JP2007305461A - Controlling method of charging or discharging for power storage device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a controlling method of charging or discharging for a power storage device easily obtaining an excellent charging or discharging cycle property without using a special device/circuit. <P>SOLUTION: The method charging or discharging the power storage device charges or discharges the power storage device. The storage device is provided with a negative electrode with a negative electrode active substance; electrolyte; and a positive electrode containing collector, and a mixture layer formed on a surface of the collector containing an organic high molecular compound which has reaction mechanism of multiple electronic reactions, in which conductive material and at least two electrons or more participate as positive electrode active substance. Consequently, the storage device charges and discharges in such a manner that capacity utilization factor is 90% or less for the positive electrode active substance. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a charge / discharge control method for an electricity storage device having excellent charge / discharge cycle characteristics and high output and high energy density.

In recent years, with the widespread use of hybrid vehicles driven using both gasoline and electricity, uninterruptible power supplies, mobile communication devices, portable electronic devices, and the like, the demand for power sources used for them has increased.
For example, a lithium ion battery or an electric double layer capacitor is used as the power source, and development for the purpose of improving the performance of the lithium ion battery or the like has been vigorously advanced.

In order to realize an electricity storage device having a high output and a high energy density, studies using an organic compound as an electrode material have been conducted. For example, Patent Document 1 proposes to use an organic compound having a π-electron conjugated cloud as a new active material capable of rapid charge and discharge.
JP 2004-111374 A

  In an electricity storage device that uses an organic compound having a π-electron conjugated cloud as a positive electrode active material, the capacity of the positive electrode active material may be reduced in repeated charge and discharge due to dissolution of the positive electrode active material in the electrolyte as the charge and discharge reaction proceeds. . On the other hand, the use of a high molecular weight organic compound can suppress the solubility of the active material in the electrolytic solution. However, when charging and discharging are repeated in a range including a high voltage region, the capacity tends to decrease. There was a problem.

  Therefore, in order to solve the above-described conventional problems, the present invention, when an organic polymer compound having a reaction mechanism of multi-electron reaction is used as a positive electrode active material, without using a special device or circuit, It aims at providing the charging / discharging control method of the storage battery device from which the outstanding charging / discharging cycling characteristics are obtained easily.

The discharge control method for an electricity storage device according to the present invention includes a negative electrode having a negative electrode active material; an electrolyte; a current collector and a multi-electron reaction involving a conductive material and at least two electrons formed on the surface of the current collector. A positive electrode containing an organic polymer compound having a reaction mechanism as a positive electrode active material;
The power storage device is charged and discharged so that the capacity utilization rate of the positive electrode active material is 90% or less.

  By using the positive electrode active material in the above-mentioned range, when using an organic polymer compound as the active material, the reaction potential is controlled by limiting the utilization rate of the active material, and the deterioration of the active material due to the potential is suppressed. It becomes possible.

The negative electrode capacity of the negative electrode with respect to the positive electrode capacity of the positive electrode is preferably 90% or less.
By designing the negative electrode capacity to be within the above range with respect to the positive electrode capacity, it is possible to limit the utilization rate of the positive electrode active material without using a special circuit or device.

It is preferable to set the upper limit voltage during charging to be equal to or lower than the maximum reaction voltage of the charging voltage curve.
When an active material having a multi-electron reaction mechanism is used as the positive electrode active material, the charge / discharge curve has a plurality of flat portions. The maximum reaction voltage means the voltage of the flat portion located on the highest voltage side in the charging voltage curve. By setting the upper limit voltage at the time of charging using the steps between a plurality of flat portions in this charging voltage curve, the usage rate of the active material is limited by a simple method without using a special device or circuit. It becomes possible.

The organic compound preferably has a π electron conjugated cloud.
In the present invention, the organic polymer compound having a reaction mechanism of a multi-electron reaction involving at least two electrons is preferably a compound having a π-electron conjugated cloud in the molecule. A compound having a π-electron conjugated cloud contributes to an electrochemical reaction (charge / discharge reaction) by coordination of ions to a π-electron conjugated cloud in the molecule. Thus, since there is no structural change such as molecular bonding / cleavage in the charge / discharge reaction, it is possible to suppress deterioration associated with the charge / discharge reaction.

