CN113937345B - 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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- CN113937345B CN113937345B CN202010670267.7A CN202010670267A CN113937345B CN 113937345 B CN113937345 B CN 113937345B CN 202010670267 A CN202010670267 A CN 202010670267A CN 113937345 B CN113937345 B CN 113937345B
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 162
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 239000011325 microbead Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims description 31
- 230000000171 quenching effect Effects 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 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
- 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
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000000034 method Methods 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
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 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
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052582 BN Inorganic materials 0.000 description 11
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 11
- 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
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910018091 Li 2 S Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910020346 SiS 2 Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002500 ions Chemical class 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
- 239000000075 oxide glass Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002203 sulfidic glass Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910020343 SiS2 Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 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
- 230000003247 decreasing effect Effects 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
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 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
- 239000002904 solvent Substances 0.000 description 1
Classifications
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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
- 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
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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)
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- 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 state electrolyte comprising an oxide glassy electrolyte matrix and sulfide glassy electrolyte microbeads dispersed in the oxide glassy electrolyte matrix. The composite solid electrolyte glass can simultaneously have 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, unstable deposition process of lithium metal and dendrite growth cause a series of safety problems, which also seriously hamper the development of lithium metal cathodes. The solid state electrolyte can match a lithium metal negative electrode with a high voltage positive electrode to form an all solid state lithium battery cell (ASSLBs) of higher energy density than a liquid electrolyte.
Most of the existing solid electrolyte glasses are oxide solid electrolyte and sulfide solid electrolyte, but each solid electrolyte glass has the advantages and inherent defects, such as high mechanical strength and air stability, but low ionic conductivity; the sulfide solid electrolyte has high ionic conductivity, but is unstable in air, low in strength and easy to crack.
It is therefore a key issue in the development of solid state batteries to find a solid state electrolyte that combines high strength, high processability, high ionic conductivity and high stability in air.
Disclosure of Invention
The purpose of the present disclosure is to provide a solid electrolyte with 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 body is oxide glassy electrolyte, so that the main body electrolyte is stable in air and high in strength, sulfide glassy electrolyte microbeads are embedded into the oxide glassy electrolyte body after being subjected to composite modification by sulfide glassy electrolyte, and the sulfide glassy electrolyte has high ionic conductivity and plays a role in improving the ionic conductivity in the oxide glassy electrolyte body, so that the composite solid electrolyte glass forms a structure similar to microcrystalline glass, and the ionic conductivity is improved, namely the microcrystalline glass microbeads. Finally, the structure enables the composite solid electrolyte glass to have high strength, high stability and high ionic conductivity.
Alternatively, the sulfide glassy electrolyte microbeads have a diameter of 1nm to 5 μm; preferably 50-500nm.
Alternatively, the sulfide glassy electrolyte microbeads are contained in an amount of 0.01 to 20 parts by weight with respect 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 inverse perovskite glassy electrolyte; the sulfide glassy electrolyte microbeads are selected from a thiosulfate 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 the group consisting of thiosilicate glassy electrolytes.
Optionally, the oxide glassy electrolyte matrix contains halogen, wherein the halogen is at least one of fluorine, chlorine, bromine and iodine.
A second aspect of the present disclosure provides a method of preparing a composite solid electrolyte, the method comprising the steps of:
s1, mixing and grinding oxide glassy electrolyte and 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 a pre-high temperature treatment and a post-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 inverse 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 a thiosilicate glassy electrolyte.
Optionally, the mass ratio of the oxide glassy electrolyte to the sulfide glassy electrolyte is 1:0.01-0.25, preferably 1:0.01-0.05.
Optionally, in step S2, the conditions of the early high temperature treatment include: under inert gas, the temperature is 600-1600 ℃, the time is 5-60min, and the heating rate is 0.3-10 ℃/min; the conditions of the cooling treatment 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 selected from single medium quenching, double medium quenching, classification quenching, surface quenching and isothermal quenching.
A third aspect of the present disclosure provides an all-solid-state battery comprising a positive electrode, a negative electrode, and a solid-state electrolyte, the solid-state electrolyte being the above-described composite solid-state electrolyte. Compared with the traditional liquid electrolyte battery, the solid-state battery has higher safety due to the existence of the composite solid-state 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-state electrolyte glass has high flexibility like a diaphragm.
