CN113937345A - Composite solid electrolyte, preparation method thereof and all-solid-state battery - Google Patents
Composite solid electrolyte, preparation method thereof and all-solid-state battery Download PDFInfo
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- CN113937345A CN113937345A CN202010670267.7A CN202010670267A CN113937345A CN 113937345 A CN113937345 A CN 113937345A CN 202010670267 A CN202010670267 A CN 202010670267A CN 113937345 A CN113937345 A CN 113937345A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 150
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 239000011325 microbead Substances 0.000 claims abstract description 23
- 238000010791 quenching Methods 0.000 claims description 31
- 230000000171 quenching effect Effects 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 16
- 229910052582 BN Inorganic materials 0.000 description 20
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002203 sulfidic glass Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229910020343 SiS2 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000075 oxide glass Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910001216 Li2S Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- 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
- H01M10/0562—Solid materials
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The present disclosure relates to a composite solid electrolyte including an oxide glassy electrolyte matrix and sulfide glassy electrolyte microbeads dispersed in the oxide glassy electrolyte matrix. The composite solid electrolyte glass can simultaneously give consideration to high strength, high stability and high ionic conductivity.
Description
Technical Field
The application relates to the field of lithium ion batteries, in particular to a composite solid electrolyte, a preparation method thereof and an all-solid-state battery.
Background
With the rapid development of electric vehicles, lithium metal batteries with high energy density are receiving more and more attention. However, in the conventional liquid electrolyte, the unstable deposition process of lithium metal and the dendrite growth cause a series of safety problems, which also seriously hinder the development of the lithium metal negative electrode. Solid-state electrolytes can match lithium metal negative electrodes and high-voltage positive electrodes to make higher energy density all-solid-state lithium battery cells (ASSLBs) than liquid electrolytes.
Most of the existing solid electrolyte glasses are oxide solid electrolytes and sulfide solid electrolytes, but each solid electrolyte glass has the advantages and the inherent defects, for example, the oxide solid electrolyte has higher mechanical strength and is stable in air, but the ionic conductivity is very low; the sulfide solid electrolyte has high ionic conductivity, but is unstable in air, low in strength and easy to crack.
The search for a solid electrolyte that combines high strength, high processability, high ionic conductivity and high stability in air is therefore a key issue in the development of solid-state batteries.
Disclosure of Invention
The purpose of the present disclosure is to provide a solid electrolyte having high stability and high ionic conductivity.
In order to achieve the above object, a first aspect of the present disclosure provides a composite solid electrolyte including an oxide glassy electrolyte matrix and sulfide glassy electrolyte microbeads dispersed in the oxide glassy electrolyte matrix. The composite solid electrolyte main body is an oxide glassy electrolyte, so that the main body electrolyte is stable in air and has higher strength, sulfide glassy electrolyte microbeads are embedded in the oxide glassy electrolyte main body after the composite modification of the sulfide glassy electrolyte, and the sulfide glassy electrolyte has higher ionic conductivity and plays a role of improving the ionic conductivity in the oxide glassy electrolyte main body, so that the composite solid electrolyte glass forms a structure similar to microcrystalline glass, and the microcrystalline but the sulfide glass microbeads improve the ionic conductivity. Finally, the composite solid electrolyte glass has high strength, high stability and high ionic conductivity.
Optionally, the diameter of the sulfide glassy electrolyte microbeads is between 1nm and 5 μm; preferably 50-500 nm.
Optionally, the sulfide glassy electrolyte microbeads are present in an amount of 0.01 to 20 parts by weight relative to 100 parts by weight of the composite solid electrolyte; preferably 1 to 5 parts by weight.
Optionally, the oxide glassy electrolyte matrix is selected from at least one of a phosphate glassy electrolyte, a silicate glassy electrolyte, a borate glassy electrolyte, and an anti-perovskite glassy electrolyte; the sulfide glassy electrolyte microbeads are selected from a thiosilicate glassy electrolyte and/or a thiophosphate glassy electrolyte;
preferably, the oxide glassy electrolyte matrix is selected from phosphate glassy electrolytes; the sulfide glassy electrolyte microbeads are selected from a thiosilicate glassy electrolyte.
