CN102306806B - Ternary composite matrix anode material for molten carbonate fuel cell (MCFC) and preparation method of ternary composite matrix anode material - Google Patents
Ternary composite matrix anode material for molten carbonate fuel cell (MCFC) and preparation method of ternary composite matrix anode material Download PDFInfo
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- CN102306806B CN102306806B CN201110243588.XA CN201110243588A CN102306806B CN 102306806 B CN102306806 B CN 102306806B CN 201110243588 A CN201110243588 A CN 201110243588A CN 102306806 B CN102306806 B CN 102306806B
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- 239000011159 matrix material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000446 fuel Substances 0.000 title claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 7
- 239000010405 anode material Substances 0.000 title abstract 5
- 239000011206 ternary composite Substances 0.000 title abstract 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 50
- 239000010406 cathode material Substances 0.000 claims description 44
- 239000002105 nanoparticle Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 37
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 36
- 229910012820 LiCoO Inorganic materials 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 33
- 239000000725 suspension Substances 0.000 claims description 29
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 28
- 229910010586 LiFeO 2 Inorganic materials 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000001962 electrophoresis Methods 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000009841 combustion method Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 abstract description 16
- 238000000151 deposition Methods 0.000 abstract description 7
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- 229910010584 LiFeO2 Inorganic materials 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 34
- 238000004090 dissolution Methods 0.000 description 14
- 238000009826 distribution Methods 0.000 description 10
- 238000012876 topography Methods 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229910001453 nickel ion Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229910013733 LiCo Inorganic materials 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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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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Abstract
The invention discloses a ternary composite matrix anode material for a molten carbonate fuel cell (MCFC) and a preparation method of the ternary composite matrix anode material. The preparation method comprises the following steps of: depositing two nano ceramic particles with high properties on a porous nickel matrix simultaneously; and sintering under an inert atmosphere, and thus obtaining a composite matrix anode, wherein the nano ceramic particles mainly comprise LiCoO2 and one of LiFeO2 and CeO2, and the deposited polynary nano ceramic particle layer is uniformly distributed on the surface of the porous nickel matrix and has high bonding force together with the matrix. The ternary composite matrix anode material has high mechanical strength, high deformation resistance, high dissolving resistance, a simple preparation process and extremely short preparation time and can be used for MCFC stack actual industries.
Description
Technical field
The invention belongs to new energy materials technical field, be specifically related to a kind of molten carbonate fuel cell tri compound substrate cathode material and preparation method thereof.
Background technology
Molten carbonate fuel cell (MCFC) is because it has efficiently, cleans, fuel source extensively and not needs to use noble metal to make the advantages such as catalyst, becomes one of the Blast Furnace Top Gas Recovery Turbine Unit (TRT) that chemical energy is converted into the tool application prospect of electric energy.And realized and having commercially produced.The slow dissolving of right its negative electrode and the battery short circuit problem causing thereof are the principal elements that affects battery life and hinder its further large-scale commercial always.Ideal cathode material should possess good toughness and mechanical strength, good anti-deformation, antilysis and chemical property.At present, not yet find to substitute completely the one-component material of traditional lithiated nickel oxide negative electrode, therefore, composite cathode material becomes study hotspot because having the premium properties of each material concurrently.Most multi-element composite material is all to form with mixed sinterings such as ceramic powders, need fully to mix to prevent material component inequality, and made composite cathode has certain fragility in making.And the electrode material area using in actual MCFC industry is large and thin thickness, thereby this just requires material to have good mechanical strength and toughness is conducive to battery pile installation, to be avoided affecting battery life because of the too early destruction of material.In addition, preparation time is also one of important indicator realizing suitability for industrialized production.
Summary of the invention
The object of the invention is to prepare at short notice there is good mechanical strength, good anti-deformation and the polynary composite cathode material of antilysis performance, can be applicable to actual MCFC battery pile industrial production.
For achieving the above object, the technical solution used in the present invention is: prepare the nano-ceramic particle of several function admirables, two kinds of nanoparticulate dispersed are wherein made to suspension in applicable dispersant.Take nickel porous material as negative electrode, platinum electrode is anode, adopt electrophoretic deposition technique, control the parameters such as suitable suspension concentration, pH of suspension value, electrophoretic voltage and electrophoresis time, by nano-particle modified in porous Ni-base surface, and in inert atmosphere, process 1 hour, make tri compound substrate cathode material.
