CN102447116B - Preparation method for membrane electrode - Google Patents
Preparation method for membrane electrode Download PDFInfo
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- CN102447116B CN102447116B CN2010106187210A CN201010618721A CN102447116B CN 102447116 B CN102447116 B CN 102447116B CN 2010106187210 A CN2010106187210 A CN 2010106187210A CN 201010618721 A CN201010618721 A CN 201010618721A CN 102447116 B CN102447116 B CN 102447116B
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Abstract
The invention relates to a preparation method for a membrane electrode, belonging to the technical field of a low temperature fuel cell; the preparation method comprises the step of combining and preparing a cathode, an anode and a Nafion middle membrane into a sandwich structure, wherein a preparation method of the cathode comprises the following steps of: (1) forming a nanowire polymer catalyst precursor on the surface of a carbon layer diffusion layer in an electrochemistry polymerization manner; (2) carrying out activating treatment on the polymer catalyst precursor under the protection of argon to obtain a polymer catalyst; (3) respectively adding activated carbon to a Nafion emulsion and a PTFE (Polytetrafluoroethylene) emulsion, dispersing the Nafion emulsion and the PTFE emulsion through ultrasonic waves, respectively and repeatedly spraying the Nafion emulsion and the PTFE emulsion by using a spray gun in different directions in a stagger manner, and carrying out vacuum drying after the completion of each spraying; and (4) then spraying an adhesive layer Nafion emulsion to prepare an outer adhesive layer and the cathode. The nanowire polymer forms a substrate with the ordered structure; all the materials are immiscible, thereby facilitating channels to form; and the channels are ordered and have good comprehensive transmission performance, and therefore, the performance of the membrane electrode is ensured.
Description
Technical field
The present invention relates to a kind of preparation method of membrane electrode, belong to the low-temperature fuel cell technical field.
Background technology
Membrane electrode is core and the key component of fuel cell, and the quality of its performance directly affects the quality of fuel battery performance.So the preparation method of membrane electrode and technical study are one of most important problems of fuel cell field always.In fuel cell, the reaction on electrode of fuel and oxidant is very complicated electrocatalytic reaction, as, negative electrode is from the mass transfer aspect, oxygen arrives negative electrode by diffusion layer, electrocatalytic reduction occurs on cathod catalyst surface to be obtained electronics and is combined generation water with the proton that anode passes over by proton exchange membrane, electrode reaction is gas-solid-liquid three-phase reaction system, so good gas delivery passage, fluid transfer, electron propagation ducts and proton transport passage must be arranged in negative electrode.Yet gas-fluid transport is again conflicting, and hydrophobic channel is favourable to oxygen transmission, and just poor to the transmittability of the water of polarity, vice versa; Electronics-proton transport is also conflicting, the good conductor confrontation insulating sublayer of electronics, and the conductor of proton also insulate to electronics.Therefore, the preparation of membrane electrode is not that to pursue that aspect best, but many-side will take into account, and strives reaching coordinated balance.The optimal structure of membrane electrode preparation should be that mass transfer channel, electron channel and proton channel build separately and do not influence each other.As adopting the CNT (carbon nano-tube) of vertical arrangement on proton exchange membrane, CNT (carbon nano-tube) (electronic conductor) one side deposits Pt nano particle (catalytic reaction position), there is Nafion resin (proton conductor) to form hydrophobic structure zone (gas passage) between particle, another side, carry out carbonylation without CNT (carbon nano-tube) and form hydrophilic area (fluid transfer).
The preparation method of existing membrane electrode has: be coated with cream method, spread coating, spraying process, turn platen press, self-assembly method etc., gas delivery passage in negative electrode, fluid transfer, electron propagation ducts and proton transport passage are not very orderly, the comprehensive transmission poor performance, affect the performance of membrane electrode.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of new-type membrane electrode, the membrane electrode gas delivery passage of acquisition, fluid transfer, electron propagation ducts and proton transport passage are orderly, and the comprehensive transmission performance is good, has guaranteed the performance of membrane electrode.
