CN1947835A - Pulse electrodeposition method for producing catalyst for direct methanol fuel cell - Google Patents
Pulse electrodeposition method for producing catalyst for direct methanol fuel cell Download PDFInfo
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- CN1947835A CN1947835A CNA2006101129208A CN200610112920A CN1947835A CN 1947835 A CN1947835 A CN 1947835A CN A2006101129208 A CNA2006101129208 A CN A2006101129208A CN 200610112920 A CN200610112920 A CN 200610112920A CN 1947835 A CN1947835 A CN 1947835A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title abstract description 54
- 239000000446 fuel Substances 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 19
- 235000019241 carbon black Nutrition 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000003223 protective agent Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000002407 reforming Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000011865 Pt-based catalyst Substances 0.000 abstract 1
- 238000006056 electrooxidation reaction Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000000366 colloid method Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
一种直接甲醇燃料电池用催化剂的制备方法，涉及到以Pt为基础的直接甲醇燃料电池催化剂的制备，其特征在于：将Pt直接沉积在活性炭黑/离子乳液载体上。通过调整前驱体的初始浓度以及脉冲电沉积的电流密度、电流的通断时间比、脉冲频率等控制参数，合成出Pt催化剂。本发明不是采用以化学试剂作为还原剂的化学合成的方法，不需要将金属前体进行预处理，也不需要任何表面活性剂或其它保护剂、还原剂，而是采用通过施加电信号、计算机控制的电化学合成方法，方法简单，可控性强，合成的Pt催化剂纳米颗粒的形貌为花状多孔纳米团簇，具有大的比表面积，能大幅度提高催化剂的甲醇电氧化催化活性，所制备的产品不仅可以用于直接甲醇燃料电池阳极催化剂，同时还可以用于其它燃料电池阴、阳极催化剂，以及气体重整、有机物裂解、污染物治理等许多领域。
A method for preparing a catalyst for a direct methanol fuel cell relates to the preparation of a Pt-based catalyst for a direct methanol fuel cell, and is characterized in that the Pt is directly deposited on an activated carbon black/ionic emulsion carrier. The Pt catalyst was synthesized by adjusting the initial concentration of the precursor, the current density of the pulse electrodeposition, the on-off time ratio of the current, and the pulse frequency and other control parameters. The present invention is not a chemical synthesis method using chemical reagents as reducing agents, and does not require pretreatment of metal precursors, nor does it require any surfactants or other protective agents or reducing agents, but uses electrical signals, computer The controlled electrochemical synthesis method is simple and highly controllable. The morphology of the synthesized Pt catalyst nanoparticles is a flower-like porous nano-cluster with a large specific surface area, which can greatly improve the catalytic activity of the catalyst for methanol electrooxidation. The prepared product can be used not only as an anode catalyst for direct methanol fuel cells, but also as cathode and anode catalysts for other fuel cells, as well as in many fields such as gas reforming, organic matter cracking, and pollutant treatment.
Description
Technical field
The invention belongs to the technical field and the fuel cell field of producing catalyst with the chemical method, specially refer to DMFC Preparation of catalysts method based on platinum.
