JPS61111908A - Material for electrode - Google Patents

Abstract

PURPOSE:To provide an electrode material giving a pollution-free cell, having an H/C atomic ratio of falling within a specific range, and prepared by baking poly(alpha-halogenated acrylonitrile), poly(beta-halogenated acrylonitrile), etc. CONSTITUTION:A compound selected from poly(alpha-halogenated acrylonitrile), poly(beta-halogenated acrylonitrile), poly(halogenated dicyanoethylene), poly(cyanoacetylene) and poly(dicyanoacetylene) or their mixture is baked to obtain a carbonaceous material having an H/C atomic ratio of 0.010-0.55, and the material is used as the objective electrode material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Objectives) The present invention relates to an electrode material that has a high energy density and a high maximum output density, and which enables a non-polluting battery.

(Prior Art) In recent years, there has been a rapid movement in research and development aimed at improving the performance of batteries. One example of this is research into rechargeable secondary batteries using electrochemical doping using carbonaceous materials as electrodes.

For example, if Li metal is used for the negative electrode and graphite is used for the positive electrode,
Anions such as ctOa-1BF can be doped between the graphite layers by charging, and the electromotive force generated at this time can be used as a battery. During discharge, these ions are dedoped from between the graphite layers, and a current is extracted.

In this way, it can be used as a secondary battery that can be charged and discharged repeatedly (='!, Gas Chemistry 46, 438 (1978), etc.).

However, in this case, there is a limit to the amount of doping, probably due to repulsion between ions doped between the graphite layers, and the energy density is low, making graphite insufficient as a positive electrode. Furthermore, Li metal as a negative electrode is insufficient as a negative electrode because it cannot increase the number of charge/discharge cycles due to dendrites that grow on the Li metal electrode as charge/discharge cycles are repeated.

Furthermore, when graphite is used as a negative electrode, cations such as Li+ ions can be doped between the layers, but it is extremely unstable in the electrolyte and reacts with the electrolyte, making it unsuitable as an electrode material ( J.

Electrochem, 5ociety, 125
．． 687 (197B).

Surface 21+112 (1983), etc.).

In addition, a battery using activated carbon fibers with a large specific surface area of 100 to 2 s o On"/y for both electrodes was published in Japanese Patent Application Laid-open No.
This is proposed in Japanese Patent No. 35881. However, this has the problem of being prone to self-discharge and not being able to withstand long-term discharge, and the charge efficiency of charging and discharging decreases, making it difficult to obtain a high-performance and highly reliable battery. This is because activated carbon fibers used as positive electrodes have relatively good electrode properties, but doping and dedoping of cations to the activated carbon fibers on the negative electrode side are not successful, so good battery properties cannot be obtained. be.

Therefore, a battery that uses Li metal as the negative electrode and activated carbon fiber as the positive electrode has these problems improved compared to a battery that uses activated carbon fiber as both electrodes, but in this case, Li metal Due to dendrites growing on the electrodes, the number of charge/discharge cycles cannot be increased.

This is the reason why a negative electrode material that can replace Li metal is required.

On the other hand, there is also a great deal of interest in research into rechargeable secondary batteries that utilize electrochemical doping with conductive polymers such as polyacetylene as electrodes. for example,
JP-A-57-121168 proposes a battery using an acetylene polymer. However, polyacetylene is unstable due to oxidative deterioration in the air, and deteriorates when reacting with trace amounts of moisture and oxygen contained in the solvent, resulting in poor stability as an electrode. In particular, the polyacetylene used as the negative electrode
Severe deterioration in electrolyte.

Therefore, a battery using polyacetylene for both electrodes has severe self-discharge and poor charging/discharging efficiency, making it difficult to obtain a high-performance, highly reliable battery.

In batteries that use Li metal as the negative electrode and polyacetylene as the positive electrode, problems such as self-discharge and charge efficiency during charging and discharging are improved compared to batteries that use polyacetylene as both electrodes. Again, the number of charging and discharging cycles cannot be increased because of dendrites that grow on the Li metal electrode as the charging and discharging process continues.

- (Summary of the Invention) In view of the current situation, the present inventors have developed a non-polluting secondary battery that is lightweight, has a high energy density, and has a high maximum output density. We recognize that it is important to have good positive and negative electrode materials that can be doped with large amounts of ions, and that the most important point is to develop materials that have excellent performance as negative electrodes. We have worked hard to develop it. As a result, we have arrived at the present invention.

