Specification
TECHNICAL FIELD
[1] [Cross Reference to Related Application]
[2] This application claims the benefit of priority based on Korean Patent
Application No. 10-2020-0071071 filed on June 11, 2020, the entire contents
10 of which are incorporated herein by reference.
[3] [Technical Field]
[4] The present invention relates to a negative electrode and a secondary battery
comprising the same.
BACKGROUND ART
15 [5] In recent years, along with the fast spread of electronic devices using batteries
such as mobile phones, notebook computers, and electric vehicles, demand for
secondary batteries that are small in size, light in weight, and relatively high
in capacity has rapidly increased. In particular, a lithium secondary battery
is light in weight and has a high energy density, and is receiving attention as
20 a driving power source of a portable device. Accordingly, research and
development efforts for improving the performance of lithium secondary
batteries have been actively pursued.
[6] Generally, lithium secondary batteries include a positive electrode, a negative
electrode, a separator interposed between the positive electrode and the
25 negative electrode, an electrolyte, an organic solvent, etc. Further, in the
2
positive electrode and the negative electrode, an active material layer
containing the positive electrode active material or the negative electrode
active material may be formed on a current collector. A lithium-containing
metal oxide such as LiCoO2 or LiMn2O4 is generally used as a positive
electrode active material for the positive electrode, 5 and thus a carbon-based
active material or silicon-based active material containing no lithium is used
as a negative electrode active material for the negative electrode.
[7] Among the negative electrode active materials, a silicon-based active material
has attracted attention in that it has a capacity as high as about 10 times as that
10 of a carbon-based active material and have excellent high-speed charging
characteristics. However, the silicon-based active material has a large
degree of volume expansion/contraction due to charging/discharging, and
there is a problem that an electrical short circuit between the active materials
is likely to occur as charging/discharging is repeated, and the lifetime
15 characteristics of the negative electrode are deteriorated. When a binder is
used in a large amount to suppress this, it is difficult to realize a desired high
capacity electrode, and resistance is increased, so it is not widely used.
[8] Korean Patent Publication No. 10-0794192 relates to a method for preparing
a carbon-coated silicon-graphite composite negative electrode material for a
20 lithium secondary battery and a method for preparing a secondary battery
comprising the same, but there is a limitation in solving the above problems.
[9] [Prior Art Document]
[10] [Patent Document]
[11] Korean Patent Publication No. 10-0794192
25 DETAILED DESCRIPTION OF THE INVENTION
3
TECHNICAL PROBLEM
[12] An object of the present invention is to provide a secondary battery that
exhibits improved capacity characteristics, lifetime characteristics, and fast
charging characteristics.
5 TECHNICAL SOLUTION
[13] The present invention provides a negative electrode comprising: a negative
electrode current collector; and a negative electrode active material layer
formed on the negative electrode current collector, wherein the negative
electrode active material layer comprises a silicon-based active material, a
10 binder, a first conductive material, and a second conductive material; a
specific surface area of the second conductive material is larger than a specific
surface area of the first conductive material; the first conductive material is
contained in the negative electrode active material layer in an amount of 9.68
% by weight to 9.83 % by weight; and the second conductive material is
15 contained in the negative electrode active material layer in an amount of 0.17
to 0.32 % by weight.
[14] The present invention also provides a secondary battery comprising the abovedescribed
negative electrode; a positive electrode opposite to the negative
electrode; a separator interposed between the negative electrode and the
20 positive electrode; and an electrolyte.
ADVANTAGEOUS EFFECTS
[15] The negative electrode of the present invention is a negative electrode using a
silicon-based active material, and is characterized by containing specific
contents of a conductive material having a small specific surface area (a first
4
conductive material) and a conductive material having a large specific area (a
second conductive material). The first conductive material allows the
conductive network to be preferably maintained between the active materials
even when the silicon-based active material undergoes volume
expansion/contraction through charging/di 5 scharging. In addition, the
second conductive material can be adsorbed on the surface of the silicon-based
active material to improve the conductivity of the surface of the silicon-based
active material. Therefore, the negative electrode in which the first conductive
material and the second conductive material are contained in specific contents
10 can improve the lifetime characteristics by preventing damage to the
conductive network due to the volume expansion/contraction of the siliconbased
active material and the electrical short circuit between the active
materials, and the excellent capacity characteristics and the fast charging
characteristics of the silicon-based active material can be preferably realized.
