JP2002175803A - Anode for all-solid polymer battery, the total-solid polymer battery using the same and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anode for a total-solid polymer battery which is superior in electricity-charging/discharging characteristics, the all-solid polymer battery using the anode for the all-solid polymer battery, and manufacturing method of them. SOLUTION: The total-solid polymer battery and its manufacturing method are constituted of an anode active material, a crosslinked polyether, the anode for the all-solid polymer battery containing a non-crosslinked polyether, an electrolyte layer, and a cathode.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an all solid polymer battery, and more particularly, to an all solid polymer battery having an improved charge / discharge capacity and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, polymer electrolyte batteries have attracted attention because of the absence of electrolyte leakage, the ability to be small and thin, and the excellent shape flexibility. However, the polymer electrolyte battery has a problem that the charge and discharge capacity of the battery is low because the electrolyte does not penetrate into the inside of the electrode.

[0003] Polymer electrolyte batteries are classified into an all solid polymer battery in which the electrolyte comprises only a polymer and an electrolyte salt, and a gel polymer electrolyte battery in which a plasticizer such as an organic solvent is added to the all solid polymer battery to improve ionic conductivity. Of these, gel polymer electrolyte batteries are
JP-A-9-274933 and JP-A-11-3070
As disclosed in Japanese Patent Publication No. 82, a technique for improving the charge / discharge characteristics of a battery by previously incorporating a polymer electrolyte into an electrode to form a composite electrode has been developed.

[0004]

However, in the case of the all solid polymer battery, a polymer electrolyte is previously contained in the electrode, and for example, a composite electrode comprising a negative electrode active material made of a carbon material and a polymer electrolyte is also used.
The charge / discharge characteristics could not be improved.

In view of the above problems, an object of the present invention is to provide a negative electrode for an all-solid polymer battery having excellent charge / discharge characteristics.

Another object of the present invention is to provide an all solid polymer battery using the negative electrode for an all solid polymer battery and a method for producing the same.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that the negative electrode active material, the ion-conductive crosslinked polyether, and the crosslinked polyether The present inventors have found that the production of a composite electrode composed of a polyether that does not chemically crosslink can provide an all-solid-state polymer battery having excellent charge / discharge characteristics, and completed the present invention. That is, the present invention for achieving the above object is configured as follows for each claim.

[0008] According to the first aspect of the present invention, there is provided an anode active material,
A negative electrode for an all solid polymer battery comprising a crosslinked polyether and a non-crosslinkable polyether.

According to a second aspect of the present invention, there is provided the negative electrode for an all solid polymer battery according to the first aspect, wherein the negative electrode active material comprises a carbon material.

A third aspect of the present invention is the negative electrode for an all solid polymer battery according to the second aspect, wherein the carbon material has an average particle size of 1 to 20 μm.

The invention according to claim 4 is characterized in that the non-crosslinkable polyether is a linear polyethylene oxide or polypropylene oxide, or a copolymer thereof. 4. The negative electrode for an all solid polymer battery according to item 1.

According to a fifth aspect of the present invention, the non-crosslinkable polyether has the following structural formula (1):

[0013]

Embedded image

(Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl, methoxy, hydroxy, amino or aromatic compound group; n
Is 10 to 100,000). The negative electrode for an all solid polymer battery according to any one of claims 1 to 4, wherein

The invention according to claim 6 is characterized in that the amount of the non-crosslinkable polyether added is 2 to 50% by mass based on the crosslinked polyether. 2. The negative electrode for an all-solid polymer battery according to item 1.

A seventh aspect of the present invention is an all solid polymer battery using the all solid polymer battery negative electrode according to any one of the first to sixth aspects.

[0017] According to the present invention, an electrolyte layer containing a crosslinked polyether is formed on the negative electrode for an all solid polymer battery according to any one of claims 1 to 6; Forming a positive electrode comprising a positive electrode active material and a crosslinked polyether.

According to a ninth aspect of the present invention, an electrolyte layer containing a crosslinked polyether is formed on a positive electrode containing a positive electrode active material and a crosslinked polyether, and the electrolyte layer is formed on the electrolyte layer. A method for producing an all-solid-state polymer battery, comprising forming the negative electrode according to any one of the above items.