Molten carbonate fuel cell tri compound substrate cathode material in the present invention is porous (nano-LiCoO
2-CeO
2)-Ni or porous (nano-LiCoO
2-LiFeO
2)-Ni material, its porosity is 65%～75%; Wherein to account for the mass percent of complex matrix cathode material be 1.2～2.2% to nano-ceramic particle coating; Described nano-ceramic particle coating is nano-LiCoO
2-CeO
2or nano-LiCoO
2-LiFeO
2.
The preparation method of above-mentioned material comprises the following steps:
Step 1. adopts gel combustion method, controls 600 ℃～700 ℃ of calcining heats, prepares LiCoO
2, CeO
2and LiFeO
2nano particle;
Step 2. is scattered in nano particle group in dispersant, to make suspension;
Described nano particle group is LiCoO
2/ CeO
2or LiCoO
2/ LiFeO
2; When nano particle group is LiCoO
2/ CeO
2time, LiCoO
2with CeO
2mol ratio be 3～6:1, its corresponding dispersant is isopropyl alcohol and ethylene glycol mixture, the volume ratio of isopropyl alcohol and ethylene glycol is 2～5:1; When nano particle group is LiCoO
2/ LiFeO
2time, LiCoO
2with LiFeO
2mol ratio be 4～8:1, its corresponding dispersant is isopropyl alcohol;
Described nano particle group and suspension ratio are: 0.1g～0.5g/50ml;
Step 3. regulates pH value to 2～6 of suspension;
In the suspension that step 4. is made in step 3, take nickel porous as negative electrode, and platinized platinum is anode, and electrode distance is 2 centimetres～3.5 centimetres, controlling electrophoretic voltage and be 35 volts～100 volts, electrophoresis time is 1 minute～5 minutes, and nano particle group is modified to porous nickel surface;
The sample that step 5 makes step 4 in 600 ℃～700 ℃ sintering 1 hour, is made tri compound substrate cathode material in inert atmosphere.
In said method, the electrode distance in step 4 is preferably 2.5 centimetres, and electrophoretic voltage is preferably 55 volts～75 volts, electrophoresis time and is preferably 1.5 minutes～and 2.5 minutes.
Compared with prior art, the invention has the beneficial effects as follows:
Tri compound substrate cathode has good toughness and intensity, and be convenient to MCFC battery pile and install, and the tri compound work negative electrode that energy converted in-situ is function admirable startup stage of MCFC.Compare with traditional porous Ni-base negative electrode, tri compound substrate cathode demonstrates good anti-deformation and antilysis performance in simulation is MCFC startup stage.The nano particle coating on composite cathode material surface is evenly fine and close, good with porous Ni-base material bond strength.Thickness of coating is very thin, can the original loose structure of fine maintenance.Tri compound substrate cathode material preparation process is simple, and feed liquid can be recycled, easy to operate and repetition.Manufacturing cycle is extremely short, is easy to realize large-scale industrial production.
The preparation method of complex matrix negative electrode of the present invention is simple, and controlled and repeated high, manufacturing cycle is short.Utilize the toughness that metal and nano-ceramic particle are good, be applicable to MCFC actual industrial.
Accompanying drawing explanation
Fig. 1 is the LiCoO of preparation
2-CeO
2the scanning electron microscope (SEM) photograph of-Ni tri compound substrate cathode material.
Fig. 2 is the LiCoO of preparation
2-CeO
2the energy dispersive spectrogram of-Ni tri compound substrate cathode material.
Fig. 3 is the LiCoO of preparation
2-CeO
2the inflection curves of-Ni tri compound substrate cathode material under simulation MCFC Start-up and operating performance condition.
Fig. 4 is LiCoO
2-CeO
2-Ni substrate cathode material is the scanning electron microscope (SEM) photograph after deformation/dissolution experiment in position.
Fig. 5 is LiCoO
2-CeO
2-Ni substrate cathode material is the Ni distribution diagram of element after deformation/dissolution experiment in position.
Fig. 6 is LiCoO
2-CeO
2-Ni substrate cathode material is the Co distribution diagram of element after deformation/dissolution experiment in position.
Fig. 7 is LiCoO
2-CeO
2-Ni substrate cathode material is the Ce distribution diagram of element after deformation/dissolution experiment in position.
