CN1242506C - Preparation method of direct alcohol kind fuel battery negative electrode - Google Patents
Preparation method of direct alcohol kind fuel battery negative electrode Download PDFInfo
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- CN1242506C CN1242506C CNB03157808XA CN03157808A CN1242506C CN 1242506 C CN1242506 C CN 1242506C CN B03157808X A CNB03157808X A CN B03157808XA CN 03157808 A CN03157808 A CN 03157808A CN 1242506 C CN1242506 C CN 1242506C
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- alcohol
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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
The present invention relates to a method of preparing negative electrodes of direct alcohol fuel batteries, which mainly comprises: carbon fiber, an adhesive, a platinum or noble metal catalyst, alcohol, water, etc. are directly mixed in proportion (without using carbon paper), and then, an electrode is processed through casting, drying, rolling and die cutting. The preparing method of the present invention has the advantages of easy control of the electrode thickness, convenient regulation of the concentration gradient of catalysts in the thickness direction, favorable consistency of prepared electrodes, low preparing cost and favorable electrode properties, and the raw material utilization rate of platinum or noble metal reaches more than 90%. Simultaneously, the preparing method is suitable for mechanical scale production.
Description
Technical field
The present invention relates to a kind of manufacture method of electrode, particularly the manufacture method of direct alcohol fuel battery negative pole belongs to the fuel cell technology field.
Background technology
In view of small molecular alcohol class A fuel As such as methyl alcohol, ethanol have that the source is abundant, low price, toxicity are little, normal temperature is liquid down, outstanding advantages such as being easy to carry, storing and replenish, and corresponding directly alcohol fuel battery has the job stability height, need not good characteristics such as charging, noiselessness, and direct alcohol fuel battery is particularly suitable as the supporting power supply of small portable electronic device.In fact, direct alcohol fuel battery is a kind of as Proton Exchange Membrane Fuel Cells, except the fuel difference that adopts, miscellaneous part material and electric pile structure and Proton Exchange Membrane Fuel Cells are all basic identical, have also inherited the process characteristic and the technology path of Proton Exchange Membrane Fuel Cells on the preparation method substantially.
In order to improve the performance of Proton Exchange Membrane Fuel Cells negative pole, people have proposed a variety of preparation methods, as spraying process, knife coating, commentaries on classics platen press, filtration sedimentation, silk screen print method etc., these methods can form to a certain extent relatively and approach and uniform Catalytic Layer, help making full use of of platinum.But experiment showed, that the platinum or the noble metal utilance of close proton exchange membrane are the highest, reduce significantly away from the platinum or the noble metal utilance of proton exchange membrane.In addition, the content height of the ionic conduction high polymer of close film can increase the adhesion of film and catalyst, and improves proton by the diffusion velocity of catalyst surface to film.If but, can hinder the diffusion of reactant on the contrary to internal accelerator away from the too high levels of the ionic conduction high polymer of film.
And directly the alcohol fuel battery negative pole is as one of its core component, and the quality of its performance and the height of cost of manufacture will directly have influence on the performance and the price of direct alcohol fuel battery.Yet still do not prepare the special process technology of direct alcohol fuel battery negative pole at present, existing preparation technology still continues to use the preparation method of Proton Exchange Membrane Fuel Cells negative pole, but there is following shortcoming in these methods: the homogeneity of (1) electrode is relatively poor; (2) utilization rate of raw materials is lower, thereby causes higher cost of manufacture.Therefore, should manage on the thickness of electrode direction, to cause the concentration gradient of precious metal salt and ionic conduction high polymer to improve the utilance of platinum and precious metal salt, and then improve the performance of electrode.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of direct alcohol fuel battery negative pole, improve the homogeneity between thickness of electrode and the electrode, on the thickness direction of electrode, cause simultaneously the concentration gradient of platinum or precious metal salt and ionic conduction high polymer, improve the utilances of raw material in electrode manufacturing process and actual use such as platinum or precious metal salt, improve the performance of electrode, and reduce the cost of manufacture of electrode.The content of corresponding invention can be described below:
The first step: get the raw materials ready as following weight percent: platinum or noble metal catalyst 1～10%, carbon fiber 1～10%, binding agent 0.1～5%, alcohol 60～90%, water 5～15%.At first mixed carbon fibre, catalyst and alcohol 5～35 minutes in ultrasonic-wave crushing machine and planetary type precise machine mixer, hybrid adhesive and water 5～35 minutes in the same device of another one simultaneously; Then the homogeneous mixture of binding agent and water is joined in the mixed liquor of scattered carbon fiber, catalyst and alcohol and continue to stir 5～35 minutes.Used binding agent is one or more in perfluorinated sulfonic acid solution, Kynoar, the polyvinyl alcohol, and used alcohol is small molecule alcohols such as methyl alcohol, ethanol.
Second step: the even mixed liquor that the first step is made places the slurry bucket of casting machine, adopts the carrier of plastic films such as polyethylene or polypropylene as the negative pole wet film, and the thickness of control wet film is at 30～320 μ m.
