JPH02121258A - Secondary cell - Google Patents

Abstract

PURPOSE:To improve the cell capacity and the self-discharge property by making an active substance with lithium or an alkaline metal including lithium as the main component, and a holding body with a composite material obtained by making an organic metal compound including a metal to alloy with an active substance react to a specific carbonaceous substance. CONSTITUTION:The active substance is lithium or an alkaline metal including lithium as the main component, and the active substance holding body has the atomic ratio of hydrogen/carbon less than 0.15; the surface interval of the 002 surface on the X-ray wide-angle diffraction method 3.37Angstrom or more; and the size of the crystalline in the c axis direction less than 150Angstrom . Under the condition an organic metal compound including a metal to alloy with an active substance is contacted to such a carbonaceous substance, a composite material of a carbonaceous substance obtained by pyrolyzing the organic metal compound and the metal to alloy with the active substance is used to form the cell. As a result, the charge and discharge cycle is extended, and the charge and discharge property under a large current is also improved.

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 chalcogen compound of a transition metal such as T i S 2 or Mo S 2, and the negative electrode body is L
BACKGROUND ART Efforts are being made to commercialize secondary batteries, which are alkali metals mainly composed of L or Ll, and have a high energy density.

Further, secondary batteries using a conductive polymer such as polyacetylene for the positive electrode and an alkanometal mainly composed of Ll or 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 foil itself is an alkali metal foil mainly composed of Ll or Ll.

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. If this continues to grow, the dendrite-like metal Li deposits will eventually penetrate the separator and reach the positive electrode body, 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 the negative electrode by using a carbonaceous material carrier prepared by firing an organic compound 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 i71 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.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the present inventors have conducted intensive research on negative electrode bodies, and have found that the negative electrode body is constructed by carrying an active material on a support having the characteristics described below. Then, they discovered that it is effective for achieving the above-mentioned object, and arrived at the present invention.

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 support has (a) a hydrogen/carbon atomic ratio of less than 0.015;

and a carbonaceous material in which the interplanar spacing ([''oo2) of the (002) plane determined by the Dr) XFA wide f/'1 diffraction method is 337 Å or more: 8, and the crystallite size (Lc) in the C-axis direction is 150 Å or less. A composite of a carbonaceous material and a metal that can be alloyed with the active material, which is obtained by thermally decomposing the organometallic compound while in contact with the organometallic compound containing the metal that can be alloyed with the active material. It is characterized by being made of 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 support for the active material constituting the negative electrode body in the present invention is produced by heating an organometallic compound containing a metal that can be alloyed with the active material in a state where the carbonaceous material having the characteristics described below is brought into contact with the organometallic compound containing a metal that can be alloyed with the active material. Consists of a composite material of carbonaceous material and metal obtained by decomposition.

That is, the carbonaceous material used in the present invention has a hydrogen/carbon atomic ratio (H/C) of less than 0.15, and xtji
l Planar spacing d of (002) plane by wide-angle diffraction method. . 2 is 3
．． 37 Å or more, the crystallite size (Lc) in the C-axis direction is 1
It has the characteristic that it is 50 Å or less.

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.

1-1/C is preferably less than 0.10, more preferably less than 0.07, particularly preferably less than 0.05.6 Also, the interplanar spacing (doo2) of the (002) plane is preferably 339 to 3. .75 people, more preferably 3,41-3
．． 70 people, particularly preferably 345 to 3.70 people, 1 good is also preferably 3.51 to 3.70 people: the crystallite size in the C axis direction is 1, c is preferably 5 to 150 people, More preferably 10 to 80 people, particularly preferably 12 to 7 people
There are 0 people.

If any of these parameters, namely H/C, d, o2, and Lc, deviate from the above range, the overvoltage during charging and discharging in the negative electrode body will increase, and as a result, gas will be generated from the negative electrode body. This not only significantly impairs the safety of the battery (charge/discharge characteristics also deteriorate).

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

That is, in Raman spectrum analysis using argon ion laser light with a wavelength of 5145, the G value defined by the following formula is preferably less than 2.5,
More preferably less than 20, particularly preferably 02
That's 12 outstanding results.

Here, the G value is the wavelength of 5145 for the carbonaceous material mentioned above.
In the spectrum intensity curve recorded on the chart when Raman spectrum analysis was performed using human argon ion laser light, the integral value (area intensity) of the spectrum intensity within the range of wave number 1580 ± 100 cm-' is calculated as wave number 1
It refers to the value divided by the area intensity within the range of 360±100C (11-'), and corresponds to a measure of the degree of graphitization of the carbonaceous material.