The preparation method of membrane electrode of the present invention, at first prepare negative electrode and anode, then negative electrode, anode and Nafion intermediate coat are made up the structure that sandwiches, and it is characterized in that the preparation method of negative electrode is as follows:
(1) adopt the electrochemical polymerization mode to form the regularly arranged nano wire polyalcohol catalyst precursor of one deck on carbon paper diffusion layer surface;
(2) with the polyalcohol catalyst precursor under argon shield,, through 200～300 ℃ of activation processing 2h, obtain polyalcohol catalyst;
(3) Nafion emulsion and PTFE emulsion are added respectively activated carbon, disperse 2h under ultrasonic wave, with spray gun in different directions staggered spraying Nafion emulsion and PTFE emulsion repeatedly, rest in 5～15 times respectively, each spraying is completed and is all needed vacuumize;
(4) use again glue-line Nafion Emulsion Spraying, through vacuumize, make outer glue-line, make negative electrode.
Wherein:
Diffusion layer is conventional diffusion layer, and the paste blade coating that is comprised of carbon dust, polytetrafluoroethylene (PTFE), isopropyl alcohol and water forms.Its preparation method is: the PTFE emulsion of 5～15wt% (U.S. Du pont company) 15mL, add the 15mL isopropyl alcohol, the activated carbon (XC-72) that under agitation adds 50mg, ultrasonic dispersion 2h, obtain finely dispersed suspension-turbid liquid, be concentrated into paste under 60～70 ℃ of air dry ovens, with the method for brushing, cover with paint, lacquer, colour wash, etc. 2 * 2cm
2T-90 carbon paper surface (toray company), coating layer thickness, at 0.2～0.5mm, dries naturally, at 200 ℃～300 ℃ heating 2h, acquisition has the carbon paper of diffusion layer in electric furnace.
The nano wire polymer has doped polypyrrole transition metal, Polyaniline Doped transition metal, polymerized phthalocyanine complex and polymerization metalloporphyrin complex etc.
The electrochemical polymerization mode of polypyrrole is:
Environmental condition: solvent is pure water, and electrolyte is lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is saturated calomel electrode;
Lead to nitrogen 15～35min in the pyrroles's of containing 0.3～0.5mol/L solution, then, constant potential polymerase 17 0～120s, obtain polypyrrole nano line under 0.7～0.9V.
The method of the catalyst precarsor of polypyrrole nano line containing transition metal element is:
The polypyrrole nano line that obtains in metal salt solution under 0.5～0.9V electro-deposition obtain the catalyst precarsor of polypyrrole nano line containing transition metal element, transition metal ions selects Fe
2+, Fe
3+, Co
2+, Ni
2+, Mn
2+, or Pt
2+Control the amount of metal deposition according to the time length of electro-deposition.
The electrochemical polymerization mode of polyaniline is:
Environmental condition: solvent is pure water, and electrolyte is lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is saturated calomel electrode;
Be logical nitrogen 15～35min in the solution of aniline of 0.5～0.8mol/L to concentration, then, constant potential polymerization 120～149s, obtain polyaniline nano-line under 0.7～0.90V.
The method of the catalyst precarsor of polyaniline nano-line containing transition metal element is:
The polyaniline nano-line that obtains in metal salt solution under 0.5～0.9V electro-deposition obtain the catalyst precarsor of polyaniline nano-line containing transition metal element, transition metal ions selects Fe
2+, Fe
3+, Co
2+, Ni
2+, Mn
2+, or Pt
2+
In the polymerized phthalocyanine complex:
In the polymerized phthalocyanine complex, (transition metal ions selects Fe to the polymerized phthalocyanine transition metal
2+, Fe
3+, Co
2+, Ni
2+, Mn
2+, or Pt
2+) the electrochemical polymerization mode of complex:
Take the carbon paper that scribbles diffusion layer as work electrode, think solvent, electrolyte is the tetrabutylammonium perchlorate, Ag/AgCl is reference electrode, logical N before polymerization
2Deoxygenation, adopt 4,4 of 0.1～0.5mol/L ', 4 ", 4 ' " in tetramino phthalocyanine transient metal complex dimethyl formamide solution, tetrabutylammonium perchlorate's concentration is 0.2～1.0mol/L, polymerization current potential 0.8～1.5V, polymerization time 30～200min.
