Specification
[0001] This application claims the benefit of Korean Patent
Application No. 10-2018-0041812, filed on April 10, 2018, in
the Korean Intellectual Property Office, the disclosure of
10 which is incorporated herein in its entirety by reference.
Technical Field
[0002] The present invention relates to a lithium secondary
battery and a method of preparing the same, and more
particularly, to a lithium secondary battery including a gel
15 polymer electrolyte and a method of preparing the same.
BACKGROUND ART
[0003] Demand for secondary batteries as an energy source
has been significantly increased as technology development
and demand with respect to mobile devices have increased, and,
20 among these secondary batteries, lithium secondary batteries
having high energy density, high operating potential, long
cycle life, and low self-discharging rate have been
commercialized and widely used.
[0004] Also, recently, in line with growing concerns about
25 environmental issues, a significant amount of research into
2
electric vehicles (EVs) and hybrid electric vehicles (HEVs),
which may replace vehicles using fossil fuels, such as
gasoline vehicle and diesel vehicle, one of major causes of
air pollution, has been conducted.
5 [0005] Nickel-metal hydride (Ni-MH) secondary batteries or
lithium secondary batteries having high energy density, high
discharge voltage, and output stability have been used as
power sources of the electric vehicles (EVs) and hybrid
electric vehicles (HEVs), wherein, in a case in which the
10 lithium secondary batteries are used in the electric vehicles,
since the lithium secondary batteries must be used for more
than 10 years under harsh conditions in addition to high
energy density and ability to provide high output in a short
period of time, energy density, safety, and long-term life
15 characteristics, which are significant better than those of a
conventional small-sized lithium secondary battery, are
inevitably required.
[0006] In general, a lithium secondary battery is prepared
by using a negative electrode, a positive electrode, a
20 separator disposed between them, and an electrolyte as a
transfer medium of lithium ions, wherein an electrolyte in a
liquid state, particularly, an ionic conductive organic
liquid electrolyte, in which a salt is dissolved in a nonaqueous organic solvent, has been mainly used in a
25 conventional secondary battery.
3
[0007] However, in a case in which the electrolyte in a
liquid state is used, the possibilities of degrading an
electrode material and volatizing the organic solvent are not
only high, but also there is a problem in safety, for example,
5 combustion caused by increases in ambient temperature and
temperature of the battery itself. In particular, the
lithium secondary battery has limitations in that, since gas
is generated in the battery due to the decomposition of a
carbonate organic solvent and/or a side reaction between the
10 organic solvent and an electrode during charge and discharge,
a thickness of the battery increases. Thus, degradation of
performance and safety of the battery essentially occurs.
[0008] In general, it is known that battery safety improves
in the order of a liquid electrolyte, a gel polymer
15 electrolyte, and a solid polymer electrolyte, but battery
performance decreases in the same order. Currently, it is
known that the solid polymer electrolyte has not been
commercialized yet due to poor battery performance.
[0009] The separator used in the lithium secondary battery
20 is an inert material that does not participate in an
electrochemical reaction, but a material which provides a
path through which lithium ions move to operate the battery
and separates physical contact between the positive electrode
and the negative electrode, wherein it is one of the key
25 materials that greatly affect performance and stability of
4
the battery.
[0010] With respect to the lithium secondary battery, heat
may be easily generated due to kinetic energy generated
during repeated charge and discharge, wherein the separator
5 is vulnerable to this heat. Particularly, with respect to a
separator using polyethylene (PE), a 'shut down' phenomenon
may occur in which melting starts at about 130°C to close
pores, and if the separator melts completely above 150°C so
that it may not prevent an internal short circuit and a
10 thermal runaway phenomenon occurs, the lithium secondary
battery may be collapsed (meltdown or mechanical integrity
failure).
[0011] In order to address this limitation, studies for
enhancing durability, for example, the use of a dip coating
15 method in which inorganic particles and a polymer binder are
coated on a surface of the separator, have recently been
continued.
[0012] In addition to the above-described limitation, in a
case in which a separator having a coating layer including a
20 gel polymer electrolyte and inorganic particles formed
thereon is used together, since adhesion between the coating
layer and the electrolyte is low, there is a limitation in
that the stability and performance of the secondary battery
are degraded.
25 [0013] Therefore, there is a need to develop a secondary
5
battery which may improve safety and capacity characteristics
of the battery by using a separator having excellent adhesion
to the gel polymer electrolyte as well as excellent
durability.
5 [0014] (Patent Document 1) Korean Patent Application Laidopen Publication No. 10-2015-0131513
DISCLOSURE OF THE INVENTION
TECHNICAL PROBLEM
[0015] An aspect of the present invention provides a lithium
10 secondary battery which may improve capacity characteristics
and safety of the battery by increasing adhesion between a
gel polymer electrolyte and a separator.
TECHNICAL SOLUTION
[0016] According to an aspect of the present invention,
15 there is provided a lithium secondary battery including a
positive electrode; a negative electrode; a separator which
includes a coating layer including an organic binder and
inorganic particles; and a gel polymer electrolyte formed by
polymerization of an oligomer, wherein the organic binder and
20 the gel polymer electrolyte are bonded by an epoxy ringopening reaction.
[0017] The organic binder may include an epoxy group, a
functional group capable of undergoing a ring-opening
reaction with the epoxy group, or a combination thereof.
25 [0018] The oligomer may include an epoxy group, a functional
6
group capable of undergoing a ring-opening reaction with the
epoxy group, or a combination thereof.
[0019] The functional group capable of undergoing a ringopening reaction with the epoxy group may include at least
5 one functional group selected from the group consisting of a
hydroxyl group (OH), a carboxylic acid group (COOH), an amine
group, an isocyanate group, a mercaptan group, and an imide
group.
