CN117728008A - Material and solid-state lithium battery including the same - Google Patents
Material and solid-state lithium battery including the same Download PDFInfo
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- CN117728008A CN117728008A CN202311206268.6A CN202311206268A CN117728008A CN 117728008 A CN117728008 A CN 117728008A CN 202311206268 A CN202311206268 A CN 202311206268A CN 117728008 A CN117728008 A CN 117728008A
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- 239000000463 material Substances 0.000 title claims abstract description 85
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 43
- 239000002223 garnet Substances 0.000 claims abstract description 37
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 25
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 22
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 21
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 7
- 239000002019 doping agent Substances 0.000 claims description 42
- 239000013078 crystal Substances 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims 2
- 239000000203 mixture Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 239000002243 precursor Substances 0.000 description 17
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 11
- 239000010955 niobium Substances 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000006641 stabilisation Effects 0.000 description 9
- 238000011105 stabilization Methods 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002001 electrolyte material Substances 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- -1 al 3+ Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical class [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to materials and solid state lithium batteries including the same. The lithium garnet material has a formula of Li 7+δ La 3 Zr 2‑x‑y‑ z M1 x M2 y M3 z O 12 Wherein M1 is one or a combination of (Y, in, mg, ca, ba, sc, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, sn, si) having an oxidation number (valence) equal to +4, provided that 0<x≤1，0<y≤1，0≤z≤2，0<x+y+z is less than or equal to 2 and is-0.2<δ<0.2. Also provided is a lithium garnet material which is the same as the aforementioned lithium garnet material except for the following: m1 is one or a combination of (Y, in, mg, ca, ba, sr, ru) and M2 is one or a combination of (Bi, ta, nb, mo, sb, te, W). The lithium oxide solid electrolyte material has the same formula as the aforementioned lithium garnet material, but also includes Ge for M3.
Description
Cross reference to related applications
The present application is based on and claims priority from U.S. provisional application No.63/407,528 filed by the U.S. patent and trademark office at day 2022, 9, and 16, and U.S. provisional application No.63/421,281 filed by day 2022, 11, and the disclosures of which are incorporated herein by reference in their entirety.
Technical Field
The material according to the embodiment relates to a solid electrolyte material for Li solid-state batteries.
Background
Solid electrolyte materials are an essential component of solid state Li-ion batteries because they enable Li ion transport while hindering the formation of Li metal dendrites that can short the device. Oxide-based solid electrolytes are particularly desirable due to advantageous properties such as high hardness, and electrochemical stability to air and Li metal. However, oxide electrolytes typically have lower conductivities for Li ions relative to liquid, gel, or sulfide electrolytes, limiting the use of these materials.
Due to its high conductivity and broad electrochemical stability window, li-garnet (LLZO) is one of the most promising kinds of oxide materials for use as solid electrolytes for Li solid state batteries.
However, undoped Li-garnet (Li 7 La 3 Zr 2 O 12 ) A tetragonal crystal structure is adopted at room temperature, which does not provide sufficient Li ion conductivity for practical use in a solid-state battery.
The main strategy to address this is to introduce alternative (substitutional) dopants that stabilize the high temperature cubic crystal structure, which can produce room temperature conductivities in excess of 1 mS/cm.
