CN114497710A - Cubic phase garnet type solid electrolyte material, composite solid electrolyte, solid lithium battery and preparation method thereof - Google Patents
Cubic phase garnet type solid electrolyte material, composite solid electrolyte, solid lithium battery and preparation method thereof Download PDFInfo
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- CN114497710A CN114497710A CN202111591983.7A CN202111591983A CN114497710A CN 114497710 A CN114497710 A CN 114497710A CN 202111591983 A CN202111591983 A CN 202111591983A CN 114497710 A CN114497710 A CN 114497710A
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- Prior art keywords
- solid electrolyte
- electrolyte material
- lithium
- source
- composite
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 204
- 239000000463 material Substances 0.000 title claims abstract description 107
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002223 garnet Substances 0.000 title claims abstract description 46
- 239000007787 solid Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 239000012528 membrane Substances 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 33
- 239000003792 electrolyte Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000002001 electrolyte material Substances 0.000 claims description 16
- 238000007731 hot pressing Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
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- 229910052719 titanium Inorganic materials 0.000 claims description 4
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- 229910019142 PO4 Inorganic materials 0.000 claims description 3
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- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
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- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
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- 239000010452 phosphate Substances 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 5
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- 238000004898 kneading Methods 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 70
- 229910052808 lithium carbonate Inorganic materials 0.000 description 39
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 33
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 28
- 229910001416 lithium ion Inorganic materials 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 16
- 239000000395 magnesium oxide Substances 0.000 description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 15
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 15
- 239000002033 PVDF binder Substances 0.000 description 14
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910013716 LiNi Inorganic materials 0.000 description 12
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 12
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
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- 210000001787 dendrite Anatomy 0.000 description 4
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
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- 210000004027 cell Anatomy 0.000 description 2
- 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 2
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- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
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- 238000001238 wet grinding Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention relates to the technical field of lithium batteries, and discloses a cubic phase garnet type solid electrolyte material, a composite solid electrolyte, a solid lithium battery and a preparation method thereof. The crystal structure of the solid electrolyte material satisfies: i is(422)Maximum peak value, I(422)/I(211)>1.05，1.05≤I(422)/I(420)Less than or equal to 1.3. The crystal structure characteristics of the solid electrolyte material enable the solid electrolyte material to have high ionic conductivity and stability.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a cubic phase garnet type solid electrolyte material, a composite solid electrolyte, a solid lithium battery and a preparation method thereof.
Background
The positive, electrolyte and negative electrodes of a solid-state lithium battery are all composed of solid-state materials, wherein the solid-state electrolyte conducts lithium ions, but is electronically insulating. The solid electrolyte is high temperature resistant, non-flammable, non-corrosive and non-volatile, and can basically eliminate the risk of spontaneous combustion of the battery. The solid electrolyte has a high young's modulus, can suppress the formation of lithium dendrites, and can use metallic lithium having a high specific capacity as a negative electrode. In addition, the solid electrolyte has a wider electrochemical window, can bear higher oxidation potential, and is matched with a high-specific-capacity positive electrode. Therefore, the solid-state lithium battery with high safety and high energy density has great hope for solving the pain points of frequent safety problems and mileage anxiety of new energy automobiles.
Among all potential solid-state electrolytes, the cubic-phase garnet-type Li7La3Zr2O12(LLZO) at its higher room temperature ionic conductivity (> 10)-4S/cm) and wide electrochemical window (not less than 5.5V/Li)+/Li), and excellent chemical and electrochemical stability for lithium metal negative electrodes, and is one of the most promising solid electrolytes. However, storage of LLZO under normal environmental conditions poses significant challenges, especially structural and stoichiometric instability. Moisture in the air can easily induce lithium and proton exchange mechanisms, leading to lithium defect stoichiometry (i.e., Li)7-xHxLa3Zr2O12) And formation of LiOH and Li2CO3Impurities.
CN108511797A discloses a Li7La3Zr2O12The preparation method of the solid electrolyte comprises the steps of synthesizing a LLZO electrolyte precursor by using ethanol as a solvent and using a non-hydrolytic sol-gel method, then grinding and sintering to obtain the LLZO electrolyte material, wherein an XRD result shows more impure phases; the dilute nitric acid introduced in the process contains oxynitride groups, and toxic and harmful oxynitride can be produced in the subsequent sintering process, so that the dilute nitric acid is harmful to human bodies, equipment and the environment.
CN109935901A discloses a Nb and Ta co-doped garnet-type LLZO solid electrolyte and a preparation method thereof, in the process of synthesizing the LLZO electrolyte material, a lanthanum source needs to be pre-sintered to remove moisture, so that the sintering activity of lanthanum oxide can be reduced, and further, wet ball milling and mixing with isopropanol as a medium need to be used to reduce the sintering difficulty.
Therefore, the research and development of a solid electrolyte material and a low-cost preparation method thereof have important significance.
Disclosure of Invention
The purpose of the invention is to solve the problems ofOvercomes the defect of low ionic conductivity of the solid electrolyte in the prior art, and aims at the problems that the synthesis of a cubic phase garnet type solid electrolyte material is difficult, the wet ball milling with isopropanol as a medium has high cost, and the LiOH and Li on the surface2CO3The problem of a plurality of impurities is solved, and a cubic phase garnet type solid electrolyte material, a composite solid electrolyte, a solid lithium battery and a preparation method thereof are provided.
In order to achieve the above object, a first aspect of the present invention provides a cubic phase garnet type solid electrolyte material, wherein the solid electrolyte material has a crystal structure satisfying: i is(422)Maximum peak value, I(422)/I(211)>1.05，1.05≤I(422)/I(420)≤1.3。
In a second aspect, the invention provides a preparation method of the solid electrolyte material, where the preparation method includes:
(1) mixing, grinding and drying a lithium source, a lanthanum source, a zirconium source, an M 'source and an M' source to obtain a mixture;
(2) and under a dry atmosphere, performing gradient sintering on the mixture, and then crushing, sieving and removing iron to obtain the solid electrolyte material.
A third aspect of the present invention provides a composite solid-state electrolyte, wherein the composite solid-state electrolyte comprises the solid-state electrolyte material, a binder, a monomer, and a lithium salt.
The fourth aspect of the present invention provides a method for preparing the aforementioned composite solid electrolyte, wherein the method for preparing the composite solid electrolyte comprises:
(1) mixing a solid electrolyte material, a binder, a monomer and a lithium salt;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1) to obtain the composite solid electrolyte.
In a fifth aspect, the invention provides a solid-state lithium battery, which comprises a positive electrode, an electrolyte and a negative electrode, wherein the electrolyte is the composite solid-state electrolyte.
Through the technical scheme, the invention has the following advantages:
(1) the technical scheme of the invention can effectively regulate and control the crystal characteristics of the garnet type solid electrolyte material, wherein I in the crystal structure(422)Strongest, I(422)/I(211)>1.05，1.05≤I(422)/I(420)Less than or equal to 1.3, is beneficial to lithium ion transmission and has high ionic conductivity;
(2) the garnet type solid electrolyte material provided by the invention is easy to form a cubic phase, has a stable structure, has no impurities such as lithium carbonate on the surface, and is beneficial to improving the stability of the garnet type solid electrolyte material in air and an NMP solvent (N-methylpyrrolidinone is also called 1-methyl 2-pyrrolidone, and is called NMP for short);
(3) the monomer in the composite solid electrolyte provided by the invention can effectively activate a transmission channel of lithium ions, and reduce the interface impedance between an electrode and the electrolyte;
(4) the composite solid electrolyte provided by the invention adopts a solvent-free mode, can effectively improve the dispersion uniformity of the garnet electrolyte material in the composite solid electrolyte, can better inhibit the formation of lithium dendrites, and improves the battery cyclicity.
