JPH07307152A - Negative electrode for lithium secondary battery and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a negative electrode for a lithium secondary battery with excellent cycle life, high electromotive force, high capacity, and high energy density and provide its manufacturing method. CONSTITUTION:A negative electrode for a lithium secondary battery contains Li, X, (X shows at least one element selected from the group comprising Zn, Ag, Mg, Cd, In, Pb, Pt, Pd, Ge, Te, Sn, Al, Bi, Sb, Ga, and Ca.) and C. The negative electrode is manufactured in such a way that each raw material gas of Li, X, and C is vapor-deposited on a substrate, a Li-X-C synthetic film is formed on a Li-X matrix by reacting C atoms, an X-C compound layer is formed on a Li matrix, or X-C compound particles are dispersed in a Li matrix.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode for a lithium secondary battery and a method for producing the same, and more specifically, it suppresses dendrite generation and has excellent cycle life, and high electromotive force.
The present invention relates to a negative electrode for a lithium secondary battery having high charge / discharge capacity and high energy density, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Generally, secondary batteries are required to have high energy density and high output density.
Examples include low self-discharge rate, low cost, high energy efficiency, and long cycle life. As a secondary battery having such performance, a non-aqueous electrolyte battery using electric energy due to the movement of lithium ions,
So-called lithium secondary batteries are known to have a high energy density.

[0003]

In this lithium secondary battery, metallic lithium (pure lithium), carbon, lithium alloy or the like is used as a negative electrode material. When the negative electrode is composed of the above pure lithium, the negative electrode can have the highest capacity, but when charging and discharging are repeated, an energy-active point is formed on the surface of the negative electrode during charging, from which Li is generated. There is a problem that deposition occurs, so-called dendrite occurs, short-circuits with the positive electrode, and ignition occurs. On the other hand, when carbon or a lithium alloy is used, dendrite is generated less than in the case of pure lithium, but since it contains a large amount of components other than lithium, it has the drawback of lowering the capacity and lowering the battery voltage. It was Therefore, in a lithium secondary battery, a negative electrode having a composition as close as possible to pure lithium and in which dendrite is less likely to occur is required.

An object of the present invention is to provide a negative electrode for a lithium secondary battery which satisfies the above-mentioned problems, has excellent cycle life by suppressing generation of dendrites, and has high electromotive force, high capacity and high energy density. To do. Another object of the present invention is to provide a method for producing the above negative electrode for a lithium secondary battery.

[0005]

The present inventors have found that the above objects can be achieved by the present invention described below. That is, the present invention has the following gist. (1) Li, X (where X is Zn, Ag, Mg, Cd,
In, Pb, Pt, Pd, Ge, Te, Sn, Al, B
A negative electrode for a lithium secondary battery containing C and one or more elements selected from i, Sb, Ga and Ca) and C. (2) Li-X-C based compound (where X is Zn, A
g, Mg, Cd, In, Pb, Pt, Pd, Ge, T
e, Sn, Al, Bi, Sb, Ga, Ca, one or more elements selected from the following). (3) Li-X-C-based compound is prepared by depositing Li raw material gas, X raw material gas and C raw material gas on a substrate, for use in a lithium secondary battery according to (2) above. Negative electrode. (4) The negative electrode for a lithium secondary battery according to (2), wherein the Li-X-C-based compound is a Li-X matrix reacted with C atoms. (5) Li and an X-C compound (where X is Zn, Ag,
Mg, Cd, In, Pb, Pt, Pd, Ge, Te, S
A negative electrode for a lithium secondary battery having a composite with one or more elements selected from n, Al, Bi, Sb, Ga and Ca. (6) A composite of Li and an X-C compound is formed by forming an X-C compound layer on a Li matrix, or L
The negative electrode for a lithium secondary battery according to (5) above, wherein the X-C compound particles are dispersed in an i matrix. (7) Lithium secondary according to any one of the above (1) to (6), wherein the composition of Li is 70 to 99.9 mol% and the total composition of X and C is 0.1 to 30 mol%. Negative electrode for batteries.

