JPH08171939A - Secondary battery - Google Patents

Abstract

PURPOSE: To provide a battery with ease of manufacture, high electromotive force and high energy density by using positive electrode active material containing N-fluoropyridinium salt to make the positive electrode active material and a negative electrode serve as respective charging electrodes. CONSTITUTION: Powdered N-fluoropyridinium salt is molded into a desired shape by a pressing machine or mixed with binder or conductive agent and molded into a desired shape together with collective material by a pressing machine to manufacture positive electrode active material 8. A battery consists of the positive electrode active material, a negative electrode 2 made of lithium, a separator 5 and electrolyte formed of lithium tetrafluoroborate. In this way, electrochemical reaction between the positive electrode active material 8 with high oxidizing force and the negative electrode active material smoothly and retroactively proceeds. The active material 8 and the negative electrode 2 serve as an anode and a cathode, respectively, during charging, so that the battery with high electromotive force and high energy density is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a secondary battery. More specifically, the present invention relates to a secondary battery having a high electromotive force and a high energy density, which is composed of a positive electrode active material composed of an N-fluoropyridinium salt which is easy to handle and has high environmental acceptability, a positive electrode current collector, an electrolytic solution, a separator and a negative electrode. More specifically, the present invention relates to a secondary battery in which the positive electrode active material and the negative electrode both serve as charging electrodes, and the positive electrode active material serves as an anode and the negative electrode serves as a cathode during charging.

[0002]

2. Description of the Related Art Batteries have become indispensable as a simple electric energy source for consumer use or as an important energy source for advanced equipment, and their types vary widely depending on the required performance. Is being studied. Further, with the situation where 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. Generally, positive electrode active materials for these batteries include manganese dioxide, cobalt dioxide, vanadium pentoxide and lithium manganese oxide, heavy metal oxides such as lithium cobalt oxide, iodine, inorganic compounds such as thionyl chloride and fluorinated graphite, polyaniline, polypyrrole. Also, organic polymers such as polythiophene are used. However, since the above-mentioned heavy metal oxides are usually insoluble in a solvent, they cannot be said to be easily molded or processed. Further, whether the inorganic compound is a toxic compound,
Also, it has heavy metals that are not preferable from the viewpoint of protection of the natural environment, and it has many problems in the manufacture of batteries because it has no ionic and electronic conductivity like graphite fluoride, and it has a secondary problem. It couldn't be a battery. Further, in the above organic polymer, a so-called doping step is necessary because the organic polymer alone cannot be a high electromotive force positive electrode material, which complicates the battery manufacturing process, and moreover as a positive electrode active material in general. When synthesizing this polymer, an electrolytic polymerization method is used, but since this polymer can be formed only on the electrode by this method, there is a great limitation in manufacturing various batteries that can meet various requirements. receive.

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

As a means for solving these drawbacks, the present inventors have found a method of using a compound having an NF bond in the molecule as a positive electrode active material, and previously filed a patent application. According to this method, it is possible to easily manufacture a battery that is satisfactory in terms of environmental acceptability, electromotive force, energy density, and the like.

However, there is a demand for a positive electrode active material having a higher electromotive force, a higher energy density, good workability and durability, and which can be used in a secondary battery with little deterioration.

[0007]

The present invention provides a positive electrode active material containing an N-fluoropyridinium salt, which has high environmental acceptability and is easy to handle, and a high electromotive force comprising the positive electrode active material. And to provide a secondary battery having a high energy density.

[0008]

The present invention provides a positive electrode current collector,
A battery comprising a positive electrode active material containing an N-fluoropyridinium salt, an electrolytic solution, a separator and a negative electrode, wherein the positive electrode active material and the negative electrode each serve as a charging electrode, and the positive electrode active material serves as an anode and a negative electrode during charging. Relates to a secondary battery which can be a cathode.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The battery of the present invention comprises a positive electrode current collector / a positive electrode composed of a positive electrode active material / electrolyte / separator / negative electrode.

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).