Drawings
FIG. 1 is an X-ray diffraction pattern of the garnet-type solid electrolyte material prepared in example 1 and comparative example 1 and a cubic phase standard card PDF # 80-0457;
FIG. 2 is a scanning electron microscope image of the garnet-type solid electrolyte material prepared in example 1;
FIG. 3 is a scanning electron microscope image of the garnet-type solid electrolyte material prepared in comparative example 1;
FIG. 4 is a scanning electron micrograph of a composite solid electrolyte prepared according to example 1;
FIG. 5 is a scanning electron micrograph of a composite solid electrolyte prepared in comparative example 1;
fig. 6 is a schematic cycle diagram of the solid lithium batteries prepared in example 1 and comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the present invention provides, in a first aspect, a cubic phase garnet type solid electrolyte material, wherein the solid electrolyte material has a crystal structure satisfying: i is(422)Maximum peak value, I(422)/I(211)>1.05，1.05≤I(422)/I(420)≤1.3。
The inventors of the present invention found that: when in the crystal structure I(422)The peak value is large and satisfies I(422)/I(211)>1.05，1.05≤I(422)/I(420)When the concentration of lithium ions in the crystal is less than or equal to 1.3, the crystal structure has stable cubic phase and high ionic conductivity at the same time, and the lithium ion concentration in the crystal and the optimum balance point of a lithium ion transmission channel are reached.
According to the present invention, it is preferable that the crystal structure of the solid electrolyte material satisfies: 1.1 is less than or equal to I(422)/I(211)≤1.4，1.05≤I(422)/I(420)Less than or equal to 1.25; more preferably, 1.14. ltoreq.I(422)/I(211)≤1.34，1.09≤I(422)/I(420)Less than or equal to 1.20; the crystal features more favorable for lithium ion transmission, higher ionic conductivity and better stability.
According to the invention, the solid-state electrolyte material comprises cubic-phase garnet-type Li7La3Zr2O12(LLZO) and a metal and/or a non-metal doped therein, and in the present invention, the chemical expression of the solid electrolyte material is:
Li7-δM’αLa3-βM”βZr2-γM”’γO12；
wherein-1 < delta <2, 0< alpha <1, 0< beta <3, 0< gamma < 2;
wherein M' is selected from Mg, Ca, Al, Ga, Sm, Tm or Y;
wherein M' is selected from Bi, Ce, Er, Gd or Ho;
wherein M' "is selected from Zn, Cu, Ce, Co, Ge, Hf, Ir, Mn, Mo, Ti, Ru, Se, Te, W, Sn, Sb, Nb or Ta.
According to the invention, it is preferred that-0.5. ltoreq. delta. ltoreq.1, 0. ltoreq. alpha. ltoreq.0.5, 0. ltoreq. beta. ltoreq.1.5, 0. ltoreq. gamma. ltoreq.1.
According to the invention, more preferably, 0. ltoreq. delta. ltoreq.0.6, 0. ltoreq. alpha. ltoreq.0.2, 0. ltoreq. beta. ltoreq.0.2, 0.1. ltoreq. gamma. ltoreq.0.3.
According to the present invention, it is further preferred that at least one of α or β is 0.
According to the invention, M' is preferably selected from Mg or Al; m' is selected from Bi or Er; m' "is selected from Co, Hf, Mn, Ti, Sn or Nb.
According to the present invention, more preferably, the solid electrolyte material includes: li6.6Mg0.2La3Zr1.8Nb0.2O12、Li6.6Mg0.2La3Zr1.7Hf0.3O12、Li6.4Al0.2La3Zr1.7Ti0.1O12、Li6.4Al0.2La3Zr1.7Ti0.1O12、Li7La2.8Er0.2Zr1.9Sn0.2O12And Li6.9La2.8Bi0.2Zr1.7Nb0.3O12One or more of (a).
In the invention, the inventor researches and discovers that the ratio I with peak intensity is obtained by introducing M ', M ' and M ' into a multi-element cathode material(422)/I(211)>1.05，1.05≤I(422)/I(420)1.3 or less of the solid electrolyte material. Of course, the person skilled in the art can also make the ratio of the peak intensities of the obtained solid electrolyte material satisfy the above conditions in other ways, andthe invention is not limited to this, but the ratio of the peak intensities I(422)/I(211)>1.05，1.05≤I(422)/I(420)Solid electrolyte materials less than or equal to 1.3 are all within the protection scope of the invention.
The compound with the chemical expression is introduced with M ', M' and/or M 'elements, so that the Li content and unit cell parameters can be adjusted by doping and substituting the isovalent/isovalent elements at Li, La or/and Zr positions in the garnet-type solid electrolyte material to reach the optimal balance point of the lithium ion concentration and a lithium ion transmission channel, and at the moment, I' in the crystal structure(422)Maximum peak value, I(422)/I(211)>1.05，1.05≤I(422)/I(420)Less than or equal to 1.3, stable cubic phase is obtained and simultaneously high ionic conductivity is achieved. In particular, the tetrahedron [ Li ] in the crystal structure can be improved under the synergistic effect of doping substitution elements at Li, La or/and Zr sites1O4]And octahedra [ Li ]2O6]Coplanarity, reducing the distance between Li and Li, obviously improving the lithium ion conductivity of the garnet solid electrolyte material, reducing the side reaction between the garnet solid electrolyte material and water and carbon dioxide in the air, and improving stability.
The solid electrolyte material is obtained by multi-point element collaborative doping; in addition, the sintering temperature and the sintering time are controlled in the preparation process; preferably, the temperature of the first sintering is 300-750 ℃, the heating rate is 0.5-10 ℃/min, and the heat preservation time is 0.5-5 h; the temperature of the second sintering is 800-.
In a second aspect, the invention provides a preparation method of the solid electrolyte material, where the preparation method includes:
(1) mixing, grinding and drying a lithium source, a lanthanum source, a zirconium source, an M 'source and an M' source to obtain a mixture;
(2) and under a dry atmosphere, performing gradient sintering on the mixture, and then crushing, sieving and removing iron to obtain the solid electrolyte material.
The inventors of the present invention found that: the mixture with matched granularity is obtained by grinding single raw material or mixed raw materials together by adopting a dry method or a wet method. In the sintering process, the garnet electrolyte material with specific crystal structure and narrow particle size distribution is prepared and obtained by multi-point element collaborative doping and sintering temperature and sintering time control. The electrolyte material is easy to form cubic phase, has stable structure, basically has no impurities such as lithium carbonate on the surface, is more stable to air and NMP solvent, can adopt water as a wet grinding medium, and has low industrialization cost. The garnet electrolyte material with a specific crystal structure and a narrow particle size distribution is beneficial to obtaining an oxide solid electrolyte sheet with high density and ionic conductivity by subsequent sintering.
