JP3481593B2 - Composite polymer electrolyte membrane and fuel cell using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a low cost composite polymer electrolyte membrane having excellent power generation performance, good adhesion to electrodes, and a fuel cell using the same.

[0002]

2. Description of the Related Art Due to the depletion of petroleum resources and serious environmental problems such as global warming, fuel cells have attracted attention as a clean power source for electric motors and have been extensively developed.
Some have been put to practical use. It is preferable to use a polymer electrolyte membrane type fuel cell especially when the fuel cell is mounted in an automobile, etc., but as the polymer electrolyte membrane, a perfluoroalkylene sulfonic acid polymer compound such as Nafion is widely used. Has been done. Although Nafion has excellent power generation performance and chemical resistance, it is very expensive.

Polymer electrolytes include sulfonated non-perfluoro hydrocarbons (for example, polyether ether ketone) in addition to the above perfluoroalkylene sulfonic acid polymers. Since sulfonated non-perfluoro hydrocarbons are cheap starting materials and have low synthesis costs, it is expected that inexpensive electrolyte membranes can be obtained for polymer electrolyte fuel cells. However, since the polymer electrolyte composed of sulfonated non-perfluoro hydrocarbon has low adhesion to the electrode, the contact resistance between the polymer electrolyte and the electrode becomes high, and a fuel cell having high power generation performance cannot be obtained.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a low cost composite polymer electrolyte membrane having excellent power generation performance, good adhesion to electrodes, and a fuel cell using the same. That is.

[0005]

As a result of earnest research in view of the above object, a polymer electrolyte is formed from a mixture of two or more sulfonated non-perfluoro hydrocarbons, and at least a sulfonated polyarylene polymer is used. As a result, it was discovered that a polymer electrolyte membrane having excellent power generation performance, good adhesion to electrodes, and low cost can be obtained, and the present invention was conceived.

That is, the composite polymer electrolyte membrane of the present invention has two or more kinds of non-perfluoroalkylene sulfonic acid type polymer electrolytes, and at least one kind of non-perfluoroalkylene sulfonic acid type polymer electrolyte is sulfonated. Poly
Made of an arylene polymer, said sulfonated polyaryl
The polymer skeleton of the ren polymer has the following general formula (1)

[Chemical formula 5] And the following general formula (2)

[Chemical formula 6] Structural unit represented by (provided that the general formula (1) and
In (2), part of C in the aromatic ring may be substituted with N, and A _{1 to} A ₁₂ are —F, —CN, —CHO,
-COR, -CR = NR ', -OR, -SR, -SO ₂
R, -OCOR, -CO ₂ R, -NRR ', -N = CR
R ′, —NRCOR ′, —CONRR ′ and R, which may be the same or different, and X is —Z—, —Z—Ph— and —Ph—Z—Ph.
R and R ′ are at least one selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group and a substituted heteroaryl group. , Which may be the same or different, Ph represents a substituted or unsubstituted phenylene group, Z represents —O—, —S—, —NR, —O
_{(CO) -, - O (} CO 2) -, - (CO) NH (C
O)-, -NR (CO)-, phthalimide, pyromellitic imide, -CO-, -SO-, -SO _2- , -P
_{(O) R -, - CH} 2 -, - CF 2 - and -CRR'-
Represents a divalent group selected from the group consisting of ) Less
Also, it is characterized in that it is configured by one or both .

In particular, the composite polymer electrolyte membrane of the present invention is a composite polymer electrolyte membrane containing first and second non-perfluoroalkylene sulfonic acid polymer electrolytes, wherein the first polymer electrolyte is sulfonated. Polyarylene polymerization
The sulfonated polyarylene polymer
The rimer skeleton has the following general formula (1)

[Chemical formula 7] And the following general formula (2)