[0011]

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[0012]

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[0013]

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[0014]

[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'
-May be formed, and 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 ′} are the same or different and are all hydrogen atoms,
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, an alkoxy group having 1 to 5 carbon atoms, or an aryloxy having 6 to 10 carbon atoms A group, a group substituted with an acyl group having 1 to 5 carbon atoms, an acyloxy group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms; an alkenyl group having 1 to 15 carbon atoms or a halogen atom or carbon atom for the alkenyl group. A group substituted with an aryl group having 6 to 10 carbon atoms; an alkynyl group having 1 to 15 carbon atoms or a group having the alkynyl group substituted with a halogen atom or an aryl group having 6 to 10 carbon atoms; or 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 the acyl group The number of carbon atoms 2; group substituted with Gen atoms
15 alkoxycarbonyl group 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 a halogen atom or 1 carbon atom A group substituted with an alkyl group having 5 to 5 carbon atoms; an alkylsulfonyl group having 1 to 15 carbon atoms or a halogen atom or 6 carbon atoms in the alkylsulfonyl group.
A group substituted with an aryl group having 10 to 10; 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; 6 to 15 carbon atoms
Arylsulfinyl group or a group in which the arylsulfinyl group is substituted with a halogen atom or an alkyl group having 1 to 5 carbon atoms; an alkoxy 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 a group; an aryloxy group having 6 to 15 carbon atoms or a group obtained by substituting the aryloxy group with a halogen atom or an alkyl group having 1 to 5 carbon atoms;
15 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 A group in which an oxy group is substituted with a halogen atom or an aryl group having 6 to 10 carbon atoms; an arenesulfonyloxy group having 6 to 15 carbon atoms or the arenesulfonyloxy group is substituted with a halogen atom or an alkyl group having 1 to 5 carbon atoms Group; carbamoyl group substituted with an alkyl group having 1 to 5 carbon atoms or a group obtained by substituting the alkyl-substituted carbamoyl group with an aryl group having 6 to 10 carbon atoms; carbamoyl group substituted with an aryl group having 6 to 10 carbon atoms Or by substituting the aryl-substituted carbamoyl group with an alkyl group having 1 to 5 carbon atoms Group; an amino group substituted with an acyl group having 1 to 5 carbon atoms or a group obtained by substituting the acyl substituted amino group with a halogen atom; an N-alkylpyridinium base having 6 to 15 carbon atoms or the N-alkylpyridinium base having halogen Group substituted with an atom, an aryl group having 6 to 10 carbon atoms or an alkyl group having 1 to 5 carbon atoms; 11 to 1 carbon atoms
5 N-arylpyridinium base or a group in which the N-arylpyridinium base is substituted 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 , 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 ′} may form a ring structure in various combinations with or without a heteroatom, and in the formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
One of R ⁸ and R ⁹

[0016]

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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 ⁸
Two of R ⁹ and R ⁹ form a polymer chain with a single bond, and the repeating units represented by the formula (IV) may be the same or different. Also

[0018]

[Outside 1]

Is a conjugate base of Bronsted acid.

[0020]

[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-one-6-sulfonic acid, 1-hydroxy-p-menthane-2-sulfonic acid, p-styrenesulfonic acid, β-
Sulfonic acids such as styrene sulfonic acid, vinyl sulfonic acid, perfluoro-3,6-dioxa-4-methyl-7-octene sulfonic acid; poly (vinyl sulfonic acid), poly (p-styrene sulfonic acid), poly (2 -Acrylamido-2-methyl-1-propanesulfonic acid) and copolymers of these with styrene, poly (perfluoro-
3,6-dioxa-4-methyl-7-octene sulfonic acid) and polysulfonic acids such as copolymers of these with tetrafluoroethylene; mineral acids such as sulfuric acid, phosphoric acid, nitric acid; hydrogen fluoride, hydrogen fluoride Halogen acids such as acids, hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydroiodic acid, perchloric acid, perbromic acid, periodic acid, chloric acid, bromic acid; monomethyl sulfuric acid, Monoalkyl sulfuric acid such as 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;

[0022]

[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 ,

[0024]

[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,

[0027]

[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.

[0029] 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.

Among the N-fluoropyridinium compounds, the compounds represented by the formula (I) include, for example, Table I
However, the present invention is not limited to these.

