CN113937346B - Solid electrolyte, preparation method thereof and all-solid-state battery - Google Patents
Solid electrolyte, preparation method thereof and all-solid-state battery Download PDFInfo
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- CN113937346B CN113937346B CN202010670273.2A CN202010670273A CN113937346B CN 113937346 B CN113937346 B CN 113937346B CN 202010670273 A CN202010670273 A CN 202010670273A CN 113937346 B CN113937346 B CN 113937346B
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title description 3
- 239000002203 sulfidic glass Substances 0.000 claims abstract description 51
- 239000000654 additive Substances 0.000 claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- 230000005496 eutectics Effects 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 40
- 239000003792 electrolyte Substances 0.000 claims description 39
- 238000010791 quenching Methods 0.000 claims description 35
- 230000000171 quenching effect Effects 0.000 claims description 35
- 238000000227 grinding Methods 0.000 claims description 20
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 239000005365 phosphate glass Substances 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000005368 silicate glass Substances 0.000 claims description 8
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 6
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000010128 melt processing Methods 0.000 claims description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 238000004090 dissolution Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 description 16
- 229910052582 BN Inorganic materials 0.000 description 14
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 229910018091 Li 2 S Inorganic materials 0.000 description 4
- 229910020346 SiS 2 Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 230000000630 rising effect Effects 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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)
- Conductive Materials (AREA)
- Glass Compositions (AREA)
Abstract
The present disclosure relates to a solid electrolyte comprising an oxide solid electrolyte, a sulfide solid electrolyte, and an oxide additive; wherein the oxide solid electrolyte, the sulfide solid electrolyte, and the oxide additive form a glassy eutectic. The solid electrolyte realizes the mutual dissolution of the oxide solid electrolyte and the sulfide solid electrolyte, and has high ionic conductivity, high strength and high air stability.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to a solid electrolyte, a preparation method thereof and an all-solid-state battery.
Background
The solid electrolyte refers to a solid material having high ion conductivity. The lithium ion battery currently used contains combustible liquid organic matters, lithium metal dendrites and uneven deposition occur in circulation, along with the continuous development of lithium ion battery technology, the requirements for high-safety and high-energy-density batteries are greatly increased, and the solid battery composed of solid electrolyte can well solve the problems. In an inorganic all-solid-state battery, the solid-state electrolyte glass can be compatible with the existing production process due to better processability.
Most of the existing solid electrolyte glasses are phosphates, silicates, borates, thiosilicates and thiophosphates, but each solid electrolyte glass has the advantages and inherent defects, such as high mechanical strength, stability in air and low ionic conductivity of oxides such as phosphates, silicates and borates; however, the ion conductivity of the thiosilicate and the thiophosphate is high, but the thiosilicate and the thiophosphate are unstable in air, have lower strength and are easier to break. Therefore, finding a solid electrolyte that combines high strength, high processability, high ionic conductivity and high stability in air is a major problem in the development of solid-state batteries.
Disclosure of Invention
An object of the present disclosure is to provide a solid electrolyte that combines strength, processability, high ionic conductivity and stability in air.
To achieve the above object, a first aspect of the present disclosure provides a solid electrolyte including an oxide solid electrolyte, a sulfide solid electrolyte, and an oxide additive; wherein the oxide solid electrolyte, the sulfide solid electrolyte, and the oxide additive form a glassy eutectic.
The oxide additive is used for realizing the mutual dissolution of the oxide solid electrolyte and the sulfide solid electrolyte, so that the oxide solid electrolyte and the sulfide solid electrolyte can form the oxide-sulfide solid electrolyte, wherein the sulfide solid electrolyte has higher ionic conductivity, and the oxide solid electrolyte has higher stability and strength in air, so that the solid electrolyte disclosed by the disclosure can simultaneously have high strength, high processability, high ionic conductivity and high stability in air.
Alternatively, the content of the oxide additive is 0.01 to 20 parts by weight, the content of the oxide solid electrolyte is 50 to 100 parts by weight, and the content of the sulfide solid electrolyte is 5 to 50 parts by weight, relative to 100 parts by weight of the solid electrolyte;
Preferably, the content of the oxide additive is 1 to 5 parts by weight, the content of the oxide solid electrolyte is 60 to 80 parts by weight, and the content of the sulfide solid electrolyte is 5 to 20 parts by weight, relative to 100 parts by weight of the solid electrolyte.