(8) The Li-X-C based compound film is formed by depositing a Li source gas, an X source gas and a C source gas on a substrate to form a Li-X-C based compound film. ) The method for producing the negative electrode for a lithium secondary battery described in (9) Li source gas, X source gas and C in the reaction vessel
A negative electrode for a lithium secondary battery according to (1) or (2) above, wherein a raw material gas is introduced and a Li-X-C-based compound film is formed on the substrate in the container by plasma reaction. Production method. (10) Li-X matrix reacted with C atom to form Li
A method for producing a negative electrode for a lithium secondary battery according to the above (1) or (2), characterized in that a composite film of X and C is formed. (11) For a lithium secondary battery according to (1) or (5) above, wherein an X-C compound layer is formed on a Li matrix or X-C compound particles are dispersed in a Li matrix. Method for manufacturing negative electrode.

[0007]

The negative electrode for a lithium secondary battery of the present invention comprises lithium containing a metal such as Zn and Ag and carbon. These metals and carbon, as these compounds, have an action of diffusing Li, so that Li deposited during charging diffuses inside the negative electrode, and as a result, generation of dendrites is suppressed.

The metals such as Zn and Ag and carbon are
Even when it is contained in a lithium negative electrode, the capacity and electromotive force are not significantly reduced. Therefore, the negative electrode of the present invention has high capacity and high electromotive force close to those of a negative electrode made of pure lithium.

The method for producing a negative electrode for a lithium secondary battery of the present invention is, for example, produced by depositing a Li-X-C-based compound on a substrate by chemical vapor deposition or physical vapor deposition of a raw material gas. This makes the composite a homogeneous mixture of Li, X and C at the atomic level. In addition, a Li-X-C-based compound is produced by reacting C atoms with a Li-X matrix, and thereby the compound becomes a homogeneous compound in which C atoms are uniformly dispersed. In addition, for example, a composite of Li and an X-C compound is prepared by forming an X-C compound layer on a Li matrix or by dispersing X-C compound particles in a Li matrix. Therefore, the composite becomes a homogeneous one in which X-C compound particles are uniformly dispersed.

As the material for the negative electrode of the present invention, for example, A) Li-X-C based compound (where X is Zn, Ag,
Mg, Cd, In, Pb, Pt, Pd, Ge, Te, S
n, Al, Bi, Sb, Ga, Ca, or one or more elements selected from Ca), B) Li and an X-C compound (where X is Zn, Ag, M).
g, Cd, In, Pb, Pt, Pd, Ge, Te, S
and one or more elements selected from n, Al, Bi, Sb, Ga, and Ca).

The above-mentioned A) Li-X-C-based compound includes A1) Li, X, and C source gases deposited on a substrate, and A2) Li-X matrix with C atoms. And the like.

According to the aspect of A1), L
Plasma CVD, MOCV for three components i, X and C
D, chemical vapor deposition such as low pressure CVD, sputtering, RF
Mixing at the atomic level by dry processes such as magnetron sputtering, three-way cluster ion beam deposition, three-way ion plating, reactive ion plating, reactive electron beam deposition, pulse plasma deposition, and physical vapor deposition such as plasma flash deposition. And the like.

According to the embodiment of A2), Li-X obtained by chemical vapor deposition or physical vapor deposition similar to the above
Compound obtained by implanting carbon ions into an alloy film, L
After forming a carbon thin film on the i-X alloy film, a compound obtained by ion beam mixing, a compound obtained by dynamic ion beam mixing in which the above two methods are used in combination, and the vapor deposition and the ion implantation are alternately performed. The compound etc. which are obtained are mentioned.

