CN1255886C - Method for preparing diaphragm of molten carbonate fuel cell - Google Patents
Method for preparing diaphragm of molten carbonate fuel cell Download PDFInfo
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- CN1255886C CN1255886C CNB2003101052541A CN200310105254A CN1255886C CN 1255886 C CN1255886 C CN 1255886C CN B2003101052541 A CNB2003101052541 A CN B2003101052541A CN 200310105254 A CN200310105254 A CN 200310105254A CN 1255886 C CN1255886 C CN 1255886C
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- carbonate fuel
- diaphragm
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- molten carbonate
- fuel battery
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The present invention relates to a method for preparing a diaphragm of a fused carbonate fuel cell. The present invention has the steps of slurry preparing, diaphragm casing from bands, drying and hot pressing. The present invention is characterized in that water is used as a solvent of the slurry, polyvinyl alcohol (PVA) is used as adhesive, lactic acid is used as a dispersing agent, the mixture of glycerol, glycerol triacetate and glycol is used as a plasticizing agent, and alpha-LiAlO2 with a certain thickness proportion is used as powder materials; the present invention has a recipe that according to weight portions, the powder materials take 45.0 portions (wherein coarse powder materials with the grain diameter of larger than 1 mu m take 80-95%, and fine powder materials with the grain diameter of smaller than 1 mu m take 5 to 20%), the adhesive takes 7.0 to 12.0 portions, the dispersing agent takes 1.5 to 3.0 portions, the plasticizing agents takes 4.0 to 8.0 portions and the content of the solvent is 2.5 to 4.5 times of that of the powder materials. Because the present invention uses the water as the solvent, the prepared diaphragm has the advantages of uniform texture, uniform thickness, high mechanical strength, high void ratio (>=50%), high diaphragm choke capability (>=0.9MPa) in the fused carbonate fuel cell, small maximum pore diameter (<=1 mu m) and high electrochemical performance (which is not lower than that of diaphragms prepared by organic solvents).
Description
Technical field:
The invention belongs to the fuel cell technology field, the preparation method of diaphragm for molten carbonate fuel battery is provided especially.
Background technology:
Molten carbonate fuel cell is in the commercialization stage in the world at present, and some countries are solving the technical problem in its commercialization process.In preparation battery diaphragm technical process, generally use band casting system film, and also in a large number with an organic solvent, as n-butanol, ethanol and chloroform etc.Though these organic solvent low toxicities, a large amount of use produces serious harm and surrounding environment caused severe contamination human body.In order to overcome these problems, some state's service water replace organic solvents such as the U.S. are also still used band casting system film.As:
Document 1.Method of making matrix for carbonate fuel cells, USP 5,997, and 794.This patent is people's such as U.S. FCE (original name ERC) Huang Chaoming a patent of invention, and it is solvent with water to the effect that, prepares diaphragm for molten carbonate fuel battery with the band casting.In order to make fuel cell-green energy resource contain more true meanings, with water solvent, substitute a large amount of in the past organic solvents that use.This is the starting point of this patent of invention.But from concrete technical consideration, also have many weak points, during as barrier film hot pressing, hypertonia is up to 2000PSI (14.06MPa).No matter heating up or in room temperature, under high pressure like this, barrier film is pressing not yet.This explanation system film formulation defectiveness.
Document 2.Preparation of electrolyte matrix structure by aqueous andnon-aqueous tape casting method for MCFC, Bull.Electrochemistry, 15 (9-10), 1999:400-403. this is India Pores, people such as S.Joseph are solvent with water also, prepare the article of diaphragm for molten carbonate fuel battery with the band casting.The no big difference of the rerum natura of barrier film and general diaphragm for molten carbonate fuel battery, but that his usefulness is γ-LiAlO
2Powder.This powder is under the molten carbonate fuel cell service conditions, and mutability is α-LiAlO
2Prepare γ-LiAlO simultaneously
2Powder has brought the difficulty of long-time 900 ℃ of roastings on technology.