(transition metal ions selects Fe to the polymerization porphyrin transition metal complexes
2+, Fe
3+, Co
2+, Ni
2+, Mn
2+, or Pt
2+) the electrochemical polymerization mode:
Take the carbon paper that scribbles diffusion layer as work electrode, take dimethyl formamide as solvent, electrolyte is the tetrabutylammonium perchlorate, and Ag/AgCl is reference electrode, adopts 5 of 0.1～0.6mol/L, 10, in 15,20-tetramino porphyrin transition metal complexes dimethyl formamide solution, tetrabutylammonium perchlorate's concentration is 0.1～0.6mol/L, polymerization current potential 0.88～1.25V, polymerization time 60～200min.
In the emulsion of spraying:
The weight concentration of Nafion emulsion is that the weight concentration of 1～3%, PTFE emulsion is 2～4%, and the activated carbon addition is the 5-10mg/5mL emulsion.
Different directions staggered spraying Nafion emulsion and PTFE emulsion, as a spraying from left to right, a spraying from right to left, hocket successively, and repeatedly spraying, generally rest in 5～15 times, do not surpass 200nm at every turn.
The weight concentration of glue-line Nafion emulsion is preferably 3～5%.
The vacuumize temperature of spraying emulsion is 70～120 ℃.
Compared with prior art, the present invention has the following advantages:
The nano wire polymer has formed the matrix of ordered structure, each material is immiscible, convenient each passage that forms, belong to catalytic reaction zone at the nano wire polymer, be again electron channel, the activated carbon part also can form electron channel, and the Nafion resin-shaped becomes hydrophilic proton conduction district, hydrophilic pores on every side forms the transmission channels of water, and the space around the PTFE resin forms gas (oxygen) transmission channel.
The formation principle is: have between regular nano wire catalytic reaction zone respectively towards fixing a direction spraying Nafion emulsion and PTFE emulsion, in the heat drying process, the Nafion emulsion of polarity forms hydrophilic region; Form hydrophobic region in nonpolar PTFE emulsion dry run, both because polarity is different, mutually repel, can not mix.Hydrophobic region and the hydrophilic area can formation rule arranged of the result of spraying repeatedly, thus realize that transmission channels and hydrophilic area Nafion matrix that the hydrophilic area space forms water form the proton transfer passage.Between hydrophobic region, space forms the gas transfer passage.The nano wire polymer is catalytic reaction zone, and with the activated carbon that adds as electron channel.Various passages require nano wire polymer catalytic reaction zone to converge, thereby reach the requirement of various aspects of performance equilibrium.
Gas delivery passage, fluid transfer, electron propagation ducts and proton transport passage are orderly, and the comprehensive transmission performance is good, have guaranteed the performance of membrane electrode.
Be applicable to (comprise PEMFC and DMFC) in polymer-membrane fuel battery, phosphoric acid type fuel cell, metal air fuel cell, alkaline fuel cell etc., also can be used for the fields such as ultracapacitor and electrochemical sensor.
With negative electrode and the common spraying of preparation or be coated with the anode that the cream method obtains and the Nafion film (Nafion 117 etc.) of processing is combined into sandwich structure, the Nafion film is in centre.Hot pressing 80～120s can obtain membrane electrode under 13～15MPa.
The membrane electrode that obtains is adopted and well known to a person skilled in the art method assembling monocell, adopt fuel battery test system to test, then can obtain the performance of battery.The catalyst that the performance of battery and chemical synthesis process obtain, use conventional methods the membrane electrode that obtains, and battery performance improves 8～12% under similarity condition.
The battery performance order from high to low of different catalysts preparation is: polymerized phthalocyanine iron＞polymerized phthalocyanine cobalt＞polymerization PORPHYRIN IRON＞polymerization Cobalt Porphyrin＞polypyrrole cobalt＞polypyrrole iron＞polyaniline cobalt＞polyaniline iron.