15 MODES OF THE INVENTION
[16] The terms or words used in the specification and claims should not be
construed as being limited to ordinary or dictionary meanings, and should be
construed as a meaning and concept that complies with the technical concept
of the present invention given the principle that the inventors can
20 appropriately define the concepts of the terms in order to explain their own
invention in the best way.
[17] The terminology used herein is used for the purpose of describing exemplary
embodiments only and is not intended to be limiting of the invention. The
articles “a” and “an” include plural referents unless the context clearly dictates
25 otherwise.
5
[18] In this specification, the terms "comprising", "including", "having" etc. are
intended to designate the presence of the implemented features, numbers,
steps, components, or combinations thereof, and are not to be understood as
precluding the possibility of the presence or addition of one or more other
5 features or numbers, steps, components or combinations thereof.
[19] In the present specification, the average particle diameter (D50) can be defined
as a particle diameter corresponding to 50 % of the cumulative volume in the
particle diameter distribution curve of the particles. The average particle
diameter (D50) can be measured using, for example, a laser diffraction method.
10 The laser diffraction method generally enables measurement of a particle
diameter of from a submicron region to about several millimeters, and results
of high reproducibility and high resolvability can be obtained.
[20]
[21] The present invention relates to a negative electrode, specifically, a negative
15 electrode for a lithium secondary battery.
[22] Specifically, the negative electrode of the present invention includes a
negative electrode current collector; and a negative electrode active material
layer formed on the negative electrode current collector, wherein the negative
electrode active material layer includes a silicon-based active material, a
20 binder, a first conductive material, and a second conductive material; a
specific surface area of the second conductive material is larger than a specific
surface area of the first conductive material; the first conductive material is
contained in the negative electrode active material layer in an amount of 9.68
% by weight to 9.83 % by weight; and the second conductive material is
6
contained in the negative electrode active material layer in an amount of 0.17
to 0.32 % by weight.
[23] Conventionally, a silicon-based active material has advantages of high
capacity and fast charging characteristics, but since the silicon-based active
material has a large degree 5 of volume expansion/contraction due to
charging/discharging, and as charging and discharging continues, the active
materials in the negative electrode lose contact with each other, and thus it is
difficult to transfer lithium between active materials, and there are problems
of lithium precipitation and fast deterioration of lifetime characteristics.
10 [24] In order to solve such problems, the negative electrode of the present invention
is a negative electrode using a silicon-based active material and is
characterized in that it contains specific contents of a conductive material
having a small specific surface area (a first conductive material) and a
conductive material having a large specific area (a second conductive
15 material). The first conductive material allows the conductive network
between the active materials to be preferably maintained even when the
silicon-based active material undergoes volume expansion/contraction
through charging/discharging. In addition, the second conductive material
can be adsorbed on the surface of the silicon-based active material to improve
20 the conductivity of the silicon-based active material surface. Therefore, the
negative electrode in which the first conductive material and the second
conductive material are contained in specific contents can improve the lifetime
characteristics by preventing damage to the conductive network due to the
volume expansion/contraction of the silicon-based active material and the
25 electrical short circuit between the active materials, and the excellent capacity
7
characteristics and the fast charging characteristics of the silicon-based active
material can be preferably realized.
[25] The negative electrode current collector may include at least one selected from
copper, stainless steel, aluminum, nickel, titanium, calcined carbon, and an
aluminum-cadmium alloy 5 , and preferably may include copper.
[26] The thickness of the negative electrode current collector may typically range
from 3 μm to 500 μm, preferably from 5 to 30 μm.
[27] The negative electrode current collector may be formed with fine irregularities
on its surface to enhance the binding force of the negative electrode active
10 material. For example, a negative electrode current collector in various
forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven
fabric etc., may be used.
[28] The negative electrode active material layer is formed on the negative
electrode current collector. Specifically, the negative electrode active
15 material layer may be formed on at least one surface of the negative electrode
current collector, specifically, on one surface or both surfaces of the negative
electrode current collector.
[29] The negative electrode active material layer contains a silicon-based active
material, a binder, and a conductive material.
20 [30] The silicon-based active material may contain a compound represented by the
following Chemical formula 1.
