CN117594869B - Sulfide and preparation method thereof, solid electrolyte, all-solid-state battery and electric equipment - Google Patents
Sulfide and preparation method thereof, solid electrolyte, all-solid-state battery and electric equipment Download PDFInfo
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000007784 solid electrolyte Substances 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 100
- 239000011164 primary particle Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 230000006837 decompression Effects 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 239000011163 secondary particle Substances 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- -1 sulfide compound Chemical class 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 23
- 238000001354 calcination Methods 0.000 description 22
- 239000013078 crystal Substances 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 230000019086 sulfide ion homeostasis Effects 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002203 sulfidic glass Substances 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of solid-state batteries, in particular to a sulfide and a preparation method thereof, a solid-state electrolyte, an all-solid-state battery and electric equipment. The sulfide comprises lithium element and sulfur element, and at least one of phosphorus element and halogen element is also contained in the sulfide; the primary particles of sulfide are flaky in shape; the sulfide is mainly prepared from raw materials through pressurization heat treatment and decompression heat treatment, wherein the pressure P 1 of the pressurization heat treatment meets 110kPa < P 1 <130kPa, and the pressure P 2 of the decompression heat treatment meets 0kPa < P 2 <1kPa. The primary particles of the sulfide are in the form of flakes, which have better wet air stability.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a sulfide and a preparation method thereof, a solid-state electrolyte, an all-solid-state battery and electric equipment.
Background
Lithium ion secondary batteries play an extremely important role in modern society, and especially, new energy automobiles and the development of large-scale energy storage are pushed to unprecedented heights. Along with the continuous improvement of the energy density and safety requirements of the power battery, the existing liquid lithium ion battery system is close to the upper limit of the energy density, and the potential safety hazard of the high-specific-energy liquid lithium ion battery is more prominent due to the combustible organic electrolyte. The all-solid-state battery using the nonflammable inorganic solid material as the electrolyte not only can eliminate potential safety hazards caused by leakage of the electrolyte and thermal runaway in the battery in the use process, but also can be used under extreme conditions of high temperature, low temperature and the like. The use of lithium metal anodes will also further increase the energy density of all-solid lithium secondary batteries. Solid-state electrolytes are the most critical materials in all-solid batteries, and the development of inorganic solid-state electrolytes with high stability and high lithium ion conductivity is a key in the development of all-solid batteries with high performance.
Among the many solid electrolyte materials currently being studied are sulfide solid electrolytes with great potential for use. The main reason is that sulfide electrolytes have ion conductivity comparable to liquid electrolytes. However, sulfide solid electrolyte has poor wet air stability, and is easy to react to produce toxic H 2 S gas when contacted with water in the air, and meanwhile, the ionic conductivity of the electrolyte is reduced. Therefore, the sulfide solid electrolyte must be prepared and used in inert environments such as glove boxes, which results in extremely high production and use costs and limits the use of the sulfide solid electrolyte in large scale.
In view of this, the present invention has been made.
Disclosure of Invention
The first aim of the invention is to provide a sulfide, wherein the control of the surface morphology of the sulfide can be realized by regulating and controlling the protective gas pressure in the two heat treatment processes, the preparation of the nano flaky sulfide solid electrolyte is realized, and primary particles of the sulfide are flaky, so that the sulfide has better wet air stability. Solves the problem of poor wet air stability of sulfide solid electrolyte prepared by the prior art.
A second object of the present invention is to provide a method for producing a sulfide.
A third object of the present invention is to provide a solid electrolyte.
A fourth object of the present invention is to provide an all-solid battery.
A fifth object of the present invention is to provide a powered device.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention firstly provides a sulfide, wherein the sulfide comprises lithium element and sulfur element, and at least one of phosphorus element and halogen element is also contained in the sulfide;
The sulfide comprises secondary particles formed by agglomeration of primary particles, and the shape of the primary particles is flaky;
the sulfide is mainly prepared from raw materials through pressurization heat treatment and depressurization heat treatment, wherein the pressure P 1 of the pressurization heat treatment meets 110kPa < P 1 <130kPa, and the pressure P 2 of the depressurization heat treatment meets 0kPa < P 2 <1kPa.
Preferably, the primary particles have a thickness H <100nm.