Background technology
DMFC (DMFC) is because of its energy density height, liquid fuel are easy to transportation and storage, running temperature is low, and has vast potential for future development in fields such as portable power supply, electric automobiles.One of critical material of DMFC is an electrode catalyst, its active performance that directly influences battery.Noble metal platinum also has excellent catalytic performance under low temperature (＜80 ℃) service condition, so the used eelctro-catalyst of DMFC all is main component with platinum at present.But because the platinum resource-constrained costs an arm and a leg the requirement that its utilization rate in DMFC does not also reach commercial applications.Therefore in the past few years, in order further to improve the activity of unit mass platinum catalyst, researchers study several different methods, thereby have the Pt catalyst that high-specific surface area has the nanoscale of high catalytic activity in the hope of synthesizing.At present; what adopt usually is the method for electronation; mainly comprise infusion process and colloid method; as document M.G tz; H.Wendt; Binary and ternary anodecatalyst formulations including the elements W; Sn and Mo for PEMFCs operated onmethanol or reformate gas; Electrochimica Acta; it is catalyst based to adopt infusion process and colloid method to prepare Pt respectively among 43 (1998) 3637-3644; studies show that the catalyst performance that colloid method synthesizes is better, the catalytic performance of methanol electro-oxidizing is better than the catalyst that infusion process synthesizes, but this method need adopt larger molecular organics to make surperficial protective agent and reducing agent; also must in the anhydrous and oxygen-free system, prepare simultaneously; complex operation, process are difficult for accurately control, and the Preparation of Catalyst cost is higher.Compare with the method for electronation, adopt the research of electrochemical reduction less, document J.J.Whalen III, J.D.Weiland, P.C Searson, Electrochemical Deposition of Platinum from Aqueous AmmoniumHexachloroplatinate Solution, Journal of The Electrochemical Society, propose on golden film, to adopt potentiostatic method to carry out electro-deposition among 152 (11) (2005) C738-C743, contrasted respectively current potential constant when the different potentials value, the particle of the Pt that electro-deposition goes out, pattern, but particle size is all bigger, thereby Pt activity of such catalysts surface area ratio is less, causes catalytic activity lower.
Summary of the invention
The present invention proposes to adopt the pulse electrodeposition method, and Pt directly is deposited on activated carbon black and the carrier that the ion emulsion is mixed.The initial concentration by adjusting presoma and the current density of pulse electrodeposition, the make-and-break time ratio (t of electric current
On/ t
Off), control such as pulse frequency parameter, to prepare pattern on activated carbon black/ion emulsion carriers be flower-shaped porous nano cluster and have than bigger serface, thereby possess the Pt catalyst metals particle of high methanol electro-oxidizing-catalyzing activity.The present invention not only can increase substantially the methanol electro-oxidizing activity of catalyst, and reaction temperature is lower, and preparation process is simple, and electric impulse signal is adopted in operation, and controllability is good.
Preparation process of the present invention may further comprise the steps:
1, activated carbon black was heated 10～60 minutes in 500～700 ℃ of air atmospheres, ratio according to 3～8 milligrams of activated carbon blacks of every milliliter of ethanol adding places ethanol with activated carbon black then, to contain the alcohol suspending liquid of activated carbon black and mass percent again and be 5% ion emulsion and make mixed liquor in 100: 1 by volume～100: 7, the mixed liquor ultrasonic wave was disperseed 30～80 minutes, form the carbon slurry;
2, pipette 120～300 μ L carbon slurry by every square centimeter of matrix area, drip on graphite, carbon paper or other the conductive matrix surface, after treating that ethanol evaporation is intact, make working electrode used in the electrodeposition process, with working electrode 50～80 ℃ of vacuum drying 3～15 hours;
3, in the electrolyte of preparation in advance, as negative electrode, platinum electrode is as anode with working electrode, saturated calomel electrode (SCE) is formed three-electrode system as reference electrode, carries out pulse electrodeposition, the temperature of electro-deposition is 20～70 ℃, and the current density of pulse electrodeposition is 0.4～50.0mA/cm
2, electric current make-and-break time ratio t
On/ t
OffBe 1: 0.5～10.
The argon gas that leads to 20～60min before the pulse electrodeposition earlier in electrolyte in the process of carrying out pulse electrodeposition, feeds argon gas to eliminate the influence of dissolved oxygen in the solution always in electrolyte.On working electrode, platinum ion is reduced to metal platinum, obtains nano level platinum catalyst.
The above-mentioned electrolyte of preparing is: 0.5molL
-1H
2SO
4With 0.5～4.0mmolL
-1The mixed solution of chloroplatinic acid.
The Pt catalyst that the present invention synthesizes is not owing to be to adopt with the chemical synthesis process of chemical reagent as reducing agent, but adopt by applying the electrochemical method for synthesizing of the signal of telecommunication, therefore method is simple, controllability is strong, the pattern of synthetic Pt catalyst nano particle is flower-shaped porous nano cluster, having big specific area and high methanol electro-oxidizing-catalyzing activity, is 1.0molL in concentration
-1CH
3High methanol electroxidation peak current density in the OH solution can reach 516mA mg
-1, the catalyst that utilizes the preparation of this method demonstrates active preferably to the electroxidation of methyl alcohol.
