CN114497712A - Electron-ion mixed conductor electrolyte, preparation method thereof and all-solid-state battery - Google Patents
Electron-ion mixed conductor electrolyte, preparation method thereof and all-solid-state battery Download PDFInfo
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- 239000011533 mixed conductor Substances 0.000 title claims abstract description 41
- 239000003792 electrolyte Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002203 sulfidic glass Substances 0.000 claims description 56
- 229910052723 transition metal Inorganic materials 0.000 claims description 50
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 47
- 229910052744 lithium Inorganic materials 0.000 claims description 47
- -1 transition metal sulfide Chemical class 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 21
- 239000011812 mixed powder Substances 0.000 claims description 19
- 229910001216 Li2S Inorganic materials 0.000 claims description 18
- 239000007784 solid electrolyte Substances 0.000 claims description 13
- 238000013329 compounding Methods 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052762 osmium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052706 scandium Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052713 technetium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 claims description 3
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 description 34
- 238000001816 cooling Methods 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 8
- 229910003092 TiS2 Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/007—Titanium sulfides
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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Abstract
The invention discloses an electron-ion mixed conductor electrolyte, a preparation method thereof and an all-solid battery, relating to the field of all-solid batteries.
Description
Technical Field
The invention relates to a solid-state battery technology, in particular to an electron-ion mixed conductor electrolyte, a preparation method thereof and an all-solid-state battery.
Background
With the rapid development of the fields of electric automobiles, large-scale energy storage and the like, higher requirements are put forward on the energy density, the power density, the service life and the safety performance of the lithium ion battery. The current commercialized lithium ion battery has a serious safety problem due to flammable organic liquid electrolyte, and the battery can cause fire or explosion accidents due to overheating of electrolyte caused by overcharge, internal short circuit and the like. At present, the problem of safety of liquid electrolyte is still not solved. In order to thoroughly solve the safety problem of lithium ion batteries, all solid-state lithium ion secondary batteries using solid electrolytes have received extensive attention.
The all-solid-state lithium ion secondary battery comprises a positive electrode, a negative electrode and a solid-state electrolyte, and the all-solid-state battery has higher energy density because the structures can be tightly combined. The solid electrolyte may be classified into an inorganic solid electrolyte, a solid polymer electrolyte, and a composite solid electrolyte, in which a sulfide electrolyte among the inorganic solid electrolytes has an ion conductivity comparable to that of a liquid electrolyte and is receiving attention.
However, although the conventional sulfide solid electrolyte has a high ionic conductivity, when the oxide positive electrode is in contact with the sulfide solid electrolyte, lithium ions have a large chemical potential difference between the two, and the lithium ions move from the sulfide solid electrolyte side to the oxide positive electrode material side, and the positive electrode and the electrolyte form a space charge layer at the same time, but the low electronic conductivity of the sulfide solid electrolyte layer makes the charge layer on the positive electrode side disappear, and the lithium ion chemical potential on the electrolyte side reaches a balance and inevitably moves to the positive electrode direction, so that the space charge layer continues to be generated, and a very large resistance is formed.
In order to solve the problems and improve the performance of the all-solid-state battery, the invention provides the electronic-ionic mixed conductor sulfide solid electrolyte, the preparation method thereof and the all-solid-state battery matched with the sulfide solid electrolyte.
Disclosure of Invention
The invention aims to provide an electron-ion mixed conductor electrolyte, a preparation method thereof and an all-solid-state battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an electronic-ionic mixed conductor electrolyte is prepared through compounding transition metal sulfide, lithium-contained sulfide and sulfide solid electrolyte, heat treating, and reacting between said sulfide and sulfide to generate sulfide of lithium-contained transition metal.
Preferably, the lithium-containing transition metal sulfide includes LixMy1Sz1Wherein x is more than or equal to 1 and less than or equal to 10, Y1 is more than or equal to 1 and less than or equal to 5, z is more than or equal to 1 and less than or equal to 16, and M comprises at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg.