Preferably, the primary particles have a width L >500nm.
Preferably, the ratio of the width L of the primary particles to the thickness H of the primary particles satisfies: L/H is more than or equal to 10 and less than or equal to 100.
Preferably, the halogen element includes at least one of Cl element, br element and I element.
Preferably, the chemical formula of the sulfide is Li 7-aPS6-aXa, wherein X is a halogen element, and a is more than or equal to 0 and less than or equal to 1.7.
Preferably, in an X-ray diffraction pattern obtained by X-ray powder diffraction of the sulfide using cukα rays, diffraction peaks are present at positions 2θ=25.7±1.0°,2θ=30.1±1.0° and 2θ=31.6±1.0°.
Preferably, the pressurized heat treatment and the depressurized heat treatment are performed in an inert atmosphere.
Preferably, the temperature of the pressurizing heat treatment is 200-350 ℃, and the heat preservation time of the pressurizing heat treatment is 3-8 hours.
Preferably, the temperature of the reduced pressure heat treatment is 400-600 ℃, and the heat preservation time of the reduced pressure heat treatment is 10-48 h.
Preferably, after the pressure heat treatment, the temperature of the material is reduced to below 50 ℃ and then the pressure-reduced heat treatment is performed.
The invention further provides a preparation method of the sulfide, which comprises the following steps:
sequentially carrying out pressurizing heat treatment and depressurizing heat treatment on the mixed raw materials, and cooling to obtain the sulfide;
Wherein the pressure P 1 of the pressure-increasing heat treatment is 110kPa < P 1 <130kPa, and the pressure P 2 of the pressure-decreasing heat treatment is 0kPa < P 2 <1kPa.
Preferably, the mixed raw material includes lithium element and sulfur element, and the raw material further contains at least one of sulfur element and halogen element.
Preferably, the raw materials are mixed and ground prior to the pressurized heat treatment.
Preferably, the linear speed of grinding is 7.5-16 m/s, and the grinding time is 10-24 h.
The invention also provides a solid electrolyte comprising the sulfide.
The invention further provides an all-solid-state battery comprising the solid-state electrolyte.
The invention also provides electric equipment, which comprises the all-solid-state battery.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, through regulating and controlling the pressure of the pressurizing heat treatment and the depressurizing heat treatment, P 1 is enabled to meet 110kPa < P 1<130kPa,P2 and 0kPa < P 2 <1kPa, flaky sequential particles can be obtained, the number of (111) crystal faces exposed on the surface of the particles is increased, the number of (011) crystal faces is reduced, and the wet air stability of sulfide is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the comparison of crystal planes exposed by a spherical primary particle and a flaky primary particle according to the present invention;
FIG. 2 is an SEM image of the sulfide produced in example 1 provided by the invention;
FIG. 3 is an enlarged view of a portion of FIG. 2;
FIG. 4 is an XDR pattern of sulfide produced in example 1 provided by the present invention;
FIG. 5 is an SEM image of the sulfide produced in comparative example 1 provided by the present invention;
FIG. 6 is a graph comparing the ionic conductivity of the sulfide prepared in example 1 and the sulfide prepared in comparative example 1 provided herein in a dew point environment at-30℃with exposure time.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the present invention, unless specifically stated otherwise, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity or as implicitly indicating the importance or quantity of the indicated technical feature. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
In the present invention, "one or more" or "at least one" means any one, any two or more of the listed items unless specifically stated otherwise. Wherein "several" means any two or more.
In a first aspect, the present invention provides a sulfide for a solid-state lithium ion battery having a layered structure, the sulfide including a lithium element and a sulfur element, and the sulfide further including at least one of a phosphorus element and a halogen element.
The sulfide comprises secondary particles formed by agglomeration of primary particles, and the primary particles are flaky in shape. That is, the sulfide is a secondary particle formed by agglomerating sheet-like primary particles.
The sulfide is mainly prepared from raw materials through pressurization heat treatment and depressurization heat treatment, wherein the pressure P 1 of the pressurization heat treatment meets 110kPa < P 1 <130kPa, and the pressure P 2 of the depressurization heat treatment meets 0kPa < P 2 <1kPa.
