CN114079054A - Lithium battery negative electrode material and preparation method thereof - Google Patents

Lithium battery negative electrode material and preparation method thereof Download PDF

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CN114079054A
CN114079054A CN202010796415.XA CN202010796415A CN114079054A CN 114079054 A CN114079054 A CN 114079054A CN 202010796415 A CN202010796415 A CN 202010796415A CN 114079054 A CN114079054 A CN 114079054A
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negative electrode
electrode material
organic polymer
silicon
lithium battery
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CN114079054B (en
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陈青华
姚林林
房冰
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Lanxi Zhide New Energy Materials Co ltd
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/052—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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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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Abstract

The invention discloses a lithium battery cathode material which comprises a silicon-based material core and an organic polymer coating layer on the surface of the core, wherein the surface of the organic polymer contains hydroxyl, carboxyl and sulfydryl active groups. The organic matter coating layer is insoluble in water or alkaline water, and can be suitable for a water system homogenate system, so that the production cost is reduced. In addition, the organic polymer with a specific functional group is used as a coating layer, so that the interface combination of the negative electrode material and the current collector can be enhanced; on the other hand, the organic polymer can stabilize an SEI film, reduce impedance, and simultaneously has certain elasticity, so that the volume expansion of the silicon-based material in the charging and discharging processes can be relieved, and the material pulverization and falling off can be prevented, thereby enabling the cathode material to have excellent cycle performance and processability. The preparation method is simple and easy to implement, low in cost and suitable for large-scale production.