Optionally, the oxide glassy electrolyte matrix contains a halogen, the halogen being at least one of fluorine, chlorine, bromine, and iodine.
A second aspect of the present disclosure provides a method for preparing a composite solid electrolyte, including the steps of:
s1, mixing and grinding the oxide glassy electrolyte and the sulfide glassy electrolyte to obtain a first mixed material;
s2, carrying out melting treatment and quenching treatment on the first mixed material; the melting treatment comprises early-stage high-temperature treatment and later-stage cooling treatment.
Alternatively, the oxide glassy electrolyte matrix may be selected from at least one of a phosphate glassy electrolyte, a silicate glassy electrolyte, a borate glassy electrolyte, and an anti-perovskite glassy electrolyte; the sulfide glassy electrolyte may be selected from a thiosilicate glassy electrolyte and/or a thiophosphate glassy electrolyte; preferably, the oxide glassy electrolyte matrix may be selected from phosphate glassy electrolytes; the sulfide glassy electrolyte may be selected from the group consisting of thiosilicate glassy electrolytes.
Optionally, the mass ratio of the oxide glassy electrolyte to the sulfide glassy electrolyte is 1: 0.01 to 0.25, preferably 1: 0.01-0.05.
Optionally, in step S2, the conditions of the high-temperature pretreatment include: under inert gas, the temperature is 600 ℃ and 1600 ℃, the time is 5-60min, and the heating rate is 0.3-10 ℃/min; the cooling treatment conditions comprise: under inert gas, the temperature is 500-1300 ℃, the time is 5-60min, and the cooling rate is 0.3-5 ℃/min; the inert gas is one of argon, nitrogen and helium; the quenching treatment mode is one of single medium quenching, double medium quenching, staged quenching, surface quenching and isothermal quenching.
A third aspect of the present disclosure provides an all-solid-state battery including a positive electrode, a negative electrode, and a solid electrolyte that is the composite solid electrolyte described above. Compared with the traditional liquid electrolyte battery, the solid-state battery has higher safety due to the existence of the composite solid electrolyte, can be matched with a high-voltage positive electrode and a lithium negative electrode, improves the energy density, and can be compatible with the existing production process due to the fact that the solid electrolyte glass has high flexibility as a diaphragm.
Through the technical scheme, the composite solid electrolyte glass has the advantages that the composite solid electrolyte glass is high in strength, stability and ionic conductivity.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
A first aspect of the present disclosure provides a composite solid electrolyte including an oxide glassy electrolyte matrix and sulfide glassy electrolyte microbeads dispersed in the oxide glassy electrolyte matrix.
According to the composite solid electrolyte disclosed by the invention, the oxide glassy electrolyte and the sulfide glassy electrolyte which cannot be mutually dissolved originally are physically taken as a matrix, and sulfide glassy electrolyte microbeads are embedded in the matrix. The structure enables the sulfide glass state electrolyte to be uniformly dispersed in the oxide glass electrolyte matrix, and the oxide glass state electrolyte has high strength and high stability, and the sulfide glass state electrolyte has higher ionic conductivity, so that the composite solid electrolyte glass has high strength, high stability and high ionic conductivity at the same time.
According to the first aspect of the present disclosure, the diameter of the sulfide glassy electrolyte microbeads may be 1nm to 5 μm; preferably 50-500 nm. The sulfide glassy state electrolyte micro-beads in the present disclosure can play a role in improving the ionic conductivity of oxide glass, while not reducing the structural strength of the oxide glassy state electrolyte matrix.
According to the first aspect of the present disclosure, the sulfide glassy electrolyte microbeads may be contained in an amount of 0.01 to 20 parts by weight, relative to 100 parts by weight of the composite solid electrolyte; preferably 1 to 5 parts by weight. In the present disclosure, a suitable sulfide glassy electrolyte bead content does not affect the physical properties of the oxide glassy electrolyte matrix while significantly increasing the ionic conductivity.