Compared with prior art, the present invention does not need metal precursor is carried out preliminary treatment, without any need for surfactant or other protective agent, reducing agent yet.Because deposition process is by applying the electrochemical reduction that pulse signal carries out Pt, the signal of telecommunication can adopt computer control, so process is easy to control, simple efficient, reaction temperature is low, can carry out electro-deposition under the room temperature condition, makes that the Preparation of catalysts cost is lower.
The prepared product of the present invention not only can be used for the DMFC anode catalyst, simultaneously can also be used for other fuel cell cathode and anode catalyst, and gas reforming, organic matter cracking, pollutant control, and organic many fields such as synthetic.
Description of drawings
Fig. 1 amplifies 10,000 times ESEM shape appearance figure for embodiment 2 synthetic catalyst.
Fig. 2 amplifies 200,000 times ESEM shape appearance figure for embodiment 2 synthetic catalyst.
Fig. 3 is the anodic oxidation of methanol cyclic voltammetry curve of the synthetic catalyst of embodiment 1
Fig. 4 is the anodic oxidation of methanol cyclic voltammetry curve of the synthetic catalyst of embodiment 2.
Fig. 5 is the anodic oxidation of methanol cyclic voltammetry curve of the synthetic catalyst of embodiment 3.
Fig. 6 is the anodic oxidation of methanol cyclic voltammetry curve of commodity Pt/C catalyst.
The specific embodiment
In order to make test data have comparativity, so under identical test condition variant catalyst is carried out the cyclic voltammetric test, i.e. test condition unification is:
Working electrode: the graphite electrode of having coated Catalytic Layer;
Anode: platinum electrode; Reference electrode: saturated calomel electrode (SCE);
Electrolyte: 0.5molL
-1H
2SO
4And 1.0molL
-1CH
3The mixed solution of OH;
Potential scanning speed=10mVs
-1Electrolyte temperature: 30 ℃.
Embodiment 1:
Activated carbon black Vulcan XC-72 was heated 60 minutes at 500 ℃ in advance.Take by weighing 40 milligrams of activated carbon blacks and place 10 milliliters of ethanol, add 350 μ L mass percents and be 5% ion emulsion Nafion solution, the mixed liquor ultrasonic wave was disperseed 80 minutes, form the carbon slurry.Get 100 μ L carbon slurry, drip on the graphite matrix, after treating that ethanol evaporation is intact, with electrode 75 ℃ of following vacuum drying 5 hours, make the working electrode that electro-deposition is adopted, working electrode is carried out electro-deposition, the employing platinum electrode is an anode, saturated calomel electrode (SCE) is a reference electrode, and electrolyte is 0.5molL
-1H
2SO
4And 0.5mmolL
-1The mixed solution of chloroplatinic acid, the temperature of electro-deposition are 45 ℃, and the argon gas of logical 20min is to eliminate the influence of dissolved oxygen in the solution in the electro-deposition forward direction electrolyte.When carrying out electro-deposition, in electrolyte, feed argon gas always.The current density that pulse electrodeposition adopts is 4.0mA/cm
2, t
On/ t
OffBe 100ms/400ms.Make the nano level Pt/C catalyst of high degree of dispersion, loading reaches 144 μ g/cm
2
Embodiment 2:
Activated carbon black Vulcan XC-72 was heated 30 minutes at 600 ℃ in advance.Take by weighing 50 milligrams of activated carbon blacks and place 10 milliliters of ethanol, add 200 μ L mass percents and be 5% ion emulsion Nafion solution, the mixed liquor ultrasonic wave was disperseed 30 minutes, form the carbon slurry.Get 100 μ L carbon slurries, drip on the graphite matrix, treat that ethanol evaporation is intact after, with 60 ℃ of vacuum drying of electrode 8 hours, make the working electrode that electro-deposition is adopted.Adopting platinum electrode is to electrode, and saturated calomel electrode (SCE) is a reference electrode, and electrolyte is 0.5molL
-1H
2SO
4And 1.0mmolL
-1The mixed solution of chloroplatinic acid, the temperature of electro-deposition are 65 ℃.The argon gas of logical 30min is to eliminate the influence of dissolved oxygen in the solution in the electro-deposition forward direction electrolyte.When carrying out electro-deposition, in electrolyte, feed argon gas.The current density of pulse electrodeposition is 6.0mA/cm
2, t
On/ t
OffBe 1s/5s.Make the nano level Pt/C catalyst of high degree of dispersion, loading is 110 μ g/cm
2SEM experimental result among Fig. 1, Fig. 2 shows that noble metal is uniformly dispersed on carrier, be the flower-shaped porous nano cluster particle with bigger serface about 100 nanometers.
