An Electrochemical Device Comprising A Gel Polymer Electrolyte
Abstract:
An electrochemical device comprising a gel polymer electrolyte, wherein the gel polymer
electrolyte comprising a diacrylamide compound as a precursor for formation of a crosslinked
polymer which is formed by crosslinking of a diacrylamide monomer and/or oligomer; wherein
the diacrylamide compound is a monomer represented by Formula I or an oligomer thereof-wherein R" and R2 are each independently hydrogen or an unsubstituted or substituted
CI-Cs alkyl, and R1 and R2 may be taken together to form a saturated or unsaturated ring; and
n is an integer of 0 to 4, and a direct bond is formed if n is 0.
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Notices, Deadlines & Correspondence
105- 1403 Samsung Pureun Apt. Jeonmin-dong Yuseong-gu Daejeon 305- 727 Republic of Korea
2. EUN YOUNG KIM
1648-5 Bongeheon 11- dong Gwanak-gu Seoul 151- 850
3. JOO-HWAN SUNG
8-1102 Sujeong Town Apt. 909 Dunsan-dong Seo-gu Daejeon 302- 120
4. DONGMYUNG KIM
103- 1401 Hwangsil Apt. Wolpyeong dong Seo-Gu Daejeon 302- 280
Specification
GEL-TYPED POLYMER ELECTROLYTE CONTAINING
IACRYL AMIDE-BASED POLYMERIC MATERIAL AND
ELECTROCHEMICAL DEVICE COMPRISING THE SAME
FIELD OF THE INVENTION
The present invention relates to a gel polymer electrolyte containing a
diacrylamde-based polymeric material and a secondary battery comprising the same.
More specifically, the present invention relates to a secondary battery which is capable
10 of achieving a significant reduction of thickness swelling by incorporation of a certain
diacrylamide-based polymeric material into an electrolyte solvent and is also capable of
achieving improved safety of the battery by';prevention of electrolyte leakage from the
battery.
BACKGROUND OF T][JT; INVENTION
15 Technological development and increased demand for mobile equipment have
led to a rapl.. increase in the demand for batteries as an energy source . In order to cope
with such a trend, a great deal of research and study has been focused on batteries which
are capable of meeting various demands. Among other things , there has been an
increasing demand for lithium secondary batteries such as lithium-ion batteries , lithium-
20 ion polymer batteries and the like, which have high-energy density, high-discharge
voltage and superior power output stability.
Generally, lithium secondary batteries may be classified into lithium-ion
batteries containing liquid electrolytes per se, lithium-ion polymer batteries containing
liquid electrolytes in the form of gels, and lithium polymer batteries containing solid
electrolytes, depending upon types of electrolytes to be employed. Particularly, the
5 lithium-ion polymer batteries (or gel polymer batteries) have various advantages such as
high safety due to lower probability of fluid leakage as compared to liquid electrolyte
batteries, and feasible ultra-thinning and compactness of the battery shape and
substantial weight reduction of the battery, which thereby lead to increased demands
thereof.
10 As representative methods for fabrication of the lithium-ion polymer battery,
there 'are largely a fabrication method of a non-c osslinked polymer battery and a
fabrication method of a directly-crosslinked polymer battery, depending upon kinds of
matrix material for electrolyte impregnation. As the polymer matrix material, acrylateand
methacrylate-based materials having excellent radical polymerization reactivity,
15 and ether-based materials having superior electrical conductivity are largely used. In
particular, the latter directly-crosslinked polymer battery fabrication method is a method
of fabricating a battery by placing a Jelly-roll type or stack type electrode assembly
composed of electrode plates and a porous separator in a pouch, injecting a thermally
polymerizable polyethylene oxide (PEO)-based monomer or oligomer crosslinking
20 agent and`--an, electrolyte composition thereto, and thermally curing the injected
materials. The thus-fabricated battery has advantages of manufacturing processes in that
plates and separators of conventional lithium-ion batteries can be directly employed
without particular modifications or alterations. However, this method is known to suffer
from disadvantages in that when the crosslinking agent is not completely cured and
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remained in the electrolyte, it is difficult to achieve uniform impregnation due to an
increased viscosity, thereby significantly decreasing characteristics of the battery.
Further, secondary batteries containing such a gel polymer electrolyte suffer
from problems associated with deterioration of the battery safety due to leakage of the
5 electrolyte which results from the occurrence of localized swelling of the battery
thickness due to the precipitation of lithium metals from an anode during repeated
charge/discharge cycles of the battery, since uniform distribution of the electrolyte into
the electrode assembly is not achieved (see FIG. 1).
Therefore, there is a strong need in the art for the development of a technology
10 which is capable of securing the battery safety by preventing the thickness swelling
while maintaining the battery performance.
