CN100336861C

CN100336861C - Electric conducting mateiral of non-water proton of polyvinyl alcohol tetrazole with acid being adulterated and preparation method

Info

Publication number: CN100336861C
Application number: CNB2004100823113A
Authority: CN
Inventors: 浦鸿汀; 叶盛; 杨正龙
Original assignee: Tongji University
Current assignee: Tongji University
Priority date: 2004-12-30
Filing date: 2004-12-30
Publication date: 2007-09-12
Anticipated expiration: 2024-12-30
Also published as: CN1660934A

Abstract

The present invention belongs to the technical filed of high molecular material and electrochemical material, more specifically polymer nonaqueous proton electric conducting material suitable for electrochemical devices, such as moderate temperature fuel batteries, etc., and a method of preparing the polymer nonaqueous proton electric conducting material. The nonaqueous proton electric conducting material is obtained by compounding polyvinyl alcohol tetrazolium and protonic acid in a certain molar proportion, the polyvinyl alcohol tetrazolium has the molecular weight of 5000 to 300000, and the protonic acid can provide protons (H<+>) and can be dissolved in organic acid or inorganic acid of polyvinyl alcohol tetrazolium. The preparing method has the advantages of simplicity and convenient control, and the proton electrical conductivity is favorable.

Description

Acid doping polyvinyl alcohol tetrazole non-aqueous proton conducting material and preparation method thereof

Technical field

The invention belongs to macromolecular material and technical field of electrochemistry, be specifically related to a kind of polymer non-aqueous proton conducting material that is applicable to electrochemical devices such as intermediate temperature fuel cell and preparation method thereof.

Background technology

Proton Exchange Membrane Fuel Cells (PEMFC) has advantages such as not containing corrosive liquid, be easy to make, can bear big pressure difference, the life-span is long, is studied in recent years at most, is most possibly produced in enormous quantities and uses.The perfluorinated sulfonic acid proton exchange membrane (PEM) such as Nafion, Dow that are used for PEMFC have shortcomings such as complex management, the working temperature of water in price height, the film be restricted.Characteristics have caused people's attention to polymer non-aqueous proton conducting material so that its specific conductivity height, operating temperature range be wide etc., can be used for electrochemical devices such as intermediate temperature fuel cell.The polymer non-aqueous proton electrical conductor of studying at most at present is the compound system of polymkeric substance and protonic acid, more representational system has the compound system (BozkurtA of benzoglyoxaline base polymer and phosphoric acid, Ise M, Kreuer K D, et al.Solid State Ionics, 1999,125:225), but the benzoglyoxaline base polymer infusibility indissoluble of main chain belt nitrogen heterocyclic, the film forming difficulty is big, introduce side chain or side group if can will play the nitrogen heterocyclic of electric action, then both can obtain higher proton conductive performance, can obtain film forming properties preferably again.Polyvinyl alcohol tetrazole (PVT) promptly is such base polymer, in the document to more (the Gaponik P.N. of the research of its synthetic method, Ivashkevich O.A., and Karavai V.P., et al, Die Angewandte Makromol.Chem., 1994,219:77), but also do not have polyvinyl alcohol tetrazole (PVT) to be used for the open report of the research of proton conducting material.

Summary of the invention

The objective of the invention is to propose a kind of be suitable for electrochemical devices such as intermediate temperature fuel cell based on novel non-aqueous polymer proton conducting material of protonic acid doping polyvinyl alcohol tetrazole and preparation method thereof.

The acid doping polyvinyl alcohol tetrazole non-aqueous proton conducting material that the present invention proposes, by polyvinyl alcohol tetrazole and protonic acid is compound obtains, it is composed as follows:

1 part of polyvinyl alcohol tetrazole (repeating unit mole number)

Protonic acid 0.1-5 part (mole number)

Described polyvinyl alcohol tetrazole (PVT) can be to be raw material synthetic, number-average molecular weight (M according to document with polyacrylonitrile (PAN) _n) be 5000～300000, become the ring rate to be the polyvinyl alcohol tetrazole of 50%～100wt%, or by vinyl tetrazolium monomer direct polymerization, number-average molecular weight (M _n) be 5000～300000, become ring rate 100wt% polyvinyl alcohol tetrazole (Gaponik P.N., Ivashkevich O.A., and Karavai V.P., et al, Die Angewandte Makromol.Chem., 1994,219:77).