Wherein the pressure P 1 of the pressurized heat treatment includes, but is not limited to, a point value of any one of 111kPa, 113kPa, 115kPa, 118kPa, 120kPa, 123kPa, 125kPa, 127kPa, 129kPa, or a range value therebetween.
The pressure P 2 of the reduced pressure heat treatment includes, but is not limited to, a point value of any one of 0.1kPa, 0.2kPa, 0.3kPa, 0.5kPa, 0.7kPa, 0.9kPa or a range value between any two. By controlling the pressure P 2 of the reduced pressure heat treatment within the above range, fusion can be generated between specific crystal faces of adjacent crystal nuclei to form a sheet structure, and simultaneously, the crystallinity and the ionic conductivity can be improved.
In sulfide solid state electrolytes, the S element is typically present in both P-S polyhedral and free S, where free S is more reactive with water. The two forms of S are different in content in different exposed crystal planes and thus have differences in water stability. As is known from the analysis of the crystal structure of the sulfide solid-state electrolyte, the (111) crystal plane contains only PS 4 tetrahedra, while the (011) crystal plane contains both PS 4 tetrahedra and free S atoms. Therefore, in order to improve the wet air stability of the sulfide solid electrolyte, the invention can increase the number of (111) crystal faces exposed on the surface of the sulfide particles and reduce the number of (011) crystal faces by respectively regulating and controlling the pressure in the compression heat treatment and the decompression heat treatment to ensure that P 1 meets 110kPa < P 1<130kPa,P2 and 0kPa < P 2 <1kPa, thereby improving the wet air stability of the sulfide.
Referring to fig. 1, which shows a comparison of the exposed crystal planes of the spheroid (polyhedral) primary particles with those of the plate-like primary particles, it can be seen that the number of exposed (111) crystal planes is greater when the primary particles are plate-like.
In some specific embodiments, the primary particles have a thickness H <100nm.
In some embodiments, the primary particles have a width L >500nm.
The sulfide primary particles prepared by the method have a thin thickness and a wide width, and are in an obvious lamellar structure, and it is understood that the lamellar surface (namely, the surface corresponding to the length multiplied by the width) in the lamellar structure is a (111) crystal face, and the surface corresponding to the thickness is a (011) crystal face. Obviously, the sulfide prepared by the method has a large number of exposed (111) crystal faces and a small number of exposed (011) crystal faces, so that the sulfide has good stability.
In some embodiments, the ratio of the width L of the primary particles to the thickness H of the primary particles satisfies: L/H is more than or equal to 10 and less than or equal to 100; wherein L/H includes, but is not limited to, a point value of any one of 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or a range value between any two.
In some embodiments, the halogen element includes at least one of Cl element, br element, and I element.
In some specific embodiments, the sulfide has a chemical formula of Li 7-aPS6-aXa, wherein X is a halogen element, 0.ltoreq.a.ltoreq.1.7; wherein a includes, but is not limited to, a point value of any one of 0, 0.3, 0.5, 0.8, 1, 1.2, 1.5, 1.7 or a range value therebetween.
In some specific embodiments, the sulfide has a retention of ionic conductivity of greater than or equal to 80% after 48 hours of exposure to a dew point environment at-30 ℃, wherein the retention = ionic conductivity of the sulfide before exposure/ionic conductivity of the sulfide after 48 hours of exposure x 100%.
Thus, the sulfide provided by the invention has excellent wet air stability.
In some specific embodiments, the sulfide has diffraction peaks at 2θ=25.7±1.0°,2θ=30.1±1.0° and 2θ=31.6±1.0° in an X-ray diffraction pattern obtained by X-ray powder diffraction of the sulfide using cukα rays.
In some specific embodiments, the pressurized heat treatment and the depressurized heat treatment are performed in an inert atmosphere.
In some specific embodiments, the temperature of the heat treatment is 200 ℃ to 350 ℃, including but not limited to any one of 200 ℃, 220 ℃, 250 ℃, 280 ℃, 300 ℃, 330 ℃, 350 ℃ or a range of values between any two.
The heat preservation time of the pressurizing heat treatment is 3-8 hours; including but not limited to a point value of any one of 3h, 4h, 5h, 6h, 7h, 8h, or a range value between any two.
