CN115117434A - Composite material, preparation method thereof, solid-state battery and electric equipment - Google Patents
Composite material, preparation method thereof, solid-state battery and electric equipment Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 57
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- 239000010439 graphite Substances 0.000 claims abstract description 83
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
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- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 description 30
- 238000002156 mixing Methods 0.000 description 17
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- 239000002994 raw material Substances 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
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- 238000005245 sintering Methods 0.000 description 9
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- 239000002184 metal Substances 0.000 description 8
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
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- 229910010093 LiAlO Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 6
- 229910021617 Indium monochloride Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
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- 239000010703 silicon Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
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- 229910005839 GeS 2 Inorganic materials 0.000 description 2
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- 229910020346 SiS 2 Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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Images
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
-
- 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
-
- 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 application discloses a composite material, a preparation method thereof, a solid-state battery and electric equipment. The composite material comprises an inner core and a coating layer arranged on the surface of the inner core; the material of the inner core comprises graphite; the material of the cladding layer comprises a sulfide solid state electrolyte. The preparation method of the composite material comprises the following steps: and adding the sulfide solid electrolyte and graphite into a first solvent, and performing dispersion and heating treatment to obtain the composite material. A solid-state battery includes a positive electrode, a solid-state electrolyte layer, and a negative electrode including a binder, a conductive agent, a first sulfide solid-state electrolyte, and the composite material. The composite material can promote the wettability of electrolyte in the negative electrode, is beneficial to the full contact of the electrolyte and the negative electrode, and can solve the problems of poor cycle stability of a solid-state battery and complex preparation process of the negative electrode.
Description
Technical Field
The application belongs to the field of secondary batteries, and relates to a composite material, a preparation method thereof, a solid-state battery and electric equipment.
Background
Solid-state batteries have been extensively studied by enterprises and universities due to their excellent safety and high energy density. The solid electrolyte is used in the solid battery to replace volatile and combustible liquid electrolyte and a diaphragm in the traditional lithium ion battery. Compared with liquid electrolyte, the solid electrolyte has the advantages of no exertion, nonflammability, no corrosion, high mechanical strength and the like, avoids the dangers of electrolyte leakage, electrode short circuit and the like in the traditional lithium ion battery, reduces the sensitivity of the battery pack to temperature, can effectively prevent dendritic crystal growth of lithium due to high mechanical strength of the solid electrolyte, and has extremely high safety in the use process. At present, the anode materials for all solid-state lithium ion batteries mainly include four types of metal lithium, metal lithium indium, silicon and graphite. The lithium metal or the lithium indium metal reacts with most sulfide solid electrolytes, so that the interface resistance is continuously increased, and the cycle performance of the battery is seriously influenced. When the metal lithium or the metal lithium indium is used for the all-solid-state battery, the metal lithium or the metal lithium indium needs to be processed into a metal foil with micron-sized thickness, and the complex preparation process causes the price to be extremely high. During the use process, the silicon negative electrode is subjected to lithium intercalation to cause huge expansion of the volume of the silicon negative electrode, so that the active material is pulverized, and the cycle performance of the silicon negative electrode is seriously influenced. The graphite is used as a common cathode material of the lithium ion battery, has the advantage of stable structure in the lithium intercalation/lithium deintercalation process, and has good cycling stability. However, in the solid-state battery, if graphite and a solid-state electrolyte are simply mixed, the solid-state electrolyte cannot be fully contacted with the graphite, so that the solid-state electrolyte cannot be well infiltrated into the graphite material, and the charge and discharge capacity performance of the negative electrode active material and the cycle stability of the battery are greatly influenced.
Based on this, it is desirable to provide a composite material that can be in sufficient contact with a solid electrolyte.
Disclosure of Invention
The purpose of the application is to provide a composite material and a preparation method thereof, a solid-state battery and electric equipment. The method aims to solve the technical problem that the electrochemical performance of the battery is poor due to poor contact between a cathode material and a solid electrolyte in the existing solid battery.
In order to achieve the above object, a first aspect of the present application provides a composite material including an inner core and a coating layer disposed on a surface of the inner core;
the inner core comprises graphite;
the material of the cladding layer comprises a solid electrolyte.
In the composite material, the particle size Dv50 of the graphite may be 2 to 8 μm.
In the present application, the particle size Dv50 of the graphite may specifically include 5 μm, 8 μm, 10 μm, or 5 to 8 μm.
