CN113948764A - Preparation method and application of sulfide solid electrolyte material - Google Patents
Preparation method and application of sulfide solid electrolyte material Download PDFInfo
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- 239000002203 sulfidic glass Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 61
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000003825 pressing Methods 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000131 polyvinylidene Polymers 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910005228 Ga2S3 Inorganic materials 0.000 claims description 3
- 229910001216 Li2S Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910010785 LiFexMn1-xPO4 Inorganic materials 0.000 claims description 2
- 229910010782 LiFexMn1−xPO4 Inorganic materials 0.000 claims description 2
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 2
- 229910013361 LiNixCoyAl1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910004956 Li10SiP2S12 Inorganic materials 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910020343 SiS2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
-
- 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
Abstract
The invention discloses a preparation method and application of a sulfide solid electrolyte material. The electrolyte has Li10GeP2S12Type structure of general formula LiaMbPcSd(M is one or more of Al, Ga, In and Ta, a, b, c and d>0)。Li10GeP2S12Solid-state electrolytes of the type have the highest lithium ion conductivity, however, such solid-state electrolytes currently being developed are costly, preventing their further practical use. Novel Li reported in this patent10GeP2S12The solid electrolyte greatly reduces the cost on the premise of not sacrificing the conductivity of the lithium ion. So that the all-solid-state battery based on the sulfide solid electrolyte has low cost, high safety and high energy densityAnd (4) degree.
Description
Technical Field
The invention belongs to the technical field of energy materials, and relates to a method for preparing a composite materialA preparation method and application of a sulfide solid electrolyte material applied to the field of solid batteries, in particular to a sulfide electrolyte material LiaMbPcSd(M is one or more of Al, Ga, In and Ta, a, b, c and d>0) A preparation method and application thereof in all-solid-state batteries.
Background
The lithium ion battery has the characteristics of high energy density and high power density, and is widely applied to markets of mobile electronic equipment, electric automobiles and the like. Due to the existence of flammable liquid electrolyte, the current commercial lithium battery has safety problems. Electric vehicles require safer, higher energy density lithium batteries to extend driving distances, provide higher power densities to shorten charging times, and maintain longer cycle life to reduce maintenance costs. Higher energy densities are achieved by increasing the cell size or number of packaged cells, which also means increasing the amount of flammable electrolyte in the device, thereby raising more serious safety concerns. Replacing flammable liquid electrolytes with flame-retardant inorganic solid electrolytes is a viable approach to improving battery safety. The use of solid electrolytes also simplifies cell design without hazardous and mobile organic solvents. The multilayer solid-state batteries are directly stacked in one package, so that higher working voltage can be provided, the effective battery volume is saved, and a road is paved for the application of electric automobiles.
However, one of the key issues in the development of solid-state batteries is to obtain a solid electrolyte with high lithium ion conductivity at room temperature. In recent years, much effort has been devoted to exploring new families of inorganic solid electrolytes, including sulfides, nitrides, hydrides, halides, phosphates, and oxides. And O2-In contrast, S2-Has larger ionic radius and higher polarizability, so that the sulfide solid electrolyte has higher ionic conductivity than the oxide solid electrolyte and can reach 10 at room temperature-3S/cm。
Meanwhile, the Chinese patent with the publication number of CN201911384502, namely 'a solid electrolyte sheet and a preparation method of the sulfide solid electrolyte sheet', discloses a sulfide solid electrolyte with a core-shell structure and a preparation method thereof, wherein the structure of the solid electrolyte sheet can improve the strength of the solid electrolyte and is beneficial to improving the preparation success rate of the electrolyte sheet, and the sulfide solid electrolyte sheet prepared by adopting a polymer fiber framework has great strength and structural stability, so that the thickness of the solid electrolyte sheet is beneficial to reducing the thickness of the solid electrolyte sheet, and the possibility is provided for further preparing a sulfide all-solid-state battery with high energy density. But has a disadvantage in that the fibrous skeleton contained in the solid electrolyte causes a great increase in the thickness of the solid electrolyte sheet, thereby greatly limiting the energy density of the assembled all-solid battery; in addition, the element such as Ge contained in the solid electrolyte causes an excessively high cost, and thus it is difficult to apply the solid electrolyte on a large scale.
Disclosure of Invention
The invention aims to provide a sulfide solid electrolyte material LiaMbPcSd(M is one or more of Al, Ga, In and Ta, a, b, c and d>0) A preparation method and application thereof in all-solid-state batteries. The all-solid-state battery based on the solid electrolyte has the characteristics of low cost, high safety, high charge-discharge specific capacity, excellent cycling stability and the like.