SUMMARY OF THE INV NTION
Therefore, it is an object of the present invention to solve the above problems,
and other technical problems that have yet to be resolved.
15 As a result of a variety of extensive and intensive studies and experiments to
solve the problems as described above, the inventors of the present invention have
surprisingly discovered that, upon the preparation of a gel polymer electrolyte via
thermal polymerization using diacrylamide monomers and/or oligomers, it is possible to
secure the battery safety by significant suppression of thickness swelling of the battery
20 to thereby prevent the electrolyte leakage, while having capacity performance
comparable to that of conventional batteries utilizing liquid electrolytes. The present
invention has been completed based on these findings.
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ESCRIPTJIGN OF THE DRAWINGS
The above and other objects, features and other advantages of the present
invention will be more clearly understood from the following detailed description taken
in conjunction with the accompanying drawings, in which:
5 FIG. 1 is a view depicting an increase of a battery cell thickness in a
conventional prismatic battery cell with respect to repeated cycles; and
FIG. 2 is a graph showing changes in charge capacity and battery cell thickness
with respect to increasing cycles, in test of Experimental Example I using batteries
fabricated in Examples and Comparative Examples.
10 DETAILED DESCRIPTION OF PREFERRED EM 0 IMENTS
In accordance with an aspect of the present invention, the above and other
objects can be accomplished by the provision of a gel polymer electrolyte comprising
a diacrylamide compound as a precursor for formation of a crosslinked polymer. That
is, the gel polymer electrolyte of the present invention comprises the electrolyte in the
15 form of gel, using, as a matrix material, a crosslinked polymer formed by crosslinking
of the diacrylamide compound as the precursor.
Therefore, it is possible to prevent the electrolyte leakage by inhibiting the
thickness swelling of the battery resulting from the precipitation of lithium metals from
an anode during repeated charge/discharge cycles of the battery, due to non-uniform
20 distribution of the electrolyte into the electrode assembly, consequently improving the
safety of the battery containing such an electrolyte.
More specifically, the diacrylamide compound has acrylamide groups and
therefore exhibits high reactivity with radicals. Therefore, it is believed that the
diacrylamide compound improves electrochemical stability of the final gel polymer
electrolyte via an improved extent of reaction. Consequently, because a contact area of
5 the electrolyte in contact with electrodes is decreased upon repeating charge/discharge
of the battery, the thickness swelling of the battery is suppressed by inhibition of side
reactions between the electrodes and the electrolyte arising from the decreased contact
area of the electrolyte in contact with the electrodes, and by the reduced vapor pressure
due to a gel polymer form of the electrolyte.
10 Further, it is possible' to minimize degradation of the battery performance,
since there is no dissociation and decreased migration of lithium ions, which may occur
in conventional gel polymer electrolytes, due to the presence of the polar functional
groups, i. e. acrylamide groups.
The crosslinked polymer utilized in the present invention refers to crosslinked
15 products formed by polymerization of a diacrylamide monomer, an oligomer thereof, or
the monomer and oligomer. That is, the crosslinked polymer of the present invention
may be formed by crosslinking polymerization of the monomers or oligomers alone, or
otherwise may be formed by simultaneous crosslinking polymerization of both the
monomer and oligomer. As used herein, the term "oligomer" refers to a low-
20 polymerization degree, linear polymer consisting of more than two monomers and
having a viscosity to an extent that can be injected in the form of a solution.
However, single use of the oligomer compound may lead to a difficulty to
control physical properties, whereas single use of the monomer may result in a
difficulty to obtain desired levels of mechanical properties. Therefore, a mixture of the
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high-molecular weight oligomeric compound and the monomeric compound may be
preferably used to overcome such problems. In this case, a mixing ratio of the monomer
and the oligomer may be in the range of 10:90 to 90:10 (w/w),
Preferred examples of the diacrylamide compounds may include, but are not
5 limited to, monomers represented by Formula I below and oligomers thereof:
)<1 R O
(CH2)n (1)
wherein R1 and R2 are each independently hydrogen or an unsubstil.uted or
substituted CI-C6 alkyl, and R' and R2 may be taken, together to form a saturated or
unsaturated ring; and
10 n is an integer of 0 to 4, and a direct bond is formed if n is 0.
Particularly preferred examples of the diacrylamide compound may include
monomers represented by Formulae II and III below and oligomers thereof:
0
NH HN
(III)
15 The above-mentioned compounds according to the present invention may be
easily prepared by those skilled in the art, based on the chemical structure thereof, and
therefore the details of preparation thereof are not provided herein.
In one preferred embodiment, the gel polymer electrolyte may further
comprise a compound that is polymerizable with the diacrylamide compound as a
precursor for formation of a crosslinked polymer.
There is no particular limit to the above-polymerizable compound, as long as
5 such a compound is polymerizable with the diacrylamide compound. Preferably,
mention may be made of (meth)acrylic ester compounds, unsaturated carboxylic
compounds, vinyl compounds and mixtures thereof without being limited thereto.