[0020] The organic binder may include a unit containing at
10 least one selected from the group consisting of an alkylene
group having 1 to 5 carbon atoms which is substituted with at
least one halogen element, an alkylene oxide group having 1
to 5 carbon atoms, an alkylene oxide group having 1 to 5
carbon atoms which is substituted with at least one halogen
15 element, an imide group, and celluloid, wherein an epoxy
group, a functional group capable of undergoing a ringopening reaction with the epoxy group, or a combination
thereof may be substituted into a main chain composed of the
unit.
20 [0021] The oligomer may include at least one unit selected
from the group consisting of a unit containing an alkylene
oxide group and a unit containing an amine group, wherein an
epoxy group, a functional group capable of undergoing a ringopening reaction with the epoxy group, or a combination
25 thereof may be substituted into a main chain composed of the
7
unit.
[0022] According to another aspect of the present invention,
there is provided a method of preparing a lithium secondary
battery which includes: inserting an electrode assembly
5 composed of a positive electrode, a negative electrode, and a
separator, which includes a coating layer including inorganic
particles and an organic binder that includes an epoxy group,
a functional group capable of undergoing a ring-opening
reaction with the epoxy group, or a combination thereof, into
10 a battery case; and performing thermal polymerization after
injecting a composition for a gel polymer electrolyte, which
includes an oligomer including the epoxy group, the
functional group capable of undergoing a ring-opening
reaction with the epoxy group, or the combination thereof,
15 into the battery case.
[0023] The composition for a gel polymer electrolyte may not
include an initiator.
[0024] The composition for a gel polymer electrolyte may be
composed of a lithium salt, a non-aqueous organic solvent,
20 and the oligomer including the epoxy group, the functional
group capable of undergoing a ring-opening reaction with the
epoxy group, or the combination thereof.
ADVANTAGEOUS EFFECTS
[0025] In a lithium secondary battery according to the
25 present invention, since a gel polymer electrolyte and an
8
organic binder in a separator coating layer are bonded by an
epoxy ring-opening reaction, adhesion between the gel polymer
electrolyte and the separator is excellent.
[0026] When the adhesion between the gel polymer electrolyte
5 and the separator is improved, since an increase in
interfacial resistance between the electrolyte and the
separator may be suppressed, capacity characteristics may be
improved and mechanical safety and high-temperature safety
may also be improved.
10 MODE FOR CARRYING OUT THE INVENTION
[0027] Hereinafter, the present invention will be described
in detail.
[0028] It will be understood that words or terms used in the
specification and claims shall not be interpreted as the
15 meaning defined in commonly used dictionaries. It will be
further understood that the words or terms should be
interpreted as having a meaning that is consistent with their
meaning in the context of the relevant art and the technical
idea of the invention, based on the principle that an
20 inventor may properly define the meaning of the words or
terms to best explain the invention.
[0029] The terms used in the present specification are used
to merely describe exemplary embodiments, but are not
intended to limit the invention. The terms of a singular
25 form may include plural forms unless referred to the contrary.
9
[0030] It will be further understood that the terms
“include,” “comprise,” or "have" in this specification
specify the presence of stated features, numbers, steps,
elements, or combinations thereof, but do not preclude the
5 presence or addition of one or more other features, numbers,
steps, elements, or combinations thereof.
[0031] Unless otherwise specified in the present invention,
the expression “*” denotes the same or different atom or a
portion connected between ends of a formula.
10 [0032] In the present invention, the expression “weightaverage molecular weight” may denote a standard polystyreneequivalent value measured by gel permeation chromatography
(GPC), and, unless otherwise specified, a molecular weight
may denote the weight-average molecular weight. For example,
15 in the present invention, GPC conditions are as follows: the
weight-average molecular weight is measured by using 1200
series by Agilent Technologies, a PL mixed B column by
Agilent Technologies may be used in this case, and
tetrahydrofuran (THF) may be used as a solvent.
20
[0033]
[0034] A lithium secondary battery according to the present
invention includes a positive electrode, a negative electrode,
a separator, which includes a coating layer including an
25 organic binder and inorganic particles, and a gel polymer
10
electrolyte formed by polymerization of an oligomer. In this
case, the organic binder and the gel polymer electrolyte are
bonded by an epoxy ring-opening reaction.
5 [0035] First, the separator will be described.
[0036] The separator includes a base material and a coating
layer formed on a surface of the based material, wherein the
coating layer includes an organic binder and inorganic
particles.
10
[0037] A porous based material may be used as the base
material, and, typically, any porous base material may be
used without particular limitation as long as it may be used
as a separator material of an electrochemical device. The
15 porous based material, for example, includes a nonwoven
fabric or porous polymer film formed of at least one selected
from polymer resins, such as polyolefin, polyethylene
terephthalate, polybutylene terephthalate, polyacetal,
polyamide, polycarbonate, polyimide, polyether ether ketone,
20 polyether sulfone, polyphenylene oxide, polyphenylene sulfide,
and polyethylene naphthalene, or a laminate of two or more
thereof, but the porous base material is not particularly
limited thereto.
25 [0038] The coating layer is to improve adhesion between the
11
separator and the gel polymer electrolyte and enhance
durability of the battery by coating the inorganic particles
on the base material, wherein the coating layer is formed on
the surface of the based material and includes an organic
5 binder and inorganic particles.
[0039] In this case, the coating layer may have a thickness
of 0.1 μm to 20 μm, preferably 0.5 μm to 20 μm, and more
preferably 1.0 μm to 20 μm. In a case in which the thickness
of the coating layer is formed within the above range,
10 durability of the separator and the adhesion to the
electrolyte may be maintained at a predetermined level or
more, an increase in resistance of the battery may be
prevented, and movement of lithium ions may be smoothly
maintained.
