CN116190574A - Composite negative electrode suitable for all-solid-state battery and preparation method thereof - Google Patents

Composite negative electrode suitable for all-solid-state battery and preparation method thereof Download PDF

Info

Publication number
CN116190574A
CN116190574A CN202310140023.1A CN202310140023A CN116190574A CN 116190574 A CN116190574 A CN 116190574A CN 202310140023 A CN202310140023 A CN 202310140023A CN 116190574 A CN116190574 A CN 116190574A
Authority
CN
China
Prior art keywords
negative electrode
solid
composite
indium
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310140023.1A
Other languages
Chinese (zh)
Inventor
王在发
方志强
赵昌泰
梁剑文
赵尚骞
方志林
黄建宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Youyan Guangdong New Material Technology Research Institute
Original Assignee
Youyan Guangdong New Material Technology Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Youyan Guangdong New Material Technology Research Institute filed Critical Youyan Guangdong New Material Technology Research Institute
Priority to CN202310140023.1A priority Critical patent/CN116190574A/en
Publication of CN116190574A publication Critical patent/CN116190574A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a composite negative electrode suitable for an all-solid-state battery and a preparation method thereof, comprising the following steps: ball-milling and mixing the negative electrode active material; ball-milling and mixing the mixed anode active material with solid electrolyte under the protection of inert gas to obtain a composite anode; indium particles are distributed in a dot shape in the whole composite anode. Aiming at the defects existing in the prior art, the invention creatively improves, develops a novel negative electrode structure suitable for all-solid-state batteries, and solves the problems of low lithium intercalation rate of a graphite negative electrode or a silicon-carbon negative electrode, easy occurrence of lithium precipitation during charging and poor electrochemical performance under high multiplying power. The preparation method is simple, is easy for large-scale production, and can realize stable circulation of the all-solid-state lithium battery under high multiplying power.

Description

Composite negative electrode suitable for all-solid-state battery and preparation method thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a composite negative electrode suitable for an all-solid-state battery and a preparation method thereof.
Background
With the rapid development of science and technology and the continuous improvement of living standard, people have higher requirements on lithium ion batteries, such as high safety, high energy density, high-rate quick charge and the like. In order to meet the requirement, the nonflammable solid electrolyte is adopted to replace the flammable organic liquid electrolyte, and meanwhile, the high-energy anode and the high-energy cathode are matched, so that further improvement of safety and energy density is expected to be realized. However, in the solid-state battery, it is limited by the low diffusion rate of lithium ions (such as graphite and silicon carbon) in the negative electrode and the difficulty in continuous ion transport network inside the negative electrode, lithium precipitation easily occurs during high-rate charging, causing interfacial lithium deposition, thus causing irreversible capacity loss and even short circuit of the battery.
There are two current solutions to the above problem.
First, the appropriate modification of the negative electrode material can improve the rate performance, such as the artificial graphite negative electrode treated by high-temperature nitridation in chinese patent CN111584866A, CN108807996a and CN110841595A, and although the rate performance can be improved, in the charging process of the all-solid-state lithium battery, lithium ions cannot be uniformly and rapidly distributed inside the whole negative electrode, and lithium deposition still easily occurs at the interface of the negative electrode and the solid electrolyte under high rate.
Secondly, aiming at the problem of lithium deposition at the interface under high multiplying power, the problem can be relieved by modifying the interface between the negative electrode and the solid electrolyte, but the problem is still obvious under high multiplying power, for example, the interface between the negative electrode and the solid electrolyte is modified by using flexible gel electrolyte in Chinese patent CN111952663A, and the modification of the interface can prevent lithium from being embedded into the negative electrode, so that the multiplying power performance is reduced.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the invention provides a composite negative electrode suitable for an all-solid-state battery and a preparation method thereof, which solve the problem that the electrochemical performance of the all-solid-state battery is poor at high multiplying power.
The invention is realized by the following technical scheme:
a preparation method of a composite negative electrode suitable for an all-solid-state battery comprises the following steps:
step 1, ball-milling and mixing a negative electrode active material;
step 2, ball-milling and mixing the mixed anode active material with solid electrolyte under the protection of inert gas to obtain a composite anode;
the anode active material includes indium and a carbon material, or the anode active material includes indium, a carbon material, and a silicon material.