Fig. 8 is the LiCoO of preparation
2-LiFeO
2the scanning electron microscope (SEM) photograph of-Ni tri compound substrate cathode material.
Fig. 9 is the LiCoO of preparation
2-LiFeO
2the energy dispersive spectrogram of-Ni tri compound substrate cathode material.
Figure 10 is the LiCoO of preparation
2-LiFeO
2the inflection curves of-Ni tri compound substrate cathode material under simulation MCFC Start-up and operating performance condition.
Figure 11 is LiCoO
2-LiFeO
2-Ni substrate cathode material is the scanning electron microscope (SEM) photograph after deformation/dissolution experiment in position.
Figure 12 is LiCoO
2-LiFeO
2-Ni substrate cathode material is the Ni distribution diagram of element after deformation/dissolution experiment in position.
Figure 13 is LiCoO
2-LiFeO
2-Ni substrate cathode material is the Co distribution diagram of element after deformation/dissolution experiment in position.
Figure 14 is LiCoO
2-LiFeO
2-Ni substrate cathode material is the Fe distribution diagram of element after deformation/dissolution experiment in position.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but the scope of protection of present invention is not limited to the scope that embodiment expresses.
Embodiment 1
Tri compound substrate cathode in the present embodiment obtains by following steps:
Adopt gel combustion method, control the calcining heat of 650 ℃, prepare LiCoO
2and CeO
2two kinds of nano particles.The 0.2g LiCoO that is 4:1 by mol ratio
2/ CeO
2it is in the isopropyl alcohol of 3:1 and the mixed liquor of ethylene glycol that mixture of nanoparticles is scattered in 50ml volume ratio, makes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of making, take nickel porous as negative electrode, platinized platinum is anode, and electrode distance is 2.5 centimetres, and controlling electrophoretic voltage and be 65 volts, electrophoresis time is 2 minutes, and nano particle group is modified to porous nickel surface.In inert atmosphere, in 650 ℃ of sintering 1 hour, make porous (nano-LiCoO
2-CeO
2)-Ni tri compound substrate cathode material.
The surface topography of the complex matrix negative electrode of preparation is measured by scanning electron microscopy, as shown in Figure 1.The nano-ceramic particle of deposition is evenly distributed on porous Ni-base surface, forms fine and close coated coating.Even in hole, coating is still evenly fine and close.Thickness of coating is thin, and complex matrix negative electrode maintains original loose structure well.
The element of complex matrix cathode material forms by X ray energy dispersive spectrum to be measured, as shown in Figure 2.Except nickel element, in material, also there is cobalt, cerium and oxygen element.This result shows, LiCoO
2and CeO
2two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Deformation/the solubility property of complex matrix cathode material is by self-built original position deformation test macro and Atomic Absorption Spectrometry.Complex matrix cathode material is (CO in negative electrode atmosphere
2: O
2: N
2for 0.20:0.15:0.65) in 650 ℃ and 3.51 * 10
5nm
-2inflection curves under bearing a heavy burden as shown in Figure 3.Fig. 3 shows, traditional porous Ni-base negative electrode is under simulation MCFC Start-up and operating performance condition, and deformation is obvious, especially start first 20 hours, with nickel porous, gradate as lithiated nickel oxide work negative electrode, and deformation slows down.Comparing with traditional porous Ni-base negative electrode, there is not obvious deformation in tri compound substrate cathode.After experiment, melt nickel ion concentration measurement result in salt and show, nickel porous material is in position in deformation process, and nickel stripping is serious (2.8936mg/L); And trielement composite material only has micro-nickel stripping (0.5178 mg/L).Result shows, compares with traditional porous Ni-base negative electrode, and the tri compound substrate cathode of preparation has good anti-deformation/antilysis performance.
The surface topography of complex matrix negative electrode after deformation/dissolution experiment measured by scanning electron microscopy, as shown in Figure 4.Compare with traditional nickel porous material, composite material in position after deformation/dissolution experiment its surface topography there is not obvious change, surface is still closely being coated nano-ceramic particle.Particle size increases to some extent, is mainly owing to being converted at basis material in the process of work negative electrode, LiCoO
2ceramic particle and matrix nickel have formed LiCo
yni
1-yo cenotype.