[31] [Chemical formula 1]
[32] SiOx
8
[33] In the Chemical formula 1, 0≤x<2. In the case of SiO2, it does not react with
lithium ions and cannot store lithium. Therefore, x is preferably within the
above range.
[34] Specifically, the silicon-based active material may contain Si.
Conventionally, Si is advantageous in 5 that the capacity is about 2.5 to 3 times
higher than that of silicon oxide (e.g. SiOx (0
[74] The present invention also provides a negative electrode slurry. The
15 negative electrode slurry may be applied onto a negative electrode current
collector to form the negative electrode described above. Specifically, the
negative electrode can be prepared by applying the negative electrode slurry
on the negative electrode current collector and drying and rolling it.
[75] The negative electrode slurry contains silicon-based active material, a binder,
20 a first conductive material, and a second conductive material; the specific
surface area of the second conductive material is larger than that of the first
conductive material; the first conductive material are contained in an amount
of 9.68 % by weight to 9.83 % by weight based on the solid content; and the
second conductive material is contained in an amount of 0.17 % by weight to
25 0.32 % by weight based on the solid content.
20
[76] The negative electrode slurry is characterized in that two kinds of conductive
material having different specific surface areas (the first conductive material
and the second conductive material) are contained in specific contents, and
thus, the first and second conductive materials can be uniformly distributed in
the slurry without occurrence 5 of a clumping phenomenon, and the first and
second conductive materials are uniformly distributed in the negative
electrode upon production of a negative electrode, so that the conductive
network at the silicon-based active material surface and between the active
materials can be smoothly maintained.
10 [77] The description of the silicon-based active material, the binder, the first
conductive material, and the second conductive material may be the same as
described in the negative electrode described above.
[78] The negative electrode slurry may further include a solvent for forming the
negative electrode slurry. The solvent for forming the negative electrode
15 slurry may contain, for example, at least one selected from the group
consisting of distilled water, ethanol, methanol and isopropyl alcohol,
preferably distilled water from the viewpoint of facilitating the dispersion of
the silicon-based active material, the binder and the conductive material.
[79] The solvent for forming a negative electrode slurry may be contained in the
20 negative electrode slurry so that the concentration of the solid content in the
negative electrode slurry ranges from 15 % by weight to 45 % by weight,
preferably from 20 % by weight to 30 % by weight in consideration of the
viscosity, coatability, dispersibility, etc. of the negative electrode slurry.
[80] The viscosity of the negative electrode slurry at 25 °C may range from 4,200
25 cP to 8,500 cP, preferably from 4,800 cP to 7,200 cP, more preferably from
21
5,200 cP to 6,800 cP, and more preferably 6,000 cP to 6,600 cP. When the
viscosity is in the above range, the problem of sedimentation of the negative
electrode slurry due to an excessively low viscosity can be prevented, a
problem of deterioration of coatability and workability such as mixing can be
avoided due to an excessively high 5 viscosity, and the dispersibility of the
above-described first conductive material and the second conductive material
is improved, whereby it is possible to produce a negative electrode having
improved lifetime characteristics and fast charging performance.
[81] The viscosity of the negative electrode slurry at 25 °C may be the viscosity of
10 a negative electrode slurry that has been rotated at a 1,500 shear rate (1/s) for
at least 250 seconds using a viscometer or the like and then allowed to rest for
80 to 120 seconds. Specifically, the viscosity of the negative electrode slurry
at 25 °C may be that of a negative electrode slurry that has been rotated for
300 seconds at a 1,500 shear rate (1/s) using a viscometer or the like, and then
15 allowed to rest for 100 seconds.
[82]
[83] The present invention provides a secondary battery, specifically a lithium
secondary battery. Specifically, the secondary battery may include the
above-described negative electrode.
20 [84] Specifically, the secondary battery may include a negative electrode; a
positive electrode opposite to the negative electrode; a separator interposed
between the negative electrode and the positive electrode; and an electrolyte.
The negative electrode may be the negative electrode described above.
22
[85] The positive electrode may include a positive electrode current collector and
a positive electrode active material layer formed on the positive electrode
current collector.
[86] The positive electrode current collector is not particularly limited as long as it
has high conductivity without causing a chemical 5 change in the battery.
Specifically, as the positive electrode current collector, copper, stainless steel,
aluminum, nickel, titanium, calcined carbon, or copper or stainless steel
whose surface is treated with carbon, nickel, titanium or silver, an aluminumcadmium
alloy or the like may be used.
