CN117525365A - Double-carbon coated silica controllable prelithiation material and preparation method and application thereof - Google Patents

Double-carbon coated silica controllable prelithiation material and preparation method and application thereof Download PDF

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CN117525365A
CN117525365A CN202311702419.7A CN202311702419A CN117525365A CN 117525365 A CN117525365 A CN 117525365A CN 202311702419 A CN202311702419 A CN 202311702419A CN 117525365 A CN117525365 A CN 117525365A
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double
slurry
carbon
coated silica
mixture
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霍锋
钱程
郭真真
刘凡
刘景博
柴丰涛
刘艳侠
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Longzihu New Energy Laboratory
Zhengzhou Institute of Emerging Industrial Technology
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Zhengzhou Institute of Emerging Industrial Technology
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • H01M4/36—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
    • 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 double-carbon coated silica controlled pre-lithiation material, a preparation method and application thereof, belongs to the technical field of lithium ion batteries, and aims to solve the technical problem of low capacity retention rate of a silicon-based material negative electrode lithium ion battery. The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps: (1) mixing silicon oxide with a lithium source to prepare a mixture; (2) Dispersing and dissolving carbon nano tubes and organic carbon sources in a solvent to prepare slurry; (3) And mixing the mixture with the slurry, spray-drying to obtain powder, and calcining the powder in an inert gas atmosphere to obtain the double-carbon coated silica controllable prelithiation material. The invention further enhances the conductivity of electrons between particles and on the surface through the combined action of double carbon, inhibits the volume expansion of the material and improves the cycle stability of the battery. By controlling the pre-lithiation degree, the material is applied to a lithium ion battery to improve the coulombic efficiency, and the capacity retention rate of the battery is improved.

Description

Double-carbon coated silica controllable prelithiation material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a double-carbon coated silica controllable prelithiation material, and a preparation method and application thereof.
Background
In recent years, in order to solve the environmental pollution and energy crisis problems faced by the human society, development of novel energy technology has been widely progressed. The lithium ion battery is used as a representative of green energy technology and is widely applied to the fields of portable electronic products, electric automobiles and the like. However, with the continuous development of industrial scale, people put higher demands on longer service time of electronic products and longer driving distance of electric automobiles, and the traditional graphite anode only has 372mAh g -1 Is unable to meet the demand, so researchers have begun to study extensively with 3580mAh g -1 The high theoretical capacity Si negative electrode of (c) replaces the conventional graphite material.
However, commercialization of silicon anodes is currently not possible, which is that silicon materials undergo serious volume changes (+.300%) during electrochemical reaction due to intercalation/deintercalation of lithium ions, which can lead to their detachment from the current collector, and formation of unstable Solid Electrolyte Interface (SEI), fromResulting in severe capacity fade. Among silicon-based negative electrode materials, nano-silicon materials are attracting attention for their excellent reversible capacity, cycle performance and cost effectiveness, however, several key problems of silicon-based negative electrodes have prevented their commercial application in lithium ion batteries. One of the outstanding challenges is to suppress the volume expansion of the silicon-based material, to increase the cycle life of the battery, and the other is to lower Initial Coulombic Efficiency (ICE), due to the lithium silicate (Li 2 SiO 3 、Li 2 Si 2 O 5 And Li (lithium) 4 SiO 4 ) And Li (lithium) 2 The composition of O, these reactions being irreversible and inactive in subsequent cycles, results in a loss of the actual energy density of the battery. The current research mainly focuses on poor conductivity of the silicon-oxygen cathode, so that the carbon added plays a role in enhancing electron conduction and regulating volume expansion, but lower coulombic efficiency still exists, and the capacity retention rate is reduced.
Disclosure of Invention
Aiming at the technical problem of low capacity retention rate of a silicon-based material negative electrode lithium ion battery, the invention provides a double-carbon coated silica controllable pre-lithiation material, a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
(1) Mixing silicon oxide with a lithium source to prepare a mixture;
(2) Dispersing and dissolving carbon nano tubes and organic carbon sources in a solvent to prepare slurry; the solvent is water;
(3) And mixing the mixture with the slurry, spray-drying to obtain powder, and calcining the powder in an inert gas atmosphere to obtain the double-carbon coated silica controllable prelithiation material. And the material is not subjected to high temperature by spray drying granulation, so that the material is not easy to break and defect.
The lithium source is any one or more than two of lithium hydroxide, lithium carbonate, lithium nitride or lithium sulfide; the mass ratio of the silicon oxide to the lithium source is (30-50): 1.
the organic carbon source is more than two of sucrose, chitosan, glucose or urea; the mass ratio of the silicon oxide, the carbon nano tube and the organic carbon source is (10-40): (0.01-0.1): (1-10); the concentration of the organic carbon source in the slurry is 0.5-3wt%.