There is no particular limit to the (meth)acrylic ester compounds, as long as
they contain acrylate group(s). Preferred are compounds containing two or more
10 acrylate groups in the molecular structure.
In one preferred embodiment, the (meth)acrylic ester compounds having two or
more acrylate groups in the molecular structure may be diacrylate corripounds.
According to the results of the experiments conducted by the present inventors,
it was confirmed that more flexible physical properties can be obtained upon
15 preparation of the gel polymer electrolyte, by the combined use of a diacrylate
compound in conjunction with the diacrylamide compound. That is, the gel polymer
electrolyte is obtained which has combination of electrochemical properties and
mechanical properties of each material, by the co-use of the diacrylamide compound
having supe-1-110'r binding force with the diacrylate compound having superior elasticity,
20 as a precursor of a crosslinked polymer.
Of course, the diacrylate compound, in conjunction with the diacrylamide
compound, may form various forms of copolymers, for example random copolymers,
block copolymers, graft copolymers and the like.
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Preferred examples of the diacrylate compound may include, but are not
limited to, monomers represented by Formula IV below, and oligomers thereof:
R3
0
wherein R3, R4 and R5 are each independently hydrogen, or an unsubstituted or
substituted C1®C4 alkyl; and
m is an integer of 1 to 20.
Examples of the (meth)acrylic ester compounds having two or more acrylate
groups in the-molecular structure may include, but are'not limited'to, diethylene glycol
diacrylate (Di(EG)DA), diethylene glycol dimethacrylate (Di(EG)DM), ethylene glycol
10 , dimethacrylate (EGDM), dipropylene glycol diacrylate (Di(PG)DA), dipropylene glycol
dimethacrylate (Di(PG)DM), ethylene glycol divinyl ether (EGDVE), ethoxylated (6)
trimethylolpropane triacrylate (ETMPTA), diethylene glycol divinyl ether
(Di(EG)DVE), triethylene glycol dimethacrylate (Tri(EG)DM), dipentaerythrito1
pentaacrylate (DPentA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane
15 trimethacrylate (TMPTM), propoxylated (3) trimethylolpropane triacrylate
(PO(3)TMPTA), propoxylated (6) trimethylolpropane triacrylate (PO(6)TMPTA),
poly(ethylene glycol)diacrylate (PA1, Mn = 700, see Formula III), poly(ethylene glycol)
dimethacrylate and mixtures thereof.
Preferably, the gel polymer electrolyte contains a polymerization initiator, an
20 electrolyte and a lithium salt.
Examples of the polymerization initiator may include azo compounds such as
2,2-azobis(2-cyanobutane), 2,2-azobis(rnethylbutyronitrile), 2,2 ' -azoisobutyronitrile
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(AIBN), azobisdimethyl-valeronitrile (AIMVN) and the, like, peroxy compounds such as
benzoyl peroxide , acetyl peroxide , dilauryl peroxide , di-tent-butyl peroxide, cumyl
peroxide, hydrogen peroxide and the like, and hydroperoxides. Preferably , AIBN, 2,2'-
azobis(2,4-dimethyl valeronitrile ) (V65), Di-(4-ter-t-butyleyclohexyl)--peroxydicarbonate
5 (DEC), or the like may be employed.
The polymerization initiator is decomposed at a certain temperature of 40 to
80'C to form radicals, and may react with monomers via the free radical polymerization
to form a gel polymer electrolyte. Generally, the free radical polymerization is carried
out by sequential reactions consisting of the initiation involving formation of transient
10 molecules having high reactivity or active sites, the propagation involving re-formation
of active sites at the ends of chains by addition of monomers to active chain ends, the
chain transfer involving transfer of the active sites to other molecules, and the
termination involving destruction of active chain centers. On the other hand, it is, of
course, possible to carry out polymerization without use of the polymerization initiator.
15 The electrolyte may also serve as a plasticizer. As examples of the electrolyte
that can be used in the present invention, mention may be made of non-protic organic
solvents such as N-methyl-2-pyrollidinone, propylene carbonate (PC), ethylene
carbonate (EC), butylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate
(DEC), ethylmethyl carbonate (EMC), gamma-butyrolactone, 1,2-dimethoxy ethane,
20 tetrahydroxy Franc, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane,
formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate,
methyl acetate, phosphoric acid triester, trimethoxy methane, dioxolane derivatives,
sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate
derivatives, tetrahydrofuran derivatives, ether, methyl propionate and ethyl propionate.