Optionally, the oxide additive is selected from at least one of B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2.
Optionally, the oxide solid electrolyte is selected from at least one of a phosphate glass solid electrolyte, a silicate glass solid electrolyte, and an anti-perovskite glass solid electrolyte; the sulfide solid state electrolyte is selected from a thiosilicate glass solid state electrolyte and/or a thiophosphate glass solid state electrolyte;
Preferably, the oxide solid electrolyte is selected from phosphate glass solid electrolytes; the sulfide solid state electrolyte is selected from the group consisting of thiosilicate glass solid state electrolytes.
Optionally, the oxide solid electrolyte contains halogen, and 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 solid electrolyte, the method comprising the steps of:
S1, mixing and grinding an oxide solid electrolyte, a sulfide solid electrolyte and an oxide additive to obtain a first mixed material;
S2, carrying out melting treatment and quenching treatment on the first mixed material.
Optionally, the oxide solid electrolyte is selected from at least one of a phosphate glass solid electrolyte, a silicate glass solid electrolyte, and an anti-perovskite glass solid electrolyte; the sulfide solid state electrolyte is selected from a thiosilicate glass solid state electrolyte and/or a thiophosphate glass solid state electrolyte; the oxide additive is selected from at least one of B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2.
Preferably, the oxide solid electrolyte is selected from phosphate glass solid electrolytes; the sulfide solid state electrolyte is selected from a thiosilicate glass solid state electrolyte; the additive is selected from at least one of B 2O3、Nb2O5 and SnO 2.
Further preferably, the oxide solid electrolyte contains halogen, and the halogen is at least one of fluorine, chlorine, bromine and iodine.
Optionally, the mass ratio of the oxide solid electrolyte precursor, the sulfide solid electrolyte precursor, and the oxide additive is 1:0.01-1:0.0001-0.25, preferably 1:0.05-0.25:0.01-0.1.
Optionally, in step S2, the conditions of the melting process include: under inert gas, the temperature is 300-1600 ℃ and the time is 5-60min; the quenching treatment mode is selected from the following treatment modes: single medium quenching, dual medium quenching, staged quenching, surface quenching and isothermal quenching; the inert gas is one of argon, nitrogen and helium.
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 described above. Compared with the traditional liquid electrolyte battery, the solid-state battery has higher safety due to the existence of the 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 solid electrolyte provided by the disclosure realizes the mutual dissolution of the oxide solid electrolyte glass and the sulfide solid electrolyte glass due to the existence of the oxide additive, so that the oxide solid electrolyte glass can be formed into the oxide-sulfide solid electrolyte glass. The sulfide solid electrolyte can improve the ionic conductivity of an oxide system, and the oxide solid electrolyte can improve the stability and strength of sulfide in air, so that the solid electrolyte can simultaneously have high strength, high processability, high ionic conductivity and high stability in air.
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 solid state electrolyte comprising an oxide solid state electrolyte, a sulfide solid state electrolyte, and an oxide additive; wherein the oxide solid electrolyte, the sulfide solid electrolyte, and the oxide additive form a glassy eutectic.
The solid electrolyte provided by the present disclosure is a mixed system solid electrolyte that is compatible with both oxide solid electrolytes and sulfide solid electrolytes. The conventional oxide solid electrolyte glass and sulfide solid electrolyte glass cannot be mutually dissolved in a high-temperature molten state, and the inventor obtains that the polarity and bond energy of additive molecules are between the two through a large number of experiments, and the addition of the oxide additive can realize the mutual dissolution of the oxide solid electrolyte and the sulfide solid electrolyte, so that the oxide solid electrolyte can form the oxide-sulfide mixed system solid electrolyte glass, the sulfide solid electrolyte can improve the ionic conductivity of an oxide system, and the oxide solid electrolyte can improve the stability and strength in the air of sulfide, thereby constructing the mixed system solid electrolyte, greatly improving the physical properties of the solid electrolyte, and enabling the solid electrolyte to have high ionic conductivity, high strength, high processability and high air stability.