Sodium carboxymethyl cellulose is also added into the slurry, and the concentration of the sodium carboxymethyl cellulose in the slurry is 0.01-0.5wt%. The dispersibility of the carbon nano tube is improved by adding sodium carboxymethyl cellulose, so that the uniformity is improved, agglomeration is avoided, and the subsequent coating effect is further influenced. Meanwhile, the sodium hydroxymethyl cellulose has a bonding effect, so that the carbon nano tube and the silica are bonded together, and further the problem of poor conductivity of the silica material is solved.
The slurry is also added with an acidic reagent, wherein the acidic reagent is hydrochloric acid, formic acid, acetic acid, lactic acid, malic acid and ascorbic acid; the mass ratio of the acidic reagent to the organic carbon source is 1: (0.5-2). The addition of the acidic reagent activates the organic carbon source in the slurry.
The calcining temperature is 700-900 ℃ and the heat preservation time is 10-30min; the inert gas is argon or nitrogen. The double carbon source is polymerized with silicon oxide and lithium compound through calcination, so that the binding force is stronger, and the structural stability of the subsequent material is ensured.
An electrode slice is prepared by mixing a double-carbon coated silica controlled pre-lithiation material, a conductive agent and a binder and then coating the mixture on a current collector.
The mass ratio of the carbon-coated silica material to the conductive agent to the binder is (7-9.3): (0.3-2): (0.4-1), wherein the conductive agent is any one of acetylene black, ketjen black, conductive graphite or Super P; the adhesive comprises styrene-butadiene rubber, sodium carboxymethyl cellulose and polyacrylic acid.
A lithium ion battery has the negative electrode plate.
The invention has the beneficial effects that: according to the invention, two different types of organic carbon sources are added, then high-temperature reaction is carried out, and the organic carbon sources are subjected to activation treatment, so that the combination with a silicon oxygen material and a lithium compound is tighter, and the subsequent coating effect is better. The invention further enhances the conductivity of electrons between particles and on the surface through the combined action of double carbon, inhibits the volume expansion of the material and improves the cycle stability of the battery. By controlling the pre-lithiation degree, the material is applied to a lithium ion battery to improve the coulombic efficiency, form a more stable interface SEI, improve the capacity retention rate of the battery, and enable the double carbon coating of a final product to be uniform and controllable in pre-lithiation in the preparation process of the technology, so that the material can be adopted by the battery manufacturing industry.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Figure 1 is an XRD pattern of silicon oxide.
FIG. 2 shows the double carbon coated silica prelithiation of SiO at different heat treatment temperatures according to the present invention x XRD pattern of/C/Li.
FIG. 3 shows the double carbon coated silica prelithiation of SiO at different heat treatment times according to the present invention x XRD pattern of/C/Li.
FIG. 4 shows a dual carbon coated silica prelithiation SiO according to the present invention x SEM image of/C/Li.
FIG. 5 is a double carbon coated silica pre-lithium SiO of the present invention x Capacity voltage curve of/C/Li.
FIG. 6 is a cycle chart of the samples prepared in example 1 and comparative examples 2, 3, 4.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of chitosan and 0.25g of sucrose, putting the chitosan and the sucrose into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely the double-carbon coated silicon-oxygen controllable prelithiation material (SiO X /C/Li)。
Example 2
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of chitosan and 0.25g of sucrose, putting the chitosan and the sucrose into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely the double-carbon coated silicon-oxygen controllable prelithiation material (SiO X /C/Li)；
Example 3
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of chitosan and 0.25g of sucrose, putting the chitosan and the sucrose into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 750 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely the double-carbon coated silicon-oxygen controllable prelithiation material (SiO X /C/Li)；
Example 4
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of chitosan and 0.25g of sucrose, putting the chitosan and the sucrose into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely the double-carbon coated silicon-oxygen controllable prelithiation material (SiO X /C/Li)；
Example 5
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of chitosan and 0.25g of sucrose, putting the chitosan and the sucrose into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing powder D into a tube furnace, introducing argon atmosphere, heating to 800 deg.C at a heating rate of 5 deg.C/min, maintaining for 20 min, addingStopping the procedure after the heat is finished, and taking out the product after the temperature is reduced to room temperature to obtain a product E, namely the double-carbon coated silica controlled prelithiation material (SiO X /C/Li)。
Example 6
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of chitosan and 0.25g of sucrose, putting the chitosan and the sucrose into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 30 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely the double-carbon coated silicon-oxygen controllable prelithiation material (SiO X /C/Li)。
Example 7
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide were mixed according to 30:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of chitosan and 0.25g of sucrose, putting the chitosan and the sucrose into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely the double-carbon coated silicon-oxygen controllable prelithiation material (SiO X /C/Li)。
Example 8
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide were mixed according to 50:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of chitosan and 0.25g of sucrose, putting the chitosan and the sucrose into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely the double-carbon coated silicon-oxygen controllable prelithiation material (SiO X /C/Li)。
Example 9
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide were mixed according to 50:1, respectively weighing 10g and 0.20g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 0.1g of carbon nanotube is weighed, 50g of water is added, ultrasonic treatment is carried out for 5 minutes, 0.6g of acetic acid (HAC) is added, and then the mixture is put into a magnetic stirrer to be uniformly stirred, so as to obtain slurry B.
