CN103730678B - The single part low-temperature solid oxide fuel cell manufactured with rare earth oxide composite with LiMn2O4 - Google Patents
The single part low-temperature solid oxide fuel cell manufactured with rare earth oxide composite with LiMn2O4 Download PDFInfo
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- CN103730678B CN103730678B CN201310747475.2A CN201310747475A CN103730678B CN 103730678 B CN103730678 B CN 103730678B CN 201310747475 A CN201310747475 A CN 201310747475A CN 103730678 B CN103730678 B CN 103730678B
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- oxide
- rare earth
- limn2o4
- fuel cell
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000000446 fuel Substances 0.000 title claims abstract description 47
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 title claims abstract description 34
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 29
- 239000007787 solid Substances 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 229910052788 barium Inorganic materials 0.000 claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 28
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 25
- 229910002651 NO3 Inorganic materials 0.000 claims description 21
- -1 rare earth compound Chemical class 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 18
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 2
- 239000002023 wood Substances 0.000 claims 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims 1
- 238000009841 combustion method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 229910052772 Samarium Inorganic materials 0.000 description 7
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 7
- 239000004111 Potassium silicate Substances 0.000 description 5
- 230000001419 dependent effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- 229910052913 potassium silicate Inorganic materials 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- 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 4
- 238000011161 development Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 229910006251 ZrOCl2.8H2O Inorganic materials 0.000 description 2
- BRSGXJFLRBKDFE-UHFFFAOYSA-N [Zr].[O].[Cl] Chemical compound [Zr].[O].[Cl] BRSGXJFLRBKDFE-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910013391 LizN Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019427 Mg(NO3)2-6H2O Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 229940115440 aluminum sodium silicate Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses one LiMn2O4 and manufacture single part low-temperature solid oxide fuel cell with rare earth oxide composite, its electrolyte single part material is MULTIPLE COMPOSITE material, 1, any two or the metal-oxide of two or more element in Li, Na, K, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Si or Sn, molar ratio is 1 99%；2, the rare earth oxide composition composite of 1 95% is added further；3, the LiMn2O4 further adding 1 95% forms MULTIPLE COMPOSITE material.Prepared by above-mentioned MULTIPLE COMPOSITE material sol-gal process and combustion method.The MULTIPLE COMPOSITE material of the present invention is assembled into single part fuel cell, can be at 300 550 DEG C of output power density 30 220 milliwatts/square centimeters.Make raw material owing to have employed cheap LiMn2O4, make SOFC obtain low cost, operating temperature low.Using effect is good.It is easy to large-scale popularization use.
Description
Technical field
The invention belongs to SOFC (SOFC) technical field, be specifically related to one LiMn2O4 and rare earth
Oxide composite manufactures single part low-temperature solid oxide fuel cell.
Background technology
The research and development main flow of SOFC (SOFC) fuel cell is middle temperature (600-800 DEG C), low temperature at present
(300-600 DEG C) operation reduces cost.Owing to being limited by electrolyte, most of development activities are only limitted to use conventional high-temperature
(1000 DEG C) yttria stabilized zirconia (YSZ) material prepares micron-sized thin film to reduce the resistance of electrolyte, to reach
To the purpose reducing fuel cell operating temperatures.But micron order thin-film electrolyte cannot ensure performance and the repetition of fuel cell
Property, and due to the restriction of YSZ electrical conductivity, it is still desirable to the operation of 700 DEG C of temperatures above.Therefore, new oxide electricity is researched and developed
Solving material is the basic guarantee realizing low temperature (300-600 DEG C) SOFC.
The electroless matter fuel cell of a kind of new configurations occurred recently, simply parts, not electrolyte membrance
Without anode, electrolyte, cathode construction three configurations of components, its simple structure and technology, eliminate electrolyte restriction and
Requirement to operation temperature, it is shown that huge business opportunity and the prospect of fuel cell industrialization.