10 [87] The positive electrode current collector may typically have a thickness of 3 to
500 μm.
[88] The positive electrode current collector may be formed with fine irregularities
on the surface to enhance the binding force of the positive electrode active
material. For example, a positive electrode current collector in various forms
15 such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven fabric
etc., may be used.
[89] The positive electrode active material layer may contain a positive electrode
active material.
[90] The positive electrode active material is a compound capable of reversible
20 intercalation and deintercalation of lithium, and may specifically include a
lithium-transition metal composite oxide containing lithium and at least one
transition metal selected from nickel, cobalt, manganese, and aluminum,
preferably a lithium-transition metal composite oxide including lithium and a
transition metal including nickel, cobalt, and manganese.
23
[91] More specifically, examples of the lithium-transition metal composite oxide
include lithium-manganese-based oxides (e.g., LiMnO2, LiMn2O4, etc.),
lithium-cobalt-based oxides (e.g., LiCoO2, etc.), lithium-nickel-based oxides
(e.g., LiNiO2, etc.), lithium-nickel-manganese-based oxides (e.g., LiNi1-
YMnYO2 (wherein, 0
[118] Example 1: Manufacture of Negative Electrode
[119] Si (average particle diameter (D50): 2.3 μm) as a silicon-based active material,
a first conductive material, a second conductive material and a copolymer of
polyvinyl alcohol and polyacrylic acid as a binder (containing a vinyl alcohol25
derived unit and an acrylic acid-derived unit at 66:34, weight-average
30
molecular weight: about 360,000 g/mol) were added to distilled water as a
solvent for forming a negative electrode slurry in a weight ratio of
85.00:9.78:0.22:5.00 to prepare a negative electrode slurry (solid content
concentration: 25 % by weight).
[120] The first conductive material was plate-like graphite 5 (specific surface area: 17
m2/g, average particle diameter (D50): 3.5 μm, aspect ratio: 1.95), and the
second conductive material was a single-walled carbon nanotube (specific
surface area: 520 m2/g, diameter: 0.0015 μm (1.5 nm), length: 15 μm and
aspect ratio; 10,000).
10 [121] On both sides of a copper current collector (thickness: 15 μm) as a negative
electrode current collector, the negative electrode slurry was applied at a
loading amount of 80.5 mg/25cm2, roll-pressed, and dried in a vacuum oven
at 130 °C for 10 hours to form a negative electrode active material layer
(thickness: 29 μm), which was used as a negative electrode (thickness of
15 negative electrode: 44 μm, porosity of negative electrode: 38.0 %).
[122] Example 2: Manufacture of Negative Electrode
[123] A negative electrode of Example 2 was produced in the same manner as in
Example 1 except that the negative electrode slurry was formed by mixing the
silicon-based active material, the first conductive material, the second
20 conductive material and the binder at a weight ratio of 85.0:9.8:0.2:5.0.
[124] Comparative Example 1: Manufacture of Negative Electrode
[125] A negative electrode of Comparative Example 1 was prepared in the same
manner as in Example 1 except that the negative electrode slurry was formed
by mixing the silicon-based active material, the first conductive material, the
31
second conductive material and the binder at a weight ratio of
85.00:9.96:0.04:5.00.
[126] Comparative Example 2: Manufacture of Negative Electrode
[127] A negative electrode of Comparative Example 2 was produced in the same
manner as in Example 1 except that the negative 5 electrode slurry was formed
by mixing the silicon-based active material, the first conductive material, the
second conductive material and the binder at a weight ratio of
85.00:9.92:0.08:5.00.
[128] Comparative Example 3: Manufacture of Negative Electrode
10 [129] A negative electrode of Comparative Example 3 was produced in the same
manner as in Example 1 except that the negative electrode slurry was formed
by mixing the silicon-based active material, the first conductive material, the
second conductive material and the binder at a weight ratio of
85.00:9.88:0.12:5.00.
15 [130] Comparative Example 4: Manufacture of Negative Electrode
[131] A negative electrode of Comparative Example 4 was produced in the same
manner as in Example 1 except that the negative electrode slurry was formed
by mixing the silicon-based active material, the first conductive material, the
second conductive material and the binder at a weight ratio of
20 85.00:9.86:0.14:5.00.