In particular, some approaches include the following: (1) Ta-LLZO/Nb-LLZO: has a cubic phase stabilized byIs a Li-garnet of (C): substituting Ta or Nb for Zr induces Li vacancies. The composition includes Li 7-x La 3 Ta x Zr 2-x O 12 And Li (lithium) 7-x La 3 Nb x Zr 2- x O 12 Wherein x is 0.4. (2) Al-LLZO/Ga-LLZO: li-garnet having a cubic phase stabilized by: al or Ga is used instead of Li. The composition includes Li 7-3x Al x La 3 Zr 2 O 12 And Li (lithium) 7-3x Ga x La 3 Zr 2 O 12 Wherein x is 0.2. (3) Li (Li) 7- 3x M1 x M2 y M3 2-y M4O 12 ，M1：Al，M2：Nb、Ta、Sb、Bi，M3：Zr，M4：La。
A widely accepted method for improving Li ion conductivity of Li-garnet is substitution doping, which induces Li vacancies exceeding 0.4 per formula unit (cell), resulting in stabilization of the high Wen Lifang LLZO phase at room temperature. Examples of Zr site doping: li (Li) 6.5 La 3 Zr 1.5 Ta 0.5 O 12 、Li 6.5 La 3 Zr 1.5 Nb 0.5 O 12 . Examples of Li site doping: li (Li) 6.4 Al 0.2 La 3 Zr 2 O 12 、Li 6.4 Ga 0.2 La 3 Zr 2 O 12 。
In particular, a widely used method for stabilizing the cubic LLZO structure is by substitution of higher valence elements, which induce the formation of Li vacancies of at least 0.5/formula unit, e.g., at Z r4+ Having Ta in the site 5+ Li of dopant 6.5 La 3 Zr 1.5 Ta 0.5 O 12 And in Li + Having Al in the site 3+ Li of dopant 6.4 Al 0.2 La 3 Zr 2 O 12 。
However, disadvantages of the doping method inducing Li vacancies include: a reduction in achievable conductivity due to reduced Li content; li site dopants (e.g., al 3+ 、Fe 3+ 、Ga 3+ ) Li can be reduced by occupying sites for Li ion hoppingIon conductivity; and the higher cost of many elements for substitution doping.
Therefore, there is a need for improvement of materials used as solid electrolytes for Li solid-state batteries.
The information disclosed in this background section is already known or available to the inventors before or during the course of carrying out an embodiment of the present application or is technical information obtained during the course of carrying out an embodiment. Thus, it may contain information that does not form the prior art already known to the public
Disclosure of Invention
The disclosure provides a material used as a solid electrolyte for a Li solid-state battery according to an embodiment.
According to one embodiment, there is a lithium garnet material composition with a new doping strategy that introduces multiple dopants into the parent Li 7 La 3 Zr 2 O 12 In the material, it stabilizes the cubic LLZO structure without inducing Li vacancies. The potential benefits of this multi-dopant strategy are: (1) higher conductivity due to higher retained Li content, (2) higher stability due to entropy benefits associated with larger amounts of dopants, and (3) lower cost because the synergistic effect of multiple dopants allows for the use of lower cost elements.
One embodiment includes a new cubic phase lithium garnet material composition by: substitution of precursor Li with multiple aliovalent cationic dopants 7 La 3 Zr 2 O 12 Zr in the material such that the total Li content remains 7/chemical formula unit. To stabilize the cubic LLZO phase, at least one dopant is selected from +2 and +3 cations (Y, in, mg, ca, ba, sc, sr, ru) and at least one dopant is selected from +5 and +6 cations (Ta, nb, mo, sb, te) such that the total oxidation state of all Zr substitutes averages +4 and the Li stoichiometry of the material is unchanged. Entropy stabilization can also be enhanced by additional substitution of Zr with equivalent dopants by group (Hf, ti, sn, si) as long as stabilization of the cubic LLZO phase is maintained.
One embodiment demonstrates a way to stabilize a cubic garnet having a Li content of 7/formula units by: zr (+4) is replaced with a combination of subtance (+2 and +3) and superance (superance) cations (+5, +6) to maintain the overall charge balance in the Zr sites.
Thus, one embodiment includes a material having the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sc, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te, W) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, ge, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
Another embodiment of the material includes a lithium garnet material having the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sc, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
Another embodiment of the material includes a lithium garnet material having the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te, W) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
Another embodiment of the material includes a lithium oxide solid state electrolyte material comprising:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
wherein:
m1 is one or a combination of sub-valent +2 or +3Zr dopants (Y, in, mg, ca, ba, sc, sr, ru),
m2 is one or a combination of supervalent +5 or +6Zr dopants (Bi, ta, nb, mo, sb, te), M3 is one or a combination of equivalent +4Zr dopants (Ti, hf, ge, sn, si),
0< x < 1,0< y < 1,0< z < 2,0< x+y+z < 2, and-0.2 < delta <0.2, and
the material has a cubic LLZO crystal structure that is stable at room temperature.