China Patent No. 201010593786.4 proposes employing doped cerium oxide and Li, the metal-oxide such as Ni, Cu, Zn
This single part fuel cell of composite material structure, and achieve good performance.But metal oxide materials is also widely
It is far from application.Lithium manganate material is to use more a kind of material in lithium battery anode, and the bigger price of volume of production is just
Preferably, have not yet seen so far about using it to realize 300-600 DEG C of low-temperature solid oxide fuel cell, be more not used in list
The relevant report of parts fuel cell.
Summary of the invention
It is an object of the invention to the low-temperature solid oxide fuel using LiMn2O4 to manufacture with rare earth oxide composite
Battery, solves the technical problem that SOFC fuel cell operates under low temperature (300-600 DEG C).
The present invention is realized in.The material of the fuel cell single part of the present invention is MULTIPLE COMPOSITE material, its composition
For:
1, any two or two or more in Li, Na, K, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Si or Sn
The metal-oxide of element, the molar fraction of the element of the most each selected metal-oxide selects between 1%-99%, and institute
The molar fraction sum having element is 100%；
2) the rare earth oxide composition, adding the percentage ratio 5 95% accounting for above-mentioned chosen elements integral molar quantity further is multiple
Condensation material；
3) after, further adding upper step 2, the LiMn2O4 of the percentage by weight 5 95% of mixture forms MULTIPLE COMPOSITE
Material.
Specifically comprise the following steps that
1, will in Li, Na, K, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Si or Sn any two or two kinds with
The nitrate of upper element or dissolve in the compound of nitric acid, is configured to mixed at 0.01-1.0M of total ion concentration with deionized water
Close solion；The molar fraction of the most each selected ion selects (such as: 40Li between 1%-99%+/60Zn2+,30K+/
70Zn2+,20Ca2+/60Zn2+/20Al3+), and the molar fraction sum of all ions is 100%；；
2, rare earth compound is added
In described step 1 chosen elementsMixed ion solutionsIn, add by the 5%-95% of its chosen elements integral molar quantity
Entering rare earth compound, this rare earth compound includes nitrate compound cerous nitrate, samaric nitrate or the Yttrium trinitrate of rare earth, or various ion
Doped cerium oxide, lanthana and technical grade mixed rare earth carbonate, or mixed rare earth carbonate is through 1-10 hour gained of 800 DEG C of calcinings
The mixed rare-earth oxide arrived, then add citric acid or carbamide by 1-4 times of step 1 chosen elements integral molar quantity, or it is not added with lemon
Lemon acid or carbamide；After stirring, dryout and obtain fine powder；By the fine powder of gained 700-850 DEG C sinter 1-20 hour, i.e.
Obtain the another kind of the present invention by the hybrid ceramic electrolyte of chosen elements oxide and rare earth oxide；
Described burning process also can be carried out step by step, i.e. is placed in groom's stove by the gel of thickness and is heated to 300-500 DEG C, material
Combustible is removed in body burning, obtains fluffy fine powder；Continue to be heated to 700-850 DEG C, sinter 1-20 hour, finally
Obtain the fluffy bi-component of quality or multi-component metal oxide and the complex with rare earth, be and can be used for 300-600
The electrolyte of DEG C low temperature SOFC.
3, composite is prepared with LiMn2O4 further
Dry method directly mixes
The metal-oxide of the ionic conduction of above-mentioned preparation-rare earth oxide composite mixed solution is dryouied, obtains
Fine powder；Fine powder and LiMn2O4 being weighed according to different weight ratios, the trickleest powder accounts between the 5-95% of gross weight；Will
Two kinds of materials directly mixed, solubilizer such as ethanol, acetone etc., with ball mill grinding 24 hours.Obtain containing LiMn2O4 5-
The complex rare-earth oxidate containing valuable metal of 95% various weight and the composite of LiMn2O4.