Aiming at the defects existing in the prior art, the invention creatively improves, develops a novel negative electrode structure suitable for all-solid-state batteries, and solves the problems of low lithium intercalation rate of a graphite negative electrode or a silicon-carbon negative electrode, easy occurrence of lithium precipitation during charging and poor electrochemical performance under high multiplying power. The preparation method is simple, is easy for large-scale production, and can realize stable circulation of the all-solid-state lithium battery under high multiplying power.
Specifically, the invention aims at the problem of poor electrochemical performance of the all-solid-state battery under high multiplying power in the prior art, indium powder, other negative electrode active substances and solid electrolyte are mixed by step ball milling in a step manner by adding the indium powder into the negative electrode, so that indium is uniformly dispersed in the whole composite negative electrode in a dot shape, lithium ions are rapidly and uniformly distributed in the whole negative electrode by utilizing the high ion conductivity of the indium, lithium deposition at the interface between the negative electrode and the solid electrolyte is avoided, and the cycle performance of the battery under high multiplying power is effectively improved.
Preferably, the composite negative electrode suitable for the high-rate all-solid-state battery is an indium-carbon composite negative electrode or an indium-silicon-carbon composite negative electrode.
Further alternatively, in step 2, the ratio of the mass of indium in the total mass of the composite anode may be 10% -45%.
The invention further optimizes the proportion parameters of indium and other anode active materials, and successfully obtains the all-solid-state battery with high multiplying power and long cycle performance.
Further alternatively, indium particles having a particle size of 0.1 μm to 50 μm are used.
Further alternatively, the mixed anode active material and the solid electrolyte are mixed according to a mass ratio of 6:4-9:1.
Further optionally, in step 1, the ball milling mixing parameter design includes: the ball milling rotating speed is 100-200 revolutions, and/or the ball milling time is 2-3 hours, and/or the ball material ratio is 15:1-40:1;
and/or in the step 2, the ball milling mixing parameter design comprises: the ball milling rotating speed is 300-500 revolutions, and/or the ball milling time is 1.5-3 hours, and/or the ball-material ratio is 15:1-40:1.
A composite negative electrode suitable for all-solid-state battery, the raw materials include negative electrode active material and solid electrolyte;
the anode active material includes indium and a carbon material, or the anode active material includes indium, a carbon material, and a silicon material; indium particles are distributed in a dot shape in the whole composite anode.
The composite anode is more preferably such that indium particles are uniformly distributed in a dot shape throughout the inside of the anode.
According to the invention, indium particles are uniformly dispersed in the cathode, and the lithium intercalation potential of indium is 0.3V-0.62V and is higher than that of graphite and silicon, so that lithium ions are preferentially intercalated in indium in the initial stage of charging, so that the lithium ions are uniformly dispersed in the whole cathode, and along with the progress of charging, the lithium ions are uniformly intercalated in the silicon or the graphite in the whole cathode, thereby effectively avoiding interfacial lithium deposition.
Further alternatively, the mass of indium may be 10% -45% of the total mass of the composite anode; and/or the mass ratio of the mixed anode active material to the solid electrolyte is 6:4-9:1.
Further alternatively, indium powder is used as the raw material, and the particle size of the indium powder particles is 0.1 μm to 50 μm.
Further optionally, the carbon material comprises at least one of graphite, carbon nanotubes, graphene, and mesophase carbon microbeads;
and/or the solid electrolyte includes any one of a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, and a halide solid electrolyte. More preferably, the sulfide solid state electrolyte is Thio-LISICON, li 11-x M 2-x P 1+x S 12 (m=ge, sn, si) and Li 6 PS 5 X (x=cl, br, I), preferably Li 6 PS 5 Cl。
An all-solid-state battery comprises a battery anode and a battery cathode, wherein the battery cathode adopts a composite electrode obtained by the preparation method of the composite cathode suitable for the all-solid-state battery, or adopts the composite cathode suitable for the all-solid-state battery; the battery anode comprises a ternary system, a lithium cobaltate system, a lithium iron phosphate system and a lithium manganate system.
The invention has the following advantages and beneficial effects:
1. the invention develops a novel negative electrode structure suitable for an all-solid-state battery, and the problems that the lithium intercalation rate of a graphite negative electrode or a silicon-carbon negative electrode is low, lithium precipitation is easy to occur during charging and the electrochemical performance is poor under high multiplying power are solved by adding indium powder into the negative electrode, and indium particles are uniformly distributed in the whole composite negative electrode in a dot shape. The preparation method is simple, is easy for large-scale production, and can realize stable circulation of the all-solid-state lithium battery under high multiplying power; and further optimizing the proportion parameters of the anode material and indium, and successfully obtaining the all-solid-state battery with high multiplying power and long cycle performance.
