JP2000235812A - Proton conductive high polymer solid electrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a high proton conductivity stabilized for a long time, excellent film forming property, temperature stability, heat resistance, and mechanical strength by composing the solid electrolyte of the polymer and the sulfonic acid compound. SOLUTION: A polymer expressed with a formula I and the sulfonic acid compound expressed with a formula II or III are dissolved by the common solvent for mixture, and thereafter, a film-like formation by casting or pressurizing formation after the mixing is performed so as to obtain the electrolyte. (In formula I, II, III; R1, R2, R3 means an organic residual group having 1-20 carbon, and they can include hetero atom of N, O, P, S', F, Cl, Br, I or the like; (m)=0.01-4; (n) means an integer capable of satisfying the relation P>=2.) Desirably, R1 means the organic residual group containing the aromatic group such as aliphatic alkyl group of carbon number 2-6, R2 means an organic residual group containing the aromatic group such as perfluoroalkyl group, and R3 means an organic residual group containing the aromatic group such as thiophenylene group. Since the solid electrolyte is composed of the polymer having high polarity, low glass transition temperature, high acid resistance and high affinity with acid compound and the sulfonic acid compound having a high degree of acid dissociation and high acid resistance, an excellent characteristic can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a proton conductive polymer solid electrolyte, and more particularly to a proton conductive polymer solid electrolyte for a secondary battery, a fuel cell and the like.

[0002]

2. Description of the Related Art As an electrolyte of a secondary battery or a fuel cell,
Conventionally, a solution in which a protonic acid, an alkali metal salt, or the like is dissolved in water or a polar organic solvent (ethylene carbonate, propylene carbonate, or the like) has been used.
However, in recent years, attempts have been made to replace the electrolyte solution with a solid electrolyte in order to prevent leakage of the electrolyte solution and to make the battery thinner and more laminated.

The properties required for the proton conductive solid electrolyte include (1) high proton conductivity of 10 ⁻² S / cm or more, (2) conductivity does not decrease even at 100 ° C. or more, and (3) heat of 200 ° C. or more. Decomposition temperature (4) A film can be formed by dissolving in a solvent.

[0004] As a proton conductive inorganic solid electrolyte, β
Hydrates such as alumina, uranyl phosphate, zirconium phosphate, tin oxide, and antimonic acid are known (JP-A-8-249923, JP-A-10-203825).
No.). However, it is pointed out that these have poor moldability.

[0005] As the proton conductive organic solid electrolyte,
Until now, cation exchange resins have been mainly used,
For example, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyaryl sulfonic acid, polyacryl sulfonic acid, polyacrylic acid and the like can be mentioned. Also, a mixture of a polar polymer such as polyacrylamide, polyethyleneimine, polyvinyl alcohol, and polyethylene oxide and an inorganic acid such as sulfuric acid, phosphoric acid, and hydrochloric acid has been used (JP-A-6-196016, JP-A-8-196016). -53614).

These organic solid electrolytes can be formed into a film by a solution casting method or the like. However, the proton conductivity is low because the degree of dissociation of the acid functional group is small. Degree decreases.

Although polyperfluorosulfonic acid and polyperfluorocarboxylic acid, which have a high degree of dissociation and are excellent in heat resistance, are also being studied, since they exhibit proton conductivity only in a water-containing state, they cannot be used at low temperatures. It has been pointed out that the mobility of hydronium carrier decreases due to freezing of water, and the density of hydronium carrier decreases due to evaporation of water at a high temperature, resulting in a problem that proton conductivity and physical properties of a membrane decrease.

[0008]

The first problem is that the proton conductivity is low. The reason is that the degree of dissociation of an acid functional group such as a carboxylic acid, a sulfonic acid and a phosphoric acid group is small, and the proton carrier density is small. In addition, even in polyperfluorosulfonic acid (Nafion) having a high degree of dissociation, the sulfonic acid introduction rate is low, so that the proportion occupied by the site responsible for film formation increases, the carrier density is low, and the conduction path is limited. This is because

[0009] The second problem is that the heat resistant temperature is low. The reason is that aliphatic or aromatic carboxylic acids,
Alternatively, sulfonic acid causes a decomposition reaction such as decarboxylation or desulfonic acid at 100 to 200 ° C.