The element of complex matrix negative electrode after deformation/dissolution experiment distributes and measures by X ray energy dispersive spectrum, as shown in Fig. 5, Fig. 6 and Fig. 7.Element distributes relevant with the loose structure of material, and hole inner region is darker, is due to ray produce power loss when hole internal reflection goes out.Cobalt and Ce elements in material distribute very evenly, and distribute consistent with nickel element in matrix.Result shows, after Deformation Experiments, the nano ceramics coating of composite material is still coated fine and close at matrix surface, and therefore greatly degree has slowed down deformation and the dissolving of material.
Embodiment 2
Tri compound substrate cathode in the present embodiment obtains by following steps:
Adopt gel combustion method, control the calcining heat of 650 ℃, prepare LiCoO
2and CeO
2two kinds of nano particles.The 0.2g LiCoO that is 3:1 by mol ratio
2/ CeO
2it is in the isopropyl alcohol of 2:1 and the mixed liquor of ethylene glycol that mixture of nanoparticles is scattered in 50ml volume ratio, makes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of making, take nickel porous as negative electrode, platinized platinum is anode, and electrode distance is 2.5 centimetres, and controlling electrophoretic voltage and be 55 volts, electrophoresis time is 2 minutes, and nano particle group is modified to porous nickel surface.In inert atmosphere, in 650 ℃ of sintering 1 hour, make porous (nano-LiCoO
2-CeO
2)-Ni tri compound substrate cathode material.
Surface topography and the element of the tri compound substrate cathode material of preparation forms similar to material prepared in embodiment 1.The nano-ceramic particle coating even compact of deposition; Element in material comprises nickel element, cobalt element, Ce elements and oxygen element, i.e. LiCoO
2and CeO
2two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Equally, complex matrix negative electrode does not have obvious deformation to occur in Deformation Experiments, melts nickel ion concentration in salt and be determined as 0.6257mg/L after experiment.After element distribution image demonstration Deformation Experiments after experiment, the nano ceramics coating of composite material is still coated fine and close at matrix surface, has largely slowed down deformation and the dissolving of material.
Embodiment 3
Tri compound substrate cathode in the present embodiment obtains by following steps:
Adopt gel combustion method, control the calcining heat of 650 ℃, prepare LiCoO
2and CeO
2two kinds of nano particles.The 0.2g LiCoO that is 6:1 by mol ratio
2/ CeO
2it is in the isopropyl alcohol of 5:1 and the mixed liquor of ethylene glycol that mixture of nanoparticles is scattered in 50ml volume ratio, makes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of making, take nickel porous as negative electrode, platinized platinum is anode, and electrode distance is 2.5 centimetres, and controlling electrophoretic voltage and be 75 volts, electrophoresis time is 2 minutes, and nano particle group is modified to porous nickel surface.In inert atmosphere, in 650 ℃ of sintering 1 hour, make porous (nano-LiCoO
2-CeO
2)-Ni tri compound substrate cathode material.
Surface topography and the element of the tri compound substrate cathode material of preparation forms similar to material prepared in embodiment 1.The nano-ceramic particle coating even compact of deposition; Element in material comprises nickel element, cobalt element, Ce elements and oxygen element, i.e. LiCoO
2and CeO
2two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Equally, complex matrix negative electrode does not have obvious deformation to occur in Deformation Experiments, melts nickel ion concentration in salt and be determined as 0.3016mg/L after experiment.After element distribution image demonstration Deformation Experiments after experiment, the nano ceramics coating of composite material is still coated fine and close at matrix surface, and greatly degree has slowed down deformation and the dissolving of material.
Embodiment 4
Tri compound substrate cathode in the present embodiment obtains by following steps:
Adopt gel combustion method, control the calcining heat of 650 ℃, prepare LiCoO
2and LiFeO
2two kinds of nano particles.The 0.2g LiCoO that is 6:1 by mol ratio
2/ LiFeO
2mixture of nanoparticles is scattered in the isopropyl alcohol of 50ml, makes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of making, take nickel porous as negative electrode, platinized platinum is anode, and electrode distance is 2.5 centimetres, and controlling electrophoretic voltage and be 65 volts, electrophoresis time is 2 minutes, and nano particle group is modified to porous nickel surface.In inert atmosphere, in 650 ℃ of sintering 1 hour, make porous (nano-LiCoO
2-LiFeO
2)-Ni tri compound substrate cathode material.
