JPH08124556A - Positive electrode and battery formed of the positive electrode - Google Patents

Abstract

PURPOSE: To provide a battery having high energy density and high electromotive force by using a positive electrode formed by sticking a compound having the N-F bond to a porous material. CONSTITUTION: A compound having the N-F bond is stuck to a porous material, to form a positive electrode. As the porous material, fiber material, conductive material, non-conductive material, flexible material, etc., are used. As the compound having the N-F bond, an N-fluoropyridinium compound, N- fluorosulfonamide compound, N-fluorodisulfonimide compound, etc., are used. By sticking the compound having N-F connection to the porous material, a positive electrode of uniform quality with desired thickness can be manufactured in a desired shape. As the porous material, a sponge-shaped and sheet-shaped fiber or the like are preferable. As the raw material of the porous material, foaming polystyrene, sponge-shaped carbon, etc., are preferable. By the battery using this positive electrode, desired electromotive force can be obtained, and the battery can be used in a wide temperature range.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive electrode used for generating electric energy and a battery comprising the positive electrode. Specifically, the present invention relates to a positive electrode in which a compound having an NF bond having high environmental receptivity is attached to a porous body, and a battery having the high positive electrode and the high energy density and high electromotive force.

[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 depending on the required performance. Is being studied.

Under such circumstances, the thinning of the battery has become indispensable especially with the advent of thin information devices such as IC cards.

A typical structure of a battery consists of positive electrode current collector / positive electrode / electrolyte / negative electrode. In order to reduce the thickness of the battery, it is naturally required to reduce the thickness of the positive electrode, which is one of these constituent components.

Inorganic oxides such as manganese dioxide and vanadium oxide, and organic polymers such as polyacetylene and polyaniline have been known as materials used for the positive electrodes of these thin type batteries. However, these inorganic oxides or organic polymers are often difficult to liquefy, and there are many problems when industrially producing a uniform thin film type positive electrode using these materials. was there.

For example, in order to produce a thin film of the above-mentioned inorganic oxide, a method is known in which a pressure-sensitive adhesive is added to this inorganic oxide and uniformly mixed and rolled. However, when the thin film is industrially manufactured using this method, it is difficult to obtain a product having a uniform thickness. On the other hand, in order to produce a thin film of the organic polymer, it is common to use an electrolytic polymerization method. However, in this electrolytic polymerization method, the polymer thin film is formed only on the electrode, and there is a problem that it is greatly restricted in producing a thin film type positive electrode for a battery having a required size.

As described above, according to the method of manufacturing a thin film type positive electrode in the prior art, when it is attempted to industrially manufacture a positive electrode having a desired thickness and size, the simplicity of manufacturing and the manufactured positive electrode There was a problem in terms of homogeneity.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a positive electrode used for generating electric energy, particularly a positive electrode which is easy to manufacture and has excellent homogeneity and is highly environmentally receptive. And a battery having a high energy density and a high electromotive force, which is composed of the positive electrode.

[0009]

The present invention relates to a positive electrode in which a compound having an N--F bond is attached to a porous body.

The present invention also relates to a positive electrode in which the porous body is made of a fiber material.

The present invention also relates to the positive electrode, wherein the porous body is made of a conductive material.

Further, the present invention relates to a positive electrode in which the porous body is made of a non-conductive material.

Further, the present invention relates to a positive electrode in which the porous body is a flexible material.

Furthermore, the present invention relates to a battery comprising a positive electrode having a compound having an N--F bond attached to a porous body.

[0015]

FUNCTION AND EXAMPLE The positive electrode in the present invention comprises a positive electrode active material and a positive electrode material. The positive electrode active material is a compound having an N—F bond, and the positive electrode material is a porous body.

Examples of the compound having an NF bond, which is the positive electrode active material used in the present invention, include N-fluoropyridinium compounds, N-fluorosulfonamide compounds, N-fluoroquinuclidinium compounds, and N-fluoro-1. , 4-diazoniabicyclo [2.2.2] octane compound, N-fluorodisulfonimide compound, N-
Examples thereof include fluoroamide compounds, N-fluorocarbamate compounds and N-fluoropyridone compounds.

Many of the compounds having NF bonds are known as fluorinating agents (Japanese Patent Publication No. 2-33707, JP-A-63-295610, JP-A-3-99).
062, Bull. Chem. Soc. Jp
n. , 64 , 1081 (1991), Z. Chem. ,
5 , 64 (1965), EP-A-470669, first.
Proceedings of 7th Fluorochemical Symposium (Osaka, 1992), 129-130, J. Fluorine Che
m. , 54 , 207 (1991), EP-A-5268.
49), JP-A-4-504124, J. Fluo
line Chem. , 55 , 207 (1991),
J. Chem. Soc. Chem. Commun, 1
992 , 595, J. Org. Chem. , 58 , 27
91 (1993), J. Am. Am. Chem. Soc. , 1
06 , 452 (1984), J. Am. Am. Chem. So
c. , 108 , 2445 (1986), J. Fluor
ine Chem. , 46 , 297 (1990), Te
trahedron Lett, 32 , 1779 (19)
91), Tetrahedron Lett. , 29 ,
6087 (1988), J. Am. Chem. So
c. , 109 , 7194 (1987), JP-A-62-2.
6264, Synlett, 1991 , 187,
Tetrahedron Lett. , 32 , 1631
(1991), Tetrahedron, 47 , 744.
7 (1991), Tetrahedron, 48 , 15
95 (1992), J. Org. Chem. , 34 , 2
840 (1969), J. Org. Chem. , 35 ,
1545 (1970), J. FluorineChe
m. 52 , 389 (1991), J. Am. Fluorin
e Chem. , 34 , 281 (1986).

The present invention has been completed by discovering that a positive electrode having a desired thickness and a homogeneous shape can be produced in a desired shape by attaching such a compound having an NF bond to a porous body.

Among the compounds having an N—F bond which can be used in the present invention, preferred compounds as the N-fluoropyridinium compound are the following formulas (I), (II) and (I
II) and (IV).

[0020]

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[0021]

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[0022]

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[0023]

[Chemical 4]