The Li-X-C-based compound, when formed into a film, is usually 1 to 100 μm, preferably 3 to.
The film is formed to a thickness of 50 μm, particularly preferably 5 to 20 μm. When the thickness of the Li-X-C-based compound is less than 1 μm, dendrite tends to occur,
On the other hand, when the thickness exceeds 100 μm, a portion unrelated to the battery reaction tends to increase, which is not preferable.

Further, as B) a composite of an X-C type compound with Li, B1) a Li matrix in which X-C type compound particles are dispersed, or B2) an X-C type compound on a Li matrix. The thing formed by forming a system compound layer is illustrated.

According to the embodiment of B1) above, B11) a matrix of X-C compound particles dispersed on the surface of a Li matrix, and B12) a matrix of X-C compound particles dispersed in a Li matrix. B13) X-C compound particles are dispersed in the surface of the Li matrix and in the Li matrix.

Examples of the above B11) include those in which X-C compound particles are sprinkled on a Li matrix, and those in which X-C compound particles are electrodeposited on a Li matrix. It Examples of the above B12) include, for example, a Li matrix in which X-C compound particles are injected by a spray gun, Li
Examples include those obtained by repeatedly sprinkling, rolling, and folding X-C-based compound particles on a matrix, and those obtained by continuously casting liquid Li in which X-C-based compound particles are dispersed. Also has a mode in which X-C compound particles are dispersed on the surface of the Li matrix (mode of B13 above).

Examples of the embodiment B2) include those formed by forming an X-C compound layer on the surface of a Li matrix by various PVD methods or CVD methods.

Examples of the above X-C compound include ZnC ₂ ,
Metal acetylides such as Ag ₂ C ₂ and MgC ₂ and Mg ₂ C
₃ etc. are illustrated.

The total mol% of X and C in the above negative electrode material is
0.1 to 30 mol%, preferably 5 to 20 mol%, particularly preferably 5 to 15 mol% is suitable. If the total mol% of X and C is less than 0.1 mol%, dendrites tend to be generated, while if it exceeds 30 mol%, the electromotive force of the negative electrode tends to decrease. In addition,
When the proportion of metallic lithium in the negative electrode increases, the degree of alloying of the negative electrode decreases, and the effect of suppressing the generation of dendrites tends to decrease. On the contrary, when the proportion of metallic lithium decreases, the content of metallic lithium in the alloy decreases, and the effect of suppressing the decrease in energy density tends to decrease.

The method for producing the negative electrode for a lithium secondary battery of the present invention will be described below. As the material for the negative electrode of the present invention,
As described above, A) Li-X-C based compound (where X is Zn, Ag,
Mg, Cd, In, Pb, Pt, Pd, Ge, Te, S
n, Al, Bi, Sb, Ga, Ca, or one or more elements selected from Ca), B) Li and an X-C compound (where X is Zn, Ag, M).
g, Cd, In, Pb, Pt, Pd, Ge, Te, S
Examples thereof include a compound with one or more elements selected from n, Al, Bi, Sb, Ga, and Ca), and these are manufactured as follows.

The above A) Li-X-C-based compound is prepared by vapor-depositing each raw material gas of A1) Li, X, and C on a substrate, and A2) reacting C atoms with a Li-X matrix. And the like.

In the above method A1), Li--X--C
The compound of the system is a chemical vapor deposition method such as plasma CVD, MOCVD, low pressure CVD, sputtering, RF magnetron sputtering, ternary cluster ion beam deposition, ternary ion plating, or reaction of three components of Li, X and C, for example. It is manufactured by forming a film on the substrate in the container by a dry process such as physical ion deposition, reactive electron beam vapor deposition, pulse plasma vapor deposition, physical vapor deposition such as plasma flash vapor deposition.

More specifically, for example, Li source gas, X
The raw material gas and C raw material gas are introduced into a reaction vessel together with a carrier gas such as argon gas, and RF power
The target Li-X-C based ternary alloy can be formed on the substrate in the container by plasma reaction at 500 W.

