CN111763081A - Pyrophosphate composite electrolyte and preparation method thereof - Google Patents
Pyrophosphate composite electrolyte and preparation method thereof Download PDFInfo
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- CN111763081A CN111763081A CN201911393398.9A CN201911393398A CN111763081A CN 111763081 A CN111763081 A CN 111763081A CN 201911393398 A CN201911393398 A CN 201911393398A CN 111763081 A CN111763081 A CN 111763081A
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- Prior art keywords
- pyrophosphate
- composite electrolyte
- metaphosphate
- metal
- calcination
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 235000011180 diphosphates Nutrition 0.000 title claims abstract description 66
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 125000005341 metaphosphate group Chemical group 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 39
- 238000001354 calcination Methods 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- BDVMTRCCIQHRBL-UHFFFAOYSA-J phosphonato phosphate;titanium(4+) Chemical compound [Ti+4].[O-]P([O-])(=O)OP([O-])([O-])=O BDVMTRCCIQHRBL-UHFFFAOYSA-J 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- DTEMQJHXKZCSMQ-UHFFFAOYSA-J phosphonato phosphate;zirconium(4+) Chemical class [Zr+4].[O-]P([O-])(=O)OP([O-])([O-])=O DTEMQJHXKZCSMQ-UHFFFAOYSA-J 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 14
- 239000012298 atmosphere Substances 0.000 abstract description 6
- 239000004449 solid propellant Substances 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 21
- 238000000227 grinding Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000000446 fuel Substances 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 5
- 229940099402 potassium metaphosphate Drugs 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002001 electrolyte material Substances 0.000 description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K Indium trichloride Inorganic materials Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 229910004856 P—O—P Inorganic materials 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 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 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- VUDJAFZYSMINQA-UHFFFAOYSA-L zinc metaphosphate Chemical compound [Zn+2].[O-]P(=O)=O.[O-]P(=O)=O VUDJAFZYSMINQA-UHFFFAOYSA-L 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910003873 O—P—O Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910002851 Sn0.9In0.1P2O7 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- XNJIKBGDNBEQME-UHFFFAOYSA-L barium(2+);dioxido(oxo)phosphanium Chemical compound [Ba+2].[O-][P+]([O-])=O.[O-][P+]([O-])=O XNJIKBGDNBEQME-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 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
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- RHJYKEDKMHDZBL-UHFFFAOYSA-L metaphosphoric acid (hpo3), magnesium salt Chemical compound [Mg+2].[O-]P(=O)=O.[O-]P(=O)=O RHJYKEDKMHDZBL-UHFFFAOYSA-L 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229940093956 potassium carbonate Drugs 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- RYSQYJQRXZRRPH-UHFFFAOYSA-J tin(4+);dicarbonate Chemical compound [Sn+4].[O-]C([O-])=O.[O-]C([O-])=O RYSQYJQRXZRRPH-UHFFFAOYSA-J 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229940043825 zinc carbonate Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
-
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Abstract
The invention provides an inorganic composite electrolyte, which is compounded by doped pyrophosphate and metaphosphate. The composite electrolyte obtained by compounding the doped pyrophosphate and the metaphosphate has good medium-temperature conductivity, has high ionic conductivity and negligible electronic conductivity in the double chemical atmosphere of the cathode and the anode, and can be stable for a long time. The composite electrolyte has good compactness, can form a compact film, and ensures that gas permeation does not occur at the operation and working temperature. The composite electrolyte has good mechanical strength and toughness, can meet the use requirements of solid fuel cells, is easy to process and has lower preparation cost.
Description
Technical Field
The invention relates to the field of solid fuel cell materials, in particular to a pyrophosphate and pyrophosphate composite electrolyte and a preparation method thereof.
Background
Compared with high-temperature and low-temperature fuel cells, the medium-temperature fuel cell has wider selectivity in the aspects of sealing materials, connecting materials, electrolyte materials and the like. Among them, development of an electrolyte material having high conductivity at a medium temperature has been a hot research point for medium-temperature fuel cells.
