JP3514080B2 - Positive electrode active material additive, positive electrode active material-containing composition obtained by blending the same, and battery using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a positive electrode active material additive used for generating electric energy, a positive electrode active material- containing composition prepared by mixing the same , and a battery using the same.

[0002]

2. Description of the Related Art Batteries are indispensable as a simple electric energy source for consumer use or as an important energy source for advanced equipment, and various types of batteries are available according to required performance. Researched and developed.

Further, under the situation that cordless electronic and electric devices are becoming more and more popular, batteries with higher energy density are required. Furthermore, from the aspect of protecting the natural environment, batteries having high environmental acceptability are required.

Conventionally, as a battery having a high energy density, a lithium battery using lithium as a negative electrode, a lithium ion battery using a lithium compound, and the like are known.

In general, as a positive electrode active material for such a battery, heavy metal oxides such as manganese dioxide, cobalt dioxide, vanadium pentoxide, lithium manganese oxide and lithium cobalt oxide, iodine, thionyl chloride and graphite fluoride are used. Inorganic compounds, organic polymers such as polyaniline, polypyrrole and polythiophene are used.

However, the above-mentioned heavy metal oxides are
Usually, since it is not soluble in a solvent, it cannot be said that molding and processing are easy. Further, the above-mentioned inorganic compounds are toxic compounds, or have heavy metals which are not preferable from the viewpoint of protecting the natural environment (that is, low environmental acceptability), and further, for example, fluorinated graphite, Since it has neither ionic conductivity nor electronic conductivity, it has various problems at the time of battery production, and cannot be a secondary battery. Further, the above-mentioned organic polymers cannot be a high-electromotive force positive electrode material only by this organic polymer, so that a so-called doping step and charging step are required, which complicates the battery manufacturing step, Generally, when synthesizing this kind of polymer as a positive electrode active material, an electropolymerization method is used. According to this method, however, since this polymer can be formed only on the electrode, it is possible to meet various requirements. There are great limitations in manufacturing batteries.

As described above, the positive electrode active material used in the conventional battery having high electromotive force and high energy has various problems.

[0008]

As a means for solving these drawbacks, the inventor of the present invention can easily produce a battery satisfying the above-mentioned environmental acceptability, electromotive force, energy density and the like. A method of using a compound having an F bond as a positive electrode active material has been found (see JP-A-7-6756).

Further, the present inventor has found that as a positive electrode active material,
Among the compounds having an NF bond, in a battery containing an N-fluoropyridinium salt, halogen, an interhalogen compound, a polyhalide, and an in-situ by a reaction are added as additives for obtaining a battery with higher performance. A compound capable of generating the halogen, the interhalogen compound, and the polyhalogen compound was found [Japanese Patent Application No. 8-203497 and Proceedings of the 72nd Annual Meeting of the Chemical Society of Japan (II), page 1299, 3K243 (1997). ) Reference: Hereinafter, it may be referred to as the above invention].

However, although these additives have excellent functions as additives for obtaining high-performance batteries, they are substances that are highly toxic and corrosive, and gas that is highly toxic and corrosive. Alternatively, since it is a substance that generates steam, when it is attempted to industrialize it, there are practically large restrictions in terms of handling and corrosion.

[0011] The present invention has been made in view of the conventional circumstances described above, and its object is as a cathode active material N-
In a battery containing a fluoropyridinium salt, a positive electrode active material additive that enables high performance of battery characteristics and has extremely low toxicity and corrosiveness, and a positive electrode active material containing the same
An object of the present invention is to provide a containing composition and a battery using the same.

[0012]

As a result of intensive studies to solve the above problems, the present inventor has found that a specific halo compound having extremely low toxicity and corrosivity is used as an additive for a positive electrode active material. It has been found that a positive electrode active material- containing composition having excellent battery characteristics (for example, internal resistance, discharge capacity, etc.) and low toxicity and corrosiveness and high environmental acceptability can be produced.

That is, the present invention is an additive to a positive electrode active material containing an N-fluoropyridinium salt, which is at least one halo selected from the group consisting of haloalkanes, haloalkenes, N-haloamides and N-haloimides. The present invention relates to a positive electrode active material additive composed of a compound (hereinafter referred to as an additive of the present invention).

The present invention also provides N- as a positive electrode active material.
Fluoro pyridinium salt, haloalkane, haloalkene, N- haloamides and N- least one halo compound selected from the group consisting of haloimide is formed by blending a positive electrode active material-containing formulation (hereinafter, a positive electrode active material containing the present invention
It is called a compound . ).

[0015] In addition, the positive electrode active material containing of the present invention, the present invention
As a battery using the compounded compound, a compound containing a positive electrode active material, which is prepared by compounding an N-fluoropyridinium salt with at least one halo compound selected from the group consisting of haloalkanes, haloalkenes, N-haloamides and N-haloimides.
The present invention relates to a battery using an object (hereinafter, referred to as a battery of the present invention).

The additive of the present invention realizes high performance of battery characteristics to the extent that it is superior or inferior to the additives of the halogen, interhalogen compound, polyhalide and the like in the preceding invention, and also has toxicity and toxicity. Since corrosiveness is extremely small, when manufacturing high performance batteries using this, manufacturing safety and handling problems, manufacturing equipment and battery case material problems, and battery safety and storage It is possible to solve the problems, such as the problem of sex, which were a big limitation in the previous invention.

In the battery of the present invention, since the N-fluoropyridinium salt effective as the positive electrode active material has an ionic structure, it can also serve as an electrolyte.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION As the battery of the present invention, for example,
A battery composed of positive electrode current collector / positive electrode / electrolyte / separator / negative electrode can be constituted, and the positive electrode is composed of the positive electrode active material and the negative electrode is composed of the negative electrode active material.

However, when the positive electrode active material also has a performance as an electrolyte, the electrolyte may not be used, and the interface between the positive electrode and the negative electrode may not be short-circuited by a protective film formed by the reaction. May not use a separator. In addition, when the positive electrode active material acts as a positive electrode current collector, the positive electrode current collector may not be used, and when it is convenient to use the negative electrode current collector, the negative electrode current collector should be used. You can

The positive electrode active material-containing formulations of the present invention, N- fluoro pyridinium salt, haloalkane, haloalkene, at least one halo compound selected from the group consisting of N- haloamides and N- haloimides (hereinafter, halo compound May be referred to as "."). Further, in order to reduce the internal resistance, it is preferable to add a conductive agent, a polar compound, etc., and a binder (binder) etc. May be.

The positive electrode reaction of the N-fluoropyridinium salt according to the present invention is expected to be as follows.

[Chemical 1]

First, the N-fluoropyridinium salt that can be used in the present invention will be described.

Preferred compounds as the N-fluoropyridinium salt include compounds represented by the following general formulas (1), (2), (3) and (4).

