CN113346050A - Silicon-carbon negative pole piece and preparation method and application thereof - Google Patents

Silicon-carbon negative pole piece and preparation method and application thereof Download PDF

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CN113346050A
CN113346050A CN202110430746.6A CN202110430746A CN113346050A CN 113346050 A CN113346050 A CN 113346050A CN 202110430746 A CN202110430746 A CN 202110430746A CN 113346050 A CN113346050 A CN 113346050A
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silicon
pole piece
carbon
carbon negative
preparation
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赵小欢
刘冯新
娄永文
李奎
张明杰
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Kunshan Ju Innovative Energy Technology 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
    • H01M4/13—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
    • 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
    • H01M4/13—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
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    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
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Abstract

The invention provides a preparation method of a silicon-carbon negative pole piece, which comprises the steps of firstly preparing slurry from porous silicon, an organic carbon nitrogen source and the like, coating the slurry on the surface of a current collector, then carrying out pyrolysis treatment, and generating a nitrogen-doped silicon-carbon material in situ on the surface of the current collector to form the silicon-carbon negative pole piece, so that the damage to the structure and the appearance of the silicon-carbon material in the process of preparing the silicon-carbon material into the slurry and coating the slurry on the surface of the current collector is avoided, the electronic conductivity and the ionic conductivity of the silicon-carbon negative pole piece are improved due to the doping of nitrogen element in the nitrogen-doped silicon-carbon material, the pyrolysis treatment is carried out on the coated pole piece in a protective gas atmosphere, the organic carbon nitrogen source is carbonized, and meanwhile, the oxidation of the negative current collector is also avoided. The silicon-carbon negative pole piece prepared by the preparation method has the advantages of good structural morphology uniformity of the silicon-carbon material, small volume change in the charge-discharge process of the pole piece, good cycle performance, and capacity retention rate of over 84% after 1000 cycles.

Description

Silicon-carbon negative pole piece and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon-carbon negative electrode plate and a preparation method and application thereof.
Background
Lithium ion batteries are a type of battery that uses a material containing lithium as an electrode and relies on lithium ions to move between a positive electrode and a negative electrode to operate. Lithium ion batteries have many advantages such as high energy density, high power density, and long cycle life, and thus have drawn great attention in the fields of portable electronic devices, power batteries, energy storage batteries, and the like. With the rapid development of large-scale energy storage systems of electric bicycles, electric automobiles and hybrid electric automobiles, higher requirements are put forward on the performances of the lithium ion battery, such as the cycle stability, the energy density, the charge and discharge performance and the like.
The negative electrode material of the traditional lithium ion battery mainly comprises a carbon material, such as natural graphite, artificial graphite, graphitized mesocarbon microbeads and the like, however, the capacity of the carbon material is close to the theoretical capacity (372mAh/g), and the carbon negative electrode material becomes the bottleneck of capacity improvement of the lithium ion battery. Silicon is used as one of the lithium ion battery cathode materials, and is considered as a new generation of lithium ion battery cathode material with great potential due to the characteristics of high theoretical specific capacity (4200mAh/g), environmental friendliness, abundant reserves and the like. However, the electronic conductivity and the ionic conductivity of silicon are low, so that the dynamic performance of the electrochemical reaction is poor; the pure silicon has serious volume expansion in the charging and discharging process, which causes the differentiation and falling off of material particles, so the cycle stability is poor. Aiming at the problems of the silicon negative electrode material, the current improvement mode mainly adopts the silicon carbon negative electrode material to be coated on a current collector to form a negative electrode pole piece, but the structural morphology of the silicon carbon material is easily damaged in the pole piece preparation process, so that the performance of the silicon carbon material is influenced.
Disclosure of Invention
Therefore, a silicon-carbon negative electrode plate with a stable structure and good cycle performance, and a preparation method and application thereof are needed to be provided.
