CN111081992B - Preparation method of binder-free lithium ion battery negative electrode material - Google Patents

Preparation method of binder-free lithium ion battery negative electrode material Download PDF

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CN111081992B
CN111081992B CN201910980596.9A CN201910980596A CN111081992B CN 111081992 B CN111081992 B CN 111081992B CN 201910980596 A CN201910980596 A CN 201910980596A CN 111081992 B CN111081992 B CN 111081992B
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lithium ion
ion battery
cathode material
preparation
milling
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CN111081992A (en
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刘进
王丽
郝延蔚
孙瑞敏
周永恒
师兆忠
赵辉
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Kaifeng University
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • 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
    • H01M4/36—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
    • 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
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The invention belongs to the field of battery energy, and particularly relates to a preparation method of a binderless lithium ion battery cathode material. Under the protection of argon, directly sintering waste silicon powder generated by cutting off single crystals, and performing ball milling; and step two, adding sodium silicate, mixing, adding ammonium chloride, ball-milling and drying. Step three, adding asphalt and sintering; soaking in hydrofluoric acid, and washing with water to neutrality; step five, adding nano titanium dioxide particles, adding carbon nano tubes and carrying out ball milling; and step six, tabletting by using a tablet press to obtain the flaky silicon-based lithium ion battery cathode material.