The purpose of the invention is realized by the following technical scheme:
the invention relates to Li10GeP2S12Sulfide-type solid electrolyte with chemical formula of LiaMbPcSdWherein M is one or more of Al, Ga, In and Ta, a, b, c and d>0。
The invention is realized by the reaction of conventional Li10GeP2S12Ge element in the sulfide solid electrolyte is replaced to form a novel solid electrolyte.
As an embodiment of the present invention, the raw material of the solid electrolyte comprises the following components:
a Li source: LiH, Li2S2、Li2One or more compositions of S;
s source: s, H2S、P2S5、P4S9、P4S3、Li2S2、Li2S、M2S3One or more of the compositions of (a);
and (3) P source: p, P2S5、P4S9、P4S3、P4S6、P4S5One or more of the compositions of (a);
the M source is: in2S2、In2S3、Al2S3、Ga2S3、Ta2S3One or more of the compositions of (a).
As an embodiment of the present invention, the mass ratio of Li to M in the solid electrolyte is 2 to 10: 1.
The invention also relates to Li10GeP2S12The preparation method of the sulfide solid electrolyte comprises the following steps:
s1, mixing Li, S, P and M sources, and ball-milling to obtain initial solid electrolyte powder;
s2, tabletting the initial solid electrolyte powder obtained in the step S1 under the pressure of 300-900 MPa to obtain an initial solid electrolyte sheet;
s3, sealing the initial solid electrolyte sheet obtained in the step S2 in a quartz tube or a glass tube, and vacuum sealing the tube (10-10)–4Pa), the calcining temperature is 500-650 ℃, and the time is 12-60 h, so as to obtain the sulfide solid electrolyte material.
In some embodiments, the appropriate molar ratio of Li in step S12S、P2S5、M2S3Mixing and ball-milling to obtain initial solid electrolyte powder.
As an embodiment of the invention, the ball milling is high-energy mechanical ball milling, the rotation speed of the ball milling is 500-650 rpm, and the ball milling time is 12-60 h.
The invention also relates to Li10GeP2S12The application of the sulfide solid electrolyte in preparing all-solid batteries.
The invention specifically comprises the following steps:
a1, positive electrode material, conductive carbon black and Li10GeP2S12Mixing the solid electrolyte materials of the type sulfide, and grinding the mixture uniformly to obtain anode powder; dispersing the anode powder into a 4% polyvinylidene fluoride-N-methyl pyrrolidone solution, uniformly stirring by magnetic force, and coating on an aluminum foil to obtain an anode plate;
a2, mixing Li10GeP2S12And finally, attaching a lithium foil to the other side of the solid electrolyte, and pressing the solid electrolyte into the all-solid-state battery.
As an embodiment of the present invention, the thickness of the solid electrolyte sheet is 200-.
The invention also relates to a sulfide-based all-solid-state battery comprising a positive electrode part, a negative electrode part and an electrolyte part; at least one of the positive electrode part, the negative electrode part and the electrolyte part comprises the Li10GeP2S12Type sulfide solid electrolyte.
As an embodiment of the present invention, the positive electrode part is composed of a positive electrode active material and the Li10GeP2S12The positive electrode active material is spinel-type transition metal oxide, lithium transition metal oxide having a layered structure, olivine, or a mixture of two or more of these materials.
As an embodiment of the present invention, Li in the positive electrode part10GeP2S12The weight of the type sulfide solid electrolyte accounts for 0-40 wt% of the total weight of the positive electrode part.
As an embodiment of the present invention, the positive electrode active material is LiCoO2、LiFePO4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2、LiNi0.5Mn1.5O4、LiFexMn1-xPO4One or a mixture of two or more of them.
As an embodiment of the present invention, the negative electrode part is composed of a negative electrode active material and the Li10GeP2S12The type sulfide solid electrolyte is constructed by mixing, and the negative active substance is a carbon series material, a Si-containing carbon series material or an olivine structure transition metal material; the carbon series material is artificial graphite, natural graphite, hard carbon or graphene; the olivine structure transition metal material is Li4Ti5O12Or LiNbTi2O7。
As an embodiment of the present invention, Li in the negative electrode part10GeP2S12The weight of the sulfide solid electrolyte accounts for 0-40 wt% of the total weight of the negative electrode part.
