CN104638218A - Method for preparing environment-friendly molten carbonate fuel cell diaphragm - Google Patents
Method for preparing environment-friendly molten carbonate fuel cell diaphragm Download PDFInfo
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- CN104638218A CN104638218A CN201510058896.3A CN201510058896A CN104638218A CN 104638218 A CN104638218 A CN 104638218A CN 201510058896 A CN201510058896 A CN 201510058896A CN 104638218 A CN104638218 A CN 104638218A
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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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for preparing an environment-friendly molten carbonate fuel cell diaphragm. The method comprises the following steps of (1) fully ball-milling and mixing diaphragm powder lithium metaaluminate LiAlO2 and a water soluble dispersant in solvent distilled water to form an uniform slurry; (2) adding a water-soluble binder, a water-soluble plasticizer and a small number of water-soluble de-foaming agents into the uniform slurry for continuously milling until to form a diaphragm slurry; (3) naturally spreading the diaphragm slurry on a horizontal glass pane, controlling environment temperature and humidity until the diaphragm slurry is dried to form the diaphragm; and (4) cutting the dried diaphragm into a demanded shape, and preparing the molten carbonate fuel cell diaphragm by 3-6 hot-pressing diaphragms. For the molten carbonate fuel cell diaphragm prepared by the method, a large number of organic solvents can be saved, so that the preparation cost of the diaphragm is greatly reduced, the prepared diaphragm is relatively high in mechanical strength, and the molten carbonate fuel cell diaphragm is very beneficial for assembling molten carbonate fuel cell stacks.
Description
Technical field
The invention belongs to molten carbonate fuel cell technical field, be specifically related to a kind of preparation method of environment-friendly type diaphragm for molten carbonate fuel battery.
Background technology
Fuel cell is a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) in electrochemical reaction mode, the chemical energy of fuel directly being become electric energy without burning, its maximum feature is that course of reaction does not relate to burning, therefore energy conversion efficiency is not by the restriction of " Carnot cycle ", and combined cycle generation efficiency is up to 80% ~ 90%.Molten carbonate fuel cell is a kind of high-temperature fuel cell, relative to low-temperature fuel cell its to have fuel source extensive, do not use noble metal, the technological merits such as combined cycle generation can be realized, being the after thermoelectricity, water power and nuclear power the 4th kind of generally acknowledged generation mode, is the first-selection of following clear energy sources generating.
Barrier film is one of core component of molten carbonate fuel cell, needs to adopt a large amount of organic solvents when preparing barrier film at present, not only increase the preparation cost of barrier film, and preparation process also not environmentally, is even harmful to the health of people.Chinese patent (97111018.2) adopts n-butanol and ethanol as barrier film solvent, successfully prepare diaphragm for molten carbonate fuel battery, but n-butanol and ethanol are organic solvent, its use amount is up to 70%, not only increase the preparation cost of barrier film, and whole preparation process is also very harmful to human body; It take distilled water as the preparation method of solvent barrier film that Chinese patent (200310105254.1) also discloses a kind of, but prepared barrier film is easily curled, and should not use in actual applications, is also not suitable for mechanization continuous seepage.
Summary of the invention
In order to solve above-mentioned prior art Problems existing, the object of the present invention is to provide a kind of preparation method of environment-friendly type diaphragm for molten carbonate fuel battery, can avoid using a large amount of organic solvent, what greatly reduce barrier film prepares preparation cost, and prepared barrier film has higher mechanical strength, advantageously in the assembling of molten carbonate fuel cell heap.The pore diameter range of barrier film is 0.1 ~ 0.4 μm, and the overall porosity of barrier film is 50 ~ 70%.
