NONAQUEOUS ELECTROLYTE SOLUTION CONTAINING SILYL ESTER
GROUPCONTAINING PHOSPFIONIC ACID DERIVATIVE, AND LITHIUM
SECONDARY BATTERY
Technical Field
[00011 The present invention relates to a non aqueous electrolyte solution having excellent
output characteristics; a lithium secondary battery utilizing the non aqueous electrolyte
solution; and an additive for lithium secondary batteries which is useful as an additive for
electrolyte solutions. More particularly, the present invention relates to a non aqueous
electrolyte solution which comprises, as a specific component, a phosphoric acid derivative
containing at least a silyl ester group, and a lithium secondary battery utilizing the
non=aqueous electrolyte solution.
Background Art
[0002] In recent years, the application range of lithium secondary battery (hereinafter, also
referred to as "lithiurn4on secondary battery") has been increasingly broadened not only in
portable electronic devices such as mobile telephones and laptop computers,, but also as a
large power source for electric cars and electric power storage. Particularly recently, there is
a strong demand for a battery that can be installed in hybrid cars and electronic cars and has
high capacity, high output and high energy density.
[0003] Such lithium=ion secondary battery is mainly constituted by a negative electrode
composed of lithium metal and/or a carbon material (such as graphite) having excellent
lithium absorbing and releasing properties; a positive electrode composed of a complex oxide
of lithium and a transition metal; and a non aqueous electrolyte solution.
Examples of positive electrode active material used in such positive electrode include
lithium metal oxides such as LiCoO2, LiMnO2, LiNiO2 and LiFePO4.
Furthermore, as the non aqueous electrolyte solution, for example, a solution in
which a lithium salt such as LiPF6, LiBF4, LiN(SO2CF3)2 or LiN(SO2C2F5)2 is added to a
mixed solvent of a highly dielectric cyclic carbonate, such as propylene carbonate or ethylene
carbonate, and a low viscosity chain carbonate, such as diethyl carbonate, methylethyl
carbonate or dimethyl carbonate, is generally used.
Meanwhile, as negative electrode active material used in the negative electrode,
lithium metal, metal compounds (such as elemental metals, oxides and alloys formed with
lithium) that are capable of absorbing and releasing lithium and carbon materials are known
and, in particular, lithiuin4on secondary batteries utilizing a coke, artificial graphite and/or
natural graphite, which is capable of absorbing and releasing lithium, have been put into
practical use.
[0004] In recent years, in terms of the battery performance, not only a high capacity but also
a high output are desired; therefore, there is a demand for a method of reducing the battery
resistance under a variety of conditions.
As a factor of increasing the battery resistance, film formation on the surface of the
negative electrode by a degradation product of the solvent or an inorganic salt, which is
caused by reductive decomposition reaction of the electrolyte solution, is considered. When
such reductive reaction occurs continuously, the film amount is increased and the battery
resistance is consequently increased, so that the charge discharge efficiency is decreased and
the energy which can be extracted from the battery is reduced.
[0005] Furthermore, other problems to be solved include deterioration of the battery
performance in a high^temperature environment. Deterioration of a litliiuin4on secondary
battery in a high temperature environment is caused by a variety of factors such as
degradation of lithium transition metal oxide, degradation of the electrolyte solution and
destruction of the film formed. on the negative electrode surface. Therefore, there is also a
demand for a method of inhibiting such deterioration of the battery performance in a
high^temperature environment.
[0006] In order to solve these problems, it has been attempted to improve the storage
properties and resistance of a battery by adding vinylene carbonate (SIC) to a non aqueous
electrolyte solution (see, for example, Japanese Patent Application Laid^Open (JP^A) No.
H5 13088).
Furthermore, there have been proposed techniques for allowing a non aqueous
electrolyte solution to contain a compound having phosphorus (P) as a constituent element.
Examples of such compound include chain phosphoric acid esters (see, for example, JP^A No.
2009224258, JP^A No. 2000164251 and JP^A No.I411 219711), cyclic anhydrides of
phosphoric acid (see, for example, JP^A No. 200866062), cyclic phosphonic acid esters (see,
for example, JP-ANo. 2001.351681) and phosphoric acid silyl esters (see, for example, JP-A
No. 2001 319685).
SUMMARY OF INVENTION
Technical Problem
[0007] Flowever, vinylene carbonate (VC) camumot be said to be sufficient fromi1 the viewpoint
of inhibiting an increase in the battery resistance. Fruhhef°moLe, conventional compounds
having phosphorus (P) as a constituent element also cannot be said to be sufficient how the
viewpoints of inhibiting an increase in the battery resistance, and. inhibiting deterioration of
performance in a. high temperature environment; therefore, a further improvement is required.
The present invention was made in view of the above^doscribed problems and an
object of the present invention is to provide a non aqueous electrolyte solution which can
improve the output characteristics of a battery by reducing the battery resistance, and inhibit
deterioration of performance in a high^temperature environment; a lithium secondary battery
utilizing the non=aqueous electrolyte solution;, and an additive for lithium secondary batteries
which is useful for the non aqueous electrolyte solution.
Solution to Problem
[0008] In the process of investigation carried out to solve the above described problems the
present inventors discovered that the battery resistance can be reduced and the storage
properties in a high temperature environment can be improved by an addition of a silyl ester
group containing phosphonic acid derivative, thereby completing the present invention.
That is, specific means for solving the above described problems are as follows.
[0009] <1> A non aqueous electrolyte solution, comprising a silyl ester group containing
phosphonic acid derivative.
[0010] <2> The non aqueous electrolyte solution according to <1>, wherein the silyl ester
group=containing phosphonic acid derivative is a compound represented by the following
Formula (1):
[0011]
11
[0012] wherein, in the Formula (1), in represents 0 or 1; n represents 1 or 2; in + n - 2;
R' represents
a hydrogen atom,
an alkyl group having; 1 to 12 carbon atoms,
a lialoalkyl group having 1 to 12 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which way be substituted with a halogen
atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon
atoms),
an alkenyl group having 2 to 12 carbon atoms,
an alkyl group having 1 to 6 carbon atoms, which is substituted with at least one
^SiR'8R19R20 group (wherein R18, Rig and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a haloalkyl group having 1 to 6 carbon atoms, which is substituted with at least one
^SiR18R19R20 group (wherein Rib, Rig and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a or 6^membered heterocyclic group (which may or may not be substituted), or
a group represented by any one of the following Formulae (34) to (310);
R2 represents
a hydrogen atom,
an alkyl group having 1 to 6 carbon atoms,
a haloalkyl group having 1 to 6 carbon atoms,
an alkenyl group having 2 to 6 carbon atoms, or
a phenyl group (which may be substituted with a halogen atom, an alkyl group
having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms);
R3 represents
an alkyl group having 1 to 6 carbon atoms,
an alkenyl group having 2 to 6 carbon atoms,
an alkoxy group having 1 to 6 carbon atoms,
a phenyl group,
a ^fSiR6R'R8 group (wherein R6, R7 and R$ each independently represent an alkyl
group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy
group having 1 to 6 carbon atoms or a phenyl group), or
a group in which, when n is 2, two Ras are linked with each other to form an
alkylene group having 1 to 3 carbon atoms or (wherein R16 and R' ;
independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group; and p
represents an integer of 1 to 3); and
R4 and R5 each independently represent
an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon
4
atoms, analkoxy group having 1 to 6 carbon atones, a phenyl group or a ^O^SiR6R'R$ group
(wherein R6, R7 and Rs each independently represent an alkyl group having 1 to 6 carbon
atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon
atoms or a phenyl group):
[0013]
B (e.
O EI.I O _Rb (34)
O
(3wa( )
(3"°)
O
(a)
(3F)
(31OO))
[0014] wherein, in Formulae (3 01) to (3 10), Ra represents a divalent hydrocarbon group
having 1 to 12 carbon atoms which may be substituted with a halogen atom; and Re represents
a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen
atom, or a ^SiR21R22R23 group (wherein R21, R22 and R23 each independently represent an
alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atones, are
alkoxy group having 1 to 6 carbon atoms or a phenyl group).
[0015] <3> The non=aqueous electrolyte solution according to <2>, wherein m is 0 and n is
2 in the Formula (1).
[0016] <4> The non aqueous electrolyte solution according to <3>, wherein, in the Formula
(1),
R1 is
an alkyl group having 1 to 6 carbon acorns,
5
a fluoroalkyl group having 1 to 6 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which may be substituted with a fluorine
atom, an alkyl group having 1 to "6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon
atoms),
an alkenyl group having 2 to 6 carbon atoms,
an alkyl group having 1 to 6 carbon atoms , which is substituted with one
^SiR'sR19R2° group (wherein Rib, R19 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a fluoroalkyl group having 1 to 6 carbon atoms,, which is substituted with one
SiRISR19R20 group (wherein R189 R19 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkox y group
having 1 to 6 carbon atoms or a phenyl group),
a 5^ or 6^membered heterocyclic group (wherein the heterocyclic group is a furyl
group, a thienyi group, a pyrrolyl group, an oxazolyl group , an isoxazolyl group, a thiazolyl
group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group , a triazolyl group, a
tetrazolyl group, a pyridyl group , a pyrimidinyl group , a pyrazinyl group, a pyridazinyl group
or a triazinyl group and n-lay be substituted with a fluorine atom , an alkyl group having 1 to 6
carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms), or
a group represented by any one of the Formulae ( 3-1), (3-9) and (3-10), with the
proviso that, in the Formulae (3-1), (3-9) and (3-10), Ra is an alkylene group having 1 to 6
carbon atoms, a fluoroalkylene group having 1 to 6 carbon atoms, a phenylene group (which
may be substituted with a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a
fluoroalkyl group having 1 to 6 carbon atoms) or an alkenylene group having 2 to 6 carbon
atoms, and Rb is an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6
carbon atoms, a phenyl group (which may be substituted with a fluorine atom, an alkyl group
having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms), an alkenyl
group hha.vingg 2- to 6 carbon atoms , or a -SiR21R22R23 group (wherein R21, R22 and R23 are each
independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6
carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group).
[0017] In the norm-aqueous electrolyte solution according to <3> or <4>, it is particularly
preferred that
R1 be
a methyl group, an ethyl group, a linear or branched propyl group , a linear or
branched butyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group,
6
a perfluoroethyl group,
a phenyl group (which may be substituted with a fluorine atom, a methyl group, an
ethyl group, a propyl group, a butyl group or a trifluoromethyl group),
a vinyl group, a propenyl group, an ally! group,
a methyl group which is substituted with one ^SiR18R19R2° group (wherein RI8, R'9
and R20 are each independently a methyl group, an ethyl group, a linear or branched propyl
group, a linear or branched butyl group, a vinyl group, an ally! group or a phenyl group),
a fluoromethyl group which is substituted with one ^SiR18R19R2° group (wherein R'$,
R19 and R20 are each independently a methyl group, an ethyl group, a linear or branched
propyl group, a linear or branched butyl group, a vinyl group, an alkyl group or a phenyl
group),
a difluoromethyl group which is substituted with one ^SiR'$R19R2° group (wherein
R18, R19 and R20 are each independently a methyl group, an ethyl group, a linear or branched
propyl group, a linear or branched butyl group, a vinyl group, an allyl group or a phenyl
group),
a thienyl group (which may be substituted with a fluorine atom, an alkyl group
having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms),
a pyridyl group (which may be substituted with a fluorine atom, an alkyl group
having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms), or
a group represented by any one of the Formulae (3-1), (3^9) and (310), with the
proviso that, in the Formulae (3-1), (3^9) and (31O), Ra is a methylene group, an ethylene
group, a propylene group, a butylene group, a fluoromethylene group, a difluoromethylene
group, a perfluoroethylene group or a phenylene group (which may be substituted with a
fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group or a
trifluoromethyl group), and R'' is a methyl group, an ethyl group, a propyl group, a butyl
group, a trifluoromethyl group, a perfluoroethyl group, a phenyl group (which may be
substituted with a fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group
or a fluoromethyl group), a vinyl group, a propenyl group, or a wSiR21R22R23 group (wherein
R21, R22 and R23 are each independently a methyl group, an ethyl group, a linear or branched
propyl group, a linear or branched butyl group, a vinyl group, a propenyl group, an allyl group,
a methoxy group, an ethoxy group or a phenyl group).
[0014] <5> The non aqueous electrolyte solution according to <3> or , wherein, in the
Formula (1),
RI is
an alkyl group having 1 to 6 carbon atoms,
7
a fluoroalkyl group having 1 to 6 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which may be substituted with a fluorine
atom, an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon
atoms),
an alkenyl group having 2 to 6 carbon atoms,
an alkyl group having 1 to 6 carbon atoms, which is substituted with one
=SiR18R19R20 group (wherein R'8, R'9 and R20 are each independently an alkyl group having 1
to 6 carbon atoms),
a fluoroalkyl group having 1 to 6 carbon atoms which is substituted with one
=SiR'8R'9R20 group (wherein Res, R'9 and R20 are each independently an alkyl group having 1
to 6 carbon atoms), or
a group represented by any one of the Formulae (3=1), (3=9) and (3=10), with the
proviso that, in the Formulae (3=1), (3=9) and (3=10), Ra is an alkylene group having 1 to 6
carbon atoms and R'' is an alkyl group having 1 to 6 carbon atoms or a =SiR21R22R23 group
(wherein R21, R22 and R23 are each independently an alkyl group having 1 to 6 carbon atoms);
and
R3, R4 and R5 are each independently an alkyl group having 1 to, 6 carbon atoms, an
alkenyl group having 2 to 6 carbon atoms or a phenyl group.
[0019] <6> The non aqueous electrolyte solution according to any one of <3> to <5>,
wherein the compound represented by the Formula (1) is
methylphosphonic acid bis(trimethylsilyl) ester,
methylphosphonic acid bis(tert=butyldimcthylsilyl) ester,
methylphosphonic acid bis(allyldimethylsilyl) ester,
methylphosphonic acid bis(triphenylsilyl) ester,
phenylphosphonic acid bis(trimethylsilyl) ester,
vinylphosphonic acid bis(trimethylsilyl) ester,
1=propenylphosphonic acid bis(trimethylsilyl) ester,
[difluoro(trimethylsilyl)methyl]phosphonic acid bis(trimethylsilyl) ester,
[(trimethylsilyloxy)methyl]phosphonic acid bis(trirnetlhylsilyl) ester,
[(methanesulfonyl.oxy)methyl]phosphoric acid bis(trimethylsilyl) ester,
methylenebisphosphonic acid tetrakis(trimethylsilyl) ester, or
2,4,4,6,6=pentamethyl=1,3,5=trioxa=2nphospha=4,6wdisilacyclohexane=2=oxide.
[0020] <7> The non=aqueous electrolyte solution according to any one of to <6>,
wherein the content of the silyl ester group=containing phosphonic acid derivative is 0.001%
by mass to 10% by mass.
<8> The non aqueous electrolyte solution according to any one of <1> to <7>,
further comprising a tetrafluoroborate.
<9> The non aqueous electrolyte solution according to <8>, wherein the
tetrafluoroborate is lithium tetrafluoroborate (LiBF4).
<10> The non aqueous electrolyte solution according to claim <4> or <9>, wherein
the concentration of the tetrafluoroborate is 0.0001 mol/L to 2 mol/L.
[0021] <11> An additive for lithium secondary batteries, comprising a compound
represented by the following F'orm'ula (1):
[0022]
n
[0023] wherein, in the F'ormula(1), m represents 0 or 1; n represents 1 or 2; m + n = 2;
Rl represents
a hydrogen atom,
an alkyl group having 1 to 12 carbon atoms,
a haloalkyl group having 1 to 12 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which may be substituted with a halogen
atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon
atoms),
an alkenyl group having 2 to 12 carbon atoms,
an alkyl group having 1 to 6 carbon atoms, which is substituted with at least one
^SiRi8Ri9R2° group (wherein R18, R19 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a haloalkyl group having 1 to 6 carbon atoms, which is substituted with at least one
^SiR1IIB19R20 group (wherein R189 R'9 and R2° each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy grroup
having 1 to 6 carbon atoms or a phenyl group),
a5 u or 6 membered heterocyclic group (which may or may not be substituted), or
9
a group represented by any one of the following Formulae (3-1) to (3-10);
R2 represents
a hydrogen atom,
an alkyl group having 1 to 6 carbon atoms,
a haloalkyl group having 1 to 6 carbon atoms,
an alkenyl group having 2 to 6 carbon atoms, or
a phenyl group (which may be substituted with a halogen atom, an alkyl group
having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms);
R3 represents
an alkyl group having 1 to 6 carbon atoms,
an alkenyl group having 2 to 6 carbon atoms,
an alkoxy group having 1 to 6 carbon atoms,
a phenyl group,
a -O-SiR6R'R3 group (wherein R6, R7 and R8 each independently represent an alkyl
group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy
group having 1 to 6 carbon atoms or a phenyl group), or
a group in which, when n is 2, two Ras are linked with each other to form -0-, an
alkylene group having 1 to 3 carbon atoms or -O-(SiR16R1 O)p^ (wherein R.16 and R"
independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group; and p
represents an integer of 1 to 3); and
R4 and R5 each independently represent
an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon
atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a -O-SiR6R7R8 group
(wherein R6, R7 and R8 each independently represent an alkyl group having 1 to 6 carbon
atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon
atoms or a phenyl group):
[0024]
10
-R,b (3-1) , (, ....Nb p
0
11
0
(1)1
0I
0
(3-7)
(3---)
(3-)
(3- 10)
[0025] wherein, in Formulae (3-1) to (3-10), Ra represents a divalent hydrocarbon group
having I to 12 carbon atoms which may be substituted with a halogen atom; and Rb represents
a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen
atom, or a'-SiR21R22 R23 group (wherein R21, R22 and R23 each independently represent an
alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms or a phenyl group).
