JP3385115B2 - Gel electrolyte and lithium secondary battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gel electrolyte and a lithium secondary battery using the gel electrolyte.

[0002]

2. Description of the Related Art Since conductive polyacetylene was discovered by Shirakawa et al. In 1971, when a conductive polymer was used as an electrode material, a light-weight, high-energy-density battery, a large-area electrochromic device, and a microelectrode were used. Since an electrochemical element such as a biochemical sensor used can be expected, conductive polymer electrodes are being actively studied. Since polyacetylene is unstable and impractical as an electrode, other π-electron conjugated conductive polymers have been studied, and relatively stable polymers such as polyaniline, polypyrrole, polyacene, and polythiophene have been developed. Lithium secondary batteries used for the positive electrode have been developed. Also,
An organic disulfide compound is proposed in U.S. Pat. No. 4,833,048 as an organic material that can be expected to have a high energy density. This organic disulfide compound is most simply represented as R-S-S-R (R is an aliphatic or aromatic organic group, and S is sulfur). The S—S bond is cleaved by electrolytic reduction to form a salt represented by R—S ⁻ M ⁺ with a cation (M ⁺ ) in the electrolytic bath. This salt returns to the original RSSR by electrolytic oxidation. A metal-sulfur secondary battery combining a metal M that supplies and traps cations (M ⁺ ) and an organic disulfide compound has been proposed in the aforementioned U.S. Patent.

[0003] Conductive polymer electrodes such as polyaniline, polypyrrole, polyacene and polythiophene take in not only cations but also anions in the electrolyte during the electrode reaction, so that the electrolyte acts as an ion transfer medium in the battery. In addition, it is necessary to supply an amount of electrolyte corresponding to the battery capacity into the battery because it is involved in the battery reaction as well. Then, there is a problem that the energy density of the battery is reduced accordingly. Energy density is 2
At about 0 to 50 Wh / kg, there is a problem that it is as small as about half that of a normal secondary battery such as a nickel-cadmium storage battery and a lead storage battery. Proposed organic disulfide compounds are described in, for example, [(C ₂ H ₅ ) ₂ N], as reported by the inventors in US Pat. No. 4,833,048.
CSS ^-] In the _second electrolysis, the potential of oxidation and reduction is very slow cell reaction are separated one volt or more (J. Electrochem.
Soc, Vol. 136, No. 9, p. 2570-2575 (1989)). Therefore, near room temperature, a large current suitable for practical use, for example, 1 m
It is difficult to extract a current of A / cm ² or more.
Limited to use at high temperatures of 00-200 ° C. Further, since the organic disulfide compound itself does not have conductivity, it is necessary to add a conductive agent such as a carbon material, a metal, or a conductive polymer to form a composite electrode for use as an electrode.

[0004] In order to solve these problems, a positive electrode using polyaniline as a conductive agent and complexed with an organic disulfide compound has been proposed. When a composite of polyaniline and an organic disulfide compound was used for the positive electrode, a battery capable of extracting a large current suitable for practical use at room temperature became possible. When the organic disulfide compound and polyaniline are uniformly compounded, the battery reaction is further improved. When the organic disulfide compound monomer and polyaniline are dissolved in N-alkyl-2-pyrrolidone, applied, and dried, the monomer organic disulfide compound and polyaniline can be uniformly compounded.

[0005]

A lithium battery using a membrane in which an organic disulfide compound and polyaniline are combined as a positive electrode and a membrane obtained by gelling an electrolyte solution obtained by dissolving a lithium salt in an organic solvent as an electrolyte has a high capacity. Operates as a secondary battery. However, there is a problem that the discharge capacity is greatly reduced with the charge / discharge cycle of the battery. Further, there is a problem of a decrease in storage characteristics such as a decrease in discharge capacity after long-term storage of the battery. The present invention solves such a problem, does not impair the feature of the high energy density of the organic disulfide compound, can take out a large current even at room temperature, and furthermore has a gel electrolyte with little deterioration in charge / discharge cycle characteristics and lithium using the same. An object is to provide a secondary battery.