Description

Lithium battery negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a lithium battery negative electrode material and a preparation method thereof.
Background
With the rapid development of economy and science and technology, energy and environmental problems become more severe, and lithium ion batteries are receiving much attention as a new energy industry. The driving anxiety of electric vehicles and the light weight of consumer electronics such as mobile phones all force lithium ion batteries to pursue higher energy density. The current commercialized negative electrode material is mainly graphite, the specific capacity of which is already close to the theoretical value (372mAh/g), and a negative electrode active material with higher specific energy is required. The silicon-based negative electrode material is a recognized next-generation negative electrode material with extremely high specific capacity (3580mAh/g), low lithium-intercalation/deintercalation potential, rich reserve capacity, no toxicity and harmlessness. However, the application of the silicon-based material is limited by the problems of huge volume expansion (about 400%) of the silicon-based material in the circulation process, instability of an SEI film, low conductivity and the like.
Disclosure of Invention
In view of the above, the invention provides a lithium battery negative electrode material and a preparation method thereof. The battery made of the cathode material has good processing performance and excellent cycle performance.
In one embodiment, the application provides a lithium battery negative electrode material, which comprises a silicon-based material core and an organic polymer coating layer on the surface of the core, wherein the surface of the organic polymer contains hydroxyl, carboxyl and sulfhydryl active groups.
In one embodiment, the present application also provides a preparation method of the above negative electrode material for lithium batteries, comprising the steps of:
s1: uniformly mixing a silicon-based material and an organic polymer precursor in solvent water to obtain mixed slurry with the solid content of 20-40%;
s2: drying the mixed slurry to obtain the negative electrode material;
wherein, a curing agent may be further added in the step S1.
The beneficial effect of this application:
the negative electrode material realizes coating synthesis in solvent water, and the finished material is insoluble in water or alkaline water, so that the negative electrode material is applicable to a water-based homogenate system, reduces the production cost and is environment-friendly. The negative electrode material adopts an organic polymer with a specific functional group as a coating layer, so that on one hand, the adhesive force of the negative electrode material and the conductive agent with the adhesive can be enhanced, and the interface combination with the current collector can be enhanced; on the other hand, the organic polymer can stabilize an SEI film, reduce impedance, has excellent tensile strength and elongation, can relieve volume expansion of a silicon-based material in the charging and discharging processes, and prevents the material from being pulverized and falling off, so that the cathode material has excellent cycle performance and processability.
Additional aspects and advantages of embodiments of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of embodiments of the present application.
Drawings
Fig. 1 EIS diagram of button cells made from example 1 and comparative example 1 negative electrode materials after 100 cycles.
Detailed Description
Embodiments of the present application will be described in detail below. The embodiments of the present application should not be construed as limiting the application.
In the present application, amounts, ratios, and other numerical values are presented in a range format, with the understanding that such range format is used for convenience and brevity and should be flexibly understood to include not only the numerical values explicitly specified as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly specified.
In the claims and the detailed description, a list of items linked by the term "at least one of" or other similar terms may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means a only; only B; or A and B. Item a may comprise a single element or multiple elements and item B may comprise a single element or multiple elements.
The embodiment provides a lithium battery negative electrode material, which comprises a silicon-based material core and an organic polymer coating layer on the surface of the core, wherein the organic polymer coats the silicon-based material through in-situ polymerization, the surface of the organic polymer contains hydroxyl, carboxyl and sulfydryl active groups, and the specific active groups can enhance the interface bonding strength of the negative electrode material and a current collector.
In some embodiments, the organic polymer is crosslinked by a curing agent or self-crosslinked by a resin to form a water-insoluble three-dimensional network structure, so as to ensure that the negative electrode material is suitable for an aqueous homogenization system, thereby reducing the production cost.
In some embodiments, the crosslinking degree of the organic polymer is 20% to 70%, preferably 30% to 60%, the organic polymer with too low crosslinking degree has low tensile strength and is easy to swell, and the organic polymer with too high crosslinking degree is fragile and easy to break; the tensile strength is 5-30 MPa, preferably 7-20 MPa; the elongation is 20-800%, preferably 150-400%, the organic polymer is easy to break in the cyclic expansion process of the silicon-based material if the elongation is too low, and the large viscosity particles of the organic polymer are easy to agglomerate if the elongation is too high.
In some embodiments, the organic polymer comprises at least one of sodium alginate, natural caraya resins and modifications thereof, isocyanate resins and modifications thereof, polyurethanes and modifications thereof, epoxy resins and modifications thereof, acrylic resins and modifications thereof, phenolic resins and modifications thereof, polyester resins and modifications thereof, and alkyd resins and modifications thereof.
In some embodiments, the silicon-based material comprises elemental silicon (e.g., nanosilicon, silicon nanowires, metallic silicon), silicon compounds (e.g., Si)3N4SiC), silicon carbon composites (Si-X, e.g., Si-C), silicon alloys (Si-M, e.g., Si-Sn), silicon oxide SiOx(wherein 0 < x < 2), at least one of silicon oxides (doping elements such as Li and Mg) modified by doping with a doping element; the doping of the element is to improve the first coulombic efficiency of the material, and includes but is not limited to elements such as Li, Mg and the like, the doping amount of the element is not particularly limited, specifically, the mass of the metal element accounts for 1.5% -30%, preferably 2% -15%, based on 100% of the total mass of the negative electrode material; the form of doping of the metal element is not particularly limited,generally in the form of silicates, in particular Li2SiO3、Li2Si2O5、Li4SiO4、Li6Si2O7、MgSiO3、Mg2SiO4、Mg4SiO6。
