CN1314142C - Method for preparing melting carbonate fuel cell membrane using water-based flow casting technique - Google Patents
Method for preparing melting carbonate fuel cell membrane using water-based flow casting technique Download PDFInfo
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- CN1314142C CN1314142C CNB2005100296622A CN200510029662A CN1314142C CN 1314142 C CN1314142 C CN 1314142C CN B2005100296622 A CNB2005100296622 A CN B2005100296622A CN 200510029662 A CN200510029662 A CN 200510029662A CN 1314142 C CN1314142 C CN 1314142C
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- water
- fuel cell
- carbonate fuel
- lialo
- cell membrane
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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 present invention relates to a method for preparing fused carbonate fuel cell diaphragm by a water-based flow casting technique, which belongs to the technical field of energy sources. The present invention adopts alpha-bias aluminum lithium powder in submicron order as raw materials which are added in a water solution of polyvinyl alcohol PVA adhesive for ball milling granulation; then, Al2O3 fiber and water are simultaneously added in the mixture, and after stirred, slurry with alpha-LiAlO2, PVA and Al2O3 fiber is obtained; the slurry is cast into a diaphragm; after the diaphragm is dried, three pieces of diaphragms are hot pressed into a diaphragm sheet, and the desired fused carbonate fuel cell diaphragm is obtained. The present invention uses water as a solvent to prepare the slurry, so the consumption of chemical agents is reduced. Because the water is used as the solvent, the environmental pollution is greatly reduced, the work environment is improved, and the production cost is reduced.
Description
Technical field
That the present invention relates to is the preparation method in a kind of fuel cell technology field, particularly a kind of method with preparing melting carbonate fuel cell membrane using water-based flow casting technique.
Background technology
Molten carbonate fuel cell is negative electrode with the porous nickel oxide, and porous-metal nickel is an anode, lithium carbonate/potash (Li
2CO
3/ K
2CO
3) or lithium carbonate/sodium carbonate (Li
2CO
3/ Na
2CO
3) eutectic mixture formed is as electrolyte, the electrolyte after the fusing is dispersed in aluminium lithate (α-LiAlO by the α of submicron order-partially
2) or γ-inclined to one side aluminium lithate (γ-LiAlO
2) in the barrier film that makes of powder.When negative electrode bubbling air and carbon dioxide, behind the coal gas after the anode feeding hydrogen or the reformation gas of natural gas, biogas, the purification, will produce electric current at external circuit, need not be through burning or mechanical work done, be a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) of efficient, cleaning.The carrying fused carbonate is by inclined to one side aluminium lithate LiAlO
2The barrier film that powder makes is one of critical material of battery.The performance of this barrier film as porosity, aperture, mechanical strength etc., all directly has influence on the performance and the life-span of battery.Generally make barrier film with The tape casting.
Through the literature search of prior art is found, the patent of invention of Chinese patent application numbers 97111018.2, this patent is LiAlO
2Powder is put in the mixed organic solvents of n-butanol and ethanol composition, adds polyvinyl butyral resin and di-n-octyl phthalate bonding agent again, the White Meat oil dispersant, and silicon oil foam killer, ball milling are after 33 hours, the slurry casting film-forming.Hot pressing after three film-stack that obtain after the drying has just obtained the barrier film of molten carbonate fuel cell.This method has the most tangible weak point, is to have adopted a large amount of organic substances, has not only improved cost of manufacture, and, cause the pollution of environment in the preparation process.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, a kind of method of preparing melting carbonate fuel cell membrane using water-based flow casting technique is provided, make it allocate slurry as solvent with water, reduced the use amount of chemical reagent, the prior water that is to use is as solvent, significantly reduced environmental pollution, improved operational environment, reduced production costs.
The present invention is achieved by the following technical solutions, and the present invention adopts the α-inclined to one side aluminium lithate (α-LiAlO of submicron order
2) powder is raw material, raw material added in the aqueous solution of polyvinyl alcohol (PVA) bonding agent, carries out the ball milling granulation, adds Al then simultaneously
2O
3Fiber and water after the stirring, obtain containing α-LiAlO
2, PVA and Al
2O
3The slurry of fiber after this slurry casting film-forming and drying, is hot pressed into a film with three films, just obtains the barrier film of needed molten carbonate fuel cell.