Preferably, the sulfide solid electrolyte includes at least one of a binary sulfide solid electrolyte, an LGPS type crystal sulfide solid electrolyte, a Thio-LiSICON series, a digermite type crystal sulfide solid electrolyte;
the binary sulfide solid electrolyte is Li2S-P2S5As a host, specifically (100-a) Li2S·a P2S5，a＝20-40； b Li2S·a P2S5·c LiBr·d LiI，b:a＝3～4，(c+d)/(a+b+c+d)＝5～50％。
Preferably, the transition metal sulfide comprises My2Sz2(Y2 is more than or equal to 1 and less than or equal to 5, z2 is more than or equal to 1 and less than or equal to 9, and M comprises at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg.
Preferably, the lithium-containing sulfide includes Li2S、Li2S2、Li2S4、Li2S6、Li2S8At least one of (1).
Preferably, the transition metal sulfide, lithium-containing sulfide and sulfide solid electrolyte are mixed in the following weight parts (1-30): (1-30): (40-98) compounding.
An electron-ion mixed conductor electrolyte and a preparation method thereof, comprising the following steps:
fully and uniformly mixing a sulfide solid electrolyte, a transition metal sulfide and a lithium-containing sulfide;
and step two, carrying out heat treatment on the mixed powder, and reacting the transition metal sulfide with the lithium-containing sulfide to obtain the lithium-containing transition metal sulfide, thereby obtaining the solid electrolyte of the electronic-ionic mixed conductor sulfide of the lithium-containing transition metal sulfide.
Preferably, the heat treatment temperature in the second step is 160-680 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-30 h.
Preferably, the mixed powder ground in the first step is sieved by a 100-mesh sieve.
An all-solid-state battery comprises a positive electrode, a negative electrode and an electron-ion mixed conductor electrolyte containing lithium transition metal sulfide as described above, which is arranged between the positive electrode and the negative electrode.
Compared with the prior art, the electron-ion mixed conductor electrolyte, the preparation method thereof and the all-solid-state battery have the advantages that:
(1) the lithium-containing transition metal sulfide is generated by compounding transition metal sulfide, lithium-containing sulfide and sulfide solid electrolyte, reacting the lithium-containing sulfide with the transition metal sulfide after heat treatment, and the lithium-containing transition metal sulfide and the sulfide solid electrolyte are mutually embedded to form the electron-ion mixed conductor solid electrolyte containing the lithium-containing transition metal sulfide, so that the electron conductivity of the solid electrolyte is greatly improved, and the solid electrolyte is mixed with an oxide anode to construct an anode with an ion-electron mixed network. After the oxide positive electrode is contacted with the solid electrolyte, the problem that excessive lithium ions move towards the positive electrode can be effectively solved, a space charge layer is prevented from being generated continuously, interface resistance can be reduced, and battery performance is improved.
(2) The sulfide solid electrolyte prepared by the method can be applied to all-solid-state batteries and has better electrochemical performance.
Detailed Description
The present invention will be described in further detail with reference to examples.
An all-solid-state battery includes a positive electrode, a negative electrode, and an electron-ion mixed conductor electrolyte containing a lithium transition metal sulfide disposed between the positive electrode and the negative electrode.
The electronic-ionic mixed conductor electrolyte is prepared by compounding transition metal sulfide, lithium-containing sulfide and sulfide solid electrolyte, and reacting the transition metal sulfide with the lithium-containing sulfide after heat treatment to generate the lithium-containing transition metal sulfide. . Transition metal sulfide, lithium-containing sulfide and sulfide solid electrolyte are prepared according to the following weight parts (1-30): (1-30): (40-98) compounding.
Specifically, the lithium-containing transition metal sulfide includes LixMy1Sz1Wherein x is more than or equal to 1 and less than or equal to 10, Y1 is more than or equal to 1 and less than or equal to 5, z is more than or equal to 1 and less than or equal to 16, and M comprises at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg.
