JP2005174560A - Conductive reformer and battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive reformer of an electrode capable of maintaining superior conductivity even in the case of being exposed to an atmosphere composed of a temperature region equal to or lower than the freezing point of water, and provide a battery using it. <P>SOLUTION: The conductive reformer 14 is at least constituted of a conductive polymer gel which has water as a main component, and contains a conductive conjugate polymer, a surfactant, and/or alcohol. Furthermore, in the battery 1 provided with at least a positive electrode 11, a negative electrode 12, and an electrolyte, at least one electrode surface of the positive electrode 11 and the negative electrode 12 has a constitution of being covered by the conductive reformer 14 which has water as the main component, and is constituted of the conductive polymer gel containing the conductive conjugate polymer, the surfactant, and/or the alcohol. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a conductive modifier for electrodes and a battery using the same.

In general, in a battery, a positive electrode and a negative electrode are immersed in an electrolytic solution in a state where they are opposed to each other. Since the electrolyte has a function of exerting conductivity, if the battery is exposed to a temperature range below the freezing point of water, the conductivity may become unstable or the conductivity may not be secured. It was.
In addition, a battery using a gel polymer electrolyte composed of a conductive polymer impregnated with an electrolytic solution instead of the electrolytic solution has been proposed (see Patent Document 1).
The gel polymer electrolyte is excellent in the ability to impregnate the electrolyte, not only prevents the mechanical properties from being lowered when the electrolyte is added, but also has excellent ionic conductivity and adhesion to the electrode. . For this reason, it is disclosed that the use of the gel polymer electrolyte improves the charge / discharge characteristics and efficiency, the battery life and the high temperature storage characteristics.
However, even in a battery using the gel polymer electrolyte, since the gel polymer electrolyte contains an electrolyte solution and the electrolyte solution has a function of exerting conductivity, the water is below the freezing point. When exposed to this temperature range, the conductivity may become unstable or the conductivity may not be ensured. That is, it has been difficult for conventional gel-like polymer electrolytes to maintain good conductivity in a low temperature atmosphere below the freezing point of water.
JP 2003-17128 A

  The object of the present invention has been made in view of the above circumstances. That is, an object is to provide an electrode conductivity modifier capable of maintaining good conductivity even when exposed to an atmosphere having a temperature range below the freezing point of water, and a battery using the same. And

That is, the conductive modifier according to the present invention is composed at least of a conductive polymer gel containing water as a main component and containing a conductive conjugated polymer, a surfactant and / or alcohol. It is a feature.
As a result, a stable electrolytic stimulus response (conductivity) can be obtained under severe conditions such that the outside air is below the freezing point of water. For this reason, the electroconductivity of an electrode surface can be improved by coat | covering and using electrodes, such as a battery, as a conductive modifier.
In addition, when the conductive modifier is exposed to an atmosphere having a temperature range higher than the freezing point of water, ion conductivity also works in addition to electronic conduction, thereby providing further excellent conductivity. It becomes possible.

In the structure of the conductive modifier, the conductive conjugated polymer is characterized by being doped with a dopant.
Thereby, the density | concentration of the carrier of a conductive polymer gel can be raised, and electroconductivity can be improved.

In the structure of the conductive modifier, the conductive polymer gel includes an electrolyte.
As a result, the electrolyte component can be held at a certain concentration in the conductive polymer gel, and the ionic species of the electrolyte component is distributed in a high concentration near the surface of the electrode coated with the conductive modifier. It can also be made. For this reason, even at a low temperature, the ionic species of the electrolyte component can be rapidly supplied to the electrode surface.

The battery according to the present invention is a battery comprising at least a positive electrode, a negative electrode, and an electrolyte, and at least one of the positive electrode and the negative electrode has a water as a main component, a conductive conjugated polymer, a surfactant, and It is characterized by being covered with a conductive modifier composed of a conductive polymer gel containing alcohol.
In the conductive modifier, a stable electrolytic stimulation response (conductivity) can be obtained under severe conditions such that the outside air is below the freezing point of water. Therefore, a battery whose electrode surface is coated with the conductive modifier. Provides excellent low temperature characteristics.

