CN102174208A - Method for preparing novel ultra-thin plasma polymerization anion exchange membrane - Google Patents
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Abstract
The invention provides a method for preparing a novel ultra-thin plasma polymerization anion exchange membrane, comprising the following steps: putting an electrode which is used as a plasma polymerization anion exchange membrane deposition substrate into a plasma discharge area, carrying out plasma modification on the surface of the electrode for a certain time, introducing a plasma polymerization monomer by taking hydrogen as carrier gas, carrying out radio-frequency plasma polymerization under a certain condition to form an ultra-thin plasma polymerization film, and carrying out quaternary ammonium treatment on the plasma polymerization film to finally prepare the ultra-thin plasma polymerization anion exchange membrane. The novel ultra-thin plasma polymerization anion exchange membrane prepared by adopting the method has good electrical conductivity, high alcohol resistance, good chemical stability and prolonged service life and use time when being applied to a fuel cell, and the production cost of the fuel cell is reduced.
Description
Technical field
The present invention relates to the Proton Exchange Membrane Fuel Cells technical field, be specifically related to new type superthin plasma polymerization anion-exchange membrane and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell, i.e. PEMFC) is an ionogen with the proton exchange membrane, is characterized in that noiselessness, zero pollutes, the no burn into life-span is long.Owing to have plurality of advantages such as power density height, efficiency of conversion high and low temperature start, volume is little, be particularly suitable for as removable power supply, be one of ideal source that is applied to by military project and civil area such as electromobile and underwater propulsion submarine etc., promise to be the first-selected power supply in space flight, military affairs, power truck and regional power station most.What the fuel of PEMFC generally adopted at present is hydrogen and methyl alcohol.But hydrogen is difficult for storing, and safety factors is scarcely arranged when using and transport, and has had a strong impact on the performance of total system.The hydrogen source problem becomes one of obstruction PEMFC widespread use and business-like major reason.Therefore, be the focus that the fuel cell of direct fuel becomes research and development with methyl alcohol.Direct methanol fuel cell (Direct Methanol Fuel Cell, i.e. DMFC) grows up on the Proton Exchange Membrane Fuel Cells basis, and it is directly to adopt methyl alcohol to act as a fuel to move.
DMFC mainly is made of anode, negative electrode and solid polymer dielectric film three parts.Electrode is made up of diffusion layer and catalyst layer, and catalyst layer is the place that electrochemical reaction takes place, and anode commonly used and electrocatalyst for cathode are respectively PtRu/C and Pt/C precious metal; Diffusion layer plays the effect of supporting Catalytic Layer, collected current and conduction reactant, is generally made by conductive porous material, and that uses now mostly is carbon paper or the carbon cloth that the surface scribbles carbon dust.Solid polymer dielectric film is commonly referred to as proton exchange membrane, and it only allows proton to pass through, and stops electronic conduction, prevents that simultaneously methyl alcohol and other material osmosis are to another electrode region.Proton exchange membrane mostly adopts the perfluorinated sulfonic acid Nafion series membranes that du pont company is produced at present.Diffusion layer, Catalytic Layer and polymeric film are collectively referred to as membrane electrode (MEA), and it is the core of DMFC, are the keys of decision DMFC performance.Problem and challenge that current direct methanol fuel cell faces have: (1) catalyzer cost height, anode methanol oxidation kinetics are slow.At present Pt is best anode catalyst, but its activity is still not high enough, and the price of Pt is higher, therefore causes the cost of the catalyzer that DMFC uses higher, is unfavorable for the commercialization of DMFC.And generate class CO intermediate in the methyl alcohol anode electrochemical oxidising process, and cause eelctro-catalyst to be poisoned, make the electrochemical oxidation speed of methyl alcohol reduce; (2) the methanol crossover problem of film.The alcohol-rejecting ability of normally used proton exchange membrane is relatively poor, cause fuel methanol to pass film by the film anode side and migrate to negative electrode by concentration diffusion and electromigration, at negative electrode and catalyzer generation electrochemical oxidation, and constitute short circuit battery with the electrochemical reduction of oxygen, produce mixed potential at negative electrode, and reduced the open circuit voltage of DMFC, reduce the current efficiency of battery; (3) when adopting methanol aqueous solution to do fuel, the anolyte compartment has been full of water, and DMFC proton exchange membrane anode side can remain under the good water saturation state.When DMFC worked, water can be moved to negative electrode (each proton can transmit 19 water moleculess) from anode by electrodialysis, and oxygen can produce water again when cathodic reduction simultaneously.Negative electrode need be discharged the water that generates much larger than electrochemical reaction like this, make the cathode side drainage load increase, and negative electrode is serious by the situation of water logging.In order to solve the problem that DMFC faces, the researchist mainly studies and explores from