The sulfide solid electrolyte comprises at least one of binary sulfide solid electrolyte, LGPS type crystal sulfide solid electrolyte, Thio-LiSICON series and chalcogenide type crystal sulfide solid electrolyte;
binary sulfide solid electrolyte with Li2S-P2S5As a host, specifically (100-a) Li2S·a P2S5，a＝20-40； b Li2S·a P2S5·c LiBr·d LiI，b:a＝3～4，(c+d)/(a+b+c+d)＝5～50％。
Transition metal sulfides include My2Sz2(Y2 is more than or equal to 1 and less than or equal to 5, z2 is more than or equal to 1 and less than or equal to 9, and M comprises at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg.
Sulfur containing lithiumThe compound comprising Li2S、Li2S2、Li2S4、Li2S6、Li2S8At least one of (1).
An electron-ion mixed conductor electrolyte and a preparation method thereof, comprising the following steps:
fully and uniformly mixing a sulfide solid electrolyte, a transition metal sulfide and a lithium-containing sulfide, and sieving mixed powder through a 100-mesh sieve;
and step two, carrying out heat treatment on the mixed powder, and reacting the transition metal sulfide with the lithium-containing sulfide to obtain the lithium-containing transition metal sulfide, thereby obtaining the solid electrolyte of the electronic-ionic mixed conductor sulfide of the lithium-containing transition metal sulfide. Wherein the heat treatment temperature is 160-680 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-30 h.
Examples 1,
Transition metal sulfide TiS2Lithium-containing sulfide Li2S and binary sulfide Li7P3S11Uniformly mixing the mixed powder according to the molar ratio of 5:5:90, placing the mixed powder in a sintering furnace for heat treatment, wherein the heat treatment temperature is 270 ℃, the heating rate is 1 ℃/min, the sintering time is 10h, and cooling to room temperature to obtain the electronic-ionic mixed conductor sulfide solid electrolyte.
Examples 2,
Transition metal sulfide TiS2Lithium-containing sulfide Li2S and binary sulfide Li7P3S11Uniformly mixing the mixed powder according to the molar ratio of 30:30:40, placing the mixed powder in a sintering furnace for heat treatment, wherein the heat treatment temperature is 270 ℃, the heating rate is 1 ℃/min, the sintering time is 10h, and cooling to room temperature to obtain the electronic-ionic mixed conductor sulfide solid electrolyte.
Examples 3,
Transition metal sulfide TiS2Lithium-containing sulfide Li2S and binary sulfide Li7P3S11Uniformly mixing the materials according to the molar ratio of 1:1:98, and placing the mixed powder into a sintering furnace for heat treatmentThe heat treatment temperature is 270 ℃, the heating rate is 1 ℃/min, the sintering time is 10h, and the electronic-ionic mixed conductor sulfide solid electrolyte is obtained after the temperature is cooled to the room temperature.
Examples 4,
Transition metal sulfide TiS2Lithium-containing sulfide Li2S and binary sulfide Li7P3S11Uniformly mixing the mixed powder according to the molar ratio of 1:1:98, placing the mixed powder in a sintering furnace for heat treatment, wherein the heat treatment temperature is 160 ℃, the heating rate is 1 ℃/min, the sintering time is 30h, and cooling to room temperature to obtain the electronic-ionic mixed conductor sulfide solid electrolyte.
Examples 5,
Transition metal sulfide TiS2Lithium-containing sulfide Li2S and binary sulfide Li7P3S11Uniformly mixing the mixed powder according to the molar ratio of 1:1:98, placing the mixed powder in a sintering furnace for heat treatment, wherein the heat treatment temperature is 680 ℃, the heating rate is 10 ℃/min, the sintering time is 1h, and cooling to room temperature to obtain the electronic-ionic mixed conductor sulfide solid electrolyte.
Examples 6,
Transition metal sulfide Nb2S3Lithium-containing sulfide Li2S and binary sulfide Li7P3S11Uniformly mixing according to the molar ratio of 1:1:98, and mixing. And (3) placing the mixed powder in a sintering furnace for heat treatment, wherein the heat treatment temperature is 270 ℃, the heating rate is 1 ℃/min, the sintering time is 10h, and after cooling to the room temperature, the electronic-ionic mixed conductor sulfide solid electrolyte is obtained.