Document 3.Method of making carbonate fuel cell ceramic matrix tape, USP4,478,776. this be the patent that human band castings such as Maricle Donald L. prepare barrier film.From patent, the system film formulation is more complete.For flowability and the film rate of drying that improves the film slurry, solvent is halogenated hydrocarbons and alcohols mixed solvent.Halogenated hydrocarbons and alcohols use in a large number, and human body is produced serious harm, and environment is caused severe contamination.
Document 4.Method for drying ceramic tape, USP 3,953, and 703. in this patent, and people such as Hurwitt Steven directly heat barrier film with microwave on the barrier film base plate, make barrier film rapid draing.Heating power is 1W/inch
2Directly heating on negative easily produces bubble in the film, reduce membrane properties.With the heating of microwave large tracts of land, easily cause unsafe factors such as microwave leakage.
In a word, the existing in prior technology common problem is:
1. with an organic solvent cause in a large number to the human body serious harm with to severe environmental pollution;
2. in the system film formulation, all solvable the or major part of components dissolves in alcohols or halogenated hydrocarbons;
3. in the system film formulation, most of component is poisonous to human body, and minority or a small amount of component are to the human body low toxicity;
4. during hot pressing, even high pressure also is difficult to the pressing barrier film;
5. barrier film needs to store in the dried equipment of special guarantor.
Summary of the invention:
In order to make fuel cell-green energy resource contain more true meaning, also in film-forming process, use a large amount of organic solvents simultaneously, to avoid causing severe contamination to human body generation serious harm with to environment in order to eliminate.The object of the present invention is to provide a kind of is the method that solvent substitutes a large amount of organic solvent band casting system films that use with water, and guarantees that the quality of prepared barrier film is not less than the barrier film that with an organic solvent makes.
The present invention specifically provides a kind of preparation method of diaphragm for molten carbonate fuel battery, comprise pulp preparation, be with and cast film, drying, heat-press step, it is characterized in that described slurry is solvent with water, with polyvinyl alcohol (PVA) is binding agent, with lactic acid is dispersant, with glycerine and glyceryl triacetate and ethylene glycol mixture is plasticizer, so that the α-LiAlO of certain thickness ratio to be arranged
2Be powder, filling a prescription is parts by weight:
Powder: 45.0 parts, the meal material 80-95% of particle diameter＞1 μ m wherein, the fine powder material 5-20% of particle diameter＜1 μ m;
Binding agent: 7.0～12.0 parts;
Dispersant: 1.5～3.0 parts;
Plasticizer: 4.0～8.0 parts;
Solvent: 2.5～4.5 times of powder.
Among the preparation method of diaphragm for molten carbonate fuel battery of the present invention, can add 0.6～1.2 part of polyether compound in the described formula of size as defoamer.
Among the preparation method of diaphragm for molten carbonate fuel battery of the present invention, glycerine and glyceryl triacetate preferably respectively account for 1/4～1/3 in the described plasticizer.
Among the preparation method of diaphragm for molten carbonate fuel battery of the present invention, the process of described slurry preparation step is as follows: part meal material, partial solvent, fine powder material, dispersant ball milling add residue meal material after 30～50 hours again; Behind the ball milling 50～70 hours, add binding agent, plasticizer, defoamer and residual solvent at last; Ball milling to 80～100 hour.
Wherein, the amount of described part meal material is preferably 70～90% of meal material.
Among the preparation method of diaphragm for molten carbonate fuel battery of the present invention, described drying steps is, barrier film is placed the parcel of porous material, under 20～30 ℃, keeps 20～30 hours.
Among the preparation method of diaphragm for molten carbonate fuel battery of the present invention, described heat-press step comprises precompressed and final pressure:
Prefabricating condition is 70～100 ℃, 4～7MPa, 2～4 minutes;
The final pressure condition is 70～100 ℃, 6～9MPa, 2～4 minutes.
Wherein, preferably first preheating before the precompressed, preheating condition is 70～100 ℃, 2～5MPa, 2～4 minutes; Preferably first preheating before the final pressure, preheating condition is 70～100 ℃, 2～5MPa, 2～4 minutes.
Adopt above system film formulation and technological process, with the band casting make all more even with thickness membranously, mechanical strength is higher.Its voidage 〉=50%, in battery the membrane gas barrier ability higher (〉=0.9MPa), the maximum diameter of hole is≤1 μ m, and higher chemical property is arranged simultaneously.Its chemical property is not less than the film that makes with organic solvent.Therefore to prepare diaphragm for molten carbonate fuel battery with water to replace organic solvent be successful in the present invention, and it is respond well.