15
[0040] Typically, in order to improve the durability and
conductivity of the separator, inorganic particles on the
surface of the base material have been used and a binder has
been used to prevent detachment of the inorganic particles.
20 However, since the conventional binder does not have a
functional group capable of undergoing a b o n d i n g reaction
with a gel polymer electrolyte, adhesion between the
electrolyte and the separator is low, and thus, internal
resistance between the electrode and the electrolyte is high
25 and there is a safety problem such as the occurrence of an
12
internal short circuit of the battery if an impact is applied
to the outside of the battery.
[0041] In the present invention, in order to solve the
above-described problem, a coating layer is formed using an
5 organic binder which may be bonded with the gel polymer
electrolyte by an epoxy ring-opening reaction.
[0042] In order for the epoxy ring-opening reaction to occur,
the organic binder includes an epoxy group, a functional
group capable of undergoing a ring-opening reaction with the
10 epoxy group, or a combination thereof, and the oligomer also
includes an epoxy group, a functional group capable of
undergoing a ring-opening reaction with the epoxy group, or a
combination thereof. However, in a case in which only the
epoxy group exists in both the organic binder and the
15 oligomer or in a case in which only the functional group
capable of undergoing a ring-opening reaction with the epoxy
group is included, since the epoxy ring-opening reaction may
not be performed, the oligomer must include the functional
group capable of undergoing a ring-opening reaction with the
20 epoxy group in the case that only the epoxy group exists in
the organic binder. In contrast, in the case that only the
functional group capable of undergoing a ring-opening
reaction with the epoxy group exists in the organic binder,
the oligomer must include the epoxy group.
25 [0043] When the separator and the gel polymer electrolyte
13
are bonded by the epoxy ring-opening reaction, since the gel
polymer electrolyte is uniformly adhered to a separator
interface, interfacial resistance may be reduced and transfer
characteristic of lithium ions may be improved to improve
5 capacity characteristics of the battery.
[0044] Also, when the adhesion between the separator and the
gel polymer electrolyte is improved, since mechanical
strength of the secondary battery may be improved to prevent
a short-circuit phenomenon of the battery even when an
10 external impact is applied and to suppress a thermal runaway
phenomenon or ignition phenomenon, safety of the battery may
be improved.
[0045] The functional group capable of undergoing a ringopening reaction with the epoxy group may include at least
15 one functional group selected from the group consisting of a
hydroxyl group (OH), a carboxylic acid group (COOH), an amine
group, an isocyanate group, a mercaptan group, and an imide
group.
[0046] Specifically, the amine group may be represented by -
20 NR1R2, wherein R1 and R2 may each independently be at least
one selected from the group consisting of hydrogen (H), a
substituted or unsubstituted chain alkyl group having 1 to 10
carbon atoms, and a substituted or unsubstituted cyclic alkyl
group having 1 to 10 carbon atoms.
25 [0047] More specifically, the imide group may be represented
14
by -R3-CO-N(R4)-CO-R5, wherein R3 to R5 may each independently
be at least one selected from the group consisting of
hydrogen (H), a substituted or unsubstituted chain alkyl
group having 1 to 10 carbon atoms, and a substituted or
5 unsubstituted cyclic alkyl group having 1 to 10 carbon atoms.
[0048] Common organic binders well known in the art, for
example, binders, in which an epoxy group and/or a functional
group capable of undergoing a ring-opening reaction with the
10 epoxy group is substituted into poly(vinylidene fluoride)
(PVdF) or PVdF-co-HFP (copolymer of poly(vinylidene fluoride)
and hexafluoropropylene), may be used as the organic binder.
Specifically, the organic binder may further include a unit
containing at least one selected from the group consisting of
15 an alkylene group having 1 to 5 carbon atoms which is
substituted with at least one halogen element (fluorine (F),
chlorine (Cl), bromine (Br), and iodine (I)), an alkylene
oxide group having 1 to 5 carbon atoms, an imide group, and
celluloid, in addition to the above functional group.
20 [0049] In this case, the epoxy group, the functional group
capable of undergoing a ring-opening reaction with the epoxy
group, or a combination thereof may be substituted into a
main chain composed of the above unit. Specifically,
hydrogen (H) in the main chain may be substituted with the
25 epoxy group, the functional group capable of undergoing a
15
ring-opening reaction with the epoxy group, or the
combination thereof, and a degree of substitution may be
calculated in mol%. However, the number or position of the
attached functional groups is not specified.
5 [0050] For example, the unit containing the alkylene group
substituted with at least one halogen element may be
represented by at least one selected from units represented
by Formulae X-1 and X-2 below.
[0051] [Formula X-1]
10
[0052] In Formula X-1, m1 is an integer of 1 to 10,000,
preferably 1 to 7,500, and more preferably 1 to 5,000.
[0053] [Formula X-2]
15 [0054] In Formula X-2, m2 and m3 are each independently an
integer of 1 to 10,000, preferably 1 to 7,500, and more
preferably 1 to 5,000.
16
[0055] For example, the unit containing the alkylene oxide
group may be represented by Formula X-3 below.
[0056] [Formula X-3]
5 [0057] In Formula X-3, m4 is an integer of 1 to 10,000,
preferably 1 to 7,500, and more preferably 1 to 5,000.
[0058] For example, the unit containing the alkylene oxide
group substituted with a halogen element may be represented
by Formula X-4 below.
10 [0059] [Formula X-4]
[0060] In Formula X-4, m5 is an integer of 1 to 10,000,
preferably 1 to 7,500, and more preferably 1 to 5,000.