novel proton exchange membranes two aspects of developing highly active catalyzer and the high alcohol-rejecting ability of preparation.Because two hang-ups that the proton exchange membrane direct methanol fuel cell faces, it is electrolytical imagination that some investigators have proposed to use anion-exchange membrane in DMFC, this imagination not only combines Proton Exchange Membrane Fuel Cells (simple in structure), the advantage of alkaline fuel cell (oxidation rate is fast) and direct methanol fuel cell (high-energy-density), and avoided the shortcoming of these three kinds of fuel cells.After adopting the basic anion exchange membrane, the performance of battery can be improved: (1) methyl alcohol oxidation rate under alkaline condition than under acidic conditions is accelerated; (2) under the alkaline condition, do not exist reaction intermediate that electrode catalyst is poisoned, so the catalysis electrode of used in battery can be selected some common electrodes for use, as silver, nickel etc. have reduced the battery system manufacturing cost; (3) owing to be to transmit OH in the alkaline methanol operation of fuel cells process from the negative electrode anode
-Ion, just the direction with methanol crossover is opposite, has increased the transport resistance of methyl alcohol, has reduced the methanol permeation amount.Reduced the potential loss that methanol crossover causes; (4) because anode is pointed in the water migration that the migration of film intermediate ion causes, help the water balance of fuel cell, the battery performance that can avoid DMFC to cause because negative electrode suffers water logging descends.
Core component at the fuel cell of alkaline condition operation is an anion-exchange membrane, and it has played the dual function that the conduction hydroxide ion is isolated the cathode and anode chamber.The performance of anion-exchange membrane will directly influence battery performance, efficient and the work-ing life of basic anion exchange membrane direct methanol fuel cell.Therefore seek to be the target that a lot of scientists pursue with the approximate excellent anionic exchange membrane of business-like Nafion film properties.
Basic anion exchange membrane direct methanol fuel cell is as follows to the specific requirement of anion-exchange membrane: (1) has higher ionic activity and good ionic conductivity, guarantees that under high current density, the ohmic resistance of film is low, to improve battery efficiency; (2) advantages of higher tensile strength and good visco-elasticity are arranged, can bear the pressure reduction of film both sides, and better binding ability is arranged, to guarantee to make effective membrane electrode with catalyzer; (3) higher hydratability is arranged.Water molecules to avoid local lack of water, improves the anti-dry ability of film little perpendicular to the direction electroosmosis of face and to be parallel on the direction of face diffusion strong.The dried wet conversion performance of film will be got well, battery can make film dry out in the course of processing, and in the operational process of battery in order to obtain maximum ionic conductance, the basic anion exchange membrane will worked under full wet condition, therefore require the dimensional stabilizing of film, have and well do wet conversion performance; (4) the mould material molecular weight is fully big, and the poly-mutually and crosslinking degree height of material to reduce the superpolymer hydrolytic action, can stop polymkeric substance to be degraded under battery operated condition effectively; Need enough thermostabilitys and long work-ing life simultaneously; (5) fuel and oxygenant are had the good isolation effect, promptly fuel and the oxygenant perviousness in film is as far as possible little, directly reacts at electrode surface to avoid the two, causes the local superheating phenomenon, and has a strong impact on the electrical efficiency and the work-ing life of battery; (6) low methyl alcohol penetrate coefficient, methyl alcohol not only causes the loss of raw material to the infiltration of negative plate, and produces mixed potential on oxygen cathode, and battery performance is reduced.At present to be used for the anion-exchange membrane of fuel cell mainly be to be used for other electrochemical field to bibliographical information, as electrodialysis etc., and as Tokuyama Soda company, Solay company etc.The anion-exchange membrane (AHA, A 006, AMX etc.) of the band quaternary ammonium group that Tokuyama company produces is a commercialization film the most frequently used in alkaline film fuel battery system.Current, the greatest problem that the basic anion exchange membrane is applied to face in the fuel cell system be film under alkaline environment, the stability problem when temperature raises particularly.The instability of film mainly is that amine groups is by OH
-Ion substitution causes.OH
-It is good nucleophilic reagent, it mainly is by direct nucleophilic substitution or when β-H exists, the methyl that links to each other with amido by the Hoffman degraded reacts, generate Trimethylamine 99 and methyl alcohol, when the basic anion exchange membrane is used for direct methanol fuel cell (DMFC), DMFC is as compact power, and the operating temperature of these batteries will be lower than 60 ℃, to reduce DeR.Basic anion exchange membrane (AAEM) is one of basic anion exchange membrane direct methanol fuel cell (AMDMFC) technology key in application parts, the good AMDMFC system performance that affects of its performance.Therefore to be more suitable in the mould material of fuel cell than existing commercial anion-exchange membrane be the problem that people pay close attention to always in exploitation.