The organic polymer compound preferably includes a structure having a π electron conjugated cloud represented by the general formula (1) or the general formula (2).
General formula (1):

In the formula (1), X is a sulfur atom or an oxygen atom, R ^{1 to} R ⁴ are each independently a chain aliphatic group, a cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group Group or nitroso group, R ⁵ and R ⁶ are each independently a hydrogen atom, a chain aliphatic group or a cyclic aliphatic group, and the aliphatic group includes an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, It can contain at least one selected from the group consisting of a phosphorus atom, a boron atom and a halogen atom.
General formula (2):

In the formula (2), X is a nitrogen atom, and R ^{1 to} R ⁴ are each independently a chain aliphatic group, a cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, or a nitroso group. The groups R ⁵ and R ⁶ are each independently a hydrogen atom, a chain-like aliphatic group or a cyclic aliphatic group, and the aliphatic group includes an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, It can contain at least one selected from the group consisting of boron atoms and halogen atoms.
The organic polymer compound preferably includes a structure having a π electron conjugated cloud represented by the general formula (3).
General formula (3):

In formula (3), X ^{1 to} X ⁴ are each independently a sulfur atom, oxygen atom, selenium atom or tellurium atom, and R ¹ and R ² are each independently a chain aliphatic group or a cyclic aliphatic group. The aliphatic group may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom.

  According to the present invention, when an organic polymer compound having a reaction mechanism of a multi-electron reaction is used as a positive electrode active material, an electrical storage device that can easily obtain excellent cycle characteristics without using a special apparatus or circuit. The charge / discharge control method can be provided.

The best mode for carrying out the present invention will be described below with reference to the drawings.
(Embodiment 1)
FIG. 1 is a schematic longitudinal sectional view of an electricity storage device of the present invention. As shown in FIG. 1, the positive electrode 19 includes a positive electrode current collector 12 and a positive electrode mixture layer 13 containing an organic polymer compound in which at least two electrons are involved in the reaction as an active material. The separator 14 is arrange | positioned on the said positive electrode 19, and electrolyte solution is contained as needed. The negative electrode 20 includes a negative electrode current collector 17 and a negative electrode mixture layer 16 containing a negative electrode active material. The negative electrode 20 is disposed on the positive electrode 19 through the separator 14 so that the negative electrode mixture layer 16 and the positive electrode mixture layer face each other. The negative electrode 20, the separator 14, and the positive electrode 19 are accommodated in the case 11, and the inside of the case 11 is sealed by caulking the peripheral edge of the sealing plate 15 through the gasket 18 at the open end of the case 11. .

As the active material, an organic polymer compound in which at least two electrons are involved in the reaction can be used. The organic polymer compound in which two or more electrons are involved in the reaction is not particularly limited, and examples thereof include an organic polymer compound having a π electron conjugated cloud as an electrode active site.
In general, a polymer compound means a compound having a molecular weight of 10,000 or more, but the organic polymer compound in the present invention is a compound having a repetitive bond unit (a monomer unit comprising an organic compound), even if the molecular weight is less than 10,000. Any monomer unit composed of repetitive organic compounds may be combined to form a polymer.
Examples of the organic polymer compound include those having a structure having a π electron conjugated cloud represented by the following general formula (1).
General formula (1):

In the formula (1), X is a sulfur atom or an oxygen atom, R ^{1 to} R ⁴ are each independently a chain aliphatic group, a cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group Group or nitroso group, R ⁵ and R ⁶ are each independently a hydrogen atom, a chain aliphatic group or a cyclic aliphatic group, and the aliphatic group is a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, It can contain at least one selected from the group consisting of a silicon atom, a phosphorus atom, a boron atom and a halogen atom.

Examples of the compound represented by the general formula (1) include a compound represented by the general formula (4) or a compound represented by the chemical formula (5).
General formula (4):

In the formula (4), R ^{1 to} R ⁴ and R ^{7 to} R ¹⁰ are each independently a chain aliphatic group, a cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group or It is a nitroso group, and the aliphatic group may contain at least one selected from the group consisting of hydrogen atom, oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom and halogen atom.
Chemical formula (5):

In addition, in general formula (4), the energy levels at which electrons are extracted from two five-membered rings approach each other due to the presence of two benzene rings positioned in two five-membered rings, and the reaction is as if it were a one-electron reaction. proceed. Accordingly, the reaction rate is faster than in the case where R ⁵ and R ⁶ do not contain a benzene ring in the general formula (1). As typical examples of the compound of the general formula (4), compounds represented by the chemical formula (6) to the chemical formula (9) are preferable compounds.
Chemical formula (6):