Example 7,
Transition metal sulfide Nb2S3Lithium-containing sulfide Li2S8With binary sulfides Li7P3S11Uniformly mixing according to the molar ratio of 1:1:98, and mixing. And (3) placing the mixed powder in a sintering furnace for heat treatment, wherein the heat treatment temperature is 270 ℃, the heating rate is 1 ℃/min, the sintering time is 10h, and after cooling to the room temperature, the electronic-ionic mixed conductor sulfide solid electrolyte is obtained.
Comparative examples 1,
Weighing prepared binary sulfide Li7P3S11And placing the mixture in a sintering furnace for sintering, wherein the sintering temperature is 270 ℃, the sintering time is 2 hours, and the sulfide solid electrolyte is obtained after cooling to the room temperature.
Example 8,
Transition metal sulfide Nb2S3Lithium-containing sulfide Li2S8With sulfide solid electrolyte Li10GeP2S12Uniformly mixing according to the molar ratio of 1:1:98, and mixing. And (3) placing the mixed powder in a sintering furnace for heat treatment, wherein the heat treatment temperature is 500 ℃, the heating rate is 1 ℃/min, the sintering time is 10h, and after cooling to the room temperature, the electronic-ionic mixed conductor sulfide solid electrolyte is obtained.
Examples 9,
Transition metal sulfide Nb2S3Lithium-containing sulfide Li2S8With sulfide solid electrolyte Li10GeP2S12And uniformly mixing according to the molar ratio of 20:20:60, and mixing. And (3) placing the mixed powder in a sintering furnace for heat treatment, wherein the heat treatment temperature is 500 ℃, the heating rate is 1 ℃/min, the sintering time is 10h, and obtaining the electron-ion mixed conductor sulfide solid electrolyte after cooling to the room temperature.
Example 10
Transition metal sulfide Nb2S3Lithium-containing sulfide Li2S and sulfide solid electrolyte Li10GeP2S12Uniformly mixing according to the molar ratio of 1:1:98, and mixing. And (3) placing the mixed powder in a sintering furnace for heat treatment, wherein the heat treatment temperature is 500 ℃, the heating rate is 1 ℃/min, the sintering time is 10h, and after cooling to the room temperature, the electronic-ionic mixed conductor sulfide solid electrolyte is obtained.
Comparative examples 2,
Sulfide solid Li which has been prepared10GeP2S12Sintering in a sintering furnace at 500 deg.C for 10 hr, and cooling to room temperature to obtain sulfide solid electrolyteAnd (4) decomposing the materials.
Example 11
Transition metal sulfide Nb2S3Lithium-containing sulfide Li2S and sulfide solid electrolyte Li6PS5And uniformly mixing Cl according to the molar ratio of 1:1:98, mixing, heating at 400 ℃, heating at the rate of 2 ℃/min for 10h, and cooling to room temperature to obtain the electronic-ionic mixed conductor sulfide solid electrolyte.
Comparative example 3
Prepared sulfide electrolyte Li6PS5And placing Cl in a sintering furnace for sintering, wherein the sintering temperature is A ℃, the sintering time is Ah, and cooling to room temperature to obtain the sulfide solid electrolyte.
Example 12
Transition metal sulfide MnS2Lithium-containing sulfide Li2S and sulfide solid electrolyte Li5.4PS4.4Cl1.6Uniformly mixing the materials according to the molar ratio of 1:1:98, heating the mixture at 450 ℃, heating the mixture at a rate of 5 ℃/min for 20h, and cooling the mixture to room temperature to obtain the electronic-ionic mixed conductor sulfide solid electrolyte.
Comparative example 4
Prepared sulfide solid electrolyte Li5.4PS4.4Cl1.6And placing the mixture in a sintering furnace for sintering, wherein the sintering temperature is 450 ℃, the sintering time is 20 hours, and the sulfide solid electrolyte is obtained after cooling to the room temperature.