[0026] <12> A lithium secondary battery, comprising:
a positive electrode;
a negative electrode containing, as a negative electrode active material, at least one
selected from lithium metal, lithium-containing alloys, metals or alloys that are capable of
forming an alloy with lithium, oxides capable of doping/dedoping lithium ions, transition
metal nitrides capable of doping/dedoping lithium ions and carbon materials capable of
doping/dedoping lithium ions; and
the non-aqueous electrolyte solution according to any one of <1> to <10>.
[0027] <13> A lithium secondary battery, which is obtained by charging/discharging a
lithium secondary battery comprising:
a positive electrode;
1"1
a negative electrode containing, as a negative electrode active material, at least one
selected from lithium metal, lithium-containing alloys, metals or alloys that are capable of
forming an alloy with lithium, oxides capable of doping/dedoping lithium ions, transition
metal nitrides capable of doping/dedoping lithium ions and carbon materials capable of
doping/dedoping lithium ions; and
the non-aqueous electrolyte solution according to any one of <1> to <10>.
Advantageous Effects of Invention
[0028] According to the present invention, a non-aqueous electrolyte solution which can
improve the output characteristics of a battery by reducing the battery resistance, and inhibit
deterioration of performance in a high temperature environment; a lithium secondary battery
utilizing the non-aqueous electrolyte solution; and an additive for lithium secondary batteries
which is useful for the non-aqueous electrolyte solution can be provided.
BRIEF DESCRIPTION OF DRAWINGS
[0029] Fig. I is a schematic cross-sectional view of a coin-type battery showing one
example of the lithium secondary battery according to the present invention.
DESCRIPTION OF EMBODIMENTS
[0030] Hereinafter, the non-aqueous electrolyte solution, the lithium secondary battery and
the additive for lithium secondary batteries according to the present invention will be
described in detail.
[0031]
The non-aqueous electrolyte solution of the present invention contains a silyl ester
group-containing phosphoric acid derivative as an additive.
When used as a non-aqueous electrolyte solution of a battery (for example, a lithium
secondary battery), the non-aqueous electrolyte solution of the present invention reduces the
battery resistance and improves the storage properties of the battery in a high temperature
environment. Therefore, by using the non-aqueous electrolyte solution of the present
invention, an extended battery service life can be realized.
[0032] (Silyl ester group-containing phosphonic acid derivative)
The phosphonic acid derivative containing a silyl ester group in the present invention
(hereinafter, also referred to as "silyl ester group-containing phosphonic acid derivative") is
not particularly restricted; however, from the viewpoint of attaining the effects of the present
invention more effectively (particularly, from the viewpoint of further improving the battery
12
storage properties in a high-ternperature environment), the silyl ester group-containing
phosphonic acid derivative is preferably a compound represented by the following Formula
M.
[0033]
I
[0034] lit the Formula (1), m_ represents 0 to 1, n represents 1 or 2, and m + n = 2;
R1 represents a hydrogen atom or a monovalent organic group having I to 36 carbon
atoms.
R2 represents a hydrogen atom , an alkyl group having 1 to 6 carbon atoms, a
haloalkyl group having I to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or a
phenyl group (which may be substituted with a halogen atom , an alkyl group having 1 to 6
carbon atoms or a haloalkyl group having I to 6 carbon atoms).
R3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms., a phenyl group, a
-O-SiR6R7R$ group (wherein R6, R7 and R8 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group ) or a group in which, when n is 2, two Ras are
linked with each other to form aO-, an alkylene group having 1 to 3 carbon atoms or
-0-(SiR16R" O)1,- (wherein R16 and R17 independently represent an alkyl group having 1 to 6
carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6
carbon atoms or a phenyl group; and p represents an integer of I to 3).
That is, when the above-described n is 2, ( 1) two Ras may each independently be an
alkyl group having I to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an
alkoxy group having I to 6 carbon atoms, a phenyl group or the above-described -O-SiR6R7R8
group , or (2) two Ras may be linked with each other to become -Oa, an alkylene group having
I to 3 carbon atoms or the above-described -.O (SiR16R17. O),,-, thereby forming a ring
containing a P atom, an 0 atom and a Si atom.
RI and R' each independently represent an alkyl group having I to 6 carbon atoms,
13
an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a
phenyl group or a -O-SiR6R7R8 group (wherein R6, R7 and R8 each independently represent an
alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms or a phenyl group).
[0035] Among the compounds represented by the Formula (1), a compound in which n is 2
and "two Ras are linked with each other to form -0-, an alkylene group having I to 3 carbon
atoms or -O-(SiR16R1 0)1_ (wherein R16 and R'' independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group; and p represents an integer of 1 to 3)" is
represented by the following Formula (2).
[0036]
[0037] In the Formula (2),
R1 has the same definitions as R1 in the Formula (1);
R9 R10 R11 and R12 each independently represent
an alkyl group having 1 to 6 carbon atoms,
an alkenyl group having 2 to 6 carbon atoms,
an alkoxy group having 1 to 6 carbon atoms,
a phenyl group, or
a -O-SiR13R14R1' group (wherein R13, R' 4 and R15 each independently represent an
alkyl group having I to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms or a phenyl group); and
X represents
an oxygen atom,
an alkylene group having 1 to 3 carbon atoms, or
a -0-(SiR_16 R1 7_0)j, _ group (wherein R16 and RI i each independently represent am
alkyl group having 1 to 6 carbon atoms, an alkenyl group having ). to 6 carbon atoms, an
1
alkoxy group having 1 to 6 carbon atoms or a phenyl group; and p represents an integer of 1
to 3).
[0038] In R1 of the Formula (1) (including the case of the Formula (2); the same applies
hereinafter), as the "monovalent organic group having 1 to 36 carbon atoms", a group having
C, 14, 0, N, P, 5, Si and a halogen element as constituent elements is preferred.
The above-described R1 is more preferably
a hydrogen atom,
an alkyl group having 1 to 12 carbon atoms,
a haloalkyl group having 1 to 12 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which may be substituted with a halogen
atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon
atoms),
an alkenyl group having 2 to 12 carbon atoms,
an alkyl group having 1 to 6 carbon atoms, which is substituted with at least one
siR18R19R20 group (wherein R13, R'9 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a haloalkyl group having 1 to 6 carbon atoms, which is substituted with at least one
-SiR18R19820 group (wherein R18, R19 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a 5 or 6-membered heterocyclic group (which may or may not be substituted), or
a group represented by any one of the later-described Formula (3-1) to (3 10).
[0039] In R1 of the Formula (1), examples of the "an alkyl group having 1 to 12 carbon
atoms" include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
isobutyl group, sec butyl group, tent-butyl group, pentyl group, 2dmethylbutyl group,
1-methylpentyl group, neopentyl group, 1-ethylpropyl group, hexyl group, 3,3-dimethylbutyl
group, heptyl group, octyl group, nonyl group, undecanyl group and dodecanyl group.
[0040] In R1 of the Formula (1), examples of the "haloalkyl group having 1 to 12 carbon
atoms" include fluoromethyl group, difluoromethyl group, trifluoromethyl group,
2,2,2-trifluoroethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group,
perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group,
perfluorononyl group, perfluorodecyl group, perfluoroundecanyl group, perfluorododecanyl
group, perfluoroisopropyl group, perfluoroisobutyl group, chlorornethyl group, chloroethyl
group, claloropropyl group, bromnomethyl group, bromoethyl group, bromopropyl group,
1
iodomethyi group, iodoethyl group and iodopropyl group.
[0041] In R' of the Formula (1), examples of the "aryl group having 6 to 14 carbon atoms
(which may be substituted with ahalogen atomn, an alkyl group having 1 to 6 carbon atoms or
a haloalkyl group having 1 to 6 carbon atoms)" include phenyl group, methylphenyl group,
dimethylphenyl group, trimethylphenyl group, tetramethylphenyl group, ethylphenyl group,
nvpropylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group,
sec-butylphenyl group, tent-butylphenyl group, pentylphenyl group, hexylphenyl group,
fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group,
pentafluorophenyl group, chlorophenyl group, bromophenyl group, naphthyl group,
nlethylnaphthyl group, ethylnaphthyl group and anthryl group.
[0042] In R' of the Formula (1), examples of the "alkenyl group having 2 to 12 carbon
atoms" include vinyl group, 1-propenyl group, allyl group, butenyl group, butene-.3 dyl group,
pentenyl group, pentene-4-yl group, hexenyl group, hexene-5 yl group, heptenyl group,
octenyl group, nonenyl group, decenyl group, undecenyl group and dodecenyl group.
10043] In R' of the Formula (1), examples of the "alkyl group having 1 to 6 carbon atoms,
which is substituted with at least one -SiR18R19R20 group (wherein R's, R19 and R20 each
independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group)" or the
"haloalkyl group having 1 to 6 carbon atoms, which is substituted with at least one
-SiR18R19R2O group (wherein R18, R19 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group)" include (trimethylsilyl)methyl group,
(triethylsilyl)Inethyl group, ((ri-n-propylsilyl)methyl group, (triisopropylsilyl)rnethyl group,
(tri-n-butylsilyl)rnethyl group, (triisobutylsilyl)methyl group, (tri-sec-butylsilyl)methyl group,
(tri-tert-butylsilyl)methyl group, (tripentylsilyl)mnethyl group, (trihexylsilyl)methyl group,
(triphenylsilyl)methyl group, (tertbutyldimethylsilyl)methyl group,
(dimethylphenylsilyl)methyl group, (methyldiphenylsilyl)methyl group,
(ethyldirnethylsilyl)mnethyl group, (dimethylpropylsilyl)methyl group,
(tert-butyldimethylsilyl)methyl group, (hexyl(timethylsilyl)methyl group,
(dimethylphenylsilyl)methyl group, (methyldiphenylsilyl)methyl group,
(dimnethylvinylsilyl)rnethyl group, (allyldimethylsilyl)rnethyl group,
(dinnethyh 1 propenylsilyl)methyl group, (butenyldinmethylsilyl)mnethyl group,
((Iirriethylpentenylsilyl)methyl group, (hexenyldirnethylsilyl)methyl group,
(rnethoxydimnethylsilyl)mnethyl group, (ethoxydimethylsilyl)met:hyl group,
(butoxydimnethylsilyl)rrmethyl group, (dimethylphenoxysilyl)mnethyl group,
16
(diethoxynm.ethylsilyl)methyl group, (methyldiphenoxysilyl)methyl group,
(trimethylsilyl)fluoromethyl group, (trimethylsilyl)difluoromethyl group,
(trimethylsilyl)chlorornethyl group, (trimethylsilyl)dichloromethyl group,
(trimethylsilyl)bromomethyl group, (trimethylsilyl)dibromomethyl group,
(trimethylsilyl)perfluoroethyl group, (trimethylsilyl)perfluoropropyl group,
(trimethylsilyl)perfluorobutyl group, (trimethylsilyl)perfluoropentyl group,
(trimethylsilyl)perfluorohexyl group, (triphenylsil),l)difluoromethyl group and
(trimethoxysilyl)difluoromethyl group.
[0044] In R' of the Formula (1), examples of the "Sm or 6-membered heterocyclic group
(which may or may not be substituted)" include heterocyclic groups containing an oxygen
atom, a nitrogen atom and a sulfur atom as constituent elements. Specific examples thereof
include furyl group, thienyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl
group, isothiazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group,
pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group and triazinyl group.
[00/15] Furthermore, it is also preferred that R1 in the Formula (1) be a group represented by
any one of the following Formulae (3=1) to (3=10).
[0046]
l a C ,lib
0
-p 0
_:b
:a
4)
3)
`1 )
17
[0047] In the Formulae (3-1) to (3x10), R" represents a divalent hydrocarbon group having 1
to 12 carbon atoms which may be substituted with a halogen atorn. Rb represents a
hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen
atom, or a =S1R21R22R23 group (wherein R21, R22 and R23 each independently represent an
alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms or a phenyl group).
[0048] In R' of the Formulae (3=1) to (3=10), examples of the "divalent hydrocarbon group
having 1 to 12 carbon atoms which may be substituted with a halogen atom" include alkylene
groups having 1 to 12 carbon atoms, haloalkylene groups having 1 to 12 carbon atoms,
alkenylene groups having I to 12 carbon atoms and phenylene groups (which may be
substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl.
group having 1 to 6 carbon atoms).
More specific examples include methylene group, ethylene group, propylene group,
butylene group, pentylene group, 2-methylbutylene group, 1-methylpentylene group,
aeopentylenie group, 1=ethylpropylene group, hexylene group, 3,3-dimethylbutylene group,
heptylene group, octylene group, nonylene group, undecanylene group, dodecanylene group,
fluoromethylene group, difluoromethylene group, fluoroethylene group, 112-difluoroethylene
group, trifluoroethylene group, perfluoroethylene group, perfluoropropylene group,
perfluorobutylene group, perfluoropentylene group, perfluorohexylene group,
perfluoroheptylene group, perfluorooctylene group, perfluorononylene group,
perfluorodecylene group, perfluoroundecanylene group, perfluorododecanylene group,
perfluoroisopropylene group, perfluoroisobutylene group, chloromethylene group,
chloroethylene group, chloropropylene group, bromomethylene group, bromoethylene group,
bromopropylene group, iodomethylene group, iodoethylene group, iodopropylene group,
vinylene group, l=propenylene group, allylene group, butenylene group, butene-=3-ylene group,
pentenylene group, pentene-4-ylene group, hexenylene group, hexene=5=ylene group,
heptenylene group, octenylene group, nonenylene group, decenylene group, undecenylene
group, dodecenylene group, phenylene group, methylphenylene group, ethylphenylene group,
propylphenylene group, butylphenylene group, hexylphenylene group, fluorophenylene group,
chlorophenylene group, bromophenylene group, iodophenylene group,
(fluoromethyl)phenylerre group, (difluoromethyl)phenylene group and
(trifluoromethyl)phenylene group.
[0049] in Rb of the Formulae (3=1) to (3=10), examples of the "hydrocarbon group having 1
to 12 carbon atoms which may be substituted with a halogen atom" include alkyl groups
having 1 to 12 carbon atoms, haloalkyl groups having 1 to 12 carbon acorns alkenyl groups
18
having 1 to 12 carbon atoms and phenyl groups (which may be substituted with a halogen
atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having I to 6 carbon
atoms).
More specific examples include methyl group, ethyl group, n-propyl group, isopropyl
group, n-butyl group, isobutyl group, sec-butyl group, tent-butyl group, pentyl group,
2-methylbutyl group, 1 -methylpentyl group, neopentyl group, 1 -ethylpropyl group, hexyl
group, 3,3-dimethylbutyl group, heptyl group, octyl group, nonyl group, undecanyl group,
dodecanyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group,
2,2,2-trifluoroethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group,
perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group,
perfluorononyl group, perfluorodecyl group, perfluoroundecanyl group, perfluorododecanyl
group, perfluoroisopropyl group, perfluoroisobutyl group, chloromethyl group, chloroethyl
group, chloropropyl group, bromomethyl group, bromoethylgroup, bromopropyl group,
iodomethyl group, iodoethyl group, iodopropyl group, vinyl group, 1 -propenyl group, alkyl
group, butenyl group, butene-3-y1 group, pentenyl group, pentene-4 yl group, hexenyl group,
hexene=5=yl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl
group, dodecenyl group, phenyl group, nzethylphenyl group, dirnethylphenyl group,
trimethylphenyl group, tetrarnethylphenyl group, ethylphenyl group, n-propylphenyl group,
isopropylphenyl group, butylphenyl group, isobutylphenyl group, sec-butylphenyl group,
tent-butylphenyl group, pentylphenyl group, hexylphenyl group, fluorophenyl group,
difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl
group, chlorophenyl group and bronlophenyl group.
[0050] In Rb of the formulae (3-1) to (3-10), examples of the "-SiR.21R22R23 group (wherein
R21, R22 and R23 each independently represent an alkyl group having 1 to 6 carbon atoms, an
alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a
phenyl group)" include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group,
triisopropylsilyl group, tri n-butylsilyl group, triisobutylsilyl group, tri-sec-butylsilyl group,
tri-tert-butylsilyl group, tripentylsilyl group, trihexylsilyl group, triphenylsilyl group,
ethyldimethylsilyl group, dimethylpropylsilyl group, tent-butyldimethylsilyl group,
hexyldimethylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group,
dimethylvinylsilyl group, allyldirnethylsilyl group, dimethylw 1 apropenylsilyl group,
butenyldimethylsilyl group, dimethylpentenylsilyl group, hexenyldimethylsilyl group,
rnetthoxydirrlethylsilyl group, ethoxydimethylsilyl group, butoxydimethylsilyl group,
dimethylphenoxysilyl group, diethoxymethylsilyl group and rnethyldiphenoxysilyl group.