In other words, this carbonaceous material has a crystalline portion and an amorphous portion, and the G value can be said to be a parameter indicating the ratio of the crystalline portion in this carbonaceous structure. If so, it is desirable that the following conditions be satisfied.

That is, the interplanar spacing (d, 8102 times the distance a o (= 2 d +
to) is preferably 2.38 to 2.47 people, more preferably 2.39 to 2.46A: the crystallite size La in the a-axis direction is preferably 10 Å or more, more preferably 15 people to 150 people, particularly preferably 19 to 7 people
There are 0 people.

The carbonaceous material used for the carrier of the negative electrode body according to the present invention preferably has a volume average particle size of 500 μm or less, more preferably 05 μm or more and 300 μm or less, particularly preferably 11 m or more and 150 μm or less, and most preferably 5 μm or less.
Particles with a size of 5 m or more and 100 μm or less.

Further, the carbonaceous material particles have pores inside, and the total pore volume is preferably 1.5xlO-"mff/g or more, more preferably 2,QxlO-"mff/g or more.
3m! 27g or more, more preferably 3, Qx 10-
'3mj2/g or more, particularly preferably 4, OXIO-3
mβ/g or more. In addition, the average pore radius is 8 to 10
Preferably 0 people, more preferably 10 to 80 people
More preferably 12 to 60 people, particularly preferably 14 to 40 people.

The total pore volume and average pore radius were calculated using the constant volume method.
It is determined by measuring the amount of gas adsorbed on a sample under pressure.

That is, in the present invention, the total pore volume and average pore radius mean those determined as follows.

The total pore volume is the relative pressure P/P determined using the constant volume method, assuming that the pores are filled with liquid nitrogen, for example.
, = 0.995 (P: vapor pressure of adsorbed gas, Po: saturated vapor pressure of adsorbed gas at cooling temperature), calculate the total volume (V, .5) of nitrogen gas adsorbed, and then use the following equation, [Equation P is the atmospheric pressure fkgf/cm2), T is the measurement temperature (K), and V is the molecular volume of the adsorbed gas (cm3).
1 mol; 34.7 for N2), V, is the liquid nitrogen volume (am3), and the amount of liquid nitrogen filled in the pores (V,
, ql.

Next, the average pore radius (γ,) is calculated from vll obtained from the above equation (1) and the BET specific surface area (S) of the sample.
It is calculated by converting using the following formula. Note that the pores are assumed to be cylindrical.

Further, the carbonaceous material used for the carrier of the negative electrode body according to the present invention has an average cross-sectional radius of 1 mm or less, preferably 500 μm or less, more preferably 0.2 μm or more and 200 μm or less, and even more preferably 0.5 μm or more. 100μ
m or less, particularly preferably 2 μm or more and 50 μm or less,
Fiber-like or rod-like materials are also desirable.

In addition, the fibers of these carbonaceous materials also have pores, as in the case of the particulate carbonaceous materials described above, and the total pore volume is 1.5XlO-3mQ/g or more, Preferably, the average pore radius is between 8 and 100 pores.

The above-mentioned carbonaceous material can be obtained by carbonizing an organic compound by heating and decomposing it at a temperature of 300 to 3000° C. usually under an inert gas (M).

Examples of the if compound as a starting source include, for example, cell [J-S, phenolic resin: polyacrylonitrile, acrylic resin such as poly(α-halogenated acrylonitrile), polyvinyl chloride, polychlorinated Vinylidene, halogenated vinyl resins such as polychlorinated vinyl chloride, polyamideimide resins, polyamide resins, polyacetylene,
Any organic polymer compound such as conjugated resin such as poly(p-phenylene) 1 For example, naphthalene. Phenanthrene, anthracene, triphenylene.

Iifm with three or more members such as pyrene, chrysene, naphthacene, bisene, perylene, pentaphene, and pentacene
A fused cyclic hydrocarbon compound formed by condensing two to seven hydrocarbon compounds, or a derivative of the above compound such as carboxylic acid, carboxylic acid anhydride, or carboxylic acid imide, or a mixture of the above compounds as the main component. Various pitches such as: intole, isoindole, quinoline, isoquinoline.

At least two or more heteroheavy ring compounds having three or more members such as quinoxaline, fuclazine, carbazole, acunodine, phenazine, and zenatridine are bonded to each other,
or fused heterocyclic compounds formed by bonding with one or more 3-membered or F monocyclic hydrocarbon compounds; derivatives of the above compounds such as carboxylic acids, carboxylic acid anhydrides, and carboxylic acid imides; Derivatives thereof such as carboxylic acids, carboxylic acid anhydrides, carboxylic acid imides, i.e. 1
．． ．． Examples include 2.4.5-tetracarboxylic acid, its anhydride or its diimide, toluene, and xylene.

