CN111039333A - 钙钛矿材料、其制备方法以及包括钙钛矿材料的二次电池 - Google Patents
钙钛矿材料、其制备方法以及包括钙钛矿材料的二次电池 Download PDFInfo
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- CN111039333A CN111039333A CN201910921293.XA CN201910921293A CN111039333A CN 111039333 A CN111039333 A CN 111039333A CN 201910921293 A CN201910921293 A CN 201910921293A CN 111039333 A CN111039333 A CN 111039333A
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- 239000000463 material Substances 0.000 title claims abstract description 159
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 27
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 25
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 22
- 229910052788 barium Inorganic materials 0.000 claims abstract description 22
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 22
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 20
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 20
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 19
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 19
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 19
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 18
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 18
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 16
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 14
- 229910052718 tin Inorganic materials 0.000 claims abstract description 14
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 13
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 13
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052745 lead Inorganic materials 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 9
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims description 242
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 72
- 229910005831 GeO3 Inorganic materials 0.000 claims description 68
- 229910002785 ReO3 Inorganic materials 0.000 claims description 68
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 68
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 66
- 238000010438 heat treatment Methods 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- 239000011572 manganese Substances 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 230000004888 barrier function Effects 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 239000011651 chromium Substances 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 15
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 14
- 239000010948 rhodium Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 229910052793 cadmium Inorganic materials 0.000 claims description 8
- 150000002642 lithium compounds Chemical class 0.000 claims description 8
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- 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
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910052798 chalcogen Inorganic materials 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910002449 CoO3−δ Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- MBXOOYPCIDHXGH-UHFFFAOYSA-N 3-butylpentane-2,4-dione Chemical compound CCCCC(C(C)=O)C(C)=O MBXOOYPCIDHXGH-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 2
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 claims description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 230000007547 defect Effects 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 2
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 claims description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 2
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 2
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 claims description 2
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- YTYSNXOWNOTGMY-UHFFFAOYSA-N lanthanum(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[La+3].[La+3] YTYSNXOWNOTGMY-UHFFFAOYSA-N 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 claims description 2
- 239000003570 air Substances 0.000 description 51
- 239000010410 layer Substances 0.000 description 47
- 239000000047 product Substances 0.000 description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 21
- 229910001416 lithium ion Inorganic materials 0.000 description 21
- 239000011734 sodium Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 239000005518 polymer electrolyte Substances 0.000 description 16
- 239000010955 niobium Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000007784 solid electrolyte Substances 0.000 description 13
- 229910003002 lithium salt Inorganic materials 0.000 description 12
- 159000000002 lithium salts Chemical class 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000011135 tin Substances 0.000 description 12
- 239000011133 lead Substances 0.000 description 11
- -1 or Dy) Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000010931 gold Substances 0.000 description 9
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 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 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052773 Promethium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 6
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 6
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 6
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Abstract
本发明涉及钙钛矿材料、其制备方法以及包括钙钛矿材料的二次电池。由式1表示的钙钛矿材料,其中在式1中,0<x≤1,0<y≤1,0<x+y<1,0<z≤1.5,0≤δ≤1,A为H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、或其组合,且M为Ni、Pd、Pb、Fe、Ir、Co、Rh、Mn、Cr、Ru、Re、Sn、V、Ge、W、Zr、Mo、Hf、U、Nb、Th、Ta、Bi、Li、H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、Mg、Al、Si、Sc、Zn、Ga、Ag、Cd、In、Sb、Pt、Au、或其组合。式1LixAyMzO3‑δ。
Description
相关申请的交叉引用
本申请要求于2018年10月11日提交的美国临时申请No.62/744,614和于2018年10月12日提交的韩国专利申请No.10-2018-0122041的优先权和权益、以及由其产生的所有权益,将其内容全部通过引用引入本文中。
技术领域
本公开内容涉及钙钛矿材料、制备所述钙钛矿材料的方法以及包括所述钙钛矿材料的二次电池。
背景技术
金属-空气电池例如可包括:空气中存在的氧气在其处被还原的正极、锂在其处被氧化的负极、以及插入在所述正极和所述负极之间的电解质。金属-空气电池可为包括锂薄膜作为负极的锂-空气电池。锂-空气电池可充当高容量电池而无需在电池中存储氧气。
锂-空气电池的正极可包括碳质材料和有机电解质。然而,碳质材料和有机电解质可被锂氧化物(Li2O2)分解(所述锂氧化物是在锂-空气电池的放电期间产生的反应产物),由此产生二氧化碳,其可引起正极的劣化。二氧化碳也可通过有机电解质被转移到负极,随后与负极中的锂反应,由此引起负极和锂-空气电池的充电和放电特性的劣化。因此,需要在这些方面改善锂-空气电池。
发明内容
提供钙钛矿材料及其制备方法。
提供包括所述钙钛矿材料的二次电池。
另外的方面将部分地在随后的描述中阐明,并且部分地将从所述描述明晰,或者可通过呈现的实施方式的实践而获知。
根据一种实施方式的方面,钙钛矿材料由式1表示:
式1
LixAyMzO3-δ
其中,在式1中,0<x≤1,0<y≤1,0<x+y<1,0<z≤1.5,和0≤δ≤1,
A为氢(H)、钠(Na)、钾(K)、铷(Rb)、铯(Cs)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、或其组合,且
M为镍(Ni)、钯(Pd)、铅(Pb)、铁(Fe)、铱(Ir)、钴(Co)、铑(Rh)、锰(Mn)、铬(Cr)、钌(Ru)、铼(Re)、锡(Sn)、钒(V)、锗(Ge)、钨(W)、锆(Zr)、钼(Mo)、铪(Hf)、铀(U)、铌(Nb)、钍(Th)、钽(Ta)、铋(Bi)、锂(Li)、氢(H)、钠(Na)、钾(K)、铷(Rb)、铯(Cs)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、镁(Mg)、铝(Al)、硅(Si)、钪(Sc)、锌(Zn)、镓(Ga)、银(Ag)、镉(Cd)、铟(In)、锑(Sb)、铂(Pt)、金(Au)、或其组合。
根据另一实施方式的方面,钙钛矿材料为由式3表示的复合物,并且具有小于1的在46.5°±2.5°的衍射角2θ处的峰强度对在32.5°±2.5°的衍射角2θ处的峰强度的比率。
式3
LixAyMzO3-δ
其中,在式3中,0<x≤1,0<y≤1,0<x+y<1,0<z≤1.5,和0≤δ≤1,
A为氢(H)或者第2族至第16族元素的至少一种,且
M为第2族至第16族元素的至少一种。
所述钙钛矿材料可具有小于1的在57.5°±2.5°的衍射角2θ处的峰强度对在32.5°±2.5°的衍射角2θ处的峰强度的比率。
根据一种实施方式的方面,制备钙钛矿材料的方法包括:提供包括锂化合物、含A元素的化合物、含M元素的化合物和溶剂的混合物;第一热处理所述混合物以形成经第一热处理的混合物;粉碎经第一热处理的混合物以获得成形产物;和第二热处理所述成形产物以形成所述钙钛矿材料,
其中所述第二热处理的温度高于所述第一热处理的温度,
其中所述含A元素的化合物的A为H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、或其组合,且
所述含M元素的化合物的M为Ni、Pd、Pb、Fe、Ir、Co、Rh、Mn、Cr、Ru、Re、Sn、V、Ge、W、Zr、Mo、Hf、U、Nb、Th、Ta、Bi、Li、H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、Mg、Al、Si、Sc、Zn、Ga、Ag、Cd、In、Sb、Pt、Au、或其组合。
根据一种实施方式的方面,二次电池包括所述钙钛矿材料。
还公开了二次电池,其包括:正极;负极;以及插入在所述正极和所述负极之间的气体阻挡层,其中所述正极、或者所述正极和所述气体阻挡层各自包括所述钙钛矿材料。
还公开了二次电池,其包括:正极;负极;以及插入在所述正极和所述负极之间的电解质,其中所述正极、或者所述正极和所述电解质各自包括所述钙钛矿材料。
附图说明
由结合附图考虑的实施方式的以下描述,这些和/或其它方面将变得明晰和更容易领会,其中:
图1为说明根据实施方式的钙钛矿材料的晶体结构的示意图;
图2为说明使用包括根据实施方式的钙钛矿材料的正极的锂-空气电池结构的示意图;
图3说明图2的正极的区域内的锂离子和电子的传导;
图4A-4C为强度(任意单位,a.u.)对衍射角(度,二西塔(2θ)的图,其分别显示实施例1-6和对比例1中制备的钙钛矿材料的X射线衍射(XRD)分析的结果;