[0051] In I22 of the Formula (1), examples of the "alkyl group having 1 to 6 carbon atoms"
19
include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl
group, sec-butyl group, tert-butyl group, phenyl group, 2-methylbutyl group, 1-methylpentyl
group, neopentyl group, 1-ethylpropyl group, hexyl group and 3,3-dimethylbutyl group.
[0052] In R2 of the Formula (1), examples of the "haloalkyl group having 1 to 6 carbon
atoms" include fluoromethyl group, difluoromethyl group, trifluoromethyl group,
2,2,2-trifluoroethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group,
perfluoropentyl group, perfluorohexyl group, perfluoroisopropyl group, perfluoroisobutyl
group, chloromethyl group, chloroethyl group, chloropropyl group, bronrornethyl group,
bromoethyl group, bromopropyl group, iodomethyl group, iodoethyl group and iodopropyl
group.
[0053] In R2 of the Formula (1), examples of the "alkenyl group having 2 to 6 carbon atoms"
include vinyl group, I-propenyl group, allyl group, butenyl group, butene-3-yl group,
pentenyl group, pentene-4-yl group, hexenyl group and hexene-5-y1 group.
[0054] In R2 of the Formula (1), examples of the "phenyl group (which may be substituted
with a halogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1
to 6 carbon atoms)" include phenyl group, methylphenyl group, dimethylphenyl group,
trimethylphenyl group, tetramethylphenyl group, pentamethylphenyl group, ethylphenyl
group, n-propylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl
group, sec-butylphenyl group, tent-butylphenyl group, pentylphenyl group, hexylphenyl group,
fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group,
pentafluorophenyl group, chlorophenyl group, bromophenyl group,
(monofluoromethyl)phenyl group, (difluoromethyl)phenyl group and (trifluoromethyl)phenyl
group.
[0055] In R3, R4 and R5 of the Formula (1), examples of the "alkyl group having I to 6
carbon atoms" include methyl group, ethyl group, n-propyl group, isopropyl group, nabutyl
group, isobutyl group, sec-butyl group, tert-butyl group, phenyl group, 2-methylbutyl group,
1 -methylpentyl group, neopentyl group, 1 -ethylpropyl group, hexyl group and
3,3-dimethylbutyl group.
[0056] In R3, R4 and R5 of the Formula (1), examples of the "allcenyl group having 2 to 6
carbon atoms" include vinyl group, 1 -propenyl group, allyl group, butenyl group, butene-3 -yl
group, pentenyl group, pentene-4 -yl group, hexenyl group and hexene-.5-yl group.
[005'!] In R3, R4 and R5 of the Formula (1), examples of the "alkoxy group having 1 to 6
carbon atoms" include niethoxy group, ethoxy group, propyloxy group, isopropyloxy group,
butyloxy group, isobutyloxy group, sec-butyloxy group, tertt-butyloxy group, pentyloxy group,
2crnethylbutyloxy group, 1 mrriethylpentyloxy group, neopentyloxy group,
20
3,3-dimethylbutyloxy group and hexyloxy group.
[0058] In R3, R4 and R5 of the Formula (1), examples of the "-®t siR6R7R8 group (wherein
R6, R7 and R8 each independently represent an alkyl group having 1 to 6 carbon atoms, an
alkenyl group having 2 to 6 carbon atoms, an alkoxy group having I to 6 carbon atoms or a
phenyl group)" include trirnethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy
group, triisopropylsilyloxy group, tri-n-butylsilyloxy group, triisobutylsilyloxy group,
tri-sec-butylsilyloxy group, tri-tert-butylsilyloxy group, tripentylsilyloxy group,
trihexylsilyloxy group, triphenylsilyloxy group, ethyldimethylsilyloxy group,
dimethylpropylsilyloxy group, tert-butyldimethylsilyloxy group, hexyldimethylsilyloxy group,
dimethylphenylsilyloxy group, methyldiphenylsilyloxy group, dimethylvinylsilyloxy group,
allyldimethylsilyloxy group, dimethylh 1 -propenylsilyloxy group, butenyldimethylsilyloxy
group, dimethylpentenylsilyloxy group, hexenyldimethylsilyloxy group,
methoxydimethylsilyloxy group, ethoxydimethylsilyloxy group, butoxydimethylsilyloxy
group, dimethylphenoxysilyloxy group, diethoxymethylsilyloxy group and
nmethyldiphenoxysilyloxy group.
[0059] As form and n in the Formula (1), there are two types of combinations, which are a
combination where m is 0 and n is 2 (hereinafter, also indicated as "") and a
combination where m is 1 and n is 1 (hereinafter, also indicated as "").
[0060] In R9, Rio R'' and R12 of the Formula (2), examples of "an alkyl group having 1 to 6
carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6
carbon atoms, a phenyl group or a -O SiR13R14R15 group (wherein R13, R14 and R15 each
independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group)" include
the same substituents as those exemplified for R3, R4 and R5 of the Formula (1).
[0061] In X of the Formula (2), examples of the "alkylene group having 1 to 3 carbon
atoms" include methylene group, ethylene group, propylene group and 1 =methylethylene
group.
[0062] In X of the Formula (2), examples of R16 and R17 in the "-O (SiR16R'7 O)1,- group
(wherein R16 and R' 7 each independently represent an alkyl group having 1 to 6 carbon atoms,
an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a
phenyl group; and p represents an integer of 1 to 3)" include methyl group, ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec butyl group, tert-butyl
group, pentyl group, 2-methylbutyl group, 1=methylpentyl group, neopentyl group,
l-ethylpropyl group, hexyl group, 3,3-dhnethylbutyl group, rnethoxy group, ethoxy group,
propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, sec'butyloxy group,
21
test-butyloxy group, pentyloxy group, 2-methylbutyloxy group, 1-mothylpentyloxy group,
neopentyloxy group, 3,3-dimethylbutyloxy group, hexyloxy group and phenyl group.
Specific examples of X are not particularly restricted; however, they include the
following Formulae (X.1) to (X-26).
[0063]
22
GH3 C,2H5
Si 1-1
P -) Si o , N,
I I
C:H3 C
(X.-1) (X°2)
G,;1 iy (-4H9
0 ^„O.. 1. C
1
G311
(X-3)
(X)
c5H91 ^G 13
0"' 1 Ca 011 1 0
GSHt1
) (X.°0)
G21-15 G^I15
(X- 10) (X-11) (X-12)
G{13 GH3
0" 1 0,n ^ . cMa
G,1-19
(X-8)
(Xr4)
C'1 A, C 2H5
I I]
(X-13)
(X-.19)
(X-23)
Ocat-J,, OC;H3 0CH3 0GH3 OC,I-I3
(X.,1'4,) (X-15
2
(X-,2,0)
-(X
O -O", o E ,,^O,, , O.,, (. "C
(X... 1 6) (X--1 7) (X-18)
CH, I I GHb
I o a - ,...,v. I . 0
81,
G21'5 1 1 Gs1μ15
I
(X.-?1) (X-22)
(X-2) (X-26)
[0064] Preferred scope of R' in the Formulae (1) and (2) will now be described from the
viewpoints of enabling to attain an improvement in the battery output characteristics by
reducing, the battery resistance, and inhibiting deterioration of performance in a
high=temperature enviroluaerit.
[0065] As described in the above, an example of R' is "an alkyl group having 1 to 12 carbon
atoms"; however, R' is more preferably an alkyl group having 1 to 6 carbon atoms,
particularly preferably a methyl group, an ethyl group, a linear or branched propyl group, or a
linear or branched butyl group.
[0066] Furthermore, as described in the above, an example of R' is "a haloalkyl group
having 1 to 12 carbon atoms "; however, R' is more preferably a fluoroalkyl group having 1 to
6 carbon atoms, particularly preferably a fluoromethyl group, a difluoromethyl group, a
trifluoromethyl group or a perfluoroethyl group.
[0067] Furthermore, as described in the above, an example of R' is "an aryl group having 6
to 14 carbon atoms (which may be substituted with a halogen atom, an alkyl group having 1
to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms)"; however, R' is more
preferably an aryl group having 6 to 14 carbon atoms (which may be substituted with a
fluorine atom, an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6
carbon atoms), particularly preferably a phenyl group (which may be substituted with a
fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group or a
trifluoromethyl group).
[0068] Furthermore, as described in the above, an example of R' is "an alkenyl group having
2 to 12 carbon atoms"; however, R' is preferably an alkenyl group having 2 to 6 carbon atoms,
more preferably a vinyl group, propenyl group or an alkyl group.
[0069] Furthermore, as described in the above, examples of R' include "an alkyl group
having 1 to 6 carbon atoms, which is substituted with at least one °SiR18R19R20 group
(wherein R18, R19 and R20 each independently represent an alkyl group having 1 to 6 carbon
atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having I to 6 carbon
atoms or a phenyl group)" and "a haloalkyl group having 1 to 6 carbon atoms, which is
substituted with at least one -SiR18R19R20 group (wherein R18, R'9 and R20 each independently
represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon
atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group)".
However, R' is more preferably "an alkyl group having 1 to 6 carbon atoms, which is
substituted with one -SiR18R19R20 group (wherein R'8, R'9 and R20 each independently
represent a methyl group, an ethyl group, a linear or branched propyl group, a linear or
branched butyl group, a vinyl group, an allyl group, a methoxy group, an ethoxy group, a
phenoxy group or a phenyl group)" or "a fluoroalkyl group having 1 to 6 carbon atoms, which
is substituted with one •SiR18R19R20 group (wherein R'8, R'9 and R20 each independently
represent a methyl group, an ethyl group, a linear or branched propyl group, a linear or
branched butyl group, a vinyl group, an allyl group, a netthoxy group, an ethoxy group, a
24
phenoxy group or a phenyl group)".
R1 is particularly preferably "a methyl group which is substituted with one
SiR13R19R20 group (wherein R", R'9 and R20 each independently represent a methyl group,
an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a vinyl
group, an allyl group or a phenyl group)", "a fluoromethyl group which is substituted with one
-SiR18R19R20 group (wherein R18, R19 and R20 each independently represent a methyl group,
an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a vinyl
group, an allyl group or a phenyl group)" or "a difluoromethyl group which is substituted with
one -SiR1IIR19R20 group (wherein R18, R19 and R20 each independently represent a methyl
group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a
vinyl group, an allyl group or a phenyl group)".
[0070] Furthermore, as described in the above, an example of R1 is "a 5 or 6-membered
heterocyclic group (which may or may not be substituted) ; however, R1 is more preferably "a
5- or 6-membered heterocyclic group (wherein the heterocyclic group is a furyl group, a
thienyl group, a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an
isothiazolyl group, an imidazolyl group, a pyrazolyl group, a thazolyl group, a tetrazolyl
group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group or a
triazinyl group and may be substituted with a fluorine atom, an alkyl group having 1 to 6
carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms)", particularly preferably "a
thienyl group (which may be substituted with a fluorine atom, an alkyl group having 1 to 6
carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms) or a pyridyl group (which
may be substituted with a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a
fluoroalkyl group having 1 to 6 carbon atoms)".
[0071] Furthermore, as described in the above, an example of R1 is "a group represented by
any one of the Formulae (3-1) to (3-10)" and R in the Formulae (3-1) to (3-10) is "a divalent
hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen
atom".
R" is preferably an alkylene group having 1 to 6 carbon atoms, a . fluoroalkylene
group having 1 to 6 carbon atoms, a phenylene group (which may be substituted with a
fluorine atom, an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6
carbon atoms) or an alkenylene group having 2 to 6 carbon atoms . R" is more preferably a
methylene group, an ethylene group, a propylene group, a butylene group, a fluoromethylene
group, a difluorornethylene group, a perfluoroethylene group or a phenylene group (which
may be substituted with a fluorine atom , a methyl group, an ethyl group, a propyl group, a
butyl group or a trifluoro _rnethyl group).
[0072] Furthermore, as described in the above, an example of R1 is "a group represented by
any one of the Formulae (3-1) to (3-10)" and Rb in the Formulae (3-1) to (3-10) is "a
hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen
atom or a -SiR21R22R23 group (wherein R21, R22 and R23 each independently represent an alkyl
group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy
group having 1 to 6 carbon atoms or a phenyl group)".
Rb is preferably an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group
having 1 to 6 carbon atoms, a phenyl group (which may be substituted with a fluorine atom,
an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms),
an alkenyl group having 2 to 6 carbon atoms or a -SiR21R22R23 group (wherein R21, R22 and
R23 are each independently an alkyl group having I to 6 carbon atoms, an alkenyl group
having 2 to 6 carbon atoms, an alkoxy group having I to 6 carbon atoms or a phenyl group).
Rh is more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a
trifluoromethyl group, a perfluoroethyl group, a phenyl group (which may be substituted with
a fluorine uiomn, a methyl group, an ethyl group, a propyl group, a butyl group or a
trifluoromethyl group), a vinyl group, a propenyl group or a -SiR21R22R23 group (wherein R2 ,
R22 and R23 are each independently a methyl group, an ethyl group, a linear or branched
propyl group, a linear or branched butyl group, a vinyl group, a propenyl group, an allyl group,
a methoxy group, an ethoxy group or a phenyl group).
[0073] As for m and n in the Formula (1), as described in the above, there are two types of
combinations, and ; however, the combination of is more preferred.
[0074] Preferred combinations of m, n, R1 and R3 to R5 in the Formula (1) will glow be
described from the viewpoints of enabling to attain an improvement in the battery output
characteristics by reducing the battery resistance, and inhibiting deterioration of performance
in a high-temperature environment.
[0075] Examples of preferred combinations in the Formula (1) include those in which
in is 0; n is 2;
R1 is
an alkyl group having 1 to 6 carbon atoms,
a fluoroalkyl group having 1 to 6 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which may be substituted with a fluorine
atom, an alkyl group having I to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon
atoms),
an alkenyl group having 2 to 6 carbon atomns,
26
an alkyl group having 1 to 6 carbon atoms, which is substituted with one
-,SiR18R19R20 group (wherein R18, R19 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a fluoroalkyl group having 1 to 6 carbon atoms, which is substituted with one
°SiR18R19R20 group (wherein R18, R'9 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a 5- or 6-membered heterocyclic group (wherein the heterocyclic group is a furyl
group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl
group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a
tetrazolyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group
or a triazinyl group and may be substituted with a fluorine atom, an alkyl group having 1 to 6
carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms), or
a group represented by any one of the Formulae (3=1), (3=9) and (3--10), with the
proviso that, in the Formulae (3=1), (3=9) and (3=10), Ra is an alkylene group having 1 to 6
carbon atoms, a fluoroalkylene group having 1 to 6 carbon atoms, a phenylene group (which
may be substituted with a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a
fluoroalkyl group having 1 to 6 carbon atoms) or an alkenylene group having 2 to 6 carbon
atoms, and R' is an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6
carbon atoms, a phenyl group (which may be substituted with a fluorine atom, an alkyl group
having 1 to 6 carbon atoms or a fluoroalkyl group having I to 6 carbon atoms), an alkenyl
group having 2 to 6 carbon atoms or a °SiR21R22B23 group (wherein R21, R22 and F23 are each
independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6
carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group); and
R3 to R5 have the same definitions as described in the above.
[0076] Among the above=described combinations, a particularly preferred combination is
one in which
m is 0; n is 2;
RI is
an alkyl group having 1 to 6 carbon atoms,
a fluoroalkyl group having 1 to 6 carbon atoms,
an aryl group having 6 to 1 /1, carbon atoms (which may be substituted with a fluorine
atom, an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon
atoms),
7
an alkenyl group having 2 to 6 carbon atoms,
an alkyl group having 1 to 6 carbon atoms, which is substituted with one
-SiR18R19R20 group (wherein R'8, R'9 and R20 are each independently an alkyl group having 1
to 6 carbon atoms),
a fluoroalkyl group having 1 to 6 carbon atoms, which is substituted with one
SiR'3R'9R20 group (wherein R18, R19 and R20 are each independently an alkyl group having I
to 6 carbon atoms), or
a group represented by any one of the Formulae (3=1), (3-9) and (3=10), with the
proviso that, in the Formulae (3=1), (3-9) and (3-10), Ra is an alkylene group having 1 to 6
carbon atoms, and Rb is an alkyl group having 1 to 6 carbon atoms or a -SiR21R22R23 group
(wherein R21, R22 and R23 are each independently an alkyl group having 1 to 6 carbon atoms);
and
R3, R4 and R5 are each independently an alkyl group having 1 to 6 carbon atoms, an
alkenyl group having 2 to 6 carbon atoms or a phenyl group.
[0077] Specific examples of the compound represented by the Formula (1) will now be
provided; however, the present invention is not restricted thereto
The following examples are shown by the combination of in and n.
The following Formula (1 a) represents a compound having a combination of in the Formula (1) and Compound Nos. Ito 143 (hereinafter, also referred to as
"Example Compounds 1 to 143", respectively) are specific examples thereof.
The following Formula (I b) represents a compound having a combination of in the Formula (1) and Compound Nos, 144 to 169 (hereinafter, also referred to as
"Example Compounds 144 to 1613", respectively) are specific examples thereof.
It is noted here that, in the Compound Nos. 1 to 168 (Example Compounds Ito 168),
"Me", "Et", "t-Bull, "Ph", "Vinyl" and "Allyl" represent a methyl group, an ethyl group, a
teat-butyl group, a phenyl group, a vinyl group and an alkyl group, respectively.