Below the inventive method is further described, method step is as follows:
(1) PVA is dissolved in 50 ~ 100 ℃ the hot water, is made into the PVA solution of 0.02wt% ~ 0.06wt%, α-LiAlO of 0.01 ~ 0.3 μ m
210 ~ 50 gram fine powders join in the above-mentioned 100 gram solution, and after stirring, dry under 50 ~ 100 ℃, ball milling is 1 ~ 4 hour then.Carry out so repeatedly 2 ~ 4 times.
(2) α-LiAlO behind the ball milling
2Add Al in the powder
2O
3Fiber, water, three's ratio α-LiAlO
2: Al
2O
3Fiber: water=10: 1: 5 forms slurry, casting film-forming.Al
2O
3Fiber is a polycrystalline structure.
(3) this film 50 ~ 100 ℃ down dry remove moisture after, get on the press that three films overlay 60 ~ 100 ℃, pressure is 1 ~ 3MPa, preheating 3 ~ 4 minutes, then, with the pressure of 4 ~ 5Mpa, hot pressing 4 ~ 5 minutes has just obtained the barrier film of molten carbonate fuel cell.The thickness of this barrier film is between the 0.6-1 millimeter, average pore size 0.3-0.4 μ m, mean porosities 50-60%.
α-LiAlO that the present invention adopts at submicron order
2The ceramic particle outside repeatedly coats water soluble adhesive PVA, carries out the ball milling granulation simultaneously, adds Al at last
2O
3Fiber and water have formed and have contained (α-LiAlO
2), PVA and Al
2O
3The slurry of fiber, casting film-forming, dry back three films are hot pressed into the needed barrier film of molten carbonate fuel cell.Adopt water miscible bonding agent PVA to coat the α-LiAlO of submicron order for many times
2Ceramic particle can be avoided in the prior art simultaneously, greatly having improved operational environment with a large amount of organic solvents and for obtaining other chemical reagent such as dispersant that the homogeneous slurry adds in addition.Al
2O
3The adding of fiber has not only improved the mechanical strength of barrier film, simultaneously, in actual use and carbonate electrolyte generation chemical reaction, has also had the ability of catching micro-fractures.
Embodiment
Provide following examples in conjunction with content of the present invention:
Embodiment one
PVA is dissolved in 50 ℃ the hot water, is made into the PVA solution of 0.02wt%, α-LiAlO of 0.01 ~ 0.3 μ m
210 gram fine powders join in the above-mentioned 100 gram solution, and after stirring, dry under 50 ℃, ball milling is 1 hour then.Carry out so repeatedly 2 times.α-LiAlO behind the ball milling
2Add Al in the powder
2O
3Fiber adds entry, three's ratio α-LiAlO
2: Al
2O
3Fiber: water=10: 1: 5 forms slurry, casting film-forming.This film is behind 50 ℃ of dry down removal moisture, get on the press that three films overlay 60 ℃, pressure is 1MPa, preheating 3 minutes, then, with the pressure of 4Mpa, hot pressing 4 minutes, just having obtained thickness is 0.6 millimeter, average pore size 0.3 μ m, the barrier film of mean porosities 50% molten carbonate fuel cell.
Embodiment two
PVA is dissolved in 75 ℃ the hot water, is made into the PVA solution of 0.04wt%, α-LiAlO of 0.01 ~ 0.3 μ m
230 gram fine powders join in the above-mentioned 100 gram solution, and after stirring, dry under 75 ℃, ball milling is 2.5 hours then.Carry out so repeatedly 3 times.α-LiAlO behind the ball milling
2Add Al in the powder
2O
3Fiber adds entry, three's ratio α-LiAlO
2: Al
2O
3Fiber: water=10: 1: 5 forms slurry, casting film-forming.This film is behind 75 ℃ of dry down removal moisture, get on the press that three films overlay 80 ℃, pressure is 2MPa, preheating 3.5 minutes, then, with the pressure of 4.5Mpa, hot pressing 4.5 minutes, just having obtained thickness is 0.8 millimeter, average pore size 0.35 μ m, the barrier film of mean porosities 55% molten carbonate fuel cell.