[0019]

According to the present invention configured as described above, the following effects can be obtained for each claim.

According to the first aspect of the present invention, there is provided a composite electrode comprising a negative electrode active material, an ion-conductive crosslinked polyether, and a polyether which is not chemically crosslinked to the crosslinked polyether. As a result, a negative electrode for an all-solid polymer battery having excellent charge / discharge characteristics can be obtained.

According to the second aspect of the invention, by using a carbon material as the negative electrode active material, a negative electrode for an all solid polymer battery having higher performance can be obtained.

According to the third aspect of the invention, by defining the average particle size of the carbon material, a negative electrode for an all solid polymer battery having excellent charge / discharge characteristics and productivity can be obtained.

In the inventions according to claims 4 to 6, the charge / discharge characteristics can be further improved by defining the suitable non-crosslinkable polyether contained in the negative electrode and the amount of addition.

According to the invention of claims 7 to 9, the all solid polymer battery having improved charge / discharge characteristics by using the anode for all solid polymer battery according to the present invention as the negative electrode of the all solid polymer battery. Can be obtained.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION A first invention of the present application is directed to a negative electrode for an all solid polymer battery, comprising a negative electrode active material, a crosslinked polyether having ionic conductivity, and a non-crosslinkable polyether. It is.

FIG. 1 shows an embodiment of a negative electrode for an all solid polymer battery according to the present invention. In the figure, 1 is a negative electrode active material, 2
Denotes an ion conductive polymer composed of a crosslinked polyether and a non-crosslinkable polyether, and 3 denotes a negative electrode current collector.

The negative electrode active material 1 is preferably made of a carbon material capable of inserting and extracting lithium ions. Specific examples of the carbon material include natural graphite, artificial graphite made of an organic sintered body, carbon black, activated carbon, carbon fiber, and the like. It is possible to use various materials other than the carbon material, and examples thereof include lithium metal, a wood alloy, and a lithium alloy such as a Li-Al alloy, but are not limited thereto.

In view of the effect of the particle size on the charge / discharge characteristics and the usability in manufacturing, the size of the carbon material is as follows:
It is preferable to use one having an average particle size of 1 to 20 μm.
The average particle size can be measured by a method for measuring various particle size distributions such as a sieving test or a sedimentation method.

In the present invention, the crosslinked polyether is a three-dimensionally crosslinked polymer having a crosslinked portion in a part of a linear polymer having an ether bond (—R—O—R′—) in the main chain. The linear polymer having an ether bond includes polyethylene oxide, polypropylene oxide,
These copolymers are exemplified. The crosslinked portion can be appropriately selected according to the type or use of the target polymer, and includes, for example, a hydroxy group, a carboxyl group, an amino group, and the like, but is not limited thereto. The degree of cross-linking is preferably such that the number of carbon atoms existing between one cross-linking portion and an adjacent cross-linking portion is a loose cross-link of about 50 to 300.

In the present invention, the term "non-crosslinkable polyether" refers to a polyether which does not chemically react with a crosslinked portion provided in the crosslinked polyether and is added to the negative electrode as another component. As the non-crosslinkable polyether, polyethylene oxide, polypropylene oxide, and copolymers thereof are preferably used.

Further, the following structural formula (1):

[0032]

Embedded image

(Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, a methoxy group, a hydroxy group, an amino group, or a group of an aromatic compound;
Is 10 to 100,000). In order to obtain more preferable charge / discharge characteristics, the number of repetitions n is more preferably 20 or more. The upper limit of the number of repetitions n is 1000
It is preferably 0 or less, more preferably 1000 or less, and particularly preferably 500 or less.

As the group of the aromatic compound, a phenyl group
(C₆H_Five-), Tolyl group (CH_ThreeC₆H _Four−), Xylyl
Group (CH_Three)_TwoC₆H_Three-), Benzyl group (C₆H_FiveCH
_Two-), Phenethyl group (C₆H_FiveCH_TwoCH_Two−), Α-me
Tylbenzyl group (C₆H_FiveCH (CH_Three)-), Bifeni
Group (C₆H_Five-C₆H_Four-), Naphthyl group (C_TenH
₇-) And their derivatives.
It is not limited to them.