A novel intermediate temperature proton conductor pyrophosphate MP from 20062O7(M is Sn, Ti, Ce or Si) has a proton conductivity of 10 in a range of 50 to 300 ℃ in an atmosphere without humidifying air-3～10-1S·cm-1It has attracted the attention of researchers. In the research, a liquid phase synthesis method is adopted, and H is utilized3PO4Reaction with tin dioxide to form SnP2O7. SnO has also been studied2、H3PO4Adding into deionized water, stirring at 220 deg.C for 1 hr, stirring at 250 deg.C to obtain paste which is difficult to stir, calcining at 650 deg.C for 2.5 hr to obtain SnP2O7. The tin pyrophosphate film is used as a fuel cell electrolyte which operates at 200-300 ℃, and a sintering process is needed to obtain the required mechanical strength. However, due to SnP2O7Can lead to a severe drop in proton conductivity, or phosphorus oxide release. The single pyrophosphate has inherent defects in stability, compactness and the like. To overcome these problems, the construction of composite electrolyte systems has become a focus of research. Wherein, porous SnO is used2Substrate, then with H3PO4Subjecting it to surface treatment to form SnP2O7-SnO2Composite ceramics.
In the existing research, gallium Ga doped single pyrophosphate Sn is obtained at the heat treatment temperature of 600 DEG C1-xGaxP2O7In a series of electrolyte samples, the dopant ion concentration x was found to have a significant effect on the sample conductivity. Wherein, at 175 ℃, Sn0.91Ga0.09P2O7Electrolyte samples in dry air and humid H2In the atmosphere, the electrical conductivity reaches the maximum value of 2.9 × 10- 2S·cm-1、4.6×10-2S·cm-1(J.Power Sources,2010,195: 5596-. In addition, Sn was prepared1-xScxP2O7Series of electrolyte samples, wherein Sn0.94Sc0.06P2O7Sample at humidity H2The conductivity reaches the maximum value of 2.8 × 10 at 200 ℃ in the atmosphere-2S·cm-1(J.Power Sources,2011,196:683-687.) these series of samples meet the Arrhenius relationship at room temperature to 200 deg.C, and the temperature continues to rise, but the conductivity decreases due to inherent defects of stability, compactness, etc.
In addition, indium doped single pyrophosphate Sn1-XInXP2O7After heat treatment at 1000 ℃, the conduction of conducting ions is discontinuous due to the lack of pyrophosphate in the system, the conductivity is low, and the use requirement of the Solid fuel cell is difficult to meet (Solid State ion.,2011(183): 26-31; Solid State ion.,2009(180): 148-.
In order to improve the stability of the solid electrolyte and expand the range of the use temperature, a medium-temperature electrolyte with excellent conductivity is urgently needed to be further developed, and meanwhile, the compactness, the mechanical and mechanical properties, the chemical stability, the thermal stability and other properties of the electrolyte also need to meet the use requirements of the electrolyte.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: the application temperature range of the pyrophosphate electrolyte can be expanded to 400-700 ℃ by the composite electrolyte formed by the pyrophosphate and the metaphosphate, the pyrophosphate electrolyte has excellent electrical property in the temperature range, the compactness is improved, and the mechanical strength and the mechanical property can meet the use requirements of the solid fuel cell, thereby completing the invention.
The invention aims to provide an inorganic composite electrolyte, which is compounded by doped pyrophosphate and metaphosphate.
Wherein the content of the first and second substances,
the pyrophosphate is metal pyrophosphate and is selected from tetravalent metal pyrophosphate;
the metaphosphate is a metal metaphosphate with a low valence state.
Another object of the present invention is to provide a method for preparing the above inorganic composite electrolyte, comprising the steps of:
step 1, mixing a pyrophosphate metal source, a doping atom source, concentrated phosphoric acid and a metal inorganic salt, and heating to obtain a cured material;
and 3, tabletting the composite powder and then carrying out secondary calcination to obtain the composite electrolyte sheet.
Optionally, the method further comprises the following steps:
and 4, processing and shaping the composite electrolyte sheet.
The pyrophosphate composite electrolyte provided by the invention has the following beneficial effects:
(1) the raw materials are wide in source, the doped pyrophosphate is prepared by a solid phase method, the method is suitable for large-scale industrial production, and the modification process is simple to operate and easy to realize.
(2) The process for preparing the composite electrolyte and the operation are simple.
(3) Compared with single doped pyrophosphate, the composite electrolyte has good electrochemical performance and obviously enhanced mechanical strength.
(4) The composite electrolyte has good medium-temperature proton conductivity.
