CN116314834A - Composite anode material, preparation method thereof and all-solid-state battery - Google Patents
Composite anode material, preparation method thereof and all-solid-state battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- 239000010703 silicon Substances 0.000 claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 42
- 239000002001 electrolyte material Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 24
- 239000011268 mixed slurry Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 230000008020 evaporation Effects 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
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- 239000007787 solid Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 6
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
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- 239000003792 electrolyte Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a composite anode material, a preparation method thereof and an all-solid-state battery, and relates to the technical field of solid-state batteries. The preparation method of the composite anode material comprises the following steps: dissolving an electrolyte material in an organic solvent, and then mixing the electrolyte material with a silicon anode material to obtain mixed slurry; evaporating the mixed slurry to obtain a mixed precursor; and sintering the mixed precursor to obtain the composite anode material. The all-solid-state battery comprises the composite anode material prepared by the preparation method. According to the preparation method, the solid electrolyte and the silicon negative electrode material are mixed by using a solvent wet mixing and evaporation sintering preparation method, so that a good ion-electron conductive network and a rich solid-solid contact interface are built, carriers are rapidly diffused through the negative electrode, and the composite negative electrode material exerts higher capacity in the all-solid-state battery.
Description
Technical Field
The application relates to the technical field of solid-state batteries, in particular to a composite anode material, a preparation method thereof and an all-solid-state battery.
Background
At present, sulfide solid-state electrolyte is one of the most probable technical routes for realizing all-solid-state batteries because of the ultrahigh ionic conductivity and excellent mechanical properties. In order to further improve the energy density of the sulfide all-solid-state battery and promote the application of the sulfide all-solid-state battery, the silicon anode material with the theoretical specific capacity being close to 10 times (3759 mAh/g) of that of graphite has excellent application prospect.
The silicon negative electrode material has a suitable lithium intercalation potential (0.4V, vs. Li + Li), can avoid lithium deposition, has better safety than lithium metal and graphite materials, and has the advantages of huge natural reserves, wide acquisition path, low cost and the like. However, to realize the application of the silicon negative electrode in the sulfide all-solid-state battery, the following disadvantages are overcome at present: since conventional silicon negative electrode batteries rely on infiltration of a liquid electrolyte to achieve rapid conduction of ions, in solid state batteries, conduction of lithium ions is achieved mainly by solid-solid contact of an electrode active material with a solid electrolyte, and although construction of an ion path can be achieved by simple two-phase mixing, such contact tends to be insufficient, resulting in a large interfacial resistance between the active material and the solid electrolyte. Therefore, it is highly desirable to prepare a negative electrode material suitable for use in a solid-state battery, which is capable of reducing the interfacial resistance between an active material and a solid-state electrolyte.
Disclosure of Invention
The purpose of the application is to provide a composite anode material, a preparation method thereof and an all-solid-state battery, wherein sulfide solid electrolyte and the anode material are combined by using solvent mixing, evaporating and sintering methods, so that a good ion-electron conductive network and a rich solid-solid contact interface are built, and the electrochemical performance of the all-solid-state battery is improved.
In order to achieve the above object, the technical scheme of the present application is as follows:
the application provides a preparation method of a composite anode material, which comprises the following steps:
dissolving an electrolyte material in an organic solvent, and then mixing the electrolyte material with a silicon anode material to obtain mixed slurry;
evaporating the mixed slurry to obtain a mixed precursor;
and sintering the mixed precursor to obtain the composite anode material.
Preferably, the preparation method satisfies at least one of the following conditions:
a. the organic solvent comprises an alcohol solvent;
b. the electrolyte material includes a sulfide electrolyte material;
c. the particle size of the electrolyte material is 1-4 mu m;
d. the silicon anode material comprises a silicon-carbon composite material or a pure silicon material;
e. the particle size of the silicon anode material is 10-20 mu m;
f. both the dissolution and the mixing are carried out in an atmosphere of inert gas.
Further preferably, the preparation method further satisfies at least one of the following conditions:
g. the alcohol solvent comprises at least one of methanol, ethanol, isopropanol, n-propanol and ethylene glycol;
h. the sulfide electrolyte material includes Li 6 PS 5 Cl、 Li 7 S 3 Cl 11 、Li 10 GeP 2 S 12 、Li 3 PS 4 And Na (Na) 2 Ge 2 S 5 At least one of (a) and (b);
i. the particle size of the silicon anode material is 5-10 times of that of the electrolyte material.