The thickness of the coating layer can be 50-150 nm, and specifically can include 50nm, 125nm, 130nm, 150nm, 50-125 nm, 50-130 nm, 125-130 nm or 125-150 nm.
In one embodiment, the solid-state electrolyte comprises one or more of a sulfide solid-state electrolyte, a halide solid-state electrolyte, a metal oxide solid-state electrolyte.
In the above composite material, the sulfide solid electrolyte includes glassy xLi 2 S·(100-x)P 2 S 5 Li-P-S glass-ceramics, Geigo-TiAl type Li 6 PS 5 X、Li 11-c M 2-c P 1+c S 12 Wherein X is more than or equal to 20 and less than or equal to 80, X is selected from at least one of Cl, Br and I, M is selected from at least one of Ge, Sn and Si, and c is 0-5.
In the above composite material, the sulfide solid electrolyte may be selected from Li 6 PS 5 Cl、Li 3 PS 4 、70Li 2 S·30P 2 S 5 、Li 11 Si 2 P 1 S 12 And Li 10 GeP 2 S 12 At least one of (1).
In the present application, the Li is prepared 6 PS 5 Cl as follows: mixing raw material Li 2 S、P 2 S 5 And LiCl, ball-milling at 500-600rpm/min according to the molar ratio, and sintering at high temperature of 500-600 ℃ to synthesize Li 6 PS 5 Cl；
Preparation of the Li 3 PS 4 The method comprises the following steps: performing ball milling on raw materials Li2S, P2S5 and LiCl at a speed of 500-600rpm/min according to a molar ratio, and sintering at a high temperature of 300-450 ℃ to synthesize Li 3 PS 4 ；
Preparation of the 70Li 2 S·30P 2 S 5 The method comprises the following steps: mixing raw material Li 2 S、P 2 S 5 Ball milling at 500-600rpm according to the molar ratio, and sintering at 200-350 ℃ to synthesize 70Li 2 S·30P 2 S 5 ；
Preparation of the Li 11 Si 2 P 1 S 12 The method comprises the following steps: mixing raw material Li 2 S、P 2 S 5 、SiS 2 Ball milling at 500-600rpm according to the molar ratio, sintering at 400-600 ℃ and synthesizing to obtain the Li 11 Si 2 P 1 S 12 ；
Preparation of the Li 10 GeP 2 S 12 The method comprises the following steps: raw material Li 2 S、P 2 S 5 、GeS 2 Ball milling at 500-600rpm according to the molar ratio, sintering at 400-600 ℃ and synthesizing to obtain the Li 11 Si 2 P 1 S 12 。
In the composite material, the graphite is in at least one of granular shape, phosphorus flake shape, flake shape and block shape;
the solid electrolyte exists in a surface coating and/or point coating mode on the graphite surface.
In the composite material, based on the mass of the composite material, the content of the graphite can be 85% -95%, and the content of the solid electrolyte can be 5-15%.
In a second aspect, the present application provides a method for preparing the above composite material, comprising the following steps: and adding the solid electrolyte and graphite into a first solvent, and performing dispersion and heating treatment to obtain the composite material.
In the preparation method, the steps of adding the solid electrolyte and the graphite into the first solvent, and performing dispersion and drying treatment to obtain the composite material comprise:
adding the solid electrolyte into a first solvent to obtain a first mixed solution;
adding the graphite into the first mixed solution, and performing dispersion treatment to obtain a second mixed solution;
and heating the second mixed solution at a first preset temperature, and evaporating the first solvent to dryness to obtain the composite material.
In the preparation method, the first solvent comprises absolute ethyl alcohol and/or N-methyl pyrrolidone, and the first preset temperature is 70-85 ℃.
Herein, every 0.1 gram of the solid electrolyte is mixed with every 1-20mL of the first solvent.
In the present application, the treatment employs ultrasound.
A third aspect of the present application provides an anode comprising a binder, a conductive agent, a first sulfide solid electrolyte, and the composite material described above.
In the application, the negative electrode comprises the following components in percentage by mass, and the total mass of the negative electrode is 100 percent:
85% -95% of the composite material;
0.5 to 2 percent of binder;
3 to 10 percent of conductive agent;
the balance being the first solid electrolyte.
In the negative electrode, the binder is at least one selected from PTFE, SBR, NBR, and PVDF, and is preferably PTFE;
the conductive agent is selected from at least one of SuperP, acetylene black, Ketjen black, carbon nanotubes, graphene and carbon fibers.
In the application, the negative electrode is specifically prepared from the following components in percentage by mass, and the total amount is 100%:
90% of the composite material;
1% of the binder;
4% of a conductive agent;
5% of solid electrolyte.
In the present application, the thickness of the negative electrode may be 100 to 300 μm, and specifically may be 100 μm, 150 μm, 200 μm, 300 μm, 100 to 150 μm, 150 to 200 μm, 200 to 300 μm, 100 to 200 μm, or 150 to 300 μm.
A fourth aspect of the present application provides a method for producing the above negative electrode, including the steps of: 1) ball-milling and mixing the composite material, the binder, the conductive agent and the first solid electrolyte according to a ratio to obtain a ball-milled mixed raw material;
2) and rolling the mixed raw materials subjected to ball milling to obtain the cathode.
In the preparation method, the rotation speed of the ball milling in the step 1) can be 200-350rpm/min, and the ball milling time can be 30-60 min;
the ball milling is carried out in a zirconia ball milling tank by adopting zirconia balls with the diameter of 2-10 mm;
in the step 2), the rolling is carried out in a roller press;
the rolling conditions were as follows:
the distance between the upper roller and the lower roller of the roller press can be 100-300 mu m;
the roll speed may be 1-3 m/min.
A fifth aspect of the present application provides a solid-state battery including a positive electrode, a first solid-state electrolyte layer, and the above-described negative electrode.
A sixth aspect of the present application provides an electric device, which includes the above solid-state battery, wherein the solid-state battery is used as a power supply source of the electric device.
The application has the following beneficial effects:
1. the composite material is used for preparing the negative electrode, and the solid electrolyte is coated on the surface of graphite, so that the solid electrolyte is in full contact with the graphite, and the capacity of a negative electrode active material (graphite) is promoted to be exerted, so that the first effect of the battery is improved, and the cycle performance of the battery is improved; and secondly, the flexible graphite cathode is in more effective contact with the solid electrolyte layer, so that the interface resistance is reduced, and the lithium ion transmission at the interface is promoted.
2. The method for preparing the cathode by adopting the composite material utilizes the binder to be easy to fibrillate and form a film under the action of high-speed shearing force, and the self-supporting cathode with micron-sized thickness can be formed by mixing and rolling the raw materials; the preparation method is simple, a toxic solvent is not required to be used for forming the negative electrode, the steps of drying the toxic solvent and post-treating the solvent are avoided, the steps of preparing the negative electrode are greatly reduced, and the harm of the toxic solvent to the environment and people in the process of preparing the negative electrode is avoided.
3. The negative electrode structure is beneficial to the transmission of ions and electrons, and a copper foil is not needed to be used as a current collector, so that the overall weight of the solid-state battery can be reduced and the cost is saved when the negative electrode structure is used as the negative electrode of the solid-state battery.
Drawings
Fig. 1 is a schematic structural view of composite particles according to example 1 of the present application, in which a is graphite and B is a composite material having graphite coated with a solid electrolyte.
Fig. 2 is a schematic view of a solid-state battery according to embodiment 1 of the present application.
The individual labels in FIG. 2 are as follows:
1, a negative electrode; 2 a solid electrolyte layer; 3 positive electrode.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The application firstly provides a composite material, which comprises an inner core and a coating layer arranged on the surface of the inner core;
the inner core comprises graphite;
the material of the cladding layer comprises a solid electrolyte.
The graphite is coated by the solid electrolyte, so that the contact performance of the solid electrolyte and the surface of the graphite can be improved, the solid electrolyte is effectively soaked into the graphite, and the capacity of the active material is favorably exerted.
Further, in order to improve the wettability of electrolyte in an electrode and avoid insufficient contact caused by too large or too small graphite particle size so as to influence lithium ion transmission at an interface, the particle size Dv50 of the graphite may include 2-8 μm;
the thickness of the coating layer can be 50-150 nm, and specifically can be 50nm, 125nm, 130nm and 150 nm.
The solid electrolyte includes one or more of a sulfide solid electrolyte, a polymer solid electrolyte, a halide solid electrolyte, a metal oxide solid electrolyte. Wherein the halide solid electrolyte comprises Li 3 InCl 6 、Li 3 YCl 6 、Li 3 TbCl 6 、Li 3 ErCl 6 (ii) a The metal oxide solid electrolyte comprises LiAlO 2 、Li 2 ZrO 3 、Li 4 Ti 5 O 12 . Since the sulfide solid electrolyte has excellent conductivity, the present application employs the sulfide solid electrolyte as a coating material.
Further, in order to facilitate electron transport without using copper foil as a current collector to reduce the weight of the negative electrode for manufacturing a solid-state battery while saving costs, the sulfide solid-state electrolyte may include Li 6 PS 5 Cl、Li 3 PS 4 、70Li 2 S·30P 2 S 5 、Li 10 GeP 2 S 12 、Li 11 Si 2 P 1 S 12 。
In the following examples, the Li was prepared 6 PS 5 Cl as follows: mixing raw material Li 2 S、P 2 S 5 And LiCl is subjected to ball milling at 500-600rpm/min according to the molar ratio, and then is sintered at a high temperature of 500-600 ℃ to synthesize Li 6 PS 5 Cl；
Preparation of the Li 3 PS 4 The method comprises the following steps: mixing raw material Li 2 S、P 2 S 5 And LiCl is subjected to ball milling at 500-600rpm/min according to the molar ratio and then sintered at a high temperature of 300-450 ℃ to synthesize Li 3 PS 4 ；
Preparation of the 70Li 2 S·30P 2 S 5 The method comprises the following steps: mixing raw material Li 2 S、P 2 S 5 Ball milling at 500-600rpm/min according to the molar ratio of 7:3, and sintering at 200-350 ℃ to synthesize 70Li 2 S·30P 2 S 5 ；
Preparation of the Li 11 Si 2 P 1 S 12 The method comprises the following steps: mixing raw material Li 2 S、P 2 S 5 、SiS 2 Ball milling at 500rp-600m/min according to the molar ratio, sintering at a high temperature of 400-600 ℃, and synthesizing to obtain the Li 11 Si 2 P 1 S 12 ；
Preparation methodThe above Li 10 GeP 2 S 12 The method comprises the following steps: mixing raw material Li 2 S、P 2 S 5 、GeS 2 Ball milling at 500-600rpm/min according to the molar ratio, sintering at 400-600 ℃ and synthesizing to obtain the Li 11 Si 2 P 1 S 12 。
Further, in order to make the flexible negative electrode contact the solid electrolyte layer more effectively, the shape and coating form of graphite in at least one of a granular shape, a phosphorus flake shape, a flake shape, and a block shape are preferable;
the solid electrolyte exists in a surface coating and/or point coating mode on the graphite surface.
In the composite material, the mass percentage of the graphite coated by the solid electrolyte is 85-95%, and the mass percentage of the sulfide solid electrolyte is 5-15%.
In order to prepare the composite material, the preparation method comprises the following steps:
adding the solid electrolyte into absolute ethyl alcohol to obtain a first mixed solution;
adding the graphite into the first mixed solution, and performing ultrasonic dispersion treatment to obtain a second mixed solution;
and heating the second mixed solution at 70-85 ℃, and evaporating absolute ethyl alcohol to dryness to obtain the composite material.
And mixing every 0.1 gram of the sulfide solid electrolyte with every 1-20ml of the anhydrous ethanol.
The application also provides a negative electrode, which comprises a binder, a conductive agent, a first solid electrolyte and the composite material. In the present application, the kind of the first solid electrolyte and the kind of the solid electrolyte are the same.
The negative electrode is specifically prepared from the following components in percentage by mass, and the total mass of the negative electrode is 100 percent:
85% -95% of the composite material;
0.5 to 2 percent of binder;
3 to 10 percent of conductive agent; the first solid electrolyte accounts for 1-8%.
The application also provides a preparation method of the cathode, which comprises the following steps: 1) ball-milling and mixing the composite material, the binder, the conductive agent and the first solid electrolyte according to a ratio to obtain a ball-milled mixed raw material;
2) and rolling the mixed raw materials subjected to ball milling to obtain the cathode.
In the preparation method, the rotation speed of the ball milling in the step 1) can be 200 and 350rpm/min, and the ball milling time can be 30-60 min;
in order to provide enough shearing force to fiberize the binder, the ball milling is carried out in a zirconia ball milling tank by using zirconia balls with the diameter of 2-10 mm;
in the step 2), in order to obtain the required thickness of the negative electrode, the distance between an upper roller and a lower roller of a roller press is controlled, and the distance between the upper roller and the lower roller of the roller press can be 100-300 mu m;
in order to make the prepared cathode have better supporting performance, the following rolling parameters are optimized, and the rolling speed can be 1-3 m/min.
The application also provides a solid-state battery, which comprises a positive electrode, a solid-state electrolyte layer and the negative electrode. Wherein the solid electrolyte layer comprises a second solid electrolyte, and the second solid electrolyte is the same as the first solid electrolyte and the solid electrolyte in the coating layer.
In another embodiment, the solid-state electrolyte in the coating layer, the first solid-state electrolyte in the negative electrode, and the second solid-state electrolyte in the solid-state electrolyte layer have different particles Dv50 and different specific surface areas, wherein the particles Dv50 are, in order from large to small, the second solid-state electrolyte in the solid-state electrolyte layer, the solid-state electrolyte in the coating layer, and the first solid-state electrolyte in the negative electrode. The particles of the first solid electrolyte in the negative electrode are in a nanometer level, the Dv50 of the particles is 5-35 nm, and the specific surface area of the particles is 200-350 m 2 (iv) g; the particles Dv50 of the second solid electrolyte are 8-15 μm, and the specific surface area is 12-28 m 2 (ii)/g; the particles of the solid electrolyte in the coating layer are nano-scale, and the Dv50 of the particles is 50-150nm, and a specific surface area of 80-130 m 2 (ii) in terms of/g. The particles Dv50 of the first solid-state electrolyte in the negative electrode are minimal, which can be effectively filled between the composite materials, improving the lithium ion conducting and electron conducting properties of the negative electrode. The second solid electrolyte in the solid electrolyte layer serves as a site for lithium ion transport, and if Dv50 of the second solid electrolyte is too large, a lithium ion diffusion path becomes too long, while if Dv50 is too small, side reactions are likely to occur, and the performance of the battery is not favorably exhibited.
The application also provides electric equipment which comprises the solid-state battery, wherein the solid-state battery is used as a power supply source of the electric equipment.
The present application will be described in detail with reference to the following examples and accompanying drawings.
Example 1
1. Preparing a composite material:
(1) 0.415g of Li 6 PS 5 Dispersing Cl (abbreviated as LPSC) in 50mL of absolute ethyl alcohol to form a first mixed solution;
(2) dispersing 4.585g of graphite with Dv50 of 4 μm in the first mixed solution, and performing ultrasonic dispersion treatment for 1h to form a second mixed solution;
(3) vacuum drying the second mixed solution at 80 ℃, evaporating anhydrous ethanol to obtain Li 6 PS 5 A composite material of Cl-coated graphite (LPSC @ Gr), wherein the graphite content in the composite material accounts for 91.7 percent, and Li 6 PS 5 The Cl content is 8.3%, and the thickness of the coating layer is 120 nm.
2. Preparation of a negative electrode:
(1) mixing the prepared composite material, a binder (PTFE), a conductive agent (graphene) and LPSC according to a proportion of 90: 1: 4: 5g and 5g, putting the weighed raw materials into a zirconia ball milling tank, and then adding 50g of zirconia balls with the diameter of 10mm for ball milling, wherein the ball milling speed is 200rpm/min, and the ball milling time is 30 min.
(2) And rolling the ball-milled raw materials by using a roller press, adjusting the distance between an upper roller and a lower roller to be 100 mu m, adjusting the roller speed to be 1m/min, and cutting and cold-pressing to obtain the cathode with the thickness of 100 mu m.
3. Preparation of solid-state battery
(1) Preparation of solid electrolyte sheet
A sulfide solid electrolyte (LPSC) was placed in a mold, and a solid electrolyte sheet having a thickness of 100 μm and a diameter of 10mm was prepared by applying a pressure of 10 MPa.
(2) Preparation of the Positive electrode
In a glove box, according to the mass ratio of 70: 30 weighing the positive electrode material LNO @ NCM622 and sulfide solid electrolyte (LPSC), grinding and mixing uniformly, wherein the LNO @ NCM622 refers to LiNbO 3 Coated LiNi 2 Co 2 Mn 2 O 2 And in the positive electrode material LiNbO 3 The coating amount of (2) is 0.5-1%. Weighing 20mg of the mixed material, placing the mixed material in a solid battery mould with the diameter of 10mm, applying the pressure of 10MPa to obtain a positive electrode pressing sheet, and placing a carbon-coated aluminum foil wafer with the diameter of 10mm on the side of the positive electrode pressing sheet as a current collector to obtain a positive electrode.
(3) Preparation of solid-state batteries
The above-described positive electrode 3, solid electrolyte sheet (i.e., sulfide solid electrolyte layer) 2, and negative electrode 1 were assembled into a solid-state battery (see fig. 2 for the structure of the solid-state battery).