[Chemical 2]

Here, the general formulas (1), (2),
In (3) and (4), adjacent R ¹ and R ² , R ²
And R ³ , R ³ and R ^4, or R ⁴ and R ⁵ may be linked to each other to form the following structure. ^{-CR 6 = CR 7 -CR 8 =} CR 9 - Further, in the general formula (3), adjacent R ^{1 'and} R ^2', R ^{2 'and} R ^3', R ^{3 'and} R ^4' or R ^{4 ′} and R ^{5 ′} may be linked to each other to form the following structure. ^{-CR 6 '= CR 7' -CR} 8 '= CR 9' -

However, in the above general formulas and structures, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
^{R 8, R 9, R 1} ', R 2', R 3 ', R 4', R 5 ', R 6', R
^{7 ′} , R ^{8 ′} and R ^{9 ′} are at least two identical or
Alternatively, they are all different groups, and may be a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a cyano group, a carbamoyl group, or other substituents described later. )

Examples of the substituent include an alkyl group having 1 to 15 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and a carbon atom. An acyl group having 1 to 5 carbon atoms, an acyloxy group having 1 to 5 carbon atoms, and 6 to 10 carbon atoms
Alkyl group having 1 to 15 carbon atoms having at least one substituent selected from the group consisting of aryl groups, alkenyl group having 1 to 15 carbon atoms, halogen atom, and 6 to 10 carbon atoms. 1 carbon atom having at least one substituent selected from the group consisting of aryl groups of
To alkenyl group having 1 to 15 carbon atoms, alkynyl group having 1 to 15 carbon atoms, halogen atom, and 6 to 10 carbon atoms
Alkynyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, or a halogen atom, or 1 to 5 carbon atoms having at least one substituent selected from the group consisting of 6 to 6 carbon atoms having at least one substituent selected from the group consisting of
15 aryl groups, or acyl groups having 1 to 15 carbon atoms, or 1 to 1 carbon atoms substituted with halogen atoms
5 acyl group, or an alkoxycarbonyl group having 2 to 15 carbon atoms, a halogen atom, or 6 to 1 carbon atoms
An alkoxycarbonyl group having 2 to 15 carbon atoms having at least one substituent selected from the group consisting of 0 aryl groups, or an aryloxycarbonyl group having 7 to 15 carbon atoms, or a halogen atom or a carbon atom. Number 1-5
An aryloxycarbonyl group having 7 to 15 carbon atoms having at least one substituent selected from the group consisting of alkyl groups, an alkylsulfonyl group having 1 to 15 carbon atoms, a halogen atom, and the number of carbon atoms. An alkylsulfonyl group having 1 to 15 carbon atoms having at least one substituent selected from the group consisting of 6 to 10 aryl groups, or an arylsulfonyl group having 6 to 15 carbon atoms, or a halogen atom or carbon. Arylsulfonyl group having 6 to 15 carbon atoms having at least one substituent selected from the group consisting of alkyl groups having 1 to 5 atoms, or alkylsulfinyl group having 1 to 15 carbon atoms, or halogen atom. Having 1 to 15 carbon atoms having at least one substituent selected from the group consisting of aryl groups having 6 to 10 carbon atoms Ruki Rusuru arylsulfinyl group, or,
An arylsulfinyl group having 6 to 15 carbon atoms, or an arylsulfinyl group having 6 to 15 carbon atoms, which has at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 5 carbon atoms, Alternatively, an alkoxy group having 1 to 15 carbon atoms, or a halogen atom, an alkoxy group having 1 to 15 carbon atoms having at least one substituent selected from the group consisting of aryl groups having 6 to 10 carbon atoms, Alternatively, an aryloxy group having 6 to 15 carbon atoms, or an aryloxy group having 6 to 15 carbon atoms having at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 5 carbon atoms. Group, an acyloxy group having 1 to 15 carbon atoms, an acyloxy group having 1 to 15 carbon atoms substituted with a halogen atom, or a carbon atom C15 acylthio group, or an acylthio group of 1-15 carbon atoms substituted with a halogen atom or alkanesulfonyloxy group having 1 to 15 carbon atoms, or a halogen atom, carbon atoms 6-10
C1 to C15 alkanesulfonyloxy group having at least one substituent selected from the group consisting of aryl groups, or C6 to C15 arenesulfonyloxy groups, or a halogen atom or a carbon atom. Number 1
An arenesulfonyloxy group having 6 to 15 carbon atoms having at least one substituent selected from the group consisting of 5 alkyl groups, or a carbamoyl group substituted with an alkyl group having 1 to 5 carbon atoms, or 6 to 10 carbon atoms
The carbamoyl group substituted with an aryl group, a carbamoyl group substituted with an aryl group having 6 to 10 carbon atoms, or the carbamoyl group substituted with an alkyl group having 1 to 5 carbon atoms, or carbon Number of atoms 1-5
An amino group substituted with an acyl group, or the amino group substituted with a halogen atom, or 6 to 15 carbon atoms
N-alkylpyridinium base of, or a halogen atom,
Aryl group having 6 to 10 carbon atoms and 1 to 5 carbon atoms
The N-alkylpyridinium base having at least one kind of substituent selected from the group consisting of alkyl groups, an N-arylpyridinium base having 11 to 15 carbon atoms, a halogen atom, and 6 to 10 carbon atoms. The N-arylpyridinium base having at least one substituent selected from the group consisting of the aryl group and an alkyl group having 1 to 5 carbon atoms, or an organic polymer chain.

The R ¹ , R ² , R ³ , R ⁴ and
^{R 5, R 6, R 7} , R 8, R 9, R 1 ', R 2', R 3 ', R
^{4 ′} , R ^{5 ′} , R ^{6 ′} , R ^{7 ′} , R ^{8 ′} and R ^{9 ′} can be variously combined and are different atoms (hetero atoms) from each other.
A ring structure may be formed with or without intervening, and in the general formula (2), R ¹ , R ² , R ³ and R
^{One of 4} , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is
It is a group represented by the following general formula (a).

[Chemical 3] (However, in the general formula (a), R is a single bond or an alkylene group having 1 to 5 carbon atoms.)

In the general formula (3), R ¹ ,
One of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , R ^{6 '} ,
One of R ^{7 ′} , R ^{8 ′} and R ^{9 ′} forms a bonding chain with a single bond.

In the general formula (4), R ¹ ,
^{Two of} R ² , R ³ , R ⁴ and R ⁵ may be a single bond to form a polymer chain, and the repeating units represented by the general formula (4) may be the same. It may be different.

In each of the above formulas, a base represented by the following formula A

[Chemical 4] Is a conjugate base of Bronsted acid.

Examples of the Bronsted acid for producing the conjugated base represented by the above formula A include methanesulfonic acid,
Butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, trinitrobenzenesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, perfluorobutanesulfonic acid Fluoro (2-ethoxyethane) sulfonic acid, perfluoro (4-ethylcyclohexane)
Sulfonic acid, trichloromethanesulfonic acid, difluoromethanesulfonic acid, trifluoroethanesulfonic acid, fluorosulfonic acid, chlorosulfonic acid, camphorsulfonic acid, bromocamphorsulfonic acid, Δ ⁴ -cholesten-3-one-6-sulfonic acid, 1-hydroxy-p-
Menthane-2-sulfonic acid, p-styrenesulfonic acid,
Sulfonic acids such as β-styrene sulfonic acid, vinyl sulfonic acid, perfluoro-3,6-dioxa-4-methyl 7-octene sulfonic acid; poly (vinyl sulfonic acid),
Poly (p-styrenesulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid), poly (perfluoro-3,6-dioxa-4-methyl-7-)
Octene sulfonic acid) and poly (styrene-vinyl sulfonic acid), which is a copolymer with styrene or tetrafluoroethylene, poly (styrene-styrene sulfonic acid), poly [styrene- (2-acrylamido-2-methyl-1 -Propanesulfonic acid)], poly [tetrafluoroethylene- (perfluoro-3,6-dioxa-4)
-Methyl-7-octene sulfonic acid)] and the like; mineral acids such as sulfuric acid, phosphoric acid and nitric acid; hydrogen fluoride,
Hydrofluoric acid, hydrogen chloride, hydrochloric acid, perchloric acid, perbromic acid,
Periodic acid, chloric acid, bromic acid, and other halogen acids; monomethyl sulfuric acid, monoethyl sulfuric acid, and other monoalkyl sulfuric acids; acetic acid, formic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, dichloroacetic acid, acrylic acid, and other carboxylic acids ; Polyacrylic acid, poly (perfluoro-
3,6-dioxa-4-methyl-7-octenoic acid), and polycarboxylic acids such as copolymers of these with tetrafluoroethylene; HAlF ₄ , HBF ₄ , HB ₂ F ₇ ,
HPF ₆ , HSbF ₄ , HSbF ₆ , HSb ₂ F ₁₁ , H
AsF ₆ , HAlCl ₄ , HAlCl ₃ F, HAlF ₃
Cl, HBCl ₄ , HBCl ₃ F, HBBr ₃ F, HS
a compound of a Lewis acid such as bCl ₆ or HSbCl ₅ F and a hydrogen halide; an aryl-substituted boron compound represented by the following structural formula (b),