In formula (I), formula (II), formula (III) and formula (IV), adjacent R ¹ and R ² , R ² and R ³ , R
³ and R ⁴ or R ⁴ and R ⁵ are linked to each other, and -CR ⁶ = CR
⁷ -CR ⁸ = CR ⁹ - and also, R ^{1 'and} R ^2', R
^{2 'and} R ^3', R ^{3 'and} R ^4' or R ^{4 'and} R ^5' are ^{linked, -CR 6 '= CR 7'} -CR 8 '= CR 9'
R ^{1 to} R ⁹ and R ^{1 ′ to} R may be formed.
^{9 ′} are the same or different and each is a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a cyano group or a carbamoyl group; an alkyl group having 1 to 15 carbon atoms or a halogen atom, a hydroxyl group, or 1 carbon atom To an alkoxy group having 5 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an acyl group having 1 to 5 carbon atoms, a group substituted with an acyloxy group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms; To 15 alkenyl group or a group in which the alkenyl group is substituted with a halogen atom or an aryl group having 6 to 10 carbon atoms; an alkynyl group having 1 to 15 carbon atoms or a halogen atom or an aryl group having 6 to 10 carbon atoms. A group substituted with C6; an aryl group having 6 to 15 carbon atoms or a group in which the aryl group is substituted with a halogen atom or an alkyl group having 1 to 5 carbon atoms; An acyl group having 1 to 15 carbon atoms or a group in which the acyl group is substituted with a halogen atom; 2 to 15 carbon atoms
Or a group in which the alkoxycarbonyl group is substituted with a halogen atom or an aryl group having 6 to 10 carbon atoms; an aryloxycarbonyl group having 7 to 15 carbon atoms or the aryloxycarbonyl group having 1 to 5 carbon atoms. A group substituted with an alkyl group of 5; an alkylsulfonyl group having 1 to 15 carbon atoms or a halogen atom or an alkylsulfonyl group having 6 to 6 carbon atoms
A group substituted with an aryl group having 10 carbon atoms; an arylsulfonyl group having 6 to 15 carbon atoms or a group having the arylsulfonyl group substituted with a halogen atom or an alkyl group having 1 to 5 carbon atoms; an alkylsulfinyl group having 1 to 15 carbon atoms or A group in which the alkylsulfinyl group is substituted with a halogen atom or an aryl group having 6 to 10 carbon atoms; an arylsulfinyl group having 6 to 15 carbon atoms or the arylsulfinyl group is substituted with a halogen atom or an alkyl group having 1 to 5 carbon atoms Group; an alkoxy group having 1 to 15 carbon atoms or a group in which the alkoxy group is substituted with a halogen atom or an aryl group having 6 to 10 carbon atoms; an aryloxy group having 6 to 15 carbon atoms or a halogen atom or carbon Group substituted with an alkyl group having 1 to 5 carbon atoms: 1 to 1
5 acyloxy group or a group in which the acyloxy group is substituted with a halogen atom; an acylthio group having 1 to 15 carbon atoms or a group in which the acylthio group is substituted with a halogen atom; an alkanesulfonyloxy group having 1 to 15 carbon atoms or the alkanesulfonyl group Oxy group is a halogen atom or has 6 carbon atoms
A group substituted with an aryl group having 10 to 10; an arenesulfonyloxy group having 6 to 15 carbon atoms or a group having the arenesulfonyloxy group substituted with a halogen atom or an alkyl group having 1 to 5 carbon atoms; alkyl having 1 to 5 carbon atoms A carbamoyl group substituted with a group or a group in which the alkyl-substituted carbamoyl group is substituted with an aryl group having 6 to 10 carbon atoms; a carbamoyl group substituted with an aryl group having 6 to 10 carbon atoms or the aryl-substituted carbamoyl group A group substituted with an alkyl group having 1 to 5; an amino group substituted with an acyl group having 1 to 5 carbon atoms or a group having an acyl-substituted amino group substituted with a halogen atom; an N-alkylpyridinium base having 6 to 15 carbon atoms Alternatively, the N-alkylpyridinium base is a halogen atom, an aryl group having 6 to 10 carbon atoms or an alkyl group having 1 to 5 carbon atoms. Group substituted with group; carbon atoms 11-15
N-arylpyridinium base, or a group obtained by substituting the N-arylpyridinium base with a halogen atom, an aryl group having 6 to 10 carbon atoms or an alkyl group having 1 to 5 carbon atoms; or an organic polymer chain, R ^{1 to} R ⁹ and R
^{1 ′ to} R ^{9 ′} may form a ring structure in various combinations with or without a heteroatom, and in the formula (II), one of R ^{1 to} R ⁹ is

[0025]

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(R is a single bond or an alkylene group having 1 to 5 carbon atoms), and in the formula (III), R ¹ , R ² ,
One of 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 ',} R ^7', and one of R ^{8 'and} R ^9' forms a linking chain by a single bond, and in formula ^{(IV), R 1, R 2, R} 3, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R
Two of ⁸ and R ⁹ form a polymer chain with a short bond, and the repeating units represented by the formula (IV) may be the same or different. Also

[0027]

[Outside 1]

Is a conjugate base of Bronsted acid.

[0029]

[Outside 2]

Examples of the Bronsted acid for producing methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, trinitrobenzenesulfonic acid, trifluoromethanesulfonic acid, perfluoro Butanesulfonic acid, perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, perfluoro (4-ethylcyclohexane) sulfonic acid, trichloromethanesulfonic acid, difluoromethanesulfonic acid, trifluoroethanesulfonic acid, fluorosulfone Acid, chlorosulfonic acid, camphorsulfonic acid, bromcamphorsulfonic acid, Δ ⁴ -cholestene-
3-on-6-sulfonic acid, 1-hydroxy-p-methane-2-sulfonic acid, p-styrenesulfonic acid, β-styrenesulfonic acid, vinylsulfonic acid, perfluoro-
Sulfonic acids such as 3,6-dioxa-4-methyl-7-octene sulfonic acid; poly (vinyl sulfonic acid), poly (p-styrene sulfonic acid), poly (2-acrylamido-2-methyl-1-propane sulfone) Acid) and copolymers of these with styrene, poly (perfluoro-3,
6-dioxa-4-methyl-7-octenesulfonic acid)
And polysulfonic acids such as copolymers of these with tetrafluoroethylene; mineral acids such as sulfuric acid, phosphoric acid and nitric acid;
Hydrogen fluoride, hydrofluoric acid, hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydroiodic acid, perchloric acid, perbromic acid, periodic acid, chloric acid, bromic acid, etc. Halogen acid; monoalkyl sulfuric acid such as monomethyl sulfuric acid and monoethyl sulfuric acid; acetic acid, formic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, dichloroacetic acid,
Carboxylic acid such as acrylic acid; polyacrylic acid, poly (perfluoro-3,6-dioxa-4-methyl-7-
Octene acid) and polycarboxylic acids such as copolymers thereof with tetrafluoroethylene; HBF ₄ , HP
F ₆ , HSbF ₄ , HSbF ₆ , HAsF ₆ , HBCl
A compound of a hydrogen halide with a Lewis acid such as ₃ F, HSbCl ₆ , or HSbCl ₅ F;

[0031]

[Chemical 6]

Aryl-substituted boron compounds such as; (FS
O ₂ ) ₂ NH, (PhSO ₂ ) ₂ NH, (CF ₃ S
O ₂ ) ₂ NH, (C ₄ F ₉ SO ₂ ) ₂ NH, CF ₃ SO
₂ NHSO ₂ C ₆ F ₁₃ ,

[0033]

[Chemical 7]

Acidic amide compounds such as; (FSO ₂ ) _{3
CH, (CF 3 SO 2)} 3 CH, (PhOSO 2) 3 C
_{H, (CF 3 SO 2)} 2 CH 2, (CF 3 SO 2) 3 C
H, (C ₄ F ₉ SO ₂ ) ₃ CH, (C ₈ F ₁₇ SO ₂ ) ₃
Examples thereof include carbonic acid compounds such as CH.

In order to use a compound having a highly stable NF bond,

[0036]

[Outside 3]

As a conjugate base of Bronsted acid having an acidity stronger than that of acetic acid (pKa of 4.56) is particularly preferable.