Example 2
The same as in example 1 of the present application, except that 0.325g of Li was added during the preparation of the composite material 6 PS 5 Cl and 4.675g of graphite, the content of graphite in the prepared composite material is 93.5 percent, and Li 6 PS 5 The Cl content was 6.5%, and the thickness of the coating layer was 85 nm.
Examples 3,
The same as in example 1 of the present application, except that 0.25g of Li was added during the preparation of the composite material 6 PS 5 Cl and 4.75g of graphite, the content of graphite in the prepared composite material is 95 percent, and Li 6 PS 5 The Cl content is 5%, and the thickness of the coating layer is 50 nm.
Examples 4,
The same as in example 1 of the present application, except that 0.375g of Li was added during the preparation of the composite material 6 PS 5 Cl and 4.625g of graphite to prepareThe graphite content in the prepared composite material is 92.5 percent, and Li 6 PS 5 The Cl content was 7.5%, and the thickness of the coating layer was 100 nm.
Examples 5,
The same as in example 1 of the present application, except that 0.75g of Li was added during the preparation of the composite material 6 PS 5 Cl and 4.25g of graphite, wherein the content of graphite in the prepared composite material is 85 percent, and Li 6 PS 5 The Cl content is 15%, and the thickness of the coating layer is 150 nm.
Example 6
The same as in example 1 of the present application, except that the graphite Dv50 was 2 μm in the preparation of the composite material.
Example 7
The same as in example 1 of the present application, except that the graphite Dv50 was 5 μm during the preparation of the composite material.
Example 8
The same as in example 1 of the present application, except that the graphite Dv50 was 6 μm during the preparation of the composite material.
Example 9
The same as in example 1 of the present application, except that the graphite Dv50 was 8 μm during the preparation of the composite material.
Example 10
The same as in example 1 of the present application, except that the graphite Dv50 was 1 μm during the preparation of the composite material.
Example 11
The same as in example 1 of the present application, except that the graphite Dv50 was 10 μm during the preparation of the composite material.
Example 12
In the same manner as in example 1 of the present application, except that the interval between the upper and lower rolls was adjusted to 125 μm in the preparation of the negative electrode, a negative electrode having a thickness of 125 μm was obtained.
Example 13
In the same manner as in example 1 of the present application, except that in the preparation of the negative electrode, the distance between the upper and lower rolls was adjusted to 200 μm, a negative electrode having a thickness of 200 μm was obtained.
Example 14
In the same manner as in example 1 of the present application, except that the interval between the upper and lower rolls was adjusted to 300 μm in the preparation of the negative electrode, a negative electrode having a thickness of 300 μm was obtained.
Example 15
In the same manner as in example 1 of the present application, except that the interval between the upper and lower rolls was adjusted to 75 μm in the preparation of the negative electrode, a negative electrode having a thickness of 75 μm was obtained.
Example 16
The same as in example 1 of the present application, except that in the preparation of the negative electrode, the distance between the upper and lower rolls was adjusted to 350 μm, and a negative electrode having a thickness of 350 μm was obtained.
Application example 17
As in example 5 of the present application, except that in the preparation of the composite material: the sulfide solid electrolyte is Li 3 PS 4 (abbreviated as LPS) to obtain Li 3 PS 4 Coated graphite (LPS @ Gr).
The preparation steps of the negative electrode are as follows:
and (2) adjusting the distance between the upper roller and the lower roller to be 200 mu m, and adjusting the roller speed to be 1m/min to obtain the cathode with the thickness of 200 mu m.
In the preparation step of the solid-state battery:
except that the sulfide solid electrolyte is LPS.
Example 18
The same as in example 1 of the present application, except that in the preparation step of the composite material:
0.5g sulfide solid electrolyte Li 10 GeP 2 S 12 (LGPS for short); 4.5g of Dv50 was 10 μm graphite, obtaining Li 10 GeP 2 S 12 Coated graphite (LGPS @ Gr) (90% graphite by mass and 10% LGPS by mass), wherein the LGPS layer has a thickness of 125 nm.
The preparation steps of the negative electrode are as follows:
and (2) adjusting the distance between the upper roller and the lower roller to be 150 mu m to obtain the cathode with the thickness of 150 mu m.
The preparation steps of the solid-state battery are as follows:
except that the sulfide solid electrolyte was LGPS.