Drawings
Fig. 1 shows an XRD test pattern of the pyrophosphate composite electrolyte in example 2 of the present invention;
FIG. 2 shows a Raman test chart of a pyrophosphate composite electrolyte in example 2 of the present invention;
FIG. 3 shows a scanning electron micrograph of the surface of a pyrophosphate composite electrolyte sheet in example 2 of the present invention;
FIG. 4 shows a scanning electron micrograph of a cross section of a pyrophosphate composite electrolyte sheet in example 2 of the present invention;
FIG. 5 shows a conductivity test chart of a pyrophosphate composite electrolyte in example 2 of the present invention;
FIG. 6 is a graph showing the current-voltage-power density (I-V-P) relationship of a pyrophosphate composite electrolyte in example 2 of the present invention;
FIG. 7 shows a single electrolyte Sn in comparative example 1 of the present invention1-xScxP2O7(x＝0.03,0.06,0.09) of the fuel cell.
Detailed Description
The present invention will now be described in detail by way of specific embodiments, and features and advantages of the present invention will become more apparent and apparent from the following description.
The invention provides an inorganic composite electrolyte, which is compounded by doped pyrophosphate and metaphosphate.
In the present invention, the pyrophosphate is selected from tetravalent metal pyrophosphates, such as those of metals such as tin, titanium, germanium, zirconium, etc., preferably tin pyrophosphate or titanium pyrophosphate, more preferably tin pyrophosphate.
The doping element is selected from transition metals such as nickel, zinc, cerium, ytterbium and the like, metal elements of IIA-IVA such as magnesium, aluminum, indium, tin and the like, nonmetal elements such as silicon, tellurium, arsenic or selenium, preferably selected from nickel, magnesium or aluminum, and more preferably nickel.
In a preferred embodiment of the present invention, the chemical composition of the nickel-doped tin pyrophosphate is Sn1- xNixP2O7Wherein x is more than or equal to 0.01 and less than or equal to 0.3, and the chemical composition of the nickel-doped tin pyrophosphate is preferably Sn0.90Ni0.10P2O7。
The metaphosphate is a low-valence metal metaphosphate, such as copper metaphosphate, magnesium metaphosphate, barium metaphosphate, iron metaphosphate, nickel metaphosphate, cobalt metaphosphate, manganese metaphosphate, zinc metaphosphate, aluminum metaphosphate, potassium metaphosphate, preferably zinc metaphosphate, sodium metaphosphate or potassium metaphosphate, more preferably potassium metaphosphate.
The molar ratio of the pyrophosphate to the metaphosphate in the composite electrolyte is (0.5-5): 1, preferably (1-4): 1, and more preferably (2-3): 1.
The inventor finds that the single doped pyrophosphate has the problems of low density, poor mechanical strength and the like, and when the doped pyrophosphate is compounded with metaphosphate, the electrochemical performance of the obtained compound is improved, and the density and the mechanical strength of the compound are remarkably enhanced, so that the doped pyrophosphate and the metaphosphate are selected to be compounded.
According to another object of the present invention, there is provided a method for preparing the above composite electrolyte, comprising the steps of:
step 1, mixing a pyrophosphate metal source, a doping atom source, concentrated phosphoric acid and a metal inorganic salt, and heating to obtain a cured product.
The pyrophosphate metal source is selected from tetravalent metals such as tin, titanium, germanium, zirconium, preferably tin or titanium, more preferably tin. In order to ensure the conductivity of the electrolyte, the high-temperature fuel cell must be operated at a high temperature (900-1000 ℃), so that the requirements on each component of the cell are very strict, the cost is high, in order to reduce the operating temperature and the cost, the electrolyte is required to have excellent conductivity at a medium temperature (400-750 ℃), the conductivity of the fuel cell is ensured, and the production cost is reduced. Among them, tin pyrophosphate has very good medium-temperature electric properties.
The tin source is selected from tin oxide, tin carbonate, tin nitrate, and the like, and is preferably tin oxide.
The doping atoms are selected from transition metals such as nickel, zinc, cerium, ytterbium and the like, metal elements of IIA-IVA such as magnesium, aluminum, indium and the like, nonmetal elements such as silicon, tellurium, arsenic or selenium, preferably selected from nickel, magnesium or aluminum, and more preferably nickel. The addition of the doping atoms can improve the compactness of the electrolyte material. This is because, in the subsequent calcination process, the dopant atoms are easily diffused on the surface of the crystal grains to form a liquid glass phase, so that viscous flow occurs, rearrangement of the crystal grains is accelerated in the calcination process, and the growth of the crystal grains is promoted, thereby accelerating the calcination process and increasing the density. The nickel salt has wide source, low cost and Ni2+Radius and Sn4+The radii (0.069nm) are the same, and Sn is more easily replaced4+After doping, the crystal lattice is not easy to twist and the deformation is small.
