CN100580989C - Molten carbonate fuel cell with solid carbon anode - Google Patents

Molten carbonate fuel cell with solid carbon anode Download PDF

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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
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China
Prior art keywords
fuel cell
solid carbon
anode
carbonate fuel
molten carbonate
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CN200710072467A
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CN101090159A (en
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王贵领
曹殿学
吕艳卓
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Harbin Engineering University
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Harbin Engineering University
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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

Abstract

This invention provides a solid carbon anode melt carbonate fuel cell taking Nil-xLixO as the cathode, Li2CO3+K2CO3 as the electrolyte and gammaLiAlO2 as the electrolyte carrier membrane and solid carbon as the anode, in which, the mol ratio of LiCO3 : K2CO3 is 56%-68% : 44%-32%, which applies solid carbon as the anode and fuel to replace hydrogen, coal gas, and natural gas to make up of a melt carbonate fuel cell to increase its efficiency.

Description

Molten carbonate fuel cell with solid carbon anode
(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.
CN200710072467A 2007-07-06 2007-07-06 Molten carbonate fuel cell with solid carbon anode Expired - Fee Related CN100580989C (en)

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CN100580989C true CN100580989C (en) 2010-01-13

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Publication number Priority date Publication date Assignee Title
WO2014151194A1 (en) * 2013-03-15 2014-09-25 Exxonmobil Research And Engineering Company Integrated power generation and chemical production 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 High-power-density molten carbonate direct coal/carbon fuel cell

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