[Chemical formula 8] Structural unit represented by (provided that the general formula (1) and
In (2), part of C in the aromatic ring may be substituted with N, and A _{1 to} A ₁₂ are —F, —CN, —CHO,
-COR, -CR = NR ', -OR, -SR, -SO ₂
R, -OCOR, -CO ₂ R, -NRR ', -N = CR
R ′, —NRCOR ′, —CONRR ′ and R, which may be the same or different, and X is —Z—, —Z—Ph— and —Ph—Z—Ph.
And R and R ′ are at least one selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group and a substituted heteroaryl group. , Which may be the same or different, Ph represents a substituted or unsubstituted phenylene group, Z represents —O—, —S—, —NR, —O
_{(CO) -, - O (} CO 2) -, - (CO) NH (C
O)-, -NR (CO)-, phthalimide, pyromellitic imide, -CO-, -SO-, -SO _2- , -P
_{(O) R -, - CH} 2 -, - CF 2 - and -CRR'-
Represents a divalent group selected from the group consisting of ) Less
Also it consists of one or both, the second polyelectrolyte is preferably composed of sulfonated polyether polymer. The content of the sulfonated polyarylene polymer in the composite polymer electrolyte membrane is preferably 50 to 95% by weight based on the whole.

Further, the fuel cell of the present invention is characterized by having the above-mentioned composite polymer electrolyte membrane.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION [1] Composite Polymer Electrolyte Membrane The composite polymer electrolyte membrane of the present invention comprises a mixture of two or more non-perfluoroalkylenesulfonic acid-based polymer electrolytes, and contains at least one non-perfluoroalkylenesulfonic acid-based polymer electrolyte. The fluoroalkylene sulfonic acid-based polymer electrolyte is a sulfonated polyarylene-based polymer. Here, the sulfonated polyarylene polymer is referred to as a first polymer electrolyte, and the other non-perfluoroalkylenesulfonic acid polymer electrolytes are referred to as a second polymer electrolyte.

(A) Sulfonated polyarylene polymer (first polyelectrolyte) The polyarylene polymer contains at least one or both of the structural units represented by the following general formula (1) or (2). . The sulfonated polyarylene polymer may be a homopolymer or a copolymer.

[Chemical 1]

One of the above general formulas (1) and (2), one of the aromatic ring C
Parts may be replaced with N. Where A₁~ A₁₂Is -F,
-CN, -CHO, -COR, -CR = NR ', -OR, -SR, -SO₂R, -OCOR,
-CO ₂R, -NRR ', -N = CRR', -NRCOR ', -CONRR' and R
Selected from the same group, whether they are the same or different
good. R and R ′ are hydrogen, an alkyl group and a substituted alkyl
Group, aryl group, substituted aryl group, heteroaryl group and
And at least one selected from the group consisting of substituted heteroaryl groups.
Both are one kind and may be the same or different.

Examples of the alkyl group or substituted alkyl group represented by -R include methyl, ethyl, propyl, n-
Butyl, t-butyl, dodecanyl, trifluoromethyl,
Perfluoro-n-butyl, 2,2,2-trifluoroethyl,
Benzyl, 2-phenoxyethyl and the like can be mentioned.

Examples of the aryl group or substituted aryl group represented by -R include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, naphthyl, biphenyl, 4-phenoxyphenyl, 4-fluorophenyl and 3-carbo. Methoxyphenyl, 4-carbomethoxyphenyl and the like can be mentioned.

Examples of the ketone group represented by -COR include acetyl, propionyl, t-butylcarbonyl and 2-
Ethylhexylcarbonyl, phenylcarbonyl (benzoyl), phenoxyphenylcarbonyl, 1-naphthylcarbonyl, 2-naphthylcarbonyl, nicotinoyl, isonicotinoyl, 4-methylphenylcarbonyl, 2-fluorophenylcarbonyl, 3-fluorophenylcarbonyl, 4-fluorophenylcarbonyl Etc.

Examples of the imine group represented by -CR = NR 'include phenyl-N-methylimino, methyl-N-methylimino, phenyl-N-phenylimino and the like.

Examples of the alkoxy group represented by —OR include methoxy, ethoxy, 2-methoxyethoxy,
Examples include t-butoxy and the like.

Examples of the aryloxy group represented by -OR include phenoxy, naphthoxy, phenylphenoxy, 4-methylphenoxyethoxy and the like.