Propyllithium is used as the Li source gas.
System, secondary butyl lithium, t-butoxy lithium
When the X source gas is, for example, a Zn source gas
Is for Ag source gas such as diethyl zinc, dimethyl zinc, etc.
Is Ag (HFA), etc.
Gnesium or the like is CH as the C source gas_Four, C₂H
₆, C₃H₈, C_FourH_Ten, C₂H_FourEtc.
(Note that the above HFA is hexafluoro-2,4-pepylene.
(Indicating an intergionant).

This Li-X-C-based compound is usually 1 to 100 μm, preferably 3 to 50 when formed into a film.
The film is formed to a thickness of μm, particularly preferably 5 to 20 μm.

In the production of the above Li-X-C type compound, it is important to mix the three components of Li, X and C at the atomic level by a dry process such as chemical vapor deposition and physical vapor deposition.

In the above reaction, Li-X-on the substrate
A C-based alloy is deposited, and the negative electrode current collector can be used as the substrate at this time. In this case, a substrate having excellent conductivity is preferable, and a Ni substrate, an Al substrate,
Examples include Cu substrates, Fe substrates, stainless steel substrates, or the above various metal substrates plated with Ni.
Of these, a Ni substrate is preferable.

In the above method A2), Li-X-C is used.
The compound of the system is obtained by injecting carbon ions into a Li-X alloy film obtained by chemical vapor deposition or physical vapor deposition similar to the above, and forming a carbon thin film on the Li-X alloy film, and then performing ion beam mixing. Dynamic ion beam mixing using the above two methods together,
It can be obtained by alternately performing the above vapor deposition and ion implantation.

Further, B) a composite of Li and an X-C type compound is prepared by dispersing X-C type compound particles in a B1) Li matrix, or by forming an X-C type compound layer on a B2) Li matrix. It can be obtained by forming.

In the method of B1), the composite of Li and the X-C type compound is, specifically, B11) by dispersing the X-C type compound particles on the surface of the Li matrix, B12) in the Li matrix. And the like. Dispersing X-C compound particles in B.) B13) Dispersing X-C compound particles in the Li matrix surface and in the Li matrix.

The above method B11) is carried out, for example, by sprinkling X-C type compound particles on a Li matrix, electrodeposition of X-C type compound particles on a Li matrix, and the like. The method of the above B12) is, for example, driving X-C compound particles into a Li matrix with a spray gun, repeating the steps of sprinkling the X-C compound particles on the Li matrix, rolling and folding, and X. -C-based compound particles are dispersed by continuously casting liquid Li, and in these methods, the X-C-based compound particles are also dispersed on the surface of the Li matrix (method of B13 above). it can.

In the above method B2), a composite of Li and an X-C compound is obtained by forming an X-C compound layer on the surface of a Li matrix by, for example, various PVD methods or CVD methods.

The negative electrode formed by complexing the above X-C compound with Li is usually 1 to 100 μm when formed into a film,
The thickness is preferably about 3 to 50 μm.

The shape and size of the negative electrode of the present invention are not particularly limited, and can be arbitrarily determined according to the form (button type, cylindrical type, rectangular type, etc.) and size of the battery.

The negative electrode for a lithium secondary battery of the present invention is used, for example, in a lithium secondary battery having a structure as shown in FIG.

The positive electrode material constituting the positive electrode of the lithium secondary battery is not particularly limited, and a positive electrode material usually used for the positive electrode of the lithium secondary battery can be used. Specifically, for example, V ₂ O ₅ , MnO ₂ , LiMn ₂ O ₄ , LiCoO ₂ ,
LiNi _0.5 Co _0.5 O ₂ , LiNiO ₂ , TiS ₂ ,
Examples of the positive electrode material include MoS ₂ and MoO ₃ as active materials. Further, in addition to the above, at least one selected from the group consisting of lithium phosphate, lithium cobalt phosphate, cobalt oxide and lithium cobalt oxide, and the content of lithium, cobalt and phosphorus, A positive electrode material using a material in which cobalt exceeds 0.1 mol and phosphorus exceeds 0.2 mol per mol of lithium as an active material can particularly increase the electromotive force and charge / discharge voltage of a secondary battery. It is exemplified as a more preferable one.