Furthermore, in the column of R', "(3-1)" to "(3-10)" represents the Formulae (3-1)
to (3=10), respectively. The columns of Ra and R'' represent Ra and Rb in the Formulae (3-1)
to (3=10), respectively.
[0078]
28
0
P11 -(O-R2
3,,- \ _.
R
0
R3
1 11
),2
\ R15
Compound
No. R a R b R 3 R 4 R R
I
2
H
Me -
Me
Me
Me
Me
Me
Me
3 Me Me Me t-Bu
4 Me Me Me Vinyl
5 Me -® -- I Me Me ] Allyl
6
7
Me
Me
Me
Me
Me
Ph
Ph
Ph
3
-9 - ^
Me
Et
- - 1 ^
Ph
- Me
Ph
Me
Ph
Me
10 (
11
Et
CH3CH2CH2
--
--
--- Ph
Me
Ph
Me
Ph
Me
12 l Bu Me Me Me
13 CH2F Me Me Me
14
15
16
CHF2
CF3
CBrF2
---
°
Me
Me
Me
Me
Me ^
Me
Me
_-Me
Me
17
18
19
CF3CH2
Ch3CF2
Ph
Me
Me
Me
Me
Me
Me
Mc
Me
Me
20
21
Ph
Ph
_- r Me
Me
Me
Me
Vinyl
Allyl
22
23
24
Ph
Ph
(4 F)Ph
-- Me
Ph
Me
Me
Ph
Me
Ph
Ph
Me
25 (4--CI)Ph --
-
Me
M
Me
M
t Me
26 Me
27
(4-Me)Ph
(4-Et)Ph 1 ° -
e
Me
e
Me Me
28
29
(4-t-F3u)Ph
(4-CF3)Ph -°
Me
Me
Me
Me
Me
Me
30 M
31
CH2-CFI
CH3 CH=CH
:=4 I = Me
Me
Me
Me
e
Me
32 CH2 C{ l-CH2 Me Me Me
[0079]
29
C)
/ I^3
11
k'-[) Q-Si ----R (1 a)
Compound 1
R F b F^ 3 R
f a
{ e
No.
33 (Me3S1)CI-12 Me Me Me
34 (Me3S1)CF2 Me Me Me
35 (Me3Si )CH2CH2 m^- Me Me Me
36 J e3SDOF2CF2 Me Me Me
37 (E't3Si)C Me Me Me
33 (Et3Si )CF2 Me Me Me
39 (Ph3S 1)C 112CF i2 - _ Me Me J Me
40 (Ph3Si )CF2CF2
--_,
Me Me Me
41 Me Me Me
42 Me Me Mo
43
M
Me Me Me
44
OCI
--- Me Me Me
45 Me Me Me
N
46 N\^/ - Me Me Me
47 I Me Me Me
48 \ -^ Me Me Me
49 I Me Me Me
[0080]
30
O R3
1 R -P11 0-111jl-R4 0 a)
R' 2
Compound
R'
Ra Rb R3
R4 R5
No.
C
F3
50 I
N
Me Me Me
51 G S A a -- Me Me
52 \ Me Me Me
S
53
C \^
- Me Me Me
54 (3-1) CH2 Me Me Me Me
55 (3- 1) CH2CH2 Me Me Me Me
56 (3- 1) GF2 Me Me Me Me
57 (3-1) CH2 SiMe3 Me Me Me
58
59
(3-1)
(3-1)
(1 -12
CI-12
SiMe3
SiMe2(t-Bu)
Me
Me
Me
Me
t.-Fu
Me
60 (3-1) CI-12 SiMe3 Ph Ph Ph
61 (3-2) CH2 Me Me Me
M
Me
62 (3-2) CH2 Et Me e Me
63 (3-2) CH2 Ph Me Me Me
64 (3-2 ) Phenylene Me Me Me Me
65
66
(3-2 )
(3-3)
Phenylene
CH2
CF3
Me
Me
Me
Me
Me
Me
Me
67 (3-3) CH, Et Me Me Me
68 (3-3) Phenylene Me Me Me Me
69 (3-3) Phenylene SiMe3 Me Me Me
70 (3-4) CH2 Me Me Me Me
71 (3-4) Phenylene Me Me Me Me
72 (3-5) CH2 Me Me Me Me
73 (3-5 ) CH2 Ph Me Me Me
[0081]
C---R2) 0 / 13
o II I
R __P - 0--Si-R4 (1 a)
I
I
I \ R 2
R3i ^ 1 'R5
R^
Compound R1 Ra Rb R3 RA R5
No.
74
75
(3-6 )
(3-6)
CH2
CH2
Me
Et
Me
Me
Me
Me
Me
Me
76 (3-6) CH2 Ph Me Me Me
77
78
(3-6)
(3-6 )
C1-I2
CF2
SiMe3
Me
Me
Me
Me
Me
Me
Me
79 (3-6 ) CF, Et Me
J
Me Me
80
-
(3-6) CF=2
Cs'
Ph
SiMe
Me
Me
Me
Me
Me
81 Me
82
(3-6)
(3-6)
2
GF2
3
SiPh3 Me Me Me
83 (3-7 ) CH2 Me Me Me Me
84 (3-7) CH2 Et Me Me Me
85 (3-7) CH2 Ph Me Me Me
86 (3-7 ) CF'2 Me Me ] Me Me
87 (3-7) CFz Et Me ^ Me Me
88 (3-7) Phenylene Ph Me Me Me
89 (3 -8) 0112 f I
CH
Me
Et
Me
M
Me I
Me
. Me
90 Me
91
(3-8 ) -
(3-8)
2
CI=12 Me
e
Me Me Me
92
93
(3-8)
(3-8)
Chit
Phenylene
Et
Me
Me
Me
Me
Me
Me
Me
94 (3-8 ) Phenylene Ph Me Me Me^
95 (3 -9 ) C1-12
CH
Me
Et
Me
M
Me
Me
Me
96 (3- 9 ) 2 e Me
97 (3-9) C112 CF3 Me Me Me
98 (3-9 ) CH2 Ph Me Me Me
99 (3-9) CN2 SiMe3 Me Me Me
100 (3-9) CI-12CH2 Me Me l Me Me
7
101 (3 9) CId2Cl 12 CF3 Me Me Me
102 (3-9 ) CH2CH2 (4-Me)Ph Me Me Me
103 (3-9 ) Phenylene
II
Me Me Me Me
104 (3-9 ) Phenylene CI3 Me Me Me
105 (3-9 ) Phenylene (4 -Me)Ph Me Mo Me
106 (3-9) CP2 Me Me M^ Me
107 (3-9) CF'2 Ph Me Me Me
[0082]
0n
R3/ j AP5)
I1 4 2
0 ( R
I i P11 ._x 0-Si---E2`^ (l a)
Compound
No H1
Pa
R5 R 3 R4 R5
10€3
109
110
111
(3-10)
(3-10 )
(3-10)
(3- 10)
CH2
CH2 (
CF2 ]
CP2
Et
SiMe3
Et
SiMe3
Me
Me
Me
Me
Me
Me
Me
Mes
Me
Me
Me
Me
112
113
(3- 10)
(3-10)
CH CH2
CH2CH2
Pt
SiMe3
Me
Me
Me
Me
MVI e
Me
114
115
(3-1)
(3-1)
CH2
CP2
Me
Me
Me
Ph
Me
Ph
t-Bu
Ph
116 (3-2) CH2 Me [ Me Me t Bu
117 (3-2) CI-12 Me ^ Me Me Ph
118 (3 - 2) Phenylene Me Me Me t-Bu
119 (3-3) CI-12 Me Me Me t-Bu
120 (3 3 )
_
CI 12 f Me _ Ph Ph Ph
121 (3 -4) CH2 Me Ph Ph Ph
122 (3 4) Phonylene J Me Ph Ph Ph
123
124
(3-5)
(3-6 )
CI-12
r CH2
CH
Me
Me
M
Me
Me
M
Me
Me
M
t-Bu
t. Bu
125 Ph
126
(3-6)
(3-6)
2
C112
e
Me
e
Me
e
Ph Ph
127
128
(3-6 )
(3-7)
CH2
CI-12
CF'
Me
Me
M
Ph
Me
M
Ph
Me
M
Ph
t-Bu
129 t-B
'
(3-7) 2
CF
e
M
e
M
e
M
u
130 Ph
131
(3-7 )
(3-7)
2
CP2
e
Me
e
Ph
e
Ph Ph
132
133 j
134
135
136
(3-8 )
(3-8)
(3-9)
(3-9 )
(3-9)
CH2
CH2
CH2
CH2
CH
Me
Et
Me
Me
CF
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
t--13u
9:--Bu
t--Bu
Ph
t-Bu
137 (3-9 )
2
CF12
3
CP3 Me Me Ph
138 (3- 10) CH2
011
Et
S Ph I
Me
Ph
me
Ph
t-Hu
139 (3 10) 2 i 3 Ph
[0083]
33
P3
1 11 (1 a)
Compo und
No.
^ a b 3 4 5
140 Me J_ [ Me Me lv OMe
141 Me Me Me0 OMe
142 Mc MeO Me0 OMe
143 Me Me Me OSiMe3
[0084]
0
R3r' IRS
\ 14
1
1
ON
Compound 1 R 6 2 62 3 t2 4 f3 5 f
No.
144 Me Me Me Me Me
145 Me Et Me Me Me
146
147
Me
Me
Ph
OF3
Me
Me
Me
Me
Me
Me
148 Me Aliyl Me Me Me
149 Ph Me Me Me Me
150 Ph OE3 Me Me Me
151
152
Ph
Ph
Ph
Et
Me
Me
Me
Me
M
Me
t-Bu
153 Ph
154
Ph
Ph C
Et
Et
Me
Ph
e
Ph Ph
155
-
-...,^ Et Me Me Me
156 C^ -_-- -- Et Me Me Me
157 Et Me M0 Me
N
158
159
(3-1)
(3--2 )
CHi2
OH2
Me
Me
Et
Et
Me
Me
Me
Me
Me
Me
160 (3-3) OH2 Me Et Me Me Me
1 6 1 (3-4) GH2 Me Et Me Me Me
162
163
(3-5)
(3-6)
CH2
OH2
Me
Me
Et
Et
Me
Me
Me
Me
Me
Me
164
165
(3-7 )
(3-8)
0112
CH2
Me
Me
Et
L
Me
Me
M
Me
Me
M
Me
Me
166 (3-9 ) CH2 Me Et e e Me
167 (3--10) OH2 Me Et Me Mn Me
168 (3-4)
OH2 _ a Ei
-
I - MF Me
[0085] Among the compounds having a combination of in the
above-described Formula (1), specific examples of the compound represented by the
above-described formula (2) (Compound Nos. 169 to 202; hereinafter, also referred to as
"Example Compounds 169 to 202", respectively) will now be provided; however, the present
invention is not restricted thereto.
It is noted here that, in the Example Compounds 169 to 202, "Me" , "Et", Ili-Pr"
I
"t-Bu", "Ph", "Vinyl" and "Allyl" represent a methyl group, an ethyl group, an isopropyl
group, a tert-butyl group, a phenyl group, a vinyl group and an allyl group, respectively.
Furthermore, in the column of X, "(X-1)" to "(X-26)" represent the above-described Formulae
(X-1) to (X-26), respectively.
[0086]
(2)
Compound
No.
R1 Ra Hb
x
R9 R10 R11 R12
169 Me 0 Me Me M : Me
170 Me 0H2
( H
Me Me
M
Me
M
Me
111 M
172
Me
Me
GH2 , 2
0H2('I-12CH2
Me
Me
e
Me )
e
Me f
e
Me
173 Me m.. 0 Vinyl Me Vinyl Me
171
1 75
Me
Me -^ -^
-
0
0
Allyl
i Pr
Me
iPr
Allyl [
i-Pr
U
Me
i Pr
176 Ph
177
178
Me
Ph
Ph
-^ 0
0
O i-12
Ph
Me
Me
Ph
Me
Me
P h
Me
Me
Me
Me
179 Ph CH2OH2 Me Me Me Me
180 CF3 0 Me Me Me Me
181 Vinyl -^-- -- 0 Me Me Me Me
182 l \ -- -- 0 Me Me Me Me
183 1
N
- -- 0 Me Me Me Me
184 (3-1) CH2 Me 0 Me Me Me J Me
185 (3-1) OH2 SiMe3 0
0
Me
M
Me
M
Me
Me
Me
186 Me
187
188
(3-2)
(3-3)
(3-4)
OH2
C OH2
CH21
Me
Me
Me
0
e
Me
Me
e
Me
Me
Me
Me
Me
Me
189 (3--5) (%H2 Me 0 Me Me Me Me
190 (3 6) 01-12 Me 0 Mc Me Me Me
[0081]
36
(2)
Compound
No.
I R a V 9 1o I1 12
191 (3-7) C1-12 Me 0 Me Me Me Me
192 (3-8) CH2 Me 1 0 Me Me Me Me
193 (3-9 Ch12 Me 0 Me Me Me Me
194 (3-10) CH2 Me 0 Me Me Me Me
195
196
Me
Me -_
(X 1)
(X-10)
-
Me
Me
Me
Me
Me
Me
Me
Mo
197
198
Me
Me
(X 14)
(X-19)
Me
Me
Me
Me
Me
Me
Me
Me
199
200
Me
(3- 1) C1-1 2 Me
(X- 20)
(X- I)
Me
Mc
Me
Me
Me
Me
Me
Me
201
- -^
(3-7 ) -.^ CIH2
I
Me (X__0 F
-
Me Me Me Me
202 (3-9) ()F12 Me ( X- I r Me Me Me Me
[0088] The compounds having a combination of in the above-described
Formula (1) (including the compound represented by the Formula (2)) can be produced by a
method described in the following known documents; however, the production method is not
restricted thereto.
Tetrahedron Letters, 1977,p155-158
Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science
(English Translation), 1961, p952 -956
Journal of the American Chemical Society, 1994, p1737-1741
Journal of Organic Chemistry, 1986, p4768-4779
[0089] Furthermore, those compounds having a combination of in the
Formula (1) can be, for example, synthesized by the following reaction route and then isolated
and purified by an existing method such as distillation, recrystallization or column
chromatography.
[0090]
37
" 0
-PI I-- OI
[0091] The compound represented by the Formula (1) (including the compound represented
by the Formula (2)) is useful as an additive for lithium secondary batteries, and particularly as
an additive for the non-aqueous electrolyte solution of lithium secondary batteries that will be
described below. By adding this additive to a non-aqueous electrolyte solution, the battery
resistance can be reduced and the battery storage properties in a high-temperature
environment can be improved, so that an extended battery service life can be realized.
That is, the additive for lithium secondary batteries of the present invention is an
additive for lithium secondary batteries containing the compound represented by the formula
M.
Furthermore, the additive for lithium secondary batteries of the present invention
may contain, if necessary, other components in addition to the compound represented by the
formula (I).
As these other components, from the viewpoint of attaining the above=described
effects more effectively, for example, at least one selected from the group consisting of a
tetrafluoroborate that will be described below, a compound represented by Formula (III) that
will be described below, a compound represented by Formula (IV) and a compound
represented Formula (V) that will be described below can be used.
[0092] The non-aqueous electrolyte solution of the present invention may contain only one
kind of the silyl ester group-containing phosphonic acid derivative described above or may
contain two or more kinds thereof.
The total content of the above-described silyl ester group-containing phosphonic acid
derivative in the non-aqueous electrolyte solution of the present invention is preferably
0.001% by mass to 10% by mass, and more preferably in the range of 0.05% by mass to 5%
by mass. In this range, an increase in battery resistance over time can be suppressed and an
extended service life can be attained.
[0093] Next, other components of the non--aqueous electrolyte solution of the present
38
invention will be described. Generally, a non--aqueous electrolyte solution contains an
electrolyte and a non-aqueous solvent.
[0094.] (Non=aqueous solvent)
The above-described non-aqueous solvent can be selected as appropriate from a
variety of known non.-aqueous solvents; however, it is preferably a cyclic aprotic solvent
and/or a chain aprotic solvent.
In the case of promoting an increase of the flash point of the solvent for an
enhancement of the safety of batteries, it is preferable to use a cyclic aprotic solvent as the
non-aqueous solvent.
[0095] [Cyclic aprotic solvent]
As the above-described cyclic aprotic solvent, a cyclic carbonate, a cyclic carboxylic
acid ester, a cyclic sulfone or a cyclic ether can be used.
The cyclic aprotic solvent may be used individually or plural thereof may be used in
combination.
The mixing ratio of the cyclic aprotic solvent in the non-aqueous solvent is 10% by
mass to 100% by mass, more preferably 20% by mass to 90% by mass, particularly preferably
30% by mass to 80% by mass. By controlling the mixing ratio in this range, the
conductivity of an electrolyte solution, which relates to the battery charge-, discharge
characteristics, can be increased.
Specific examples of the cyclic carbonate include ethylene carbonate, propylene
carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate and
2,3-pentylene carbonate. Thereamong, ethylene carbonate and propylene carbonate that
have a high dielectric constant are suitably used. In the case of a battery in whicl^i graphite is
used as a negative electrode active material, ethylene carbonate is more preferred.