[Chemical 5] Alternatively, (FSO ₂ ) ₂ NH, (PhSO ₂ ) ₂ NH,
(CF ₃ SO ₂ ) ₂ NH, (C ₄ F ₉ SO ₂ ) ₂ NH,
Acidic amide compounds such as CF ₃ SO ₂ NHSO ₂ C ₆ F ₁₃ and compounds represented by the following structural formula (c);

[Chemical 6] Alternatively, (FSO ₂ ) ₃ CH, (CF ₃ SO ₂ ) ₃ CH,
(PhOSO ₂ ) ₃ CH, (CF ₃ SO ₂ ) ₂ CH ₂ ,
(C ₄ F ₉ SO ₂ ) ₃ CH, (C ₈ F ₁₇ SO ₂ ) ₃ CH
Carbonic acid compounds such as

In particular, in order to use a highly stable N-fluoropyridinium salt, acetic acid (pKa = 4.56) is used as the conjugate base of the Bronsted acid represented by the formula A.
It is preferable to use a conjugate base of Bronsted acid having a stronger acidity.

[0033] As the conjugate base of the Bronsted acid of the formula A, for ^{_{example, - BF 4, - PF 6}} , - As
^{_{F 6, - SbF 6, -}} AlF 4, - AlCl 4, - Sb
^{_{Cl 6, - SbCl 5 F,}} - Sb 2 F 11, - B 2 F 7,
^{_{- OClO 3, - OSO 2 F}} , - OSO 2 Cl, - OS
^{_{O 2 OH, - OSO 2 OCH}} 3, - OSO 2 CH 3, -
^{_{OSO 2 CF 3, - OSO 2}} CCl 3, - OSO 2 C 4
^{_{F 9, - OSO 2 C 6}} H 5, - OSO 2 C 6 H 4 C
^{_{H 3, - OSO 2 C 6}} H 4 NO 2, - N (SO 2 C
F ₃ ) _{2 and the} like are particularly preferable.

Next, among the N-fluoropyridinium salts, examples of the compound represented by the following general formula (1) include, for example, substituents R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and further brene. Preferable examples of the conjugated base of the Sted acid are shown in Tables 1 to 17 below, but the conjugated base is not limited thereto. However, in Tables 1 to 17, k is an integer of 1 to 10, l is an integer of 10 to 100,000, and m is
Is an integer of 10 to 10,000, p and q are positive integers, and 1 <p + q ≦ 1000.

[Chemical 7]

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

[Table 9]

[0044]

[Table 10]

[0045]

[Table 11]

[0046]

[Table 12]

[0047]

[Table 13]

[0048]

[Table 14]

[0049]

[Table 15]

[0050]

[Table 16]

[0051]

[Table 17]

Next, among the N-fluoropyridinium salts, the compounds represented by the following general formula (2) include, for example, substituents R ¹ , R ² , R ³ , R ⁴ and R ⁵ shown below. Although those shown in Table 18 and Table 19 are preferred,
It is not limited to these.

[Chemical 7]

[0053]

[Table 18]

[0054]

[Table 19]

Next, among the N-fluoropyridinium salts, examples of the compound represented by the general formula (3) include:
Substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹ ',
Preferable examples of the conjugate bases of R ² ′, R ³ ′, R ⁴ ′, R ⁵ ′ and Bronsted acid are shown in Tables 20 and 21 below, but not limited thereto.
However, “single bond” in the table indicates a binding site that is bound by a single bond.

[Chemical 8]

[0056]

[Table 20]

[0057]

[Table 21]

Next, among the N-fluoropyridinium salts, examples of the compound represented by the general formula (4) include compounds represented by the following structural formulas (d-1) to (d-19). However, the present invention is not limited to these. However, n is an arbitrary natural number, preferably 2 or more.

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

The N-fluoropyridinium salt-containing polymer containing the repeating unit represented by the general formula (4) is an unsubstituted or substituted phenylene, naphthalenediyl, thiophenediyl, pyrrolediyl, or flange as a copolymerization component. Units such as files may be included.
However, preferred examples of the substituent include a lower alkyl group and a halogen atom.

The N-fluoropyridinium salt-containing polymer may be a binary or ternary or more copolymer having different N-fluoropyridinium salts as copolymerization components. Further, this copolymer Further, one or more kinds of components other than the N-fluoropyridinium salt may be copolymerized. Further, the copolymer may be a block copolymer, a random copolymer, or a craft copolymer.

When the N-fluoropyridinium salt-containing polymer is a copolymer, the content (molar fraction) of the unit represented by the general formula (4) is at least 50 from the viewpoint of the electric capacity of the battery. % Or more, and more preferably 60% or more. In addition, the N-fluoropyridinium salt-containing polymer containing the repeating unit represented by the general formula (4) has an average molecular weight of 50 from the viewpoint of easy production.
Those up to 10,000 are preferred.

Further, the N-fluoropyridinium salt-containing polymer is at least a pyridine-containing polymer represented by the following general formula (5) selected from the group consisting of Bronsted acid, Bronsted acid salt and Lewis acid. It is prepared by reacting with fluorine (F ₂ ) in the presence of one acid or salt.

When the reaction between the pyridine-containing polymer and fluorine is incomplete in this reaction, the unit represented by the following general formula (5) and / or the unit represented by the following general formula (6) is When a Lewis acid contained in the N-fluoropyridinium salt-containing polymer and represented by the following formula B is used, the following general formula (5), the following general formula (6) and / or the following general formula The repeating unit represented by (7) is N-
Included in polymers containing fluoropyridinium salts.

[Chemical 14]

Further, as the N-fluoropyridinium salt, N-fluoropyridinium pyridine heptafluorodiborate whose structural formula (compositional formula) is represented by the following structural formula (e) can also be mentioned.

[Chemical 16]

As the N-fluoropyridinium salt, N-fluoropyridinium pyridine trifluoroboron hydroxytrifluoroborate whose structural formula (compositional formula) is represented by the following structural formula (f) can also be mentioned.

[Chemical 17]

Among the N-fluoropyridinium salts that can be used in the present invention, particularly preferable compounds are the following general formula (1a), general formula (2a), general formula (3a) and general formula (4a). The compound represented by

[0067]

[Chemical 18] [However, in the general formula (1a), R ^1a , R ^2a , R
^At least two of ^3a , R ^4a and R ^5a are the same;
Or all different groups, each of which is a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a halogen atom, a methyl or halogen substituent or an unsubstituted phenyl group, a lower alkoxy group, a lower acyl group, a lower acyloxy group, A lower alkoxycarbonyl group, a cyano group or a nitro group. ]

[0068]

[Chemical 19] [However, in the general formula (2a), R ^1a , R ^2a , R
^{One of 3a} , R ^4a and R ^5a is a group represented by the following general formula (g), and at least two are the same or all different groups, each of which is a hydrogen atom, a lower alkyl group or a lower group. It is a haloalkyl group or a halogen atom.

[Chemical 20] (However, in the general formula (g), r is an integer of 0 to 5.)]

Here, in the general formula (1a) and the general formula (2a), the lower alkyl group, the lower haloalkyl group, the lower alkoxy group, the lower acyl group, the lower acyloxy group and the lower alkoxycarbonyl group. Has a carbon atom number in the range of 1 to 4, r is an integer of 0 to 2, and the conjugate base of the Bronsted acid represented by the following formula A ′ in the general formula (1a) is pKa. = 4.56 or less of the conjugate base of Bronsted acid is still more preferred.