  Chemical formula (7):

  Chemical formula (8):

  Chemical formula (9):

Examples of the organic polymer compound having the structure represented by the general formula (5) include, for example, the general formula (10) in which the compound of the general formula (5) is combined with another polymer such as polyacetylene or polymethyl methacrylate. Or the compound represented by General formula (11) is mentioned. These are preferable in terms of high stability in the electrolyte solution.
General formula (10):

In formula (10), n is an integer of 2 or more.
General formula (11):

In formula (11), n is an integer of 2 or more.
Examples of the organic polymer compound include those containing a structure having a π-electron conjugated cloud represented by the following general formula (2).
General formula (2):

In the formula (2), X is a nitrogen atom, and R ^{1 to} R ⁴ are each independently a chain aliphatic group, a cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, or a nitroso group. Groups R ⁵ and R ⁶ are each independently a hydrogen atom, a chain aliphatic group or a cyclic aliphatic group, and the aliphatic group is a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, It can contain at least one selected from the group consisting of phosphorus atom, boron atom and halogen atom.
Examples of the compound represented by the general formula (2) include a compound represented by the chemical formula (12).
Chemical formula (12):

Examples of the organic polymer compound include those having a structure having a π-electron conjugated cloud represented by the following general formula (3).
General formula (3):

In formula (3), X ^{1 to} X ⁴ are each independently a sulfur atom, oxygen atom, selenium atom or tellurium atom, and R ¹ and R ² are each independently a chain aliphatic group or a cyclic aliphatic group. The aliphatic group may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom.
Examples of the compound represented by the general formula (3) include compounds represented by the general formulas (13) to (16).
General formula (13):

In formula (13), X ^{1 to} X ⁴ are each independently a sulfur atom, oxygen atom, selenium atom or tellurium atom, and R ³ and R ⁶ are each independently a chain aliphatic group or a cyclic aliphatic group. , A hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group or a nitroso group, and the aliphatic group is selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. It may contain at least one selected.
General formula (14):

In formula (14), X ^{1 to} X ⁴ are each independently a sulfur atom, oxygen atom, selenium atom, or tellurium atom, and Y and Z are each independently a sulfur atom, oxygen atom, selenium atom, tellurium atom, or methylene. It is a group.
Formula (15):

In formula (15), X ^{1 to} X ⁴ are each independently a sulfur atom, oxygen atom, selenium atom, or tellurium atom, and R ⁵ and R ⁶ are each independently a chain aliphatic group or a cyclic aliphatic group. Group, hydrogen atom, hydroxyl group, cyano group, amino group, nitro group or nitroso group, and the aliphatic group consists of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom 1 or more types chosen from a group can be included, and n is 1 or more.
Formula (16):

In formula (16), X < ¹ > -X < ⁴ > is a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom each independently.
Moreover, as an organic polymer compound containing the structure represented by General formula (3), the organic polymer compound which has the compound represented by General formula (3) in a side chain is mentioned, for example. Examples of such an organic polymer compound include a compound represented by the general formula (17) in which the main chain skeleton is polyvinyl alcohol and the side chain is carboxytetrathiafulvalene.
Formula (17):

In formula (17), n is an integer of 2 or more.
In the form in which the above various compounds are used for the positive electrode 19, for the purpose of imparting electron conductivity to the positive electrode mixture layer 13, a carbon material such as carbon black, graphite, acetylene black, or a conductive material such as polyaniline, polypyrrole, or polythiophene. A polymer may be included in the positive electrode mixture layer 13. Further, a solid electrolyte made of polyethylene oxide or the like, or a gel electrolyte made of polymethyl methacrylate or the like may be included in the positive electrode mixture layer 13 as an ion conductive auxiliary agent.

Furthermore, in order to improve the binding property of the positive electrode active material, a binder such as polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-polytetrafluoroethylene, polyethylene, polyimide, polyacrylic acid or the like is added. You may include in a positive mix layer.
As the current collector, a metal foil, a metal mesh, a resin film containing a conductive filler, or the like is used as in a general battery.

  The electrolyte is used as a solution containing an electrolyte, and the electrolyte solution is a polymer electrolyte containing polyacrylonitrile, an acrylate monomer or a methacrylate monomer, a polymer electrolyte gelled with a copolymer of ethylene and acrylonitrile, or a solid electrolyte. In the case of an electrolyte solution, it is preferable to impregnate the separator with the electrolyte solution.

