CN117727985B - Electrolyte powder and preparation method and application thereof - Google Patents
Electrolyte powder and preparation method and application thereof Download PDFInfo
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- CN117727985B CN117727985B CN202410172795.8A CN202410172795A CN117727985B CN 117727985 B CN117727985 B CN 117727985B CN 202410172795 A CN202410172795 A CN 202410172795A CN 117727985 B CN117727985 B CN 117727985B
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- acetylacetonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 97
- 239000000843 powder Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 55
- 239000000446 fuel Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims description 34
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 26
- 229910052706 scandium Inorganic materials 0.000 claims description 20
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 18
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 17
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- GAXDEROCNMZYCS-QXMHVHEDSA-N (z)-n,n-dimethyloctadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(C)C GAXDEROCNMZYCS-QXMHVHEDSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-MDZDMXLPSA-N Elaidamide Chemical compound CCCCCCCC\C=C\CCCCCCCC(N)=O FATBGEAMYMYZAF-MDZDMXLPSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- 150000008431 aliphatic amides Chemical class 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 22
- 238000005245 sintering Methods 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 53
- 239000002245 particle Substances 0.000 description 28
- 239000013078 crystal Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000003292 glue Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- -1 oxygen ions Chemical class 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 2
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- YOLBPRFHRRGRGO-UHFFFAOYSA-N cerium;pentane-2,4-dione Chemical compound [Ce].CC(=O)CC(C)=O YOLBPRFHRRGRGO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- DKQGUFYCPQCGKJ-UHFFFAOYSA-N pentane-2,4-dione;scandium Chemical compound [Sc].CC(=O)CC(C)=O DKQGUFYCPQCGKJ-UHFFFAOYSA-N 0.000 description 1
- SGNLDVYVSFANHW-UHFFFAOYSA-N pentane-2,4-dione;zirconium Chemical compound [Zr].CC(=O)CC(C)=O SGNLDVYVSFANHW-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- DBTMQFKUVICLQN-UHFFFAOYSA-K scandium(3+);triacetate Chemical compound [Sc+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBTMQFKUVICLQN-UHFFFAOYSA-K 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Fuel Cell (AREA)
- Conductive Materials (AREA)
Abstract
The invention belongs to the field of fuel cells, and particularly discloses electrolyte powder, a preparation method and application thereof. According to the invention, acetylacetone metal salt and a specific organic solvent are used as reaction raw materials, and electrolyte powder with uniform size, easy dispersion, high purity and good sintering activity can be obtained by controlling the proportion of the reaction raw materials and the two heat treatment processes.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to electrolyte powder, and a preparation method and application thereof.
Background
The fuel cell is an electrochemical device capable of directly converting chemical energy into electric energy, wherein the solid oxide fuel cell has higher working temperature, can realize cogeneration by utilizing waste heat while generating electricity, has high energy utilization efficiency and has wide application prospect. Solid oxide fuel cells generally consist of three parts, an anode, a cathode and an electrolyte, wherein the electrolyte serves to transfer oxygen ions from the cathode to the anode for combination with fuel while isolating air.
In order to ensure high performance operation of the solid oxide fuel cell, the electrolyte needs to have higher strength and good conductivity, and the uniformity of the crystal grain size and the granularity of the powder of the electrolyte also meet certain requirements, and the performances are determined by the preparation method and the process.
Zirconia is one of the most common electrolyte materials in solid oxide fuel cells, which conducts electricity with oxygen vacancies as carriers. At present, the preparation method of the zirconia-based electrolyte mainly comprises a high-temperature solid-phase method, a sol-gel method, a hydrothermal method, a coprecipitation method and the like. However, the existing technology is easy to form large particle aggregates in the preparation process, so that electrolyte particles are uneven, further the strength and conductivity of the electrolyte particles are poor, and meanwhile, the defects of overhigh cost, complex technology and toxicity of the adopted raw materials exist, so that the mass production of electrolyte powder is not facilitated. Therefore, there is a need to develop a method for preparing electrolyte powder having a uniform size and being easily dispersed.