The 3rd step: above-mentioned wet film and carrier are entered drying process device through the machinery pulling, control temperature at 60～100 ℃, time 1～12min.Dried is carried out in inert atmospheres such as the argon gas that flows, helium, nitrogen.
The 4th step: dried negative electrode film and carrier are continued by a roll squeezer, and roll-in pressure is 20～80kg/cm
2
The 5th step: the making for variable concentrations gradient negative pole on the thickness direction need repeat the first step to the corresponding steps in four steps, general 3～5 times, regulate the allocation ratio of catalyst, carbon fiber, binding agent, alcohol and water simultaneously, increase or reduce the ratio of catalyst according to the concentration gradient that on thickness direction, increases successively or reduce successively.
The 6th step: at last negative electrode film and carrier are peeled off, negative electrode film enters stamping machine and adopts the punch die of required size to carry out die-cut.
The present invention is owing to adopted above technical scheme, promptly adopted the slurry of optimal components ratio to form, and the The tape casting that can accurately control wet-film thickness prepares wet film, in conjunction with dry, means such as roll-in, increase successively or the platinum that reduces successively or the concentration gradient of noble metal on thickness direction, have been formed, can improve the utilances of raw material in electrode manufacturing process and actual use such as platinum or noble metal greatly, improved the performance of electrode, reduce the cost of manufacture of direct alcohol fuel battery negative pole significantly, guaranteed the homogeneity between thickness of electrode and the electrode simultaneously.
Embodiment
Further specify the specific embodiment of the present invention below by embodiment.
Embodiment 1:
The first step: take by weighing 1.5g PtRu/C catalyst, 1.8g carbon fiber, 0.5g perfluorinated sulfonic acid solution, 40g ethanol and 4.5g water.At first mixed carbon fibre, catalyst and ethanol 20 minutes in ultrasonic-wave crushing machine and planetary type precise machine mixer mixed perfluorinated sulfonic acid solution and water 20 minutes simultaneously in the same device of another one; Then the homogeneous mixture of perfluorinated sulfonic acid and water is joined in the mixed liquor of scattered carbon fiber, catalyst and ethanol and continue to stir 20 minutes.
Second step: the even mixed liquor that the first step is made places the slurry bucket of casting machine, adopts the carrier of polyacrylic film as the negative pole wet film, and the thickness of control wet film is at 90 μ m.
The 3rd step: above-mentioned wet film and carrier are entered drying process device by the machinery pulling, and the control temperature is at 75 ℃, and time 3min carries out dried in flowing nitrogen.
The 4th step: dried negative electrode film and carrier are continued by a roll squeezer, and roll-in pressure is 32kg/cm
2Subsequently negative electrode film and polypropylene carrier are peeled off, negative electrode film enters stamping machine and adopts the punch die of 100mm * 100mm to carry out die-cut.So far, negative pole is made and is finished.
Embodiment 2:
The first step: take by weighing 1.8g PtRu/C catalyst, 2.0g carbon fiber, 0.6g perfluorinated sulfonic acid solution, 45g ethanol and 5.0g water.At first mixed carbon fibre, catalyst and ethanol 20 minutes in ultrasonic-wave crushing machine and planetary type precise machine mixer mixed perfluorinated sulfonic acid solution and water 20 minutes simultaneously in the same device of another one; Then the homogeneous mixture of perfluorinated sulfonic acid and water is joined in the mixed liquor of scattered carbon fiber, catalyst and ethanol and continue to stir 20 minutes.
Second step: the even mixed liquor that the first step is made places the slurry bucket of casting machine, adopts the carrier of polyacrylic film as the negative pole wet film, and the thickness of control wet film is at 90 μ m.
The 3rd step: above-mentioned wet film and carrier are entered drying process device by the machinery pulling, and the control temperature is at 75 ℃, and time 5min carries out dried in the argon gas that flows.
The 4th step: dried negative electrode film and carrier are continued by a roll squeezer, and roll-in pressure is 32kg/cm
2
The 5th step: the making for three kinds of concentration catalyst negative poles on the thickness direction need repeat the corresponding steps in four steps of the first step to the 2 times, while is reduced to 1.2g and 0.6g with the content of catalyst successively, and the weight of carbon fiber, perfluorinated sulfonic acid solution, second alcohol and water is identical with ground floor; The THICKNESS CONTROL of second layer wet film is at 150 μ m; The THICKNESS CONTROL of the 3rd layer of wet film is at 210 μ m.
The 6th step: at last negative electrode film and polypropylene carrier are peeled off, negative electrode film enters stamping machine and adopts the punch die of 100mm * 100mm to carry out die-cut.So far, negative pole is made and is finished.
Embodiment 3:
The first step: take by weighing 0.6g PtRu/C catalyst, 2.0g carbon fiber, 0.6g perfluorinated sulfonic acid solution, 45g ethanol and 5.0g water.At first mixed carbon fibre, catalyst and ethanol 20 minutes in ultrasonic-wave crushing machine and planetary type precise machine mixer mixed perfluorinated sulfonic acid solution and water 20 minutes simultaneously in the same device of another one; Then the homogeneous mixture of perfluorinated sulfonic acid and water is joined in the mixed liquor of scattered carbon fiber, catalyst and ethanol and continue to stir 20 minutes.