Through the technical scheme, the composite solid electrolyte is provided, and the composite solid electrolyte glass can be high in strength, high in stability and high in ionic conductivity.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
A first aspect of the present disclosure provides a composite solid state electrolyte comprising an oxide glassy electrolyte matrix and sulfide glassy electrolyte microbeads dispersed in the oxide glassy electrolyte matrix.
The composite solid electrolyte of the present disclosure has oxide glassy electrolyte and sulfide glassy electrolyte which are not mutually soluble, and sulfide glassy electrolyte beads are embedded in the matrix by using the oxide glassy electrolyte as the matrix in a physical mode. The structure enables sulfide glassy electrolyte to be uniformly dispersed in an oxide glass electrolyte matrix, and the sulfide glassy electrolyte has high strength and high stability, so that the composite solid electrolyte glass has high strength, high stability and high ionic conductivity.
According to a first aspect of the present disclosure, the sulfide glassy electrolyte microbeads may have a diameter of 1nm to 5 μm; preferably 50-500nm. The sulfide glassy electrolyte microbeads in the present disclosure can function to increase the ionic conductivity of oxide glass without decreasing the structural strength of the oxide glassy 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 with respect to 100 parts by weight of the composite solid electrolyte; preferably 1 to 5 parts by weight. In the present disclosure, the appropriate sulfide glassy electrolyte microbead content does not affect the physical properties of the oxide glassy electrolyte matrix while significantly enhancing 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 inverse 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 a material having the formula Li aXbYcZdPOe, wherein 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. Silicate glasses may comprise a material having the formula Li aXbYcZdSiOe, where 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 a material having the formula Li aXbYcZdBOe, where 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, 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 anti-perovskite glass may comprise a material having the formula Li 3-xM0.5x OZ, where x is between 0 and 1.5, M is one or more of Be, mg, ca, sr, 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, and c is between 0.1 and 30. The thiophosphate has the formula α (Li 2S)-β(P2S5) - γ (LiX), where X is one or more of F, cl, br and I, a is between 40 and 75, β is between 25 and 60, and c is between 0.1 and 50.
In a preferred embodiment of the present disclosure, the oxide glassy electrolyte matrix is selected from phosphate glassy electrolytes; the sulfide glassy electrolyte microbeads are selected from the group consisting of thiosilicate glassy electrolytes.
In a preferred embodiment of the present disclosure, the oxide glassy electrolyte matrix contains a halogen, which is at least one of fluorine, chlorine, bromine, and iodine. The halogen-containing oxide glassy electrolytes of the present disclosure can further improve oxide glass ionic conductivity.
A second aspect of the present disclosure provides a method of preparing a composite solid electrolyte, the method comprising the steps of:
S1, mixing and grinding an oxide glassy electrolyte precursor and a 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 a pre-high temperature treatment and a post-cooling treatment.
According to a second aspect of the present disclosure, the mass ratio of the oxide glassy electrolyte precursor and the sulfide glassy electrolyte precursor may be 1:0.01-0.25, preferably 1:0.01-0.05.
According to a 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 inverse 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 a thiosilicate glassy electrolyte.
According to a second aspect of the present disclosure, in step S2, the conditions of the preliminary high temperature treatment may include: under inert gas, the temperature is 600-1600 ℃, the time is 5-60min, and the heating rate is 0.3-10 ℃/min; the conditions of the cooling treatment 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, dual medium quenching, staged quenching, surface quenching and isothermal quenching; .
A third aspect of the present disclosure provides an all-solid-state battery comprising a positive electrode, a negative electrode, and a solid-state electrolyte, the solid-state electrolyte being the above-described composite solid-state electrolyte.
The all-solid-state battery has higher safety compared with the traditional liquid electrolyte battery due to the existence of the composite solid electrolyte, can be matched with a high-voltage positive electrode and a lithium negative electrode, improves energy density, and can be compatible with the existing production process due to the fact that the solid electrolyte glass has high flexibility like a diaphragm.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
Materials, reagents, instruments and equipment used in the examples of the present disclosure are commercially available unless otherwise specified. The operation of the examples of the present disclosure was performed under an argon atmosphere.