Disclosure of Invention
Aiming at the problems of poor conductivity, strength, grain size uniformity, powder granularity and the like of the electrolyte related to the prior art, the invention provides electrolyte powder and a preparation method and application thereof.
In order to achieve the above purpose, the method specifically comprises the following technical scheme:
the preparation method of the electrolyte powder comprises the following steps:
(1) Zirconium acetylacetonate, scandium acetylacetonate, cerium acetylacetonate and a solvent are mixed to obtain a mixed solution; the molar ratio of zirconium acetylacetonate to scandium acetylacetonate to cerium acetylacetonate is zirconium acetylacetonate to scandium acetylacetonate to cerium acetylacetonate=1 (0.11-0.17) to (0.02-0.08); the solvent comprises at least one of aliphatic amine, aliphatic amide, aliphatic amine oxide and aliphatic amine containing N heteroatom group;
(2) Performing primary heat treatment on the mixed solution under a vacuum condition to obtain a precursor;
(3) And carrying out secondary heat treatment on the precursor under inert gas, and washing and drying to obtain the electrolyte powder.
According to the invention, acetylacetone metal salt and a specific organic solvent are used as reaction raw materials, and electrolyte powder with uniform size, easy dispersion, high purity and good sintering activity can be obtained by controlling the proportion of the reaction raw materials and the two heat treatment processes. Meanwhile, the method disclosed by the invention is simple in process, low in cost, beneficial to large-scale production and very suitable for preparing the electrolyte sheet of the solid oxide fuel cell.
The solvent of the invention is an amphiphilic structure compound which is not dissociated into ionic state in water, and is a nonionic solvent, and the solvent can play the role of both solvent and surfactant, so the solvent is also a nonionic surfactant.
The zirconia-based nano electrolyte powder is prepared by the method of the invention, and has the characteristics of uniform grain size, easy dispersion of powder, high purity and good sintering activity, wherein in the method of the invention, at least one of acetylacetone metal salts such as zirconium acetylacetonate, scandium acetylacetonate and cerium acetylacetonate is used as a solvent, and at least one of nonionic surfactants is used as a solvent, and the solvent can play a role of the surfactant, and compared with other metal salts such as zirconium, scandium and cerium, the decomposition speed of the acetylacetone salt in the high-temperature reaction process is relatively mild, the C-O bond breakage and the nucleation process are slower, the solvent is easier to selectively adsorb around the zirconia crystal nucleus, the aggregation of crystal nuclei is prevented, and the formation of large particle aggregates is easier to be inhibited. Compared with cationic surfactants and anionic surfactants, the nonionic surfactants are better in combination with crystal nucleus, and if the cationic surfactants are adopted, the crystal nucleus cannot be effectively coated due to electrostatic repulsive force, so that the dispersing effect is poor; if the anionic surfactant is adopted, the particle size is smaller, the shrinkage rate is too high in subsequent sintering, the product can generate corrugated fluctuation, and the product requirement cannot be met.
Preferably, in the step (1), the molar ratio of zirconium acetylacetonate, scandium acetylacetonate and cerium acetylacetonate is zirconium acetylacetonate to scandium acetylacetonate to cerium acetylacetonate=1 (0.13-0.16): (0.03-0.05), and the electrolyte powder is better in conductivity and strength when the molar ratio of zirconium acetylacetonate, scandium acetylacetonate and cerium acetylacetonate is adopted.