[0061] For example, the unit containing the imide group may
15 be represented by Formula X-5 below.
[0062] [Formula X-5]
17
[0063] In Formula X-5, m6 is an integer of 1 to 10,000,
preferably 1 to 7,500, and more preferably 1 to 5,000.
[0064] For example, the unit containing the celluloid may be
5 represented by Formula X-6 below.
[0065] [Formula X-6]
[0066] In Formula X-6, m7 is an integer of 1 to 10,000,
preferably 1 to 7,500, and more preferably 1 to 5,000.
10
[0067] The organic binder may be included in an amount of 1
part by weight to 80 parts by weight, preferably 5 parts by
weight to 60 parts by weight, and more preferably 5 parts by
weight to 40 parts by weight based on 100 parts by weight of
15 the coating layer. In a case in which the organic binder is
included in an amount within the above range, the detachment
18
of the inorganic particles included in the coating layer may
be prevented, and adhesion to the oligomer constituting the
gel polymer electrolyte may also be maintained at a
predetermined level or more.
5 [0068] The inorganic particles form a space (interstitial
volume) between the particles to form micropores and also
serve as a kind of spacer capable of maintaining a physical
shape at the same time. Also, since the inorganic particles
may transmit and transfer lithium ions, lithium ion
10 conductivity may be improved. In this case, micropores may
be formed by controlling a size of the inorganic particles
and an amount of the inorganic particles, and a pore size and
porosity may be controlled.
[0069] The inorganic particles may include inorganic
15 particles commonly used in the art. For example, the
inorganic particles may include at least one element selected
from the group consisting of silicon (Si), aluminum (Al),
titanium (Ti), zirconium (Zr), tin (Sn), cerium (Ce),
magnesium (Mg), calcium (Ca), zinc (Zn), yttrium (Y), lead
20 (Pb), barium (Ba), hafnium (Hf), and strontium (Sr), and may
preferably include at least one element selected from the
group consisting of Si, Al, Ti, and Zr.
[0070] Specifically, the inorganic particles may include
SiO2, Al2O3, TiO2, ZrO2, SnO2, CeO2, MgO, CaO, ZnO, Y2O3,
25 Pb(Zr,Ti)O3 (PZT), Pb(1-a1)Laa1Zr(1-b1)Tib1O3 (PLZT, where, 0≤a1≤1
19
and 0≤b1≤1), PB(Mg3Nb2/3)O3-PbTiO3 (PMN-PT), BaTiO3, HfO2
(hafnia), and SrTiO3, and the inorganic materials listed
above generally have a property that their physical
properties do not change even at a high temperature of 200°C
5 or higher. More preferably, the inorganic particles may
include at least one inorganic material selected from the
group consisting of SiO2, Al2O3, TiO2, and ZrO2.
[0071] The inorganic particles may be included in an amount
of 20 parts by weight to 99 parts by weight, preferably 40
10 parts by weight to 95 parts by weight, and more preferably 60
parts by weight to 95 parts by weight based on 100 parts by
weight of the coating layer. In a case in which the
inorganic particles are included in an amount within the
above range, the durability of the separator for a secondary
15 battery may be improved while the detachment of the inorganic
particles from the coating layer may be prevented.
[0072] Next, the gel polymer electrolyte will be described.
[0073] The gel polymer electrolyte may be disposed between
20 the positive electrode, the negative electrode, and the
separator, and is formed by polymerization of an oligomer.
[0074] Specifically, the oligomer includes an epoxy group, a
functional group capable of undergoing a ring-opening
reaction with the epoxy group, or a combination thereof. In
25 a case in which the oligomer is used, the oligomer may be
20
thermally polymerized by an epoxy ring-opening reaction
between the oligomers and may also be bonded to the organic
binder included in the separator coating layer by an epoxy
ring-opening reaction.
5 [0075] With respect to an oligomer polymerized by
conventional radical polymerization, the oligomers may be
bonded by a polymerization reaction only when a
polymerization initiator is essentially used. However, azobased and peroxide-based compounds used as a radical
10 polymerization initiator have a limitation in that the
compounds reduce the safety of the battery by generating gas
in the battery during a curing reaction.
[0076] The oligomer used in the gel polymer electrolyte of
the present invention is an oligomer polymerized by an epoxy
15 ring-opening reaction, wherein the polymerization reaction
may be performed without using a polymerization initiator
which is used when a conventional oligomer is polymerized.
Thus, since gas is not generated in the battery even during
curing through the polymerization reaction, swelling of the
20 battery and an electrode short-circuit phenomenon induced by
the swelling may be prevented in advance to improve the
safety of the battery.
[0077] Specifically, the oligomer includes at least one unit
selected from the group consisting of a unit containing an
25 alkylene oxide group and a unit containing an amine group,
21
wherein the epoxy group, the functional group capable of
undergoing a ring-opening reaction with the epoxy group, or
the combination thereof may be substituted into a main chain
composed of the above unit.
5 [0078] For example, the oligomer may include at least one
compound selected from the group consisting of compounds
represented by Formula 2 and Formula 3 below.
[0079] [Formula 2]
10 [0080] n1 may be an integer of 2 to 10,000, preferably 2 to
7,500, and more preferably 2 to 5,000.
[0081] [Formula 3]
[0082] In Formula 3, R6 to R11 are a substituted or
15 unsubstituted alkylene group having 1 to 5 carbon atoms, and
R12 to R16 are each independently at least one selected from
the group consisting of hydrogen (H), a substituted or
unsubstituted alkyl group having 1 to 10 carbon atoms, -
NR17R18, and –R19NR20R21, wherein R19 is a substituted or
22
unsubstituted alkylene group having 1 to 5 carbon atoms, and
R17, R18, R20, and R21 are each independently hydrogen (H), a
substituted or unsubstituted alkyl group having 1 to 5 carbon
atoms, and –R22NH2, wherein R22 is a substituted or
5 unsubstituted alkylene group having 1 to 5 carbon atoms, and
n2 is an integer of 1 to 10,000, preferably 1 to 7,500, and
more preferably 1 to 5,000.
