JPH0268860A - Secondary battery - Google Patents

Abstract

PURPOSE:To enable stable high-capacity discharge by using lithium or alkarine metal chiefly containing lithium as active material and forming a carrier from mixture of specific carbon material and metal able to be alloyed with the active material. CONSTITUTION:Active material is lithium or alkaline metal chiefly containing it and a carrier is formed from mixture of both a carbon material having the face-to-face spacing (d002 between face (002) of 3.37A or more by the X-ray wide-angle diffraction method and the crystal element in the (c) direction of 150A or less in size, and metal able to be alloyed with active material. so the mixture material thermally discomposes organic compound into carbon and simultaneously thermal discomposes the organic metal compound containing metal able to be alloyed with the active material. Since lithium(Li) which functions as active material at the time of charging or alkaline metal chiefly containing lithium may be fixed stable to the carrier, the high capacity current may be discharged stably.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a secondary battery, and more particularly to a secondary battery that is small, has a long charge/discharge cycle life, and has a stable high capacity.

(Prior art) The main component of the positive electrode body is a transition metal chalcogen compound such as T i S z or MoS x, and the negative electrode body is made of Li.
Efforts are being made to commercialize secondary batteries made of alkali metals mainly composed of Li, which have high energy density.

Further, secondary batteries using a conductive polymer such as polyacetylene for the positive electrode and Li or an alkali metal mainly composed of Li for the negative electrode are also being studied.

(Problem to be solved by the invention) However, in such a secondary battery, the negative electrode body is
Problems arise due to the fact that the i-foil or the foil itself is an alkali metal foil mainly composed of Li.

That is, when the battery is discharged, Li from the negative electrode body becomes Li ions and moves into the electrolyte solution, and during charging, these Li ions become metal Li and are deposited on the negative electrode body again, but this charge-discharge cycle is repeated. As a result, the metal Li deposited becomes dendrite-like. Since this dendrite-like Li is an extremely active substance, it decomposes the electrolyte, resulting in the disadvantage that the charge/discharge cycle characteristics of the battery deteriorate. Furthermore, this is growing (
Finally, this dendrite-like metal Li deposit penetrates the separator and reaches the positive electrode body, causing a problem of causing a short circuit phenomenon. In other words, the problem arises that the charge/discharge cycle life is short.

In order to avoid such problems, attempts have been made to construct a negative electrode by using a carbonaceous material obtained by firing an organic compound as a carrier, and supporting Li or an alkali metal mainly composed of Li.

By using such a negative electrode body, the precipitation of Li dendrites has been prevented, but on the other hand, a battery incorporating this negative electrode body has a much higher discharge capacity than a primary battery of the same size. Furthermore, the magnitude of self-discharge was not necessarily reduced to a satisfactory level.

Under such circumstances, the present invention aims to provide a secondary battery having a larger battery capacity and improved self-discharge characteristics.

[Structure of the Invention] (Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted extensive research on negative electrode bodies, and have developed an active material onto a carrier having the characteristics described below. The present invention has been achieved based on the discovery that it is effective to achieve the above-mentioned object by carrying the structure.

That is, the secondary battery of the present invention includes a negative electrode body consisting of an active material and a carrier supporting the active material, and (a) the active material is lithium or an alkali metal mainly composed of lithium. (b) The carrier has a lattice spacing (do. 2) of the (002) plane determined by X-ray wide-angle diffraction method.
) is 3.37 Å or more: and the crystallite size (Lc) in the C-axis direction is 150 Å or less; and a metal that can be alloyed with the active material. It is characterized in that it is obtained by thermally decomposing an organic compound and carbonizing it, and simultaneously thermally decomposing an organometallic compound containing a metal that can be alloyed with the active material.

The battery of the present invention is characterized in that the negative electrode body has the above-described configuration, and other elements may be the same as conventional secondary batteries.