[0031]

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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.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

[Table 5]

[0038]

[Table 6]

[0039]

[Table 7]

[0040]

[Table 8]

[0041]

[Table 9]

[0042]

[Table 10]

[0043]

[Table 11]

[0044]

[Table 12]

[0045]

[Table 13]

[0046]

[Table 14]

[0047]

[Table 15]

[0048]

[Table 16]

[0049]

[Table 17]

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

[0051]

[Chemical 9]

[0052]

[Table 18]

[0053]

[Table 19]

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

[0055]

[Chemical 10]

[0056]

[Table 20]

[0057]

[Table 21]

As an example of the compound represented by the formula (IV) among the N-fluoropyridinium compounds, for example, those having a structural formula represented by the following formula are preferably mentioned, but not limited thereto.

[0059]

[Chemical 11]

[0060]

[Chemical 12]

[0061]

[Chemical 13]

[0062]

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The N-fluoropyridinium salt-containing polymer containing the repeating unit represented by the formula (IV) contains a unit of substituted or unsubstituted phenylene, naphthalenediyl, thiophenediyl, pyrrolediyl, furandiyl etc. 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):

[0064]

[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):

[0066]

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The unit represented by

[0068]

[Outside 4]

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

[0070]

[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.

[0073]

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Among the compounds having an N—F bond, a particularly preferred compound as the N-fluorosulfonamide compound is the following formula (VIII):

[0075]

[Chemical 19]

(In the formula, R ^a and R ^b are the same or different and each is 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

[0077]

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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):

[0080]

[Chemical 21]

Is indicated by (

[0082]

[Outside 5]

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

[0084]

[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):

[0087]

[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,

[0089]

[Outside 6]

Is the conjugate base of the same or different Bronsted acids as described above). In particular

[0091]

[Chemical formula 24]

And the like.

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

[0094]

[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,

[0096]

[Chemical formula 26]

And the like.

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

[0099]

[Chemical 27]

(In the formula, R ^f and R ^g are the same or different and each is 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

[0101]

[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):

[0104]

[Chemical 29]

(In the formula, R ^h and R ⁱ 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 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

[0106]

Embedded image

And the like.

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

[0109]

[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

[0111]

Embedded image

And the like.

Further, as the compound having an N--F bond,

[0114]

[Chemical 33]

You may use the like.

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):

[0117]

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(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):

[0119]

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

[0121]

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(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 an N-fluoropyridinium compound, 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.

[0123]

[Outside 7]

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

[0125]

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(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 ',

[0127]

[Outside 8]

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

[0129]

[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 10 carbon atoms, or a halogen atom, R
^{1a to} R ^5a , two of them form a polymer chain with a single bond,

[0131]

[Outside 9]

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

The N-fluoropyridinium compound represented by the formula (I) includes N-fluoropyridinium trifluoromethanesulfonate, N-fluoropyridinium tetrafluoroborate, N-fluoropyridinium hexafluoroantimonate and N-fluoro. 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.

Next, a battery composed of a positive electrode active material composed of an N-fluoropyridinium salt, a positive electrode current collector, an electrolytic solution, a separator and a negative electrode will be described.

[Preparation of Positive Electrode Made of Positive Electrode Active Material] If the N-fluoropyridinium salt is in the form of powder, it is shaped into a desired shape such as with a press, or if necessary, mixed with a binder or a conductive agent, for example. Then, it is molded into a desired shape with a current collector together with a current collector. As the binder, for example, a normal binder such as polytetrafluoroethylene powder, carboxymethyl cellulose, polyvinyl alcohol, etc., and as the conductive agent, for example, nickel powder, metal powder such as platinum powder, various metal fine fibers and graphite, graphite, etc. Carbon black such as graphite and acetylene black, carbon such as carbon fiber, pitch and tar are preferably used.

When the N-fluoropyridinium salt can be formed into a film or a plate, such as when it is composed of a high molecular weight compound such as a polymer, or a material which can be formed into a film or a plate by a film forming agent. In that case, the film may be formed as it is, or may be formed into a plate, or if necessary, a binder, a conductive agent, or an additive described below may be added to form a film or a plate, which is then combined with a current collector. To produce a positive electrode. As the film-forming agent, for example, a polymer material such as polyethylene oxide, polyethylene, polytetrafluoroethylene, polyvinyl acetate, polyacrylonitrile, polymethyl acrylate, or gelatin is preferable.