According to a first aspect of the present disclosure, the oxide glassy electrolyte matrix may be selected from at least one of a phosphate glassy electrolyte, a silicate glassy electrolyte, and an anti-perovskite glassy electrolyte; the sulfide glassy electrolyte microbeads may be selected from a thiosilicate glassy electrolyte and/or a thiophosphate glassy electrolyte.
Wherein the phosphate glass may comprise Li having a chemical formulaaXbYcZdPOeWherein a is between 0.5 and 6, X is one or more of Al, Y, Ca, Cr, In, Fe, Se and La, b is between 0 and 0.3, Y is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V and the element Hf, c is between 0 and 0.9, Z is one or more of F, Cl, Br and I, and d is between 0 and 1.5. The silicate glass may comprise Li having the formulaaXbYcZdSiOeWherein a is between 0.3 and 6, X is one or more of Na, K, Ca, Ba and Al, b is between 0 and 0.5, Y is one or more of Ti, Zr, La, Y, Sb, Sc, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, c is between 0 and 0.8, Z is one or more of F, Cl, Br and I, and d is between 0 and 1.5. The borate glass may comprise Li having the formulaaXbYcZdBOeWherein a is between 0.5 and 6, X is one or more of Na, K, Ca, Ba and Al, b is between 0 and 0.5, and Y is Ti, Zr, La, Y, Sb, Sc, V, Cr, Mn, Fe, Co, Al,One or more of Ni, Cu and Zn, c is between 0 and 0.8, Z is one or more of F, Cl, Br and I, and d is between 0 and 1.5. The anti-perovskite glass may comprise Li having the formula3-xM0.5xOZ, wherein x is between 0 and 1.5, M is one or more of Be, Mg, Ca, Sr and Ba, and Z is one or more of F, Cl, Br and I. The thiosilicate has the formula a (Li)2S)-b(SiS2) -c (LiX), wherein X is one or more of F, Cl, Br and I, a is between 20 and 70, b is between 30 and 80, c is between 0.1 and 30. The thiophosphate has the chemical formula alpha (Li)2S)-β(P2S5) - γ (LiX), wherein X is one or more of F, Cl, Br and I, a is between 40 and 75, β is between 25 and 60, c is between 0.1 and 50.
In a preferred embodiment of the present disclosure, the oxide glassy electrolyte matrix is selected from the group consisting of phosphate glassy electrolytes; the sulfide glassy electrolyte microbeads are selected from a thiosilicate glassy electrolyte.
In a preferred embodiment of the present disclosure, the oxide glassy electrolyte matrix contains a halogen, and the halogen is at least one of fluorine, chlorine, bromine, and iodine. The oxide glassy electrolytes containing halogen of the present disclosure can further improve the oxide glass ionic conductivity.
A second aspect of the present disclosure provides a method for preparing a composite solid electrolyte, including the steps of:
s1, mixing and grinding the oxide glassy electrolyte precursor and the sulfide glassy electrolyte to obtain a first mixed material;
s2, carrying out melting treatment and quenching treatment on the first mixed material; the melting treatment comprises early-stage high-temperature treatment and later-stage cooling treatment.
According to the second aspect of the present disclosure, the mass ratio of the oxide glassy electrolyte precursor to the sulfide glassy electrolyte precursor may be 1: 0.01 to 0.25, preferably 1: 0.01-0.05.
According to the second aspect of the present disclosure, the oxide glassy electrolyte may be selected from at least one of a phosphate glassy electrolyte, a silicate glassy electrolyte, a borate glassy electrolyte, and an anti-perovskite glassy electrolyte; the sulfide glassy electrolyte may be selected from a thiosilicate glassy electrolyte and/or a thiophosphate glassy electrolyte; preferably, the oxide glassy electrolyte matrix may be selected from phosphate glassy electrolytes; the sulfide glassy electrolyte may be selected from the group consisting of thiosilicate glassy electrolytes.
