CN114023941A - Rice hull-based silicon oxide/graphene aerogel composite negative electrode material and preparation method and application thereof - Google Patents

Rice hull-based silicon oxide/graphene aerogel composite negative electrode material and preparation method and application thereof Download PDF

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CN114023941A
CN114023941A CN202111318910.0A CN202111318910A CN114023941A CN 114023941 A CN114023941 A CN 114023941A CN 202111318910 A CN202111318910 A CN 202111318910A CN 114023941 A CN114023941 A CN 114023941A
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silicon oxide
negative electrode
electrode material
graphene aerogel
acid
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杨宏训
孙孟飞
马娇娇
徐明航
邹旭飞
吴帅霆
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Jiangsu University of Science and 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a rice hull-based silicon oxide/graphene aerogel composite negative electrode material which is a three-dimensional porous frame structure formed by mutually connecting random oriented sheet structures with a fold structure and macropores/mesopores, wherein the particle diameter of the silicon oxide is 40-200 nm and is uniformly dispersed in the interior and on the surface of a three-dimensional graphene aerogel network; according to the percentage, silicon accounts for 8-23%, oxygen accounts for 47-82%, and carbon accounts for 10-30%; the BET specific surface area is 160 to 210m2(ii) in terms of/g. The rice hull based silicon oxide/graphene aerogel composite negative electrode material is applied toThe lithium ion battery has the advantages of long cycle life, high specific capacity and the like, and is wide in raw material source, convenient for large-scale production, low in price, safe in operation, easy in recycling of byproducts and capable of realizing green pollution-free production. The invention also discloses a preparation method and an application method of the rice hull silicon oxide/graphene aerogel composite negative electrode material.

Description

Rice hull-based silicon oxide/graphene aerogel composite negative electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of new energy storage, relates to a lithium ion battery cathode material and preparation and application thereof, and more particularly relates to a rice hull-based silicon oxide/graphene aerogel composite cathode material and a preparation method and application thereof.
Background
With the continuous development of lithium ion battery technology, the lithium ion battery plays an increasingly important role in the fields of military, aerospace, civil use and the like, is widely applied to the fields of electronic equipment, power automobiles, static energy storage and the like, particularly new energy automobiles, is one of the emerging industries of national strategy, and has a huge market in the future. The cathode material, as an important component of the lithium ion battery, determines the performance and safety of the lithium ion battery. The capacity of the anode material which is most widely applied on the market at present is close to the theoretical capacity 372mAh g-1The lifting space is very limited, and the low energy density of the lithium ion battery severely limits the wide application of the lithium ion battery. Therefore, the development of a lithium ion battery with high specific energy, long service life and low cost is an urgent problem to be solved, and is also a key way for solving the mileage anxiety of the electric automobile.
The silicon-based negative electrode material such as pure silicon and silicon oxide has the advantages of high specific capacity, low lithium removal potential and the like, and is considered to be a negative electrode material with great application prospect in the next generation of lithium ion batteries. However, the silicon-based negative electrode material has high production cost and large volume change in the lithium intercalation and deintercalation process, which leads to material pulverization, exfoliation and capacity attenuation, which limits the wide application of the material in lithium ion batteries, especially the complicated production process, can greatly increase the cost, and is not beneficial to the marketization of the silicon-based lithium ion batteries. How to reduce the cost of the silicon-based material while improving the performance of the silicon-based material is a research hotspot in the market. For example, from the viewpoint of production cost, a cheap silicon source can be searched, the production process can be simplified, and from the viewpoint of material performance, the material can be nanocrystallized and compounded with other materials.