The electronic-ionic mixed conductor sulfide solid electrolyte prepared in the above embodiment and the solid electrolyte prepared in proportion are subjected to ion conductivity and electronic conductivity performance tests, and assembled into a battery to test the battery performance, and the test results are as follows.
The assembly mode of the all-solid-state battery is as follows: the surface loading of the positive electrode NCM811 is 2mAh/cm2, the N/P ratio is 1.2, the electrolyte content in the positive electrode and the negative electrode is 30 wt%, the thickness of an electrolyte layer is 100 mu m, the charging and discharging voltage is 3.0-4.25V, the first circle is circulated for 0.05C, the second circle is started to perform charging and discharging circulation for 200 times at 0.5C, and the larger the discharge capacity retention ratio after 200 weeks is, the better the circulation performance is.
Although preferred embodiments of the present invention have been described in detail hereinabove, it should be clearly understood that modifications and variations of the present invention are possible to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An electron-ion mixed conductor electrolyte, characterized in that: the method comprises the steps of compounding transition metal sulfide, lithium-containing sulfide and sulfide solid electrolyte, reacting the transition metal sulfide with the lithium-containing sulfide after heat treatment to generate the lithium-containing transition metal sulfide, and further constructing the electronic-ionic mixed conductor sulfide solid electrolyte of the lithium-containing transition metal sulfide which is embedded with each other.
2. The electron-ion mixed conductor electrolyte of claim 1, wherein: the lithium-containing transition metal sulfide includes LixMy1Sz1Wherein x is more than or equal to 1 and less than or equal to 10, Y1 is more than or equal to 1 and less than or equal to 5, z is more than or equal to 1 and less than or equal to 16, and M comprises at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg.
3. The electron-ion mixed conductor electrolyte of claim 1, wherein: the sulfide solid electrolyte comprises at least one of a binary sulfide solid electrolyte, an LGPS type crystal sulfide solid electrolyte, a Thio-LiSICON series and a langugite type crystal sulfide solid electrolyte;
the binary sulfide solid electrolyte is Li2S-P2S5As a host, specifically (100-a) Li2S·a P2S5，a＝20-40；b Li2S·a P2S5·c LiBr·d LiI，b:a＝3～4，(c+d)/(a+b+c+d)＝5～50％。
4. The electron-ion mixed conductor electrolyte of claim 2, wherein: the transition metal sulfide includes My2Sz2Wherein Y2 is more than or equal to 1 and less than or equal to 5, z2 is more than or equal to 1 and less than or equal to 9, M comprises at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg.
5. The electron-ion mixed conductor electrolyte of claim 2, wherein: the lithium-containing sulfide includes Li2S、Li2S2、Li2S4、Li2S6、Li2S8At least one of (1).
6. The electron-ion mixed conductor electrolyte of claim 1, wherein: the transition metal sulfide, lithium-containing sulfide and sulfide solid electrolyte are prepared from the following components in parts by mole (1-30): (1-30): (40-98) compounding.
7. An electron-ion mixed conductor electrolyte and a preparation method thereof are characterized in that: the method comprises the following steps:
fully and uniformly mixing a sulfide solid electrolyte, a transition metal sulfide and a lithium-containing sulfide;
and step two, carrying out heat treatment on the mixed powder, and reacting the transition metal sulfide with the lithium-containing sulfide to obtain the lithium-containing transition metal sulfide, thereby obtaining the solid electrolyte of the electronic-ionic mixed conductor sulfide of the lithium-containing transition metal sulfide.
8. The electron-ion mixed conductor electrolyte and the method for preparing the same according to claim 7, wherein: and the heat treatment temperature in the second step is 160-680 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-30 h.
9. The electron-ion mixed conductor electrolyte and the method for preparing the same according to claim 7, wherein: and sieving the powder mixed in the step one through a 100-mesh sieve.
10. An all-solid-state battery characterized by: an electron-ion mixed conductor electrolyte comprising a positive electrode, a negative electrode and the lithium-containing transition metal sulfide according to any one of claims 1 to 6 disposed between the positive electrode and the negative electrode.
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