Or wet-mixed
WillLiMn2O4 weighs between 5-95 DEG C according to different weight, adds in the mixed solution of above-mentioned steps 2,90
DEG C heating is sufficiently stirred.The mixing LiMn2O4 obtained and the pasty solutions of metal-oxide complex rare-earth oxidate containing valuable metal.
Again in the above-mentioned mixing pasty solutions containing RE composite and LiMn2O4, add by weight 1-4 times of LiMn2O4
Citric acid or carbamide, or not adding citric acid or carbamide；After stirring, dryout and obtain fine powder；The fine powder of gained is existed
500-850 DEG C sinters 1-20 hour, i.e. obtains the material of single part fuel cell；
Described combustion process also can be carried out step by step, i.e. is placed in Muffle furnace by the gel of thickness and is heated to 300-500 DEG C,
Combustible is removed in material body burning, obtains fluffy fine powder；Continue to be heated to 500-850 DEG C, sinter 1-20 hour, i.e.
Obtain the material of single part fuel cell.
The method according to the invention, from alternative ion Li, Na, K, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti,
Si or Sn selects any 2 kinds, 3 kinds or multiple element, can construct thousand, the formula of ten thousand kind of material.These formula do not depend on
In using what chemicals, be also not dependent on how preparing, it is important to comprise element described above, and by 2,3 or
These elementary composition multiple component oxide materials multiple.Change by this thinking and method obtain for single part material from
The composite oxide material of electronic conduction, belongs to the protection category of the present invention.
By the material of above-mentioned preparation according to different fuel cell configurations, 1) with the composite oxide of metal of above-mentioned preparation be
The single part fuel cell of electrolyte and preparation；2) the single part material structure single part battery of above-mentioned preparation.Use dry method powder
Body at 10-30MPa forming under the pressure lamellar fuel cell, and be coated with on this battery two sides silver slurry obtain fuel cell for colelctor electrode
Device.At 600 DEG C, 0.5-2.0 hour sintering of presintering also can not sinter directly measurement.The latter is typically substrate by nickel foam
Carry out dry powder compacting.
Compared with existing oxide fuel cell material, the present invention has an advantage highlighted below:
1. the present invention uses cheap lithium manganate material to prepare fuel cell, is conducive to being substantially reduced cost.
2. the single part fuel cell in the present invention, it is to avoid and solve anode of fuel cell, electrolyte and the moon of complexity
The complicated structure of pole, it also avoid a coupling difficult problem for these materials the most chemically and physically characteristic
3. the use of single part fuel cell, can be advanced further towards low temperature, high-performance by the technology of SOFC undoubtedly, reduces
Manufacturing cost, the product for development further with market competitiveness SOFC opens a new way.
4., because single part composite, the fuel cell of its structure does not has a coupling difficult problem for material, does not has tradition yet
SOFC pottery hot-short splits that shortcoming makes low temperature, the realization of high-performance SOFC technology has more expanded it at traffic and portable power source, dynamic
The application of power, and it is not limited only to traditional SOFC range at stationary electric power plant.
5. the present invention propose new design of material and development method, broken traditional SOFC structure electrolyte necessary
With the restriction of oxygen ion conductor, and use various double, many/answer the oxide of component, it is provided that wide new function material is sent out
Exhibition space and degree of freedom.
The present invention has developed the functional material as base with two components or multicomponent total oxygen compound material further, and uses
Cheap lithium manganate material, it is achieved that high performance 300-600 DEG C of low-temperature solid oxide fuel cell, has not yet seen so far
LiMn2O4 is used to have the relevant report that fuel cell is similar.Low temperature (the 300-of all these all solid state oxide materials structure
600 DEG C) fuel cell material is with low cost, does colelctor electrode and catalyst without noble metal,.The invention of these materials is solid oxygen
Compound fuel cell is made that the real contribution breaking property to low temperature, commercialization.The thousands of example experimental results done confirm the present invention
There is universality and superiority.