In some specific embodiments, the temperature of the reduced pressure heat treatment is 400 ℃ to 600 ℃, including, but not limited to, any one of the point values or a range of values between any two of 400 ℃, 430 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃.
The heat preservation time of the reduced pressure heat treatment is 10 h-48 h, including but not limited to any one point value or any range value between any two of 10h, 12h, 15h, 18h, 20h, 24h, 28h, 32h, 36h, 40h, 44h and 48 h.
The adoption of the heating temperature and the heat preservation time is beneficial to further promoting the formation of a lamellar structure, so that the wet air stability of sulfide is improved.
In some embodiments, after the pressure heat treatment, the temperature of the material after the pressure heat treatment is reduced to below 50 ℃, and then the pressure heat treatment is performed. Each raw material is subjected to preliminary reaction to form a large number of crystal nuclei, and the further growth of the crystal nuclei can be limited by cooling. Otherwise, the nuclei will continue to grow to form polyhedral or spheroidal particles.
In some embodiments, the sulfide produced by the invention is a solid solution phase sulfide solid electrolyte material.
In a second aspect, the present invention provides a method for preparing the sulfide, comprising the steps of:
And (3) sequentially carrying out pressurizing heat treatment and depressurizing heat treatment on the mixed raw materials, and cooling to obtain the sulfide.
Wherein the pressure P 1 of the pressure-increasing heat treatment is 110kPa < P 1 <130kPa, and the pressure P 2 of the pressure-decreasing heat treatment is 0kPa < P 2 <1kPa.
The wet air stability of the sulfide obtained by the preparation method of the sulfide provided by the invention is good, and the ion conductivity of the sulfide is not easy to be reduced even if the sulfide is contacted with air and water.
In addition, the preparation method is simple to operate, the raw materials are easy to obtain, the process flow is short, the production cost is low, and the large-scale production can be realized.
In some embodiments, the mixed raw material includes lithium element and sulfur element, and the raw material further includes at least one of sulfur element and halogen element.
In some embodiments, the raw materials are mixed and ground prior to the pressurized heat treatment.
The grinding can fully and uniformly mix the materials, thereby improving the reactivity.
In some embodiments, the linear velocity of the grinding is 7.5m/s to 16m/s, including but not limited to a point value of any one of 7.5m/s, 8m/s, 9m/s, 10m/s, 12m/s, 14m/s, 16m/s, or a range value between any two; the grinding time is 10-24 h, including but not limited to any one of 10h, 12h, 14h, 18h, 20h, 22h and 24h or any range between the two.
In some embodiments, the milling is performed in a ball milling pot.
In a third aspect, the present invention provides a solid state electrolyte comprising the sulfide.
It is understood that the solid electrolyte may contain only the sulfide, or may contain other electrolyte materials used in combination with the sulfide, which is not limited in the present invention.
In a fourth aspect, the present invention provides an all-solid battery comprising said solid electrolyte.
In some embodiments, the all-solid battery is a lithium secondary battery that includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer.
In a fifth aspect, the present invention provides a powered device comprising the all-solid-state battery.
The electric equipment provided by the invention can be widely applied to various fields, such as the fields of vehicles, electronic products, aerospace, medical or energy storage, and the like.
The electric equipment comprises any equipment, device or system with the all-solid-state battery.
As examples, the electric devices include, but are not limited to, electric automobiles, electric motorcycles, electric bicycles, electric tools, energy storage systems, electronic products, office equipment, and the like.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method of the sulfide provided by the embodiment comprises the following steps:
(1) In a glove box, li 2S、P2S5 and LiCl were weighed according to the element ratio in Li 5.7PS4.7Cl1.3, the above raw materials were placed in a 50ml zirconia ball mill pot, and 50g zirconia pellets having a diameter of 5mm were added. And placing the sealed ball milling tank on a ball mill for ball milling, wherein the linear speed of grinding is 14.0m/s, and the grinding time is 16 hours.
(2) Collecting the ball-milled material in the step (1), sealing the ball-milled material in a tube furnace, performing first-stage calcination, namely pressurized heat treatment, wherein the calcination temperature is controlled by adopting temperature programming, the temperature is raised to 300 ℃ from room temperature at a temperature raising rate of 3 ℃/min, the temperature is kept for 6 hours, argon is introduced into the furnace, and the pressure P 1 of the pressurized heat treatment is controlled at 123kPa. After the pressurized heat treatment is completed, the temperature is reduced to 50 ℃, and the pressure is controlled to be reduced to be less than 1.0kPa.