The plasma polymerization anion-exchange membrane has the not available advantage of anion-exchange membrane of conventional wet chemosynthesis: (1) has ultra-thin, fine and close, amorphous three-dimensional crosslinking structure; (2) ultrafine plasma body polymeric membrane allow the fuel cell miniaturization and and electrode between combine closely; (3) highly cross-linked structure makes polyelectrolyte membrane have the chemistry of height and the low-permeability of thermostability and organic liquid such as methyl alcohol; Highly cross-linked structure can effectively solve the degradation problem of film again.
Just propose to adopt built-in flat capacitor coupled discharge Plasma Polymerization to prepare anion-exchange membrane as far back as the S.Roualdes of France in 2006 and the study group of J.Durand, but do not report the specific performance of film.The Zempachi Ogumi of Kyoto Univ Japan in 2008 etc. are that monomer adopts built-in flat capacitor coupled plasma success polymerization to make plasma polymerization film with the 4-vinylpridine, handle obtaining anion-exchange membrane through quaternized, alkali lye.But the specific conductivity of film has only 5.4 * 10
-4S cm
-1Employing deposits film forming between two parallel built-in disk electrodes, although this method synthetic film can suppress methanol permeation effectively, its electric conductivity is lower.With respect to electric capacity glow discharge mode, after glow photocapacitance discharge mode can reduce electron pair polymerization reaction monomer destruction in various degree, has improved the integrity of monomer structure, thereby significantly improves the content of functional group in the plasma polymerization film.Therefore Plasma Polymerization synthetic anionic exchange membrane is one of current most promising novel method.How to improve the specific conductivity of plasma polymerization anion-exchange membrane, reduce methanol permeability, solve film under alkaline environment, the stability problem when temperature raises particularly, developing the new type superthin anion-exchange membrane of high-performance and low-cost, is a great technical barrier of exploitation high-performance direct methanol fuel cell.Therefore, the present invention be intended to research and preparation have excellent electrical conductivity, the ultra-thin anion-exchange membrane of high alcohol-rejecting ability and chemical stability.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of preparation method of new type superthin plasma polymerization anion-exchange membrane, the anion-exchange membrane that the inventive method makes has excellent electrical conductivity, high alcohol-rejecting ability and good chemical stability.
The technical solution used in the present invention is as follows for achieving the above object:
A kind of preparation method of new type superthin plasma polymerization anion-exchange membrane is characterized in that: specifically may further comprise the steps:
(1) modification of electrode surface plasma body is a plasma polymerization anion-exchange membrane deposition substrate with the electrode, puts into plasma reactor vacuum chamber chip bench, is evacuated to background air pressure 10
-3Below the Pa, logical Ar gas to pressure in vacuum tank reaches about 20Pa, and the substrate negative bias is controlled at 10-30V, at radio frequency power is to carry out the radio-frequency plasma discharge under the condition of 100-300W, and the counter electrode surface is carried out plasma body and modified 5-10 minute;
(2) plasma polymerization film formation reaction adjusting Ar airshed to reactor pressure in vacuum tank reaches 10-20Pa, is that carrier gas feeds plasma polymerization monomer, polymerization reaction monomer gas/H to vacuum chamber then with hydrogen
2The mixed gas dividing potential drop is controlled at 5-15Pa (polymerization reaction monomer gas/H
2Intrinsic standoff ratio is 1: 1-1: 5), the substrate negative bias is controlled at 10-30V, at radio frequency power is to carry out plasma polymerization under the condition of 10-300W, reaction times 1-4 hour, obtains the ultrathin plasma polymeric membrane;
(3) the quaternized processing of trimethylamine solution 2-4 days that mass concentration is 25-35wt% is at room temperature put into the plasma polymerization film that obtains in the step (2) in the quaternized processing of plasma polymerization film, then at 1-2mol L
-1Alkalinisation treatment in the KOH solution obtains ultrathin plasma polymerization anion-exchange membrane at last.