According to the conductive modifier of the present invention, even if the conductive conjugated polymer of the conductive polymer gel constituting the conductive modifier brings about conductivity, even if it is used in a temperature range below the freezing point of water. Since the electron conduction functions, good conductivity is ensured. Therefore, the conductive modifier of the present invention can provide stable conductivity even when used under severe conditions where the outside air is below the freezing point of water. For this reason, it is applied to the surface of a battery electrode, an electrode of an electrochemical sensor of a gas concentration detection element in which an ion conductive solid electrolyte such as zirconia or an electrolyte is provided between a pair of electrodes, and a multifunctional biomedical electrode. When coated, the conductive modifier of the present invention contributes to improving the stability of conductive characteristics such as impedance characteristics of various electrodes.
Further, when exposed to an atmosphere having a temperature range higher than the freezing point of water, ion conductivity also functions in addition to electronic conduction, so that much more excellent conductivity can be obtained.

  According to the battery of the present invention, the conductivity on the electrode surface can be improved by covering the electrode surface with the conductive modifier of the present invention, and the outside air is particularly below the freezing point of water. Under such severe conditions, stable and excellent output characteristics (low temperature characteristics) can be obtained.

Hereinafter, the battery according to the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a battery 1 of the present invention. The battery 1 includes at least a positive electrode (positive electrode plate) 11, a negative electrode (negative electrode plate) 12, and an electrolyte solution 13 disposed between the positive electrode 11 and the negative electrode 12. In the battery 1 shown as an example in FIG. 1, the positive electrode plate 11 and the negative electrode plate 12 are immersed in the electrolyte solution 13 so as to face each other.
Note that a porous membrane separator may be provided between the positive electrode 11 and the negative electrode 12 to prevent the positive electrode 11 and the negative electrode 12 from coming into contact with each other and causing an internal short circuit.

  The positive electrode 11 is composed of a conductive current collector and a positive electrode active material provided on the surface of the current collector. The negative electrode 12 is composed of a conductive current collector and a negative electrode active material provided on the current collector surface.

The above-described positive electrode active material and negative electrode active material are not particularly limited, and known materials can be applied.
For example, like a manganese battery, manganese dioxide can be used as the positive electrode active material and zinc can be used as the negative electrode active material. Moreover, like an alkaline battery, at least one or more selected from manganese dioxide, mercury oxide, silver oxide, and nickel oxyhydroxide can be used as the positive electrode active material, and zinc can be used as the negative electrode active material.
Moreover, like a lead acid battery, lead dioxide can be used as a positive electrode active material, and lead can be used as a negative electrode active material. Further, like a nickel-cadmium battery, nickel oxyhydroxide can be used as the positive electrode active material, and cadmium can be used as the negative electrode active material.
Further, like a nickel metal hydride battery, nickel oxyhydroxide can be used as the positive electrode active material, and a hydrogen storage alloy can be used as the negative electrode active material.

The electrolytic solution 13 is not particularly limited, and a known one can be applied according to the positive electrode active material or the negative electrode active material, and examples thereof include an electrolytic solution such as sulfuric acid and potassium hydroxide.
Instead of the electrolytic solution 13, a solid electrolyte in which the electrolytic solution 13 is impregnated with a polymer material may be applied.

The surface of the positive electrode 11 and the negative electrode 12 described above is coated with a conductive modifier 14. The conductive modifier 14 that is the gist of the present invention will be described in detail below.
FIG. 3A is an explanatory view schematically showing a colloidal aqueous dispersion of poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (hereinafter also referred to as PEDOT / PSS). FIG. 3B shows an example of the conductive polymer gel 2 of the present invention obtained by adding a surfactant 23 to the colloidal aqueous dispersion of PEDOT / PSS shown in FIG. It is explanatory drawing which shows this typically.
As shown in FIG. 3A, the PEDOT / PSS colloidal aqueous dispersion has PEDOT / PSS molecules dispersed in water 21. By adding the surfactant 23 to the PEDOT / PSS colloidal aqueous dispersion and placing it under gelation conditions, a three-dimensional network is formed via the surfactant 23 as shown in FIG. It is formed and gels easily by including water 21 therein, whereby the conductive polymer gel 2 is obtained.

As shown in FIG. 3B, the conductive modifier 14 of the present invention is composed of water 21 as a main component, and includes a conductive conjugated polymer 22, a surfactant 23 and / or an alcohol. At least from the conductive polymer gel 2.
The conductive polymer gel 2 is formed by gelling the conductive conjugated polymer 22 itself with the surfactant 23 and / or alcohol, and has been proposed in, for example, Japanese Patent Application No. 2003-19120 Etc. are applicable.
The conductive modifier 14 may be coated only on the surface of one of the positive electrode 11 and the negative electrode 12.