Alternatively, a carbonaceous material such as carbon black may be used as a starting source and further heated to appropriately advance carbonization to form the carbonaceous material constituting the negative electrode body according to the present invention.

The carrier for the active material constituting the negative electrode body according to the present invention is prepared by contacting the above-mentioned specific carbonaceous material with an organometallic compound containing a metal that can be alloyed with the active material. Since it is made of a composite material of a carbonaceous material and a metal obtained by thermal decomposition, the organometallic compound containing a metal that can be alloyed with the active material will be described next.

Since the active material is Li or an alkanometal mainly composed of Li, the organometallic compound containing a metal that can be alloyed with the active material is usually an organometallic compound containing a metal that can be alloyed with Li.

Examples of such organometallic compounds include aluminum (At), lead (PB), zinc (2nl), and tin (2nl).
Sn), bismuth (old), indium (Inl, magnesium fMgl, gallium (Ga), cadmium (Cd)
), silicon (Si), antimony (sb), palladium (fPd), boron (B), silver (fAg), etc., and preferably AI, Pb, In
, an organometallic compound containing Bi and Cd,
More preferably A1. It is an organometallic compound containing Pb or Bi, and particularly preferably an organometallic compound containing AI.

The above organometallic compound has the general formula: MRo (M
represents the above-mentioned metal, and R, , represents n alkyl groups bonded to the metal M). Organometallic compounds are often used.

In the above formula, examples of the alkyl group represented by R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5ec-butyl group, tert-butyl group, pentyl group, and hexyl group.

Specific examples of particularly preferred organometallic compounds include organoaluminum compounds such as triethylaluminum, tripropylaluminum, tributylaluminum, and tripentylaluminum.

The above-mentioned organometallic compounds can be used alone or in combination of two or more.

Further, the above-mentioned organometallic compound may be used in combination with a small proportion of another organometallic compound containing a metal other than the metal that can be alloyed with the active material.

The active material carrier constituting the negative electrode body according to the present invention is made of a mixture material obtained by thermally decomposing the above-mentioned organometallic compound while the above-mentioned carbonaceous material is in contact with the organometallic compound. .

Here, thermally decomposing the organometallic compound in a state where the organometallic compound is in contact with the carbonaceous material means thermally decomposing the organometallic compound so that at least a portion of the organometallic compound is in contact with the above-mentioned carbonaceous material, For example, a method of impregnating a carbonaceous material with an organometallic compound and thermally decomposing it, or a method of dissolving the organometallic compound in a stable and inert organic solvent up to its decomposition temperature, and immersing the carbonaceous material in this solution and thermally decomposing it. etc. are used. At this time, the organometallic compound is usually used in a weight ratio of 0.03 to 10 to 1 of the carbonaceous material.

The heating temperature during thermal decomposition is below the melting point of the metal contained in the organometallic compound, preferably 1.0 below the melting point of the metal.
The temperature is 0°C or more lower, more preferably 200°C or more lower than the melting point of the metal. Specifically, when an organoaluminum compound is used, preferably 1
50°C or more and 500°C or less, more preferably 200°
C or more and 400°C or less, particularly preferably 250°C or more3
Select a pyrolysis temperature below 80°C.

Heating time varies depending on the organometallic compound used, but
When an organoaluminum compound is used, the heating time is 30 seconds to 10 hours, more preferably 1 minute to 3 hours, and even more preferably 3 hours.
The time period is from minutes to 1 hour, particularly preferably from 5 minutes to 30 minutes.

The atmosphere during heating is usually an inert gas atmosphere such as N2 or Ar.

Next, the forms that the mixture material obtained by pyrolysis takes include, for example, a composite form in which the surface of a carbonaceous material is coated with a metal, and a form in which a metal is precipitated in the form of particles on the surface of a carbonaceous material. Examples include a composite form or a composite form in which both are mixed. These composite forms can be adjusted by selecting production conditions such as the ratio of the carbonaceous material to the organometallic compound, the concentration of the organometallic compound, and the decomposition temperature of the organometallic compound.

The content of the metal that can be alloyed with the active material in the above kneaded material is preferably 3% by weight or more and less than 70% by weight, more preferably 5% by weight or more and less than 50% by weight, particularly preferably 10% by weight or more and less than 30% by weight. less than %.

Further, 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 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, such as a powder such as a polyolefin resin, can be added.