The thioether group represented by —SR includes, for example, thiomethyl, thiobutyl, thiophenyl and the like.

Examples of the sulfonyl group represented by —SO ₂ R include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, tolylsulfonyl and the like.

Examples of the ester group represented by -OCOR include phenylcarboxy, 4-fluorophenylcarboxy, 2-ethylphenylcarboxy and the like.

Examples of the ester group represented by —CO ₂ R include methoxycarbonyl, benzoyloxycarbonyl, phenoxycarbonyl, naphthyloxycarbonyl, ethylcarboxy and the like.

As the amine group represented by —NRR ′,
Examples thereof include amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

Examples of the imine group represented by -N = CRR 'include dimethylimino, methylimino, phenylimino and the like.

Examples of the amide group represented by -NRCOR 'include N-acetylamino, N-acetylmethylamino, N-benzoylamino, N-benzoylmethylamino and the like.

Examples of the amide group represented by -CONRR 'include N, N-dimethylaminocarbonyl, N-butylaminocarbonyl, N-phenylaminocarbonyl, N, N-diphenylaminocarbonyl, N-phenyl-N- Methylaminocarbonyl and the like can be mentioned.

Among these, acetyl, benzoyl,
Carbomethoxy, formyl, phenoxy, phenoxybenzoyl, phenyl and the like are preferable, and phenoxybenzoyl is particularly preferable.

X in the structural unit of the general formula (2) is -Z.
-, -Z-Ph-, -Ph-Z-Ph- and the like. Where Z
Is -O-, -S-, -NR, -O (CO)-, -O (CO ₂ )-,-(CO) NH (CO)
-, -NR (CO)-, Phthalimide, Pyromellitimide, -CO
-, - SO -, - SO 2 -, - P (O) R -, - CH 2 -, - a and a divalent group selected from the group consisting of -CRR'- - CF _2. However, Ph represents a substituted or unsubstituted phenylene group.

Examples of Z include those derived from bisphenol A such as -oxy-1,4-phenylene-2,2-isopropylidene-1,4-phenylene-oxycarbonyl-, bisphenol AF and other bisphenols. good. Further, -hexafluoroisopropylidene-2,2-diyl, -isopropylidene-2,2-diyl, 2-phenyl-1,1,1-trifluoroethylidene-2,2'-diyl and the like can be mentioned.

Examples of -Ph-Z- Ph -type esters and amides include-(phenylene-CONH-phenylene-NHCO)-
Phenylene-,-(phenylene-CONH-phenylene)-,
-(Phenylene-COO-phenylene-OCO) -phenylene-,-(phenylene-carbonyl) -phenylene-,-
(Phenylene-carbonyl-phenylene-oxo-phenylene-carbonyl-phenylene- and the like.

Further, polyamide, polyarylate, polyarylene oxide, polycarbonate, polydimethylsiloxane, polyester, polyetherketone, polyphenylene, substituted polyphenylene, polyphenylene sulfide, polystyrene and the like can be mentioned.

Polyamides include, for example, 1,4-butanediamine, 1,6-hexanediamine, 4,4'methylenedianiline,
Some are formed by the usual condensation of diamines such as 1,3-phenylenediamine and 1,4-phenylenediamine with diacids such as adipic acid, isophthalic acid, terephthalic acid and succinic acid.

Polyarylates are formed, for example, from terephthalic acid or isophthalic acid and diols such as bisphenol A (2,2'-isopropylidenediphenol), resorcinol, hydroquinone, 4,4'-dihydroxybiphenyl and the like. There is something.

Examples of the polyarylene oxide include poly (2,6-dimethyl-1,4-phenylene oxide) and poly (2,6).
-Diphenyl-1,4-phenylene oxide), poly (oxy
-2,3,5,6-tetrafluorophenylene), poly (oxy-
2,6-pyridinediyl) and the like.

Examples of the polyester include diols such as ethylene glycol, 1,6-hexane glycol, hydroquinone, propylene glycol and resorcinol,
Some are formed by the usual condensation reaction with a diacid such as adipic acid, isophthalic acid, terephthalic acid, succinic acid.