The invention also relates to a preparation method of the all-solid-state battery; firstly, preparing a positive electrode material, and mixing the electrode material, conductive carbon black and a sulfide solid electrolyte material according to a certain ratio (such as 2-3:1: 5-6); grinding and uniformly mixing the mixture to obtain anode powder; dispersing the anode powder into 4% polyvinylidene fluoride-N-methyl pyrrolidone solution, and coating the solution on an aluminum foil after magnetic stirring to obtain the anode plate. The reason why the sulfide electrolyte is complexed with the positive electrode is to improve the ionic conductivity.
Secondly, placing the sulfide solid electrolyte material powder in a tabletting mold, pressing into a solid electrolyte sheet, then placing the positive plate on one side of the solid electrolyte, pressing under pressure, finally attaching a lithium foil on the other side of the solid electrolyte, and pressing into the all-solid-state battery with a sandwich structure.
Compared with the prior art, the invention has the following beneficial effects:
(1) the prepared sulfide solid electrolyte material has better chemical stability;
(3) the prepared solid electrolyte is applied to all-solid batteries, so that the cycling stability of the batteries is improved;
(4) the sulfide solid electrolyte is introduced when the anode is prepared, so that the overall electrochemical performance of the battery is improved;
(5) the cost of the raw materials needed by the prepared sulfide electrolyte is low, and the large-scale industrial production is promoted.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is Li prepared according to example 110InP2S12XRD pattern of sulfide solid electrolyte;
fig. 2 is a cycle performance of an all-solid battery prepared according to example 1;
fig. 3 is a graph illustrating the first charge and discharge of the all-solid battery manufactured according to example 1;
FIG. 4 is a graph showing conductivity curves of electrolytes prepared according to examples 1 to 4 and comparative examples 1 to 3; wherein, (A) is the impedance spectrum of the stainless steel symmetrical battery assembled by the prepared electrolyte; (B) calculating the lithium ion conductivity of the prepared electrolyte;
fig. 5 is a 50 th cycle charge and discharge graph of the all-solid batteries manufactured according to examples 1 to 4 and comparative examples 1 to 3.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1
The present example relates to Li10InP2S12Preparing a sulfide solid electrolyte and an all-solid-state battery thereof; the method comprises the following steps:
(1) determining that M is In, and mixing Li In proper molar ratio2S、P2S5And dopant In2S3Mixing and high-energy planetary ball millingThe rotational speed and time of the planetary ball mill were 500rpm and 48 hours, thereby obtaining an initial solid electrolyte material.
(2) And (2) placing 40mg of the powder obtained in the step (1) in a tabletting mold with the diameter of 12mm, and pressing the powder into a solid electrolyte sheet at 600 MPa.
(3) Putting the sheet electrolyte obtained in the step (2) into a quartz tube in an argon atmosphere, and sealing the tube in vacuum (about 10)–4Pa)。
(4) And (4) carrying out heat treatment on the solid electrolyte sheet obtained in the step (3) at 550 ℃ for 12h to obtain the sulfide solid electrolyte material.
(5) And (4) mixing 112mg of the sulfide solid electrolyte material obtained in the step (4), 48mg of lithium iron phosphate and 20mg of conductive carbon black, and grinding the mixture uniformly to obtain positive electrode powder. Dissolving the anode powder in 500mg of 4% polyvinylidene fluoride-N-methyl pyrrolidone solution, and coating the solution on an aluminum foil after uniformly stirring by magnetic force.
(6) And placing the powder of the sulfide solid electrolyte material in a tabletting mold, pressing into a solid electrolyte sheet with the thickness of about 500 micrometers, then placing the positive plate on one side of the solid electrolyte, pressing under pressure, finally attaching a lithium foil on the other side of the solid electrolyte, and pressing into the all-solid-state battery.
Example 2
Addition of dopant Al2S3Otherwise, the same procedure as in example 1 was repeated.
Example 3
Doped Ga2S3Otherwise, the same procedure as in example 1 was repeated.
Example 4
Doped with Ta2S3Otherwise, the same procedure as in example 1 was repeated.
Comparative example 1
This comparative example relates to Li10SiP2S12Sulfide solid electrolyte and preparation thereof; the method comprises the following steps:
(1) mixing Li2S、P2S5And dopant SiS2Mixing and high-energy planetary ball milling at 550rpm for 48h to obtain the initial solid electrolyte material.