Furthermore, these cyclic carbonates may be used as mixtures of two or more kinds.
[0096] Specific examples of cyclic carboxylic acid esters include y-butyrolactone,
6-valerolactone, and alkyl-substituted compounds such as methyl-y butyrolactone,
ethyhy-butyrolactone, and ethyhb-valerolactone.
The cyclic carboxylic acid esters have low vapor pressures, low viscosities, and high
dielectric constants. These compounds can lower the viscosity of an electrolyte solution
without lowering the flash point of the electrolyte solution and the degree of dissociation of
the electrolyte. For this reason, the cyclic carboxylic acid esters have a feature that the
conductivity of the electrolyte solution, which is an index related to the discharge
characteristics of a battery, can be increased without increasing inflammability of the
electrolyte solution. Therefore, in the case of promoting an increase in the flash point of the
9
solvent, it is preferable to use a cyclic carboxylic acid ester as the cyclic aprotic solvent.
y- butyrolactone is most preferred.
Furthermore, the cyclic carboxylic acid ester is preferably used as a mixture with
another cyclic aprotic solvent. For example, a mixture of a cyclic carboxylic acid ester and a
cyclic carbonate and/or a chain carbonate may be used.
[0097] Specific examples of such combination of a cyclic carboxylic acid ester, a cyclic
carbonate and/or a chain carbonate include combinations of. y-butyrolactone and ethylene
carbonate; y-butyrolactone, ethylene carbonate and dimethyl carbonate; y-butyrolactone,
ethylene carbonate and methylethyl carbonate; y-butyrolactone, ethylene carbonate and
diethyl carbonate; y-butyrolactone and propylene carbonate; y-butyrolactone, propylene
carbonate and dimethyl carbonate; y-butyrolactone, propylene carbonate and methylethyl
carbonate; y-butyrolactone, propylene carbonate and diethyl carbonate; y-butyrolaetone,
ethylene carbonate and propylene carbonate; y-butyrolactone, ethylene carbonate, propylene
carbonate and dimethyl carbonate; y-butyrolactone, ethylene carbonate, propylene carbonate
and methyiethyl carbonate; y-butyrolactone, ethylene carbonate, propylene carbonate and
diethyl carbonate; y-butyrolactone, ethylene carbonate, dimethyl carbonate and methylethyl
carbonate; y-butyrolactone, ethylene carbonate, dimethyl carbonate and diethyl carbonate;
y-butyrolactone, ethylene carbonate, methylethyl carbonate and diethyl carbonate;
y-butyrolactone, ethylene carbonate, dimethyl carbonate, rnethylethyl carbonate and diethyl
carbonate; ymbutyrolactone, ethylene carbonate; propylene carbonate, dimethyl carbonate and
methylethyl carbonate; y-butyrolactone, ethylene carbonate, propylene carbonate, dirnethyl
carbonate and diethyl carbonate; y-butyrolactone, ethylene carbonate, propylene carbonate,
methylethyl carbonate and diethyl carbonate; y-butyro lactone, ethylene carbonate,, propylene
carbonate, dimethyl carbonate, methylethyl carbonate and diethyl carbonate; y-butyrolactone
and sulfolane; y-butyrolactone, ethylene carbonate and sulfolane; y-butyrolactone, propylene
carbonate and sulfolane; y-butyrolactone, ethylene carbonate, propylene carbonate and
sulfolane; and y-butyrolactone, sulfolane and dimethyl carbonate.
Examples of the cyclic sulfone include sulfolanes, 2amethylsulfolane,
3-methylsulfolaile, dimethylsulfone, diethyl sulfone, dipropyl sulfone, methylethyl sulfone
and methylpropyl sulfone.
Examples of the cyclic ether include dioxolanes.
[0098] [Chain aprotic solvent]
As the above-described chain aprotic solvent, for example, a chain carbonate, a chain
carboxylic acid ester, a chain ether or a chain phosphoric acid ester can be used.
The mixing ratio of the chain aprotic solvent in the non-aqueous solvent is 10% by
40
mass to 100% by mass, more preferably 20% by mass to 90% by mass, particularly preferably
30% by mass to 80% by mass.
Specific examples of the chain carbonate include dimethyl carbonate, methylethyl
carbonate, diethyl carbonate, methylpropyl carbonate, methylisopropyl carbonate, ethylpropyl
carbonate, dipropyl carbonate, methylbutyl carbonate, ethylbutyl carbonate, dibutyl carbonate,
methylpentyl carbonate, ethylpentyl carbonate, dipentyl carbonate, methylheptyl carbonate,
ethylheptyl carbonate, diheptyl carbonate, methylhexyl carbonate, ethylhexyl carbonate,
dihexyl carbonate, methyloctyl carbonate, ethyloctyl carbonate, dioctyl carbonate and
methyltrifluoroethyl carbonate. These chain carbonates may be used as mixtures of two or
more kinds.
Specific examples of the chain carboxylic acid ester include methyl pivalate.
Specific examples o (' the chain ether include dimethoxyethanes.
Specific examples of the chain phosphoric acid ester include trimethyl phosphate.
[0099] [Combination of solvents]
The non-aqueous solvent used in the non-aqueous electrolyte solution of the
invention may be used singly or as a mixture of plural kinds. Furthermore, one kind or
plural kinds of only cyclic aprotic solvents may be used, one kind or plum! kinds of only
chain aprotic solvents may be used, or a mixture of a cyclic aprotic solvent and a chain aprotic
solvent may also be used. When it is intended to enhance the load characteristics and low
temperature characteristics of a battery in particular, it is preferable to use a combination of a
cyclic aprotic solvent and a chain aprotic solvent as the non-aqueous solvent.
Furthermore, in view of the electrochemical stability of the electrolyte solution, it is
most preferable to apply a cyclic carbonate to the cyclic aprotic solvent, and to apply a chain
carbonate to the linear aprotic solvent. Also, a combination of a cyclic carboxylic acid ester
with a cyclic carbonate and/or a chain carbonate can also increase the conductivity of the
electrolyte solution, which is related to the charge-discharge characteristics of the battery.
[0100] Specific examples of combination of a cyclic carbonate and a chain carbonate
include combinations of: ethylene carbonate and dimethyl carbonate; ethylene carbonate and
methylethyl carbonate; ethylene carbonate and diethyl carbonate; propylene carbonate and
dimethyl carbonate; propylene carbonate and methylethyl carbonate; propylene carbonate and
diethyl carbonate; ethylene carbonate, propylene carbonate and methylethyl carbonate;
ethylene carbonate, propylene carbonate and diethyl carbonate; ethylene carbonate, dimethyl
carbonate and methylethyl carbonate; ethylene carbonate, dimethyl carbonate and diethyl
carbonate; ethylene carbonate, methylethyl carbonate and diethyl carbonate; ethylene
carbonate, dimethyl carbonate, methylethyl carbonate and diethyl carbonate; ethylene
4.1
carbonate, propylene carbonate, dimethyl carbonate and methylethyl carbonate; ethylene
carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate; ethylene carbonate,
propylene carbonate, methylethylcarbonate and diethyl carbonate; and ethylene carbonate,
propylene carbonate, dimethyl carbonate, methylethyl carbonate and diethyl carbonate.
The mixing ratio of the cyclic carbonate and the chain carbonate is such that, when
expressed as a mass ratio, the ratio of cyclic carbonate : chain carbonate is 5 : 95 to 80 : 20,
more preferably 10 : 90 to 70 : 30, and particularly preferably 15 : 85 to 55 : 45. When such
a ratio is used, an increase in the viscosity of the electrolyte solution is suppressed, and the
degree of dissociation of the electrolyte can be increased. Therefore, the conductivity of the
electrolyte solution related to the charge-discharge characteristics of the battery can be
increased. Furthermore, the solubility of the electrolyte can be further increased.
Accordingly, an electrolyte solution having excellent electrical conductivity at normal
temperature or low temperatures can be obtained, and therefore, the load characteristics of a
battery from normal temperature to low temperatures can be improved.
['0101] [Other solvent]
In addition to the above-described solvents, the non-aqueous electrolyte solution of
the present invention may also contain other solvent as non-aqueous solvent. Specific
examples of the other solvent include amides such as dimethyl formaride; chain carbamates
such as methyl-N,N-dimethyl carbamate; cyclic amides such as N-methyl pyrrolidone; cyclic
ureas such as N,N-dimethylimidazolidinone; boron compounds such as trimethyl borate,
triethyl borate, tributyl borate, trioctyl borate and trirnethylsilyl borate; and polyethylene
glycol derivatives represented by the following Formulae.
HO(CH2CH2O)aH
HO[CH2CH(CH3)O]bH
CH3O(CH2CH2O),H
CH3O[CH2CH(CH3)O]dH
CH3O(CH2CH2O),CH3
CH3O[CH2CH(CH3)O]1CH3
C9H19PhO(CH2CH2O)g[CH(CH3)O]1iCH3 (Ph is a phenyl group)
CH3O[CH2CH(C1-13)O];CO[OCH(CH3)CH2].;OCH3
In the Formulae, a to f are each an integer from 5 to 250; g to j are each an integer
from 1 to 249; 5 < g + h < 250; and 5 < i + j < 250.
[0102] (Electrolyte)
The non-aqueous electrolyte solution of the present invention may contain a variety
of known electrolytes and any electrolyte may be used as long, as it is normally used as an
42
electrolyte for a non-aqueous electrolyte solution.
[0103] Specific examples of such electrolyte include tetra alkyl aurnnoniurn salts such as
(C2II5)4NPF6,(C2FI5)4NBF4, (C2H5)4NC104, (C2FI5)4NAsF6, (C2H5)4N2SiF6,
(C2FI5)4NOS02CkF(2k+l) (k = an integer of 1 to 8) and (C2FI5)4NPF„[CkF(21,+1)](6-„) (n = 1 to 5
and k = an integer of 1 to 8); lithium salts such as LiPF6, LiC1O4, LiAsF6, Li2SiF6,
LiOSO2CkF(21+I) (k = an integer of I to 8), LiPF„[CkF(2k+u](6_„) (n = 1 to 5 and k = an integer
of 1 to 8), LiC(S02R24)(SO2R25)(S02R26), LiN(S020R21)(S020R28) and
LiN(S02R29)(SO2R30) (wherein R24 to R30 may be the same or different and are each a
perfluoroalkyl group having 1 to 8 carbon atoms); and tetrafluoroborates such as LiBF4,
NaBF4, KBF4, (C4H9)4NBF4, CH3(C2H5)3NBF4 and imidazolium tetrafluoroborate.
[0104] Examples of tetrafluoroborates include, as described in the above, LiBF4, NaBF4,
KBF4, (C4.FIg)4NBF4, CFI3(C2145)3NBF4 and imidazolium tetrafluoroborate; however,
considering the cost and the ease of handling, LiBF4 is preferred.
[0105] As the electrolyte in the present invention, the above-described electrolytes may be
used singly, or two or more kinds thereof may be used in combination,
In cases where the electrolyte is used singly, it is preferably LiBF6 or LiBF4.
In cases where two or more kinds of electrolytes are used in combination, the
combination is preferably that of a lithium salt and a tetrafluoroborate, more preferably that of
LiPF6 and a tetrafluoroborate, particularly preferably that of LiPF6 and LiBF4.
[0106] The total electrolyte concentration in the non-aqueous electrolyte solution of the
present invention is usually 0.1 mol/L to 3 mol/L, preferably 0.5 mol/L to 2 mol/L.
[0107] Furthermore, it is preferred that the electrolyte of the present invention contain at
least one kind of tetrafluoroborate. This is because a reaction product generated by a
reaction between the above-described silyl ester group-containing phosphoric acid derivative
and the tetrafluoroborate ion modifies a coating film formed by an organic substance on the
electrode surface into a coating film having an affinity for ions and, as a result, an increase in
battery resistance can be further suppressed. Moreover, such a modified coating film of the
electrode surface has further improved thermal stability, so that capacity reduction after
storage at high temperature can be further suppressed.
In cases where the electrolyte contains at least one kind of tetrafluoroborate, the total
electrolyte concentration, which is the concentration of the contained tetrafluoroborate and
other electrolytes combined, may be any value as long as it is in the above-described range;
however, it is desired that the concentration of the tetrafluoroborate be in the range of 0.0001
mol/L to 2 mot/L.
As long as the concentration of the tetrafluoroborate is not lower than 0.0001 mot/L,
43
a higher concentration of the reaction product generated by a reaction between the
above-described silyl ester group-containing phosphonic acid derivative and the
tetra fluoroborate ion is attained, so that the above-described effects can be attained more
effectively.
[0108] (Compound represented by Formula (III))
From the viewpoint of forming a coating film on the negative electrode surface, it is
preferred that the non-aqueous electrolyte solution of the present invention contain a
compound represented by Formula (III).
[0 109]
[0110] In the Formula (111), Y1 and Y2 independently represent a hydrogen atom, a methyl
group, an ethyl group or a propyl group.
Examples of the compound represented by the Formula (III) include vinylene
carbonate, methylvinylene carbonate, ethylvinylene carbonate, propylvinylene carbonate,
dimethylvinylene carbonate, diethylvinylene carbonate and dipropylvinylene carbonate.
Therearnong, vinylene carbonate is most preferred.
In cases where the non-aqueous electrolyte solution of the present invention contains
a compound represented by the Formula (III), the content thereof in the non-aqucous
electrolyte solution of the present invention can be selected as appropriate in accordance with
the purpose thereof; however, it is preferably 0.001% by mass to 10% by mass, more
preferably 0.05% by mass to 5% by mass.
[0111] (Compound represented by Formula (IV))
From the viewpoint of forming a coating film on the negative electrode surface, it is
preferred that the non-aqueous , electrolyte solution of the present invention contain a
compound represented by Formula (IV).
[0112]
[0113] In the Formula (IV), X' X2, X3 and X4 each independently represent a hydrogen
atom, a fluorine atom, a chlorine atom or an alkyl group having 1 to 3 carbon atoms which
may be substituted with a fluorine atom. It is noted here, however, that all of X' to X4 never
are hydrogen atoms at the same time.
Examples of the alkyl group having 1 to 3 carbon atoms represented by XI to X4 in
the Formula (IV), which may be substituted with a fluorine atom, include fluoromethyl,
difluoromethyl, trifluoromethyl, pentafluoroethyl and heptafluoropropyl.
As the compound represented by the Formula (IV), a known one can be used, and
examples thereof include fluoroethylene carbonates in which 1 to 4 hydrogens in ethylene
carbonate are substituted with fluorine, such as 4-fluoroethylene carbonate,
4,4-difluoroethylene carbonate, 4, 5-difluoroethylene carbonate, 4,4,5-trifluoroethylene
carbonate and 4,4,5,5-tetrafluoroethylene carbonate. Thereamong, most preferred are
4,5adifluoroethylene carbonate and 4-fluoroethylene carbonate.
In cases where the non-aqueous electrolyte solution of the present invention contains
a compound represented by the Formula (IV), the content thereof in the non-aqueous
electrolyte solution of the present invention can be selected as appropriate in accordance with
the purpose thereof; however, it is preferably 0,001% by mass to 10% by mass, more
preferably 0.05% by mass to 5% by mass.
[0114] (Compound represented by Formula V)
From the viewpoint of forming a coating film on the surfaces of the positive and
negative electrodes, it is preferred that the non-aqueous electrolyte solution of the present
invention contain a compound represented by Formula (V).
[0115]
[0116] In the Formula (V), Z', Z2, Z3 and Z4 are each independently an alkyl group having 1
to 12 carbon atoms which may contain a fluorine atom, a hydrogen atom or a fluorine atom,
and n represents an integer of 0 to 3. When n is 2 or 3, the plural Z3 and Z4 may be the same
or different.
Exarnples of the alkyl group having 1 to 12 carbon atoms represented by Z' to Z4,
which may contain a fluorine atom, include methyl group, ethyl group, n-propyl group,
isopropyl group, n-butyl group, isobutyl group, sec butyl group, tert-butyl. group, pentyl group,
2-methylbutyl group, 1-methylpentyl group, neopentyl group, l-ethylpropyl group, hexyl
group, 3,3-dimethylbutyl group, heptyl group, octyl group, nonyl group, undecanyl group,
dodecanyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group,
2,2,2-trifluoroethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group,
perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group,
perfluorononyl group, perfluorodecyl group, perfluoroundecanyl group, perfluorododecanyl
group, perfluoroisopropyl group and perfluoroisobutyl group.
The number of carbon atoms in Z' to Z4 is preferably 1 to 12; however, from the
viewpoint of the solubility to the electrolyte solution, it is more preferably not more than 4,
still more preferably not more than 2. It is most preferred that Z' to Z4 be all hydrogen
atoms.
The n is preferably 1 or 2, more preferably 1.
As the compound represented by the Formula (V), a known one can be used, and
examples thereof include 1,3-prop-l-ene sultone, 3-methyhh1,3-prop-I-ene sultone,
4-methyl-1,3-prop-l-ene sultone, 5-methyl-1,3-prop-1 ene sultone and 1,4=butene-I-ene
sultone. Thereamong, most preferred is 1,3-prop-l-ene sultone in which Z' to Z4 are all
hydrogen atoms and n is 1.