[0083] In a case in which the oligomer includes both the
10 compound represented by Formula 2 and the compound
represented by Formula 3, the compound represented by Formula
2 and the compound represented by Formula 3 may be mixed in a
weight ratio of 30:70 to 100:0, for example, 40:60 to 95:5.
When the oligomer is used by mixing the compound represented
15 by Formula 2 and the compound represented by Formula 3 in the
above ratio, mechanical properties of the polymer formed of
the oligomer may be improved to prevent leakage of the gel
polymer electrolyte and to improve adhesion to the separator.
20 [0084] Specifically, the compound represented by Formula 3
may include at least one compound selected from the group
consisting of compounds represented by Formulae 3-1 to 3-3
below.
[0085] [Formula 3-1]
23
[0086] In Formula 3-1, n2 is an integer of 1 to 10,000.
[0087] [Formula 3-2]
5 [0088] In Formula 3-2, n2 is an integer of 1 to 10,000.
[0089] [Formula 3-3]
[0090] In Formula 3-3, n2 is an integer of 1 to 10,000.
[0091] n2 may preferably be an integer of 1 to 10,000, and
10 may more preferably be an integer of 1 to 7,500.
[0092] The oligomer represented by Formula 2 or Formula 3
24
may have a weight-average molecular weight (Mw) of about 100
to about 1,000,000, preferably 100 to 900,000, and more
preferably 300 to 800,000. If the oligomer has the above
range of the weight-average molecular weight, since the gel
5 polymer electrolyte formed by curing may be stably formed to
improve mechanical performance of the battery, heat
generation and ignition phenomena, which may be caused by the
external impact of the battery, may be suppressed and an
explosion phenomenon, which may be caused by the heat and
10 ignition, may also be controlled. Also, since an electrolyte
leakage phenomenon and an electrolyte volatilization
phenomenon may be suppressed, high-temperature safety of the
lithium secondary battery may be significantly improved.
15 [0093] The composition for a gel polymer electrolyte may
include a lithium salt and a non-aqueous organic solvent in
addition to the oligomer.
[0094] Any lithium salt typically used in an electrolyte for
a lithium secondary battery may be used as the lithium salt
20 without limitation. For example, the lithium salt may
include Li+ as a cation, and may include at least one
selected from the group consisting of F-, Cl-, Br-, I-, NO3
-,
N(CN)2
-, BF4
-, ClO4
-, AlO4
-, AlCl4
-, PF6
-, SbF6
-, AsF6
-, BF2C2O4
-,
BC4O8
-, (CF3)2PF4
-, (CF3)3PF3
-, (CF3)4PF2
-, (CF3)5PF-, (CF3)6P-,
CF3SO3
-, C4F9SO3
-, CF3CF2SO3 25 -, (CF3SO2)2N-, (F2SO2)2N-,
25
CF3CF2(CF3)2CO-, (CF3SO2)2CH-, CF3(CF2)7SO3
-, CF3CO2
-, CH3CO2
-, SCN-,
and (CF3CF2SO2)2N- as an anion. One or, if necessary, a
mixture of two or more thereof may be used as the lithium
salt. The lithium salt may be included in a concentration of
5 0.8 M to 2 M, for example, 0.8 M to 1.5 M in the composition
for a gel polymer electrolyte. However, the concentration is
not necessarily limited to the above range, and the lithium
salt may be included at a high concentration of 2M or more
depending on other components in the composition for a gel
10 polymer electrolyte.
[0095] Any non-aqueous organic solvent typically used in an
electrolyte solution for a lithium secondary battery may be
used as the non-aqueous organic solvent without limitation.
For example, an ether compound, an ester compound, an amide
15 compound, a linear carbonate compound, or a cyclic carbonate
compound may be used alone or as a mixture of two or more
thereof. Among them, the non-aqueous organic solvent may
typically include the cyclic carbonate compound, the linear
carbonate compound, or a mixture thereof.
20 [0096] Specific examples of the cyclic carbonate compound
may be any one selected from the group consisting of ethylene
carbonate (EC), propylene carbonate (PC), 1,2-butylene
carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate,
2,3-pentylene carbonate, vinylene carbonate, and
25 fluoroethylene carbonate (FEC), or a mixture of two or more
26
thereof. Also, specific examples of the linear carbonate
compound may be any one selected from the group consisting of
dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl
carbonate, ethylmethyl carbonate (EMC), methylpropyl
5 carbonate, and ethylpropyl carbonate, or a mixture of two or
more thereof, but the present invention is not limited
thereto.
[0097] In particular, cyclic carbonates, such as ethylene
carbonate and propylene carbonate, which are known to well
10 dissociate the lithium salt in the electrolyte due to high
permittivity as highly viscous organic solvents, among the
carbonate-based organic solvents may be used, and an
electrolyte solution having high electrical conductivity may
be prepared when the cyclic carbonate is mixed with low
15 viscosity, low permittivity linear carbonate, such as
dimethyl carbonate and diethyl carbonate, in an appropriate
ratio.
[0098] Also, as the ether compound among the non-aqueous
organic solvents, any one selected from the group consisting
20 of dimethyl ether, diethyl ether, dipropyl ether, methylethyl
ether, methylpropyl ether, and ethylpropyl ether, or a
mixture of two or more thereof may be used, but the present
invention is not limited thereto.