[Chemical 21]

[0070]

[Chemical formula 22] [However, in the general formula (3a), R ^1a , R ^2a , R
^3a , R ^4a , R ^5a , R ^1a ′, R ^2a ′, R ^3a ′, R ^4a ′ and R ^5a ′ are at least two the same or all different groups, each of which is a hydrogen atom or a lower group. An alkyl group,
A lower haloalkyl group, a halogen atom, a methyl or halogen-substituted or unsubstituted phenyl group, a lower alkoxy group, a lower acyl group, a lower acyloxy group, a lower alkoxycarbonyl group, a cyano group or a nitro group. Further, one of R ^1a , R ^2a , R ^3a , R ^4a and R ^5a and one of R ^1a ′, R ^2a ′, R ^3a ′, R ^4a ′ and R ^5a ′ are bonded by a single bond. The conjugate base of the Bronsted acid represented by the formula A has a pKa =
It is a conjugate base of Bronsted acid of 4.56 or less. ]

In the general formula (3a), the lower alkyl group, the lower haloalkyl group, the lower alkoxy group, the lower acyl group, the lower acyloxy group and the lower alkoxycarbonyl group have 1 to 10 carbon atoms. It is preferably within the range of 4.

[0072]

[Chemical formula 23] [Here, in the general formula (4a), R ^1a , R ^2a ,
At least two of R ^3a , R ^4a and R ^5a are the same or all are different groups, and each is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 carbon atom, It is an aryl group having 6 to 8 carbon atoms or a halogen atom. Further, in R ^1a , R ^2a , R ^3a , R ^4a and R ^5a , two of them form a polymer chain with a single bond,
The conjugate base of Bronsted acid represented by the formula A ′ is
It is a conjugate base of Bronsted acid having a pKa of 4.56 or less. ]

Next, the above general formulas (1), (2),
Preferred compounds are specifically listed in (3) and (4).

First, as the N-fluoropyridinium salt represented by the general formula (1), N-fluoropyridinium trifluoromethanesulfonate, N-fluoropyridinium tetrafluoroborate, N-fluoropyridinium hexafluoroantimonate, N-fluoropyridinium hexafluorophosphate, N-fluoropyridinium hexafluoroarsenate, N-fluoro (methyl) pyridinium tetrafluoroborate,
N-fluoro (ethyl) pyridinium tetrafluoroborate, N-fluoro (propyl) pyridinium tetrafluoroborate, N-fluoro (methoxy) pyridinium tetrafluoroborate, N-fluorodimethylpyridinium tetrafluoroborate, N-fluorotrimethyl Pyridinium trifluoromethanesulfonate,
N-fluorotrimethylpyridinium tetrafluoroborate, N-fluorocyanopyridinium tetrafluoroborate, N-fluoronitropyridinium tetrafluoroborate, N-fluorochloropyridinium tetrafluoroborate, N-fluorodichloropyridinium trifluoromethanesulfonate, Alternatively, N-fluorodichloropyridinium tetrafluoroborate and the like are particularly preferable.

Next, as the N-fluoropyridinium salt represented by the general formula (2), N-fluoropyridinium sulfonate, N-fluorochloropyridinium sulfonate, N-fluoro (methyl) pyridinium sulfonate, N -Fluoro (trifluoromethyl) pyridinium sulfonate or N-fluoro (dimethyl)
Particularly preferred is pyridinium sulfonate.

Further, as the N-fluoropyridinium salt represented by the general formula (3), N, N'-difluorobipyridinium bis (tetrafluoroborate), N,
N'-difluorobipyridinium bis (hexafluorophosphate), N, N'-difluorobipyridinium bis (hexafluoroarsenate), N, N'-difluorobipyridinium bis (hexafluoroantimonate), N, N'-difluorobipyridinium Bis (trifluoromethanesulfonate), N, N'-difluorodimethylbipyridinium bis (tetrafluoroborate), N, N'-difluorodichlorobipyridinium bis (tetrafluoroborate) and the like are particularly preferable.

Further, N- represented by the general formula (4) is
As the fluoropyridinium salt, poly (N-fluoropyridinium tetrafluoroborate-diyl), poly (N-fluoropyridinium hexafluorophosphate-diyl), poly (N-fluoropyridinium hexafluoroarsenate-diyl), poly ( N-fluoropyridinium hexafluoroantimonate-diyl), poly (N-fluoropyridinium trifluoromethanesulfonate-diyl), poly [N, N'-difluorobipyridinium bis (tetrafluoroborate)-
Diyl], poly [N, N'-difluorobipyridinium bis (hexafluorophosphate) -diyl], poly [N, N'-difluorobipyridinium bis (hexafluoroarsenato) -diyl], poly [N, N'- Difluorobipyridinium bis (hexafluoroantimonate) -diyl], poly [N, N'-difluorobipyridinium bis (trifluoromethanesulfonate)-
Diyl], poly [N, N′-difluorodimethylbipyridinium bis (tetrafluoroborate) -diyl],
Poly [N, N'-difluorodichlorobipyridinium bis (tetrafluoroborate) -diyl], poly [N,
N'-difluorodihexylbipyridinium bis (tetrafluoroborate) -diyl] and the like are particularly preferable.

The positive electrode active material which can be used in the present invention, which is prepared by blending a halo compound with an N-fluoropyridinium salt, or the positive electrode active material which also serves as an electrolyte, is solid,
It may be in the form of powder, film, or liquid. The halo compounds may be used alone or as a mixture of two or more kinds.

The haloalkane used as the positive electrode active material additive in the present invention preferably has at least one iodine atom or bromine atom. In particular, it is preferable to have at least one iodine atom. The number of carbon atoms is preferably within the range of 1-10.

To show this haloalkane specifically, for example,
For example, CH₃I, CH₂I₂, CHI₃, CI_Four, CH₃
Br, CH₂Br₂, CHBr₃, CBr_Four, CH₂B
rI, CHBr₂I, CBr₃I, CBr₂I₂, CB
rI₃, C₂H_FiveI, C₂H _FourI₂, C₂H₂I_Four, C
₂I₆, C₂Br_FourI₂, C₂H_FiveBr, C₂H_FourBr
₂, C₂Cl_FourI₂, C₂F_FourI₂, C₂F_FourBr₂,
C₂Br₆, C₃H₇I, C₃H₆I₂, C₃H
_FiveI₃, C₃H_FourI_Four, C₃I₈, C₃Br₂I₆, C
₃Cl₆I₂, C₃F₇I, C₃F₆I₂, C_FourH
₉I, C_FourH₈I₂, C_FourH₆I_Four, C_FourH_FourI₆, C
_FourH₂I₈, C_FourI_Ten, C_FourBr₆I_Four, C_FourCl₆I
_Four, C_FourF₆I_Four, C_FiveH_TenI₂, C₆H₁₂I₂, C₇
H₁₄I₂, C₈H₁₆I₂, C₉H₁₈I₂, C_TenH
₂₀I₂, C_FiveH₈I₂(Diiodocyclopentane), C
₆H_TenI₂(Diiodocyclohexane), C₇H₁₂I₂
(Diiodocycloheptane), C₈H₁₄I₂(The iodine
Cyclooctane), C₉H₁₆I₂(Diiodocyclonona
), C_TenH₁₈I₂(Diiodocyclodecane) and others
You can

The haloalkene used as the positive electrode active material additive of the present invention preferably has at least one iodine atom or bromine atom. In particular,
It preferably has at least one iodine atom. The number of carbon atoms is preferably within the range of 1-10.