(2) And (2) placing 40mg of the solid electrolyte initial material obtained in the step (1) in a tabletting mould with the diameter of 12mm, and pressing the solid electrolyte initial material into a solid electrolyte sheet at 600 MPa.
(3) Putting the sheet electrolyte obtained in the step (2) into a quartz tube in an argon atmosphere, and sealing the tube in vacuum (about 10)–4Pa)；
(4) And (4) carrying out heat treatment on the solid electrolyte sheet obtained in the step (3) at 550 ℃ for 24h to obtain the sulfide solid electrolyte material.
(5) And (4) mixing 112mg of the sulfide solid electrolyte material obtained in the step (4), 48mg of lithium iron phosphate and 20mg of conductive carbon black, and grinding the mixture uniformly to obtain positive electrode powder. Dissolving the anode powder in 500mg of 4% polyvinylidene fluoride-N-methyl pyrrolidone solution, and coating the solution on an aluminum foil after uniformly stirring by magnetic force.
(6) And placing the powder of the sulfide solid electrolyte material in a tabletting mold, pressing into a solid electrolyte sheet with the thickness of about 500 micrometers, then placing the positive plate on one side of the solid electrolyte, pressing under pressure, finally attaching a lithium foil on the other side of the solid electrolyte, and pressing into the all-solid-state battery.
Comparative example 2
Doping SnS2Otherwise, the same procedure as in comparative example 1 was repeated.
Comparative example 3
GeS doping2Otherwise, the same procedure as in comparative example 1 was repeated.
Performance testing
The all-solid-state batteries prepared in the above examples 1 to 4 and comparative examples 1 to 3 were placed in a glove box and tested in a special battery testing device to test the battery performance, and the assembled batteries were subjected to a 0.5C constant current battery charge and discharge test at room temperature in an environment of 25 ℃ with a charge and discharge interval of 2 to 4.2V.
The sulfide solid electrolyte prepared in example 1 was subjected to XRD testing, and the results are shown in fig. 1. The all-solid-state battery manufactured in example 1 was a button battery of a 2032 type, and the battery was subjected to a constant current charge and discharge test at 0.5C, with a charge and discharge voltage interval of 2 to 4.2V, a test temperature of 25 ℃, a charge and discharge cycle as shown in fig. 3, and a first charge and discharge curve as shown in fig. 2. Further, the conductivity curves (fig. 4) of the electrolytes prepared in comparative examples 1 to 4 and comparative examples 1 to 3 were compared, and the conductivity of each electrolyte is shown in table 1. The 50 th cycle charge and discharge graph (fig. 5) of the all-solid batteries prepared in comparative examples 1 to 4 and comparative examples 1 to 3; as can be seen from fig. 5, the battery of example 1 has the highest capacity under the same test conditions. And the capacity was decreased in order from example 1 to comparative example 3, which is consistent with the conductivity test results.
Table 1 conductivity of the electrolytes prepared according to examples 1 to 4 and comparative examples 1 to 3.
| Electrolyte | Conductivity mS/cm2 |
| Example 1 | 11.3 |
| Example 2 | 6.7 |
| Example 3 | 3.7 |
| Example 4 | 1.84 |
| Comparative example 1 | 0.26 |
| Comparative example 2 | 0.33 |
| Comparative example 3 | 0.29 |
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. Li10GeP2S12The sulfide-type solid electrolyte is characterized in that the chemical general formula of the sulfide-type solid electrolyte is LiaMbPcSdWherein M is one or more of Al, Ga, In and Ta, a, b, c and d>0。
2. Li according to claim 110GeP2S12Sulfide-type solid electrolyte, characterized in that the raw material of the solid electrolyte comprises the following components:
a Li source: LiH, Li2S2、Li2One or more compositions of S;
s source: s, H2S、P2S5、P4S9、P4S3、Li2S2、Li2S、M2S3One or more of the compositions of (a);
and (3) P source: p, P2S5、P4S9、P4S3、P4S6、P4S5One or more of the compositions of (a);
the M source is: in2S2、In2S3、Al2S3、Ga2S3、Ta2S3One or more of the compositions of (a).
3. Li according to claim 110GeP2S12Type sulfide solid electrolyte, whichCharacterized in that the mass ratio of Li to M in the solid electrolyte is 2-10: 1.