The nickel source is selected from nickel oxide, nickel nitrate, nickel chloride or nickel sulfate, preferably nickel oxide or nickel nitrate, more preferably nickel nitrate. In the subsequent calcination process, the nickel nitrate can form a liquid phase at the grain edge, so that the wettability among grains is increased, the grain positions are rearranged and contacted, the grain boundary sliding is accelerated, the material is densified, the volume fraction of the grain boundary is reduced, and the resistance of the grain boundary is reduced, so that the total conductivity and the conductivity of the grain boundary of the electrolyte can be improved.
The concentration of the concentrated phosphoric acid is 14.6mol/L, and the molar weight of the phosphoric acid radical is the molar weight of the concentrated phosphoric acid. Upon acidification of the concentrated phosphoric acid, the pyrophosphate metal source may be converted to pyrophosphate.
The metal inorganic salt is a metal carbonate selected from copper carbonate, magnesium carbonate, barium carbonate, iron carbonate, nickel carbonate, cobalt carbonate, manganese carbonate, zinc carbonate, aluminum carbonate, sodium carbonate or potassium carbonate, preferably zinc carbonate, sodium carbonate or potassium carbonate, more preferably sodium carbonate or potassium carbonate. The carbonate is added into a reaction system, metaphosphate can be obtained under the action of phosphoric acid and high temperature, and the pyrophosphate and metaphosphate composite electrolyte can be obtained through further treatment.
Only one phase of the single electrolyte promotes ion conduction, and in the composite electrolyte, in addition to the pyrophosphate phase, the other metaphosphate phase is formed by ions (H)+And O2-) Flow therein is fast, promoting H+And O2-And the conduction provides a large-area transmission channel for high ion conduction, effectively reduces the interface polarization impedance and can greatly improve the electrochemical performance. This mixed ion transport in the composite electrolyte helps to improve conductivity. The metaphosphate phase is distributed between the pyrophosphate electrolyte crystal boundary and fills a single electrolyte gap, so that the density of the sample is increased.
The pyrophosphate metal source, the doping atom source and the metal inorganic salt are uniformly mixed and then ground, and manual grinding or mechanical grinding can be carried out, wherein the particle size of the ground mixture is 0.1-3 μm, preferably 0.2-2 μm, and more preferably 0.5-1.5 μm. The particle size of the raw material is controlled, so that the density of a cured substance after subsequent calcination is improved, the treatment temperature is reduced, and the treatment time is shortened. And after the grinding is finished, adding concentrated phosphoric acid and then mixing and grinding.
In a preferred mode, the materials can be pre-ground, and are respectively ground into small particles and then mixed and ground, so that the problems that the original particle sizes of the raw materials are different greatly and the grinding is insufficient are solved. The concentrated phosphoric acid can be added to the mixture after the end of the pre-grinding.
The heating treatment is high-temperature treatment of the mixture of a metal source of the pyrophosphate, a source of the doping atoms, concentrated phosphoric acid and metal inorganic salt.
The heating treatment temperature is 150-550 ℃, preferably 250-450 ℃, and more preferably 300-400 ℃. At the temperature, the metal pyrophosphate source and the doping atom source are dehydrated at high temperature under the acidity of concentrated phosphoric acid to form doped pyrophosphate, and the metal inorganic salt is dehydrated at high temperature under the acidity of concentrated phosphoric acid to form metaphosphate, as shown in reaction formulas (1) and (2). In this process, a small portion of the pyrophosphate is converted to pyrophosphate due to the presence of carbonate, as shown in equation (3).
SnO2+2H3PO4＝SnP2O7+3H2O (1)；
2H3PO4+K2CO3＝3H2O+2KPO3+CO2↑ (2)；
SnP2O7+K2CO3＝SnO2+2KPO3+CO2↑ (3)。
The pyrophosphate metal source, the doping atom source and the metal inorganic salt react with the concentrated phosphoric acid, so that the conversion process of pyrophosphate and metaphosphate is completed on one hand, and the concentrated phosphoric acid can be consumed on the other hand, so that the raw materials are melted and solidified, and the subsequent calcination process is convenient to carry out.