The technology of the present invention both can be used to prepare diaphragm for molten carbonate fuel battery, also can be used to prepare the diaphragm seal of catalytic membrane and pressure vessels for the chemical industry.Because in the filming technology process, be solvent with water, avoid using a large amount of organic solvents, overcome cause thus to the human body serious harm with to problems such as severe environmental pollutions, make fuel cell-green energy resource contain more true meaning.Therefore will come into one's own day by day and more and more widely be applied in the technical process of various system films.In a word:
1. to prepare barrier film be unique solvent with water in the present invention, replaces preparing a large amount of organic solvents that use of barrier film in the past, eliminated to the human body serious harm with to problems such as severe environmental pollutions.
2. in the system film formulation, most of and a large amount of components are nontoxic to human body, and minority and a small amount of component are to the human body low toxicity.
3. during hot pressing, low-temp low-pressure can be with the barrier film pressing.
4. when barrier film was stored, barrier film can be placed in room temperature and atmosphere, need not the dried equipment of special guarantor.
Description of drawings:
Fig. 1 is charging sequence and the technological process that solvent prepares barrier film with water;
The precompressed schematic diagram of Fig. 2 film, wherein 1: mylar, 2: film.
The final pressure schematic diagram of Fig. 3 film, wherein 1: mylar, 2: film.
Embodiment:
1. prepare burden
α-LiAlO
2: 45.0 grams (coarse fodder (particle diameter＞1 μ m) 80～95%, fines (particle diameter＜1 μ m) 5～20%)
Polyvinyl alcohol (PVA): 7.0～12.0 grams
Lactic acid: 1.5～3.0 grams
Glycerine and glyceryl triacetate and ethylene glycol mixture (glycerine and glyceryl triacetate respectively account for 1/4～1/3): 4.0-8.0
Polyether compound: 0.6～1.2 gram
Water: α-LiAlO
22.5～4.5 times of powder
In order to make the barrier film powder really meet the rerum natura requirement of ceramic powder, α-LiAlO
2Powder has certain thickness ratio.Polyvinyl alcohol (PVA), lactic acid, glycerine and glyceryl triacetate and ethylene glycol mixture are respectively binding agent, dispersant and mixed plasticizer.The relative citric acid acidity of lactic acid is more weak, can reduce α-LiAlO
2Powder hydrolysis rate at room temperature has the effect of stabilizing powder state.What use in this prescription is mixed plasticizer, and it has water storage plasticising, the effect of blend component and stabilising system.
2. technological process
In order to make the barrier film powder really meet the rerum natura requirement of ceramic powder, charging sequence and filming technology flow process are undertaken by Fig. 1.70～90% coarse fodder is added when ball milling begins, and all the other coarse fodders are added after 30～50 hours at ball milling.Behind ball milling to 80～100 hour, more than feeding intake just becomes slurry.As the increase that feeds intake, the proper extension ball milling time.
3. with band casting film forming
Filter slurry with 100 order stainless (steel) wires.Under 0.09～0.099MPa vacuum and stirring (50～60 rev/mins), remove the bubble in the slurry, 25～40 minutes time; Amount of slurry for a long time, the proper extension mixing time.Bubble-free slurry band is cast from the glass plate of completing mylar and level glass plate area 50 * 50cm
2
4. the drying of film
More than the barrier film that makes left standstill 1～2 hour, bubble residual or that bring into can break voluntarily in the film.For the composition in the barrier film is fixed up fast, film is wanted rapid draing, otherwise the inorganic powder in the film is sunken to the bottom.Around glass plate, put a frame and (make Outside Dimensions 50 * 50cm, interior hole dimension 48 * 48cm), loam cake porous body by porous material.Porous body can be cardboard, foamed plastics or other porous material etc.The height that props up frame is the height of slurry top small space.This is highly the smaller the better, exceeds to touch slurry.Limited solvent vapo(u)r makes this small space saturated very soon in the film, and barrier film is in the saturated environment of solvent vapo(u)r all the time, can make barrier film rapid draing and does not split.Be aided with suitable heating, keep 20～30 ℃ around it, through 20～30 hours, film was just dry.