图5为离子传导率(西门子/厘米,S/cm)的对数(log)对电子传导率(S/cm)的对数的图,其说明实施例1-6和对比例1中制备的钙钛矿材料的电子传导率和离子传导率之间的关系;
图6为实施例7和8以及对比例2中制造的锂空气电池的电势(伏特,V)对容量(毫安-时,mAh)的图;
图7为循环伏安图且为对于实施例1的钙钛矿材料的电流(安,A)对电势(V)的图;以及
图8为循环伏安图且为对于实施例3的钙钛矿材料的电流(A)对电势(V)的图。
具体实施方式
现在将详细介绍实施方式,其实例在附图中说明,其中相同的附图标记始终表示相同的元件。在这方面,本实施方式可具有不同的形式并且不应解释为限于本文中阐述的描述。因此,下面仅通过参照附图描述实施方式以说明方面。
本文中所使用的术语仅仅是为了描述具体实施方式且不意图为限制性的。如本文中所使用的,单数形式“一种(个))(不定冠词,a,an)”和“所述(该)”意图包括复数形式,包括“至少一种(个)”,除非内容清楚地另外说明。“至少一种(个)”不应被解释为限制“一种(个)”。“或”意味着“和/或”。如本文中所使用的,术语“和/或”包括相关所列项目的一个或多个的任意和全部组合。将进一步理解,术语“包括”和/或“包含”当用在本说明书中时则表示存在所述的特征、区域、整体、步骤、操作、元件和/或组分,但不排除存在或添加一种或多种另外的特征、区域、整体、步骤、操作、元件、组分和/或其集合。如本文中所使用的,术语“和/或”包括相关所列项目的一个或多个的任意和全部组合。表述如“…的至少一种(个)”当在要素列表之前或之后时修饰整个要素列表,而不是修饰所述列表的单独要素。
如本文中所使用的“约”或“大约”包括所陈述的值且意味着在如由本领域普通技术人员考虑到所讨论的测量和与具体量的测量有关的误差(即,测量系统的限制)而确定的对于具体值的可接受的偏差范围内。例如,“约”可意味着在所述值的一种或多种标准偏差内,或者在所述值的±30%、20%、10%或5%内。
除非另外定义,否则在本文中所使用的所有术语(包括技术和科学术语)的含义与本公开内容所属领域的普通技术人员通常理解的相同。将进一步理解,术语,例如在常用字典中定义的那些,应被解释为其含义与它们在本公开内容和相关领域的背景中的含义一致,并且将不以理想化或过度形式的意义进行解释,除非在本文中清楚地如此定义。
在本文中参照作为理想化实施方式的示意图的横截面图描述示例性实施方式。因此,将预计到作为例如制造技术和/或公差的结果的与图示的形状的变化。因而,本文中描述的实施方式不应解释为限于本文中所示区域的具体形状,而是包括由例如制造所造成的形状上的偏差。例如,图示或描述为平坦的区域可具有粗糙的和/或非线性的特征。此外,所图示的尖锐的角可为圆形的。因而,图中所示的区域在本质上是示意性的,并且它们的形状不意图说明区域的精确形状,并且不意图限制本权利要求的范围。
在下文中,将更详细地描述钙钛矿材料、其制备方法以及包括所述钙钛矿材料的二次电池。
根据一个方面,提供由式1表示的钙钛矿材料。
式1
LixAyMzO3-δ
在式1中,0<x≤1,0<y≤1,0<x+y<1,0<z≤1.5,0≤δ≤1,A可为氢(H)、钠(Na)、钾(K)、铷(Rb)、铯(Cs)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、或其组合。
在其中A包括组合的实施方式中,A可由A1 aA2 (a-1)表示,其中0<a<1,且A1和A2各自独立地为氢(H)、钠(Na)、钾(K)、铷(Rb)、铯(Cs)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、或铒(Er)。
M可为镍(Ni)、钯(Pd)、铅(Pb)、铁(Fe)、铱(Ir)、钴(Co)、铑(Rh)、锰(Mn)、铬(Cr)、钌(Ru)、铼(Re)、锡(Sn)、钒(V)、锗(Ge)、钨(W)、锆(Zr)、钼(Mo)、铪(Hf)、铀(U)、铌(Nb)、钍(Th)、钽(Ta)、铋(Bi)、锂(Li)、氢(H)、钠(Na)、钾(K)、铷(Rb)、铯(Cs)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、镁(Mg)、铝(Al)、硅(Si)、钪(Sc)、锌(Zn)、镓(Ga)、银(Ag)、镉(Cd)、铟(In)、锑(Sb)、铂(Pt)、金(Au)、或其组合。
在其中M包括组合的实施方式中,M可由M1 mM2 (m-1)表示,其中0<m<1,且M1和M2各自独立地为镍(Ni)、钯(Pd)、铅(Pb)、铁(Fe)、铱(Ir)、钴(Co)、铑(Rh)、锰(Mn)、铬(Cr)、钌(Ru)、铼(Re)、锡(Sn)、钒(V)、锗(Ge)、钨(W)、锆(Zr)、钼(Mo)、铪(Hf)、铀(U)、铌(Nb)、钍(Th)、钽(Ta)、铋(Bi)、锂(Li)、氢(H)、钠(Na)、钾(K)、铷(Rb)、铯(Cs)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、镁(Mg)、铝(Al)、硅(Si)、钪(Sc)、锌(Zn)、镓(Ga)、银(Ag)、镉(Cd)、铟(In)、锑(Sb)、铂(Pt)、或金(Au)。
在式1中,A和M可彼此相同或不同。例如,A可为La、Ce、Pr、Gd、Ca、Sr、Ba、或其组合,且M可为例如Mn、Ni、Ru、Cr、Co、Ru、Ir、Fe、Pd、Pb、Rh、Sn、V、Re、Ge、W、Zr、Mo、Nb、Ta、Hf、Bi、或其组合。
在式1中,x可满足0.1<x≤0.5、例如0.1<x≤0.45、0.2<x≤0.5、或0.3<x≤0.4的范围;y可满足0.2<y≤0.7、例如0.4<y≤0.7、或0.52<y≤0.67的范围;且z可满足0.8<z≤1.2、例如0.9<z≤1.1的范围。x和y之和可为0.3至0.99、例如0.4至0.98、例如0.6至0.97、例如0.7至0.93、例如0.75至0.89。在式1中,0.2<x≤0.5,0.2<y≤0.7,和0.8<z≤1.2,例如0.3<x≤0.4,0.4<y≤0.7,和0.9<z≤1.1。
在式1中,δ表示氧空位,且选择δ的值以使所述钙钛矿材料是电中性的。
在式1中,x对y的比率可为例如约1:0.5至约1:7、或约1:1至约1:6、或约1:2至约1:5。
所述钙钛矿材料可为电中性的。所述钙钛矿材料可具有小于约4电子伏特、例如约3.5电子伏特(eV)或更小、或者约3eV或更小、或者约2.5eV或更小、例如0eV至约3.5eV、或0eV至3eV、或约0.1eV至约3eV、或约0.5eV至约2.5eV的氧空位形成能。供参考,作为包括钛的钙钛矿材料的Li0.34La0.55TiO3可具有约3.59eV的氧空位形成能,因此,所述钙钛矿材料可具有小于Li0.34La0.55TiO3的氧空位形成能的氧空位形成能,例如小于约3.59eV、例如0eV至小于约3.59eV的氧空位形成能。如本文中所使用的,“氧空位形成能”可通过使用量子计算方法来定义。不受理论限制,理解,所述钙钛矿材料的氧空位形成能越小,可越容易由于氧空位而形成过剩电子,由此提高所述钙钛矿材料的电子传导率。
用于定义氧空位形成能的量子计算方法可为如下的方法:其与Emery等(AntoineA.Emery,Chris Wolverton,“High-throughput DFT calculations of formationenergy,stability and oxygen vacancy formation energy of ABO3perovskites,”Scientific Data 4,文章号170153(2017),在下文中“Emery”)(将其内容全部通过引用引入本文中)公开的方法相同或基本上类似。氧空位形成能为等于单独存在的式A2B2O5的成分和氧的总能量与由氧和A2B2O5共同存在导致的两个ABO3分子的能量之间的差的值,如下面方程1中所示。
方程1
在方程1中,为氧空位形成能,E(A2B2O5)为A2B2O5的能量,μo为氧的化学势,且E(ABO3)为ABO3的能量。在方程1中,A2B2O5为如下的结构:其中氧原子已从A2B2O6除去,并且A和B位点与Emery等中定义的相同。
由式1表示的钙钛矿材料可为由式2表示的化合物。
式2
LixA1yM1zO3-δ
在式2中,0.3<x≤1,0<y≤0.7,0<z≤1,0<x+y<1,0≤δ≤1,A1可为La、Ce、Pr、Gd、Ca、Sr、Ba、或其组合,且M1可为Mn、Ni、Ru、Cr、Co、Ru、Ir、Fe、Pd、Pb、Rh、Sn、V、Re、Ge、W、Zr、Mo、Nb、Ta、Hf、Bi、或其组合。
在式2中,A1可为例如La、Ca、或其组合,且M1可为例如Ru、Mn、Ni、Cr、Ir、Co、其中0<a<1的Mn1-aWa、或其组合。
锂-空气电池包括包含碳质材料和有机电解质的正极(cathode)。在这样的锂-空气电池中,当源自负极的锂与引入正极的氧气反应时的放电期间产生锂氧化物(Li2O2),然后在氧被还原时Li2O2沉积在正极的孔中。在放电期间,由于所述锂氧化物在正极的孔中的沉积,碳质材料和有机电解质可分解,并且所得的分解产物可使锂-空气电池的寿命特性劣化。
为了解决这些缺点,已经有利地发现钙钛矿材料,其能够确保锂离子和电子的同时传导并且其不易被所述锂氧化物放电产物分解。
所述钙钛矿材料可具有ABO3相,其包括在氧位点处的空位并且其中锂占据A位点的一部分。所述钙钛矿材料也可具有斜方、立方、单斜或三斜晶相,其拥有氧缺陷。所述钙钛矿材料可由于优化的在A位点处的锂集中(浓度,concentration)而具有改善的锂离子传导率,以及由于具有低的氧空位形成能的金属M引入B位点中而具有提高的电子传导率。
所述钙钛矿材料可具有约1X 10-6西门子/厘米(S/cm)或更大、或者约1X10-5S/cm或更大、或者约1X 10-3S/cm或更大、例如约1X 10-5S/cm至约1X 10-1S/cm、或者约1X 10-4S/cm至约1X 10-2S/cm、或更特别地约2.6X 10-4S/cm至约5.6X 10-2S/cm的电子传导率,以及约1X 10-7S/cm或更大、或者约2X 10-6S/cm或更大、或者约1X 10-6S/cm或更大、例如约1X 10- 7S/cm至约1X 10-5S/cm、或者约5X 10-6S/cm至约5X 10-5S/cm、或更特别地约2.0X 10-6S/cm至约8.8X 10-5S/cm的离子传导率。
图1为说明根据实施方式的钙钛矿材料的晶体结构的示意图。在图1中,所述钙钛矿材料可为具有式1的结构的钙钛矿材料,其中A为镧(La)。
所述钙钛矿材料可具有包括共角MO6八面体的结构,如图1中所示,其中六个氧原子可限定顶点并且M位于八面体的中心。MO6八面体的顶点限定其中镧(La)、锂(Li)和空位无规分布的空间。在所述钙钛矿材料中,锂离子可通过跳跃(hopping)转移到空位中,并且电子可转移到金属(M)离子层。在图1中,镧(La)可用钙(Ca)代替,且M可为例如Ru、Mn、Ni、Cr、Ir、Co、W、或其组合。所述钙钛矿材料可呈现具有约23°、例如约23.0°±2.5°的X射线衍射(XRD)角2θ的峰。尽管不希望受理论束缚,但理解,在约23.0°±2.5°处的峰是由各层中La的排列产生的,如图1中所示。
如通过X射线衍射测量的,所述钙钛矿材料可在32.5°±2.5的衍射角2θ处具有主峰,并且在46.5°±2.5°的衍射角2θ和/或57.5°±2.5°的衍射角2θ处具有次峰。所述主峰是指最高峰,例如具有最大强度,且所述次峰是指具有低于主峰强度的强度的峰。
所述钙钛矿材料可具有小于1、例如小于0.9、例如小于0.8、例如约0.1至约0.8、例如约0.2至约0.8、例如约0.2至约0.6的在46.5°±2.5°的衍射角2θ处的峰强度(I(46.5°±2.5°):Ib)对在32.5°±2.5°的衍射角2θ处的峰强度(I(32.5°±2.5°):Ia)的比率(Ib/Ia)。在一种或多种实施方式中,所述钙钛矿材料可具有小于1、例如小于0.9、例如小于0.8、例如约0.1至约0.8、例如约0.2至约0.8、例如约0.2至约0.4的在57.5°±2.5°的衍射角2θ处的峰强度(I(57.5°±2.5°):Ic)对在32.5°±2.5°的衍射角2θ处的峰强度(I(32.5°±2.5°):Ia)的比率(Ic/Ia)。
根据另一方面,钙钛矿材料可为由式3表示的复合物,其具有小于1的在46.5°±2.5°的衍射角2θ处的峰强度(I(46.5°±2.5°):Ib)对在32.5°±2.5°的衍射角2θ处的峰强度(I(32.5°±2.5°):Ia)的比率(Ib/Ia)。
式3
LixAyMzO3-δ
在式3中,0<x≤1,0<y≤1,0<x+y<1,0<z≤1.5,0≤δ≤1,
A可为氢(H)或者元素周期表的第1族至第16族元素的至少一种元素,且
M可为元素周期表的第1族至第16族元素的至少一种。
所述钙钛矿材料可具有小于1.0的在57.5°±2.5°的衍射角2θ处的峰强度(I(57.5°±2.5°):Ic)对在32.5°±2.5°的衍射角2θ处的峰强度(I(32.5°±2.5°):Ia)的比率(Ic/Ia)。
在式3中,A可为例如H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、或其组合,且M可为例如Ni、Pd、Pb、Fe、Ir、Co、Rh、Mn、Cr、Ru、Re、Sn、V、Ge、W、Zr、Mo、Hf、U、Nb、Th、Ta、Bi、Li、H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、Mg、Al、Si、Sc、Zn、Ga、Ag、Cd、In、Sb、Pt、Au、或其组合。
例如,上述X射线衍射角特性可归因于例如其中A为La且晶体结构中的M如图1中所示的由式3表示的钙钛矿材料。
所述钙钛矿材料可具有约5nm至约500微米(μm)、例如约100nm至约15μm、例如约300nm至约10μm的平均粒径。在一种或多种实施方式中,所述钙钛矿材料可具有约0.01平方米/克(m2/g)至约1000m2/g、例如约0.5m2/g至约100m2/g、或者约5m2/g至约75m2/g的比表面积。
所述钙钛矿材料可为例如Li0.34La0.55MnO3、Li0.34La0.55NiO3、Li0.34La0.55CrO3、Li0.34La0.55CoO3、Li0.34La0.55IrO3、Li0.34La0.55RuO3、Li0.34La0.55FeO3、Li0.34La0.55PdO3、Li0.34La0.55PbO3、Li0.34La0.55RhO3、Li0.34La0.55SnO3、Li0.34La0.55VO3、Li0.34La0.55ReO3、Li0.34La0.55GeO3、Li0.34La0.55WO3、Li0.34La0.55ZrO3、Li0.34La0.55MoO3、Li0.34La0.55NbO3、Li0.34La0.55TaO3、Li0.34La0.55HfO3、Li0.34La0.55BiO3;Li0.10La0.63MnO3、Li0.10La0.63NiO3、Li0.10La0.63CrO3、Li0.10La0.63CoO3、Li0.10La0.63IrO3、Li0.10La0.63RuO3、Li0.10La0.63FeO3、Li0.10La0.63PdO3、Li0.10La0.63PbO3、Li0.10La0.63RhO3、Li0.10La0.63SnO3、Li0.10La0.63VO3、Li0.10La0.63ReO3、Li0.10La0.63GeO3、Li0.10La0.63WO3、Li0.10La0.63ZrO3、Li0.10La0.63MoO3、Li0.10La0.63NbO3、Li0.10La0.63TaO3、Li0.10La0.63HfO3、Li0.10La0.63BiO3;Li0.20La0.60MnO3、Li0.20La0.60NiO3、Li0.20La0.60CrO3、Li0.20La0.60CoO3、Li0.20La0.60IrO3、Li0.20La0.60RuO3、Li0.20La0.60FeO3、Li0.20La0.60PdO3、Li0.20La0.60PbO3、Li0.20La0.60RhO3、Li0.20La0.60SnO3、Li0.20La0.60VO3、Li0.20La0.60ReO3、Li0.20La0.60GeO3、Li0.20La0.60WO3、Li0.20La0.60ZrO3、Li0.20La0.60MoO3、Li0.20La0.60NbO3、Li0.20La0.60TaO3、Li0.20La0.60HfO3、Li0.20La0.60BiO3;Li0.30La0.57MnO3、Li0.30La0.57NiO3、Li0.30La0.57CrO3、Li0.30La0.57CoO3、Li0.30La0.57IrO3、Li0.30La0.57RuO3、Li0.30La0.57FeO3、Li0.30La0.57PdO3、Li0.30La0.57PbO3、Li0.30La0.57RhO3、Li0.30La0.57SnO3、Li0.30La0.57VO3、Li0.30La0.57ReO3、Li0.30La0.57GeO3、Li0.30La0.57WO3、Li0.30La0.57ZrO3、Li0.30La0.57MoO3、Li0.30La0.57NbO3、Li0.30La0.57TaO3、Li0.30La0.57HfO3、Li0.30La0.57BiO3;Li0.40La0.53MnO3、Li0.40La0.53NiO3、Li0.40La0.53CrO3、Li0.40La0.53CoO3、Li0.40La0.53IrO3、Li0.40La0.53RuO3、Li0.40La0.53FeO3、Li0.40La0.53