TECHNICAL FIELD
Cross-reference to Related Applications
5 [0001] This application claims the benefit of Korean Patent
Application Nos. 2014-0131746, filed on September 30, 2014,
and 2015-0124201, filed on September 2, 2015, in the Korean
Intellectual Property Office, the disclosure of which is
incorporated herein in its entirety by reference.
10 Technical Field
[0002] The present invention relates to a method of
preparing a lithium secondary battery which may
simultaneously improve output characteristics and lifetime
characteristics of the lithium secondary battery.
15 BACKGROUND ART
[0003] Recently, in line with the development of information
and telecommunications industry, electronic devices are being
miniaturized, light-weighted, reduced in thickness, and
portable. As a result, the need for high energy density
20 batteries used as power sources of such electronic devices
has increased. Currently, research into lithium secondary
batteries, as batteries that may best satisfy the above need,
has actively conducted.
[0004] A lithium secondary battery is a battery which is
25 composed of a positive electrode, a negative electrode, and
2
an electrolyte and a separator which provide movement paths
of lithium ions between the positive electrode and the
negative electrode, wherein electrical energy is generated by
oxidation and reduction reactions that occur when lithium
5 ions are stored in and released from the positive electrode
and the negative electrode.
[0005] A lithium secondary battery has an average discharge
voltage of about 3.6 V to about 3.7 V, and one of the
advantages of the lithium secondary battery is that it has a
10 higher discharge voltage than other alkaline batteries and a
nickel-cadmium battery. In order to achieve such a high
operating voltage, an electrolyte composition, which is
electrochemically stable in a charge and discharge voltage
range of 0 V to 4.2 V, is required.
15 [0006] Lithium ions released from a positive electrode
active material, such as lithium metal oxide, during initial
charging of a lithium secondary battery move to a negative
electrode active material, such as a graphite-based material,
to be intercalated into interlayers of the negative electrode
20 active material. In this case, since lithium is highly
reactive, lithium reacts with an electrolyte and carbon
constituting the negative electrode active material on a
surface of the negative electrode active material, such as a
graphite-based material, to form a compound such as Li2CO3,
25 Li2O, or LiOH. These compounds may form a solid electrolyte
3
interface (SEI) film on the surface of the negative electrode
active material such as a graphite-based material.
[0007] The SEI film may only pass lithium ions by acting as
an ion tunnel. Due to the effect of the ion tunnel, the SEI
5 film may prevent the destruction of a negative electrode
structure due to the intercalation of organic solvent
molecules having a high molecular weight, which move with
lithium ions in the electrolyte, into the interlayers of the
negative electrode active material. Thus, it has been
10 reported that the decomposition of the electrolyte does not
occur by preventing the contact between the electrolyte and
the negative electrode active material, and stable charge and
discharge may be maintained by reversibly maintaining the
amount of lithium ions in the electrolyte.
15 [0008] However, the SEI film of the lithium secondary
battery may be unstable due to an additive or an organic
solvent included in the electrolyte, and although the SEI
film may be stably formed, gas may be generated due to the
decomposition of the residual additive.
20 [0009] Even in a case of using an imide-based salt which may
improve high-temperature storability and low-temperature
output characteristics by minimizing an increase in viscosity
of the organic solvent at low temperature and improving the
mobility of the lithium ions, there is a significant
25 limitation in using the lithium secondary battery due to the
4
possibility of corrosion.
[0010] Thus, there is an urgent need to develop a method of
improving output characteristics and lifetime characteristics
of the lithium secondary battery while forming a robust and
5 uniform SEI film and selectively selecting and using an
electrolyte.
DISCLOSURE OF THE INVENTION
TECHNICAL PROBLEM
[0011] The present invention provides a method of preparing
10 a lithium secondary battery which may simultaneously improve
output characteristics and lifetime characteristics of the
lithium secondary battery by preparing an electrode on which
an SEI film is formed through a pretreatment process, putting
an electrode assembly including the electrode in a battery
15 case, and injecting an electrolyte thereinto.
TECHNICAL SOLUTION
[0012] According to an aspect of the present invention,
there is provided a method of preparing a lithium secondary
battery including: performing a pretreatment in which an SEI
20 (solid electrolyte interphase) film is formed on an electrode
by impregnating the electrode in a composition for forming an
SEI film, which includes a lithium salt, a non-aqueous
organic solvent, and an SEI film-forming agent capable of
forming the SEI film by an electrochemical oxidation or
25 reduction decomposition reaction, and applying a voltage to
5
the electrode; and preparing an electrode assembly using the
electrode having the SEI film formed thereon, putting the
electrode assembly in a battery case, and performing an
assembly process of electrolyte injection and charging one or
5 more times.
[0013] According to another aspect of the present invention,
there is provided a lithium secondary battery prepared by the
above method.
[0014] According to another aspect of the present invention,
10 there is provided a battery module including the lithium
secondary battery as a unit cell and a battery pack including
the battery module.
[0015] Particularities of other embodiments of the present
invention are included in the following detailed description.
15 ADVANTAGEOUS EFFECTS
[0016] According to a method of preparing a lithium
secondary battery according to an embodiment of the present
invention, output characteristics and lifetime
characteristics of a lithium secondary battery may be further
20 improved by forming an SEI film on an electrode in advance
through a pretreatment of the electrode, putting an electrode
assembly including the electrode having the SEI film formed
thereon in a battery case, and stepwise injecting an
electrolyte one or more times.
25 [0017] Also, an amount of an expensive additive used may be
6
reduced by using only a small amount of the additive required
for the formation of the SEI film in a pretreatment step, the
release of a gas generated in the battery case may be
facilitated, and various electrolytes may be selectively used
5 by the stepwise injection of the electrolyte. Thus, the
performance of the lithium secondary battery may be further
improved by overcoming limitations due to the typical use of
a lithium salt and an additive.