In cases where the nonaqueous electrolyte solution of the present invention contains
46
a compound represented by the Formula (V), the content thereof in the non-aqueous
electrolyte solution of the present invention can be selected as appropriate in accordance with
the purpose thereof; however, it is preferably 0.001% by mass to 10% by mass, more
preferably 0.05% by mass to 5% by mass.
[0117] The non-aqueous electrolyte solution of the present invention is not only suitable as a
non-aqueous electrolyte solution for lithium secondary batteries, but can also be used as a
non-aqueous electrolyte solution for primary batteries, a non-aqueous electrolyte solution for
electrochemical capacitors, and an electrolyte solution for electric double-layer capacitors and
aluminum electrolytic condensers.
[0118]
The lithium secondary battery of the present invention is constituted to essentially
include a negative electrode, a positive electrode, and the non-aqueous electrolyte solution of
the invention, and usually, a separator is provided between the negative electrode and the
positive electrode.
[3119] (Negative electrode)
As a negative electrode active material constituting the negative electrode, at least
one of lithium metal, lithium-containing alloys, metals or alloys that are capable of forming
an alloy with lithium, oxides capable of doping/dedoping lithium ions, transition metal
nitrides capable of doping/dedoping lithium ions and carbon materials capable of
doping/dedoping lithium ions may be used.
Examples of the metals or alloys that are capable of forming an alloy with lithium ion
include silicon, silicon alloys, tin and tin alloys. Examples of the oxides capable of
doping/dedoping lithium ions include titanium-based oxides.
Thereamong, a carbon material capable of doping/dedoping lithium ions is preferred.
Such carbon material may be a carbon black, an activated carbon, an artificial graphite, a
natural graphite or an amorphous carbon and may also take any of a fibrous form, a spherical
form, a potato-shape and a flake form.
[0120] Specific examples of the above-described amorphous carbon material include hard
carbon, cokes, mesocarbon microbeads (MCMB) calcinated at 1,500°C or lower and
mesophase pitch carbon fiber (MCF).
Examples of graphite material include natural gra_phites and artificial graphites and,
as an artificial graphite, a graphitized MCMB, a graphitized MCF or the like is used.
Furthermore, as a graphite material, a boron-containing graphite material or the like may be
used and a graphite material coated with a metal such as gold, platinum, silver, copper or tin,
an amorphous carbon-coated graphite material or a mixture of amorphous carbon and graphite
7
may also be used.
[0121] These carbon materials may be used singly, or two or n2ore kinds may be used as a
mixture. As the carbon material, particularly, one having an interplanar spacing d(002)
between the (002) planes of not larger than 0.340 rum as measured by an X-ray analysis is
preferred, and a graphite having a true density of not less than 1.70 g/cm3 or a highly
crystalline carbon material having properties similar to those of the graphite is preferred. By
using such a carbon material, the energy density of a battery can be increased.
[0122] (Positive electrode)
Examples of a positive electrode active material constituting the above-described
positive electrode include transition metal oxides and transition metal sulfides such as MoS2,
TiS2, Mn02 and V205; complex oxides composed of lithium and transition metals such as,
LiCoO2, LiMnO2, LiMn2O/1, LiNiO2, LiNixCo(iex)O2 [0 < X < 1] and LiFePOLG; and
el ectroconductive polymer materials such as polyaniline, polythiophene, polypyrrole,
polyacetylene, polyacene and dilnercaptothiadiazole/polyaniline complex.
Thereamong, complex oxides composed of lithium and transition metals are
particularly preferred.
In cases where the negative electrode is lithium metal or a lithium alloy, a carbon
material may be used as the positive electrode. Furthermore, as the positive electrode, a
mixture of a complex oxide composed of lithium and transition metals and a carbon material
may also be used.
The positive electrode active material may be used singly, or two or more kinds may
be used as a mixture. Since positive electrode active materials usually have insufficient
conductivity, a positive electrode is constructed by using a positive electrode active material
together with a conductive auxiliary agent. Examples of the conductive auxiliary agent
include carbon materials such as carbon black, amorphous whisker, and graphite.
[0123] (Separator)
As the above-described separator, a film which electrically insulates the positive and
negative electrodes from each other and allows lithium ions to pass therethrough can be used,
and examples of such separator include a porous film and a polymer electrolyte.
As the above-described porous film, a microporous polymer film is suitably used,
and examples of the material thereof include polyolefin, polyimide, polyvinylidene fluoride
and polyester.
Particularly, a porous polyolefin is preferred, and specific examples thereof include a
porous polyethylene film, a porous polypropylene film and a rnultilayer film containing a
porous polyethylene film and a polypropylene film. On the porous polyolefin film, other
resin having excellent thermostability may also be coated.
Examples of the above-described polymer electrolyte include a polymer in which a
lithium salt is dissolved and a polymer swollen with an electrolyte solution.
The non-aqueous electrolyte solution of the present invention may also be used for
the purpose of swelling a polymer to obtain a polymer electrolyte.
[0124] (Configuration of battery)
The lithium secondary battery of the present invention includes the negative
electrode active material, positive electrode active material, and separator described above.
The lithium secondary battery of the present invention may adopt various known
shapes, and can be formed into a cylindrical shape, a coin shape, a box shape, a film shape, or
any other shape. However, the fundamental structure of the battery is the same irrespective
of the shape, and modification in the design can be applied in accordance with the purpose.
An example of the lithium secondary battery of the present invention may be a coin
type battery illustrated in fig. 1.
In the coin type battery shown in fig. 1, a disc-shaped negative electrode 2, a
separator 5 in which a. non-aqueous electrolyte solution formed by dissolving a non-aqueous
electrolyte in a non-aqueous solvent has been injected, a disc-shaped positive electrode 1, and
optionally spacer plates 7 and 8 formed of stainless steel, aluminum or the like are
accommodated, in the state of being laminated in this order, between a positive electrode can
3 (hereinafter, also referred to as "battery can") and a sealing plate 4 (hereinafter, also referred
to as "battery can lid"). The positive electrode can 3 and the sealing plate 4 are sealed by
caulking with a gasket 6.
[0125] The applications of tlhe non-aqueous electrolyte solution of the exemplary
embodiment of the present invention and a lithium secondary battery using the non-aqueous
electrolyte solution are not particularly limited, and the non-aqueous electrolyte solution and
the lithium secondary battery can be used in various known applications. For example, they
can be widely used in small-sized portable equipment as well as large-sized equipment, such
as laptop computers, mobile computers, mobile telephones, headphone stereo cassette players,
video movie recorders, liquid crystal TV sets, handy cleaners, electronic organizers,
calculators, radios, backup power supply applications, motors, automobiles, electric cars,
motorcycles, electric motorcycles, bicycles, electric bicycles, lighting equipment, game
machines, time pieces, electric tools, and cameras.
Examples
[0126] The present invention will now be described more concretely byway of exar
49
)les
thereof, however, the present invention is not restricted to these examples. It is noted here
that, in the following examples, "%" means % by mass.
[0127]
(Synthesis of Example Compound 95)
(Hydroxymethyl)phosphonic acid diethyl ester (20 mmol, 3.36 g) and triethyl amine
(24 mrnol, 2.42 g) were dissolved in methylene chloride and the resulting solution was cooled
to 5°C. Then, methanesulfonyl chloride (24 mmol, 2.75 g) was added thereto dropwise.
After stirring the resultant at 5°C for 0.5 hour and then at room temperature for 1 hour,
insoluble matters were removed by filtration. The thus obtained filtrate was washed with IN
hydrochloric acid, aqueous sodium bicarbonate solution and saturated saline, and then dried
with magnesium sulfate. This magnesium sulfate was removed by filtration and an oily
matter obtained by concentrating the filtrate was purified by silica gel column
chromatography (ethyl acetate/n=hexane) to obtain colorless and transparent
(methanesulfonyloxymethyl)phosphoric acid diethyl ester (yield: 3.77 g, 77%). The result
of 'EI=NMaR measurement of this compound is shown below.
[0128] 'I1=NMR (270 MHz, CDC13) 6 (ppm): 4.44 4.41 (211, d, J = 8.9 Hz), 4.25=4.17 (AH,
dt, J = 1.1, 7.0 Hz), 3.12 (3H, s), 1.41°1.35 (6H, t, J = 7.011z)
[0129] The thus obtained (methanesulfonyloxymethyl)phosphoric acid diethyl ester (4.1
mmol, 1.0 g) was dissolved in 10 ml of dry methylene chloride and trimethylsilyl bromide
(12.2 mmol, 1.86 g) was added thereto dropwise at room temperature. The resultant was
stirred at room temperature for 5 hours and concentrated under reduced pressure. The
resulting oily matter was vacuum=distilled (112 to 118°C/0.1 kPa) to obtain Example
Compound 95 (yield: 0.87 t , 64%). The result of 114-NMR measurement of the Fxample
Compound 95 is shown below.
[0130] 'I1=NMR (270 MHz, CDC13) 6 (ppm): 4.284.24 (2H, d, J = 9.5 Hz), 3.05 (3H, s),
0.27 (18H, s)
[0131] (Synthesis of Example Compound 2)
Methylphosphonic acid dimethyl ester (16.1 mmol, 2.0 g) was dissolved in 20 ml of
dry methylene chloride and trimethylsilyl bromide (3 eq., 48.4 mmol, 7.4 g) was added
thereto dropwise at room temperature. The resultant was stirred at room temperature for 5
hours and concentrated under reduced pressure. The resulting oily matter was
vacuum =distilled (51 to 52°C/0.3 kPa) to obtain Example Compound 2 (yield: 2.46 g, 64%).
The result of 'H=NMR measurement of the Example Compound 2 is shown below.
IFI°NMR (270 MHz, CDC13) o (ppm): 1.41°1.35 (3H, d, .I = 17.8 Hz), 0.23 (18H, s)
[0132] (Synthesis of Exarraple Compound 3)
50
In a flask equipped with Dean-Stark apparatus, methylphosphonic acid (15.6 mmol,
1.5 g) and tertmbutyldimethyl silanol (2.1 eq., 32.8 mmol) were dissolved in 50 ml of dry
n-hexane and the resultant was allowed to react under heating to reflux while isolating and
eliminating distillated water. The thus obtained reaction solution was concentrated under
reduced pressure (120°C/5.3 kPa) and the resulting oily matter was vacuum=distilled (97 to
100°C/0.2 kPa) to obtain Example Compound 3 (yield: 3.80 g, 75%). The result of 'H=h1MR
measurement of the Example Compound 3 is shown below.
'H=NMR (270 MHz, CDC13) d (ppm): 1.411.34 (3H, d, J = 17.8 Hz), 0.87 (18H, s), 0.20-.0.19
(12H, d, J = 2.4 Hz)
[0133] (Synthesis of Example Compound 5)
Methylphosphonic acid dimethyl ester (3.0 mmol, 0.37 g) was dissolved in 10 ml of
dry methylene chloride and allyldimethylsilyl bromide (3 eq., 9.0 mmol, 1.62 g) was added
thereto dropwise at room temperature. The resultant was stirred at room temperature for 5
hours and concentrated under reduced pressure. The resulting oily matter was
vacuum=distilled (87 to 92°C/0.2. kPa) to obtain Example Compound 5 (yield: 0.47 g, 54%).
The result of 'H=INMR measurement of the Example Compound 5 is shown below.
'I-1.,h1MR (270 MHz, CDCl3) d (ppm): 5.87-5.71 (2H, n ►), 5.00=4.83 (4H, yi), 1.77=1.75 (4H, d,
J = 7.8 Hz), 1.481.41 (3H, d, J = 18.4 Hz), 0.30 (12H, s)
[0134] (Synthesis of Example Compound 8)
Methylphosphonic acid (10.0 mmol, 0.96 g) and ethoxytriphenyl silane (2.0 eq., 20.0
mmol, 6.09 g) were dissolved in 10 ml of dry o-xylene and the resultant was allowed to react
under heating to reflux while distilling out distilled ethanol. The thus obtained reaction
solution was cooled to room temperature and after adding thereto 40 ml of diethyl ether, the
resultant was filtered to obtain a solid. The thus obtained solid was recrystallized from hot
toluene to obtain Example Compound 8 (yield: 2.16 g, 35%). The result of 'H=NMR
measurement of the Example Compound 8 is shown below.
IH=NMR (270 MHz, CDC13) 8 (ppm): 7.587.54 (12H, in), 7.467.39 (6H, in), 7.36=7.25 (12H,
nn), 1.28=1.21 (3H, d, J = 18.1 Hz)
[0135] (Synthesis of Example Compound 19)
Example Compound 19 was synthesized in the same mariner as the Example
Compound 2, except that methylphosphonic acid dimethyl ester was changed to
phenylphosphonic acid dimethyl ester and the conditions of the vacuum=distillation were
changed to 85 to 91 °C/0.2 1cPa (yiel(l: 41 °/0). The result of ' EH=NMR measurement of the
Example Compound 19 is shown below.
'H--NMR (270 MHz, CDC13) 6 (ppm): 7.807.71 (2I-1, iin) , 7.52- 7. 38 (3H, rn), 0.25 (18H, s)
[0136] (Synthesis of Example Compound 30)
Example Compound 30 was synthesized in the same manner as the Example
Compound 2, except that methylphosphonic acid dimethyl ester was changed to
vinylphosphonic acid diethyl ester and the conditions of the vacuum -distillation were changed
to 78 to 82°C/0.8 kPa (yield: 73%). The result of 1H-NMR measurement of the Example
Compound 30 is shown below.
'kI-NMR (270 MHz, CDC13) 6 (ppm): 6.12-5.76 ( 314, m), 0.23 (1811, s)
[0137] (Synthesis of Example Compound 31)
Example Compound 31 was synthesized in the same maimer as the Example
Compound 2, except that methylphosphonic acid dimethyl ester was changed to
1-propenylphosphonic acid diethyl ester and the conditions of the vacuum-distillation were
changed to 62 to 69°C/0.2 kPa (yield: 79%). The result of 'H-NMR measurement of the
Example Compound 31 is shown below.
'H-NMR (270 MHz , CDC13) 6 (ppm): 6.636.41 (1H, m), 5 .795.65 ( 1H, ddd , J = 27, 17, 1.6
Hz), 1.83-i .79 (31, m), 0.23 ( 1814, s)
[0138] (Synthesis of Example Compound 34)
Example Compound 34 was synthesized in the same manner as the Example
Compound 2, except that methylphosphonic acid dimethyl ester was changed to
(trimethylsilyldifluoromethyl )phosphoric acid diethyl ester and the conditions of the
vacuum-distillation were changed to 95 to 103°C/0.1 kPa (yield: 40%). The result of
'H-NMR measurement of the Example Compound 34 is shown below.
'H-NMR (270 MHz, CDC13) 6 (ppm): 0.26 (18H, s), 0.19 (911, s)
[0139] (Synthesis of Example Compound 57)
Example Compound 57 was synthesized in the same manner as the Example
Compound 2, except that methylphosphonic acid dirnethyl ester was changed to
(trimethylsilyloxy-methyl)phosphonic acid diethyl ester and the conditions of the
vacuum-distillation were changed to 61 to 71°C/0.2 kPa (yield: 84%). The result of
'H-NMR measurement of the Example Compound 57 is shown below.
iH-NMR (270 MHz, CDC13) 6 (ppm): 3.713.67 (2H, d, J = 8.9 Hz), 0.23 (18H, s), 0.08 (911,
s)
[0140] (Synthesis of Example Compound 109)
Example Compound 109 was synthesized in the same manner as the Example
Compound 2, except that rriethylphosphonic acid dimethyl ester was changed to
rnethylenediphosphonic acid tetraethyl ester, that the amount of trimethylsilyl bromide was
increased to 6 eel. and that the conditions of the vacuuixi-distillation were changed to I18 to
123°C/0.2 kPa (yield: 89%). The result of'H•NMR measurement of the Example
Compound 109 is shown below.
'H-NMR (270 MHz, CDC13) 6 (ppm): 2.32-2.16 (2H, t, J = 21.6 Hz), 0.25 (36H, s)
[0141] (Synthesis of Example Compound 169)
A mixed solution of methylphosphonic acid ( 12 minol, 1.15 g) and
1,3-diethoxy-1 , 1,3,3-tetramethyl disiloxane (10 mmol , 2.22 g) was heated at 100°C for 3
hours . The resulting reaction solution was vacuum-distillated (141 to 145°C/0.1 kPa) to
obtain Example Compound 169 (yield: 0.63 g, 23%/methylphosphonic acid). The result of
'H-NMR measurement of the Example Compound 169 is shown below.
'H-NMR (270 MHz, CDC13) d (ppm): 1.54-1.47 (3H, d, J = 18.4 Hz), 0.23 (18H, s)
[0142]
A. lithium secondary battery was prepared by the following procedures.
(Preparation of negative electrode)
First, 20 parts by mass of an artificial graphite, 80% by mass of a natural
graphite-based graphite, 1 part by mass of carboxymethyl cellulose and 2 parts by mass of
SBR latex were kneaded in an aqueous solvent to prepare a negative electrode mixture slurry
in the form of a paste.
Then, after coating and drying the thus obtained negative electrode mixture slurry on
a negative electrode collector made of a band-shaped copper foil having a thickness of 18 lmrm,
the resultant was compressed using a roll press to obtain a sheet-form negative electrode
composed of the negative electrode collector and a negative electrode active material layer.
Here, the negative electrode active material layer had a coating density of 10 mg/cm2 and a
packing density of 1.5 g/ml.