In one aspect of the invention, a preparation method of a silicon-carbon negative pole piece is provided, which comprises the following steps:
ultrasonically stirring porous silicon, an organic carbon nitrogen source, a binder, a dispersing agent and a solvent to obtain slurry, wherein the organic carbon nitrogen source is selected from at least one of polyfurfuryl alcohol, aminoguanidine, urea, aliphatic amine and aromatic amine;
coating the slurry on a current collector, drying and rolling to obtain a coated pole piece;
and pyrolyzing the coated pole piece in a protective gas atmosphere, and cooling to obtain the silicon-carbon negative pole piece.
In some embodiments, the porous silicon has a particle size of 50nm to 10 μm, a porosity of 20% to 80%, a pore diameter of 10nm to 500nm, and a specific surface area of 50m2/g～300m2/g。
In some of these embodiments, the binder is selected from at least one of styrene-butadiene rubber, polyacrylonitrile multipolymer emulsion, and polyvinylidene fluoride.
In some of these embodiments, the dispersant is selected from at least one of sodium carboxymethylcellulose, polyacrylic acid, sodium alginate, polyvinyl alcohol, polyallyl alcohol natural oil, higher alcohol or dimethicone, dimethyl sulfoxide, and ethyl acetate.
In some of these embodiments, the solvent is selected from at least one of N-methylpyrrolidone, N-dimethylformamide, deionized water, and anhydrous ethanol.
In some embodiments, the mass ratio of the porous silicon to the organic carbon nitrogen source to the binder to the dispersant to the solvent is 1: (0.05-1): (0.015 to 0.1): (0.015 to 0.08): (1-2.5).
In some of these embodiments, the current collector is one of a copper foil, a carbon cloth, a nickel foil, and a titanium foil.
In some embodiments, the ultrasonic stirring time is 1-5 h, and the ultrasonic frequency is 20-50 kHz.
In some embodiments, the pyrolysis treatment is carried out at a temperature of 300-900 ℃ for 0.5-3 h.
In some embodiments, before the step of pyrolyzing the coated pole piece in a protective gas atmosphere, the method further comprises the following steps:
and rolling and slitting the coating pole piece.
On the other hand, the invention also provides a silicon-carbon negative pole piece obtained by the preparation method of the silicon-carbon negative pole piece.
In another aspect of the invention, a lithium ion battery is also provided, and the negative electrode plate adopts the silicon-carbon negative electrode plate.
According to the preparation method of the silicon-carbon negative pole piece, firstly, the porous silicon, the organic carbon nitrogen source and the like are prepared into slurry to be coated on the surface of the current collector, then pyrolysis treatment is carried out, the nitrogen-doped silicon-carbon material is generated on the surface of the current collector in situ, the silicon-carbon negative pole piece is formed, the damage to the structure and the appearance of the silicon-carbon material in the process that the silicon-carbon material is prepared into the slurry and then coated on the surface of the current collector is avoided, the structure of the silicon-carbon material is stable, the nitrogen-doped silicon-carbon material is doped with nitrogen elements, the electronic conductivity and the ionic conductivity of the silicon-carbon negative pole piece are improved, the coated pole piece is subjected to pyrolysis treatment in a protective gas atmosphere, the organic carbon nitrogen source is carbonized, and meanwhile, the oxidation of the negative current collector is also avoided. The silicon-carbon negative pole piece prepared by the preparation method has the advantages of good structural morphology uniformity of the silicon-carbon material, small volume change in the charge-discharge process of the pole piece, good cycle performance, and capacity retention rate of over 84% after 1000 cycles.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a silicon-carbon negative electrode plate according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, a schematic flow chart of a method for manufacturing a silicon-carbon negative electrode plate according to an embodiment of the invention is shown. A preparation method of a silicon-carbon negative pole piece comprises the following steps of S100-S140:
step S100: and ultrasonically stirring the porous silicon, the organic carbon nitrogen source, the binder, the dispersant and the solvent to obtain slurry. The organic carbon nitrogen source refers to an organic substance containing carbon and nitrogen elements, and in the embodiment of the present invention, the organic carbon nitrogen source is at least one selected from polyfurfuryl alcohol, aminoguanidine, urea, aliphatic amine and aromatic amine.