BRIEF DESCRIPTION OF THE DRAWINGS
10 [0018] The following drawings attached to the specification
illustrate preferred examples of the present invention by
example, and serve to enable technical concepts of the
present invention to be further understood together with
detailed description of the invention given below, and
15 therefore the present invention should not be interpreted
only with matters in such drawings.
[0019] FIG. 1 is a flowchart illustrating a method of
preparing a lithium secondary battery according to an
embodiment of the present invention;
20 [0020] FIG. 2 is a flowchart illustrating an electrode
injection and charging step of step II in the method of
preparing a lithium secondary battery according to the
embodiment of the present invention;
[0021] FIG. 3 is a graph illustrating experimental results
25 of output characteristics of lithium secondary batteries
7
prepared in Examples 1 and 2 and Comparative Examples 1 and
4; and
[0022] FIG. 4 is a graph illustrating experimental results
of lifetime characteristics of lithium secondary batteries
5 prepared in Examples 1 to 5 and Comparative Examples 1 to 4.
MODE FOR CARRYING OUT THE INVENTION
[0023] Hereinafter, the present invention will be described
in more detail to allow for a clearer understanding of the
present invention.
10 [0024] It will be understood that words or terms used in the
specification and claims shall not be interpreted as the
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
15 meaning in the context of the relevant art and the technical
idea of the invention, based on the principle that an
inventor may properly define the meaning of the words or
terms to best explain the invention.
[0025] A method of preparing a lithium secondary battery
20 according to an embodiment of the present invention includes:
performing a pretreatment in which an SEI film is formed on
an electrode by impregnating the electrode in a composition
for forming an SEI film, which includes a lithium salt, a
non-aqueous organic solvent, and an SEI film-forming agent
25 forming the SEI film by an electrochemical oxidation-
8
reduction decomposition reaction, and applying a voltage to
the electrode (step I ) ; and preparing an electrode assembly
using the electrode having the SEI film formed thereon,
putting the electrode assembly in a battery case, and
5 performing a process of electrolyte injection and charging
one or more times (step II).
[0026] According to the method of preparing a lithium
secondary battery according to the embodiment of the present
invention, output characteristics and lifetime
10 characteristics of a lithium secondary battery may be further
improved by forming an SEI film on an electrode in advance
through a pretreatment of the electrode, putting the
electrode having the SEI film formed thereon in a battery
case, and stepwise injecting an electrolyte one or more times.
15 [0027] Also, an amount of an expensive additive used may be
reduced by using only a small amount of the additive required
for the formation of the SEI film in the pretreatment step,
the release of a gas generated in the battery case may be
facilitated, and various electrolytes may be selectively used
20 by the stepwise injection of the electrolyte. Thus, the
performance of the lithium secondary battery may be further
improved by overcoming limitations due to the typical use of
a lithium salt and an additive.
[0028] FIG. 1 is a flowchart illustrating the method of
25 preparing a lithium secondary battery according to the
9
embodiment of the present invention. However, FIG. 1 is only
an example for describing the present invention and the
present invention is not limited thereto.
[0029] Hereinafter, the present invention will be described
5 in more detail for each step with reference to FIG. 1. In
the method of preparing a lithium secondary battery according
to the embodiment of the present invention, step I, as a
pretreatment step for preparing a secondary battery, may
include forming an SEI film on an electrode using a
10 composition for forming an SEI film.
[0030] That is, step I is a step of forming an SEI film on a
positive electrode or a negative electrode by putting the
electrode, i.e., the positive electrode or the negative
electrode, in a composition for forming an SEI film, which
15 includes an SEI film-forming agent capable of easily forming
the SEI film due to good wettability with respect to an
electrolyte as well as forming the SEI film by an
electrochemical oxidation or reduction decomposition reaction,
and applying a voltage to perform the electrochemical
20 reaction.
[0031] In general, since an electrode used in a lithium
secondary battery is strongly lipophilic, the electrode has
poor wetting with an electrolyte having a hydrophilic
property. In a case where activation of the battery is
25 performed in a state in which the electrolyte does not
10
sufficiently wet the electrode, since an SEI film is not
properly formed on the electrode, the lifetime
characteristics of the battery may be degraded.
[0032] In the present invention, since the electrode
5 pretreatment is performed by using the composition for
forming an SEI film which may improve the wetting with the
electrolyte, an SEI film may be sufficiently formed on the
electrode in advance due to the good wettability.
[0033] The composition for forming an SEI film is not
10 particularly limited so long as it is a solution including a
compound which may form the SEI film on the electrode, and
may specifically include an SEI film-forming agent, a lithium
salt, and a non-aqueous organic solvent.
[0034] The lithium salt usable in the preparation of the
15 composition for forming an SEI film is a source of lithium
ions, wherein the lithium salt may be used without particular
limitation as long as it is a compound capable of providing
lithium ions. Specific examples of the lithium salt may be
LiPF6, LiAsF6, LiCF3SO3, LiBF4, LiBF6, LiSbF6, LiAlO4, LiAlCl4,
20 LiSO3CF3, or LiClO4, and any one thereof or a mixture of two
or more thereof may be used.
[0035] Also, the lithium salt may be included in a
concentration of 0.5 mol/l to 2 mol/l in the composition for
forming an SEI film. In a case in which the concentration of
25 the lithium salt is less than 0.5 mol/l, an amount of lithium
11
ions provided is not sufficient, and in a case in which the
concentration of the lithium salt is greater than 2 mol/l,
since viscosity of the composition for forming an SEI film
may be increased, formability of the SEI film may be reduced.
5 When considering conductivity of the lithium ions in the SEI
film and the formability of the SEI film, the lithium salt,
for example, may be included in a concentration of 0.5 mol/l
to 1.6 mol/l in the composition for forming an SEI film.