The heating treatment time is 10-60 min, preferably 20-50 min, and more preferably 25-40 min. Within the heating treatment time range, the reaction materials can be fully subjected to melting reaction, and energy waste is avoided.
And 2, carrying out primary calcination on the condensate, cooling and crushing to obtain composite powder.
The calcination is carried out in air. The density of the solidified body can be improved by calcination, the substance state is changed from particle aggregates to a crystal grain combination, solid particles are mutually bonded by matching with the calcination temperature and the calcination time, crystal grains grow up, pores are reduced, the substances are transferred at the calcination temperature, the density is increased, a polycrystalline sintered body can be formed, and the mechanical property of electrolyte can also be improved.
The primary calcination temperature is 400-550 ℃, preferably 450-530 ℃, more preferably 480-510 ℃, and the calcination time is 30-80 min, preferably 45-70 min, more preferably 55-65 min. If the temperature is too low, there is an excessive amount of phosphoric acid, metaphosphoric acid remaining, resulting in a decrease in sample stability. If the temperature is too high, the phosphate and metaphosphate are volatilized excessively, the ion conduction is discontinuous, and the conductivity is reduced.
After the heating treatment in step 1, the raw materials react with each other to form a pyrophosphate and a metaphosphate, and a cured product is formed. In the primary calcination process of the condensate, pyrophosphate is converted from particle aggregates to crystal grain combination, and the pyrophosphate exists in the composite electrolyte in the form of crystals after calcination as can be known from X-ray diffraction (XRD) analysis of a sample; meanwhile, metaphosphate moves among pyrophosphate crystal boundaries under the action of high temperature to form an amorphous metaphosphate phase. Relative to H in the pyrophosphate crystal phase+And O2-The conduction is faster in the amorphous metaphosphate phase, the interface polarization impedance can be effectively reduced, and the electrochemical performance is greatly improved.
After calcination, the product is pulverized and milled to obtain a composite powder, and the milling may be performed manually or mechanically. The grinding can make the calcined material components uniformly distributed in the composite powder, the particle size of the ground composite powder is reduced and uniform, and the calcination of the composite powder with small particle size can improve the density of the calcined sintered body, improve the compactness, reduce the calcination temperature and shorten the calcination time.
The particle size of the composite powder after grinding is 0.1-3 μm, preferably 0.2-2 μm, and more preferably 0.5-1.5 μm.
And 3, tabletting the composite powder and then carrying out secondary calcination to obtain the composite electrolyte sheet.
The pressure condition of the composite powder tabletting is 100-300 MPa, preferably 150-280 MPa, more preferably 180-220 MPa, and the tabletting time is 0.5-15 min, preferably 1.5-10 min, more preferably 2-5 min.
The conditions under which the tablets are made directly affect their conductivity. First, the material composition needs to be uniformly distributed during the tabletting process. On one hand, the problem that the conductivity is reduced due to the fact that the pressed tablet density is not uniform after pressing caused by nonuniform mass distribution of materials is avoided. In actual operation, under the same pressure, the density of places with more materials is high, the compactness is good, the density of places with less materials is low, the compactness is poor, and the difference of the compactness directly influences the phase change of the composite electrolyte in secondary calcination, so that the difference of the tabletting conductivity at different positions is large. On the other hand, the internal components of the material need to be uniformly distributed within the laminate.
In the invention, the appropriate tabletting conditions can improve the compactness of tabletting and ensure the uniformity of the compactness, so that the powder particles are effectively and regularly contacted, and the uniform change of microstructures in the secondary calcining process is facilitated.
The temperature of the secondary calcination is 600-800 ℃, preferably 650-750 ℃, more preferably 680-720 ℃, and the calcination time is 30-80 min, preferably 45-70 min, more preferably 55-65 min. Because the tabletting is made of composite powder, the specific surface area of the powder raw material is large, the surface free energy is high, and various crystal defects exist in the powder, the temperature can play a role in overcoming energy barrier in the calcining process, and the integral tabletting is formed by melting, so that the processing is convenient, and the use requirement of the solid fuel cell is met. And the particles are fused in the secondary calcining process, so that the hardness of the tabletting can be increased, and the stability and the density of the tabletting can be improved. If the temperature is too low, the density and conductivity are high, but the stability is lowered. If the temperature is too high, the density and conductivity will be reduced.
The mole ratio of the pyrophosphate to the metaphosphate in the composite electrolyte sheet is (0.5-5): 1, preferably (1-4): 1, and more preferably (2-3): 1.