That is, the present invention provides one or more of poly(α-halogenated acrylonitrile), poly(β-halogenated acrylonitrile), poly(halogenated dicyanoethane), poly(cyanoacetylene), and poly(dicyanoacetylene).
Obtained by thermally firing a mixture of more than one species, the atomic ratio of hydrogen/carbon atoms determined from elemental analysis is 0.010 to 0.55.
The electrode material is in the range of .

The negative electrode is an electrode that is connected to the cathode of an external power source, into which electrons are sent, and which is doped with cations during charging. On the other hand, the positive electrode refers to the electrode that is connected to the anode of an external power source to extract electrons and is doped with anions during charging.

The electrode material of the present invention exhibits excellent battery performance when used as a negative electrode.

It is also possible to use the electrode material of the present invention as a positive electrode.

(Specific explanation) In the present invention, materials to be subjected to thermal calcination include poly(α-halogenated acrylonitrile), poly(β-halogenated acrylonitrile), poly(β-
Halogenated acrylonitrile) is obtained by polymerizing α-halogenated acrylonitrile and β-halogenated acrylonitrile, and there are homopolymers of α-halogenated acrylonitrile and β-halogenated acrylonitrile. Also,
Contains those copolymerized with a small proportion of other monomers. Other comonomers that can be used include those having a nitrile group such as acrylonitrile, and halogenated vinyl compounds such as vinyl heptafluoride. α-halogenated acrylonitrile is represented by formula (1), and β-halogenated acrylonitrile is represented by formula (2).

HC CoN HCC Tubori (α-halogenated acrylonitrile), poly(β-
Halogenated acrylonitrile) is usually obtained by radical polymerization of α-halogenated acrylonitrile and β-halogenated acrylonitrile, respectively.

Poly(halogenated dicyanoethylene) is a polymer of norogenated dicyanoethylene, and includes a homopolymer of halogenated dicyanoethylene and a small proportion of copolymerized with other comonomers. The halogenated dicyanoethylene is a heptamine represented by formula (3).

Poly(cyanoacetylene) and poly(dicyanoacetylene) are polymers of cyanoacetylene and dicyanoacetylene expressed by the formula T41 (5), and are preferably homopolymers, but may be copolymerized with a small proportion of other comonomers. Including things that are.

H-C=C-C (3) N=C-CTC-CmiN (4) The electrode material of the present invention includes the above-mentioned poly(α-halogenated acrylonitrile), poly(β-halogenated acrylonitrile), A stone obtained by thermally firing one type or a mixture of 2 m or more of poly(halogenated dicyanoethylene), poly(cyanoacetylene), and poly(dicyanoacetylene). From the viewpoint of ease of industrial production of monomers and polymers, it is used as a precursor for thermal sintering of poly(α-halogenated acrylonitrile), poly(β-halogenated acrylonitrile), especially poly(α-) and halogenated acrylonitrile). It is preferable to use Particularly preferred are poly(α-fluoroacrylonitrile) and poly(α-chloroacrylonitrile).

Poly(α-halogenated acrylonitrile), poly(β-
Pyridine, DBU (halogenated acrylonitrile) and poly(halogenated dicyanoethylene) are
1,8-diazabicyclo(4,3゜0) undecene-7
), tertiary amine compounds such as triethylamine, benzene-trimethylammonium hydroxide, sodium amide (used in liquid ammonia), alkali hydroxide (used under high temperature and pressure), potassium butoxide, butyl lithium, aqueous alkaline solutions and amine compounds A preferred method is to obtain the electrode material of the present invention by treating the electrode material with a phase transfer catalyst component such as , crown nityl, etc., carrying out a dehydrohalogenation reaction, and then thermally calcining it.

Thermal firing is performed in vacuum or inert gas, argon e.
tc) flowing down or oxidizing gas (!2 gas etc.) flowing down,
Or it is carried out under a mixed gas flow of both. It is usually thermally fired under vacuum or under a flow of inert gas.

Closely related to the atomic ratio of hydrogen/carbon atoms in the polymer conjugated system produced at the thermal firing temperature, this atomic ratio is 0.015.
The thermal firing temperature is selected to match the range of .about.0.55. Usually, the firing temperature is selected in the range of 180 to 2000°C.

The polymer before thermal baking is used in various forms such as fibrous, powder, granular, and film forms.