[0036] Typically, an SEI film may also be formed by an
10 electrochemical oxidation-reduction reaction of an
electrolyte including a lithium salt and a non-aqueous
organic electrolyte. However, the SEI film formed by the
decomposition of the non-aqueous organic electrolyte is thick
and has a high resistance.
15 [0037] In contrast, in the present invention, since a
thickness of the formed SEI film is reduced but density is
increased by using an additive for forming an SEI film, an
SEI film having improved properties may be formed, for
example, resistance in the SEI film is decreased.
20 [0038] In the method of preparing a lithium secondary
battery according to the embodiment of the present invention,
the SEI film-forming agent usable in the preparation of the
composition for forming an SEI film, as a compound capable of
forming the SEI film by an electrochemical oxidation or
25 reduction decomposition reaction, may specifically include a
12
cyclic carbonate-based compound containing an unsaturated
bond; a cyclic or chain carbonate-based compound containing a
halogen atom; a lithium salt containing an oxalato complex as
an anion; an imide-based lithium salt; a fluorophosphate-
5 based lithium salt; a fluoroborate-based lithium salt; a 6-
membered aromatic heterocyclic compound containing at least
two nitrogen atoms in a molecule; a sultone-based compound;
or an acrylate-based compound, and any one thereof or a
mixture of two or more thereof may be used. Unless otherwise
10 specified in the present invention, the SEI film-forming
agent is a compound different from a lithium salt and a nonaqueous
organic solvent used in the preparation of the
composition for forming an SEI film and described below.
[0039] In the SEI film-forming agent, the cyclic carbonate-
15 based compound containing an unsaturated bond may
specifically be a vinylene carbonate-based compound such as
vinylene carbonate, methyl vinylene carbonate, ethyl vinylene
carbonate, propyl vinylene carbonate, dimethyl vinylene
carbonate, or vinylene ethylene carbonate; or a vinyl
20 ethylene carbonate-based compound, such as vinyl ethylene
carbonate, and any one thereof or a mixture of two or more
thereof may be used.
[0040] Also, in the SEI film-forming agent, the cyclic or
chain carbonate-based compound containing a halogen atom may
25 specifically be a cyclic carbonate-based compound containing
13
at least one halogen atom in a molecule such as
fluoroethylene carbonate or difluoroethylene carbonate; and a
chain carbonate-based compound containing at least one
halogen atom in a molecule such as fluoromethyl methyl
5 carbonate or bis(fluoromethyl)carbonate, and any one thereof
or a mixture of two or more thereof may be used.
[0041] Furthermore, in the SEI film-forming agent, as the
lithium salt containing an oxalato complex as an anion, any
lithium salt may be used without limitation as long as an
10 anionic compound containing an oxalate group and lithium ions
form a complex through coordination bonds. Specific examples
of the lithium salt containing an oxalato complex as an anion
may be lithium difluoro(oxalato)borate (LiODFB), lithium
tetrafluoro(oxalato) phosphate (LiTFOP), lithium
15 tris(oxalate)phosphate (LTOP), or lithium bis(oxalato)borate
(LiBOB), and any one thereof or a mixture of two or more
thereof may be used.
[0042] In the SEI film-forming agent, an imide-based lithium
salt such as lithium bisfluorosulfonyl imide (LiFSI), lithium
20 bis trifluoromethanesulfonyl imide (LiTFSI), or lithium
bis(perfluoroethylsulfonyl)imide (LiBETI); and a
fluorophosphate-based lithium salt, such as LiBF4, lithium
difluorophosphate (LiF2O2P), or lithium monofluorophosphate
(Li2PO3F), may be used as the lithium salt for forming an SEL
25 film in addition to the lithium salt containing an oxalato
14
complex as an anion, and the above compounds may be used
alone or in a mixture of two or more thereof.
[0043] The lithium salt containing an oxalato complex as an
anion, the imide-based lithium salt, or the fluorophosphate-
5 based salt, which may be used as the SEI film-forming agent,
may also be used as the lithium salt in the composition for
forming an SEI film. In this case, the lithium salt
containing an oxalato complex as an anion, the imide-based
lithium salt, or the fluorophosphate-based salt may be
10 included in an amount in which a total concentration of the
lithium salt included in the composition for forming an SEI
film simultaneously satisfies a condition of lithium salt
concentration in the composition for forming an SEI film and
a condition of the amount of the SEI film-forming agent.
15 [0044] Also, in the SEI film-forming agent, the 6-membered
aromatic heterocyclic compound containing at least two
nitrogen atoms in a molecule may specifically be pyrimidine
and 1,3,5-triazine, and any one thereof or a mixture of two
or more thereof may be used.
20 [0045] Furthermore, in the SEI film-forming agent, the
sultone-based compound may specifically be 1,3-propane
sultone (PS), 1,4-butane sultone, or 1,3-propene sultone, and
any one thereof or a mixture of two or more thereof may be
used.
25 [0046] The SEI film-forming agent may be included in an
15
amount of 0.1 wt% to 10 wt% based on a total weight of the
composition for forming an SEI film. When the amount of the
SEI film-forming agent is within the above range, a uniform
and thin film derived from the additive for forming an SEI
5 film may be formed on the electrode after the electrical
reaction, and an amount of a gas generated by charging may be
minimized. Also, when considering an effect of improving
physical properties of the SEI film formed according to the
use of the SEI film-forming agent, the SEI film-forming agent
10 may specifically be included in an amount of 0.25 wt% to 5
wt%, for example, 0.5 wt% to 3 wt%, based on the total weight
of the composition for forming an SEI film.
[0047] In the composition for forming an SEI film, the nonaqueous
organic solvent functions as a medium through which
15 ions involved in the electrochemical reaction may move,
wherein any non-aqueous organic solvent, which may be
minimally decomposed by an oxidation reaction or the like
during charging and discharging of the battery and may
exhibit desired characteristics with the SEI film-forming
20 agent, may be appropriate.