The carrier can be manufactured, for example, by compression molding the above-mentioned materials as they are or by adding a binder or the like.

Methods for further supporting the active material on the support obtained in this way include chemical methods, electrochemical methods, and physical methods. 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 alkali 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 such active material may be supported not only on the carrier of the negative electrode body but also on the carrier of the positive electrode body or on both electrodes.

Further, the amount of active material supported on the carrier of the negative electrode body according to the present invention is preferably as follows.

■ 1 to 20% by weight, more preferably 3 to 10% by weight based on the above carbonaceous material; and ■ 1 to 80% by mole, more preferably 1 to 80% by weight based on the metal that can be alloyed with the active material. 5-60 mol%, particularly preferably 10-60 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 be small. The volume change of the negative electrode 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 structure of the secondary battery of the present invention will be explained with reference to the drawings. In Fig. 1, a positive electrode body (2) is attached to the bottom of the positive electrode can (H) in a positive electrode can (1) which also serves as a positive electrode terminal. This positive electrode body is not particularly limited, but for example,
It is preferable to use a metal chalcogen compound that releases or acquires alkali metal cations such as Li ions during charging and discharging reactions. Such metal chalcogen compounds include vanadium oxide, vanadium sulfide, molybdenum oxide, molybdenum sulfide, manganese oxide, chromium oxide, titanium oxide, titanium sulfide, and these. Examples include composite oxides and composite sulfides. Preferably.

Cri Oa, Va 0S, Va O+z, vo2
,CraOs,MnO2,Tiot,MoVz
Os, T i Sa, Va Ss, vo32, M
oSi, vS2, Cr a, zsV o, ts S
2, Cro, s vo, s S2, etc. Also, L
I Mn204, L 10H・Mn0i, L
i Oxides such as COO2 and WOx, Cu S, Fe
It is also possible to use sulfides such as a, asVo, tss z, Nao, +Cr5s, phosphorus compounds such as N1PSx, FePSs, and selenium compounds such as VSea and Nb5es.

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) is made of LiCl20. .

LIBF4. It is impregnated with a non-aqueous electrolyte of a predetermined concentration in which an electrolyte such as LtAsFs or LtPFa 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) has an active material supported on a support made of a composite material of the above-mentioned carbonaceous material and a metal that can be alloyed with the active material. It is installed in

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 -1 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.

The secondary battery of the present invention allows the negative electrode body to support a large amount of the active material by using a carrier made of a composite material of the above-mentioned carbonaceous material and a metal that can be alloyed with the active material. In addition, the active material can be smoothly loaded and released repeatedly during charging and discharging, resulting in an unprecedentedly large capacity and excellent charging and discharging characteristics.

In the present invention, elemental analysis and X-ray wide-angle diffraction measurements were carried out by the following methods.

"Elemental Analysis" Samples were dried under reduced pressure at 120°C for approximately 15 hours, then dried on a hot plate in a dry box at 100°C for 1 hour. Then, the sample was collected in an aluminum cup in an argon atmosphere, and the carbon generated by combustion was collected.
The carbon content can be determined from the weight of O□ gas, and the generated H2
Determine the hydrogen content from the weight of O. In the Examples of the present invention described later, measurements were made using a PerkinElmer 240C elemental analyzer.

"X-ray wide-angle diffraction" (1) Interplanar spacing of (002) plane (dooal and (11
0) 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 approximately 15% by weight based on the sample. Silicon powder is added as an internal standard substance, mixed, packed into a sample cell, and made monochromatic with a graphite monochromator. A wide-angle X-ray diffraction curve is measured using the reflection diffraction meter method as a radiation source. 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. i.e. (002), and (+, 1.O)
A baseline of a curve corresponding to diffraction is drawn, and the real intensity from the baseline is plotted again to obtain correction curves for the (002) plane and the (110) plane. 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. d by the following Black formula from the α-ray elongation to Cu. . 2 and d
Find 116.

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

K −Eβ 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) Manufacture of positive electrode body 5 g of MnO2 powder calcined at 470°C and 0.5 g of powdered polytetrafluoroethylene were kneaded, and the resulting mixed wire was roll-formed to a thickness of 0.411+ m. It was made into a sheet.

One side of this sheet was crimped to a current collector, a stainless steel net with a wire diameter of 0.1 and 60 mesh, to form a positive electrode body.

(2) Manufacture of negative electrode body Crystalline cellulose particles were set in an electric heating furnace, heated to 1000°C at a heating rate of 200°C/hr under N2 gas flow, and further held at 1000°C for 1 hour. The particles of carbonaceous material obtained by cooling this were set in a separate electric heating furnace, and heated to 1800°C under a flow of N2 gas at a heating rate of ], OOO°C/hr, and further heated to 1800°C. It was held for 1 hour.

