CN108370025A - 用于储能,催化,光伏和传感器应用的合成表面官能化酸化金属氧化物材料 - Google Patents
用于储能,催化,光伏和传感器应用的合成表面官能化酸化金属氧化物材料 Download PDFInfo
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- CN108370025A CN108370025A CN201680070252.9A CN201680070252A CN108370025A CN 108370025 A CN108370025 A CN 108370025A CN 201680070252 A CN201680070252 A CN 201680070252A CN 108370025 A CN108370025 A CN 108370025A
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- Prior art keywords
- metal oxide
- solid metal
- battery electrode
- amo
- electrode according
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 67
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000006557 surface reaction Methods 0.000 title description 20
- 238000006555 catalytic reaction Methods 0.000 title description 5
- 238000004146 energy storage Methods 0.000 title description 3
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000002086 nanomaterial Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 235000019647 acidic taste Nutrition 0.000 description 20
- 239000002243 precursor Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 238000005580 one pot reaction Methods 0.000 description 9
- 229910052718 tin Inorganic materials 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- FYQZIUWOAGROCR-MRMRLACISA-N amotin Natural products CC(C)[C@]1(O)[C@@H]2OC(=O)[C@H]1[C@@H]3CC[C@]4(O)C(=O)O[C@H]2[C@]34C FYQZIUWOAGROCR-MRMRLACISA-N 0.000 description 7
- LPGWZGMPDKDHEP-NVDFJPPOSA-N vinleurosine Chemical compound C([C@]1([C@@H]2O1)CC)N(CCC=1C3=CC=CC=C3NC=11)C[C@@H]2C[C@]1(C(=O)OC)C1=CC([C@]23[C@H]([C@@]([C@H](OC(C)=O)[C@]4(CC)C=CCN([C@H]34)CC2)(O)C(=O)OC)N2C)=C2C=C1OC LPGWZGMPDKDHEP-NVDFJPPOSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 150000001450 anions Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003930 superacid Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 3