Embodiment three
PVA is dissolved in 100 ℃ the hot water, is made into the PVA solution of 0.06wt%, α-LiAlO of 0.01 ~ 0.3 μ m
250 gram fine powders join in the above-mentioned 100 gram solution, and after stirring, dry under 100 ℃, ball milling is 4 hours then.Carry out so repeatedly 4 times.α-LiAlO behind the ball milling
2Add Al in the powder
2O
3Fiber adds entry, three's ratio α-LiAlO
2: Al
2O
3Fiber: water=10: 1: 5 forms slurry, casting film-forming.This film is behind 100 ℃ of dry down removal moisture, get on the press that three films overlay 100 ℃, pressure is 3MPa, preheating 4 minutes, then, with the pressure of 5Mpa, hot pressing 5 minutes, just having obtained thickness is 1 millimeter, average pore size 0.4 μ m, the barrier film of mean porosities 60% molten carbonate fuel cell.
Diaphragm for molten carbonate fuel battery embodiment two obtains is equipped with K
2CO
3/ Na
2CO
3Electrolytic salt, two ends are put negative electrode and anode, negative electrode one end bubbling air and carbon dioxide, and anode one end feeds hydrogen, and battery is heated to 650 ℃, and can obtain open circuit voltage is 1.06V, at 50mA/cm
2Under the current density, cell voltage is 0.93V, at l00mA/cm
2Under the current density, cell voltage is 0.85V, at 150mA/cm
2Under the current density, cell voltage is 0.78V.
Claims (8)
1, a kind of method of preparing melting carbonate fuel cell membrane using water-based flow casting technique is characterized in that, step is as follows:
(1) polyvinyl alcohol is dissolved in the hot water, is made into poly-vinyl alcohol solution, adopt the α-LiAlO of submicron order
2Powder is a raw material, with α-LiAlO
2Fine powder joins in the poly-vinyl alcohol solution, after stirring, and drying, ball milling carries out 2-4 time so repeatedly then;
(2) α-LiAlO behind the ball milling
2Add Al in the powder
2O
3Fiber, water obtain containing α-LiAlO
2, polyvinyl alcohol and Al
2O
3The slurry of fiber, casting film-forming;
(3) with the film that obtains in the step (2) is dry remove moisture after, get three films and overlay on the press, hot pressing after the preheating obtains the barrier film of molten carbonate fuel cell.
2, the method for preparing melting carbonate fuel cell membrane using water-based flow casting technique according to claim 1, it is characterized in that, in the step (1), polyvinyl alcohol is dissolved in 50 ~ 100 ℃ the hot water, is made into the poly-vinyl alcohol solution of percentage by weight 0.02% ~ 0.06%.
3, according to the method for claim 1 or 2 described preparing melting carbonate fuel cell membrane using water-based flow casting techniques, it is characterized in that, in the step (1), α-LiAlO
210 ~ 50 gram fine powders join in the 100 gram poly-vinyl alcohol solutions, 50 ~ 100 ℃ of baking temperatures, ball milling 1 ~ 4 hour.
4, the method for preparing melting carbonate fuel cell membrane using water-based flow casting technique according to claim 1 is characterized in that, in the step (2), and α-LiAlO
2: Al
2O
3Fiber: water=10: 1: 5.
5, according to the method for claim 1 or 4 described preparing melting carbonate fuel cell membrane using water-based flow casting techniques, it is characterized in that described α-LiAlO
2Particle diameter be 0.01～0.3 μ m, Al
2O
3Fiber is a polycrystalline structure.
6, the method for preparing melting carbonate fuel cell membrane using water-based flow casting technique according to claim 1 is characterized in that, in the step (3), baking temperature is 50 ~ 100 ℃.