The preparation method of described plasma polymerization anion-exchange membrane, it is characterized in that: the described plasma polymerization monomer of step (2) is selected from any in 2-vinyl pyridine, 4-vinylpridine, 2-1-chloro-4-methyl-benzene, the 4-1-chloro-4-methyl-benzene, and described any monomer heated volatile temperature is 30-60 ℃.
The preparation method of described plasma polymerization anion-exchange membrane is characterized in that, described plasma reactor adopts particle energy controlled coupling of after glow photocapacitance or after glow photoelectricity sense coupled plasma polymerizing reactor.
The preparation method of described plasma polymerization anion-exchange membrane is characterized in that, described plasma reactor is connected to the inlet system stable, that flow velocity is controlled.
Advantage that the present invention has and positively effect:
(1) the plasma polymerization anion-exchange membrane has the crosslinking structure of height, makes it have higher thermostability and chemical stability than ordinary method polymeric film, thereby has increased its life-span and working hour in fuel cell.Its highly cross-linked structure also makes it that fuel is had low perviousness.
(2) superthin structure of plasma polymerization anion-exchange membrane makes that it and electrode can perfect adaptations, has reduced the resistance and the OH of film
-Conducting path, improved fuel cell performance; Strengthened the back diffusion ability (also promptly have from moistening capacity) of product water from the anode side to the cathode-side, thereby simplified battery structure, reduced cost.
(3) if it combines as the sputtering sedimentation of catalystic material with other film deposition process, the membrane electrode assemblies of micro fuel cell can be achieved by the successive deposition process, thereby improve membrane electrode three phase boundary (film, electrode, catalyzer) contact performance, improve the utilization ratio of catalyzer.
(4) because plasma technology can make the fuel cell miniaturization, thereby its scale operation cost reduces greatly.
(5) adopt after glow photocapacitance coupled plasma discharge mode or after glow photoelectricity sense coupled plasma discharge mode, can effectively reduce the destructiveness of polymerization reaction monomer in the plasma discharge process, improve the content of functional group in the plasma polymerization anion-exchange membrane, thereby improve the specific conductivity of film.
Description of drawings
Fig. 1: plasma polymerization anion-exchange membrane composition principle figure.
Introduce practical example of the present invention below
Embodiment
A kind of preparation method of new type superthin plasma polymerization anion-exchange membrane, concrete steps are as follows:
(1) modification of electrode surface plasma body is a plasma polymerization anion-exchange membrane deposition substrate with the electrode, puts into plasma reactor vacuum chamber chip bench, is evacuated to background air pressure 10
-3Below the Pa, logical Ar gas to pressure in vacuum tank reaches about 20Pa, and the substrate negative bias is controlled at 30V, at radio frequency power is to carry out the radio-frequency plasma discharge under the condition of 100W, and the counter electrode surface is carried out plasma body and modified 5 minutes;
(2) plasma polymerization film formation reaction adjusting Ar airshed to reactor pressure in vacuum tank reaches 20Pa, is that carrier gas feeds 4-1-chloro-4-methyl-benzene monomer, 4-1-chloro-4-methyl-benzene monomer gas/H to vacuum chamber then with hydrogen
2The mixed gas dividing potential drop is controlled at 10Pa (4-1-chloro-4-methyl-benzene monomer gas/H
2Intrinsic standoff ratio is 1: 5), the substrate negative bias is controlled at 10V, at radio frequency power is to carry out plasma polymerization under the condition of 50W that 4 hours reaction times obtained the ultrathin plasma polymeric membrane;
(3) at room temperature the plasma polymerization film that obtains in the step (2) to be put into mass concentration be 30% the quaternized processing of trimethylamine solution 3 days to the quaternized processing of plasma polymerization film, then at 1mol L
-1Alkalinisation treatment in the KOH solution obtains ultrathin plasma polymerization anion-exchange membrane at last.The new type superthin plasma polymerization anion-exchange membrane that obtains has good OH
-Electroconductibility, specific conductivity reach 14.8mS cm
-1The order of magnitude has lower methanol permeability simultaneously (10
-12m
2s
-1The order of magnitude).
