CN100580989C - Solid carbon anode molten carbonate fuel cell - Google Patents
Solid carbon anode molten carbonate fuel cell Download PDFInfo
- Publication number
- CN100580989C CN100580989C CN200710072467A CN200710072467A CN100580989C CN 100580989 C CN100580989 C CN 100580989C CN 200710072467 A CN200710072467 A CN 200710072467A CN 200710072467 A CN200710072467 A CN 200710072467A CN 100580989 C CN100580989 C CN 100580989C
- Authority
- CN
- China
- Prior art keywords
- fuel cell
- molten carbonate
- solid carbon
- carbonate fuel
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 239000007787 solid Substances 0.000 title claims abstract description 32
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910010093 LiAlO Inorganic materials 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003245 coal Substances 0.000 abstract description 8
- 239000003345 natural gas Substances 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000003034 coal gas Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000004880 explosion Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000003610 charcoal Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002309 gasification Methods 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Fuel Cell (AREA)
Abstract
本发明提供一种固体炭阳极熔融碳酸盐燃料电池，它是一种以Ni1-xLixO为阴极、Li2CO3+K2CO3为电解质、γLiAlO2为电解质载体隔膜，以固体炭作为阳极制备的熔融碳酸盐燃料电池，其中Li2CO3∶K2CO3摩尔比为56%-68%∶44-32%。本发明采用熔融碳酸盐燃料电池的阴极、电解质、隔膜和金属极板等结构，以固体炭取代氢气、煤气和天然气等做为阳极和燃料，构成熔融碳酸盐燃料电池。以固体炭直接为阳极的熔融碳酸盐燃料电池其电效率高，实际效率可达80%，无需对煤等固体炭进行重整气化；可有效的避免阴极NiO溶解导致两极短路的问题；炭来源丰富，价格低廉；炭的化学性质稳定，没有爆炸的危险。The invention provides a solid carbon anode molten carbonate fuel cell, which is a kind of Ni 1-x Li x O as a cathode, Li 2 CO 3 +K 2 CO 3 as an electrolyte, γLiAlO 2 as an electrolyte carrier diaphragm, and A molten carbonate fuel cell prepared with solid carbon as an anode, wherein the molar ratio of Li 2 CO 3 : K 2 CO 3 is 56%-68%: 44-32%. The invention adopts the structure of cathode, electrolyte, diaphragm and metal plate of the molten carbonate fuel cell, and replaces hydrogen, coal gas and natural gas with solid carbon as the anode and fuel to form the molten carbonate fuel cell. The molten carbonate fuel cell with solid carbon directly as the anode has high electrical efficiency, the actual efficiency can reach 80%, and there is no need to reform and gasify solid carbon such as coal; it can effectively avoid the problem of short circuit caused by the dissolution of cathode NiO; The source of carbon is abundant and the price is low; the chemical properties of carbon are stable and there is no danger of explosion.
Description
(1) technical field
The present invention relates to the fuel cell technology field, be specifically related to a kind of with the fuel cell of solid carbon as anode.
(2) background technology
Fuel cell is a kind of electrochemical device that directly chemical energy efficiently, environmental friendliness is changed into electric energy, is a kind of green energy conversion equipment, can solve energy-conservation simultaneously and environmental protection two big world difficult problems.Molten carbonate fuel cell is the fuel cell that is made of porous cathode, porous ceramic electrolyte membrance, porous metals anode, metal polar plate.Its electrolyte is a molten state carbonate, reaction principle schematically as follows:
Anode: 2H
2+ 2CO
3 2-→ 2CO
2+ 2H
2O+4e
-
Negative electrode: O
2+ 2CO
2+ 4e
-→ 2CO
3 2-
Overall reaction: O
2+ 2H
2→ 2H
2O
Molten carbonate fuel cell is a kind of high-temperature battery (600～700 ℃), and plurality of advantages such as have that efficient height, noise are low, pollution-free, UTILIZATION OF VESIDUAL HEAT IN is worth height and the battery structure material is inexpensive is a kind of green power station.
At present, the anode fuel of molten carbonate fuel cell is mainly hydrogen, coal gas and natural gas etc. both at home and abroad, and these fuel have very big shortcoming.Hydrogen exists the danger of blast, and the output of hydrogen only can be satisfied with Chemical Manufacture such as synthetic fertilizer and oil hydrogenation; Coal gas needs by the coal gasification preparation, and this process exists to be polluted and energy consumption problem; Natural gas need be converted into hydrogen-rich gas (H through reforming
2+ the use that just can act as a fuel after CO), interior reformation has increased the structure of battery to a certain extent than renaturation, has reduced its job stability, the industrial chemicals that natural gas is still valuable, its reserves are limited.Molten carbonate fuel cell is in long-term hot operation in addition, and negative electrode NiO can be dissolved in the fused carbonate, the Ni of generation
2+Near dissolved H when being diffused into the anode
2Be reduced into metal Ni particulate, accumulate gradually and be interconnected into the Ni bridge, cause short circuit between negative electrode and anode, thereby limited useful life.Can consult Takao Watanabe, Yoshiyuki Izaki and Yoshihiro Mugikura etc., Applicability ofmolten carbonate fuel cells to various fuels.Journal of Power Sources 160 (2006) 868-871, and Andrew L.Dicks, Molten carbonate fuel cells.Current Opinion in Solid State and Materials Science8 (2004) 379-383.