25 These materials may be used alone or in any combination thereof.
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The lithium salt is a material that is dissolved in the non-aqueous electrolyte to
thereby resulting in dissociation of lithium ions. Examples of the lithium salt may
include, for example, LiC1, LiBr, Lit, LiC1®4, LiBF4, LiB10C110, LiPF6, LiCF3SO3,
LiCF3CO2, LiAsF6, LiSbF6, LiA1C14, CH3SO3Li, CF3SO3Li, (CF3SO2)2NLi,
5 chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate
and imide. These materials may be used alone or in any combination thereof.
Additionally, in order to improve charge/discharge characteristics and flame
retardancy, for example, pyridine, triethylphosphite, triethanolamine, cyclic ether,
ethylenediamine, n®glyme, hexaphosphoric triamide, nitrobenzene derivatives, sulfur,
10 quinone imine dyes, N-substituted oxazolidirione, N,Nmsubstituted imidazolidine,
ethylene glycol dialkyl ether, ammonium salts, pyrrol`e, 2-methoXy ethanol, aluminum
trichloride or the like may be added to the electrolyte. If necessary, in order to impart
incombustibility, the electrolyte may further include halogen-containing solvents such
as carbon tetrachloride and ethylene trifluoride. Further, in order to improve high-
15 temperature storage characteristics, the electrolyte may additionally include carbon
dioxide gas.
Since the gel polymer electrolyte according to the present invention is
included in the gel-type, instead of a liquid phase, the ratio of the electrolyte : the
crosslinked polymer formed by crosslinking of the diacrylamide compound is important
20- in order to achieve uniform application of the electrolyte to the electrodes.
Although there is no particular limit to a content of the diacrylamide
compound, it is preferred to contain the diacrylamide compound in an amount of 0.1 to
10% by weight based on the total weight of the electrolyte.
m10®
Where the ratio of the crosslinked polymer is lower than 0.1% by weight, it is
not easy to form a gel polymer, consequently resulting in significant swelling of the
battery which occurs upon use of the liquid electrolyte, and it may also be difficult to
prepare a matrix material having a given thickness. On the other hand, where the
5 content of the crosslinked polymer exceeds 10% by weight , an increased density of the
gel polymer may lead to a decreased transfer rate of lithium ions, which in turn causes
the precipitation of lithium ions, consequently resulting in the deterioration of the
battery performance, and may also lead to an increased viscosity , thereby presenting a
difficulty to achieve uniform application thereof to target sites. Addition of the
10 diacrylate compound to the diacrylamide compound also suffers from the same
problems as described above. That is, the total weight of the diaerylamide compound
and the diacrylate compound is preferably 1 to 10% by weight, based on the total
weight of the electrolyte.
In accordance with another aspect of the present invention, there is provided
15 an electrochemical device comprising the above-mentioned gel polymer electrolyte.
The electrochemical device encompasses all kinds of devices that undergo
electrochemical reactions. As specific examples of the electrochemical device, mention
may be made of all kinds of primary batteries, secondary batteries, fuel cells, solar
cells, capacitors and the like. Preferred are secondary batteries.
20 Generally, the secondary battery is fabricated by inclusion of the electrolyte in
an electrode assembly composed of a cathode and an anode, which are faced opposite
to each other with a separator therebetween.
The cathode is, for example, fabricated by applying a mixture of a cathode
active material, a conductive material and a binder to a cathode current collector,
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followed by drying and pressing. If necessary, a. filler may be further added to the
above mixture.
The cathode current collector is generally fabricated to have a thickness of 3 to
500 /gym. There is no particular limit to materials for the cathode current collector, so
5 long as they have high conductivity without causing chemical changes in the
fabricated battery. As examples of the materials for the cathode current collector,
mention may be made of stainless steel, aluminum, nickel, titanium, sintered carbon,
and aluminum or stainless steel which was surface-treated with carbon, nickel,
titanium or silver. The current collector may be fabricated to have fine irregularities
10 on the surface thereof so as to enhance adhesion to the cathode active material. In
addition, the current collector may take various forms including films, sheets, foils,
nets, porous structures, foams and nonwoven fabrics.
Examples of the cathode active materials that can be used in the present
invention may include, but are not limited to, layered compounds such as lithium
15 cobalt oxide (LiCoO2) and lithium nickel oxide (LiNi02),: or compounds substituted
with one or more transition metals; lithium manganese oxides such as compounds of
Formula Lil+xMn2_xO4 (0 x<0.33), LiMnO3, LiMn2O3 and LiMnO2; lithium copper
oxide (Li2CuO2); vanadium oxides such as LiV3O8, V205 and Cu2V2O7; Ni-site type
lithium nickel oxides of Formula LiNil_,tM,,02 (M = Co, Mn, Al, Cu, Fe, Mg, B or Ga,
20 and 0.015x<0.3); lithium manganese composite oxides of Formula LiMn2_xMxO2 (M =
Co, Ni, Fe, Cr, Zn or Ta, and 0.01
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