The polyether ketone is, for example, poly (oxy 1,4-phenylene-oxy-1,4-phenylene-carbonyl-1,4-phenylene), polyether ether ketone,
There are polyether ketone, polyether ketone ketone and the like. Specific examples of such polyarylene include compounds represented by the following general formula.

[Chemical 2]

By introducing a substituent having an ion-exchange function into the polymer having the above-mentioned skeleton, the function as a polymer electrolyte can be exerted. In particular, it is preferable to use the above polymer after sulfonation. This is because the function as an ion exchange resin is improved. The sulfonation method is not particularly limited, and a method of synthesizing a polymer having a sulfonic acid group by introducing a sulfonic acid group into a monomer and then polymerizing it, and introducing a sulfonic acid group after polymerizing a monomer into a polymer There are ways to do it.

The ion exchange capacity of the sulfonated polyarylene polymer (which is a standard for sulfonation) is 1.5 to 3.0 meq.
It is preferably / g. The ion exchange capacity is determined by neutralization titration. If the ion exchange capacity is less than 1.5 meq / g,
If the ionic conductivity is insufficient, and if it exceeds 3.0 meq / g, the mechanical strength, thermal decomposition resistance, and high temperature / high humidity resistance are insufficient.

(B) Second Polymer Electrolyte The second polymer electrolyte is not particularly limited, but a sulfonated polyether polymer electrolyte is preferable. This is because the structure of the sulfonated polyarylene polymer, which is the first polyelectrolyte, is relatively rigid, and the polyelectrolyte having a structure with rich bending castability that alleviates the drawbacks is mixed. Is desirable. By relaxing the rigidity, the adhesion is improved.

Here, the polyether polymer has a main chain of —O—, —S at a ratio of 0.5 or more per one phenylene group.
-, -CO-, -CONH-, -COO-, -SO- and -SO _2-, etc.,
It is a polymer having a structure that is considerably more flexible than the first polymer electrolyte. As such a second polymer electrolyte, for example, -Ph-O-, -Ph-O-Ph-CO, -Ph-O-Ph-O-Ph-CO
-, -Ph-O-Ph-CO-Ph-CO-, -Ph-O-Ph-O-Ph-CO-Ph-CO-, -P
hO-Ph-CO-Ph-O-Ph-CO-Ph-CO-, -Ph-O-Ph-CO-Ph-CO-Ph-
Examples thereof include polymer compounds containing repeating units such as O-Ph-CO-Ph-CO- and -Ph-Ph-O-Ph-CO-Ph-CO-, alone or in combination. Also, -O- may be -S-.
These polymer compounds can be produced by a known production method.

Specific examples of such polyether polymer compounds include polyether ether ketone (PEE
K), polyether sulfone (PES), polysulfone (PS
F), polyetherimide (PEI), polyphenylene sulfide (PPS), polyphenylene oxide (PPO) and the like. Particularly preferred are polyphenylene oxide, polyether ether ketone and polyether sulfone. These polymer compounds may be homopolymers or copolymers.

Polyether ether ketone (PEEK) has the general formula:

[Chemical 3] It has a basic structure represented by The benzene ring forming the skeleton may have a substituent such as an alkyl group.

The sulfonation of the polyether polymer can be carried out in the same manner as the above-mentioned first polymer electrolyte. The ion exchange capacity of the sulfonated polyether polymer (which is a guide for sulfonation) is preferably 1.0 to 2.5 meq / g. If the ion exchange capacity is less than 1.0 meq / g, the ionic conductivity is insufficient, and if it exceeds 2.5 meq / g, the mechanical strength, thermal decomposition resistance and high temperature / humidity resistance are insufficient. . The more preferable ion exchange capacity of polyether ether ketone is 1.0 to 2.0 meq / g.

(C) Weight ratio The weight ratio of the sulfonated polyarylene polymer (first polymer electrolyte) to the sulfonated polyether polymer (second polymer electrolyte) is 50:50 to 95 :. It is preferably 5. When the weight ratio is less than 50:50, the ionic conductivity of the composite polymer electrolyte membrane is insufficient, and the thermal stability and chemical stability are poor. On the other hand, if it exceeds 95: 5, the flexibility of the composite polymer electrolyte membrane is insufficient due to the rigidity of the sulfonated polyarylene polymer itself, and the adhesion between the electrode and the electrolyte membrane is poor. A more preferable weight ratio is 60:40 to 95: 5, particularly 70:30 to 90:10.