In the negative electrode body according to the present invention, the active material is Li or L.
This active material, which is mainly an alkali metal containing i, moves in and out of the negative electrode body in response to charging and discharging of the battery.

The carrier for the active material constituting the negative electrode body in the present invention is made of a mixture material of a carbonaceous material having the characteristics described below and a metal that can be alloyed with the active material.

That is, the carbonaceous material constituting the mixture material has a (002) plane spacing d 002 of 3.
37A or more, crystallite size (Lc) in the C-axis direction is 15
It has the characteristic that it is 0 Å or less.

The spacing (dooz) of the (002) plane is preferably 3.3
9 to 3.75 people, more preferably 3.41 to 3.70 people
A, particularly preferably 3.45 to 3.70 people, most preferably 3.51 to 3.70 people: the crystallite size Lc in the C axis direction is preferably 5 to 150 people, more preferably 10 ~80 people, particularly preferably 12-70 people.

These parameters, namely d. . If either 2 or Lc deviates from the above range, the overvoltage at the negative electrode during charging and discharging will increase, and as a result, gas will be generated from the negative electrode, significantly impairing the safety of the battery. In addition, the charge/discharge cycle characteristics also deteriorate.

Further, the carbonaceous material constituting the mixture material used for the carrier of the negative electrode body according to the present invention preferably has the following characteristics.

The hydrogen/carbon atomic ratio (H/C) is preferably less than 0.10, more preferably less than 0.07.

Particularly preferably less than 0.05.

Other atoms such as nitrogen, oxygen, halogen, etc. may be present in this carbonaceous material in a proportion of preferably 7 mol% or less, more preferably 4 mol% or less, particularly preferably 2 mol% or less. good.

Furthermore, it is desirable that the carbonaceous material constituting the mixture material used for the carrier of the negative electrode body according to the present invention satisfies the following conditions.

In other words, the distance a 6 (= 2 d
zo) is preferably 2.38 to 2.47 people, more preferably 2.39 to 2.46 people: the crystallite size La in the a-axis direction is preferably 108 or more, more preferably 15 The range is from 150 people to 150 people, particularly preferably from 19 to 70 people.

In addition, in Raman spectrum analysis using argon ion laser light with a wavelength of 5145 nm, the G value defined by the integral value of the spectral intensity in the wave number range of 1580 ± 100 cm-' is less than 2.5. It is preferably less than 2.0, particularly preferably 0.2 or more and less than 1.2.

Here, the G value is the wavelength of 5145 for the carbonaceous material mentioned above.
In the spectral intensity curve recorded on the chart when Raman spectrum analysis was performed using human argon ion laser light, the wave number was 1580±100cn+-'
It refers to the value obtained by dividing the integral value of the spectral intensity (area intensity) within the range of 1360±100cn+-' by the area intensity within the wave number range of 1360±100cn+-', and corresponds to a measure of the degree of graphitization of the carbonaceous material.

That is, this carbonaceous material has a crystalline portion and an amorphous portion, and the G value can be said to be a parameter indicating the proportion of the crystalline portion in this carbonaceous structure.

The carbonaceous material constituting the mixture material used for the carrier of the negative electrode body according to the present invention preferably consists of particles having a volume average particle diameter of 100 μm or less and a specific surface area of 1 rri''/g or more, more preferably Volume average particle size is 5μ
m or more and 70 μm or less, specific surface area of 3 rn'/g or more, particularly preferably volume average particle size of LOum or more and 50 L
tm or less, and the specific surface area is 5rn''78 or more.

Next, the metal that can be alloyed with the active material and that constitutes the mixture material used for the carrier of the negative electrode body according to the present invention is
Alternatively, an alkali metal mainly composed of Li, usually a metal that can be alloyed with Li, is used. For example, aluminum (At
), lead (pb), zinc (Zn), tin (Sn), bismuth fBi), indium (1 mouth), magnesium f
Mg), gallium (Gal, cadmium (Cd),
Silver (Ag), silicon fsi), boron (B), gold (Au
), platinum [Ptl, palladium FPdl, antimony (Sb1, etc.), preferably /1.1.Pb,
In, Bi and Cd, more preferably A
1. These are Pb and In, and particularly preferably AI.

