JP2003297364A - Electrode material for electrochemical cell and electrochemical cell using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode material for fabricating a cell having a high energy density and capable of forming an electrode having excellent reversibility and provide a lithium battery having an excellent rate performance using the electrode material. <P>SOLUTION: The electrode material for the lithium battery is an organic sulfur compound capable of making an electrolytic oxidative and reductive reaction, wherein each molecule of the organic sulfur compound has a phenanthrene structure. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electrode material for an electrochemical cell having a disulfide group.

[0002]

2. Description of the Related Art As an electrode material for an electrochemical cell which can be expected to have a high energy density, a disulfide compound which is an organic sulfur compound is disclosed in U.S. Pat. No. 4,833,048. This organic sulfur compound is most simply R-
S—S—R (R is a hydrocarbon, S is sulfur), the S—S bond is cleaved by an electrolytic reduction reaction, and is represented by 2R ⁻ · M ⁺ with a metal ion M ⁺ in the electrolyte. To produce a metal salt. This metal salt is converted to the original R-S- by the electrolytic oxidation reaction.
Return to SR. Metal M that supplies and captures metal ions M ⁺
A metal-disulfide secondary battery, which is a combination of a disulfide-based compound and a disulfide-based compound, has been proposed in the aforementioned US patent. This battery can be expected to have a high energy density of 150 Wh / kg or more.

[0003]

However, since the metal salt is easily dissolved in an organic electrolytic solution, for example, when it is used as an electrode material for an electrochemical cell using an organic electrolytic solution, particularly a secondary battery, It was difficult.

[0004]

The present invention, as described in claim 1, is an organic sulfur compound capable of electrolytic redox reaction, wherein the organic sulfur compound has a phenanthrene structure in its molecule. It is an electrode material for electrochemical cells characterized by having.

That is, the redox-reducible organic sulfur compound is
By having a phenanthrene structure, solubility in an electrolytic solution can be suppressed. Also. Since it has a phenanthrene structure, it is well suited when a carbon material is used as the conductive agent, and the transfer of electrons between the organic sulfur compound and the conductive agent easily proceeds.

The present invention also provides 3,6-phenanthrenedithiol, 1,10 as described in claim 2.
-An electrode material for an electrochemical cell comprising dithiophenanthrene, 4,5-dithiophenanthrene, or a metal salt thereof.

3,6-phenanthrene thiol, 1,
10-dithiophenanthrene, 4,5-dithiophenanthrene, or a metal salt thereof is relatively easy to synthesize.

Further, the present invention provides an electrochemical cell using these electrode materials for an electrochemical cell as described in claim 3. The electrode material of the present invention can be used in electrochemical cells such as capacitors and batteries. As a battery, a proton battery or an aproton battery can be used.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, description will be made assuming that the electrode material of the present invention is used as an electrode material for a lithium battery, but the present invention is not limited by the following description.

When the electrode material for an electrochemical cell of the present invention is used as a positive electrode active material for a lithium battery, the negative electrode active material may be any material generally used for negative electrodes for lithium batteries. For example, lithium-containing alloys such as lithium metal, lithium-aluminum, lithium-lead, lithium-tin, lithium-aluminum-tin, lithium-gallium, and wood alloys, and the following carbon materials can be mentioned. For example, there are natural graphite, artificial graphite, amorphous carbon, fibrous carbon, powdery carbon, petroleum pitch carbon, and coal coke carbon. These carbon materials are preferably particles or fibers having a diameter or fiber diameter of 0.01 to 10 μm and a fiber length of several μm to several mm. In particular, the carbon material is analyzed by X-ray diffraction or the like; Lattice plane spacing (d ₀₀₂ ) 0.333 to 0.350 nm Crystallite size in the a-axis direction La 20 nm or more Crystallite size in the c-axis direction Lc 20 nm As described above, graphite having a true density of 2.00 to 2.25 g / cm ³ is preferable because it exhibits a high capacity. However, it is not limited to these ranges.

Further, the carbon material can be modified by adding a metal oxide such as tin oxide or silicon oxide, or by adding phosphorus or boron. Also, by using graphite in combination with lithium metal, a lithium-containing alloy, or by performing electrochemical reduction in advance,
It is also possible to insert lithium into the carbonaceous material used in the present invention in advance.