PdO3、Li0.40La0.53PbO3、Li0.40La0.53RhO3、Li0.40La0.53SnO3、Li0.40La0.53VO3、Li0.40La0.53ReO3、Li0.40La0.53GeO3、Li0.40La0.53WO3、Li0.40La0.53ZrO3、Li0.40La0.53MoO3、Li0.40La0.53NbO3、Li0.40La0.53TaO3、Li0.40La0.53HfO3、Li0.40La0.53BiO3;Li0.45La0.52MnO3、Li0.45La0.52NiO3、Li0.45La0.52CrO3、Li0.45La0.52CoO3、Li0.45La0.52IrO3、Li0.45La0.52RuO3、Li0.45La0.52FeO3、Li0.45La0.52PdO3、Li0.45La0.52PbO3、Li0.45La0.52RhO3、Li0.45La0.52SnO3、Li0.45La0.52VO3、Li0.45La0.52ReO3、Li0.45La0.52GeO3、Li0.45La0.52WO3、Li0.45La0.52ZrO3、Li0.45La0.52MoO3、Li0.45La0.52NbO3、Li0.45La0.52TaO3、Li0.45La0.52HfO3、Li0.45La0.52BiO3;Li0.34Ce0.55MnO3、Li0.34Ce0.55NiO3、Li0.34Ce0.55CrO3、Li0.34Ce0.55CoO3、Li0.34Ce0.55IrO3、Li0.34Ce0.55RuO3、Li0.34Ce0.55FeO3、Li0.34Ce0.55PdO3、Li0.34Ce0.55PbO3、Li0.34Ce0.55RhO3、Li0.34Ce0.55SnO3、Li0.34Ce0.55VO3、Li0.34Ce0.55ReO3、Li0.34Ce0.55GeO3、Li0.34Ce0.55WO3、Li0.34Ce0.55ZrO3、Li0.34Ce0.55MoO3、Li0.34Ce0.55NbO3、Li0.34Ce0.55TaO3、Li0.34Ce0.55HfO3、Li0.34Ce0.55BiO3;Li0.10Ce0.63MnO3、Li0.10Ce0.63NiO3、Li0.10Ce0.63CrO3、Li0.10Ce0.63CoO3、Li0.10Ce0.63IrO3、Li0.10Ce0.63RuO3、Li0.10Ce0.63FeO3、Li0.10Ce0.63PdO3、Li0.10Ce0.63PbO3、Li0.10Ce0.63RhO3、Li0.10Ce0.63SnO3、Li0.10Ce0.63VO3、Li0.10Ce0.63ReO3、Li0.10Ce0.63GeO3、Li0.10Ce0.63WO3、Li0.10Ce0.63ZrO3、Li0.10Ce0.63MoO3、Li0.10Ce0.63NbO3、Li0.10Ce0.63TaO3、Li0.10Ce0.63HfO3、Li0.10Ce0.63BiO3;Li0.20Ce0.60MnO3、Li0.20Ce0.60NiO3、Li0.20Ce0.60CrO3、Li0.20Ce0.60CoO3、Li0.20Ce0.60IrO3、Li0.20Ce0.60RuO3、Li0.20Ce0.60FeO3、Li0.20Ce0.60PdO3、Li0.20Ce0.60PbO3、Li0.20Ce0.60RhO3、Li0.20Ce0.60SnO3、Li0.20Ce0.60VO3、Li0.20Ce0.60ReO3、Li0.20Ce0.60GeO3、Li0.20Ce0.60WO3、Li0.20Ce0.60ZrO3、Li0.20Ce0.60MoO3、Li0.20Ce0.60NbO3、Li0.20Ce0.60TaO3、Li0.20Ce0.60HfO3、Li0.20Ce0.60BiO3;Li0.30Ce0.57MnO3、Li0.30Ce0.57NiO3、Li0.30Ce0.57CrO3、Li0.30Ce0.57CoO3、Li0.30Ce0.57IrO3、Li0.30Ce0.57RuO3、Li0.30Ce0.57FeO3、Li0.30Ce0.57PdO3、Li0.30Ce0.57PbO3、Li0.30Ce0.57RhO3、Li0.30Ce0.57SnO3、Li0.30Ce0.57VO3、Li0.30Ce0.57ReO3、Li0.30Ce0.57GeO3、Li0.30Ce0.57WO3、Li0.30Ce0.57ZrO3、Li0.30Ce0.57MoO3、Li0.30Ce0.57NbO3、Li0.30Ce0.57TaO3、Li0.30Ce0.57HfO3、Li0.30Ce0.57BiO3;Li0.40Ce0.53MnO3、Li0.40Ce0.53NiO3、Li0.40Ce0.53CrO3、Li0.40Ce0.53CoO3、Li0.40Ce0.53IrO3、Li0.40Ce0.53RuO3、Li0.40Ce0.53FeO3、Li0.40Ce0.53PdO3、Li0.40Ce0.53PbO3、Li0.40Ce0.53RhO3、Li0.40Ce0.53SnO3、Li0.40Ce0.53VO3、Li0.40Ce0.53ReO3、Li0.40Ce0.53GeO3、Li0.40Ce0.53WO3、Li0.40Ce0.53ZrO3、Li0.40Ce0.53MoO3、Li0.40Ce0.53NbO3、Li0.40Ce0.53TaO3、Li0.40Ce0.53HfO3、Li0.40Ce0.53BiO3;Li0.45Ce0.52MnO3、Li0.45Ce0.52NiO3、Li0.45Ce0.52CrO3、Li0.45Ce0.52CoO3、Li0.45Ce0.52IrO3、Li0.45Ce0.52RuO3、Li0.45Ce0.52FeO3、Li0.45Ce0.52PdO3、Li0.45Ce0.52PbO3、Li0.45Ce0.52RhO3、Li0.45Ce0.52SnO3、Li0.45Ce0.52VO3、Li0.45Ce0.52ReO3、Li0.45Ce0.52GeO3、Li0.45Ce0.52WO3、Li0.45Ce0.52ZrO3、Li0.45Ce0.52MoO3、Li0.45Ce0.52NbO3、Li0.45Ce0.52TaO3、Li0.45Ce0.52HfO3、Li0.45Ce0.52BiO3;Li0.34Pr0.55MnO3、Li0.34Pr0.55NiO3、Li0.34Pr0.55CrO3、Li0.34Pr0.55CoO3、Li0.34Pr0.55IrO3、Li0.34Pr0.55RuO3、Li0.34Pr0.55FeO3、Li0.34Pr0.55PdO3、Li0.34Pr0.55PbO3、Li0.34Pr0.55RhO3、Li0.34Pr0.55SnO3、Li0.34Pr0.55VO3、Li0.34Pr0.55ReO3、Li0.34Pr0.55GeO3、Li0.34Pr0.55WO3、Li0.34Pr0.55ZrO3、Li0.34Pr0.55MoO3、Li0.34Pr0.55NbO3、Li0.34Pr0.55TaO3、Li0.34Pr0.55HfO3、Li0.34Pr0.55BiO3;Li0.10Pr0.63MnO3、Li0.10Pr0.63NiO3、Li0.10Pr0.63CrO3、Li0.10Pr0.63CoO3、Li0.10Pr0.63IrO3、Li0.10Pr0.63RuO3、Li0.10Pr0.63FeO3、Li0.10Pr0.63PdO3、Li0.10Pr0.63PbO3、Li0.10Pr0.63RhO3、Li0.10Pr0.63SnO3、Li0.10Pr0.63VO3、Li0.10Pr0.63ReO3、Li0.10Pr0.63GeO3、Li0.10Pr0.63WO3、Li0.10Pr0.63ZrO3、Li0.10Pr0.63MoO3、Li0.10Pr0.63NbO3、Li0.10Pr0.63TaO3、Li0.10Pr0.63HfO3、Li0.10Pr0.63BiO3;Li0.20Pr0.60MnO3、Li0.20Pr0.60NiO3、Li0.20Pr0.60CrO3、Li0.20Pr0.60CoO3、Li0.20Pr0.60IrO3、Li0.20Pr0.60RuO3、Li0.20Pr0.60FeO3、Li0.20Pr0.60PdO3、Li0.20Pr0.60PbO3、Li0.20Pr0.60RhO3、Li0.20Pr0.60SnO3、Li0.20Pr0.60VO3、Li0.20Pr0.60ReO3、Li0.20Pr0.60GeO3、Li0.20Pr0.60WO3、Li0.20Pr0.60ZrO3、Li0.20Pr0.60MoO3、Li0.20Pr0.60NbO3、Li0.20Pr0.60TaO3、Li0.20Pr0.60HfO3、Li0.20Pr0.60BiO3、Li0.30Pr0.57MnO3、Li0.30Pr0.57NiO3、Li0.30Pr0.57CrO3、Li0.30Pr0.57CoO3、Li0.30Pr0.57IrO3、Li0.30Pr0.57RuO3、Li0.30Pr0.57FeO3、Li0.30Pr0.57PdO3、Li0.30Pr0.57PbO3、Li0.30Pr0.57RhO3、Li0.30Pr0.57SnO3、Li0.30Pr0.57VO3、Li0.30Pr0.57ReO3、Li0.30Pr0.57GeO3、Li0.30Pr0.57WO3、Li0.30Pr0.57ZrO3、Li0.30Pr0.57MoO3、Li0.30Pr0.57NbO3、Li0.30Pr0.57TaO3、Li0.30Pr0.57HfO3、Li0.30Pr0.57BiO3;Li0.40Pr0.53MnO3、Li0.40Pr0.53NiO3、Li0.40Pr0.53CrO3、Li0.40Pr0.53CoO3、Li0.40Pr0.53IrO3、Li0.40Pr0.53RuO3、Li0.40Pr0.53FeO3、Li0.40Pr0.53PdO3、Li0.40Pr0.53PbO3、Li0.40Pr0.53RhO3、Li0.40Pr0.53SnO3、Li0.40Pr0.53VO3、Li0.40Pr0.53ReO3、Li0.40Pr0.53GeO3、Li0.40Pr0.53WO3、Li0.40Pr0.53ZrO3、Li0.40Pr0.53MoO3、Li0.40Pr0.53NbO3、Li0.40Pr0.53TaO3、Li0.40Pr0.53HfO3、Li0.40Pr0.53BiO3;Li0.45Pr0.52MnO3、Li0.45Pr0.52NiO3、Li0.45Pr0.52CrO3、Li0.45Pr0.52CoO3、Li0.45Pr0.52IrO3、Li0.45Pr0.52RuO3、Li0.45Pr0.52FeO3、Li0.45Pr0.52PdO3、Li0.45Pr0.52PbO3、Li0.45Pr0.52RhO3、Li0.45Pr0.52SnO3、Li0.45Pr0.52VO3、Li0.45Pr0.52ReO3、Li0.45Pr0.52GeO3、Li0.45Pr0.52WO3、Li0.45Pr0.52ZrO3、Li0.45Pr0.52MoO3、Li0.45Pr0.52NbO3、Li0.45Pr0.52TaO3、Li0.45Pr0.52HfO3、Li0.45Pr0.52BiO3;Li0.10Ca0.80MnO3、Li0.10Ca0.80NiO3、Li0.10Ca0.80CrO3、Li0.10Ca0.80CoO3、Li0.10Ca0.80IrO3、Li0.10Ca0.80RuO3、Li0.10Ca0.80FeO3、Li0.10Ca0.80PdO3、Li0.10Ca0.80PbO3、Li0.10Ca0.80RhO3、Li0.10Ca0.80SnO3、Li0.10Ca0.80VO3、Li0.10Ca0.80ReO3、Li0.10Ca0.80GeO3、Li0.10Ca0.80WO3、Li0.10Ca0.80ZrO3、Li0.10Ca0.80MoO3、Li0.10Ca0.80NbO3、Li0.10Ca0.80TaO3、Li0.10Ca0.80HfO3、Li0.10Ca0.80BiO3;Li0.20Ca0.60MnO3、Li0.20Ca0.60NiO3、Li0.20Ca0.60CrO3、Li0.20Ca0.60CoO3、Li0.20Ca0.60IrO3、Li0.20Ca0.60RuO3、Li0.20Ca0.60FeO3、Li0.20Ca0.60PdO3、Li0.20Ca0.60PbO3、Li0.20Ca0.60RhO3、Li0.20Ca0.60SnO3、Li0.20Ca0.60VO3、Li0.20Ca0.60ReO3、Li0.20Ca0.60GeO3、Li0.20Ca0.60WO3、Li0.20Ca0.60ZrO3、Li0.20Ca0.60MoO3、Li0.20Ca0.60NbO3、Li0.20Ca0.60TaO3、Li0.20Ca0.60HfO3、Li0.20Ca0.60BiO3;Li0.25Ca0.50MnO3、Li0.25Ca0.50NiO3、Li0.25Ca0.50CrO3、Li0.25Ca0.50CoO3、Li0.25Ca0.50IrO3、Li0.25Ca0.50RuO3、Li0.25Ca0.50FeO3、Li0.25Ca0.50PdO3、Li0.25Ca0.50PbO3、Li0.25Ca0.50RhO3、Li0.25Ca0.50SnO3、Li0.25Ca0.50VO3、Li0.25Ca0.50ReO3、Li0.25Ca0.50GeO3、Li0.25Ca0.50WO3、Li0.25Ca0.50ZrO3、Li0.25Ca0.50MoO3、Li0.25Ca0.50NbO3、Li0.25Ca0.50TaO3、Li0.25Ca0.50HfO3、Li0.25Ca0.50BiO3;Li0.30Ca0.40MnO3、Li0.30Ca0.40NiO3、Li0.30Ca0.40CrO3、Li0.30Ca0.40CoO3、Li0.30Ca0.40IrO3、Li0.30Ca0.40RuO3、Li0.30Ca0.40FeO3、Li0.30Ca0.40PdO3、Li0.30Ca0.40PbO3、Li0.30Ca0.40RhO3、Li0.30Ca0.40SnO3、Li0.30Ca0.40VO3、Li0.30Ca0.40ReO3、Li0.30Ca0.40GeO3、Li0.30Ca0.40WO3、Li0.30Ca0.40ZrO3、Li0.30Ca0.40MoO3、Li0.30Ca0.40NbO3、Li0.30Ca0.40TaO3、Li0.30Ca0.40HfO3、Li0.30Ca0.40BiO3;Li0.40Ca0.20MnO3、Li0.40Ca0.20NiO3、Li0.40Ca0.20CrO3、Li0.40Ca0.20CoO3、Li0.40Ca0.20IrO3、Li0.40Ca0.20RuO3、Li0.40Ca0.20FeO3、Li0.40Ca0.20PdO3、Li0.40Ca0.20PbO3、Li0.40Ca0.20RhO3、Li0.40Ca0.20SnO3、Li0.40Ca0.20VO3、Li0.40Ca0.20ReO3、Li0.40Ca0.20GeO3、Li0.40Ca0.20WO3、Li0.40Ca0.20ZrO3、Li0.40Ca0.20MoO3、Li0.40Ca0.20NbO3、Li0.40Ca0.20TaO3、Li0.40Ca0.20HfO3、Li0.40Ca0.20BiO3;Li0.10Sr0.80MnO3、Li0.10Sr0.80NiO3、Li0.10Sr0.80CrO3、Li0.10Sr0.80CoO3、Li0.10Sr0.80IrO3、Li0.10Sr0.80RuO3、Li0.10Sr0.80FeO3、Li0.10Sr0.80PdO3、Li0.10Sr0.80PbO3、Li0.10Sr0.80RhO3、Li0.10Sr0.80SnO3、Li0.10Sr0.80VO3、Li0.10Sr0.80ReO3、Li0.10Sr0.80GeO3、Li0.10Sr0.80WO3、Li0.10Sr0.80ZrO3、Li0.10Sr0.80MoO3、Li0.10Sr0.80NbO3、Li0.10Sr0.80TaO3、Li0.10Sr0.80HfO3、Li0.10Sr0.80BiO3;Li0.20Sr0.60MnO3、Li0.20Sr0.60NiO3、Li0.20Sr0.60CrO3、Li0.20Sr0.60CoO3、Li0.20Sr0.60IrO3、Li0.20Sr0.60RuO3、Li0.20Sr0.60FeO3、Li0.20Sr0.60PdO3、Li0.20Sr0.60PbO3、Li0.20Sr0.60RhO3、Li0.20Sr0.60SnO3、Li0.20Sr0.60VO3、Li0.20Sr0.60ReO3、Li0.20Sr0.60GeO3、Li0.20Sr0.60WO3、Li0.20Sr0.60ZrO3、Li0.20Sr0.60MoO3、Li0.20Sr0.60NbO3、Li0.20Sr0.60TaO3、Li0.20Sr0.60HfO3、Li0.20Sr0.60BiO3;Li0.25Sr0.50MnO3、Li0.25Sr0.50NiO3、Li0.25Sr0.50CrO3、Li0.25Sr0.50CoO3、Li0.25Sr0.50IrO3、Li0.25Sr0.50RuO3、Li0.25Sr0.50FeO3、Li0.25Sr0.50PdO3、Li0.25Sr0.50PbO3、Li0.25Sr0.50RhO3、Li0.25Sr0.50SnO3、Li0.25Sr0.50VO3、Li0.25Sr0.50ReO3、Li0.25Sr0.50GeO3、Li0.25Sr0.50WO3、Li0.25Sr0.50ZrO3、Li0.25Sr0.50MoO3、Li0.25Sr0.50NbO3、Li0.25Sr0.50TaO3、Li0.25Sr0.50HfO3、Li0.25Sr0.50BiO3;Li0.30Sr0.40MnO3、Li0.30Sr0.40NiO3、Li0.30Sr0.40CrO3、Li0.30Sr0.40CoO3、Li0.30Sr0.40IrO3、Li0.30Sr0.40RuO3、Li0.30Sr0.40FeO3、Li0.30Sr0.40PdO3、Li0.30Sr0.40PbO3、Li0.30Sr0.40RhO3、Li0.30Sr0.40SnO3、Li0.30Sr0.40VO3、Li0.30Sr0.40ReO3、Li0.30Sr0.40GeO3、Li0.30Sr0.40WO3、Li0.30Sr0.40ZrO3、Li0.30Sr0.40MoO3、Li0.30Sr0.40NbO3、Li0.30Sr0.40TaO3、Li0.30Sr0.40HfO3、Li0.30Sr0.40BiO3;Li0.40Sr0.20MnO3、Li0.40Sr0.20NiO3、Li0.40Sr0.20CrO3、Li0.40Sr0.20CoO3、Li0.40Sr0.20IrO3、Li0.40Sr0.20RuO3、Li0.40Sr0.20FeO3、Li0.40Sr0.20PdO3、Li0.40Sr0.20PbO3、Li0.40Sr0.20RhO3、Li0.40Sr0.20SnO3、Li0.40Sr0.20VO3、Li0.40Sr0.20ReO3、Li0.40Sr0.20GeO3、Li0.40Sr0.20WO3、Li0.40Sr0.20ZrO3、Li0.40Sr0.20MoO3、Li0.40Sr0.20NbO3、Li0.40Sr0.20TaO3、Li0.40Sr0.20HfO3、Li0.40Sr0.20BiO3;Li0.10Ba0.80MnO3、Li0.10Ba0.80NiO3、Li0.10Ba0.80CrO3、Li0.10Ba0.80CoO3、Li0.10Ba0.80IrO3、Li0.10Ba0.80RuO3、Li0.10Ba0.80FeO3、Li0.10Ba0.80PdO3、Li0.10Ba0.80PbO3、Li0.10Ba0.80RhO3、Li0.10Ba0.80SnO3、Li0.10Ba0.80VO3、Li0.10Ba0.80ReO3、Li0.10Ba0.80GeO3、Li0.10Ba0.80WO3、Li0.10Ba0.80ZrO3、Li0.10Ba0.80MoO3、Li0.10Ba0.80NbO3、Li0.10Ba0.80TaO3、Li0.10Ba0.80HfO3、Li0.10Ba0.80BiO3;Li0.20Ba0.60MnO3、Li0.20Ba0.60NiO3、Li0.20Ba0.60CrO3、Li0.20Ba0.60CoO3、Li0.20Ba0.60IrO3、Li0.20Ba0.60RuO3、Li0.20Ba0.60FeO3、Li0.20Ba0.60PdO3、Li0.20Ba0.60PbO3、Li0.20Ba0.60RhO3、Li0.20Ba0.60SnO3、Li0.20Ba0.60VO3、Li0.20Ba0.60ReO3、Li0.20Ba0.60GeO3、Li0.20Ba0.60WO3、Li0.20Ba0.60ZrO3、Li0.20Ba0.60MoO3、Li0.20Ba0.60NbO3、Li0.20Ba0.60TaO3、Li0.20Ba0.60HfO3、Li0.20Ba0.60BiO3;Li0.25Ba0.50MnO3、Li0.25Ba0.50NiO3、Li0.25Ba0.50CrO3、Li0.25Ba0.50CoO3、Li0.25Ba0.50IrO3、Li0.25Ba0.50RuO3、Li0.25Ba0.50FeO3、Li0.25Ba0.50PdO3、Li0.25Ba0.50PbO3、Li0.25Ba0.50RhO3、Li0.25Ba0.50SnO3、Li0.25Ba0.50VO3、Li0.25Ba0.50ReO3、Li0.25Ba0.50GeO3、Li0.25Ba0.50WO3、Li0.25Ba0.50ZrO3、Li0.25Ba0.50MoO3、Li0.25Ba0.50NbO3、Li0.25Ba0.50TaO3、Li0.25Ba0.50HfO3、Li0.25Ba0.50BiO3;Li0.30Ba0.40MnO3、Li0.30Ba0.40NiO3、Li0.30Ba0.40CrO3、Li0.30Ba0.40CoO3、Li0.30Ba0.40IrO3、Li0.30Ba0.40RuO3、Li0.30Ba0.40FeO3、Li0.30Ba0.40PdO3、Li0.30Ba0.40PbO3、Li0.30Ba0.40RhO3、Li0.30Ba0.40SnO3、Li0.30Ba0.40VO3、Li0.30Ba0.40ReO3、Li0.30Ba0.40GeO3、Li0.30Ba0.40WO3、Li0.30Ba0.40ZrO3、Li0.30Ba0.40MoO3、Li0.30Ba0.40NbO3、Li0.30Ba0.40TaO3、Li0.30Ba0.40HfO3、Li0.30Ba0.40BiO3;Li0.40Ba0.20MnO3、Li0.40Ba0.20NiO3、Li0.40Ba0.20CrO3、Li0.40Ba0.20CoO3、Li0.40Ba0.20IrO3、Li0.40Ba0.20RuO3、Li0.40Ba0.20FeO3、Li0.40Ba0.20PdO3、Li0.40Ba0.20PbO3、Li0.40Ba0.20RhO3、Li0.40Ba0.20SnO3、Li0.40Ba0.20VO3、Li0.40Ba0.20ReO3、Li0.40Ba0.20GeO3、Li0.40Ba0.20WO3、Li0.40Ba0.20ZrO3、Li0.40Ba0.20MoO3、Li0.40Ba0.20NbO3、Li0.40Ba0.20TaO3、Li0.40Ba0.20HfO3、Li0.40Ba0.20BiO3;Li0.25La0.50MnO3、Li0.25La0.50NiO3、Li0.25La0.50CrO3、Li0.25La0.50CoO3、Li0.25La0.50IrO3、Li0.25La0.50RuO3、Li0.25La0.50FeO3、Li0.25La0.50PdO3、Li0.25La0.50PbO3、Li0.25La0.50RhO3、Li0.25La0.50SnO3、Li0.25La0.50VO3、Li0.25La0.50ReO3、Li0.25La0.50GeO3、Li0.25La0.50WO3、Li0.25La0.50ZrO3、Li0.25La0.50MoO3、Li0.25La0.50NbO3、Li0.25La0.50TaO3、Li0.25La0.50HfO3、Li0.25La0.50BiO3;Li0.05La0.82Mn0.70O3、Li0.10La0.80Mn0.70O3、Li0.20La0.77Mn0.70O3、Li0.05La0.82Nb0.70O3、Li0.10La0.80Nb0.70O3、Li0.20La0.77Nb0.70O3、Li0.05La0.82Ta0.70O3、Li0.10La0.80Ta0.70O3、Li0.20La0.77Ta0.70O3、Li0.05La0.82V0.70O3、Li0.10La0.80V0.70O3、Li0.20La0.77V0.70O3;Li0.05La0.82W0.70O3、Li0.10La0.80W0.70O3、Li0.20La0.77W0.70O3、Li0.05La0.82Mo0.70O3、Li0.10La0.80Mo0.70O3、Li0.20La0.77Mo0.70O3、Li0.05La0.82Bi0.70O3、Li0.10La0.80Bi0.70O3、Li0.20La0.77Bi0.70O3、Li0.05La0.82Cr0.70O3、Li0.10La0.80Cr0.70O3、Li0.20La0.77Cr0.70O3,或其组合。
所述钙钛矿材料可为其中在任何以上列举的材料中O3-δ(其中0<δ≤1)代替O3的材料。
所述钙钛矿材料可为例如Li0.34La0.55RuO3-δ(其中0≤δ≤1)、Li0.34La0.55MnO3-δ(其中0≤δ≤1)、Li0.34La0.55NiO3-δ(其中0≤δ≤1)、Li0.34La0.55CrO3-δ(其中0≤δ≤1)、Li0.34La0.55IrO3-δ(其中0≤δ≤1)、Li0.34La0.55CoO3-δ(其中0≤δ≤1)、Li0.34Ca0.58(Mn0.5W0.5)O3-δ(其中0≤δ≤1)、或其组合。例如,所述钙钛矿材料可为其中在以上列举的式中δ为0的任何材料,例如Li0.34La0.55RuO3、Li0.34La0.55MnO3、Li0.34La0.55NiO3、Li0.34La0.55CrO3、Li0.34La0.55IrO3、Li0.34La0.55CoO3、或其组合。
在下文中,将进一步描述制备实施方式的钙钛矿材料的方法。
可提供锂化合物、含A元素的化合物、含M元素的化合物和溶剂的混合物。接着,可对所述混合物进行第一热处理以提供经第一热处理的混合物。所述溶剂可为所述含A元素的化合物和所述含M元素的化合物可溶解和/或分散在其中的任何合适的溶剂。例如,所述溶剂可为乙醇、水、乙二醇或异丙醇的至少一种。所述溶剂的量可为约3重量份至约1,000重量份、或约200重量份至约800重量份、例如约300重量份至约600重量份,相对于100重量份所述锂化合物、所述含A元素的化合物和所述含M元素的化合物的总重量。
在所述含A元素的化合物中,A可为氢(H)或者周期表的第1族至第16族元素的至少一种元素,且M可为周期表的第1族至第16族元素的至少一种。例如,所述含A元素的化合物的A和所述含M元素的化合物的M可与以上式1中对于A和M定义的那些相同。也就是说,所述含A元素的化合物的A可为H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、或其组合,且所述含M元素的化合物的M可为Ni、Pd、Pb、Fe、Ir、Co、Rh、Mn、Cr、Ru、Re、Sn、V、Ge、W、Zr、Ti、Mo、Hf、U、Nb、Th、Ta、Bi、Li、H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、Mg、Al、Si、Sc、Zn、Ga、Ag、Cd、In、Sb、Pt、Au、或其组合。
所述混合物的提供可包括将所述锂化合物、所述含A元素的化合物、所述含M元素的化合物和所述溶剂组合并且混合以形成所述混合物。所述混合可通过任何合适的方法例如研磨、共混、搅拌、或其组合进行。所述研磨可使用例如球磨机、空气喷射研磨机、珠磨机、辊磨机、或其组合进行。
所述第一热处理可以约1摄氏度/分钟(℃/分钟)至约10℃/分钟的加热速率进行,并且所述第一热处理的温度可在约600℃至约900℃、或约650℃至约900℃或约650℃至约750℃的范围内。在所述第一热处理期间,CO3和OH可被除去。在所述第一热处理过程之后,可通过进行将在后面进一步描述的第二热处理过程而获得钙钛矿材料。当所述第一热处理的加热速率在上述范围内时,所述第一热处理可足以使得能够在将在后面进一步描述的第二热处理过程之后形成具有所选择的晶体结构的钙钛矿材料。
所述第一热处理可在氧化气体气氛中进行。
所述氧化气体气氛可使用例如环境空气或纯氧气产生。所述第一热处理的时间可取决于所述第一热处理温度而变化,并且可为例如约1至20小时、例如约1至10小时、例如约2至5小时。
所述锂化合物可为例如氧化锂(Li2O)、碳酸锂、氯化锂、硫化锂、硝酸锂、磷酸锂或氢氧化锂的至少一种。
所述含A元素的化合物可为例如如下的至少一种:氧化镧、碳酸镧、氯化镧、硫化镧、硝酸镧、磷酸镧、氢氧化镧、氧化钇、碳酸钇、氯化钇、硫化钇、氧化铈、碳酸铈、氯化铈、硫化铈、硝酸铈、磷酸铈、氢氧化铈、氧化钙、碳酸钙、氯化钙、硫化钙、硝酸钙、磷酸钙、氢氧化钙、氧化钡、碳酸钡、氯化钡、硫化钡、硝酸钡、磷酸钡、氢氧化钡、氧化锶、碳酸锶、氯化锶、硫化锶、硝酸锶、磷酸锶或氢氧化锶。
所述含M元素的化合物可为例如如下的至少一种:氧化镍、氢氧化镍、氧化钴、氢氧化钴、氧化钌、氢氧化钌、氧化铬、氢氧化铬、氧化铱、氢氧化铱、氧化锰或氢氧化锰。
可化学计量地控制所述锂化合物、所述含A元素的化合物、和所述含M元素的化合物的量以获得由式1表示的钙钛矿材料。
接着,可将来自所述第一热处理的产物粉碎以获得成形产物。所述成形产物可为例如包括颗粒的粉末。所述成形产物(颗粒)可具有约10μm或更小、例如约5μm或更小、或者约1μm或更小的颗粒尺寸。当所述成形产物的颗粒尺寸在该范围内时,颗粒尺寸可小到足以确保充分的粉碎和混合,由此使在所述钙钛矿材料中的晶相的形成容易。本文中使用的表述“颗粒尺寸”在颗粒在形状上为球形时是指平均粒径,并且在颗粒为非球形时是指沿长轴的长度(最长尺寸)。颗粒尺寸可使用任何合适的方法例如扫描电子显微镜或颗粒尺寸分析仪测量。
根据一种或多种实施方式的方法可包括使用第二热处理加热所述成形产物以形成所述钙钛矿材料。所述第二热处理的加热速率可为约1℃/分钟至约10℃/分钟。所述第二热处理的温度可例如高于所述第一热处理的温度。
在所述第二热处理之前,可将所述成形产物(颗粒)压制成片(pellet)形式。当将所述成形产物压制成片形式并且然后随后使用所述第二热处理加热时,加热的成形产物中的热扩散距离减小,并且可使钙钛矿材料的形成容易。另一方面,当所述成形产物的颗粒为粉末形式而不是片形式时,热扩散距离可大于当所述成形产物为片形式时,并且结果,与对片形式进行所述第二热处理时相比,可提高所述第二热处理的时间和温度以形成钙钛矿材料。
可根据式1中M的预定氧化数来调节所述第二热处理的条件。例如,所述第二热处理可在氧化气体气氛、还原气体气氛或惰性气体气氛中进行。可例如使用环境空气或氧气产生所述氧化气体气氛。可使用还原气体如氢气产生所述还原气体气氛,并且可使用气体如氮气、氩气和/或氦气产生所述惰性气体气氛。
所述第二热处理可在约900℃至约1500℃、或约1000℃至约1400℃、或约1100℃至约1200℃的温度下进行。第二热处理时间可取决于所述第二热处理的温度而变化。所述第二热处理时间可为例如约1小时至约50小时、例如约6小时至约48小时、或约10小时至约36小时。
通过所述第二热处理,可形成钙钛矿材料。在根据一种或多种实施方式的制备方法中,如果所述第二热处理的温度低于所述第一热处理的温度,则可难以获得具有晶相的钙钛矿材料。当所述第二热处理的时间和温度在上述范围内时,所述第二热处理可能够形成具有结晶结构的钙钛矿材料,并且所述钙钛矿材料的合成时间可短到足以在经济上和在商业上为有益的。
根据另一方面,二次电池包括根据任意上述实施方式的钙钛矿材料。所述二次电池可包括正极、负极以及插入在所述正极和所述负极之间的电解质。所述正极、或者所述正极和所述电解质各自可包括根据任意上述实施方式的钙钛矿材料。
所述二次电池可为例如锂-空气电池、锂离子电池或全固态锂二次电池。所述二次电池的形状没有限制并且可具有多种形状的任一种,例如像硬币、钮扣、片、堆、圆柱、平面或角的形状。所述二次电池还可用作用于电动车的大型电池。
所述二次电池可为例如锂-空气电池。所述锂-空气电池可包括包含根据任意上述实施方式的钙钛矿材料的正极、气体阻挡层(例如,氧气阻挡层)和含锂负极。由于所述锂-空气电池的正极包括根据任意上述实施方式的钙钛矿材料,所以所述锂-空气电池可具有改善的充电和放电特性。所述正极也可充当电解质。
图2为说明包括根据上述实施方式之一的钙钛矿材料的锂-空气电池10的结构的示意图。
参照图2,作为根据实施方式的二次电池的锂-空气电池10可具有包括如下的结构:包括所述钙钛矿材料的正极11、负极13、以及插入在正极11和负极13之间的气体阻挡层12。气体阻挡层12可为例如不透氧气的层。正极11可基本上由所述钙钛矿材料组成或由所述钙钛矿材料组成而没有任何粘合剂或电解质。
图3是图2的正极11的局部放大图。
参照图3,在正极11中,所述钙钛矿材料促进锂离子(Li+)和电子(e-)的同时传导。所述钙钛矿材料是具有优化的离子传导率和电子传导率二者的混合传导材料。由于结晶结构的优异的耐化学品性和稳定性,所述钙钛矿材料也可充当正极中间层。所述钙钛矿材料可不在任何程度上被放电期间形成且沉积在正极11的孔中的锂氧化物(Li2O2)分解。因此,所述钙钛矿材料防止由如下引起的锂-空气电池的寿命特性的劣化:在包括其的正极中碳质材料和有机聚合物电解质的分解。
正极11可通过如下制造:在约500℃至约1400℃、或约600℃至约1300℃、或约750℃至约1200℃的温度下热处理(加热)根据任意上述实施方式的钙钛矿材料。当热处理温度在该范围内时,制造的正极11可具有优异的离子传导率和电子传导率。
如上所述制造的正极11的重量和厚度没有限制。例如,正极11可具有约0.1毫克(mg)至约1000mg、或约1mg至约750mg、或约10mg至约500mg的重量,以及约0.1μm至约1000μm、或约1μm至约800μm、或约100μm至约500μm的厚度。
接着,在将正极11设置在气体阻挡层12的表面上之后,可将负极13设置在气体阻挡层12的与正极11相反的表面上。
在将正极11和负极13设置在气体阻挡层12上之后,可进行热处理。热处理温度可为例如约500℃至约1000℃、或约600℃至约1300℃、或约750℃至约1200℃。
负极13可为含锂负极。例如,负极13可为锂金属薄膜和/或基于锂的合金薄膜。基于锂的合金可为锂与例如铝、锡、镁、铟、钙、钛或钒的至少一种的合金。
气体阻挡层12充当锂离子传导性固体电解质膜,并且还可起到用于防止锂金属负极和杂质如氧气之间的直接反应的保护层的作用。例如,所述锂离子传导性固体电解质膜可为包括无机材料例如锂离子传导性玻璃、锂离子传导性晶体(例如陶瓷或玻璃-陶瓷)、或其组合的层。然而,实施方式不限于此。例如,可使用具有锂离子传导性、不透氧气且能够保护负极的任何固体电解质膜。例如,考虑到化学稳定性,所述锂离子传导性固体电解质膜可包括金属氧化物。