2. Compared with the existing graphite negative electrode or silicon-carbon negative electrode, the preparation method of the indium-silicon-carbon composite negative electrode provided by the invention has the advantages of strong operability, simple material process and practical value, and can be applied to large-scale industrial production. In addition, the composite negative electrode has good lithium ion transmission performance, can ensure that lithium ions are firstly and rapidly uniformly distributed on the whole negative electrode in the charging process, avoids lithium deposition at an interface, and ensures high stability and long service life in the charging and discharging process under high multiplying power.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention. In the drawings:
FIG. 1 is a schematic view of a composite negative electrode structure of the present invention; wherein 1 represents an active material and a solid electrolyte, and 2 represents indium particles.
Fig. 2 is a charge-discharge curve of all solid-state lithium ion batteries of the negative electrodes prepared in example 1 and comparative example 1 of the present invention.
Fig. 3 is the cycle capacity of all solid state lithium ion batteries of the negative electrode prepared in example 1, example 2 and example 3 of the present invention.
Fig. 4 shows the rate performance of the all-solid-state lithium ion battery of the negative electrode prepared in example 3 of the present invention.
Fig. 5 is a charge curve of the all-solid-state lithium ion battery of the negative electrode prepared in comparative example 1 of the present invention at 2C rate.
Fig. 6 shows the long cycle performance of the all-solid-state lithium ion battery of the negative electrode prepared in example 3 of the present invention.
Fig. 7 is a charge-discharge curve of all solid-state lithium ion batteries of the negative electrode prepared in example 4 and comparative example 2 of the present invention.
FIG. 8 is a charge-discharge curve of 0.2C and 0.3C of comparative example 2 of the present invention.
Fig. 9 is a graph showing the rate performance of the all-solid-state lithium ion battery of the negative electrode prepared in example 4 of the present invention.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
Example 1
The embodiment provides a composite negative electrode suitable for an all-solid-state battery, in particular an indium-carbon negative electrode, which is prepared by the following method:
(1) Indium powder (D50=50 μm) and graphite powder (D50=6.5 μm) are weighed according to the mass ratio of 1:1 and then placed in a ball milling tank, ball milling is carried out for 2 hours at 200r/min, and the raw material A-11 which is uniformly mixed is obtained.
(2) In an argon glove box, raw materials A-11 and sulfide solid electrolyte are weighed according to the mass ratio of 9:1, then are placed in a ball milling tank, ball milling is carried out for 2 hours at 400r/min under the argon environment, and an indium-carbon negative electrode is obtained and marked as InC-11.
Example 2
The embodiment provides a composite negative electrode suitable for an all-solid-state battery, in particular an indium-carbon negative electrode, which is prepared by the following method:
(1) Indium powder (D50=50 μm) and graphite powder (D50=6.5 μm) are weighed according to the mass ratio of 1:3 and then placed in a ball milling tank, ball milling is carried out for 2 hours at 200r/min, and a uniformly mixed raw material A-13 is obtained.
(2) In an argon glove box, raw materials A-11 and sulfide solid electrolyte are weighed according to the mass ratio of 9:1, then are placed in a ball milling tank, ball milling is carried out for 2 hours at 400r/min under the argon environment, and an indium-carbon negative electrode is obtained and marked as InC-13.
Example 3
The embodiment provides a composite negative electrode suitable for an all-solid-state battery, in particular an indium-carbon negative electrode, which is prepared by the following method:
(1) Indium powder (D50=50 μm) and graphite powder (D50=6.5 μm) are weighed according to the mass ratio of 1:4 and then placed in a ball milling tank, ball milling is carried out for 2 hours at 200r/min, and the raw material A-14 which is uniformly mixed is obtained.
(2) In an argon glove box, raw materials A-11 and sulfide solid electrolyte are weighed according to the mass ratio of 9:1, then are placed in a ball milling tank, ball milling is carried out for 2 hours at 400r/min under the argon environment, and an indium-carbon negative electrode is obtained and marked as InC-14.