[2] Method for Producing Composite Polymer Electrolyte Membrane (A) Preparation of Sulfonated Polyarylene Polymer A polyarylene polymer is dissolved in concentrated sulfuric acid and reacted to be sulfonated. The obtained sulfonated polyarylene polymer is dissolved in an organic solvent such as N-methylpyrrodoline to obtain a uniform solution.

(B) Preparation of Sulfonated Polyether Polymer After sulfonation of the polyether polymer by the same method as in the above (A), it is dissolved in an organic solvent such as N-methylpyrrodoline, Make a homogeneous solution.

(C) Membrane formation A solution of a sulfonated polyarylene polymer and a solution of a sulfonated polyether ether ketone are uniformly mixed in the above solid content weight ratio, and the obtained homogeneous solution is cast into a flat mold. And dry.

[3] Electrode Structure The electrode structure that constitutes each cell of the fuel cell includes the above-mentioned composite polymer electrolyte membrane and electrodes on both sides thereof (air electrode and fuel electrode).
And a diffusion layer that supports each electrode. The diffusion layer is obtained by applying a slurry of carbon black on a support layer made of carbon paper or the like. The electrodes are
It can be obtained by uniformly mixing the catalyst particles in which platinum particles are supported on carbon black with the ion conductive binder, and applying the obtained catalyst paste on the diffusion layer.
An integrated electrode structure is produced by hot pressing with the diffusion layers arranged with the electrodes inside on both sides of the composite polymer electrolyte membrane.

[0048]

The present invention will be described in more detail by the following examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of polymer electrolyte membrane The following structural formula:

[Chemical 4] Poly (4'-phenoxybenzoyl-1,4-phenylene) represented by the formula (3) was sulfonated with concentrated sulfuric acid to an ion exchange capacity of 2.3 meq / g. The obtained sulfonated poly (4′-phenoxybenzoyl-1,4-phenylene) was dissolved in N-methylpyrrodrine. In the same way, polyetheretherketone (PEEK) was added with concentrated sulfuric acid to obtain an ion exchange capacity of 1.8 meq /
Sulfonated to g. The obtained sulfonated polyether ether ketone was dissolved in N-methylpyrrodrine.

Both solutions were mixed so that the solid content weight ratio of sulfonated poly (4'-phenoxybenzoyl-1,4-phenylene) / sulfonated polyether ether ketone was 95: 5, and the polymer electrolyte solution was mixed. Was produced. A composite polymer electrolyte membrane having a dry film thickness of 50 μm was produced from this polymer electrolyte solution by a casting method.

(2) Preparation of catalyst paste Platinum particles were supported on carbon black (furnace black) at a platinum / carbon weight ratio of 1: 1 to obtain catalyst particles. Nafion (manufactured by DuPont) was used as the ion conductive binder, and the catalyst particles were uniformly mixed in the solution of Nafion to prepare a catalyst paste. The catalyst particle / Nafion weight ratio in the catalyst paste was 8: 5.

(3) Preparation of Diffusion Layer Carbon black and polytetrafluoroethylene (PTFE) particles having a weight ratio of 4: 6 are uniformly dispersed in ethylene glycol, and a slurry is applied to one side of carbon paper and dried. An underlayer was formed by forming a diffusion layer composed of carbon paper and the underlayer.

(4) Preparation of electrode The catalyst paste obtained in (2) above was screen-printed on the underlayer of the diffusion layer so that the amount of platinum was 0.5 mg / cm ^2, and 60
Drying was performed at 10 ° C for 10 minutes and vacuum drying at 120 ° C to prepare an air electrode and a fuel electrode.