[0099] As the ester compound among the non-aqueous organic
25 solvents, any one selected from the group consisting of
27
linear esters such as methyl acetate, ethyl acetate, propyl
acetate, methyl propionate, ethyl propionate, propyl
propionate, and butyl propionate; and cyclic esters such as
γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ5 valerolactone, and ε-caprolactone, or a mixture of two or
more thereof may be used, but the present invention is not
limited thereto.
[00100] Next, the positive electrode will be described.
10 [00101] Specifically, the positive electrode may be prepared
by coating a positive electrode collector with a positive
electrode active material slurry including a positive
electrode active material, a binder, a conductive agent, and
a solvent.
15 [00102] The positive electrode collector generally has a
thickness of 3 μm to 500 μm and is not particularly limited
so long as it has conductivity without causing adverse
chemical changes in the battery, wherein, for example,
stainless steel, aluminum, nickel, titanium, fired carbon, or
20 aluminum or stainless steel that is surface-treated with one
of carbon, nickel, titanium, silver, or the like may be used.
[00103] The positive electrode active material is a compound
capable of reversibly intercalating and deintercalating
lithium, wherein the positive electrode active material may
25 specifically include a lithium composite metal oxide
28
including lithium and at least one metal such as cobalt,
manganese, nickel, or aluminum. Specifically, the lithium
composite metal oxide may include lithium-manganese-based
oxide (e.g., LiMnO2, LiMn2O4, etc.), lithium-cobalt-based
5 oxide (e.g., LiCoO2, etc.), lithium-nickel-based oxide (e.g.,
LiNiO2, etc.), lithium-nickel-manganese-based oxide (e.g.,
LiNi1-Y1MnY1O2 (where 0
[00117] Next, a method of preparing a lithium secondary
battery according to the present invention will be described.
20 The method of preparing a lithium secondary battery includes
the steps of: (1) inserting an electrode assembly composed of
a positive electrode, a negative electrode, and a separator
into a battery case, and (2) performing thermal
polymerization after injecting a composition for a gel
25 polymer electrolyte including an oligomer into the battery
34
case. Since a functional group of an organic binder and a
functional group of the oligomer undergo an epoxy ringopening reaction in the step of performing thermal
polymerization, the organic binder and the oligomer are
5 bonded to each other. Hereinafter, each step will be
described.
[00118] (1) Step of Inserting Electrode Assembly
[00119] First, a positive electrode, a negative electrode,
10 and a separator, which includes a coating layer containing in
organic particles and an organic binder that includes an
epoxy group, a functional group capable of undergoing a ringopening reaction with the epoxy group, or a combination
thereof, are prepared. Thereafter, an electrode assembly is
15 prepared by disposing the separator between the positive
electrode and the negative electrode. In this case, the
prepared electrode assembly is inserted into the battery case.
As the battery case, various battery cases used in the art
may be used without limitation, and, for example, a
20 cylindrical type, prismatic type, pouch type, or coin type
battery case may be used.
[00120] Since configurations of the prepared positive
electrode, negative electrode, and separator are the same as
those described above, detailed descriptions thereof will be
25 omitted.
35
[00121] (2) Step of Performing Thermal Polymerization After
Injecting Composition for Gel Polymer Electrolyte
[00122] Next, after injecting a composition for a gel polymer
5 electrolyte containing an oligomer, which includes the epoxy
group, the functional group capable of undergoing a ringopening reaction with the epoxy group, or the combination
thereof, into the battery case into which the electrode
assembly is inserted, thermal polymerization is performed by
10 heating.
[00123] With respect to a conventional gel polymer
electrolyte, a polymerization initiator was used to form the
gel polymer electrolyte by curing a composition containing an
oligomer. However, with respect to a peroxide-based compound
15 used as a thermal/photopolymerization initiator, since gas
was generated as a by-product during the reaction to cause a
swelling phenomenon of a battery, there was a limitation in
that high-temperature safety of the battery was deteriorated.
[00124] However, in a case in which a gel polymer electrolyte
20 is formed by thermal polymerization using an epoxy ringopening reaction as in the present invention, since the epoxy
ring-opening reaction proceeds without the
thermal/photopolymerization initiator when heat is applied,
the oligomer may be polymerized to form a gel polymer
25 electrolyte. Since the functional group of the organic
36
binder and the functional group of the oligomer may also
undergo an epoxy ring-opening reaction during the thermal
polymerization of the oligomer, the organic binder and the
oligomer may be bonded to each other.
5 [00125] Thus, the composition for a gel polymer electrolyte
may be cured without using a polymerization initiator to form
a gel polymer electrolyte, and, simultaneously, the organic
binder on the coating layer included in the separator may be
bonded together to improve the adhesion between the separator
10 and the gel polymer electrolyte.
Mode for Embodiments
[00126] Hereinafter, the present invention will be described
in more detail, according to specific examples. However, the
15 following examples are merely presented to exemplify the
present invention, and the scope of the present invention is
not limited thereto. It will be apparent to those skilled in
the art that various modifications and alterations are
possible within the scope and technical spirit of the present
20 invention, and such modifications and alterations fall within
the scope of claims included herein.
[00127] [Examples]
[00128] 1. Example 1
25 [00129] (1) Base Material Preparation
37
[00130] 100 g of polyethylene and 20 g of polyvinyl alcohol,
as a pore-forming agent, were mixed to prepare a mixture.
The mixture was dissolved in dimethylformamide, as a polar
solvent, in a weight ratio of about 1:10 to form a polymer
5 solution. The polymer solution was cast on a glass plate,
put in an oven at about 100°C, and dried for about 30 minutes
to obtain a polymer film. Thereafter, polyvinyl alcohol
(PVA) was extracted by immersing the polymer film in water to
prepare a porous base material.