当所述锂离子传导性固体电解质膜含有大的百分比的锂离子传导性晶体时,可获得高的离子传导率。例如,所述锂离子传导性固体电解质膜可包括约50重量%或更多、例如约55重量%或更多、或者约60重量%或更多的锂离子传导性晶体,基于所述锂离子传导性固体电解质膜的总重量。
所述锂离子传导性晶体可包括例如Li3N、锂超离子导体(LISICON)、或具有钙钛矿结构和锂离子传导性的晶体例如La0.55Li0.35TiO3;具有NASICON型结构的LiTi2P3O12;Li1+x+y(Al,Ga)x(Ti,Ge)2-xSiyP3-yO12(其中0≤x≤1和0≤y≤1,例如0≤x≤0.4和0<y≤0.6,或0.1≤x≤0.3和0.1<y≤0.4);能够沉淀这些晶体的玻璃-陶瓷;或其组合。
锂离子传导性玻璃-陶瓷的非限制性实例可包括锂-铝-锗-磷酸盐(LAGP)、锂-铝-钛-磷酸盐(LATP)、锂-铝-钛-硅-磷酸盐(LATSP)、或其组合。例如,当通过热处理使具有Li2O-Al2O3-TiO2-SiO2-P2O5组成的母玻璃结晶时,所得的初晶相可为Li1+x+yAlxTi2-xSiyP3- yO12(其中0≤x≤1和0≤y≤1)。例如,在Li1+x+yAlxTi2-xSiyP3-yO12的式中,x和y可满足例如0≤x≤0.4和0<y≤0.6、例如0.1≤x≤0.3和0.1<y≤0.4。
气体阻挡层12的锂离子传导性玻璃-陶瓷可包括Li1+x+yAlxTi2-xSiyP3-yO12(其中0≤x≤1和0≤y≤1、例如0≤x≤0.4和0<y≤0.6、例如0.1≤x≤0.3和0.1<y≤0.4)、或Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12(其中0≤x≤2和0≤y≤3)。例如,气体阻挡层12可为包括LATP(Li1.4Ti1.6Al0.4P3O12)的固体电解质膜。
在一种或多种实施方式中,所述锂-空气电池可进一步包括在正极11和气体阻挡层12之间的正极中间层(未显示)。所述锂-空气电池可进一步包括在气体阻挡层12和负极13之间的负极中间层(未显示)。所述正极中间层和所述负极中间层可抑制可在所述正极或所述负极与气体阻挡层12之间发生的副反应。所述正极中间层和所述负极中间层可各自具有例如约0.1μm至约10μm、或约1μm至约10μm、或约1μm至约7.5μm的厚度。
所述正极中间层和所述负极中间层可各自包括电解质,所述电解质包括液体电解质、凝胶电解质或固体电解质的至少一种。
所述液体电解质、所述凝胶电解质或所述固体电解质没有特别限制,且可为适于锂-空气电池的任何电解质。
例如,所述液体电解质可包括溶剂和锂盐。所述溶剂可包括有机溶剂、离子液体或低聚物的至少一种。然而,实施方式不限于此。可使用在室温(25℃)下为液体形式的任何溶剂。
所述有机溶剂可包括如下的至少一种:基于醚的溶剂、基于碳酸酯的溶剂、基于酯的溶剂或基于酮的溶剂。例如,所述有机溶剂可包括如下的至少一种:碳酸亚丙酯、碳酸亚乙酯、碳酸氟代亚乙酯、碳酸乙烯基亚乙酯、碳酸亚丁酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸甲基异丙基酯、碳酸二丙酯、碳酸二丁酯、苄腈、乙腈、四氢呋喃、2-甲基四氢呋喃、γ-丁内酯、二氧戊环、4-甲基二氧戊环、二甲基乙酰胺、二甲亚砜、二烷、1,2-二甲氧基乙烷、环丁砜、二氯乙烷、氯苯、硝基苯、丁二腈、二甘醇二甲醚(DEGDME)、四甘醇二甲醚(TEGDME)、聚乙二醇二甲醚(PEGDME,Mn=~500)、二甲醚、二乙醚、二丁醚、或二甲氧基乙烷。然而,实施方式不限于此。所述有机溶剂可为在室温下为液体形式的任何有机溶剂。
所述锂盐可包括如下的至少一种:LiTFSI、LiPF6、LiBF4、LiAsF6、LiClO4、LiNO3、双(草酸)硼酸锂(LiBOB)、LiCF3SO3(三氟甲烷磺酸锂,三氟甲磺酸锂,LiTfO)、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO3CF3)2、LiC4F9SO3、或LiAlCl4、然而,实施方式不限于此。可使用适合用作锂盐的任何材料。所述锂盐的浓度可为约0.01摩尔浓度(M)至约3.0M。然而,实施方式不限于此。所述锂盐的浓度可根据需要适当地调节。
所述固体电解质的非限制性实例可包括如下的至少一种:离子传导性聚合物、聚合物离子液体(PIL)、无机电解质、聚合物基质或电子传导性聚合物。所述聚合物基质可不具有离子传导性或电子传导性。
所述固体电解质可包括如下的至少一种:聚环氧乙烷(PEO)、包括具有低的玻璃化转变温度(Tg)的至少两个聚合物嵌段的固体接枝共聚物、聚双(三氟甲磺酰)亚胺(二烯丙基二甲基铵)/(聚(二烯丙基二甲基铵)TFSI)、Cu3N、Li3N、锂磷氧氮化物(LiPON)、Li3PO4·Li2S·SiS2、Li2S·GeS2·Ga2S3、Li2O·11Al2O3、Na2O·11Al2O3、(Na,Li)1+xTi2-xAlx(PO4)3(其中0.1≤x≤0.9)、Li1+xHf2-xAlx(PO4)3(其中0.1≤x≤0.9)、Na3Zr2Si2PO12、Li3Zr2Si2PO12、Na5ZrP3O12、Na5TiP3O12、Na3Fe2P3O12、Na4NbP3O12、Na-硅酸盐、Li0.3La0.5TiO3、Na5MSi4O12(其中M可为稀土元素,例如Nd、Gd、或Dy)、Li5ZrP3O12、Li5TiP3O12、Li3Fe2P3O12、Li4NbP3O12、Li1+x(M,Al,Ga)x(Ge1-yTiy)2-x(PO4)3(其中0≤x≤0.8,0≤y≤1.0,且M可为Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、或Yb)、Li1+x+yQxTi2-xSiyP3-yO12(其中0≤x≤0.4,0<y≤0.6,且Q可为Al或Ga)、Li6BaLa2Ta2O12、Li7La3Zr2O12、Li5La3Nb2O12、Li5La3M2O12(其中M可为Nb或Ta)、或Li7+xAxLa3- xZr2O12(其中0<x<3且A可为Zn)。
作为离子传导性聚合物,所述固体电解质可包括离子传导性重复单元,所述离子传导性重复单元可为如下的至少一种:基于醚的单体、基于丙烯酰基的单体、基于甲基丙烯酰基的单体或基于硅氧烷的单体。
所述离子传导性聚合物可为如下的至少一种:聚环氧乙烷、聚环氧丙烷、聚(甲基丙烯酸甲酯)、聚(甲基丙烯酸乙酯)、聚二甲基硅氧烷、聚丙烯酸酯、聚丙烯酸乙酯、聚(丙烯酸2-乙基己基酯)、聚(甲基丙烯酸丁酯)、聚(甲基丙烯酸2-乙基己基酯)、聚(丙烯酸癸酯)或聚乙烯乙酸乙烯酯。所述离子传导性聚合物可为包括离子传导性重复单元和结构性重复单元的共聚物。所述离子传导性重复单元可得自如下的至少一种单体:丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸2-乙基己基酯、甲基丙烯酸丁酯、甲基丙烯酸2-乙基己基酯、丙烯酸癸酯、乙烯乙酸乙烯酯、环氧乙烷或环氧丙烷。例如,所述结构性重复单元可得自如下的至少一种单体:苯乙烯、4-溴苯乙烯、叔丁基苯乙烯、二乙烯基苯、甲基丙烯酸甲酯、甲基丙烯酸异丁酯、丁二烯、乙烯、丙烯、二甲基硅氧烷、异丁烯、N-异丙基丙烯酰胺、氟乙烯、丙烯腈、4-甲基-1-戊烯、对苯二甲酸丁二醇酯、对苯二甲酸乙二醇酯或乙烯基吡啶。所述离子传导性聚合物可为包括离子传导性相和结构性相的嵌段共聚物。所述包括离子传导性相和结构性相的嵌段共聚物的实例可包括在美国专利No.8,269,197和8,563,168、以及美国专利公开No.2011/0206994中公开的嵌段共聚物,将其各自的内容全部通过引用引入本文中。
所述负极中间层可包括固体聚合物电解质。例如,所述固体聚合物电解质可为掺杂有锂盐的聚环氧乙烷(PEO),其中所述锂盐的非限制性实例可为如下的至少一种:LiN(SO2F)2、LiBF4、LiPF6、LiSbF6、LiAsF6、LiClO4、LiCF3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO3CF3)2、LiC4F9SO3、或LiAlCl4。所述负极中间层可为通过混合聚环氧乙烷和锂盐制备的聚合物电解质。
所述正极中间层可为例如通过混合聚(氧乙烯)甲基丙烯酸酯和聚(二甲基硅氧烷)共聚物和锂盐制备的聚合物电解质。
所述锂-空气电池可进一步包括电解质。所述电解质可具有包括浸渍有固体聚合物电解质的隔板的结构体。具有浸渍有固体聚合物电解质的隔板的结构体可通过如下制备:将固体聚合物电解质膜设置在隔板的一个或两个表面上并且同时辊压隔板-膜结构体。在一些实施方式中,可通过将包括锂盐的液体电解质注入隔板中而制备所述结构体。
接着,在将所述负极安装在壳的内侧上之后,可将在其上具有所述气体阻挡层的所述正极设置在所述负极上。可在所述负极和所述气体阻挡层之间进一步设置所述负极中间层(当存在时)。可在所述气体阻挡层和所述正极之间进一步设置所述正极中间层(当存在时)。所述气体阻挡层可为氧气阻挡层。
接着,可在所述正极上设置包括金属或碳的气体扩散层,由此完成锂-空气电池的制造。
现在将参照以下实施例详细描述本发明构思的一种或多种实施方式。然而,这些实施例仅用于说明的目的,并且不意图限制本发明构思的一种或多种实施方式的范围。
实施例
实施例1:钙钛矿材料(Li0.34La0.55RuO3-δ)(0≤δ≤1)的制备
将Li2CO3、La2O3和RuO2粉末以提供Li0.34La0.55RuO3-δ(其中0≤δ≤1)的组成的化学计量的量添加到乙醇中,然后混合。然后将所得混合物放入球磨混合器中并且粉碎和混合约4小时。将所得混合物干燥,然后以约5℃/分钟的加热速率加热至约800℃,随后在相同温度下在空气气氛中进行连续第一热处理约4小时。
将在所述第一热处理后获得的所得的经加热的混合物粉碎成具有约0.3μm颗粒尺寸的粉末(一次颗粒)。然后将该粉末压制以形成具有约1.3厘米(cm)直径、约0.5cm高度和约0.3克(g)重量的圆柱形片。然后将所述片在空气气氛中在约1200℃的温度下经受第二热处理约24小时以获得目标产物。对于所述第二热处理,以约5℃/分钟的加热速率将温度升至1200℃。所述目标产物是Li0.34La0.55RuO3-δ,其中δ=0和/或0<δ≤1。
实施例2:钙钛矿材料(Li0.34La0.55NiO3-δ)(0≤δ≤1)的制备
以与实施例1中相同的方式获得目标产物,除了如下之外:使用Ni(OH)2代替RuO2。所述目标产物为Li0.34La0.55NiO3-δ,其中δ=0和/或0<δ≤1。
实施例3:钙钛矿材料(Li0.34La0.55MnO3-δ)(0≤δ≤1)的制备
以与实施例1中相同的方式获得目标产物,除了如下之外:使用MnO2代替RuO2。所述目标产物为Li0.34La0.55MnO3-δ,其中δ=0和/或0<δ≤1。
实施例4:钙钛矿材料(Li0.34La0.55CrO3-δ)(0≤δ≤1)的制备
以与实施例1中相同的方式获得目标产物,除了如下之外:使用Cr2O3代替RuO2。所述目标产物为Li0.34La0.55CrO3-δ,其中δ=0和/或0<δ≤1。
实施例5:钙钛矿材料(Li0.34La0.55CoO3-δ)(0≤δ≤1)的制备
以与实施例1中相同的方式获得目标产物,除了如下之外:使用Co2O3代替RuO2。所述目标产物为Li0.34La0.55CoO3-δ,其中δ=0和/或0<δ≤1。
实施例6:钙钛矿材料(Li0.34La0.55IrO3-δ)(0≤δ≤1)的制备
以与实施例1中相同的方式获得目标产物,除了如下之外:使用IrO2代替RuO2。所述目标产物为Li0.34La0.55IrO3-δ,其中δ=0和/或0<δ≤1。
对比例1:钙钛矿材料(Li0.34La0.55TiO3)的制备
以与实施例1中相同的方式获得目标产物,除了如下之外:使用TiO2代替RuO2并且所述第一热处理和所述第二热处理二者均在约1000℃下进行。
实施例7:锂-空气电池的制造
通过如下制造具有约5毫克/平方厘米(mg/cm2)的每单位面积的重量和约10μm厚度的正极:在约1000℃下在空气气氛下加热根据实施例1制备的钙钛矿材料Li0.34La0.55RuO3-δ(其中0≤δ≤1)约60分钟。
将具有约250μm厚度的锂-铝-钛-磷酸盐(LATP)层(可得自Ohara Corp.,Japan)作为气体阻挡层设置在所述正极的下表面上,并且将具有所述气体阻挡层的所述正极的下表面在约900℃下加热约60分钟。
将作为负极中间层的聚合物电解质设置在所述气体阻挡层之下。通过如下制备所述聚合物电解质:将聚环氧乙烷(Mn=100,000道尔顿)和作为锂盐的双(三氟甲磺酰)亚胺锂(LiTFSI)以20:1的EO/Li摩尔比混合。
将锂金属箔设置在所述聚合物电解质之下,并且将气体扩散层(GDL)(25BC,可得自SGL)附着至所述正极的上表面。将镍网设置在GDL上,然后用能够将空气转移到所述正极的压制构件进行压制以固定单元电池,由此制造锂-空气电池。
实施例8:锂-空气电池的制造
以与实施例7中相同的方式制造锂-空气电池,除了如下之外:使用根据实施例3制备的钙钛矿材料Li0.34La0.55MnO3-δ(其中0≤δ≤1)代替实施例1的钙钛矿材料Li0.34La0.55RuO3-δ(其中0≤δ≤1)。
实施例9:锂-空气电池的制造
通过如下制造具有约5mg/cm2的每单位面积的重量和约10μm厚度的正极:在约1000℃下在空气气氛下加热根据实施例1制备的钙钛矿材料Li0.34La0.55RuO3-δ(其中0≤δ≤1)约60分钟。
将作为正极中间层的聚合物电解质设置在具有约250μm厚度并且充当气体阻挡层的锂-铝-钛-磷酸盐(LATP)层(可得自Ohara Corp.,Japan)的表面上。通过如下制备该聚合物电解质:将聚(氧乙烯)甲基丙烯酸酯和聚二甲基硅氧烷的共聚物(Mn=100,000道尔顿)(聚(氧乙烯)甲基丙烯酸酯和聚二甲基硅氧烷的重量比=7:3)和作为锂盐的双(三氟甲磺酰)亚胺锂(LiTFSI)以20:1的EO/Li摩尔比混合。
随后,将作为负极中间层的聚合物电解质设置在所述气体阻挡层的相反表面上。通过如下制备该聚合物电解质:将聚环氧乙烷(Mn=600,000道尔顿)和作为锂盐的双(三氟甲磺酰)亚胺锂(LiTFSI)以20:1的EO/Li摩尔比混合。
将锂金属箔设置在所述聚合物电解质之下,并且将气体扩散层(GDL)(25BC,可得自SGL)附着至所述正极的上表面。将镍网布置在GDL上,然后用能够将空气转移到所述正极的压制构件进行压制以固定单元电池,由此制造锂-空气电池。
实施例10
以与实施例9中相同的方式制造锂-空气电池,除了如下之外:使用根据实施例3制备的钙钛矿材料Li0.34La0.55MnO3-δ(其中0≤δ≤1)代替实施例1的钙钛矿材料Li0.34La0.55RuO3-δ(其中0≤δ≤1)。
实施例11
以与实施例1中相同的方式制备钙钛矿材料,除了如下之外:变化Li2CO3、La2O3、和RuO2的量以提供表1中所示的钙钛矿材料。
表1
实施例11的样品 | 钙钛矿材料的组成 |
11-1 | Li<sub>0.20</sub>La<sub>0.60</sub>RuO<sub>3-δ</sub>(0≤δ≤1) |
11-2 | Li<sub>0.30</sub>La<sub>0.57</sub>RuO<sub>3-δ</sub>(0≤δ≤1) |
11-3 | Li<sub>0.40</sub>La<sub>0.53</sub>RuO<sub>3-δ</sub>(0≤δ≤1) |
11-4 | Li<sub>0.45</sub>La<sub>0.52</sub>RuO<sub>3-δ</sub>(0≤δ≤1) |
实施例12
以与实施例3中相同的方式制备钙钛矿材料,除了如下之外:变化Li2CO3、La2O3、和MnO2的量以提供表2中所示的钙钛矿材料的组成。
表2
实施例12的样品 | 钙钛矿材料的组成 |
12-1 | Li<sub>0.20</sub>La<sub>0.60</sub>MnO<sub>3-δ</sub>(0≤δ≤1) |
12-2 | Li<sub>0.30</sub>La<sub>0.57</sub>MnO<sub>3-δ</sub>(0≤δ≤1) |
12-3 | Li<sub>0.40</sub>La<sub>0.53</sub>MnO<sub>3-δ</sub>(0≤δ≤1) |
12-4 | Li<sub>0.45</sub>La<sub>0.52</sub>MnO<sub>3-δ</sub>(0≤δ≤1) |
对比例2:锂-空气电池的制造
以与实施例7中相同的方式制造锂-空气电池,除了如下之外:使用根据对比例1制备的钙钛矿材料Li0.34La0.55TiO3-δ(其中0≤δ≤1)代替实施例1的钙钛矿材料Li0.34La0.55RuO3-δ(其中0≤δ≤1)。
评价实施例1:X射线衍射分析
通过X射线衍射(XRD)分析来分析实施例1-6和对比例1的钙钛矿材料。X射线衍射分析的结果示于图4A-4C中。在图4A-4C中,Ti、Mn、Co、Ir、Cr、Ni、和Ru分别对应于对比例1、实施例2、实施例6、实施例5、实施例4、实施例3和实施例1的钙钛矿材料中存在的元素。
使用利用Cu Kα辐射的Bruker D8 Advance衍射仪进行XRD光谱法。基于对钙钛矿材料各自的XRD光谱法的结果,计算在46.5°±2.5°的衍射角2θ处的峰强度(I(46.5°±2.5°):Ib)对在32.5°±2.5°的衍射角2θ处的峰强度(I(32.5°±2.5°):Ia)的比率(Ib/Ia)、以及在57.5°±2.5°的衍射角2θ处的峰强度(I(57.5°±2.5°):Ic)对在32.5°±2.5°的衍射角2θ处的峰强度(I(32.5°±2.5°):Ia)的比率(Ic/Ia)。结果示于表3中。