4. Li according to any one of claims 1 to 310GeP2S12A method for producing a sulfide-type solid electrolyte, comprising the steps of:
s1, mixing and ball-milling Li, S, P and M sources to obtain initial solid electrolyte powder, wherein the ball-milling rotation speed is 500-;
s2, tabletting the initial solid electrolyte powder obtained in the step S1 under the pressure of 300-900 MPa to obtain an initial solid electrolyte sheet;
s3, sealing the initial solid electrolyte sheet obtained in the step S2 in a quartz tube or a glass tube, and vacuum sealing the tube (10-10)– 4Pa), the calcining temperature is 500-650 ℃, and the time is 12-60 h, so as to obtain the sulfide solid electrolyte material.
5. Li according to any one of claims 1 to 310GeP2S12The application of the sulfide solid electrolyte in preparing all-solid batteries.
6. The application according to claim 6, specifically comprising:
a1, positive electrode material, conductive carbon black and Li10GeP2S12Mixing the solid electrolyte materials of the type sulfide, and grinding the mixture uniformly to obtain anode powder; dispersing the anode powder into a 4% polyvinylidene fluoride-N-methyl pyrrolidone solution, uniformly stirring by magnetic force, and coating on an aluminum foil to obtain an anode plate;
a2, mixing Li10GeP2S12And finally, attaching a lithium foil to the other side of the solid electrolyte, and pressing the solid electrolyte into the all-solid-state battery.
7. The use according to claim 7, wherein the thickness of the solid electrolyte sheet is 200-800 μm.
8. The sulfide-based all-solid battery according to claim 10, wherein the positive electrode active material is LiCoO2、LiFePO4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2、LiNi0.5Mn1.5O4、LiFexMn1-xPO4One or a mixture of two or more of them.
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| PCT/CN2022/113370 WO2023030026A1 (en) | 2021-09-01 | 2022-08-18 | Method for preparing sulfide solid electrolyte material and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114789993A (en) * | 2022-05-05 | 2022-07-26 | 上海屹锂新能源科技有限公司 | Modified GeAg sulfide type solid electrolyte and preparation method and application thereof |
| CN114899480A (en) * | 2022-05-13 | 2022-08-12 | 上海屹锂新能源科技有限公司 | Sulfide-doped solid electrolyte and preparation method and application thereof |
| CN115304377A (en) * | 2022-09-14 | 2022-11-08 | 吉林师范大学 | LGPS ceramic chip, preparation method thereof and pressing die of LGPS ceramic chip |
| WO2023030026A1 (en) * | 2021-09-01 | 2023-03-09 | 上海屹锂新能源科技有限公司 | Method for preparing sulfide solid electrolyte material and application thereof |
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| CN109361019A (en) * | 2018-09-15 | 2019-02-19 | 中国科学院青岛生物能源与过程研究所 | A kind of all solid state lithium metal battery and its chemical property improvement method |
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| JP5742562B2 (en) * | 2011-08-02 | 2015-07-01 | トヨタ自動車株式会社 | Solid electrolyte material-containing body and battery |
| CN103401018B (en) * | 2013-08-09 | 2016-08-10 | 宁德时代新能源科技股份有限公司 | Solid electrolyte material of lithium ion battery |
| JP7010011B2 (en) * | 2018-01-17 | 2022-01-26 | トヨタ自動車株式会社 | Sulfide solid electrolyte |
| CN113948764A (en) * | 2021-09-01 | 2022-01-18 | 上海屹锂新能源科技有限公司 | Preparation method and application of sulfide solid electrolyte material |
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| CN109361019A (en) * | 2018-09-15 | 2019-02-19 | 中国科学院青岛生物能源与过程研究所 | A kind of all solid state lithium metal battery and its chemical property improvement method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023030026A1 (en) * | 2021-09-01 | 2023-03-09 | 上海屹锂新能源科技有限公司 | Method for preparing sulfide solid electrolyte material and application thereof |
| CN114789993A (en) * | 2022-05-05 | 2022-07-26 | 上海屹锂新能源科技有限公司 | Modified GeAg sulfide type solid electrolyte and preparation method and application thereof |
| CN114789993B (en) * | 2022-05-05 | 2024-01-30 | 上海屹锂新能源科技有限公司 | Modified sulfur silver germanium mineral solid electrolyte and preparation method and application thereof |
| CN114899480A (en) * | 2022-05-13 | 2022-08-12 | 上海屹锂新能源科技有限公司 | Sulfide-doped solid electrolyte and preparation method and application thereof |
| CN115304377A (en) * | 2022-09-14 | 2022-11-08 | 吉林师范大学 | LGPS ceramic chip, preparation method thereof and pressing die of LGPS ceramic chip |
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