[0048] Specifically, the non-aqueous organic solvent may be
a cyclic carbonate-based solvent such as ethylene carbonate
(EC), propylene carbonate (PC), and butylene carbonate (BC);
a linear carbonate-based solvent such as dimethyl carbonate
25 (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC),
16
ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC),
and ethylpropyl carbonate (EPC); an ester-based solvent such
as methyl acetate, ethyl acetate, γ-butyrolactone, and ε-
caprolactone; an ether-based solvent such as dibutyl ether or
5 tetrahydrofuran; or a ketone-based solvent, such as
cyclohexanone, and any one thereof or a mixture of two or
more thereof may be used. Among the above solvents, the
organic solvent may be a mixture of cyclic carbonate and
linear carbonate in consideration of the formability of the
10 SEI film, and, for example, may be a mixture in which the
linear carbonate is mixed in a larger amount than the cyclic
carbonate. Specifically, a mixing volume ratio of the linear
carbonate to the cyclic carbonate may be in a range of 5:5 to
8:2.
15 [0049] The non-aqueous organic solvent may be included in
such an amount that the composition for forming an SEI film
has a viscosity which facilitates the formation of the SEI
film.
[0050] The electrode pretreated by the composition for
20 forming an SEI film may be a positive electrode or a negative
electrode.
[0051] Specifically, in a case in which the electrode is a
positive electrode, the usable positive electrode may include
a structure in which a positive electrode active material
25 layer is stacked on a current collector such as a thin film
17
formed of aluminum or an aluminum-based alloy. In this case,
the positive electrode active material layer may include a
positive electrode active material, a conductive agent, and a
binder, and the positive electrode active material and the
5 conductive agent may be stacked on the current collector by
the binder.
[0052] The positive electrode active material is a compound
(lithiated intercalation compound) capable of reversibly
intercalating and deintercalating lithium, wherein the
10 positive electrode active material may specifically be a
lithium transition metal oxide including lithium and a
transition metal such as cobalt, manganese, nickel, or
aluminum. Furthermore, the lithium transition metal oxide
may be selected form the group consisting of lithium-nickel-
15 manganese-cobalt-based oxide, lithium-manganese-based oxide,
lithium-nickel-manganese-based oxide, and lithium-manganesecobalt-
based oxide, and, for example, may include LiCoO2,
LiNiO2, LiMnO2, LiMn2O4, Li(NiaCobMnc)O2 (where 0
[00133] A composition for forming a positive electrode was
prepared by adding 96 wt% of Li(Ni0.33Co0.33Mn0.33)O2 as a
positive electrode active material, 2 wt% of carbon black as
25 a conductive agent, and 2 wt% of polyvinylidene fluoride
44
(PVdF) as a binder to N-methyl-2-pyrrolidone (NMP) as a
solvent. A 20 μm thick aluminum (Al) thin film as a positive
electrode collector was coated with the composition for
forming a positive electrode and dried, and the Al thin film
5 was then roll-pressed to prepare a positive electrode.
[00134] Also, a composition for forming a negative electrode
was prepared by adding 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 to NMP as a solvent.
10 A 10 μm thick copper (Cu) thin film as a negative electrode
collector was coated with the composition for forming a
negative electrode and dried, and the Cu thin film was then
roll-pressed to prepare a negative electrode.
[00135]
15 [00136] A composition for forming an SEI film was prepared by
adding LiPF6, as a lithium salt, at a concentration of 1.0 M
to a non-aqueous organic solvent having a composition, in
which a volume ratio of ethylene carbonate (EC):ethylmethyl
carbonate (EMC):dimethyl carbonate (DMC) was 3:3:4, and then
20 adding 1 wt% of vinylene carbonate (VC) based on a total
weight of the composition for forming an SEI film.
[00137]
[00138] The composition for forming an SEI film and negative
electrode thus prepared were put in a 15 mL bath and an
25 electrochemical reaction was then performed using a lithium
45
metal foil as a counter electrode. For the electrochemical
reaction, a constant current of 0.05 C was applied to the
negative electrode and the counter electrode within a voltage
range of 2.5 V to 0.005 V, and, when the voltage was 0.005 V,
5 an SEI film was formed on the negative electrode by applying
a current under a constant voltage condition until a current
value became 1/20 C.
[00139] Step II: Electrolyte Injection and Charging Step
(Twice Injection)
10 [00140] Step i) First Electrolyte Injection Step
[00141]
[00142] A first electrolyte was prepared by adding 0.25 ml of
1M LiPF6, as a lithium salt, and 1 wt% of 1,3-propane sultone
(PS), as an additive, based on a total weight of a non-
15 aqueous electrolyte solution to a non-aqueous organic solvent
having a composition in which a volume ratio of propylene
carbonate (PC):ethylene carbonate (EC):ethylmethyl carbonate
(EMC) was 3:3:4.
[00143]
20 [00144] An electrode assembly was prepared by disposing a
separator formed of three layers of
polypropylene/polyethylene/polypropylene (PP/PE/PP) between
the positive electrode prepared in step I and the negative
electrode having the SEI film formed thereon, the electrode
25 assembly was put in a battery case, and the first electrolyte
46
was then injected.
[00145] Step ii) First Charging Step
[00146] As a first charging process, first charging was
performed at a constant current of 0.1 C up to 4.2 V in a
5 state in which an electrolyte injection hole of the battery
case obtained in step i) was not sealed.
[00147] Step iii) Second Electrolyte Injection Step
[00148]
[00149] A second electrolyte was prepared by adding 0.25 ml
10 of 1M LiFSI, as a lithium salt, based on the total weight of
the non-aqueous electrolyte solution to a non-aqueous organic
solvent having a composition, in which a volume ratio of
propylene carbonate (PC):ethylene carbonate (EC):ethylmethyl
carbonate (EMC) was 3:3:4, and the second electrolyte was
15 then injected into the electrode assembly first charged in
step i i ).