Moreover, the above-mentioned polycyanoacetylene and polydicyanoacetylene can be obtained by thermally polymerizing cyanoacetylene or dicyanoacetylene, respectively, at an appropriate temperature of 200 to 1000°C, and the thermally polymerized product can be further thermally calcined at an appropriate temperature. It can be manufactured continuously.

The electrode material of the present invention has an atomic ratio of hydrogen/carbon atoms determined from elemental analysis in the range of 0.010 to 0.55, preferably 0.015 to 0.50, more preferably 0.02.
Q is in the range of 0.45. If the atomic ratio of hydrogen/carbon atoms exceeds the upper and lower limits, stable charge/discharge characteristics and storage characteristics cannot be obtained as an electrode material.

Furthermore, the electrode material of the present invention has an absorbance ratio A of 0.60 or less, which is expressed by the following formula and determined from an infrared spectrum.
Preferably, a value of 0.50 or less is appropriate.

A=A2080~2280/Al450 #165G
A 110110-2280 is the absorbance of the maximum peak in the range of 2080 to 2280 cm in the infrared absorption spectrum. Strictly speaking, 2200-2240c
It is the absorbance of absorption based on the nitrile group of m.

A1450-16501f is the absorbance of the maximum absorption peak in the range of 1450 to 1650 cM''1 in the infrared absorption spectrum.It is considered to be an absorption peak based on a conjugated system.

The absorbance ratio A becomes smaller as the nitrile group cyclizes and the conjugated system grows.

If the absorbance ratio A exceeds 0.60, stable charging/discharging charge efficiency and good storage characteristics cannot be obtained as an electrode material.

In addition, when the conjugate system expands, C! ! ! ! Absorption of the N group is no longer observed, and the absorption peak in the range of 1450 to 165 oi1 becomes broad, making it impossible to accurately calculate the absorbance ratio A. In this case, the absorbance ratio (absorbance A20
80 to 2280 can be regarded as almost 0) is determined to be approximately 0.

Furthermore, the electrode material of the present invention has a t value of 19.900 to 19.900 determined from an electron spin resonance spectrum (measured at 23°C).
It is preferable to have a signal in the range of 20,100 and a line width (ΔHPP) of the signal in the range of 3 to 1500 Gauss.

Although the electrode material of the present invention may have two or more electron spin resonance spectrum signals in some cases,
The t value of at least one of the signals is 1.99
00 to 2.0100, the signal width (ΔH,,) is 3 Gauss or more, and F13 to 1500
in the Gaussian range.

The electrode material according to the present invention can be used as an electrode in various shapes either alone or in combination with a conductive material such as carbon fiber, a reinforcing material, etc.

A battery using the electrode material of the present invention has the following configuration. That is, the electrode material of the present invention is used as the main active material for the negative electrode, and an electrode material having relatively good characteristics as a positive electrode, such as activated carbon fiber, is selected for the positive electrode.

When using another electrode material for the negative electrode and the positive electrode material of the present invention for the positive electrode, it is also possible to use the electrode material of the present invention for the positive electrode and the negative electrode.

Electrolyte is 1ictO4, LiCA, LiPFg
, K.C.N.S.

NaPFa + LiBF4. N(Bu)4CtO4,
Known salts such as alkali metal salts such as N(Bu)4C6, alkaline earth metal salts, and tetraalkylammonium salts are combined with propylene carbonate, ethylene carbonate, acetonitrile, γ-butyrolactone, dimethylformamide, dimethylsulfoxide, and ethyl ether. ,
Usually, a solvent dissolved in one or a mixed solvent of two or more organic solvents commonly used in batteries, such as tetrahydrofuran and glymes, is used.

From the viewpoint of using a solvent with a high decomposition voltage, propylene carbonate, ethylene carbonate, etc. are preferable as the organic solvent. Further, in order to obtain a compact battery that does not leak, it is preferable to use an electrolyte that is solid at room temperature or the operating temperature of the battery.

When a battery with the above configuration is charged by applying a constant voltage to both poles from an external power supply or by regulating the voltage so that a constant current flows, anions are generated at the positive electrode and positive at the negative electrode. When doped with ions, the P-type electrode and desk-type electrode can be used as a battery by utilizing the electromotive force generated at these two electrodes. During discharge, each electrolyte ion is dedoped from its respective electrode, allowing current to flow out. By repeating such charging and discharging cycles, it can be used as a secondary battery.