Accompanying drawing explanation
Fig. 1 a, b, c and d are respectively a kind of exemplary complex oxide LiZn oxide parcel samarium doping cerium oxide of the present invention
(being designated as LZSDC) composite, LiMn2O4 and composite (the scanning electron microscope photograph of dry powder c and wet method d) that they eventually form
Sheet.
Fig. 2 is the material phase analysis result of material, the XRD figure of the composite of LiMn2O4 and LiMn2O4-LZSDC.
Fig. 3 is a typical LiZSDC composite and the dry mixed material of LiMn2O4 different ratio of the present invention
The single part fuel cell current-voltage (I-V) at 550 DEG C of structure and current-power (I-P) curve.
Fig. 4 a is three parts and the organigram of single part fuel-cell device；Fig. 4 b and 4c is the electricity of fuel cell
Stream-voltage (I-V) and current-power (I-P) curve, wherein 4b is LZSDC/LiMnO prepared by three parts battery wet methods
30% composite is anode and negative electrode and LZSDC is electrolyte, and Fig. 4 c is wet method LZSDC/LiMnO 30% composite
Single part fuel cell is in the performance of 550 DEG C of actual measurements.
Detailed description of the invention
Below in conjunction with the accompanying drawings, by more embodiment, the present invention is specifically described in detail.
Part I: can be used for the ion conductor rare earth-oxide composite of single part
Embodiment 1: prepared by the solution of metal-oxide
1) chosen elements is the nitrate of Li, Na, K, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Si or Sn, such as LiNO3
Deng or oxyhydroxide, such as LiOH etc..；
2) from above-mentioned preferred element, any 2 kinds, 3 kinds or multiple are selected, according to selected each element or ion in choosing
Determine in the total amount of element or ion shared molar fraction in 1%-99% scope, preparation concentration be 0.01-1.0M mixing from
Sub-solution；
Mixed solution formula:
Take 0.025 mole of M (NO3)y(y=1 or 2；M=Li, Na, K, Ca, Sr or Ba) and 0.025 mole other 2,3 or
4 valence metal ions: be typically Zn2+、Mg2+、Al32+、Bi3+Or Zr4+Water-soluble compound such as Zn (NO3)26H2O、Mg
(NO3)2 6H2O、Al(NO3)3 9H2O、Bi(NO3)3 9H2O or ZrOCl2 8H2O, with deionized water or distilled water be deployed into according to
Total concentration of metal ions is the liquid of 0.5M, such as:
1), Zn base, to Zn (NO3)2.6H2O, takes 0.025 mole, and additionally takes 0.025 mole of M (NO respectively3)y(M=Li,
Na, K, Ca, Sr or Ba, y=1 or 2), any of which M is deployed into 1-6 kind difference M ion and Zn2+The hybrid metal of ion
Ion concentration is the solution of 0.25M. it is true that due to above-mentioned chosen elements Zn, Li, Na, K, Ca, Sr or Ba, its each component institute
The molar fraction accounted for can select at 1-99%, thus can have thousand, ten thousand kind of formula, the wherein 50:50 enumerated here
A kind of all component formula (lower with)；
2), Mg base, to Mg (NO3)2.6H2O, takes 0.025 mole, and additionally takes 0.025 mole of M (NO respectively3)y(M=Li,
Na, K, Ca, Sr or Ba, y=1 or 2), any of which M is deployed into No. 6-12 different M ions and Mg2+The hybrid metal of ion
Ion concentration is the solution of 0.5M.