Description of drawings
Fig. 1, polypyrrole nano line micro-structure diagram of the present invention.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
The preparation method of membrane electrode of the present invention, at first prepare negative electrode and anode, then negative electrode, anode and Nafion intermediate coat are made up the structure that sandwiches, and the preparation method of its negative electrode is as follows:
(1) adopt the electrochemical polymerization mode to form one deck nano wire polyalcohol catalyst precursor on carbon paper diffusion layer surface;
Environmental condition: solvent is pure water, and electrolyte is lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is saturated calomel electrode;
Lead to nitrogen 25min in the pyrroles's of containing 0.3mol/L solution, then, constant potential polymerization 100s, obtain polypyrrole nano line under 0.85V.To polypyrrole nano line in the cobalt acetate solution of 0.5mol/L, saturated calomel electrode is reference electrode, and the carbon paper of the polypyrrole nano line electrode of working is arranged, electro-deposition 120s obtains the catalyst precarsor of polypyrrole nano line cobalt under 0.75V.
(2) with the polyalcohol catalyst precursor under argon shield,, through 250 ℃ of activation processing 2h, obtain polyalcohol catalyst.
(3) be that 1% Nafion emulsion and weight concentration are that 2% PTFE emulsion adds respectively activated carbon with weight concentration, addition is the 6mg/5mL emulsion, disperse 2h under ultrasonic wave, then respectively with spray gun different directions staggered spraying Nafion emulsion and PTFE emulsion each 5 times, the Nafion emulsion sprays from left to right, the PTFE emulsion sprays from right to left, and each spraying is completed and all needed vacuumize, and the vacuumize temperature is 120 ℃.
(4) with weight concentration be again 5% glue-line Nafion Emulsion Spraying, make outer glue-line, make negative electrode.
The adulterate catalyst precarsor of other transition metal, method is the same, just cobalt acetate solution is changed into other metal salt solution and gets final product.
Embodiment 2
Electrochemical polymerization method prepares polyaniline nano-line, and its method, with embodiment 1, just changes the pyrroles into aniline, sample solution concentration, polymerization current potential and asynchronism(-nization).Concentration of aniline is 0.5mol/L, under 0.89V (vs.SCE), and constant potential polymerization 134s.
The electro-deposition method of polyaniline nano-line containing transition metal element is with embodiment 1.Polyaniline cobalt (PANI-Co) structural formula of nano wire polyaniline (PANI) and doping cobalt element thereof is as follows:
The adulterate catalyst precarsor of other transition metal, method is the same, just cobalt acetate solution is changed into other metal salt solution, gets final product.
Embodiment 3
Electrochemical polymerization method prepares polymerized phthalocyanine complex nano wire.
The preparation method of poly-phthalocyanine complex nano wire is with embodiment 1, just aqueous solvent is changed into dimethyl formamide (DMF) and (will carry out purifying and decompression distillation before using, to remove moisture and impurity), support electrolyte tetrabutylammonium perchlorate (TBAP), reference electrode Ag/AgCl.DMF solution 50mL at the TBAP of 0.5mol/L, add 4,4 of 0.025mmol ', 4 ", 4 ' " tetramino FePC, be made into the solution of 0.5mol/L, logical high-purity N before polymerization
230min is with the oxygen except in solution, under current potential 1.0V (vs.Ag/AgCl) constant potential, and polymerization 1h.Can obtain the polymerized phthalocyanine Fe nanowire.
The preparation method of the polymerized phthalocyanine nano wire of other central metallic ions coordination is the same, just 4,4 ', 4 ", 4 ' " tetramino FePC changes 4,4 into ', 4 ", 4 ' " other metal complex of tetramino phthalocyanine, get final product.
Embodiment 4
The preparation of polymerization metalloporphyrin complex nano wire.
The preparation method of polymerization Cobalt Porphyrin nano wire is with embodiment 3, just 4,4 ', 4 ", 4 ' " the tetramino FePC changes 5,10,15,20-tetramino Cobalt Porphyrin into, gets final product.
The preparation method of the polymerization metalloporphyrin complex nano wire of other central metallic ions coordination is with embodiment 3, just just 4,4 ', 4 ", 4 ' " the tetramino FePC changes other metal complex of 5,10,15,20-tetramino porphyrin into, gets final product.
Embodiment 5
The activation of nano wire polyalcohol catalyst precursor.
The catalyst precarsor (together with the carbon paper that diffusion layer is arranged) of embodiment 1～4 preparation, under the high-purity argon gas protection, 300 ℃ of activation 2h.
