JPH1197020A - Manufacture of negative electrode, and lithium secondary cell employing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the manufacture of a negative electrode and a lithium secondary cell which is high in energy density, high in charging/discharging capacity, and is provided with cell characteristics giving a long cyclic life to the cell. SOLUTION: In this manufacture, negative electrode mix composed of negative electrode active material, conductive material, and of binding material, is distributed into organic solvent so as to be coated over a negative electrode current collector, so that a negative electrode is thereby manufactured. In this case, the negative electrode which is primarily lithium contained transition metallic nitride, and is manufactured by means of a manufacturing process where the aforesaid organic solvent is at least to be one kind out of an alphatic hydrogen carbide group and an aromatic hydrogen carbide group, is used for a lithium secondary cell. By this constitution, there occurs no reaction among the negative electrode active material, the organic solvent and the binding material, and since they are sufficiently combined with one another, deterioration in the quality of material such as the formation of irreverseible material and the like will hardly be seen, and since the negative electrode will never be peeled off and so on, a very long cyclic life can thereby be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a negative electrode and a lithium secondary battery using the negative electrode, and more particularly to a battery having a high energy density, a large charge / discharge capacity and a long cycle life. The present invention relates to a method for producing a negative electrode having characteristics and a lithium secondary battery using the same.

[0002]

2. Description of the Related Art In recent years, electronic devices have become smaller, lighter and more portable, and there has been a demand for the development of batteries having a high energy density as power sources. As a battery that meets such demands, a lithium secondary battery is expected.

[0003] Lithium secondary batteries are basically various types of commercially available secondary batteries, for example, nickel cadmium batteries,
It has higher voltage and higher energy density than lead storage batteries and the like. However, in general, a lithium secondary battery using lithium metal as a negative electrode active material generates needle-like lithium at the time of charging, and this needle-like lithium is cut off at the time of discharging and falls off from the electrode base, so that it does not contribute to charging and discharging, and is dead. Lithium is produced. For this reason, a battery using lithium metal as the negative electrode active material has a problem that the cycle life is short.

[0004] As a new negative electrode active material replacing lithium metal, carbonaceous materials such as natural graphite, artificial graphite and amorphous carbon have been studied. These materials utilize the intercalation reaction of lithium ions, and hold lithium in an ionized state in the skeletal structure, eliminating the formation of dendrites (needle-like lithium) found in lithium metal. Cycle life is improved. These carbonaceous materials can stably insert and desorb lithium ions in a range of a base electrode potential of 0 to 1 V with respect to a lithium metal reference electrode, and have a charge and discharge capacity of 200 to 370 mAh / g. In fact, lithium ion secondary batteries using a carbonaceous material as the negative electrode active material have been put to practical use. However, the carbonaceous material has a problem in that the capacity is smaller than that of lithium metal, and the energy density of a battery using the carbonaceous material for the negative electrode is considerably smaller than that of a battery using lithium metal for the negative electrode. .

[0005]

Recently, as a new negative electrode active material replacing these carbonaceous materials, Li ₃ FeN ₂ , L
Attention has been paid to lithium-containing transition metal nitrides such as i ₇ MnN ₄ and Li _2.5 Co _0.5 N. These lithium-containing transition metal nitrides have a voltage of 0 to 2.0 V with respect to the lithium metal reference electrode.
Lithium ion can be stably inserted and desorbed in the range of the lower electrode potential of 200 to 1000 mAh /
g of very large charge / discharge capacity. However,
Since these lithium-containing transition metal nitrides have a very strong reducing power like lithium metal, they tend to react with binders, conductive materials and organic solvents. It has been difficult to produce a negative electrode by applying it to the body.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a method for producing a negative electrode having a battery characteristic having a high energy density, a large charge / discharge capacity, and a long cycle life. An object of the present invention is to provide a lithium secondary battery.