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 150000003891 oxalate salts Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 oxygen anion Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000003113 alkalizing effect Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000003050 experimental design method Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229910002919 BO3 Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910006130 SO4 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- YVIMHTIMVIIXBQ-UHFFFAOYSA-N [SnH3][Al] Chemical compound [SnH3][Al] YVIMHTIMVIIXBQ-UHFFFAOYSA-N 0.000 description 1
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical group [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003283 colorimetric indicator Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- NTIGMHLFJNXNBT-UHFFFAOYSA-N manganese tin Chemical compound [Mn].[Sn] NTIGMHLFJNXNBT-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 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
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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Abstract
一种酸化的金属氧化物(“AMO”)材料,优选呈单分散纳米颗粒形式,尺寸为20nm或更小,当以5wt%悬浮于水溶液中时pH<7,至少在其上表面上哈米特函数H0>‑12。AMO材料在电池电极,催化剂或光伏组件等应用中有用。
Description
背景技术
本发明属于用于化学能源存储和电力装置的材料领域,例如但不限于电池。更具体地,本发明涉及用于诸如电化学电池材料(电池),催化剂,光伏组件和传感器等应用的合成酸化金属氧化物(“AMO”)纳米材料。
金属氧化物是氧与金属键合的化合物,具有通式MmOx。它们存在于自然界中,但可以人工合成。在合成金属氧化物中,合成方法可以对表面的性质,包括其酸/碱特性具有广泛的影响。表面特性的变化可改变氧化物的特性,影响催化活性和电子迁移率等特征。然而,表面控制反应性的机制并不总被很好的表征或理解。例如,在光催化中,表面羟基被认为促进电子从导带转移到化学吸附的氧分子。
尽管表面特性的重要性,金属氧化物文献,包括科学论文和专利,都主要致力于创造新型纳米级结晶形式的金属氧化物,以改善能源储存和电力应用。金属氧化物表面特性被忽视,并且在化学催化文献外,针对控制或改变已知金属氧化物的表面以实现性能目标的创新非常少。
化学催化文献主要致力于创造“超强酸”——酸度大于纯硫酸(18.4M H2SO4)——通常用于烃裂解等大规模反应。超强酸性不能在传统的pH值上进行测量,而是用哈米特数进行量化。哈米特数(H0)可被认为是将pH范围扩展到0以下的负数。纯硫酸的H0为-12。
然而,有许多反应体系和应用中,超强酸性太强。例如,超强酸性可降解系统组分或催化不需要的副反应。然而,酸性在这些应用中提供增强的反应性和速率特性或和改善的电子迁移率可能仍然是有用的。
电池文献教导说,酸性基团在电池中是有害的,它们可以攻击金属集流体和外壳并导致其他电极部件的劣化。此外,现有技术教导了活性催化电极表面导致电解质分解,这可导致电池中产生气体并最终导致电池失效。
存在对呈酸性但至少在其表面上不具有超强酸性的合成金属氧化物的需要。
发明内容