According to the first aspect of the present disclosure, the content of the oxide additive may be 0.01 to 20 parts by weight, the content of the oxide solid electrolyte may be 50 to 100 parts by weight, and the content of the sulfide solid electrolyte may be 5 to 50 parts by weight, relative to 100 parts by weight of the solid electrolyte. The presence of a small amount of oxide additive molecules in the present disclosure can connect the oxide and sulfide solid state electrolyte glass networks to make them miscible.
In a preferred embodiment of the present disclosure, the oxide additive may be contained in an amount of 1 to 5 parts by weight, the oxide solid electrolyte may be contained in an amount of 60 to 80 parts by weight, and the sulfide solid electrolyte may be contained in an amount of 5 to 20 parts by weight, relative to 100 parts by weight of the solid electrolyte.
According to a first aspect of the present disclosure, the additive may be selected from at least one of B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2. The polarity and bond energy of the oxide additive are between the oxide solid electrolyte molecules and the sulfide solid electrolyte molecules, so that the oxide solid electrolyte molecules and the sulfide solid electrolyte molecules can be well connected to form a space network structure.
According to the first aspect of the present disclosure, the oxide solid electrolyte may be selected from at least one of a phosphate glass solid electrolyte, a silicate glass solid electrolyte, and an inverse perovskite glass solid electrolyte; the sulfide solid state electrolyte may be selected from a thiosilicate glass solid state electrolyte and/or a thiophosphate glass solid state electrolyte.
According to the first aspect of the present disclosure, phosphate glass solid electrolytes, silicate glass solid electrolytes, and anti-perovskite glass solid electrolytes may be well known to those skilled in the art. For example, the phosphate glass solid state electrolyte may comprise a material having the formula Li aXbYcZdPOe, where 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 solid electrolyte 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.
In a preferred embodiment of the present disclosure, the oxide solid electrolyte is selected from phosphate glass solid electrolytes; the sulfide solid state electrolyte is selected from the group consisting of thiosilicate glass solid state electrolytes.
In a preferred embodiment of the present disclosure, the oxide solid electrolyte may contain a halogen therein, so that the ion conductivity of the solid electrolyte may be further increased, wherein the halogen may be at least one of fluorine, chlorine, bromine and iodine.
A second aspect of the present disclosure provides a method of preparing a solid electrolyte, the method comprising the steps of:
S1, mixing and grinding an oxide solid electrolyte, a sulfide solid electrolyte and an oxide additive to obtain a first mixed material;
S2, carrying out melting treatment and quenching treatment on the first mixed material.
The solid electrolyte prepared by the method realizes the mutual dissolution of the oxide solid electrolyte and the sulfide solid electrolyte, so that the oxide solid electrolyte and the sulfide solid electrolyte can form an oxide-sulfide mixed system solid electrolyte. The sulfide solid electrolyte can improve the ion conductivity of the oxide solid electrolyte, and the oxide solid electrolyte can improve the stability and strength of the sulfide solid electrolyte in the air, so that the sulfide solid electrolyte glass meets the requirements of high strength, high stability and high ion conductivity.
According to a second aspect of the present disclosure, the oxide solid electrolyte may be selected from at least one of a phosphate glass solid electrolyte, a silicate glass solid electrolyte, and an inverse perovskite glass solid electrolyte; the sulfide solid state electrolyte may be selected from a thiosilicate glass solid state electrolyte and/or a thiophosphate glass solid state electrolyte; the oxide additive may be selected from at least one of B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2. Preferably, the oxide solid electrolyte may be selected from phosphate glass solid electrolytes; the sulfide solid state electrolyte may be selected from a thiosilicate glass solid state electrolyte; the additive may be selected from at least one of B 2O3、Nb2O5 and SnO 2.
According to a second aspect of the present disclosure, the oxide solid electrolyte may contain halogen therein, and the halogen may be at least one of fluorine, chlorine, bromine, and iodine. The present disclosure may further increase the ionic conductivity of the solid electrolyte by introducing a halogen element into the oxide solid electrolyte precursor.