[0007]

In order to achieve the above object, a method of manufacturing a negative electrode according to the present invention comprises dispersing a negative electrode mixture composed of a negative electrode active material, a conductive material and a binder in an organic solvent to form a negative electrode current collector. a negative electrode manufacturing method to be applied to, the anode active material, the composition formula Li _{1 +} x M _y N (where, M represents an element belonging to the transition metal, x is -0.2～2.0 Wherein y is in the range of 0.1 to 0.5), and the organic solvent is selected from aliphatic hydrocarbons and aromatic hydrocarbons. It is characterized by at least one kind.

Further, a lithium secondary battery according to the present invention comprises a negative electrode manufactured by dispersing a negative electrode mixture comprising a negative electrode active material, a conductive material and a binder in an organic solvent and coating the mixture on a negative electrode current collector; a positive electrode comprising a positive active material that reversibly deintercalation of a lithium secondary battery comprising a lithium ion conductive electrolyte, the negative electrode active material, the composition formula Li 1 _{+ x} M _y N (where, M is , Represents an element belonging to a transition metal, x is in the range of -0.2 to 2.0, and y is 0.
(In the range of 1 to 0.5), wherein the organic solvent is at least one of aliphatic hydrocarbons and aromatic hydrocarbons. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

As described above, since the negative electrode active material in the present invention has a very strong reducing power like lithium metal, it easily reacts with a binder, a conductive material or an organic solvent, and thus has been applied to a current collector. Although it was not possible to produce a negative electrode in the form, as the organic solvent for dispersing the negative electrode mixture, when using at least one of the above-described aliphatic hydrocarbons and aromatic hydrocarbons, the negative electrode active material No reaction of the organic solvent was observed, and the negative electrode could be produced in a form applied to the negative electrode current collector. Furthermore, when at least one of the above-mentioned styrene-butadiene rubber, butadiene rubber, acrylic rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber or a modified product thereof is used as the binder, the negative electrode active material and the binder are used. Was not observed, and a homogeneous and smooth coated negative electrode having excellent adhesion between the negative electrode and the negative electrode current collector could be produced. In addition, it has been found through experiments that this negative electrode has a high-capacity charge / discharge region and a long cycle life at an electrode potential of 2.0 V or less with respect to the lithium reference electrode.

This phenomenon occurs because these organic solvents have excellent reduction resistance and do not react with the negative electrode active material.
Furthermore, since these binders also have excellent reduction resistance, it is thought that the anode performance could be brought out without reacting with the anode active material. In addition, since these binders have high adhesiveness, it is considered that the adhesive force between the negative electrode active materials and the adhesive force between the negative electrode current collector and the negative electrode were sufficiently obtained, and exhibited good cycle characteristics. ing.

[0012] Negative electrode active material used in the present invention, the composition formula Li _{1 +} x M _y N (where, M represents an element belonging to the transition metal, x is in the range of -0.2～2.0 Yes, y is 0.1 ~
0.5 (in the range of 0.5).

The transition metal referred to in the present invention has an element number of 2
1 from Sc of element number 30, Zn of element number 30, Y of element number 39, Cd of element number 48, La of element number 57, and Hg of element number 80.

In the above-mentioned composition formula, if x is less than -0.2, the negative electrode active material may be decomposed. If x exceeds 2, Li metal or Li ₃ N 2 may be formed on the grain boundaries or on the surface of the negative electrode active material. Precipitates and the characteristics deteriorate. Further, when y is less than 0.1, the insulating property is increased, the battery characteristics are deteriorated, and the negative electrode active material may be decomposed. When y exceeds 0.5, solid solution of the transition metal becomes difficult. Battery characteristics are degraded.

As the organic solvent used in the present invention, at least one of aliphatic hydrocarbons and aromatic hydrocarbons, which are commercially available products, can be used, but those which are sufficiently dehydrated are preferable. Examples of the aliphatic hydrocarbon used in the present invention include pentane, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, heptane, octane, nonane, decane, Alternatively, it can be at least one selected from dodecane.