  The electrolyte may be any electrolyte that can be used for lithium ion batteries and non-aqueous electric double layer capacitors. Specifically, salts formed by combinations of cations and anions listed below can be used. As the cation species, alkali metal cations such as lithium, sodium and potassium, alkaline earth metal cations such as magnesium, quaternary ammonium cations such as tetraethylammonium and 1,3-ethylmethylimidazolium can be used. Anionic species include halide anions, perchlorate anions and trifluoromethanesulfonate anions, tetraborofluoride anions, trifluorophosphoric hexafluoride anions, trifluoromethanesulfonate anions, bis (trifluoromethanesulfonyl) imide anions, bis (per Fluoroethylsulfonyl) imide anion, and the like. These can be used alone or in combination.

When the electrolyte itself is in the form of a solution, it can be used alone without necessarily mixing it with a solvent. When the electrolyte itself is solid, it is necessary to use it by dissolving it in the following solvent.
The solvent for forming the electrolyte solution may be any solvent that can be used for lithium ion batteries and non-aqueous electric double layer capacitors. Specifically, nonaqueous solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyl lactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, and acetonitrile are preferable. These can be used alone or in combination.

Solid electrolytes include Li ₂ S—SiS ₂ , Li ₂ S—B ₂ S ₅ , Li ₂ S—P ₂ S ₅ —GeS ₂ , sodium / alumina (Al ₂ O ₃ ) amorphous or low phase transition temperature ( Tg) polyether, amorphous vinylidene fluoride-6-fluoropropylene copolymer, heterogeneous polymer blend polyethylene oxide and the like.

  The negative electrode active material is not particularly limited, but carbon materials such as graphite and amorphous carbon, lithium metal, lithium-containing composite nitride, lithium-containing titanium oxide, a composite of tin and carbon, tin and other metals And carbon materials having electric double layer capacity such as silicon, silicon oxide, and activated carbon can be used.

Next, the effect obtained by charging / discharging the electricity storage device so that the capacity utilization of the positive electrode active material is 90% or less in the method for controlling charge / discharge of the electricity storage device in the present invention will be described.
The capacity here means current capacity, and the capacity utilization is the capacity actually used in the charge / discharge reaction with respect to the theoretical capacity calculated based on the weight of the active material contained in the electrode. Mean percentage. The theoretical capacity of the active material is determined by the following equation with respect to the number of reaction electrons per polymer repeating unit (n) and the molecular weight (Mw) of the polymer repeating unit.
Theoretical capacity (mAh / g) = (n × 96500 / Mw) × (1000/3600)

  The case where the organic high molecular compound represented by General formula (17) is used for a positive electrode active material is demonstrated below. When tetrathiafulvalene is used as an active material as the low molecular weight material represented by the general formula (3), it has been confirmed that capacity degradation is caused by repeated charge / discharge tests due to elution of the active material accompanying the charge / discharge reaction. It has been confirmed that the use of such a polymer compound as an active material suppresses a decrease in capacity due to dissolution of the active material. However, a tendency has been confirmed that capacity deterioration occurs due to deterioration factors other than dissolution of the active material. As a result of the study by the present inventors, the knowledge that deterioration due to repeated oxidation-reduction reaction in a high potential state is obtained, and the capacity reduction is remarkably suppressed by using the electricity storage device at a capacity utilization rate of 90% or less. I found out that

(Embodiment 2)
The charge / discharge control method for an electricity storage device according to the present embodiment is a storage device using an organic polymer compound having a reaction mechanism of a multi-electron reaction involving at least two electrons per repeating unit as a positive electrode active material. The proportion of the negative electrode capacity is 90% or less.
When the negative electrode capacity is 90% or less with respect to the positive electrode capacity, the capacity of the electric storage device is inevitably regulated by the negative electrode capacity. For this reason, in this Embodiment, the capacity utilization factor of a positive electrode will be restrict | limited to 90% or less, and it becomes possible to suppress a capacity | capacitance fall similarly to Embodiment 1. FIG.