表3
参照表3和图4A-4C,在11.3±0.5°的衍射角处的峰出现在对比例1的钙钛矿材料中,而未出现在实施例1-6的钙钛矿材料中。不受理论限制,理解对比例1的钙钛矿材料在结晶结构中具有单独的贫La和富La层,而实施例1-6的钙钛矿材料具有未分离成贫La和富La层的La层,如图1中所示,表明实施例1-6的钙钛矿材料具有与对比例1的钙钛矿材料不同的结晶结构。
评价实施例2:电子传导率和离子传导率
测量实施例1-6和对比例1的钙钛矿材料的电子传导率和离子传导率。结果示于表4和图5中。
表4
实施例 | 钙钛矿材料的组成 | 电子传导率(S/cm) | 离子传导率(S/cm) |
实施例1 | Li<sub>0.34</sub>La<sub>0.55</sub>RuO<sub>3</sub> | 5.6X 10<sup>-2</sup> | 2.1X 10<sup>-5</sup> |
实施例2 | Li<sub>0.34</sub>La<sub>0.55</sub>NiO<sub>3</sub> | 2.8X 10<sup>-2</sup> | 3.0X 10<sup>-6</sup> |
实施例3 | Li<sub>0.34</sub>La<sub>0.55</sub>MnO<sub>3</sub> | 2.0X 10<sup>-3</sup> | 8.8X 10<sup>-5</sup> |
实施例4 | Li<sub>0.34</sub>La<sub>0.55</sub>CrO<sub>3</sub> | 2.6X 10<sup>-4</sup> | 2.0X 10<sup>-6</sup> |
实施例5 | Li<sub>0.34</sub>La<sub>0.55</sub>CoO<sub>3</sub> | 4.5X 10<sup>-4</sup> | 4.6X 10<sup>-6</sup> |
实施例6 | Li<sub>0.34</sub>La<sub>0.55</sub>IrO<sub>3</sub> | 4.3X 10<sup>-3</sup> | 1.7X 10<sup>-5</sup> |
对比例1 | Li<sub>0.34</sub>La<sub>0.55</sub>TiO<sub>3</sub> | 3.8X 10<sup>-9</sup> | 1.2X 10<sup>-5</sup> |
参照表4和图5,与对比例1的钙钛矿材料相比,发现实施例1-6的钙钛矿材料具有令人满意的离子传导率以及显著改善的电子传导率。
评价实施例3:充电和放电特性的评价
将实施例7和8以及对比例2的锂空气电池在约60℃和1个大气压(atm)的氧气压力的条件下以0.01毫安/平方厘米(mA/cm2)的恒定电流放电,直到达到相对于Li的2.0伏(V)的电压。然后以相同的电流将所述锂-空气电池充电,直到达到4.3V的电压(第1次充电和放电循环)。在第1次充电和放电循环的充电和放电测试的结果示于图6中。
参照图6,与对比例2的锂-空气电池的充电和放电特性相比,发现实施例7和8的锂空气电池具有改善的充电和放电特性。
还以与应用于实施例7和实施例8的锂空气电池的相同的方式评价实施例9和实施例10的锂空气电池的充电和放电特性。作为充电和放电特性评价的结果,发现实施例9和10的锂空气电池的充电和放电特性几乎与实施例7和8的锂空气电池的那些类似。
评价实施例4:电化学稳定性评价
在单独地粉碎实施例1和3的钙钛矿材料后,将85重量%粉碎产物、10重量%作为导电剂的炭黑、和5重量%作为粘合剂的聚偏氟乙烯(PVDF)在用作溶剂的N-甲基-2-吡咯烷酮(NMP)中一起混合以制备浆料。将所述浆料涂覆在铝箔上,然后干燥以制造工作电极。将所述工作电极和作为对电极的锂金属箔与设置在所述工作电极和所述对电极之间的隔板一起组装,所述隔板浸渍有液体电解质(在碳酸亚丙酯(PC)中的1M LiTFSI),由此完成半单元电池的制造。
通过循环伏安法(CV)评价各自涂覆在锂金属上的钙钛矿材料各自的电化学稳定性,其中将在约2V至约4V(相对于Li)的范围内的电压以约0.1毫伏/秒(mV/sec)的扫描速率施加至所述半单元电池。结果示于图7和8中。图7和8分别是关于实施例1和实施例3的钙钛矿材料的循环伏安法的结果。
如图7和8中所示,发现实施例1和3的钙钛矿材料是电稳定的,而不产生由副反应引起的过电流。
如上所述,根据一种或多种实施方式,包括含有根据任意上述实施方式的钙钛矿材料的正极的二次电池可具有改善的充电和放电特性。
应理解,本文中描述的实施方式应仅在描述的意义上考虑且不用于限制的目的。各实施方式内的特征或方面的描述应被认为可用于其它实施方式中的其它类似特征或方面。
尽管已经参照附图描述了实施方式,但是本领域普通技术人员将理解,在不背离如由所附权利要求所限定的精神和范围的情况下,可在其中进行形式和细节方面的多种变化。
Claims (27)
1.由式1表示的钙钛矿材料:
式1
LixAyMzO3-δ
其中,在式1中,0<x≤1,0<y≤1,0<x+y<1,0<z≤1.5,和0≤δ≤1,
A为H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、或其组合,且
M为Ni、Pd、Pb、Fe、Ir、Co、Rh、Mn、Cr、Ru、Re、Sn、V、Ge、W、Zr、Mo、Hf、U、Nb、Th、Ta、Bi、Li、H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、Mg、Al、Si、Sc、Zn、Ga、Ag、Cd、In、Sb、Pt、Au、或其组合。
2.如权利要求1所述的钙钛矿材料,其中式1中的A和M不同。
3.如权利要求1所述的钙钛矿材料,其中式1中的A为La、Ce、Pr、Gd、Ca、Sr、Ba、或其组合,且式1中的M为Mn、Ni、Ru、Cr、Co、Rb、Ir、Fe、Pd、Pb、Rh、Sn、V、Re、Ge、W、Zr、Mo、Nb、Ta、Hf、Bi、或其组合。
4.如权利要求1所述的钙钛矿材料,其中,在式1中,0.2<x≤0.5,0.2<y≤0.7,和0.8<z≤1.2。
5.如权利要求1所述的钙钛矿材料,其中,在式1中,0.3<x≤0.4,0.4<y≤0.7,和0.9<z≤1.1。
6.如权利要求1所述的钙钛矿材料,其中,在式1中,x对y的比率为1:0.5至1:7。
7.如权利要求1所述的钙钛矿材料,其中所述钙钛矿材料具有0至小于4电子伏特的氧空位形成能。
8.如权利要求1所述的钙钛矿材料,其中所述由式1表示的钙钛矿材料为由式2表示的化合物:
式2
LixA1yM1zO3-δ
其中,在式2中,0.3<x≤1,0<y≤0.7,0<z≤1,0<x+y<1,和0≤δ≤1,
A1为La、Ce、Pr、Gd、Ca、Sr、Ba、或其组合,且
M1为Mn、Ni、Ru、Cr、Co、Ru、Ir、Fe、Pd、Pb、Rh、Sn、V、Re、Ge、W、Zr、Mo、Nb、Ta、Hf、Bi、或其组合。
9.如权利要求1所述的钙钛矿材料,其中所述钙钛矿材料为Li0.34La0.55MnO3、Li0.34La0.55NiO3、Li0.34La0.55CrO3、Li0.34La0.55CoO3、Li0.34La0.55IrO3、Li0.34La0.55RuO3、Li0.34La0.55FeO3、Li0.34La0.55PdO3、Li0.34La0.55PbO3、Li0.34La0.55RhO3、Li0.34La0.55SnO3、Li0.34La0.55VO3、Li0.34La0.55ReO3、Li0.34La0.55GeO3、Li0.34La0.55WO3、Li0.34La0.55ZrO3、Li0.34La0.55MoO3、Li0.34La0.55NbO3、Li0.34La0.55TaO3、Li0.34La0.55HfO3、Li0.34La0.55BiO3,
Li0.10La0.63MnO3、Li0.10La0.63NiO3、Li0.10La0.63CrO3、Li0.10La0.63CoO3、Li0.10La0.63IrO3、Li0.10La0.63RuO3、Li0.10La0.63FeO3、Li0.10La0.63PdO3、Li0.10La0.63PbO3、Li0.10La0.63RhO3、Li0.10La0.63SnO3、Li0.10La0.63VO3、Li0.10La0.63ReO3、Li0.10La0.63GeO3、Li0.10La0.63WO3、Li0.10La0.63ZrO3、Li0.10La0.63MoO3、Li0.10La0.63NbO3、Li0.10La0.63TaO3、Li0.10La0.63HfO3、Li0.10La0.63BiO3,
Li0.20La0.60MnO3、Li0.20La0.60NiO3、Li0.20La0.60CrO3、Li0.20La0.60CoO3、Li0.20La0.60IrO3、Li0.20La0.60RuO3、Li0.20La0.60FeO3、Li0.20La0.60PdO3、Li0.20La0.60PbO3、Li0.20La0.60RhO3、Li0.20La0.60SnO3、Li0.20La0.60VO3、Li0.20La0.60ReO3、Li0.20La0.60GeO3、Li0.20La0.60WO3、Li0.20La0.60ZrO3、Li0.20La0.60MoO3、Li0.20La0.60NbO3、Li0.20La0.60TaO3、Li0.20La0.60HfO3、Li0.20La0.60BiO3,
Li0.30La0.57MnO3、Li0.30La0.57NiO3、Li0.30La0.57CrO3、Li0.30La0.57CoO3、Li0.30La0.57IrO3、Li0.30La0.57RuO3、Li0.30La0.57FeO3、Li0.30La0.57PdO3、Li0.30La0.57PbO3、Li0.30La0.57RhO3、Li0.30La0.57SnO3、Li0.30La0.57VO3、Li0.30La0.57ReO3、Li0.30La0.57GeO3、Li0.30La0.57WO3、Li0.30La0.57ZrO3、Li0.30La0.57MoO3、Li0.30La0.57NbO3、Li0.30La0.57TaO3、Li0.30La0.57HfO3、Li0.30La0.57BiO3,
Li0.40La0.53MnO3、Li0.40La0.53NiO3、Li0.40La0.53CrO3、Li0.40La0.53CoO3、Li0.40La0.53IrO3、Li0.40La0.53RuO3、Li0.40La0.53FeO3、Li0.40La0.53PdO3、Li0.40La0.53PbO3、Li0.40La0.53RhO3、Li0.40La0.53SnO3、Li0.40La0.53VO3、Li0.40La0.53ReO3、Li0.40La0.53GeO3、Li0.40La0.53WO3、Li0.40La0.53ZrO3、Li0.40La0.53MoO3、Li0.40La0.53NbO3、Li0.40La0.53TaO3、Li0.40La0.53HfO3、Li0.40La0.53BiO3,
Li0.45La0.52MnO3、Li0.45La0.52NiO3、Li0.45La0.52CrO3、Li0.45La0.52CoO3、Li0.45La0.52IrO3、Li0.45La0.52RuO3、Li0.45La0.52FeO3、Li0.45La0.52PdO3、Li0.45La0.52PbO3、Li0.45La0.52RhO3、Li0.45La0.52SnO3、Li0.45La0.52VO3、Li0.45La0.52ReO3、Li0.45La0.52GeO3、Li0.45La0.52WO3、Li0.45La0.52ZrO3、Li0.45La0.52MoO3、Li0.45La0.52NbO3、Li0.45La0.52TaO3、Li0.45La0.52HfO3、Li0.45La0.52BiO3,
Li0.34Ce0.55MnO3、Li0.34Ce0.55NiO3、Li0.34Ce0.55CrO3、Li0.34Ce0.55CoO3、Li0.34Ce0.55IrO3、Li0.34Ce0.55RuO3、Li0.34Ce0.55FeO3、Li0.34Ce0.55PdO3、Li0.34Ce0.55PbO3、Li0.34Ce0.55RhO3、Li0.34Ce0.55SnO3、Li0.34Ce0.55VO3、Li0.34Ce0.55ReO3、Li0.34Ce0.55GeO3、Li0.34Ce0.55WO3、Li0.34Ce0.55ZrO3、Li0.34Ce0.55MoO3、Li0.34Ce0.55NbO3、Li0.34Ce0.55TaO3、Li0.34Ce0.55HfO3、Li0.34Ce0.55BiO3,
Li0.10Ce0.63MnO3、Li0.10Ce0.63NiO3、Li0.10Ce0.63CrO3、Li0.10Ce0.63CoO3、Li0.10Ce0.63IrO3、Li0.10Ce0.63RuO3、Li0.10Ce0.63FeO3、Li0.10Ce0.63PdO3、Li0.10Ce0.63PbO3、Li0.10Ce0.63RhO3、Li0.10Ce0.63SnO3、Li0.10Ce0.63VO3、Li0.10Ce0.63ReO3、Li0.10Ce0.63GeO3、Li0.10Ce0.63WO3、Li0.10Ce0.63ZrO3、Li0.10Ce0.63MoO3、Li0.10Ce0.63NbO3、Li0.10Ce0.63TaO3、Li0.10Ce0.63HfO3、Li0.10Ce0.63BiO3,
Li0.20Ce0.60MnO3、Li0.20Ce0.60NiO3、Li0.20Ce0.60CrO3、Li0.20Ce0.60CoO3、Li0.20Ce0.60IrO3、Li0.20Ce0.60RuO3、Li0.20Ce0.60FeO3、Li0.20Ce0.60PdO3、Li0.20Ce0.60PbO3、Li0.20Ce0.60RhO3、Li0.20Ce0.60SnO3、Li0.20Ce0.60VO3、Li0.20Ce0.60ReO3、Li0.20Ce0.60GeO3、Li0.20Ce0.60WO3、Li0.20Ce0.60ZrO3、Li0.20Ce0.60MoO3、Li0.20Ce0.60NbO3、Li0.20Ce0.60TaO3、Li0.20Ce0.60HfO3、Li0.20Ce0.60BiO3,
Li0.30Ce0.57MnO3、Li0.30Ce0.57NiO3、Li0.30Ce0.57CrO3、Li0.30Ce0.57CoO3、Li0.30Ce0.57IrO3、Li0.30Ce0.57RuO3、Li0.30Ce0.57FeO3、Li0.30Ce0.57PdO3、Li0.30Ce0.57PbO3、Li0.30Ce0.57RhO3、Li0.30Ce0.57SnO3、Li0.30Ce0.57VO3、Li0.30Ce0.57ReO3、Li0.30Ce0.57GeO3、Li0.30Ce0.57WO3、Li0.30Ce0.57ZrO3、Li0.30Ce0.57MoO3、Li0.30Ce0.57NbO3、Li0.30Ce0.57TaO3、Li0.30Ce0.57HfO3、Li0.30Ce0.57BiO3,
Li0.40Ce0.53MnO3、Li0.40Ce0.53NiO3、Li0.40Ce0.53CrO3、Li0.40Ce0.53CoO3、Li0.40Ce0.53IrO3、Li0.40Ce0.53RuO3、Li0.40Ce0.53FeO3、Li0.40Ce0.53PdO3、Li0.40Ce0.53PbO3、Li0.40Ce0.53RhO3、Li0.40Ce0.53SnO3、Li0.40Ce0.53VO3、Li0.40Ce0.53ReO3、Li0.40Ce0.53GeO3、Li0.40Ce0.53WO3、Li0.40Ce0.53ZrO3、Li0.40Ce0.53MoO3、Li0.40Ce0.53NbO3、Li0.40Ce0.53TaO3、Li0.40Ce0.53HfO3、Li0.40Ce0.53BiO3,
Li0.45Ce0.52MnO3、Li0.45Ce0.52NiO3、Li0.45Ce0.52CrO3、Li0.45Ce0.52CoO3、Li0.45Ce0.52IrO3、Li0.45Ce0.52RuO3、Li0.45Ce0.52FeO3、Li0.45Ce0.52PdO3、Li0.45Ce0.52PbO3、Li0.45Ce0.52RhO3、Li0.45Ce0.52SnO3、Li0.45Ce0.52VO3、Li0.45Ce0.52ReO3、Li0.45Ce0.52GeO3、Li0.45Ce0.52WO3、Li0.45Ce0.52ZrO3、Li0.45Ce0.52MoO3、Li0.45Ce0.52NbO3、Li0.45Ce0.52TaO3、Li0.45Ce0.52HfO3、Li0.45Ce0.52BiO3,
Li0.34Pr0.55MnO3、Li0.34Pr0.55NiO3、Li0.34Pr0.55CrO3、Li0.34Pr0.55CoO3、Li0.34Pr0.55IrO3、Li0.34Pr0.55RuO3、Li0.34Pr0.55FeO3、Li0.34Pr0.55PdO3、Li0.34Pr0.55PbO3、Li0.34Pr0.55RhO3、Li0.34Pr0.55SnO3、Li0.34Pr0.55VO3、Li0.34Pr0.55ReO3、Li0.34Pr0.55GeO3、Li0.34Pr0.55WO3、Li0.34Pr0.55ZrO3、Li0.34Pr0.55MoO3、Li0.34Pr0.55NbO3、Li0.34Pr0.55TaO3、Li0.34Pr0.55HfO3、Li0.34Pr0.55BiO3,