Examples of the aromatic hydrocarbon include, for example, at least one selected from benzene, toluene, xylene, ethylbenzene, butylbenzene, styrene, cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane.

The binder used in the present invention may be a commercially available styrene-butadiene rubber, butadiene rubber, acrylic rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber or a modified product thereof as described above. At least one of them can be used.

The content of the binder in the negative electrode is 0.1 to
When the content of the binder is less than 0.1% by weight, the binding property between the negative electrode and the current collector deteriorates, the resistance of the negative electrode increases, or the negative electrode is removed from the substrate. Peeled off, failing to provide good battery life. On the other hand, when the content exceeds 15% by weight, the resistance of the negative electrode is increased because the binder is an insulator, and good battery characteristics cannot be obtained.

The conductive material used in the present invention is not fundamentally limited, and those conventionally used in lithium batteries can be effectively used. Further, the negative electrode current collector is not basically limited either, and a conventionally used negative electrode current collector can be effectively used.

The composition formula Li _{1 + x} which is the negative electrode active material of the present invention
_MyN (where M represents an element belonging to a transition metal, x
Is in the range of -0.2 to 2.0, and y is 0.1 to 0.5
The lithium-containing transition metal nitride represented by the formula (1) can be synthesized as follows. Starting materials include lithium (Li) or lithium nitride (Li ₃
N) and can be used a transition metal or a transition metal nitride, the composition of these starting materials formula Li 1 _{+ x} M _y N (where,
M represents an element belonging to a transition metal, and x is -0.2 to
2.0, and y is in the range of 0.1 to 0.5). After weighing and mixing, the mixture can be synthesized by firing in a nitrogen atmosphere using a normal firing method.

The electrolyte used in the present invention includes a non-aqueous electrolyte,
A polymer electrolyte, an inorganic solid electrolyte, or a molten salt electrolyte is suitable. The non-aqueous electrolyte generally includes a solvent and a lithium salt dissolved in the solvent. Examples of the solvent for the non-aqueous electrolyte include ethylene carbonate (EC),
Chain esters such as propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (MEC);
γ-lactones such as γ-butyrolactone, chain ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE) and ethoxymethoxyethane (EME), and cyclic ethers such as tetrahydrofuran And at least one solvent selected from nitriles such as acetonitrile and the like. Also,
As a solute of the non-aqueous electrolyte, LiAsF ₆ , LiBF ₄ ,
LiPF ₆ , LiAlCl ₄ , LiClO ₄ , LiCF ₃ S
O ₃ , LiSbF ₆ , LiSCN, LiCl, LiC ₆ H ₅
SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ )
₃ , lithium salts such as C ₄ F ₉ SO ₃ Li and mixtures thereof can be used.

As the polymer electrolyte, for example, a polyether compound such as polyethylene oxide is used, and LiCF is used.
A system in which a lithium salt such as ₃ SO ₃ is dissolved, or a system in which the above-mentioned non-aqueous electrolyte is impregnated with a polymer latex can be used,
As the inorganic solid electrolyte, Li ₂ S—SiS ₂ —Li ₃ PO ₄ or Li ₄ SiO ₄ —Li ₃ VO ₄ can be used. Further, as the molten salt electrolyte, for example, AlCl ₃
-1-butylpyridinium chloride-LiCl or Al
Cl _{3-1-ethyl-3-methylimidazolium} chloride -LiCl system can be used.

Further, when the negative electrode active material of the present invention is used in a lithium secondary battery, the positive electrode active material includes titanium, molybdenum, tungsten, niobium, vanadium, manganese,
Oxides, sulfides, sulfates, and the like of transition metals such as iron, chromium, nickel, and cobalt can be used. Also,
A transition metal complex acid such as titanium, molybdenum, tungsten, niobium, vanadium, manganese, iron, chromium, nickel, or cobalt containing lithium, a complex sulfide, a complex sulfide, or the like can be used. In particular, LiMn ₂ O ₄ , L has an electrode potential of 3 V or more with respect to a lithium metal electrode, and can be expected to have high voltage and high energy density.
iCoO ₂ and LiNiO ₂ are suitable as the positive electrode active material.