In some embodiments, the thickness of the organic polymer coating layer is 0.5-50 nm, preferably 1-20 nm, and more preferably 1-5 nm, and too thin a coating layer may cause the coating layer to crack during the cyclic expansion of the silicon-based material, thereby accelerating the cell capacity attenuation; if the coating layer is too thick, the resistivity of the negative electrode material is increased, and the performance of the material is affected.
In some embodiments, the mass ratio of the organic polymer coating layer is 0.1% to 5%, preferably 0.25% to 2%, based on 100% of the total mass of the negative electrode material.
In some embodiments, the negative electrode material has a resistivity of 0.002 Ω -cm to 120 Ω -cm, preferably 0.005 Ω -cm to 80 Ω -cm, under a pressure of 30MPa, and a suitable resistivity ensures that the material has good electrical properties.
Next, a method for producing an anode material, which is produced by:
s1: uniformly mixing a silicon-based material and an organic polymer precursor in solvent water to obtain mixed slurry with the solid content of 20-40%;
s2: drying the mixed slurry to obtain the negative electrode material;
wherein, a curing agent may be further added in the step S1.
In some embodiments, the drying process may be achieved by spray drying, microwave vacuum drying, vacuum oven drying, double cone vacuum drying, single cone vacuum drying, air flow drying, and the like. The temperature and time of the drying treatment are not particularly limited, and can be determined according to the selected drying mode under the premise of considering the yield and the energy consumption, preferably, the spray drying mode is adopted, the temperature is 70-300 ℃, and the treatment time is 0.5-10 h.
The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited thereto.
Example 1
First, 100g of SiO material and 0.1g of waterborne polyurethane are fully mixed in deionized water to obtain mixed slurry with the solid content of 33%. And then carrying out spray drying on the mixed slurry at the drying temperature of 200 ℃ for 1h to obtain the final negative electrode material.
Example 2
Firstly, 100g of silicon-carbon composite material, 1g of epoxy resin and 1g of phenolic resin are fully mixed in deionized water, and 0.1g of epoxy polyamine curing agent is added to obtain mixed slurry with the solid content of 20%. And then, passing the mixed slurry through a centrifugal spray dryer, wherein the drying temperature is 100 ℃, and the drying time is 1h, so as to obtain the final cathode material.
Example 3
First, 100g of Li-doped SiO and 5g of acrylic resin are fully mixed in deionized water to obtain mixed slurry with the solid content of 40%. And then, drying the mixed slurry in a single-cone vacuum dryer at the drying temperature of 80 ℃ for 5 hours to obtain the final cathode material.
Comparative example 1
The organic polymer coating negative electrode material without special functional groups: 100g of the same SiO material as in example 1 and 5g of acrylonitrile resin were thoroughly mixed in deionized water to obtain a mixed slurry with a solid content of 40%. And then, drying the mixed slurry in a single-cone vacuum dryer at the drying temperature of 80 ℃ for 5 hours to obtain the final cathode material.
Comparative example 2
The same SiO material as in example 1 is selected, and cracking carbon coating is carried out on the surface of SiO by a chemical vapor deposition method, so as to obtain the carbon-coated cathode material.
The negative electrode materials prepared in the examples and comparative examples were used to prepare button cells as follows: according to the mass ratio of 93: 2.5: 1.5: 3, mixing a negative electrode material, SBR (styrene butadiene rubber): CMC (sodium carboxymethylcellulose): SP mixed and stirred continuously for 8h to be pasty by a magnetic stirrer. The stirred slurry was poured onto a copper foil having a thickness of 9 μm, coated with an experimental coater, and dried at 85 ℃ under vacuum (-0.1MPa) for 6 hours. The pole pieces were rolled to 100 μm on a manual roll-to-roll machine. And (4) carrying out peel strength test on the obtained pole piece by using a strong double-faced adhesive tape 180-degree peeling method.
And (3) preparing the rolled pole piece into a wafer with the diameter of 12mm by using a sheet punching machine, drying the wafer at 85 ℃ in vacuum (-0.1MPa) for 8 hours, testing the thickness of the wafer, and weighing to calculate the weight of the active substance. A CR2032 button cell is assembled in a glove box, a metal lithium sheet is taken as a counter electrode, a polypropylene microporous membrane is taken as a diaphragm, and 1mol/L LiPF6 in EC (ethyl carbonate) = DEC (diethyl carbonate) =1:1 is taken as electrolyte.
Standing the battery for 12h at room temperature, performing constant-current charge and discharge test on a blue test system, performing charge and discharge at 0.1C current, removing lithium, cutting off voltage of 1.5V, circulating for 100 circles, and performing EIS test. And disassembling the recycled battery, testing the thickness of the pole piece, and calculating the expansion rate of the pole piece.
TABLE 1 test results of negative electrode materials prepared in examples and comparative examples
Description of the samples Pole piece peel strength (N/m) First reversible specific capacity (mAh/g) Capacity retention after 100 cycles Expansion rate of pole piece
Example 1 10.22 1405.3 84.9% 105%
Example 2 10.36 1420.6 85.3% 106%
Example 3 10.04 1429.2 89.7% 107%
Comparative example 1 6.91 1424.7 82.1% 133%
Comparative example 2 6.12 1417.6 80.6% 165%
As can be seen from table 1, example 1 having the organic coating layer with a specific functional group has higher peel strength than comparative example 1 having no organic coating layer with a specific functional group, indicating that the negative electrode material having the organic coating layer with a specific functional group has stronger adhesion to the current collector. Example 1 compared to comparative example 2 with only carbon coating, example 1 has more excellent capacity retention and the pole piece has less swelling after 100 cycles.
Fig. 1 is an EIS diagram of the button cell prepared from the negative electrode materials of example 1 and comparative example 1 after 100 cycles, and the battery of example 1 has lower SEI film resistance after 100 cycles, which indicates that the battery has better cycle performance.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the above description is not intended to limit the invention, and the invention is not limited to the above disclosed and described embodiments, and modifications and variations of the invention, such as equivalent substitutions of each raw material and addition of auxiliary components, selection of specific modes, etc., made by those skilled in the art within the spirit of the embodiments, should also fall within the scope of the claims of the present invention.