Example 4
The embodiment provides a composite negative electrode suitable for an all-solid-state battery, in particular an indium-silicon-carbon negative electrode, which is prepared by the following method:
(1) Silicon powder (D50=1 mu m) and graphite powder (D50=6.5 mu m) are weighed according to the mass ratio of 44.4:55.5, and then are placed in a ball milling tank, ball milling is carried out for 2 hours at 200r/min, so that a uniformly mixed raw material A is obtained, the theoretical capacity of silicon-graphite is 1500mAh/g, and the theoretical specific capacity can be regulated and controlled by changing the proportion of silicon and graphite in the process.
(2) Indium powder (D50=50μm) and raw material A are weighed according to the mass ratio of 1:4 respectively, and then are placed in a ball milling tank for ball milling for 2 hours at 200r/min, so as to obtain raw material B which is uniformly mixed.
(3) In an argon glove box, weighing a raw material B and sulfide solid electrolyte according to a mass ratio of 9:1, placing the raw material B and sulfide solid electrolyte in a ball milling tank, and ball milling for 2 hours at 400r/min under an argon environment to obtain an indium-silicon-carbon negative electrode, wherein the negative electrode is marked as InSiC-1500.
Comparative example 1
The comparative example provides a graphite anode which is prepared by the following method:
in an argon glove box, 0.2g of graphite is weighed and placed in a ball milling tank, and then a certain amount of sulfide solid electrolyte is weighed according to the mass ratio of the graphite to the sulfide solid electrolyte of 9:1. Ball milling is carried out for 2 hours at a rotating speed of 200r/min in an argon environment, and then ball milling is carried out for 2 hours at a rotating speed of 400r/min, so that a graphite cathode is obtained and marked as C.
Comparative example 2
The comparative example provides a silicon-carbon negative electrode, which is prepared by the following method:
(1) Preparation of silicon-carbon negative electrode: firstly, silicon powder (D50=1 mu m) and graphite powder (D50=6.5 mu m) are weighed according to the mass ratio of 44.4:55.5 respectively and then placed in a ball milling tank, ball milling is carried out for 2 hours at 200r/min, and a uniformly mixed raw material A is obtained, wherein the theoretical silicon-carbon capacity is 1500mAh/g, and the theoretical specific capacity can be regulated and controlled by changing the proportion of silicon and carbon in the process.
(2) In an argon glove box, weighing a raw material A and sulfide solid electrolyte according to a mass ratio of 9:1, placing the raw material A and sulfide solid electrolyte in a ball milling tank, and ball milling for 2 hours at 400r/min under an argon environment to obtain a silicon-carbon negative electrode, wherein the silicon-carbon negative electrode is marked as SiC-1500.
Application example
The negative electrodes prepared in examples 1 to 4 and comparative examples 1 to 2 were assembled into all solid-state lithium ion batteries, and their electrochemical properties were tested:
placing 80mg of sulfide solid electrolyte powder into a self-made mold, applying 380MPa pressure, adding a composite positive electrode on one side, wherein the positive electrode is a ternary system (NMC 811) or lithium cobaltate, applying 760MPa pressure, placing a prepared negative electrode on the other side, applying 380MPa, and screwing a battery screw to obtain the all-solid lithium ion battery.
The cathodes prepared in example 1 and comparative example 1 were subjected to electrochemical analysis test, and as a result, as shown in fig. 2, the charge-discharge voltage window was 2.1 to 4.3V, charge-discharge was performed at a current density of 1C, positive electrode NMC811 matched with the full-cell first-turn discharge capacity of the cathode of example 1 to be 146mAh/g, and matched with the full-cell first-turn discharge capacity of the cathode of comparative example 1 to be 61mAh/g.
The negative-electrode-matched positive electrode NMC811 prepared in example 1, example 2 and example 3 was subjected to a cycle stability test at a current density of 1C, and example 3 exhibited the best cycle stability with a 500-cycle capacity maintained at 75% as shown in table 1 and fig. 3.
Table 1 all solid-state battery test results obtained in examples 1 to 3 and comparative example 1
Figure BDA0004087164320000051
Full cell rate tests of the negative electrode prepared in accordance with example 3 were conducted at 1C, 1.5C, 2C, 3C and 5C for 5 weeks, respectively, with a current density of 1C of about 2.2mA/cm 2 A high capacity of 116mAh/g was maintained even at a 5C rate as shown in fig. 4, while the full cell of the negative electrode of comparative example 1 was short-circuited at 2C charge as shown in fig. 5.
The full cell of matching example 3 had a capacity retention of 5600 cycles at 1C rate of 68%, as shown in fig. 6, demonstrating that the obtained indium-carbon anode of the present invention has high capacity, high rate performance and excellent cycle performance.