10 [00131] (2) Coating Layer Composition Preparation
[00132] 27 g of aluminum oxide (Al2O3), as inorganic
particles, and 3 g of polyvinylidene fluoride (hereinafter,
referred to as “PVdF”, weight-average molecular weight:
50,000) substituted with 0.5 mol% of an epoxy group, as an
15 organic binder, were put in 72.1 ml of an N-methylpyrrole
solution to prepare a coating layer composition.
[00133] (3) Preparation of Separator for Secondary Battery
[00134] The coating layer composition was coated on the
porous base material, and dried for about 30 seconds to
20 prepare a separator for a secondary battery.
[00135] 2. Example 2
[00136] A separator for a secondary battery was prepared in
the same manner except that PVdF (weight-average molecular
25 weight: 100,000) substituted with 0.5 mol% of an ethylene
38
imide group was used as an organic binder in Example 1.
[00137] [Comparative Examples]
[00138] 1. Comparative Example 1
5 [00139] In Example 1, a porous base material, on which a
coating layer was not formed, was prepared as a separator for
a secondary battery.
[00140] 2. Comparative Example 2
10 [00141] A separator for a secondary battery was prepared in
the same manner except that PVdF (weight-average molecular
weight: 50,000), which an epoxy group does not substitute,
was used as an organic binder in Example 1.
15 [00142] [Preparation Example] Lithium Secondary Battery
Preparation
[00143] 94 wt% of Li(Ni0.8Mn0.1Co0.1)O2 as a positive electrode
active material, 3 wt% of carbon black as a conductive agent,
and 3 wt% of polyvinylidene fluoride (PVdF), as a binder,
20 were added to N-methyl-2-pyrrolidone (NMP), as a solvent, to
prepare a positive electrode active material slurry. An
about 20 μm thick aluminum (Al) thin film, as a positive
electrode collector, was coated with the positive electrode
active material slurry and dried, and the coated Al thin film
25 was then roll-pressed to prepare a positive electrode.
39
[00144] 96 wt% of carbon powder as a negative electrode
active material, 3 wt% of PVdF as a binder, and 1 wt% of
carbon black, as a conductive agent, were added to NMP, as a
solvent, to prepare a negative electrode active material
5 slurry. A 10 μm thick copper (Cu) thin film, as a negative
electrode collector, was coated with the negative electrode
active material slurry and dried, and the coated Cu thin film
was then roll-pressed to prepare a negative electrode.
[00145] A gel polymer electrolyte composition was prepared by
10 adding 5 g of a mixture, in which the compound represented by
Formula 2 (weight-average molecular weight (Mw) = 500) and
the compound represented by Formula 3-3 (weight-average
molecular weight (Mw) = 10,000) were mixed in a weight ratio
of 7:3, to 94.99 g of an organic solvent in which 1 M LiPF6
15 was dissolved in ethylene carbonate (EC) : ethyl methyl
carbonate (EMC) (=3:7 (volume ratio)) and stirring to
completely dissolve the mixture.
[00146] After the positive electrode/separator/negative
electrode were sequentially stacked (each of the separators
20 prepared according to Examples 1 and 2 and Comparative
Examples 1 and 2 were used as the above separator), the stack
was accommodated in a case for a lithium secondary battery,
the composition for a gel polymer electrolyte was injected
into the case for a lithium secondary battery, and the case
25 was then stored at room temperature for 2 days. Thereafter,
40
the case was heated (thermal polymerization process) at 60°C
for 24 hours to prepare each lithium secondary battery
according to Examples 1 and 2 and Comparative Examples 1 and
2.
5
[00147] [Experimental Examples]
[00148] 1. Experimental Example 1: Initial Capacity
Measurement Test
[00149] After formation was performed on each of the lithium
10 secondary batteries prepared in Examples 1 and 2 and the
lithium secondary batteries prepared in Comparative Examples
1 and 2 at a current of 100 mA (0.1 C rate), 3rd discharge
capacity, which was measured after constant current/constant
voltage (CC/CV) charging at 334 mA (0.3 C, 0.05 C cut-off) to
15 4.2 V and CC discharging at 333 mA (0.3 C) to 3 V were
repeated 3 times, was selected as initial capacity. The
results thereof are presented in Table 1.
[00150] [Table 1]
Initial capacity (mAh)
Example 1 2.00
Example 2 2.01
Comparative Example 1 1.95
Comparative Example 2 1.97
20 [00151] Referring to Table 1, with respect to the lithium
41
secondary batteries of Examples 1 and 2, it may be confirmed
that, since the gel polymer electrolyte was stably formed and
adhesion to the separator was high, interfacial
characteristics were improved, and thus, initial capacities
5 were higher. In contrast, with respect to the lithium
secondary batteries of Comparative Examples 1 and 2, it may
be confirmed that, since adhesion between the gel polymer
electrolyte and the separator was low to increase interfacial
resistance, initial capacities of the lithium secondary
10 batteries were measured low.
[00152] 2. Experimental Example 2: Nail Penetration Test
[00153] After metal nails having a diameter of 2.5 mm were
dropped at a speed of 600 mm/min to the fully charged lithium
15 secondary batteries prepared in Examples 1 and 2 and
Comparative Examples 1 and 2, a thermocouple was attached to
a surface of each lithium secondary battery to measure the
temperature generated, and whether or not ignition occurred
was evaluated. The test results are presented in Table 2.