Second step: the even mixed liquor that the first step is made places the slurry bucket of casting machine, adopts the carrier of polyacrylic film as the negative pole wet film, and the thickness of control wet film is at 60 μ m.
The 3rd step: above-mentioned wet film and carrier are entered drying process device by the machinery pulling, and the control temperature is at 75 ℃, and time 5min carries out dried in flowing nitrogen.
The 4th step: dried negative electrode film and carrier are continued by a roll squeezer, and roll-in pressure is 32kg/cm
2
The 5th step: the making for three kinds of concentration catalyst negative poles on the thickness direction need repeat the corresponding steps in four steps of the first step to the 2 times, while is increased to 1.2g and 1.8g with the content of catalyst successively, and the weight of carbon fiber, perfluorinated sulfonic acid solution, second alcohol and water is identical with ground floor; The THICKNESS CONTROL of second layer wet film is at 120 μ m; The THICKNESS CONTROL of the 3rd layer of wet film is at 210 μ m.
The 6th step: at last negative electrode film and polypropylene carrier are peeled off, negative electrode film enters stamping machine and adopts the punch die of 100mm * 100mm to carry out die-cut.So far, negative pole is made and is finished.
Claims (6)
1, a kind of Direct Alcohol Fuel Cell Anode Preparation Method, it is characterized in that: carbon fiber, binding agent, platinum or noble metal catalyst, alcohol and water are got the raw materials ready as following weight percent: platinum or noble metal catalyst 1～10%, carbon fiber 1～10%, binding agent 0.1～5%, alcohol 60～90%, water 5～15%, the order that slurry mixes is: A, mixed carbon fibre, platinum or noble metal catalyst and alcohol, hybrid adhesive and water simultaneously in ultrasonic-wave crushing and mechanical agitation process; B, the even mixed liquor of binding agent and water joined continue in scattered carbon fiber, catalyst and the pure mixed liquor to stir, until all mixing; Adopt The tape casting to form wet film then, the control wet-film thickness is 30～320 μ m, in the inert atmosphere that flows this wet film is carried out dried 1～12min again and obtains dry film, at last dry film is carried out roll-in and die-cutly prepares direct alcohol fuel battery negative pole.
2, by the described preparation method of claim 1, it is characterized in that different requirements according to electrode concentration gradient on thickness direction, curtain coating and roll process more than 3 or 3 are set, catalyst content increases successively or reduces in each operation.
3, by the described preparation method of claim 1, the carrier that it is characterized in that used negative pole wet film is one or more in the plastic films such as polypropylene, polyethylene.
4, by the described preparation method of claim 1, it is characterized in that used binding agent is one or more in perfluorinated sulfonic acid solution, Kynoar, the polyvinyl alcohol.
5, by the described preparation method of claim 1, the inert atmosphere that it is characterized in that the dried employing is one or more in argon gas, helium, the nitrogen.
6, by the described preparation method of claim 1, the pressure limit that it is characterized in that roll-in is 20～80kg/cm
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03157808XA CN1242506C (en) | 2003-04-17 | 2003-08-27 | Preparation method of direct alcohol kind fuel battery negative electrode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN03113246.4 | 2003-04-17 | ||
| CN03113246 | 2003-04-17 | ||
| CNB03157808XA CN1242506C (en) | 2003-04-17 | 2003-08-27 | Preparation method of direct alcohol kind fuel battery negative electrode |
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| Publication Number | Publication Date |
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| CN1514505A CN1514505A (en) | 2004-07-21 |
| CN1242506C true CN1242506C (en) | 2006-02-15 |
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| CNB03157808XA Expired - Fee Related CN1242506C (en) | 2003-04-17 | 2003-08-27 | Preparation method of direct alcohol kind fuel battery negative electrode |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100337353C (en) * | 2005-06-16 | 2007-09-12 | 哈尔滨工业大学 | Method for preparing Pt-Ru-NI/C catalyst in use for fuel cell of direct alcohols |
| CN111326752A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院大连化学物理研究所 | Solid powder of fuel cell catalyst layer and preparation method and application thereof |
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Assignee: Jiangsu Shuangde Group Co., Ltd. Assignor: Jiangsu Shuangdeng Power Supply Co., Ltd. Contract fulfillment period: 2009.3.1 to 2019.3.1 contract change Contract record no.: 2009320000349 Denomination of invention: Preparation method of direct alcohol kind fuel battery negative electrode Granted publication date: 20060215 License type: Exclusive license Record date: 2009.3.13 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.3.1 TO 2019.3.1; CHANGE OF CONTRACT Name of requester: JIANGSU SHUANGDENG GROUP CO.,LTD. Effective date: 20090313 |
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Granted publication date: 20060215 Termination date: 20100827 |