According to a second aspect of the present disclosure, the mass ratio of the oxide solid electrolyte precursor, the sulfide solid electrolyte precursor, and the oxide additive may be 1:0.01-1:0.0001-0.25, preferably 1:0.05-0.25:0.01-0.1.
According to a second aspect of the present disclosure, in step S2, the conditions of the melt processing may include: under inert gas, the temperature is 300-1600 ℃ and the time is 5-60min; the quenching treatment may be performed in a manner selected from the group consisting of: one of single medium quenching, dual medium quenching, staged quenching, surface quenching and isothermal quenching; the inert gas may be one of argon, nitrogen and helium.
A third aspect of the present disclosure provides an all-solid state battery including a positive electrode, a negative electrode, and a solid state electrolyte.
The all-solid-state battery has higher safety compared with the traditional liquid electrolyte battery due to the existence of the 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 examples of the present disclosure were all 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 solid 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 die for quenching, and obtaining the sulfide solid electrolyte.
Grinding 80% of oxide solid electrolyte, 5% of B 2O3% of sulfide solid electrolyte and 15% of sulfide solid electrolyte, grinding and uniformly mixing, placing into a boron nitride crucible, heating to 1150 ℃ along with a furnace, heating at a rate of 5 ℃/min, keeping for 20 minutes, taking out, pouring into a stainless steel die, and quenching to obtain the 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 solid 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 die for quenching, and obtaining the sulfide solid electrolyte.
Grinding 80% of oxide solid electrolyte, 5% of B 2O3% of sulfide solid electrolyte and 15% of sulfide solid electrolyte, grinding and uniformly mixing, placing into a boron nitride crucible, heating to 1150 ℃ along with a furnace, heating at a rate of 5 ℃/min, keeping for 20 minutes, taking out, pouring into a stainless steel die, and quenching to obtain the solid electrolyte of the embodiment.
Example 3
The oxide solid electrolyte and sulfide solid electrolyte of this example were prepared in the same manner as in example 1.
Grinding 94% of oxide solid electrolyte, 1% of B 2O3% of sulfide solid electrolyte, grinding, uniformly mixing, placing into a boron nitride crucible, heating to 1150 ℃ along with a furnace, heating at a rate of 5 ℃/min, keeping for 20 minutes, taking out, pouring into a stainless steel die, and quenching to obtain the solid electrolyte of the embodiment.
Example 4
The oxide solid electrolyte and sulfide solid electrolyte of this example were prepared in the same manner as in example 1.
Grinding the oxide solid electrolyte with the mass ratio of 50%, the B 2O3 with the mass ratio of 20% and the sulfide solid electrolyte with the mass ratio of 30%, grinding and uniformly mixing, placing into a boron nitride crucible, heating to 1150 ℃ along with a furnace, heating at a speed of 5 ℃/min, taking out after 20 minutes, pouring into a stainless steel die, and quenching to obtain the solid electrolyte of the embodiment.
Example 5
The oxide solid electrolyte and sulfide solid electrolyte of this example were prepared in the same manner as in example 1.
Grinding 80% of oxide solid electrolyte, 5% of SiO 2% of sulfide solid electrolyte and 15% of sulfide solid electrolyte, grinding and uniformly mixing, placing into a boron nitride crucible, heating to 1150 ℃ along with a furnace, heating at a rate of 5 ℃/min, keeping for 20 minutes, taking out, pouring into a stainless steel die, and quenching to obtain the solid electrolyte of the embodiment.
Comparative 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 solid 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 die for quenching, and obtaining the sulfide solid electrolyte.
Grinding oxide solid electrolyte with the mass ratio of 80% and sulfide solid electrolyte with the mass ratio of 20%, grinding and mixing uniformly, placing into a boron nitride crucible, heating to 1150 ℃ along with a furnace, heating at a rate of 5 ℃/min, taking out after 20 minutes, pouring into a stainless steel die, and quenching to obtain the solid electrolyte of the comparative example.