根据本发明的材料是合成的,酸化的金属氧化物(“AMO”),优选呈单分散纳米颗粒形式(尺寸为20nm或更小),当以5wt%悬浮于水溶液中时具有pH<7,并且至少在其表面上哈米特函数H0>-12。AMO材料在诸如电池电极,催化剂,光伏组件或传感器等的应用中是有用的。
优选地,合成和表面官能化是在“单釜”水热法中完成的,其中当金属氧化物由合适的前体合成时,所述金属氧化物的表面被官能化。这种单釜法不需要任何超出那些合成金属氧化物本身所需步骤外的酸化步骤,并产生具有期望表面酸度(但不是超强酸性)的AMO材料。
在优选的实施例中,表面官能化的发生采用强吸电子基团(“EWGs”)——例如SO4,PO4,或卤素——无论单独使用或与彼此的一些组合。表面官能化也可使用比SO4,PO4或卤素弱的EWG。例如,合成的金属氧化物可以用乙酸盐(CH3COO),草酸盐(C2O4)和柠檬酸盐(C6H5O7)表面官能化。
附图说明
图1示出了用本发明公开的方法制备的AMO和市售的非AMO锡比较,相对于锂循环时的循环伏安图中的差异。
图2示出了AMO氧化锡的总反射率不同于市售的非AMO氧化锡。
图3是X射线光电子能谱(XPS)数据,其示出了由本发明公开的合成方法内生的表面官能化。显示的数字是以%表示的原子浓度。最右栏列出了以5wt%分散在在水溶液中时测量的合成纳米颗粒的相应pH值。
图4显示了相同条件下(除了使用不同的官能团外)合成的AMO纳米颗粒之间的形态差异。
图5显示了相同条件下(除了具有两个不同的总反应时间)合成的AMO纳米颗粒的形态和性能的差异。
图6是显示了球形和细长(针状或杆状)AMO在相对锂循环时表现差异的代表性半电池数据。
图7是使用两个一强(含磷)和一弱(乙酸盐)吸电子基团AMO合成的纳米颗粒的表面的X射线光电子能谱分析,其表明磷的原子浓度比与乙酸酯基团相关联的键的原子浓度更大。
图8A示出了一AMO,其在可见光中比另一AMO更活跃。
图8B示出了一AMO,其在紫外光下比其他AMO更具活性。
图9是比较两种AMO的图表,一种具有较高的容量,适于首次(一次性使用)电池应用,另一种具有较高的可循环性,适用于二次(可充电)电池应用。
图10示出了AMOs可提高电池性能,而不会恶化电池组件或产生气体。
定义
为了本公开的目的,以下术语具有以下含义:
酸性氧化物——科学文献中通用的术语,指氧与非金属元素的二元化合物。一个例子是二氧化碳,CO2。一些类金属(例如Si,Te,Po)的氧化物在其纯分子状态下同样具有弱酸性。
酸化金属氧化物(“AMO”)——在本文用来表示氧和金属的二元化合物的术语,其经过合成或更改而比其天然矿物状态具有更大酸度并且哈米特函数,H0>-12(不是超强酸)。平均粒径尺寸也小于天然矿物态下的尺寸。天然的矿物学形式不属于本发明的AMO材料的范围。然而,合成金属氧化物在本公开的范围内比其最丰富的矿物学形式(具有等效的化学计量比)酸度更大但不是落在本公开的范围内的超强酸,可以说是AMO材料,只要它满足本公开中讨论的某些其他条件即可。
酸性——在科学文献中通用的术语,指在水溶液中的PH值小于7的化合物。
吸电子基团(“EWG”)——将电子密度吸引到自己的原子或分子基团。EWG的强度是基于其在化学反应中的已知表现。例如,卤素已知是强EWG。有机酸基团已知是弱吸电子的。
哈米特函数——在高浓度酸溶液和超强酸中定量酸度的额外方法,其酸度由下式定义:H0=pKBH++log([B]/[BH+])。在此比例下,纯的18.4摩尔H2SO4具有-12的H0值。纯硫酸酸值H0=-12不能解释为pH=-12,而是表示存在的酸性物质在虚拟(理想)浓度为1012mol/L时具有等于H3O+的质子化能力,通过其质子化弱碱的能力来测量的。哈米特酸度函数在其方程中避免了水分。它在此用于提供从超强酸区分AMO材料的定量手段。哈米特函数可以与比色指示剂测试和程序升温脱附结果相关。
金属氧化物——在科学文献中用来指氧与金属元素的二元化合物的通用术语。根据它们在元素周期表中的位置,金属氧化物在其纯分子状态下从弱碱性到两性(同时显示酸性和碱性)变化。弱碱性金属氧化物是锂,钠,镁,钾,钙,铷,锶,铟,铯,钡和碲的氧化物。两性氧化物是铍,铝,镓,锗,砹,锡,锑,铅和铋的氧化物。
单分散——以均一尺寸的颗粒为特征,这些颗粒基本上彼此分离,不聚集成较大颗粒。
pH——一种科学文献中通用的功能性数值标度,用于指定水溶液的酸度或碱度。它是水合氢离子[H3O+]浓度的对数的负数。如本文所用,它描述了悬浮在水溶液中的纳米颗粒的相对酸度。
表面官能化——将小原子或分子基团附着到材料表面。
超强酸——比100%H2SO4酸性更强的物质,具有哈米特函数,H0<-12。