When the electrode material for an electrochemical cell of the present invention is used as the negative electrode active material of a lithium battery, the positive electrode active material may be a material generally used for a positive electrode for lithium batteries. For example, materials such as lithium-containing transition metal oxides and phosphates that exhibit a discharge voltage of 3 V or more with respect to lithium are preferably used. In particular, a material that can obtain a discharge potential of 4 V or higher is more preferable because a high battery voltage is obtained and the energy density is improved. Examples of the lithium-containing transition metal oxide include, for example, the general formula Li _y Co _1-x M
_x O ₂ , Li _y Mn _2-x M _X O ₄ {M is a group I to VIII metal (for example, Li, Ca, Cr, Ni, Fe, Co,
One or more kinds of elements such as Mn), and the x value indicating the substitution amount of different elements is effective up to the maximum substitutionable amount, but 0 ≦ x ≦ 1 is preferable from the viewpoint of discharge capacity. As for the y value indicating the amount of lithium, the maximum amount that can reversibly use lithium is effective, but 0 <y ≦ 2 is preferable from the viewpoint of discharge capacity. }, But is not limited thereto. However, since the electrode material of the present invention has a relatively noble potential when used for the negative electrode, a positive electrode active material that operates at a more noble potential is preferable.

The above-mentioned lithium-containing transition metal oxide is
Other active materials can be further mixed and used. example
For example, CuO, Cu₂O, Ag₂O, CuS, CuSO_FourNa
Which group I metal compound, TiS₂, SiO₂, SnO, etc.
Group IV metal compound, V₂O_Five, V₆O₁₂, VO_x, Nb
₂O_Five, Bi₂O₃, Sb₂O₃Group V metal compounds such as Cr
O ₃, Cr₂O₃, MoO₃, MoS₂, WO₃, SeO₂Na
Which group VI metal compound, MnO₂, Mn₂O₃VI such as
Group I metal compound, Fe₂O₃, FeO, Fe₃O_Four, FeP
O_Four, Ni₂O₃, NiO, CoO₃, CoO, etc. VII
Examples thereof include Group I metal compounds. In addition, poly pillow
Le, polyaniline, polyparaphenylene, polyacetylene
Conductive polymer compounds such as
Lafite structure carbonaceous materials may be used,
It is not limited to.

Examples of the method for forming the electrode material of the present invention include roller coating for applicator rolls, screen coating, doctor blade method,
It is desirable, but not limited to, to coat the current collector in any thickness and in any shape using a means such as spin coating or a bar coder.
When these means are used, it is possible to increase the actual surface area of the electrochemically active substance that comes into contact with the electrolyte layer and the current collector.

In the electrode material of the present invention, a conductive agent, a binder, a filler and the like can be added to the electrode mixture as needed.

The conductive agent may be any electron conductive material that does not adversely affect the battery performance. Normal,
Natural graphite (scaly graphite, flake graphite, earthy graphite, etc.), artificial graphite, carbon black, acetylene black, Ketjen black, carbon whiskers, carbon fiber and metal (copper, nickel, aluminum, silver, gold, etc.) powder, A conductive material such as a metal fiber or a conductive ceramic material may be contained as one kind or a mixture thereof. Of these, acetylene black is preferable from the viewpoint of conductivity and coatability. The addition amount is preferably 1 to 50% by weight, and particularly preferably 2 to 30% by weight. These mixing methods are physical mixing, and ideally, they are homogeneous mixing. Therefore, a powder mixer such as a V-type mixer, an S-type mixer, a grinder, a ball mill, and a planetary ball mill can be mixed in a dry or wet manner.

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

The filler may be any material as long as it does not adversely affect the battery performance. Usually, olefin polymers such as polypropylene and polyethylene, aerosil, zeolite, glass, carbon and the like are used. The amount of the filler added is preferably 0 to 30% by weight.

It is also possible to add a chalcogen element such as sulfur, selenium or tellurium to the electrode material of the present invention. The chalcogen element is added to the S—S bond of the disulfide group contained in the electrode material to further increase the electrochemical capacity. The amount of the chalcogen element added is preferably 30% by weight or less based on the electrode material of the present invention.