The cathodes prepared in example 4 and comparative example 2 were subjected to electrochemical tests, and as shown in fig. 7-8 and table 2, the charge-discharge voltage window was 2.5-4.3V, and the charge-discharge at 0.1C current density, the initial-cycle discharge capacity of the full battery, which was matched with the cathodes of example 4 and lithium cobaltate as the positive electrode, was 143mAh/g, and the initial-cycle coulomb efficiency was 92%. The first-cycle discharge capacity of the full battery with the cathode and the lithium cobaltate of the matched pair ratio 2 as the anode is 117mAh/g, and the first-cycle coulomb efficiency is only 74%.
Table 2 test results of all solid-state batteries prepared in example 4 and comparative example 2
Figure BDA0004087164320000061
Full cell rate tests of the negative electrode and the positive electrode made of lithium cobaltate according to the matching example 4 were conducted at 0.2C, 0.3C, 1C, 2C, 3C, 5C, 7C and 10C for 5 weeks, respectively, with a current density of 1C of about 2.2mA/cm 2 The high capacity of 123mAh/g can be maintained at 1C multiplying power, the capacity of 125mAh/g can be obtained after the 10C circulation is completed and the 1C circulation is completed, as shown in figure 9, the indium-silicon-carbon anode has excellent multiplying power performance, and interfacial lithium deposition is avoided.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. A method for preparing a composite negative electrode suitable for an all-solid-state battery, comprising the steps of:
step 1, ball-milling and mixing a negative electrode active material;
step 2, ball-milling and mixing the mixed anode active material with solid electrolyte under the protection of inert gas to obtain a composite anode;
the anode active material includes indium and a carbon material, or the anode active material includes indium, a carbon material, and a silicon material.
2. The method for manufacturing a composite anode suitable for an all-solid battery according to claim 1, wherein in step 2, the mass ratio of indium in the total mass of the composite anode is 10% -45%.
3. The method for producing a composite negative electrode for all-solid-state batteries according to claim 1, wherein indium particles having a particle diameter of 0.1 μm to 50 μm are used.
4. The method for producing a composite anode suitable for an all-solid battery according to claim 1, wherein the mixed anode active material and the solid electrolyte are mixed in a mass ratio of 6:4 to 9:1.
5. The method for preparing a composite anode suitable for an all-solid-state battery according to claim 1, wherein in step 1, the ball milling mixing parameter design comprises: the ball milling rotating speed is 100-200 revolutions, and/or the ball milling time is 2-3 hours, and/or the ball material ratio is 15:1-40:1;
and/or in the step 2, the ball milling mixing parameter design comprises: the ball milling rotating speed is 300-500 revolutions, and/or the ball milling time is 1.5-3 hours, and/or the ball-material ratio is 15:1-40:1.
6. A composite negative electrode suitable for an all-solid-state battery, characterized in that the raw materials include a negative electrode active material and a solid electrolyte;
the anode active material includes indium and a carbon material, or the anode active material includes indium, a carbon material, and a silicon material; indium particles are distributed in a dot shape in the whole composite anode.
7. The composite anode suitable for all-solid-state batteries according to claim 1, wherein in step 2, the ratio of the mass of indium to the total mass of the composite anode may be 10% -45%; and/or the mass ratio of the mixed anode active material to the solid electrolyte is 6:4-9:1.
8. The composite negative electrode for all-solid-state battery according to claim 1, wherein indium powder is used as the raw material, and the particle size of the indium powder particles is 0.1 μm to 50 μm.
9. The composite negative electrode for an all-solid battery according to claim 1, wherein the carbon material comprises at least one of graphite, carbon nanotubes, graphene, and mesophase carbon microbeads;
and/or the solid electrolyte includes any one of a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, and a halide solid electrolyte.
10. An all-solid-state battery comprising a battery positive electrode and a battery negative electrode, wherein the battery negative electrode is a composite electrode obtained by the method for producing a composite negative electrode suitable for an all-solid-state battery according to any one of claims 1 to 5, or a composite negative electrode suitable for an all-solid-state battery according to any one of claims 6 to 9;
the battery anode comprises a ternary system, a lithium cobaltate system, a lithium iron phosphate system and a lithium manganate system.
