Embodiment
Fig. 1 is a flow chart of the present invention, below in conjunction with embodiment the present invention is specified.
Embodiment 1: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material carbon dust 15g, binding agent polyvinyl butyral resin (PVB) 25g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant fish oil 4g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 8%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1450 ℃ of sintering 2 hours, realize electrolytical densification, exerting pressure during sintering is 750Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printing Pd-YSZ cathode functional on the solid oxide fuel half-cell after the densification, the weight ratio of Pd and YSZ 6.6: 94, YSZ is 8%mol Y
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1300 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(5%H in the mist reducing atmosphere
2+ 95%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 11 hours, obtain the metallic nickel support type solid oxide fuel cell.
Fig. 2 is the SEM sectional view of embodiment 1 prepared metallic nickel support type SOFC, as can be seen from the figure, behind high temperature sintering, these other assemblies of cell support body and battery contact well, do not have layering or crackle at the interface and occur, dielectric substrate is very fine and close, no significant defect, and supporter and anode functional layer all present loose structure, help the gas transmission.
Fig. 3 is the X ray diffracting spectrum of embodiment 1 prepared metallic nickel support type SOFC anode layer, as can be seen, the basic Restore All of nickel oxide is a nickel, thus show the nickel oxide supporter 750 ℃ after 11 hours reduction reaction, can be reduced to the metallic nickel supporter of porous.
Fig. 4 be embodiment 1 prepared metallic nickel support type SOFC at 650-800 ℃ of measured V-I curve and P-I curve, test result shows, this battery is respectively 0.23,0.38,0.64 and 0.81w/cm at 650,700,750,800 ℃ maximum power density
2The result shows that the metallic nickel support type SOFC of the present invention's preparation possesses excellent electric performance.
Embodiment 2: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 200g, pore creating material carbon dust 10g, binding agent polyvinyl butyral resin (PVB) 22g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 22g, dispersant fish oil 3g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 96g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 4 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique printed anode functional layer NiO-YSZ and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 8%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 650Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer Pd-YSZ on the solid oxide fuel half-cell after the densification, the weight ratio of Pd and YSZ 7: 93, YSZ is 8%mol Y
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1300 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(4%H in the mist reducing atmosphere
2+ 96%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Fig. 5 is the SEM sectional view of embodiment 2 prepared metallic nickel support type SOFC, as can be seen, when sintering temperature is 1370 ℃, the dielectric substrate of sintering is just very fine and close, the reduction of sintering temperature can prevent that not only supporter is too fine and close when burning altogether, increase reduction difficulty subsequently, and can avoid growing up of anode layer particle, reduce battery performance.
Embodiment 3: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 200g, pore creating material starch 10g, binding agent methylcellulose 22g, plasticizer adipic acid propylene glycol polyester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 22g, dispersant glyceryl tristearate 3g, organic solvent styrene/absolute ethyl alcohol (weight ratio, 1: 1) 96g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 70: 30, and YSZ is 8%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 4: 96, LSCN is the LaCoO that 10%mol Sr and 10%mol Ni mix
3, YSZ is 8%mol
Y
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1150 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H
2With (10%H in the Ar mist reducing atmosphere
2+ 90%Ar vol.%), to the reduction of nickel oxide through 7 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 4: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 200g, pore creating material starch 10g, binding agent methylcellulose 22g, plasticizer adipic acid propylene glycol polyester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 22g, dispersant glyceryl tristearate 3g, organic solvent styrene/absolute ethyl alcohol (weight ratio, 1: 1) 96g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 70: 30, and YSZ is 8%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 8: 92, LSCN is the LaCoO that 10%mol Sr and 10%mol Ni mix
3, YSZ is 8%molY
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1150 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H
2With (10%H in the Ar mist reducing atmosphere
2+ 90%Ar vol.%), to the reduction of nickel oxide through 7 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 5: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material starch 15g, binding agent polyacrylate 25g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant fatty acid polyethylene glycol ester 4g, organic solvent triethanolamine/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 50: 50, and YSZ is 8%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 4: 96, LSCN is the LaCoO that 30%mol Sr and 30%mol Ni mix
3, YSZ is 8%molY
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H
2With (4%H in the Ar mist reducing atmosphere
2+ 96%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 6: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 8%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 8: 92, LSCN is the LaCoO that 30%mol Sr and 30%mol Ni mix
3, YSZ is 8%molY
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(5%H in the mist reducing atmosphere
2+ 95%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 7: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 200g, pore creating material starch 10g, binding agent polyacrylate 22g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 22g, dispersant fatty acid polyethylene glycol ester 3g, organic solvent triethanolamine/absolute ethyl alcohol (weight ratio, 1: 1) 96g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 10%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 4: 96, LSCN is the LaCoO that 30%mol Sr and 30%mol Ni mix
3, YSZ is 10%molY
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1150 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H
2With (6%H in the Ar mist reducing atmosphere
2+ 94%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 8: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material starch 15g, binding agent polyacrylate 25g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant fatty acid polyethylene glycol ester 4g, organic solvent triethanolamine/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 70: 30, and YSZ is 10%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 8: 92, LSCN is the LaCoO that 30%mol Sr and 30%mol Ni mix
3, YSZ is 10%molY
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H
2With (6%H in the Ar mist reducing atmosphere
2+ 94%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 9: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material starch 15g, binding agent polyacrylate 25g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant fatty acid polyethylene glycol ester 4g, organic solvent triethanolamine/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 50: 50, and YSZ is 10%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1390 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 8: 92, LSCN is the LaCoO that 10%mol Sr and 10%mol Ni mix