Described protonic acid is meant can provide proton (H ⁺), non-volatile, the mineral acid or the organic acid that can be dissolved in polyvinyl alcohol tetrazole, as phosphoric acid, sulfuric acid etc., but be not limited thereto.

The preparation method of non-aqueous proton conducting material of the present invention can adopt a kind of in following two kinds of methods, and concrete steps are as follows:

(1) be that 5000～300000 polyvinyl alcohol tetrazole is dissolved in N with molecular weight, dinethylformamide is made the solution of 5～8wt%.Add protonic acid by above-mentioned mol ratio, fully stir, make homogeneous phase solution.Solution is poured on the polyfluortetraethylene plate, and automatically levelling is put into the vacuum drying oven oven dry then and can be obtained film sample, and the doping X of protonic acid is the protonic acid mole number and the ratio of PVT repeating unit mole number.

(2) be that 5000～300000 polyvinyl alcohol tetrazole is dissolved in N with molecular weight, dinethylformamide is made the solution of 5～8wt%, solution is poured on the polyfluortetraethylene plate, and levelling is put into the vacuum drying oven oven dry then automatically, weigh, it was immersed in the solution of protonic acid 1-10 hour oven dry.Can calculate in the film doping X of acid according to the increase of film weight, i.e. the ratio of protonic acid mole number and PVT repeating unit mole number.

The present invention has studied the proton conductive performance of different types of polyvinyl alcohol tetrazole after acid is mixed, and finds that its specific conductivity raises with the increase of protonic acid doping amount, raises with the rising of envrionment temperature, can reach 10 ^-3S/cm.By the film forming properties of research protonic acid doping polyvinyl alcohol tetrazole, find that sour doping in 0.1-5 part (mol ratio) scope, has good film forming properties.Applicable to electrochemical devices such as intermediate temperature fuel cells.

Description of drawings

Fig. 1 is the alternating-current impedance figure of phosphate-doped polyvinyl alcohol tetrazole composite membrane.

Fig. 2 is the real part of plural specific conductivity of the phosphate-doped polyvinyl alcohol tetrazole composite membrane variation diagram with frequency under inconsiderate temperature, X=1.5.

Fig. 3 is the real part of plural specific conductivity of the phosphate-doped polyvinyl alcohol tetrazole composite membrane variation diagram with frequency under differing temps, X=1.0.

Fig. 4 is that the proton conductivity of phosphate-doped polyvinyl alcohol tetrazole composite membrane is with variation of temperature figure.

Embodiment

Following examples are only for further specifying the present invention, are not violating under the purport of the present invention, and the present invention should be not limited to the content that following experimental example is specifically expressed.

Embodiment 1

Raw materials used as follows:

Polyvinyl alcohol tetrazole (M _n18130～136000) adopting molecular weight is that 18131.5～136000 polyacrylonitrile (Fluka company product) is according to document self-control (Gaponik P.N., Ivashkevich O.A., and Karavai V.P., et al, Die Angewandte Makromol.Chem., 1994,219:77).

Diisopropyl azodicarboxylate, reagent company of traditional Chinese medicines group product.

Trichloromethane, reagent company of traditional Chinese medicines group product.

N, dinethylformamide, Shanghai development chemical industry one factory's product.

The phosphoric acid of 85wt%, Shanghai amalgamation factory products.

The phosphoric acid of 95～98wt%, Shanghai amalgamation factory products.

37% hydrochloric acid, reagent company of traditional Chinese medicines group product.

Raw materials used proportioning is as follows:

PVT (adopts the PAN preparation, M _n, 18130) and 1 part (repeating unit mole number)

Phosphatase 11 .5 part (mole number)

The preparation of composite membrane:

PVT is dissolved in N, and dinethylformamide is made the solution of 5～8wt%, and the proportioning of pressing X=1.5 adds phosphoric acid, fully stirs, and makes homogeneous phase solution.Solution is poured on the polyfluortetraethylene plate, behind the levelling, puts into the vacuum drying oven oven dry and can obtain the composite membrane sample automatically.

The mensuration of composite membrane proton conductive performance:

Composite membrane two sides metal spraying is handled with as electrode, used alternating current impedance instrument (EG ﹠amp with 273 type potentiostat/galvanostats and 5210 type lock-in amplifiers; G Princeton Applied Research Co.) composite impedance of mensuration composite membrane changes into proton conductivity by calculating again.The proton conductive performance of composite membrane such as Fig. 1, Fig. 2 and shown in Figure 4.