Another embodiment of the material includes a lithium oxide solid state electrolyte material comprising:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
wherein:
m1 is one or a combination of sub-valent +2 or +3Zr dopants (Y, in, mg, ca, ba, sr, ru),
m2 is one or a combination of supervalent +5 or +6Zr dopants (Bi, ta, nb, mo, sb, te, W),
m3 is one or a combination of equivalent +4Zr dopants (Ti, hf, ge, sn, si),
0< x < 1,0< y < 1,0< z < 2,0< x+y+z < 2, and-0.2 < delta <0.2, and
the material has a cubic LLZO crystal structure that is stable at room temperature.
Another embodiment of the material includes a material that maintains a cubic LLZO phase at room temperature and has the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sc, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
Another embodiment of the material includes a material that maintains a cubic LLZO phase at room temperature and has the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te, W) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
Another embodiment is a solid state lithium battery, comprising: a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer, wherein the solid electrolyte layer comprises any of the foregoing materials.
Drawings
The patent or application document contains at least one drawing produced in color. Copies of this patent or patent application publication with color drawings will be provided by the office upon request and payment of the necessary fee.
Example embodiments of the inventive concepts will be more clearly understood from the following detailed description considered in conjunction with the accompanying drawings, in which:
figure 1 is an XRD pattern with a Rietveld finish for example 3,
figure 2 is an XRD pattern with a litverdet finish for example 4,
FIG. 3 is an XRD pattern with a Riteville finish for comparative example 2, an
Fig. 4 is an XRD pattern with a ritverdet finish for comparative example 7.
Detailed Description
The embodiments of the disclosure described herein are example embodiments, and thus, the disclosure is not limited thereto, and may be implemented in a variety of other forms. The implementations provided in the following description each do not preclude association with one or more features of additional examples or additional implementations that are also or are not provided herein but are consistent with the disclosure. For example, even if a substance (thing) described in one specific example or embodiment is not described in a different example or embodiment thereof, the substance (thing) may be understood as being related to or combined with the different example or embodiment unless otherwise mentioned in the description thereof. Further, it is to be understood that all statements of the principles, aspects, examples, and embodiments of the present disclosure are intended to encompass both structural and functional equivalents thereof. Additionally, these equivalents should be understood to include not only currently known equivalents but also equivalents developed in the future.
As used herein, the expression "at least one of" when preceding or following a list of elements, modifies the entire list of elements and does not modify individual elements of the list. For example, the expression "at least one (a)," of a, b and c "should be understood to include: only a, only b, only c, both a and b, both a and c, both b and c, or all of a, b and c. In this document, when the term "same" is used to compare the dimensions of two or more elements, the term may cover "substantially the same" dimensions.
Li-garnet materials have great technical utility (relevance) due to their potential application as solid electrolyte materials for Li-ion batteries, due to their high hardness, broad electrochemical stability and high Li-ion conductivity. However, base material Li 7 La 3 Zr 2 O 12 A tetragonal crystal structure of low conductivity is formed at room temperature, and thus needs to be changed to achieve Li ion conductivity sufficient for application as a solid electrolyte. As described above, a widely used method for improving the conductivity of Li garnet is by introducing a dopant inducing Li vacancies, which results in stabilization of the cubic phase of high conductivity. The most relevant example for this is with Ta 5+ Or Nb (Nb) 5+ Replacement of Zr 4+ (e.g. Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 、Li 6.5 La 3 Zr 1.5 Nb 0.5 O 12 ) Or with Al 3+ 、Fe 3+ Or Ga 3+ Substitution of Li + (e.g. Li 6.4 Al 0.2 La 3 Zr 2 O 12 、Li 6.4 Fe 0.2 La 3 Zr 2 O 12 、Li 6.4 Ga 0.2 La 3 Zr 2 O 12 ). Stabilization of cubic garnet by this method has been shown to occur when Li vacancies of at least 0.5/formula unit are induced instead.