Although an electromotive force is generated even when IYT type or P type electrodes having different doping levels are used, the electromotive force is lower than when P type or H type electrodes are used for both poles.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples. In addition, elemental analysis, infrared spectrum measurement, and electron spin resonance spectrum measurement were performed by the following methods.

[Elemental analysis]

After drying the sample under reduced pressure at 120°C for about 15 hours, it was dried at 1o on a hot plate in a dry box.

℃, vacuum dried for 1 hr, tempered in an aluminum cup under argon, and packed with PerkinElmer 240.
Measured using a C-type elemental analyzer.

[Infrared spectrum measurement]

The sample was mixed with KBr tablets in a mortar and powdered.

This powder was pressed into a sheet.

This sheet-like number is manufactured by Di gi lab Qua
Measurement was performed using a limatic Fourier transform infrared spectrophotometer.

[Electron spin resonance spectrum measurement]

The first-order differential absorption vector of electron spin resonance is JEOL
Measurement is performed in the X band using a JEB-Pg IX ESR spectrometer. Powdered samples are left as they are, fine flake samples are pulverized in an agate mortar, placed in a capillary tube with an outer diameter of 2 m, and then the capillary tube is placed in an ES tube with an outer diameter of 511 Ill.
Put it in the R tube. The modulation width of the high-frequency magnetic field is assumed to be 6.3 Gauss. All of the above is carried out at 23° C. in an air atmosphere. The line width (ΔHpp) between the peaks of the −th order differential absorption spectrum is M
n”/MgO standard data.

(The following is a blank space) Example 1 After dissolving poly(α-fluoroacrylonitrile) in an acetone solvent, it was cast on a glass plate and air-dried to obtain a film with a thickness of 20 μm. This film was placed in a quartz glass tube and degassed under vacuum. Furthermore, the quartz glass tube containing this film was set in an electric heating furnace, and the temperature was raised to 300° C. at a rate of 7 minutes under vacuum for 10 minutes. Further under vacuum 300
It was kept at ℃ for 1 hour. In this way, a black film-like substrate was obtained. The infrared absorption spectrum of this film-like substrate is shown in FIG.

In addition, Table 1 shows the assumed atomic ratio determined from elemental analysis measured using a PerkinElmer 24QC elemental analyzer. Further, FIG. 2 shows the ESR spectrum of the heat-sintered film-like substrate. Based on these data, the hydrogen/carbon atomic ratio of the above film-like substrate is 0.45.The absorbance ratio obtained from the infrared absorption spectrum is A=A201G"w tt
so/),,! sso ~1sso is 0.40. Determined from electron spin resonance spectrum? The half width (Δ■) of the signal with a value of 2.0 O12 was 6.8 Gauss.

Table 1 [Battery using the above film-like substrate as a negative electrode] The above film-like substrate 11 cape was wrapped in a 55-mesh platinum wire mesh and used as one electrode. In addition, phenolic activated carbon fiber felt (ACN 504-15 manufactured by Nippon Kynor Co., Ltd.) 1
1y was similarly wrapped in a 55-mesh platinum wire mesh to serve as the other electrode.

A glass fiber filter paper with a thickness of 0.5 yma was placed between both electrodes as a diaphragm. A platinum wire was connected between both electrodes as a lead wire. An electrode made of the above film-like substrate wrapped in a platinum wire mesh is connected to the cathode of a potentiostat/galvanostat (HA-501 manufactured by Hokuto Denko Co., Ltd.), and an electrode made of a phenolic activated carbon fiber felt wrapped in a platinum wire mesh is connected to the anode. Then, charge it by passing a constant current of 0.15 mA between both electrodes. Charging was terminated when a charge of 2.0 coulombs was reached as indicated by the coulomb meter.

[Battery performance]

4. Measure the open circuit voltage of the battery after the above charging. I got Ov.

Immediately after the above charging, a constant resistance discharge was carried out by connecting an IKΩ resistor between the two electrodes, and the electric charge was discharged until the potential between the two electrodes reached 0.IV, and the amount of electric charge was 1.54 coulombs.

The above-described charging and discharging operations are repeated until the fourth charge amount is 2. The discharge charge amount was 1.50 coulombs relative to Q coulombs. After the 5th charge, leave it for 15 hours and then
A constant resistance discharge of KΩ was performed, and a discharged charge amount of 1.23 coulombs was obtained for a charged charge amount of 2.0 coulombs.