Optionally, the method further comprises the following steps:
and 4, processing and forming the composite electrolyte sheet.
In order to test the conductivity of the prepared composite electrolyte sheet, the composite electrolyte sheet was processed into an electrolyte separator. The size of the electrolyte membrane is based on the requirement of different fuel cells on the shape of the electrolyte membrane, such as the electrolyte membrane with the diameter of 18.0mm and the thickness of 1.1 mm.
The electrolyte membrane is used as a core component of the solid fuel cell, and the electrolyte provided by the invention has the following beneficial effects:
(1) the electrolyte has high ionic conductivity and negligible electronic conductivity in a dual chemical atmosphere of the cathode and anode, and is stable for a long time.
(2) Within the working temperature range of 400-700 ℃, the electrolyte has good chemical stability, crystal form stability and overall dimension stability in oxidation and reduction environments.
(3) At operating and preparation temperatures, chemical compatibility with the electrode material, thermal expansion matching, and no chemical interaction are required.
(4) The electrolyte is compact, a compact film can be formed, and the compactness at the operation and working temperature can be ensured.
(5) The composite electrolyte has good mechanical strength and toughness, can meet the use requirement, is easy to process and has lower preparation cost.
Examples
Example 1
SnO2、Ni(NO3)214.6mol/L of concentrated H3PO4And K2CO3Taking materials according to the molar ratio of 2.7:0.3:7:0.5, and respectively carrying out SnO treatment2、Ni(NO3)2And K2CO3Pre-grinding, adding concentrated H3PO4Grinding (final molar ratio of Sn)0.9Ni0.1P2O7：KPO33: 1) uniformly mixing, and completely curing after heat preservation for 30min at 350 ℃ to obtain a cured substance.
And (3) heating the cured substance in a box type resistance furnace at 500 ℃ for about 1 hour, cooling to room temperature, taking out, grinding into fine powder, and grinding uniformly to obtain the composite powder.
Example 2
The compound powder was compressed into tablets under a pressure of 200MPa for 3 min.
Putting the pressed wafer on a gasket, covering a ceramic crucible, and putting the wafer in an electric furnace to be burnt for 1h at 700 ℃ to obtain Sn0.9Ni0.1P2O7/KPO3In which Sn0.9Ni0.1P2O7And KPO3Is 3: 1.
The sample was processed into an electrolyte separator 18.0mm in diameter and 1.1mm in thickness and used for the test of the medium-temperature electrical properties in a dry nitrogen atmosphere.
Comparative example
Comparative example 1
SnO2、Sc2O3And 14.6mol/L concentrated phosphoric acid were taken out in a molar ratio, ground in the same grinding method as in example 1, mixed with stirring at 350 ℃ until a solid mixture was formed, ground into a powder, and kept at 350 ℃ for 30 min.
The solid powder was pressed at 300MPa into tablets with a diameter of 12mm and a thickness of 1.2 mm. Placing the condensate in a box-type resistance furnace to heat at 500 ℃, calcining for about 2h, cooling to room temperature, and taking out to obtain Sn1-xScxP2O7Tabletting (x ═ 0.03,0.06 or 0.09). The both sides of the pellet were covered with platinum paste, heated at 250 ℃ for 30min, and the platinum wire was packaged, and subjected to electrical performance test in a humid hydrogen atmosphere, as shown in fig. 5.
Comparative example 2
SnO214.6mol/L concentrated phosphoric acid and In2O3According to molar ratio SnO2:In2O3:H3PO4The reaction mixture was taken out and ground at 0.9:0.05:3.0 and added to the reaction vessel.
Adding 100mL of deionized water, and maintaining at 300 deg.CStir warm until a viscous slurry is obtained. Calcining the viscous slurry at 650 ℃ for 2.5h to obtain Sn0.9In0.1P2O7And (5) grinding the powder.
Making into tablet under 200MPa, wherein the tablet has a diameter of 12mm and a thickness of 1.2 mm. And putting the pressed sheet on a gasket, covering a ceramic crucible, and putting the pressed sheet in an electric furnace for burning for 2 hours at 650 ℃. The resulting pellets were subjected to electrical property testing in a dry nitrogen atmosphere, as shown in FIG. 5.
Comparative example 3
To InCl3Adding dilute hydrochloric acid and SnCl into the aqueous solution in sequence4·5H2O, dilute hydrochloric acid is added to inhibit hydrolysis of tin chloride, and (NH) is added last4)2HPO4An aqueous solution of (a). SnCl4·5H2O、InCl3And (NH)4)2HPO4Is 0.92:0.08: 3.