An alternative route to stabilization of cubic garnet without significant Li vacancy generation is the following embodiment: which includes stabilization by cubic garnet without the generation of significant amounts of Li vacancies as follows: substitution of Zr in lithium garnet structures with multiple aliovalent cations 4+ . The multiple cation substitutions create disorder that stabilizes the cubic garnet phase at room temperature while maintaining the Li content at about 7/chemical formula unit. The key approach to this embodiment is to include at least one over-valence (+5 and +6) dopant and at least one sub-valence (+2 and +3) dopant (taken from the list in table 1 below) such that the overall charge balance is maintained without changing the Li content of the material.
Table 1: list of candidate dopants
The benefits of the multi-cation substitution method are:
1) Higher conductivity of cubic Li-garnet electrolyte due to higher retained Li content relative to cubic garnet stabilized via Li vacancy formation;
2) Due to the higher configurational entropy, the resistance to electrochemical decomposition is increased, leading to thermodynamic stabilization of the material; and
3) The ability to introduce sub-valent +2 and +3 dopants into Zr sites has potential benefits to cost or desirable secondary properties of the material. Substitution of Zr with a divalent element is generally not feasible in this material, as charge balancing would require Li >7, which is very energetically unfavorable.
Thus, in general, one embodiment includes a material having the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sc, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te, W) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, ge, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
The materials in one embodiment are thus those of the cubic LLZO phase that maintain high conductivity at room temperature and have the compositional formula of the form:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sc, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
The materials in another embodiment are thus those of the cubic LLZO phase that maintain high conductivity at room temperature and have the compositional formula of the form:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te, W) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
Accordingly, one embodiment includes a lithium garnet material having the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sc, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
Another embodiment includes a lithium garnet material having the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is one or a combination of (Y, in, mg, ca, ba, sr, ru) having an oxidation number (valence) below +4, M2 is one or a combination of (Bi, ta, nb, mo, sb, te, W) having an oxidation number (valence) above +4, and M3 is one or a combination of (Hf, ti, sn, si) having an oxidation number (valence) equal to +4, provided that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
Another embodiment includes a lithium oxide solid state electrolyte material comprising:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
wherein:
m1 is one or a combination of sub-valent +2 or +3Zr dopants (Y, in, mg, ca, ba, sc, sr, ru),
m2 is one or a combination of supervalent +5 or +6Zr dopants (Bi, ta, nb, mo, sb, te), M3 is one or a combination of equivalent +4Zr dopants (Ti, hf, ge, sn, si),
0< x < 1,0< y < 1,0< z < 2,0< x+y+z < 2, and-0.2 < delta <0.2, and
the material has a cubic LLZO crystal structure that is stable at room temperature.
Another embodiment includes a lithium oxide solid state electrolyte material comprising:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
wherein:
m1 is one or a combination of sub-valent +2 or +3Zr dopants (Y, in, mg, ca, ba, sr, ru),
m2 is one or a combination of supervalent +5 or +6Zr dopants (Bi, ta, nb, mo, sb, te, W),
m3 is one or a combination of equivalent +4Zr dopants (Ti, hf, ge, sn, si),
0< x < 1,0< y < 1,0< z < 2,0< x+y+z < 2, and-0.2 < delta <0.2, and
the material has a cubic LLZO crystal structure that is stable at room temperature.
M1 is preferably one or a combination of two or more of Y, mg, and Ca. In a preferred embodiment, M1 is one or a combination of Y and Mg, or one or a combination of Ca and Mg. In a preferred embodiment, M1 is one of Y, mg, and Ca. In a preferred embodiment, M1 is Y. In another preferred embodiment, M1 is Mg. In a further preferred embodiment, M1 is Ca.
M2 is preferably one or a combination of two or more of Ta, nb, and Sb. In a preferred embodiment, M2 is one of Ta, nb, and Sb. In a preferred embodiment, M2 is Ta. In another preferred embodiment, M2 is Nb. In a further preferred embodiment, M2 is Sb.
M3 is preferably one or a combination of two or more of Sn, hf, and Ge. In a preferred embodiment, M3 is Sn.