A third problem is that in the case of a water-containing proton conductive polymer, the conductivity changes with temperature, and the proton conductivity gradually decreases at high temperatures. The reason is that the proton carrier density and the physical properties of the polymer membrane decrease because the proton carrier density decreases due to evaporation at a high temperature and freezing at a low temperature.

[Purpose] An object of the present invention is to prevent decomposition over a wide temperature range from a low temperature to a high temperature, exhibit a stable high proton conductivity for a long period of time, and form a film, flexibility, adhesion and mechanical properties. To provide a proton conductive polymer solid electrolyte having excellent mechanical strength.

[0012]

According to the present invention, a solid polymer electrolyte comprises a polymer represented by the general formula (1) and a sulfonic acid compound represented by the general formula (2) or (3). Provided is a proton conductive polymer solid electrolyte comprising:

[0013]

Embedded image

In the formula, R ¹ represents all organic residues having 1 to 20 carbon atoms, and may contain a hetero atom such as N, O, P, S, F, Cl, Br or I. n is an integer of 2 or more and indicates the degree of polymerization.

[0015]

Embedded image

In the formula, R ² represents any organic residue having 1 to 20 carbon atoms, and may contain a hetero atom such as N, O, P, S, F, Cl, Br, or I.

[0017]

Embedded image

In the formula, R ³ represents any organic residue having 1 to 20 carbon atoms, and may contain a hetero atom such as N, O, P, S, F, Cl, Br or I. m is 0.01 to 4 and indicates the amount of sulfonic acid group introduced. p represents a degree of polymerization as an integer of 2 or more.

[0019]

Embodiments of the present invention will be described below in detail.

According to the present invention, a polymer (general formula (1)) having high polarity, low glass transition temperature, excellent acid resistance, and high affinity with an acid compound, has a large acid dissociation degree, and has a high acid resistance. A proton-conductive polymer solid composed of an excellent sulfonic acid compound (general formula (2) or (3)) and having high proton conductivity, high heat resistance, excellent temperature stability, and good film formability. An electrolyte can now be provided.

R ¹ in the general formula (1) represents all organic residues having 1 to 20 carbon atoms, and N, O, P, S, F, Cl, B
It may contain a hetero atom such as r or I. Carbon number 1
Are unstable, and it is difficult to synthesize derivatives having 11 or more carbon atoms. Therefore, derivatives having 2 to 10 carbon atoms are preferable. In particular, in the case of an aliphatic alkyl group having 2 to 6 carbon atoms (an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and an isomer group thereof), the polymer has a high dielectric constant, and the sulfonic acid compound and Because of the excellent compatibility of
Most preferred.

Although n in the general formula (1) is not particularly limited,
Preferably it is 30,000 to 100,000, more preferably 10 to 100
It is ten thousand. If the degree of polymerization is less than 3, film formability and mechanical strength will be low. If it exceeds 100,000, it will be difficult to dissolve or swell in a solvent. The polymer may have a linear structure,
It may have a branched, cross-linked, or cyclic structure, or may be a copolymer or a mixture thereof.

The method for producing the polymer is not particularly limited.
It can be obtained by a known reaction. For example, polymerization of an epoxy compound and carbon dioxide using a triethylaluminum or triethylzinc catalyst (Macromol.Ch)
em. , 130, 210-220 (1969)), ring-opening polymerization of cyclic carbonate compounds (J. Am. Chem.
Soc. , 52, 314, 326 (1930), Mac
rmol. RapidCommum, 17, 865-
870 (1996)) and the like.

As the polymer used in the proton conductive solid polymer electrolyte of the present invention, a polymer having one or more units of the general formula (1) can be used. Can also be used. In the proton-conductive polymer solid electrolyte of the present invention, the polymer as a structural material can be composed of only a polymer having a unit of the general formula (1). In addition to the polymer having units, it may be composed of a polymer blend in which another polymer compatible with the polymer is blended. In this case, examples of the other polymer include a polar polymer such as polyoxyethylene and polyethyleneimine.
In addition, the proportion of the blend, proton conductivity and flexibility required for proton conductive polymer solid electrolyte film,
It can be appropriately determined according to the mechanical strength and the like.

Next, R ² in the general formula (2) will be described in detail.