Step three: weighing 0.5g of chitosan and 0.5g of sucrose, putting into a deaeration machine for uniform dispersion, operating the machine for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain the slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 750 ℃ at a heating rate of 4 ℃/min, preserving heat for 20 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely SiO X /C/Li；
Example 10
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 0.125g of carbon nanotube is weighed, 45g of water is added, ultrasonic treatment is carried out for 5 minutes, 0.8ml of acetic acid (HAC) is added, and then the mixture is put into a magnetic stirrer to be uniformly stirred, so as to obtain slurry B.
Step three: 1g of chitosan and 0.25g of glucose are weighed, put into a deaerator for uniform dispersion, the apparatus is operated for 10 minutes, the dispersed mixture is added into slurry B, and the mixture A is added after uniform stirring, thus obtaining slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 850 ℃ at a heating rate of 4 ℃/min, preserving heat for 30 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely SiO X /C/Li；
Example 11
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide were mixed according to 30:1, respectively weighing 10g and 0.33g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 1g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: 0.2g of chitosan and 0.1g of urea are weighed, put into a deaerator for uniform dispersion, the apparatus is operated for 10 minutes, the dispersed mixture is added into slurry B, and the mixture A is added after uniform stirring, so as to obtain slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely SiO X /C/Li；
Example 12
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide were mixed according to 50:1, respectively weighing 10g and 0.33g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: 0.2g of chitosan and 0.3g of urea are weighed, put into a deaerator for uniform dispersion, the apparatus is operated for 10 minutes, the dispersed mixture is added into slurry B, and the mixture A is added after uniform stirring, so as to obtain slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, and introducing argonHeating to 800 deg.C at a heating rate of 5 deg.C/min in gas atmosphere, maintaining for 10min, stopping the procedure after heating, taking out when the temperature is reduced to room temperature, and taking out when the temperature is reduced to room temperature to obtain product E, namely SiO X /C/Li；
Example 13
Step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.33g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.9 acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of sucrose and 0.25g of urea, putting into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 20 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely SiO X /C/Li；
Example 14
Step one: silica and lithium hydroxide were mixed according to 50:1, respectively weighing 10g and 0.33g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.4 acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.3g of sucrose and 0.2g of urea, putting into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 30 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely SiO X /C/Li。
Comparative example 1
Silicone material (SiOx), conductive agent (Super P), binder (sodium carboxymethyl cellulose CMC) and binder (styrene-butadiene latex SBR) according to 8:1:0.4: 0.4g, 0.05g, 0.02g and 0.03g are respectively weighed according to the proportion of 0.6, then the materials are put into a ball milling tank for ball milling for 30 minutes to prepare sizing agent, the sizing agent is uniformly coated on copper foil by a film coating machine, and then the sizing agent is dried for 12 hours at 100 ℃ in a vacuum drying oven; and (3) obtaining an electrode plate, assembling the electrode plate into a button battery, performing constant-current charge and discharge test on the battery by adopting a blue electrochemical workstation, wherein the test voltage is 0.01V-2.0V, assembling the electrode plate into a lithium ion battery, and performing electrochemical performance test.
Comparative example 2
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: weighing 0.25g of chitosan and 0.25g of sucrose, putting the chitosan and the sucrose into a deaerator for uniform dispersion, operating the deaerator for 10 minutes, adding the dispersed mixture into the slurry B, stirring uniformly, and adding the mixture A to obtain a slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 0min, stopping the procedure after heating, and cooling to room temperatureTaking out to obtain a product E, namely the double-carbon coated silica controlled prelithiation material (SiO X /C/Li)。
Comparative example 3
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 1.25g of carbon nanotube slurry (dispersed in an aqueous solution containing 0.6wt% of sodium carboxymethylcellulose, carbon nanotube content of 0.4 wt%) was weighed, 45g of water was added, followed by ultrasonic treatment for 5 minutes, 0.5g of acetic acid (HAC) was added, and then the mixture was placed in a magnetic stirrer and stirred uniformly to obtain slurry B.