(Embodiment 3)
The charge / discharge control method for an electricity storage device in the present embodiment charges an upper limit voltage during charging in an electricity storage device using an organic polymer compound having a reaction mechanism of a multi-electron reaction involving at least two electrons as a positive electrode active material. Set it below the maximum reaction voltage of the voltage curve.
The maximum reaction voltage at the time of charging means the voltage of the flat part located on the highest voltage side in the charging voltage curve when the voltage curve at the time of charging has a plurality of flat parts. And it becomes possible to control the oxidation state of an active material by setting the upper limit voltage at the time of charge to below the maximum reaction voltage.

  Here, in FIG. 2, a polymer compound represented by the general formula (17) having a polyethylene oxide skeleton as a main chain and a tetrathiafulvalene skeleton as a side chain via a carboxyl group is used as a positive electrode active material. It is a charging voltage curve when Li is used for. When such an organic polymer compound is used for the positive electrode active material, the charging voltage curve has two flat portions (flat portions existing in the regions a and b). It is considered that the reaction from 0 to 1 valence proceeds in the low voltage region (region a in FIG. 2), and the reaction from 1 to 2 valence proceeds in the high voltage region (region b in FIG. 2).

For example, the maximum reaction voltage of the charging voltage curve shown in FIG. 2 is such that when the flat portion is inclined like the flat portion of the region b (3.65 to 3.9 V in FIG. 2), the flat portion of the region b It is a voltage near 3.9 V located on the high voltage side. And, by setting the voltage of 3.5V located near the inflection point of the two flat portions as the upper limit voltage, it becomes possible to limit the oxidation state of the active material to monovalent, and the capacity reduction accompanying the charge / discharge cycle Can be suppressed.
Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.

Example 1
(1) Production of positive electrode As the positive electrode active material, an organic compound represented by the above general formula (17) (number average molecular weight: 4050) was used. The above compound was synthesized by reacting polyvinyl alcohol (Aldrich) and carboxytetrathiafulvalene by dehydration condensation. 30 mg of the above compound and 30 mg of acetylene black were uniformly mixed, and 1 mg of N-methyl-2-pyrrolidone was further added to obtain a slurry. Next, 5 mg of polyvinylidene fluoride was added to the slurry and mixed to obtain a slurry-like positive electrode mixture. Further, the above positive electrode mixture was applied as a positive electrode current collector plate 12 onto an aluminum foil, vacuum-dried, and then punched and cut into a disk shape having a diameter of 13.5 mm. A positive electrode 19 on which the agent layer 13 was formed was produced. At this time, the coating weight of the positive electrode active material was 1.7 mg / cm ² per unit area.

(2) Production of Negative Electrode As a negative electrode active material, 15 mg of powdery graphite and 6 mg of acetylene black were uniformly mixed, and 6 mg of polyvinylpyrrolidone and 250 g of methanol were further added to obtain a slurry. This slurry-like negative electrode mixture is cast on an aluminum foil as a negative electrode current collector plate 17, vacuum-dried, and punched and cut into a disk shape having a diameter of 13.5 mm. A negative electrode 20 on which the mixture layer 16 was formed was produced.

(3) Production of Storage Battery Device A porous polyethylene sheet was used for the separator 14. As the electrolytic solution, a solution obtained by dissolving lithium borofluoride at a concentration of 1M in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a weight ratio of 1: 1 was used. In order to make the comparison easier, in this example, an electrolytic solution having a large capacity drop in the charge / discharge cycle was selected. Using the above positive electrode, negative electrode, separator, and electrolytic solution, the same coin-type electricity storage device as that in FIG. 1 was obtained.
In the above negative electrode production, negative electrodes having different capacities were prepared by controlling the thickness at the time of casting, and the negative electrode capacity with respect to the positive electrode capacity was changed to 30%, 50%, 70% and 90%, respectively. Produced. Samples having negative electrode capacities of 30%, 50%, 70%, and 90% with respect to the positive electrode capacities were produced as Samples 1, 2, 3, and 4. As comparative examples, coin-type electricity storage devices using a negative electrode having a negative electrode capacity of 100% and 150% with respect to the positive electrode capacity were prepared as Samples A and B.

  A charge / discharge cycle test was performed on each power storage device obtained above. The test conditions were a charge / discharge current value of 0.5 mA, an upper limit voltage of 4.0 V during charging, and a lower limit voltage of 3.0 V during discharge. About each electrical storage device, charging / discharging was performed 500 cycles, and the charge capacity maintenance rate per positive electrode active material at the time of the first, 50, 100, 300, 500 cycles was investigated. The capacity retention rate was expressed as a percentage of the initial capacity of sample A. The test results are shown in Table 1.