(5) Preparation of Electrode Structure The electrolyte membrane obtained in (1) above is sandwiched between the air electrode and fuel electrode obtained in (4) above, and a primary hot press is performed at 80 ° C., 5 MPa for 2 minutes. Then, secondary hot pressing was performed under the conditions of 160 ° C., 4 MPa, and 1 minute to produce an electrode structure.

(6) Evaluation of characteristics (a) Measurement of Q value Using a cell in which one side of the electrode structure is in contact with a sulfuric acid aqueous solution having pH 1 and the counter side is in contact with nitrogen gas, the voltage is changed from -0.5V to 1V. Scanning was performed to determine the Q value (charge, C / cm ² ) from the peak area on the adsorption side of protons. The results are shown in Table 1.

(B) Measurement of power generation potential A cell having a current density of 0.2 A / cm ² when the above electrode structure is used as a single cell, air is used as an air electrode and pure hydrogen is used as a fuel electrode to generate power. The potential (V) was measured. The power generation conditions for both electrodes were a pressure of 100 kPa, a utilization rate of 50%, a relative humidity of 50%, and a temperature of 85 ° C. The results are shown in Table 1.

(C) Evaluation of hot water resistance The ion exchange capacity after immersing the above electrode structure in hot water at 95 ° C. for 200 hours is A (meq / g), and the initial ion exchange capacity is B (meq / g). In this case, (A / B) × 100 (%) is defined as hot water resistance. The results of hot water resistance obtained are shown in Table 1.

Example 2 A composite was prepared in the same manner as in Example 1 except that the solid content weight ratio of sulfonated poly (4'-phenoxybenzoyl-1,4-phenylene) / sulfonated polyether ether ketone was 90:10. A polymer electrolyte membrane was prepared and evaluated. The results are shown in Table 1.

Example 3 A composite was prepared in the same manner as in Example 1 except that the solid content weight ratio of sulfonated poly (4'-phenoxybenzoyl-1,4-phenylene) / sulfonated polyether ether ketone was 85:15. A polymer electrolyte membrane was prepared and evaluated. The results are shown in Table 1.

Example 4 A composite was prepared in the same manner as in Example 1 except that the solid content weight ratio of sulfonated poly (4'-phenoxybenzoyl-1,4-phenylene) / sulfonated polyether ether ketone was 80:20. A polymer electrolyte membrane was prepared and evaluated. The results are shown in Table 1.

Example 5 A composite was prepared in the same manner as in Example 1 except that the solid content weight ratio of sulfonated poly (4'-phenoxybenzoyl-1,4-phenylene) / sulfonated polyether ether ketone was 70:30. A polymer electrolyte membrane was prepared and evaluated. The results are shown in Table 1.

Example 6 A composite was prepared in the same manner as in Example 1 except that the solid content weight ratio of sulfonated poly (4'-phenoxybenzoyl-1,4-phenylene) / sulfonated polyether ether ketone was 60:40. A polymer electrolyte membrane was prepared and evaluated. The results are shown in Table 1.

Comparative Example 1 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 1 except that only sulfonated poly (4′-phenoxybenzoyl-1,4-phenylene) was used. The results are shown in Table 1.

[0064]

[Table 1] Note: (1) Sulfonated poly (4'-phenoxybenzoyl-
Solids weight ratio of 1,4-phenylene) / sulfonated polyetheretherketone.

As is clear from Table 1, the composite polymer electrolyte membrane of the present invention has excellent power generation performance and Q value as well as excellent hot water resistance.

[0066]

The composite polymer electrolyte membrane of the present invention comprises two or more kinds of non-perfluoroalkylene sulfonic acid type polymer electrolytes, and at least one kind of non-perfluoroalkylene sulfonic acid type polymer electrolyte is sulfonated polyarylene. Since it is a polymer, it has excellent power generation performance and hot water resistance. Further, since it is made of a non-fluorine-based polymer electrolyte, cost reduction can be achieved.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H01M 8/02 H01M 8/02 P (72) Inventor Nagayuki Kanaoka 1-4-1, Chuo, Wako, Saitama Honda Motor Co., Ltd. Inside the Research Institute (72) Hiroshi Soma 1-4-1 Chuo 1-chome, Wako City, Saitama Prefecture Inside the Honda R & D Co., Ltd. (72) Inventor Nobuhiro Saito 1-4-1 Chuo 1 Wako City, Saitama Prefecture (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo, JRS Co., Ltd. (72) Inventor Masayuki Takahashi 2-11-24 Tsukiji, Chuo-ku, Tokyo (JR) (56) ) Reference Japanese Patent Laid-Open No. 10-21943 (JP, A) Japanese Patent Publication No. 10-507574 (JP, A) International Publication 00/024796 (WO, A1) International Publication 00/027513 (WO, A1) (58) ) Fields surveyed (Int.Cl. ⁷ , DB name) H01B 1/06 H01M 8/02