As shown in FIG. 2, PEDOT / PSS, which is an example of the conductive conjugated polymer 22, is poly (3,4-ethylenedioxythiophene) (hereinafter also referred to as PEDOT) and polystyrene sulfonic acid as a dopant. (Hereinafter also referred to as PSS).
As shown in FIG. 3, gelation is carried out by adding surfactant 23 (and / or alcohol) to a colloidal aqueous dispersion of PEDOT / PSS and placing it under gelation conditions, either physically or chemically. It is thought that this is due to the formation of a three-dimensional network, and that the resulting gel exhibits conductivity is due to electronic conductivity and / or ionic conductivity. Of course, it is not limited to these ideas.

  Examples of the conductive conjugated polymer 22 include polyacetylene, polyphenylene, polypyrrole, polythiophene, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyaniline, polyphenylene vinylene, polythiophene vinylene, polyperiphthalene, polyanthracene, poly Examples include at least one selected from naphthalene, polypyrene, polyazulene, and derivatives thereof. Among them, polypyrrole or polythiophene shown in FIG. 2 is preferable because it is highly stable and reliable and easily available. Used.

The conductive conjugated polymer 22 is preferably doped with a dopant, whereby the carrier concentration of the conductive polymer gel 2 is increased, and the conductivity can be improved.
Examples of the dopant include at least one selected from iodine, arsenic fluoride, iron chloride, perchloric acid, sulfonic acid, perfluorosulfonic acid, polystyrene sulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, and derivatives thereof. However, among them, polystyrene sulfonic acid is preferable because high conductivity can be easily adjusted.

  Specifically, the colloidal dispersion of the conductive conjugated polymer 22 is obtained, for example, by polymerizing 3,4-ethylenedioxythiophene in the presence of a catalyst such as iron (III) toluenesulfonate. Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) colloidal aqueous dispersion (hereinafter referred to as PEDOT / PSS) (trade name: BaytronP, conductive polymer (PEDOT / PSS) concentration of about 1. 3% by mass, manufactured by Bayer).

The surfactant 23 is not particularly limited, and may be a known cationic surfactant, anionic surfactant, amphoteric surfactant, nonionic surfactant, or a mixture of two or more thereof. At least one selected surfactant can be used.
Examples of the cationic surfactant include quaternary alkyl ammonium salts and alkyl pyridinium halides.
Examples of the anionic surfactant include alkyl sulfuric acid or its ester salt, polyoxyethylene alkyl ether sulfuric acid or its salt, alkyl benzene sulfonic acid or its salt, alkyl naphthalene sulfonic acid or its salt, alkyl sulfosuccinic acid or its salt, alkyl Examples thereof include diphenyl ether disulfonic acid or a salt thereof, fatty acid or a salt thereof, naphthalenesulfonic acid or a formalin condensate thereof.
Examples of amphoteric surfactants include alkyl betaines, amine oxides, and hydrolyzed collagens.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene rubitol fatty acid ester, polyoxyethylene fatty acid ester , Polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanolamide, or derivatives thereof.

Among these surfactants 23, long-chain alkylbenzene sulfonic acids are particularly preferred because gelation efficiency is improved.
The addition amount of the surfactant 23 used in the present invention in the conductive polymer gel 2 is not particularly limited, but is usually 0.1 to 30 parts by mass with respect to 1 part by mass of the conductive polymer. Preferably, it is 0.5-10 mass parts more preferably.
If it is less than 0.1 parts by mass, it may not be gelled, and if it exceeds 30 parts by mass, it may not gelate.

The alcohol is not particularly limited, and at least one alcohol selected from known monohydric alcohols and polyhydric alcohols or a mixture of two or more thereof can be used.
Examples of monohydric alcohols include branched or linear alcohols such as ethanol, isopropyl alcohol, and butanol, cyclic alcohols, polymeric alcohols, and mixtures of two or more thereof.
Examples of the polyhydric alcohol include glycols such as ethylene glycol and propylene glycol, chain polyhydric alcohols such as glycerin, erythritol, xylitol, and sorbitol, cyclic polyhydric alcohols such as glucose and scroll, polyethylene glycol, and polyvinyl alcohol. A polymeric polyhydric alcohol or a mixture of two or more of these may be used.
Among these alcohols, isopropyl alcohol, ethylene glycol, and polyethylene glycol can be preferably used. Among them, polyhydric alcohols such as ethylene glycol and polyethylene glycol are preferable for the following reasons. Ethylene glycol has an effect of gelation even at a low concentration and can be particularly preferably used because it is not volatile. Further, the molecular weight of polyethylene glycol is not particularly limited, but a molecular weight of 1000 is more preferable than a molecular weight of 400 because gelation occurs even if the addition amount is small.