According to the second aspect of the present disclosure, in step S2, the conditions of the front-end high-temperature treatment may include: under inert gas, the temperature is 600 ℃ and 1600 ℃, the time is 5-60min, and the heating rate is 0.3-10 ℃/min; the cooling treatment conditions may include: under inert gas, the temperature is 500-1300 ℃, the time is 5-60min, and the cooling rate is 0.3-5 ℃/min; the inert gas is one of argon, nitrogen and helium; the conditions of the third quenching treatment may include: single medium quenching, double medium quenching, graded quenching, surface quenching and isothermal quenching; .
A third aspect of the present disclosure provides an all-solid-state battery including a positive electrode, a negative electrode, and a solid electrolyte that is the composite solid electrolyte described above.
The all-solid-state battery has higher safety compared with the traditional liquid electrolyte battery due to the existence of the composite solid electrolyte, and can be matched with a high-voltage anode and a lithium cathode to improve the energy density.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The materials, reagents, instruments and equipment used in the examples of the present disclosure are commercially available, unless otherwise specified. The example operations of the present disclosure were performed under an argon atmosphere.
Example 1
16mmol of LiCl and 24mmol of P2O5And 16mmol Li2CO3Adding into mortar, grinding and mixing. And placing the mixed powder into a boron nitride crucible, placing the boron nitride crucible into a muffle furnace heated to 800 ℃, taking out the boron nitride crucible after 10 minutes, pouring the boron nitride crucible into a stainless steel mold, and quenching to obtain the oxide glassy electrolyte.
40mmol of SiS2And 60mmol of Li2And S, adding the materials into a mortar for grinding, mixing fully, placing the materials into a boron nitride crucible, heating the materials to 950 ℃ along with a furnace, keeping the temperature at the rate of 5 ℃/min for 30 minutes, taking the materials out after full melting, pouring the materials into a stainless steel mold, and quenching to obtain the sulfide glassy electrolyte.
Grinding 95 mass percent of oxide glassy electrolyte and 5 mass percent of sulfide glassy electrolyte, grinding, uniformly mixing, placing into a boron nitride crucible, heating to 1300 ℃ along with the furnace, heating at a rate of 5 ℃/min, keeping for 10 minutes, cooling to 1100 ℃, taking out, pouring into a stainless steel mold, and quenching to obtain the composite solid electrolyte of the embodiment.
Example 2
24mmol of P2O5And 16mmol Li2CO3Adding into mortar, grinding and mixing. And placing the mixed powder into a boron nitride crucible, placing the boron nitride crucible into a muffle furnace heated to 800 ℃, taking out the boron nitride crucible after 10 minutes, pouring the boron nitride crucible into a stainless steel mold, and quenching to obtain the oxide glassy electrolyte.
40mmol of SiS2And 60mmol of Li2And S, adding the materials into a mortar for grinding, mixing fully, placing the materials into a boron nitride crucible, heating the materials to 950 ℃ along with a furnace, keeping the temperature at the rate of 5 ℃/min for 30 minutes, taking the materials out after full melting, pouring the materials into a stainless steel mold, and quenching to obtain the sulfide glassy electrolyte.
Grinding 95 mass percent of oxide glassy electrolyte and 5 mass percent of sulfide glassy electrolyte, grinding, uniformly mixing, placing into a boron nitride crucible, heating to 1300 ℃ along with the furnace, heating at a rate of 5 ℃/min, keeping for 10 minutes, cooling to 1100 ℃, taking out, pouring into a stainless steel mold, and quenching to obtain the composite solid electrolyte of the embodiment.
Example 3
The oxide glassy electrolyte and the sulfide glassy electrolyte of this example were prepared in the same manner as in example 1.
Grinding 80 mass percent of oxide glassy electrolyte and 20 mass percent of sulfide glassy electrolyte, grinding, uniformly mixing, placing into a boron nitride crucible, heating to 1300 ℃ along with the furnace, heating at a rate of 5 ℃/min, keeping for 10 minutes, cooling to 1100 ℃, taking out, pouring into a stainless steel mold, and quenching to obtain the composite solid electrolyte of the embodiment.