5. hot pressing
The film of above drying toasted 6～8 hours in 60～70 ℃ of baking ovens, and part moisture in the evaporation membranes is to avoid following hot pressing or barrier film modification when the start battery.
Hot pressing divides precompressed and final pressure.Dry face (hair side) opposite unites two into one, and carries out precompressed by Fig. 2.The preheating of precompressed elder generation, the condition of preheating is 70～100 ℃, 2～5MPa, 2～4 minutes; Then precompressed, the condition of precompressed is 70～100 ℃, 4～7MPa, 2～4 minutes.
After the precompressed, the control cooling rate, temperature is reduced to about 60 ℃ after 15～30 minutes.Carry out final pressure by Fig. 3.The film 2～4 layers (opening) that above pressure is crossed carries out preheating, and the condition of preheating is the same.The condition of final pressure is 70～100 ℃, 6～9MPa, 2～4 minutes; With same condition cooling.The film of final pressure is battery diaphragm, thickness 0.6～0.8mm, bulk density 1.75～2.00/cm
3
Embodiment 1: prepare burden by prescription:
α-LiAlO
2: 45.0 grams (coarse fodder (particle diameter＞1 μ m) 95%, fines (particle diameter＜1 μ m) 5%)
Polyvinyl alcohol (PVA): 9.0 grams
Lactic acid: 2.3 grams
Glycerine and glyceryl triacetate and ethylene glycol mixture (glycerine and glyceryl triacetate respectively account for 1/4 and 1/3): 5.0 grams
Polyether compound: 0.8 gram
Water: α-LiAlO
24.0 times of powder
Charging sequence and filming technology flow process are undertaken by Fig. 1.Obtaining battery diaphragm thickness after hot pressing is 0.69mm, and bulk density is 1.84g/cm
3
Simulated battery heats up and logical oxygen condition slowly, makes the film specimen.Record its maximum diameter of hole≤1 μ m, voidage 〉=50%.
With one of such film, the porous sintered nickel plate is that negative electrode and sintered porous nickel-chromium alloy plate are that anode is assembled into battery.Heat up slowly and logical oxygen condition under, organic substance volatilization and burning in the film, film becomes the porous film body.At 500 ℃, the carbonate that is put in inside battery in advance begins fusion and soaks in the film.If battery does not have leakage and does not have gas blowby, the logical H in the anode chamber
2+ CO
2(H
2/ CO
2=80/20) gaseous mixture is at the logical O of cathode chamber
2+ CO
2(O
2/ CO
2=40/60) gaseous mixture.Utilance at reaction gas is 20%, and reaction pressure is 0.9MPa, 200 and 364.3mA/cm
2During discharge, cell output voltage is respectively 0.870 and 0.682V.
Embodiment 2
By above prescription batching, make barrier film by Fig. 1 charging sequence and technological process.After hot pressing, the thickness of barrier film is 0.74mm, and its bulk density is 1.81g/cm
3Again by above condition assembling and operation monocell.200 and 392.9mA/cm
2Discharge, cell output voltage are respectively 0.882 and 0.638V.
Embodiment 3
By above system film formulation batching, make barrier film by Fig. 1 charging sequence and technological process.After hot pressing, store, also can directly store (when needing hot pressing afterwards, can in 60-70 ℃ of baking oven, toast hot repressing after 1 hour) without hot pressing in baking oven baking back.The barrier film of above gained is assembled by above condition and the operation monocell store 1 wheat harvesting period in room temperature and air after again.200 and 300mA/cm
2Discharge, cell output voltage are respectively 0.817 and 0.677V.Compare with make and store the barrier film of identical time in room temperature and air with organic solvent, it is much higher with water to be that solvent makes the chemical property of barrier film.
Comparative example 1
People such as U.S. FCE (original name ERC) Huang Chaoming are solvent with water, and polyvinyl alcohol (PVA) is a binding agent, and citric acid is a dispersant, and glycerine is that plasticizer makes barrier film.The rerum natura of barrier film and most of diaphragm for molten carbonate fuel battery basic identical.Even but barrier film is under very high pressure, up to 2000PSI (14.06MPa), barrier film also is difficult to pressing as pressure.