The concentration of the alcohol used in the present invention in the conductive polymer gel 2 is not particularly limited, but is usually preferably 1 to 70 parts by weight, more preferably 10 parts per 1 part by weight of the conductive polymer. -50 mass parts.
If it is less than 1 part by mass, it may not be gelled, and if it exceeds 70 parts by mass, it may become too thin to be gelled.
In the present invention, the surfactant 23 and the alcohol can be used alone, but they can also be used in combination at any ratio.
In the present invention, the ratio of the surfactant 23 and the alcohol when used in combination is not particularly limited.

As a method of gelling the conductive conjugated polymer 22 with the surfactant 23 and / or alcohol, the following methods can be applied.
First, the surfactant 23 and / or alcohol as an additive is added to a colloidal dispersion liquid and / or a conductive conjugated polymer solution in which the conductive conjugated polymer 22 is colloidally dispersed in water 21. Pour in and add to avoid bubbles.
Next, it is left in an open space or sealed space in a normal atmospheric pressure without being subjected to vibration for a predetermined time (hereinafter referred to as stationary).
As described above, a three-dimensional network is formed and easily gelled, and the conductive polymer gel 2 can be obtained stably.
Here, the conductive conjugated polymer solution is obtained by dissolving the conductive conjugated polymer 22 in, for example, water or an organic solvent. In the present invention, the conductive conjugated polymer colloid dispersion liquid and the conductive conjugated polymer solution can be used alone, but they can also be used in combination at any ratio.

In the conductive polymer gel 2, the conductive conjugated polymer 22 constituting the conductive polymer gel 2 provides conductivity, so that even if it is used in a temperature range below the freezing point of water, electron conduction functions, so that it is good. Conductivity is ensured.
Therefore, the conductive modifier 14 of the present invention can provide stable conductivity even when used under severe conditions where the outside air is below the freezing point of water. For this reason, when it coat | covers on the electrode surface etc., the electroconductive modifier 14 of this invention contributes to the improvement of stability of electroconductive characteristics, such as an impedance characteristic of various electrodes.
In particular, in the case of a battery in which an oxide having poor electronic conductivity such as manganese dioxide or lead dioxide is used as the positive electrode active material or the negative electrode active material, the conductivity of the electrode surface can be greatly improved.
Further, when exposed to an atmosphere having a temperature range higher than the freezing point of water, ion conductivity also functions in addition to electron conduction, so that a further excellent conductivity can be obtained.

As a method of providing the conductive modifier 14 on the electrode surface, for example, a colloidal dispersion and / or a conductive conjugated polymer solution in which the conductive conjugated polymer 22 is first dispersed in a colloidal form in the water 21. In addition, the surfactant 23 and / or alcohol as an additive is poured and added so as not to generate bubbles to prepare a precursor solution. Next, this precursor solution is applied to the electrode surface, and is left in an open space or sealed space in a normal atmospheric pressure atmosphere without applying vibration for a predetermined time.
As described above, a three-dimensional network is formed on the electrode surface and gels easily, and the conductive polymer gel 2 can be obtained stably. Thereby, a thin film layer of the conductive modifier 14 composed of at least the conductive polymer gel 2 is formed on the electrode surface.
In this way, an electrode in which the surface of the electrode is coated with the conductive modifier 14 can be formed.
The thickness of the thin film layer made of the conductive modifier 14 provided on the surface of the electrode is preferably 0.01 μm or more and 50 μm or less, whereby the conductivity of the electrode surface can be greatly improved.

  Moreover, the ionic conductivity and electronic conductivity of the conductive polymer gel 2 are derived from the molecular structure. For this reason, the desired conductivity can be obtained by appropriately selecting the chemical species used as the conductive conjugated polymer 22, the surfactant 23 and / or the alcohol and the dopant, and adjusting the content of the dopant. In addition, the ionic conductivity and electronic conductivity of the conductive polymer gel 2 can be adjusted.