Claims (4)
1. the preparation method of a new type superthin plasma polymerization anion-exchange membrane is characterized in that: specifically may further comprise the steps:
(1) modification of electrode surface plasma body is a plasma polymerization anion-exchange membrane deposition substrate with the electrode, puts into plasma reactor vacuum chamber chip bench, is evacuated to background air pressure 10
-3Below the Pa, logical Ar gas to pressure in vacuum tank reaches about 20Pa, and the substrate negative bias is controlled at 10-30V, at radio frequency power is to carry out the radio-frequency plasma discharge under the condition of 100-300W, and the counter electrode surface is carried out plasma body and modified 5-10 minute;
(2) plasma polymerization film formation reaction adjusting Ar airshed to reactor pressure in vacuum tank reaches 10-20Pa, is that carrier gas feeds plasma polymerization monomer, polymerization reaction monomer gas/H to vacuum chamber then with hydrogen
2The mixed gas dividing potential drop is controlled at 5-15Pa (polymerization reaction monomer gas/H
2Intrinsic standoff ratio is 1: 1-1: 5), the substrate negative bias is controlled at 10-30V, at radio frequency power is to carry out plasma polymerization under the condition of 10-300W, reaction times 1-4 hour, obtains the ultrathin plasma polymeric membrane;
(3) the quaternized processing of trimethylamine solution 2-4 days that mass concentration is 25-35wt% is at room temperature put into the plasma polymerization film that obtains in the step (2) in the quaternized processing of plasma polymerization film, then at 1-2mol L
-1Alkalinisation treatment in the KOH solution obtains ultrathin plasma polymerization anion-exchange membrane at last.
2. the preparation method of plasma polymerization anion-exchange membrane according to claim 1, it is characterized in that: the described plasma polymerization monomer of step (2) is selected from any in 2-vinyl pyridine, 4-vinylpridine, 2-1-chloro-4-methyl-benzene, the 4-1-chloro-4-methyl-benzene, and described any monomer heated volatile temperature is 30-60 ℃.
3. the preparation method of plasma polymerization anion-exchange membrane according to claim 1 is characterized in that, described plasma reactor adopts particle energy controlled coupling of after glow photocapacitance or after glow photoelectricity sense coupled plasma polymerizing reactor.
4. the preparation method of plasma polymerization anion-exchange membrane according to claim 3 is characterized in that, described plasma reactor is connected to the inlet system stable, that flow velocity is controlled.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970629A (en) * | 2019-11-08 | 2020-04-07 | 苏州卫鹏机电科技有限公司 | Fuel cell membrane electrode CCM and preparation method and device thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191174A (en) * | 1996-11-12 | 1998-08-26 | 全培赫 | Method of enhancing releasing effect of mold using low temperature plasma processes |
| CN1687149A (en) * | 2005-02-01 | 2005-10-26 | 中国科学院等离子体物理研究所 | Method of plasma for initiating polymerization of vinyl monomer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191174A (en) * | 1996-11-12 | 1998-08-26 | 全培赫 | Method of enhancing releasing effect of mold using low temperature plasma processes |
| CN1687149A (en) * | 2005-02-01 | 2005-10-26 | 中国科学院等离子体物理研究所 | Method of plasma for initiating polymerization of vinyl monomer |
Non-Patent Citations (1)
| Title |
|---|
| 《Thin Solid Films》 20101127 Jue Hu 等 Plasma-polymerized alkaline anion-exchange membrane: Synthesis and 2155-2162 1-4 第519卷, 第7期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970629A (en) * | 2019-11-08 | 2020-04-07 | 苏州卫鹏机电科技有限公司 | Fuel cell membrane electrode CCM and preparation method and device thereof |
| CN110970629B (en) * | 2019-11-08 | 2022-07-26 | 苏州卫鹏机电科技有限公司 | Fuel cell membrane electrode CCM and preparation method and device thereof |
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