Specific examples of this haloalkene include, for example, CH ₂ = CHI, CH ₂ = CI ₂ , CHI = C.
I ₂ , CI ₂ = CI ₂ , CHBr = CHI, CBrI =
CI ₂ , CBr ₂ = CI ₂ , CBr ₂ = CBrI, CB
r ₂ = CBr ₂ , CIBr = CIBr, CCl ₂ = CC
lI, CClI = CClI, CI ₂ = CCl ₂ , CI ₂
= CICl, CHI = CICH ₃ , CHI = CICH ₂
I, CH ₂ = CHCH ₂ I, CI ₂ = CICH ₃ , CI
Br = CICH ₃ , CI ₃ CI = CI ₂ , CH ₂ ICH
= CHCH ₂ I, CH ₂ ICH = CHCH ₂ Br, CH
₂ ICHICH = CH ₂ , CI ₃ CI = CICI ₃ , C
_{I 2 = CI-CI = CI} 2, CH 3 CI = CICH 3,
CH ₂ ICH = C (CH ₃ ) CH ₂ I, CHI = CIC
₃ H ₇ , CHI = CIC ₄ H ₉ , CHI = CIC
₅ H ₁₁ , CHI = CIC ₆ H ₁₃ , CHI = CIC
₇ H ₁₅ , CHI = CIC ₈ H ₁₇ ,

[Chemical formula 24] And so on.

The N-haloamides used as the positive electrode active material additive in the present invention include N-iodoamide and N-haloamide.
Examples thereof include bromoamide and N-chloroamide. Among them, N-iodoamide or N-bromoamide is preferable, and N-iodoamide is more preferable. The number of carbon atoms is preferably within the range of 1-10.

Specific compounds include, for example, HCO
_{NHI, HCON (CH 3) I} , CH 3 CONHI, C
_{H 3 CON (CH 3) I} , CH 3 CON (CH 3) B
r, CH ₃ CON (CH ₃ ) Cl, CH ₃ CON (C ₂
H ₅ ) I, CH ₃ CON (C ₃ H ₇ ) I, CH ₃ CON
(C ₄ H ₉ ) I, C ₂ H ₅ CONHI, C ₂ H ₅ CON
(CH ₃ ) I, C ₃ H ₇ CONHI, C ₃ H ₇ CON
(CH ₃ ) I, C ₄ H ₉ CONHI, C ₅ H ₁₁ CONH
I, C ₆ H ₁₃ CONHI, C ₆ H ₅ CON (CH ₃ )
I, C ₆ H ₅ CON (C ₂ H ₅ ) I, C ₆ H ₅ CON
(C ₃ H ₇ ) I,

[Chemical 25] And so on.

The N-haloimide used as the positive electrode active material additive in the present invention includes N-iodoimide and N-haloimide.
Examples thereof include bromoimide and N-chloroimide. Among them, N-iodoimide or N-bromoimide is preferable, and N-iodoimide is more preferable. The number of carbon atoms is preferably within the range of 1-10.

Specific compounds include, for example, CH ₃
CONICOCH ₃ , CH ₃ CONBrCOCH ₃ , C
H ₃ CONClCOCH ₃ , CH ₃ CONICOC ₂ H
₅ , C ₂ H ₅ CONICOC ₂ H ₅ , C ₃ H ₇ CONI
COC ₃ H ₇ , C ₄ H ₉ CONICOC ₄ H ₉ ,

[Chemical formula 26] , C ₆ H ₅ CONICOCH ₃ , C ₆ H ₄ (CO) ₂ N
I _{(N-iodophthalimide), C 6 H 4 (CO} ) 2 N
Br (N-bromophthalimide) etc. are mentioned.

Next, examples of the method of blending the halo compound with the N-fluoropyridinium salt will be described for the following methods (1) to (3), but the method is not limited to these methods. The compound obtained by mixing the N-fluoropyridinium salt with the halo compound can be produced, for example, by the following methods alone or by the combination of the following methods.

(1) By mechanically compounding a N-fluoropyridinium salt with a halo compound (if necessary, further components), and with or without addition of a solvent and / or a liquid electrolyte, The formulation can be manufactured.

Specific examples of the mechanical mixing method include a mixing method using shearing force, a mixing method using ultrasonic waves, and a mixing method by applying vibration.

More specifically, in the method of blending by shearing force, it may be blended while being crushed with a pestle in a mortar, or may be blended with a stirring rod. In addition, in the method of blending using ultrasonic waves, the blending may be performed with a pestle using a stirring rod or a mortar while applying ultrasonic waves. Also,
In the method of blending by applying vibration, blending may be carried out by applying a vibrator, or blending may be carried out by a pestle using a stirring rod or a mortar while vibrating with a vibrator.

In the above-mentioned mechanical compounding method,
A solvent or liquid electrolyte described below may be added as appropriate.

(2) Part or all of the halo compound is dissolved in a solvent or a liquid electrolyte, and this is added to an N-fluoropyridinium salt (additional other components are added if necessary).
It is possible to mix them to prepare a composition in which a halo compound is mixed with an N-fluoropyridinium salt.

It is desirable that the solvent is capable of at least partially dissolving a halo compound, and examples thereof include nitriles such as acetonitrile and propionitrile, nitroalkanes such as nitromethane and nitroethane, diethyl ether and dipropyl. Ether, dibutyl ether, tetrahydrofuran, dimethoxyethane, 1,4-
Ethers such as dioxane and 1,3-dioxolane,
Methyl acetate, methyl acetate, methyl formate, ethyl formate, γ
-Butyrolactone, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and other esters, benzene, toluene, halobenzene, nitrobenzene and other aromatic compounds, acetone, methyl ethyl ketone, dipropyl ketone and other ketones, methanol, ethanol,
Examples thereof include alcohols such as propanol, isopropanol, butanol, secondary butyl alcohol, tertiary butyl alcohol, trifluoroethanol, hexafluoroisopropanol, nonafluoro-t-butyl alcohol, water, and the like, or a mixture thereof.

As the liquid electrolyte, the liquid electrolyte described later can be used.

As a specific method for compounding the above-mentioned compound,
For example, the halo compound may be partially or wholly dissolved in the solvent or the liquid electrolyte and then mixed with the N-fluoropyridinium salt, or the N-fluoropyridinium salt and the halo compound may be contained in the same container. In addition to, preferably mechanically (physically) blending, a solvent or liquid electrolyte may be added to dissolve or blend a part or all of the halo compound. The dissolution in a solvent or liquid electrolyte may be carried out under heating, if necessary. In addition, the above formulation is
It can be achieved by compounding by the above-mentioned shearing force, compounding by using ultrasonic waves, compounding by applying vibration, or a combination thereof.

In the method of dissolving a part or all of the halo compound in the solvent or liquid electrolyte and then blending it with the N-fluoropyridinium salt, the solvent or liquid in which part or all of the halo compound is dissolved is used. Electrolyte, N
It may be impregnated with a positive electrode active material containing a fluoropyridinium salt.

(3) Producing a blend of the N-fluoropyridinium salt and the halo compound by exposing the N-fluoropyridinium salt (and optionally other components) to the vapor of the halo compound. You can

As an example of the method of exposing to steam, a method in which an N-fluoropyridinium salt and a halo compound are allowed to coexist in a closed container and the mixture is exposed to the steam of the halo compound while heating or cooling if necessary, Alternatively, a method of exposing a mixed gas of an inert gas such as nitrogen gas, helium gas or argon gas and a halo compound vapor to an N-fluoropyridinium salt, if necessary, may be used.

Next, in the present invention, the compounding ratio of the halo compound to the N-fluoropyridinium salt [molar ratio: halo compound / N-fluoropyridinium salt] is 0.00.
It is preferably in the range of 01 to 0.5.

If the compounding ratio is less than 0.0001,
A drop in voltage may occur due to an increase in internal resistance,
In addition, stable discharge tends not to be obtained. Further, if the compounding ratio is larger than 0.5, the electric capacity may decrease, and it may be difficult to form a battery having a high energy density.

The range of the compounding ratio is 0.000.
It is preferably in the range of 5 to 0.3, and further,
It is preferably in the range of 0.0005 to 0.2,
Furthermore, it is particularly preferable that it is in the range of 0.001 to 0.1.

In the present invention, it may be desirable to add an additive made of a polar compound to the positive electrode active material obtained by mixing the halo compound with the N-fluoropyridinium salt.

Particularly, one or two or more polar compounds are added in an amount of 0.5 to 0.5 with respect to the weight of the N-fluoropyridinium salt.
It is preferable to add 30% by weight, more preferably 0.5 to 20% by weight, further preferably 1 to 15% by weight.
By blending it, it may be possible to obtain a positive electrode active material having a further smaller internal resistance.

Examples of such polar compounds include:
Dimethyl sulfone, diphenyl sulfone, methylphenyl sulfone, 1,3-dioxolane, γ-butyrolactone, sulfolane, methylsulfolane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, methyl formate, ethyl formate, methyl acetate, Ethyl acetate, tetraethylene glycol dimethyl ether,
Triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethoxyethane, ethylene glycol, diethylene glycol, methanol,
Diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, nitromethane, nitroethane, nitrobenzene, dinitrobenzene, trinitrobenzene,
Chlorodinitrobenzene, fluorodinitrobenzene,
Acetonitrile, propionitrile, benzonitrile,
Pyridinium trifluoromethanesulfonate, pyridinium tetrafluoroborate, pyridinium hexafluorophosphonate, pyridinium hexafluoroarsenate, pyridinium hexafluoroantimonate, 2,6-dichloropyridinium tetrafluoroborate, 3,5-dichloropyridinium tetrafluoroborate And polar organic compounds such as 2,4,5-trimethylpyridinium terafluoroborate.

Examples of the polar compound include lithium trifluoromethanesulfonate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroantimonate, lithium tetrachloroaluminate, and perchlorine. Lithium acid, sodium perchlorate, potassium perchlorate, ammonium trifluoromethanesulfonate, ammonium tetrafluoroborate, ammonium chloride, sodium trifluoromethanesulfonate, sodium tetrafluoroborate, potassium tetrafluoroborate, cesium tetrafluoroborate Mention may be made of polar inorganic compounds such as salts and water.

Next, in the present invention, a preferable battery structure example using a composition obtained by compounding an N-fluoropyridinium salt with a halo compound and an example of a manufacturing method thereof will be described in the following (I) and (II). . Of course, it is not limited to these structures and manufacturing methods.

(I) In the case of a battery using a mixture prepared by blending an N-fluoropyridinium salt with a halo compound

First, the material used for the positive electrode and its manufacturing method will be described.

When the mixture of the N-fluoropyridinium salt and the halo compound is in the form of powder, it can be molded into a desired shape with a press or the like, and if necessary, for example, a binder or a conductive agent, and further added. It may be mixed with an agent or the like and preferably molded into a desired shape together with the positive electrode current collector with a press or the like.

As the binder, for example, a binder such as polytetrafluoroethylene powder, polyvinylidene fluoride powder, carboxydimethyl cellulose, polyvinyl alcohol or the like can be used.

As the conductive agent, for example, nickel powder, fine metal fibers, graphite such as graphite and graphite, carbon black such as acetylene black, carbon fiber, carbonaceous materials such as pitch and tar can be used.

Examples of the positive electrode current collector include:
Graphite, graphite such as graphite, carbon black such as acetylene black, carbon-based substances such as carbon fiber, pitch and tar, nets such as platinum, gold, nickel, stainless steel, iron and copper, foil laths, punching metal (foamed metal) ), A metal fiber network, etc. are preferable.

Examples of the additives include the polar organic compounds and polar inorganic compounds shown above.

The amount of the binder may be appropriately selected depending on the kind of the compound containing the N-fluoropyridinium salt and the halo compound and the kind of the binder. For example,
10% by weight of binder, based on the total weight of the formulation
It is preferably below, and more preferably below 5% by weight. If the amount of the binder exceeds 10% by weight based on the total weight of the formulation, it may cause an increase in internal resistance.

Further, the amount of the conductive agent may be appropriately selected depending on the kind of the compound containing the N-fluoropyridinium salt and the halo compound, the kind of the conductive agent and the like. For example, the conductive agent is preferably about 1 to 80% by weight, more preferably 2 to 50% by weight, based on the total weight of the compound. If the amount of the conductive agent is less than this range, the effect of the conductive agent may be reduced, while if it is more than this range, the electromotive force tends to decrease and the electric capacity becomes small.

When the compound of the N-fluoropyridinium salt and the halo compound can be formed into a film or can be formed into a film by a film forming agent, it is formed into a film as it is, or if necessary, the above-mentioned film is formed. A binder, a conductive agent, and further additives are mixed to form a film,
Preferably, a positive electrode can be produced by combining with a positive electrode current collector.

As the film-forming agent as the additive, for example, a polymer material such as polyethylene oxide, polyethylene, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl acetate, polyacrylonitrile, polymethyl acrylate, or gelatin is preferable. . The amount of the additive compounded is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total weight of the compounded mixture of the N-fluoropyridinium salt and the halo compound. If it is more than this amount, the internal resistance may increase.

When the mixture of the N-fluoropyridinium salt and the halo compound is in a liquid state, it may be used as it is, or may be used by impregnating it into a porous body having a desired shape. Further, if necessary, the binder, the conductive agent, and the additives described above may be added, and it is also possible to mix them to form a desired shape. Examples of the porous body include a porous fiber material, a porous conductive or non-conductive material, and a porous flexible material. The porous conductive material also serves as a current collector. It is also possible to let. The binder, conductive agent, and additives used here may be the same types and amounts as those described above.

In addition, the N-fluoropyridinium salt and the halo compound may be blended with another known positive electrode active material.

As such a positive electrode active material, for example,
Examples thereof include metal oxides such as manganese dioxide, lithium manganese oxide, cobalt dioxide, lithium cobalt oxide, nickel dioxide and lithium nickel oxide, and organic polymers such as polyaniline, polypyrrole and polyphenylene.

Such another positive electrode active material is 1 to 1 for the blend of the N-fluoropyridinium salt and the halo compound.
It is preferable to contain 80% by weight, and 2 to 50% by weight
It is more preferable to contain it.

Next, materials that can be used for the electrolyte will be described. As the electrolyte, those commonly used can be used regardless of whether they are liquid (that is, liquid electrolyte) or solid (that is, solid electrolyte).

Preferred liquid electrolytes include, for example, lithium perchlorate, tetrabutylammonium perchlorate,
Lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroantimonate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) amide, LiC (SO ₂ C
F _{3) 3,} N-fluoro pyridinium ethylene carbonate dissolved solutes such as salts, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, propylene carbonate, sulfolane, methyl sulfolane, .gamma.-butyrolactone, 1,3-dioxolane, 2-methyl Tetrahydrofuran, diethyl ether, tetrahydrofuran, dimethoxyethane, diethoxyethane, diglyme, triglyme, tetraglyme, acetonitrile, methyl formate, ethyl formate, dimethyl sulfite, dimethyl 2,2-difluoromalonate, 2,
Examples thereof include diethyl 2-difluoromalonate, methyl 2,2-difluoroacetoacetate, ethyl 2,2-difluoroacetoacetate, and a mixture of two or more kinds of these solvents.

The solid electrolyte may be, for example, a polymer solid electrolyte such as a gel electrolyte containing lithium trifluoromethanesulfonate or a highly ionic conductive non-aqueous electrolyte, or an N-fluoropyridinium salt or an N-fluoropyridinium salt. / Lithium salt mixture [for example, N-fluoropyridinium tetrafluoroborate / LiBF ₄ mixture and the like].

Next, the material used for the negative electrode (negative electrode active material) will be described.

As the negative electrode active material, alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, amphoteric compounds such as aluminum, transition metals such as zinc, cadmium, copper and lead,
Lithium-aluminum, lithium-tin, lithium-
Lead, lithium-gold, lithium-platinum, lithium-zinc,
Various lithium alloys such as lithium-cadmium, lithium-silver, lithium-magnesium and lithium-wood metal can be used. In particular, lithium, lithium alloys, calcium, from the viewpoint that it can generate a high electromotive force and easily applied to a flexible thin battery,
Negative electrode active materials such as magnesium, aluminum and zinc are preferable.

Next, the separator will be described.

When a separator is required, for example, a conventionally used cloth such as a polyamide-based or polypropylene-based woven cloth, a non-woven cloth, or a cellulose fiber can be used. A battery can be assembled by a usual method using the above-mentioned structure.

(II) A mixture of an N-fluoropyridinium salt and a halo compound is used as a positive electrode active material and an electrolyte,
For batteries used as positive electrodes

First, a positive electrode which also serves as a positive electrode active material and an electrolyte can be produced in the same manner as the above-described method for producing a positive electrode. Also in this case, various additives such as a conductive agent may be used.

As the negative electrode material, those mentioned above can be used. In addition, the separator is not necessary in principle because the interface between the positive electrode and the negative electrode often does not become a short circuit state due to the protective film formed by the reaction between the materials forming the electrodes. Moreover, what was mentioned above should just be used as needed.

Such a battery can be assembled by a usual method without using a separator between the positive electrode and the negative electrode, using the positive electrode as a material that also serves as the positive electrode active material and the electrolyte. You may use a separator according to.

[0133] As another example of a method for manufacturing a battery using a formulation halo compound is an additive, which are incorporated in the N- fluoropyridinium salt of the present invention, then, the positive electrode active containing N- fluoropyridinium salt An example of a method for producing a battery in the case of using an electrolyte in which a part or all of a halo compound is dissolved in a battery using a substance- containing composition will be described.

In this battery, the electrolyte in which the halo compound is dissolved permeates or diffuses into the N-fluoropyridinium salt, which is the positive electrode active material. Therefore, in this battery , the halo compound is mixed with the N-fluoropyridinium salt. A battery using a formulation containing a positive electrode active material.

The positive electrode was prepared by the method (I) described above.
Made according to the method described above, except that instead of using a blend of a fluoropyridinium salt with a halo compound, only the N-fluoropyridinium salt is used, where the halo compound is dissolved in the electrolyte. can do. The separator and the negative electrode may be manufactured according to the method described above, and the battery according to the present invention can be assembled by a usual method using such constituent materials.

The amount of the halo compound added to the electrolyte is 0.0001 to a compounding ratio [molar ratio: (halo compound) / (N-fluoropyridinium salt)] with respect to the total amount of the N-fluoropyridinium salt used in the battery. It is preferably in the range of 0.5, more preferably in the range of 0.0005 to 0.3, and then 0.0005 to 0.
The range of 2 is more preferably within the range of 0.001 to 0.1.

When the compounding ratio (molar ratio) is smaller than the above range (that is, less than 0.0001), the internal resistance is increased to lower the voltage and stable discharge cannot be obtained. Tend. On the other hand, if it is larger than the above-mentioned range (that is, exceeds 0.5), the electric capacity is lowered, and a battery having a high energy density may not be achieved.

The battery of the present invention may be formed in a generally used battery shape such as a cylindrical shape, a square shape, a button shape, and a coin shape, and may have a size and shape suitable for the usage form. Batteries can also be made.

The batteries of the present invention can be used, for example, in commuter tickets, cash cards, pacemakers, watches, calculators, electronic toys, small radios, electronic writers, cameras, electronic thermometers, medical equipment, greeting cards, etc.
Hearing aid, pager, electronic notebook, keyless entry,
RAM memory, IC memory, mobile phone, notebook computer, portable AV equipment, solar battery backup, power source for cards, etc.

[0140]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

Examples 1 to 5 <Preparation of Positive Electrode Active Material (Positive Electrode)> N-fluoropyridinium salts, halo compounds and other constituents shown in Table 22 below were added in the amounts shown in Table 22 (% by weight). ) And weighed and blended it sufficiently in a mortar until it became a uniform fine powder.

Next, this was rolled by a pressing machine and punched into a circular pellet having a diameter of 16 mm to obtain a positive electrode active material. The total weight of the positive electrode active material is also shown in Table 22 below. The binder used as a constituent component of the positive electrode active material was a polytetrafluoroethylene binder (F-104 manufactured by Daikin Industries, Ltd.), and the acetylene black was Gunbai manufactured by Denki Kagaku Kogyo Co., Ltd. As acetylene black containing tetrafluoroethylene, TAB-2 manufactured by Hosen Co., Ltd. was used. In addition, the separator is Celgard # made by Hosen Co., Ltd.
2400 was used.

<Fabrication of Battery> Next, the fabrication process of the battery in this example will be described with reference to FIG.

First, the separator shown in Table 22 below was superposed on the surface of the positive electrode (positive electrode active material) 8 on the negative electrode side, and 1 M (mol / liter) as a liquid electrolyte was placed thereon.
LiBF ₄ mixed solution of propylene carbonate (PC): dimethyl carbonate (DMC) = 1: 1 about 0.09 to 0.10 m
About 0.13 mL of L or γ-butyrolactone was impregnated to form a separator / electrolyte layer 5.

Then, on this, as a negative electrode (negative electrode active material), a disk shape having a diameter of 16.5 mm (thickness 0.38 mm)
Of the nickel foil lath (Product No. Ni-HO1-200-030: thunk Co., Ltd.) welded to a negative electrode can (negative electrode terminal) 1 as a negative electrode current collector after stacking the lithium plates 2 of
(Same) 3 coated this. Also, as the positive electrode current collector,
After providing the nickel foil lath 3 on the positive electrode can (positive electrode terminal) 6,
Graphite paste 7 was applied on this, and a button type lithium battery 9 was produced according to a usual method. In addition,
The open circuit voltage, DC internal resistance, and electric capacity (discharge capacity) of the manufactured battery are also shown in Table 22 below.

FIG. 1 shows a partial cross-sectional side view of this battery. That is, in this button type battery 9, the positive electrode side is
A nickel foil lath 3 as a positive electrode collector and a graphite paste 7 are provided in this order on the positive electrode terminal 6, and a positive electrode 8 is further provided on the nickel foil lath 3 and the graphite paste 7. The negative electrode side has a laminated structure including a nickel foil lath 3 provided on the negative electrode terminal 1 and a lithium plate 2 as a negative electrode. And, between the lithium plate 2 and the positive electrode 8,
A separator / electrolyte layer 5 is provided, of course,
The negative electrode can (negative electrode terminal) 1 and the positive electrode can (positive electrode terminal) 6 are packed by an insulating layer 4.

The DC internal resistance in Table 22 was measured using a device having the circuit shown in FIG.
From open circuit voltage and 1MΩ to 510kΩ, 100k
Under an external load of Ω, 51 kΩ, 30 kΩ, and 10 kΩ, the battery voltage after 1 minute or the battery voltage having a substantially constant value was measured, and the minimum value of 2 from the current value and the voltage value of each resistance was measured. Calculated by multiplication.

However, in FIG. 2, in order to measure the DC internal resistance of the button type lithium battery 9, the battery 9, the switch 11, the external load 12, and the voltmeter 10 are wired 13.
Are connected as shown in FIG.

The open circuit voltage (V), the internal DC resistance (kΩ), and the electric (discharge) capacity (mAh / g) of 2.5 V or more, which were measured as described above, are described in the following tables for Examples 1 to 5. 22 is also shown. However, in Table 22, [B] /
[A] represents a molar ratio [(halo compound) / (N-fluoropyridinium salt)].

However, the electric capacity is 300 μ at a temperature of 20 ° C.
It was determined by performing constant current discharge of A. The discharge curve obtained at this time is shown in FIG. That is, FIG.
It is a curve which shows the change of the voltage with time in 300 microamperes constant current discharge in ° C. In addition, FIG. 3 also shows the discharge curve of Comparative Example 1 below.