Embodiment 6
The preparation of negative electrode.Add respectively the activated carbon (XC-72 of 5mg in the PTFE emulsion (Dupont) of the Nafion of 5mL 2wt% emulsion (Du pont) and 5mL 3%, Cabot) under helping, ultrasonic wave disperses 2h, adopt respectively spray gun at different directions, as: Nafion from right to left, PTFE from left to right, spray in turn 5 times, the direction of each spraying is consistent, and each spraying is completed all and need to be processed 35min under 100 ℃ of vacuum drying chambers, and each thickness surpasses 200nm.Finally, be with 5% Nafion Emulsion Spraying, thickness 100nm, cathode portion can be completed.
Adopt and use the same method, can obtain the anode of different situations, just respectively the mass concentration of Nafion emulsion and PTFE solution is changed, the techniques such as number of times that the activated carbon quality that adds changes or change spraying get final product.
Embodiment 7
The preparation of novel membrane electrode.With the negative electrode of embodiment 6 preparation with adopt spraying or be coated with the anode that the cream method obtains that (anode Pt carrying capacity is 2mg/cm
2) being combined into sandwich structure with the Nafion film (Nafion 117) of processing, the Nafion film is in centre.Hot pressing 120s can obtain membrane electrode under 13.5MPa.
Adopting uses the same method can obtain the membrane electrode of different parameters, and the parameter and the kind that just change negative electrode, anode and film get final product.It the results are shown in Table 1.
Battery assembling and battery performance test.Membrane electrode assembling monocell embodiment obtains, adopt fuel battery test system to test.Then can obtain the performance of battery.It the results are shown in Table 1.
Claims (8)
1. the preparation method of a membrane electrode, at first prepare negative electrode and anode, then negative electrode, anode and Nafion intermediate coat are made up the structure that sandwiches, and it is characterized in that the preparation method of negative electrode is as follows:
(1) the nano wire polyalcohol catalyst precursor that adopts the electrochemical polymerization mode to arrange in carbon paper diffusion layer surface formation rule, wherein, the nano wire polymer has doped polypyrrole transition metal, Polyaniline Doped transition metal, polymerized phthalocyanine complex and polymerization metalloporphyrin complex;
(2) with the polyalcohol catalyst precursor under argon shield,, through 200-300 ℃ of activation processing 2h, obtain polyalcohol catalyst;
(3) Nafion emulsion and PTFE emulsion are added respectively activated carbon, disperse 2h under ultrasonic wave, with spray gun in relative direction staggered spraying Nafion emulsion and PTFE emulsion repeatedly, each spraying is completed and is all needed vacuumize respectively;
(4) use again glue-line Nafion Emulsion Spraying, make outer glue-line, make negative electrode.
2. the preparation method of membrane electrode according to claim 1 is characterized in that the electrochemical polymerization mode of polypyrrole:
Environmental condition: solvent is pure water, and electrolyte is lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is saturated calomel electrode;
Lead to nitrogen 15～35min in the pyrroles's of containing 0.3～0.5mol/L solution, then, under 0.7～0.9V, constant potential polymerase 17 0～120s, obtain polypyrrole nano line, the polypyrrole nano line that obtains in metal salt solution under 0.5～0.9V electro-deposition obtain the catalyst precarsor of polypyrrole nano line containing transition metal element.
3. the preparation method of membrane electrode according to claim 1 is characterized in that the electrochemical polymerization mode of polyaniline:
Environmental condition: solvent is pure water, and electrolyte is lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is saturated calomel electrode;
Be logical nitrogen 15～35min in the solution of aniline of 0.5～0.8mol/L to concentration, then, constant potential polymerization 120～149s under 0.7～0.90V, obtain polyaniline nano-line, the polyaniline nano-line that obtains in metal salt solution under 0.5～0.9V electro-deposition obtain the catalyst precarsor of polyaniline nano-line containing transition metal element.