[00150] Step iv) Second Charging Step
[00151] An electrolyte injection hole of the battery case
obtained in step iii) was sealed, and, as a second charging
20 process, second charging was then performed at a constant
current of 0.2 C up to 4.2 V.
[00152] Example 2
[00153] A lithium secondary battery was prepared in the same
manner as in Example 1 except that the electrolyte injection
25 and charging step of step II in Example 1 was performed only
47
one time as follows:
[00154] Step II: Electrolyte Injection and Charging Step
(Single Injection)
[00155] Step i) First Electrolyte Injection Step
5 [00156]
[00157] A first electrolyte was prepared by adding 0.5 ml of
1M LiPF6, as a lithium salt, and 1 wt% of 1,3-propane sultone
(PS), as an additive, based on a total weight of a nonaqueous
electrolyte solution to a non-aqueous organic solvent
10 having a composition in which a volume ratio of propylene
carbonate (PC):ethylene carbonate (EC):ethylmethyl carbonate
(EMC) was 3:3:4.
[00158]
[00159] An electrode assembly was prepared by disposing a
15 separator formed of three layers of
polypropylene/polyethylene/polypropylene (PP/PE/PP) between
the positive electrode prepared in step I and the negative
electrode having the SEI film formed thereon, the electrode
assembly was put in a battery case, and the first electrolyte
20 was then injected.
[00160] Step ii) First Charging Step
[00161] As a first charging process, first charging was
performed at a constant current of 0.1 C up to 4.2 V in a
state in which an electrolyte injection hole of the battery
25 case obtained in step i) was not sealed.
48
[00162] Examples 3 to 8
[00163] Lithium secondary batteries were prepared in the same
manner as in Example 1 except that compositions for forming
an SEI film and first and/or second electrolytes were
5 prepared according to formulations listed in the following
Table 1 and used.
[00164] Comparative Example 1
[00165] i) Electrolyte Injection Step
[00166]
10 [00167] An electrolyte was prepared by adding a total of 0.5
ml of 0.5M LiPF6 and 0.5 M LiFSI, as a lithium salt, based on
a total weight of a non-aqueous electrolyte solution to a
non-aqueous organic solvent having a composition in which a
volume ratio of propylene carbonate (PC):ethylene carbonate
15 (EC):ethylmethyl carbonate (EMC) was 3:3:4.
[00168]
[00169] A composition for forming a positive electrode was
prepared by adding 96 wt% of Li(Ni0.33Co0.33Mn0.33)O2 as a
positive electrode active material, 2 wt% of carbon black as
20 a conductive agent, and 2 wt% of polyvinylidene fluoride
(PVdF) as a binder to N-methyl-2-pyrrolidone (NMP) as a
solvent. A 20 μm thick aluminum (Al) thin film as a positive
electrode collector was coated with the composition for
forming a positive electrode and dried, and the Al thin film
25 was then roll-pressed to prepare a positive electrode.
49
[00170] Also, a composition for forming a negative electrode
was prepared by adding 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 to NMP as a solvent.
5 A 10 μm thick copper (Cu) thin film as a negative electrode
collector was coated with the composition for forming a
negative electrode and dried, and the Cu thin film was then
roll-pressed to prepare a negative electrode.
[00171] An electrode assembly was prepared by disposing a
10 separator formed of three layers of
polypropylene/polyethylene/polypropylene (PP/PE/PP) between
the positive electrode and negative electrode thus prepared,
the electrode assembly was put in a battery case, and the
electrolyte was then injected.
15 [00172] ii) Charging Step
[00173] An electrolyte injection hole of the battery case
obtained in step i) was sealed, and, as a first charging
process, charging was then performed at a constant current of
0.1 C up to 4.2 V.
20 [00174] Comparative Example 2
[00175] Step i) First Electrolyte Injection Step
[00176]
[00177] A first electrolyte was prepared by adding 0.25 ml of
1M LiPF6, as a lithium salt, and 1 wt% of 1,3-propane sultone
25 (PS), as an additive, based on a total weight of a non-
50
aqueous electrolyte solution to a non-aqueous organic solvent
having a composition in which a volume ratio of propylene
carbonate (PC):ethylene carbonate (EC):ethylmethyl carbonate
(EMC) was 3:3:4.
5 [00178]
[00179] An electrode assembly was prepared by disposing a
separator formed of three layers of
polypropylene/polyethylene/polypropylene (PP/PE/PP) between
the positive electrode and negative electrode prepared in
10 Comparative Example 1, the electrode assembly was put in a
battery case, and the first electrolyte was then injected.
[00180] Step ii) First Charging Step
[00181] As a first charging process, first charging was
performed at a constant current of 0.1 C up to 4.2 V in a
15 state in which an electrolyte injection hole of the battery
case obtained in step i) was not sealed.
[00182] Step iii) Second Electrolyte Injection Step
[00183]
[00184] A second electrolyte was prepared by adding 0.25 ml
20 of 1M LiFSI, as a lithium salt, based on the total weight of
the non-aqueous electrolyte solution to a non-aqueous organic
solvent having a composition, in which a volume ratio of
propylene carbonate (PC):ethylene carbonate (EC):ethylmethyl
carbonate (EMC) was 3:3:4, and the second electrolyte was
25 then injected into the electrode assembly first charged in
51
step i i ).
[00185] Step iv) Second Charging Step
[00186] An electrolyte injection hole of the battery case
obtained in step iii) was sealed, and, as a second charging
5 process, second charging was then performed at a constant
current of 0.2 C up to 4.2 V.