R ² represents all organic residues having 1 to 20 carbon atoms, and may contain a hetero atom such as N, O, P, S, F, Cl, Br or I. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group,
Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, fluoromethyl group, fluoroethyl group, fluoropropyl group, fluorobutyl group, fluoropentyl group, fluorohexyl group, fluoroheptyl group, fluorooctyl group, Fluorononyl group, fluorodecyl group, fluoroundecyl group, fluorododecyl group, chloromethyl group, chloroethyl group, chloropropyl group, chlorobutyl group, chloropentyl group, chlorohexyl group, chloroheptyl group, chlorooctyl group, chlorononyl group, Chlorodecyl group, chloroundecyl group, chlorododecyl group, bromomethyl group, bromoethyl group, bromopropyl group, bromobutyl group, bromopentyl group, bromohexyl group, bromoheptyl group, bromooctyl group,
Bromononyl group, bromodecyl group, bromoundecyl group, bromododecyl group, iodomethyl group, iodoethyl group, iodopropyl group, iodobutyl group, iodopentyl group, iodohexyl group, iodoheptyl group, iodooctyl group, iodononyl group, iododecyl group, Iodoundecyl group, iodododecyl group, perfluoromethyl group, perfluoroethyl group, perfluoropropyl group,
Perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, perfluoroundecyl, perfluorododecyl, perchloromethyl , Perchloroethyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchloroheptyl, perchlorooctyl, perchlorononyl, perchlorodecyl, perchloroundecyl Group, perchlorododecyl group, perbromomethyl group, perbromoethyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromoheptyl group, perbromooctyl group, perbromononyl Group, Perbro Decyl group, perbromoundecyl group, perbromododecyl group, periodomethyl group, periodoethyl group, periodopropyl group, periodobutyl group, periodopentyl group, periodohexyl group, periodoheptyl group, par Iodooctyl group, periodononyl group, periododecyl group, periodundecyl group, periodododecyl group, phenyl group, toluyl group, xylyl group, biphenyl group, naphthyl group, fluorophenyl group, fluorotoluyl group, fluoroxy Silyl group, fluorobiphenyl group, fluoronaphthyl group, chlorophenyl group, chlorotoluyl group, chloroxylyl group, chlorobiphenyl group, chloronaphthyl group, bromophenyl group, bromotoluyl group, bromoxylyl group, bromobiphenyl group, bromonaphthyl group, iodo Phenyl group, iodotolyl group, iodoxylyl group, iodobiphenyl group, iodonaphthyl group, perfluorophenyl group, perfluorotoluyl group, perfluoroxylyl group, perfluorobiphenyl group, perfluoronaphthyl group, perchlorophenyl group, perchloro Toluyl group, perchloroxylyl group, perchlorobiphenyl group, perchloronaphthyl group, perbromophenyl group, perbromotoluyl group, perbromoxylyl group, perbromobiphenyl group, perbromonaphthyl group, periodophenyl group,
Examples include a periododolyl group, a periodoxyl group, a periodobiphenyl group, and a periodnaphthyl group. Among these, a perfluoroalkyl group having a high degree of dissociation of sulfonic acid, excellent thermal stability, and excellent compatibility with the polymer is preferable.

Next, R ³ in formula (3) will be described in more detail.

