CN102447116A - Preparation method for membrane electrode - Google Patents
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- CN102447116A CN102447116A CN2010106187210A CN201010618721A CN102447116A CN 102447116 A CN102447116 A CN 102447116A CN 2010106187210 A CN2010106187210 A CN 2010106187210A CN 201010618721 A CN201010618721 A CN 201010618721A CN 102447116 A CN102447116 A CN 102447116A
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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 membrane electrode preparation method, belong to the low-temperature fuel cell technical field.
Background technology
Membrane electrode is the core and the key component of fuel cell, and the quality of its performance directly affects the quality of fuel battery performance.So membrane electrode preparation method and technical study are one of most important problems of fuel cell field always.The reaction on electrode of fuel and oxidant is very complicated electrocatalytic reaction in the fuel cell; As; Negative electrode is from the mass transfer aspect; Oxygen arrives negative electrode through diffusion layer; Obtain electronics in the reaction of cathod catalyst surface generation electrical catalyze reduction and combine to generate water with the proton that anode passes over through PEM, 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-liquid transfer 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 also is 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 make up separately and do not influence each other.As be employed in the CNT of vertical arrangement on the PEM; CNT (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 the particle; Another side, no CNT carry out carbonylation and form hydrophilic area (fluid transfer).
Existing membrane electrode preparation method has: be coated with cream method, spread coating, spraying process, commentaries on classics platen press, self-assembly method etc.; Gas delivery passage in the negative electrode, fluid transfer, electron propagation ducts and proton transport passage are not very orderly; The comprehensive transmission poor performance influences the performance of membrane electrode.
Summary of the invention
The object of the present invention is to provide a kind of new-type membrane electrode preparation method, 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.
Membrane electrode preparation method of the present invention at first prepares negative electrode and anode, again negative electrode, anode and Nafion intermediate coat is made up the structure that sandwiches, and it is characterized in that the preparation method of negative electrode is following:
(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 activated carbon respectively, under ultrasonic wave, disperse 2h, with spray gun in the staggered spraying of different directions Nafion emulsion and PTFE emulsion repeatedly, grasp at 5～15 times respectively, spray completion all needs vacuumize at every turn;
(4) again with the spraying of glue-line Nafion emulsion, glue-line outside vacuumize makes makes negative electrode.
Wherein:
Diffusion layer is conventional diffusion layer, and the paste blade coating of being made up 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 obtains finely dispersed suspension-turbid liquid; Under 60～70 ℃ of air dry ovens, be concentrated into paste, cover with paint, lacquer, colour wash, etc. 2 * 2cm with the method for brushing
2T-90 carbon paper surface (toray company), coating layer thickness dries at 0.2～0.5mm 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 a pure water, and electrolyte is a lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is a saturated calomel electrode;
Logical nitrogen 15～35min in the pyrroles's of containing 0.3～0.5mol/L solution, then, constant potential polymerase 17 0～120s obtains 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 a pure water, and electrolyte is a lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is a saturated calomel electrode;
To concentration is logical nitrogen 15～35min in the solution of aniline of 0.5～0.8mol/L, and then, constant potential polymerization 120～149s obtains 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:
(transition metal ions selects Fe to the polymerized phthalocyanine transition metal in the polymerized phthalocyanine complex
2+, Fe
3+, Co
2+, Ni
2+, Mn
2+, or Pt
2+) the electrochemical polymerization mode of complex:
Carbon paper to scribble diffusion layer is a work electrode, thinks solvent, and electrolyte is the tetrabutylammonium perchlorate, and Ag/AgCl is a reference electrode, logical N before the polymerization
2Deoxygenation is adopted 4,4 of 0.1～0.5mol/L ', 4 ", 4 ' " in the tetramino phthalocyanine transient metal complex dimethyl formamide solution, tetrabutylammonium perchlorate's concentration is 0.2～1.0mol/L, polymerization 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:
Carbon paper to scribble diffusion layer is a work electrode, is solvent with the dimethyl formamide, and electrolyte is the tetrabutylammonium perchlorate; Ag/AgCl is a reference electrode, adopts 5,10 of 0.1～0.6mol/L; 15, in the 20-tetramino porphyrin transition metal complexes dimethyl formamide solution, tetrabutylammonium perchlorate's concentration is 0.1～0.6mol/L; Polymerization potential 0.88～1.25V, polymerization time 60～200min.
In the emulsion of spraying:
The weight concentration of Nafion emulsion is 1～3%, and the weight concentration of 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, like a spraying from left to right, a spraying from right to left hockets successively, and repeatedly spraying is generally grasped at 5～15 times, does 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, and 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: having between the regular nano wire catalytic reaction zone respectively towards fixing direction spraying Nafion emulsion and PTFE emulsion, and in the heat drying process, the Nafion emulsion of polarity formation hydrophilic region; Form hydrophobic region in the nonpolar PTFE emulsion dry run, the two repels because polarity is different each other, can not mix.Hydrophobic region and the hydrophilic area can formation rule arranged of the result of spraying repeatedly, thus realize that the hydrophilic area space forms the transmission channels and hydrophilic area Nafion matrix formation proton transfer passage of water.The space forms the gas transfer passage between the hydrophobic region.The nano wire polymer is a 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 balanced requirement of various aspects of performance.