In the negative electrode for a lithium secondary battery of the present invention, since the negative electrode active material is basically made of lithium, one containing no Li as the positive electrode active material (V ₂ O ₅ , MnO ₂ , TiS ₂ , MoS ₂ , MoO ₃
Etc. may be used, but a positive electrode active material containing Li (L
If iCoO ₂ , LiNiO ₂ or the like) is used, the amount of the negative electrode active material can be reduced.

The positive electrode active material is mixed with a conductive material such as acetylene black, Ketjen black and graphite, and a binder such as polytetrafluoroethylene, polyvinylidene fluoride and polyethylene.

The positive electrode mixture obtained by mixing the positive electrode active material with a conductive material and a binder is molded into an appropriate shape and size by any method such as casting, compression molding, roll molding, Used as a positive electrode for lithium secondary batteries.

Further, the electrolyte is not particularly limited as long as the object of the present invention can be achieved, and for example, an electrolytic solution in which salts are dissolved in an organic solvent or a solid electrolyte can be used.
When the electrolyte is an electrolytic solution, the salts include LiC.
lO ₄ , LiBF ₄ , LiPF ₆ , LiAsF ₆ , Li
AlCl ₄ , Li (CF ₃ SO ₂ ) ₂ N, etc. can be used,
Ethylene carbonate, propylene carbonate, dimethyl sulfoxide, sulfolane, γ-butyrolactone,
1,2-dimethoxyethane, N, N-dimethylformamide, tetrahydrofuran, 1,3-dioxolane, 2
-Dissolved in an organic solvent such as methyltetrahydrofuran, diethyl ether, dimethyl carbonate, diethyl carbonate and a mixture thereof to prepare a concentration of 0.1 to 3 mol / liter for use. This electrolytic solution is used by impregnating or filling a separator such as a porous polymer or a glass filter.

When the electrolyte is a solid electrolyte, the above-mentioned salts are mixed with polyethylene oxide, polypropylene oxide, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol and the like, and their derivatives, mixtures and complexes. This solid electrolyte also serves as a separator for the positive electrode and the negative electrode.

In this lithium secondary battery,
When the positive electrode, the separator (or the solid electrolyte), the negative electrode and the like are wound into a roll, a lithium battery having a higher electric capacity can be obtained.

The negative electrode for a lithium secondary battery having the above structure is L
Since i, X, and C are contained, Li deposited on the negative electrode during charging is diffused by the X, C, or X—C-based compound and enters into the negative electrode, whereby dendrite is formed. Is prevented from occurring.

Further, even if X and C are added to Li, the decrease in capacity and electromotive force is very small. Therefore, the negative electrode containing Li, X, and C has a high level close to that of pure lithium. Has capacity and high electromotive force.

Further, according to the above method for producing a negative electrode for a lithium secondary battery, the Li—X—C-based compound is produced by vapor-depositing the source gas on the substrate by chemical vapor deposition or physical vapor deposition. , A homogeneous negative electrode in which Li, X, and C are mixed at the atomic level is obtained. Alternatively, for example, carbon ions are injected into a Li-X alloy, or a carbon vapor deposition film formed on the surface of the alloy is produced by dispersing C atoms by ion beam mixing or the like. A negative electrode can be obtained. In addition, a composite of Li and an X-C compound is, for example, a Li sheet with X
Since the -C-based compound particles are dispersed, rolled, and then folded, the process is repeated, so that a homogeneous negative electrode in which the X-C-based compound particles are uniformly dispersed can be obtained.