The proportion of zirconium acetylacetonate, scandium acetylacetonate and cerium acetylacetonate is controlled within a proper range, and the crystal structure of the electrolyte powder can be regulated and controlled to stabilize the electrolyte material. Scandium ions can replace zirconium ions and introduce oxygen vacancies in the lattice through research. Oxygen vacancies distributed around zirconium ions not only reduce the repulsive force between local oxygen and oxygen, so that the coordination layer generates larger distortion, but also can release partial interlayer stress and promote the stability of the generated cubic zirconia, thereby ensuring that the high Wen Lifang phase of the zirconia is reserved to room temperature. If the scandium content is low enough to promote the stability of the zirconia, the phase structure of the zirconia material is changed, so that the grain size is large and the grain size difference is large, and the strength and the conductivity of the electrolyte sheet are further affected; when the scandium content is higher, along with the increase of the sintering temperature, oxygen vacancies are easy to enrich towards the interface with low symmetry, and the increase of vacancies in the zirconia material promotes the diffusion of scandium ions to a certain extent, and finally, the oxygen vacancies and scandium ions undergo a composite reaction at the interface, so that the vacancies in the zirconia material are reduced, and the stability of the electrolyte powder is also reduced.
Cerium ions can promote the high-temperature diffusion process of oxygen vacancies and avoid grain boundary segregation, so that the high-temperature mechanical property and chemical stability of the electrolyte powder are improved, and if the content of cerium element is low, the high-temperature mechanical property and chemical stability of the electrolyte powder are not sufficiently improved; when the content of cerium element is too high, the diffusion rate of oxygen vacancies is too high, which may affect the phase structure stability of zirconia, and thus the strength and conductivity of the electrolyte sheet.
Preferably, the molar concentration of zirconium acetylacetonate in the mixed solution is 0.05-0.25mol/L.
Further preferably, in the step (1), the molar concentration of zirconium acetylacetonate in the mixed solution is 0.1 to 0.2mol/L.
The concentration of zirconium acetylacetonate in the mixed solution system, namely the ratio of the quantity of zirconium acetylacetonate substances to the volume of the solvent, is too high, so that the solvent can only be selectively adsorbed around part of zirconia crystal nuclei to prevent aggregation of part of zirconia crystal nuclei, and large particle aggregates still exist in the finally obtained electrolyte powder, which is not beneficial to ensuring the uniformity of particle sizes. The concentration of zirconium acetylacetonate in the mixed system is too low, so that the temperature consistency of each position in the reaction system is not guaranteed, the phenomenon of partial high or low temperature exists, and the size consistency of electrolyte powder particles is also not guaranteed, so that the particle size consistency is better and the conductivity and strength of the electrolyte sheet prepared from the electrolyte powder are better when the concentration of zirconium acetylacetonate is adopted.
Preferably, the aliphatic groups include saturated aliphatic groups and unsaturated aliphatic groups, the aliphatic groups having a carbon chain length of from C9 to C20, and the N-heteroatom containing groups include N, N-dimethyl groups.
Preferably, in step (1), the solvent has a relative molecular mass between 260 and 330 and a boiling point greater than 350 ℃; further preferably, the solvent comprises at least one of Z-N, N-dimethyl-9-octadecenamide, erucamide, N-oxo-N, N-dimethyl-9-octadecenamide, 9-octadecenamide.
When the solvent is selected, the functional group contained in the solvent has a proper relative molecular mass, has a good binding force with zirconia crystal nucleus, can achieve a good dispersing effect, has a proper boiling point and a good thermal stability, and cannot volatilize or decompose in the reaction.
In the step (2), the temperature of the first heat treatment is 100-120 ℃, the time of the first heat treatment is 0.5-1h, and the heating rate of the first heat treatment is 20-30 ℃/min.
The first heat treatment in the step (2) can remove the moisture and low boiling point impurities in the reaction system, and avoid affecting the synthesis process.
Preferably, in step (3), the temperature of the second heat treatment is 270 to 350 ℃, preferably the temperature of the second heat treatment is 280 to 340 ℃, and more preferably the temperature of the second heat treatment is 280 to 300 ℃.