The metal that can be alloyed with the above active material preferably has a volume average particle size of 50 μm or less, more preferably 30 μm or less,
Particularly preferred are fine particles with a diameter of 10 um or less.

In the mixture material constituting the carrier of the negative electrode body, the mixed form of the carbonaceous substance and the metal that can be alloyed with the active material includes a form in which the carbonaceous substance adheres to the surface of the metal particles and the metal particles are coated with the carbonaceous substance. , a form in which several metal fine particles are dispersed inside carbonaceous material particles, a form in which carbonaceous material particles and metal particles exist independently, etc. can be taken.

Furthermore, the ratio of carbonaceous substances in this mixture material is 2
0 to 98% by weight, preferably 50 to 95% by weight, more preferably 70 to 90% by weight, and the proportion of the metal that can be alloyed with the active material is 2 to 80% by weight, preferably 5 to 50% by weight, and Preferably it is 10 to 30% by weight.

In the present invention, the above-mentioned mixture material is obtained by thermally decomposing an organic compound and carbonizing it, and at the same time thermally decomposing an organometallic compound containing a metal that can be alloyed with the active material. It is characterized by

In order to obtain the mixture material that constitutes the carrier.

There are two methods described below.

First, the first method will be described.

Organic compounds used include, for example, benzene or its carboxylic acids or anhydrides, derivatives such as carboxylic acid imides, i.e. 1.2,4.5-
Tetracarboxylic acid, its dianhydride or its diimide, etc.: Toluene, xylene, etc.: For example, naphthalene, phenanthrene.

Monocyclic hydrocarbon compounds with three or more members such as anthracene, triphenylene, pyrene, chrysene, naphthacene, bicene, perylene, pentaphene, and pentacene are
A fused cyclic hydrocarbon compound formed by condensing two or more cyclic hydrocarbons, or
Various pitches whose main components are derivatives of the above compounds such as carboxylic acids, carboxylic acid anhydrides, and carboxylic acid imides, and mixtures of the above compounds: for example, indole, isoindole, quinoline, isoquinoline, and quinoxaline.

Phthalazine, carbazole, acridine, phenazine,
A condensed heterocyclic compound formed by at least two or more 3-membered or more-membered monocyclic compounds bonded to each other, or bonded to one or more 3- or more-membered monocyclic hydrocarbon compounds, such as zenatridine, each of the above. Examples include derivatives of compounds such as carboxylic acids, carboxylic acid anhydrides, and carboxylic acid imides.

The above-mentioned organic compound is thermally decomposed and carbonized to obtain the above-mentioned carbonaceous material. At this time, an organometallic compound having a metal that can be alloyed with the active material is simultaneously thermally decomposed in the same space.

As the organometallic compound containing a metal that can be alloyed with the active material used, a compound in which a metal that can be alloyed with the active material exemplified above and an arbitrary organic substituent are bonded can be used, Preferably, MR, --R, (M represents the above-mentioned metal.

R1...R, represents n alkyl groups bonded to metal M). Specific examples include triethylaluminum, diethylaluminum hydride, tripropylaluminum, and tributylaluminum.

The mixture material constituting the carrier of the negative electrode body according to the present invention contains the above-mentioned organic compound and the above-mentioned organometallic compound.
It is obtained by thermal decomposition and carbonization under a flow of inert gas such as N2 and argon simultaneously in the same space. Also,
Thermal decomposition and carbonization can be carried out under reduced pressure, or when the organic group of the organometallic compound has an oxygen-containing group such as an alkoxy group, in order to prevent the oxidation of the metal produced, Thermal decomposition and carbonization can also be carried out in an atmosphere of a reducing gas such as hydrogen.