[00187] Comparative Example 3
[00188] A lithium secondary battery was prepared in the same
manner as in Comparative Example 2 except that, in the method
10 of preparing the lithium secondary battery of Comparative
Example 2, LiFSI, instead of LiPF6, was used as a lithium
salt during the preparation of the first electrolyte, LiPF6,
instead of LiFSI, was used as a lithium salt during the
preparation of the second electrolyte, and 1,3-propane
15 sultone (PS) was further used as an additive.
[00189] Comparative Example 4
[00190] A lithium secondary battery was prepared in the same
manner as in Comparative Example 1 except that, in the method
of preparing the lithium secondary battery of Comparative
20 Example 1, an electrolyte, which was prepared by adding 0.5
ml of 1M LiPF6, as a lithium salt, and 1 wt% of 1,3-propane
sultone (PS) and 1 wt% of vinylene carbonate (VC), as an
additive, based on a total weight of a non-aqueous
electrolyte solution to a non-aqueous organic solvent having
25 a composition in which a volume ratio of propylene carbonate
52
(PC):ethylene carbonate (EC):ethylmethyl carbonate (EMC) was
3:3:4, was used.
[00191] Comparative Example 5
[00192] A lithium secondary battery was prepared in the same
5 manner as in Comparative Example 3 except that, in the method
of preparing the lithium secondary battery of Comparative
Example 3, an electrolyte, which was prepared by adding 0.5
ml of 1M LiPF6, as a lithium salt, and 1 wt% of vinylene
carbonate (VC), as an additive, based on a total weight of a
10 non-aqueous electrolyte solution to a non-aqueous organic
solvent having a composition in which a volume ratio of
propylene carbonate (PC):ethylene carbonate (EC):ethylmethyl
carbonate (EMC) was 3:3:4, was used.
[00193] The compositions for forming an SEI film and the
15 compositions of the first and second electrolytes, which were
used in Examples 1 to 8 and Comparative Examples 1 to 5, are
listed in the following Table 1.
[00194] [Table 1]
Example 1
Example 2
Composition
for forming a
negative
electrode SEI
film
(Composition
A)
(Composition
First electrolyte
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
o
(PC/EC/EMC=3/3/4,
Second
electrolyte
(PC/EC/EMC=3/3/4,
LiFSI 1M)
×
53
Example 3
Example 4
Example 5
Example 6
Example 7
Example 8
Comparative
Example 1
Comparative
Example 2
Comparative
Example 3
Comparative
Example 4
A)
(Composition
B)
(Composition
C)
(Composition
D)
(Composition
E)
(Composition
F)
(Composition
G)
x
x
x
x
LiPF6 1M, PS 1
wt%)
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
(PC/EC/EMC=3/3/4,
LiPF6 0.5M, LiFSI
0.5M)
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
(PC/EC/EMC=3/3/4,
LiFSI 1M)
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
(PC/EC/EMC=3/3/4,
LiFSI 1M)
x
(PC/EC/EMC=3/3/4,
LiFSI 1M)
x
(PC/EC/EMC=3/3/4,
LiFSI 1M)
x
x
(PC/EC/EMC=3/3/4,
LiFSI 1M)
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
x
54
Comparative
Example 5
×
wt%, VC 1 wt%)
o
(EC/EMC/DMC
=3/3/4, LiPF6 1M,
VC 1 wt%)
o
(PC/EC/EMC=3/3/4,
LiPF6 1M, PS 1
wt%)
[00195] In Table 1, the mixing ratio of the solvents was
based on a volume ratio, and
[00196] Composition A: EC/EMC/DMC=3/3/4, LiPF6 1 M, VC 1 wt%;
5 [00197] Composition B: EC/EMC/DMC=3/3/4, LiPF6 1 M, FEC 1
wt%;
[00198] Composition C: EC/EMC/DMC=3/3/4, LiPF6 0.9 M, LiODFB
0.1 M;
[00199] Composition D: EC/EMC/DMC=3/3/4, LiPF6 0.9 M, LiFSI
10 0.1 M;
[00200] Composition E: EC/EMC/DMC=3/3/4, LiPF6 0.9 M, LiF2O2P
0.1 M;
[00201] Composition F: EC/EMC/DMC=3/3/4, LiPF6 1 M,
pyrimidine 0.5 wt%; and
15 [00202] Composition G: EC/EMC/DMC=3/3/4, LiPF6 1 M, PS 0.5
wt%.
[00203] Experimental Example 1: Output Characteristics Test
[00204] Outputs were calculated from voltage differences
which were obtained by discharging the lithium secondary
20 batteries of Examples 1 and 2 and Comparative Examples 1 and
4 at 0.5 C for 10 seconds for the state of charge (SOC) at
55
room temperature. The results thereof are presented in FIG.
3.
[00205] As illustrated in FIG. 3, output characteristics of
the lithium secondary batteries of Examples 1 and 2 subjected
5 to the pretreatment step of forming an SEI film on the
electrode were significantly improved in comparison to those
of the lithium secondary batteries of Comparative Examples 1
and 4 which were not subjected to the pretreatment step of
forming an SEI film.
10 [00206] Specifically, with respect to Example 1 in which the
electrolyte injection and charging step was performed twice
while performing the pretreatment step of forming an SEI film
on the electrode, it may be understood that the output
characteristics were improved by about 15% to about 70% at
15 90% SOC in comparison to those of Comparative Examples 1 and
4.
[00207] Also, when comparing Example 2 and Comparative
Example 4, it may be understood that the output
characteristics of Comparative Example 4, which was not
20 subjected to the pretreatment step of forming an SEI film on
the electrode, were decreased by about 15% to about 20% in
comparison to those of Example 2.
[00208] Thus, it may be understood that the output
characteristics were significantly improved when the
25 pretreatment step of forming an SEI film on the electrode was
56
performed before the electrolyte injection and charging step.