If the temperature of the second heat treatment is too high, the solvent gradually decomposes, and the amount of the solvent selectively adsorbed around the zirconia crystal nuclei is small, so that the zirconia crystal nuclei are liable to aggregate, and thus the zirconia large-particle agglomerates are formed. When the zirconium oxide large particles are used for preparing the electrolyte sheet, the sintering activity of the zirconium oxide large particles is slightly poor, and the shrinkage consistency in the sintering process of the electrolyte sheet is influenced, so that the strength and the conductivity of the electrolyte sheet are influenced. If the temperature of the second heat treatment is too low, the formation of zirconia particle aggregates can be effectively inhibited under the action of a solvent to obtain zirconia particles with uniform size, but the particle size is smaller, the shrinkage rate is too high in the subsequent sintering, the product can generate corrugated fluctuation, an electrolyte sheet with the corrugated fluctuation is easy to crack, and in the process of combining with a cathode and an anode of a battery to form a single battery, the electrode thickness difference is large, the current is uneven, the strength and the conductivity of the battery are affected, so that the electrolyte sheet with the corrugated fluctuation cannot meet the product requirement. Within the second heat treatment temperature, the electrolyte powder is better in conductivity and strength.
Preferably, in step (3), the time of the second heat treatment is 0.5 to 3 hours, preferably the time of the second heat treatment is 1 to 2 hours, and more preferably the time of the second heat treatment is 1 to 1.7 hours.
If the second heat treatment time in the step (3) is too short, the obtained zirconia particles have smaller size, and the electrolyte sheet can also generate ripple fluctuation, which is not beneficial to the improvement of the product performance. If the second heat treatment in step (3) is too long, the obtained zirconia particles have a larger size, and when the zirconia particles are used for producing an electrolyte sheet, the pores are difficult to migrate to the vicinity of the grain boundaries and discharge even after plastic flow, so that the internal porosity of the product is high, and the strength and conductivity of the product are poor, and therefore, the conductivity and strength of the electrolyte sheet produced from the electrolyte powder are better within the second heat treatment time.
Preferably, in the step (3), the heating rate of the second heat treatment is 10-50 ℃/min, and more preferably, the heating rate of the second heat treatment is 10-40 ℃/min.
In the step (3), if the temperature rising rate of the second heat treatment is too fast, the temperature consistency of each position in the reaction system is poor, so that the difference of the particle growth rates of zirconia at different positions is caused, the consistency of electrolyte powder particles is not facilitated, and zirconia particle aggregates are usually present, which can influence the shrinkage consistency in the sintering process, and further influence the strength and the conductivity of the electrolyte sheet; if the temperature rising rate of the second heat treatment is too slow, the time consumption is long, the production efficiency is reduced, and the production cost is increased, although the temperature consistency of each position in the reaction system is good, so that when the temperature rising rate is adopted, the conductivity and the strength of the electrolyte sheet prepared from the electrolyte powder are better, the efficiency is higher, and the cost is relatively lower.
In the step (3), the solvent used for washing comprises at least one of ethanol, isopropanol, cyclohexane, acetone, chloroform, carbon tetrachloride, methanol and toluene.
In the step (3), the inert gas comprises at least one of argon, nitrogen and helium.
The average grain size of the electrolyte powder prepared by the method is 55-65nm, the variance among grains is less than 25%, the D50 of the electrolyte powder is 0.5-1 mu m, and the D100 of the electrolyte powder is 2-4 mu m.
The invention also provides application of the electrolyte powder in preparation of the fuel cell electrolyte sheet.
Preferably, the application of the electrolyte powder in preparing the electrolyte sheet of the fuel cell comprises the following steps:
(1) Uniformly mixing the electrolyte powder, the adhesive, the dispersing agent and the solvent to obtain slurry;
(2) And the slurry is subjected to tape casting, molding, glue discharging and sintering in sequence to obtain the electrolyte sheet.
Preferably, the binder content is 15-25wt%, the dispersant content is 15-20wt%, the plasticizer content is 5-10wt%, and the solvent content is 20-30wt%, based on the mass of the electrolyte.