(3) And (3) sealing the cooled material obtained in the step (2) in a tubular furnace for second-stage calcination, namely, reduced pressure heat treatment, wherein the temperature of the second-stage calcination is controlled by adopting temperature programming, the temperature is raised to 540 ℃ at a temperature raising rate of 3 ℃/min, the temperature is kept for 24 hours, argon is introduced into the furnace, and the pressure P 2 of the reduced pressure heat treatment is controlled at 0.5kPa. And cooling to 50 ℃ after the decompression heat treatment is completed, and crushing to obtain sulfide.
Example 2
The sulfide production method provided in this example is substantially the same as that in example 1, except that in step (3), the pressure P 2 of the reduced-pressure heat treatment was replaced with 0.3kPa.
Example 3
The sulfide production method provided in this example is substantially the same as that in example 1, except that in step (2), the holding time of the heat treatment under pressure is replaced with 7.5 hours.
Example 4
The sulfide production method provided in this example is substantially the same as that in example 1, except that in step (3), the holding time of the reduced pressure heat treatment is replaced with 16 hours.
Example 5
The preparation method of the sulfide provided by the embodiment comprises the following steps:
In a glove box, li 2 S and P 2S5 were weighed according to the element ratio in Li 7PS6, the above raw materials were placed in a 50ml zirconia ball mill pot, and 50g zirconia pellets having a diameter of 5mm were added. And placing the sealed ball milling tank on a ball mill for ball milling, wherein the linear speed of grinding is 10.0m/s, and the grinding time is 12 hours.
Collecting ball-milled materials, sealing the ball-milled materials in a tube furnace for calcination, namely, pressurizing heat treatment, wherein the calcination temperature is controlled by adopting temperature programming, the temperature is raised to 240 ℃ from room temperature at a temperature raising rate of 3 ℃/min, the temperature is kept for 6 hours, argon is introduced into the furnace, and the pressure P 1 of the pressurizing heat treatment is controlled at 115kPa. After the pressurized heat treatment is completed, the temperature is reduced to 50 ℃, and the pressure is controlled to be reduced to be less than 1.0kPa.
And then sealing the cooled material in a tube furnace for second-stage calcination, namely, reduced pressure heat treatment, wherein the temperature of the second-stage calcination is controlled by adopting temperature programming, the temperature is raised to 410 ℃ at a temperature raising rate of 3 ℃/min, the temperature is kept for 24 hours, argon is introduced into the furnace, and the pressure P 2 of the reduced pressure heat treatment is controlled at 0.5kPa. And cooling to 50 ℃ after the decompression heat treatment is completed, and crushing to obtain sulfide.
Example 6
The preparation method of the sulfide provided by the embodiment comprises the following steps:
In a glove box, li 2S、P2S5 and LiCl were weighed according to the element ratio in Li 6PS5 Cl, the above raw materials were placed in a 50ml zirconia ball mill pot, and 50g zirconia pellets with a diameter of 5mm were added. And placing the sealed ball milling tank on a ball mill for ball milling, wherein the linear speed of grinding is 13.0m/s, and the grinding time is 16 hours.
Collecting ball-milled materials, sealing the ball-milled materials in a tube furnace for calcination, namely, pressurizing and heat treatment, wherein the calcination temperature is controlled by adopting temperature programming, the temperature is raised from room temperature to 280 ℃ at a temperature raising rate of 3 ℃/min, the temperature is kept for 6 hours, argon is introduced into the furnace, and the pressure P 1 of the pressurizing and heat treatment is controlled at 120kPa. After the pressurized heat treatment is completed, the temperature is reduced to 50 ℃, and the pressure is controlled to be reduced to be less than 1.0kPa.
And then sealing the cooled material in a tube furnace for second-stage calcination, namely, reduced pressure heat treatment, wherein the temperature of the second-stage calcination is controlled by adopting temperature programming, the temperature is raised to 550 ℃ at a temperature raising rate of 3 ℃/min, the temperature is kept for 24 hours, argon is introduced into the furnace, and the pressure P 2 of the reduced pressure heat treatment is controlled to be 0.5kPa. And cooling to 50 ℃ after the decompression heat treatment is completed, and crushing to obtain sulfide.