As the positive electrode current collector and the negative electrode current collector, any electron conductor may be used so long as it does not adversely affect the constructed battery. For example, as the positive electrode current collector, aluminum, titanium, stainless steel, nickel, baked carbon,
In addition to conductive polymers, conductive glass, etc., adhesiveness, conductivity,
For the purpose of improving the oxidation resistance, a material obtained by treating the surface of aluminum, copper or the like with carbon, nickel, titanium, silver or the like can be used. As the negative electrode current collector, copper, nickel,
Iron, stainless steel, titanium, aluminum, calcined carbon,
In addition to conductive polymers, conductive glass, Al-Cd alloys, etc., those obtained by treating the surface of copper or the like with carbon, nickel, titanium, silver or the like for the purpose of improving adhesiveness, conductivity, and oxidation resistance. Can be used. It is also possible to oxidize the surface of these materials. With respect to these shapes, in addition to the foil shape, a film shape, a sheet shape, a net shape, a punched or expanded material, a lath body, a porous body, a foamed body, a fiber group formed body or the like is used. The thickness is not particularly limited, but one having a thickness of 1 to 500 μm is used.
Among these current collectors, the positive electrode is an aluminum foil having excellent oxidation resistance, the negative electrode is stable in a reducing field, and has excellent conductivity, and an inexpensive copper foil, nickel foil, iron foil, And alloy foils containing a part thereof are preferred. Furthermore, it is desirable that the foil has a rough surface and a surface roughness of 0.2 μmRa or more, which has excellent adhesion between the electrochemically active substance layer and the current collector. Electrolytic foils are excellent for the purpose of obtaining such a rough surface.

A metal can made of iron, stainless steel, aluminum or the like can be used as an outer casing material for a battery using the electrode material of the present invention. From the viewpoint of weight energy density, a metal foil and a resin film are used. A laminated metal resin composite film is preferred. Examples of the metal foil include aluminum, iron, nickel, copper, SUS, titanium, gold, silver, etc.
Although any foil without pinholes may be used, lightweight and inexpensive aluminum foil is preferable. Further, a resin film having an excellent puncture strength such as a polyethylene terephthalate film or a nylon film on the outer surface, and a thermoplastic and fusible film such as a polyethylene film or a nylon film on the inner surface is preferably used. . From the viewpoint of solvent resistance, it is desirable to seal the opening of such a resin film with a thermoplastic resin.

As the battery separator using the electrode material of the present invention, it is possible to use a microporous membrane or nonwoven fabric of polyolefin type, polyester type, polyacrylonitrile type, polyphenylene sulfide type, polyimide type, and fluororesin type. . Among them, it is preferable that the microporous film having poor wettability is treated with a surfactant or the like.

From the viewpoint of strength, the porosity of the separator is preferably 98% by volume or less. From the viewpoint of charge / discharge characteristics, the porosity is preferably 20% by volume or more.

The ionic compound used as the electrolyte in the battery using the electrode material of the present invention is, for example, LiC.
lO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF
₃ SO ₃ , LiCF ₃ CO ₂ , LiSCN, LiBr, Li
I, Li ₂ SO ₄ , Li ₂ B ₁₀ Cl ₁₀ , NaClO ₄ , Na
I, NaSCN, NaBr, KClO ₄ , KSCN, and other inorganic ion salts containing one of Li, Na or K, L
iN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , (C
H ₃ ) ₄ NBF ₄ , (CH ₃ ) ₄ NBr, (C ₂ H ₅ ) ₄ NC
_{lO 4, (C 2 H 5} ) 4 NI, (C 3 H 7) 4 NBr, (n-
_{C 4 H 9) 4 NClO 4} , (n-C 4 H 9) 4 NI, (C 2 H
₅ ) ₄ N-maleate, (C ₂ H ₅ ) ₄ N-benzo
ate, quaternary ammonium salts such as (C ₂ H ₅ ) ₄ N-phthalate, and organic ionic salts such as lithium stearyl sulfonate, lithium octyl sulfonate, and lithium dodecylbenzene sulfonate.

The ionic compound can be used by dissolving it in an organic solvent or the like. Examples of the organic solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, chloroethylene carbonate and vinylene carbonate; cyclic esters such as γ-butyrolactone and γ-valerolactone; dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate. Chain ester carbonates; methyl acetate, methyl butyrate and other chain esters; tetrahydrofuran or its derivatives, ethers such as 1,3-dioxane, 1,2-dimethoxyethane and methyldiglyme; nitriles such as acetonitrile and benzonitrile It is also possible to add a group; dioxalane or a derivative thereof; sulfolane, sultone or a derivative thereof alone or a mixture of two or more thereof. However, it is not limited to these. By adding such an organic solvent, battery characteristics such as cycle characteristics and stability can be improved.