Preferably, the binder comprises polyvinyl butyral.
Preferably, the dispersant comprises glycerol trioleate.
Preferably, the plasticizer comprises dioctyl phthalate.
Preferably, the solvent comprises at least one of toluene and ethanol.
Preferably, the temperature of the glue discharging is 350-450 ℃, and the time of the glue discharging is 40-60h.
Preferably, the sintering temperature is 1350-1550 ℃, and the sintering time is 20-50h.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, acetylacetone metal salt and a specific organic solvent are used as reaction raw materials, and electrolyte powder with uniform size, easy dispersion, high purity and good sintering activity can be obtained by controlling the proportion of the reaction raw materials and the two heat treatment processes. Meanwhile, the method has simple process and lower cost, is favorable for large-scale production, and is very suitable for preparing the electrolyte sheet of the solid oxide fuel cell.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described by means of specific examples. The test methods used in examples and/or comparative examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are all commercially available.
Example 1
S1, adding acetylacetone metal salt into a 9-octadecylenamine solvent to form a mixed system, and fully and uniformly stirring, wherein the acetylacetone metal salt contains 84.75% of acetylacetone zirconium, 11.86% of acetylacetone scandium and 3.39% of acetylacetone cerium, based on 100% of the molar percentage of the acetylacetone metal salt; the concentration of the zirconium acetylacetonate in the mixed system is 0.16mol/L;
s2, carrying out primary heat treatment on the mixed system under the vacuum condition, wherein the primary heat treatment comprises the following specific steps: heating to 100 ℃ at room temperature at a heating rate of 20 ℃/min and preserving heat for 0.5h;
S3, introducing argon into the system, and carrying out secondary heat treatment on the mixed system in an argon atmosphere, wherein the secondary heat treatment specifically comprises the following steps: heating from 100 ℃ to 300 ℃ at a heating rate of 30 ℃/min and preserving heat for 2 hours;
and S4, cooling the mixed system to room temperature, washing with ethanol, and drying to obtain electrolyte powder.
After the electrolyte powder is prepared, the electrolyte powder is also required to be prepared into an electrolyte sheet for further testing, and the preparation steps are as follows:
(1) Pulping: mixing electrolyte powder (60 kg), a binder (polyvinyl butyral (PVB, 19.8 wt%), a dispersant (glycerol trioleate, 16.9 wt%), a plasticizer (dioctyl phthalate, 8.3 wt%) and a solvent (toluene and ethanol volume ratio is toluene: ethanol=1:1, 24.2 wt%), wherein the amounts of the binder, the dispersant, the plasticizer and the solvent are calculated as mass percent of the electrolyte powder; sand grinding and dispersing for 48 hours to form slurry which has certain fluidity and is not easy to settle and stable;
(2) Casting: coating the prepared slurry on a base film through a slurry injection port of a casting device, and drying to form a film strip with a certain thickness;
(3) And (3) forming: cutting the film strip into films with certain size and thickness (the length of the film is 120mm, the width of the film is 120mm, and the thickness of the film is 80 mu m) by using a cutting machine table, and obtaining a blank to be subjected to glue discharging after molding;
(3) And (3) glue discharging: removing organic components such as adhesive, dispersant, plasticizer and the like in the green body in an air atmosphere, ensuring high-temperature sintering quality, wherein the glue discharging temperature is 400 ℃, and the glue discharging time is 50 hours;
(4) Sintering: and (3) carrying out high-temperature treatment on the product after the glue discharge, thereby obtaining the electrolyte sheet with high mechanical strength and excellent electrical performance, wherein the sintering temperature is 1450 ℃, and the sintering time is 38 hours.
Examples 2 to 16
The preparation steps of examples 2 to 16 were identical to example 1 except that the content of the components of the acetylacetonate metal salt, the kind of the solvent, and the concentration of the solute in the mixed system in step S1 were as shown in Table 1.