Step S120: and coating the slurry on a current collector, drying and rolling to obtain the coated pole piece.
Step S140: and (3) pyrolyzing the coated pole piece in a protective gas atmosphere, and cooling to obtain the silicon-carbon negative pole piece.
According to the preparation method of the silicon-carbon negative pole piece, the porous silicon, the organic carbon nitrogen source and the like are prepared into slurry to be coated on the surface of the current collector, then pyrolysis treatment is carried out, the nitrogen-doped silicon-carbon material is generated on the surface of the current collector in situ, the silicon-carbon negative pole piece is formed, the damage to the structure and the appearance of the silicon-carbon material in the process that the silicon-carbon material is prepared into the slurry and then coated on the surface of the current collector is avoided, the nitrogen-doped silicon-carbon material is doped with nitrogen elements, the electronic conductivity and the ionic conductivity of the silicon-carbon negative pole piece are improved, the coating pole piece is subjected to pyrolysis treatment in a protective gas atmosphere, the organic carbon nitrogen source is carbonized, and meanwhile, the oxidation of the negative current collector is also avoided. The silicon-carbon negative pole piece prepared by the preparation method has the advantages of good structural morphology uniformity of the silicon-carbon material, small volume change in the charge-discharge process of the pole piece, good cycle performance, and capacity retention rate of over 84% after 1000 cycles.
The porous silicon is a novel one-dimensional nano photonic crystal material, has a quantum sponge-shaped microstructure with nano silicon atomic clusters as a framework, and can be formed by electrochemical anodic corrosion or chemical corrosion of monocrystalline silicon. Due to the porous structure, the problem of volume expansion of the pole piece can be relieved to a certain extent in the charging and discharging process, the damage of the pole piece material is avoided, and the circulation stability of the lithium ion battery is ensured. In some embodiments, the porous silicon has a particle size of 50nm to 10 μm, a porosity of 20% to 80%, a pore diameter of 10nm to 500nm, and a specific surface area of 50m2/g～300m2(ii) in terms of/g. The porosity of the porous silicon with the size is high, and the large volume change of the pole piece can be avoided in the lithium intercalation and lithium deintercalation process.
Optionally, the porous silicon has a D50 particle size (corresponding to a particle size distribution percentage of 50%) of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii) in terms of/g. Optionally, the porous silicon has a D50 particle size of 50nm, a porosity of 50%, a pore diameter of 10nm, and a specific surface area of 300m2(ii) in terms of/g. Optionally, the porous silicon has a D50 particle size of 5 μm, a porosity of 20%, a pore diameter of 250nm, and a specific surface area of 150m2(ii) in terms of/g. Optionally, the porous silicon has a D50 particle size of 10 μm, a porosity of 80%, a pore diameter of 500nm, and a specific surface area of 50m2/g。
In some of these embodiments, the binder is selected from at least one of styrene butadiene rubber, polyacrylonitrile multipolymer emulsion, and polyvinylidene fluoride.
In some of these embodiments, the dispersing agent is selected from at least one of sodium carboxymethylcellulose, polyacrylic acid, sodium alginate, polyvinyl alcohol, polyallyl alcohol natural oil, higher alcohol or dimethicone, dimethyl sulfoxide, and ethyl acetate. Further, the dispersant is sodium carboxymethyl cellulose.
In some of these embodiments, the solvent is selected from at least one of N-methylpyrrolidone, N-dimethylformamide, deionized water, and anhydrous ethanol.
In some embodiments, the mass ratio of the porous silicon to the organic carbon nitrogen source to the binder to the dispersant to the solvent is 1: (0.05-1): (0.015 to 0.1): (0.015 to 0.08): (1-2.5). Optionally, the mass ratio of the porous silicon to the organic carbon nitrogen source to the binder to the dispersant to the solvent is 1: 0.08: 0.02: 0.012: 1.1. optionally, the mass ratio of the porous silicon to the organic carbon nitrogen source to the binder to the dispersant to the solvent is 1: 0.5: 0.05: 0.04: 1.25. optionally, the mass ratio of the porous silicon to the organic carbon nitrogen source to the binder to the dispersant to the solvent is 1: 1: 0.1: 0.08: 2.5. optionally, the mass ratio of the porous silicon to the organic carbon nitrogen source to the binder to the dispersant to the solvent is 1: 0.05: 0.015: 0.015: 1.0.
in some of these embodiments, the current collector is one of a copper foil, a carbon cloth, a nickel foil, and a titanium foil.
In some embodiments, the ultrasonic stirring time is 1-5 h, and the ultrasonic frequency is 20-50 kHz.
In some embodiments, in the step of ultrasonic stirring, the stirring speed is 10r/min to 35r/min, and the linear velocity of the dispersion plate is 10m/s to 20 m/s.
In some embodiments, the pyrolysis treatment is carried out at a temperature of 300 ℃ to 900 ℃ for 0.5h to 3 h. Optionally, the temperature of the pyrolysis treatment is 300-550 ℃, 550-700 ℃ or 700-900 ℃. Further, the temperature of the pyrolysis treatment is 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃.
In some of these embodiments, the protective gas is at least one of argon and nitrogen.
In some embodiments, before the step of pyrolyzing the coated pole piece in the protective gas atmosphere, the method further comprises the step of rolling and slitting the coated pole piece, and slitting the pole piece into a proper size.
The invention further provides a silicon-carbon negative pole piece prepared by the preparation method of the silicon-carbon negative pole piece.
The invention also provides a lithium ion battery, and the negative pole piece of the lithium ion battery adopts the silicon-carbon negative pole piece.
The silicon-carbon negative electrode plate and the preparation method thereof provided by the invention are further illustrated by specific examples below.
Example 1:
(1) porous silicon, polyfurfuryl alcohol, Styrene Butadiene Rubber (Polymerized Styrene Butadiene Rubber, hereinafter abbreviated as SBR), sodium carboxymethylcellulose (hereinafter abbreviated as CMC) and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 2:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.5: 0.05: 0.04: 1.25 adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 3:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 1: 0.1: 0.08: 2.5, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 4:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.05: 0.015: 0.015: 1.0, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 5:
(1) will be porousSilicon, polyfurfuryl alcohol, SBR, CMC and deionized water according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 50nm, a porosity of 50%, a pore diameter of 10nm, and a specific surface area of 300m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 6:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 5 μm, a porosity of 20%, a pore diameter of 250nm, and a specific surface area of 150m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 7:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 10 μm, a porosity of 80%, a pore diameter of 500nm, and a specific gravitySurface area of 300m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 8:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 20%, a pore diameter of 10nm, and a specific surface area of 50m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 9:
(1) porous silicon, aminoguanidine, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 10:
(1) porous silicon, urea, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 11:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and a solvent are mixed according to a mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the solvent is a mixture of N-methyl pyrrolidone and deionized water according to a ratio of 5: 100; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 12:
(1) porous silicon, polyfurfuryl alcohol, polyvinylidene fluoride, CMC and N-methyl pyrrolidone are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 13:
(1) porous silicon, polyfurfuryl alcohol, polyacrylonitrile multipolymer emulsion, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 14:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 1h, the ultrasonic frequency is 50kHz, the rotating speed of a stirring revolution paddle is 35r/min, and the linear velocity of a dispersion disc is 20 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 15:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 5h, the ultrasonic frequency is 20kHz, the rotating speed of a stirring revolution paddle is 10r/min, and the linear velocity of a dispersion disc is 10 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 16:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein said porous siliconD50 particle size was 2 μm, porosity was 35%, pore diameter was 50nm, specific surface area was 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 3h at 300 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Example 17:
(1) porous silicon, polyfurfuryl alcohol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, the rotating speed of a stirring revolution paddle is 25r/min, and the linear velocity of a dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece at 900 ℃ in an argon atmosphere for 0.5h, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Comparative example 1:
the silicon-carbon negative pole piece is prepared according to the following steps:
(1) porous silicon, polyethylene glycol, SBR, CMC and deionized water are mixed according to the mass ratio of 1: 0.08: 0.02: 0.012: 1.1, adding the mixture into a stirring tank, and ultrasonically stirring to obtain uniformly mixed slurry; wherein the porous silicon has a D50 particle size of 2 μm, a porosity of 35%, a pore diameter of 50nm, and a specific surface area of 100m2(ii)/g; the ultrasonic stirring time is 2h, the ultrasonic frequency is 30kHz, and the stirring revolution is carried outThe rotating speed of the paddle is 25r/min, and the linear speed of the dispersion disc is 18 m/s.