Thermal decomposition and carbonization are usually carried out at a temperature of 200 to 1000°C, preferably 200°C to (the melting point of the metal to be produced).

Furthermore, after carrying out the above pyrolysis and carbonization, 1
000°C ~ (boiling point of metal produced), preferably 10
Carbonization is further advanced by heating at a temperature of 00°C to (the boiling point of the metal to be produced -300°C), more preferably 1000°C to (the boiling point of the metal to be produced -500°C), and the above-mentioned carbonaceous material is It can be adjusted as much as possible.

In the first method, specifically, for example, in the same reaction vessel,
This can be carried out by introducing the above-mentioned organic compound and organometallic compound in a gas phase together with an inert gas flow and heating them to perform thermal decomposition and carbonization to form a mixture of carbonaceous material and metal particles.

Next, the second method will be described.

Organic compounds used here include, for example, cellulose resins: phenolic resins: acrylic resins such as polyacrylonitrile and poly(α-halogenated acrylonitrile); halogenated resins such as polyvinyl chloride, polyvinylidene chloride, and polychlorinated vinyl chloride. Vinyl resin; polyamide-imide resin: polyamide resin: polyacetylene, poly(
Examples include arbitrary organic polymer compounds such as conjugated resins such as p-phenylene).

When the organic compound described above is thermally decomposed and carbonized, the organic metal compound used in the first method described above can be simultaneously thermally decomposed in the same space to obtain a mixture material constituting the support. can.

Thermal decomposition and carbonization are usually carried out at 200 to 1000°C under a flow of inert gas. Furthermore, after that, under an inert gas atmosphere, under normal pressure or a pressure of 1 to 10 kg/cm2, the temperature is preferably 1000°C to 1500°C (the boiling point of the metal to be formed). boiling point -300
℃), more preferably at a temperature of 1600°C to 500°C (boiling point of the metal to be produced) to advance carbonization, and can be adjusted to obtain the carbonaceous material described below.

In the second method, for example, an organometallic compound is premixed with an organic compound or impregnated with the organic compound and heated under a flow of inert gas or under reduced pressure to thermally decompose and carbonize. This can be carried out by making a mixture of Note that the organometallic compound may be dissolved in a suitable solvent and used as a solution.

(Thus, a mixture material of the carbonaceous material which is the material of the support and a metal that can be alloyed with the active material is obtained.

In addition, the mixture material constituting the carrier of the negative electrode body according to the present invention may contain a conductive agent, a binder, etc. in addition to the above-mentioned mixture of carbonaceous material and metal that can be alloyed with the active material. .

As the conductive agent, expanded graphite, metal powder, etc. can be added in an amount usually less than 50% by weight, preferably less than 30% by weight.

Further, as the binder, less than 50% by weight, preferably less than 30% by weight, particularly preferably 5% by weight or more and less than 10% by weight of powder such as polyolefin resin can be added.

The carrier can be formed by compression molding the above-mentioned materials as they are, or by adding a binder, etc., or by mixing the above-mentioned materials with a binder, etc. dissolved or suspended in a solvent. It can be manufactured by a method of coating and molding on a wire mesh or the like of a current collector.

Methods for further supporting the active material on the support obtained in this way include chemical methods, electrochemical methods, physical methods, etc. A method of electrolytic impregnation in which the above-mentioned support is immersed in an electrolytic solution and lithium is used as a counter electrode, and this support is used as an anode.Simply, the above-mentioned support and lithium are electrically contacted. , a method of immersing the carrier in an electrolytic solution, a method of mixing lithium powder in the process of obtaining a molded body of the carrier, etc. can be applied.

In this way, Li ions or alkano metal ions are doped into the carbonaceous material of the support, and are further contained in at least a portion of the metal that can be alloyed with the active material in the support, and are supported therein. .