Examples 17 to 30
The preparation steps of examples 17 to 30 were identical to those of example 1 except that the second heat treatment in step S3 was different in temperature (T 2), temperature rise rate (r 2), and holding time (T 2), as shown in Table 2.
Comparative examples 1 to 4
The preparation steps of comparative examples 1 to 4 were identical to those of example 1 except that the content of the components of the acetylacetonate metal salt, the kind of the solvent, and the concentration of the solute in the mixed system in step S1 were as shown in Table 1.
Comparative example 5
Comparative example 5 differs from example 1 only in that a metal acetate was used instead of the metal acetylacetonate in comparative example 5, wherein the metal acetate contained 84.75% of zirconium acetate, 11.86% of scandium acetate and 3.39% of cerium acetate, the molar ratio was 1:0.14:0.04, the concentration of zirconium acetate was 0.1mol/L, and the other process steps and process parameters of comparative example 5 were identical to those of example 1, based on 100% of the molar percentage of the metal acetate.
Comparative example 6
The procedure of comparative example 6 was identical to that of example 1, except that the solvent in step S1 was octadecenoic acid, as shown in Table 1.
TABLE 1
TABLE 2
After preparing the electrolyte powder, the electrolyte powder of each example and comparative example was tested for grain size, grain uniformity, and grain size; after the electrolyte sheets were prepared, the strength and conductivity of the electrolyte sheets of each example and comparative example were tested, the specific test methods and qualification criteria are shown in table 3, and the test results are shown in table 4.
TABLE 3 Table 3
TABLE 4 Table 4
The electrolyte powder prepared by the invention is a zirconia-based electrolyte, the grain size is uniform, the grain size is moderate, wherein the average grain size is 55-65nm, the variance of the grain size is less than 25%, the D50 of the powder is 0.5-1 mu m, and the D100 is 2-4 mu m. The electrolyte sheet prepared by the invention has good strength and conductivity, wherein the strength is more than 0.6kgF, and the conductivity is more than 150mS/cm.
As is clear from examples 1, 8 to 12 and comparative examples 1 to 4, the scandium acetylacetonate of comparative examples 1 to 2 was added at too high or too low a ratio, which resulted in instability of zirconia in the electrolyte powder, failed variance of the crystal grain size of the electrolyte powder, and poor strength of the electrolyte sheet; the cerium acetylacetonate of comparative examples 3 to 4 was added at too low or too high a ratio, which resulted in poor high-temperature mechanical properties and stability of zirconia, and failed in the variance of the crystal grain size of the electrolyte powder, and failed in the strength of the electrolyte sheet.
As is clear from examples 1 to 7, the concentration of zirconium acetylacetonate in the mixed system has a certain influence on the electrolyte powder, and the crystal grain size and particle size of examples 6 and 7 are slightly increased as compared with examples 1 to 5, and the strength and conductivity of the electrolyte sheet are slightly inferior to those of examples 1 to 5, so that the concentration of zirconium acetylacetonate can be selected to be 0.05 to 0.25mol/L, and more preferably 0.1 to 0.2mol/L. In example 6, zirconium acetylacetonate concentration was smaller than the further preferable range, the dispersibility of the mixed system was deteriorated, agglomeration was present, zirconium acetylacetonate concentration was higher than the further preferable range in example 7, and the temperature uniformity of the mixed system was poor, so that the crystal grain sizes and particle sizes of example 6 and example 7 were slightly increased, and the strength and conductivity of the electrolyte sheet were slightly inferior to those of examples 1 to 5.
From examples 1 and 17 to 30, it is known that the temperature, time and heating rate of the second heat treatment have a certain influence on the strength and conductivity of the electrolyte sheet, and the heat treatment temperature can be selected to be 270 to 350 ℃, and more preferably 280 to 300 ℃; the time of the second heat treatment is selected to be 0.5 to 3 hours, more preferably 1 to 1.7 hours; the rate of temperature rise in the second heat treatment may be selected to be 10 to 50 c/min, more preferably 10 to 40 c/min, and the strength and conductivity of the electrolyte sheet are more excellent when the temperature, time, and rate of temperature rise in the second heat treatment are adopted.