Example 19
The same as in example 1 of the present application, except that the sulfide solid electrolyte was 70Li 2 S·30P 2 S 5 。
Example 20
The same as in example 1 of the present application, except that the sulfide solid electrolyte was Li 11 Si 2 P 1 S 12 。
Example 21
1. The preparation method of the composite material comprises the following steps:
(1) 0.75g of sulfide solid electrolyte Li 6 PS 5 Dispersing Cl in 45mL of N-methylpyrrolidone (NMP) to form a first mixed solution;
(2) dispersing 4.25g of graphite with the Dv50 of 5 mu m in the solution A, and carrying out ultrasonic treatment for 1h to form a second mixed solution;
(3) vacuum drying the second mixed solution at 80 ℃ to obtain Li 6 PS 5 Cl-coated graphite (LPSC @ Gr) (85% graphite content, Li) 6 PS 5 Cl content of 15%), wherein the thickness of the LPSC layer was 150 nm.
2. The preparation steps of the negative electrode are as follows:
the same as in example 1, except that 40g of zirconia balls with a diameter of 10mm were added in step (1) and ball milling was carried out, wherein the ball milling rotation speed was 200rpm/min and the ball milling time was 30 min.
And (2) adjusting the distance between the upper roller and the lower roller to be 300 mu m, and adjusting the roller speed to be 1m/min to obtain the cathode with the thickness of 300 mu m.
Example 22
As in example 1 of the present application, except that,
1. in the preparation of the composite, 0.6g of sulfide solid electrolyte Li 6 PS 5 Cl, 4.4g of graphite having a Dv50 of 10 μm, Li being obtained 6 PS 5 Cl-coated graphite (LPSC @ Gr), wherein the thickness of the LPSC layer is 130 nm.
2. Preparation of a negative electrode:
(1) 40g of zirconia balls having a diameter of 10mm were added and ball-milled.
(2) The distance between the upper roller and the lower roller is adjusted to be 150 mu m, the roller speed is adjusted to be 1m/min, and the cathode with the thickness of 150 mu m is obtained.
Example 23
1. Preparing a composite material: LiCl and InCl are added 3 And graphite are uniformly dispersed in water, and then the water is evaporated by heating and stirring at 60 ℃ to obtain Li 3 InCl 6 A graphite-coated composite material. Wherein the graphite Dv50 of the composite material is 4 μm, the graphite content accounts for 91.7 percent, and Li 3 InCl 6 The content of the coating layer is 8.3 percent, and the thickness of the coating layer is 120 nm.
2. The negative electrode was prepared as in example 1.
3. Preparation of solid-state batteries: the same as in example except that the solid electrolyte was Li 3 InCl 6 。
Example 24
1. Preparing a cathode material by mixing Al with the mass ratio of 1:2 2 O 3 、Li 2 CO 3 Ball-milling, uniformly mixing, calcining at 800 ℃ for 10h in a vacuum tube furnace, and cooling to obtain LiAlO 2 Mixing LiAlO with the mass ratio of 1:9 2 Uniformly dispersing graphite in absolute ethyl alcohol, evaporating the absolute ethyl alcohol to obtain a cathode material precursor, carrying out sintering on the cathode material precursor in a vacuum tube furnace at 400 ℃ to obtain LiAlO 2 A graphite-coated negative electrode material. Wherein the graphite Dv50 of the composite material is 4 μm, the graphite content accounts for 91.7 percent, and LiAlO 2 The content of the coating layer is 8.3 percent, and the thickness of the coating layer is 120 nm.
2. The negative electrode was prepared as in example 1.
3. Preparation of solid-state batteries: same as example 1, except that the solid electrolyte was LiAlO 2 。
Comparative example 1
Unlike example 1, in the preparation of the anode material, 0.415g of Li was added 6 PS 5 Cl and 4.585g of graphite, replaced by 5gAnd preparing graphite to obtain the graphite negative electrode material without the sulfide solid electrolyte coating.
The relevant parameters of the composite materials and the negative electrode prepared in examples 1 to 24 and comparative example 1 are recorded in table 1, and the prepared solid-state battery is subjected to a full battery performance test, wherein the test method comprises the following steps: and (4) carrying out rate charging and rate discharging on the solid-state battery by using the Xinwei test cabinet. The battery test multiplying power is 0.1C, the working voltage range is 2.75-4.3V, and the cycle is 100 circles.
The above solid-state battery test data were summarized to obtain table 2.