3), Al base, equally, to Al (NO3)3.9H2O M (NO3)y(M=Li, Na, K, Ca, Sr or Ba, y=1 or 2), its
Any one of M be deployed into No. 13-18 different M ions and Al3+The solution of the mixing 0.5M of ion；
4) 0.025 mole of M (NO, similarly, is taken3)y(M=Li, Na, K, Ca, Sr or Ba；Y=1 or 2), any of which one
Plant 0.015 mole of Al (NO of M3)3.9H2O and 0.01 mole of Bi (NO3)3.9H2O mix, be deployed into No. 19-24 different M ions with
Al3+/Bi3+Ar ion mixing forms the solution 5 that total ion concentration is 1.0M), take 0.025 mole of M (NO3)y(M=Li, Na, K, Ca,
Sr or Ba, y=1 or 2), any of which M and 0.015 mole of Al (NO3)3.9H2O and 0.01 mole of ZrOCl2.8H2O mixes,
It is deployed into No. 25-30 different M ions and Al3+/Zr4+Ar ion mixing forms the solution 6 that total ion concentration is 0.5M), take 0.025
Mole M (NO3)y(M=Li, Na, K, Ca, Sr or Ba, y=1 or 2), any of which M and 0.015 mole of Zn (NO3)2.6H2O
With 0.01 mole of ZrOCl2.8H2O mixes, and is deployed into No. 31-36 different M ions and Zn2+/Zr4+Total ion of Ar ion mixing
Concentration is the solution of 0.25M
Embodiment 2: the 37-47# formula is as follows:
37, with 0.02mol potassium silicate to 0.02mol zinc nitrate, it is deployed into K+/Si4+/Zn2+Ar ion mixing always from
Sub-concentration is the solution of 0.05M.
38, with 0.02mol aluminium silicate to 0.02mol zinc nitrate, it is deployed into Al3+/Si4+/Zn2+Ar ion mixing total
Ion concentration is the solution of 0.1M.
39, with 0.02mol sodium silicate to 0.01mol zinc nitrate and 0.01mol stannic chloride, it is deployed into Na+/Si4+/Zn2+/
Sn2+Ar ion mixing forms the solution that total ion concentration is 0.25M.
40, with 0.02mol aluminium silicate to 0.01mol zinc nitrate and 0.01mol stannic chloride, it is deployed into Al3+/Si4+/Zn2+/
Sn2+Ar ion mixing forms the solution that total ion concentration is 0.3M.
41, with 0.02mol silmag to 0.02mol potassium nitrate, it is deployed into Si4+/Mg2+/K+Ar ion mixing forms always
Ion concentration is the solution of 0.5M.
42, use 0.01mol zinc nitrate and 0.01mol silmag to 0.02mol potassium nitrate, be deployed into Si4+/Mg2+/
Zn2+/K+The solution of the mixing 0.5M of ion.
43, with 0.01mol zinc nitrate and 0.01mol silmag, it is deployed into Si4+/Mg2+/Zn2+Ar ion mixing forms
Total ion concentration is the solution of 1.0M.
44,0.01 potassium silicate: 0.01 magnesium nitrate, is deployed into Si4+/Mg2+/K+It is 1.0M that Ar ion mixing forms total ion concentration
Solution.
45,0.01 aluminium silicate: 0.01 oxygen chlorine zirconium, is deployed into Si4+/Al3+/Zr4+The total ion concentration of Ar ion mixing is
The solution of 0.5M.
46,0.01 potassium silicate: 0.01 magnesium nitrate, is deployed into Si4+/K+/Mg2+The total ion concentration of Ar ion mixing is
The solution of 0.5M.
47,0.01 potassium silicate: 0.01 oxygen chlorine zirconium, is deployed into Si4+/K+/Zr4+The total ion concentration of Ar ion mixing is
The solution of 0.25M.
Above-mentioned cited silicate is potassium silicate, sodium silicate, aluminium silicate and silicon magnesium compound, and they are all good systems
The carrier of standby oxide containing silicon；If meeting insufficient hydrolysis, can separately add appropriate acid dissolving.
In short, by above-mentioned ion: in Li, Na, K, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Si or Sn any 2
Kind, 3 kinds or multiple element and different component score, it is possible to construct thousand, ten thousand kind of formula, it is impossible to be all described one by one.