Li0.10Pr0.63MnO3、Li0.10Pr0.63NiO3、Li0.10Pr0.63CrO3、Li0.10Pr0.63CoO3、Li0.10Pr0.63IrO3、Li0.10Pr0.63RuO3、Li0.10Pr0.63FeO3、Li0.10Pr0.63PdO3、Li0.10Pr0.63PbO3、Li0.10Pr0.63RhO3、Li0.10Pr0.63SnO3、Li0.10Pr0.63VO3、Li0.10Pr0.63ReO3、Li0.10Pr0.63GeO3、Li0.10Pr0.63WO3、Li0.10Pr0.63ZrO3、Li0.10Pr0.63MoO3、Li0.10Pr0.63NbO3、Li0.10Pr0.63TaO3、Li0.10Pr0.63HfO3、Li0.10Pr0.63BiO3,
Li0.20Pr0.60MnO3、Li0.20Pr0.60NiO3、Li0.20Pr0.60CrO3、Li0.20Pr0.60CoO3、Li0.20Pr0.60IrO3、Li0.20Pr0.60RuO3、Li0.20Pr0.60FeO3、Li0.20Pr0.60PdO3、Li0.20Pr0.60PbO3、Li0.20Pr0.60RhO3、Li0.20Pr0.60SnO3、Li0.20Pr0.60VO3、Li0.20Pr0.60ReO3、Li0.20Pr0.60GeO3、Li0.20Pr0.60WO3、Li0.20Pr0.60ZrO3、Li0.20Pr0.60MoO3、Li0.20Pr0.60NbO3、Li0.20Pr0.60TaO3、Li0.20Pr0.60HfO3、Li0.20Pr0.60BiO3,
Li0.30Pr0.57MnO3、Li0.30Pr0.57NiO3、Li0.30Pr0.57CrO3、Li0.30Pr0.57CoO3、Li0.30Pr0.57IrO3、Li0.30Pr0.57RuO3、Li0.30Pr0.57FeO3、Li0.30Pr0.57PdO3、Li0.30Pr0.57PbO3、Li0.30Pr0.57RhO3、Li0.30Pr0.57SnO3、Li0.30Pr0.57VO3、Li0.30Pr0.57ReO3、Li0.30Pr0.57GeO3、Li0.30Pr0.57WO3、Li0.30Pr0.57ZrO3、Li0.30Pr0.57MoO3、Li0.30Pr0.57NbO3、Li0.30Pr0.57TaO3、Li0.30Pr0.57HfO3、Li0.30Pr0.57BiO3,
Li0.40Pr0.53MnO3、Li0.40Pr0.53NiO3、Li0.40Pr0.53CrO3、Li0.40Pr0.53CoO3、Li0.40Pr0.53IrO3、Li0.40Pr0.53RuO3、Li0.40Pr0.53FeO3、Li0.40Pr0.53PdO3、Li0.40Pr0.53PbO3、Li0.40Pr0.53RhO3、Li0.40Pr0.53SnO3、Li0.40Pr0.53VO3、Li0.40Pr0.53ReO3、Li0.40Pr0.53GeO3、Li0.40Pr0.53WO3、Li0.40Pr0.53ZrO3、Li0.40Pr0.53MoO3、Li0.40Pr0.53NbO3、Li0.40Pr0.53TaO3、Li0.40Pr0.53HfO3、Li0.40Pr0.53BiO3,
Li0.45Pr0.52MnO3、Li0.45Pr0.52NiO3、Li0.45Pr0.52CrO3、Li0.45Pr0.52CoO3、Li0.45Pr0.52IrO3、Li0.45Pr0.52RuO3、Li0.45Pr0.52FeO3、Li0.45Pr0.52PdO3、Li0.45Pr0.52PbO3、Li0.45Pr0.52RhO3、Li0.45Pr0.52SnO3、Li0.45Pr0.52VO3、Li0.45Pr0.52ReO3、Li0.45Pr0.52GeO3、Li0.45Pr0.52WO3、Li0.45Pr0.52ZrO3、Li0.45Pr0.52MoO3、Li0.45Pr0.52NbO3、Li0.45Pr0.52TaO3、Li0.45Pr0.52HfO3、Li0.45Pr0.52BiO3,
Li0.10Ca0.80MnO3、Li0.10Ca0.80NiO3、Li0.10Ca0.80CrO3、Li0.10Ca0.80CoO3、Li0.10Ca0.80IrO3、Li0.10Ca0.80RuO3、Li0.10Ca0.80FeO3、Li0.10Ca0.80PdO3、Li0.10Ca0.80PbO3、Li0.10Ca0.80RhO3、Li0.10Ca0.80SnO3、Li0.10Ca0.80VO3、Li0.10Ca0.80ReO3、Li0.10Ca0.80GeO3、Li0.10Ca0.80WO3、Li0.10Ca0.80ZrO3、Li0.10Ca0.80MoO3、Li0.10Ca0.80NbO3、Li0.10Ca0.80TaO3、Li0.10Ca0.80HfO3、Li0.10Ca0.80BiO3,
Li0.20Ca0.60MnO3、Li0.20Ca0.60NiO3、Li0.20Ca0.60CrO3、Li0.20Ca0.60CoO3、Li0.20Ca0.60IrO3、Li0.20Ca0.60RuO3、Li0.20Ca0.60FeO3、Li0.20Ca0.60PdO3、Li0.20Ca0.60PbO3、Li0.20Ca0.60RhO3、Li0.20Ca0.60SnO3、Li0.20Ca0.60VO3、Li0.20Ca0.60ReO3、Li0.20Ca0.60GeO3、Li0.20Ca0.60WO3、Li0.20Ca0.60ZrO3、Li0.20Ca0.60MoO3、Li0.20Ca0.60NbO3、Li0.20Ca0.60TaO3、Li0.20Ca0.60HfO3、Li0.20Ca0.60BiO3,
Li0.25Ca0.50MnO3、Li0.25Ca0.50NiO3、Li0.25Ca0.50CrO3、Li0.25Ca0.50CoO3、Li0.25Ca0.50IrO3、Li0.25Ca0.50RuO3、Li0.25Ca0.50FeO3、Li0.25Ca0.50PdO3、Li0.25Ca0.50PbO3、Li0.25Ca0.50RhO3、Li0.25Ca0.50SnO3、Li0.25Ca0.50VO3、Li0.25Ca0.50ReO3、Li0.25Ca0.50GeO3、Li0.25Ca0.50WO3、Li0.25Ca0.50ZrO3、Li0.25Ca0.50MoO3、Li0.25Ca0.50NbO3、Li0.25Ca0.50TaO3、Li0.25Ca0.50HfO3、Li0.25Ca0.50BiO3,
Li0.30Ca0.40MnO3、Li0.30Ca0.40NiO3、Li0.30Ca0.40CrO3、Li0.30Ca0.40CoO3、Li0.30Ca0.40IrO3、Li0.30Ca0.40RuO3、Li0.30Ca0.40FeO3、Li0.30Ca0.40PdO3、Li0.30Ca0.40PbO3、Li0.30Ca0.40RhO3、Li0.30Ca0.40SnO3、Li0.30Ca0.40VO3、Li0.30Ca0.40ReO3、Li0.30Ca0.40GeO3、Li0.30Ca0.40WO3、Li0.30Ca0.40ZrO3、Li0.30Ca0.40MoO3、Li0.30Ca0.40NbO3、Li0.30Ca0.40TaO3、Li0.30Ca0.40HfO3、Li0.30Ca0.40BiO3,
Li0.40Ca0.20MnO3、Li0.40Ca0.20NiO3、Li0.40Ca0.20CrO3、Li0.40Ca0.20CoO3、Li0.40Ca0.20IrO3、Li0.40Ca0.20RuO3、Li0.40Ca0.20FeO3、Li0.40Ca0.20PdO3、Li0.40Ca0.20PbO3、Li0.40Ca0.20RhO3、Li0.40Ca0.20SnO3、Li0.40Ca0.20VO3、Li0.40Ca0.20ReO3、Li0.40Ca0.20GeO3、Li0.40Ca0.20WO3、Li0.40Ca0.20ZrO3、Li0.40Ca0.20MoO3、Li0.40Ca0.20NbO3、Li0.40Ca0.20TaO3、Li0.40Ca0.20HfO3、Li0.40Ca0.20BiO3,
Li0.10Sr0.80MnO3、Li0.10Sr0.80NiO3、Li0.10Sr0.80CrO3、Li0.10Sr0.80CoO3、Li0.10Sr0.80IrO3、Li0.10Sr0.80RuO3、Li0.10Sr0.80FeO3、Li0.10Sr0.80PdO3、Li0.10Sr0.80PbO3、Li0.10Sr0.80RhO3、Li0.10Sr0.80SnO3、Li0.10Sr0.80VO3、Li0.10Sr0.80ReO3、Li0.10Sr0.80GeO3、Li0.10Sr0.80WO3、Li0.10Sr0.80ZrO3、Li0.10Sr0.80MoO3、Li0.10Sr0.80NbO3、Li0.10Sr0.80TaO3、Li0.10Sr0.80HfO3、Li0.10Sr0.80BiO3,
Li0.20Sr0.60MnO3、Li0.20Sr0.60NiO3、Li0.20Sr0.60CrO3、Li0.20Sr0.60CoO3、Li0.20Sr0.60IrO3、Li0.20Sr0.60RuO3、Li0.20Sr0.60FeO3、Li0.20Sr0.60PdO3、Li0.20Sr0.60PbO3、Li0.20Sr0.60RhO3、Li0.20Sr0.60SnO3、Li0.20Sr0.60VO3、Li0.20Sr0.60ReO3、Li0.20Sr0.60GeO3、Li0.20Sr0.60WO3、Li0.20Sr0.60ZrO3、Li0.20Sr0.60MoO3、Li0.20Sr0.60NbO3、Li0.20Sr0.60TaO3、Li0.20Sr0.60HfO3、Li0.20Sr0.60BiO3,
Li0.25Sr0.50MnO3、Li0.25Sr0.50NiO3、Li0.25Sr0.50CrO3、Li0.25Sr0.50CoO3、Li0.25Sr0.50IrO3、Li0.25Sr0.50RuO3、Li0.25Sr0.50FeO3、Li0.25Sr0.50PdO3、Li0.25Sr0.50PbO3、Li0.25Sr0.50RhO3、Li0.25Sr0.50SnO3、Li0.25Sr0.50VO3、Li0.25Sr0.50ReO3、Li0.25Sr0.50GeO3、Li0.25Sr0.50WO3、Li0.25Sr0.50ZrO3、Li0.25Sr0.50MoO3、Li0.25Sr0.50NbO3、Li0.25Sr0.50TaO3、Li0.25Sr0.50HfO3、Li0.25Sr0.50BiO3,
Li0.30Sr0.40MnO3、Li0.30Sr0.40NiO3、Li0.30Sr0.40CrO3、Li0.30Sr0.40CoO3、Li0.30Sr0.40IrO3、Li0.30Sr0.40RuO3、Li0.30Sr0.40FeO3、Li0.30Sr0.40PdO3、Li0.30Sr0.40PbO3、Li0.30Sr0.40RhO3、Li0.30Sr0.40SnO3、Li0.30Sr0.40VO3、Li0.30Sr0.40ReO3、Li0.30Sr0.40GeO3、Li0.30Sr0.40WO3、Li0.30Sr0.40ZrO3、Li0.30Sr0.40MoO3、Li0.30Sr0.40NbO3、Li0.30Sr0.40TaO3、Li0.30Sr0.40HfO3、Li0.30Sr0.40BiO3,
Li0.40Sr0.20MnO3、Li0.40Sr0.20NiO3、Li0.40Sr0.20CrO3、Li0.40Sr0.20CoO3、Li0.40Sr0.20IrO3、Li0.40Sr0.20RuO3、Li0.40Sr0.20FeO3、Li0.40Sr0.20PdO3、Li0.40Sr0.20PbO3、Li0.40Sr0.20RhO3、Li0.40Sr0.20SnO3、Li0.40Sr0.20VO3、Li0.40Sr0.20ReO3、Li0.40Sr0.20GeO3、Li0.40Sr0.20WO3、Li0.40Sr0.20ZrO3、Li0.40Sr0.20MoO3、Li0.40Sr0.20NbO3、Li0.40Sr0.20TaO3、Li0.40Sr0.20HfO3、Li0.40Sr0.20BiO3,
Li0.10Ba0.80MnO3、Li0.10Ba0.80NiO3、Li0.10Ba0.80CrO3、Li0.10Ba0.80CoO3、Li0.10Ba0.80IrO3、Li0.10Ba0.80RuO3、Li0.10Ba0.80FeO3、Li0.10Ba0.80PdO3、Li0.10Ba0.80PbO3、Li0.10Ba0.80RhO3、Li0.10Ba0.80SnO3、Li0.10Ba0.80VO3、Li0.10Ba0.80ReO3、Li0.10Ba0.80GeO3、Li0.10Ba0.80WO3、Li0.10Ba0.80ZrO3、Li0.10Ba0.80MoO3、Li0.10Ba0.80NbO3、Li0.10Ba0.80TaO3、Li0.10Ba0.80HfO3、Li0.10Ba0.80BiO3,
Li0.20Ba0.60MnO3、Li0.20Ba0.60NiO3、Li0.20Ba0.60CrO3、Li0.20Ba0.60CoO3、Li0.20Ba0.60IrO3、Li0.20Ba0.60RuO3、Li0.20Ba0.60FeO3、Li0.20Ba0.60PdO3、Li0.20Ba0.60PbO3、Li0.20Ba0.60RhO3、Li0.20Ba0.60SnO3、Li0.20Ba0.60VO3、Li0.20Ba0.60ReO3、Li0.20Ba0.60GeO3、Li0.20Ba0.60WO3、Li0.20Ba0.60ZrO3、Li0.20Ba0.60MoO3、Li0.20Ba0.60NbO3、Li0.20Ba0.60TaO3、Li0.20Ba0.60HfO3、Li0.20Ba0.60BiO3,
Li0.25Ba0.50MnO3、Li0.25Ba0.50NiO3、Li0.25Ba0.50CrO3、Li0.25Ba0.50CoO3、Li0.25Ba0.50IrO3、Li0.25Ba0.50RuO3、Li0.25Ba0.50FeO3、Li0.25Ba0.50PdO3、Li0.25Ba0.50PbO3、Li0.25Ba0.50RhO3、Li0.25Ba0.50SnO3、Li0.25Ba0.50VO3、Li0.25Ba0.50ReO3、Li0.25Ba0.50GeO3、Li0.25Ba0.50WO3、Li0.25Ba0.50ZrO3、Li0.25Ba0.50MoO3、Li0.25Ba0.50NbO3、Li0.25Ba0.50TaO3、Li0.25Ba0.50HfO3、Li0.25Ba0.50BiO3,
Li0.30Ba0.40MnO3、Li0.30Ba0.40NiO3、Li0.30Ba0.40CrO3、Li0.30Ba0.40CoO3、Li0.30Ba0.40IrO3、Li0.30Ba0.40RuO3、Li0.30Ba0.40FeO3、Li0.30Ba0.40PdO3、Li0.30Ba0.40PbO3、Li0.30Ba0.40RhO3、Li0.30Ba0.40SnO3、Li0.30Ba0.40VO3、Li0.30Ba0.40ReO3、Li0.30Ba0.40GeO3、Li0.30Ba0.40WO3、Li0.30Ba0.40ZrO3、Li0.30Ba0.40MoO3、Li0.30Ba0.40NbO3、Li0.30Ba0.40TaO3、Li0.30Ba0.40HfO3、Li0.30Ba0.40BiO3,
Li0.40Ba0.20MnO3、Li0.40Ba0.20NiO3、Li0.40Ba0.20CrO3、Li0.40Ba0.20CoO3、Li0.40Ba0.20IrO3、Li0.40Ba0.20RuO3、Li0.40Ba0.20FeO3、Li0.40Ba0.20PdO3、Li0.40Ba0.20PbO3、Li0.40Ba0.20RhO3、Li0.40Ba0.20SnO3、Li0.40Ba0.20VO3、Li0.40Ba0.20ReO3、Li0.40Ba0.20GeO3、Li0.40Ba0.20WO3、Li0.40Ba0.20ZrO3、Li0.40Ba0.20MoO3、Li0.40Ba0.20NbO3、Li0.40Ba0.20TaO3、Li0.40Ba0.20HfO3、Li0.40Ba0.20BiO3,
Li0.25La0.50MnO3、Li0.25La0.50NiO3、Li0.25La0.50CrO3、Li0.25La0.50CoO3、Li0.25La0.50IrO3、Li0.25La0.50RuO3、Li0.25La0.50FeO3、Li0.25La0.50PdO3、Li0.25La0.50PbO3、Li0.25La0.50RhO3、Li0.25La0.50SnO3、Li0.25La0.50VO3、Li0.25La0.50ReO3、Li0.25La0.50GeO3、Li0.25La0.50WO3、Li0.25La0.50ZrO3、Li0.25La0.50MoO3、Li0.25La0.50NbO3、Li0.25La0.50TaO3、Li0.25La0.50HfO3、Li0.25La0.50BiO3,