Example 1
16Mmol LiCl, 24mmol P 2O5 and 16mmol Li 2CO3 were added to a mortar and ground to mix well. Placing the mixed powder into a boron nitride crucible, placing the crucible into a muffle furnace which is heated to 800 ℃, taking out the crucible after 10 minutes, pouring the crucible into a stainless steel die, and quenching to obtain the oxide glassy electrolyte.
Adding 40mmol SiS 2 and 60mmol Li 2 S into a mortar for grinding, mixing thoroughly, placing into a boron nitride crucible, heating to 950 ℃ along with a furnace, keeping the temperature rising speed at 5 ℃/min for 30 minutes, taking out after full melting, pouring into a stainless steel mold for quenching, and obtaining the sulfide glassy electrolyte.
Grinding oxide glassy electrolyte with the mass ratio of 95% and sulfide glassy electrolyte with the mass ratio of 5%, grinding and mixing uniformly, placing into a boron nitride crucible, heating to 1300 ℃ along with a furnace, heating at a rate of 5 ℃/min, cooling to 1100 ℃ after keeping for 10 minutes, taking out, pouring into a stainless steel die, and quenching to obtain the composite solid electrolyte of the embodiment.
Example 2
24Mmol of P 2O5 and 16mmol of Li 2CO3 are added into a mortar for grinding and mixing uniformly. Placing the mixed powder into a boron nitride crucible, placing the crucible into a muffle furnace which is heated to 800 ℃, taking out the crucible after 10 minutes, pouring the crucible into a stainless steel die, and quenching to obtain the oxide glassy electrolyte.
Adding 40mmol SiS 2 and 60mmol Li 2 S into a mortar for grinding, mixing thoroughly, placing into a boron nitride crucible, heating to 950 ℃ along with a furnace, keeping the temperature rising speed at 5 ℃/min for 30 minutes, taking out after full melting, pouring into a stainless steel mold for quenching, and obtaining the sulfide glassy electrolyte.
Grinding oxide glassy electrolyte with the mass ratio of 95% and sulfide glassy electrolyte with the mass ratio of 5%, grinding and mixing uniformly, placing into a boron nitride crucible, heating to 1300 ℃ along with a furnace, heating at a rate of 5 ℃/min, cooling to 1100 ℃ after keeping for 10 minutes, taking out, pouring into a stainless steel die, and quenching to obtain the composite solid electrolyte of the embodiment.
Example 3
The oxide glassy electrolyte and sulfide glassy electrolyte of this example were prepared in the same manner as in example 1.
Grinding oxide glassy electrolyte with the mass ratio of 80% and sulfide glassy electrolyte with the mass ratio of 20%, grinding and mixing uniformly, placing into a boron nitride crucible, heating to 1300 ℃ along with a furnace, heating at a rate of 5 ℃/min, cooling to 1100 ℃ after keeping for 10 minutes, taking out, pouring into a stainless steel die, and quenching to obtain the composite solid electrolyte of the embodiment.
Example 4
The oxide glassy electrolyte and sulfide glassy electrolyte of this example were prepared in the same manner as in example 1.
Grinding oxide glassy electrolyte with the mass ratio of 99% and sulfide glassy electrolyte with the mass ratio of 1%, grinding and mixing uniformly, placing into a boron nitride crucible, heating to 1300 ℃ along with a furnace, heating at a rate of 5 ℃/min, cooling to 1100 ℃ after keeping for 10 minutes, taking out, pouring into a stainless steel die, and quenching to obtain the composite solid electrolyte of the embodiment.
Comparative example 1
The preparation method of the composite solid electrolyte of the embodiment is the same as that of the embodiment 1, except that the oxide glassy electrolyte precursor with the mass ratio of 95% and the sulfide glassy electrolyte precursor with the mass ratio of 5% are ground and then are ground and mixed uniformly, the ground and mixed uniformly is placed into a boron nitride crucible, the temperature is raised to 1100 ℃ along with the furnace, the heating rate is 5 ℃/min, the mixture is kept for 10 minutes, and then the mixture is taken out and poured into a stainless steel die to be quenched, so that the composite solid electrolyte of the embodiment is obtained.
Comparative example 2
16Mmol LiCl, 24mmol P 2O5 and 16mmol Li 2CO3 were added to a mortar and ground to mix well. Placing the mixed powder into a boron nitride crucible, placing the crucible into a muffle furnace which is heated to 800 ℃, taking out the crucible after 10 minutes, pouring the crucible into a stainless steel die, and quenching to obtain the solid electrolyte of the comparative example.