Step three: 0.5g of chitosan is weighed, placed into a deaerator for uniform dispersion, the instrument is operated for 10 minutes, the dispersed mixture is added into the slurry B, and the mixture A is added after uniform stirring, so as to obtain the slurry C. And then placing the slurry C into a spray dryer for spray drying to obtain powder D.
Step four: placing the powder D into a tube furnace, introducing argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 minutes, stopping the procedure after heating, and taking out the powder D when the temperature is reduced to room temperature to obtain a product E, namely the double-carbon coated silicon-oxygen controllable prelithiation material (SiO X /C/Li)。
Comparative example 4
The preparation method of the double-carbon coated silica controlled prelithiation material comprises the following steps:
step one: silica and lithium hydroxide according to 40:1, respectively weighing 10g and 0.25g according to the mass ratio, and performing ball milling for 30 minutes to obtain a mixture A;
step two: 0.25g of chitosan and 0.25g of sucrose are weighed, placed into a deaerator for uniform dispersion, the apparatus is operated for 10 minutes, 45g of water is added into the dispersed mixture, ultrasonic treatment is carried out for 5 minutes, 0.5g of acetic acid (HAC) is added into the mixture, and a magnetic stirrer is used for uniform stirring, so that slurry B is obtained. And then placing the slurry B into a spray dryer for spray drying to obtain powder C.
Step three: placing the powder C into a tube furnace,introducing argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 minutes, stopping the procedure after heating, and taking out the product when the temperature is reduced to room temperature to obtain a product D, namely the double-carbon coated silica controlled prelithiation material (SiO) X /C/Li)。
Application example
Electrode slice
Preparation of double carbon coated silica controlled Pre-lithiation Material (SiO) from example 1 X Coating the product SiO according to the mass ratio of/C/Li) X /C/Li: uniformly ball-milling a conductive agent (Super P) adhesive (CMC) adhesive (SBR) according to the mass ratio of 8:1:0.4:0.6 to prepare slurry, uniformly coating the slurry on a copper foil by using a film coater, and drying for 12 hours at 100 ℃ in a vacuum drying oven; the lithium ion battery is characterized in that the lithium ion battery is a required electrode plate, the electrode plate is assembled into a lithium ion half battery, a blue electrochemical workstation is used for carrying out constant-current charge and discharge test on the battery, the test voltage is 0.01V-2.0V, and the obtained material is assembled into a button battery to test the performance of the lithium ion battery cathode material.
By adopting the mode, the pre-lithiated materials prepared in examples 2-7 and comparative examples 1-4 are prepared into button cells in sequence to test the performance of the lithium ion battery cathode material.
First, the silica used in the above examples was characterized, and FIG. 1 is a raw material silica SiO x XRD pattern of/C, demonstrating the presence of silica. Table 1 shows the relevant parameters for selecting silica as the starting material, with a particle size D50 of about 5.0.+ -. 1.0. Mu.m, and a lower initial efficiency of only 69% under 0.1C test conditions.
Table 1: relevant parameters of silica used as raw materials
Fig. 2: changing the technological parameters, and respectively keeping the temperature at 700, 750, 800 and 900 ℃ for 10 minutes at four different heat treatment temperatures in examples 1-4 to obtain the double-carbon coated silica prelithiation SiO x XRD pattern of/C/Li, with Si standard cards PDF#27-1402 and SiO 2 As can be seen from comparison of the standard cards PDF #89-3608 of (c), as the reaction temperature increases,the diffraction peak becomes sharper because the crystallinity becomes stronger, while the diffraction peak of 2θ at 28.4 ° increases in intensity and sharper with the rise in temperature, which corresponds to the formation of a phase of Si, indicating that this reaction mainly occurs at 800 ℃, and when the heat treatment temperature reaches 900 ℃, a large number of impurity peaks appear.
Fig. 3: the reaction temperature is kept at 800 ℃ for different time to obtain the double-carbon coated silica pre-lithium SiO x The XRD patterns of/C/Li, the samples obtained in comparative example 2, examples 1, 5 and 6 at 0, 10, 20 and 30 minutes, can find that the crystal phase of Si is in a growth state for 0-10 minutes, the intensity of diffraction peak increases, and the intensity of diffraction peak does not change much after the heat preservation time is continued to be prolonged, thus proving that the growth process can be completed within 10 minutes after the Si reacts.