(2) And (2) uniformly coating the slurry obtained in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece.
(3) Coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling and cutting the pole piece into the required size.
(4) And (3) pyrolyzing the cut pole piece for 2 hours at 550 ℃ in an argon atmosphere, and cooling to obtain the lithium battery silicon-carbon negative pole piece.
Comparative example 2:
the silicon-carbon negative pole piece is prepared according to the following steps:
(1) adding 100 parts of porous silicon, 8 parts of polyfurfuryl alcohol, 2 parts of SBR and 1.2 parts of CMC (carboxy terminated polybutadiene) into 110 parts of deionized water according to the mass parts, and uniformly stirring to prepare uniform negative electrode slurry; wherein the porous silicon material has D50 particle diameter of 2 μm, porosity of 35%, pore diameter of 50nm, and specific surface area of 100m2/g；
(2) Uniformly coating the slurry in the step (1) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece;
(3) coating the pole piece at a ratio of 1.2g/cm3And (5) compacting the density, rolling, and then cutting to obtain the lithium battery silicon-carbon negative pole piece.
Comparative example 3:
the silicon-carbon negative pole piece is prepared according to the following steps:
(1) mixing 100 parts of porous silicon and 8 parts of polyfurfuryl alcohol according to the mass parts, drying, and calcining at 550 ℃ for 2 hours to obtain a silicon-carbon material;
(2) adding 100 parts of silicon-carbon material, 2 parts of SBR and 1.2 parts of CMC (carboxy terminated polyurethane) into 110 parts of deionized water according to the mass parts, and uniformly stirring to prepare uniform negative electrode slurry; wherein the porous silicon material has D50 particle diameter of 2 μm, porosity of 35%, pore diameter of 50nm, and specific surface area of 100m2/g；
(3) Uniformly coating the slurry in the step (2) on a copper foil, and drying and rolling at 80 ℃ to obtain a coated pole piece;
(4) coating the pole piece at a ratio of 1.2g/cm3Compacting the density, rolling and cutting to obtain the lithium batterySilicon carbon negative pole piece.
The positive pole piece adopts a traditional lithium battery positive pole piece and is prepared according to the following steps:
adding 96.5 parts of NCM622, 0.5 part of conductive carbon black, 1 part of carbon nano tube and 2 parts of PVDF into 33.8 parts of N-methyl pyrrolidone in parts by mass, uniformly stirring to prepare uniform anode slurry, coating the uniform anode slurry on two sides of a 12 mu m aluminum foil, drying, and then coating the aluminum foil with the weight of 3.5g/cm3And rolling and cutting the compacted density to obtain the required positive pole piece.
The negative electrode plates of examples 1 to 17 and comparative examples 1 to 3 were respectively subjected to baking, packaging, liquid injection, sealing, formation and capacity grading with the positive and negative electrode plates prepared above to prepare 2Ah soft-package lithium ion batteries. The electrochemical properties of the lithium ion battery prepared are shown in table 1.