The surface topography of the complex matrix negative electrode of preparation is measured by scanning electron microscopy, as shown in Figure 8.The nano-ceramic particle of deposition is evenly distributed on porous Ni-base surface, forms fine and close coating layer.Even in hole, coating is still evenly fine and close.Thickness of coating is thin, and complex matrix negative electrode maintains original loose structure well.
The element of complex matrix cathode material forms by X ray energy dispersive spectrum to be measured, as shown in Figure 9.Except nickel element, in material, also there is cobalt, iron and oxygen element.This result shows, LiCoO
2and LiFeO
2two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Deformation/the solubility property of complex matrix cathode material is by self-built original position deformation test macro and Atomic Absorption Spectrometry.Complex matrix cathode material is (CO in negative electrode atmosphere
2: O
2: N
2for 0.20:0.15:0.65) in 650 ℃ and 3.51 * 10
5nm
-2inflection curves under bearing a heavy burden as shown in figure 10.Figure 10 shows, traditional porous Ni-base negative electrode is under simulation MCFC Start-up and operating performance condition, and deformation is obvious, especially start first 20 hours, with nickel porous, gradate as lithiated nickel oxide work negative electrode, and deformation slows down.Comparing with traditional porous Ni-base negative electrode, there is not obvious deformation in tri compound substrate cathode.After experiment, melt nickel ion concentration measurement result in salt and show, nickel porous material is in position in deformation process, and nickel stripping is serious (2.8936mg/L); And trielement composite material only has the nickel stripping (0.1783mg/L) of denier.Result shows, compares with traditional porous Ni-base negative electrode, and the tri compound substrate cathode of preparation has good anti-deformation/antilysis performance, and compares with 3 with embodiment 1,2, melts in salt nickel ion concentration lower, is due to LiFeO
2the solubility of component in melting salt is extremely low.
The surface topography of complex matrix negative electrode after deformation/dissolution experiment measured by scanning electron microscopy, as shown in figure 11.Compare with traditional nickel porous material, composite material in position after deformation/dissolution experiment its surface topography there is not obvious change, surface is still closely being coated nano-ceramic particle.Particle size increases to some extent, is mainly owing to being converted at basis material in the process of work negative electrode, LiCoO
2ceramic particle and matrix nickel have formed LiCo
yni
1-yo cenotype.
The element of complex matrix negative electrode after deformation/dissolution experiment distributes and measures by X ray energy dispersive spectrum, as shown in Figure 12, Figure 13 and Figure 14.Element distributes relevant with the loose structure of material, and hole inner region is darker, is due to ray produce power loss when hole internal reflection goes out.Cobalt and ferro element in material distribute very evenly, and distribute consistent with nickel element in matrix.Result shows, after Deformation Experiments, the nano ceramics coating of composite material is still coated fine and close at matrix surface, and greatly degree has slowed down deformation and the dissolving of material.
Embodiment 5
Tri compound substrate cathode in the present embodiment obtains by following steps:
Adopt gel combustion method, control the calcining heat of 650 ℃, prepare LiCoO
2and LiFeO
2two kinds of nano particles.The 0.2g LiCoO that is 4:1 by mol ratio
2/ LiFeO
2mixture of nanoparticles is scattered in the isopropyl alcohol of 50ml, makes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of making, take nickel porous as negative electrode, platinized platinum is anode, and electrode distance is 2.5 centimetres, and controlling electrophoretic voltage and be 55 volts, electrophoresis time is 2 minutes, and nano particle group is modified to porous nickel surface.In inert atmosphere, in 650 ℃ of sintering 1 hour, make porous (nano-LiCoO
2-LiFeO
2)-Ni tri compound substrate cathode material.
Surface topography and the element of the tri compound substrate cathode material of preparation forms similar to material prepared in embodiment 4.The nano-ceramic particle coating even compact of deposition; Element in material comprises nickel element, cobalt element, ferro element and oxygen element, i.e. LiCoO
2and LiFeO
2two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Equally, complex matrix negative electrode does not have obvious deformation to occur in Deformation Experiments, melts nickel ion concentration in salt and be determined as 0.1088mg/L after experiment.After element distribution image demonstration Deformation Experiments after experiment, the nano ceramics coating of composite material is still coated fine and close at matrix surface, and therefore very big degree has slowed down deformation and the dissolving of material.