[0038] As the conjugated ^{base, -} BF _^4, - PF
_{^{6, - AsF 6, - SbF}} 6, - AlCl 4, - SbC
_{^{l 6, - SbCl 5 F,}} - Sb 2 F 11, - B 2 F 7, -
_{^{OClO 3, - OSO 2 F,}} - OSO 2 Cl, - OSO
_{^{2 OH, - OSO 2 OCH 3}} , - OSO 2 CH 3, - O
_{^{SO 2 CF 3, - OSO 2}} CCl 3, - OSO 2 C 4 F
_{^{q, - OSO 2 C 6 H}} 5, - OSO 2 C 6 H 4 CH 3,
^- such as OSO ₂ C ₆ H ₄ NO ₂ are particularly preferred.

The compounds represented by the formula (I) among the N-fluoropyridinium compounds are shown in Table I, for example.
However, the present invention is not limited to these.

[0040]

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In Table I, k is an integer from 1 to 10, n is an integer from 10 to 100,000, and m is 10 to 10,000.
, P and q are positive integers, and 1 <p + q ≦ 1000.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6]

[0048]

[Table 7]

[0049]

[Table 8]

[0050]

[Table 9]

[0051]

[Table 10]

[0052]

[Table 11]

[0053]

[Table 12]

[0054]

[Table 13]

[0055]

[Table 14]

[0056]

[Table 15]

[0057]

[Table 16]

[0058]

[Table 17]

Of the N-fluoropyridinium compounds, the compounds represented by the formula (II) are preferably those shown in Table II, but are not limited thereto.

[0060]

[Chemical 9]

[0061]

[Table 18]

[0062]

[Table 19]

Of the above N-fluoropyridinium compounds, examples of the compound represented by the formula (III) are preferably, but not limited to, those shown in Table III.

[0064]

[Chemical 10]

[0065]

[Table 20]

[0066]

[Table 21]

Of the N-fluoropyridinium compounds, examples of the compound represented by the formula (VI) are preferably those having a structural formula represented by the following formula, but are not limited thereto.

[0068]

[Chemical 11]

[0069]

[Chemical 12]

[0070]

[Chemical 13]

[0071]

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The N-fluoropyridinium salt-containing polymer containing the repeating unit represented by the formula (IV) contains a unit such as substituted or unsubstituted phenylene, naphthalenediyl, thiophenediyl, pyrrolediyl and furandiyl as a copolymerization component. It may be. Preferred examples of the substituents include a lower alkyl group and a halogen atom. Further, the N-fluoropyridinium salt-containing body may be a binary or ternary or more copolymer having different N-fluoropyridinium salts as a copolymerization component, and the N-fluoropyridinium salt-containing body may further contain the above N-fluoropyridinium salt. One or more components other than the fluoropyridinium salt may be copolymerized. Further, the copolymer may be a block copolymer, a random copolymer or a graft copolymer. In the case of a copolymer, the content (molar fraction) of the unit represented by the formula (IV) is at least 50% or more, preferably 60% or more, from the viewpoint of the electric capacity of the battery. The average molecular weight of the N-fluoropyridinium salt-containing polymer containing the repeating unit represented by the formula (IV) is preferably up to 500,000 from the viewpoint of easy production. Furthermore, this N-fluoropyridinium salt-containing polymer has the following formula (V):

[0073]

[Chemical 15]

A pyridine-containing polymer corresponding to Bronsted acid and / or Bronsted acid salt, and / or
Alternatively, it is produced by reacting with fluorine (F ₂ ) in the presence of a Lewis acid. When the reaction is incomplete at this time, the unit represented by the above formula (V),
And / or the following formula (VI):

[0075]

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The unit represented by

[0077]

[Outside 4]

When the following formula (V) and / or formula (VI) and / or the following formula (VI) are used,
I):

[0079]

[Chemical 17]

The unit represented by is included in the N-fluoropyridinium salt-containing polymer.

Further, as the N-fluoropyridinium compound, N-fluoropyridinium pyridine heptafluorodiborate having a structural formula represented by the following formula can also be exemplified.

[0082]

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Of the compounds having an NF bond, a particularly preferable compound as the N-fluorosulfonamide compound is the following formula (VIII):

[0084]

[Chemical 19]

(In the formula, R ^a and R ^b are the same or different, and are an alkyl group having 1 to 15 carbon atoms, or a group in which the alkyl group is substituted with a halogen atom or an aryl group having 6 to 10 carbon atoms; 15 aryl group or a group obtained by substituting the aryl group with a halogen atom, a nitro group, a cyano group, an acyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms, a pyridyl group or a halogen atom for the pyridyl group. in a substituted group, to R ^a and R ^b may form a ring structure without the intervention or through a hetero atom, and, R ^b
Can also be a hydrogen atom. ). In particular

[0086]

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And the like.

Among the compounds having an NF bond, a particularly preferable compound as the N-fluoroquinuclidinium compound is the following formula (IX):

[0089]

[Chemical 21]

Is indicated by (

[0091]

[Outside 5]

Is a conjugate base of the above Bronsted acid). In particular,

[0093]

[Chemical formula 22]

And the like.

Among the compounds having an NF bond, a particularly preferred compound as the N-fluoro-1,4-diazoniabicyclo [2.2.2] octane compound is the following formula (X):

[0096]

[Chemical formula 23]

(R ^c is a carbon number of 1 to
An alkyl group of 15 or a halogen atom for the alkyl group,
A group substituted with a nitro group, a cyano group, an acyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms,

[0098]

[Outside 6]

Are the conjugate bases of the same or different Bronsted acids mentioned above). In particular

[0100]

[Chemical formula 24]

And the like.

Of the compounds having an NF bond, a particularly preferred compound as the N-fluorodisulfonimide compound is the following formula (XI):

[0103]

[Chemical 25]

(In the formula, R ^d and R ^e are the same or different, an alkyl group having 1 to 15 carbon atoms, or a group in which the alkyl group is substituted with a halogen atom or an aryl group having 6 to 16 carbon atoms; An aryl group of 10 to 10 or a halogen atom, a nitro group, a cyano group, a carbon number of 1 to 5
Is an acyl group or a group substituted with an alkyl group having 1 to 5 carbon atoms, and R ^d and R ^e may have a cyclic structure with or without a heteroatom, or R ^d and R ^e
e is an integral unit of an aromatic ring structure having 6 to 10 carbon atoms or a halogen atom, a nitro group, a cyano group, an acyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Forming a substituted structure). In particular,

[0105]

[Chemical formula 26]

And the like.

Of the compounds having an N—F bond, a particularly preferred compound as the N-fluoroamide compound is the following formula (XII):

[0108]

[Chemical 27]

(In the formula, R ^f and R ^g are the same or different and each represents a hydrogen atom, a halogen atom, an amino group or a group in which the amino group is substituted with an alkyl group having 1 to 5 carbon atoms, or 1 carbon atom.
To 15 alkyl group or a group in which the alkyl group is substituted with a halogen atom or an aryl group having 6 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms or a halogen atom, a nitro group, a cyano group, or a carbon number It is a group substituted with an acyl group having 1 to 5 or an alkyl group having 1 to 5 carbon atoms, and R ^f and R ^g may form a cyclic structure with or without a hetero atom. ), Specifically

[0110]

[Chemical 28]

And the like.