TABLE 1
Figure BDA0003031256840000171
Figure BDA0003031256840000181
As can be seen from the data in table 1, compared with comparative examples 1 to 3, the lithium ion batteries prepared from the negative electrode plates provided in examples 1 to 17 have higher capacity retention rate, the capacity is maintained at more than 97% in 300 cycles of charge and discharge, and the capacity is still maintained at more than 85% after 1000 cycles of charge and discharge, which is higher than that of the lithium ion batteries composed of the negative electrode plates of comparative examples 1 to 3. In addition, the lithium ion battery prepared by the negative electrode plate provided by the embodiment 1-17 has higher first charge-discharge efficiency which can reach over 84%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of a silicon-carbon negative pole piece is characterized by comprising the following steps:
ultrasonically stirring porous silicon, an organic carbon nitrogen source, a binder, a dispersing agent and a solvent to obtain slurry, wherein the organic carbon nitrogen source is selected from at least one of polyfurfuryl alcohol, aminoguanidine, urea, aliphatic amine and aromatic amine;
coating the slurry on a current collector, drying and rolling to obtain a coated pole piece;
and pyrolyzing the coated pole piece in a protective gas atmosphere, and cooling to obtain the silicon-carbon negative pole piece.
2. The preparation method of the silicon-carbon negative electrode plate as claimed in claim 1, wherein the particle size of the porous silicon is 50nm to 10 μm, the porosity is 20 to 80%, the pore diameter is 10nm to 500nm, and the specific surface area is 50m2/g～300m2/g。
3. The preparation method of the silicon-carbon negative electrode plate as claimed in claim 1, wherein the binder is at least one selected from styrene-butadiene rubber, polyacrylonitrile multipolymer emulsion and polyvinylidene fluoride;
and/or the dispersing agent is at least one selected from sodium carboxymethylcellulose, polyacrylic acid, sodium alginate, polyvinyl alcohol, polypropylene alcohol natural oil, higher alcohol or dimethyl silicone oil, dimethyl sulfoxide and ethyl acetate;
and/or the solvent is at least one selected from N-methyl pyrrolidone, N-dimethylformamide, deionized water and absolute ethyl alcohol.
4. The preparation method of the silicon-carbon negative electrode plate as claimed in any one of claims 1 to 3, wherein the mass ratio of the porous silicon to the organic carbon nitrogen source to the binder to the dispersant to the solvent is 1: (0.05-1): (0.015 to 0.1): (0.015 to 0.08): (1-2.5).
5. The method for preparing the silicon-carbon negative electrode plate according to claim 1, wherein the current collector is one of copper foil, carbon cloth, nickel foil and titanium foil.
6. The preparation method of the silicon-carbon negative electrode plate according to any one of claims 1 to 3 and 5, wherein the ultrasonic stirring time is 1-5 h, and the ultrasonic frequency is 20-50 kHz.
7. The preparation method of the silicon-carbon negative electrode plate as claimed in any one of claims 1 to 3 and 5, wherein the temperature of the pyrolysis treatment is 300-900 ℃ and the time is 0.5-3 h.
8. The preparation method of the silicon-carbon negative electrode plate as claimed in any one of claims 1 to 3 and 5, characterized by further comprising the following steps before the step of subjecting the coated electrode plate to pyrolysis treatment in a protective gas atmosphere:
and rolling and slitting the coating pole piece.
9. The silicon-carbon negative electrode plate prepared by the method of any one of claims 1 to 8.
10. A lithium ion battery, characterized in that, the negative pole piece adopts the silicon-carbon negative pole piece of claim 9.
CN202110430746.6A 2021-04-21 2021-04-21 Silicon-carbon negative pole piece and preparation method and application thereof Pending CN113346050A (en)

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CN111342014A (en) * 2020-03-05 2020-06-26 上海电气集团股份有限公司 Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof
CN112110448A (en) * 2020-09-21 2020-12-22 中山大学 Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof

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CN111342014A (en) * 2020-03-05 2020-06-26 上海电气集团股份有限公司 Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof
CN112110448A (en) * 2020-09-21 2020-12-22 中山大学 Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof

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