Note that supporting the active material as described above is not limited to the carrier of the negative electrode body, but may also be carried out on the carrier of the positive electrode body or both electrodes. The supported amount of the active material is preferably: (1) 1 to 20% by weight, more preferably 3 to 10% by weight, based on the above carbonaceous material; 1 to 80 mol%, more preferably 5 to 60 mol%, particularly preferably 10 to 60 mol%
50 mol%, most preferably 20-50 mol%.

If the amount of active material supported in the negative electrode body is smaller than the range limited in above ■ and ■, the amount of active material supported will be too small and the battery capacity will decrease; if it is larger than this range, the negative electrode will deteriorate during charging and discharging. The change in volume of the body becomes large, resulting in poor current collection, and lithium dendrites are easily formed, resulting in a significant reduction in charge/discharge cycle life.

Next, the configuration of the secondary battery of the present invention will be explained with reference to the drawings. In Figure 1, a positive electrode body (2) is attached to the bottom of the positive electrode can (1) inside the positive electrode can (1) which also serves as a positive electrode terminal. The cathode body stored is not particularly limited, but for example,
It is preferable to consist of a metal chalcogen compound that releases or acquires alkali metal cations such as Li ions during charge/discharge reactions. Examples of such metal chalcogen compounds include vanadium oxide, vanadium sulfide, and molybdenum oxide. , molybdenum sulfide, manganese oxide, chromium oxide, titanium oxide, titanium sulfide, and composite oxides and composite sulfides of these. Preferably Cr3O8, V20s, V-01
3, VO2, Cr, 0-1M n O2, TlO2, M
OV 20 a, T i S z, V2S5. Mo52
, M o S 3, vS2, Cr Q, 2SV. 7.
S2, Cr o, s Vo, s S z, etc. In addition, oxides such as Li Co Oz and Wo 3, Cu
S, F eo, i, Vo7ss 2, Nao, +C
Sulfides such as r5z, Ni PS! , FePSa, etc., phosphorus, sulfur compounds, VSez, N b S e 1
It is also possible to use serrene compounds such as the following. It is also possible to use amorphous metal chalcogen compounds, especially amorphous V2C.

A positive electrode body (2) and a negative electrode body (4) are opposed to each other with a separator (3) interposed therebetween.

The separator (3) that holds the electrolyte is made of a material with excellent liquid retention properties, such as a nonwoven fabric made of polyolefin resin. This separator (3) contains brobylene carbonate 1-. LiCj20.
.

LiBF4. LiAsF5. It is impregnated with a nonaqueous electrolyte solution of a predetermined concentration in which an electrolyte such as LiPFe is dissolved.

Furthermore, a solid electrolyte that is a conductor of Li or alkali metal ions can be interposed between the positive electrode body and the negative electrode body.

The negative electrode body (4) is made of a carrier made of a mixture material of a carbonaceous material having the above-mentioned characteristics, an active material, and a metal that can be alloyed with.
It supports an active material and is installed in a negative electrode can (5) which also serves as a negative electrode terminal.

These positive electrode body (2), separator (3), and negative electrode body (4) constitute a power generation element as a whole. Then, this power generation element is housed in a battery container consisting of a positive electrode can (1) and a negative electrode can (5), and a battery is assembled.

6 is an insulating backing that separates the positive and negative electrode bodies, and the battery is sealed by bending the opening of the positive electrode can (1) inward.

In the secondary battery of the present invention, Li ions (or alkali metal ions mainly composed of Li) supported in the negative electrode body are released during discharge, and Li ions are transferred to the carbonaceous material in the carrier during charging. Due to the accumulation of Li ions in the metal that can be alloyed with the dope, Li ions are supported on the carrier of the negative electrode body.

By carrying and releasing Li ions in this manner, the charge/discharge cycle of the battery is repeated.