According to the invention, the M 'source, the M' source are each independently selected from one or more of the oxides, hydroxides, carbonates, oxalates, acetates and citrates of M ', M';
according to the invention, preferably, the M ' source, the M ' source and the M ' source are all nano-scale, and the specific surface area is more than or equal to 20M2(ii)/g; in the more preferable case, it is preferable that,
according to the invention, D of the M 'source, M' source50The same or different, each of which is 20-200nm, and has a specific surface area of 50-500m2/g。
According to the invention, D of the mixture after grinding and drying501-5 μm, D of the mix100Is 4-10 μm.
According to the invention, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide and lithium nitrate. In the present invention, the ratio of the actual amount of the lithium salt to the stoichiometric amount is 1 to 1.2 to compensate for lithium volatilization during sintering.
According to the invention, the lanthanum source is selected from one or more of lanthanum oxide, lanthanum hydroxide, lanthanum carbonate, lanthanum oxalate, lanthanum acetate and lanthanum citrate.
According to the invention, the zirconium source is selected from one or more of zirconium oxide, zirconium hydroxide, zirconium carbonate, zirconium oxalate, zirconium acetate and zirconium citrate.
According to the invention, the gradient sintering comprises a first sintering and a second sintering.
According to the invention, the temperature of the first sintering is 300-750 ℃, the heating rate is 0.5-10 ℃/min, and the heat preservation time is 0.5-5 h; the temperature of the second sintering is 800-.
According to the invention, preferably, the temperature of the first sintering is 400-; the temperature of the second sintering is 900-.
According to the present invention, the drying atmosphere may be formed of dry air, dry oxygen, dry nitrogen, or the like.
According to the invention, the specific operations of mixing (mixing), grinding, crushing, sieving, iron removal are not particularly limited, as long as the requirements are met. In the invention, the mixing can be realized by adopting a high-speed mixer, a V-shaped mixer, a double-cone mixer or a coulter mixer; the grinding can be realized by adopting a stirring ball mill, a planetary ball mill or a sand mill; the crushing can be realized by adopting a double-roller crushing mode, a ball mill mode, an air flow mill mode or a mechanical milling mode; the screening can adopt an ultrasonic vibration screen; the iron removal can be realized by an electromagnetic iron remover.
A third aspect of the present invention provides a composite solid-state electrolyte, wherein the composite solid-state electrolyte comprises the solid-state electrolyte material, a binder, a monomer, and a lithium salt.
According to the present invention, based on the total weight of the composite solid electrolyte, the content of the solid electrolyte material is 60 to 90 wt%, the content of the binder is 2 to 20 wt%, the content of the monomer is 3 to 60 wt%, and the content of the lithium salt is 5 to 60 wt%.
According to the present invention, it is preferable that the content of the solid electrolyte material is 70 to 80% by weight, the content of the binder is 5 to 10% by weight, the content of the monomer is 5 to 40% by weight, and the content of the lithium salt is 10 to 40% by weight, based on the total weight of the composite solid electrolyte.
According to the invention, the binder is selected from one or more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polytetrafluoroethylene, polyethylene oxide, polyether, polymethyl methacrylate, polyacrylonitrile, polyethylene carbonate and polypropylene carbonate.
According to the invention, the monomer is selected from one or more of unsaturated carbonates and halides thereof with a dielectric constant of more than 10, phosphates with a dielectric constant of more than 10, carboxylic esters with a dielectric constant of 2-10 and ethers with a dielectric constant of 5-10. In the invention, the monomer in the composite solid electrolyte provided by the invention can effectively activate a transmission channel of lithium ions, and reduce the interface impedance between the electrode and the electrolyte.
According to the present invention, preferably, the carbonate is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate and halides thereof.
According to the present invention, preferably, the phosphate ester is selected from one or more of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tributyl phosphate and halides thereof.
According to the present invention, preferably, the carboxylic acid ester is selected from one or more of γ -butyrolactone, methyl formate, methyl acetate, methyl butyrate and ethyl propionate.
According to the present invention, preferably, the ethers are selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxy ether, 1, 2-dimethoxyethane, diglyme and 12-crown-4 ether.
According to the invention, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulphonylimide, lithium bistrifluorosulphonylimide, lithium bisoxalato borate, lithium difluorooxalato borate and lithium trifluoromethanesulfonate.
According to the invention, the particle size D of the solid electrolyte material50Is 0.05-5 μm.
The fourth aspect of the present invention provides a method for preparing the aforementioned composite solid electrolyte, wherein the method for preparing the composite solid electrolyte comprises:
(1) mixing a solid electrolyte material, a binder, a monomer and a lithium salt;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1) to obtain the composite solid electrolyte.
According to the preparation method of the composite solid electrolyte, the preparation method is solvent-free preparation, the dispersion uniformity of the garnet electrolyte material in the composite solid electrolyte can be effectively improved by adopting a solvent-free mode, the formation of lithium dendrite can be well inhibited, and the battery cyclicity is improved.
According to the invention, the mixing conditions include: the temperature is 0.5-2Tm(ii) a Wherein, TmIs the melting point of the binder; the mixing time is such that the mixer torque reaches a steady state.
According to the present invention, the conditions of the hot pressing include: the temperature is 0.5-2Tm(ii) a Wherein, TmIs the melting point of the binder; the hot pressing pressure may be adjusted according to the desired electrolyte membrane thickness.
According to the invention, the composite solid electrolyte is in the form of a membrane having a thickness of 2 to 20 μm, preferably 4 to 15 μm.
In a fifth aspect, the invention provides a solid-state lithium battery, which comprises a positive electrode, an electrolyte and a negative electrode, wherein the electrolyte is the composite solid-state electrolyte.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
performing phase and crystal structure analysis by using an X-ray automatic diffractometer manufactured by Rigaku corporation of Japan;
observing the morphology by using an S-4800 type scanning electron microscope manufactured by Hitachi corporation of Japan;
particle size distribution testing was performed using a Mastersizer 2000 laser particle sizer from Malvern, where only the D of the material was characterized50；
Adopting CT-3008 of Newwei electronics Limited company to carry out charge-discharge and cycle tests on the solid-state battery;
the AC impedance and electrochemical window tests were carried out using the SP-150 electrochemical workstation from Bio-logic, France.
The raw materials mentioned in the invention are commercial products meeting related national standards or industry standards.
Example 1
This example illustrates a solid electrolyte material and a composite solid electrolyte and a solid lithium battery prepared by the method of the present invention (Li-2 valence doping, Zr-valence aliovalent doping, dry mixing, one-stage firing).