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 solid electrolytes obtained in examples 1 to 5 and comparative examples 1 to 3 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 5 and comparative examples 1 to 3 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 | Whether or not it is a homogeneous phase |
| Example 1 | 10-5-10-4S/cm | 7ppm | 120° | Is that |
| Example 2 | 10-6-10-5S/cm | 5ppm | 160° | Is that |
| Example 3 | 10-6-10-5S/cm | 2ppm | 135° | Is that |
| Example 4 | 10-5-10-4S/cm | 53ppm | 90° | Is that |
| Example 5 | 10-6S/cm | 7ppm | 120° | Is that |
| Comparative example 1 | 10-7-10-6S/cm | 565ppm | 30° | Whether or not |
| Comparative example 2 | 10-8-10-7S/cm | 0ppm | 160° | Is that |
| Comparative example 3 | 10-4-10-3S/cm | 1383ppm | 60° | Is that |
From the data in table 2, it can be seen that: examples 1-5 were excellent in ionic conductivity and generally higher in stability and strength; the heterogeneous phase of the product obtained in comparative example 1 has significantly reduced conductivity, stability and strength; comparative example 2 is an oxide solid electrolyte, and although the stability and strength are high, the ionic conductivity is low; comparative example 3 is a sulfide solid state electrolyte, which is low in stability and strength, although the ionic conductivity is high. From this, it can be seen that the 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 (8)
1. A solid electrolyte, wherein the solid electrolyte comprises an oxide solid electrolyte, a sulfide solid electrolyte, and an oxide additive;
wherein the oxide solid electrolyte, the sulfide solid electrolyte, and the oxide additive form a glassy eutectic;
The content of the oxide additive is 1-5 parts by weight, the content of the oxide solid electrolyte is 60-80 parts by weight, and the content of the sulfide solid electrolyte is 5-20 parts by weight, relative to 100 parts by weight of the solid electrolyte;
The oxide solid electrolyte is selected from at least one of phosphate glass solid electrolyte, silicate glass solid electrolyte and anti-perovskite glass solid electrolyte; the sulfide solid state electrolyte is selected from a thiosilicate glass solid state electrolyte and/or a thiophosphate glass solid state electrolyte;
the oxide solid electrolyte contains halogen, wherein the halogen is at least one of fluorine, chlorine, bromine and iodine;
the oxide additive is selected from at least one of B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3、SiO2.
2. The solid electrolyte of claim 1, wherein the oxide solid electrolyte is selected from phosphate glass solid electrolytes; the sulfide solid state electrolyte is selected from the group consisting of thiosilicate glass solid state electrolytes.
3. A method for producing the solid electrolyte according to any one of claims 1 to 2, characterized by comprising the steps of:
S1, mixing and grinding an oxide solid electrolyte, a sulfide solid electrolyte and an oxide additive to obtain a first mixed material;
S2, carrying out melting treatment and quenching treatment on the first mixed material.
4. A method according to claim 3, wherein the oxide solid electrolyte is selected from at least one of a phosphate glass solid electrolyte, a silicate glass solid electrolyte, and an inverse perovskite glass solid electrolyte;
The sulfide solid state electrolyte is selected from a thiosilicate glass solid state electrolyte and/or a thiophosphate glass solid state electrolyte;
The oxide additive is selected from at least one of B2O3、GeO2、Al2O3、ZnO、BeO、PbO、Nb2O5、Ta2O5、La2O3、SnO2、Bi2O3 and SiO 2.
5. The method of claim 4, wherein the oxide solid electrolyte is selected from phosphate glass solid electrolytes; the sulfide solid state electrolyte is selected from a thiosilicate glass solid state electrolyte; the oxide additive is selected from at least one of B 2O3、Nb2O5 and SnO 2.
6. The method of claim 5, wherein the oxide solid electrolyte contains a halogen, the halogen being at least one of fluorine, chlorine, bromine, and iodine.
7. A method according to claim 3, wherein in step S2, the conditions of the melt processing include: under inert gas, the temperature is 300-1600 ℃ and the time is 5-60min; the quenching treatment mode is one selected from single medium quenching, double medium quenching, classification quenching, surface quenching and isothermal quenching; the inert gas is one of argon, nitrogen and helium.
8. An all-solid battery comprising a positive electrode, a negative electrode, and a solid electrolyte, wherein the solid electrolyte is the solid electrolyte according to any one of claims 1 to 2.
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