Table 2 shows the charge efficiency in each cycle.

(Left below) Example 2 The film-like substrate obtained in Example 1 was further heated at 20°C under nitrogen flow.
The temperature was raised to SOO°C at a rate of 1/min. Furthermore, SO under nitrogen flow
It was held at 0° C. for 1 hour. In this way, a black film-like substrate was obtained. The infrared spectrum of this film-like substrate is
Figures and values of elemental analysis are shown in Table 1. Further, an electron spin resonance spectrum (ESB spectrum) is shown in FIG. Based on these data, the hydrogen/carbon atomic ratio of the above film-like substrate is 0.40, and the absorbance ratio determined from the infrared absorption spectrum is A = Aj ~! 1110 /A15110
N165G is 0.37, and the half width (ΔH) of the signal with an f value of 2.0011 determined from the electron spin resonance spectrum
is 6.3 Gauss and 90 [Battery using the above film-like substrate as the negative electrode] A battery was constructed in the same manner as in Example 1 except that the above-mentioned film-like substrate 11■ was used as the negative electrode. Make sure to charge it in the same way as step 1. Charging was terminated when a charge of 2.0 coulombs was charged as indicated by the coulomb meter.

[Battery performance]

Immediately after the above charging, a constant resistance discharge was performed by connecting a resistor of IKΩ between the two electrodes, and the amount of charge discharged until the potential between the two electrodes reached o, iV was 1.56 coulombs.

The above-described charging and discharging operations were repeated, and the amount of discharged charge was 1.57 coulombs compared to the fourth charge amount of 2.0 coulombs. After the 5th charge, leave it for 15 hours and then
A constant resistance discharge of KΩ was performed, and the discharged charge amount was 1.27 coulombs compared to the charged charge amount of 2.0 coulombs.

Comparative Example 1 A battery was constructed in the same manner as in Example 1, except that phenolic activated carbon fiber felt (manufactured by Nippon Kynol Co., Ltd. eN504-15) 1119 was used as the negative electrode, and charged in the same manner as in the experiments. . 2 with the coulomb meter reading.
When it was charged with a charge of 0 coulombs, it stopped charging.

[Battery performance]

Immediately after the above charging, a constant resistance discharge was carried out by connecting a resistor of IKΩ between the two electrodes, and the amount of charge discharged until the potential between the two electrodes reached 0.1 V was 1.48 coulombs.

The above-described charging and discharging operations were repeated, and the discharged charge amount was 0.76 coulombs compared to the fourth charge amount of 2.0 coulombs. After the 5th charge, leave it for 15 hours and then
A constant resistance discharge of KΩ was performed, and a discharged charge amount of 0.47 coulombs was obtained for a charged charge amount of 2.0 coulombs.

Comparative Example 2 [Preparation of polyacetylene film] Using Ti(0-nBu)4A4(Et)s as a catalyst and toluene as a solvent, acetylene gas was blown into a 1-ton glass autoclave, and the method of Hakushu et al. (J, P .

S, Polymer Chemistry Edi
tion Vol 12 11-20 (1974)
A polyacetylene film was obtained by a known method described in et al.

[Battery using the above polyacetylene film as the negative electrode] A battery was constructed in the same manner as in Example 1 except that the above polyacetylene film 11q was used as the negative electrode.
The coulomb meter reading was 2.0 when charged in the same manner as above.
When the coulomb charge was charged, the charge was stopped.

[Battery performance]

Immediately after the queen charging, a constant resistance discharge was performed by connecting an IKΩ resistor between the two electrodes, and the amount of charge discharged until the potential between the two electrodes reached 0.1 V was 1.40 coulombs.

The above-described charging and discharging operations were repeated, and while the fourth charge amount was 2.0 coulombs, the discharged charge amount was 0.70 coulombs. After charging for the 5th time, leave it for 15 hours.
A constant resistance discharge of KΩ was performed, and a discharged charge amount of 0.43 coulombs was obtained for a charged charge amount of 2.0 coulombs.

Comparative Example 3 A poly(α-fluoroacrylonitrile) film cast from an acetone solution in the same manner as in Example 1 was placed in a quartz glass tube, and this was set in an electric heating door. The temperature was increased to 3000°C at a rate of 30°C/min under nitrogen flow. Further nitrogen flow, aoo.

It was kept at ℃ for 30 minutes. In this way, a black film-like substrate was obtained. This film-like substrate was prepared using PerkinElmer 240C
The atomic ratio of hydrogen/carbon atoms determined from elemental analysis using a type elemental analyzer is shown in Table 1, and the atomic ratio of hydrogen/carbon atoms was less than 0.010.

[Battery using the above film substrate as the negative electrode] E Example 1 except that the above film substrate 11119 was used as the negative electrode.
A battery was constructed in the same manner as in Example 1, and charged in the same manner as in Example 1. Charging was terminated when a charge of 2.0 coulombs was charged as indicated by the coulomb meter.

[Battery performance]

Immediately after charging, constant resistance discharge was performed by connecting an IKΩ resistor between the two electrodes, and the amount of charge discharged until the potential between the two electrodes reached 0.1 V was 0.92 coulombs.

The above charging and discharging operations were repeated, and the discharged charge amount was 0.60 coulombs compared to the fourth charge amount of 2.0 coulombs. After the fifth charge, the battery was left to stand for 15 hours, and then constant resistance discharge of IKΩ was performed to obtain a discharged charge of 0.31 coulombs for a charged charge of 2.0 coulombs.

Comparative Example 4 A poly(a-fluoroacrylonitrile) film cast from an acetone solution in the same manner as in Comparative Example 3 was placed in a quartz glass tube, and this was set in an electric heating door. The temperature was increased to 180°C at a rate of 10°C/min under nitrogen flow. Further, the temperature was maintained at 180° C. for 30 minutes under nitrogen flow. The atomic ratio of hydrogen/carbon atoms determined from the elemental analysis value of the film-like substrate thus obtained was 0.59, and the absorbance ratio determined from the infrared spectrum was A = Axtao-ggso / A1550.
~1m5o was 1.2.

[Battery using the above film-like substrate as the negative electrode] A battery was constructed in the same manner as in Example 1, except that the above-mentioned film-like substrate 11 was used as the negative electrode, and charged in the same manner as in Example 1. Charging was terminated when a charge of 2.0 coulombs was charged as indicated by the coulomb meter.

[Battery performance]

Immediately after the above charging, a resistor of IKΩ is connected between the two electrodes and a constant resistance discharge is performed, so that the potential between the two electrodes becomes 0. Although the battery was discharged to IV, the amount of discharged charge was less than 0.40 coulombs.

[Comparison of Example 1.2 and Comparative Example 1.2] 1 cy in Table 2
cle, 4 cycle, 5 cycle (1
Example 1.2 of the charging/discharging electric vehicle (5 hours discharge)
is higher than Comparative Example 1.2, indicating that it is an excellent battery. That is, it can be seen that a battery using the organic polymer electrode material of the present invention as a negative electrode is far superior to a battery using known activated carbon fiber or polyacetylene as a negative electrode.

[Comparison of numbers between Example 1.2 and Comparative Example 3] 1 cy in Table 2
cle, 4 cycle, 5 cycle (
It can be seen that the charge efficiency of Example 1.2 is higher than that of Comparative Example 3.4 in both charging and discharging charge efficiencies (after being left for 15 hours), indicating that it is an excellent battery. In other words, a battery using the organic polymer-based electrode material of the present invention as a negative electrode is superior to a battery using an organic polymer-based electrode material as a negative electrode having an atomic ratio of hydrogen/carbon atoms that is outside the scope of the claims of the present invention. It can be seen that the battery is

[Brief explanation of the drawings] Fig. 1 is an infrared absorption spectrum diagram of the film-like substrate obtained in Example-1, Fig. 2 is an ESR spectrum diagram of the same film-like substrate, and Figs. 2 is an infrared absorption spectrum diagram and an ESR spectrum diagram of the film-like substrate obtained in Example 2. FIG. Patent applicant Mitsubishi Yuka Co., Ltd. agent Patent attorney Hidetoshi Furukawa (and 1 other person) Ichigo Tsubochi (cm-9 Figure 2)

Claims (1)

[Claims] 1. Poly(α-halogenated acrylonitrile), poly(
One or two selected from β-halogenated acrylonitrile), poly(halogenated dicyanoethylene), poly(cyanoacetylene), and poly(dicyanoacetylene)
Electrode material 2 obtained by thermally calcining a mixture of more than one species and having an atomic ratio of hydrogen/carbon atoms in the range of 0.010 to 0.55 Patent obtained by thermally calcining poly(α-halogenated acrylonitrile) Electrode material according to claim 1