Abstract:
The present invention pertains to a non aqueous electrolyte that contains a non aqueous electrolyte solvent a supporting electrolyte and a sulfonate represented by a predetermined formula and is characterized by the concentration of the sulfonate being at least 0.001 wt% and less than 0.2 wt% with respect to the total mass of the non aqueous electrolyte.
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Notices, Deadlines & Correspondence
c/o NEC Corporation 7 1 Shiba 5 chome Minato ku Tokyo
1088001
2. NAKAMURA Akinobu
c/o NEC Corporation 7 1 Shiba 5 chome Minato ku Tokyo
1088001
3. UTSUGI Koji
c/o NEC Corporation 7 1 Shiba 5 chome Minato ku Tokyo
1088001
Specification
NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY
Technical Field
[OOOll
The present invention relates to a non-aqueous electrolyte secondary
battery excellent in stability.
Background Art
[0002l
The uses of a lithium ion secondary battery among secondary batteries
have been spreading not only as a power source for consumer products such
as notebook computers and mobile devices including a cellular phone but also,
in recent years, as a power source for driving machines such as an electric
vehicle, an electric motor cycle, and a power-assisted bicycle, a power source
for small electrically driven machine, and a power source for a power storage
system making use of its characteristics such as small and light weight and
high energy density.
[00031
As a substance capable of desorbing and inserting a lithium ion, a
lithium based complex oxide of a transition metal, a carbon material, lithium
metal, an alloy based compound, and an oxide carbon material are generally
used for a material for positive and negative electrode active materials of a
lithium ion secondary battery. Moreover, a carbonate based solvent and a
lithium salt as a supporting salt are generally used as a non-aqueous
electrolyte.
[00041
In a charging and discharging process of the secondary battery, a
desorption and insertion reaction of a lithium ion occurs a t an interface of an
electrode and an electrolyte. However, besides the reaction, an electrolyte
solvent or the supporting salt causes a decomposition reaction to form a
coating film having a high resistance on the surface of the electrode, which
inhibits the desorption and insertion reaction of the lithium ion that
primarily should occur. As a result thereof, irreversible lowering of
discharging capacity or the like is accelerated, which leads to deterioration of
the battery. Therefore, various ideas have been devised to suppress the
deterioration.
[00051
As one of the ideas, a method for suppressing the decomposition
reaction by forming a protective film on the surface of the electrode is
included, and the means thereof proposes adding an additive having coating
film-forming capability to the electrolyte. Patent Literatures 1 to 3, for
example, discloses that when a cyclic monosulfonic acid ester is used as an
additive, a coating film is formed on the surface of the electrode to improve
battery properties. A proposal to use a cyclic disulfonic acid ester has also
been made recently as shown by Patent Literature 4 because the cycle
properties and the storage properties (suppression of an increase in
resistance and the suppression of lowering in a capacity holding ratio) can be
more improved than those for the secondary battery using the cyclic
monosulfonic acid ester. As described herein, a sulfonic acid ester-based
compound is useful as an electrolyte additive having a coating film-forming
capability.
Citation List
Patent Literature
[00061
Patent Literature 1: Japanese Patent Laid-Open No. 63-102173
Patent Literature 2: Japanese Patent Laid-Open No. 2000-3724
Patent Literature 3: Japanese Patent Laid-Open No. 11-339850
Patent Literature 4: Japanese Patent Laid-Open No. 2004-281368
Summary of Invention
Technical Problem
[00071
However, when the non-aqueous electrolyte containing the sulfonic acid
ester-based additive is used for production of the secondary battery after the
non-aqueous electrolyte is left standing under, for example, a high
temperature, there has been a problem that the lowering of the battery
capacity or the deterioration of storage and cycle properties for the secondary
battery occurs.
Solution to Problem
[0008l
The present invention relates to a non-aqueous electrolyte comprising a
non-aqueous electrolyte solvent, a supporting salt, and a sulfonate
represented by the following general formula (1):
[00091
wherein R1 and R2 each independently represent a hydrogen atom, a halogen
atom, or C1 to C5 alkyl group, alkenyl group or alkoxy group, and M
represents an alkali metal or an alkaline earth metal,
wherein the concentration of the sulfonate is 0.001 wt% or more and
less than 0.2 wt% based on the total mass of the non-aqueous electrolyte.
Advantageous Effects of Invention
[00101
According to the present invention, the charging and discharging
efficiency, the cycle properties, and so on of a non-aqueous electrolyte
secondary battery can be improved.
Brief Description of Drawing
[00111
Figure 1 is a schematic drawing of a non-aqueous electrolyte secondary
battery of the present invention.
Description of Embodiments
[0012l
According to the present embodiment, the battery life in a cycle test or
a storage evaluation test can be improved particularly in a non-aqueous
electrolyte secondary battery using a non-aqueous electrolyte containing a
sulfonic acid ester-based compound.