The above electrolytic solution may be poured after the separator of the present invention is sandwiched between electrodes to be laminated or rolled up. As the injection method, it is possible to inject at normal pressure, but a vacuum impregnation method or a pressure impregnation method may be used.

As the electrolyte of the battery using the electrode material of the present invention, a lithium ion conductive solid electrolyte which is solid or solid at a temperature of −20 to 60 ° C. can be used. The solid electrolyte is a polyethylene oxide derivative in which the above ionic compound is dissolved or a polymer containing at least the derivative, a polypropylene oxide derivative or a polymer containing at least the derivative, polyphosphazene or the derivative, a polymer containing an ion dissociative group, phosphorus. Ion such as acid ester polymer derivative, polyvinyl pyridine derivative, bisphenol A derivative, polyacrylonitrile, polyvinylidene fluoride, polymer matrix material (gel electrolyte) containing non-aqueous electrolyte in fluororubber, and inorganic solid electrolyte A conductive compound can be used.

As an electrode of a battery using the electrode material of the present invention, it is preferable to use it in combination with the solid electrolyte in order to secure sufficient ionic conductivity while suppressing the elution of the electrode material into the electrolyte. . For example, 3,6-phenanthrene thiol obtained by the method described below and acetylene black which is a conductive agent are kneaded, and acrylate-modified polyethylene glycol which is the polyethylene oxide derivative and LiN which is the ionic compound are kneaded.
(CF ₃ SO ₂ ) ₂ and azobisisobutyronitrile as a radical initiator are added and kneaded, and a paste-like substance made by adding acetonitrile is applied on an aluminum foil,
Examples include a method of heating to about 80 ° C. to remove acetonitrile, and further performing thermal crosslinking at about 100 ° C. to use as an electrode. As a method for crosslinking, in addition to thermal crosslinking using a radical initiator and UV crosslinking, a method using active rays is also preferable. It is also possible to previously subject the organic sulfur compound, which is the electrode material of the present invention, to an oxidation treatment and a disulfide treatment. When used as an electrode material of a lithium battery, active protons of thiol react with lithium to generate hydrogen gas, so it is desirable to perform oxidation treatment in advance.

[0029]

EXAMPLES [3,6-phenanthrenedithiol (36
Synthesis of PDT] 3,6-PDT was synthesized in six steps using para-bromotoluene as a starting material.

[Step 1: Synthesis of para-bromobenzyl bromide] 20.6 ml of para-bromotoluene (168.
5 mmol) in 200 ml of carbon tetrachloride, and 30 g (168.5 mmol) of N-bromosuccinimide,
α, α'-Azobisisobutyronitrile (AIBN)
0.3 g (1.8 mmol) was added and the mixture was refluxed at 80 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature, insoluble matter was removed with Celite, and the filtrate was concentrated to recrystallize the obtained crude crystal to obtain para-bromobenzyl bromide.

[Second Step: Synthesis of Parabromobenzaldehyde] 8.5 g of parabromobenzyl bromide (50
mmol) in 50 ml of chloroform, and with stirring, 9.09 g of hexamethylenetetramine (65 m
(mol) was gradually added and dissolved. A white precipitate (para-bromobenzyl bromide hexamethylenetetramine salt) begins to precipitate when stirring is continued at room temperature for about 3 hours, and this was collected by filtration and air-dried for about 30 minutes. White precipitate 1 obtained
2.12 g (31 mmol) of acetic acid aqueous solution 100 ml
(90 ml of acetic acid, 10 ml of water)
Reflux for hours. Then 100m of water while maintaining the temperature
After adding 1 and continuing heating and stirring for about 10 minutes, when cooled to room temperature, para-bromobenzaldehyde begins to precipitate as crystals, so it is filtered off, washed well with water and saturated aqueous sodium hydrogencarbonate in this order, and dried in air to remove para-bromobenzaldehyde. Benzaldehyde was obtained.

[Third step: Synthesis of parabromobenzyl bromide triphenylphosphine salt] 11.89 g (47.6 mmol) of parabromobenzyl bromide was dissolved in 50 ml of acetone, and 13.11 g (50 mmol) of triphenylphosphine was stirred while stirring. Was gradually added and dissolved. When stirring was continued at room temperature for about 2 hours, the desired product began to precipitate, and this was collected by filtration and sufficiently air-dried to obtain para-bromobenzyl bromide triphenylphosphine salt.