[0047]

EXAMPLES Hereinafter, the present invention will be described more specifically by showing examples. Needless to say, the present invention is not limited to this. Examples 1 to 2 (Preparation of Negative Electrode) 18 m in diameter in an RF plasma reactor.
A nickel substrate having a thickness of 0.1 mm and a thickness of 0.1 mm was installed, and propyllithium was used as a Li source, diethylzinc was used as a Zn source, and CH ₄ was used as a carbon source as Ar gas carriers. 100μ
m of Li-Zn-C based synthetic material was obtained and used as a negative electrode. The flow rate of each source gas was 10% for propyllithium.
0 ml / min, diethyl zinc 120 ml / min, CH ₄ 160 ml
/ min.

(Production of Positive Electrode) Commercially available crystalline vanadium pentoxide (purity 99.9%) was crushed and sieved to 20 μm.
A positive electrode active material having a thickness of m or less was used. This positive electrode active material 80
mg, acetylene black 10 mg and polytetrafluoroethylene 10 mg are mixed well and the diameter is 15 mm.
A positive electrode was produced by molding into a disk shape of φ.

(Production of Battery) A microporous separator made of polypropylene (diameter 19 mm, thickness 25 μm) was sandwiched between the negative electrode and the positive electrode to produce a coin type test cell shown in FIG. Before sealing the test cell, an electrolyte solution in which 1 mol / liter of lithium perchlorate was dissolved in a solution of propylene carbonate and diethyl carbonate in a volume ratio of 50:50 was injected into the test cell. I saved it.

(Charge / Discharge Test) The above battery was in a charged state, and first discharged to a constant current value of 2.8 V and then rested for 1 hour. Then, the battery was charged to 3.8 V at a constant current value and then rested for 1 hour. This was set as one set, and discharging and charging were repeated. In addition, in this charge and discharge,
The current values of 1 mA and 10 mA are referred to as Example 1 and Example 2, respectively. The test battery obtained in this example had an electromotive force of 3.4 V and a high electromotive force similar to the battery using the metal lithium negative electrode.

COMPARATIVE EXAMPLES 1-2 The same procedure as in the above examples was used except that a Li sheet having a diameter of 18 mm and a thickness of 100 μm was pressed onto a nickel substrate to form a negative electrode instead of the Li—Zn—C type synthetic material. Then, a test cell was prepared and a charge / discharge test was conducted. In this charging / discharging, the current values of 1 mA and 10 mA were designated as Comparative Example 1 and Comparative Example 2, respectively.

Examples 3 to 4 ZnC ₂ particles were deposited by electrophoresis on a 100 μm-thick Li sheet in a liquid in which ZnC ₂ particles having an average particle diameter of 0.1 μm were dispersed. This sheet is 18m in diameter
m, and a thickness of 50 μm was punched out into a disk shape, and this was pressed onto an expanded metal (18 mmφ) made of nickel to produce a negative electrode. The same positive electrode as in Example 1 except that the above negative electrode was used,
A coin-type test cell was prepared using the electrolytic solution, and this battery was subjected to a charge / discharge test in the same manner as in Example 1 with current values of 1 mA (Example 3) and 10 mA (Example 4). The test battery obtained in this example had an electromotive force of 3.4 V and a high electromotive force similar to the battery using the metal lithium negative electrode.

Examples 5 to 10 In the above Example 1, instead of diethylzinc, Ag (HFA) was used as the Ag source (Example 5), dimethylmagnesium was used as the Mg source (Example 6), and tritylindium (as the In source). Example 7), tetramethylgermanium (Example 8) as a Ge source, tetramethyltin (Example 9) as an Sn source, and tripropylaluminum (Example 10) as an Al source, respectively, and a Li-X-C system. A test cell was prepared and a charge / discharge test was conducted in the same manner except that the synthetic material of was prepared.