Also, it may be used in combination with other known positive electrode active materials.

Further, by adding one or more polar compounds to the N-fluoropyridinium salt,
A positive electrode active material capable of producing a positive electrode having a lower internal resistance can be obtained.

Further, in the compound having the NF 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, Examples of polar inorganic compounds include sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, zinc tetrafluoroborate, magnesium trifluoromethanesulfonate, magnesium tetrafluoroborate, and water.

The thickness of the positive electrode is appropriately selected depending on the type of battery to be manufactured, desired model, electric capacity and the like.

[Positive Electrode Current Collector] Examples of the positive electrode current collector include graphite, graphite such as graphite, carbon black such as acetylene black, carbon such as carbon fiber, pitch and tar, platinum, gold, nickel, stainless steel, A plate made of iron, copper or the like, a net, a punching 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.
The thickness may be appropriately selected, but in the case of a thin battery, the thickness is not limited to these, but is preferably about 0.1 to 0.01 mm.

[Electrolytic Solution] As the electrolytic solution, a commonly used one can be used. Examples of preferred electrolytic solutions include lithium tetrafluoroborate, lithium hexafluoroantimonate, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, tetrabutylammonium perchlorate, and lithium trifluoromethanesulfonate. Dissolved ethylene carbonate, propylene carbonate, sulfolane, 2-methylsulfolane, 2,4-dimethylsulfolane, γ-butyrolactone, 1,3-dioxolane,
2-Methyltetrahydrofuran, diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, acetonitrile and the like, or a mixture thereof.

[Negative Electrode] Examples of the negative electrode active 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. , Lithium, calcium, magnesium, zinc and lithium alloys are preferably used. If necessary, the negative electrode active material may be used together with the negative electrode current collector. As the negative electrode current collector, the same one as the positive electrode current collector can be used.

The thickness of the negative electrode may be appropriately selected depending on the type of battery. It may be determined according to the desired model, electric capacity and the like.

[Separator] The separator used in the present invention is a non-conductive material such as paper, cloth or film made of synthetic resin such as polyolefin, vinylon, polyamide, vinylon and rayon, and various kinds of paper and cloth made of natural fiber. Materials or fibrous materials can be exemplified.

In the present invention, in order to obtain a secondary battery having a high electromotive force and a high energy density, the positive electrode active material is a non-substituted N-containing compound containing a conductive compound such as a polar compound or acetylene black as an additive. Fluoropyridinium salt,
Alternatively, an N-fluoropyridinium salt having an electron-withdrawing group is selected, while the negative electrode is preferably lithium or a lithium alloy. In order to obtain a secondary battery with higher energy density, N-fluoropyridinium salt is used as N-
It is preferable to select N-fluoropyridinium sulfonate in which the anionic part of the fluoropyridinium salt is bound to the pyridine skeleton. The positive electrode current collector is preferably carbon or nickel, and the electrolytic solution is preferably an organic solvent in which a lithium salt such as lithium tetrafluoroborate is dissolved.

The above constituent materials may be assembled into a battery by a usual method.

Applications of the battery obtained by the present invention include, but are not limited to, commuter passes, cash cards, pacemakers, watches, calculators, electronic toys,
Small radios, electronic lighters, cameras, electronic thermometers, medical devices, greeting cards, hearing aids, pagers,
Electronic notebook, keyless entry, RAM memory, IC
Memory, mobile phone, laptop, portable AV
Equipment, solar battery backup, power supply for cards, etc.

[0151]