In the secondary battery of the present invention, by using a carrier made of a mixture material of the above-mentioned carbonaceous material and a metal that can be alloyed with the active material in the negative electrode body, a large amount of the active material can be supported on the negative electrode body. Moreover, since it is possible to smoothly repeat loading and releasing the active material during charging and discharging, it exhibits unprecedented large capacity and excellent charging and discharging characteristics.

In addition, in the present invention, elemental analysis and xI! Each measurement of wide-angle diffraction was carried out by the following method.

"Elemental analysis" Samples were dried under reduced pressure at 120°C for about 15 hours, then dried on a hot plate in a dry box at 100°C for 1 hour.6The samples were then sampled in an aluminum cup in an argon atmosphere to analyze CO generated by combustion.
□ Calculate the carbon content from the weight of the gas, and also calculate the generated H, O
Determine the hydrogen content from the weight of. In the Examples of the present invention described later, measurements were made using a PerkinElmer 240C elemental analyzer.

"X#! Wide-angle diffraction" (1) Interplanar spacing (doaz) of (002) plane and (1,
10) Interplanar spacing (d,,.) If the carbonaceous material is a powder, it is used as it is, or if it is in the form of minute pieces, it is powdered in an agate mortar, and the amount of high purity for X-ray standards is about 15% by weight based on the sample. Silicon powder is added as an internal standard substance, mixed, packed into a sample cell, monochromated with a graphite monochromator, and α-rays are used as a radiation source, and wide-angle X-ray diffraction curves are measured using the reflection diffractometer method.6 curves For the correction, the following simple method is used without making corrections for so-called Lorentz factors, polarization factors, absorption factors, atomic scattering factors, etc. That is, baselines of curves corresponding to (002) and (110) diffraction are drawn, and the real intensities from the baseline are plotted again to obtain correction curves for the (002) and (110) planes. Find the midpoint of the line segment where a line parallel to the angular axis drawn at two-thirds of the peak height of this curve intersects with the diffraction curve, correct the angle at the midpoint using an internal standard, and calculate this. The wavelength of the CuKa line should be twice as long as it should be. ,
and do by the following Bragg equation. 2 and d,.

seek.

E: 1.5418 people θ, θ′: d Q (l R, d Diffraction angle corresponding to I I O (2) Size of crystallite in c-axis and a-axis directions:
Lc: La In the corrected diffraction curve obtained in the previous section, the size of the crystallites in the C-axis and a-axis directions is determined from the following equation using the so-called half value β at a position half the peak height.

β・cosθ β・cosθ′ There are various discussions about the shape factor K, but K=0.90
was used. Well, θ and θ' have the same meaning as in the previous section.

(Example) The present invention will be explained below with reference to Examples.

(1) Production of positive electrode body 5 g of M n Ox powder calcined at 470°C and 0.5 g of powdered polytetrafluoroethylene are kneaded, and the resulting mixed wire is roll-formed to a thickness of 0.4 mm. It was made into a sheet.

One side of this sheet is a current collector with a wire diameter of 0. 1mm, 6
(2) Manufacture of negative electrode body 500 rng of naphthalene-1,4,5,8-tetracarboxylic dianhydride powder was impregnated with triisobutylaluminum. Set in an electric heating furnace and under Ar gas flow, 1
Raise the temperature to 350°C at a heating rate of 5°C/min, and then
Hold at 50°C for 30 minutes, naphthalene-1,4,5,
Thermal decomposition and carbonization of 8-tetracarboxylic dianhydride and decomposition of triisobutylaluminum were carried out.

Thereafter, this was further heated to 600°C at a heating rate of 15°C/min.
The temperature was raised to 600° C. and maintained at 600° C. for 30 minutes to further advance carbonization.

In this way, a mixture material containing 90% by weight of carbonaceous material and 10% by weight of AI2 metal was obtained.

As a result of X-ray wide-angle diffraction analysis, the carbonaceous material in this mixture material has the following properties: d = 3.66 people, Lc = 13.5
It was a person.