(3) summary of the invention
The purpose of this invention is to provide a kind of manyly as difficult blast, output height, the reserves of anode with solid carbon, molten carbonate fuel cell does not need to reform and transforms the molten carbonate fuel cell with solid carbon anode of anode fuel.
The object of the present invention is achieved like this: it is a kind of with Ni
1-xLi
xO is negative electrode, Li
2CO
3+ K
2CO
3Be electrolyte, γ LiAlO
2Be electrolyte carrier barrier film, with the molten carbonate fuel cell of solid carbon as anode preparation, wherein Li
2CO
3: K
2CO
3Mol ratio is 56%-68%: 44-32%, the Ni of described negative electrode for being obtained after in-situ oxidation and lithiumation by foam Ni
1-xLi
xO.
The present invention also has some technical characterictics like this:
1, described anode solid carbon is that chemical constituent is the material of carbon, comprises the solid carbon that derives from coal, oil, natural gas, biomass, graphite, plastics or organic waste;
2, described anode solid carbon is the solid carbon of carbon rod, carbon plate, charcoal particle or carbon powder.
Essence of the present invention is to replace hydrogen, coal gas and natural gas etc. as anode with solid carbon, constitutes molten carbonate fuel cell, and when the working temperature of battery was 800 ℃, the actual energy transformation efficiency of battery can reach 80%.The present invention adopts solid carbon such as coal directly to do the fuel of fuel cell, does not directly burn, and without the overheated machine transfer process, need not the gasification of reforming of solid carbon such as coal.Chemical energy with being stored in the solid carbon such as coal by electrochemical oxidation reactions, directly changes into electric energy.
Operation principle of the present invention is:
Anode: C+2CO
3 2-→ 3CO
2+ 4e
-
Negative electrode: O
2+ 2CO
2+ 4e
-→ 2CO
3 2-
Overall reaction: C+O
2→ 2CO
2
The invention has the advantages that with solid carbon directly be the molten carbonate fuel cell of anode, its electrical efficiency height, actual efficiency can reach about 80%, and being higher than with the natural gas is 55% of fuel; Need not during for fuel with the solid carbon the charcoal gasification of reforming, because the present invention is 800 ℃ in the working temperature of battery, be molten condition this moment such as powdered carbon, so need not its gasification of reforming; Can effectively avoid negative electrode Ni
1-xLi
xThe O dissolving causes the two poles of the earth problem of short-circuit, wherein Ni
1-xLi
xO can be NiO etc.; Carbon source is abundant, and is cheap, except that coal, also can utilize the charcoal in reproducible biomass (stalk, shell, cereal cot, grass etc.) even the organic waste; The chemical property of charcoal is stable, does not have the danger of blast.
(4) embodiment
For effect of the present invention is described better, be illustrated with specific embodiment below.
Embodiment 1:
Employing is an anode by the powdered carbon of coal preparation, 62%Li
2CO
3+ 38%K
2CO
3(mol ratio) is electrolyte, and NiO is negative electrode (being obtained through in-situ oxidation and lithiumation by foam Ni), 0.5atm O
2/ CO
2Be oxidant at=1: 2, γ-LiAlO
2Film is an electrolyte carrier barrier film, and preparation is the molten carbonate fuel cell of fuel with the solid carbon, and at 800 ℃, under the 0.75V voltage, current density reaches 80mA/cm
2, corresponding power density reaches 60mW/cm
2
Embodiment 2:
Employing is an anode by the powdered carbon of pine preparation, 62%Li
2CO
3+ 38%K
2CO
3(mol ratio) is electrolyte, and NiO is negative electrode (being obtained through in-situ oxidation and lithiumation by foam Ni), 0.5atm O
2/ CO
2Be oxidant at=1: 2, γ-LiAlO
2Film is an electrolyte carrier barrier film, and preparation is the molten carbonate fuel cell of fuel with the solid carbon, and at 800 ℃, under the 0.78V voltage, current density reaches 84mA/cm
2, corresponding power density reaches 66mW/cm
2
Embodiment 3
Employing is an anode by the powdered carbon of maize straw preparation, 62%Li
2CO
3+ 38%K
2CO
3(mol ratio) is electrolyte, and NiO is negative electrode (being obtained through in-situ oxidation and lithiumation by foam Ni), 0.5atm O
2/ CO
2Be oxidant at=1: 2, γ-LiAlO
2Film is an electrolyte carrier barrier film, and preparation is the molten carbonate fuel cell of fuel with the solid carbon, and at 800 ℃, under the 0.72V voltage, current density reaches 77mA/cm