TABLE 1
Table 2 performance test results of solid-state batteries
Through the examination of different parameters in table 1, the performance results of the solid-state batteries in table 2 are compared to see that:
1. according to the test data of the above examples 1 to 24 and comparative example 1, compared with the composite material coated with the solid electrolyte, the solid electrolyte-free negative electrode material has significantly reduced test performance of the solid battery, which is expressed by that the first effect is only 62.2%, and the cycle retention rate is only 71.3 for 100 cycles, because when the solid electrolyte coating is not provided, the negative electrode active material (graphite) in the solid battery cannot be in sufficient contact with the solid electrolyte, so that the solid electrolyte cannot be well infiltrated into the graphite material, and the first effect of the negative electrode active material is greatly influenced, and the cycle stability of the solid battery is influenced. In the present application, since the solid electrolyte serves as a passage for lithium ion transport, when the contact performance between the solid electrolyte and graphite is poor, the capacity of graphite is reduced to cause a decrease in the first effect, and therefore, the contact performance between the solid electrolyte and graphite can be expressed by the size of the first effect.
2. The test data of the embodiments 1 to 5 show that the percentage content of the solid electrolyte can affect the electrochemical performance of the solid battery, and when the content of the solid electrolyte is 6.5 to 8.3%, the charge-discharge first effect of the solid battery is 84.2 to 85.5%, and the capacity retention rate of 100 circles is 92.2 to 98.5%. Application for
3. Through the data examination of different graphite Dv50 in the above example 1 and examples 6-11, it can be seen that the particle size Dv50 of graphite in the composite material can be 2-8 μm, and the performance of the solid-state battery prepared by the composite material is better than that prepared by the examples 10-11, as compared with the examples 10-11, as a result, it can be seen that the lithium ion transport at the interface is affected due to insufficient contact caused by too large or too small particle size of graphite.
4. As can be seen from the test data of examples 1-22 and examples 22-23, the solid-state batteries made with sulfide solid-state electrolytes have superior electrochemical performance relative to batteries made with halide solid-state electrolytes and oxide solid-state electrolytes because sulfide solid-state electrolytes have greater electrical conductivity than halide solid-state electrolytes and oxide solid-state electrolytes.
Claims (10)
1. A composite material, which is characterized by comprising an inner core and a coating layer arranged on the surface of the inner core;
the inner core comprises graphite;
the material of the cladding layer comprises a solid electrolyte.
2. The composite material according to claim 1, wherein the graphite has a particle size Dv50 of 2 to 8 μm; the thickness of the coating layer is 50-150 nm.
3. The composite material of claim 1, wherein the solid electrolyte comprises one or more of a sulfide solid electrolyte, a halide solid electrolyte, and a metal oxide solid electrolyte.
4. The composite material of claim 2, wherein the sulfide solid state electrolyte comprises a glassy xLi 2 S·(100-x)P 2 S 5 Li-P-S glass-ceramics, Geigo-TiAl type Li 6 PS 5 X、Li 11-c M 2-c P 1+c S 12 Wherein X is more than or equal to 20 and less than or equal to 80, X is selected from at least one of Cl, Br and I, M is selected from at least one of Ge, Sn and Si, and c is 0-5.
5. The composite material of any of claims 1-4, wherein the graphite is in a shape of at least one of granular, phosphorus flake, and block;
the solid electrolyte exists in a surface coating and/or point coating mode on the graphite surface.
6. The composite material according to claim 1, wherein the graphite content is 85 to 95% and the solid electrolyte content is 5 to 15% based on the mass of the composite material.
7. A method for preparing a composite material according to any one of claims 1 to 6, comprising the steps of:
and adding the solid electrolyte and graphite into a first solvent, and performing dispersion and heating treatment to obtain the composite material.
8. The preparation method of claim 7, wherein the step of adding the solid electrolyte and the graphite into the first solvent, and performing dispersion and drying treatment to obtain the composite material comprises the following steps:
adding the solid electrolyte into a first solvent to obtain a first mixed solution;
adding the graphite into the first mixed solution, and performing dispersion treatment to obtain a second mixed solution;
and heating the second mixed solution at a first preset temperature, and evaporating the first solvent to dryness to obtain the composite material.
9. A solid-state battery comprising a positive electrode, a solid-state electrolyte layer, and a negative electrode, the negative electrode comprising a binder, a conductive agent, a first solid-state electrolyte, and the composite material according to any one of claims 1 to 6.
10. An electric device, comprising the solid-state battery according to claim 9 as a power supply source for the electric device.
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