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 in the polymer-membrane fuel battery (to comprise PEMFC and DMFC), phosphoric acid type fuel cell, metal air fuel cell, alkaline fuel cell etc. also can be used for fields such as ultracapacitor and electrochemical sensor.
With the negative electrode of preparation and common spraying or be coated with the anode that the cream method obtains and the Nafion film of handling (Nafion 117 etc.) is combined into sandwich structure, the Nafion film is in the centre.Hot pressing 80～120s can obtain membrane electrode under 13～15MPa.
Adopt the membrane electrode that obtains the method that well known to a person skilled in the art to assemble monocell, adopt fuel battery test system to test, can obtain the performance of battery then.The catalyst that the performance of battery and chemical synthesis process obtain uses 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
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
Membrane electrode preparation method of the present invention at first prepares negative electrode and anode, again negative electrode, anode and Nafion intermediate coat is made up the structure that sandwiches, and the preparation method of its negative electrode is following:
(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 a pure water, and electrolyte is a lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is a saturated calomel electrode;
Logical nitrogen 25min in the pyrroles's of containing 0.3mol/L solution, then, constant potential polymerization 100s obtains polypyrrole nano line under 0.85V.To polypyrrole nano line in the cobalt acetate solution of 0.5mol/L, saturated calomel electrode is a 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 activated carbon respectively with weight concentration; Addition is the 6mg/5mL emulsion, under ultrasonic wave, disperses 2h, then respectively with spray gun different directions staggered spraying Nafion emulsion and PTFE emulsion respectively 5 times; The Nafion emulsion sprays from left to right; The PTFE emulsion sprays from right to left, and it is 120 ℃ that each spraying completion all needs vacuumize, vacuumize temperature.
(4) using weight concentration again is the spraying of 5% glue-line Nafion emulsion, makes outer glue-line, makes negative electrode.
The mix catalyst precarsor of other transition metal, method is the same, just changes cobalt acetate solution into other metal salt solution and gets final product.
Embodiment 2
Electrochemical polymerization method prepares polyaniline nano-line, and its method just changes the pyrroles into aniline, sample solution concentration, polymerization potential and asynchronism(-nization) with embodiment 1.Aniline concentration 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 following:
The mix catalyst precarsor of other transition metal, method is the same, just changes cobalt acetate solution into other metal salt solution, gets final product.
Embodiment 3
Electrochemical polymerization method prepares polymerized phthalocyanine complex nano wire.
The preparation method who gathers the phthalocyanine complex nano wire is with embodiment 1; Just change aqueous solvent into dimethyl formamide (DMF) and (will carry out purifying and decompression distillation before using; To remove moisture and impurity), support electrolyte with tetrabutylammonium perchlorate (TBAP), reference electrode is used Ag/AgCl.", 4 ' " the tetramino FePC that at the DMF solution 50mL of the TBAP of 0.5mol/L, adds 4,4 of 0.025mmol ', 4 is made into the solution of 0.5mol/L, logical high-purity N before the polymerization
230min to be to remove the oxygen in the 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 gets 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 into, and 20-tetramino Cobalt Porphyrin 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 5,10,15 into, and other metal complex of 20-tetramino porphyrin gets final product.
Embodiment 5
The activation of nano wire polyalcohol catalyst precursor.
The catalyst precarsor (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.Activated carbon (the XC-72 that in the PTFE emulsion (Dupont) of the Nafion of 5mL 2wt% emulsion (Du pont) and 5mL 3%, adds 5mg respectively; Cabot) help dispersion 2h down at ultrasonic wave, adopt spray gun respectively 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 accomplished all need handle 35min down for 100 ℃ at vacuum drying chamber, and each thickness does not surpass 200nm.At last, use 5% Nafion emulsion spraying, thickness 100nm, cathode portion can be accomplished.
Adopt and use the same method, can obtain the anode of different situations, just change the mass concentration of Nafion emulsion and PTFE solution respectively, the activated carbon quality of adding changes or changes the technologies such as number of times that spray and gets 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 of handling (Nafion 117), the Nafion film is in the 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.Its result sees table 1.
Battery assembling and battery performance test.Membrane electrode assembling monocell embodiment obtains adopts fuel battery test system to test.Can obtain the performance of battery then.Its result sees table 1.