4. the preparation method of membrane electrode according to claim 1 is characterized in that the electrochemical polymerization mode of polymerized phthalocyanine transient metal complex in the polymerized phthalocyanine complex:
Take the carbon paper that scribbles diffusion layer as work electrode, take dimethyl formamide as solvent, electrolyte is the tetrabutylammonium perchlorate, and Ag/AgCl is reference electrode, logical N2 deoxygenation before polymerization, adopt 4,4 of 0.1～0.5mol/L ', 4 ' ', 4 ' ' '-tetramino phthalocyanine transient metal complex dimethyl formamide solution in, tetrabutylammonium perchlorate's concentration is 0.2～1.0mol/L, polymerization current potential 0.8～1.5V, polymerization time 30～200min.
5. the preparation method of membrane electrode according to claim 1 is characterized in that the electrochemical polymerization mode of polymerization porphyrin transition metal complexes:
Take the carbon paper that scribbles diffusion layer as work electrode, take dimethyl formamide as solvent, electrolyte is the tetrabutylammonium perchlorate, and Ag/AgCl is reference electrode, adopts 5 of 0.1～0.6mol/L, 10, in 15,20-tetramino porphyrin transition metal complexes dimethyl formamide solution, tetrabutylammonium perchlorate's concentration is 0.1～0.6mol/L, polymerization current potential 0.88～1.25V, polymerization time 60～200min.
6. the preparation method of according to claim 1～5 described membrane electrodes of arbitrary claim is characterized in that:
The weight concentration of Nafion emulsion is that the weight concentration of 1～3%, PTFE emulsion is 2～4%, and the activated carbon addition is 5～10mg/5mL emulsion.
7. the preparation method of membrane electrode according to claim 6, the weight concentration that it is characterized in that glue-line Nafion emulsion is 3～5wt%.
8. the preparation method of membrane electrode according to claim 6, it is characterized in that spraying different emulsions need to be according to fixing relative direction, and each direction is identical, and the vacuumize temperature of emulsion is 70～120 ℃.
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| CN102881925B (en) * | 2012-09-28 | 2015-07-15 | 孙公权 | Novel ordering membrane electrode and preparation method and application thereof |
| CN103887531B (en) * | 2012-12-21 | 2016-08-03 | 中国科学院大连化学物理研究所 | A kind of ordering gas-diffusion electrode and preparation thereof and application |
| CN104157878A (en) * | 2014-08-22 | 2014-11-19 | 南京中储新能源有限公司 | Carbon nanotube array-nano polyaniline-sulfur composite positive electrode, and preparation method and application thereof |
| CN105576264B (en) * | 2014-10-15 | 2018-12-07 | 中国科学院大连化学物理研究所 | A kind of gas-diffusion electrode and its preparation and application |
| CN106898497A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | Bifunctional electrodes and its preparation method and application |
| CN107247081A (en) * | 2017-04-26 | 2017-10-13 | 浙江理工大学 | Carbon nano-tube fibre supported metal phthalocyanine prepares electrochemical sensor |
| CN108717075B (en) * | 2018-05-21 | 2019-05-10 | 大连理工大学 | Utilize the method for the film modified electrode slice detection uric acid of electro-deposition perfluorinated sulfonic acid |
| CN110112428A (en) * | 2019-05-10 | 2019-08-09 | 南开大学 | The active carbon air cathode of nitrogen-doped carbon nano wire modified microorganism fuel cell |
| CN111096705A (en) * | 2019-12-29 | 2020-05-05 | 苏州路之遥科技股份有限公司 | Production process of detachable heating toilet seat |
| CN114976050B (en) * | 2022-05-13 | 2024-06-25 | 上海碳际实业集团有限公司 | Preparation process of gas diffusion layer for fuel cell |
| CN115974670B (en) * | 2023-01-10 | 2024-11-05 | 南京工业大学 | Method for synthesizing 2-methyl-1, 4-naphthoquinone by oxidation of polymerized cobalt phthalonitrile catalyst |
| CN116759590B (en) * | 2023-08-17 | 2023-10-31 | 安徽明天新能源科技有限公司 | Preparation method of multi-layer catalytic layer structure CCM |
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| CN1269429A (en) * | 1999-04-07 | 2000-10-11 | 中国科学院大连化学物理研究所 | Preparation of three-in-one thin-layer hydrophobic catalyst electrode and membrane electrode assembly |
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