In a preferred embodiment, 0< x.ltoreq.0.5. In another preferred embodiment, 0< x.ltoreq.0.25. In another preferred embodiment, 0.25.ltoreq.x.ltoreq.0.5. In a preferred embodiment, 0< y.ltoreq.0.5. In another preferred embodiment, 0< y.ltoreq.0.25. In another preferred embodiment, 0.25.ltoreq.y.ltoreq.0.5. In a preferred embodiment, 0.ltoreq.z.ltoreq.1.25. In another preferred embodiment, 0.ltoreq.z.ltoreq.0.75. In a further preferred embodiment, 0.ltoreq.z.ltoreq.0.50. In a further preferred embodiment, 0.ltoreq.z.ltoreq.0.25.
The method for preparing the oxide is a solid state method. In this method, precursor powders are combined in a ratio that depends on the composition of the target material. In a typical preparation, the precursor may consist of: lithium carbonate, lanthanum hydroxide, zirconium oxide, and at least one precursor containing each of the included metals M1, M2, and M3. Examples of metal precursors include metal oxides, hydroxides, carbonates, and nitrates. In particular, the compounds described in the present invention can be prepared using, for example, the following as sources of relevant metal ions: the precursors tantalum oxide, niobium oxide, bismuth oxide, molybdenum oxide, tungsten oxide, tellurium hydroxide, titanium oxide, tin oxide, hafnium oxide, germanium oxide, silicon oxide, indium oxide, scandium oxide, barium carbonate, magnesium carbonate, calcium carbonate, and strontium carbonate.
The precursor mixture may be mixed by a method such as ball milling or planetary milling to produce a homogeneous mixture. Mixing may be performed with a suitable solvent such as ethanol, isopropanol, ethylene glycol, or acetone to aid in uniform dispersion of the precursor.
The precursor mixture may then be heat treated at a temperature of 600 ℃ to 1100 ℃ for a time of 1 hour to 48 hours to produce an oxide powder having the desired composition and crystal structure.
The oxide powder may then be compressed using a uniaxial hydraulic press to form densely packed sheets (disks). Heat treatment may then be applied at a temperature of about 900-1500 ℃ for 1-48 hours to produce a dense sheet that may be used as a solid electrolyte in a solid state lithium battery cell (cell).
For example, the calcined powder may be formed into a sheet by applying a uniaxial pressure of 100-500 MPa. The sheet may then be heat treated at 1200 ℃ for 2 hours to form a dense sintered solid electrolyte suitable for use in a lithium battery cell.
As an example of manufacturing a battery full cell using a garnet solid electrolyte and a Li-metal anode, an ionic liquid electrolyte may be used as the positive electrode electrolyte (catholyte) and a garnet oxide electrolyte may be used as the Li-metal anode electrolyte (anolyte). First, 20 μm thick Li Metal (Honjo Metal co., ltd.) on a 10 μm thick Cu foil can be attached to the protonated surface of the LLZO piece by cold isostatic pressing at 250 MPa. Commercially available NCM111 electrode (Supported: 3.2g cm) -3 Active material: 93 wt.%; samsung SDI) was coated on an Al foil as a positive electrode. Ionic liquid Pyr13FSI (Kanto Chemical co.inc.) can be mixed with LiFSI salt (2M) to prepare a catholyte. The mixed solution may be dropped onto the positive electrode and then infiltrated into the positive electrode under vacuum for 2 hours. The penetration amount of the ionic liquid may be 20 wt% with respect to the weight of the positive electrode. The infiltrated positive electrode may be placed on the other side of the LLZO sheet in a 2032-coin cell. To eliminate the possibility of direct contact between the ionic liquid and the Li metal, a relatively small positive electrode (0.4 cm in diameter) may be used for the hybrid electrolyte cell. Finally, the cell use pouch may be sealed under vacuum.
A 110 micron chip of LLZO (garnet) may be used. Even thinner sheets can be desirably manufactured by a method like tape casting up to 20 microns. The garnet electrolyte may have a thickness in the range of 20-150 microns. The garnet electrolyte has an additional thickness in the range of 20-110 microns.