[00131
Hereinafter, the constitution of the non-aqueous electrolyte and the
non-aqueous electrolyte secondary battery using the non-aqueous electrolyte
of the present invention will be described.
[00141
(Non-Aqueous Electrolyte)
In the present embodiment, the non-aqueous electrolyte comprises a
non-aqueous electrolyte solvent, a supporting salt, and a sulfonate
represented by the following formula (I), and the concentration of the
sulfonate represented by the following formula (1) is 0.001 wt% or more and
less than 0.2 wt% based on the total mass of the non-aqueous electrolyte. In
addition, the sulfonate represented by the following formula (1) is hereinafter
sometimes described simply as the "sulfonate".
[00151
[00161
In the formula (I), RI and Rz each independently represent a hydrogen
atom, a halogen atom, or C1 to C5 alkyl group, alkenyl group, or alkoxy
group, and M represents an alkali metal or an alkaline earth metal,
preferably lithium.
[00171
In the formula (I), it is preferable that RI and R3 are each
independently a hydrogen atom, C1 to C5 alkyl group, or alkoxy group, more
preferably a hydrogen atom, methyl group, ethyl group, methoxy group, or
ethoxy group, further more preferably a hydrogen atom, methyl group, or
ethyl group.
[OOl8l
Examples of the compound represented by the general formula (I)
include dilithium methanedisulfonate, dilithium 1,l-ethanedisulfonate,
dilithium 1-methyl-1,l-ethanedisulfonatdei,l ithium 1,l-propanedisulfonate,
dilithium 2-methyl-1,l-propanedisulfonate, dilithium 1,l-butanedisulfonate,
dilithium methoxymethanedisulfonate, dilithium ethoxymethanedisulfonate,
dilithium 1,l-prop-2-yldisulfonateb;u t the present invention is not limited to
these. Moreover, the non-aqueous electrolyte of the present embodiment
may contain the compound represented by the general formula (1) alone or in
combinations of two or more.
[00191
The non-aqueous electrolyte of the present embodiment contains the
sulfonate represented by the formula (1) i n an amount of 0.001 wt% or more
and less than 0.2 wt% based on the total mass of the non-aqueous electrolyte,
preferably 0.001 wt% or more and 0.15 wt% or less. The inventors of the
present invention have made diligent studies and, as a result thereof, have
found that when the sulfonate concentration in the non-aqueous electrolyte is
made within the above-described range, the lowering of the capacity of the
non-aqueous electrolyte secondary battery manufactured using the nonaqueous
electrolyte is small and the battery properties are favorable. When
the concentration of the sulfonate represented by the formula (1) is 0.2 wt%
or more based on the total mass of the non-aqueous electrolyte, the
deterioration of the electrolyte becomes remarkable, and when a secondary
battery is manufactured using the non-aqueous electrolyte having a sulfonate
concentration of 0.2 wt% or more based on the total mass of the electrolyte,
the battery properties become worse in such a way that the capacity
retention ratio in the cycle property evaluation is lowered.
[0020l
It is preferable that the non-aqueous electrolyte of the present
invention contains a disulfonic acid ester compound such as a chain
disulfonic acid ester compound and a cyclic disulfonic acid ester compound.
A coating film is formed on the surface of the electrode to improve battery
properties by the electrolyte containing the disulfonic acid ester compound.
[00211
Specific examples of the disulfonic acid ester compound include, but not
limited to these in the present invention, dimethyl rnethanedisulfonate,
diethyl rnethanedisulfonate, bis(trifluoromethyl) rnethanedisulfonate,
bis(trimethylsilyl) rnethanedisulfonate, ethylene ethylenedisulfonate,
ethylene rnethanedisulfonate, methylene rnethanedisulfonate, propylene
rnethanedisulfonate, ethylene 1,l-ethanedisulfonate, and dimethyl 1,lethanedisulfonate.
The electrolyte of the present embodiment may contain
the disulfonic acid ester compound alone or in combinations of two or more.
Loo221
The concentration of the disulfonic acid ester compound in the nonaqueous
electrolyte is not particularly limited, however it is preferably 0.2
wt% or more and less than 10 wt%, more preferably 0.2 wt% or more and 5
wt% or less, further more preferably 0.2 wt% or more and 3 wt% or less.
[00231
It is considered that the sulfonate represented by the formula (1) is
generated due to the occurrence of the decomposition of the disulfonic acid
ester compound caused by the reaction of the decomposition product or the
like of the supporting salt with the disulfonic acid ester compound in the
non-aqueous electrolyte containing the disulfonic acid ester compound. On
this occasion, it is anticipated that a free acid is generated, and it is
considered that the free acid becomes a cause of the lowering of the battery
capacity and the deterioration of storage and cycle properties.