Claims (9)
1. a membrane electrode preparation method at first prepares negative electrode and anode, again negative electrode, anode and Nafion intermediate coat is made up the structure that sandwiches, and it is characterized in that the preparation method of negative electrode is following:
(1) adopts the electrochemical polymerization mode nano wire polyalcohol catalyst precursor that formation rule is arranged 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 activated carbon respectively, under ultrasonic wave, disperse 2h, with spray gun in the staggered spraying of different directions Nafion emulsion and PTFE emulsion repeatedly, spray completion all needs vacuumize at every turn respectively;
(4) again with the spraying of glue-line Nafion emulsion, make outer glue-line, make negative electrode.
2. membrane electrode preparation method according to claim 1 is characterized in that the nano wire polymer has doped polypyrrole transition metal, Polyaniline Doped transition metal, polymerized phthalocyanine complex and polymerization metalloporphyrin complex.
3. membrane electrode preparation method according to claim 2 is characterized in that the electrochemical polymerization mode of polypyrrole:
Environmental condition: solvent is a pure water, and electrolyte is a lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is a saturated calomel electrode;
Logical 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 obtains 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.
4. membrane electrode preparation method according to claim 2 is characterized in that the electrochemical polymerization mode of polyaniline:
Environmental condition: solvent is a pure water, and electrolyte is a lithium perchlorate, and work electrode is the carbon paper that scribbles diffusion layer, and reference electrode is a saturated calomel electrode;
To concentration is logical nitrogen 15～35min in the solution of aniline of 0.5～0.8mol/L; 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.
5. membrane electrode preparation method according to claim 2 is characterized in that the electrochemical polymerization mode of polymerized phthalocyanine transient metal complex in the polymerized phthalocyanine complex:
Carbon paper to scribble diffusion layer is a work electrode, is solvent with the dimethyl formamide, and electrolyte is the tetrabutylammonium perchlorate, and Ag/AgCl is a reference electrode, logical N before the polymerization
2Deoxygenation is adopted 4,4 of 0.1～0.5mol/L ', 4 ", 4 ' " in the tetramino phthalocyanine transient metal complex dimethyl formamide solution, tetrabutylammonium perchlorate's concentration is 0.2～1.0mol/L, polymerization potential 0.8～1.5V, polymerization time 30～200min.
6. membrane electrode preparation method according to claim 2 is characterized in that the electrochemical polymerization mode of polymerization porphyrin transition metal complexes:
Carbon paper to scribble diffusion layer is a work electrode, is solvent with the dimethyl formamide, and electrolyte is the tetrabutylammonium perchlorate; Ag/AgCl is a reference electrode, adopts 5,10 of 0.1～0.6mol/L; 15, in the 20-tetramino porphyrin transition metal complexes dimethyl formamide solution, tetrabutylammonium perchlorate's concentration is 0.1～0.6mol/L; Polymerization potential 0.88～1.25V, polymerization time 60～200min.
7. according to the described membrane electrode preparation method of the arbitrary claim of claim 1～6, it is characterized in that:
The weight concentration of Nafion emulsion is 1～3%, and the weight concentration of PTFE emulsion is 2～4%, and the activated carbon addition is 5～10mg/5mL emulsion.
8. membrane electrode preparation method according to claim 7, the weight concentration that it is characterized in that glue-line Nafion emulsion is 3～5wt%.
9. membrane electrode preparation method according to claim 7, it is characterized in that spraying different emulsions need be according to fixing different directions, and each direction is identical, and the vacuumize temperature of emulsion is 70～120 ℃.
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| CN102881925A (en) * | 2012-09-28 | 2013-01-16 | 孙公权 | Novel ordering membrane electrode and preparation method and application thereof |
| CN103887531A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Ordered gas diffusion electrode and preparation and application thereof |
| 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 |
| CN105576264A (en) * | 2014-10-15 | 2016-05-11 | 中国科学院大连化学物理研究所 | Gas diffusion electrode and preparation and application thereof |
| 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 |
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| CN102881925A (en) * | 2012-09-28 | 2013-01-16 | 孙公权 | Novel ordering membrane electrode and preparation method and application thereof |
| CN102881925B (en) * | 2012-09-28 | 2015-07-15 | 孙公权 | Novel ordering membrane electrode and preparation method and application thereof |
| CN103887531A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Ordered gas diffusion electrode and preparation 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 |
| CN105576264A (en) * | 2014-10-15 | 2016-05-11 | 中国科学院大连化学物理研究所 | Gas diffusion electrode and preparation and application thereof |
| 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 |
| CN108717075A (en) * | 2018-05-21 | 2018-10-30 | 大连理工大学 | The method for detecting uric acid using the film modified electrode slice of electro-deposition perfluorinated sulfonic acid |
| 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 |
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| CN116759590A (en) * | 2023-08-17 | 2023-09-15 | 安徽明天新能源科技有限公司 | Preparation method of composite CCM with high durability and low activation time and different catalytic layers |
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