Embodiment 6
Tri compound substrate cathode in the present embodiment obtains by following steps:
Adopt gel combustion method, control the calcining heat of 650 ℃, prepare LiCoO
2and LiFeO
2two kinds of nano particles.The 0.2g LiCoO that is 8:1 by mol ratio
2/ LiFeO
2mixture of nanoparticles is scattered in the isopropyl alcohol of 50ml, makes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of making, take nickel porous as negative electrode, platinized platinum is anode, and electrode distance is 2.5 centimetres, and controlling electrophoretic voltage and be 75 volts, electrophoresis time is 2 minutes, and nano particle group is modified to porous nickel surface.In inert atmosphere, in 650 ℃ of sintering 1 hour, make porous (nano-LiCoO
2-LiFeO
2)-Ni tri compound substrate cathode material.
Surface topography and the element of the tri compound substrate cathode material of preparation forms similar to material prepared in embodiment 4.The nano-ceramic particle coating even compact of deposition; Element in material comprises nickel element, cobalt element, ferro element and oxygen element, i.e. LiCoO
2and LiFeO
2two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Equally, complex matrix negative electrode does not have obvious deformation to occur in Deformation Experiments, melts nickel ion concentration in salt and be determined as 0.2376mg/L after experiment.After element distribution image demonstration Deformation Experiments after experiment, the nano ceramics coating of composite material is still coated fine and close at matrix surface, has largely slowed down deformation and the dissolving of material.
Claims (2)
1. molten carbonate fuel cell tri compound substrate cathode material preparation method, this material is porous (nano-LiCoO
2-CeO
2)-Ni or porous (nano-LiCoO
2-LiFeO
2)-Ni material, its porosity is 65%～75%; Wherein to account for the mass percent of complex matrix cathode material be 1.2～2.2% to nano-ceramic particle coating; Described nano-ceramic particle coating is nano-LiCoO
2-CeO
2or nano-LiCoO
2-LiFeO
2,
It is characterized in that the method comprises the following steps:
Step 2-1. adopts gel combustion method, controls 600 ℃～700 ℃ of calcining heats, prepares LiCoO
2, CeO
2and LiFeO
2nano particle;
Step 2-2. is scattered in nano particle group in dispersant, to make suspension;
Described nano particle group is LiCoO
2/ CeO
2or LiCoO
2/ LiFeO
2; When nano particle group is LiCoO
2/ CeO
2time, LiCoO
2with CeO
2mol ratio be 3～6:1, its corresponding dispersant is isopropyl alcohol and ethylene glycol mixture, the volume ratio of isopropyl alcohol and ethylene glycol is 2～5:1; When nano particle group is LiCoO
2/ LiFeO
2time, LiCoO
2with LiFeO
2mol ratio be 4～8:1, its corresponding dispersant is isopropyl alcohol;
Described nano particle group and suspension ratio are: 0.1g～0.5g/50ml;
Step 2-3. regulates pH value to 2～6 of suspension;
In the suspension that step 2-4. makes at step 2-3, take nickel porous as negative electrode, and platinized platinum is anode, and electrode distance is 2 centimetres～3.5 centimetres, controlling electrophoretic voltage and be 35 volts～100 volts, electrophoresis time is 1 minute～5 minutes, and nano particle group is modified to porous nickel surface;
The sample that step 2-5 makes step 2-4 in 600 ℃～700 ℃ sintering 1 hour, is made tri compound substrate cathode material in inert atmosphere.
2. preparation method according to claim 1, is characterized in that the electrode distance in the method step 2-4 is 2.5 centimetres, and electrophoretic voltage is that 55 volts～75 volts, electrophoresis time are 1.5 minutes～2.5 minutes.
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| CN101076913A (en) * | 2004-01-12 | 2007-11-21 | 燃料电池能有限公司 | Fused carbonate fuel battery cathode with mixed oxide coatings |
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| CN101076913A (en) * | 2004-01-12 | 2007-11-21 | 燃料电池能有限公司 | Fused carbonate fuel battery cathode with mixed oxide coatings |
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| 电化学法多组分修饰制备MCFC复合阴极;陈丽江等;《2009年第十五次全国电化学学术会议论文集》;20091201;第1页 * |
| 陈丽江等.电化学法多组分修饰制备MCFC复合阴极.《2009年第十五次全国电化学学术会议论文集》.2009,1-2. |
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