(1) According to Li2CO3：La2O3：ZrO2：MgO：Nb2O53.465: 1.5: 1.8: 0.2: weighing the above substances at a molar ratio of 0.1, wherein Li2CO3、La2O3And ZrO2The particle size of (3) is not required, MgO and Nb2O5D of (A)50Are all 50nm, and the specific surface area is 150m2(ii)/g; then carrying out dry grinding and mixing; d of the mixture after grinding and mixing50Is 4.2 μm, D100Is 10 μm;
(2) putting the mixture obtained in the step (1) into a roller kiln, heating to 420 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2h, then heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 8h, and naturally cooling to about 100 ℃; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron6.6Mg0.2La3Zr1.8Nb0.2O12。
FIG. 1 is an X-ray diffraction pattern of the garnet-type solid electrolyte material prepared in example 1 and comparative example 1 and a cubic phase standard card PDF # 80-0457; as shown in FIG. 1, the X-ray diffraction pattern of example 1 has a crystal structure consistent with that of the cubic phase Standard card PDF #80-0457, i.e., cubic phase garnet type crystal structure, I(422)Maximum peak value, I(422)/I(211)＝1.21，I(422)/I(420)＝1.16。
FIG. 2 is a scanning electron microscope image of the garnet-type solid electrolyte material prepared in example 1; as shown in fig. 2, the garnet-type solid electrolyte material has substantially no impurities such as lithium carbonate remaining on the surface thereof, and is advantageous for lithium ion transport and has high stability.
FIG. 4 is a scanning electron micrograph of a composite solid electrolyte prepared according to example 1; as shown in fig. 4, the garnet-type solid electrolyte material is uniformly dispersed in the composite solid electrolyte. Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 2.6 multiplied by 10-3S/cm; an SS composite solid electrolyte membrane Li test system is assembled, an electrochemical window test is carried out at 25 ℃, a scanning speed of 10mV and a voltage range of-1V to 6V, and the oxidation potential is 5.7V.
(3) According to the following steps of 80:5:5: and (2) weighing the cubic-phase garnet-type solid electrolyte material, the adhesive polyethylene oxide, the monomer ethylene carbonate and the lithium salt lithium bistrifluoromethylsulfonyl imide in the step (2) respectively according to the weight ratio of 10, mixing at 80 ℃, and hot-pressing at 100 ℃ to obtain the composite solid electrolyte membrane with the thickness of 15 mu m.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.6Co0.1Mn0.3O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 27 omega.
Fig. 6 is a schematic cycle diagram of the solid lithium batteries prepared in example 1 and comparative example 1, and as shown in fig. 6, the solid lithium battery in example 1 has a specific first discharge capacity of 192.2mAh/g at 25 ℃ at 3.0-4.3V and 0.2C; the capacity retention after 80 weeks of cycling was 81.1%.
Example 2
This example illustrates a solid electrolyte material and a composite solid electrolyte and a solid lithium battery prepared by the method of the present invention (Li-2 + doping, Zr + doping, wet mixing, single firing).
(1) According to Li2CO3：La2O3：ZrO2：MgO：HfO23.399: 1.5: 1.7: 0.2: weighing the above materials at a molar ratio of 0.3, wherein Li2CO3、La2O3And ZrO2Has a particle diameter of (1), MgO and HfO2D of (A)50Are all 50nm, and the specific surface area is 150m2(ii)/g; putting the mixture into a ball mill, carrying out wet ball milling by taking water as a medium, and finally drying; after ball milling and drying, D of the mixture501.5 μm, D100Is 4.7 μm;
(2) putting the mixture obtained in the step (1) into a roller kiln, heating to 440 ℃ at the speed of 1 ℃/min in a dry air atmosphere, preserving heat for 2h, then heating to 1000 ℃ at the speed of 3 ℃/min, preserving heat for 8h, and naturally cooling to about 100 ℃; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron6.6Mg0.2La3Zr1.7Hf0.3O12。
In addition, from the X-ray diffraction pattern, it can be derived: the crystal structure in the X-ray diffraction pattern obtained by the test is consistent with the cubic phase standard card PDF #80-0457, namely the cubic phase garnet type crystal structure, I(422)Maximum peak value, I(422)/I(211)＝1.14，I(422)/I(420)＝1.12。
In addition, from the scanning electron micrographs it can be derived: the garnet solid electrolyte material has no residual impurities such as lithium carbonate on the surface, is beneficial to lithium ion transmission, and has high stability.
(3) According to the following steps of 80:5:5: and (3) respectively weighing the cubic phase garnet type solid electrolyte material, polyvinylidene fluoride, gamma-butyrolactone and lithium bis (trifluoromethanesulfonyl) imide in the step (2) according to the weight ratio of 10, then mixing at 100 ℃ and carrying out hot pressing at 160 ℃ to obtain the composite solid electrolyte membrane with the thickness of 15 microns.
Assembling a SS composite solid electrolyte membrane SS test system by taking a stainless Steel Sheet (SS) as an electrode, and carrying out alternating current impedance test at the temperature of 25 ℃, the disturbance voltage of 10mV and the frequency range of 1 MHz-1 HzThe ion conductivity was calculated to be 3.1X 10-3S/cm; and assembling the SS composite solid electrolyte membrane | Li test system, and performing an electrochemical window test at 25 ℃, a scanning speed of 10mV and a voltage range of-1V to 6V, wherein the oxidation potential is 5.8V.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.7Co0.1Mn0.2O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on an aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 26 omega.
In addition, the first-cycle discharge specific capacity of the solid lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 196.3 mAh/g; the capacity retention after 80 weeks of cycling was 87.3%.
Example 3
This example illustrates a solid electrolyte material and a composite solid electrolyte and a solid lithium battery prepared by the method of the present invention (Li-3 + doping, Zr + doping, wet mixing, single firing).
(1) According to Li2CO3：La2O3：ZrO2：Al2O3：TiO23.296: 1.5: 1.7: 0.1: weighing the above substances at a molar ratio of 0.3, wherein Li2CO3、La2O3And ZrO2The particle diameter of (A) is not required, Al2O3And TiO2D of (A)50All are 30nm, and the specific surface area is 270m2(ii)/g; putting the mixture into a ball mill, carrying out wet ball milling by taking water as a medium, and finally drying. After ball milling and drying, D of the mixture501.2 μm, D1004.3 μm;
(2) putting the mixture obtained in the step (1) into a roller kiln, heating to 500 ℃ at the speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2h, and then keeping the temperature at the speed of 3 ℃/minHeating to 1000 ℃, preserving heat for 7h, and naturally cooling to about 100 ℃; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron6.4Al0.2La3Zr1.7Ti0.3O12。
The crystal structure in the X-ray diffraction pattern obtained by the test is consistent with the cubic phase standard card PDF #80-0457, namely the cubic phase crystal structure, I(422)Maximum peak value, I(422)/I(211)＝1.34，I(422)/I(420)＝1.18。
In addition, impurities such as lithium carbonate and the like basically do not remain on the surface of the garnet type solid electrolyte material, lithium ion transmission is facilitated, and the stability is high.
(3) According to the following steps of 80:5:5: and (3) weighing the garnet-type solid electrolyte material, polytetrafluoroethylene, diglyme and lithium bistrifluoromethylsulfonyl imide in the step (2) at a weight ratio of 10, mixing at 170 ℃, and hot-pressing at 170 ℃ to obtain a composite solid electrolyte membrane with the thickness of 15 mu m.
Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 9.3 multiplied by 10-4S/cm, assembling a SS composite solid electrolyte membrane Li test system, and performing electrochemical window test at 25 ℃, 10mV scanning speed and-1V to 6V voltage range, wherein the oxidation potential is 5.7V.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.7Co0.1Mn0.2O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 31 omega.