Embodiments of the foregoing materials may be assembled with a positive electrode active material layer and a negative electrode active material layer for use in embodiments as a solid state lithium battery comprising: a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer, wherein the solid electrolyte layer comprises any of the foregoing materials.
Examples
Embodiments will now be illustrated by the following examples, which are not in any way limiting.
Various examples of Li-garnet having various heterovalent dopants substituting for Zr were synthesized using standard solid state methods according to substitution rules in embodiments, as described below.
A broad list of the compositions tested and XRD results are included in table 2 to demonstrate the broad applicability of the heterovalent polycation doping strategy in this material. The tested compositions included in table 2 were prepared in the following manner.
Example 1
Preparation of Compound Li using precursor powders lithium carbonate, lanthanum hydroxide, zirconium oxide, yttrium oxide, and antimony oxide mixed in stoichiometric proportions 7 La 3 Y 0.25 Zr 1.5 Sb 0.25 O 12 It is the target composition of example 1, wherein 5-50% excess lithium precursor is added to mitigate lithium evaporation during heat treatment. The precursor powder was then treated in a planetary mill using zirconium dioxide mixing balls at 350rpm for 24 hours. The precursor mixture was then heat treated at 1000 ℃ for 8 hours to produce a powder of the desired composition and crystal structure.
Examples 2 to 6 and comparative examples 1 to 9
The compounds described in examples 2-6 and comparative examples 1-9 were prepared in a similar manner to that described above in example 1, but using the precursors tantalum oxide, niobium oxide, titanium oxide, tin oxide, silicon oxide, magnesium carbonate, and calcium carbonate as sources of the relevant metal ions.
The synthesized material was characterized via XRD to confirm the presence of cubic garnet phase at room temperature, and SEM/EDS to confirm that dopants had been incorporated into the parent structure. As a control, as described above, a number of samples of undoped Li garnet material and multi-doped Li garnet with Zr replaced by multiple equivalent dopants (Hf, ti, sn, si) were also synthesized. In all cases, in undoped materials or equivalent polycation doping, the materials demonstrate formation of a low conductivity tetragonal phase by XRD, confirming that the introduction of an aliovalent dopant is necessary for stabilization of the cubic phase. The results are shown in table 2 below. XRD patterns with ritwald refinement for selected samples are shown in fig. 1-4, illustrating the tetragonal structure of undoped and equivalent polycationic doped materials and the cubic structure of aliovalent polycationic doped materials. In particular, fig. 1-4 show XRD results for representative samples with a ritverdet refinement fit for cubic LLZO and tetragonal LLZO, as follows. Fig. 1 shows the positive results: by using Y 3+ 、Nb 5+ Aliovalent Zr site doped and stabilized cubic LLZO (example 3); fig. 2 shows the positive results: by using Ca 2+ 、Ta 5+ Aliovalent Zr site doped and stabilized cubic LLZO (example 4); fig. 3 shows negative results: with Ti used 4 + 、Sn 4+ Tetragonal LLZO doped with equivalent Zr sites (comparative example 2); and figure 4 shows negative results: undoped tetragonal LLZO (comparative example 7).