[0143] (Preparation of positive electrode)
First, 90 parts by mass of f,iMn2O4, 5 parts by mass of acetylene black and 5 parts by
mass of polyvinylidene fluoride were kneaded using N-methylpyrrolidinone as a solvent to
prepare a positive electrode mixture slurry in the form of a paste.
Then, after coating and drying the thus obtained positive electrode mixture slurry on
a positive electrode collector made of a band-shaped aluminum foil having a thickness of 20
rim, the resultant was compressed using a roll press to obtain a sheet=form positive electrode
composed of the positive electrode collector and a positive electrode active material layer.
Here, the positive electrode active material layer had a coating density of 30 mg/cm2 and a
packing density of 2.5 g/rill.
[0144] (Preparation of non-aqueous electrolyte solution)
As a non aqueous solvent, ethylene carbonate (EC), dimetlryl carbonate (DMC) and
methylethyl carbonate (EMC) were mixed at a ratio of 34:33:33 (mass ratio) to obtain a mixed
solvent.
In the thus obtained mixed solvent, LiPF6 as an electrolyte was dissolved such that
the LiPF6 concentration in the eventually obtained non-aqueous electrolyte solution became
1.0 mol/L.
Then, to the thus obtained solution, Example Compound 2 was added as an additive
such that the content thereof in the eventually obtained non-aqueous electrolyte solution
became 0.5% by mass.
[0145] (Preparation of coin-type battery)
The above-described negative and positive electrodes were punched out in the form
of disks having a diameter of 14 mm and 13 mm, respectively, to obtain coin-shaped
electrodes. Furthermore, a separator was obtained by punching out a 20 μm-thick
microporous polyethylene film in the form of a disk having a diameter of 17 nnm.
The thus obtained coin-shaped negative electrode, separator and coin-shaped positive
electrode were laminated in this order in a stainless steel battery can (size 2032) and 20 1tl of
the above-described non-aqueous electrolyte solution was injected thereinto to impregnate the
separator and the positive and negative electrodes with the non-aqueous electrolyte solution.
Furthermore, an aluminum plate (1.2 mm in thickness, 16 mm in diameter) and a
spring were placed on the positive electrode and the battery was then sealed by caulking the
battery can lid via a polypropylene gasket, thereby preparing a coin-type lithium secondary
battery having a diameter of 20 mm, a height of 3.2 mm and the configuration shown in Fig. 1
(hereinafter, referred to as "test battery").
For the thus obtained coin-type battery (test battery), the initial characteristics and the
characteristics after high-temperature storage were evaluated.
[0146] (Evaluation methods)
[Evaluation of battery initial characteristics and characteristics after high-temperature storage]
The test battery was charged at a constant voltage of 4.0 V. Then, the thus charged
test battery was cooled to -10°C in a thermostat chamber and the impedance thereof was
measured using impedance measuring apparatuses manufactured by Solartron
(POTENTIOGALVANOSTAT S11287 and FREQUENCY RESPONSE ANALYZER 12558).
Here, the resistance [02] at 0.2 Hz was defined as the initial battery resistance.
The results are shown in Table 1 below.
[0147] After the impedance measurement, the test battery was charged at a constant current
of 1 mA and a constant voltage of 4.2 V in a 25°C thermostat chamber. Subsequently, in this
25°C thermostat chamnber, the battery was allowed to discharge to 2.85 V at a constant current
of I mA and the discharge capacity before high temperature storage [mAh] was measured.
Then, after charging the above-described test battery at a constant current of 1 mA
and a constant voltage of 4.2 V in the 25°C thermostat chamber, the temperature of the
thermostat chamber was raised to 80°C and the test battery was stored for two days in the
80°C thermostat chamber (high-temperature storage).
After the high-temperature storage, the temperature of the thermostat chamber was
returned to 25°C and in this 25°C thermostat chamber, the test battery was allowed to
discharge to 2.85 V at a constant current of 1 mA to measure the residual discharge capacity
of the battery [mAh] (that is, the discharge capacity after high-temperature storage [mAh])
was measured.
Thereafter, using the following equation, the capacity retention rate before and after
high-temperature storage was calculated.
[0148] Capacity retention rate before and after high-temperature storage [%]
= (Discharge capacity after high-temperature storage [mAh] /Discharge capacity before
high-tempcrattire storage [nom]) X 100 [%]
[0149]
lion-aqueous electrolyte solutions were prepared and coin-type batteries were
obtained in the same manner as in Example 1, except that the respective Example Compounds
(3, 5, 8, 19, 30, 31, 34, 57, 95, 109 and 169) listed in the "Additive" Column of Table I were
added in place of the above-described Example Compound 2.
For the thus obtained coin-type batteries, the initial characteristics and the
characteristics after high-temperature storage were evaluated in the same mailer as in
Example 1. The results are summarized in Table 1 below.
[0150] The names and structures of the Examples Compounds 2, 3, 5, 9, 19, 30, 31, 34, 57,
95, 109 and 169 are shown below. In these structures of the Example Compounds shown
below, "Me" and "Ph" represent a methyl group and a phenyl group, respectively.
[0151] Example Compounds-
Example Compound 2: methylphosphonic acid bis(trimethylsilyl) ester
Example Compound 3: methylphosphonic acid bis(tert-butyldilmethylsilyl) ester
Example Compound 5: methylphosphonic acid bis(allyldimethylsilyl) ester
Example Compound 8: mcthylphosphonic acid bis(triphenylsilyl) ester
Example Compound 19: phenylphosphonic acid bis(trimethylsilyl) ester
Example Compound 30: vinylphosphonic acid bis(trimethylsilyl) ester
Example Compound 31: 1-propenylphosphonic acid bis(trimethylsilyl) ester
Example Compound 34: [difluoro(trirmthylsilyl)metl-iyl]phosphonic_; acid bis(trimmrmethylsilyl)
55
ester
Example Compound 57: [(trimethylsilyloxy)methyl]phosphonic acid bis (trirnethylsilyl) ester
Example Compound 95: [(methrinesulfonylhoxy )methyllphosphonic acid bis(trimethylsilyl)
ester
Example Compound 109: methylenebisphosphonic acid tetrakis(trimethylsilyl) ester
Example Compound 169:
2,4,4,6, 6-pentamethy1-1 , 3,5-trioxa-2-phospha-4 , 6-disilacyclohexane-2,-oxide
[0152]
me ''0°
P SIMe3
I
(Example Compound 2)
11SiMe3
0
Me'll,,0'
P
0
0
Me,,li ,0^°SiPh3
Sifh3
Ph. Il, 0,
P SIMe3
0
1"SiMe3
0
,p,0,
P SIMe3
0
SiMe3
(Example Compound 3)
(Example Compound 5)
(Example Compound 8)
i0
l^SiMe3
(Example Compound 95)
0 H2 O
Me3Si P P SIMe3
^,.0 (),ter, (Example C^ri^;,riAnd 109)
(Example Compound 19) Me3Si SiMe3
(Example Compound 30)
0
P SIMe3
0
SiMe3
F2 0
Me3Si
P
SIMe3
0"
SiMe3
(Example Compound 31)
(Example Compound 34)
H2 0
Me3Si ^C^II 0^
0 P SIMe3
(Example Compound 5 7)
0
SIMe3
O\ /0 "2 0
Me""p0 P SIMe3
0
Mee„I.10,S' .,
I I
0, 0 (Example Compound 169)
[0153]
A non-aqueous electrolyte solution was prepared and a coin-type battery was
obtained in the same manner as in Example 1 except that, in the preparation of the
non=aqueous electrolyte solution of Example 1, LiBF4 was further added such that the LiBF4
concentration in the eventually obtained non-aqueous electrolyte solution became 0.01 mol/f,.
For the thus obtained coin type battery, the initial characteristics and the characteristics after
56
high-ternporature storage were evaluated in the same manner as in Example 1.
The results are summarized in Table 1 below.
[0154]
In Comparative Example 1, a non-aqueous electrolyte solution was prepared and a
coin-type battery was obtained in the same manner as in Example 1, except that the
above-described Example Compound 2 was not added.
Furthermore, in Comparative Examples 2 to 13, non-aqueous electrolyte solutions
were prepared and coin type batteries were obtained in the same manner as in Example 1,
except that the respective Comparative Compounds shown below were added in place of the
above-described Example Compound 2.
It is noted here that, in these Comparative Compounds shown below, "Me", "Et" and
"Ph" represent a methyl group, an ethyl group and a phenyl group, respectively.
In Comparative Example 14, a non-aqueous electrolyte solution was prepared and a
coin-type battery was obtained in the same manner as in Example 1, except that the
above-described Example Compound 2 was not added and LiBF4 was added such that the
LiBF4 concentration in the eventually obtained non-aqueous electrolyte solution became 0.01
mot/L.
For the thus obtained coin-type batteries, the initial characteristics and the
characteristics after high-temperature storage were evaluated in the same manner as in
Example 1. The results are summarized in Table 1 below in the same manner as those of
Examples.
[0155] Comparative Compounds-
Comparative Compound A: methylphosphonic acid
Comparative Compound B: nlethylphosphorric acid dimethyl ester
Comparative Compound C: phenylphosphonic acid
Comparative Compound D: phenylphosphonic acid dimethyl ester
Comparative Compound E: vinylphosphonic acid
Comparative Compound F: vinylphosphonic acid diethyl ester
Comparative Compound G: 1 -propenylphosphonic acid diethyl ester
Comparative Compound H: (trimethylsilyldifluoromethyl)phosphoric acid diethyl ester
Comparative Compound I: (trimethylsilyloxy-methyl) phosphonic acid diethyl ester
Comparative Compound J: (methanesulfonyloxy-methyl) phosphonic acid diethyl ester
Comparative Compound K: methylenediphosphonic acid tetraethyl ester
Comparative Compound L: tris(trimethylsilyl)phosphate
The Comparative Compounds A to L have the following structures,
5I
[01 56]
0
11/l
H°
)E1
(Comparative Compound A)
OFI
0
Me.N1
P
,,U,M
(Comparative Compound B)
Me
0
Ph,I I ,OH
P` (Comparative Compound C)
01-1
(Comparative Compound C)
0
F 18 iMe>3
a" iMe3
(Comparative Compound 1)
(Comparative Compound J)
(Comparative Compound K)
(Comparative Compound L)
[0157]
A non-aqueous electrolyte solution was prepared and a coin type battery was
obtained in the same manner as in Example 1 except that, in the preparation of the
non-aqueous electrolyte solution of Example 1, the Example Compound 2 and vinylene
carbonate (VC) were added as additives such that the contents thereof in the eventually
obtained non-aqueous electrolyte solution each became 0.5% by mass. For the thus obtained
coin-type battery, the initial characteristics and the characteristics after high temperature
storage were evaluated in the same manner as in Example 1. The results are summarized in
Table 2 below.
[015 8]
Me
a
(Comparative Compound 0)
F2 0
C"I1"t^,
Me3Si I' 'Et (Comparative Compound 1-1)
01
'Ft
Fie. 0
Me3Si.C,,11,,0,
0
m
F
E:t
FI2 0
Me-", i..e,0P'^ °Et
Ft
0 1120
Et`-10, 1 1,C, 11,0,
F P Ft
I I
Lt`' O 0 Ft
(Comparative Compound F)
Me3"
(,)
1 1 1 1 10 ,
P Et
I (Comparative Compound F)
Uw
Et
Non-aqueous electrolyte solutions were prepared and coin-type batteries were
obtained in the same manner as in Example 14, except that the respective Example
Compounds (3, 5, 8, 19 , 30, 31, 34, 57, 95, 109 and 169) were added in place of the
above-described Example Compound 2. For the thus obtained coin-type batteries , the initial
characteristics and the characteristics after high-temperature storage were evaluated in the
same manner as in Example 14. The results are summarized in Table 2 below.
[0159]
A non-aqueous electrolyte solution was prepared and a coin-type battery was
obtained in the same manner as in Example 14 except that , in the preparation of the
non-aqueous electrolyte solution of Example 14, LiBF4 was further added such that the LiBF4
concentration in the eventually obtained non-aqueous electrolyte solution became 0.01 mol/L.
For the thus obtained coin-type battery, the initial characteristics and the characteristics after
high-temperature storage were evaluated in the same manner as in Example 14. The results
are summarized in Table 2 below.
[0160]
In Comparative Example 15, a non-aqueous electrolyte solution was prepared and a
coin-type battery was obtained in the same manner as in Example 14, except that the
above-described Example Compound 2 was not added.
Furthermore , in Comparative Examples 16 to 27, non-aqueous electrolyte solutions
were prepared and coin-type batteries were obtained in the same manner as in Example 14,
except that the above-described respective Comparative Compounds A to L were added in
place of the above-described Example Compound 2.
In Comparative Example 28 , a non-aqueous electrolyte solution was pr, ,. , red and a
coin-type battery was obtained in the same manner as in Example 14, except that the
above-described Example Compound 2 was not added and LiBF4 was added such that the
LiBF4 concentration in the eventually obtained non-aqueous electrolyte solution became 0.01
mot/L.
For the thus obtained coin-type batteries, the initial characteristics and the
characteristics after high-temperature storage were evaluated in the same manner as in
Example 14. The results are summarized in Table 2 below in the same manner as those of
Examples.
[0161] [Table 1]
Llc ctrolyt;c. Battery Discharge (apacity
Additive
(viol/0 resistance capacity retention rate
59
[ S2 ] ai.er after
high-temperature high--temperature
storage [mAh_] storage [%]
Example
Example I LiPF6 ( 1.0) Compound 2 91 3.1 77
0.5% by mass
Example
Example 2 LiPF6(1.0) Compound 3 98 3.0 76
0.5% by mass
Example
Example 3 LiPF6 ( 1.0) Compound 5 103 3.0 74
0.5% by mass
Example
Example 4 LiPF6( 1.0) Compound 8 110 3.0 74
0.5% by mass
Example
Example 5 LiPF6(1.0) Compound 19 95 3.0 74
0.5% by mass
Example -- -
Example 6 LiPF6 ( 1.0) Compound 30 92 3.1 77
0.5% by mass
Example
Example 7 LiPF6( 1.0) Compound 31 94 3.0 75
0.5% by mass
Example
Example 8 LiPF6 ( 1.0) Compound 34 99 3.0 75
0.5% by mass
Example
Example 9 LiPF6 ( 1.0) Compound 57 86 3.0 76
0.5% by mass
Example
Example 10 LiPF6(1.0) Compound 95 96 3.1 78
0.5% by mass
- --- Example ^- -
Example 11 LiPF6(1.0) 94 3.1 7
Compound 109
60
0.5% by mass
Example
Example 12 LiPF6( 1.0) Compound 169 101 3.1 73
0.5% by mass
LIPf6 (1.0 ) Example
Example 13 °'r LiBF4 Compound 2 84 3.1 76
(0.01) 0.5% by mass
Comparative
LiPf6 ( 1. 0) 177 2.8 70
Example 1
Comparative
Comparative
L.IPF6 ( 1.0) Compound A 140 2.8 66
Example 2
(.).5% by mass
Comparative
Comparative
LIPF6 ( 1.0) Compound B 151 2.9 68
Example 3
0.5% by mass
Comparative
Comparative
LiPf6( 1.0 ) Compound C 164 2.8 66
Example 4
0.5% by mass
Comparative
Comparative
LiPf6(1.0) Compound D 113 2.9 68
Example 5
0.5% by mass
Comparative
Comparative
Liff6 ( 1.0) Compound E 184 3.0 70
Example 6
0.5% by mass
Comparative
Comparative
Liff6( 1 .0) Compound f 235 2.9 67
Example 7
0.5% by mass
Comparative
Comparative
LiPf6( 1.0 ) Compound G 150 2.€3 67
Example €3
0.5% by mass
Comparative
Comparative
L. iF F6 (1.0) Compound H 136 3.0 68
Example 9
0.5% by mass
Comparative LiPF6(1.0) Comparative 121 2.7 64
61
Example 10 Compound I
0.5% by mass
Comparative
Comparative
LIPF6(1.0) Compound J 132 2.9 67
Example 11
0.5% by mass
Comparative
Comparative
LiPF6(1.0) Compound K 138 2.8 66
Example 12
0.5% by mass
Comparative
Comparative
LiPF6(1.0) Compound L 94 3,0 71
Example 13
0.5% by mass
LiPF6(1.0)
Comparative
d- LiBF4 95 2.9 68
Example 14
(0.01)
[0162] [Table 2]
- -^ Discharge Capacity
Battery capacity retention rate
Electrolyte
Additive resistance after after
( mol/L)
high temperature high-temperature
storage [m0Ah1
---
storage [%1
VC Example
Example 14 L iPF6 (1.0) 0.5% by Compound 2 83 3.3 82
mass 0.5% by mass
VC Example
Example 15 LiPF6 ( 1.0) 0.5% by Compound 3 89 3.2 81
mass 0.5% by mass
VC Example
Example 16 LIPF6 ( 1.0) 0.5% by Compound 5 94 3.2 79
mass 0.5% by mass
VC Example
Example 17 LIPF6 ( 1.0) 0.5% by Compound 8 96 3.2 79
mass 0.5% by mass
---- VC Example
Example 18 L1PF6 (1.0) 0.5% by Compound 19 86 3.2 /9
mass 0.5% by mass
62
VC Example
Example 19 LiPF66(1.0) 0.5% by Compound 30 84 3.3 82
mass 0.5% by mass
VC Example
Example 20 LiPF6 (1.0) 0.5% by Compound 31 85 3.2 80
mass 0.5% by mass
VC Example
Example 21 LiPF 6 (1.0) 0.5% by Compound 34 90 3.2 80
mass 0.5% by mass
VC Example
Example 22 LiPF6(1.0) 0.5% by Compound 57 78 3.2 81
--
mass 0.5% by mass
- - VC Example
Example 23 LiPF6 (1.0) 0.5% by Compound 95 87 3.3 83
mass 0.5% by mass
Example
VC
Compound
Example 24 LiPF6 (1.0) 0.5% by 85 3.3 83
109
mass
0.5% by mass
Example `- -
VC
Compound
Example 25 LiPF6(1.0) 0.5% by 92 3.3 79
169
mass
0.5% by mass
LiPF6(1.0) \/ CI Example
Example 26 i LiBF4 0.5% by Compound 2 76 3.3 81
(0.01) mass 0.5% by mass
VC
Comparative
LiPF6(1.0) 0.5% by - 125 2.8 72
Example 15
mass
VC Comparative
Comparative
LiPF6(1.0) 0.5% by Compound A 122 2.8 68
Example 16
mass 0.5% by Mass
VC Comparative
Comparative
LiPF6 (1.0) 0.5% by Compound B 131 2.9 70
Example 17
mass 0.5% by mass
Comparative LiPF6 (1.0) VC; Comparative 143 2.8 68
63
Example 18 0.5% by Compound C
mass 0.5% by mass
VC Comp arat ive
Comparative
LiPF"6 (1.0) 0.5% by Compound D 98 2.9 70
Example 19
mass 0.5% by mass
VC Comparative
Comparative
LiPF6(1.0) 0.5% by Compound E 160 3.0 72
Example 20
mass 0.5% by mass
VC Comparative
Comparative
LiPE6(1.0) 0.5% by Compound IF 204 2.9 69
Example 21
mass 0.5% by mass
VC; Comparative
Comparative
LiPF6 (1.0) 0.5% by Compound G 130 2.8 69
Example 22
mass 0.5% by mass
VC; Comparative
Comparative
LiPF6(1.0) 0.5% by Compound 1.1 118 3.0 70
Example 23
mass 0.5% by mass
VC Comparative
Comparative
Liff6(1.0) 0.5% by Compound 1 105 2.7 66
Example 24
mass 0.5% by mass
VC Comparative
Comparative
LiPE6(1.0) 0.5% by Compound J 115 2.9 69
Example 25
mass 0.5% by mass
VC, Comparative
Comparative
LiPE6(1.0) 0.5% by Compound K 120 2.8 68
Example 26
mass 0.5% by mass
VC; Comparative
Comparative
LiPF6(1.0) 0.5% by Compound L 82 3.0 73
Example 27
mass 0.5% by mass
LiPF'6(1.0) VC - ^'
Comparative
+LiBF4 0.5% by 83 2.9 70
Example 28
(0.01) mass
[0163] From the results shown in Table 1, comparing Examples 1 to 12 where the silyl ester
group-containing compound of the present invention was added and Comparative Example 1
where the cot-upound of the present invention was not added, it is seen that, by adding the
compound of the present invention, the battery resistance, which is an initial characteristic,
6L
can be reduced and a high capacity retention rate after high-temperature storage can be
attained. From these results, it is understood that an addition of the compound of the present
invention contributes to an extended battery service life.