The addition amount of the non-crosslinkable polyether is preferably 2 to 50% by mass, more preferably 5 to 30% by mass, based on the mass of the crosslinked polyether.
Within this range, an all-solid polymer battery having more excellent charge / discharge characteristics can be obtained.

A supporting electrolyte is contained in the ion conductive polymer 2 composed of a crosslinked polyether and a non-crosslinkable polyether. LiBF ₄ , as a supporting electrolyte,
Lewis acid salt such as LiPF ₆ , LiN (CF ₃ SO ₂ ) ₂ , L
sulfonates such as iCF ₃ SO ₃ , other LiClO ₄ ,
One or more lithium salts selected from LiCF ₃ CO _{2 and the} like can be used. The concentration of these supporting electrolytes is preferably adjusted so that the ratio of the number of lithium ions to the number of ether oxygen atoms in the crosslinked polyether (the number of lithium ions / the number of ether oxygen atoms) is 0.001 to 5, More preferably, it is 0.01 to 0.1.

As the negative electrode current collector 3, a copper foil, a nickel foil, an iron foil, a stainless steel foil or the like can be used.

By using the negative electrode for an all-solid polymer battery according to the present invention having the above-described structure, a negative electrode for an all-solid polymer battery having excellent charge / discharge characteristics can be obtained.

Next, one embodiment of a method for producing a negative electrode for an all solid polymer battery will be described.

The negative electrode active material 1, an uncrosslinked crosslinked polyether raw material, a noncrosslinkable polyether, and a supporting electrolyte are mixed, and an appropriate amount of a nonaqueous solvent such as ethylene carbonate or dimethyl carbonate is added. Disperse into a paste. This paste is applied to the negative electrode current collector 3, and the non-crosslinked crosslinked polyether raw material is subjected to a crosslinking reaction by heating or irradiation with ultraviolet rays or energy rays to form a negative electrode. In the case of performing a cross-linking reaction by heat, various polymerization initiators can be added to accelerate the cross-linking reaction. Examples of the polymerization initiator include azobisisobutylnitrile, benzoyl peroxide and the like. Examples of the polymerization initiator when a crosslinking reaction is caused by ultraviolet rays include benzyldimethyl ketal, acetophenone, and benzophenone. When a crosslinking reaction is performed by radiation, a polymerization initiator is not required, and crosslinking can be performed by direct irradiation with radiation. The initiator can be added to the paste or the like.

The second invention of the present application is an all-solid polymer battery using the above-described negative electrode. That is, it is an all-solid polymer battery including a positive electrode made of a positive electrode active material and a crosslinked polyether, an electrolyte layer, and the negative electrode.

FIG. 2 shows an embodiment of the all solid polymer battery according to the present invention. In the figure, 4 indicates a negative electrode, 5 indicates a positive electrode active material, 6 indicates a conductive additive, 7 indicates a crosslinked polyether, 8 indicates a positive electrode current collector, 9 indicates an electrolyte layer, and 10 indicates a positive electrode.

The positive electrode active material 5 absorbs and stores lithium ions.
Composed of a releasable metal oxide, such as LiCo
O ₂ , LiMn ₂ O ₄ , LiNiO ₂ , LiTiO ₂ , Li
Known materials such as FeO ₂ , LiMnO ₂ , LiRuO ₂ , and LiWO ₂ can be used.

The conductive assistant 6 may be added to improve the conductivity of the positive electrode. Examples of the conductive assistant include acetylene black, carbon black, graphite, and graphite.

As the crosslinked polyether 7, the same one as used for the negative electrode can be used. That is, a polymer obtained by three-dimensionally cross-linking a polyether made of polyethylene oxide, polypropylene oxide, a copolymer thereof, or the like via a cross-linking portion is used.

As the positive electrode current collector 8, aluminum foil,
Stainless steel foil or the like can be used.