R ³ represents all organic residues having 1 to 20 carbon atoms, and may contain a hetero atom such as N, O, P, S, F, Cl, Br or I. For example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, fluoromethylene group, fluoroethylene group, fluoropropylene group, Fluorobutylene group, fluoropentylene group,
Fluorohexylene, fluoroheptylene, fluorooctylene, fluorononylene, fluorodecylene, fluoroundecylene, fluorododecylene, chloromethylene, chloroethylene, chloropropylene, chlorobutylene Group, chloropentylene, chlorohexylene, chloroheptylene, chlorooctylene, chlorononylene, chlorodecylene, chloroundecylene, chlorododecylene, bromomethylene, bromoethylene, bromopropylene, bromobutylene, bromo Pentylene group, bromohexylene group,
Bromoheptylene group, bromooctylene group, bromononylene group, bromodecylene group, bromoundecylene group, bromododecylene group, iodomethylene group, iodoethylene group, iodopropylene group, iodobutylene group, iodopentylene group, iodohexylene group, iodoheptylene group, Iodooctylene group, iodononylene group, iododecylene group, iodoundecylene group, iodododecylene group, perfluoromethylene group, perfluoroethylene group, perfluoropropylene group, perfluorobutylene group, perfluoropentylene group, perfluorohexylene group, Perfluoroheptylene group, perfluorooctylene group, perfluorononylene group, perfluorodecylene group, perfluoroundecylene group, perfluorododecylene group, perchloromethyl Ren group, perchlorethylene group, perchlorethylene propylene group, perchlorethylene butylene,
Perchloropentylene group, perchlorohexylene group, perchloroheptylene group, perchlorooctylene group, perchlorononylene group, perchlorodecylene group, perchloroundecylene group, perchlorododecylene group, par Bromomethylene group, perbromoethylene group, perbromopropylene group, perbromobutylene group, perbromopentylene group, perbromohexylene group, perbromoheptylene group, perbromooctylene group, perbromononylene group,
Perbromodecylene group, perbromoundecylene group, perbromododecylene group, periodmethylene group, periodoethylene group, periodopropylene group, periodobutylene group, periodopentylene group, periodohexylene group, Periodic heptylene group, periodic octylene group, periodic nonylene group, periodic dodecylene group, periodic undecylene group, periodic dodecylene group, phenylene group, toluylene group, xylylene group, biphenylene group, naphthylene Group, fluorophenylene group, fluorotoluylene group, fluoroxylylene group, fluorobiphenylene group, fluoronaphthylene group, chlorophenylene group, chlorotoluylene group, chloroxylylene group, chlorobiphenylene group, chloronaphthylene group, bromophenylene group, Bromot Ylene group, a bromo-xylylene group,
Bromobiphenylene group, bromonaphthylene group, iodophenylene group, iodotoluylene group, iodoxylylene group, iodobiphenylene group, iodonaphthylene group, pyridylene group, pyrrole group, furanylene group, oxyphenylene group, thiophenylene group, carbonylphenylene group,
Iminophenylene group, oxycarbonylphenylene group,
Examples include phenylene carbonate, isopropylphenylene, sulfinylphenylene, and sulfonylphenylene. Among these, an aromatic hydrocarbon group which is excellent in thermal stability and compatibility with the above-mentioned polymer and is easy to synthesize, particularly a thiophenylene group, is preferred.

As the polymer having R ³ as a structural unit, a polymer having one or more units of the general formula (3) can be used. Can be used, as well as blends thereof.

M in the general formula (3) is preferably 0.0
1-4, more preferably 0.1-2.5. If the sulfonic acid group introduction amount is less than 0.01, sufficient proton conductivity cannot be obtained, and if it exceeds 4, the film-forming property and mechanical strength are low, and it is difficult to dissolve in an organic solvent.

Although p in the general formula (3) is not particularly limited,
Preferably it is 30,000 to 100,000, more preferably 10 to 100
It is ten thousand. If the degree of polymerization is less than 3, film formability and mechanical strength will be low. If it exceeds 100,000, it will be difficult to dissolve or swell in a solvent. The polymer may have a linear structure,
It may have a branched, cross-linked, or cyclic structure, or may be a copolymer or a mixture thereof.

The method for producing the sulfonic acid compound of the general formula (3) is not particularly limited, and can be obtained by a known reaction. For example, polymers such as polyparaphenylene, polyetheretherketone, and polysulfonium salts can be easily obtained by sulfonation using known sulfonating agents under known conditions (Macromol. Ra).
pid Commun, 15, 669-676 (1
994), Macromolecules, 25, 6
495-6499 (1992), Macromole
cules, 30, 2491-2496 (199
7)).

The polymerization ratio of the sulfonic acid compound represented by the general formula (2) or (3) to the polymer represented by the general formula (1) is usually from 95/5 to 5/95, preferably from 95/5 to 5/95. 90 / 10-20 / 80, more preferably 80 / 20-
30/70. 5% by weight of sulfonic acid compound
If it is less than 30, sufficient proton conductivity cannot be obtained.

The proton conductive polymer solid electrolyte of the present invention is prepared by mixing a polar organic solvent such as propylene carbonate, ethylene carbonate, acetonitrile, dimethylacetamide, dimethylformamide, sulfuric acid, phosphoric acid, and an appropriate amount of water. Is also good.