Comparative example 2
India Pores, people such as S.Joseph are solvent with water also, prepare diaphragm for molten carbonate fuel battery with the band casting.The rerum natura of barrier film and most of diaphragm for molten carbonate fuel battery basic identical.But his used barrier film powder is γ-LiAlO
2Powder.γ-LiAlO
2Under the battery operation condition, mutability is α-LiAlO
2
Claims (9)
1, a kind of preparation method of diaphragm for molten carbonate fuel battery, comprise pulp preparation, be with and cast film, drying, heat-press step, it is characterized in that described slurry is solvent with water, with the polyvinyl alcohol is binding agent, with lactic acid is dispersant, with glycerine and glyceryl triacetate and ethylene glycol mixture is plasticizer, so that the α-LiAlO of certain thickness ratio to be arranged
2Be powder, filling a prescription is parts by weight:
Powder: 45.0 parts, the meal material 80-95% of particle diameter＞1 μ m wherein, the fine powder material 5-20% of particle diameter＜1 μ m;
Binding agent: 7.0～12.0 parts;
Dispersant: 1.5～3.0 parts;
Plasticizer: 4.0～8.0 parts;
Solvent: 2.5～4.5 times of powder.
2,, it is characterized in that in the described formula of size adding 0.6～1.2 part of polyether compound as defoamer according to the preparation method of the described diaphragm for molten carbonate fuel battery of claim 1.
3,, it is characterized in that glycerine and glyceryl triacetate respectively account for 1/4～1/3 in the described plasticizer according to the preparation method of the described diaphragm for molten carbonate fuel battery of claim 1.
4, according to the preparation method of claim 1,2 or 3 described diaphragm for molten carbonate fuel battery, it is characterized in that described pulp preparation process is as follows: part meal material, partial solvent, fine powder material, dispersant ball milling add residue meal material after 30～50 hours again; Behind the ball milling 50～70 hours, add binding agent, plasticizer, defoamer and residual solvent at last; Ball milling to 80～100 hour.
5,, it is characterized in that described part meal material is 70～90% of a meal material according to the preparation method of the described diaphragm for molten carbonate fuel battery of claim 4.
6, according to the preparation method of the described diaphragm for molten carbonate fuel battery of claim 4, it is characterized in that described drying steps is, barrier film is placed the parcel of porous material, under 20～30 ℃, kept 20～30 hours.
7,, it is characterized in that described heat-press step comprises precompressed and final pressure according to the preparation method of the described diaphragm for molten carbonate fuel battery of claim 6:
Prefabricating condition is 70～100 ℃, 4～7MPa, 2～4 minutes;
The final pressure condition is 70～100 ℃, 6～9MPa, 2～4 minutes.
8, according to the preparation method of the described diaphragm for molten carbonate fuel battery of claim 7, it is characterized in that the preceding first preheating of described precompressed, preheating condition is 70～100 ℃, 2～5MPa, 2～4 minutes.
9, according to the preparation method of the described diaphragm for molten carbonate fuel battery of claim 7, it is characterized in that the preceding first preheating of described final pressure, preheating condition is 70～100 ℃, 2～5MPa, 2～4 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101052541A CN1255886C (en) | 2003-12-03 | 2003-12-03 | Method for preparing diaphragm of molten carbonate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101052541A CN1255886C (en) | 2003-12-03 | 2003-12-03 | Method for preparing diaphragm of molten carbonate fuel cell |
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|---|---|
| CN1624951A CN1624951A (en) | 2005-06-08 |
| CN1255886C true CN1255886C (en) | 2006-05-10 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314142C (en) * | 2005-09-15 | 2007-05-02 | 上海交通大学 | Method for preparing melting carbonate fuel cell membrane using water-based flow casting technique |
| CN102299350B (en) * | 2010-06-23 | 2014-09-03 | 中国科学院大连化学物理研究所 | Diaphragm of molten carbonate fuel cell and preparation of diaphragm with composite pore structure |
| 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 |
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2003
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