具体实施方式
这里描述的优选实施例提供了在诸如电池电极,催化剂或光伏组件的应用中有用的酸化金属氧化物(“AMO”)材料的说明性实例。这些AMO材料的表面是酸性的,但不是超强酸性。
金属氧化物的表面理想地是金属和氧中心的阵列,根据氧化物的晶体结构排序。实际上,阵列不完美,容易出现空位,变形和表面附着的影响。无论如何,任何暴露的金属中心都是阳离子(带正电的)并且可接受电子,因此发挥定义为路易斯酸位点的功能。氧中心是阴离子(带负电荷)并充当路易斯碱基位点以供电子。这导致了众所周知的金属氧化物表面的两性。
在正常的大气条件下,水蒸气的存在将分子化(水合)地或离解(羟基化)地吸附到金属氧化物表面。OH-和H+类型都可以吸附在氧化物表面上。负电荷的羟基物质将附着在金属阳离子(路易斯酸,电子受体)中心,并且H+将附着在氧阴离子(路易斯碱,电子供体)中心。两种吸附都导致金属氧化物表面上存在相同的官能团——羟基。
这些表面羟基可以用作布朗斯特酸或用作布朗斯特碱,因为这些基团可以放弃或接受质子。单个羟基为质子供体或质子受体的倾向受其所附着的金属阳离子或氧阴离子的配位的影响。金属氧化物表面的缺陷如氧空位或表面基团与其他化学物质的配位,意味着所有的阳离子和阴离子不是同样地配位。酸碱位点的数量和强度会有所不同。当在氧化物表面大致“总计”时,这可以使表面具有整体的酸性或碱性特征。
路易斯酸和碱位点的数量和强度(分别来自暴露的金属阳离子和氧阴离子)和布朗斯特酸和碱位点(来自表面羟基)——为金属氧化物增加了广泛的用途和功能以及其在化学反应和装置应用中的使用。这些位点是金属氧化物的化学反应性的强有力贡献者。它们可以作为其他化学基团的锚点,其他化学基团和甚至另外的金属氧化物可附着于其上。它们会影响表面电荷,亲水性和生物相容性。
改变金属氧化物表面的一种方法是在被称为表面官能化的方法中附着小的化学基团或吸电子基团(“EWG”)。EWG诱导氢氧键的极化并促进氢的离解。例如,更强的EWG将会产生极性更大的键并因此具有酸性更大的质子。路易斯位点的酸度可以通过诱导极化来增加,这有助于将电子提供到位点。当将如此制成的化合物置于水中时,酸性质子将解离并因此降低水性pH测量值。
尽管有些不精确,在测量固体酸/碱体系而不是液体体系时,传统的使用滴定法测量pH值的方法,pH试纸和pH探针可用于评估分散在水溶液中的金属氧化物的酸度。这些测量可以通过使用包括但不限于比色指示器,红外光谱和程序升温脱附数据的技术来补充,以建立金属氧化物表面的酸化性质。表面基团可通过标准分析技术检测,包括但不限于X射线光电子能谱。
表面官能化可在合成后完成,包括但不限于将金属氧化物暴露于酸性溶液或含有所需官能团的蒸气。它也可以通过固态方法完成,其中金属氧化物与含有所需官能团的固体混合和/或研磨。然而,所有这些方法都需要额外的表面官能化步骤或超出合成金属氧化物本身所需的步骤。
AMO材料的合成和表面官能化可在“单釜”水热合成方法或其等效方法中实现,其中当金属氧化物由合适的前体合成时金属氧化物的表面被官能化。含有EWG的前体盐被溶解,所得溶液用含有第二种EWG的酸来酸化。然后将该酸化溶液碱化,并将碱化溶液加热然后洗涤。干燥步骤产生固体AMO材料。
以举例的方式,使用以下单釜法合成了AMO形式的氧化锡并同时表面官能化的优选实施例:
1.首先,将7克氯化锡(II)二水合物(SnCl2·2H2O)溶于35毫升无水乙醇和77毫升蒸馏水的溶液中。
2.将所得溶液搅拌30分钟。
3.通过加入7mL 1.2M HCl将溶液酸化,逐滴加入,并将所得溶液搅拌15分钟。
4.通过加入1M碱的水溶液碱化溶液,滴加至溶液的pH值约为8.5。
5.然后将所得不透明白色悬浮液在搅拌下置于热水浴中(~60℃至90℃)至少2小时。
6.然后用蒸馏水和无水乙醇洗涤悬浮液。
7.将洗涤过的悬浮液在空气中100℃下干燥1小时,然后在空气中200℃下退火4小时。
该方法用氯产生表面官能化的锡的AMO,当以5wt%在水溶液及室温下测量时,其pH值约为2。根据定义它的哈米特函数,H0>-12。尽管这里描述了诸如烧瓶的开放系统,但也可以使用诸如高压灭菌器的封闭系统。
本领域技术人员将认识到,该方法的参数可以如水热合成中通常的那样变化。这些参数包括但不限于试剂的类型和浓度,酸和碱的类型和浓度,反应时间,温度和压力,搅拌速率和时间,洗涤步骤的数量和类型,干燥和煅烧的时间和温度,以及在干燥和煅烧过程中的气体暴露。可以单独或以任何组合进行变化,优选使用实验设计方法。此外,其他金属氧化物合成方法——例如喷雾热解方法,气相生长方法,电沉积方法,固态方法和水热或溶剂热方法——可用于实现与此处公开的方法相同或相似的结果。