[Fourth stage: Synthesis of trans-4,4'-dibromostilbene] 9.23 g (18) of para-bromobenzyl bromide triphenylphosphine salt under a nitrogen stream.
and 4 g of para-bromobenzaldehyde (21.
6 mmol) in dry THF (tetrahydrofuran) 10
0 ml and suspended in it, and 50 ml of dry THF and potassium tertiary butoxide (t-BuOK) 2.
The solution prepared with 63 g (23.4 mmol) was gradually added dropwise. After stirring at room temperature for about 5 hours, the reaction was stopped with water, extracted with diethyl ether, washed well with water and saturated brine, dried over sodium sulfate, and distilled under reduced pressure to obtain a crude product with chloroform. Recrystallization gave trans-4,4'-dibromostilbene.

[Step 5: Synthesis of 3,6-dibromophenanthrene] 676 mg of 4,4′-dibromostilbene
(2 mmol) is dissolved in 250 ml of cyclohexane,
A piece of iodine was added, and the mixture was irradiated with ultraviolet rays while stirring with a high pressure mercury lamp at room temperature. Thereafter, UV irradiation and stirring were continued until the color of iodine disappeared (about 3 hours). When the iodine color of the solution disappears, the ultraviolet irradiation is stopped, the solvent is removed from the reaction solution under reduced pressure, and the obtained crude product is purified by silica gel column chromatography (hexane).
6-Dibromophenanthrene was obtained.

[Sixth step: Synthesis of 3,6-phenanthrenedithiol] 3,6-dibromophenanthrene 33
6.03 mg (1 mmol) was dissolved in 50 ml of dry THF, cooled to -78 ° C, and stirred for 20 minutes. Then, 1.26 ml of 1.6 M normal butyl lithium hexane solution was slowly added dropwise while maintaining the temperature. Further, while paying attention to the temperature, the stirring was continued for about 1 hour, 64 mg (2 mmol) of sulfur which had been sublimated and purified was added, and the stirring was continued for 13 minutes thereafter. The reaction was stopped with 10% hydrochloric acid, extracted with toluene, washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over sodium sulfate, and the solvent was removed under reduced pressure to give 3,6-phenanthrenedithiol.

[1,10-Dithiophenanthrene (11
ODTP) and 4,5-dithiophenanthrene (45
DTP)] 110DTP and 45DTP are synthesized by Ashe, AJIII; Kampf, JW; Savla, PM The Reac.
tion of Sulfur with Dilithio Compounds.The Synthes
es and Structures Phenanthro [1,10-cd] -1,2-dithiole
and Phenanthro [4,5-cde] [1,2] dithiin. Heteroatom C
hem., vol.5, no.4,1994, pp.113-119.

Under nitrogen atmosphere, 13 ml of 1.6 mol / l n-butyllithium hexane solution and dry TMEDA were used.
(Tetramethylethylenediamine) 3 ml at room temperature 30
Mix for about a minute. This is designated as "solution 1". Weigh 0.9 g (5 mmol) of phenanthrene into another container,
After drying under vacuum, it is placed under a nitrogen atmosphere. The "solution 1" prepared previously is gradually added dropwise using a transfer tube. After dropping, the mixture was heated and stirred at 60 ° C. for 3 hours, returned to room temperature, diluted with 25 ml of dry THF, cooled to −78 ° C., and 1.28 g (40 mmol) of sulfur that had been sublimated and purified was added to keep the temperature. While stirring for about 3 hours, stirring was continued at room temperature for 12 hours. After that, the reaction was stopped with 10% hydrochloric acid, and the mixture was extracted with chloroform. The organic layer was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine in that order, dried over sodium sulfate, and then the solvent was removed under reduced pressure to remove silica gel. Purification by column chromatography (hexane) gave 4,5-dithiophenanthrene and 1,10-dithiophenanthrene.

(Test Cell 1) A test cell shown in FIG. 1 was manufactured. 34 PDT of 34 mg and acetylene black of 10 mg obtained above were kneaded in an agate mortar to give 12% by weight.
283 mg of an N-methylpyrrolidone solution in which polyvinylidene fluoride was dissolved was added and further kneaded. Then about 2 ml
N-methylpyrrolidone of was added to form a paste. The pasty substance is applied onto an aluminum foil as a working electrode current collector 12, heated to about 80 ° C. to remove N-methylpyrrolidone, and a working electrode material 11 containing 36 PDT on the working electrode current collector 12 A working electrode 1 was formed.