Table 2: list of synthesized compositions and XRD-fitted results
| Sample ID | Target composition | Zr doping type | LLZO phase (purity) |
| Example 1 | Li 7 La 3 Y 0.25 Zr 1.5 Sb 0.25 O 12 | Alien valence | Cube (95 wt.%) |
| Example 2 | Li 7 La 3 Y 0.25 Zr 1.5 Ta 0.25 O 12 | Alien valence | Cube (89 wt.%) |
| Example 3 | Li 7 La 3 Y 0.25 Zr 1.5 Nb 0.25 O 12 | Alien valence | Cube (94 wt.%) |
| Example 4 | Li 7 La 3 Ca 0.25 Zr 1.25 Ta 0.5 O 12 | Alien valence | Cube (97 wt.%) |
| Example 5 | Li 7 La 3 Mg 0.25 Zr 1.25 Nb 0.5 O 12 | Alien valence | Cube (98 wt.%) |
| Example 6 | Li 7 La 3 Mg 0.25 Zr 1.25 Ta 0.5 O 12 | Alien valence | Cube (98 wt.%) |
| Comparative example 1 | Li 7 La 3 Ti 0.25 Zr 1.5 Sn 0.25 O 12 | Equivalent(s) | Tetragonal (100 wt.%) |
| Comparative example 2 | Li 7 La 3 Ti 0.25 Zr 1.25 Sn 0.5 O 12 | Equivalent(s) | Tetragonal (100 wt.%) |
| Comparative example 3 | Li 7 La 3 Si 0.25 Zr 1.25 Sn 0.5 O 12 | Equivalent(s) | Square (97 wt.%) |
| Comparative example 4 | Li 7 La 3 Ti 0.25 ZrSn 0.75 O 12 | Equivalent(s) | Square (99 wt.%) |
| Comparative example 5 | Li 7 La 3 Ti 0.25 Zr 0.5 Sn 1.25 O 12 | Equivalent(s) | Tetragonal (100 wt.%) |
| Comparative example 6 | Li 7 La 3 Ti 0.5 Zr 0.5 SnO 12 | Equivalent(s) | Square (97 wt.%) |
| Comparative example 7 | Li 7 La 3 Zr 2 O 12 | Undoped, undoped | Square (99 wt.%) |
| Comparative example 8 | Li 7 La 3 Zr 2 O 12 | Undoped, undoped | Square (99 wt.%) |
| Comparative example 9 | Li 7 La 3 Zr 2 O 12 | Undoped, undoped | Square (98 wt.%) |
As shown above, table 2 presents the synthesized composition and a list showing XRD-fitted results of LLZO phase purity and crystal structure. In all cases, the aliovalent Zr site doping stabilizes the cubic LLZO while maintaining a nominal Li content of 7/formula unit, while the equivalent doped and undoped samples produce tetragonal LLZO at room temperature.
Examples 7 and 8 and comparative example 10
The compounds described in examples 7 and 8 and comparative example 10 were prepared in a similar manner to that described above in example 1, but with the use of precursor powders lithium carbonate, lanthanum hydroxide, zirconia, tantalum oxide, and magnesium carbonate in example 7, precursor powders lithium carbonate, lanthanum hydroxide, zirconia, tantalum oxide, and yttria in example 8, and precursor powders lithium carbonate, lanthanum hydroxide, and zirconia in comparative example 10 (undoped LLZO). Further, the samples were sintered at 1200 ℃ for 8 hours, and then the room temperature conductivity of each sample was measured, and the obtained results are shown in table 3 below.
Table 3: conductivity results
| Sample ID | Composition of the composition | Sintering | Conductivity at room temperature |
| Example 7 | Li 7 La 3 Zr 1.25 Mg 0.25 Ta 0.5 O 12 | 1200℃，8h | 2.8x10 -5 S/cm |
| Example 8 | Li 7 La 3 ZrY 0.5 Ta 0.5 O 12 | 1200℃，8h | 8.9x10 -6 S/cm |
| Comparative example 10 | Li 7 La 3 Zr 2 O 12 | 1200℃，8h | 2.1x10 -7 S/cm |
As can be seen from the results set forth in table 3, both Mg-Ta-LLZO and Y-Ta-LLZO compositions have significantly higher conductivities than undoped LLZO, with an improvement of >40x for Y-Ta-LLZO and >100x for Mg-Ta-LLZO. Furthermore, samples sintered at 1100 ℃ showed similar trends, but much lower conductivities than those sintered at 1200 ℃.
Experimental results demonstrate the utility of the disclosed multi-doping strategy and the superior properties of the disclosed multi-doped samples.
Thus, as described above, focus has been on having a new doping strategy (which introduces multiple dopants into the parent Li 7 La 3 Zr 2 O 12 Among materials, embodiments of new lithium garnet material compositions that stabilize the cubic LLZO structure without inducing Li vacancies) have potential advantages including: (1) higher conductivity due to higher retained Li content, (2) higher stability due to entropy benefits associated with larger amounts of dopants, and (3) lower cost, because the synergistic effect of multiple dopants allows for the use of lower cost elements.