Disclosure of Invention
The invention aims to solve the problem and defect that most of silicon element in the rice hull is wasted in the prior art, and the rice hull is changed into a raw material with high added value. And provides a rice hull-based silicon oxide/graphene aerogel composite negative electrode material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a rice hull-based silicon oxide/graphene aerogel composite negative electrode material is a three-dimensional porous frame structure formed by mutually connecting random oriented sheet structures with a fold structure and macropores/mesopores, wherein the particle diameter of the silicon oxide is 40-200 nm and is uniformly dispersed in the interior and on the surface of a three-dimensional graphene aerogel network; according to the percentage, silicon accounts for 8-23%, oxygen accounts for 47-82%, and carbon accounts for 10-30%; the BET specific surface area is 160 to 210m2/g。
In order to achieve the above object, another technical solution adopted by the present invention is:
a preparation method of a rice hull-based silicon oxide/graphene aerogel composite negative electrode material comprises the following steps:
step 1, cleaning rice hulls by adopting ultrapure water, soaking the rice hulls in an acid solution with the concentration of 0.1-5 mol/L, keeping the rice hulls at 80-100 ℃ for 8-24 hours, continuously stirring, performing centrifugal separation, washing the rice hulls by using the ultrapure water to be neutral, and drying the rice hulls in an oven;
step 2, spreading the product obtained in the step 1 in a porcelain boat, placing the porcelain boat in a tubular furnace in an inert atmosphere, keeping the porcelain boat at 400-600 ℃ for 1-4 h at a heating rate of 2-5 ℃/min, and naturally cooling the porcelain boat to room temperature;
step 3, placing the product obtained in the step 2 in a NaOH solution with the concentration of 1-3 mol/L for reflux stirring, keeping the temperature at 25-130 ℃ for 2-6 hours, and filtering to obtain a filtrate;
step 4, adding the filtrate obtained in the step 3 into the mixed solution according to the mass ratio of 1: (0.1-0.5 g) adding hexadecyl trimethyl ammonium bromide, after the solid is dissolved, dropwise adding an acid solution at 25-80 ℃ until the pH value is 1-10, keeping the pH value for 3-24 h to obtain a white precipitate, filtering the precipitate, washing the precipitate to be neutral, and drying the precipitate;
step 5, paving the product obtained in the step 4 in a porcelain boat, placing the porcelain boat in a tube furnace, keeping the porcelain boat at 400-600 ℃ for 1-6 h at a heating rate of 2-5 ℃/min in an air atmosphere, and naturally cooling the porcelain boat;
step 6, mixing the product obtained in the step 5 with aluminum powder or magnesium powder or a mixture of aluminum and magnesium powder according to a mass ratio of 1-6: 1-6, uniformly mixing, putting into a ball milling tank, ball milling for 10 min-10 h under inert gas, putting into a stainless steel closed reactor, reducing at the temperature of 650-750 ℃ for 2-6 h at the temperature rising rate of 2-15 ℃/min under the inert gas atmosphere, and naturally cooling;
step 7, soaking the product obtained in the step 6 in an acid solution with the concentration of 0.1-2 mol/L for reaction for 4-24 hours, filtering and washing to be neutral, and performing vacuum drying;
step 8, ultrasonically dispersing the product obtained in the step 7 in a graphene oxide solution with the concentration of 1-2 mg/mL for 1-2 h, performing hydrothermal reaction at 150-180 ℃ for 4-12 h, naturally cooling, filtering and washing with ultrapure water;
and 9, freeze-drying the product obtained in the step 8, placing the product in a tubular furnace, keeping the product in a hydrogen-argon mixed gas at a temperature rise rate of 2-5 ℃/min within a temperature range of 500-600 ℃ for 2-6 hours, and naturally cooling to obtain the rice hull silicon oxide/graphene aerogel composite negative electrode material.
Further preferably, the acid solution in step 1 is any one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid or a mixed acid of a plurality of the acids in any proportion.
Further preferably, the inert atmosphere in step 2 is nitrogen gas or argon gas or a nitrogen-argon mixed gas.
More preferably, the acid solution in the step 4 is any one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and the concentration is 1-15 wt%.
Further preferably, the inert atmosphere in step 6 is nitrogen gas or argon gas or a nitrogen-argon mixed gas.
Further preferably, the acid solution in step 7 is any one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid or a mixed acid of a plurality of the acids in any proportion.
More preferably, the volume fraction of hydrogen in the hydrogen-argon mixture gas in the step 9 is 5-10%.
The rice hull silicon oxide/graphene aerogel composite material is applied as a negative active material of a lithium ion battery. The method is particularly used as a CR2032 button lithium ion battery and comprises the following steps:
(A) mixing rice hull silicon oxide/graphene aerogel composite material, Keqin black and polyvinylidene fluoride according to the weight ratio of 5-8: 4-1: 1, mixing uniformly to obtain a solid mixture.