Loo241
The sulfonate represented by the formula (1) becomes liable to be
generated in the case where, for example, the non-aqueous electrolyte
containing the disulfonic acid ester compound is stored at a high temperature
for a long period of time (3 months or more at 35OC, for example) or water is
mixed into the non-aqueous electrolyte. Accordingly, it is preferable that
the non-aqueous electrolyte is stored at a low temperature (room
temperature or less, for example, preferably 10°C or less) or the water
content in the non-aqueous electrolyte is made 20 ppm or less for the purpose
of making the concentration of the sulfonate in the non-aqueous electrolyte
within the above-described range.
[00251
Examples of the supporting salt include compounds such as LiPFs,
LiBF4, LiAsFs, LiSbFs, LiC104, LiAlC14, LiN(CkFzk+lSO2)2, and
L ~ N ( C ~ F ~ ~ + ~ S O ~ ) ( C(k~, Fn,Z a~nd+ m~ SeaOch~ i)n dependently represent a
natural number), or a mixture thereof. It is preferable that the
concentration of the supporting salt in the non-aqueous electrolyte is 0.5 to
2.0 mollL. It becomes easy to adjust the density, the viscosity, the
conductivity, and so on i n an appropriate range by making the concentration
of the supporting salt within the above-described range.
[00261
In the present embodiment, examples of the non-aqueous electrolyte
solvent of the non-aqueous electrolyte include, but not particularly limited to,
cyclic carbonate compounds, chain carbonate compounds, chain carboxylic
acid ester compounds, cyclic carboxylic acid ester compounds, cyclic ether
compounds, chain ether compounds, phosphoric acid ester compounds, and
fluorinated derivatives thereof. And, among these compounds, it is
preferable that the non-aqueous electrolyte solvent of the non-aqueous
electrolyte contains a cyclic carbonate compound and more preferably
contains 10 to 60% of the cyclic carbonate compound based on 100% (volume
ratio) of the non-aqueous electrolyte solvent. The non-aqueous electrolyte
solvent may be used alone or in combinations of two or more.
[00271
Examples of the cyclic carbonate compound include ethylene carbonate
(EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate
(vc), and, among these compounds, ethylene carbonate (EC) and propylene
carbonate (PC) are more preferable.
[00281
Examples of the chain carbonate compound include dimethyl carbonate
(DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (MEC).
Examples of the chain carboxylic acid ester compound include ethyl acetate,
methyl propionate, ethyl formate, ethyl propionate, methyl butyrate, ethyl
butyrate, methyl acetate, and methyl formate. Examples of the cyclic
carboxylic acid ester compound include y-butyrolactone. Examples of the
cyclic ether compound include tetrahydrofuran and 2-methyltetrahydrofuran.
Examples of the chain ether compound include 1,2-ethoxy ethane (DEE) and
ethoxy methoxy ethane (EME). Examples of the phosphoric acid ester
compound include trimethyl phosphate, triethyl phosphate, and tributyl
phosphate.
[00291
The non-aqueous electrolyte of the present embodiment may contain a
monosulfonic acid ester compound such as 1,3-propane sultone, 1,4-butane
sultone, methyl methanesulfonate, methyl ethanesulfonate, methyl
trifluoromethanesulfonate.
[00301
Hereinafter, the constitution of the non-aqueous electrolyte secondary
battery of the present invention will be described with reference to the
drawing. Figure 1 is an example of a schematic drawing of a non-aqueous
electrolyte secondary battery of the present invention.
[00311
The battery relating to the present invention has a structure shown in
Figure 1, for example. The battery has a layered structure in which a
porous separator 16 is present between a positive electrode and a negative
electrode. The positive electrode is manufactured by forming a layer 12
containing a positive electrode active material as a film on a surface of a
positive electrode collector 11. The negative electrode is manufactured by
forming a layer 13 containing a negative electrode active material as a film
on a surface of a negative electrode collector 14.
[00321
Examples of the positive electrode active material used for the layer 12
containing a positive electrode active material include lithium-containing
complex oxides such as LiCoOz, LiNiOs, and LiMneOa which are compounds
capable of desorbing and inserting a lithium ion. Moreover, compounds in
which the portion of the transition metal in these lithium-containing complex
oxides is replaced with another element may be used.
[00331
Moreover, a lithium-containing complex oxide having a plateau at 4.5 V
or more in terms of electric potential vs. lithium metal can also be used as a
positive electrode active material. Examples of the lithium-containing
complex oxide include spinel type lithium manganese complex oxides, olivine
type lithium complex oxides, and inverse spinel type lithium-containing
complex oxides. The lithium-containing complex oxide may be, for example,
a compound represented by Li,(MxMnz-J04 (where 0