[132] Comparative Example 5: Manufacture of Negative Electrode
[133] A negative electrode of Comparative Example 5 was produced in the same
manner as in Example 1 except that the negative electrode slurry was formed
by mixing the silicon-based active material, the first conductive material, the
32
second conductive material and the binder at a weight ratio of
85.00:9.57:0.43:5.00.
[134] Comparative Example 6: Manufacture of Negative Electrode
[135] A negative electrode of Comparative Example 6 was produced in the same
manner as in Example 1 except that the negative 5 electrode slurry was formed
by mixing the silicon-based active material, the first conductive material and
the binder at a weight ratio of 85:10:5 without using the second conductive
material.
[136] Comparative Example 7: Manufacture of Negative Electrode
10 [137] A negative electrode of Comparative Example 7 was prepared in the same
manner as in Example 1 except that the negative electrode slurry was formed
by mixing the silicon-based active material, the second conductive material
and the binder at a weight ratio of 94:1:5 without using the first conductive
material.
15 [138] Table 1
First Conductive Material Second Conductive Material
Content (%
by weight,
based on
weight of
negative
electrode
active
material
layer)
Specific
Surface
Area
(m2/g)
Aspect
Ratio
Content (%
by weight,
based on
weight of
negative
electrode
active
material
layer)
Specific
Surface
Area
(m2/g)
Aspect
Ratio
Example 1 9.78 17 1.95 0.22 520 10,000
Example 2 9.80 17 1.95 0.20 520 10,000
Comparative
Example 1
9.96 17 1.95 0.04 520 10,000
Comparative
Example 2
9.92 17 1.95 0.08 520 10,000
Comparative
Example 3
9.88 17 1.95 0.12 520 10,000
Comparative
Example 4
9.86 17 1.95 0.14 520 10,000
33
Comparative
Example 5
9.57 17 1.95 0.43 520 10,000
Comparative
Example 6
10 17 1.95 0 - -
Comparative
Example 7
0 - - 1 520 10,000
[139]
[140] 1. Manufacture of Secondary Battery
[141] A positive electrode slurry was prepared by adding Li[Ni0.6Co0.2Mn0.2]O2
(average particle diameter (D50): 15 5 μm) as a positive electrode active
material, carbon black (product name: Super C65, manufactured by Timcal)
as an conductive material, and polyvinylidene fluoride (PVdF) as the binder
at a weight ratio of 97:1.5:1.5 to N-methyl-2-pyrrolidone (NMP), which is a
solvent for forming a positive electrode slurry (solid content concentration: 78
10 % by weight).
[142] On both sides of an aluminum current collector (thickness: 12 μm) as a
positive electrode current collector, the positive electrode slurry was applied
at a loading amount of 450 mg/25 cm2, roll-pressed, and dried in a vacuum
oven at 130 °C for 10 hours to form a positive electrode active material layer
15 (thickness: 54 μm), thereby producing a positive electrode (thickness of
positive electrode: 66 μm, porosity: 24 %).
[143] A polyethylene separator was interposed between the positive electrode and
the negative electrode of Example 1 and an electrolyte was injected to produce
a secondary battery of Example 1.
20 [144] The electrolyte was obtained by adding vinylene carbonate at 3 % by weight
based on the total weight of the electrolyte to an organic solvent in which
fluoroethylene carbonate (FEC) and diethyl carbonate (DMC) were mixed at
34
a volume ratio of 30:70, and adding LiPF6 as a lithium salt at a concentration
of 1 M.
[145] The secondary batteries of Example 2 and Comparative Examples 1 to 7 were
produced in the same manner as in Example 1 except that the negative
electrodes of the above-described Example 5 2 and Comparative Examples 1-7
were used.
[146] 2. N/P ratio measurement and calculation of secondary battery
[147] A coin-type half-cell containing a negative electrode of Example 1, a lithium
metal counter electrode opposite to the negative electrode, a polyethylene
10 separator interposed between the negative electrode and the lithium metal
counter electrode, and an electrolyte was produced and the discharge capacity
was determined (units: mAh/g). The discharge capacity was multiplied by
the loading amount to obtain the discharge capacity per unit area of the
negative electrode of Example 1 (units: mAh/cm2).