Examples cited are simply to illustrate that formula prepared by the material of the present invention above, are not dependent on using what chemicals, also
It is not dependent on how preparing, it is important to comprise above-mentioned element, and being combined by 2,3 or these Element generations multiple
Oxide material；So, above-mentioned citing should not be taken as limiting the invention.As long as because according to side of the present invention
Method, the most natural can preparation develops out the multifarious kind of formula preparing material of the present invention.
Prepare the composite of metal-oxide and rare earth oxide further
As it was previously stated, according to chosen elements or the 1-95% of the integral molar quantity of ion in prepared by above-mentioned mixed ion solutions
Scope adds rare earth compound.These include nitrate compound: such as cerous nitrate, samarium, yttrium, or dissolve in the compound of nitric acid；
Including rare earth oxide, this rare earth oxide can be various ion doping cerium oxide, or cerium oxide (CeO2), lanthana
(La2O3) or mixed rare earth carbonate, and mixed rare earth carbonate is through 1-10 hour obtained mischmetal oxygen of 800 DEG C of calcinings
Compound (LCP).Then according to 1-4 times of chosen elements or ion total mole number adds citric acid, 200 DEG C of heating and stir straight
It is changed into gel to liquid.Arriving this, two kinds of methods continue: 1) continue stirring, heating, and thickness is dried, until burning obtains rapidly
Fluffy fine powder；Said process can also be carried out under the higher temperature (such as 400 DEG C) in groom's stove；Or by thickness
Gel is placed and is kept 12-24 hour in 120 DEG C in an oven, generally yields the most fluffy dry glue.Last 500-850 DEG C of burning
Tie 1-20 hour, obtain bi-component or multicomponent element oxide and the complex of rare earth oxide.The most further and manganese
Acid lithium mixes, and ball milling prepares different LiMn2O4-rare earth oxide composites；2) superincumbent gel adds not
With the LiMn2O4 of weight fraction, stirring, heating, until burning obtains fluffy fine powder；Said process can also be groom
Carry out under higher temperature (such as 400 DEG C) in stove；Or place it in baking oven and keep 12-24 hour in 120 DEG C, finally exist
500-850 DEG C sinters 1-20 hour, obtains different LiMn2O4-rare earth oxide composites.Material prepared by both approaches
Material, is used equally to the single part material of the electroless matter membrance fuel cells of foregoing description.
Name the examples of implementation of some representative formulations.
Embodiment 3:
Any solution is taken according to its total metal (or quasiconductor) in representative 47 solution formulas elected
The 1%-95% of element mole adds cerous nitrate/or cerium oxide, can produce again very many formula, select 3 typical components
Formula (in molar ratio, 20% metallic element: 80% cerium；50% metallic element: 50% cerium；80% metallic element:
20% cerium) as a example by, it is sufficiently stirred for and is maintained at 100 DEG C.Repeat sol-gel process and combustion method mistake prepared by above-mentioned material
Journey；Finally sinter 1-20 hour at 500-850 DEG C, various bi-component or multi-component metal oxide-rare earth oxide can be obtained
(cerium oxide) complex, this complex prepares various component proportion with LiMn2O4 ball milling under Different Weight mark proportioning further
Single part material；Or add the LiMn2O4 of Different Weight mark proportioning at above-mentioned solution state, repeat above-mentioned material and prepare
Sol-gel process and combustion method process；Finally sinter 1-20 hour at 500-850 DEG C, prepare the multiple of various component proportion
Composite.
Embodiment 4:
Above-mentioned plain cerium oxide effect is replaced with doped cerium oxide (typical case is such as the cerium oxide of yttrium, samarium, gadolinium or La doped)
Fruit is more preferable.Such as with 10-20mol% yttrium, lanthanum, samarium, gadolinium doped-ceria, the nitrate compound of they elements or they
Oxide nitric acid dissolve and prepare mixed solution according to doping content 10-20mol% and cerous nitrate, then abundant embodiment 3
Two kinds of methods be prepared into the MULTIPLE COMPOSITE material of various component proportion.