As described above, by using the negative electrode of the present invention, a high-capacity charge / discharge region can be obtained at an electrode potential of 2.0 V or less with respect to the lithium reference electrode. Furthermore, there is almost no deterioration such as generation of an irreversible substance due to the reaction between the negative electrode active material and the binder, and there is no peeling of the negative electrode and the current collector, so that extremely stable and long-life battery characteristics can be obtained. Therefore, the negative electrode active material, the composition formula Li _{1 +} x M _y N (where, M is
Represents an element belonging to a transition metal, x is in the range of -0.2 to 2.0, and y is in the range of 0.1 to 0.5). In addition, at least one of aliphatic hydrocarbons and aromatic hydrocarbons is used as an organic solvent, and styrene-butadiene rubber, butadiene rubber, acrylic rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber or a styrene-butadiene rubber is used as a binder. By using at least one of the modified products, a lithium secondary battery having a high energy density, a large charge / discharge capacity, and a long cycle life can be provided.

[0025]

The present invention will be described in more detail with reference to the following examples.

[0026]

Embodiment 1 FIG. 1 is a sectional view of a test cell used for evaluating the performance of a negative electrode of a lithium secondary battery according to the present invention. FIG.
In the figure, reference numeral 1 denotes a counter electrode case which is formed by drawing a stainless steel plate. Reference numeral 2 denotes a counter electrode, which is obtained by punching a lithium metal foil having a predetermined thickness into a diameter of 16 mm and pressing it. 3 is a non-aqueous electrolyte, EC and D
LiClO ₄ is dissolved at 1 mol / L in a mixed solvent of EE having a volume ratio of 1: 1. Reference numeral 4 denotes a separator made of a porous film of polypropylene or polyethylene. Reference numeral 5 denotes a working electrode case formed by drawing a stainless steel plate. Reference numeral 6 denotes a working electrode using the negative electrode of the present invention. Numeral 7 denotes a gasket which keeps electrical insulation between the counter electrode case 1 and the working electrode case 5, and which has an opening edge of the working electrode case bent inward and caulked.
The battery contents are hermetically sealed.

The working electrode 6 was manufactured as follows. Li ₂ of the negative electrode active material synthesized in the above-described _{method. 6} Co _0.4 and N, graphite conductive material, the acrylic rubber binder, the weight mixing ratio of 8
The mixture was mixed at 2: 14: 4 and dispersed in dehydrated toluene of an organic solvent to obtain an appropriate viscosity to prepare a slurry. The slurry was applied to a copper foil substrate (thickness: 18 μm) of a negative electrode current collector by a doctor blade method to form a negative electrode sheet. Produced. Thereafter, a negative electrode having a diameter of 18 mm was punched from the negative electrode sheet, and the periphery was shaved off by 1 mm in width to secure a welded portion, thereby forming a working electrode. This working electrode is spot-welded to the working electrode case 5.

This test cell was subjected to a charge / discharge test in a voltage range of 0.0-1.4 V and a current of hlA. FIG. 2 shows a charge / discharge curve of the fifth cycle at this time. As is clear from the figure, this negative electrode can reversibly occlude and release lithium ions in a voltage range of 0.0 to 1.4 V, and has a capacity of 10 mA.
h were obtained. FIG. 3 shows the cycle characteristics of the test cell. As is apparent from the figure, no rapid decrease in capacity due to charge / discharge was observed, and charge / discharge was repeated stably for 500 cycles or more. After the charge / discharge test,
The test cell was disassembled and the working electrode surface was observed, but no peeling of the negative electrode was observed. The working electrode was analyzed with an X-ray diffractometer, but no deposition of lithium metal was observed.