15 [148] In addition, a coin-type half-cell containing the positive electrode prepared
above, a lithium metal counter electrode opposite to the positive electrode, a
polyethylene separator interposed between the positive electrode and the
lithium metal counter electrode, and an electrolyte was produced and the
discharge capacity was determined (units: mAh/g). The discharge capacity
20 was multiplied by the loading amount to obtain the discharge capacity per unit
area of the positive electrode (units: mAh/cm2).
[149] The N/P ratio of the secondary battery of Example 1 was determined by the
following equation 1 (N/P ratio = 2.76).
[150] [Equation 1]
35
[151] N/P ratio = {(discharge capacity per unit area of the negative electrode) /
(discharge capacity per unit area of the positive electrode)}.
[152] The N/P ratio of the secondary batteries of Example 2 and Comparative
Examples 1 to 7 was determined in the same manner as in Example 1 except
that the negative electrodes of Example 5 2 and Comparative Examples 1-7
were used.
[153] The results are shown in Table 2.
[154] Table 2
N/P ratio
Example 1 2.76
Example 2 2.69
Comparative Example 1 2.67
Comparative Example 2 2.65
Comparative Example 3 2.68
Comparative Example 4 2.68
Comparative Example 5 2.63
Comparative Example 6 2.66
Comparative Example 7 2.67
10 [155] Experimental Examples
[156] Experimental Example 1: Measurement of Resting Viscosity of Negative
Electrode Slurry
[157] The resting viscosities of the negative electrode slurries prepared in Examples
1 and 2 and Comparative Examples 1 to 7 were measured. The resting
15 viscosity was measured using a viscometer (product name: HAAKE
viscometer, manufactured by ThermoFisher Scientific).
[158] Specifically, 5 mL of the negative electrode slurries prepared in Examples 1-
2 and Comparative Examples 1-7 were prepared, and the negative electrode
slurry was put in the viscometer, rotated at a 1,500 shear rate (1/s) at 25 °C for
36
300 seconds, then, the rotation was stopped and the viscosity after resting for
100 seconds was measured.
[159] Table 3
Resting Viscosity (cP @ 25 °C)
Example 1 6,420
Example 2 5,880
Comparative Example 1 2,550
Comparative Example 2 2,570
Comparative Example 3 3,110
Comparative Example 4 3,860
Comparative Example 5 16,800
Comparative Example 6 1,560
Comparative Example 7 11,830
[160] Referring to Table 3, it can 5 be confirmed that the negative electrode slurries
of Examples 1 and 2 exhibit a favorable level of resting viscosity as compared
with Comparative Examples, and that the active material, the first conductive
material, a second conductive material and a binder are smoothly dispersed.
However, it can be confirmed that the negative electrode slurries of
10 Comparative Examples 1 to 7 have an excessively low or high resting
viscosity. When the resting viscosity is too low, there is a risk of slurry
sedimentation, and when the resting viscosity is too high, there may be a risk
that coatability is lowered, and difficulty in transfer of the slurry makes it
difficult to produce a negative electrode, which may affect the lifetime
15 characteristics of the negative electrode as described later.
[161] Experimental Example 2: Evaluation of Cycle Capacity Retention Rate
[162] The capacity retention rate of the secondary batteries produced in Examples 1
and 2 and Comparative Examples 1 to 7 was evaluated using an
electrochemical charger/discharger.
37
[163] The secondary battery was charged and discharged to the 100th cycle under
charging (1.0 C CC/CV charging 4.2 V 0.05 C cut) and discharging (0.5 C CC
discharge 3.2 V cut) conditions.
[164] The capacity retention rate was evaluated by the following formula. The
5 results are shown in Table 4 below.
[165] Capacity retention rate (%) = {(discharge capacity at 100th cycle) / (discharge
capacity at first cycle)}×100
[166] Table 4
Cycle Capacity Retention Rate (%) @
100cycle
Example 1 93.9
Example 2 92.0
Comparative Example 1 74.4
Comparative Example 2 75.8
Comparative Example 3 81.3
Comparative Example 4 86.6
Comparative Example 5 87.4
Comparative Example 6 70.8
Comparative Example 7 69.1
10 [167] Referring to Table 4, it can be seen that the secondary batteries of Examples
1 and 2 in which the first conductive material and the second conductive
material were added in a preferable amount in the negative electrode exhibited
a superior level of cycle capacity retention rate as compared to the
Comparative Examples.