(B) Mixing the solid mixture obtained in the step (A) with N-methylpyrrolidone according to a mass ratio of 18-30: 70-82, and uniformly stirring to obtain slurry.
(C) Coating the slurry obtained in the step (B) on copper foil, and drying and rolling to obtain an electrode plate of the lithium ion battery with the thickness of 11-25 mu m;
(D) taking the electrode plate of the lithium ion battery obtained in the step (C) as a working electrode, taking a lithium plate as a counter electrode, adopting a microporous polypropylene-polyethylene film as a diaphragm, and adopting 1mol/L LiPF6And (3) preparing the electrolyte into a CR2032 button type lithium ion battery in a glove box filled with argon.
The invention has the advantages and beneficial effects that:
1. according to the rice hull silicon oxide/graphene aerogel composite material and the preparation method thereof, rice hulls are directly used as raw materials, agricultural wastes are recycled, the environment is protected, the production cost is reduced, the national requirement for vigorously developing a new natural waste biomass material is met, and the economic, social and ecological benefits of the rice hulls are improved;
2. according to the rice hull silicon oxide/graphene aerogel composite material and the preparation method thereof, silicon oxide is extracted from rice hulls by means of a precipitation method, a reduction method and the like, and then the rice hull silicon oxide/graphene aerogel composite material with a three-dimensional porous structure is obtained by hydrothermal compounding with graphene, so that the conductivity of the material can be improved, the volume expansion of the material can be effectively relieved, and the cycle performance of a battery can be improved.
Drawings
Fig. 1 is a scanning electron microscope image of the rice hull silicon oxide/graphene aerogel composite negative electrode material prepared in embodiment 1 of the invention.
Fig. 2 is a transmission electron microscope image of the rice hull silicon oxide/graphene aerogel composite negative electrode material prepared in embodiment 1 of the invention.
Fig. 3 is an X-ray diffraction (XRD) spectrum of the rice hull silicon oxide/graphene aerogel composite negative electrode material prepared in example 1 of the present invention.
Fig. 4 is a raman diagram of the rice hull silicon oxide/graphene aerogel composite negative electrode material prepared in embodiment 1 of the present invention.
FIG. 5 shows that the rice hull silicon oxide/graphene aerogel composite negative electrode material prepared in example 1 of the invention is used as a negative electrode material of a lithium ion battery at 1000mA g-1Cycle performance graph below.
Detailed Description
In order to make the present invention more fully understood, the technical solutions of the present invention will be described below in detail with reference to the embodiments of the present invention and the accompanying drawings. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1. A preparation method of a rice hull-based silicon oxide/graphene aerogel composite negative electrode material comprises the following steps:
(1) cleaning 10g of rice hulls with ultrapure water, then soaking the rice hulls in 100ml of 2mol/L hydrochloric acid solution, keeping the mixture at 90 ℃ for 24 hours while stirring continuously, then performing centrifugal separation, washing the mixture with ultrapure water to be neutral, and then placing the mixture in an oven for drying.
(2) Flatly paving the product obtained in the step 1 in a porcelain boat, placing the porcelain boat in a tubular furnace in an inert atmosphere, heating to 600 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2.5 hours, and naturally cooling to room temperature;
(3) placing 2g of the product obtained in the step 2 in 40ml of 2.5mol/L NaOH solution for reflux stirring, keeping the solution at the temperature of 120 ℃ for 3 hours, cooling and filtering to obtain filtrate;
(4) adding 0.4g of hexadecyl trimethyl ammonium bromide into the filtrate obtained in the step 3, dropwise adding an acid solution at 80 ℃ until the pH value is 10 and keeping the pH value for 3 hours after the solid is dissolved to obtain a white precipitate, filtering and washing the precipitate to be neutral, and drying the precipitate at 60 ℃;
(5) flatly paving the product obtained in the step (4) in a porcelain boat, placing the porcelain boat in a tube furnace, keeping the porcelain boat at 600 ℃ for 4 hours at the heating rate of 2 ℃/min in the air atmosphere, and naturally cooling the porcelain boat;
(6) and mixing the product obtained in the step 5 with aluminum powder according to the weight ratio of 1: 1, uniformly mixing the components in a mass ratio, putting the mixture into a ball milling tank, ball milling the mixture for 20min under inert gas, putting the mixture into a stainless steel closed reactor, keeping the mixture at 700 ℃ for 3h at a heating rate of 10 ℃/min under the atmosphere of the inert gas, and naturally cooling the mixture to room temperature;
(7) soaking the product obtained in the step 6 in a hydrochloric acid solution with the concentration of 2mol/L for reaction for 24 hours, filtering and washing to be neutral, and drying the precipitate at 80 ℃ in vacuum;
(8) ultrasonically dispersing the product obtained in the step 7 in 100mL of graphene oxide solution with the concentration of 2mg/mL for 1h, carrying out hydrothermal reaction at 180 ℃ for 12h, naturally cooling, filtering and washing with ultrapure water;
(9) and (3) freeze-drying the product obtained in the step (8), placing the product in a tubular furnace, keeping the product in a hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min within the temperature range of 500 ℃ for 2 hours, and naturally cooling the product to obtain the rice hull silicon oxide/graphene aerogel composite negative electrode material.