[00209] Experimental Example 2: Lifetime Characteristics Test
[00210] The lithium secondary batteries of Examples 1 to 5
and Comparative Examples 1 to 4 were charged at 1 C to 4.2
5 V/3.25 mA at room temperature under a constant
current/constant voltage (CC/CV) condition and then
discharged at a constant current (CC) of 3 C to a voltage of
3.03 V to measure discharge capacities. The charge and
discharge were repeated 1 to 80 cycles and the measured
10 discharge capacities are presented in FIG. 4.
[00211] As illustrated in FIG. 4, it may be understood that
lifetime characteristics of Examples 1 to 5 subjected to the
pretreatment step of forming an SEI film on the electrode
according to the present invention were significantly
15 improved in comparison to those of the lithium secondary
batteries of Comparative Examples 1 to 4 which were not
subjected to the pretreatment step.
[00212] Specifically, with respect to Example 1 in which the
electrolyte injection and charging step was performed one or
20 more times while performing the pretreatment step of forming
an SEI film on the electrode, it may be understood that
initial discharge capacity was similar to that of Comparative
Examples 1 to 4, but discharge capacity after about 10 cycles
was significantly improved in comparison to that of
25 Comparative Examples 1 to 4.
57
[00213] That is, with respect to the secondary batteries of
Examples 1 to 5, slopes of the resulting graphs of lifetime
characteristics from the 1st cycle to the 80th cycle were slow
so that discharge capacities at the 80th cycle were hardly
5 decreased from the initial discharge capacities. In contrast,
with respect to Comparative Examples 1 to 4, it may be
confirmed that discharge capacities were significantly
decreased after a 30th cycle and lifetime characteristics at
the 80th cycle were decreased by about 5% to about 15% in
10 comparison to those of Example 1.
[00214] Also, when comparing Comparative Examples 1 and 2 in
which the electrolyte injection and charging step was
performed twice under the same condition, it may be observed
that the lifetime characteristics were decreased by about 11%
15 depending on whether the pretreatment step of forming an SEI
film on the electrode was performed before the electrolyte
injection and charging step or not.
[00215] Thus, it may be understood that the lifetime
characteristics were significantly improved when the
20 pretreatment step of forming an SEI film on the electrode was
performed before the electrolyte injection and charging step.
[00216] Experimental Example 3: Swelling Characteristics Test
[00217] The lithium secondary batteries of Examples 2 to 8
and Comparative Examples 4 and 5 were charged at 1 C to 4.2
25 V/3.25 mA at room temperature under a constant
58
current/constant voltage (CC/CV) condition and then put in an
oven while the temperature was increased to 85°C for 1 hour.
Then, a thickness of each battery was measured after holding
the temperature for 4 hours. Degrees of swelling from
5 initial thicknesses are presented in Table 2.
[00218] [Table 2]
Example 2
Example 3
Example 4
Example 5
Example 6
Example 7
Example 8
Comparative Example 4
Comparative Example 5
Degree of swelling (mm)
0.31
0.25
0.44
0.50
0.36
0.40
0.38
1.40
1.55
[00219] As illustrated in Table 2, it may be understood that
swelling characteristics of Examples 2 to 8 were
10 significantly reduced in comparison to those of Comparative
Examples 4 and 5.
[00220] As an example, the battery of Example 2 had a degree
of swelling of 0.31 nm and the battery of Comparative Example
4 had a degree of swelling of 1.40 nm, wherein it was
15 confirmed that the degree of swelling of the electrode of
59
Example 2 from its initial thickness was reduced by about
351% in comparison to that of Comparative Example 4.
60
I/We Claim:
1. A method of preparing a lithium secondary battery, the
method comprising:
5 performing a pretreatment in which an SEI (solid
electrolyte interphase) film is formed on an electrode by
impregnating the electrode in a composition for forming an
SEI film and applying a voltage to the electrode; and
preparing an electrode assembly using the electrode
10 having the SEI film formed thereon, putting the electrode
assembly in a battery case, and performing a combination
process of electrolyte injection and charging one or more
times,
wherein the composition for forming an SEI film
15 comprises a lithium salt, a non-aqueous organic solvent, and
an SEI film-forming agent forming the SEI film by an
electrochemical oxidation or reduction decomposition reaction.
2. The method of claim 1, wherein the SEI film-forming
20 agent comprises one selected from the group consisting of a
cyclic carbonate-based compound containing an unsaturated
bond; a cyclic or chain carbonate-based compound containing a
halogen atom; a lithium salt containing an oxalato complex as
an anion; an imide-based lithium salt; a fluorophosphate-
25 based lithium salt; a 6-membered aromatic heterocyclic
61
compound containing at least two nitrogen atoms in a
molecule; and a sultone-based compound, or a mixture of two
or more thereof.
5 3. The method of claim 1, wherein the SEI film-forming
agent comprises one selected from the group consisting of
vinylene carbonate, methyl vinylene carbonate, ethyl vinylene
carbonate, propyl vinylene carbonate, dimethyl vinylene
carbonate, and vinyl ethylene carbonate, or a mixture of two
10 or more thereof.
4. The method of claim 1, wherein the SEI film-forming
agent is included in an amount of 0.1 wt% to 10 wt% based on
a total weight of the composition for forming an SEI film.
5. The method of claim 1, wherein the lithium salt
comprises one selected from the group consisting of LiPF6,
LiAsF6, LiCF3SO3, LiBF4, LiBF6, LiSbF6, LiAlO4, LiAlCl4,
LiSO3CF3, and LiClO4, or a mixture of two or more thereof.
6. The method of claim 1, wherein the forming of the SEI
film is performed by applying a voltage of 0.005 V to 4.5 V
at a constant current of 0.01 C to 5 C.
25 7. The method of claim 1, wherein, in a case in which the
62
15
20
electrode is a positive electrode, the forming of the SEI
film is performed by applying a voltage of 1 V to 4.5 V for 1
hour to 24 hours at a constant current of 0.01 C to 5 C.