Embodiment 5:
Other rare earth element includes that scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium or gadolinium replace cerium, can be by same procedure system above
Standby, further preferred example is yttrium, lanthanum, samarium or the nitrate compound of gadolinium element or the dissolving of their oxide nitric acid, the heaviest
Multiple above step, it is possible to obtain the MULTIPLE COMPOSITE material of various component proportions.
Embodiment 6:
Rare earth oxide is raw material of industry level mixed rare earth carbonate and raw material of industry level mixed rare earth carbonate is forged through 800 DEG C
Burn 1-10 hour obtained mixed rare-earth oxide (LCP) replace above-mentioned cerous nitrate or cerium oxide, repeat step above equally
Suddenly, it is possible to obtain the MULTIPLE COMPOSITE material of various component proportions.
It is important to note that given example is simply to illustrate that the ingenious and abundant part of the present invention, implement to enumerate
I is unequal to lifting, it is impossible to be limited to this.
Embodiment 7:
Enumerate, with form, the result that some typical fuel cells are implemented to measure below, prove these materials of the present invention
Practicality and high-performance.Cited is all the fuel cell (active face of the button cell of 13 mm dias 0.64 square centimeter
Long-pending) actual measured results.Wherein SDC is samarium doping CeO2；GDC is Gd2 O3 CeO2。
Table 1. representative fuel cell measured data at different temperatures
The fuel cell using material of the present invention to be electrolyte structure, can be 450-600 DEG C of output maximum current density
250-610mA/cm2, power density 50-210mW/cm2.
These materials cited by the above embodiment of the present invention be exploitation be applicable to 300-600 DEG C SOFC and list portion
Part electroless matter functional material has been expanded thinking, has been established platform, and provide wide advanced material development space and from
By spending.
The preferred technology path of chemical preparation referred to above is wet chemistry method, main sol-gel process and combustion method
Obtain nano level metal or semiconductor element (such as silicon or stannum) oxide and with rare earth material complex for low temperature, high-performance
Ion conductive material.
Can be from following ion according to the present invention: selected Li, Na, K, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Si or Sn
Any 2 kinds, 3 kinds or multiple element construct thousand, ten thousand kind of material prescription.These formula are not dependent on using any chemicals, also
It is not dependent on how preparing, it is important to comprise above-mentioned element, and by 2,3 or multiple these are elementary composition with dilute
Soil oxide forms composite oxides, for the ion conductive material of the single part of low temperature oxide fuel battery (LTSOFC).
As long as according to method of the present invention, the most just can matching, developing out multifarious kind and prepare joining of electrolyte of the present invention
Side.
Two kinds or multi-component composite oxides obtained and and rare earth oxide formation are changed by this thinking and method
Composite, can be employed as the single part electroless matter fuel of low temperature (300-600 DEG C) oxide fuel cell (LTSOFC)
The ionic conductor material of battery, belongs to the protection category of the present invention.Obviously the present invention be first lithium manganate material is used in low
Temperature oxide single piece device, either any component is all the protection category of the present invention.
Claims (4)
1. the single part low-temperature solid oxide fuel cell manufactured with rare earth oxide composite with LiMn2O4, it is single
The material of parts is MULTIPLE COMPOSITE material, it is characterised in that consist of:
1), any two or two or more unit in Li, Na, K, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Si or Sn
The metal-oxide of element, the molar fraction of the element of the most each selected metal-oxide selects between 1%-99%, and all
The molar fraction sum of element is 100%；
2) the rare earth oxide composition composite wood of the percentage ratio 5 95% accounting for above-mentioned chosen elements integral molar quantity, is added further
Material；
3) after, further adding upper step 2, the LiMn2O4 of the percentage by weight 5 95% of mixture forms MULTIPLE COMPOSITE material
Material.