After mixing 5% by weight of polyethylene powder with an average particle size of 5μm into this mixture material, it was compression molded to a thickness of 0.5n+.
It was made into a pellet-like carrier of m.

Next, the support pellet was added to the Li ion concentration above mol/2.
The pellet is immersed in an electrolytic solution, and the pellet is used as an anode.
It was subjected to electrolytic treatment using as a cathode.

The electrolytic treatment conditions were a bath temperature of 20° C. and a current density of 0.5 mA/ba, and 12+aAh of Li was supported on the support to form a negative electrode body.

(3) Assembly of the battery The above-mentioned positive electrode body was installed in a stainless steel positive electrode can with the current collector facing down, and after placing a polypropylene nonwoven fabric as a separator on top of it, Li C420 was placed there.
4 was dissolved in propylene carbonate at a concentration of 1 mol/2 to impregnate it with a non-aqueous electrolyte. Then put the above negative electrode body on top! ! The power generation element was constructed by placing the

Note that the positive electrode body was also subjected to the same electrolytic treatment as the negative electrode body before being incorporated into a battery, so that it supported Li with a capacity of 4 mAh. The electrolytic treatment conditions were a bath temperature of 20°C and a current density of 0.5 A.
/cm''. Thus, a button-shaped secondary battery as shown in the figure was manufactured.

(4) Characteristics of the battery The battery thus manufactured was repeatedly charged and discharged at a constant current of 750 μA with a battery voltage of 3.2 V at the upper limit and 1.8 V at the lower limit for cycle evaluation. The performance at the 60th cycle and the 200th cycle is shown in the table.

compared to le (1) Manufacture of positive electrode body A positive electrode body was manufactured in the same manner as in the example.

(2) Manufacture of negative electrode body Thermal decomposition and carbonization were carried out in the same manner as in Example except that only 500 mg of naphthalene-1,4,5,8-tetracarboxylic dianhydride powder was used and tributylaluminum was not infiltrated. A carbonaceous material was obtained.

As a result of X-ray wide-angle diffraction analysis, this carbonaceous material was found to be doom
= 3.65 people, Lc = 13.7 people.

This was made into a pellet-like support in the same manner as in the example, and subjected to the same electrolytic treatment as in the example to support 12 mAh of Li to form a negative electrode body.

(3) Battery assembly A battery was assembled in the same manner as in the example.

(4) Battery characteristics Measure the battery characteristics under the same conditions as in the example,
The results are also listed in the table.

Table [Effects of the Invention] As is clear from the above explanation, the secondary battery of the present invention has a long charge-discharge cycle life, good charge-discharge characteristics at large currents, and has an active material during charging. Since Li or alkali metals mainly composed of Li can be stably fixed on the carrier, stable high capacity, that is, large current discharge is possible, and self-discharge characteristics are also good (highly reliable batteries Therefore, its industrial value is great.

Although the explanation so far has been made regarding a secondary battery having a button-shaped structure, the technical idea of the present invention is not limited to this structure (for example, it may be used in other shapes such as cylindrical, flat, square, etc.). It can also be applied to secondary batteries.

[Brief explanation of the drawing]

The figure is a longitudinal sectional view of a secondary battery having a button-shaped structure, which is an embodiment of the present invention.

Claims (1)

[Scope of Claims] A secondary battery comprising a negative electrode body comprising an active material and a carrier supporting the active material, wherein: (a) the active material is lithium or an alkali metal mainly composed of lithium; (b) The carrier has a lattice distance of (002) plane (d_0_
0_2) is 3.37 Å or more: and the crystallite size (Lc) in the c-axis direction is 150 Å or less: a mixture material of a carbonaceous material and a metal that can be alloyed with the active material, and the mixture material is A secondary battery characterized in that the secondary battery is obtained by thermally decomposing an organic compound, carbonizing it, and at the same time thermally decomposing an organic metal compound containing a metal that can be alloyed with the active material.