In order to achieve the above object, the present invention adopts following technical scheme:
A preparation method for environment-friendly type diaphragm for molten carbonate fuel battery, comprises the steps:
Step 1: by barrier film powder lithium metaaluminate LiAlO
2homogeneous slurry is formed after mixing with water soluble dispersing agent abundant ball milling in solvent distilled water;
Step 2: add water-soluble binder, water-soluble plasticizer and a small amount of water insoluble defoamer and continue ball milling, until form barrier film slurry in described homogeneous slurry;
Step 3: naturally spread on horizontal glass plate by described barrier film slurry, control environment temperature and humidity, until its drying and forming-film;
Step 4: be cut into required form after film drying, 3 ~ 6 hot pressing film forming, just can obtain diaphragm for molten carbonate fuel battery;
Described barrier film powder lithium metaaluminate LiAlO
2in barrier film slurry, occupy ratio is 15 ~ 40%, the mass ratio of described water soluble dispersing agent shared by barrier film slurry is 0.5 ~ 1%, the mass ratio of described water-soluble binder shared by barrier film slurry is 3 ~ 5%, the mass ratio of described water-soluble plasticizer shared by barrier film slurry is 1 ~ 3%, the mass ratio of described water insoluble defoamer shared by barrier film slurry is 0.1 ~ 2%, and the mass ratio of described distilled water shared by barrier film slurry is 50 ~ 75%.
Described barrier film powder lithium metaaluminate LiAlO
2for α type LiAlO
2powder, its particle size range is 0.1 ~ 10 μm.
Described water soluble dispersing agent refers to the water soluble organic substance that can play peptizaiton.
The described water soluble organic substance that can play peptizaiton is citric acid.
Described water-soluble binder refers to and can to dissolve in distilled water and can stable existence and have close-burning material.
Describedly can to dissolve in distilled water and can stable existence and to have close-burning material be sodium carboxymethylcellulose CMC.
Described water-soluble plasticizer refers to and can be dissolved in distilled water and can play the material of plasticization.
Describedly can be dissolved in distilled water and the material that can play plasticization is glycerine.
The described temperature and humidity that controls environment, ambient temperature controls at 15 ~ 30 DEG C, and humid control is 30 ~ 70%.
The condition of described hot pressing is: pressure is 2 ~ 4MPa, and hot pressing time is 1 ~ 8min, and hot pressing temperature is 85 ~ 95 DEG C.
Compared to the prior art comparatively, the present invention possesses following advantage:
The inventive method is adopted to prepare diaphragm for molten carbonate fuel battery, the preparation process environmental protection of barrier film, not only can avoid using a large amount of organic solvent, what greatly reduce barrier film prepares preparation cost, and prepared barrier film has higher mechanical strength, advantageously in the assembling of molten carbonate fuel cell heap.The pore diameter range of barrier film is 0.1 ~ 0.4 μm, and the overall porosity of barrier film is 50 ~ 70%.
Embodiment
Below in conjunction with specific embodiment, the present invention is further detailed explanation:
Embodiment one: adopt mass ratio to account for barrier film slurry 26%, particle size range is α-LiAlO between 0.1 ~ 10 μm
2particle is as barrier film powder, mass ratio is adopted to account for barrier film slurry 65% distilled water as solvent, mass ratio is adopted to account for barrier film slurry 1% citric acid as dispersant, put into ball grinder and carry out ball milling mixing, time is 10h, rotating speed is 200 revs/min, after mixing, add mass ratio to it again and account for the sodium carboxymethylcellulose of barrier film slurry 5% as binding agent, mass ratio accounts for the glycerine of barrier film slurry 2.5% as plasticizer, mass ratio accounts for the polyethers of barrier film slurry 0.5% as defoamer, mixing and ball milling forms homogeneous barrier film slurry after 20 hours, then above-mentioned uniform sizing material is laid on preprepared glass plate, natural drying film forming.
Finally above-mentioned barrier film biscuit is cut into required form, adopts 5 and be stacked together, adjustment hydraulic press pressure is 4MPa, and temperature is 90 DEG C, suppresses after 2 minutes and can film forming use.Through Mercury-injection test, the overall porosity of barrier film is 59%, and average pore size is 0.35 μm, meets battery to the requirement of barrier film various performance parameters.