AMO纳米材料的性能特征与非酸化金属氧化物纳米颗粒的性能特征不同。作为一个例子,图1显示了单釜法制备的AMO锡与市售非AMO锡相比,相对于锂循环时的循环伏安图中的差异。作为另一个例子,图2显示AMO氧化锡的总反射率不同于市售非AMO氧化锡的总反射率。数据表明AMO具有较低的带隙,因此作为光伏系统的组件具有更理想的性能。
AMO材料可被认为具有通式
MmOx/G
其中MmOx是金属氧化物,m最小为1且不大于5,x最小为1且不大于21;
G是至少一种EWG而不是氢氧化物,而且
/简单地区分金属氧化物和EWG,表示两者之间没有固定的数学关系或比率。
G可以表示单一类型的EWG,或者多于一种类型的EWG。
优选的AMO是酸化锡氧化物(SnxOy),酸化二氧化钛(TiaOb),酸化铁氧化物(FecOd)和酸化氧化锆(ZreOf)。优选的吸电子基团(“EWG”)是Cl,Br,BO3,SO4,PO4和CH3COO。无论具体的金属或EWG如何,AMO材料都是酸性的,但不是超强酸性的,当以5wt%悬浮在水溶液中时,产生的pH值小于7,至少在其表面上哈米特函数H0>-12。
AMO材料结构可以是结晶的或无定形的(或其组合),并且可以单独使用或者作为与另一材料与现在技术中已知的非酸化金属氧化物或与其他添加剂,粘合剂或导电助剂组合的复合材料。可将AMO材料以10wt%至80wt%且高达90wt%至95wt%的范围添加至导电辅助材料,例如石墨或导电碳(或其等价物)。在优选的实施例中,AMO以10wt%,33wt%,50wt%和80wt%添加。
为了使可用的总表面积最大化,AMO应为纳米颗粒形式(即,尺寸小于1微米)并且基本上是单分散的。更优选地,纳米颗粒尺寸小于100nm,甚至更优选小于20nm或10nm。
除了简单的或者二元氧化物之外,其他金属或金属氧化物存在于其中的混合金属AMO也已经被付诸实施。这些混合金属AMO可被认为具有通式
MmNnOx/G和MmNnRrOx/G
其中:
M是金属,m最小为1且不大于5;
N是金属且n大于0且不大于5;
R是金属且r大于0且不大于5;
O是与所有金属有关的总氧,x最小为1且不大于21;
/简单地区分金属氧化物和吸电子表面基团,表示两者之间没有固定的数学关系或比率;以及
G是至少一种EWG而不是氢氧化物。
G可表示单一类型的EWG,或者多于一种类型的EWG。
一些现有的混合金属氧化物体系,其中沸石是最突出的例子,它显示出强酸性,虽然每种简单的氧化物都不具有强酸性。本公开的混合金属AMO的优选实施例不同于那些系统,因为任何实施例必须包含至少一种呈简单MmOx/G形式的酸性(但不是超酸性)的AMO。优选的混合金属和金属氧化物体系是SnxFecOy+d和SnxTiyOy+b,其中y+d和y+b可以是整数或非整数值。
在一个优选的实施例中,混合金属AMO材料通过改进的单釜法产生:合成以两种金属前体盐而不是一种,以任何比例开始。例如,单釜法的步骤1可以如下改变:首先,将3.8g氯化锡(II)二水合物(SnCl2·2H2O)和0.2g氯化锂(LiCl)溶解在20mL纯乙醇和44mL蒸馏水中。
也可以以任何比例使用三种金属前体盐。根据所需的产品,金属前体盐可具有相同或不同的阴离子基团;可以在合成中的不同点引入;或者可以作为固体引入或引入溶剂中。
使用单釜法进行的实验产生了七个关键发现。首先,在所有情况下,表面官能化和酸性都是内源性产生的(见图3),而不是合成后产生。与现有技术的表面官能化方法不同,单釜法既不需要除了合成金属氧化物本身所需的步骤以外的任何额外的步骤用于表面官能化,也不需要使用含羟基的有机化合物或过氧化氢。
其次,该方法广泛地普遍适用于各种金属氧化物和EWG。使用该方法,合成了铁,锡,锑,铋,钛,锆,锰和铟的金属氧化物,并用氯化物,硫酸盐,乙酸盐,硝酸盐,磷酸盐,柠檬酸盐,草酸盐,硼酸盐和溴化物同时表面官能化。合成了锡铁,锡锰,锡锰铁,锡钛,铟锡,锑锡,铝锡,锂铁,锂锡等混合金属AMO。此外,表面官能化可使用比卤素和SO4弱的EWG完成,仍然产生酸性但不是超酸性表面。例如,该方法也被用于合成用乙酸盐(CH3COO),草酸盐(C2O4)和柠檬酸盐(C6H5O7)表面官能化的AMOs。
第三,EWG和纳米粒子的其他性质之间存在协同关系,例如尺寸,形态(如片状,球状,针状或杆状),氧化态和结晶度(无定形,结晶,或其混合物)。例如,在除了使用用于表面官能化的不同EWG之外,相同条件下合成的AMO纳米颗粒之间可能发生形态学差异(见图4)。表面官能化可能起到“固定”纳米颗粒尺寸的作用,阻止它们的生长。根据确切的合成条件,该固定可能仅发生在纳米粒子的一个维度上,或者发生在多个维度上。