【Example】

Examples 1 to 4 To the ground mixture of N-fluoropyridinium salt described in Table IV, the additive described in Table IV was added and mixed in a caloric menort mortar and sufficiently stirred, and then pressed with a hydraulic press made by RIKEN to have a diameter of 16 mm. Was formed into a disk shape and was laminated on the positive electrode current collector (disk shape) shown in Table IV. Then, as a separator, a filter paper manufactured by Nippon Rikagaku Kikai Co., Ltd. (product name: Kiriyama funnel filter paper No. 707, diameter 18 mm, thickness 0.
A circular sheet (05 mm) was superposed on the surface of the positive electrode active material and impregnated with 0.15 ml of the electrolytic solution shown in Table IV. Furthermore, lithium (diameter 15 m
m, and a disk shape having a thickness of 0.33 mm) was superposed on the surface of the separator. Then, a nickel mesh (a plate shape having a diameter of 15 mm and a thickness of 0.03 mm) was superposed on the surface of the negative electrode active material as a negative electrode current collector, and a button-type secondary battery was manufactured according to a conventional method. In the manufacture of button batteries, nickel mesh (diameter 15 mm, thickness 0.03 m) is also provided on the positive electrode collector side.
m) was used. A schematic partial cross-sectional view of the manufactured battery is shown in FIG. In FIG. 1, 1 is a negative electrode terminal (made of stainless steel), 2 is lithium, 3 is a nickel mesh, 4 is an insulating packing, 5 is a separator and an electrolytic solution, 6 is a positive electrode can (made of stainless steel), 7 is a carbon plate, 8 Is a positive electrode active material. All the weights shown in Table IV were measured in a dry box under an argon atmosphere.

The circuit voltage of the battery was measured and used as an electromotive force (V), and the circuit voltage of the device shown in FIG.
The internal resistance value was measured from the battery voltage under an external load of MΩ to 10 kΩ. In FIG. 2, 9 indicates a secondary battery, V indicates a voltmeter, and R indicates an external load. The battery voltage when an external load is applied is a constant value or a nearly constant value (about ±
The measured value was obtained when the state (measured at 0.01 V) was reached. The results are shown in Table IV. The measurement of the electric capacity was performed as follows. It carried out using the apparatus shown in FIG. A graph of the discharge (discharge curve) was created by plotting the change of the battery voltage with an external load of 10 kΩ with time as the horizontal axis, and the flowing current value was integrated to calculate the electric capacity of the positive electrode active material in the unit of mAh / g. The results are shown in Table IV. The electric capacity of, for example, 2.5 V or more shown in Table IV means the total amount of electricity flowing until the voltage of the electromotive force drops to 2.5 V. Further, 1 mAh / g corresponds to a current of 1 mA flowing for 1 hour with 1 g of the active material.

[0153]

[Table 22]

Next, the secondary batteries (Examples 1 and 2) were repeatedly charged and discharged. The result is shown in Figure 3.
And shown in FIG.

Charging / discharging was performed under a load of 110 kΩ for a certain period of time, and then a constant voltage of 4.5 V was charged for the same period (however, a constant current of 140 μA was charged until the voltage reached 4.5 V). This charging / discharging was repeated. A part of the repetition is shown in FIGS. 3 and 4. The upper line in the figure shows the change in battery voltage due to charge / discharge (the left axis of the graph represents the voltage), and the lower line shows the charging current (the left axis of the graph represents the charging current value).

[0156]

According to the present invention, since the positive electrode active material is composed of N-fluoropyridinium salt, the electrochemical reaction between the positive electrode active material having a high oxidizing power and the negative electrode active material can be carried out smoothly and reversibly. In order to proceed, a secondary battery having a high electromotive force and a high energy density in which the positive electrode active material and the negative electrode also serve as charging electrodes, respectively, and the positive electrode active material serves as an anode and the negative electrode serves as a cathode during charging. Can be provided.

[Brief description of drawings]

FIG. 1 is a schematic partial cross-sectional view of button batteries manufactured in Examples 1 to 4.

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 4.

FIG. 3 is a chart showing the results of repeated charge / discharge experiments of the battery manufactured in Example 1.

FIG. 4 is a chart showing the results of repeated charging / discharging experiments of the battery prepared in Example 2.

[Explanation of symbols]

 1 Negative Electrode Terminal 2 Lithium 3 Nickel Net 4 Insulating Packing 5 Separator and Electrolyte 6 Positive Electrode Can 7 Carbon Plate 8 Positive Electrode Active Material 9 Secondary Battery

Claims (1)

[Claims] 1. A battery comprising a positive electrode current collector, a positive electrode active material containing an N-fluoropyridinium salt, an electrolytic solution, a separator and a negative electrode, wherein the positive electrode active material and the negative electrode both serve as charging electrodes. A secondary battery in which the positive electrode active material can sometimes be the anode and the negative electrode can be the cathode.