Of the compounds having an NF bond, a particularly preferred compound as the N-fluorocarbamate compound is the following formula (XIII):

[0113]

[Chemical 29]

(In the formula, R ^h and R ⁱ are the same or different, an alkyl group having 1 to 15 carbon atoms, or a group in which the alkyl group is substituted with a halogen atom or an aryl group having 6 to 16 carbon atoms; An aryl group of 10 to 10 or a halogen atom, a nitro group, a cyano group, a carbon number of 1 to 5
Is an acyl group or a group substituted with an alkyl group having 1 to 5 carbon atoms, and R ⁱ may be a hydrogen atom,
R ^h and R ⁱ may have a cyclic structure with or without a heteroatom, or R ^h and R ⁱ together form an aromatic ring structure having 6 to 10 carbon atoms or the aromatic ring structure. A structure substituted with a halogen atom, a nitro group, a cyano group, an acyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms is formed. ). In particular

[0115]

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And the like.

Among the compounds having an NF bond, a particularly preferable compound as the N-fluoropyridone compound is the following formula (XIV):

[0118]

[Chemical 31]

(In the formula, R ^{j to m} are R ^{1 to} R in the formula (I).
^The same as the group defined in ⁵ ). In particular

[0120]

Embedded image

And the like.

Further, as the compound having an NF bond,

[0123]

[Chemical 33]

[0124] etc. may be used.

Examples of the compound having an NF bond preferably used in the present invention include N-fluoropyridinium compounds. Particularly preferred compounds include the following formula (Ia):

[0126]

Embedded image

(Wherein R ^1a , R ^2a , R ^3a , R ^4a and R ^5a are the same or different and each is a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a halogen atom), and The following formula (IIa):

[0128]

Embedded image

(Wherein one of R ^1a , R ^2a , R ^3a , R ^4a and R ^5a is

[0130]

Embedded image

(N is an integer of 0 to 5) and the other is the same or different and each is a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a halogen atom). And N-fluoropyridinium compounds, wherein the lower alkyl group has 1 to 4 carbon atoms, the lower haloalkyl group has 1 to 4 carbon atoms, and n is 0.
Is an integer from 2 to 2 of the formula (Ia) above.

[0132]

[Outside 7]

More preferred is an N-fluoropyridinium compound having a pKa of 4.56 or less, which is a conjugated base of Bronsted acid.

[0134]

Embedded image

(Where R ^1a , R ^2a , R ^3a , R ^4a , R ^5a ,
R ^{1a '} , R ^2a' , R ^{3a '} , R ^4a' and R ^{5a '} are the same or different and each is a hydrogen atom, a lower alkyl group, a haloalkyl group having 1 carbon atom, a C 1-8 or halogen atom. , and the one of R ^1a to R ^5a is R ^{1a 'to} R
Forming a binding chain with a single bond with one of ^5a ',

[0136]

[Outside 8]

Is a conjugated base of Bronsted acid having a pKa of 4.56 or less) and a compound of the following formula (IVa):

[0138]

[Chemical 38]

(Where R ^1a , R ^2a , R ^3a , R ^4a and R
^5a are the same or different and each has a hydrogen atom and a carbon number of 1
To an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 carbon atom, an aryl group having 6 to 8 carbon atoms, or a halogen atom, R ^1a
~ R ^5a , two of them are single bonds to form a polymer chain,

[0140]

[Outside 9]

Is an N-fluoropyridinium compound selected from the group consisting of compounds having a pKa of 4.56 or less, which is a conjugate base of Bronsted acid).

As the N-fluoropyridinium compound represented by the formula (I), N-fluoropyridinium trifluoromethanesulfonate, N-fluoropyridinium tetrafluoroborate, N-fluoropyridinium hexafluoroantimonate and N-fluoro are used. Pyridinium hexafluorophosphate, N-fluoro (methyl) pyridinium tetrafluoroborate, N-
Fluorodimethylpyridinium tetrafluoroborate, N-fluorotrimethylpyridinium trifluoromethanesulfonate, N-fluorotrimethylpyridinium tetrafluoroborate, N-fluorochloropyridinium tetrafluoroborate, N-fluorodichloropyridinium trifluoromethanesulfonate, or N -Fluorodichloropyridinium tetrafluoroborate and the like are particularly preferable, and as the N-fluoropyridinium compound represented by the formula (II), N-fluoropyridinium sulfonate, N-fluorochloropyridinium sulfonate, N-fluoro (methyl) Pyridinium sulfonate, N-fluoro (trifluoromethyl) pyridinium sulfonate or N-fluoro (dimethyl) pyridini And the like. As the N-fluoropyridinium compound represented by the formula (III), 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, and are represented by the formula (I
Examples of the N-fluoropyridinium compound represented by V) include poly (N-fluoropyridinium tetrafluoroborate-diyl), poly (N-fluoropyridinium hexafluorophosphate-diyl), and poly (N-fluoropyridinium hexafluoroacene). Nato-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'- The Le Oro bipyridinium bis (hexafluoroantimonate) - diyl], poly [N, N'-difluoro-bipyridinium bis (trifluoromethanesulfonate) - diyl], poly [N, N'
-Difluorodimethylbipyridinium bis (tetrafluoroborate) -diyl], poly [N, N'-difluorodichlorobipyridinium bis (tetrafluoroborate) -diyl], poly [N, N'-difluorodihexylbipyridinium bis (tetrafluoro) Borate) -diyl] and the like are particularly preferable.

The electric energy material which is a compound having an N—F bond usable in the present invention may be in the form of powder or film. In addition, the compound having an NF bond may be used alone or as a mixture of two or more kinds.

The porous body which is the positive electrode material used in the present invention has a structure capable of adhering a sufficient amount of the positive electrode active material to the porous body, and the positive electrode active material is at least near or on the surface. Any structure may be used as long as it can be attached. Further, the portion of the positive electrode active material attached to the porous body does not have to be uniformly attached in the thickness direction, and for example, most of it may be present near the surface.

As an example of the structure of the porous body, for example, a sponge-like structure in which the constituent material has a large number of communicating holes (hereinafter referred to as sponge-like. Here, although expressed as sponge-like, it does not necessarily have elasticity. The structure of the fiber material formed into a sheet with various tissues (hereinafter, referred to as a fiber structure or a fiber structure). In the fiber structure, for example, between the filaments in a structure such as a nonwoven fabric, and In a structure such as a woven fabric, there are gaps or spaces between filaments and yarns, but in the present invention, such gaps or spaces are referred to as holes), and the sponge-like or fiber structure is particularly preferable. preferable.

The pore diameter of the sponge-like porous material used in the present invention is not particularly limited, but is 200 to 200 on average.
It is about 1 μm, preferably about 150 to 5 μm on average. If the average pore size is smaller or larger than the above range, the positive electrode active material tends to be difficult to be attached sufficiently. The porosity of the sponge-like porous body (ratio of the volume of pores to the volume of the sponge-like porous body) is not particularly limited, but is 90 to 30%, preferably 80 on average.
~ 50%. If the porosity is smaller than the above range, the electric capacity is insufficient, and if it is larger than the above range, the positive electrode active material tends to be hard to adhere.