Embodiment 2

Raw materials used proportioning is as follows:

Phosphatase 11 .0 part (mole number)

The mensuration of the preparation method of composite membrane and proton conductive performance is similar to Example 1, its proton conductive performance such as Fig. 1, Fig. 3 and shown in Figure 4.：

Embodiment 3

Raw materials used proportioning is as follows:

PVT (adopts vinyl tetrazolium direct polymerization, M _n, 9600) and 1 part (repeating unit mole number)

Phosphatase 11 .0 part (mole number)

The mensuration of the preparation method of composite membrane and proton conductive performance is similar to Example 1, and its proton conductive performance and Fig. 1, Fig. 2, Fig. 3 and result shown in Figure 4 are similar.

Embodiment 4

Raw materials used proportioning is as follows:

PVT (adopts the PAN preparation, M _n, 136000) and 1 part (repeating unit mole number)

0.8 part of phosphoric acid (mole number)

The preparation method of composite membrane:

PVT is dissolved in N, dinethylformamide, make the solution of 5～8wt%, solution is poured on the polyfluortetraethylene plate, automatically behind the levelling, put into the vacuum drying oven oven dry, weigh, with 1-10h in the aqueous solution of its immersion phosphoric acid, oven dry, can calculate in the film doping X of acid according to the increase of film weight, i.e. the ratio of protonic acid mole number and PVT repeating unit mole number.

The mensuration of composite membrane proton conductive performance is similar to Example 1, and its proton conductive performance and Fig. 1, Fig. 2, Fig. 3 and result shown in Figure 4 are similar.

Embodiment 5

Raw materials used proportioning is as follows:

PVT (adopts the PAN preparation, M _n, 75000) and 1 part (repeating unit mole number)

0.8 part in sulfuric acid (mole number)

The mensuration of the preparation method of composite membrane and proton conductive performance is similar to Example 1.Its proton conductive performance and Fig. 1, Fig. 2, Fig. 3 and result shown in Figure 4 are similar.

In the foregoing description, the parameter of each component raw material and consumption and preparation process only is the representative of choosing in order to describe invention.In fact a large amount of experiments show, in summary of the invention part institute restricted portion, all can obtain the similar sour doping proton exchange of the foregoing description.

Claims

1, a kind of protonic acid doping polyvinyl alcohol tetrazole non-aqueous proton conducting material is characterized in that composed as follows:

1 part of polyvinyl alcohol tetrazole, by the repeating unit mole number, number-average molecular weight is 5000-300000,

Protonic acid 0.1-5 part is by mole number.

2, non-aqueous proton conducting material according to claim 1, it is characterized in that said polyvinyl alcohol tetrazole is to be 5000～300000, to become the ring rate to be the polyvinyl alcohol tetrazole of 50%～100wt% by polyacrylonitrile synthetic, number-average molecular weight, or by vinyl tetrazolium monomer direct polymerization, number-average molecular weight is 5000～300000, become the polyvinyl alcohol tetrazole of ring rate 100wt%.

3, non-aqueous proton conducting material according to claim 1 is characterized in that said protonic acid is for providing proton (H ⁺), nonvolatile, the inorganic or organic acid that can be dissolved in polyvinyl alcohol tetrazole.

4, a kind of preparation method of non-aqueous proton conducting material as claimed in claim 1 is characterized in that adopting a kind of in following two kinds of methods:

(1) be that 5000～300000 polyvinyl alcohol tetrazole is dissolved in N with molecular weight, dinethylformamide is made the solution of 5～8wt%, adds a protonic acid by the mole proportioning, fully stirs, and makes homogeneous phase solution; Solution is poured on the polyfluortetraethylene plate, behind the levelling, puts into the vacuum drying oven oven dry and can obtain film sample automatically;

(2) be that 5000～300000 polyvinyl alcohol tetrazole is dissolved in N with molecular weight, dinethylformamide, make the solution of 5～8wt%, solution is poured on the polyfluortetraethylene plate, and levelling is put into the vacuum drying oven oven dry then automatically, weigh, it was immersed in the solution of protonic acid 1-10 hour, and the doping of acid in the film is calculated in oven dry according to the increase of film weight.