The single part low-temperature solid that a kind of LiMn2O4 the most according to claim 1 manufactures with rare earth oxide composite
Oxide fuel cell, it is characterised in that MULTIPLE COMPOSITE material preparation process is:
1), will in Li, Na, K, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Si or Sn any two or two or more
The nitrate of element or dissolve in the compound of nitric acid, is configured to the total ion concentration mixing at 0.01-1.0M with deionized water
Solion；The molar fraction of the most each selected ion selects between 1%-99%, and the molar fraction sum of all ions
It is 100%；
2), rare earth compound is added
In the mixed ion solutions of described step 1 chosen elements, add dilute by the 5%-95% of its chosen elements integral molar quantity
Earth compounds, this rare earth compound includes nitrate compound cerous nitrate, samaric nitrate or the Yttrium trinitrate of rare earth, or various ion doping
Cerium oxide, lanthana and technical grade mixed rare earth carbonate, or mixed rare earth carbonate is obtained through 800 DEG C of calcinings 1-10 hour
Mixed rare-earth oxide；
3), MULTIPLE COMPOSITE material is prepared further with LiMn2O4
Dry method directly mixes
The metal-oxide of the ionic conduction of above-mentioned preparation-rare earth oxide composite mixed solution is dryouied, obtains fine
Powder；Trickle powder and LiMn2O4 being weighed according to different weight ratios, the trickleest powder accounts between the 5-95% of gross weight；By two kinds
Material directly mixes, and after adding solvent ethanol or acetone, with ball mill grinding 24 hours, obtains containing metal oxide--and dilute
Soil oxide--the MULTIPLE COMPOSITE material of LiMn2O4；
Or wet-mixed
Weigh the LiMn2O4 of Different Weight, join the ionic conduction metal-oxide-rare earth oxide composite wood of above-mentioned preparation
In material mixed solution, wherein, the quality of lithium carbonate accounts for lithium carbonate and metal-oxide-rare earth oxide composite gross weight
Between 5-95%；Then, sufficiently stir 90 DEG C of heating, the mixing LiMn2O4 obtained and the paste of complex rare-earth oxidate containing valuable metal
Shape solution, after stirring, dryouies and obtains fine powder；The fine powder of gained is sintered 1-20 hour at 500-850 DEG C, i.e. obtains
The MULTIPLE COMPOSITE material of containing metal oxide--rare earth oxide--LiMn2O4.
The single part low-temperature solid that a kind of LiMn2O4 the most according to claim 2 manufactures with rare earth oxide composite
Oxide fuel cell, it is characterised in that in the wet-mixed of MULTIPLE COMPOSITE material preparation process 3, described combustion process substep enters
OK, i.e. be placed in Muffle furnace by the gel of thickness and be heated to 300-500 DEG C, combustible is removed in material body burning, obtains fluffy
Fine powder；Continue to be heated to 500-850 DEG C, sinter 1-20 hour,--rare earth oxide--manganese that i.e. obtains containing metal oxide
The MULTIPLE COMPOSITE material of acid lithium.
4. the MULTIPLE COMPOSITE material of containing metal oxide--rare earth oxide--LiMn2O4 obtained according to claim 2 is used for nothing
The single part material of electrolyte membrance fuel cells.
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| CN104103842B (en) * | 2014-07-02 | 2017-01-04 | 湖北大学 | A kind of electroless matter barrier film single part fuel cell with Schottky junction type |
| CN105895933A (en) * | 2015-01-22 | 2016-08-24 | 南京蕴纳纳米科技有限公司 | High-performance fuel cell with agricultural nitric acid rare earth and transition oxide composite material as separator |
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| CN102544540A (en) * | 2010-12-17 | 2012-07-04 | 宓丹 | Fuel cell without electrolyte |
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| WO2012051280A3 (en) * | 2010-10-12 | 2012-07-26 | The Research Foundation Of State University Of New York | Composite electrodes, methods of making, and uses thereof |
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