Example 4
The oxide glassy electrolyte and the sulfide glassy electrolyte of this example were prepared in the same manner as in example 1.
Grinding and then uniformly mixing the oxide glassy electrolyte with the mass ratio of 99% and the sulfide glassy electrolyte with the mass ratio of 1%, putting the mixture into a boron nitride crucible, heating the mixture to 1300 ℃ along with a furnace, heating the mixture at a rate of 5 ℃/min, keeping the temperature for 10 minutes, then cooling the mixture to 1100 ℃, taking the mixture out, pouring the mixture into a stainless steel mold, and quenching the mixture to obtain the composite solid electrolyte of the embodiment.
Comparative example 1
The preparation method of the composite solid electrolyte in this embodiment is the same as that in embodiment 1, except that in this embodiment, 95% by mass of the oxide glassy state electrolyte precursor and 5% by mass of the sulfide glassy state electrolyte precursor are ground, then ground, uniformly mixed, placed in a boron nitride crucible, heated to 1100 ℃ along with a furnace, heated at a rate of 5 ℃/min, kept for 10 minutes, taken out, poured into a stainless steel mold, and quenched, so as to obtain the composite solid electrolyte in this embodiment.
Comparative example 2
16mmol of LiCl and 24mmol of P2O5And 16mmol Li2CO3Adding into mortar, grinding and mixing. And placing the mixed powder into a boron nitride crucible, placing the boron nitride crucible into a muffle furnace heated to 800 ℃, taking out the boron nitride crucible after 10 minutes, pouring the boron nitride crucible into a stainless steel mold, and quenching to obtain the solid electrolyte of the comparative example.
Comparative example 3
40mmol of SiS2And 60mmol of Li2S additionGrinding in a pot, mixing fully, placing in a boron nitride crucible, heating to 950 ℃ along with the furnace, keeping the temperature at the rate of 5 ℃/min for 30 minutes, taking out after full melting, pouring into a stainless steel mold, and quenching to obtain the solid electrolyte of the comparative example.
Test example 1
The diameters of the sulfide glassy electrolyte microbeads in the solid electrolytes prepared in examples 1 to 4 and comparative examples 1 to 3 were measured by the following specific measurement methods: the measurement can be directly carried out under a scanning electron microscope, and the measurement result is shown in table 1.
TABLE 1
| Group of | Diameter of sulfide glassy state electrolyte microbeads | Content of sulfide glass state electrolyte micro beads |
| Example 1 | 50～100nm | 5％ |
| Example 2 | 30～80nm | 5％ |
| Example 3 | 300-500nm | 20％ |
| Example 4 | 5-20nm | 1％ |
| Comparative example 1 | - | - |
| Comparative example 2 | - | - |
| Comparative example 3 | - | - |
Test example 2
The solid electrolytes obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to an ion conductivity test by the following method: coating conductive silver adhesive on two sides of a glass sheet in a glove box, and drying in an oven at 150 ℃ for 1h to remove the solvent. Connecting electrodes at two ends of the glass sheet coated with the conductive silver paste, and carrying out electrochemical impedance test at a frequency of 7MHz-10 mHz.
0.5g of the samples obtained in examples 1 to 4 and comparative examples 1 to 2 was placed in a closed chamber having a capacity of 10L, and tested for H using a sensor2(ii) the concentration of S, to obtain the difference in its stability in air; the thermoformed samples (thickness 200 μm) were tested for bending resistance and the angle at which they broke was recorded to obtain strength data. The specific results are shown in Table 2.