In addition, the first cycle discharge specific capacity of the solid-state lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 194.9 mAh/g; the capacity retention after 80 weeks of cycling was 88.9%.
Example 4
This example is to illustrate solid electrolyte materials and composite solid electrolytes and solid lithium batteries prepared by the method of the present invention (wet mixing, two-stage firing).
(1) According to Li2CO3：La2O3：ZrO2：Al2O3：TiO23.296: 1.5: 1.7: 0.1: weighing the above substances at a molar ratio of 0.3, wherein Li2CO3、La2O3And ZrO2The particle diameter of (A) is not required, Al2O3And TiO2D of (A)50All are 30nm, and the specific surface area is 270m2(ii) in terms of/g. Mixing Li2CO3、La2O3、ZrO2And Al2O3Putting the mixture into a ball mill, carrying out wet ball milling by taking water as a medium, and finally drying. After ball milling and drying, D of the mixture501.2 μm, D1004.3 μm;
(2) putting the mixture obtained in the step (1) into a roller kiln, heating to 600 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 1h, then heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 10h, and naturally cooling to about 100 ℃ along with a furnace body; then with the weighed TiO2Putting the mixture into a ball mill, carrying out wet ball milling by taking water as a medium, and finally drying. After ball milling and drying, D of the mixture501.2 μm, D100And 4.3 μm. Placing into roller kiln, heating to 960 deg.C at a rate of 5 deg.C/min in dry air atmosphere, maintaining for 9h, and naturally cooling to about 100 deg.C; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron6.4Al0.2La3Zr1.7Ti0.3O12。
In addition, from the X-ray diffraction pattern, it can be derived: the crystal structure in the X-ray diffraction pattern obtained by the test is consistent with the cubic phase standard card PDF #80-0457, namely the cubic phase garnet type crystal structure, I(422)Maximum peak value, I(422)/I(211)＝1.33，I(422)/I(420)＝1.20。
In addition, from the scanning electron micrographs it can be derived: the garnet solid electrolyte material has no residual impurities such as lithium carbonate on the surface, is beneficial to lithium ion transmission, and has high stability.
(3) According to the following steps of 80:5:5: and (3) weighing the garnet-type solid electrolyte material, polytetrafluoroethylene, diglyme and lithium bistrifluoromethylsulfonyl imide in the step (2) at a weight ratio of 10, mixing at 170 ℃, and hot-pressing at 170 ℃ to obtain a composite solid electrolyte membrane with the thickness of 15 mu m.
Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 4.3 multiplied by 10-3S/cm, assembling a SS composite solid electrolyte membrane | Li test system, and performing electrochemical window test at 25 ℃, 10mV scanning speed and-1V to 6V voltage range, wherein the oxidation potential is 5.8V.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.83Co0.07Mn0.1O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on an aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 35 omega.
In addition, the first cycle discharge specific capacity of the solid-state lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 205.4 mAh/g; the capacity retention after 80 weeks of cycling was 85.8%.
Example 5
This example illustrates a solid electrolyte material and a composite solid electrolyte prepared by the method of the present invention (La-position isovalent doping, Zr-position isovalent doping, one-stage sintering), and a solid lithium battery.
(1) According to Li2CO3：La2O3：ZrO2：Er2O3：SnO23.64: 1.2: 1.8: 0.3: weighing the above substances at a molar ratio of 0.2, wherein Li2CO3、La2O3And ZrO2The particle diameter of (A) is not required, Er2O3And SnO2D of (A)50All are 80nm, the specific surface area is 100m2(ii)/g; then carrying out dry grinding and mixing; d of the mixture after grinding and mixing50Is 4.2 μm, D100Is 10 μm;
(2) putting the mixture obtained in the step (1) into a roller kiln, heating to 550 ℃ at the speed of 2 ℃/min in a dry air atmosphere, preserving heat for 1h, then heating to 1050 ℃ at the speed of 3 ℃/min, preserving heat for 10h, and naturally cooling to about 100 ℃; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron7La2.4Er0.6Zr1.8Sn0.2O12。
In addition, from the X-ray diffraction pattern, it can be derived: the crystal structure in the X-ray diffraction pattern obtained by the test is consistent with the cubic phase standard card PDF #80-0457, namely the cubic phase garnet type crystal structure, I(422)Maximum peak value, I(422)/I(211)＝1.15，I(422)/I(420)＝1.09。
In addition, from the scanning electron micrographs it can be derived: the garnet solid electrolyte material has no residual impurities such as lithium carbonate on the surface, is beneficial to lithium ion transmission and has high stability.
(3) According to the proportion of 80:5:5: weighing the garnet-type solid electrolyte material, the vinylidene fluoride-hexafluoropropylene copolymer, the fluoroethylene carbonate and the lithium bis (trifluoromethylsulfonyl) imide in the step (2) at a weight ratio of 10, mixing at 120 ℃, and hot-pressing at 150 ℃ to obtain a composite solid electrolyte membrane with the thickness of 15 mu m.
Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 8.8 multiplied by 10-4S/cm; an SS composite solid electrolyte membrane Li test system is assembled, an electrochemical window test is carried out at 25 ℃, a scanning speed of 10mV and a voltage range of-1V to 6V, and the oxidation potential is 5.9V.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.95Co0.02Mn0.03O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on an aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 26 omega.
In addition, the first-cycle discharge specific capacity of the solid-state lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 224.1 mAh/g; the capacity retention after 80 weeks of cycling was 83.4%.
Example 6
This example illustrates a solid electrolyte material and a composite solid electrolyte prepared by the method of the present invention (La isovalent doping, Zr isovalent doping, one-stage sintering), and a solid lithium battery.
(1) According to Li2CO3：La2O3：ZrO2：Bi2O3：Nb2O53.465: 1.4: 1.6: 0.1: weighing the above substances at a molar ratio of 0.2, wherein Li2CO3、La2O3And ZrO2Is not required, Bi2O3And Nb2O5D of (A)50Are all 20nm, and the specific surface area is 370m2(ii)/g; putting the mixed materials into a mixing tank for dry mixing; after mixing, D of the mixture50Is 4.2 μm, D100Is 10 μm;
(2) putting the mixture obtained in the step (1) into a roller kiln, heating to 560 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2h, then heating to 990 ℃ at a speed of 3 ℃/min, preserving heat for 9h, and naturally cooling to about 100 ℃; through crushingSieving to remove iron to obtain garnet type solid electrolyte material Li6.6La2.8Bi0.2Zr1.6Nb0.4O12。
In addition, from the X-ray diffraction pattern, it can be derived: the crystal structure in the X-ray diffraction pattern obtained by the test is consistent with the cubic phase standard card PDF #80-0457, namely the cubic phase garnet type crystal structure, I(422)Maximum peak value, I(422)/I(211)＝1.25，I(422)/I(420)＝1.14。
In addition, from the scanning electron micrographs it can be derived: the garnet solid electrolyte material has no residual impurities such as lithium carbonate on the surface, is beneficial to lithium ion transmission, and has high stability.