第四,AMO的特性对合成条件和过程非常敏感。例如,在除了具有两个不同的总反应时间之外,相同的条件下合成AMO纳米粒子时可产生形态和性能的差异(见图5和6)。可以使用实验设计方法来确定最佳或最优的合成条件和程序以产生期望的特征或特征组。
第五,存在于前体盐中的阴离子和存在于酸中的阴离子都有助于AMO的表面官能化。在一个优选的实施例中,氯化锡前体和盐酸用于合成锡的AMO。这些颗粒的性能不同于使用氯化锡前体和硫酸的实施例,或者使用硫酸锡前体和盐酸的实施例。因此,匹配前体阴离子和酸性阴离子是优选的。
第六,当使用具有弱EWG和具有强EWG的酸的前体时,或反之亦然,强吸阴离子将主导表面官能化。这开辟了更广泛的合成可能性,允许使用在前体盐和酸中不易得到的离子官能化。它也可能允许用强和弱的EWG混合功能化。在一个实例中,乙酸锡前体和磷酸用于合成锡的AMO。表面的X射线光电子能谱分析表明磷的原子浓度大于与乙酸根相关的键(见图7)。
第七,最后,虽然所公开的方法是用于合成AMO的一般过程,但可以调整合成过程和条件以产生对于不同的应用被认为是所期望的大小,形态,氧化态和结晶态。作为一个实例,催化应用可能需要在可见光中更具活性的AMO材料(见图8A)或在紫外光下更具活性的AMO材料(见图8B)。
在另一个例子中,AMO材料可以用作电池电极。首次(一次性使用)电池应用可能需要具有导致最高容量特性的AMO,而二次(可充电)电池应用可能需要相同的AMO,但具有导致最高可循环性的特性(见图9)。AMO材料可以提高电池性能,而不会使电池部件劣化或产生气体(见图10)。这与现有技术所教导的完全相反。
Claims (22)
1.一种电池电极,所述电池电极包含至少一种固体金属氧化物材料,所述固体金属氧化物材料包含酸性但不是超强酸性的表面,当以5wt%悬浮于水溶液时具有pH<7并哈米特函数H0>-12。
2.根据权利要求1所述的电池电极,所述固体金属氧化物材料包括至少一种尺寸<100nm的颗粒。
3.根据权利要求1所述的电池电极,所述固体金属氧化物材料包括至少一种尺寸<20nm的颗粒。
4.根据权利要求1所述的电池电极,所述固体金属氧化物材料包括至少一种尺寸<10nm的颗粒。
5.根据权利要求1所述的电池电极,所述固体金属氧化物材料包含基本上单分散的纳米颗粒形式。
6.根据权利要求1所述的电池电极,所述pH<6。
7.根据权利要求1所述的电池电极,所述pH<5。
8.根据权利要求1所述的电池电极,所述pH<4。
9.根据权利要求1所述的电池电极,所述pH<3。
10.根据权利要求1所述的材料,还包括所述固体金属氧化物材料为氧化锡。
11.根据权利要求1所述的电池电极,还包括非酸化的固体金属氧化物材料。
12.根据权利要求1所述的电池电极,还包括粘合剂材料。
13.根据权利要求1所述的电池电极,还包括导电助剂。
14.一种固体金属氧化物纳米材料,其形式为MmOx/G,其中Mm是一种金属,Ox是总氧,MmOx是一种金属氧化物,G是至少一个吸电子表面基团,并且“/”在所述金属氧化物和所述吸电子表面基团之间构成区分,所述固体金属氧化物纳米材料以5wt%悬浮于水溶液中时pH<7并且至少在其表面上哈米特函数H0>-12。
15.根据权利要求14所述的固体金属氧化物纳米材料,还包括,所述金属氧化物包含第二不同金属“Nn”,其中n大于0且不大于5。
16.根据权利要求15所述的固体金属氧化物纳米材料,还包括,所述金属氧化物包含第三不同金属“Rr”,其中r大于0且不大于5。
17.根据权利要求14所述的固体金属氧化物纳米材料,还包括m最小为1且不大于5。
18.根据权利要求14所述的固体金属氧化物纳米材料,还包括x最小为1且不大于21。
19.根据权利要求14所述的固体金属氧化物纳米材料,还包括至少一种尺寸<100nm的颗粒。
20.根据权利要求14所述的固体金属氧化物纳米材料,还包括至少一种尺寸<20nm的颗粒。
21.根据权利要求14所述的固体金属氧化物纳米材料,还包括至少一种尺寸<10nm的颗粒。
22.根据权利要求1所述的固体金属氧化物纳米材料,还包括基本上单分散的纳米颗粒形式。
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CN108370025B (zh) | 2023-09-01 |
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