| Group of | Ionic conductivity | H2S content | Bending angleDegree of rotation |
| Example 1 | 10-5S/cm-10-4S/cm | 0.5ppm | 85° |
| Example 2 | 10-6S/cm-10-5S/cm | 0.5ppm | 95° |
| Example 3 | 10-4S/cm | 7ppm | 70° |
| Example 4 | 10-6S/cm | 0.1ppm | 110° |
| Comparative example 1 | 10-6S/cm-10-5S/cm | 533ppm | 30° |
| Comparative example 2 | 10-8S/cm-10-7S/cm | 0ppm | 160° |
| Comparative example 3 | 10-4S/cm-10-3S/cm | 1383ppm | 60° |
As can be seen from the data in table 2: examples 1 to 4 were excellent in ionic conductivity and generally increased in stability and strength, and comparative example 1 was not subjected to high-temperature heat treatment, did not form a uniformly dispersed glass bead composite structure, and could not have high stability and high strength. As can be seen from comparative examples 2 and 3, the pure oxide solid state electrolyte glass does not have high ionic conductivity, and the pure sulfide solid state electrolyte glass does not have high stability and high strength. It follows that the composite solid electrolyte of the present disclosure can simultaneously achieve high strength, high stability, and high ionic conductivity.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A composite solid electrolyte comprising an oxide glassy electrolyte matrix and sulfide glassy electrolyte microbeads dispersed in the oxide glassy electrolyte matrix.
2. A composite solid-state electrolyte according to claim 1, wherein the diameter of the sulfide glassy electrolyte microbeads is between 1nm and 5 μ ι η; preferably 50-500 nm.
3. A composite solid electrolyte according to claim 1, wherein the sulfide glassy electrolyte microbeads are contained in an amount of 0.01 to 20 parts by weight relative to 100 parts by weight of the composite solid electrolyte; preferably 1 to 5 parts by weight.
4. A composite solid electrolyte according to claim 1, wherein the oxide glassy electrolyte matrix is selected from at least one of a phosphate glassy electrolyte, a silicate glassy electrolyte, a borate glassy electrolyte, and an anti-perovskite glassy electrolyte; the sulfide glassy electrolyte microbeads are selected from a thiosilicate glassy electrolyte and/or a thiophosphate glassy electrolyte;
preferably, the oxide glassy electrolyte matrix is selected from phosphate glassy electrolytes; the sulfide glassy electrolyte microbeads are selected from a thiosilicate glassy electrolyte.
5. The method of claim 4, wherein the oxide glassy electrolyte matrix comprises a halogen, the halogen being at least one of fluorine, chlorine, bromine, and iodine.
6. A method for producing a composite solid electrolyte according to any one of claims 1 to 5, characterized by comprising the steps of:
s1, mixing and grinding the oxide glassy electrolyte and the sulfide glassy electrolyte to obtain a first mixed material;
s2, carrying out melting treatment and quenching treatment on the first mixed material; the melting treatment comprises early-stage high-temperature treatment and later-stage cooling treatment.
7. The method of claim 6, wherein the mass ratio of the oxide glassy electrolyte to the sulfide glassy electrolyte is 1: 0.01 to 0.25, preferably 1: 0.01-0.05.
8. The method of claim 6, wherein the oxide glassy electrolyte is selected from at least one of a phosphate glassy electrolyte, a silicate glassy electrolyte, a borate glassy electrolyte, and an anti-perovskite glassy electrolyte; the sulfide glassy electrolyte is selected from a thiosilicate glassy electrolyte and/or a thiophosphate glassy electrolyte;
preferably, the oxide glassy electrolyte matrix is selected from phosphate glassy electrolytes; the sulfide glassy electrolyte is selected from the group consisting of thiosilicate glassy electrolytes.
9. The method of claim 6, wherein in step S2, the conditions of the pre-high temperature treatment include: under inert gas, the temperature is 600 ℃ and 1600 ℃, the time is 5-60min, and the heating rate is 0.3-10 ℃/min; the cooling treatment conditions comprise: under inert gas, the temperature is 500-1300 ℃, the time is 5-60min, and the cooling rate is 0.3-5 ℃/min; the inert gas is one of argon, nitrogen and helium;
the quenching treatment mode is one of single medium quenching, double medium quenching, staged quenching, surface quenching and isothermal quenching.
10. An all-solid-state battery comprising a positive electrode, a negative electrode and a solid-state electrolyte, characterized in that the solid-state electrolyte is a composite solid-state electrolyte according to any one of claims 1 to 5.
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