7, according to the method for claim 1 or 6 described preparing melting carbonate fuel cell membrane using water-based flow casting techniques, it is characterized in that, in the step (3), the temperature of press is 60 ~ 100 ℃, and pressure is 1 ~ 3MPa, preheating 3 ~ 4 minutes, then, with the pressure of 4 ~ 5Mpa, hot pressing 4 ~ 5 minutes.
8, the method for preparing melting carbonate fuel cell membrane using water-based flow casting technique according to claim 1 is characterized in that, the thickness of gained barrier film is between the 0.6-1 millimeter, average pore size 0.3-0.4 μ m, mean porosities 50-60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100296622A CN1314142C (en) | 2005-09-15 | 2005-09-15 | Method for preparing melting carbonate fuel cell membrane using water-based flow casting technique |
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|---|---|---|---|
| CNB2005100296622A CN1314142C (en) | 2005-09-15 | 2005-09-15 | Method for preparing melting carbonate fuel cell membrane using water-based flow casting technique |
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|---|---|
| CN1770502A CN1770502A (en) | 2006-05-10 |
| CN1314142C true CN1314142C (en) | 2007-05-02 |
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| CNB2005100296622A Expired - Fee Related CN1314142C (en) | 2005-09-15 | 2005-09-15 | Method for preparing melting carbonate fuel cell membrane using water-based flow casting technique |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101814606A (en) * | 2010-04-01 | 2010-08-25 | 江苏工业学院 | Method for preparing NiO cathode materials of molten carbonate fuel cell by aqueous tape casting |
| CN101942677A (en) * | 2010-09-30 | 2011-01-12 | 中南大学 | Heat-insulating coating material for aluminum electrolytic inert anode and use thereof |
| CN102306812B (en) * | 2011-09-01 | 2013-06-05 | 中国华能集团清洁能源技术研究院有限公司 | Method for recycling electrolyte substrate waste material of molten carbonate fuel cell |
| CN104638218A (en) * | 2015-02-04 | 2015-05-20 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing environment-friendly molten carbonate fuel cell diaphragm |
| CN105322188A (en) * | 2015-10-28 | 2016-02-10 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing modified nickel electrode of molten carbonate fuel cell through aqueous tape casting |
| JP6670231B2 (en) * | 2016-12-22 | 2020-03-18 | I&Tニューマテリアルズ株式会社 | Electrode of power storage device, slurry for electrode of power storage device, and method of manufacturing the same |
| CN110010918B (en) * | 2019-05-06 | 2023-05-16 | 中国华能集团清洁能源技术研究院有限公司 | PET silicone oil membrane recycling device and method for producing molten carbonate fuel cell membrane |
| CN113471500B (en) * | 2021-07-16 | 2023-10-03 | 华能国际电力股份有限公司 | Salt film of molten carbonate fuel cell and preparation method thereof |
Citations (6)
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| CN1199932A (en) * | 1997-05-17 | 1998-11-25 | 中国科学院大连化学物理研究所 | Preparation of diaphragm for molten carbonate fuel battery |
| JPH10340729A (en) * | 1997-06-04 | 1998-12-22 | Yoyu Tansanengata Nenryo Denchi Hatsuden Syst Gijutsu Kenkyu Kumiai | Method for preventing corrosion of separator member for molten carbonate type fuel cell |
| US6037076A (en) * | 1995-10-03 | 2000-03-14 | Kabushiki Kaisha Toshiba | Molten carbonate fuel cell and method of manufacturing retaining material for electrolyte body of molten carbonate fuel cell |
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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 |
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| US6037076A (en) * | 1995-10-03 | 2000-03-14 | Kabushiki Kaisha Toshiba | Molten carbonate fuel cell and method of manufacturing retaining material for electrolyte body of molten carbonate fuel cell |
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| US6544676B2 (en) * | 2000-01-25 | 2003-04-08 | Kist (Korea Institute Of Science And Technology | Internal reforming molten carbonate fuel cell with membrane for intercepting carbonate vapor |
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