Embodiment two: adopt mass ratio to account for barrier film slurry 29%, particle size range is α-LiAlO between 0.1 ~ 10 μm
2particle is as barrier film powder, mass ratio is adopted to account for barrier film slurry 63% distilled water as solvent, mass ratio is adopted to account for barrier film slurry 0.8% citric acid as dispersant, put into ball grinder and carry out ball milling mixing, time is 15h, rotating speed is 240 revs/min, after mixing, add mass ratio to it again and account for the sodium carboxymethylcellulose of barrier film slurry 4.2% as binding agent, mass ratio accounts for the glycerine of barrier film slurry 2.8% as plasticizer, mass ratio accounts for the polyethers of barrier film slurry 0.2% as defoamer, mixing and ball milling forms homogeneous barrier film slurry after 25 hours, then above-mentioned uniform sizing material is laid on preprepared glass plate, natural drying film forming.
Finally above-mentioned barrier film biscuit is cut into required form, adopts 4 and be stacked together, adjustment hydraulic press pressure is 3MPa, and temperature is 95 DEG C, suppresses after 4 minutes and can film forming use.Through Mercury-injection test, the overall porosity of barrier film is 55%, and average pore size is 0.32 μm, meets battery to the requirement of barrier film various performance parameters.
Claims (10)
1. a preparation method for environment-friendly type diaphragm for molten carbonate fuel battery, is characterized in that: comprise the steps:
Step 1: by barrier film powder lithium metaaluminate LiAlO
2homogeneous slurry is formed after mixing with water soluble dispersing agent abundant ball milling in solvent distilled water;
Step 2: add water-soluble binder, water-soluble plasticizer and a small amount of water insoluble defoamer and continue ball milling, until form barrier film slurry in described homogeneous slurry;
Step 3: naturally spread on horizontal glass plate by described barrier film slurry, control environment temperature and humidity, until its drying and forming-film;
Step 4: be cut into required form after film drying, 3 ~ 6 hot pressing film forming, just can obtain diaphragm for molten carbonate fuel battery;
Described barrier film powder lithium metaaluminate LiAlO
2mass ratio shared in barrier film slurry is 15 ~ 40%, the mass ratio of described water soluble dispersing agent shared by barrier film slurry is 0.5 ~ 1%, the mass ratio of described water-soluble binder shared by barrier film slurry is 3 ~ 5%, the mass ratio of described water-soluble plasticizer shared by barrier film slurry is 1 ~ 3%, the mass ratio of described water insoluble defoamer shared by barrier film slurry is 0.1 ~ 2%, and the mass ratio of described distilled water shared by barrier film slurry is 50 ~ 75%.
2. preparation method according to claim 1, is characterized in that: described barrier film powder lithium metaaluminate LiAlO
2for α type LiAlO
2powder, its particle size range is 0.1 ~ 10 μm.
3. preparation method according to claim 1, is characterized in that: described water soluble dispersing agent refers to the water soluble organic substance that can play peptizaiton.
4. preparation method according to claim 3, is characterized in that: the described water soluble organic substance that can play peptizaiton is citric acid.
5. preparation method according to claim 1, is characterized in that: described water-soluble binder refers to and can to dissolve in distilled water and can stable existence and have close-burning material.
6. preparation method according to claim 5, is characterized in that: describedly can to dissolve in distilled water and can stable existence and to have close-burning material be sodium carboxymethylcellulose CMC.
7. preparation method according to claim 1, is characterized in that: described water-soluble plasticizer refers to and can be dissolved in distilled water and can play the material of plasticization.
8. preparation method according to claim 7, is characterized in that: describedly can be dissolved in distilled water and the material that can play plasticization is glycerine.
9. preparation method according to claim 1, is characterized in that: the described temperature and humidity that controls environment, ambient temperature controls at 15 ~ 30 DEG C, and humid control is 30 ~ 70%.
10. hot pressing film forming according to claim 1, is characterized in that: the condition of described hot pressing is: pressure is 2 ~ 4MPa, and hot pressing time is 1 ~ 8min, and hot pressing temperature is 85 ~ 95 DEG C.