  Table 1 shows that good cycle characteristics are exhibited when the negative electrode capacity is 90% or less of the positive electrode capacity, but it was confirmed that the cycle deterioration was rapid when used exceeding 100% of the positive electrode capacity.

Example 2
Using the negative electrode having a capacity of 150% of the positive electrode capacity used in Example 1 as the negative electrode, an electricity storage device was produced in the same manner as in Example 1. Regarding the electricity storage device obtained above, a charge / discharge cycle test was conducted with a charge / discharge current value of 1 mA, a lower limit voltage of 3.0 V during discharge, and an upper limit voltage of 3.65 V or 3.8 V during charge. did. In addition, as a comparative example, a charge / discharge cycle test was performed under the same conditions as described above except that the upper limit voltage during charging was set to 4.0 V, and Sample C was obtained. The test results are shown in Table 2.

  By changing the upper limit voltage during charging from Table 2, it is possible to control the utilization factor of the active material, and if the utilization factor of the positive electrode active material is 80% or less, the capacity reduction is suppressed, and the charge / discharge cycle It was found that the characteristics were improved.

  The charge / discharge control method for an electricity storage device of the present invention can be suitably used for a lithium ion battery or an electric double layer capacitor.

It is a schematic longitudinal cross-sectional view of the coin-type battery which is an example of embodiment of this invention. It is a charge voltage curve when the main chain has a polyvinyl alcohol skeleton as the positive electrode active material and a polymer having a tetrathiafulvalene skeleton in the side chain is used.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Case 12 Positive electrode collector 13 Positive electrode mixture layer 14 Separator 15 Sealing plate 16 Negative electrode mixture layer 17 Negative electrode collector 18 Gasket 19 Positive electrode 20 Negative electrode

Claims (6)

A negative electrode having a negative electrode active material;
Electrolytes;
A current collector, and a mixture layer formed on a surface of the current collector as a positive electrode active material, comprising a conductive material and an organic polymer compound having a multi-electron reaction reaction mechanism involving at least two electrons. A positive electrode containing;
A charge / discharge control method for an electricity storage device comprising:
A charge / discharge control method for an electricity storage device, wherein the electricity storage device is charged / discharged so that a capacity utilization of the positive electrode active material is 90% or less. The negative electrode capacity of the negative electrode relative to the positive electrode capacity of the positive electrode is 90% or less,
The charging / discharging control method of the electrical storage device of Claim 1 characterized by these. Set the upper limit voltage during charging to the maximum reaction voltage of the charging voltage curve,
The charging / discharging control method of the electrical storage device of Claim 1 characterized by these. The organic polymer compound has a π-electron conjugated cloud in the molecule;
The charging / discharging control method of the electrical storage device of Claim 1 characterized by these. The organic polymer compound includes a structure having a π electron conjugated cloud represented by the general formula (1) or the general formula (2).
The charging / discharging control method of the electrical storage device in any one of Claims 1-4 characterized by these.
General formula (1):

In the formula (1), X is a sulfur atom or an oxygen atom, R ^{1 to} R ⁴ are each independently a chain aliphatic group, a cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group Group or nitroso group, R ⁵ and R ⁶ are each independently a hydrogen atom, a chain aliphatic group or a cyclic aliphatic group, and the aliphatic group includes an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, It can contain at least one selected from the group consisting of a phosphorus atom, a boron atom and a halogen atom.
General formula (2):

In the formula (2), X is a nitrogen atom, and R ^{1 to} R ⁴ are each independently a chain aliphatic group, a cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, or a nitroso group. Each of the groups R ⁵ and R ⁶ is independently a hydrogen atom, a chain aliphatic group or a cyclic aliphatic group, and the aliphatic group includes an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a phosphorus atom , At least one selected from the group consisting of a boron atom and a halogen atom. The organic polymer compound includes a structure having a π electron conjugated cloud represented by the general formula (3).
The charging / discharging control method of the electrical storage device in any one of Claims 1-4 characterized by these.
General formula (3):

In formula (3), X ^{1 to} X ⁴ are each independently a sulfur atom, oxygen atom, selenium atom or tellurium atom, and R ¹ and R ² are each independently a chain aliphatic group or a cyclic aliphatic group. And the aliphatic group may contain at least one selected from the group consisting of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom and halogen atom.

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