2. The rice hull silicon oxide/graphene aerogel composite negative electrode material is used for assembling and testing performance of a CR2032 button type lithium ion battery, and comprises the following steps:
(a) uniformly mixing the rice hull silicon oxide/graphene aerogel composite negative electrode material, Ketjen black and a binder polyvinylidene fluoride according to a mass ratio of 7:2:1 to obtain a solid mixture;
(b) mixing the solid mixture obtained in the step (a) with N-methyl pyrrolidone according to the mass ratio of 25:75, and uniformly stirring to obtain slurry;
(c) coating the slurry obtained in the step (b) on copper foil, and drying and rolling to obtain a lithium ion battery electrode plate with the thickness of 10-24 microns;
(d) taking the electrode plate of the lithium ion battery obtained in the step (c) as an electrode negative plate, taking a lithium plate as an electrode positive plate, adopting a microporous polypropylene membrane as a diaphragm, and adopting 1mol/L LiPF6And the solvent is electrolyte, and the CR2032 button type lithium ion battery is assembled in a glove box filled with argon.
(e) The assembled lithium ion battery in the step (d) is controlled to be in a voltage range of 0.01-3V and the voltage is controlled to be 100mA g-1The first three cycles of charge-discharge activation are carried out. After activation, the voltage is in the range of 0.01-3V and the voltage is 1000mA g-1The charge-discharge cycle test was carried out at the current density of (2).
Example 2
1. A preparation method of a rice hull-based silicon oxide/graphene aerogel composite negative electrode material comprises the following steps:
(1) cleaning 10g of rice hulls by using ultrapure water, then soaking the rice hulls in 200ml of 1mol/L hydrochloric acid solution, keeping the mixture at 90 ℃ for 24 hours while stirring continuously, then performing centrifugal separation, washing the mixture by using the ultrapure water until the mixture is neutral, and then placing the mixture in an oven for drying.
(2) Flatly paving the product obtained in the step 1 in a porcelain boat, placing the porcelain boat in a tubular furnace in an inert atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2.5 hours, and naturally cooling to room temperature;
(3) placing 2g of the product obtained in the step 2 in 40ml of NaOH solution with the concentration of 2.5mol/L for reflux stirring, keeping the temperature at 120 ℃ for 3 hours, cooling and filtering to obtain filtrate;
(4) adding 0.4g of Cetyl Trimethyl Ammonium Bromide (CTAB) into the filtrate obtained in the step 3, dropwise adding a sulfuric acid solution at 25 ℃ until the pH value is 7 after the solid is dissolved, keeping the pH value for 3 hours to obtain a white precipitate, filtering and washing the precipitate to be neutral, and drying the precipitate at 60 ℃;
(5) flatly paving the product obtained in the step (4) in a porcelain boat, placing the porcelain boat in a tube furnace, keeping the porcelain boat at 600 ℃ for 4 hours at the heating rate of 2 ℃/min in the air atmosphere, and naturally cooling the porcelain boat;
(6) and mixing the product obtained in the step 5 with magnesium powder according to the weight ratio of 2:1, uniformly mixing the components in a mass ratio, putting the mixture into a ball milling tank, ball milling the mixture for 20min under inert gas, putting the mixture into a stainless steel closed reactor, keeping the mixture at 700 ℃ for 3h at a heating rate of 10 ℃/min under the atmosphere of the inert gas, and naturally cooling the mixture to room temperature;
(7) soaking the product obtained in the step 6 in 2mol/L hydrochloric acid solution for reaction for 24 hours, filtering and washing to be neutral, and drying the precipitate at 80 ℃ in vacuum;
(8) ultrasonically dispersing the product obtained in the step 7 in 100mL of graphene oxide solution with the concentration of 1mg/mL for 2h, carrying out hydrothermal reaction at 180 ℃ for 12h, naturally cooling, filtering and washing with ultrapure water;
(9) and (3) freeze-drying the product obtained in the step (8), placing the product in a tubular furnace, keeping the product in a hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min within the temperature range of 500 ℃ for 2 hours, and naturally cooling the product to obtain the rice hull silicon oxide/graphene aerogel composite negative electrode material.
2. The rice hull silicon oxide/graphene aerogel composite negative electrode material is used for assembling and testing the performance of the CR2032 button type lithium ion battery: a battery was assembled from the silicon-oxygen-carbon composite negative electrode material in the manner of example 1 and subjected to a charge-discharge performance test.
Example 3
1. A preparation method of a rice hull-based silicon oxide/graphene aerogel composite negative electrode material comprises the following steps:
(1) cleaning 10g of rice hulls by using ultrapure water, then soaking the rice hulls in 200ml of 1mol/L hydrochloric acid solution, keeping the mixture at 900 ℃ for 24 hours while stirring continuously, then performing centrifugal separation, washing the mixture by using the ultrapure water until the mixture is neutral, and then placing the mixture in an oven for drying.
(2) Flatly paving the product obtained in the step 1 in a porcelain boat, placing the porcelain boat in a tubular furnace in an inert atmosphere, heating to 600 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2.5 hours, and naturally cooling to room temperature;
(3) placing 2g of the product obtained in the step 2 in 40ml of 2mol/L NaOH solution for reflux stirring, keeping the solution at the temperature of 120 ℃ for 3 hours, cooling and filtering to obtain filtrate;
(4) adding 0.4g of Cetyl Trimethyl Ammonium Bromide (CTAB) into the filtrate obtained in the step 3, dropwise adding a sulfuric acid solution at 80 ℃ after the solid is dissolved until the pH value is 10 and keeping the pH value for 3 hours to obtain a white precipitate, filtering and washing the precipitate to be neutral, and drying the precipitate at 60 ℃;
(5) flatly paving the product obtained in the step (4) in a porcelain boat, placing the porcelain boat in a tube furnace, keeping the porcelain boat at 600 ℃ for 4 hours at the heating rate of 2 ℃/min in the air atmosphere, and naturally cooling the porcelain boat;
(6) and mixing the product obtained in the step 5 with magnesium powder according to the weight ratio of 1: 1, uniformly mixing the components in a mass ratio, putting the mixture into a ball milling tank, ball milling the mixture for 20min under inert gas, putting the mixture into a stainless steel closed reactor, keeping the mixture at 650 ℃ for 2h at a heating rate of 2 ℃/min under the atmosphere of the inert gas, and naturally cooling the mixture to room temperature;
(7) soaking the product obtained in the step 6 in 0.1mol/L hydrochloric acid solution for reaction for 24 hours, filtering and washing to be neutral, and drying the precipitate at 80 ℃ in vacuum;
(8) ultrasonically dispersing the product obtained in the step 7 in 100mL of graphene oxide solution with the concentration of 0.5mg/mL for 2h, carrying out hydrothermal reaction for 12h at 180 ℃, naturally cooling, filtering and washing with ultrapure water;
(9) and (3) freeze-drying the product obtained in the step (8), placing the product in a tubular furnace, keeping the product in a hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min within the temperature range of 500 ℃ for 2 hours, and naturally cooling the product to obtain the rice hull silicon oxide/graphene aerogel composite negative electrode material.
2. The rice hull silicon oxide/graphene aerogel composite negative electrode material is used for assembling and testing the performance of the CR2032 button type lithium ion battery: a battery was assembled from the silicon-oxygen-carbon composite negative electrode material in the manner of example 1 and subjected to a charge-discharge performance test.