Embodiment 3:
Activated carbon black Vulcan XC-72 was heated 20 minutes at 700 ℃ in advance.Take by weighing 70 milligrams of activated carbon blacks and place 9 milliliters of ethanol, add 500 μ L mass percents and be 5% ion emulsion Nafion solution, the mixed liquor ultrasonic wave was disperseed 50 minutes, form the carbon slurry.Get 80 μ L carbon slurries, drip on the graphite matrix, treat that ethanol evaporation is intact after, with 50 ℃ of vacuum drying of electrode 12 hours, make the working electrode that electro-deposition is adopted.Adopting platinum electrode is to electrode, and saturated calomel electrode (SCE) is a reference electrode, and electrolyte is 0.5molL
-1H
2SO
4And 4.0mmolL
-1The mixed solution of chloroplatinic acid, the temperature of electro-deposition are 25 ℃.The argon gas of logical 40min is to eliminate the influence of dissolved oxygen in the solution in the electro-deposition forward direction electrolyte.When carrying out electro-deposition, in electrolyte, feed argon gas.The current density of pulse electrodeposition is 25.0mA/cm
2, t
On/ t
OffBe 100ms/300ms.Make the nano level Pt/C catalyst of high degree of dispersion, loading is 85 μ g/cm
2
As seen Fig. 3 as a result, Fig. 4, Fig. 5 of testing by the cyclic voltammetric that the catalyst that above embodiment synthesized is carried out compare with Fig. 6 as a result of the cyclic voltammetric test that commercial catalyst carries out: compare with commodity Pt/C catalyst, the take-off potential of just sweeping the methanol electro-oxidizing peak of Pt/C catalyst is lower, and under the same scan current potential, the Pt/C catalyst obviously has higher current density, illustrate the Pt/C catalyst can be under lower current potential the more methyl alcohol generation of catalysis electrochemical reaction, promptly have better methanol electro-oxidizing-catalyzing activity.
Claims (3)
1, a kind of pulse electrodeposition prepares the method for DMFC with catalyst, it is characterized in that preparation process may further comprise the steps:
1) activated carbon black was heated 10～60 minutes in 500～700 ℃ of air atmospheres, ratio according to 3～8 milligrams of activated carbon blacks of every milliliter of ethanol adding places ethanol with activated carbon black then, to contain the alcohol suspending liquid of activated carbon black and mass percent again and be 5% ion emulsion and make mixed liquor in 100: 1 by volume～100: 7, the mixed liquor ultrasonic wave was disperseed 30～80 minutes, form the carbon slurry;
2) pipette 120～300 μ L carbon slurry by every square centimeter of matrix area, drip on graphite, carbon paper or other the conductive matrix surface, after treating that ethanol evaporation is intact, make working electrode used in the electrodeposition process, with working electrode 50～80 ℃ of vacuum drying 3～15 hours;
3) in the electrolyte of preparation in advance, as negative electrode, platinum electrode is as anode with working electrode, and saturated calomel electrode is carried out pulse electrodeposition as reference electrode, and the temperature of electro-deposition is 20～70 ℃, and the current density of pulse electrodeposition is 0.4～50.0mA/cm
2, electric current make-and-break time ratio t
On/ t
OffBe 1: 0.5～10.