The temperature of the second thermal reaction in example 20 at step S3 is higher than the further preferable range, the time of the second thermal reaction in example 26 at step S3 is out of the further preferable range, and the rate of temperature rise in example 30 at the second thermal reaction is out of the further preferable range, which leads to the formation of large particle aggregates, a large particle size or a poor uniformity of the size, and unsatisfactory strength and conductivity of the electrolyte sheet; the reaction temperature in example 21 at step S3 was lower than the further preferable range, and the reaction time in example 25 at step S3 did not reach the further preferable range, which resulted in the decrease of the particle size of the electrolyte powder and the unsatisfactory conductivity of the electrolyte sheet.
As is clear from examples 1 and 5, the acetate in comparative example 5 is decomposed more severely than the acetylacetonate metal salt, the solvent is not adsorbed around the crystal nuclei before the crystal nuclei are aggregated, resulting in large grain size of the electrolyte powder, excessively large difference in grain size, disqualification of uniformity of particle size, and poor conductivity of the electrolyte sheet.
As is evident from examples 1, 13-16 and comparative example 6, other types of surfactants have a poor effect on the zirconia nucleus compared to nonionic surfactants, resulting in unacceptable grain size and particle size, and failing to meet the subsequent product production requirements.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the electrolyte powder is characterized by comprising the following steps:
(1) Zirconium acetylacetonate, scandium acetylacetonate, cerium acetylacetonate and a solvent are mixed to obtain a mixed solution; the molar ratio of zirconium acetylacetonate to scandium acetylacetonate to cerium acetylacetonate is zirconium acetylacetonate to scandium acetylacetonate to cerium acetylacetonate=1 (0.11-0.17) to (0.02-0.08); the solvent is at least one of aliphatic amine, aliphatic amide, aliphatic amine oxide and aliphatic amine containing N heteroatom group; the molar concentration of the zirconium acetylacetonate in the mixed solution is 0.05-0.25mol/L;
(2) Performing primary heat treatment on the mixed solution under a vacuum condition to obtain a precursor; the temperature of the first heat treatment is 100-120 ℃, the time of the first heat treatment is 0.5-1h, and the heating rate of the first heat treatment is 20-30 ℃/min;
(3) Performing secondary heat treatment on the precursor under inert gas, and washing and drying to obtain the electrolyte powder; the temperature of the second heat treatment is 270-350 ℃, the time of the second heat treatment is 0.5-3h, and the temperature rising rate of the second heat treatment is 10-50 ℃/min.
2. The method for producing an electrolyte powder according to claim 1, wherein in the step (1), the molar concentration of zirconium acetylacetonate in the mixed solution is 0.1 to 0.2mol/L.
3. The method for producing an electrolyte powder according to claim 1, wherein in the step (1), the molar ratio of zirconium acetylacetonate, scandium acetylacetonate, and cerium acetylacetonate is (0.13-0.16) to (0.03-0.05) as zirconium acetylacetonate to scandium acetylacetonate to cerium acetylacetonate=1.
4. The method for producing an electrolyte powder according to claim 1, wherein in the step (3), the temperature of the second heat treatment is 280 to 300 ℃, the time of the second heat treatment is 1 to 1.7 hours, and the temperature rise rate of the second heat treatment is 10 to 40 ℃/min.
5. The method for producing an electrolyte powder according to claim 1, wherein in the step (1), the solvent is at least one of Z-N, N-dimethyl-9-octadecenamide, erucamide, N-oxo-N, N-dimethyl-9-octadecenamide, and 9-octadecenamide.
6. An electrolyte powder produced by the method for producing an electrolyte powder according to any one of claims 1 to 5.
7. Use of the electrolyte powder of claim 6 in a fuel cell electrolyte sheet.
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