Example 7
The preparation method of the sulfide provided by the embodiment comprises the following steps:
In a glove box, li 2S、P2S5 and LiCl were weighed according to the element ratio in Li 5.5PS4.5Cl1.5, the above raw materials were placed in a 50ml zirconia ball mill pot, and 50g zirconia pellets having a diameter of 5mm were added. And placing the sealed ball milling tank on a ball mill for ball milling, wherein the linear speed of grinding is 17.0m/s, and the grinding time is 16 hours.
Collecting ball-milled materials, sealing the ball-milled materials in a tube furnace for calcination, namely, pressurizing heat treatment, wherein the calcination temperature is controlled by adopting temperature programming, the temperature is raised from room temperature to 300 ℃ at a temperature raising rate of 3 ℃/min, the temperature is kept for 6 hours, argon is introduced into the furnace, and the pressure P 1 of the pressurizing heat treatment is controlled at 126kPa. After the pressurized heat treatment is completed, the temperature is reduced to 50 ℃, and the pressure is controlled to be reduced to be less than 1.0kPa.
And then sealing the cooled material in a tube furnace for second-stage calcination, namely, reduced pressure heat treatment, wherein the temperature of the second-stage calcination is controlled by adopting temperature programming, the temperature is raised to 550 ℃ at a temperature raising rate of 3 ℃/min, the temperature is kept for 24 hours, argon is introduced into the furnace, and the pressure P 2 of the reduced pressure heat treatment is controlled to be 0.5kPa. And cooling to 50 ℃ after the decompression heat treatment is completed, and crushing to obtain sulfide.
Comparative example 1
The sulfide production method provided in this comparative example is substantially the same as in example 1 except that in step (3), the pressure P 2 of the second stage calcination is replaced with 123kPa.
Comparative example 2
The sulfide production method provided in this comparative example is substantially the same as in example 1 except that in step (2), the pressure P 1 of the first stage calcination is replaced with 0.5kPa.
Comparative example 3
The sulfide production method provided in this comparative example is substantially the same as in example 1, except that in step (2) and step (3), the tube furnace is replaced with a quartz tube and evacuated, that is, the heat treatment under pressure and the heat treatment under reduced pressure are both performed under vacuum, and the degree of vacuum in the quartz tube is <0.1Mpa.
Comparative example 4
The sulfide production method provided in this comparative example was substantially the same as in example 5 except that in step (2) and step (3), the tube furnace was replaced with a quartz tube and evacuated, that is, the heat treatment under pressure and the heat treatment under reduced pressure were both carried out under vacuum, and the degree of vacuum in the quartz tube was <0.1Mpa.
Comparative example 5
The sulfide production method provided in this comparative example was substantially the same as in example 6, except that in step (2) and step (3), the tube furnace was replaced with a quartz tube and evacuated, that is, the heat treatment under pressure and the heat treatment under reduced pressure were both carried out under vacuum, and the degree of vacuum in the quartz tube was <0.1Mpa.
Comparative example 6
The sulfide production method provided in this comparative example was substantially the same as in example 7, except that in step (2) and step (3), the tube furnace was replaced with a quartz tube and evacuated, that is, the heat treatment under pressure and the heat treatment under reduced pressure were both carried out under vacuum, and the degree of vacuum in the quartz tube was <0.1Mpa.
Comparative example 7
The sulfide production method provided in this comparative example is substantially the same as in example 1 except that the pressure P 1 of the first stage calcination is replaced with 100kPa in step (2), and the pressure P 2 of the second stage calcination is replaced with 10kPa in step (3).
Comparative example 8
The sulfide production method provided in this comparative example is substantially the same as in example 1 except that the pressure P 1 of the first stage calcination is replaced with 0.5kPa in step (2), and the pressure P 2 of the second stage calcination is replaced with 123kPa in step (3).
Experimental example
The morphology of primary particles of sulfides produced in each example and each comparative example was tested, and the original ionic conductivity of each sulfide and its ionic conductivity after 48 hours of exposure to a dew point environment at-30 ℃ were measured, and the results are shown in table 1.