(3) According to the following steps of 80:5:5: and weighing the garnet-type solid electrolyte material, the vinylidene fluoride-hexafluoropropylene copolymer, the fluoroethylene carbonate and the lithium bis (trifluoromethyl) sulfonyl imide in the second step respectively according to the weight ratio of 10, then mixing at 120 ℃ and hot-pressing at 150 ℃ to obtain the composite solid electrolyte membrane with the thickness of 15 mu m.
Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 3.2 multiplied by 10-3S/cm; and assembling the SS composite solid electrolyte membrane | Li test system, and performing an electrochemical window test at 25 ℃, a scanning speed of 10mV and a voltage range of-1V to 6V, wherein the oxidation potential is 5.8V.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.95Co0.02Mn0.03O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on an aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 32 omega.
In addition, the first-cycle discharge specific capacity of the solid-state lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 223.6 mAh/g; the capacity retention after 80 weeks of cycling was 83.1%.
Example 7
A solid electrolyte material and a composite solid electrolyte and a solid lithium battery were prepared in the same manner as in example 1, except that: the amount of the doping element varies mainly, specifically:
(1) according to Li2CO3：La2O3：ZrO2：MgO：Nb2O52.94: 1.5: 1.8: 0.6: weighing the above substances at a molar ratio of 0.1, wherein Li2CO3、La2O3And ZrO2Has an undesirable particle diameter of MgO and Nb2O5D of (A)50Are all 50nm, and the specific surface area is 150m2(ii)/g; then carrying out dry grinding and mixing; d of the mixture after grinding and mixing50Is 4.2 μm, D100Is 10 μm.
(2) Putting the mixture obtained in the step (1) into a roller kiln, heating to 970 ℃ at the speed of 3 ℃/min in a dry air atmosphere, preserving heat for 8h, and naturally cooling to about 100 ℃; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron5.6Mg0.6La3Zr1.8Nb0.2O12。
In addition, from the X-ray diffraction pattern, it can be derived: the crystal structure in the X-ray diffraction pattern is consistent with the cubic phase standard card PDF #80-0457, namely the cubic phase garnet crystal structure, I(422)Maximum peak value, I(422)/I(211)＝1.17，I(422)/I(420)＝1.13。
(3) According to the following steps of 80:5:5: weighing the garnet-type solid electrolyte material, the binder polyethylene oxide, the monomer ethylene carbonate and the lithium salt lithium bistrifluoromethylsulfonyl imide in the step (2) at a weight ratio of 10, mixing at 80 ℃ and hot-pressing at 100 ℃ to obtain a composite solid electrolyte membrane with the thickness of 15 microns.
Assembling SS | composite solid electrolyte by taking stainless Steel Sheet (SS) as electrodeThe film | SS test system is used for carrying out alternating current impedance test at 25 ℃, 10mV disturbance voltage and 1 MHz-1 Hz frequency range, and the ionic conductivity is calculated to be 3.1 multiplied by 10-3S/cm; an SS composite solid electrolyte membrane Li test system is assembled, an electrochemical window test is carried out at 25 ℃, a scanning speed of 10mV and a voltage range of-1V to 6V, and the oxidation potential is 5.7V.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.6Co0.1Mn0.3O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on an aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 35 omega.
The first cycle discharge specific capacity of the solid-state lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 185.6 mAh/g; capacity retention was 78.8% after 80 weeks of cycling.
Comparative example 1
A solid electrolyte material and a composite solid electrolyte and a solid lithium battery were prepared in the same manner as in example 1, except that: mainly undoped; specifically, the method comprises the following steps:
(1) according to Li2CO3：La2O3：ZrO23.675: 1.5: 2, wherein Li2CO3、La2O3And ZrO2The grain diameter of the raw materials is not required, and the raw materials are mixed by a dry method; after mixing, D of the mixture50Is 4.2 μm, D100Is 10 μm.
(2) Putting the mixture obtained in the step (1) into a roller kiln, heating to 420 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2h, then heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 8h, and naturally cooling to about 100 ℃; and crushing, sieving and removing iron to obtain the garnet solid electrolyte material.
FIG. 1 is an X-ray diffraction pattern of a garnet-type solid electrolyte material prepared in example 1 and comparative example 1 and a cubic phase standard card PDF # 80-0457; as shown in FIG. 1, comparative example 1 has a large number of cleavage peaks in the X-ray diffraction pattern, i.e., tetragonal crystal structure, I(422)/I(211)＝0.89，I(422)/I(420)＝0.97。
In addition, fig. 3 is a scanning electron microscope image of the garnet-type solid electrolyte material prepared in comparative example 1, and as shown in fig. 3, a large amount of impurities such as lithium carbonate exist on the surface of the garnet-type solid electrolyte material, which is not good for lithium ion transmission and has poor stability.
(3) The garnet-type solid electrolyte material, polyethylene oxide, ethylene carbonate and lithium bistrifluoromethylsulfonyl imide in step (2) were weighed in a weight ratio of 80:5:5:10, respectively, and then kneaded and hot-pressed at 80 ℃ to obtain a composite solid electrolyte membrane having a thickness of 15 μm.
Fig. 5 is a scanning electron microscope image of the composite solid electrolyte prepared in comparative example 1, and as shown in fig. 5, the dispersion uniformity of the garnet-type solid electrolyte material in the composite solid electrolyte was lower than that of example 1 (fig. 4).
Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 2.3 multiplied by 10-5S/cm, assembling a SS composite solid electrolyte membrane Li test system, and performing electrochemical window test at 25 ℃ at a scanning speed of 10mV and a voltage range of-1V to 6V, wherein the oxidation potential is 4.5V. This is because the tetragonal garnet-type solid electrolyte material has difficulty in transporting lithium ions.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.6Co0.1Mn0.3O2) The acetylene black, the lithium bis (trifluoromethyl) sulfonyl imide and the polyvinylidene fluoride are dispersed in N-methyl-2-pyrrolidone according to the mass ratio of 80:5:5:10, blade-coated on an aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; charging the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode with water content and oxygen content less than 5ppmThe cell was assembled in an argon-filled glove box.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 83 omega.
Fig. 6 is a schematic cycle diagram of the solid lithium batteries prepared in example 1 and comparative example 1; as shown in FIG. 6, the first cycle specific discharge capacity of the solid lithium battery in comparative example 1 reached 175.9mAh/g at 25 ℃ at 3.0-4.3V and 0.2C; the capacity retention after 80 weeks of cycling was 61.0%.
Comparative example 2
A solid electrolyte material and a composite solid electrolyte and a solid lithium battery were prepared in the same manner as in example 1, except that: the doping amount is not limited in the scope of the invention, and specifically:
(1) according to Li2CO3：La2O3：Nb2O5: MgO is 2.415: 1.5: 1: weighing the above substances at a molar ratio of 0.2, wherein Li2CO3、La2O3Is not required, Nb2O5D of (A)50Are all 2 mu m; then carrying out dry grinding and mixing; d of the mixture after grinding and mixing50Is 4.2 μm, D100Is 10 μm.
(2) Putting the mixture obtained in the step (1) into a roller kiln, heating to 420 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2h, then heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 8h, and naturally cooling to about 100 ℃; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron4.6Mg0.2La3Nb2O12。
In addition, from the X-ray diffraction pattern, it can be derived: i in the crystal structure in the X-ray diffraction pattern obtained by testing(422)/I(211)＝0.96，I(422)/I(420)＝0.77。
In addition, from the scanning electron micrographs it can be derived: the garnet solid electrolyte material has a large amount of impurities such as lithium carbonate on the surface, which is not beneficial to lithium ion transmission and has poor stability.