As a material for the sponge-like porous material used in the present invention, sponge-like resin such as polyethylene, polystyrene, polyvinyl chloride, or sponge-like ceramics is preferable from the viewpoint of non-conductivity. Among them, expanded polystyrene is particularly preferable in that it has good flexibility and is inexpensive, while various sponge-like metals and sponge-like carbons are preferable from the viewpoint of being conductive, and among them, sponge-like carbon is economical. Is particularly preferable in that a high electromotive force can be obtained.

When a non-conductive material is used as the positive electrode material, and when it is used as a battery, it should not be shortened.
It also has the advantage that it can be stored for a long time, while
When a conductive material is used as the positive electrode material, it is possible to manufacture a battery that has a low internal resistance and therefore can generate high current and high voltage, and it is possible to construct a battery without using a positive electrode current collector. There are advantages. Examples of preferred embodiments of the positive electrode material composed of the sponge-like porous body include conductive sponge-like porous bodies such as sponge-like carbon, sponge-like nickel, sponge-like platinum, sponge-like silver and sponge-like lead, and expanded polystyrene. And the non-conductive sponge-like porous body.

As a method for producing the sponge-like porous body, a generally known firing method or the like may be used. In the case of a sponge-like metal such as sponge-like nickel, sponge-like platinum or sponge-like silver, for example. Include a method for producing a sponge-like metal by forming a metal coating on the surface layer of a planar foamed organic resin by plating or vapor deposition, then burning off the organic resin, and further treating in a reducing atmosphere. , For example, in the case of sponge-like carbon, a method of baking wood etc. in an oxygen-deficient state to make charcoal,
Or carbon with a large surface area (may be in powder form,
If desired, a binder such as polytetrafluoroethylene, carboxymethyl cellulose, polyvinyl alcohol, etc. may be added to solidify. In addition, as described above, these sponge-like porous bodies can be used even when the distribution state of the pores is not uniform in the thickness direction of the sponge-like porous body.

Examples of the fibrous porous material used in the present invention include structures such as a woven structure, a knitted structure, a braided structure, and a non-woven structure. The non-woven structure (including a structure such as a non-woven fabric) is preferable from the viewpoint of large size.

The fiber density (ratio of the volume of the fibers to the volume of the porous material having a fiber structure) of the fibrous porous material used in the present invention is 90 to 30%, preferably 80 to 5 on average.
It is 0%. When the density is lower than the above range, the electric capacity tends to be poor, while when the density is higher than the range, the impregnation force or the adhesive force tends to be poor.

The diameter of the fiber used in the porous body having the above fiber structure is preferably 200 to 0.5, and 100 to
1 is more preferred. If the diameter is smaller than the above range, the strength tends to be weak, whereas if the diameter is larger than the above range, the impregnating force or the adhesive force tends to be poor.

The cross-sectional structure of the fibers does not have to be circular, and may have, for example, an irregular cross section.

The fibers used in the porous material of the fiber structure used in the present invention include natural fibers such as cotton, wool and hemp, semi-synthetic fibers such as cellulose fibers, rayon, vinylon, polyamide, nylon and vinylon. , Synthetic fibers such as polypropylene and polyethylene, and metal fibers such as nickel fibers, platinum fibers, and silver fibers, and carbon fibers. Natural fibers and synthetic fibers are non-conductive and have good flexibility. On the other hand, conductive metal fibers such as nickel fibers, platinum fibers, and silver fibers, carbon fibers, and the like are preferable because they are conductive.
As described above, when a non-conductive material is used as the positive electrode material, when it is used as a battery, it has the advantages that it does not shorten (short-circuit) and can be stored for a long period of time. When used, there is an advantage that a battery having a low internal resistance and capable of generating a high current and a high voltage can be manufactured, and a battery can be constructed without using a positive electrode current collector.

As the method for producing the porous body having the fiber structure, any of commonly used weaving methods, knitting methods, braiding methods, non-woven methods and the like can be used. Here, in the case of the non-woven metal fiber, it is preferable to obtain it by a method of sintering the metal fiber.

The porous body used in the present invention is preferably a flexible material from the viewpoint of obtaining a flexible positive electrode.

Next, the method for producing the positive electrode of the present invention will be described.

A compound having an NF bond, which is a positive electrode active material, is mixed with a solvent, and if necessary, mixed and stirred under heating to uniformly dissolve or disperse a solution of the positive electrode active material. When the compound having an N—F bond is a liquid, this liquid can be used as it is. A method in which the solution or liquid is further added with an appropriate additive, if necessary, and then applied to the porous body that is the positive electrode material, or the porous body is immersed in the solution or liquid and added if necessary. The positive electrode is obtained by drying at room temperature or room temperature. The coating or dipping and drying may be repeated several times.

The solvent is a solvent capable of dissolving or dispersing a compound having an NF bond, and examples thereof include nitrile compounds such as acetonitrile, propionitrile and benzonitrile, methanol, ethanol, propanol, and the like.
Isopropanol, butanol, isobutanol, second
Alcohols such as butyl alcohol, tertiary butyl alcohol, trifluoroethanol, hexafluoroisopropanol, amide compounds such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, formic acid, acetic acid, propionic acid, trifluoroacetic acid, pentafluoropropionic acid, etc. Carboxylic acids, ethers such as diethyl ether, tetrahydrofuran, dioxane,
Acetone, ketones such as methyl ethyl ketone, methyl chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, halogenated hydrocarbons such as trichlorotrifluoroethane, aromatic compounds such as benzene, toluene, chlorobenzene, water or a mixture of these. A mixture can be exemplified.

The amount of the solvent to be used may be appropriately selected from the amount necessary for liquefying the compound having an N--F bond, and is not limited to these amounts, but is preferably about 15 to 99% by weight. Is about 20 to 91% by weight. Further, as described above, when the compound having an N—F bond is a liquid, it may be used without using a solvent.

The amount of the compound having an NF bond attached to the positive electrode material may be about 10 to 95% by weight, preferably about 50 to 90% by weight.

Further, in the compound having the N--F bond,
Furthermore, by adding one or more polar compounds, a positive electrode active material capable of producing a positive electrode having a lower internal resistance can be obtained. The amount of the polar compound preferably used is 0.5 to 60% by weight, preferably 1 to 50% by weight, more preferably 2 to 40% by weight, based on the weight of the compound having an NF bond. Examples of the polar compound include dimethyl sulfone, dimethyl carbonate, diphenyl sulfone, methylphenyl sulfone, 1,3-dioxolane, γ-butyrolactone, sulfolane, ethylene carbonate, propylene carbonate, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. , Dimethoxyethane, ethylene glycol, ethanol, methanol, diethyl ether, tetrahydrofuran, 2-
Methyl tetrahydrofuran, nitromethane, nitroethane, nitrobenzene, dinitrobenzene, trinitrobenzene, chlorodinitrobenzene, fluorodinitrobenzene, acetonitrile, propionitrile, benzonitrile, pyridinium trifluoromethanesulfonate, pyridinium tetrafluoroborate, pyridinium hexafluorophosphonate, Polar organic compounds such as pyridinium hexafluoroarsenate, pyridinium hexafluoroantimonate, 2,6-dichloropyridinium tetrafluoroborate, 3,5-dichloropyridinium tetrafluoroborate and 2,4,5-trimethylpyridinium tetrafluoroborate Compound, as well as lithium trifluoromethanesulfonate, lithium tetrafluorobora , Lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroantimonate, lithium perchlorate, sodium perchlorate, potassium perchlorate, ammonium trifluoromethanesulfonate, ammonium tetrafluoroborate, ammonium chloride, Illustrates polar inorganic compounds such as sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, zinc tetrafluoroborate, magnesium trifluoromethanesulfonate, magnesium tetrafluoroborate, water, or mixtures thereof. be able to.