The electrolyte layer 9 can have a structure in which a supporting electrolyte is contained in the same crosslinked polyether as that used for the negative electrode. Examples of the supporting electrolyte contained in the electrolyte layer 9 include Lewis acid salts such as LiBF ₄ and LiPF ₆ ,
Sulfonates such as (CF ₃ SO ₂ ) ₂ and LiCF ₃ SO ₃ ;
In addition, one or more lithium salts selected from LiClO ₄ , LiCF ₃ CO _{2 and the} like can be used.

The positive electrode, the negative electrode, and the electrolyte layer are not limited to those described above, and may be improved using various known techniques.

As a method for manufacturing the positive electrode, for example, the following method can be used. That is, the positive electrode active material 5, the uncrosslinked crosslinked polyether raw material, the supporting electrolyte, and the conductive additive 6 are mixed, and an appropriate amount of a non-aqueous solvent such as ethylene carbonate or dimethyl carbonate is added, and each is uniformly dispersed. Into a paste. This paste is mixed with the positive electrode current collector 8
And a non-crosslinked crosslinked polyether raw material is subjected to a crosslinking reaction by heating or irradiation of ultraviolet rays or energy rays to form a positive electrode. In the case of performing a cross-linking reaction by heat, various polymerization initiators can be added to accelerate the cross-linking reaction. Examples of the polymerization initiator include azobisisobutylnitrile, benzoyl peroxide and the like. Examples of the polymerization initiator when a crosslinking reaction is caused by ultraviolet rays include benzyldimethyl ketal, acetophenone, and benzophenone. When a crosslinking reaction is performed by radiation, a polymerization initiator is not required, and crosslinking is performed by directly irradiating radiation.
The initiator can be added to the paste or the like, and various types of supporting electrolytes that can be used for the positive electrode may be the same as those used for the negative electrode.

The following method can be used for producing the electrolyte layer 9. That is, an uncrosslinked polyether raw material and a supporting electrolyte are mixed, a suitable amount of a non-aqueous solvent such as ethylene carbonate or dimethyl carbonate is added, and each is uniformly dispersed to form a paste. This paste is applied to the prepared negative electrode, positive electrode, glass, or the like, and the non-crosslinked crosslinked polyether is crosslinked by heating or irradiation of ultraviolet rays or energy rays to form an electrolyte layer. When a crosslinking reaction is caused by heat, various polymerization initiators can be added to accelerate the crosslinking reaction. Examples of the polymerization initiator include azobisisobutylnitrile, benzoyl peroxide and the like. Examples of the polymerization initiator when a crosslinking reaction is caused by ultraviolet rays include benzyldimethyl ketal, acetophenone, and benzophenone. When a crosslinking reaction is performed by radiation, a polymerization initiator is not required, and crosslinking is performed by directly irradiating radiation. The initiator can be added to the paste or the like.

By laminating the positive electrode, the negative electrode, and the electrolyte layer manufactured by the above-described method, an all solid polymer battery according to the present invention can be obtained. An electrolyte layer made of a crosslinked polyether is formed on the negative electrode. It may be manufactured by forming a positive electrode comprising a positive electrode active material and a crosslinked polyether on the electrolyte layer, and conversely, forming an electrolyte layer comprising a crosslinked polyether on a positive electrode comprising a positive electrode active material and a crosslinked polyether. Alternatively, a negative electrode may be formed on the electrolyte layer.

In the laminating method, the positive electrode, the negative electrode, and the electrolyte layer may be separately manufactured, processed into a desired shape, and then laminated, or may be laminated and processed into a desired shape.
Further, it can be formed directly on the positive electrode, the negative electrode, and the electrolyte layer.

The crosslinked polyether and the supporting electrolyte used for the positive electrode, the negative electrode, and the electrolyte are preferably the same in consideration of the ionic conductivity at the interface. However, if sufficient battery performance can be obtained, It may be different.

[0054]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described.

Crosslinked polyethers are described in Electro
chem. Soc. , Vol. 145, No. 5, Ma
y 1998, p. 1521, a trifunctional polyether synthesized from ethylene oxide and propylene oxide, comprising three polyether chains terminated with acrylate esters. Was. Hereinafter, this synthesized trifunctional polyether was used as a crosslinked polyether raw material.

Example 1 As a carbon material as a negative electrode active material, 10 g of MCMB graphitized product (manufactured by Osaka Gas Co., Ltd.) having an average particle size of 20 μm, and a crosslinked polyether raw material 1
0 g and 2.2 g of LiBF _{4 as} a supporting electrolyte were mixed, and the following structural formula (2):

[0057]

Embedded image

The polyethylene oxide represented by
10% by mass (1 g) based on the crosslinked polyether raw material
Added to be. This mixture is added to the supporting electrolyte L
iBF _FourContaining 1 mol / l of a volume ratio of 1: 1
Ethylene carbonate (EC) and dimethyl carbonate
(DMC) and dispersed in 10 g of mixed solvent to form a paste
Was prepared. Next, a polymerization initiator is added to the negative electrode coating solution.
0.1% by mass of azobisisobutylnitrile
Applied in a thickness of 100μm on the surface of the copper foil which is the current collector
And dried at 90 ° C for 2 hours or more to produce a negative electrode
did.

Next, 10 g of the crosslinked polyether raw material and 2.2 g of LiBF _{4 serving} as a supporting electrolyte were mixed with 1 mol / liter of LiBF _{4 serving} as a supporting electrolyte.
1 and dispersed in 10 g of a mixed solvent of EC and DMC, and 0.1% by mass of benzyldimethyl ketal as a photopolymerization initiator.
This was added, applied on a glass plate, and irradiated with ultraviolet rays for 20 minutes or more to prepare a 100 μm-thick film-like electrolyte layer.

The positive electrode is made of LiMn ₂ O ₄ 1 which is a positive electrode active material.
0 g, 10 g of a crosslinked polyether raw material, 3 g of acetylene black as a conductive additive, and LiB as a supporting electrolyte.
F ₄ and 2.2g were mixed, a supporting electrolyte LiBF ₄ to 1mol / l containing the volume ratio of 1: 1 of EC and DM
C and dispersed in 10 g of a mixed solvent to prepare a paste-like positive electrode coating solution. Next, 0.1% by mass of azobisisobutylnitrile as a polymerization initiator was added to the positive electrode coating solution, and the mixture was applied to a surface of an aluminum foil as a positive electrode current collector at a thickness of 100 μm, and was heated at 90 ° C. for 2 hours or more. It dried and the positive electrode was produced.

The above-mentioned negative electrode, electrolyte layer and positive electrode were processed into appropriate sizes and bonded to obtain an all solid polymer battery.

Example 2 An all solid polymer battery was obtained in the same manner as in Example 1 except that 20% by mass (2 g) of polyethylene oxide was added to the crosslinked polyether raw material.

<Example 3> Instead of the polyethylene oxide represented by the above structural formula (2), the following structural formula (3):

[0064]

Embedded image

10% by mass (1 g) based on the crosslinked polyether raw material using polyethylene oxide represented by
Except for the addition, an all solid polymer battery was obtained in the same manner as in Example 1.

Example 4 Instead of the polyethylene oxide represented by the structural formula (2), the structural formula (3)
An all solid polymer battery was obtained in the same manner as in Example 1 except that polyethylene oxide represented by the following formula was used and 20% by mass (2 g) was added to the crosslinked polyether raw material.

Example 5 After a negative electrode was prepared in the same manner as in Example 1, 10 g of a crosslinked polyether raw material and 2.2 g of LiBF ₄ as a supporting electrolyte were contained, and 1 mol / L of LiBF ₄ as a supporting electrolyte was contained. 1: 1 volume ratio
The mixture was dispersed in 10 g of a mixed solvent of EC and DMC, and 0.1% of azobisisobutylnitrile as a polymerization initiator was added.
Was dried at a temperature of 2 hours or more to produce a negative electrode and an electrolyte layer integrally.

Next, LiMn ₂ O ₄ 10 which is a positive electrode active material is used.
g, 10 g of a crosslinked polyether raw material, 3 g of acetylene black as a conductive additive, and LiBF as a supporting electrolyte.
₄ 2.2 g, and LiBF ₄ as a supporting electrolyte was mixed with 1
EC / DMC with a volume ratio of 1: 1 containing mol / L
Was dispersed in 10 g of a mixed solvent to prepare a paste-like positive electrode coating solution. 0.1% by mass of azobisisobutylnitrile as a polymerization initiator was added to the positive electrode coating liquid, and the mixture was applied to a thickness of 100 μm on the one in which the negative electrode and the electrolyte layer were integrated. Drying was performed at a temperature of 90 ° C. for 2 hours or more to prepare an anode, an electrolyte layer, and a cathode so as to be integrated, and processed into an appropriate size to obtain an all-solid polymer battery.

Example 6 An all solid polymer battery was obtained in the same manner as in Example 5, except that 20% by mass (2 g) of polyethylene oxide was added to the crosslinked polyether raw material.

<Example 7> Instead of the polyethylene oxide represented by the above structural formula (2), the above structural formula (3)
An all solid polymer battery was obtained in the same manner as in Example 5, except that polyethylene oxide represented by the formula (1) was used and 10% by mass (1 g) was added to the crosslinked polyether raw material.

Example 8 Instead of the polyethylene oxide represented by the structural formula (2), the structural formula (3)
An all-solid-state polymer battery was obtained in the same manner as in Example 5, except that polyethylene oxide represented by the following formula was used and 20% by mass (2 g) was added to the crosslinked polyether raw material.

Example 9 A negative electrode and an electrolyte layer were integrally formed in the same manner as in Example 5.

Next, the positive electrode active material LiMn ₂ O ₄ 10
g, 10 g of a crosslinked polyether raw material, 3 g of acetylene black as a conductive additive, and LiBF as a supporting electrolyte.
₄ 2.2 g, and LiBF ₄ as a supporting electrolyte was mixed with 1
EC / DMC with a volume ratio of 1: 1 containing mol / L
And a paste-like positive electrode coating solution was prepared by dispersing the mixture in 10 g of a mixed solvent. 0.1 mass% of azobisisobutylnitrile as a polymerization initiator was added to the positive electrode coating solution, and the mixture was applied in a thickness of 100 μm to the surface of an aluminum foil as a positive electrode current collector.
After drying at a temperature of 2 ° C. for 2 hours or more, a positive electrode was prepared. In order to form a battery, an all-solid-state polymer battery was obtained by laminating the above-mentioned positive electrode with the negative electrode and the electrolyte layer integrally formed.

Example 10 An all solid polymer battery was obtained in the same manner as in Example 9 except that 20% by mass (2 g) of polyethylene oxide was added to the crosslinked polyether raw material.

<Example 11> Instead of the polyethylene oxide represented by the structural formula (2), the polyethylene oxide represented by the structural formula (3) was used, and 10% by mass ( Except for adding 1 g), an all solid polymer battery was obtained in the same manner as in Example 9.

<Example 12> Instead of the polyethylene oxide represented by the structural formula (2), the polyethylene oxide represented by the structural formula (3) was used, and 20% by mass ( Except for adding 2 g), an all solid polymer battery was obtained in the same manner as in Example 9.

Comparative Example 1 As a carbon material as a negative electrode active material, 10 g of MCMB graphitized product (manufactured by Osaka Gas Co., Ltd.) having an average particle size of 20 μm, and a crosslinked polyether raw material 1
0 g, and the mixture is mixed with LiB as a supporting electrolyte.
EC with a volume ratio of 1: 1 containing 1 mol / L of F ₄
And DMC were dispersed in 10 g of a mixed solvent to prepare a paste-like negative electrode coating solution. Next, 0.1% by mass of azobisisobutylnitrile as a polymerization initiator was added to the negative electrode coating solution, and applied to a surface of a copper foil as a negative electrode current collector in a thickness of 100 μm,
Drying was performed at a temperature of 90 ° C. for 2 hours or more to produce a negative electrode. The electrolyte layer and the positive electrode were produced in the same manner as in Example 1, and the negative electrode, the electrolyte layer, and the positive electrode were laminated to obtain an all solid polymer battery.

Table 1 summarizes the structures of the negative electrodes used in the all solid polymer batteries of Examples 1 to 12 and Comparative Example 1.

[0079]

[Table 1]

The obtained all-solid-state polymer batteries of Examples 1 to 12 and Comparative Example were charged at a constant current of 0.1 C until the battery voltage reached 4.2 V.
Constant voltage charging was performed at 2 V, and charging was performed for a total of 12 hours. Then 0.1C until battery voltage drops to 2.5V
And the initial discharge capacity was measured. Table 2 shows relative values of the discharge amount when the discharge amount of the comparative example is set to 1.

[0081]

[Table 2]

As is clear from Table 2, the all-solid-state polymer batteries of Examples 1 to 12 according to the present invention to which the linear polyether was added had much higher initial discharge capacity than Comparative Example 1. You can see that.

Although the present invention has been described based on the twelve embodiments, the present invention is not limited to these embodiments. The details such as the positive electrode active material, the method for producing the electrode, and the form of the battery to be produced can be appropriately selected, changed, and combined without departing from the gist of the present invention.

[Brief description of the drawings]

FIG. 1 is a sectional view of a negative electrode for an all solid polymer battery according to the present invention.

FIG. 2 is a cross-sectional view of the all solid polymer battery according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Negative electrode active material 2 Ion conductive polymer 3 Negative electrode current collector 4 Negative electrode 5 Positive electrode active material 6 Conductive auxiliary agent 7 Crosslinked polyether 8 Positive electrode current collector 9 Electrolyte layer 10 Positive electrode

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) H01M 10/40 H01M 10/40 B (72) Inventor Tomoaki Arimura 2 Takaracho, Kanagawa-ku, Yokohama-shi, Kanagawa Nissan F-term (Reference) 5H029 AJ02 AK03 AL06 AL07 AL08 AL12 AM07 AM16 BJ12 DJ09 EJ12 EJ14 HJ01 HJ02 HJ05 5H050 AA02 BA18 CA07 CA08 CA09 CB07 CB08 CB09 CB12 DA13 EA11 EA23 EA28 FA02 FA18 GA10

Claims (9)

[Claims] 1. A negative electrode for an all solid polymer battery comprising a negative electrode active material, a crosslinked polyether, and a non-crosslinkable polyether. 2. The negative electrode for an all solid polymer battery according to claim 1, wherein the negative electrode active material is made of a carbon material. 3. The carbon material has an average particle size of 1 to 2
The negative electrode for an all solid polymer battery according to claim 2, wherein the thickness is 0 µm. 4. The method according to claim 1, wherein the non-crosslinkable polyether is a linear polyethylene oxide or polypropylene oxide, or a copolymer thereof. Anode for solid polymer batteries. 5. The non-crosslinkable polyether has the following structural formula (1): (Wherein, R ¹ and R ² are each independently a hydrogen atom, or a methyl group, a methoxy group, a hydroxy group, an amino group, or a group of an aromatic compound, and n is 10 to 1
The negative electrode for an all solid polymer battery according to any one of claims 1 to 4, wherein the negative electrode is represented by the following formula: 6. The amount of the non-crosslinkable polyether added is:
The anode for an all solid polymer battery according to any one of claims 1 to 5, wherein the amount is 2 to 50% by mass based on the crosslinked polyether. 7. An all-solid polymer battery using the all-solid polymer battery negative electrode according to claim 1. Description: 8. An electrolyte layer containing a crosslinked polyether is formed on the negative electrode for an all solid polymer battery according to claim 1, and a positive electrode active material and a crosslinked polyether are formed on the electrolyte layer. A method for producing an all-solid polymer battery, comprising forming a positive electrode comprising ether. 9. An electrolyte layer comprising a crosslinked polyether is formed on a positive electrode comprising a positive electrode active material and a crosslinked polyether, and an electrolyte layer comprising the crosslinked polyether is formed on the electrolyte layer.
A method for producing an all-solid-state polymer battery, comprising forming the negative electrode described in the above item.