Preheating at 80 deg.C, concentrating at 200 deg.C to obtain colloidal precipitate, and calcining at 650 deg.C for 2.5h to obtain Sn0.92In0.08P2O7And (5) grinding the powder.
Making into tablet under 200MPa, wherein the tablet has a diameter of 12mm and a thickness of 1.2 mm. The tablets were placed on a pad, covered with a ceramic crucible, and calcined in an electric furnace at 1000 ℃ for 2 h. In an air atmosphere, the resulting preforms were subjected to electrical property testing, as shown in FIG. 5.
Comparative example 4
Taking SnO214.6mol/L concentrated phosphoric acid and Ga2O3Grinding, mixing, SnO214.6mol/L concentrated phosphoric acid and Ga2O3In a molar ratio of SnO2:Ga2O3:H3PO40.91:0.045:3.0, stirring and mixing at 250 ℃ until a solid mixture is formed, and burning at 500 ℃ for 2h to obtain Sn0.91Ga0.09P2O7。
Pressing into tablet under 300MPa, wherein the tablet has diameter of 12mm and thickness of 1.2 mm.
Pressure measuring and testingConductivity of the sheet at 175 ℃ the conductivity reached a maximum of 2.9 × 10 in a dry air atmosphere-2S·cm-1(ii) a In wet H2Has an electric conductivity of 4.6 × 10-2S·cm-1。
Examples of the experiments
Experimental example 1
XRD analysis was performed on the sample obtained in example 2. The XRD results of the samples are shown in fig. 1. As shown in FIG. 1, the XRD diffraction peak intensity and position and SnP of the sample of example 22O7The standard spectrogram is the same, which indicates that SnP is formed2O7Is a product of the main phase. SnO at 26.82 ° 2 θ2The weak diffraction peak of (a) suggests that the following reaction occurs during the conversion of potassium carbonate to potassium metaphosphate: SnP2O7+K2CO3＝SnO2+2KPO3+CO2×) and thus a small amount of SnO is generated2。
Diffraction peaks of potassium carbonate and potassium metaphosphate are not seen in FIG. 1, indicating that K is2CO3And SnP2O7After full reaction, the product is completely converted into KPO3KPO, and3is mainly present in the composite electrolyte in an amorphous state.
Experimental example 2
The Raman analysis was performed on the sample obtained in example 2. The Raman test results of the samples are shown in figure 2. 315cm in FIG. 2-1And 353cm-1Is PO in pyrophosphate4A bending vibration peak of tetrahedral units; 469cm-1Is (P)2O7)4-Bending and twisting of the radicals overlaps the vibrational peaks; 703cm-1Is a P-O-P bridge oxygen bond symmetric stretching vibration peak of pyrophosphate and metaphosphate; 1102cm-1The strong spectral band is the symmetric stretching vibration of P-O-P non-bridge oxygen bonds in a pyrophosphate structural unit; 1176cm-1The spectral band is phosphorus and non-bridging oxygen PO in metaphosphate structural unit2Symmetric telescopic vibration; 1261cm-1Is O-P-O non-bridge oxygen antisymmetric telescopic vibration in metaphosphate structural unit.
The raman spectrum results showed that the sample obtained in example 2 was a tin pyrophosphate and corresponding metaphosphate composite electrolyte.
Experimental example 3
The sample obtained in example 2 was subjected to SEM analysis. The SEM test results of the samples are shown in fig. 3 and 4. FIG. 3 is Sn0.9Ni0.1P2O7/KPO3Surface topography of the electrolyte sheet, FIG. 4 is Sn0.9Ni0.1P2O7/KPO3A picture of the cross-sectional morphology of the electrolyte sheet.
The photograph shows that the composite electrolyte has high compactness, and the section diagram of FIG. 4 shows that the composite electrolyte has uniform and consistent particle diameter and a small number of pores, and the pores are proved to be closed pores by an air tightness experiment. When testing the gas tightness of hydrogen, the air inlet valve and the air outlet of the fuel cell stack are closed, nitrogen can be filled into the air inlet end of the hydrogen, a certain pressure value is set, and the pressure drop value is observed after the pressure is maintained for a period of time. If not, the airtightness is proved to be good.