CN202310140023.1A 2023-02-21 2023-02-21 Composite negative electrode suitable for all-solid-state battery and preparation method thereof Pending CN116190574A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310140023.1A CN116190574A (en) 2023-02-21 2023-02-21 Composite negative electrode suitable for all-solid-state battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310140023.1A CN116190574A (en) 2023-02-21 2023-02-21 Composite negative electrode suitable for all-solid-state battery and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116190574A true CN116190574A (en) 2023-05-30

Family

ID=86451947

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310140023.1A Pending CN116190574A (en) 2023-02-21 2023-02-21 Composite negative electrode suitable for all-solid-state battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116190574A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117691096A (en) * 2024-02-04 2024-03-12 内蒙古工业大学 Silicon-based composite anode material of all-solid-state lithium battery and preparation method thereof

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08138725A (en) * 1994-11-01 1996-05-31 Matsushita Electric Ind Co Ltd All solid lithium battery
JP2006164695A (en) * 2004-12-06 2006-06-22 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery
US20100075223A1 (en) * 2008-09-23 2010-03-25 Industrial Technology Research Institute Energy storage devices
JP2014029777A (en) * 2012-07-31 2014-02-13 Ngk Spark Plug Co Ltd All-solid-state battery
CN105489931A (en) * 2015-12-24 2016-04-13 国联汽车动力电池研究院有限责任公司 Application of sulfide electrolyte in preparing all-solid-state battery
KR20160047301A (en) * 2014-10-22 2016-05-02 주식회사 포스코 Method for producing anode materials of secondary battery and anode materials for all-solid secondary battery pot for producing anode materials
KR20160086795A (en) * 2016-07-08 2016-07-20 현대자동차주식회사 A solid-state battery and a method for manufacturing it
CN107240688A (en) * 2017-06-15 2017-10-10 山东大学 A kind of silicium cathode material of sulfenyl solid electrolyte cladding and preparation method thereof
KR20180044166A (en) * 2016-10-21 2018-05-02 창원대학교 산학협력단 Method for preparing all-solid-state secondary battery having improved interfacial properties and all-solid-state secondary battery prepared thereby
CN109921090A (en) * 2019-03-08 2019-06-21 山东大学 A kind of all solid state full battery of lithium ion and preparation method thereof
CN110233298A (en) * 2019-07-09 2019-09-13 珠海冠宇电池有限公司 A kind of preparation method of novel all-solid lithium-ion battery
CN110957525A (en) * 2018-09-27 2020-04-03 比亚迪股份有限公司 Solid electrolyte, preparation method thereof and solid lithium battery
CN111566848A (en) * 2018-01-26 2020-08-21 松下知识产权经营株式会社 Negative electrode material and battery using the same
CN111653754A (en) * 2020-06-28 2020-09-11 中国华能集团清洁能源技术研究院有限公司 Preparation method of sulfide all-solid-state battery lithium cathode composite material
CN111785974A (en) * 2020-08-25 2020-10-16 中南大学 Positive electrode coating method for sulfide solid-state lithium ion battery, positive electrode and battery
CN213026226U (en) * 2020-06-28 2021-04-20 中国华能集团清洁能源技术研究院有限公司 Sulfide all-solid-state battery with lithium composite material as negative electrode
CN112713266A (en) * 2020-12-30 2021-04-27 蜂巢能源科技有限公司 Negative electrode slurry and application thereof
CN114447299A (en) * 2022-01-14 2022-05-06 中国科学院宁波材料技术与工程研究所 Method for relieving negative pole lithium separation during charging of all-solid-state lithium ion battery

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08138725A (en) * 1994-11-01 1996-05-31 Matsushita Electric Ind Co Ltd All solid lithium battery
JP2006164695A (en) * 2004-12-06 2006-06-22 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery
US20100075223A1 (en) * 2008-09-23 2010-03-25 Industrial Technology Research Institute Energy storage devices
JP2014029777A (en) * 2012-07-31 2014-02-13 Ngk Spark Plug Co Ltd All-solid-state battery
KR20160047301A (en) * 2014-10-22 2016-05-02 주식회사 포스코 Method for producing anode materials of secondary battery and anode materials for all-solid secondary battery pot for producing anode materials
CN105489931A (en) * 2015-12-24 2016-04-13 国联汽车动力电池研究院有限责任公司 Application of sulfide electrolyte in preparing all-solid-state battery
KR20160086795A (en) * 2016-07-08 2016-07-20 현대자동차주식회사 A solid-state battery and a method for manufacturing it
KR20180044166A (en) * 2016-10-21 2018-05-02 창원대학교 산학협력단 Method for preparing all-solid-state secondary battery having improved interfacial properties and all-solid-state secondary battery prepared thereby