Preferably, the mass ratio of the organic solvent is 80% -85%, the mass ratio of the electrolyte material is 3% -8%, and the mass ratio of the silicon anode material is 10% -15% based on 100% of the mass of the mixed slurry.
Preferably, the temperature of the evaporation is 60-100 ℃ and the time is 0.5-2 h.
Preferably, the sintering temperature is 350-550 ℃ and the sintering time is 3-5 h.
Preferably, the temperature rising rate of sintering is 2 ℃/min-3 ℃/min.
Preferably, both the evaporation and the sintering are performed in an inert gas atmosphere.
The application also provides a composite anode material, which is prepared by adopting the preparation method of the composite anode material.
The application also provides an all-solid-state battery which comprises the composite anode material.
The beneficial effects of this application:
the preparation method of the composite anode material has the advantages of simple production process and lower cost, and is suitable for industrial mass production. The electrolyte material is dissolved by using an organic solvent, so that the aggregation phenomenon of the electrolyte material can be reduced, the electrolyte material is uniformly dispersed and then uniformly covered on the surface of the silicon anode material, the interface contact between the electrolyte and the silicon anode material is greatly increased, and the ionic conductivity of the composite anode material is maximized; meanwhile, after the materials are mixed more uniformly, the consistency of the battery manufactured later is enhanced, and the quality and the service life of the battery product are improved. The preparation method of the composite anode material further adopts the evaporation and sintering modes, and can sinter and carbonize the residual organic solvent, so that the generated carbon can establish bridges among different silicon anode materials, and the electronic conductivity of the composite anode material is further improved.
The preparation method constructs a rich electron-ion conductive network in the composite anode material, thereby realizing faster diffusion of carriers through the anode, leading to reduced polarization and Li + The faster diffusion of (2) helps to inhibit the plating of Li, resulting in better capacity exertion and better initial efficiency.
Compared with the anode material directly subjected to mechanical dry mixing, the all-solid-state battery manufactured by using the composite anode material can exert higher charge and discharge capacity and has higher consistency.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
Fig. 1 is a first-turn charge-discharge curve of the solid-state batteries prepared in examples 1 to 3 and comparative example 1.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus. The conjunction "consisting of … …" excludes any unspecified element, step or component.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The application provides a preparation method of a composite anode material, which comprises the following steps:
s1, dissolving an electrolyte material in an organic solvent, and then mixing with a silicon anode material to obtain mixed slurry;
s2, evaporating the mixed slurry to obtain a mixed precursor;
and S3, sintering the mixed precursor to obtain the composite anode material.
In a preferred embodiment, the organic solvent in S1 comprises an alcoholic solvent.
Further preferably, the alcohol solvent includes at least one of methanol, ethanol, isopropanol, n-propanol, and ethylene glycol.
In a preferred embodiment, the electrolyte material in S1 comprises a sulfide electrolyte material.
Further preferably, the sulfide electrolyte material includes Li 6 PS 5 Cl、Li 7 S 3 Cl 11 、Li 10 GeP 2 S 12 、Li 3 PS 4 And Na (Na) 2 Ge 2 S 5 At least one of them.
In a preferred embodiment, the particle size of the electrolyte material is 1 μm to 4 μm, and may be, for example, 1 μm, 2 μm, 3 μm, 4 μm or any value between 1 μm and 4 μm.
In a preferred embodiment, the silicon negative electrode material in S1 comprises a silicon carbon composite material or a pure silicon material.
In a preferred embodiment, the particle size of the silicon anode material is 10 μm to 20 μm, and may be, for example, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm or any value between 10 μm and 20 μm.
In a preferred embodiment, both the dissolution and the mixing in S1 are carried out in an atmosphere of inert gas. Specifically, the sulfide electrolyte material and the organic solvent can be mixed in a glove box filled with argon, mechanical stirring is used until the solid electrolyte is completely dissolved in the solvent, then the silicon anode material is added, and mechanical stirring is continued for 2-5 hours, so that mixed slurry is obtained.
In a preferred embodiment, the particle size of the silicon anode material in S1 is 5 to 10 times the particle size of the electrolyte material. In this way, under the dispersion condition of the alcohol solvent, the structure of the sulfide electrolyte coated silicon anode material can be formed, the solid-solid fixation effect is better, and the obtained composite anode material also has better ionic conductivity.
In a preferred embodiment, the organic solvent is 80% -85% by mass of the mixed slurry, for example, 80%, 81%, 82%, 83%, 84%, 85% or any value between 80% -85% by mass; the electrolyte material may have a mass ratio of 3% -8%, for example, 3%, 4%, 5%, 6%, 7%, 8% or any value between 3% -8%, and the silicon anode material may have a mass ratio of 10% -15%, for example, 10%, 11%, 12%, 13%, 14%, 15% or any value between 105-15%.
In a preferred embodiment, the temperature required for evaporation in S2 is 60℃to 100℃and may be, for example, 60℃70℃80℃90℃100℃or any value between 60℃and 100℃for a period of time of 0.5h to 2h, for example, 0.5h, 1h, 1.5h, 2h or any value between 0.5h to 2h.
Specifically, the mixed slurry obtained in the step S1 is continuously placed in a glove box filled with argon, heating and evaporation are carried out, the highest evaporation temperature is set to be 100 ℃, mechanical stirring can be carried out simultaneously in the evaporation process, and after stirring for 1h, almost all organic solvents in the mixed slurry volatilize, so that a mixed precursor is obtained.
In a preferred embodiment, the temperature required for sintering in S3 is 350-550 ℃, e.g. may be 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or any value between 350-550 ℃, and the sintering time is 3-5 h, e.g. may be 3h, 4h, 5h or any value between 3h-5h.
Further preferably, the mixed precursor material is placed in a tube furnace and sintered at a temperature of 400-500 ℃.
In a preferred embodiment, during the sintering in S3, the temperature rise rate of the sintering temperature may be 2 ℃/min to 3 ℃/min, for example, at a rate of 2 ℃/min, 2.5 ℃/min, 3 ℃/min or any value between 2 ℃/min and 3 ℃/min.
In a preferred embodiment, the evaporation in S2 and the sintering in S3 are both carried out in an inert gas atmosphere, which may be, for example, an argon atmosphere, a nitrogen atmosphere or a helium atmosphere.
The application also provides a composite anode material, which is prepared by adopting the preparation method of the composite anode material.
The electrolyte material and the silicon anode material in the composite anode material prepared by the method are uniformly distributed, and the assembled parallel battery has good consistency. Specifically, after the silicon anode material is soaked with the ethanol solution containing the sulfide electrolyte, sulfide electrolyte which is easy to agglomerate to form secondary particle sediment can be mechanically stirred and dispersed further, the sulfide electrolyte is less easy to agglomerate to form secondary particles, so that the sulfide electrolyte particles can be uniformly covered on the surfaces of the silicon anode particles, and the solid-solid contact area is further increased after evaporation. Compared with the anode material prepared by directly using a simple two-phase mixing method, the composite anode material prepared by the application has higher ionic conductivity and electronic conductivity.
According to the preparation method, the evaporation and sintering modes are used, the residual organic solvent can be carbonized, and the generated carbon is dense and stable in bridge established between different silicon anode materials by controlling the evaporation temperature and time, the sintering temperature and time and the temperature rising rate in the sintering process, so that the long-term cycle performance of the composite anode material is further improved.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. 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 embodiment provides a composite anode material, and the preparation method thereof comprises the following steps:
(1) Wet mixing of raw materials: 120mg of Li 6 PS 5 Cl was dissolved in 1.6g of absolute ethanol solution and stirred with a magnetic stirrer until Li 6 PS 5 Cl is completely dissolved, and 280mg of silicon carbon powder (with the theoretical capacity of 1300 mAh/g) is added into the mixture containing Li 6 PS 5 In an ethanol solution of Cl, wherein Li 6 PS 5 The particle size of Cl is 2 mu m, the particle size of silicon carbon powder is 12 mu m, and the mechanical stirring is continued for 3 hours to obtain mixed slurry;
(2) And (3) material mixing and evaporation: evaporating the mixed slurry at 60 ℃ until the ethanol is completely evaporated to dryness, so as to obtain a precursor material;
(3) Sintering a precursor: and (3) placing the precursor material into a tube furnace, heating from room temperature to 450 ℃ at a heating rate of 2 ℃/min, continuously sintering for 4 hours, and naturally cooling to obtain the composite silicon-carbon anode material.
The embodiment also provides an all-solid-state battery, the preparation method of which comprises:
assembling a mold solid-state battery: weigh 85mg of Li 6 PS 5 The Cl solid electrolyte powder is pressed into electrolyte flakes in a die battery with the diameter of 10mm under the pressure of 360MPa and the dwell time of 1 min; continuing on the mould10mg of the composite silicon-carbon anode material prepared in the embodiment is added above a battery, and pressed into a composite electrode slice under the pressure of 360Mpa and the pressure maintaining time of 2 min; and sequentially adding an indium sheet with the diameter of 10mm and a lithium sheet with the diameter of 8mm below the die battery to obtain the die solid-state battery with the structure of the composite anode/solid electrolyte/Liin.
Example 2
The embodiment provides a composite anode material, and the preparation method thereof comprises the following steps:
(1) Wet mixing of raw materials: 75mg of Li 6 PS 5 Cl was dissolved in 1.7g of absolute ethanol solution and stirred with a magnetic stirrer until Li 6 PS 5 Cl is completely dissolved, 225mg of silicon carbon powder (theoretical capacity is 1300 mAh/g) is added into the mixture containing Li 6 PS 5 In an ethanol solution of Cl, wherein Li 6 PS 5 The particle size of Cl is 3 mu m, the particle size of silicon carbon powder is 15 mu m, and the mechanical stirring is continued for 3 hours to obtain mixed slurry;
(2) And (3) material mixing and evaporation: evaporating the mixed slurry at 80 ℃ until the ethanol is completely evaporated to dryness, so as to obtain a precursor material;
(3) Sintering a precursor: and (3) placing the precursor material into a tube furnace, heating from room temperature to 550 ℃ at a heating rate of 2 ℃/min, continuously sintering for 4 hours, and naturally cooling to obtain the composite silicon-carbon anode material.
This example provides an all-solid-state battery, which is prepared in the same manner as in example 1.
Example 3
This example provides a composite anode material, which is prepared in the same manner as in example 1, except that: li in step (1) 6 PS 5 Cl was dissolved in methanol.
This example provides an all-solid-state battery, which is prepared in the same manner as in example 1.
Comparative example 1
The comparative example provides a composite anode material, the preparation method of which comprises:
mechanical ball milling: 120mg of Li is weighed 6 PS 5 Cl and 280mg of silicon carbon powder (theoretical capacity 1300 mAh/g) were added to the argon-filled zirconiaInto a ball milling tank, 2g of ZrO was added 2 (diameter is 4 mm), the rotation speed of ball milling is 500rpm, and the ball milling is operated for 5 hours, so that the composite silicon-carbon anode material is obtained.
This comparative example provides an all-solid-state battery, which was prepared in the same manner as in example 1.
Comparative example 2
This comparative example provides a composite anode material, which was prepared in the same manner as in example 1, except that: and (3) the sintering process of the step (3) is omitted, and after the evaporation of the step (2), the obtained precursor material is crushed, so that the obtained precursor material is the composite silicon-carbon anode material.
This comparative example provides an all-solid-state battery, which was prepared in the same manner as in example 1.
Comparative example 3
This comparative example provides a composite anode material, which was prepared in the same manner as in example 1, except that: li (Li) 6 PS 5 The Cl particle size was 10 μm and the silica carbon powder particle size was 12. Mu.m.
This comparative example provides an all-solid-state battery, which was prepared in the same manner as in example 1.
3 samples of the solid-state lithium ion batteries of examples 1 to 3 and comparative examples 1 to 3 were prepared respectively for cyclic charge and discharge testing, and the specific test procedure was as follows: the battery is put at 45 ℃ and a voltage interval of 0.55V-0.9V for charge and discharge test, and is charged and discharged for one week at a multiplying power of 0.05C first, and then is continuously charged and discharged in a circulating way at a multiplying power of 0.1C. The test results of 3 solid-state battery samples in each of the examples and comparative examples are listed in table 1.
Meanwhile, the composite silicon cathodes of the above examples 1-3 and comparative examples 1-3 were subjected to electron conductivity test, and the specific test method was as follows: taking 60mg of composite silicon negative electrode, placing two stainless steel sheets on two sides of the composite silicon negative electrode in a die battery with the diameter of 10mm, assembling the composite silicon negative electrode into a model battery with a sandwich-like structure under the pressure of 360MPa and the pressure maintaining time of 1min, and recording the thickness of the pressed composite silicon negative electrode. Potentiostatic testing is carried out on the composite silicon anode by using an electrochemical workstation under the voltage of 50 mV, and the change of current is recorded, so that the electronic conductivity of the composite silicon anode is obtainedσ electron See (1):
in the method, in the process of the invention,V50 mV;Iis steady state current at 50 mV bias;pis the resistivity of the composite silicon negative electrode, and the reciprocal thereof represents the conductivity;lthe thickness of the composite silicon anode;sis the die cross-sectional area. Table 2 shows the electron conductivities of the composite silicon anodes of examples 1-3 and comparative examples 1-3.
Table 1 test results of solid-state batteries prepared in examples 1 to 3 and comparative examples 1 to 3
TABLE 2 electronic conductivity of composite silicon cathodes prepared in examples 1-3 and comparative examples 1-3
From the test results of example 1 and comparative example 1, it can be found that: the composite silicon-carbon negative electrode of the all-solid-state battery directly produced by mechanical dry mixing has low capacity exertion, and the consistency of the parallel assembled battery is poor; the composite silicon-carbon anode material prepared by the preparation method can exert higher capacity (see figure 1) in an all-solid-state battery, and has higher consistency. Meanwhile, the electron conductivity of the composite anode material is enhanced through wet mixing of an alcohol solvent and sintering carbonization, so that carriers can diffuse through the anode more quickly, and the composite anode material can exert higher capacity in an all-solid-state battery.
The preparation method of the composite anode material has the advantages that sulfide electrolyte and silicon anode material can be uniformly mixed, a good ion-electron network can be constructed, the capacity of the prepared composite anode material is higher, and the initial effect is better.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, any of the above-described claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The preparation method of the composite anode material is characterized by comprising the following steps:
dissolving an electrolyte material in an organic solvent, and then mixing the electrolyte material with a silicon anode material to obtain mixed slurry;
evaporating the mixed slurry to obtain a mixed precursor;
and sintering the mixed precursor to obtain the composite anode material.
2. The method of manufacturing according to claim 1, wherein at least one of the following conditions is satisfied:
a. the organic solvent comprises an alcohol solvent;
b. the electrolyte material includes a sulfide electrolyte material;
c. the particle size of the electrolyte material is 1-4 mu m;
d. the silicon anode material comprises a silicon-carbon composite material or a pure silicon material;
e. the particle size of the silicon anode material is 10-20 mu m;
f. both the dissolution and the mixing are carried out in an atmosphere of inert gas.
3. The method of manufacturing of claim 2, further satisfying at least one of the following conditions:
g. the alcohol solvent comprises at least one of methanol, ethanol, isopropanol, n-propanol and ethylene glycol;
h. the sulfide electrolyte material includes Li 6 PS 5 Cl、 Li 7 S 3 Cl 11 、Li 10 GeP 2 S 12 、Li 3 PS 4 And Na (Na) 2 Ge 2 S 5 At least one of (a) and (b);
i. the particle size of the silicon anode material is 5-10 times of that of the electrolyte material.
4. The method according to claim 1, wherein the mass ratio of the organic solvent is 80 to 85%, the mass ratio of the electrolyte material is 3 to 8%, and the mass ratio of the silicon anode material is 10 to 15%, based on 100% by mass of the mixed slurry.
5. The method of claim 1, wherein the evaporating temperature is 60 ℃ to 100 ℃ for 0.5h to 2h.
6. The method of claim 1, wherein the sintering is performed at a temperature of 350 ℃ to 550 ℃ for a time of 3 hours to 5 hours.
7. The method of claim 1, wherein the sintering is performed at a rate of 2 ℃/min to 3 ℃/min.
8. The method according to any one of claims 1 to 7, wherein the evaporation and the sintering are both performed in an atmosphere of inert gas.
9. A composite anode material characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. An all-solid battery comprising the composite anode material of claim 9.
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