[0029]

Example 2 The mixing ratio by weight of Example 1 was 86: 13: 1.
A working electrode 6 (negative electrode) was prepared in place of the above, and the characteristics of the negative electrode were evaluated using a test cell. Example 1 except for the weight mixing ratio
The same one was used.

This test cell was also subjected to a charge / discharge test in a voltage range of 0.0 to 1.4 V and a current of 1 mA. This negative electrode has a
In a voltage range of 0 to 1.4 V, lithium ions could be reversibly inserted and released, and a capacity of 11 mAh was obtained.
In addition, no rapid decrease in capacity due to charging / discharging was observed.
Charge and discharge were repeated stably for at least 00 cycles. further,
After completion of the charge / discharge test, the test cell was disassembled and the surface of the working electrode was observed, but no peeling of the negative electrode was observed. The working electrode was analyzed with an X-ray diffractometer, but no deposition of lithium metal was observed.

[0031]

Example 3 A working electrode 6 (negative electrode) was prepared by replacing the organic solvent of Example 1 with dehydrated cyclohexane, and the characteristics of the negative electrode were evaluated using a test cell. Except for the organic solvent, the same one as in Example 1 was used.

This test cell was also subjected to a charge / discharge test in a voltage range of 0.0 to 1.4 V and a current of 1 mA. This negative electrode has a
In a voltage range of 0 to 1.4 V, lithium ions could be reversibly inserted and released, and a capacity of 11 mAh was obtained.
In addition, no rapid decrease in capacity due to charging / discharging was observed.
Charge and discharge were repeated stably for at least 00 cycles. further,
After completion of the charge / discharge test, the test cell was disassembled and the surface of the working electrode was observed, but no peeling of the negative electrode was observed. The working electrode was analyzed with an X-ray diffractometer, but no deposition of lithium metal was observed.

[0033]

Example 4 A working electrode 6 (negative electrode) was prepared by replacing the binder of Example 1 with styrene-butadiene rubber, and the characteristics of the negative electrode were evaluated using a test cell. Except for the binder, the same material as in Example 1 was used.

This test cell was also subjected to a charge / discharge test in a voltage range of 0.0 to 1.4 V and a current of 1 mA. This negative electrode has a
In a voltage range of 0 to 1.4 V, lithium ions could be reversibly inserted and released, and a capacity of 10 mAh was obtained.
In addition, no rapid decrease in capacity due to charging / discharging was observed.
Charge and discharge were repeated stably for at least 00 cycles. further,
After completion of the charge / discharge test, the test cell was disassembled and the surface of the working electrode was observed, but no peeling of the negative electrode was observed. The working electrode was analyzed with an X-ray diffractometer, but no deposition of lithium metal was observed.

[0035]

Example 5 A working electrode 6 (negative electrode) was prepared by changing the organic solvent of Example 1 to hexane and the binder to ethylene-propylene rubber, and the characteristics of the negative electrode were evaluated using a test cell. Except for the organic solvent and the binder, the same materials as in Example 1 were used.

This test cell was also subjected to a charge / discharge test in a voltage range of 0.0 to 1.4 V and a current of 1 mA. This negative electrode has a
In a voltage range of 0 to 1.4 V, lithium ions could be reversibly inserted and released, and a capacity of 9 mAh was obtained. Also, no rapid decrease in capacity due to charge / discharge was observed,
Charge / discharge was repeated stably for 0 cycles or more. After the completion of the charge / discharge test, the test cell was disassembled and the surface of the working electrode was observed, but no peeling of the negative electrode was observed. The working electrode was analyzed with an X-ray diffractometer, but no deposition of lithium metal was observed.

[0037]

Example 6 A working electrode 6 (negative electrode) was prepared by replacing the binder of Example 1 with ethylene-propylene-diene rubber, and the characteristics of the negative electrode were evaluated using a test cell. Except for the binder, the same material as in Example 1 was used.