The carbonaceous material thus obtained was placed in a 500 mJ2 agate container, and two agate poles with a diameter of 2
Six 5mm+ agate balls and 16 agate balls 20mm in diameter were added and crushed for 3 minutes.

This carbonaceous material was analyzed by elemental analysis, X-ray wide-angle diffraction, particle size distribution,
As a result of analysis such as specific surface area measurement, it had the following characteristics.

Hydrogen/carbon (H/C) = 0.04 doo2 = 3-59 people, Lc = 14 people ao (2dzo
l = 2.41 persons, La = 25 persons Volume average particle diameter = 38 μm Specific surface area (BET) = 8.2 rn''/g Next, the above carbonaceous material was brought into contact with triisobutylaluminum and thermally decomposed. 5g of carbonaceous material was added to a 1 mol/a hexane solution of triisobutylaluminum (t8.5r).
After adding it to nJ2 and thoroughly impregnating it, it was heated for 300 minutes under a N2 stream.
Raise the temperature to ``C, further heat at 300℃ for 30 minutes,
Pyrolysis was performed.

(Therefore, 10% by weight of aluminum is mixed.

A composite material of the carbonaceous material and aluminum described above was obtained.

After mixing 7% by weight of polyethylene powder with an average particle size of 5LLm, it was compression molded to a thickness of 0. It was made into a pellet-like carrier of 5+mm.

Next, the support pellet was adjusted to a Li ion concentration of 1 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 i as a cathode.

The electrolytic treatment conditions were a bath temperature of 20°C and a current density of 0.511IA.
/c112, and 12+oAh of Li was supported on the carrier to form a negative electrode body.

(3) Assembling the battery Place the above-mentioned positive electrode body on a stainless steel positive electrode jig with the current collector facing down, place several polypropylene nonwoven fabrics as separators on top of it, and then add LiCl204 at a concentration of 1. It was impregnated with a non-aqueous electrolyte dissolved in propylene carbonate at mol/β. Then, the negative electrode body was placed thereon to form a power generation element.

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 5 mAh. The electrolytic treatment conditions are: bath temperature 20'C1 current density 0,5
It was mA/cm2. In this way, a button-shaped secondary battery as shown in the figure was manufactured.

(4) Characteristics of the Battery The battery manufactured in this way was repeatedly charged and discharged at a constant current of 8oOuA within a range of battery voltage from 3.3V to 1.8V to perform cycle evaluation. Table 1 shows the performance at the IO cycle and the 90th cycle.

Further, after the 10th cycle of charging was completed, one circuit was opened and left for 60 days, and then the 11th cycle of discharging was performed. Table 2 shows the performance at the 10th and 11th cycles.

The internal resistance of the battery immediately after assembly is 15Ω, and the internal resistance of the battery after 6 cycles of charging and discharging is 1.
It was 7Ω.

±comparison (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 Support pellets were manufactured in the same manner as in Example, except that only the carbonaceous material manufactured in the same manner as in Example was used, and the organic aluminum was not brought into contact with and thermally decomposed. .

This was subjected to the same electrolytic treatment as in the example, and 12IIIA
A negative electrode body was prepared by supporting Li of h.

(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 Tables 1 and 2.

The internal resistance of the battery immediately after assembly is 18Ω, and the internal resistance of the battery after 6 cycles of charging and discharging is 3Ω.
It was 4Ω.

Table 1 Table 2 [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 is not active during charging. Since the alkanometal, which is mainly composed of Li or Ll, can be stably fixed on the supporting material, stable high capacity, that is, large current discharge is possible, and it also has good self-discharge characteristics and is highly reliable. Since it is a battery, 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 can also be applied to secondary batteries having shapes such as cylindrical, flat, and square.

[Brief explanation of drawings]

The figure is a longitudinal sectional view of a secondary battery having a button-shaped structure, which is an embodiment of the present invention. ■...Positive electrode can 2...Positive electrode body 3...Separator 4...Negative electrode body 5...Negative electrode element 6...Insulating packing

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 support has (a) a hydrogen/carbon atomic ratio of less than 0.15; and (b) an interplanar spacing (d) of the (002) plane determined by X-ray wide-angle diffraction.
_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 state in which an organometallic compound containing a metal that can be alloyed with the active material is brought into contact with the carbonaceous material. A secondary battery comprising a composite material of a carbonaceous material obtained by thermally decomposing the organometallic compound and a metal that can be alloyed with the active material.