As the electrolyte / separator 3, an ion conductive compound supported on a non-woven fabric was used. The method for producing the electrolyte / separator 3 is as follows. That is, in order to support the ion conductive compound layer on the non-woven fabric made of polyethylene, acrylate-modified polyethylene glycol 10
Wt%, 6 wt% lithium tetrafluoroborate and 30 wt% ethylene carbonate were mixed and cast on both sides of the non-woven fabric, and the electron dose was 80 in an inert gas atmosphere.
It was irradiated with an electron beam of kGy and cured to obtain an electrolyte / separator 3. Electrolyte / separator 3 obtained by this
Had a thickness of 30 μm.

The counter electrode 2 was obtained by pressure-bonding lithium as the counter electrode material 21 onto a nickel plate as the counter electrode current collector 22. Terminals 6 and 6 were attached to the working electrode 1 and the counter electrode 2, respectively. The counter electrode 2, the electrolyte / separator 3 and the working electrode 1 are laminated in this order to form an electrochemical cell element 4, and an exterior body.
A test cell 1 was prepared by using a metal resin composite film for 5.

(Test Cell 2) A test cell 2 was obtained by assembling the test cell 1 except that the 110 PDT was used in place of the 36 PDT.

(Test Cell 3) Instead of the 36PDT,
Test cell 3 was obtained by assembling test cell 1 except that 45 PDT was used.

Cyclic voltammetry (CV) measurement was performed on the obtained test cells 1, 2, and 3. The upper and lower limits of the scanning potential are +1.5 to +3.0 V, and 10 mV /
It was measured by a linear scan at a speed of 2 cycles of sec. The results are shown in FIGS.

The following operations were performed on the test cells 1, 2, and 3 as batteries having a working electrode and a counter electrode as a positive electrode and a negative electrode, respectively. Current 0.1m for test cell 1
A, constant voltage charging with a final voltage of 4.0 V was performed, and then constant current discharging with a current of 0.1 mA and a final voltage of 1.5 V was performed. Further, the test cells 2 and 3 were subjected to constant current discharge with a current of 0.1 mA and a final voltage of 1.5 V, and then with constant current of 0.1 mA and a final voltage of 3.7 V. As a result, FIG.
The charge and discharge characteristics shown in Nos. 6 and 8 were obtained.

[0045]

As described above, by using the electrode material of the present invention, an electrode having high capacity and excellent cycle characteristics can be obtained. In addition, since the active material soluble in the solvent can be processed into the active material insoluble in the solvent at the stage of electrode preparation,
It can be applied thinly, and its applicability to batteries requiring rate is immeasurable.

[Brief description of drawings]

FIG. 1 is an external view of a test cell.

FIG. 2 is a sectional view of a test cell.

FIG. 3 is a current-potential characteristic diagram of the test cell 1.

FIG. 4 is a charge / discharge characteristic diagram of test cell 1.

5 is a current-potential characteristic diagram of the test cell 2. FIG.

FIG. 6 is a charge / discharge characteristic diagram of test cell 2.

FIG. 7 is a current-potential characteristic diagram of the test cell 3.

FIG. 8 is a charge / discharge characteristic diagram of test cell 3.

[Explanation of symbols]

1 Working pole 11 Working electrode material 12 Working electrode current collector 2 opposite poles 21 Counter electrode material 22 Counter electrode current collector 3 Electrolyte and separator 4 Electrochemical cell elements 5 exterior body 6 terminals

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor, Daisuke Yutoku             60, 1010, Sugada Kou, Sugata Town, Ozu City, Ehime Prefecture F term (reference) 5H029 AJ03 AJ05 AK02 AK03 AK15                       AL06 AL07 AL12 AL15 AM03                       AM04 AM07 HJ02                 5H050 AA07 AA08 BA15 CA02 CA07                       CA26 CB07 CB08 CB12 CB26                       HA02

Claims (3)

[Claims] 1. An electrode material for an electrochemical cell, which is an organic sulfur compound capable of electrolytic redox reaction, wherein the organic sulfur compound has a phenanthrene structure in the molecule. 2. A 3,6-phenanthrene dithiol,
An electrode material for an electrochemical cell comprising 1,10-dithiophenanthrene, 4,5-dithiophenanthrene, or a metal salt thereof. 3. A battery using the electrode material for an electrochemical cell according to claim 1 or 2.