15 [168] Experiment Example 3: Evaluation of Fast Charging Lifespan
[169] With respect to the secondary batteries produced in Examples 1 and 2 and
Comparative Examples 1 to 7, the capacity retention rate during fast charging
was evaluated using an electrochemical charger/discharger. The secondary
battery was subjected to 1) charging (0.2C CC/CV charging 4.2V 0.05C cut)
38
and discharging (0.2C CC discharge 3.2V cut), which is the first cycle, and 2)
charging and discharging to the 100th cycle from the second cycle under
charging (2.0 C CC/CV charging 4.2 V 0.05C cut) and discharging (0.5C CC
discharge 3.2V cut) conditions.
[170] The capacity retention rate was evaluated 5 by the following formula. The
results are shown in Table 5 below.
[171] Capacity retention rate (%) = {(discharge capacity at 100th cycle)/(discharge
capacity at first cycle)}×100
[172] Table 5
Cycle Capacity Retention Rate (%) @
100thcycle
Example 1 74.2
Example 2 72.4
Comparative Example 1 57.3
Comparative Example 2 57.6
Comparative Example 3 63.4
Comparative Example 4 66.7
Comparative Example 5 67.3
Comparative Example 6 53.8
Comparative Example 7 51.8
10
[173] Referring to Table 5, it can be seen that the secondary batteries of Examples
1 and 2, in which the first conductive material and the second conductive
material were added in a preferable amount in the negative electrode,
exhibited excellent levels of fast charging characteristics as compared with the
15 comparative examples.
CLAIMS
1. A negative electrode, comprising:
a negative electrode current collector; and
a negative electrode active material layer formed on the negative electrode
5 current collector,
wherein the negative electrode active material layer comprises a silicon-based
active material, a binder, a first conductive material, and a second conductive material,
a specific surface area of the second conductive material is larger than a
specific surface area of the first conductive material,
10 the first conductive material is contained in the negative electrode active
material layer in an amount of 9.68 % by weight to 9.83 % by weight, and
the second conductive material is contained in the negative electrode active
material layer in an amount of 0.17 % by weight to 0.32 % by weight.
15 2. The negative electrode according to claim 1, wherein the specific surface area
of the first conductive material is 5 m2/g to 40 m2/g.
3. The negative electrode according to claim 1, wherein the first conductive
material comprises at least one selected from the group consisting of graphite and
20 carbon black.
4. The negative electrode according to claim 1, wherein an average particle
diameter (D50) of the first conductive material is 1 μm to 20 μm.
40
5. The negative electrode according to claim 1, wherein an aspect ratio of the
first conductive material is 1.1 to 30.0.
6. The negative electrode according to claim 1, wherein a specific surface area
of the 5 second conductive material is 400 m2/g to 1,000 m2/g.
7. The negative electrode according to claim 1, wherein the second conductive
material comprises at least one selected from single-walled carbon nanotubes and
multi-walled carbon nanotubes.
10
8. The negative electrode according to claim 1, wherein an aspect ratio of the
second conductive material is 5,000 to 15,000.
9. The negative electrode according to claim 1, wherein the silicon-based active
15 material is contained in an amount of 75 % by weight to 89 % by weight.
10. The negative electrode according to claim 1, wherein an average particle
diameter (D50) of the silicon-based active material is 1 μm to 10 μm.
20 11. The negative electrode according to claim 1, wherein a ratio of an average
particle diameter (D50) of the silicon-based active material to an average particle
diameter (D50) of the first conductive material is 1:1 to 1:5.
12. The negative electrode according to claim 1, wherein the binder comprises at
25 least one selected from the group consisting of styrene-butadiene rubber, acrylonitrile41
butadiene rubber, acrylic rubber, butyl rubber, fluoro rubber, carboxymethyl cellulose,
starch, hydroxypropyl cellulose, polyvinyl alcohol, polyacrylic acid, polyethylene
glycol, polyacrylonitrile, and polyacryl amide.
13. The negative electrode according 5 to claim 1, wherein the binder is contained
in the negative electrode active material layer in an amount of 1 % by weight to 15 %
by weight.
14. A secondary battery, comprising:
10 the negative electrode according to claim 1;
a positive electrode opposite to the negative electrode;
a separator interposed between the negative electrode and the positive
electrode; and
an electrolyte.