Comparative example 3
Adding 40mmol SiS 2 and 60mmol Li 2 S into a mortar for grinding, mixing thoroughly, placing into a boron nitride crucible, heating to 950 ℃ along with a furnace, keeping the temperature rising speed at 5 ℃/min for 30 minutes, taking out after full melting, pouring into a stainless steel die for quenching, and obtaining the solid electrolyte of the comparative example.
Test example 1
The diameters of 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: can be directly measured under a scanning electron microscope, and the measurement results are shown in table 1.
TABLE 1
| Group of | Diameter of sulfide glassy electrolyte microbeads | Content of sulfide glassy electrolyte microbeads |
| 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 ion conductivity test as follows: in a glove box, conductive silver paste is coated on two sides of a glass sheet, and the glass sheet is put into an oven to be dried for 1h at 150 ℃ to remove the solvent. And connecting two ends of the glass sheet coated with the conductive silver paste with electrodes, and performing electrochemical impedance test at the frequency of 7MHz-10mHz.
0.5G of the samples obtained in examples 1 to 4 and comparative examples 1 to 2 were placed in a closed cavity having a capacity of 10L, and the concentration of H 2 S was measured using a sensor to obtain a difference in stability in air; the thermoformed sample (thickness 200 μm) was subjected to a bending resistance test, and the angle at break thereof was recorded to obtain the strength data thereof. The specific results are shown in Table 2.
| Group of | Ion conductivity | H 2 S content | Bending angle |
| 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° |
From the data in table 2, it can be seen that: 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, and a uniformly dispersed glass bead composite structure was not formed, and it was impossible to 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 ion conductivity, and the pure sulfide solid state electrolyte glass does not have high stability and high strength. From this, it can be seen that the composite solid electrolyte of the present disclosure can simultaneously combine high strength, high stability, and high ionic conductivity.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (5)
1. A composite solid electrolyte comprising an oxide glassy electrolyte matrix and sulfide glassy electrolyte microbeads dispersed in the oxide glassy electrolyte matrix; the diameter of the sulfide glassy electrolyte microbeads is 50-500nm; the content of the sulfide glassy electrolyte microbeads is 1-5 parts by weight relative to 100 parts by weight of the composite solid electrolyte;
The oxide glassy electrolyte matrix is selected from at least one of phosphate glassy electrolyte, silicate glassy electrolyte, borate glassy electrolyte and inverse perovskite glassy electrolyte; the sulfide glassy electrolyte microbeads are selected from a thiosulfate glassy electrolyte and/or a thiophosphate glassy electrolyte; the oxide glassy electrolyte matrix contains halogen, wherein the halogen is at least one of fluorine, chlorine, bromine and iodine.
2. The composite solid state electrolyte of claim 1, wherein the oxide glassy electrolyte matrix is selected from phosphate glassy electrolytes; the sulfide glassy electrolyte microbeads are selected from the group consisting of thiosilicate glassy electrolytes.
3. A method of preparing a composite solid electrolyte according to any one of claims 1 to 2, comprising the steps of:
s1, mixing and grinding oxide glassy electrolyte and 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 a pre-high temperature treatment and a post-cooling treatment; the conditions of the pre-high temperature treatment include: under inert gas, the temperature is 600-1600 ℃, the time is 5-60min, and the heating rate is 0.3-10 ℃/min; the conditions of the post cooling treatment 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 selected from single medium quenching, double medium quenching, classification quenching, surface quenching and isothermal quenching;
the mass ratio of the oxide glassy electrolyte to the sulfide glassy electrolyte is 1:0.01-0.05;
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 inverse perovskite glassy electrolyte; the sulfide glassy electrolyte is selected from a thiosilicate glassy electrolyte and/or a thiophosphate glassy electrolyte.
4. A method according to claim 3, wherein the oxide glassy electrolyte is selected from phosphate glassy electrolytes; the sulfide glassy electrolyte is selected from the group consisting of thiosilicate glassy electrolytes.
5. An all-solid-state battery comprising a positive electrode, a negative electrode, and a solid-state electrolyte, wherein the solid-state electrolyte is the composite solid-state electrolyte according to any one of claims 1 to 2.
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