3, YSZ is 10%molY
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H
2With (6%H in the Ar mist reducing atmosphere
2+ 94%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 10: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material starch 13g, binding agent polyacrylate 25g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant glycerine tristearate 4g, organic solvent styrene/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 10%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 4: 96, LSCN is the LaCoO that 10%mol Sr and 10%mol Ni mix
3, YSZ is 10%molY
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H
2With (6%H in the Ar mist reducing atmosphere
2+ 94%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 11: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 50: 50, and YSZ is 8%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN on the solid oxide fuel half-cell after the densification, LSCN are the LaCoO that 10%mol Sr and 10%molNi mix
3, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H
2With (4%H in the Ar mist reducing atmosphere
2+ 96%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 12: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 40: 60, and YSZ is 10%mol Y
2O
3The ZrO that mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN on the solid oxide fuel half-cell after the densification, LSCN are the LaCoO that 30%mol Sr and 30%molNi mix
3, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed HX and Ar mist reducing atmosphere (5%H
2+ 95%Ar vol.%), to the reduction of nickel oxide through 10 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 13: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-GDC anode functional layer and GDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and GDC weight ratio are 64: 36, and GDC is the CeO that the Gd of 20%mol mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 2: 98, LSCF is the LaFeO of the Co doping of the Sr of 30%mol and 10%mol
3, GDC is the CeO that the Gd of 20%mol mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(5%H in the mist reducing atmosphere
2+ 95%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 14: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-GDC anode functional layer and GDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and GDC weight ratio are 70: 30, and GDC is the CeO that the Gd of 20%mol mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 6: 94, LSCF is the LaFeO of the Co doping of the Sr of 30%mol and 10%mol
3, GDC is the CeO that the Gd of 20%mol mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(5%H in the mist reducing atmosphere
2+ 95%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 15: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 220g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-GDC anode functional layer and GDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and GDC weight ratio are 64: 36, and GDC is the CeO that the Gd of 10%mol mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1380 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 2: 98, LSCF is the LaFeO of the Co doping of the Sr of 30%mol and 10%mol
3, GDC is the CeO that the Gd of 10%mol mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(5%H in the mist reducing atmosphere
2+ 95%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 16: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-GDC anode functional layer and GDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and GDC weight ratio are 70: 30, and GDC is the CeO that the Gd of 10%mol mixes
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 6: 94, LSCF is the LaFeO of the Co doping of the Sr of 30%mol and 10%mol
3, GDC is the CeO that the Gd of 10%mol mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(5%H in the mist reducing atmosphere
2+ 95%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 17: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-SDC anode functional layer and SDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and SDC weight ratio are 64: 36, the CeO that SDC mixes for 10%mol Sm
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 6: 94, LSCF is the LaFeO of the Co doping of the Sr of 50%mol and 30%mol
3, GDC is the CeO that the Gd of 10%mol mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(5%H in the mist reducing atmosphere
2+ 95%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 18: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-SDC anode functional layer and SDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and SDC weight ratio are 70: 30, the CeO that SDC mixes for 10%mol Sm
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 2: 98, LSCF is the LaFeO of the Co doping of the Sr of 50%mol and 30%mol
3, GDC is the CeO that the Gd of 10%mol mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(5%H in the mist reducing atmosphere
2+ 95%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 19: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-SDC anode functional layer and SDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and SDC weight ratio are 64: 36, the CeO that SDC mixes for 20%mol Sm
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 6: 94, LSCF is the LaFeO of the Co doping of the Sr of 50%mol and 30%mol
3, GDC is the CeO that the Gd of 20%mol mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(5%H in the mist reducing atmosphere
2+ 95%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 20: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-SDC anode functional layer and SDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and SDC weight ratio are 64: 36, the CeO that SDC mixes for 20%mol Sm
2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1390 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 2: 98, LSCF is the LaFeO of the Co doping of the Sr of 50%mol and 30%mol
3, GDC is the CeO that the Gd of 20%mol mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H
2And N
2(6%H in the mist reducing atmosphere
2+ 94%N
2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 21: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and LSGM dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 10%mol Y
2O
3The ZrO that mixes
2, LSGM is the LaGaO that 10%mol Sr and 20%mol Mg mix
3, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1390 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 750Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer Pd-YSZ on the solid oxide fuel half-cell after the densification, the weight ratio of Pd and YSZ 7: 93, YSZ is 10%mol Y
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1300 ℃ of sintering temperatures 2 hours, make the soild oxide monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed reducing atmosphere (5%H
2+ 95%N
2, vol.%) in, to the reduction of nickel oxide, prepare the metallic nickel supporter of porous through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 22: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and LSGM dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 10%mol Y
2O
3The ZrO that mixes
2, LSGM is the LaGaO that 15%mol Sr and 25%mol Mg mix
3, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 750Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer Pd-YSZ on the solid oxide fuel half-cell after the densification, the weight ratio of Pd and YSZ 6.6: 94, YSZ is 10%mol Y
2O
3The ZrO that mixes
2, and, realize the sintering of cathode layer and dielectric substrate 1300 ℃ of sintering temperatures 2 hours, make the soild oxide monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed reducing atmosphere (5%H
2+ 95%N
2, vol.%) in, to the reduction of nickel oxide, prepare the metallic nickel supporter of porous through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.