The foregoing is illustrative of exemplary embodiments and is not to be construed as limiting the disclosure. Although a few exemplary embodiments have been described, those skilled in the art will readily appreciate that many modifications are possible in the above embodiments without materially departing from the disclosure.
Claims (16)
1. A material having the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
wherein M1 is Y, in, mg, ca, ba, sc, sr having an oxidation number below +4, and Ru, M2 is Bi, ta, nb, mo, sb, te having an oxidation number above +4, and W, and M3 is Hf, ti, ge, sn having an oxidation number equal to +4, and Si, with the proviso that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
2. The material of claim 1, wherein the material is a lithium garnet material having the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is Y, in, mg, ca, ba, sc, sr having an oxidation number below +4, and Ru, M2 is Bi, ta, nb, mo, sb having an oxidation number above +4, and Te, and M3 is Hf, ti, sn, and Si, having an oxidation number equal to +4, with the proviso that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
3. The material of claim 1, wherein the material is a lithium garnet material having the formula:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
where M1 is Y, in, mg, ca, ba, sr having an oxidation number below +4, and Ru, M2 is Bi, ta, nb, mo, sb, te having an oxidation number above +4, and W, and M3 is Hf, ti, sn, and Si, having an oxidation number equal to +4, with the proviso that 0< x.ltoreq.1, 0< y.ltoreq.1, 0.ltoreq.z.ltoreq.2, 0< x+y+z.ltoreq.2, and-0.2 < delta <0.2.
4. The material of claim 1, wherein the material is a lithium oxide solid electrolyte material comprising:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
wherein:
m1 is one or a combination of two or more of a valence +2 or +3Zr dopant selected from Y, in, mg, ca, ba, sc, sr, and Ru,
m2 is one or a combination of two or more of the supervalent +5 or +6Zr dopants selected from Bi, ta, nb, mo, sb, and Te,
m3 is one or a combination of two or more of the equivalent +4zr dopants selected from Ti, hf, ge, sn, and Si,
0< x < 1,0< y < 1,0< z < 2,0< x+y+z < 2, and-0.2 < delta <0.2, and
the material has a cubic LLZO crystal structure that is stable at room temperature.
5. The material of claim 1, wherein the material is a lithium oxide solid electrolyte material comprising:
Li 7+δ La 3 Zr 2-x-y-z M1 x M2 y M3 z O 12
wherein:
m1 is one or a combination of two or more of a valence +2 or +3Zr dopant selected from Y, in, mg, ca, ba, sr, and Ru,
m2 is one or a combination of two or more of the supervalent +5 or +6Zr dopants selected from Bi, ta, nb, mo, sb, te, and W,
m3 is one or a combination of two or more of the equivalent +4zr dopants selected from Ti, hf, ge, sn, and Si,
0< x < 1,0< y < 1,0< z < 2,0< x+y+z < 2, and-0.2 < delta <0.2, and
the material has a cubic LLZO crystal structure that is stable at room temperature.
6. A material as claimed in claim 2 or 3, wherein the material retains a cubic LLZO phase at room temperature.
7. The material of claim 1, wherein M1 comprises Y.
8. The material of claim 1, wherein M1 comprises Mg.
9. The material of claim 1, wherein M1 comprises Ca.
10. The material of claim 1, wherein M2 comprises Nb.
11. The material of claim 1, wherein M2 comprises Sb.
12. The material of claim 7, 8 or 9, wherein M2 comprises at least one of Sb, ta, and Nb.
13. The material of claim 7, 8 or 9, wherein M2 comprises at least one of Ta and Nb.
14. The material of claim 1, 7, 8, or 9, wherein M2 comprises Ta.
15. A solid-state lithium battery comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer, wherein the solid electrolyte layer comprises the material of any one of claims 1-14.
16. The solid state lithium battery of claim 15, wherein the solid electrolyte layer has a thickness of 20-150 microns.
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| US18/113,417 US20240097184A1 (en) | 2022-09-16 | 2023-02-23 | ALIOVALENT MULTI-CATION DOPING OF Li-GARNET FOR STABILIZATION OF CUBIC LLZO |
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