2, corresponding power density reaches 56mW/cm
2
Embodiment 4
Employing flue dust is anode, 62%Li
2CO
3+ 38%K
2CO
3(mol ratio) is electrolyte, and NiO is negative electrode (being obtained through in-situ oxidation and lithiumation by foam Ni), 0.5atm O
2/ CO
2Be oxidant at=1: 2, γ-LiAlO
2Film is an electrolyte carrier barrier film, and preparation is the molten carbonate fuel cell of fuel with the solid carbon, and at 800 ℃, under the 0.68V voltage, current density reaches 62mA/cm
2, corresponding power density reaches 42mW/cm
2
Embodiment 5
Employing is an anode by the charcoal of oil preparation, 62%Li
2CO
3+ 38%K
2CO
3(mol ratio) is electrolyte, and NiO is negative electrode (being obtained through in-situ oxidation and lithiumation by foam Ni), 0.5atm O
2/ CO
2Be oxidant at=1: 2, γ-LiAlO
2Film is an electrolyte carrier barrier film, and preparation is the molten carbonate fuel cell of fuel with the solid carbon, and at 800 ℃, under the 0.76V voltage, current density reaches 76mA/cm
2, corresponding power density reaches 58mW/cm
2
Embodiment 6
Employing is an anode by the charcoal (the high temperature anoxybiotic is removed fugitive constituent) of polyethylene powder preparation, 62%Li
2CO
3+ 38%K
2CO
3(mol ratio) is electrolyte, and NiO is negative electrode (being obtained through in-situ oxidation and lithiumation by foam Ni), 0.5atm O
2/ CO
2Be oxidant at=1: 2, γ-LiAlO
2Film is an electrolyte carrier barrier film, and preparation is the molten carbonate fuel cell of fuel with the solid carbon, and at 800 ℃, under the 0.77V voltage, current density reaches 81mA/cm
2, corresponding power density reaches 62mW/cm
2
Embodiment 7
The employing graphite powder is an anode, 62%Li
2CO
3+ 38%K
2CO
3(mol ratio) is electrolyte, and NiO is negative electrode (being obtained through in-situ oxidation and lithiumation by foam Ni), 0.5atm O
2/ CO
2Be oxidant at=1: 2, γ-LiAlO
2Film is an electrolyte carrier barrier film, and preparation is the molten carbonate fuel cell of fuel with the solid carbon, and at 800 ℃, under the 0.71V voltage, current density reaches 57mA/cm
2, corresponding power density reaches 40mW/cm
2
Embodiment 8
The employing active carbon is an anode, 62%Li
2CO
3+ 38%K
2CO
3(mol ratio) is electrolyte, and NiO is negative electrode (being obtained through in-situ oxidation and lithiumation by foam Ni), 0.5atm O
2/ CO
2Be oxidant at=1: 2, γ-LiAlO
2Film is an electrolyte carrier barrier film, and preparation is the molten carbonate fuel cell of fuel with the solid carbon, and at 800 ℃, under the 0.79V voltage, current density reaches 92mA/cm
2, corresponding power density reaches 73mW/cm
2
Claims (1)
1. molten carbonate fuel cell with solid carbon anode is characterized in that: it is that to adopt active carbon be anode, and mol ratio is 62%Li
2CO
3+ 38%K
2CO
3Being electrolyte, is negative electrode by foam Ni through the NiO of in-situ oxidation and lithiumation acquisition, 0.5atmO
2/ CO
2Be oxidant at=1: 2, γ-LiAlO
2Film is an electrolyte carrier barrier film, preparation be the molten carbonate fuel cell of fuel with the solid carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710072467A CN100580989C (en) | 2007-07-06 | 2007-07-06 | Solid carbon anode molten carbonate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710072467A CN100580989C (en) | 2007-07-06 | 2007-07-06 | Solid carbon anode molten carbonate fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101090159A CN101090159A (en) | 2007-12-19 |
| CN100580989C true CN100580989C (en) | 2010-01-13 |
Family
ID=38943389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710072467A Expired - Fee Related CN100580989C (en) | 2007-07-06 | 2007-07-06 | Solid carbon anode molten carbonate fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100580989C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014151184A1 (en) * | 2013-03-15 | 2014-09-25 | Exxonmobil Research And Engineering Company | Integrated power generation and carbon capture using fuel cells |
| CN109868168A (en) * | 2019-02-28 | 2019-06-11 | 北京科技大学 | A kind of colm high value added utilization method |
| CN110707347B (en) * | 2019-09-11 | 2021-10-22 | 华中科技大学 | A high power density molten carbonate direct coal/carbon fuel cell |
-
2007
- 2007-07-06 CN CN200710072467A patent/CN100580989C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101090159A (en) | 2007-12-19 |
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Granted publication date: 20100113 Termination date: 20120706 |