Claims (5)

(57) [Claims] 1. In a composite polymer electrolyte membrane having two or more non-perfluoroalkylene sulfonic acid type polymer electrolytes, at least one non-perfluoroalkylene sulfonic acid type polymer electrolyte is a sulfonated polyarylene polymer.
Of the sulfonated polyarylene polymer
The polymer skeleton has the following general formula (1): And a structural unit represented by the following general formula (2) : Structural unit represented by (provided that the general formula (1) and
In (2), part of C in the aromatic ring may be substituted with N, and A _{1 to} A ₁₂ are —F, —CN, —CHO,
-COR, -CR = NR ', -OR, -SR, -SO ₂
R, -OCOR, -CO ₂ R, -NRR ', -N = CR
R ′, —NRCOR ′, —CONRR ′ and R, which may be the same or different, and X is —Z—, —Z—Ph— and —Ph—Z—Ph.
And R and R ′ are at least one selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group and a substituted heteroaryl group. , Which may be the same or different, Ph represents a substituted or unsubstituted phenylene group, Z represents —O—, —S—, —NR, —O
_{(CO) -, - O (} CO 2) -, - (CO) NH (C
O)-, -NR (CO)-, phthalimide, pyromellitic imide, -CO-, -SO-, -SO _2- , -P
_{(O) R -, - CH} 2 -, - CF 2 - and -CRR'-
Represents a divalent group selected from the group consisting of ) Less
A composite polymer electrolyte membrane comprising one or both . 2. A composite polymer electrolyte membrane containing first and second non-perfluoroalkylene sulfonic acid polymer electrolytes, wherein the first polymer electrolyte is sulfonated.
Made of riaarylene polymer, said sulfonated polyary
The polymer skeleton of the ethylene polymer is represented by the following general formula (1): And a structural unit represented by the following general formula (2) : Structural unit represented by (provided that the general formula (1) and
In (2), part of C in the aromatic ring may be substituted with N, and A _{1 to} A ₁₂ are —F, —CN, —CHO,
-COR, -CR = NR ', -OR, -SR, -SO ₂
R, -OCOR, -CO ₂ R, -NRR ', -N = CR
R ′, —NRCOR ′, —CONRR ′ and R, which may be the same or different, and X is —Z—, —Z—Ph— and —Ph—Z—Ph.
And R and R ′ are at least one selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group and a substituted heteroaryl group. , Which may be the same or different, Ph represents a substituted or unsubstituted phenylene group, Z represents —O—, —S—, —NR, —O
_{(CO) -, - O (} CO 2) -, - (CO) NH (C
O)-, -NR (CO)-, phthalimide, pyromellitic imide, -CO-, -SO-, -SO _2- , -P
_{(O) R -, - CH} 2 -, - CF 2 - and -CRR'-
Represents a divalent group selected from the group consisting of ) Less
Also consists of one or both, the composite polymer electrolyte membrane wherein the second polymer electrolyte characterized by comprising the sulfonated polyether polymer. 3. The composite polymer electrolyte membrane according to claim 1, wherein the content of the sulfonated polyarylene polymer is 50 to 95% by weight of the whole. 4. The composite polymer electrolyte membrane according to claim 2, wherein the content of the sulfonated polyarylene polymer is 50 to 95% by weight based on the total weight of the composite polymer electrolyte membrane. 5. A fuel cell comprising the composite polymer electrolyte membrane according to any one of claims 1 to 4.