5 8. The method of claim 1, wherein, in a case in which the
electrode is a negative electrode, the forming of the SEI
film is performed by applying a voltage of 0.005 V to 4.5 V
for 1 hour to 24 hours at a constant current of 0.01 C to 5 C.
10 9. The method of claim 1, wherein the combination process
of electrolyte injection and charging is performed one to
three times.
10. The method of claim 1, wherein the combination process
15 of electrolyte injection and charging comprises:
a first injection step of preparing a battery cell by
injecting a first electrolyte into the battery case; and
a first charging step of charging the battery cell.
20 11. The method of claim 1, wherein the combination process
of electrolyte injection and charging comprises:
a first injection step of preparing a battery cell by
injecting a first electrolyte into a battery case;
a first charging step of charging the battery cell;
25 a second injection step of injecting a second
63
electrolyte into the charged battery cell; and
a second charging step of charging the battery cell
into which the second electrolyte is injected.
5 12. The method of claim 10 or 11, wherein the first
electrolyte comprises at least one lithium salt selected from
the group consisting of LiPF6, LiAsF6, LiCF3SO3, LiBF4, LiBF6,
LiSbF6, and LiSO3CF3,
the electrode comprises an aluminum current collector,
10 and
an AlF3 film is formed on the current collector after
the first charging step.
13. The method of claim 10 or 11, wherein the first
15 electrolyte further comprises a sulfonic acid ester-based
additive.
14. The method of claim 13, wherein the sulfonic acid
ester-based additive comprises one selected from the group
20 consisting of 1,3-propane sultone, 1,4-butane sultone, 2,4-
butane sultone, and a cyclic disulfonic acid ester, or a
mixture of two or more thereof.
15. The method of claim 11, wherein the second electrolyte
25 comprises an imide-based lithium salt.
64
16. The method of claim 15, wherein the imide-based lithium
salt comprises one selected from the group consisting of
lithium bisfluorosulfonyl imide, lithium
5 bistrifluoromethanesulfonyl imide, and lithium
bis(perfluoroethylsulfonyl)imide, or a mixture of two or more
thereof.
17. The method of claim 11, wherein the second electrolyte
10 further comprises one selected from the group consisting of a
nitrile-based compound and a phosphate-based compound, or a
mixture thereof.
18. The method of claim 10 or 11, wherein the first
15 charging step is performed by applying a voltage of 1.0 V to
4.5 V at a constant current of 0.01 C to 5 C.
19. The method of claim 11, wherein the first charging step
is performed in a state in which the battery case is not
20 sealed after the injection of the first electrolyte.
20. The method of claim 11, wherein the second charging
step is performed by applying a voltage of 2.0 V to 4.5 V at
a constant current of 0.01 C to 5 C.
25
65
21. The method of claim 11, wherein the second charging
step is performed in a state in which the battery case is
sealed after the injection of the second electrolyte.
5 22. The method of claim 10 or 11, wherein the SEI filmforming
agent comprises a cyclic carbonate-based compound
containing an unsaturated bond, and
the first electrolyte comprises at least one lithium
salt selected from the group consisting of LiPF6, LiAsF6,
10 LiCF3SO3, LiBF4, LiBF6, LiSbF6, and LiSO3CF3.
23. The method of claim 22, wherein the first electrolyte
further comprises a sulfonic acid ester-based additive.
15 24. The method of claim 11, wherein the SEI film-forming
agent comprises a cyclic carbonate-based compound containing
an unsaturated bond,
the first electrolyte comprises at least one lithium
salt selected from the group consisting of LiPF6, LiAsF6,
20 LiCF3SO3, LiBF4, LiBF6, LiSbF6, and LiSO3CF3; and a sulfonic
acid ester-based additive, and
the second electrolyte comprises an imide-based lithium
salt.
25 25. The method of claim 1, wherein the electrode assembly
66
is any one selected from the group consisting of a jelly-roll
type, a stacked type, and a stack and folding type.
26. The method of claim 1, wherein the lithium secondary
5 battery is a cylindrical type, a prismatic type, or a pouch
type.
27. A lithium secondary battery prepared by the method of
claim 1.
10
28. The lithium secondary battery of claim 27, comprising
an electrode in which an SEI film-forming agent derived SEI
film on a surface of the electrode and at least one layer of
film formed by an electrochemical oxidation or reduction
15 reaction of an electrolyte on the SEI film are formed,
wherein the SEI film-forming agent comprises one
selected from the group consisting of a cyclic carbonatebased
compound containing an unsaturated bond; a cyclic or
chain carbonate-based compound containing a halogen atom; a
20 lithium salt containing an oxalato complex as an anion; an
imide-based lithium salt; a fluorophosphate-based lithium
salt; a 6-membered aromatic heterocyclic compound containing
at least two nitrogen atoms in a molecule; and a sultonebased
compound, or a mixture of two or more thereof.
25
67
29. The lithium secondary battery of claim 27, comprising
an electrode in which an SEI film derived from a cyclic
carbonate-based compound containing an unsaturated bond on a
surface of the electrode and a sulfonic acid ester-based
5 additive derived film on the SEI film are formed.
30. The lithium secondary battery of claim 27, comprising
an electrode in which an SEI film derived from a cyclic
carbonate-based compound containing an unsaturated bond on a
10 surface of the electrode, a sulfonic acid ester-based
additive derived film on the SEI film, and an imide-based
lithium salt derived film on the sulfonic acid ester-based
additive derived film are formed.
15 31. A battery module comprising the lithium secondary
battery of claim 27 as a unit cell.
32. A battery pack comprising the battery module of claim
31.
20
33. The battery pack of claim 32, wherein the battery pack
is used as a power source of a medium and large sized device.
34. The battery pack of claim 33, wherein the medium and
25 large sized device is selected from the group consisting of
68
an electric vehicle, a hybrid electric vehicle, a plug-in
hybrid electric vehicle, and a power storage system.