This test cell was also subjected to a charge / discharge test with a voltage range of 0.0 to 1.4 V and a current of 1 mA. This negative electrode has a
In a voltage range of 0 to 1.4 V, lithium ions could be reversibly inserted and extracted, and a capacity of 9.5 mAh was obtained. In addition, no rapid decrease in capacity due to charge / discharge was observed, and charge / discharge was repeated stably for 500 cycles or more. After the completion of the charge / discharge test, the test cell was disassembled and the surface of the working electrode was observed, but no peeling of the negative electrode was observed. The working electrode was analyzed with an X-ray diffractometer, but no deposition of lithium metal was observed.

[0039]

Comparative Example 1 A working electrode 6 (negative electrode) was prepared by replacing the organic solvent of Example 1 with dehydrated acetone, but reacted vigorously with Li _2.6 Co _0.4 N as a negative electrode active material to form a negative electrode. I couldn't do that.

[0040]

Comparative Example 2 An attempt was made to produce a working electrode 6 (negative electrode) by replacing the organic solvent of Example 1 with dehydrated ethanol, but reacted violently with the negative electrode active material Li _2.6 Co _0.4 N to prepare a negative electrode. I couldn't do that.

[0041]

Comparative Example 3 A slurry was prepared using polyvinylidene fluoride as a binder and N-methyl-2-pyrrolidone as a solvent. The slurry was applied to a current collector copper foil substrate (thickness 18 μm) by a doctor blade method, and the working electrode 6 was formed. (Negative electrode) was produced. Except for the working electrode 6, the same electrode as in Example 1 was used, and the characteristics of the negative electrode were evaluated using a test cell.

This test cell was subjected to a charge / discharge test in a voltage range of 0.0 to 1.4 V and a current of 1 mA. This negative electrode
In a voltage range of 0.0 to 1.4 V, lithium ions can be reversibly inserted and released, and a capacity of 10 mAh was obtained. However, as shown in FIG. 3, the capacity gradually decreased with the cycle, and the cycle life was as short as 250 cycles.

[0043]

As described above, when the negative electrode according to the present invention is used, since there is no reaction between the negative electrode active material and the organic solvent or the binder, deterioration such as impurity generation and decomposition of the negative electrode active material is almost observed. In addition, a large charge / discharge capacity and a stable and long cycle life can be obtained in the range of a low electrode potential of 2.0 V or less with respect to the lithium metal reference electrode. Therefore, a high voltage and a high energy density can be achieved without significantly lowering the operating voltage of the battery. In addition, when the negative electrode according to the present invention is used, there is no reaction between the negative electrode active material and the organic solvent or the binder, and there is sufficient adhesive force. Since there is no peeling or the like, a very long cycle life can be obtained.

Accordingly, the present invention provides a high energy density
In addition, there is an excellent effect that a lithium secondary battery having a large charge / discharge capacity and a long cycle life can be obtained.

[Brief description of the drawings]

FIG. 1 is a sectional view of a test cell used in the present invention.

FIG. 2 is a diagram showing a charge / discharge curve at the fifth cycle of a test cell in Example 1 of the present invention.

FIG. 3 is a diagram showing cycle characteristics of test cells in Example 1 and Comparative Example 3 of the present invention.

[Explanation of symbols]

 1 Counter electrode case 2 Counter electrode 3 Non-aqueous electrolyte 4 Separator 5 Working electrode case 6 Working electrode 7 Gasket

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoji Sakurai 3-19-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Japan Telegraph and Telephone Corporation (72) Inventor Junichi Yamaki 3--19, Nishishinjuku, Shinjuku-ku, Tokyo 2 Nippon Telegraph and Telephone Corporation (72) Junichi Yamaura, Inventor 1-1, Matsushita-cho, Moriguchi-shi, Osaka Prefecture Matsushita Battery Industry Co., Ltd. (72) Shigeo Kondo 1-1-1, Matsushita-cho, Moriguchi-shi, Osaka Matsushita Inside Battery Industry Co., Ltd. (72) Shuji Tsutsumi 1-1, Matsushita-cho, Moriguchi City, Osaka Prefecture Inside Matsushita Battery Industry Co., Ltd. (72) Masaki Hasegawa 1-1-1, Matsushita-cho, Moriguchi City, Osaka Matsushita Battery Company Industry Co., Ltd.