FIG. 4 shows the preparation of double-carbon coated silica pre-lithium SiO by heat preservation at 800℃for 10min in example 1 x SEM of/C/Li, showing the microstructure of the silica-carbon coated and pre-lithium, stacked in flakes.
FIG. 5 is a schematic diagram of SiO under the condition of keeping the reaction temperature at 800℃for 10 minutes in example 1 x And LiOH are processed according to different proportions to obtain the double-carbon coated silica pre-lithium SiO x The capacity voltage curve of/C/Li shows that with the addition of lithium compound, the first-cycle discharge specific capacity is obviously reduced, but the first-cycle charge specific capacity is not greatly different, so that the first-cycle coulomb efficiency is improved, wherein the best proportion is SiO x /C:LiOH＝40：1。
As can be seen from Table 2, the electrochemical properties of the samples before and after double carbon and pre-lithiation of silica at 0.1C show that pre-lithiation can significantly improve the initial coulomb efficiency and reduce the initial discharge specific capacity, especially when SiO x Lioh=40: at 1, the first circle coulomb efficiency reaches 89.66%. This is attributed to the fact that pre-lithium in advance reduces the occurrence of side reactions during the first-turn discharge process, generating a more uniform and stable SEI film.
Table 2: under the condition that the reaction temperature is kept at 800 ℃ for 10 minutes, siO x And LiOH are processed according to different proportions to obtain the double-carbon coated silica controllable prelithiation material SiO x Electric at 0.1C/LiChemical properties
Fig. 6 is a cycle chart of the samples prepared in example 1 and comparative examples 2, 3, and 4, from which it is apparent that the product prepared in example 1 has the best cycle performance and good battery stability due to the protection of the material structure by the double carbon coating.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The preparation method of the double-carbon coated silica controlled prelithiation material is characterized by comprising the following steps of:
(1) Mixing silicon oxide with a lithium source to prepare a mixture;
(2) Dispersing and dissolving carbon nano tubes and organic carbon sources in a solvent to prepare slurry;
(3) And mixing the mixture with the slurry, spray-drying to obtain powder, and calcining the powder in an inert gas atmosphere to obtain the double-carbon coated silica controllable prelithiation material.
2. The method for preparing a double-carbon coated silica controlled prelithiation material according to claim 1, wherein the lithium source is any one or two or more of lithium hydroxide, lithium carbonate, lithium nitride and lithium sulfide; the mass ratio of the silicon oxide to the lithium source is (30-50): 1.
3. the method for preparing a double-carbon coated silica controlled prelithiation material according to claim 2, wherein the organic carbon source is more than two of sucrose, chitosan, glucose or urea; the mass ratio of the silicon oxide, the carbon nano tube and the organic carbon source is (10-40): (0.01-0.1): (1-10); the concentration of the organic carbon source in the slurry is 0.5-3wt%.
4. The method for preparing a double-carbon coated silica controlled prelithiation material according to claim 3, wherein sodium carboxymethyl cellulose is added into the slurry, and the concentration of sodium carboxymethyl cellulose in the slurry is 0.01-0.5wt%.
5. The method for preparing a double-carbon coated silica controlled prelithiation material according to claim 4, wherein an acidic reagent is added in the slurry, and the acidic reagent is hydrochloric acid, formic acid, acetic acid, lactic acid, malic acid, and ascorbic acid; the mass ratio of the acidic reagent to the organic carbon source is 1: (0.5-2).
6. The method for preparing a double-carbon coated silica controlled prelithiation material according to claim 5, wherein the calcining temperature is 700-900 ℃ and the heat preservation time is 10-30min; the inert gas is argon or nitrogen.
7. The dual carbon coated silica controlled prelithiation material made by the method of any one of claims 1-6.
8. An electrode sheet is characterized in that the double-carbon coated silica controlled prelithiation material, a conductive agent and a binder are mixed and then coated on a current collector to prepare the electrode sheet.
9. The electrode sheet of claim 8, wherein the mass ratio of the carbon-coated silicone material, the conductive agent, and the binder is (7-9.3): (0.3-2): (0.4-1); the conductive agent is any one of acetylene black, ketjen black, conductive graphite or Super P; the binder is styrene-butadiene rubber, sodium carboxymethyl cellulose and polyacrylic acid.
10. A lithium ion battery characterized in that the negative electrode is the electrode sheet of claim 9.
CN202311702419.7A 2023-12-12 2023-12-12 Double-carbon coated silica controllable prelithiation material and preparation method and application thereof Pending CN117525365A (en)

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