Example 4
1. A preparation method of a rice hull-based silicon oxide/graphene aerogel composite negative electrode material comprises the following steps:
(1) cleaning 10g of rice hulls by using ultrapure water, then soaking the rice hulls in 200ml of 2mol/L hydrochloric acid solution, keeping the mixture at 90 ℃ for 24 hours while stirring continuously, then performing centrifugal separation, washing the mixture by using the ultrapure water until the mixture is neutral, and then placing the mixture in an oven for drying.
(2) Flatly paving the product obtained in the step 1 in a porcelain boat, placing the porcelain boat in a tubular furnace in an inert atmosphere, heating to 600 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2.5 hours, and naturally cooling to room temperature;
(3) placing 2g of the product obtained in the step 2 in 40ml of 2mol/L NaOH solution for reflux stirring, keeping the solution at the temperature of 120 ℃ for 3 hours, cooling and filtering to obtain filtrate;
(4) adding 0.4g of Cetyl Trimethyl Ammonium Bromide (CTAB) into the filtrate obtained in the step 3, dropwise adding a sulfuric acid solution at 80 ℃ after the solid is dissolved until the pH value is 1, keeping the pH value for 2 hours to obtain a white precipitate, filtering and washing the precipitate to be neutral, and drying the precipitate at 60 ℃;
(5) flatly paving the product obtained in the step (4) in a porcelain boat, placing the porcelain boat in a tube furnace, keeping the porcelain boat at 600 ℃ for 4 hours at the heating rate of 2 ℃/min in the air atmosphere, and naturally cooling the porcelain boat;
(6) and mixing the product obtained in the step 5 with magnesium powder according to the weight ratio of 1: 1, uniformly mixing the components in a mass ratio, putting the mixture into a ball milling tank, ball milling the mixture for 20min under inert gas, putting the mixture into a stainless steel closed reactor, keeping the mixture at 700 ℃ for 5h at a heating rate of 10 ℃/min under the atmosphere of the inert gas, and naturally cooling the mixture to room temperature;
(7) soaking the product obtained in the step 6 in 1mol/L hydrochloric acid solution for reaction for 24 hours, filtering and washing to be neutral, and drying the precipitate at 80 ℃ in vacuum;
(8) ultrasonically dispersing the product obtained in the step 7 in 100mL of graphene oxide solution with the concentration of 1.5mg/mL for 2h, carrying out hydrothermal reaction for 12h at 180 ℃, naturally cooling, filtering and washing with ultrapure water;
(9) and (3) freeze-drying the product obtained in the step (8), placing the product in a tubular furnace, keeping the product in a hydrogen-argon mixed gas at the temperature rise rate of 2 ℃/min within the temperature range of 550 ℃ for 2 hours, and naturally cooling to obtain the rice hull silicon oxide/graphene aerogel composite negative electrode material.
2. The rice hull silicon oxide/graphene aerogel composite negative electrode material is used for assembling and testing the performance of the CR2032 button type lithium ion battery: a battery was assembled from the silicon-oxygen-carbon composite negative electrode material in the manner of example 1 and subjected to a charge-discharge performance test.
Taking the rice hull silicon oxide/graphene aerogel composite negative electrode material prepared in example 1 as an example, scanning is performed by an electron microscope, and the scanning result is shown in fig. 1, which shows an interconnected three-dimensional frame with a wrinkled structure and a macroporous/mesoporous random orientation sheet structure, namely SiOxThe nano particles are wrapped inside and on the surface of the three-dimensional graphene aerogel network, so that the dispersibility is good, and the particle size range is 40-200 nm. The structure generated by the self-assembly of the graphene oxide under the hydrothermal condition can not only provide more surface reaction sites, but also has enough space for buffering SiOxThe large volume of the nanoparticles changes during charging and discharging. Therefore, these properties are advantageous for shortening Li+The diffusion length of the lithium ion battery improves the rate capability and the cycle stability of the lithium ion battery;
FIG. 2 is a TEM image of the rice hull-based silicon oxide/graphene aerogel composite anode material of example 1, showing SiOxThe nanoparticles were uniformly distributed on the graphene aerogel nanoplatelets with wrinkles around them, consistent with SEM images.