(3) According to the following steps of 80:5:5: and weighing the garnet-type solid electrolyte material, the polyethylene oxide, the ethylene carbonate and the lithium bis (trifluoromethyl) sulfonyl imide in the second step respectively according to a weight ratio of 10, and then mixing and hot-pressing at 80 ℃ to obtain a composite solid electrolyte membrane with the thickness of 15 mu m.
Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 4.2 multiplied by 10-5S/cm; and assembling the SS composite solid electrolyte membrane | Li test system, and performing an electrochemical window test at 25 ℃, a scanning speed of 10mV and a voltage range of-1V to 6V, wherein the oxidation potential is 4.5V. This is because the garnet-type solid electrolyte material has too large lattice distortion to transmit lithium ions.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.6Co0.1Mn0.3O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on an aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 76 omega.
The first-cycle discharge specific capacity of the solid-state lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 184.1 mAh/g; capacity retention after 80 weeks of cycling was 75.8%.
Comparative example 3
A solid electrolyte material and a composite solid electrolyte and a solid lithium battery were prepared in the same manner as in example 1, except that: mainly vinyl carbonate-free esters; specifically, the method comprises the following steps:
(1) according to Li2CO3：La2O3：ZrO2：MgO：Nb2O53.465: 1.5: 1.8: 0.2: weighing the above substances at a molar ratio of 0.1, wherein Li2CO3、La2O3And ZrO2The particle diameter of (3) is not required; MgO (magnesium oxide)And Nb2O5D of (A)50Are all 50nm, and the specific surface area is 150m2(ii)/g; then dry grinding and mixing are carried out. D of the mixture after grinding and mixing50Is 4.2 μm, D100Is 10 μm;
(2) putting the mixture obtained in the step (1) into a roller kiln, heating to 420 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2h, then heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 8h, and naturally cooling to about 100 ℃; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron6.6Mg0.2La3Zr1.8Nb0.2O12。
In addition, from the X-ray diffraction pattern, it can be derived: i in the crystal structure in the X-ray diffraction pattern obtained by testing(422)/I(211)＝0.86，I(422)/I(420)＝1.52。
In addition, from the scanning electron micrographs it can be derived: impurities such as lithium carbonate and the like basically do not remain on the surface of the garnet type solid electrolyte material, and lithium ion transmission is facilitated.
(3) According to the following steps of 80: 10: the garnet-type solid electrolyte material, polyethylene oxide and lithium bistrifluoromethylsulfonyl imide in step (2) were weighed at a weight ratio of 10, respectively, and then kneaded and hot-pressed at 80 ℃ to obtain a composite solid electrolyte membrane having a thickness of 15 μm.
Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 1.1 multiplied by 10-5S/cm; and assembling the SS composite solid electrolyte membrane | Li test system, and performing an electrochemical window test at 25 ℃, a scanning speed of 10mV and a voltage range of-1V to 6V, wherein the oxidation potential is 4.6V. This is due to the difficulty of transporting lithium ions due to the absence of monomers that activate the lithium ion transport channels.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.6Co0.1Mn0.3O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyridineCoating the sheet on an aluminum foil in pyrrolidone in a blade mode, drying, punching the sheet, and drying for 12 hours in vacuum at 120 ℃; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 326 omega.
In addition, the first-cycle discharge specific capacity of the solid lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 150.7 mAh/g; capacity retention after 80 weeks of cycling was 50.6%.
Comparative example 4
A solid electrolyte material and a composite solid electrolyte and a solid lithium battery were prepared in the same manner as in example 1, except that: in step (1), the particle size of each material is not within the range defined by the invention, specifically:
(1) according to Li2CO3：La2O3：ZrO2：MgO：Nb2O53.465: 1.5: 1.8: 0.2: weighing the above substances at a molar ratio of 0.1, wherein Li2CO3、La2O3And ZrO2Has an undesirable particle diameter of MgO and Nb2O5D of (A)50Are all 50nm, and the specific surface area is 150m2(ii)/g; then dry grinding and mixing are carried out. D of the mixture after grinding and mixing508.5 μm, D100And 30 μm.
(2) Putting the mixture obtained in the step (1) into a roller kiln, heating to 420 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2h, then heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 8h, and naturally cooling to about 100 ℃; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron6.6Mg0.2La3Zr1.8Nb0.2O12。
In addition, from the X-ray diffraction pattern, it can be derived: the crystal structure in the X-ray diffraction pattern is consistent with the cubic phase standard card PDF #80-0457, namely the cubic phase crystal structure, I(422)/I(211)＝0.86，I(422)/I(420)＝0.8。
(3) According to the following steps of 80:5:5: weighing the garnet-type solid electrolyte material, the binder polyethylene oxide, the monomer ethylene carbonate and the lithium salt lithium bistrifluoromethylsulfonyl imide in the step (2) at a weight ratio of 10, mixing at 80 ℃ and hot-pressing at 100 ℃ to obtain a composite solid electrolyte membrane with the thickness of 15 microns.
Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 2.7 multiplied by 10-5S/cm; and assembling the SS composite solid electrolyte membrane | Li test system, and performing an electrochemical window test at 25 ℃, a scanning speed of 10mV and a voltage range of-1V to 6V, wherein the oxidation potential is 4.5V. This is due to I(422)Low, and is not beneficial to lithium ion transmission.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.6Co0.1Mn0.3O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 68 omega.
In addition, the first cycle discharge specific capacity of the solid-state lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 175.1 mAh/g; the capacity retention after 80 weeks of cycling was 61.8%.
Comparative example 5
A solid electrolyte material and a composite solid electrolyte and a solid lithium battery were prepared in the same manner as in example 1, except that: in step (2), the gradient sintering conditions are different, specifically:
(1) according to Li2CO3：La2O3：ZrO2：MgO：Nb2O53.465: 1.5: 1.8: 0.2: weighing at a molar ratio of 0.1The above substance, wherein Li2CO3、La2O3And ZrO2Has an undesirable particle diameter of MgO and Nb2O5D of (A)50Are all 50nm, MgO and Nb2O5D of (A)50Are all 50nm, and the specific surface area is 150m2(ii)/g; then dry grinding and mixing are carried out. D of the mixture after grinding and mixing50Is 4.2 μm, D100Is 10 μm.
(2) Putting the mixture obtained in the step (1) into a roller kiln, heating to 970 ℃ at the speed of 3 ℃/min in a dry air atmosphere, preserving heat for 8h, and naturally cooling to about 100 ℃; the garnet type solid electrolyte material Li is obtained by crushing, sieving and removing iron6.6Mg0.2La3Zr1.8Nb0.2O12。
The crystal structure in the X-ray diffraction pattern is consistent with the cubic phase standard card PDF #80-0457, namely the cubic phase crystal structure, I(422)/I(211)＝0.9，I(422)/I(420)＝1.6。
(3) According to the following steps of 80:5:5: weighing the garnet-type solid electrolyte material, the binder polyethylene oxide, the monomer ethylene carbonate and the lithium salt lithium bistrifluoromethylsulfonyl imide in the step (2) at a weight ratio of 10, mixing at 80 ℃ and hot-pressing at 100 ℃ to obtain a composite solid electrolyte membrane with the thickness of 15 microns.