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| CN201510058896.3A CN104638218A (en) | 2015-02-04 | 2015-02-04 | Method for preparing environment-friendly molten carbonate fuel cell diaphragm |
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| CN201510058896.3A CN104638218A (en) | 2015-02-04 | 2015-02-04 | Method for preparing environment-friendly molten carbonate fuel cell diaphragm |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110739160A (en) * | 2019-10-30 | 2020-01-31 | 东莞东阳光科研发有限公司 | method for preparing capacitor diaphragm by recycling waste capacitor diaphragm |
| CN111354963A (en) * | 2020-04-17 | 2020-06-30 | 中国华能集团清洁能源技术研究院有限公司 | Method for compositely preparing molten carbonate fuel cell diaphragm and electrolyte |
| CN112909276A (en) * | 2021-03-12 | 2021-06-04 | 华能国际电力股份有限公司 | Method for recovering water-based molten carbonate fuel cell diaphragm waste material |
| CN113224340A (en) * | 2021-04-29 | 2021-08-06 | 华能国际电力股份有限公司 | Molten carbonate fuel cell diaphragm and preparation method thereof |
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| CN1624951A (en) * | 2003-12-03 | 2005-06-08 | 中国科学院大连化学物理研究所 | Method for preparing diaphragm of molten carbonate fuel cell |
| CN1770502A (en) * | 2005-09-15 | 2006-05-10 | 上海交通大学 | Method for preparing melting carbonate fuel cell membrane using water-based flow casting technique |
| CN101071872A (en) * | 2007-06-07 | 2007-11-14 | 上海交通大学 | Integrated preparing method for molten carbonate fuel cell electrolyte membrane |
| CN104078634A (en) * | 2014-06-30 | 2014-10-01 | 中国华能集团清洁能源技术研究院有限公司 | High-strength molten carbonate fuel cell diaphragm and preparation method thereof |
| CN204088433U (en) * | 2014-06-30 | 2015-01-07 | 中国华能集团清洁能源技术研究院有限公司 | A kind of high strength diaphragm for molten carbonate fuel battery |
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2015
- 2015-02-04 CN CN201510058896.3A patent/CN104638218A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1624951A (en) * | 2003-12-03 | 2005-06-08 | 中国科学院大连化学物理研究所 | Method for preparing diaphragm of molten carbonate fuel cell |
| CN1770502A (en) * | 2005-09-15 | 2006-05-10 | 上海交通大学 | Method for preparing melting carbonate fuel cell membrane using water-based flow casting technique |
| CN101071872A (en) * | 2007-06-07 | 2007-11-14 | 上海交通大学 | Integrated preparing method for molten carbonate fuel cell electrolyte membrane |
| CN104078634A (en) * | 2014-06-30 | 2014-10-01 | 中国华能集团清洁能源技术研究院有限公司 | High-strength molten carbonate fuel cell diaphragm and preparation method thereof |
| CN204088433U (en) * | 2014-06-30 | 2015-01-07 | 中国华能集团清洁能源技术研究院有限公司 | A kind of high strength diaphragm for molten carbonate fuel battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110739160A (en) * | 2019-10-30 | 2020-01-31 | 东莞东阳光科研发有限公司 | method for preparing capacitor diaphragm by recycling waste capacitor diaphragm |
| CN110739160B (en) * | 2019-10-30 | 2022-03-04 | 东莞东阳光科研发有限公司 | Method for preparing capacitor diaphragm by recycling waste capacitor diaphragm |
| CN111354963A (en) * | 2020-04-17 | 2020-06-30 | 中国华能集团清洁能源技术研究院有限公司 | Method for compositely preparing molten carbonate fuel cell diaphragm and electrolyte |
| CN112909276A (en) * | 2021-03-12 | 2021-06-04 | 华能国际电力股份有限公司 | Method for recovering water-based molten carbonate fuel cell diaphragm waste material |
| CN113224340A (en) * | 2021-04-29 | 2021-08-06 | 华能国际电力股份有限公司 | Molten carbonate fuel cell diaphragm and preparation method thereof |
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Application publication date: 20150520 |