Claims (12)

[Claims] 1. A method for producing a negative electrode, comprising dispersing a negative electrode mixture comprising a negative electrode active material, a conductive material and a binder in an organic solvent and applying the mixture to a negative electrode current collector, wherein the negative electrode active material has a composition formula Li _{1 + x
MyN} (where M represents an element belonging to a transition metal, x
Is in the range of -0.2 to 2.0, and y is 0.1 to 0.5
), And the organic solvent is at least one of aliphatic hydrocarbons and aromatic hydrocarbons. 2. The method according to claim 1, wherein the binder is styrene-butadiene rubber,
The method for producing a negative electrode according to claim 1, wherein the method is at least one of butadiene rubber, acrylic rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, and a modified product thereof. Wherein M in the above composition formula Li _{1 +} x M _y N is C
3. The method for manufacturing a negative electrode according to claim 1, wherein the negative electrode is at least one of o, Ni, and Cu. 4. The method according to claim 1, wherein the aliphatic hydrocarbon is pentane, hexane, 2-methylpentane, 2,2-dimethylbutane,
2. The method according to claim 1, wherein the compound is at least one selected from 2,3-dimethylbutane, 3-methylpentane, heptane, octane, nonane, decane, and dodecane.
4. The method for producing a negative electrode according to any one of the above items. 5. The method according to claim 1, wherein the aromatic hydrocarbon is at least one selected from benzene, toluene, xylene, ethylbenzene, butylbenzene, styrene, cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane. Claims 1 to 3
A method for producing the negative electrode according to any one of the above. 6. The negative electrode has a binder content of 0.1%.
The method for producing a negative electrode according to any one of claims 1 to 5, wherein the content is from 15 to 15% by weight. 7. A negative electrode produced by dispersing a negative electrode mixture composed of a negative electrode active material, a conductive material and a binder in an organic solvent and applying it to a negative electrode current collector, reversibly inserts and removes lithium ions. a positive electrode comprising a positive active material, a lithium secondary battery comprising a lithium ion conductive electrolyte, the negative electrode active material, the composition formula Li 1 _{+ x} M _y N (where, M is an element belonging to the transition metal Wherein x is in the range of -0.2 to 2.0 and y is in the range of 0.1 to 0.5), and the organic solvent is a fatty acid. A lithium secondary battery, which is at least one of aromatic hydrocarbons and aromatic hydrocarbons. 8. The method according to claim 1, wherein the binder is styrene-butadiene rubber,
The lithium secondary battery according to claim 7, which is at least one of butadiene rubber, acrylic rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, and a modified product thereof. 9. M in the composition formula Li _{1 +} x M _y N is C
9. The lithium secondary battery according to claim 7, wherein the lithium secondary battery is at least one of o, Ni, and Cu. 10. The method according to claim 1, wherein the aliphatic hydrocarbon is pentane, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, heptane, octane, nonane, decane, or The lithium secondary battery according to any one of claims 7 to 9, wherein the lithium secondary battery is at least one selected from dodecane. 11. The method according to claim 11, wherein the aromatic hydrocarbon is benzene, toluene, xylene, ethylbenzene, butylbenzene,
The secondary battery according to any one of claims 7 to 9, wherein the secondary battery is at least one selected from styrene, cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane. 12. The method according to claim 1, wherein the content of the binder in the negative electrode is 0.1%.
The amount is 1 to 15% by weight.
2. The lithium secondary battery according to any one of the above items 1.