Assembling a SS composite solid electrolyte membrane SS test system by using a stainless Steel Sheet (SS) as an electrode, performing an alternating current impedance test at 25 ℃, 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and calculating that the ionic conductivity is 3.3 multiplied by 10-5S/cm; and assembling a SS | composite solid electrolyte membrane | Li test system, and performing an electrochemical window test at 25 ℃, a scanning speed of 10mV and a voltage range of-1V to 6V, wherein the oxidation potential is 4.5V. This is due to I(422)Lower, I(420)Higher, not beneficial to lithium ion transmission.
(4) Preparing positive electrode active material (LiNi) of lithium nickel cobalt manganese oxide0.6Co0.1Mn0.3O2) Acetylene black, lithium bistrifluoromethylsulfonyl imide and polyvinylidene fluoride in a mass ratio of 80:5:5:10 is dispersed in N-methyl-2-pyrrolidone, blade-coated on an aluminum foil and dried, and then punched and vacuum-dried at 120 ℃ for 12 hours; the positive electrode, the composite solid electrolyte membrane and the lithium metal negative electrode were assembled in an argon-filled glove box having a water content and an oxygen content of less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid lithium battery is 83 omega.
In addition, the first-cycle discharge specific capacity of the solid-state lithium battery at 3.0-4.3V, 0.2C and 25 ℃ reaches 177.1 mAh/g; the capacity retention after 80 weeks of cycling was 56.8%.
From the above results, it can be seen that:
(1) in the crystal structure of the solid electrolyte material of the present invention I(422)Maximum peak value, I(422)/I(211)>1.05，1.05≤I(422)/I(420)Less than or equal to 1.3, is beneficial to lithium ion transmission and has high ionic conductivity; the structure is stable, and impurities such as lithium carbonate and the like are basically not generated on the surface;
(2) the monomer in the composite solid electrolyte provided by the invention can effectively activate a transmission channel of lithium ions, and reduce the interface impedance between an electrode and the electrolyte;
(3) the invention can effectively improve the dispersion uniformity of the garnet electrolyte material in the composite solid electrolyte, can better inhibit the formation of lithium dendrites and improve the battery cyclicity;
(4) the cubic phase garnet type solid electrolyte material has higher ionic conductivity (more than 10)-4S/cm), higher oxidation potential.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A cubic phase garnet type solid electrolyte material, characterized in that the solid electrolyte materialThe crystal structure of the material satisfies: i is(422)Maximum peak value, I(422)/I(211)>1.05，1.05≤I(422)/I(420)≤1.3。
2. The solid state electrolyte material according to claim 1, wherein a crystal structure of the solid state electrolyte material satisfies: 1.1 is less than or equal to I(422)/I(211)≤1.4，1.05≤I(422)/I(420)≤1.25；
Preferably, 1.14 ≦ I(422)/I(211)≤1.34，1.09≤I(422)/I(420)≤1.20。
3. The solid state electrolyte material according to claim 1 or 2, wherein the chemical expression of the solid state electrolyte material is: li7-δM’αLa3-βM”βZr2-γM”’γO12；
Wherein-1 < delta <2, 0< alpha <1, 0< beta <3, 0< gamma < 2;
m' is selected from Mg, Ca, Al, Ga, Sm, Tm or Y;
m' is selected from Bi, Ce, Er, Gd or Ho;
m' "is selected from Zn, Cu, Ce, Co, Ge, Hf, Ir, Mn, Mo, Ti, Ru, Se, Te, W, Sn, Sb, Nb or Ta.
4. The solid state electrolyte material of claim 3, wherein-0.5 ≦ δ ≦ 1, 0 ≦ α ≦ 0.5, 0 ≦ β ≦ 1.5, 0 ≦ γ ≦ 1;
preferably, 0. ltoreq. delta. ltoreq.0.6, 0. ltoreq. alpha. ltoreq.0.2, 0. ltoreq. beta. ltoreq.0.2, 0.1. ltoreq. gamma. ltoreq.0.3;
and/or, M' is selected from Mg or Al;
and/or, M' is selected from Bi or Er;
and/or, M' "is selected from Co, Hf, Mn, Ti, Sn or Nb;
preferably, at least one of α or β is 0.
5. A method for producing a solid electrolyte material according to any one of claims 1 to 4, characterized in that the production method comprises:
(1) mixing, grinding and drying a lithium source, a lanthanum source, a zirconium source, an M 'source and an M' source to obtain a mixture;
(2) and under a dry atmosphere, performing gradient sintering on the mixture, and then crushing, sieving and removing iron to obtain the solid electrolyte material.
6. The method of claim 5, wherein the source of M ', source of M ", source of M'" are each independently selected from one or more of the oxides, hydroxides, carbonates, oxalates, acetates, and citrates of M ', M ", M'";
and/or the M ' source, the M ' source and the M ' source are all nano-scale, and the specific surface area is more than or equal to 20M2/g；
Preferably, D of the M 'source, M' source50The same or different, each of which is 20-200nm, and has a specific surface area of 50-500m2/g；
And/or, in step (1), D of the mix501-5 μm, D of the mix100Is 4-10 μm.
7. The production method according to claim 5, wherein the gradient sintering includes a first sintering and a second sintering;
wherein the temperature of the first sintering is 300-; the temperature of the second sintering is 800-;
preferably, the temperature of the first sintering is 400-; the temperature of the second sintering is 900-.
8. A composite solid electrolyte comprising the solid electrolyte material according to any one of claims 1 to 4, a binder, a monomer, and a lithium salt.
9. The composite solid electrolyte according to claim 8, wherein the content of the solid electrolyte material is 60 to 90 wt%, the content of the binder is 2 to 20 wt%, the content of the monomer is 3 to 60 wt%, and the content of the lithium salt is 5 to 60 wt%, based on the total weight of the composite solid electrolyte;
and/or the monomer is selected from one or more of unsaturated carbonate with a dielectric constant of more than 10 and a halogenated substance thereof, phosphate with a dielectric constant of more than 10, carboxylic ester with a dielectric constant of 2-10 and ether with a dielectric constant of 5-10;
and/or the particle size D of the solid electrolyte material50Is 0.05-5 μm.
10. A method for producing the composite solid electrolyte according to claim 8 or 9, characterized by comprising:
(1) mixing a solid electrolyte material, a binder, a monomer and a lithium salt;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1) to obtain the composite solid electrolyte.
11. The production method according to claim 10, wherein the conditions for the kneading include: the temperature is 0.5-2Tm；
And/or, the hot pressing conditions include: the temperature is 0.5-2Tm；
Wherein, TmIs the melting point of the binder;
and/or the composite solid electrolyte is in the shape of a membrane, and the thickness of the membrane is 2-20 mu m.
12. A solid-state lithium battery comprising a positive electrode, an electrolyte and a negative electrode, characterized in that the electrolyte is the composite solid-state electrolyte of claim 8 or 9.
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