[0164] Furthermore, focusing on the ester group of phosphonic acid derivative, from
comparisons between a silyl ester group-containing compound of the present invention
(Example Compound 2) and a compound in which the silyl ester group is substituted with an
OH group (Comparative Compound A) as well as a compound in which the silyl ester group
is substituted with an alkyl ester group (Comparative Compound B), it is seen that, by adding
the compound of the present invention, the battery resistance, which is an initial characteristic,
can be reduced and a high capacity retention rate after high temperature storage can be
attained. From these results, it is understood that an addition of a silyl ester group shown in
the present invention contributes to an extended battery service life.
In Comparative Example 13 where Comparative Compound L, which is silyl ester
group-substituted phosphoric acid, was used, although an effect of reducing the initial battery
resistance could be confirmed, the capacity retention rate after high-temperature storage was
lower than that of those cases where the compound of the present invention was used;
therefore, it is seen that the silyl ester group-containing phosphonic acid derivative according
to the present invention is useful.
[0165] Paying attention to Examples 1 and 13 and Comparative Example 14, it is seen that a
further reduction in the battery resistance could be achieved by further adding LiBF4 to the
compound of the present invention as compared to those cases where LiBF4 was not added.
Meanwhile, when LiBF4 was solely added, although a reduction in the battery
resistance could be attained, the capacity retention rate after high temperature storage was not
improved (Comparative Example 14). From these results, it is seen that an addition of the
silyl ester group-containing phosphonic acid derivative according to the present invention and
a tetrafluoroborate contributes to an extended battery service life.
[0166] These effects of the compound of the present invention explained with reference to
the results shown in Table I can also be confirmed from the results in Table 2 in the same
manner.
Furthermore, as clearly seen from comparisons between Examples I to 13 in Table 1
and Examples 14 to 26 in Table 2, by using the compound of the present invention and VC in
combination, the battery resistance, which is an initial characteristic, can be further reduced
and the capacity retention rate after high-temperature storage can be further improved.
[0167] The entire disclosure of Japanese Patent Application No. 2010-117404 is
incorporated in this specification by reference.
65
All publications, patent applications, and technical standards described in this
specification are herein incorporated by reference to the same extent as if each individual
publication, patent application, or technical standard was specifically and individually
indicated to be incorporated by reference.
66

CLAIMS
1. A non-aqueous electrolyte solution, comprising a silyl ester group-containing
phosphonic acid derivative.
2. The non aqueous electrolyte solution according to claim 1, wherein the silyl ester
group-containing phosphonic acid derivative is a compound represented by the following the
Formula (1):
wherein, in the Formula (1), in represents 0 or 1; n represents 1 or 2; m + n = 2;
R1 represents
a hydrogen atom,
an alkyl group having 1 to 12 carbon atoms,
a haloalkyl group having 1 to 12 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which may be substituted with a halogen
atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon
atoms),
an alkenyl group having 2 to 12 carbon atoms,
an alkyl group having 1 to 6 carbon atoms, which is substituted with at least one
=SiR'8R'9R2° group (wherein R'89 R'9 and R20 each independently "r er^ppresent an alkyl group1
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atones, an alkoxy group
having 1 to 6 carbon atornsor a phenyl group),
a haloalkyl group having 1 to 6 carbon atoms, which is substituted with at least one
SiR18R19R20 group (wherein R18, R19 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a .5- or 6-menrbered heterocyclic group (which may or may not be substituted), or
a group represented by any one of the following Forrnutae (:3-1) to (3-10);
67
R2 represents
a hydrogen atom,
an alkyl group having 1 to 6 carbon atoms,
a haloalkyl group having I to 6 carbon atones,
an alkenyl group having 2 to 6 carbon atoms, or
a phenyl group (which may be substituted with a halogen atom, an alkyl group
having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms);
R3 represents
an alkyl group having 1 to 6 carbon atoms,
an alkenyl group having 2 to 6 carbon atoms,
an alkoxy group having 1 to 6 carbon atoms,
a phenyl group,
a -O-SiR6R7R8 group (wherein R6, R7 and R8 each independently represent an alkyl
group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy
group having 1 to 6 carbon atoms or a phenyl group), or
a group in which, when n is 2, two R 3s are linked with each other to form a0-, an
alkylene group having 1 to 3 carbon atoms or -0-(SiR16R17 0),,_ (wherein R'6 and R17
independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group; and p
represents an integer of 1 to 3); and
1?4 and R5 each independently represent
an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon
atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a -O-SiR6t7R8 group
(wherein R6, R7 and R8 each independently represent an alkyl group having 1 to 6 carbon
atoms, an alkenyl group having 2 to 6 carbon aton-ms, an alkoxy group having 1 to 6 carbon
atoms or a phenyl group):
68
b (-) (3- 2)
0
0
a,_Y_rI II._R i b
0
)
7 )
0
(3-8 )
wherein, in Formulae (3-1) to (3-10), R`'represents a divalent hydrocarbon group
having 1 to 12 carbon atoms which may be substituted with a halogen atom; and Re represents
a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen
atom, or a _SiR21R22R23 group (wherein R21, R22 and R23 each independently represent an
alkyl group having I to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an
alkoxy group having I to 6 carbon atoms or a phenyl group).
3. The non aqueous electrolyte solution according to claim 2, wherein in is 0 and n is 2
in the Formula (1).
4. The non-aqueous electrolyte solution according to claim 3, wherein, in the Formula
(1),
R1 is
an alkyl group having 1 to 6 carbon atoms,
a fluoroalkyl group having I to 6 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which niay be substituted with a fluorine
atom, art alkyl group having, I to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon
69
atoms),
an alkenyl group having 2 to 6 carbon atoms,
an alkyl group having 1 to 6 carbon atoms, which is substituted with one
SiR18R19R20 group (wherein R", R'9 and R2° each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a fluoroalkyl group having 1 to 6 carbon atoms, which is substituted with one
-SiR18R19R2° group (wherein R18, R'9 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms or a phenyl group),
a 5 or 6-i-nembered heterocyclic group (wherein the heterocyclic group is a furyl
group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a (hiazolyl
group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a
tetrazolyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group
or a triazinyl group and may be substituted with a fluorine atom, an alkyl group having I to 6
carbon atoms or a fluoroalkyl group having I to 6 carbon atoms), or
a group represented by any one of the Formulae (3-1), (3-9) and (3-10), with the
proviso that, in the Formulae (3-1), (3-9) and (3-10), Ra is an alkylene group having 1 to 6
carbon atoms, a fluoroalkylene group having I to 6 carbon atoms, a phenylene group (which
may be substituted with a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a
fluoroalkyl group having 1 to 6 carbon atoms) or an alkenylene group having 2 to 6 carbon
atoms, and Rb is an alkyl group having I to 6 carbon atoms, a fluoroalkyl group having 1 to 6
carbon atoms, a phenyl group (which may be substituted with a fluorine, atom, are alkyl group
having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms), an alkenyl
group having 22 -to 6 carbon atoms, or a -SiR21R22R23 group (wherein R21 R22 and R23 are each
independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6
carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group).
5. The non-aqueous electrolyte solution according to claim 3 or 4, wherein, in the
Formula (1),
R1 is
an alkyl group having I to 6 carbon atoms,
a fluoroalkyl group having I to 6 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which may be substituted with a fluorine
atone, an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon
70
atoms
an alkenyl group having 2 to 6 carbon atoms,
an alkyl group having 1 to 6 carbon atoms, which is substituted with one
°SiR'8R19R20 group (wherein R'8 R'9 and R20 are each independently an alkyl group having 1
to 6 carbon atoms),
a fluoroalkyl group having 1 to 6 carbon atoms, which is substituted with one
-SiR18R19R20 group (wherein R'8, R19 and R20 are each independently an alkyl group having 1
to 6 carbon atoms), or
a group represented by any one of the Formulae (3 -1), (3-9) and (3x10), with the
proviso that, in the Formulae (3-1), (3-9) and (3-10), Ra is an alkylene group having 1 to 6
carbon atoms and Rb is an alkyl group having 1 to 6 carbon atoms or a -SiR2IR22R23 group
(wherein R21, R22 and R23 are each independently an alkyl group having 1 to 6 carbon atoms),
and
R3, R4 and R5 are each independently an alkyl group having 1 to 6 carbon atoms, an
alkenyl group having 2 to 6 carbon atoms or a phenyl group.
6. The non aqueous electrolyte solution according to any one of claims 3 to 5, wherein
the compound represented by the Formula (1) is
methylphosphonic acid bis(trimethylsilyl) ester,
methylphosphonic acid bis(tert-butyldimethylsilyl) ester,
methylphosphonic acid bis(allyldimethylsilyl) ester,
nnethylphosphonic acid bis(triphenylsilyl) ester,
phenylphosphonic acid bis(trimethylsilyl) ester,
vinylphosphonic acid bis(trimethylsilyl) ester,
1-propenylphosphonic acid bis(trimethylsilyl) ester,
[difhroro(trirnethylsilyl)methyl]phosphonic acid bis(trimethylsilyl) ester,
[(trimethylsilyloxy)methyl]phosphonic acid bis(trimethylsilyl) ester,
[(methanesulfonyl-oxy)methyl]phosphonic acid bis(trimethylsilyl) ester,
methylenebisphosphonic acid tetrakis(trimethylsilyl) ester, or
2,4,4,6,6-pentan°ethyl-1,3,5-trioxa-2-pliospha- 4,6-disilacyclohexane-2-oxide.
7. The non-aqueous electrolyte solution according to any one of claims 1 to 6, wherein
the content of the silyl ester group containing phosphonic acid derivative is 0.001% by mass
to 10% by mass.
71
8. The non-aqueous electrolyte solution according to any one of claims 1 to 7, further
comprising a tetrafluoroborate.
9. The non-aqueous electrolyte solution according to claim 8, wherein the
tetrafluoroborate is lithium tetrafluoroborate (LiBF4).
10. The non-aqueous electrolyte solution according to claim 8 or 9, wherein the
concentration of the tetrafluoroborate is 0.0001 rnol/L, to 2 mol/1..
11. An additive for lithium secondary batteries, comprising a compound represented by
the following Formula (1):
I
wherein, in the Formula (1), m represents 0 or 1; n represents 1 or 2; in + n = 2;
RI represents
a hydrogen atom,
an alkyl group having 1 to 12 carbon atoms,
a haloalkyl group having 1 to 12 carbon atoms,
an aryl group having 6 to 14 carbon atoms (which may be substituted with a halogen
atom, an alkyl group having I to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon
atoms),
an alkenyl group having 2 to 12 carbon atoms,
an alkyl group having 1 to 6 carbon atoms, which is substituted with at least one
-SiR18R19R20 group (wherein R18 , R19 and R2° each independently represent an alkyl group
having I to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms , an alkoxy group
having I to 6 carbon atoms or a phenyl group),
a haloalkyl group having 1 to 6 carbon atoms, which is substituted with at least one
=SiR18R19R20 group (wherein R18, R19 and R20 each independently represent an alkyl group
having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group
72
having 1 to 6 carbon atoms or a phenyl group),
a 5- or 6-membered heterocyclic group (which may or may not be substituted), or
a group represented by any one of the following Formulae (3-1) to (3-10);
R2 represents
a hydrogen atom,
an alkyl group having 1 to 6 carbon atoms,
a haloalkyl group having l to 6 carbon atoms,
an alkenyl group having 2 to 6 carbon atoms, or
a phenyl group (which may be substituted with a halogen atom, an alkyl group
having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms);
R3 represents
an alkyl group having 1 to 6 carbon atoms,
an alkenyl group having 2 to 6 carbon atoms,
an alkoxy group having 1 to 6 carbon atoms,
a phenyl group,
a -O-SiR6R1R8 group (wherein R6, R7 and R8 each independently represent an alkyl
group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy
group having 1 to 6 carbon atoms or a phenyl group), or
a group in which, when n is., two Ras are linked with each other to form -0-, an
alkylene group having 1 to 3 carbon atoms or -,O-(SiR16R17 O)u_ (wherein R16 and R17
independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group havi
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a phenyl group; and p
represents an integer of 1 to 3); and
R4 and R5 each independently represent
an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon
atoms, an alkoxy group having I to 6 carbon atoms, a phenyl group or a -O-SiR6R7R8 group
(wherein R6, R7 and R8 each independently represent an alkyl group having 1 to 6 carbon
atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon
atoms or a phenyl group):
73
Rb
1
-O-Rb
0
0 R,
0
01
(3--9)
b
0
11
11 1 )
wherein, in Formulae (3-1) to (3-10), Ra represents a divalent hydrocarbon group
having 1 to 12 carbon atoms which may be substituted with a halogen atom; and Rb represents
a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen
atom, or a-SiR21R22R23 group (wherein R21, R22 and R23 each independently represent an
alkyl group having 1 to 6 carbon atoms, an alkcnyl group having 2 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms or a phenyl group).
12. A lithium secondary battery, comprising:
a positive electrode;
a negative electrode containing, as a negative electrode active material, at least one
selected from lithium metal, lithium-containing alloys, metals or alloys that are capable of
forming an alloy with lithium, oxides capable of doping/dedoping lithium ions, transition
metal nitrides capable of doping/dedoping lithium ions and carbon materials capable of
doping/dedoping lithium ions; and
the non-aqueous electrolyte solution according to any one of claims I to 10.
13. A lithium secondary battery, which is obtained by charging/discharging a lithium
74
secondary battery comprising:
a positive electrode;
a negative electrode containing, as a negative electrode active material, at least one
selected from lithium metal, lithium-containing alloys, metals or alloys that are capable of
forming an alloy with lithium, oxides capable of doping/dedoping lithium ions, transition
metal nitrides capable of doping/dedoping lithium ions and carbon materials capable of
doping/dedoping lithium ions; and
the non-aqueous electrolyte solution according to any one of claims I to 10.