20 [00154] [Table 2]
Temperature generated
(°C)
The number of cells ignited /
the total number of cells
tested
Example 1 55 0/5
Example 2 50 0/5
Comparative Example 1 110 3/5
42
Comparative Example 2 105 2/5
[00155] A short circuit occurred in the lithium secondary
battery due to an external impact (impact caused by the metal
nail) of the lithium secondary battery and the battery
5 generated heat due to the short circuit, wherein, since the
higher the temperature generated was the higher the
possibility of ignition was, it was considered that safety
was poor. Also, in a case in which the heat generation
leaded to ignition, it was evaluated that the safety of the
10 lithium secondary battery was low. According to Table 2,
with respect to the lithium secondary batteries of Examples 1
and 2 of the present invention, it may be confirmed that the
temperatures generated were all low at 55°C or less and an
ignition phenomenon also did not occur. Alternatively, with
15 respect to the lithium secondary batteries of Comparative
Examples 1 and 2, it may be confirmed that the temperatures
generated were all 100°C or higher which were significantly
higher than those of the examples and the ignition phenomenon
also occurred. This seems to be due to the fact that, with
20 respect to the examples, since the adhesion between the
separator and the gel polymer electrolyte was more improved
than that of the comparative examples, mechanical durability
of the lithium secondary batteries was improved, and thus, an
internal short circuit phenomenon due to the external impact
43
was suppressed.
[00156] 3. Experimental Example 3: High-temperature Safety
Evaluation (Hot Box Test)
5 [00157] After the lithium secondary batteries of Examples 1
and 2 and Comparative Examples 1 and 2 were fully charged at
a state of charge (SOC) of 100%, the lithium secondary
batteries were left standing for 4 hours at 150°C to perform
tests to confirm whether or not ignition occurred and time at
10 which the ignition started when the ignition occurred. The
results thereof are presented in Table 3 below.
[00158] [Table 3]
Whether or not ignition
occurred
Ignition start time
(minutes)
Example 1 × -
Example 2 × -
Comparative Example 1 O 30
Comparative Example 2 O 120
[00159] In Table 3, × represents a case where ignition did
15 not occur during storage at 150°C, and O represents a case
where the ignition occurred during storage at 150°C.
According to Table 3, with respect to the lithium secondary
batteries of Examples 1 and 2, it may be confirmed that an
exothermic reaction was suppressed even during high20 temperature storage in a fully charged state and thermal
44
runaway phenomenon and ignition phenomenon also did not occur.
In contrast, with respect to the lithium secondary batteries
of Comparative Examples 1 and 2, since interface stability
was low due to the weak adhesion between the separator and
5 the gel polymer electrolyte, it may be confirmed that the
exothermic reaction was not suppressed during storage at
150°C and the thermal runaway phenomenon and the ignition
phenomenon occurred in series.
CLAIMS
1. A lithium secondary battery comprising:
a positive electrode;
5 a negative electrode;
a separator comprising a coating layer that includes an
organic binder and inorganic particles; and
a gel polymer electrolyte formed by polymerization of
an oligomer,
10 wherein the organic binder and the gel polymer
electrolyte are bonded by an epoxy ring-opening reaction.
2. The lithium secondary battery of claim 1, wherein the
organic binder comprises an epoxy group, a functional group
15 capable of undergoing a ring-opening reaction with an epoxy
group, or a combination thereof.
3. The lithium secondary battery of claim 1, wherein the
oligomer comprises an epoxy group, a functional group capable
20 of undergoing a ring-opening reaction with an epoxy group, or
a combination thereof.
4. The lithium secondary battery of claim 2 or 3, wherein
the functional group capable of undergoing a ring-opening
25 reaction with an epoxy group comprises at least one selected
46
from the group consisting of a hydroxyl group (OH), a
carboxylic acid group (COOH), an amine group, an isocyanate
group, a mercaptan group, and an imide group.
5 5. The lithium secondary battery of claim 1, wherein the
organic binder comprises a unit containing at least one
selected from the group consisting of an alkylene group
having 1 to 5 carbon atoms which is substituted with at least
one halogen element, an alkylene oxide group having 1 to 5
10 carbon atoms, an alkylene oxide group having 1 to 5 carbon
atoms which is substituted with at least one halogen element,
an imide group, and celluloid,
wherein an epoxy group, a functional group capable of
undergoing a ring-opening reaction with an epoxy group, or a
15 combination thereof is substituted into a main chain composed
of the unit.
6. The lithium secondary battery of claim 1, wherein the
oligomer comprises at least one unit selected from the group
20 consisting of a unit containing an alkylene oxide group and a
unit containing an amine group,
wherein an epoxy group, a functional group capable of
undergoing a ring-opening reaction with an epoxy group, or a
combination thereof is substituted into a main chain composed
25 of the unit.
47
7. A method of preparing a lithium secondary battery, the
method comprising:
Inserting into a battery case an electrode assembly
5 comprising a positive electrode, a negative electrode, and a
separator, which includes a coating layer including inorganic
particles and an organic binder that includes an epoxy group,
a functional group capable of undergoing a ring-opening
reaction with an epoxy group, or a combination thereof; and
10 performing thermal polymerization after injecting a
composition for a gel polymer electrolyte, which includes an
oligomer including the epoxy group, the functional group
capable of undergoing a ring-opening reaction with the epoxy
group, or the combination thereof, into the battery case.
15
8. The method of claim 7, wherein the functional group of
the organic binder and the functional group of the oligomer
undergo an epoxy ring-opening reaction when the oligomer is
thermally polymerized.
20
9. The method of claim 7, wherein the composition for a
gel polymer electrolyte does not comprise an initiator.
10. The method of claim 7, wherein the composition for a
25 gel polymer electrolyte comprises a lithium salt, a non-
48
aqueous organic solvent, and the oligomer including the epoxy
group, the functional group capable of undergoing a ringopening reaction with the epoxy group, or the combination
thereof.