Wherein retention of ionic conductivity = original ionic conductivity of sulfide/ionic conductivity of sulfide x 100% after 48h exposure in a dew point environment at-30 ℃.
The ionic conductivity was measured using Electrochemical Impedance Spectroscopy (EIS).
TABLE 1 results of Performance test of sulfides produced in examples and comparative examples
The mixed morphology in table 1 refers to a mixed morphology in which the primary particles are flaky and spheroid.
Further, as shown in fig. 2, an SEM image of the sulfide produced in example 1 is shown, fig. 3 is a partially enlarged view of fig. 2, and as shown in fig. 4, an XDR image of the sulfide produced in example 1 is shown. FIG. 5 is an SEM image of the sulfide produced in comparative example 1. FIG. 6 is a graph comparing the ionic conductivity of the sulfide prepared in example 1 and the sulfide prepared in comparative example 1 in a dew point environment at-30℃with exposure time.
It can be seen from table 1 and the figures that nano-platelet shaped sulfides can be obtained using the method of the present invention, and that the morphology of sulfides shows higher wet air stability as solid electrolyte materials.
The primary particles of the sulfides obtained in each comparative example were spherical or mixed in morphology and had poor wet air stability.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (11)
1. A sulfide, wherein the sulfide contains lithium element and sulfur element, and at least one of phosphorus element and halogen element;
The sulfide comprises secondary particles formed by agglomeration of primary particles, and the shape of the primary particles is flaky; the chemical formula of the sulfide is Li 7-aPS6-aXa, wherein X comprises halogen elements, and a is more than or equal to 0 and less than or equal to 1.7; the thickness H of the primary particles is <100nm; the primary particles have a width L >500nm; the ratio of the width L of the primary particles to the thickness H of the primary particles satisfies: L/H is more than or equal to 10 and less than or equal to 100;
The sulfide is mainly prepared from raw materials through compression heat treatment and decompression heat treatment, wherein the pressure P 1 of the compression heat treatment meets 110kPa < P 1 <130kPa, and the pressure P 2 of the decompression heat treatment meets 0kPa < P 2 <1kPa; the temperature of the pressurizing heat treatment is 200-350 ℃, and the heat preservation time of the pressurizing heat treatment is 3-8 hours; the temperature of the reduced pressure heat treatment is 400-600 ℃, and the heat preservation time of the reduced pressure heat treatment is 10-48 h; after the pressure heat treatment, the temperature of the material is reduced to below 50 ℃ and then the pressure reduction heat treatment is performed.
2. The sulfide of claim 1, wherein the halogen element includes at least one of Cl element, br element, and I element.
3. Sulfide as claimed in claim 1, characterized in that, in the X-ray diffraction pattern obtained by X-ray powder diffraction of the sulfide using cukα rays, diffraction peaks are present at the positions 2θ=25.7±1.0°,2θ=30.1±1.0° and 2θ=31.6±1.0°.
4. Sulfide according to claim 1, characterized in that the pressurized heat treatment and the depressurized heat treatment are performed in an inert atmosphere.
5. The method for producing a sulfide as claimed in any one of claims 1 to 4, comprising the steps of:
sequentially carrying out pressurizing heat treatment and depressurizing heat treatment on the mixed raw materials, and cooling to obtain the sulfide;
Wherein the pressure P 1 of the pressure-increasing heat treatment is 110kPa < P 1 <130kPa, and the pressure P 2 of the pressure-decreasing heat treatment is 0kPa < P 2 <1kPa.
6. The method according to claim 5, wherein the mixed raw material contains lithium element and sulfur element, and the raw material further contains at least one of sulfur element and halogen element.
7. The method for producing a sulfide compound according to claim 5, wherein each raw material is mixed and ground before the press heat treatment.
8. The method for producing a sulfide according to claim 7, wherein the linear velocity of grinding is 7.5m/s to 16m/s, and the time of grinding is 10 hours to 24 hours.
9. A solid electrolyte comprising the sulfide according to any one of claims 1 to 4.
10. An all-solid battery comprising the solid electrolyte of claim 9.
11. An electrical device comprising an all-solid-state battery as recited in claim 10.
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