[0151]

[Table 22]

Comparative Examples 1 and 2 Button type batteries were prepared using the constituent materials shown in Table 23 below (that is, in the same manner as in Examples 1 to 4 except that the halo compound was not used). This was designated as Comparative Example 1. Comparative Example 2 is Example 5 except that no halo compound is used.
A button-type battery having the same structure as that of 1.

Also in Comparative Examples 1 and 2, the open circuit voltage, the DC internal resistance, and the electric capacity (discharge capacity) were measured in the same manner as in the above Example, and the measurement results are also shown in Table 23 below. . Regarding Comparative Example 1, a constant current discharge curve of 300 μA at a temperature of 20 ° C. is also shown in FIG.

[0154]

[Table 23]

Example 6 and Comparative Example 3 Batteries similar to those of Example 1 were prepared and the temperature was set to −20 ° C.
Constant current discharge at 100 μA was performed. This was set as Example 6 and the obtained discharge curve is shown in FIG. That is, in FIG.
It is a curve which shows the change of the voltage with time in 100 microamperes constant current discharge in -20 ° C. Further, a battery similar to that of Comparative Example 1 was prepared, and this was similarly subjected to temperature-
A constant current discharge at 20 ° C. and 100 μA was performed. This was designated as Comparative Example 3, and the obtained discharge curve is also shown in FIG.

<Evaluation> Comparison between Examples 1 to 4 and Comparative Example 1, Example 5 and Comparative Example 2
From comparison with Example 6 and Comparative Example 3 (Table 2
2, Table 23, FIG. 3 and FIG. 4), the battery of this example using the positive electrode active material- containing composition containing an N-fluoropyridinium salt and a halo compound was a battery containing no halo compound (Comparative Example 1). It can be seen that the open circuit voltage (electromotive force), the internal resistance, and the discharge capacity are remarkably superior to those of 2 and 2).

Further, as shown in FIG. 3, in the battery of this example, the discharge time and discharge voltage were the same as those of Comparative Example 1 in which no halo compound was used.
Excellent results have been obtained compared to. Furthermore, from FIG. 4, it can be seen that the battery of this example exhibits superior performance and operates effectively even in an environment of a temperature of -20 ° C as compared with Comparative Example 3 in which no halo compound is used. .

When tetrabromomethane was used as the halo compound as in Example 4, as compared with Comparative Example 1 (1.16 kΩ) in the case where the halo compound was not used, the DC internal resistance (1 .26 kΩ) is slightly higher, but as can be seen from the discharge curve of Example 4 in FIG. 3, the internal resistance after discharge is lower than in Comparative Example 1, and as a result, both the discharge voltage and the discharge capacity are higher than in Comparative Example 1. Obviously superior.

[0159]

The additive of the present invention comprises at least one halo compound selected from the group consisting of haloalkanes, haloalkenes, N-haloamides and N-haloimides, and has a smooth electron flow. Since it is excellent in the function as a mediator that causes it to operate at the same time as it has low toxicity and corrosiveness, when manufacturing a battery using this, there are manufacturing safety and handling problems, as well as manufacturing equipment and It is possible to solve the problem of the material of the battery case and further the problems of safety and storability, and thus to provide a battery having excellent battery characteristics and high environmental acceptability.

Further, the positive electrode active material- containing composition of the present invention and the battery of the present invention include at least one selected from the group consisting of N-fluoropyridinium salts and haloalkanes, haloalkenes, N-haloamides and N-haloimides. A compound containing a positive electrode active material containing a halo compound and a battery containing the same can be added to the positive electrode material or the flow of electrons between the active material molecules of the N-fluoropyridinium salt that is the positive electrode active material. Electron flow between the conductive agent and the positive electrode active material can be smoothly carried out by the halo compound, and excellent battery characteristics such as electromotive force, internal resistance and discharge capacity, and at the same time, a positive electrode active material having high environmental acceptability. Substance- containing formulations ,
Furthermore, a battery using this positive electrode active material- containing composition can be provided.

[Brief description of drawings]

FIG. 1 shows a partial cross-sectional side view of a button type battery manufactured in this example.

FIG. 2 is a circuit diagram used for measuring the battery characteristics of the battery.

FIG. 3 is a graph showing discharge curves of a battery of this example and a battery of a comparative example.

FIG. 4 is a graph showing another discharge curve of the same.

[Explanation of symbols]

1 ... Negative electrode terminal 2 ... Negative electrode (lithium plate) 3 ... Nickel foil lath 4 ... Insulating packing 5 ... Separator and electrolyte 6 ... Positive electrode terminal 7 ... Graphite paste 8 ... Positive electrode 9 ... Button type battery 10 ... Voltmeter 11 ... Switch 12 ... External load 13 ... Wiring

Front page continuation (51) Int.Cl. ⁷ Identification code FI H01M 10/40 H01M 10/40 A // C07D 213/22 C07D 213/22 213/26 213/26 213/30 213/30 213/50 213 / 50 213/65 213/65 213/79 213/79 213/80 213/80 213/81 213/81 213/82 213/82 213/84 213/84 (56) Reference JP-A-7-118480 ( JP, 57-3374 (JP, A) JP, 8-171939 (JP, A) JP, 7-296820 (JP, A) JP, 7-6756 (JP, A) (58) ) Fields surveyed (Int.Cl. ⁷ , DB name) H01M 4/00-4/04 H01M 4/36-4/62 H01M 6/00-6/22 H01M 10/40

Claims (17)

(57) [Claims] 1. An additive to a positive electrode active material containing an N-fluoropyridinium salt, the positive electrode comprising at least one halo compound selected from the group consisting of haloalkanes, haloalkenes, N-haloamides and N-haloimides. Active material additive. 2. The halo compound having 1 to 10 carbon atoms.
The positive electrode active material additive according to claim 1, which is within the range. 3. The positive electrode active material additive according to claim 1, wherein the haloalkane and the haloalkene contain at least one iodine atom and / or bromine atom. 4. The N-haloamide is N-iodoamide or N-bromoamide, and the N-haloimide is N-haloamide.
-Iodoimide or N-bromoimide.
The positive electrode active material additive described in 1. 5. A positive electrode active material- containing composition comprising an N-fluoropyridinium salt and at least one halo compound selected from the group consisting of haloalkanes, haloalkenes, N-haloamides and N-haloimides. 6. The halo compound having 1 to 10 carbon atoms.
The positive electrode active material- containing composition according to claim 5, which is within the range of
Compound 7. The positive electrode active material- containing composition according to claim 5, wherein the haloalkane and the haloalkene contain at least one iodine atom and / or bromine atom. 8. The N-haloamide is N-iodoamide or N-bromoamide, and the N-haloimide is N-haloamide.
-Iodoimide or N-bromoimide.
The positive electrode active material- containing composition described in 1. 9. The molar ratio [(halo compound) / (N-fluoropyridinium salt)] of the halo compound to the N-fluoropyridinium salt is in the range of 0.0001 to 0.5. Positive electrode active material- containing compound described in
Thing . 10. The positive electrode active material- containing compound according to claim 5, further comprising an additive composed of a polar compound.
Thing . 11. The positive electrode active material- containing blend according to claim 10, wherein the polar compound is blended in an amount of 0.5 to 30 wt% with respect to the N-fluoropyridinium salt. 12. The positive electrode active material- containing composition according to claim 5, further comprising a conductive agent. 13. A battery using a positive electrode active material- containing composition comprising an N-fluoropyridinium salt and at least one halo compound selected from the group consisting of haloalkanes, haloalkenes, N-haloamides and N-haloimides. . 14. The battery according to claim 13, wherein the N-fluoropyridinium salt also serves as an electrolyte. 15. The battery according to claim 13, wherein the positive electrode active material- containing composition further comprising an additive composed of a polar compound is used. 16. The battery according to claim 15, wherein the polar compound is blended in an amount of 0.5 to 30% by weight with respect to the N-fluoropyridinium salt. 17. The battery according to claim 13, wherein a conductive agent is added to the positive electrode active material- containing composition.