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Ca-doping medium-low-temperature solid oxide fuel battery cathode material

A fuel cell cathode and solid oxide technology, which is applied to solid electrolyte fuel cells, battery electrodes, circuits, etc., can solve the problems of reduced conductivity and electrochemical performance, reduced thermal expansion coefficient, and high thermal expansion coefficient, so as to improve electrical conductivity, Reduced thermal expansion coefficient and excellent performance

Inactive Publication Date: 2017-02-22
JIANGSU UNIV
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Problems solved by technology

The cobalt-based perovskite structure cathode material has high oxygen ion-electron conductivity characteristics and good catalytic activity, but its thermal expansion coefficient is quite different from that of the electrolyte (T.V.Aksenova, L.Yu.Gavrilova, A.A.Yaremchenko, V.A.Cherepanov,V.V.Kharton,Oxygen nonstoichiometry,thermal expansion and high-temperature electrical properties of layered NdBaCo 2 o 5+δ and SmBaCo 2 o 5+δ ), the thermal matching between the cathode and the electrolyte material is poor, and the high thermal expansion coefficient of the cobalt-based double perovskite cathode material is mainly related to C o 3+ content related
Zhiwen Zhu et al. found that the thermal expansion coefficient of B-site Cu doping decreased significantly, but the electrical conductivity and electrochemical performance decreased simultaneously (Zhiwen Zhu, ZetianTao, Lei Bi, Wei Liu, Investigation of SmBaCuCoO 5+d double-perovskite as cathode for proton-conducting solid oxide fuel cells, Materials Research Bulletin 2010, 45:1771)

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Example 1: PrBa 0.999 Ca 0.001 CoCuO 5+δ Powder preparation

[0019] Weigh 11.6869g of EDTA (analytical pure) and add it to deionized water, add ammonia water dropwise to adjust the pH of the solution to 6, and obtain mixed solution A; weigh 16.8112g of citric acid (analytical pure) and add it to deionized water, add ammonia water dropwise to adjust the pH of the solution value is 6, to obtain the mixed solution B; weigh Pr(NO 3 ) 3 ·6H 2 O (analytical pure) 4.3501g, Ba (NO 3 ) 2 (analytical pure) 2.6108g, Ca(NO 3 ) 2 4H 2 O (analytical pure) 0.00024g, Co (NO 3 ) 2 ·6H 2 O (analytical pure) 2.9103g and Cu (NO 3 ) 2 ·3H 2 O (analytical pure) 2.416g was dissolved in deionized water to obtain metal salt solution C; metal salt solution C and mixed solution B were added to mixed solution A, then heated and stirred in a water bath at 80°C for 12 hours, and evaporated to dryness to obtain a gel ; The resulting gel was treated at a low temperature of 250°C to ob...

Embodiment 2

[0020] Example 2: 80wt.% PrBa 0.4 Ca0.6 CoCuO 5+δ -20wt.%Gd 0.1 Ce 0.9 o 1.95 Powder preparation

[0021] Weigh 11.6869g of EDTA (analytical pure) and add it to deionized water, add ammonia water dropwise to adjust the pH of the solution to 6, and obtain mixed solution A; weigh 16.8112g of citric acid (analytical pure) and add it to deionized water, add ammonia water dropwise to adjust the pH of the solution value is 6, to obtain the mixed solution B; weigh Pr(NO 3 ) 3 ·6H 2 O (analytical pure) 4.3501g, Ba (NO 3 ) 2 (Analytical pure) 1.4635g, Ca(NO 3 ) 2 4H 2 O (analytical pure) 0.8502g, Co (NO 3 ) 2 ·6H 2 O (analytical pure) 2.9103g and Cu (NO 3 ) 2 ·3H 2 O (analytical pure) 2.4160g was dissolved in deionized water to obtain metal salt solution C; metal salt solution C and mixed solution B were added to mixed solution A, then heated and stirred in a water bath at 80°C for 12 hours, and evaporated to dryness to obtain a gel ; The resulting gel was treated at ...

Embodiment 3

[0024] Example 3 50wt.% PrCaCoCuO 5+δ -50wt.%Sm 0.2 Ce 0.8 o 1.9

[0025] Weigh 11.67g of EDTA (analytical pure) and add it to deionized water, add ammonia water dropwise to adjust the pH of the solution to 7, and obtain mixed solution A; weigh 16.8112g of citric acid (analytical pure) and add it to deionized water, add ammonia water dropwise to adjust the pH of the solution value is 7, to get the mixed solution B; weigh Pr(NO 3 ) 3 ·6H 2 O (analytical pure) 4.3501g, Ca (NO 3 ) 2 4H 2 O (analytical pure) 2.3616g, Co (NO 3 ) 2 ·6H 2 O (analytical pure) 2.9103g and Cu (NO 3 ) 2 ·3H 2 O (analytical pure) 2.4160g was dissolved in deionized water to obtain metal salt solution C; metal salt solution C and mixed solution B were added to mixed solution A, then heated and stirred in a water bath at 80°C for 12 hours, and evaporated to dryness to obtain a gel ; The obtained gel was treated at a low temperature of 350°C to obtain the battery cathode material—PrCaCoCuO 5+δ...

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Abstract

The invention provides a Ca-doping medium-low-temperature solid oxide fuel battery cathode material, which has the composition general formula of yPrBa1-xCaxCoCuO5+delta-(1-y)M, wherein x is 0.001 to 1.0; delta is 0 to 1.0; y is 10 weight percent to 100 weight percent; M is one or the combination of more than one of Gd0.1Ce0.9O1.95, Gd0.2Ce0.8O1.9, Sm0.1Ce0.9O1.95, Sm0.2Ce0.9O1.9, Y0.16Zr0.92O2.08 and Sc0.2Ce0.01Zr0.89O2.1. The cathode material provided by the invention has the advantages that the Ca is doped into a site A of Pr BaCuCoO5+delta so as to improve the material electric conductivity and the electric chemical performance; meanwhile, the heat expansion coefficient of the material is reduced; the SOFC cathode material with excellent performance can be obtained, so that the cathode material has high oxygen catalytic reduction activity and electric conductivity in the medium-low temperature range; the polarization impedance at 700 DEG C is only 0.014 ohm cm<2>; the maximum output power of the corresponding single battery is as high as 1331 mW cm<-2> at 800 DEG C.

Description

technical field [0001] The invention belongs to the field of battery cathode material preparation, and in particular relates to a cathode material suitable for medium and low temperature calcium-doped medium and low temperature solid oxide fuel cells. Background technique [0002] With the over-exploitation and low-efficiency use of fossil energy, the environment is deteriorating day by day, and these problems seriously restrict the sustainable development of the economy. As a green energy conversion device, solid oxide fuel cell (SOFC) is expected to alleviate the above problems due to its high energy conversion efficiency and wide range of fuel applications. Reducing the operating temperature of SOFC to the medium and low temperature range (500-800°C) and having better thermal matching performance are the keys to realize its commercialization. However, as the operating temperature decreases, the oxygen catalytic reduction activity of conventional cathode materials decreas...

Claims

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Application Information

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IPC IPC(8): H01M4/86H01M4/90H01M8/10
CPCH01M4/86H01M4/9016H01M8/10Y02E60/50
Inventor 庞胜利沈湘黔苏彦靖王文智
Owner JIANGSU UNIV
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