Li0.05La0.82Mn0.70O3、Li0.10La0.80Mn0.70O3、Li0.20La0.77Mn0.70O3、Li0.05La0.82Nb0.70O3、Li0.10La0.80Nb0.70O3、Li0.20La0.77Nb0.70O3、Li0.05La0.82Ta0.70O3、Li0.10La0.80Ta0.70O3、Li0.20La0.77Ta0.70O3、Li0.05La0.82V0.70O3、Li0.10La0.80V0.70O3、Li0.20La0.77V0.70O3、Li0.05La0.82W0.70O3、Li0.10La0.80W0.70O3、Li0.20La0.77W0.70O3、Li0.05La0.82Mo0.70O3、Li0.10La0.80Mo0.70O3、Li0.20La0.77Mo0.70O3、Li0.05La0.82Bi0.70O3、Li0.10La0.80Bi0.70O3、Li0.20La0.77Bi0.70O3、Li0.05La0.82Cr0.70O3、Li0.10La0.80Cr0.70O3、Li0.20La0.77Cr0.70O3、或
其组合。
10.如权利要求1所述的钙钛矿材料,其中所述钙钛矿材料为其中0≤δ≤1的Li0.34La0.55RuO3-δ、其中0≤δ≤1的Li0.34La0.55MnO3-δ、其中0≤δ≤1的Li0.34La0.55NiO3-δ、其中0≤δ≤1的Li0.34La0.55CrO3-δ、其中0≤δ≤1的Li0.34La0.55IrO3-δ、其中0≤δ≤1的Li0.34La0.55CoO3-δ、其中0≤δ≤1的Li0.34Ca0.58(Mn0.5W0.5)O3-δ、或其组合。
11.如权利要求1所述的钙钛矿材料,其中所述钙钛矿材料具有小于1的在46.5°±2.5°的衍射角2θ处的峰强度对在32.5°±2.5°的衍射角2θ处的峰强度的比率。
12.如权利要求1所述的钙钛矿材料,其中所述钙钛矿材料具有1X10-6西门子/厘米或更大的电子传导率和2X10-6西门子/厘米或更大的离子传导率。
13.如权利要求1所述的钙钛矿材料,其中式1的钙钛矿材料包括在钙钛矿结构的A位点上的空位和锂、氧缺陷,且
其中所述式1的钙钛矿材料具有斜方、立方、单斜或三斜晶体结构。
14.复合钙钛矿材料,其由式3表示且具有小于1的在46.5°±2.5°的衍射角2θ处的峰强度对在32.5°±2.5°的衍射角2θ处的峰强度的比率:
式3
LixAyMzO3-δ
其中,在式3中,0<x≤1,0<y≤1,0<x+y<1,0<z≤1.5,和0≤δ≤1,
A为H或者周期表的第2族至第16族元素的至少一种,且
M为周期表的第2族至第16族元素的至少一种。
15.如权利要求1或14所述的钙钛矿材料,其中所述钙钛矿材料具有小于1的在57.5°±2.5°的衍射角2θ处的峰强度对在32.5°±2.5°的衍射角2θ处的峰强度的比率。
16.制备如权利要求1-15任一项所述的钙钛矿材料的方法,所述方法包括:
提供包括锂化合物、含A元素的化合物、含M元素的化合物和溶剂的混合物;
第一热处理所述混合物以形成经第一热处理的混合物;
粉碎所述经第一热处理的混合物以获得成形产物;和
第二热处理所述成形产物以形成所述钙钛矿材料,
其中所述第二热处理的温度高于所述第一热处理的温度,
其中所述含A元素的化合物的A为H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、或其组合,且
所述含M元素的化合物的M为Ni、Pd、Pb、Fe、Ir、Co、Rh、Mn、Cr、Ru、Re、Sn、V、Ge、W、Zr、Mo、Hf、U、Nb、Th、Ta、Bi、Li、H、Na、K、Rb、Cs、Ca、Sr、Ba、Y、La、Ce、Pr、Nd、Pm、Sm、Gd、Tb、Dy、Ho、Er、Mg、Al、Si、Sc、Zn、Ga、Ag、Cd、In、Sb、Pt、Au、或其组合。
17.如权利要求16所述的方法,其中所述第一热处理在600℃至900℃的温度下进行。
18.如权利要求16所述的方法,其中所述第二热处理在900℃至1500℃的温度下进行。
19.如权利要求16所述的方法,其中所述钙钛矿材料具有100微米或更小的颗粒尺寸。
20.如权利要求16所述的方法,其中所述溶剂为乙醇、水、乙二醇或异丙醇的至少一种。
21.如权利要求16所述的方法,其中所述锂化合物为如下的至少一种:氧化锂、碳酸锂、氯化锂、硫化锂、硝酸锂、磷酸锂或氢氧化锂。
22.如权利要求16所述的方法,其中所述含A元素的化合物为如下的至少一种:氧化镧、碳酸镧、氯化镧、硫化镧、硝酸镧、磷酸镧、氢氧化镧、氧化钇、碳酸钇、氯化钇、硫化钇、氧化铈、碳酸铈、氯化铈、硫化铈、硝酸铈、磷酸铈、氢氧化铈、氧化钙、碳酸钙、氯化钙、硫化钙、硝酸钙、磷酸钙、氢氧化钙、氧化钡、碳酸钡、氯化钡、硫化钡、硝酸钡、磷酸钡、氢氧化钡、氧化锶、碳酸锶、氯化锶、硫化锶、硝酸锶、磷酸锶或氢氧化锶。
23.如权利要求16所述的方法,其中所述含M元素的化合物为如下的至少一种:氧化镍、氢氧化镍、氧化钴、氢氧化钴、氧化钌、氢氧化钌、氧化铬、氢氧化铬、氧化铱、氢氧化铱、氧化锰或氢氧化锰。
24.如权利要求16所述的方法,进一步包括在所述第二热处理之前压制所述成形产物以形成片。
25.二次电池,包括如权利要求1-15任一项所述的钙钛矿材料。
26.如权利要求25所述的二次电池,其中所述二次电池包括:
正极;
负极;以及
插入在所述正极和所述负极之间的气体阻挡层,
其中所述正极、或者所述正极和所述气体阻挡层各自包括所述钙钛矿材料。
27.如权利要求25所述的二次电池,其中所述二次电池包括:
正极;
负极;以及
插入在所述正极和所述负极之间的电解质,
其中所述正极、或者所述正极和所述电解质各自包括所述钙钛矿材料。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112952081A (zh) * | 2021-02-04 | 2021-06-11 | 复旦大学 | 一种锂离子电池层状钙钛矿结构负极材料及其制备方法 |
CN112968254A (zh) * | 2021-01-29 | 2021-06-15 | 东莞维科电池有限公司 | 一种锂离子电池用隔膜及其制备方法和锂离子电池 |
CN114142006A (zh) * | 2021-11-16 | 2022-03-04 | 昆明理工大学 | 一种高循环稳定性锂离子电池负极材料及其制备方法 |
CN114958033A (zh) * | 2022-04-11 | 2022-08-30 | 厦门稀土材料研究所 | 一种高近红外反射彩色颜料及其制备方法和应用 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102618549B1 (ko) * | 2018-10-24 | 2023-12-27 | 삼성전자주식회사 | 혼합전도체, 이를 포함하는 전기화학 소자 및 그 제조방법 |
CN111092229B (zh) | 2018-10-24 | 2024-05-31 | 三星电子株式会社 | 混合导体、包括其的电化学装置和制备混合导体的方法 |
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US11121377B2 (en) * | 2018-12-12 | 2021-09-14 | Samsung Electronics Co., Ltd. | Ionic-electronic conductive material, method of manufacturing same, and lithium-air battery comprising same |
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US11837696B2 (en) | 2019-12-13 | 2023-12-05 | Samsung Electronics Co., Ltd. | Solid electrolyte, preparation method thereof, metal air battery including the same, and electrochemical device including the same |
CN114806575A (zh) * | 2022-05-23 | 2022-07-29 | 龙岩学院 | 一种高效铋离子激活的黄色荧光材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060254677A1 (en) * | 2005-05-10 | 2006-11-16 | Mckinnell James | Substitutionally alloyed intermetallic compounds |
TW201301352A (zh) * | 2011-06-20 | 2013-01-01 | Advanced Tech Materials | 高k值鈣鈦礦材料及其製造與使用方法 |
US20130162109A1 (en) * | 2011-07-04 | 2013-06-27 | Taiyo Yuden Co., Ltd. | Piezoelectric ceramics and multi-layered piezoelectric ceramic components |
US20160190550A1 (en) * | 2014-12-29 | 2016-06-30 | Samsung Electronics Co., Ltd. | Composite cathode active material, cathode and lithium battery containing the composite cathode active material |
CN108206277A (zh) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | 改性高镍三元正极材料及其制备方法、锂离子电池 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07169456A (ja) | 1993-03-25 | 1995-07-04 | Ngk Insulators Ltd | リチウムイオン伝導体及びリチウム電池のカソード材料 |
US8563168B2 (en) | 2006-04-04 | 2013-10-22 | The Regents Of The University Of California | High elastic modulus polymer electrolytes |
WO2009092058A1 (en) | 2008-01-16 | 2009-07-23 | Seeo, Inc | Gel polymer electrolytes for batteries |
JP5184212B2 (ja) | 2008-05-26 | 2013-04-17 | 日本電信電話株式会社 | リチウム空気二次電池およびリチウム空気二次電池製造方法 |
US8269197B2 (en) | 2009-07-22 | 2012-09-18 | Intraop Medical Corporation | Method and system for electron beam applications |
JP2016213178A (ja) | 2015-04-30 | 2016-12-15 | 旭化成株式会社 | リチウムイオン伝導体及びこれを用いたリチウムイオン電池 |
KR101907730B1 (ko) | 2015-12-07 | 2018-12-07 | 주식회사 엘지화학 | 리튬 이차전지용 양극 첨가제 및 이를 포함하는 이차전지 |
FR3046498B1 (fr) | 2015-12-31 | 2019-11-29 | I-Ten | Batterie entierement solide comprenant un electrolyte solide et une couche de materiau conducteur ionique |
WO2017147793A1 (zh) * | 2016-03-01 | 2017-09-08 | 苏州大学张家港工业技术研究院 | 基于锂离子固体电解质的锂空气电池的制备方法 |
KR20170109374A (ko) | 2016-03-21 | 2017-09-29 | 주식회사 모비엔플렉스 | 금속 공기 이차전지용 양극 및 이를 포함하는 금속 공기 이차전지 |
US11848411B2 (en) * | 2018-10-11 | 2023-12-19 | Samsung Electronics Co., Ltd. | Cathode and lithium-air battery including the cathode |
KR20200041234A (ko) | 2018-10-11 | 2020-04-21 | 삼성전자주식회사 | 양극 및 이를 포함하는 리튬-공기 전지 |
US11837696B2 (en) * | 2019-12-13 | 2023-12-05 | Samsung Electronics Co., Ltd. | Solid electrolyte, preparation method thereof, metal air battery including the same, and electrochemical device including the same |
KR20210099434A (ko) * | 2020-02-04 | 2021-08-12 | 삼성전자주식회사 | 양극, 이를 포함하는 리튬-공기 전지 및 이의 제조 방법 |
-
2019
- 2019-09-27 CN CN201910921293.XA patent/CN111039333A/zh active Pending
- 2019-09-30 US US16/587,116 patent/US12009514B2/en active Active
- 2019-10-08 EP EP19201887.7A patent/EP3659972A3/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060254677A1 (en) * | 2005-05-10 | 2006-11-16 | Mckinnell James | Substitutionally alloyed intermetallic compounds |
TW201301352A (zh) * | 2011-06-20 | 2013-01-01 | Advanced Tech Materials | 高k值鈣鈦礦材料及其製造與使用方法 |
US20130162109A1 (en) * | 2011-07-04 | 2013-06-27 | Taiyo Yuden Co., Ltd. | Piezoelectric ceramics and multi-layered piezoelectric ceramic components |
US20160190550A1 (en) * | 2014-12-29 | 2016-06-30 | Samsung Electronics Co., Ltd. | Composite cathode active material, cathode and lithium battery containing the composite cathode active material |
CN108206277A (zh) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | 改性高镍三元正极材料及其制备方法、锂离子电池 |
Non-Patent Citations (2)
Title |
---|
MINHUA FANG 等: "The investigation of lithium doping perovskite oxide LiMnO3 as possible LIB anode material", 《CERAMICS INTERNATIONAL》, vol. 44, no. 7, pages 8223 - 8231, XP085357730, DOI: 10.1016/j.ceramint.2018.02.002 * |
孟广耀等: "《低温固体氧化物燃料电池》", 中国科学技术大学出版社, pages: 143 - 144 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112968254A (zh) * | 2021-01-29 | 2021-06-15 | 东莞维科电池有限公司 | 一种锂离子电池用隔膜及其制备方法和锂离子电池 |
CN112952081A (zh) * | 2021-02-04 | 2021-06-11 | 复旦大学 | 一种锂离子电池层状钙钛矿结构负极材料及其制备方法 |
CN114142006A (zh) * | 2021-11-16 | 2022-03-04 | 昆明理工大学 | 一种高循环稳定性锂离子电池负极材料及其制备方法 |
CN114142006B (zh) * | 2021-11-16 | 2023-12-01 | 昆明理工大学 | 一种高循环稳定性锂离子电池负极材料及其制备方法 |
CN114958033A (zh) * | 2022-04-11 | 2022-08-30 | 厦门稀土材料研究所 | 一种高近红外反射彩色颜料及其制备方法和应用 |
CN114958033B (zh) * | 2022-04-11 | 2024-01-02 | 厦门稀土材料研究所 | 一种高近红外反射彩色颜料及其应用 |
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