2, pulse electrodeposition as claimed in claim 1 prepares the method for DMFC with catalyst, it is characterized in that, the argon gas of logical 20～60min in the process of carrying out pulse electrodeposition, feeds argon gas always in the pulse electrodeposition forward direction electrolyte in electrolyte.
3, pulse electrodeposition as claimed in claim 1 prepares the method for DMFC with catalyst, it is characterized in that the above-mentioned electrolyte of preparing is 0.5molL
-1H
2SO
4With 0.5～4.0mmolL
-1The mixed solution of chloroplatinic acid.
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|---|---|---|---|
| CNB2006101129208A CN100418624C (en) | 2006-09-12 | 2006-09-12 | A kind of pulse electrodeposition prepares the method for direct methanol fuel cell catalyst |
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|---|---|---|---|
| CNB2006101129208A CN100418624C (en) | 2006-09-12 | 2006-09-12 | A kind of pulse electrodeposition prepares the method for direct methanol fuel cell catalyst |
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|---|---|
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| CN100418624C CN100418624C (en) | 2008-09-17 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102235214A (en) * | 2010-04-26 | 2011-11-09 | 通用汽车环球科技运作有限责任公司 | Start-stop hybrid exothermic catalyst heating system |
| CN101471445B (en) * | 2007-12-11 | 2011-11-16 | 通用汽车环球科技运作公司 | Method of treating nanoparticles using an intermittently processing electrochemical cell |
| CN102477564A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for preparing SPE (solid polymer electrolyte) anodic oxygen evolution catalysts for water electrolysis |
| CN109234761A (en) * | 2018-10-09 | 2019-01-18 | 天津城建大学 | A kind of Co producing hydrogen for photoelectrocatalysis3O4The preparation method of/Pt laminated film |
| CN109331820A (en) * | 2018-10-29 | 2019-02-15 | 大连理工大学 | A method for preparing Pt-based catalyst by pulse electrodeposition under ultrasonic conditions |
| CN111939897A (en) * | 2020-08-26 | 2020-11-17 | 上海交通大学 | A kind of platinum nanowire particle catalyst preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6258239B1 (en) * | 1998-12-14 | 2001-07-10 | Ballard Power Systems Inc. | Process for the manufacture of an electrode for a solid polymer fuel cell |
-
2006
- 2006-09-12 CN CNB2006101129208A patent/CN100418624C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101471445B (en) * | 2007-12-11 | 2011-11-16 | 通用汽车环球科技运作公司 | Method of treating nanoparticles using an intermittently processing electrochemical cell |
| CN102235214A (en) * | 2010-04-26 | 2011-11-09 | 通用汽车环球科技运作有限责任公司 | Start-stop hybrid exothermic catalyst heating system |
| CN102235214B (en) * | 2010-04-26 | 2016-01-13 | 通用汽车环球科技运作有限责任公司 | The exothermic catalyst heating system of start-stop hybrid |
| CN102477564A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for preparing SPE (solid polymer electrolyte) anodic oxygen evolution catalysts for water electrolysis |
| CN102477564B (en) * | 2010-11-23 | 2014-11-19 | 中国科学院大连化学物理研究所 | A kind of method for preparing SPE water electrolysis anode oxygen evolution catalyst |
| CN109234761A (en) * | 2018-10-09 | 2019-01-18 | 天津城建大学 | A kind of Co producing hydrogen for photoelectrocatalysis3O4The preparation method of/Pt laminated film |
| CN109331820A (en) * | 2018-10-29 | 2019-02-15 | 大连理工大学 | A method for preparing Pt-based catalyst by pulse electrodeposition under ultrasonic conditions |
| CN111939897A (en) * | 2020-08-26 | 2020-11-17 | 上海交通大学 | A kind of platinum nanowire particle catalyst preparation method |
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|---|---|
| CN100418624C (en) | 2008-09-17 |
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