Description

Preparation method of binder-free lithium ion battery negative electrode material
Technical Field
The invention belongs to the field of battery energy, and particularly relates to a preparation method of a binderless lithium ion battery cathode material.
Background
In the field of energy storage, lithium ion batteries have attracted much attention and research because of their advantages such as high specific energy, long cycle life, moderate price, etc. The negative electrode of the battery is used as one of the core components of the battery, and plays an important role in the performance of the battery. The silicon-based negative electrode material has become the first choice of the negative electrode of the new generation of lithium ion batteries due to the advantages of high specific capacity and the like. However, since the silicon material is a semiconductor material, the conductivity is poor, and the material also has the problems of volume expansion effect and the like in the circulation process, so that the cost is relatively high in the nano preparation process, and the popularization and application of the material are influenced. The nano-tubes and nano-particles in the carbon nano-material are both in nano size, and the gap space of the nano-tubes and the nano-particles is also in nano level, so that a large amount of intercalation space can be provided for lithium ions, and the nano-tubes and the nano-particles have excellent lithium intercalation characteristics, are favorable for the charge and discharge capacity and the cycle life of a lithium ion battery, but have the defects of voltage lag, unobvious charge and discharge potential platform and the like. The high-purity silicon waste of photovoltaic enterprises is adopted as a raw material, and is introduced into the application of the lithium ion battery cathode material through researches such as purification and surface modification, on the basis of the silicon-based material, the titanium dioxide cathode material and the carbon nanotube material are combined together to form the silicon-based cathode material with a novel structure, different components complement each other in performance and can generate a synergistic effect, so that on the basis of reducing the preparation cost of the material, the comprehensive performance of the silicon-based cathode material is obviously superior to that of a single silicon-based component, and the silicon-based cathode material is expected to become an ideal cathode material of a new generation of lithium ion batteries.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the production cost of the silicon-based material is reduced, and the electrode capacity is increased; meanwhile, the use of a binder of a high molecular compound component and a current collector of a metal copper foil or an aluminum foil is avoided, the resistance in the lithium desorption process is reduced, and the charge-discharge cycle performance and other performances of the material are improved.
The technical scheme adopted by the invention is that the method comprises the following steps:
under the protection of argon, directly sintering waste silicon powder generated by cutting off a single crystal at 800 ℃ for 2 hours, and performing ball milling for 10-40 hours; and step two, adding sodium silicate, mixing for 10 minutes, adding ammonium chloride, ball-milling for 30 minutes, and drying. Step three, adding asphalt, and sintering for 4 hours at 900 ℃; soaking in hydrofluoric acid, and washing with water to neutrality; step five, adding nano titanium dioxide particles (D50 is 25-500 nanometers), adding carbon nano tubes (the length is less than 1 micrometer, and the tube diameter is 15-40 nanometers), and ball-milling for 0.5-1 hour; and step six, tabletting by using a tablet machine under the force of 800-1000 Newton to obtain the sheet-like silicon-based lithium ion battery cathode material.
And (3) directly taking the sheets after being pressed by the tablet press as the lithium ion battery cathode material, assembling the lithium ion battery cathode material into a button battery in an inert atmosphere glove box, and carrying out performance test on the button battery.
The invention has the following beneficial effects:
the preparation method disclosed by the invention is simple in process and low in production cost, and the lithium ion battery cathode material prepared by the method has a synergistic improvement effect after the carbon nano tube and the titanium dioxide are added, so that the pores of the material with the mixed structure are increased, the specific surface area of the material is effectively increased, and the electrode capacity is increased; meanwhile, the use of a binder of a high molecular compound component and a current collector of a metal copper foil or an aluminum foil is avoided, and the resistance in the lithium desorption process is effectively reduced, so that the lithium desorption/intercalation material has higher conductivity and specific capacity, good charge-discharge cycle performance, and an effectively improved material discharge platform. The process for assembling the lithium ion battery electrode by the material prepared by the method is simple, the process is easy to control, and the method is suitable for industrial production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the internal structure of the electrode material of the mixed structure of the discoid silicon-based lithium ion battery in the embodiment. Wherein (a) an overview view; (b) partial view.
Fig. 2 is a discharge curve of the electrode material of the pie-shaped silicon-based lithium ion battery hybrid structure in the embodiment, and as can be seen from the curve, the material discharges stably, and the discharge platform is obvious.
Fig. 3 is a capacity cycling curve of button cell made of electrode material with a pie-shaped silicon-based lithium ion battery mixed structure in the embodiment, and it can be seen from the graph that the capacity decays in the first 3 cycles of the material and becomes stable after about 4 times.
Detailed Description
The invention is further described below by means of preferred embodiments.
In the embodiment of the invention, the scanning electron microscope characterization analysis of the electrode material with the silicon-based lithium ion battery mixed structure is carried out by adopting a German Zeiss (Zeiss) Sigma-500 electronic scanning electron microscope.
In the embodiment of the invention, an electrochemical comprehensive analysis tester of Shenzhen New Wien is adopted to analyze and test the electrical cycle performance of the electrode material with the silicon-based lithium ion battery mixed structure.
A preparation method of a binderless lithium ion battery cathode material is characterized by comprising the following steps of:
under the protection of argon, directly sintering waste silicon powder generated by cutting off a single crystal at 800 ℃ for 2 hours, and performing ball milling for 10-40 hours; and step two, adding sodium silicate, mixing for 10 minutes, adding ammonium chloride, ball-milling for 30 minutes, and drying. Step three, adding asphalt, and sintering for 4 hours at 900 ℃; soaking in hydrofluoric acid, and washing with water to neutrality; step five, adding nano titanium dioxide particles (D50 is 25-500 nanometers), adding carbon nano tubes (the length is less than 1 micrometer, and the tube diameter is 20 nanometers), and ball-milling for 1 hour; and step six, tabletting by using a tablet press with 900 Newton force to obtain the sheet-like silicon-based lithium ion battery cathode material. The sheet obtained by pressing with a tablet press can be directly used as a lithium ion battery cathode material, and a CR 2032 button battery is assembled in a glove box in a high-purity argon inert atmosphere, wherein a counter electrode is a lithium sheet, an electrolyte is a 1mol/L Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of LiPF6 (EC: DEC: 1: 2), and a diaphragm is Celgard 2500. The assembled cell was allowed to stand for 12 hours for testing.

Claims (1)

1. A preparation method of a binderless lithium ion battery cathode material is characterized by comprising the following steps of: under the protection of argon, directly sintering waste silicon powder generated by cutting off a single crystal at 800 ℃ for 2 hours, and performing ball milling for 10-40 hours; step two, adding sodium silicate, mixing for 10 minutes, adding ammonium chloride, ball-milling for 30 minutes, and drying; step three, adding asphalt, and sintering for 4 hours at 900 ℃; soaking in hydrofluoric acid, and washing with water to neutrality; step five, adding nano titanium dioxide particles, wherein the nano titanium dioxide particles D50 are 25-500 nanometers, adding carbon nano tubes, the length of each carbon nano tube is less than 1 micrometer, the tube diameter is 15-40 nanometers, and performing ball milling for 0.5-1 hour; and step six, tabletting by using a tablet machine under 800-1000 Newton force to obtain a sheet structure, so as to obtain the lithium ion battery cathode material.
CN201910980596.9A 2019-10-12 2019-10-12 Preparation method of binder-free lithium ion battery negative electrode material Active CN111081992B (en)

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