Experimental example 4
The samples obtained in example 2, comparative example 1, comparative example 2 and comparative example 3 were subjected to conductivity tests at different temperatures, and the results of the change of the conductivity of the samples with temperature are shown in fig. 5, it can be seen that the conductivity of the sample obtained in example 2 reached a maximum of 6.9 × 10 at 700 c-2S·cm-1. According to the following formula:
the conductivity sigma (unit: S cm) of the sample is obtained by calculation-1). Wherein L is the thickness of the solid electrolyte (0.11cm), R is the bulk resistance of the sample (unit: Ω, measured by an electrochemical workstation, i.e., the AC impedance value), and S is the electrode area (0.5 cm)2). The heat treatment temperature of example 2 was 700 ℃.
In comparative example 1, the conductivity reached a maximum of 2.8 × 10 at 225 to 255 ℃-2S·cm-1。
Sn samples obtained in comparative examples 2 and 30.9In0.1P2O7And Sn0.92In0.08P2O7Because the conductivity of the conductive ions is discontinuous due to the lack of pyrophosphate in the system, the conductivity of the three pyrophosphate electrolytes is lower than that of the composite electrolyte obtained in the invention.
Experimental example 5
H is assembled by using hydrogen as fuel gas and oxygen as oxidant and using the composite electrolyte membranes prepared in example 2 and comparative example 12/O2Fuel cells were tested and the current-voltage-power density (I-V-P) relationship was determined, and the results are shown in fig. 6 and 7.
In the test, the open-circuit voltage is 1.04V, and the maximum output power density is 434mW cm at 700 DEG C-2。
Single electrolyte Sn of comparative example 11-xScxP2O7The conductivity (x ═ 0.03,0.06,0.09) reached the highest at 255 ℃, and the current-voltage-power density (I-V-P) relationship at 255 ℃ was tested, with the results shown in fig. 7. As can be seen from FIG. 7, the maximum output density at 255 ℃ does not exceed 30 mW/cm either-2It is demonstrated that the fuel cell performance of a single electrolyte is much lower than that of the composite electrolyte of pyrophosphate and metaphosphate obtained in example 2 of the present invention.
The invention has been described in detail with reference to specific embodiments and/or illustrative examples and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. An inorganic composite electrolyte, characterized in that the inorganic composite electrolyte is compounded by doped pyrophosphate and metaphosphate.
2. The composite electrolyte according to claim 1, wherein the pyrophosphate is selected from tetravalent metal pyrophosphates, such as tin, titanium, germanium, zirconium pyrophosphates, preferably tin pyrophosphate or titanium pyrophosphate, more preferably tin pyrophosphate.
3. The composite electrolyte according to claim 1, wherein the metaphosphate is a lower valence metal metaphosphate.
4. The method for producing the composite electrolyte according to any one of claims 1 to 3, characterized by comprising the steps of:
step 1, mixing a pyrophosphate metal source, a doping atom source, concentrated phosphoric acid and a metal inorganic salt, and heating to obtain a cured material;
step 2, carrying out primary calcination on the condensate, cooling and crushing to obtain composite powder;
and 3, tabletting the composite powder and then carrying out secondary calcination to obtain the composite electrolyte sheet.
5. The production method according to claim 4, wherein, in step 1,
the doping atoms are selected from transition metals, such as nickel, zinc, cerium, ytterbium, metal elements of IIA to IVA, such as magnesium, aluminium or indium, non-metal elements, such as silicon, tellurium, arsenic or selenium, preferably from nickel, magnesium or aluminium, more preferably nickel,
the metal inorganic salt is a metal carbonate.
6. The preparation method according to claim 4 or 5, wherein in the step 2, the primary calcination temperature is 400 to 550 ℃ and the calcination time is 30 to 80 min.
7. The method according to any one of claims 4 to 6, wherein in step 3, the pressure of the tablet is 100 to 300MPa, and the tabletting time is 0.5 to 15 min.
8. The preparation method according to any one of claims 4 to 7, wherein in the step 3, the temperature of the secondary calcination is 600 to 800 ℃, and the calcination time is 30 to 80 min.
9. The production method according to any one of claims 4 to 8, further comprising,
and 4, processing and forming the composite electrolyte sheet.
10. The preparation method according to any one of claims 4 to 9, wherein the molar ratio of the pyrophosphate to the metaphosphate in the composite electrolyte sheet is (0.5-5): 1, preferably (1-4): 1, and more preferably (2-3): 1.
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