CN107240688A (en) * 2017-06-15 2017-10-10 山东大学 A kind of silicium cathode material of sulfenyl solid electrolyte cladding and preparation method thereof
CN111566848A (en) * 2018-01-26 2020-08-21 松下知识产权经营株式会社 Negative electrode material and battery using the same
CN110957525A (en) * 2018-09-27 2020-04-03 比亚迪股份有限公司 Solid electrolyte, preparation method thereof and solid lithium battery
CN109921090A (en) * 2019-03-08 2019-06-21 山东大学 A kind of all solid state full battery of lithium ion and preparation method thereof
CN110233298A (en) * 2019-07-09 2019-09-13 珠海冠宇电池有限公司 A kind of preparation method of novel all-solid lithium-ion battery
CN111653754A (en) * 2020-06-28 2020-09-11 中国华能集团清洁能源技术研究院有限公司 Preparation method of sulfide all-solid-state battery lithium cathode composite material
CN213026226U (en) * 2020-06-28 2021-04-20 中国华能集团清洁能源技术研究院有限公司 Sulfide all-solid-state battery with lithium composite material as negative electrode
CN111785974A (en) * 2020-08-25 2020-10-16 中南大学 Positive electrode coating method for sulfide solid-state lithium ion battery, positive electrode and battery
CN112713266A (en) * 2020-12-30 2021-04-27 蜂巢能源科技有限公司 Negative electrode slurry and application thereof
CN114447299A (en) * 2022-01-14 2022-05-06 中国科学院宁波材料技术与工程研究所 Method for relieving negative pole lithium separation during charging of all-solid-state lithium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117691096A (en) * 2024-02-04 2024-03-12 内蒙古工业大学 Silicon-based composite anode material of all-solid-state lithium battery and preparation method thereof
CN117691096B (en) * 2024-02-04 2024-04-09 内蒙古工业大学 Silicon-based composite anode material of all-solid-state lithium battery and preparation method thereof

Similar Documents

Publication Publication Date Title
CN108461723B (en) Silicon-based composite material for lithium ion battery and preparation method thereof
CN103700820B (en) A kind of lithium ion selenium battery with long service life
CN108232156B (en) Silicon-carbon composite cathode for solid-state battery and preparation method thereof
CN109119592B (en) Lithium titanate negative electrode piece, preparation method and lithium titanate battery
CN107634208A (en) A kind of preparation method of lithium ion battery silicon-carbon cathode material
CN112909234A (en) Preparation method and application of lithium cathode or sodium cathode
CN110620224A (en) Negative electrode material for lithium battery, preparation method of negative electrode material and lithium battery
CN112133896B (en) High-capacity graphite-silicon oxide composite material and preparation method and application thereof
CN107316989B (en) Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof
CN102110813B (en) Graphite material at negative pole of lithium ion battery and preparation method thereof
CN116190574A (en) Composite negative electrode suitable for all-solid-state battery and preparation method thereof
CN107565099B (en) Positive active material, preparation method thereof and lithium ion battery
CN108682856B (en) Typha carbon-loaded vanadium sodium phosphate nano composite material and preparation method and application thereof
CN114094058B (en) Preparation method of lithium phosphide electrode based on microwave method
CN115249799A (en) Rosin-based nitrogen-doped coated hard carbon negative electrode material of sodium ion battery and preparation method of rosin-based nitrogen-doped coated hard carbon negative electrode material
CN110098384A (en) A kind of modified cobalt acid lithium and its preparation and application
CN114665068A (en) Preparation method of all-solid-state lithium battery with lithium-aluminum alloy as negative electrode
CN114695851A (en) Composite negative electrode material, negative electrode, battery and preparation method of composite negative electrode material
CN112397701A (en) Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof
CN112209430B (en) Tin dioxide/niobium doped carbon composite material for lithium ion battery and preparation method and application thereof
CN115036454B (en) Safe and stable activated negative electrode
CN114914400B (en) Hard carbon stable lithium silicon alloy negative electrode and battery
CN114242979B (en) Organic composite positive electrode material, preparation method thereof and all-solid-state battery
CN114388878B (en) Composite solid electrolyte and preparation method and application thereof
CN111261857B (en) FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination