JPH1140152A - Nonaqueous electrolyte battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a battery with high capacity and superior charging an discharging cycle property by using a covalent boned crystal which can absorb and emit lithium as a main structure constituent substance of a negative electrode active material and depositing carbon particles on the crystal surface. SOLUTION: It is preferable to use silicon having an electrical conductivity σof 10<-5> S/cm or higher at 20 deg.C and doped with impurities, such as boron as a covalent bond crystal. It is further preferable that carbon particles can absorb and emit lithium. A main solute of an electrolytic substance is a salt- containing carbon and preferably the solute has a C-F bond. It is preferable to use a salt represented by a general formula (R1Y1) (R2Y2)NLi as the salt. In the formula, R1, R2 are represented by Cn F2n+ with n 1-4, R1=R2 or R1≠R2, Y1, Y2 are each one of CO, SO, or SO2 , Y1=Y2 or Y1≠Y2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery, and more particularly, to a negative electrode for a non-aqueous electrolyte battery having a large discharge capacity and a high power density and excellent cycle characteristics.

[0002]

2. Description of the Related Art Conventionally, lithium has been typically used as a negative electrode active material for a nonaqueous electrolyte battery. However, dendritic deposition of lithium generated during charging (dendrite)
Therefore, there was a problem in terms of cycle life. In addition, the dendrite penetrates through the separator, causing an internal short circuit and causing ignition. Further, alloys with metallic lithium were also used for the purpose of preventing dendrite generated during charging as described above, but when the charge amount was increased, there were problems such as fine powdering of the negative electrode and falling off of the negative electrode active material. .

At present, attention has been paid to a battery using a carbon material for a negative electrode for the purpose of prolonging the service life and safety, and a part thereof has been put to practical use. However, the carbon material used for the negative electrode is
There were problems such as an internal short circuit and a decrease in charging efficiency during rapid charging. Since these carbon materials generally have a lithium doping potential of the carbon material close to 0 V, when rapid charging is performed, the potential becomes 0 V or less and lithium may be deposited on the electrode. This may cause an internal short circuit of the cell or lower the discharge efficiency. Although such carbon materials have been considerably improved in terms of cycle life, their relatively low density results in low capacity per volume. That is, this carbon material is still insufficient in terms of high energy density. In addition, the initial charge / discharge efficiency is reduced for those that need to form a film on carbon, and the amount of electricity used to form this film is irreversible, leading to the inability to draw out the capacity of that amount of electricity. .

On the other hand, as a negative electrode active material other than lithium metal, a lithium alloy or a carbon material, a composite oxide Li _x Si _{1- y My} O _z containing silicon and lithium (JP-A-7-230800), Crystalline chalcogen compound M ¹
It has been proposed to use M ² _p M ⁴ _q (Japanese Patent Laid-Open No. 7-288123), which is improved in terms of high capacity and high energy density.

[0005] However, the above-mentioned composite oxide has a problem in quick charging and load characteristics because the electric conductivity of the active material itself is low. Since the composite oxide itself is an oxide itself, it is considered that the reaction with lithium proceeds through the reduction of the oxide, so that irreversible reduction occurs at the initial stage and the initial charge / discharge efficiency is lowered. there were.
It is desired to develop a safe negative electrode material for a non-aqueous electrolyte battery having a higher capacity, a higher energy density, a longer cycle life, and a higher safety.

[0006]

As described above, it is understood that there are various problems when lithium, a lithium alloy, a carbon material, and an oxide are used as a negative electrode.

[0007] The present invention solves the above-mentioned problems,
Non-aqueous material with high capacity and excellent charge-discharge cycle characteristics by using a covalent crystal capable of occluding and releasing lithium as the main constituent material of the negative electrode active material and supporting carbon particles on the crystal surface. An object is to provide an electrolyte battery.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and a main constituent of a negative electrode active material used in a non-aqueous electrolyte battery is a common material capable of occluding and releasing lithium. A bonded crystal, characterized in that carbon particles are supported on the crystal surface. The covalent crystal used in the present invention has an electric conductivity σ of 10 ⁻⁵ S at 20 ° C.
It is preferably at least cm ^{−1, and} more preferably, the covalent crystal is silicon doped with an impurity such as boron.

Further, it is preferable that the above-mentioned carbon particles can occlude and release lithium.

Further, as an electrolyte in a non-aqueous electrolyte battery, a main solute is a salt containing carbon, and preferably, an electrolyte having a CF bond in the solute exhibits excellent charge / discharge characteristics. I understood. As a salt having a C—F bond, at least general formula (1) (R1Y1) (R2Y2) NLi General formula (1) (where R1 and R2 in general formula (1) are C _n F _{2n + 1} Represented,
n is a number from 1 to 4, and R1 = R2 or R1
≠ R2, and Y1 and Y2 are CO, SO, SO ₂
Y1 = Y2 or Y1 ≠ Y2. It is preferable to use the salt represented by the formula (1).

First, as a compound of lithium and silicon, Binary Alloy Phase Diagram is used.
ms (p2465), it is known that lithiation is performed with a composition up to Li ₂₂ Si ₅ . Also, Japanese Patent Application Laid-Open No. 5-74463 reports that the cycle characteristics are improved by using a single crystal of silicon for the negative electrode. However, when trying to occlude lithium in silicon as a negative electrode material of a non-aqueous electrolyte battery for rapid charge and discharge, it was found that lithium was deposited with almost no occlusion.

That is, although a compound of a covalent bond crystal such as lithium and silicon is known, silicon itself is originally an intrinsic semiconductor and has low electron conductivity as it is.
The characteristics as a battery negative electrode material were poor. Therefore, the mixture of the covalent crystal and the conductive agent such as carbon alone cannot follow the change in volume during charge and discharge, so that the negative electrode active material is isolated and the resistance is increased, thereby causing a decrease in capacity. However, it has been found that by supporting carbon particles on the silicon crystal surface, isolation between the silicon crystal and the conductive agent can be prevented, and an increase in the resistance of the negative electrode can be suppressed. Further, the covalent crystal is doped with an atom that can be a donor atom or an acceptor atom, and the electric conductivity σ is made to be 10 ⁻⁵ Scm ⁻¹ or more at 20 ° C., thereby increasing the occlusion of lithium without increasing the resistance of the negative electrode.
Release was found to occur easily. In particular, it was found that the capacity was improved by doping silicon with boron as an impurity.

The covalent crystals referred to herein include Si,
Ge, GaAs, GaP, InSb, GaP, SiC,
BN and the like. Among them, Si is particularly preferable because it has excellent charge / discharge characteristics, is abundant in resources, and has low toxicity, and thus is excellent in safety and particularly preferable. . In addition, examples of the crystal system include a single crystal, a polycrystal, and a microcrystal, but are not limited thereto.

Furthermore, the covalent crystal may contain impurities for the purpose of improving electron conductivity. The impurities referred to here are those which can be donor atoms and acceptor atoms among all elements in the periodic table, and are preferably P, Al, As, Sb, B, Ga, In, etc. It is not limited. It is also preferable to improve electron conductivity due to the existence of lattice defects not due to impurities inside the covalent crystal.

The concentration of the mixed impurities is usually a ratio of 10 ⁷ to 10 ⁶ silicon atoms to one donor or acceptor atom, but high concentration doping is preferable, and silicon atoms of 10 ⁴ to 10 ⁶ are suitable. It is desirable that the concentration is high enough to leave a face-centered cubic structure of silicon at a rate of one donor atom or one acceptor atom or more.

The covalent crystal used in the present invention preferably has an average particle size of 100 μm or less. In obtaining a predetermined shape, a pulverizer or a classifier is used to obtain a powder. For example, mortars, ball mills, sand mills, vibrating ball mills, planetary ball mills, jet mills, counter jet mills, swirling air jet mills, sieves, and the like are used. At the time of pulverization, wet pulverization in which an organic solvent such as water or hexane coexists can be used. The classification method is not particularly limited, and a sieve, an air classifier, or the like is used as needed in both dry and wet methods.

As a method for supporting the carbon particles on the covalent bond crystal used in the present invention, ordinary mixing is also possible, but preferably a sintering method, a vapor deposition method, a thermal plasma method, or a CV method.
D method, a sputtering method, a thermal decomposition method using a sol-gel method, a wet reduction method, an electrochemical reduction method, a gas phase reduction gas treatment method, a mechanofusion, and the like. Absent.

Examples of the negative electrode material that can be used in conjunction with the present invention include lithium metals, lithium alloys, and organic compounds containing lithium such as methyllithium. Further, by using a lithium metal, a lithium alloy, and an organic compound containing lithium in combination, it is possible to further insert lithium into the compound of the covalent crystal and lithium used in the present invention inside the battery.

When the covalent crystal supporting the carbon particles of the present invention is used, a conductive agent, a binder, a filler, and the like can be added as an electrode mixture. Any conductive material may be used as long as it does not adversely affect battery performance. Usually, natural graphite (flaky graphite, flaky graphite, earthy graphite, etc.), artificial graphite, carbon black, acetylene black, Ketjen black, carbon whiskers, carbon fibers and metals (copper, nickel, aluminum, silver, gold, etc.) A conductive material such as powder, metal fiber, metal deposition, and conductive ceramic material can be included as one type or a mixture thereof. The addition amount is preferably 1 to 50% by weight, particularly preferably 2 to 30% by weight.

As the binder, usually, tetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, ethylene-propylene diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluoro rubber, carboxymethyl cellulose, etc. Such as a thermoplastic resin, a polymer having rubber elasticity, a polysaccharide and the like can be used alone or as a mixture of two or more. Further, it is desirable that a binder having a functional group that reacts with lithium, such as a polysaccharide, be deactivated by, for example, methylation. The addition amount is preferably 1 to 50% by weight, particularly 2 to 50% by weight.
30% by weight is preferred.

As the filler, any material may be used as long as it does not adversely affect battery performance. Usually, olefin polymers such as polypropylene and polyethylene, aerosil, zeolite, glass, carbon and the like are used. The added amount of the filler is preferably 30% by weight or less.

The current collector of the electrode active material may be any electronic conductor that does not adversely affect the battery. For example, as the positive electrode material, aluminum,
In addition to titanium, stainless steel, nickel, calcined carbon, conductive polymer, conductive glass, etc., for the purpose of improving adhesiveness, conductivity, and oxidation resistance, the surface of aluminum, copper, etc. is coated with carbon, nickel, titanium, or the like. Those treated with silver or the like can be used. As the negative electrode material, copper, stainless steel, nickel, aluminum, titanium, calcined carbon, conductive polymer, conductive glass, Al-Cd alloy, etc.
For the purpose of improving conductivity and oxidation resistance, a material obtained by treating the surface of copper or the like with carbon, nickel, titanium, silver, or the like can be used. These materials can be oxidized on the surface. For these shapes, besides foil, film, sheet, net, punch,
Expanded, lath, porous, foam,
A fiber group formed body or the like is used. The thickness is not particularly limited, but a thickness of 1 to 500 μm is used.

The thus obtained compound of lithium and the covalent bond crystal can be used as a negative electrode active material.
On the other hand, MnO ₂ , MoO ₃ , V ₂
O ₅ , Li _x CoO ₂ , Li _x NiO ₂ , Li _x Mn ₂
Metal oxides such as O ₄ , TiS ₂ , MoS ₂ , NbSe
Metallic chalcogenides such as _{3 and the} like, graphite intercalation compounds such as polyacene, polyparaphenylene, polypyrrole, and polyaniline, and alkali metal ions such as conductive polymers and various substances capable of absorbing and releasing anions can be used.

In particular, when the compound of the present invention and the lithium compound are used as a negative electrode active material, V ₂ O ₅ , Li _x CoO ₂ , and Li _x Ni are used from the viewpoint of high energy density.
Those having an electrode potential of 3 to ₄ V, such as O ₂ and Li _x Mn ₂ O _4, are desirable. In particular, Li _x CoO ₂ , Li _x NiO
₂ , lithium-containing transition metal oxides such as Li _x Mn ₂ O ₄ are preferred.

As the electrolyte, for example, an organic electrolyte, a solid polymer electrolyte, an inorganic solid electrolyte, a molten salt, or the like can be used, and among them, an organic electrolyte is preferable. As the organic solvent of the organic electrolyte, propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, esters such as γ-butyrolactone, tetrahydrofuran, substituted tetrahydrofuran such as 2-methyltetrahydrofuran, dioxolane, Ethers such as diethyl ether, dimethoxyethane, diethoxyethane, methoxyethoxyethane, dimethylsulfoxide, sulfolane, methylsulfolane,
Acetonitrile, methyl formate, methyl acetate, N-methylpyrrolidone, dimethylformamide and the like can be mentioned, and these can be used alone or as a mixed solvent.

The main constituent solute of the electrolyte used in the present invention may be any salt containing carbon. Preferably,
Preferably, the solute has a CF bond. For example, the formula has been used in JP _{58-225045: (C n X 2n +} 1 Y) 2 N -, and those expressed by M ^+, the following formula (2), (3): (RSO 2 ) ₃ C ⁻ , M ⁺ ... General formula (2) (RSO ₂ ) O ⁻ , M ⁺ . More preferably, general formula (1) (R1Y1) (R2Y2) NLi General formula (1) (R1 and R2 in general formula (1) are represented by C _n F _{2n + 1} ,
n is a number from 1 to 4, and R1 = R2 or R1
≠ R2, and Y1 and Y2 are CO, SO, SO ₂
And Y1 = Y2 or Y1 ≠ Y2. ), And more preferably a general formula (4) (R1SO ₂ ) (R2SO ₂ ) NLi... General formula (4) is used. R
1, R2 is represented by C _n F _{2n + 1} , n is a number from 1 to 4, and R1 = R2 or R1 ≠ R2. Most preferably, R1 = R2 = C ₂ F ₅ , or R1 = C
F _3, R2 = a C ₄ F _9.

On the other hand, as the solid electrolyte, for example, an inorganic solid electrolyte, an organic solid electrolyte, an inorganic solid electrolyte, a molten salt and the like can be used. Well known inorganic solid electrolytes include lithium nitrides, halides, oxyacid salts, phosphorus sulfide compounds, and the like, and one or more of these can be used in combination. Among them, Li ₃ N, Li
_{I, Li 5 NI 2, Li} 3 N-LiI-LiOH, Li
₄ SiO ₄ , Li ₄ SiO ₄ -LiI-LiOH, xL
i ₃ PO _{4- (1-x)} Li ₄ SiO ₄ , Li ₂ SiS _{3 and the} like are effective. On the other hand, in the organic solid electrolyte, a polyethylene oxide derivative or a polymer containing at least the derivative, a polypropylene oxide derivative or a polymer containing at least the derivative, polyphosphazene or the derivative,
Polymer matrix material (gel electrolyte) containing non-aqueous electrolyte in polymer containing ion-dissociating group, phosphate ester polymer derivative, polyvinyl pyridine derivative, bisphenol A derivative, polyacrylonitrile, polyvinylidene fluoride, fluorine rubber, etc. Etc. are effective.

As the separator, an insulating thin film having excellent ion permeability and mechanical strength can be used. Olefin polymers such as polypropylene and polyethylene, glass fiber, and organic solvent resistant and hydrophobic
Sheets, microporous membranes, and nonwoven fabrics made of polyvinylidene fluoride, polytetrafluoroethylene, or the like are used. The pore size of the separator is in a range generally used for a battery, and is, for example, 0.01 to 10 μm. The same applies to the thickness, which is in the range generally used for batteries, for example, 5 to 300 μm.

When the covalent crystals supporting carbon particles of the present invention are used, it is possible to further modify at least the surface layer portion of the powder with a substance other than carbon particles. For example, plating, sintering, mechanofusion, vapor deposition, and thermal plasma of a material with good electron conductivity such as gold, silver, carbon, nickel, and copper, or a material with good ion conductivity such as lithium carbonate, boron glass, and solid electrolyte Coating by applying a technique such as a method.

The reason why such excellent charge / discharge characteristics are obtained is not necessarily clear, but is considered as follows. That is, it can be seen that the crystal having a covalent bond can occlude lithium, and that the compound has a high lithium abundance ratio. However, since a crystal having a covalent bond is a semiconductor but an intrinsic semiconductor, the electric conductivity at room temperature is low and the polarization during charge and discharge is relatively large. On the other hand, when impurities that can be donor atoms and acceptor atoms are doped into the covalent bond crystal, electron conductivity is improved, polarization during charge and discharge is reduced, and electrons can be easily given to lithium ions. The occluded lithium oxide can easily release electrons and release lithium ions. In other words, it is presumed that the flow of electrons in the covalent bond crystal becomes smoother by obtaining a mechanism for flowing electrons, thereby facilitating occlusion and release of lithium. In addition, since the crystal structure of silicon or gallium is the same face-centered cubic structure as diamond, the bonding of crystals is very strong,
Following the expansion and contraction associated with the insertion and extraction of lithium, no miniaturization or falling off of the active material itself was observed, suggesting that the reversibility of charge and discharge has been improved. In addition, by supporting carbon particles on the crystal surface, the electron conductivity between the particles is improved, and when lithium is inserted and extracted, lithium can be temporarily accumulated on the carbon particles. It is considered that the discharge characteristics are improved.

Further, the following is considered as a reason why the use of a salt containing carbon as the main solute used in the electrolyte improves the charge / discharge efficiency. Conventionally, carbon-free salts typified by LiPF ₆ used in nonaqueous electrolyte batteries react with a small amount of water inside the battery to generate hydrogen fluoride. This hydrogen fluoride is used for surface treatment of silicon or the like, and is considered to have a function of eroding a film existing on the silicon surface. Therefore, it is considered that the hydrogen fluoride present inside the battery and the film on the silicon surface react with each other, remain as a compound having low ion conductivity at the interface, and increase the resistance of the negative electrode, thereby lowering the charge / discharge efficiency. . On the contrary, it is considered that the salt containing carbon as represented by the general formula (1) hardly generates hydrogen fluoride, thereby suppressing the increase in the resistance of the negative electrode and improving the charge / discharge efficiency. .

As described above, the present invention provides a nonaqueous electrolyte battery characterized in that the main constituent material of the negative electrode active material is a covalent bond crystal capable of occluding and releasing lithium, and carbon particles are supported on the crystal surface. By using a salt containing carbon as the main constituent solute of the electrolyte, lithium can be inserted and released in the range of at least 0 to 2 V with respect to metallic lithium, and since the crystal is strong, it is usually used. Fine powdering during charge and discharge and partial isolation of the negative electrode active material, which are observed in alloys, are suppressed, and by using such a salt as a nonaqueous electrolyte, the charge and discharge efficiency is excellent and the cycle characteristics are good. It can be used as a negative electrode of a non-aqueous electrolyte battery having excellent charge / discharge characteristics. In particular, by supporting carbon particles capable of storing and releasing lithium, lithium can be smoothly stored and released into silicon, and the charge / discharge rate characteristics are improved. In addition, high energy density is achieved because of its large capacity.

[0033]

Embodiments of the present invention will be described below.

(Invention) Silicon polycrystalline powder (electron conductivity σ is 0.8 Scm ⁻¹ at 20 ° C.), which is a p-type semiconductor doped with 10 ⁴ silicon atoms and 1 B atom, and artificial graphite ( (D002) = 3.37 °, crystal size Lc = 360 ° in the c-axis direction) was mixed at a weight ratio of 85:10, and partially sintered at 1500 ° C. under a nitrogen atmosphere. The obtained sintered powder was pulverized with a mortar to obtain a negative electrode active material which is a covalent crystal supporting carbon particles. This negative electrode active material and polytetrafluoroethylene powder were mixed at a weight ratio of 95: 5, and toluene was added and kneaded sufficiently. This was formed into a sheet having a thickness of 0.1 mm by a roller press.
Next, this was punched into a circle having a diameter of 16 mm,
After drying at 0 ° C. for 15 hours, a negative electrode 2 was obtained. The negative electrode 2 was used by being pressed against a negative electrode can 5 provided with a negative electrode current collector 7. The positive electrode 1 is
LiCoO ₂ , acetylene black and polytetrafluoroethylene powder as a positive electrode active material were mixed at a weight ratio of 85: 1.
The mixture was mixed at 0: 5, and toluene was added and kneaded well. This was formed into a 0.8 mm thick sheet by a roller press. Next, this was punched out into a circle having a diameter of 16 mm and dried under reduced pressure at 200 ° C. for 15 hours to obtain a positive electrode 1. Positive electrode 1
Was press-bonded to a positive electrode can 4 having a positive electrode current collector 6. 1 m of (C ₂ F ₅ SO ₂ ) ₂ NLi was added to a mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1.
ol / l dissolved electrolytic solution was used, and a microporous polypropylene membrane was used for the separator 3. 20 mm in diameter and 1.6 m in thickness using the above positive electrode, negative electrode, electrolyte and separator.
m was manufactured. This battery is referred to as Battery (A) of the present invention.

(Comparative Example 1) A polycrystalline silicon powder which is a p-type semiconductor doped with 10 ⁴ silicon atoms and 1 B atom without carrying carbon particles as a negative electrode active material (electron conductivity σ is A battery was fabricated in the same manner as in the present invention except that 0.8 Scm ^-1 ) was used at 20 ° C. The obtained battery is referred to as a comparative battery (B).

Comparative Example 2 As a solute of the electrolytic solution, (C ₂
A battery was fabricated in the same manner as in the present invention except that LiBF ₄ was used instead of F ₅ SO ₂ ) ₂ NLi. The obtained battery is referred to as a comparative battery (C).

The battery of the present invention (A), the comparative batteries (B) and (C) thus produced were subjected to a charge / discharge cycle test. The test conditions were as follows: charge current 5 mA, charge end voltage 4.1 V, discharge current 5 mA, discharge end voltage 3.
0 V was applied. Table 1 shows the results of the charge / discharge test of these batteries.

[0038]

[Table 1]

As can be seen from Table 1, the battery of the present invention (A) using a covalent crystal in which carbon particles are supported on a negative electrode active material.
Indicates that the battery characteristics such as charge / discharge efficiency and cycle characteristics are superior to the comparative battery (B) using a covalent bond crystal in which carbon particles are not supported on the negative electrode active material. In addition, the battery (A) of the present invention using a salt containing carbon as the solute of the electrolytic solution has excellent charge / discharge characteristics as compared with the comparative battery (C) using LiBF ₄ as the solute of the electrolytic solution.
The decrease after cycling was small.

Although the reasons for these results are not clear, it is considered that the transfer of electrons and ions occurring on the silicon crystal surface has a large effect on the battery characteristics. In other words, by supporting carbon particles on the silicon surface, the electron conductivity between the particles is improved, and the carbon particles themselves occlude and release lithium, thereby smoothly absorbing and releasing lithium into silicon, The use of a salt containing carbon that does not easily produce hydrogen fluoride in the electrolyte prevents the formation of compounds with relatively low ionic conductivity generated on the surface of the negative electrode active material, resulting in excellent charge / discharge efficiency and cycle characteristics. It is also considered that a high-output, high-energy-density nonaqueous electrolyte battery was obtained. Silicon is considered to be a material with low toxicity and excellent safety.

In the above embodiment of the present invention, silicon is used as a covalent bond crystal and (C ₂ F ₅
Although SO ₂ ) ₂ NLi was mentioned, the same effect was confirmed for other carbon-containing salts. The present invention is not limited to the starting materials, the production method, the positive electrode, the negative electrode, the electrolyte, the separator, the shape of the battery, and the like of the active material described in the above-described embodiment.

[0042]

Since the present invention is constructed as described above, it exhibits excellent charge / discharge efficiency, charge / discharge cycle characteristics, and rapid charge / discharge characteristics, and has high output, high capacity, and high energy density.
A highly safe nonaqueous electrolyte battery can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view of a coin-type nonaqueous electrolyte battery according to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 positive electrode 2 negative electrode 3 separator 4 positive electrode can 5 negative electrode can 6 positive electrode current collector 7 negative electrode current collector 8 insulating packing

Claims (8)

[Claims] 1. A non-aqueous electrolyte battery characterized in that the main constituent material of the negative electrode active material is a covalent crystal capable of inserting and extracting lithium, and carbon particles are supported on the surface of the crystal. 2. The non-aqueous electrolyte battery according to claim 1, wherein the carbon particles are carbon particles capable of inserting and extracting lithium. 3. The non-aqueous electrolyte battery according to claim 1, wherein the main solute used for the electrolyte is a salt containing carbon. 4. The method according to claim 1, wherein the salt containing carbon is at least CF.
4. The non-aqueous electrolyte battery according to claim 3, wherein the non-aqueous electrolyte battery has a bond. 5. The carbon-containing salt according to claim 1, wherein at least one of the general formula (1) (R1Y1) (R2Y2) NLi... General formula (1) (wherein R1 and R2 in the general formula (1) are C _n F _{2n + 1}
n is a number from 1 to 4, and R1 = R2 or R1
≠ R2, and Y1 and Y2 are CO, SO, SO ₂
Y1 = Y2 or Y1 ≠ Y2. 4. The non-aqueous electrolyte battery according to claim 3, wherein a salt represented by the formula (1) is used. 6. The electric conductivity σ of the covalent crystal is 2
2. The non-aqueous electrolyte battery according to claim 1, wherein the temperature is 10 ^-5 Scm ^-1 or more at 0 ° C. 7. The non-aqueous electrolyte battery according to claim 1, wherein the covalent crystal is made of silicon, and is doped with boron as an impurity. 8. The non-aqueous electrolyte battery according to claim 1, wherein a main constituent material of the positive electrode active material is a lithium-containing transition metal oxide.