In order to prepare the proton conductive polymer solid electrolyte of the present invention, for example, a sulfonic acid compound and a polymer represented by the general formula (1) are dissolved in a common solvent and mixed, and then the film is formed by casting. And a method in which both components are mixed and then molded by applying pressure. Further, a polymer serving as a precursor may be mixed and cast with a polymer represented by the general formula (1) to form a film, and then sulfonated by reacting with a sulfonating reagent.

Here, as the common solvent, for example, methanol, ethanol, dichloromethane, chloroform,
Tetrahydrofuran, acetonitrile, nitromethane,
Examples include benzene, nitrobenzene, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and the like.

[0037]

Next, the present invention will be described in more detail by way of examples.

Example 1 Perfluorooctanesulfonic acid and polypropylene carbonate (number average molecular weight 26
000) in a weight ratio of 3/1 was cast on a platinum electrode and dried under reduced pressure to prepare a composite membrane. This composite film was obtained as a transparent film, and the thermal decomposition onset temperature under nitrogen was 260 ° C.

{Evaluation method}
It is sandwiched between gold electrodes and sealed in a closed cell under a dry atmosphere.
Peedance Analyzer (Yokogawa Hewlett and
Using HP4194A manufactured by Packard, a frequency of 10
0 to 15 MHz, absolute value and phase of sample impedance
Measure angles, create complex impedance plots,
Ton conductivity was calculated. Proton conductivity at 30 ° C
4 × 10^-Five2 × 10 at S / cm, 200 ° C.^-3S / cm
It became. The sample was placed in a 50% humidity atmosphere at 12:00.
When left for a while, the water content becomes 16 wt% and proton conduction
The degree is 2 × 10 at 30 ° C. ^-2S / cm, 1 at 100 ° C
× 10^-2S / cm.

Example 2 Perfluorooctane sulfo
Acid and polyethylene carbonate (number average molecular weight 500
00) was mixed in a weight ratio of 2/1 in dimethylforma.
The amide solution is cast on a platinum electrode and dried under reduced pressure.
A composite membrane was made. This composite membrane is obtained as a transparent film
The thermal decomposition onset temperature under nitrogen was 292 ° C.
Was. Place the composite membrane sandwiched between platinum electrodes in a closed
Sealed in an impedance analyzer (HP419
4A), using a sample of 100
Measures absolute value and phase angle of impedance, complex impedance
A proton plot was created and the proton conductivity was calculated. Step
Roton conductivity is 1 × 10 at 30 ° C.^-FiveS / cm, 20
6 × 10 at 0 ° C^-FourS / cm. In addition, the same sample
After measuring for 12 hours in a 50% humidity atmosphere,
Moisture content becomes 20 wt%, and 1 × 10 at 30 ° C. ^-2S / c
m, 8 × 10 at 100 ° C.^-3S / cm.

Example 3 Perfluorobutanesulfonic acid and polybutylene carbonate (number average molecular weight 3500
0) was mixed on a platinum electrode with a chloroform solution mixed at a weight ratio of 4/1, and dried under reduced pressure to form a composite membrane. This composite film was obtained as a transparent film, and the thermal decomposition onset temperature under nitrogen was 278 ° C. The composite membrane sandwiched between platinum electrodes is sealed in a closed cell under a dry atmosphere,
Using an impedance analyzer (HP4194A), the absolute value and the phase angle of the impedance of the sample were measured at a frequency of 100 to 15 MHz, a complex impedance plot was created, and the proton conductivity was calculated. The proton conductivity is 3 × 10 ⁻⁶ S / cm at 30 ° C. and 8 × at 200 ° C.
It became 10 ^-4 S / cm. When the sample was left standing in an atmosphere of 50% humidity for 12 hours and measured, the water content was 20 watts.
6 × 10 ⁻³ S / cm at 30 ° C., 100 ° C.
In this case, it was 9 × 10 ⁻³ S / cm.

(Example 4) The amount of sulfonic acid group introduced was 1.8.
/ Unit mol of polythiophenylenesulfonic acid and polybutylene carbonate (number average molecular weight 35,000)
Was mixed on a platinum electrode with a dimethylformamide solution mixed at a weight ratio of 2/1, and dried under reduced pressure to prepare a composite membrane. This composite membrane is obtained as a transparent film,
The thermal decomposition onset temperature under nitrogen was 267 ° C. The composite membrane sandwiched between platinum electrodes is sealed in a closed cell under a dry atmosphere, and an impedance analyzer (HP4194A)
, The absolute value and phase angle of the impedance of the sample were measured at a frequency of 100 to 15 MHz, a complex impedance plot was created, and the proton conductivity was calculated. The proton conductivity was 2 × 10 ⁻⁵ S / cm at 30 ° C. and 1 × 10 ⁻³ S / cm at 200 ° C. In addition, the same sample was subjected to a humidity of 5
When measured after being left in a 0% atmosphere for 12 hours, the water content was 22 wt%, and 2 × 10 ⁻² S / cm, 1
At 00 ° C., it was 3 × 10 ⁻² S / cm.

(Comparative Example 1) In the same manner as in Example 1, instead of polyvinyl sulfuric acid, a perfluorosulfonic acid polymer (weight per sulfonic acid group: 1100) and a molecular weight of 1
000 polyoxyethylene composite membrane with a weight ratio of perfluorosulfonic acid polymer and polyoxyethylene of 2:
Created in 1. Proton conductivity is 3 × 1 at room temperature 30 ° C.
^0-8 S / cm, 4 × 10 ^-5 S / cm at 200 ° C., and a sample left for 12 hours under a relative humidity of 50% are 6 ° C. at 30 ° C.
It showed a proton conductivity of ^10-4 S / cm and 3 ^10-5 S / cm at 100 ° C.

Table 1 shows the results of Examples 1 to 4 and Comparative Example 1.

[0045]

[Table 1]

[0046]

As described above, according to the proton conductive polymer solid electrolyte of the present invention, a polymer having high polarity, low glass transition temperature, excellent acid resistance, and high affinity with an acid compound is obtained. By comprising a general formula (1) and a sulfonic acid compound (general formula (2) or general formula (3)) having a large acid dissociation degree and excellent acid resistance, a high proton conductivity is stably exhibited for a long time. It has excellent effects on film forming properties, temperature stability and heat resistance.

Continuing on the front page (72) Inventor Masaki Fujiwara 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Shinako Okada 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation In-company (72) Inventor Masato Kurosaki 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Hidetoshi Tsuchida 2--10-10 Sekicho, Nerima-ku, Tokyo (72) Inventor Shinji Takeoka 3-40-16 Tamagawa, Setagaya-ku, Tokyo Forest 404 (72) Inventor Kenji Miyatake 405-48 Mizuno, Sayama-shi, Saitama (72) Inventor Kazuaki Fukushima 1-2-chome Takada, Toshima-ku, Tokyo 15 Maison M103 F term (reference) 5G301 CA30 CD01 5H026 AA06 CX04 EE18 EE19 5H029 AJ02 AJ15 AM03 AM04 AM16 EJ14

Claims (5)

[Claims] 1. A proton conductive solid polymer electrolyte comprising a polymer represented by the general formula (1) and a sulfonic acid compound represented by the general formula (2) or (3). Embedded image (In the formula, R ¹ represents all organic residues having 1 to 20 carbon atoms, and may include a hetero atom such as N, O, P, S, F, Cl, Br, or I. n is 2 The degree of polymerization is indicated by the above integer.) (Wherein, R ² represents all organic residues having 1 to 20 carbon atoms, and may contain a hetero atom such as N, O, P, S, F, Cl, Br, or I). ] (Wherein, R ³ represents all organic residues having 1 to 20 carbon atoms, and may include a hetero atom such as N, O, P, S, F, Cl, Br, or I. m is 0. 0.01 to 4, indicating the amount of sulfonic acid group introduced. P is an integer of 2 or more indicating the degree of polymerization.) 2. The proton conductive polymer solid electrolyte according to claim 1, wherein R ¹ is an aliphatic alkyl group having 2 to 6 carbon atoms. 3. The proton conductive solid polymer electrolyte according to claim 1, wherein R ² is a perfluoroalkyl group. 4. The proton conductive polymer solid electrolyte according to claim 1, wherein R ³ is an organic residue containing an aromatic group. 5. The method according to claim 1, wherein R ³ is a thiophenylene group.
Or the proton-conductive polymer solid electrolyte according to 2 or 4.