The thickness of the positive electrode is appropriately selected depending on the type of battery to be manufactured, but in the case of a thin battery, the thickness is not limited to this but is 2 to 0.01 mm.
The degree is preferably about 1 to 0.05 mm.

Next, the constitution of the battery of the present invention comprising the positive electrode in which the compound having an N—F bond is attached to the porous body will be explained, but the present invention is not limited to these.

[Preparation of Positive Electrode] The porous body to which the compound having an NF bond is attached according to the above method is cut into a size necessary for the positive electrode of a desired battery, and pressed into a required thickness. And make a positive electrode. The order of the cutting process and the pressing process may be reversed. In addition, in the case of a battery that requires a positive electrode current collector, the cutting or pressing process may be performed together with the positive electrode current collector.

As another example of the method for producing the positive electrode, a compound having an N—F bond is prepared in advance by cutting a porous body cut into a size necessary for the positive electrode of a desired battery and subjecting the porous body to the above process. Are adhered, press-bonded to a required thickness, and if necessary, further cut and / or pressed to obtain a positive electrode. In addition, in the case of a battery requiring a positive electrode current collector, these processes may be performed together with the positive electrode. The preferable configuration and structure of the positive electrode are as described above.

[Positive Electrode Current Collector] Examples of the positive electrode current collector include graphite, graphite such as graphite, carbon black such as acetylene black, carbon fiber, carbon such as pitch and tar, platinum, gold, nickel, stainless steel, A plate made of iron, copper, aluminum or the like, a net, a patching metal (foamed metal), a metal fiber net, or the like is preferably used.

The thickness of the positive electrode current collector depends on the type of battery.
It may be selected as appropriate, but in the case of a thin battery, it is not limited to these, but 0.5 to 0.01 mm is suitable.

When the porous body is a conductive porous body, there are cases where the positive electrode current collector is not used.

[Electrolyte] As the electrolyte, those commonly used can be used regardless of whether they are liquid or solid. Preferred liquid electrolytes include, for example, lithium perchlorate, tetrabutylammonium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphonate, lithium trifluoromethanesulphonate, magnesium chloride, zinc chloride, ammonium chloride and the like dissolved therein. Ethylene carbonate, propylene carbonate, sulfolane, γ-butyrolactone, 1,3-dioxirane, 2-
Examples include methyltetrahydrofuran, diethyl ether, tetrahydrofuran, dimethoxyethane, acetonitrile, methanol, ethanol, water, or a mixture thereof, and the solid electrolytes include, for example, lithium trifluoromethanesulfonate and highly ion conductive non-aqueous electrolyte gel. Polymer solid electrolytes and the like.

The compound having an N—F bond used in the present invention is N-fluoropyridinium compound, N-fluoroquinuclidinium compound, N-fluoro-1,4-diazoniabicyclo [2.2.2]. In the case of a salt structure such as an octane compound, since the compound having an NF bond also has the property of an electrolyte, it is not always necessary to use an electrolyte, and these are dissolved in a polar solvent. The solution can also be used as the electrolyte.

[Negative Electrode] Examples of the negative electrode material include 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, lithium-cadmium, lithium-silver, lithium-magnesium, lithium-wood metal, and various other lithium alloys can be used. Materials such as lithium, lithium alloys, calcium, and magnesium are preferable because they can generate high electromotive force and can be easily applied to flexible thin batteries.

The thickness of the negative electrode may be appropriately selected depending on the type of battery, but in the case of a thin battery, it is not limited to these, but generally about 1 to 0.01 mm is suitable.

[Separator] When a separator is used, for example, a woven or non-woven fabric such as a polyamide type or a polypropylene type, a cellulose fiber or the like which has been conventionally used can be employed.

When the porous material used in the present invention is a non-conductive material, the separator is not always necessary. This is because the separator is used to prevent a short circuit between the positive electrode and the negative electrode, and the compound having the NF bond reacts with the metal of the negative electrode to form a solid protective film (from metal fluoride) on the interface. This is because the short circuit is less likely to occur because the protective film) is formed, and when the porous body is a non-conductive material, the short circuit does not occur.

Thickness of separator (when used)
May be appropriately selected, but in the case of a thin battery, it is not limited to these, but is generally 0.2 to 0.02 m.
Those of about m are suitable.

The above constituent materials may be appropriately assembled into a battery by an ordinary method.

NF that can be used in the present invention
In order to show the characteristics of the compound having a bond as an electric energy material, first, a compound having various N—F bonds is used as a positive electrode (the compound having the N—F bond also serves as a solid electrolyte. The all-solid-state battery, which was prepared without using the porous body as the positive electrode material), was prepared in the following manner, and the electromotive force of this battery was measured. Hereinafter, all experiments were performed at room temperature.

Reference Examples 1 to 8 The compounds having NF bond shown in Table IV were well ground,
A positive electrode in which a positive electrode current collector was adhered was prepared by pressing on a 1 cm × 1 cm platinum plate to form a thin layer of the compound having a thickness of about 0.1 mm. If a thin layer with good adhesion cannot be successfully formed, about 5 to 10% by weight of sulfolane as an adhesive is mixed with the compound having NF bond to form a thin layer on a platinum plate by the same method as described above. did.

Then, on the surface of the thin layer, about 1 cm × 1 c
A metal plate described in Table IV of m was provided, and a laminated structure of a platinum plate / a compound having an N—F bond / the metal plate was produced.

The platinum plate and the metal were sandwiched by a pinch cock so that the laminated structure was sufficiently adhered to each other to prepare an all-solid-state battery, and the open circuit voltage was measured by a voltmeter. The results are shown in Table IV.

[0182]

[Table 22]

Reference Examples 9 to 15 Reference Example 1 was repeated except that compounds having various substituents on the pyridine ring of the N-fluoropyridinium compounds shown in Table V were used as the compounds having the NF bond. ~ 8
An all-solid-state battery was prepared by the same method as described above, and the open circuit voltage was measured with a voltmeter. The results are shown in Table V.

[0184]

[Table 23]

According to the results shown in Table IV and Table V,
It can be seen that the compound having an NF bond used in the present invention has a high energy density and can be a battery having a high electromotive force, or can be a battery having a wide range of electromotive force.