Moreover, in the conductive modifier 14, the electrolyte component is dissolved in the water 21 included in the conductive polymer gel 2, and the water 21 is contained in the conductive polymer gel 2 as an electrolytic solution. Is preferred.
The electrolyte component is not particularly limited, and known ones can be applied depending on the positive electrode active material and the negative electrode active material. For example, electrolyte components for aqueous electrolytes such as zinc chloride, ammonium chloride, dilute sulfuric acid, potassium hydroxide, lithium bromide, lithium perchlorate, lithium trifluoromethanesulfonate, potassium thiocyanate, lithium hexafluorophosphate, Electrolyte components for organic non-aqueous electrolytes such as lithium hexafluoroarsenate (organic acid salts, etc.), electrolyte components for inorganic non-aqueous electrolytes such as lithium aluminum tetrachloride, lithium carbonate-potassium chloride eutectic mixture, etc. Examples include molten salts and solid electrolytes such as β-alumina.

Since the water 21 in the conductive polymer gel 2 is included in a three-dimensional network, if the electrolyte component is dissolved in the water 21, the electrolyte component is contained in the conductive polymer gel 2. In addition, it is held at a certain concentration.
For this reason, by making the conductive polymer gel 2 contain the electrolyte component in a high concentration in advance, the ionic species of the electrolyte component is made high in the vicinity of the surface of the electrode coated with the conductive modifier 14. It can also be distributed.
In general, when the battery temperature becomes low, the ionic conductivity in the electrolytic solution 13 decreases. For this reason, the ionic species of the electrolyte component is not sufficiently supplied in the vicinity of the electrode surface, the electrolyte component in the vicinity of the electrode surface becomes low in concentration, and the oxidation-reduction reaction of the active material on the electrode surface becomes difficult to occur. Discharge characteristics will deteriorate.
However, since the electrode is coated with the conductive modifier 14 containing the electrolyte component, the ionic species of the electrolyte component can be distributed in a high concentration near the surface of the electrode. In addition, the ionic species of the electrolyte component can be supplied to the electrode surface. For this reason, even if it is low temperature, ion can be supplied stably and the further outstanding low temperature characteristic is acquired.

Specific examples according to the present invention are shown below, but the present invention is not limited to these specific examples.
(Example 1)
In this example, PEDOT / PSS, which is a conductive conjugated polymer colloidal dispersion (trade name: Baytron P, a conductive polymer (PEDOT / PSS) concentration of about 1.3 mass% colloidal water dispersion, manufactured by Bayer) 100 parts by mass, 30 parts by mass of ethylene glycol (Ethyleneglycol: (CH ₂ OH) ₂ : hereinafter abbreviated as EG) as an additive, and lithium trifluoromethanesulfonate (Trifluoromethanesulfuric Acid Lithium Salt) as an electrolyte component (electrolyte) 5 parts by mass of CF ₃ SO ₃ Li (hereinafter abbreviated as TFMS-Li) was added and mixed. After stirring for about 10 minutes, the mixture was left to stand at 10 ° C., 25 ° C., and 50 ° C. Samples with different standing temperatures by standing for 1 week Conductive modifier) were prepared separately.

(Example 2)
In this example, trifluoromethanesulfonic acid silver (CF ₃ SO ₃ Ag: hereinafter abbreviated as TFMS-Ag) was used instead of TFMS-Li as an electrolyte component, and the addition amount was 5 parts by mass. Samples (conductivity modifiers) having different standing temperatures were individually produced at the standing temperatures of 10 ° C., 25 ° C., and 50 ° C., except for the above.

(Example 3)
In this example, the additive as dodecylbenzenesulfonate _{(Dodecylbenzene sulfonic acid: (C 12} H 25 C 6 H 4 SO 3 H): hereinafter, also referred to as DBS) surfactants used consisting of the addition of 2 wt A case where an electrolyte component is further added will be described.
DBS was used instead of EG as an additive, the addition amount was 2 parts by mass, TFMS-Li was used as an electrolyte component, the addition amount was 5 parts by mass, except that it was left open when allowed to stand. By operating in the same manner as in Example 1, samples (conductive modifiers) having different standing temperatures were individually produced at the standing temperatures of 10 ° C., 25 ° C., and 50 ° C.

Example 4
In this example, TFMS-Ag was used instead of TFMS-Li as an electrolyte component, and the operation was performed in the same manner as in Example 3 except that the addition amount was 5 parts by mass. The standing temperatures were 10 ° C, 25 ° C, and 50 ° C. Thus, samples (conductive modifiers) having different standing temperatures were individually prepared.

(Example 5)
In this example, the electrolyte component was not added, and DBS was used instead of EG as an additive, and the addition amount was 0.7 parts by mass, which was sealed and allowed to stand for one day, as in Example 1. In operation, samples (conductivity modifiers) having different standing temperatures were individually produced at standing temperatures of 10 ° C., 25 ° C. and 50 ° C.

  In Examples 1 to 5, the degree of gelation was examined for the samples obtained at the individual standing temperatures. At that time, the following three levels (◯ mark, Δ mark, and X mark) were used as criteria for gelation. ○ indicates a solidified and self-supporting product is obtained; △ indicates that solidification is not achieved but a highly viscous product is obtained; × indicates the above two levels (○ and △ ) Indicates cases that do not fall under.

In addition, when the gel with the above-mentioned symbol ○ was obtained, the potential difference measurement method shown below was carried out using a sample having a standing temperature of 50 ° C. to examine the potential difference of the gel.
First, the gel is transferred to a container made of an insulating material, for example, a beaker, and a copper plate and an aluminum plate are inserted into the gel and fixed as an electrode with an interval of about 1 cm.
Next, a tester is connected via both plates forming electrodes and copper lead wires to form a measurement circuit.
And the electric potential obtained immediately after connecting a measuring circuit is read with a tester.
Table 1 summarizes the gelation determination results and the potential difference measurement results.
In addition, when the potential difference of distilled water was measured by the same measuring method, it was 100 mV.

From Table 1, the following points became clear.
(A) Under the conditions where the standing temperature is 10 ° C. and 25 ° C., gelation cannot be performed with any added amount.
(B) Under a condition where the standing temperature is 50 ° C., the gel (conductivity modifier) can be gelled, solidified and self-supported in any of the examples (Examples 1 to 4). )was gotten.
(C) The potential difference in the gel (Example 1) obtained by adding the electrolyte component consisting of TFMS-Li to the additive consisting of EG is the same as that of distilled water. However, the potential difference of the gel (Example 2) obtained by replacing the electrolyte component with TFMS-Ag increased three times.
(D) The potential difference in the gel (Example 3) obtained by adding the electrolyte component consisting of TFMS-Li to the additive consisting of DBS increased by about 50%. Then, when the electrolyte component was replaced with TFMS-Ag, the potential difference was greatly increased to 4 times.

From the above results, as shown in the above (c), the conductive polymer gel 2 can maintain a solid state while enclosing the water 21 (electrolytic solution) in which the electrolyte component is dissolved. For this reason, when the conductive polymer gel 2 is coated on the electrode surface as the conductive modifier 14, the ionic species of the electrolyte component can be distributed at a high concentration in the vicinity of the surface of the electrode.
Further, it was found that stable gelation was possible when an EG or DBS surfactant 23 and an electrolyte of TFMS-Li or TFMS-Ag were used as an additive under open conditions. Moreover, it was confirmed that the addition of the electrolyte caused an improvement in the potential difference, and that the effect was particularly remarkable when an electrolyte made of TFMS-Ag was added.
For this reason, when the electroconductive polymer gel 2 is applied as the electroconductive modifier 14 of an electrode, it can be used as an electrode and electrolyte integrated primary battery or secondary battery.

  Even if the conductive modifier of the present invention is used in a temperature range below the freezing point of water, electronic conductivity functions, so that good conductivity is ensured. Therefore, the conductive modifier is applied to the electrode surface. By covering, the conductivity of the electrode at a low temperature can be improved. For this reason, it can utilize as an electroconductive modifier of electrodes, such as a battery.

It is a schematic sectional drawing which shows an example of the battery of this invention. It is a schematic diagram which shows an example of the molecular structure of a conductive conjugated polymer. (A) is explanatory drawing which shows typically the colloid aqueous dispersion of PEDOT / PSS, (B) is explanatory drawing which shows typically an example of the conductive polymer gel of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Battery, 2 ... Conductive polymer gel, 11 ... Positive electrode, 12 ... Negative electrode, 13 ... Electrolyte, 14 ... Conductive modifier, 21 ... Water, 22 ... Conductive conjugate Polymer, 23 ... surfactant.

Claims (4)

A conductive modifier comprising at least a conductive polymer gel containing water as a main component and containing a conductive conjugated polymer, a surfactant and / or an alcohol. The conductive modifier according to claim 1, wherein the conductive conjugated polymer is doped with a dopant. The conductive modifier according to claim 1, wherein the conductive polymer gel contains an electrolyte. In a battery having at least a positive electrode, a negative electrode, and an electrolyte,
Of the positive electrode and the negative electrode, at least one electrode surface is composed of a conductive polymer gel comprising water as a main component and comprising a conductive conjugated polymer, a surfactant, and / or an alcohol. A battery characterized by being coated with a material.

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