Claims (9)

1. The lithium battery negative electrode material comprises a silicon-based material core and an organic polymer coating layer on the surface of the core, and is characterized in that the surface of the organic polymer contains hydroxyl, carboxyl and sulfydryl active groups.
2. The negative electrode material for a lithium battery as claimed in claim 1, wherein the organic polymer is crosslinked by a curing agent or self-crosslinked by a resin to form a water-insoluble three-dimensional network structure.
3. The negative electrode material for the lithium battery as claimed in claim 1, wherein the organic polymer has a crosslinking degree of 20% to 70%, preferably 30% to 60%, a tensile strength of 5 to 30MPa, preferably 7 to 20MPa, and an elongation of 20% to 800%, preferably 150% to 400%.
4. The negative electrode material for a lithium battery as claimed in claim 1, wherein the organic polymer comprises at least one of sodium alginate, natural caraya resin and its modification, isocyanate resin and its modification, polyurethane and its modification, epoxy resin and its modification, acrylic resin and its modification, phenolic resin and its modification, polyester resin and its modification, and alkyd resin and its modification.
5. The negative electrode material for lithium battery as claimed in claim 1, whereinCharacterized in that the silicon-based material comprises simple substance silicon, silicon compound, silicon-carbon compound, silicon alloy and silicon oxide SiOx(wherein 0 < x < 2), and doping the modified silicon oxide compound with a doping element.
6. The negative electrode material for a lithium battery as claimed in claim 1, wherein the organic polymer coating layer has a thickness of 0.5 to 50nm, preferably 1 to 20 nm.
7. The negative electrode material for the lithium battery as claimed in claim 1, wherein the mass ratio of the organic polymer coating layer is 0.1% to 5%, preferably 0.25% to 2%, based on 100% of the total mass of the negative electrode material.
8. The negative electrode material for a lithium battery as claimed in claim 1, wherein the negative electrode material has a resistivity of 0.002 Ω -cm to 120 Ω -cm, preferably 0.005 Ω -cm to 80 Ω -cm, under a pressure of 30 MPa.
9. The method for preparing the negative electrode material for a lithium battery as claimed in any one of claims 1 to 8, comprising the steps of:
s1: uniformly mixing a silicon-based material and an organic polymer precursor in solvent water to obtain mixed slurry with the solid content of 20-40%;
s2: drying the mixed slurry to obtain the negative electrode material;
wherein, a curing agent may be further added in the step S1.
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CN114597379A (en) * 2022-03-24 2022-06-07 湖北亿纬动力有限公司 Negative electrode material, preparation method and application
CN114784260A (en) * 2022-06-02 2022-07-22 内蒙古三信科技发展有限公司 Modified silicon material for lithium ion battery and preparation method and application thereof
CN114976021A (en) * 2022-07-19 2022-08-30 山东石大胜华化工集团股份有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN116666639A (en) * 2023-08-02 2023-08-29 天津力神电池股份有限公司 Hard carbon electrode material, preparation method thereof and battery
WO2023184098A1 (en) * 2022-03-28 2023-10-05 宁德时代新能源科技股份有限公司 Silicon-containing negative electrode active material, and negative electrode plate, secondary battery and electric device comprising same
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CN114597379A (en) * 2022-03-24 2022-06-07 湖北亿纬动力有限公司 Negative electrode material, preparation method and application
CN114597379B (en) * 2022-03-24 2024-05-03 湖北亿纬动力有限公司 Negative electrode material, preparation method and application
WO2023184098A1 (en) * 2022-03-28 2023-10-05 宁德时代新能源科技股份有限公司 Silicon-containing negative electrode active material, and negative electrode plate, secondary battery and electric device comprising same
CN114784260A (en) * 2022-06-02 2022-07-22 内蒙古三信科技发展有限公司 Modified silicon material for lithium ion battery and preparation method and application thereof
CN114784260B (en) * 2022-06-02 2024-05-14 内蒙古三信科技发展有限公司 Modified silicon material for lithium ion battery and preparation method and application thereof
CN114976021A (en) * 2022-07-19 2022-08-30 山东石大胜华化工集团股份有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN114976021B (en) * 2022-07-19 2023-11-24 胜华新材料集团股份有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN116666639A (en) * 2023-08-02 2023-08-29 天津力神电池股份有限公司 Hard carbon electrode material, preparation method thereof and battery
CN116666639B (en) * 2023-08-02 2023-11-03 天津力神电池股份有限公司 Hard carbon electrode material, preparation method thereof and battery
CN118645607A (en) * 2024-08-13 2024-09-13 比亚迪股份有限公司 Negative electrode material, preparation method thereof, dry-method negative electrode plate and lithium ion battery

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