Further, the compound having the NF bond has a high environmental acceptor, and the thermal decomposition temperature of, for example, N-fluoropyridinium tetrafluoroborate is 198 ° C. or higher (having other NF bonds. Since the compound also has a high thermal decomposition temperature) and good thermal stability, the battery manufactured using the compound having the NF bond can be used in a wide temperature range and needs to contain a heavy metal or the like as a constituent component. Therefore, it can be highly environmentally acceptable. By using the positive electrode in which the porous body is impregnated with the compound having the NF bond having such excellent performance, the primary and secondary batteries can be manufactured very easily. In particular, it is advantageous for manufacturing flexible primary and secondary thin batteries.

Next, the present invention will be described based on examples, but the present invention is not limited to such examples.

Examples 1-26 N-fluoropyridinium tetrafluoroborate (manufactured by Onoda Cement Co., Ltd., trade name; Onoda Fluorinert F)
A solution of P-B500) (hereinafter referred to as FP-B500) almost saturated in acetonitrile was prepared (hereinafter, referred to as “P-B500”).
Acetonitrile solution). The FP-B500 contained 3.8% by weight of a polar compound, pyridinium tetrafluoroborate, in addition to N-fluoropyridinium tetrafluoroborate.

Next, the thin fiber material shown in Table VI, which was cut into a size of 1 cm × 1 cm, was immersed in the acetonitrile solution for about 5 minutes and then taken out, and the temperature was changed to 120 ° C.
And dried for 5 minutes. After that, the above-mentioned dipping and drying process was repeated four more times, and about 3 to 10 times the weight of FP-B500 was attached to the weight of the fiber material before dipping. Subsequently, the FP-B500-adhered fiber material was immersed in a mixed solution of sulfolane / tetrahydrofuran (weight ratio 1/9), which is a polar compound, for about 5 minutes, taken out, and dried at 120 ° C. for 5 minutes.

The above-mentioned fibrous material to which FP-B500, sulfolane and tetrahydrofuran were adhered was pressed with a pressing machine (manufactured by Aldrich Co., product number Z16912-9) to
A thin positive electrode was produced by pressurizing at a pressure of ton / cm ² for 5 minutes (without heating) (the thickness of the positive electrode is shown in Table VI).

On one surface of the positive electrode, a platinum plate (surface area 1
cm × 1 cm, thickness 0.1 mm), and a magnesium plate (surface area 1 cm × 1 cm, thickness 0.5 mm) on the other surface to form a three-layer laminate, which is the whole as shown in FIG. A solid thin battery was produced. FIG. 1 is a perspective view of the battery, 1 is a positive electrode made of a compound having an N—F bond and a porous body, 2 is a positive electrode current collector made of a platinum plate, 3
Indicates a negative electrode made of a magnesium plate.

The open circuit voltage of the battery was measured, and the internal resistance value was measured from the open circuit voltage of the device shown in FIG. 2 and the battery voltage under an external load of 1 MΩ to 10 KΩ.
In FIG. 2, 1 is a positive electrode of the battery, 2 is a positive electrode current collector of the battery, 3 is a negative electrode of the battery, V is a voltmeter, and R is an external load. The battery voltage when an external load is applied is a constant value or a nearly constant value (state that is stable at about ± 0.01 V)
When it became, it was made into the measured value. The results are shown in Table VI.

[0193]

[Table 24]

[0194]

[Table 25]

Examples 27 to 34 The compounds shown in the table were used as the compound having an NF bond, and as a fiber material, a nonwoven fabric made by Asahi Chemical Industry Co., Ltd. (product name: Clean Wipe-P) (diameter 15 mm, thickness 0) .0
5 mm) was used to manufacture a positive electrode by the same method as in Examples 1 to 26.

Subsequently, batteries were produced by the same method as in Examples 1 to 26 except that the materials shown in Table VII were used as the negative electrode material, and the electromotive force and internal resistance of the batteries were measured by the same method as described above. . The negative electrode material had a diameter of 15 mm and a thickness of 0.38 mm. The results are shown in Table VII.

[0197]

[Table 26]

Examples 35 to 37 Examples of the case of the battery of the present invention, which is a liquid or a viscous substance and is composed of the compound having the NF bond, will be shown below.

Table VII as compounds having NF bond
The compound described in I was used, and as a fiber material, a cotton non-woven fabric (product name: Clean Wipe-P) manufactured by Asahi Kasei Kogyo Co., Ltd. (surface area: 2 cm × 2 cm, thickness: 0.1 mm) was used. When the compound having an NF bond is a liquid, the compound having an NF bond can be obtained by dropping and impregnating the required amount of the compound having the NF bond into the fiber material. Also in the case of a viscous material, a platinum plate (surface area 2 cm × 2 cm, thickness) is similarly formed on one surface of the positive electrode obtained by impregnating the fiber material with a necessary amount of the compound having the N—F bond in spots. 0.1 mm), and the negative electrode material (surface area 2 cm × 2) described in Table VIII on the other surface.
cm, thickness 0.5 mm) were overlapped to produce an all-solid thin battery. However, only in the case of Example 37, about 20% by weight of a polar compound, sulfolane, was added to the compound having an N—F bond and mixed uniformly to obtain a positive electrode active material.

Subsequently, the electromotive force and internal resistance of the battery were measured by the same method as in Examples 1-34. The results are shown in Table V
Shown in III.

[0201]

[Table 27]

Example 38 An example of using a conductive material as the positive electrode material porous material in the present invention is shown below.

As the compound having an NF bond, the same N-fluoropyridinium tetrafluoroborate (2 g) used in Examples 1 to 26 and 1,1,1,3,3,3 were used.
-A solution of 3 ml of hexafluoroisopropanol in a porous carbon plate (Nikola, product name;
Carbon sheet part number C-073328) (surface area 50m
m × 50 mm, thickness 0.1 mm) was soaked for 30 minutes, then taken out and dried under reduced pressure using a vacuum pump for 1.5 hours under heating at 50 to 60 ° C. to produce a positive electrode.

The amount of N-fluoropyridinium tetrafluoroborate attached to the porous carbon plate was 176 mg.

Next, a cotton non-woven fabric (Asahi Kasei Co., Ltd.)
Made, product name; clean wipe-P) (surface area 54 mm x
54 mm, thickness 0.05 mm) was used as a separator, and the separator was impregnated with a mixed solution of N-fluoropyridinium tetrafluoroborate and sulfolane (mixing ratio 1: 5 (weight ratio)) as an electrolytic solution.

A separator impregnated with the electrolyte was superposed on one surface of the positive electrode, and a magnesium plate (surface area: 50 mm × 50 mm, thickness: 0.3 m) was further formed thereon.
m) were overlaid to prepare a battery having a structure as shown in FIG.
FIG. 3 is a perspective view of the battery, 4 is a positive electrode composed of a compound having an N—F bond and a conductive porous body, 5 is a separator, and 6 is a negative electrode.

A method similar to that of Examples 1 to 37 was applied to the above-mentioned battery (however, the battery of this embodiment was not provided with a positive electrode current collector, and the battery was provided with a separator. As a result of measuring the electromotive force and the internal resistance in Example 1 to 37), the electromotive force is 2.22 V,
The internal resistance was 1.7 KΩ.