[0006]

Means for Solving the Problems The gel electrolyte of the present invention comprises:
An organic disulfide compound in which a sulfur-sulfur bond is cleaved by electrolytic reduction to generate a sulfur-metal ion (including proton) bond, and the sulfur-metal ion bond regenerates the original sulfur-sulfur bond by electrolytic oxidation (hereinafter, simply referred to as an organic disulfide compound) An organic disulfide compound) and a solution in which a lithium salt is dissolved in an aprotic organic solvent, and a gelling agent. Further, the lithium secondary battery of the present invention comprises a positive electrode comprising a composite film containing an organic disulfide compound and polyaniline, a solution in which a lithium salt and a lithium salt of an organic disulfide compound are dissolved in an aprotic organic solvent, and a gelling agent. And a negative electrode for capturing or supplying lithium ions.

Here, the gelling agent is preferably an acrylonitrile copolymer. The amount of the organic disulfide compound or the lithium salt thereof dissolved in the solution constituting the gel electrolyte ranges from 85% to 11% of the saturation amount.
It is preferably 0%. Further, it is preferable that the composite film of the positive electrode is a coating film of an N-alkyl-2-pyrrolidone solution in which an organic disulfide compound monomer containing a thiol group and polyaniline are dissolved. Further, for the negative electrode, a metal alloy such as lithium metal, lithium-aluminum, lithium-manganese, or a carbon material capable of reversibly inserting and extracting lithium ions, a metal sulfide, a metal oxide, or a conductive polymer is used. Can be

[0008]

The organic disulfide compound becomes a monomer at the time of electrolytic reduction and a polymer at the time of electrolytic oxidation in the composite film composed of the organic disulfide compound and polyaniline of the positive electrode. Polymeric organic disulfide compounds are insoluble in organic solvents, and monomeric organic disulfide compounds are soluble in organic solvents. The monomeric organic disulfide compound dissolved in the composite membrane flows out of the composite membrane to the electrolyte due to the concentration gradient. If the organic disulfide compound flows out of the electrode, the absolute amount of the battery active material decreases,
Battery capacity decreases. The flow of the organic disulfide compound into the electrolyte causes a reduction in the capacity of the battery as the charge / discharge cycle progresses. In addition, when the battery is stored in the electrolytic reduction state, the organic disulfide compound as a monomer flows out into the electrolyte over time, and the absolute amount of the battery active material decreases, so that the capacity of the battery decreases. The dissolution of the monomeric organic disulfide compound causes a deterioration in storage characteristics.

In the structure of the present invention, by dissolving the organic disulfide compound in the gel electrolyte in advance, the elution of the monomeric organic disulfide compound out of the composite film in the composite film during electrolytic reduction can be suppressed. In addition, the electrolyte in which the organic disulfide compound is dissolved in advance also serves as a supplier for supplying the organic disulfide compound to the composite membrane. For this reason, even if the organic disulfide compound becomes inactive in the composite membrane, a decrease in capacity can be prevented by newly supplying the organic disulfide compound from the electrolyte.

[0010]

Examples The organic disulfide compounds of the present invention include:
The compound represented by the general formula (R (S) _y ) _n described in US Pat. No. 4,833,048 can be used. R is an aliphatic group or an aromatic group, S is sulfur, y is an integer of 1 or more, and n is an integer of 2 or more. HSCH ₂ CH ₂ S
Dithioglycol represented by H, is represented by C ₂ N ₂ S (SH) represented by _{2 2,5-dimercapto-1,3,4-thiadiazole, C 3 H 3 N 3 S} 3 s- triazine −2,
4,6-trithiol, 7-methyl-2,6,8-trimercaptopurine represented by C ₆ H ₆ N ₄ S ₃ or C
_For example, 4,5-diamino-2,6-dimercaptopyrimidine represented by ₄ H ₆ N ₄ S ₂ is used. In each case, commercially available products can be used as they are. As polyaniline, aniline polymerized by electrolytic or chemical oxidation is used. From the viewpoint of solubility, reduced polyaniline in the undoped state is preferable. As such a polyaniline, there is “Anilead” manufactured by Nitto Denko Corporation. The degree of reduction (RDI) of polyaniline can be represented based on an electronic absorption spectrum of a solution in which polyaniline is slightly dissolved in N-methyl-2-pyrrolidone. That is, the intensity (I ₃₄₀ ) of the absorption peak due to the para-substituted benzene structure appearing on the short wavelength side near 340 nm and 6
Ratio of absorption peak intensity (I ₆₄₀ ) attributable to the quinone diimine structure appearing on the long wavelength side near 40 nm, RDI =
I ₆₄₀ / I ₃₄₀ is used as an index. Polyaniline having an RDI of 0.5 or less is preferably used. The degree of undoping of polyaniline is represented by conductivity. Conductivity is 10 ^-5
Polyaniline of S / cm or less is preferably used. In forming a composite film, N-alkyl-2-pyrrolidone is used as a solvent for uniformly dissolving the organic disulfide compound and polyaniline. N-alkyl-2-
As pyrrolidone, N-methyl-2-pyrrolidone, N
-Ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone are preferred because they give good solubility.

As an electrolyte solution for the gel electrolyte membrane, a solution in which a lithium salt is dissolved in an aprotic organic solvent is used. LiClO ₄ , LiB
F ₄ , LiPF ₆ , LiAsF ₆ , LiCF ₃ SO ₃ , Li
N (CF ₃ SO ₂ ) ₂ or the like is used alone, or a mixed salt thereof is used. As the aprotic organic solvent, ethylene carbonate, propylene carbonate, diethylene carbonate, dimethylene carbonate, dimethoxyethane, γ-butyrolactone, sulfolane, dimethyl sulfoxide alone or a mixed solvent thereof is used. As the gelling agent for the gel electrolyte, a polyacrylonitrile-based, polyvinylidene fluoride-based, polyvinylpyrrolidone-based, polyvinylidene carbonate-based, or polyether-based polymer main chain can be used. In terms of adhesiveness between the gel electrolyte and the electrode interface, it is preferable to use a polyacrylonitrile polymer or a copolymer thereof as the gelling agent. As the organic disulfide compound dissolved in the gel electrolyte, the same organic disulfide compound as in the positive electrode composite membrane is used. When this gel electrolyte is used as an electrolyte of a lithium battery, the organic disulfide compound dissolved in the gel electrolyte is desirably a lithium salt. When the dissolution amount of the organic disulfide compound in the aprotic organic solvent is 85% to 110% with respect to the saturation amount, both the suppression of charge / discharge cycle deterioration and the improvement of storage characteristics work very effectively.

Example 1 Preparation of electrode: 2,5-dimercapto-1,3,4-thiadiazole (hereinafter referred to as DMcT) monomer powder
5 g (0.01 mol) was dissolved in 3 g (0.03 mol) of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) to prepare a viscous yellow transparent DMcT-NMP solution. To this solution was added 0.5 g (0.003 mol, RDI) of "Anilead" powder manufactured by Nitto Denko as polyaniline.
= 0.3) and heated to 80 ° C in a sealed container purged with an inert gas to obtain a sticky dark green complex. The composite was printed on a titanium foil having a size of 4 × 4 cm and a thickness of 30 μm, and then subjected to a reduced pressure heat treatment at 80 ° C. and 1 cmHg for 1 hour to obtain a composite electrode having a thickness of 20 μm. This composite electrode was cut out to a size of 1 × 1 cm and used as a positive electrode for a battery.

Preparation of DMcT-Li salt: 30 ml of an aqueous solution in which 1.6 g of LiOH was dissolved was added dropwise to 100 ml of ethanol in which 6 g of DMcT was dissolved while stirring. After stirring at room temperature for 3 hours, the mixture was concentrated with an evaporator and suction-filtered. A cream-colored powder was obtained on the filter paper. This is washed several times with acetone and then dried under vacuum.
5.2 g of McT-Li were obtained.

Preparation of electrolyte: DMcT-Li salt is saturated in 20.7 g of a propylene carbonate (hereinafter, referred to as PC) -ethylene carbonate (hereinafter, referred to as EC) (1: 1 volume ratio) solution in which 1M of LiClO ₄ is dissolved. Amount (4.
5% by weight) and dissolved. To this solution, 3.0 g of a copolymer of acrylonitrile (hereinafter, referred to as AN) and ethyl acrylate (hereinafter, referred to as EA) (AN: EA copolymerization molar ratio = 90: 10) was added, stirred, and dissolved by heating. To prepare the electrolyte solution. This electrolyte solution was cast on a glass petri dish and left at 0 ° C. for 6 hours. Thus, a 0.5 mm thick gel electrolyte membrane 1-A was obtained. For comparison, a gel electrolyte membrane containing no DMcT-Li salt was prepared. A copolymer of acrylonitrile and ethyl acrylate (AN: EA copolymer molar ratio = 90: 20.7 g) in 20.7 g of a PC-EC (1: 1 volume ratio) solution in which 1M of LiClO ₄ was dissolved.
10) 3.0 g was added, and the mixture was stirred and dissolved by heating to prepare an electrolyte solution. This electrolyte solution was cast on a glass petri dish and left at 0 ° C. for 6 hours. Thus, a 0.5 mm thick gel electrolyte membrane 1-B was obtained. Each of the electrolyte membranes 1-A and 1-B was cut into a size of 1 × 1 cm.

Preparation of Battery: Metallic lithium having a thickness of 0.3 mm was cut into a size of 1 × 1 cm to obtain a negative electrode. The composite positive electrode membrane, the gel electrolyte membrane, and the metal lithium anode were sequentially stacked to form a 1 × 1 cm square battery. Batteries 1-A1 and 1-A2 using a gel electrolyte membrane 1-A as an electrolyte, and batteries 1-B1 and 1-B2 using a gel electrolyte membrane 1-B as an electrolyte were prepared.

Example 2 Preparation of electrode: 1.5 g of DMcT monomer powder (0.01 g
Mol) with 3 g of N-methyl-2-pyrrolidone (NMP)
(0.03 mol), viscous yellow transparent DM
A cT-NMP solution was prepared. To this solution was added 0.5 g of Nitto Denko "Anilead" powder as polyaniline.
(0.003 mol, RDI value = 0.3) was added, and the mixture was heated to 80 ° C in a closed container replaced with an inert gas to obtain a sticky dark green complex. This composite was printed on a titanium foil having a size of 4 × 4 cm and a thickness of 30 μm, and then subjected to a heat treatment under reduced pressure at 80 ° C. and 1 cmHg for 1 hour.
A composite electrode having a thickness of 20 μm was obtained. This composite electrode was cut out to a size of 1 × 1 cm and used as a positive electrode for a battery.

Preparation of DMcT-Li salt: 30 ml of an aqueous solution in which 1.6 g of LiOH was dissolved was added dropwise to 100 ml of ethanol in which 6 g of DMcT was dissolved while stirring. After stirring at room temperature for 3 hours, the mixture was concentrated with an evaporator, and suction filtration was performed. A cream-colored powder was obtained on the filter paper. This is washed several times with acetone, and then dried in vacuum.
5.2 g of cT-Li salt were obtained.

Preparation of electrolyte: 20.7 g of an EC-sulfolane (hereinafter referred to as SL) -diethylene carbonate (hereinafter referred to as DEC) (1: 1: 0.5 volume ratio) solution in which 1M LiBF ₄ was dissolved was added to DMcT. -Saturated amount of Li salt
(4.5% by weight) and dissolved. To this solution was further added a copolymer of acrylonitrile and ethyl acrylate (A
3.0 g of N: EA copolymerization molar ratio = 90: 10) was added, and the mixture was stirred and dissolved by heating to prepare an electrolyte solution. This electrolyte solution was cast on a glass petri dish and left at 0 ° C. for 6 hours. Thus, a 0.5 mm thick gel electrolyte membrane 2-A was obtained. For comparison, a gel electrolyte membrane containing no DMcT-Li salt was prepared. EC-S with 1M LiBF ₄ dissolved
A copolymer of acrylonitrile and ethyl acrylate (A) was added to 20.7 g of L-DEC (1: 1: 0.5 volume ratio) solution.
(N: EA copolymerization molar ratio = 90: 10), 3.0 g, and the mixture was stirred and dissolved by heating to prepare an electrolyte solution. This electrolyte solution was cast on a glass petri dish and left at 0 ° C. for 6 hours. Thus, a 0.5 mm thick gel electrolyte membrane 2-B was obtained. Each of the electrolyte membranes 2-A and 2-B was cut into a size of 1 × 1 cm.

Preparation of battery: Metal lithium having a thickness of 0.3 mm was cut into a size of 1 × 1 cm to obtain a negative electrode. The composite positive electrode membrane, the gel electrolyte membrane, and the metal lithium anode were sequentially stacked to form a 1 × 1 cm square battery. Batteries 2-A1 and 2-A2 using the gel electrolyte membrane 2-A as the electrolyte, and batteries 2-B1 and 2-B2 using the gel electrolyte membrane 2-B as the electrolyte were prepared.

Example 3 Preparation of Electrode: 1.5 g (0.01 g) of DMcT monomer powder
Mol) with 3 g of N-methyl-2-pyrrolidone (NMP)
(0.03 mol), viscous yellow transparent DM
A cT-NMP solution was prepared. To this solution was added 0.5 g of Nitto Denko "Anilead" powder as polyaniline.
(0.003 mol, RDI value = 0.3) was added, and the mixture was heated to 80 ° C in a closed container replaced with an inert gas to obtain a sticky dark green complex. This composite was printed on a titanium foil having a size of 4 × 4 cm and a thickness of 30 μm, and then subjected to a heat treatment under reduced pressure at 80 ° C. and 1 cmHg for 1 hour.
A composite electrode having a thickness of 20 μm was obtained. This composite electrode was cut out to a size of 1 × 1 cm and used as a positive electrode for a battery.

Preparation of DMcT-Li salt: 30 ml of an aqueous solution in which 1.6 g of LiOH was dissolved was added dropwise to 100 ml of ethanol in which 6 g of DMcT was dissolved while stirring. After stirring at room temperature for 3 hours, the mixture was concentrated with an evaporator and suction-filtered. A cream-colored powder was obtained on the filter paper. This is washed several times with acetone and then dried under vacuum.
5.2 g of McT-Li salt were obtained.

Preparation of electrolyte: DMC was added to 20.7 g of PC-EC (1: 1 volume ratio) solution in which 1M LiClO ₄ was dissolved.
T-Li salt was added and dissolved in a saturated amount (4.5% by weight). An acrylonitrile polymer (3.0 g) was further added to the solution, and the mixture was stirred and dissolved by heating to prepare an electrolyte solution. This electrolyte solution was cast on a glass petri dish and left at 0 ° C. for 6 hours. Thus, a 0.5 mm thick gel electrolyte membrane 3-
A was obtained. For comparison, a gel electrolyte membrane containing no DMcT-Li salt was prepared. 3.0 g of an acrylonitrile copolymer was added to 20.7 g of a PC-EC (1: 1 volume ratio) solution in which 1 M of LiClO ₄ was dissolved, and the mixture was stirred and dissolved by heating to prepare an electrolyte solution. This electrolyte solution was cast on a glass petri dish and left at 0 ° C. for 6 hours. Thus, a thickness of 0.
A 5 mm gel electrolyte membrane 3-b was obtained. Electrolytic membrane 3-A, 3
Both -B were cut out to a size of 1 × 1 cm.

Preparation of Battery: Metallic lithium having a thickness of 0.3 mm was cut into a size of 1 × 1 cm to obtain a negative electrode. The composite positive electrode membrane, the gel electrolyte membrane, and the metal lithium anode were sequentially stacked to form a 1 × 1 cm square battery. Batteries 3-A1 and 3-A2 using a gel electrolyte membrane 3-A as an electrolyte, and batteries 3-B1 and 3-B2 using a gel electrolyte membrane 3-B as an electrolyte were prepared.

Example 4 Preparation of an electrode: 2.3 g of s-triazine-2,4,6-trithiol (hereinafter referred to as TTA) monomer powder (0.2 g).
01 mol) with N-methyl-2-pyrrolidone (NMP) 6
g (0.06 mol), viscous yellow transparent T
A TA-NMP solution was prepared. To this solution was added 0.5 g of Nitto Denko "Anilead" powder as polyaniline.
(0.003 mol, RDI value = 0.3) was added, and the mixture was heated to 80 ° C in a closed container replaced with an inert gas to obtain a sticky dark green complex. This composite was printed on a titanium foil having a size of 4 × 4 cm and a thickness of 30 μm, and then subjected to a heat treatment under reduced pressure at 80 ° C. and 1 cmHg for 1 hour.
A composite electrode having a thickness of 20 μm was obtained. This composite electrode was cut out to a size of 1 × 1 cm and used as a positive electrode for a battery.

Preparation of TTA-Li salt: TTA powder 4.5
g of ethanol dispersed in 100 ml of LiOH 1.2
g of an aqueous solution in which g was dissolved was added dropwise while stirring.
After stirring at room temperature for 3 hours, the mixture was concentrated with an evaporator, and suction filtration was performed. A cream-colored powder was obtained on the filter paper.
This was washed several times with acetone and then dried under vacuum, thus obtaining 4.0 g of a TTA-Li salt.

Preparation of electrolyte: TTA was added to 20.7 g of a PC-EC (1: 1 volume ratio) solution in which 1M of LiClO ₄ was dissolved.
A Li salt was added and dissolved in a saturated amount (2.0% by weight). 2. A copolymer of acrylonitrile and ethyl acrylate (AN: EA copolymerization molar ratio = 90: 10) was further added to this solution.
0 g was added, and the mixture was stirred and dissolved by heating to prepare an electrolyte solution. This electrolyte solution was cast on a glass Petri dish and heated at 0 ° C for 6 hours.
Left for hours. Thus, a 0.5 mm-thick gel electrolyte membrane 4-A was obtained. For comparison, a gel electrolyte membrane containing no TTA-Li salt was prepared. A copolymer of acrylonitrile and ethyl acrylate (AN: E) was added to 20.7 g of a PC-EC (1: 1 volume ratio) solution in which 1M of LiClO ₄ was dissolved.
A copolymer molar ratio = 90: 10) 3.0 g was added and stirred,
The solution was heated and dissolved to prepare an electrolyte solution. This electrolyte solution was cast on a glass petri dish and left at 0 ° C. for 6 hours.
Thus, a 0.5 mm thick gel electrolyte membrane 4-B was obtained.
Each of the electrolyte membranes 4-A and 4-B was cut into a size of 1 × 1 cm.

Preparation of Battery: Metal lithium having a thickness of 0.3 mm was cut into a size of 1 × 1 cm to obtain a negative electrode. The composite positive electrode membrane, the gel electrolyte membrane, and the metal lithium anode were sequentially stacked to form a 1 × 1 cm square battery. Batteries 4-A1 and 4-A2 using a gel electrolyte membrane 4-A as an electrolyte and batteries 4-B and 4-B2 using a gel electrolyte membrane 4-B as an electrolyte were prepared.

The following tests were conducted for each of the above batteries. (1) Test batteries 1-A1, 2-A1, 3-A1, 4-A1, and 1-B with inferior cycle.
1, 2-B1, 3-B1, and 4-B1 were discharged at a constant current of 0.1 mA in the range of 4.25 to 2.25 V, and the discharge capacity (Q, unit: mAh) in each charge / discharge cycle was determined. The electrode performance was evaluated based on the degree of decrease in the discharge capacity (Q) with the progress of the charge / discharge cycle. Table 1 shows the results. (2) Storage battery 1-A2, 2-A2, 3-A2, 4-A2, 1-B
3. 2,2-B2, 3-B2, 4-B2 were stored at room temperature in the electrolytic reduction state for 60 days, and then at a constant current of 0.1 mA.
Discharge once in the range of 25 to 2.25 V, and discharge capacity (Q,
(Unit: mAh) was measured. Storage performance was evaluated based on the degree of decrease in the discharge capacity (Q). Table 2 shows the results.

[0029]

[Table 1]

[0030]

[Table 2]

As apparent from the above results, in the lithium secondary battery using the composite electrode in which the organic disulfide compound and the polyaniline are composited, the organic disulfide compound lithium-chlorinated in Examples 1-4 according to the present invention and the lithium When a solution obtained by dissolving a salt in an aprotic organic solvent is gelled and used as an electrolyte, a decrease in discharge capacity due to the progress of a charge / discharge cycle is reduced. In addition, a decrease in discharge capacity after storage of the battery is also reduced.

[0032]

According to the present invention, it is possible to obtain a long-life lithium secondary battery capable of extracting a large current and having little deterioration in charge / discharge cycles.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) H01M 10/36-10/40 H01M 4/02-4/62

Claims (5)

(57) [Claims] 1. A sulfur-sulfur bond is cleaved by electrolytic reduction to form a sulfur-metal ion (including proton) bond,
A solution in which a sulfur-metal ion bond regenerates an original sulfur-sulfur bond by electrolytic oxidation and a lithium salt dissolved in an aprotic organic solvent, and a gel electrolyte comprising a gelling agent , wherein the solution Organic diss to
The dissolved amount of the sulfide compound is from 85% to 11
Gel electrolyte that is 0% . 2. The gel electrolyte according to claim 1, wherein the gelling agent is an acrylonitrile copolymer. 3. A sulfur-sulfur bond is cleaved by electrolytic reduction to form a sulfur-metal ion (including proton) bond,
A positive electrode comprising a composite film containing an organic disulfide compound (hereinafter simply referred to as an organic disulfide compound) and a polyaniline in which a sulfur-metal ion bond regenerates the original sulfur-sulfur bond by electrolytic oxidation, a lithium salt and a lithium salt of the organic disulfide compound And a gel electrolyte comprising a gelling agent and a solution in which a solution is dissolved in an aprotic organic solvent, and a lithium secondary battery comprising a negative electrode for capturing or supplying lithium ions , wherein an organic disulfide to the solution is provided.
Dissolution of lithium salt of compound from 85% to saturation
110% lithium secondary battery . 4. The lithium secondary battery according to claim 3 , wherein the gelling agent is an acrylonitrile copolymer. 5. A sulfur-sulfur bond is cleaved by electrolytic reduction.
To form a sulfur-metal ion (including proton) bond,
Sulfur-sulfur original with sulfur-metal ion bond by electrolytic oxidation
Organic disulfide compounds that regenerate bonds (hereinafter simply
Called disulfide compounds. ) And polyaniline
Cathode composed of composite membrane, lithium salt and organic disulfide
Dissolve the lithium salt of the compound in an aprotic organic solvent
Electrolyte comprising a solution and a gelling agent,
Lithium with a negative electrode for capturing or supplying
A um secondary battery, the composite film of the positive electrode, the coating film in <br/> Oh Brighter lithium of N- alkyl-2-pyrrolidone solution prepared by dissolving an organic disulfide compound monomer and polyaniline containing a thiol group Rechargeable battery.