[Evaluation Results] When the battery was disassembled after 100 cycles of the above test and the negative electrode was observed, no dendrite-like lithium deposition was observed in any of the batteries prepared in Examples, but the batteries of Comparative Examples Had the dendrite-like deposition of lithium, and traces of a short circuit between the positive electrode and the negative electrode due to the penetration of the separator were observed. The relationship between the discharge capacity and the number of cycles of the test batteries produced in the above Examples and Comparative Examples was as shown in Fig. 1 (note that
The discharge capacity is shown per 1 g of the positive electrode active material). Figure 1
As is clear from the above, in Example, the discharge capacity decreases with the current value, but the decrease in capacity with the number of cycles is very small. On the other hand, in the comparative example, although the initial capacity was the same as that of the example, the decrease in capacity due to the deposition of dendrite-like lithium and the short circuit between the positive electrode and the negative electrode was remarkable with the increase in the number of cycles.

[0055]

INDUSTRIAL APPLICABILITY The lithium secondary battery using the lithium alloy negative electrode of the present invention is excellent in cycle life because dendrites are prevented from being generated, and since dendrites are prevented, it is safe without ignition due to short circuit. Is also excellent. Further, it has the same high capacity and high electromotive force as a lithium secondary battery using a metal lithium negative electrode. Therefore, the present invention can provide a negative electrode for a lithium secondary battery, which has excellent cycle life, high electromotive force, high capacity, high energy density, and excellent safety. Further, according to the method for producing a negative electrode for a lithium secondary battery of the present invention, a homogeneous negative electrode can be produced, and the desired negative electrode can be efficiently obtained.

[Brief description of drawings]

FIG. 1 is a graph showing a relationship between a discharge capacity and a cycle number of a test battery manufactured in an example of the present invention.

FIG. 2 is a schematic cross-sectional view showing the structure of a test lithium secondary battery produced in an example.

Claims (11)

[Claims] 1. Li, X (where X is Zn, Ag, M
g, Cd, In, Pb, Pt, Pd, Ge, Te, S
A negative electrode for a lithium secondary battery, which contains C and one or more elements selected from n, Al, Bi, Sb, Ga, and Ca. 2. A Li—X—C-based compound (where X is Zn, Ag, Mg, Cd, In, Pb, Pt, Pd, G).
e, Te, Sn, Al, Bi, Sb, Ga, Ca, or one or more elements selected from the following). 3. A Li—X—C based compound is formed on the substrate as L.
The negative electrode for a lithium secondary battery according to claim 2, which is prepared by depositing an i source gas, a X source gas and a C source gas. 4. The negative electrode for a lithium secondary battery according to claim 2, wherein the Li—X—C-based compound is a Li—X matrix reacted with C atoms. 5. Li and an X—C compound (where X is Z
n, Ag, Mg, Cd, In, Pb, Pt, Pd, G
e, Te, Sn, Al, Bi, Sb, Ga, Ca and one or more kinds of elements) and a composite with a negative electrode for a lithium secondary battery. 6. A composite of Li and an X—C compound is L
The negative electrode for a lithium secondary battery according to claim 5, wherein the i-matrix is formed with an X-C compound layer or the Li-matrix is dispersed with X-C compound particles. 7. The composition of Li is 70 to 99.9 mol%, X
The negative electrode for a lithium secondary battery according to claim 1, wherein the total composition of C and C is 0.1 to 30 mol%. 8. The lithium according to claim 1, wherein a Li source gas, a source gas of X and a source gas of C are vapor-deposited on the substrate to form a Li—X—C based compound film. Manufacturing method of negative electrode for secondary battery. 9. A Li source gas, a source gas of X and a source gas of C are introduced into a reaction vessel, and a Li—X—C-based compound film is formed on a substrate in the vessel by a plasma reaction. The method for producing a negative electrode for a lithium secondary battery according to claim 1 or 2. 10. The method for producing a negative electrode for a lithium secondary battery according to claim 1, wherein the Li—X matrix is reacted with C atoms to form a composite film of Li, X and C. . 11. The negative electrode for a lithium secondary battery according to claim 1, wherein an X—C compound layer is formed on the Li matrix or X—C compound particles are dispersed in the Li matrix. Manufacturing method.