[0208]

INDUSTRIAL APPLICABILITY In the positive electrode in which the compound having the NF bond of the present invention is attached to the porous body, a porous body having a desired thickness and size can be selected and used as the positive electrode material. Since a positive electrode having various thicknesses and sizes that are homogeneous can be easily manufactured, and a compound having an NF bond is used as a positive electrode active material, a positive electrode having excellent environmental acceptability and heat stability can be obtained. Can be manufactured. According to the battery including the positive electrode, a high electromotive force can be obtained, and a desired electromotive force can be obtained by appropriately selecting and combining a porous body which is a positive electrode material or a compound having an N—F bond which is a positive electrode active material. In addition, it can have a high energy density, can be used in a wide temperature range, and has a long life. Further, the battery is easy to promote miniaturization, weight reduction, and thinning, and is excellent in practicality.

Further, according to the present invention, by using the porous material which is the positive electrode material as the fiber material, the positive electrode can be manufactured more easily and inexpensively.

Further, according to the present invention, a battery can be constructed without using a separator by using the non-conductive material for the porous body as the positive electrode material.

Further, according to the present invention, by using the porous material as the positive electrode material as a conductive material, a battery can be constructed without using a positive electrode current collector, and the conductive material can be used as a positive electrode. The battery used as the material can have high current and high electromotive force because of its low internal resistance. Furthermore, since the porous body that is the positive electrode material is a flexible material, a flexible battery can be manufactured.

[Brief description of drawings]

FIG. 1 is a perspective view of batteries manufactured in Examples 1-36.

FIG. 2 is a schematic explanatory diagram of a method for measuring electromotive force and internal resistance of the batteries manufactured in Examples 1 to 37.

FIG. 3 is a perspective view of a battery manufactured in Example 37.

[Explanation of symbols]

 1 Positive Electrode 2 Positive Electrode Current Collector 3 Negative Electrode 4 Positive Electrode 5 Separator 6 Negative Electrode

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[Procedure amendment]

[Submission date] December 14, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

[0038] As the conjugated ^{base, -} BF _^4, - PF
_{^{6, - AsF 6, - SbF}} 6, - AlCl 4, - SbC
_{^{l 6, - SbCl 5 F,}} - Sb 2 F 11, - B 2 F 7, -
_{^{OClO 3, - OSO 2 F,}} - OSO 2 Cl, - OSO
_{^{2 OH, - OSO 2 OCH 3}} , - OSO 2 CH 3, - O
_{^{SO 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 CH 3,
^- such as OSO ₂ C ₆ H ₄ NO ₂ are particularly preferred.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0146

[Correction method] Change

[Correction content]

The pore diameter of the sponge-like porous material used in the present invention is not particularly limited, but is 200 to 200 on average.
It is about 1 μm, preferably about 150 to 5 μm on average. If the average pore size is smaller or larger than the above range, the positive electrode active material tends to be difficult to be attached sufficiently. The porosity of the sponge-like porous body (ratio of the volume of pores to the volume of the sponge-like porous body) is not particularly limited, but is 90 to 30%, preferably 80 on average.
~ 50%. The Most porosity smaller than the range, a capacitance is insufficient, also large and the positive electrode active material tends to hardly adhere.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0154

[Correction method] Change

[Correction content]

The fibers used in the porous material of the fiber structure used in the present invention include natural fibers such as cotton, wool and hemp, semi-synthetic fibers such as cellulose fibers, rayon, vinylon, polyamide, nylon and vinylon. , Synthetic fibers such as polypropylene and polyethylene, and metal fibers such as nickel fibers, platinum fibers, and silver fibers, and carbon fibers. Natural fibers and synthetic fibers are non-conductive and have good flexibility. On the other hand, conductive metal fibers such as nickel fibers, platinum fibers, and silver fibers, carbon fibers, and the like are preferable because they are conductive.
As described above, when a non-conductive material is used as the positive electrode material, when it is used as a battery, it has the advantages that it does not cause a short circuit and can be stored for a long period of time. When used, there is an advantage that a battery having a low internal resistance and capable of generating a high current and a high voltage can be manufactured, and a battery can be constructed without using a positive electrode current collector.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0158

[Correction method] Change

[Correction content]

[0158] The compound having a N-F bond as a cathode active material, was mixed in a solvent, obtaining a solution of a more uniformly dissolved or dispersed was the positive electrode active material to mixing and stirring with heating under, if necessary. When the compound having an N—F bond is a liquid, this liquid can be used as it is. A method in which the solution or liquid is further added with an appropriate additive, if necessary, and then applied to the porous body that is the positive electrode material, or the porous body is immersed in the solution or liquid and added if necessary. The positive electrode is obtained by drying at room temperature or room temperature. The coating or dipping and drying may be repeated several times.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0167

[Correction method] Change

[Correction content]

[Positive Electrode Current Collector] Examples of the positive electrode current collector include graphite, graphite such as graphite, carbon black such as acetylene black, carbon fiber, carbon such as pitch and tar, platinum, gold, nickel, stainless steel, iron, copper, plate, such as aluminum, net, pan Chin <br/> Gumetaru (metal foam), metal fiber network is preferably used.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0170

[Correction method] Change

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[Electrolyte] As the electrolyte, those commonly used can be used regardless of whether they are liquid or solid. Preferred liquid electrolyte, such as lithium perchlorate, tetrabutylammonium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate phosphonate, lithium trifluoromethane phosphonate, magnesium chloride, and dissolved zinc chloride, ammonium chloride, etc. ethylene carbonate, propylene carbonate, sulfolane, .gamma.-butyrolactone, 1,3 Jioki Seo run, 2-
Examples include methyltetrahydrofuran, diethyl ether, tetrahydrofuran, dimethoxyethane, acetonitrile, methanol, ethanol, water, or a mixture thereof, and the solid electrolytes include, for example, lithium trifluoromethanesulfonate and highly ion conductive non-aqueous electrolyte gel. Polymer solid electrolytes and the like.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0186

[Correction method] Change

[Correction content]

[0186] Furthermore, the compounds having a N-F bond has a high environmental receptors, also for example N- Furuoropiriji <br/> Niu beam thermal decomposition temperature of the tetrafluoroborate is 198 ° C.
Above (other compounds with NF bond also have high thermal decomposition temperature
Since the battery manufactured by using the compound having the NF bond can be used in a wide temperature range and does not need a heavy metal as a constituent component, Can be highly receptive. By using the positive electrode in which the porous body is impregnated with the compound having the NF bond having such excellent performance, the primary and secondary batteries can be manufactured very easily. In particular, it is advantageous for manufacturing flexible primary and secondary thin batteries.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction content]

[0197]

[Table 26]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location H01M 6/16 Z 10/40 Z

Claims (6)

[Claims] 1. A positive electrode in which a compound having an N—F bond is attached to a porous body. 2. The positive electrode according to claim 1, wherein the porous body is made of a fiber material. 3. The positive electrode according to claim 1, wherein the porous body is made of a conductive material. 4. The positive electrode according to claim 1, wherein the porous body is made of a non-conductive material. 5. The positive electrode according to claim 1, 2, 3 or 4, wherein the porous body is a flexible material. 6. A battery comprising a positive electrode in which a compound having an N—F bond is attached to a porous body.