The XRD spectrum of experimental example 1 is shown in FIG. 3, and has a broad peak at 20-26 deg. and amorphous SiOxAnd overlapping with the graphene aerogel. In addition, the significant peaks near 28.5 °, 47.2 °, 56.2 °, 69.1 ° and 76.5 ° correspond to the (111), (220), (311), (400) and (331) lattice planes of the Si crystal phase, further confirming successful preparation of the material.
FIG. 4 is a Raman spectrum of the rice hull-based silicon oxide/graphene aerogel composite anode material of example 1, which is shown to be at-517 cm-1The peak at (b) corresponds to the peak of crystalline silicon, indicating that nanocrystalline Si is dispersed in SiOxIn the nano-particles. Furthermore, at-1350 and-1604 cm-1Is provided with two broad characteristic peaks respectively corresponding to sp2Pi-bonded delocalized D-band and G-band. I isD/IGThe value is about 1.07, which indicates that the material contains a large number of defects, the defects can provide more active sites for the reaction, and shorten Li+The transmission path of (2) improves material performance.
FIG. 5 is a cycle performance diagram of the rice hull silicon oxide/graphene aerogel composite negative electrode material of example 1 as a negative electrode material of a lithium ion battery at 1000mA/g, and the discharge capacity is 923mAh g after 380 cycles of cycle-1And the material is far higher than the current commercial graphite cathode material, and shows excellent cycle performance.
The lithium battery performance results of examples 1-4 are shown in table 1.
Table 1 shows that the lithium ion batteries of examples 1-4 are operated at 1000mA g-1The capacity obtained at the 4 th and 380 th circles was measured by charging and discharging at a current.
TABLE 1
Figure BDA0003344786140000081
As can be seen from Table 1, the rice hull silicon oxide/graphene aerogel composite negative electrode material is used as an electrode material and applied to a lithium ion battery at 1000mA g-1Then, the charging capacity is 923mAh g after 380 cycles of circulation-1The graphite anode material has good cycle performance which is far higher than that of the current commercialized graphite anode material.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims.

Claims (9)

1. The rice hull-based silicon oxide/graphene aerogel composite negative electrode material is characterized in that the composite negative electrode material is a three-dimensional porous frame structure formed by mutually connecting random oriented sheet structures with a fold structure and macropores/mesopores, wherein the particle diameter of the silicon oxide is 40-200 nm, and the silicon oxide is uniformly dispersed in the interior and on the surface of a three-dimensional graphene aerogel network; according to the percentage, silicon is 8-23%, oxygen is 47-82%, and carbon is 10-30%; the BET specific surface area is 160 to 210m2/g。
2. The preparation method of the rice hull silicon oxide/graphene aerogel composite negative electrode material according to claim 1, which is characterized by comprising the following steps:
step 1, cleaning rice hulls by adopting ultrapure water, soaking the rice hulls in an acid solution with the concentration of 0.1-5 mol/L, keeping the rice hulls at 80-100 ℃ for 8-24 hours, continuously stirring, performing centrifugal separation, washing the rice hulls by using the ultrapure water to be neutral, and drying the rice hulls in an oven;
step 2, spreading the product obtained in the step 1 in a porcelain boat, placing the porcelain boat in a tubular furnace in an inert atmosphere, keeping the porcelain boat at 400-600 ℃ for 1-4 h at a heating rate of 2-5 ℃/min, and naturally cooling the porcelain boat to room temperature;
step 3, placing the product obtained in the step 2 in a NaOH solution with the concentration of 1-3 mol/L for reflux stirring, keeping the temperature at 25-130 ℃ for 2-6 hours, and filtering to obtain a filtrate;
step 4, adding the filtrate obtained in the step 3 into the mixed solution according to the mass ratio of 1: (0.1-0.5 g) adding Cetyl Trimethyl Ammonium Bromide (CTAB), after the solid is dissolved, dropwise adding an acid solution at 25-80 ℃ until the pH value is 1-10, keeping the pH value for 3-24 h to obtain a white precipitate, filtering the precipitate, washing the precipitate to be neutral, and drying the precipitate;
step 5, paving the product obtained in the step 4 in a porcelain boat, placing the porcelain boat in a tube furnace, keeping the porcelain boat at 400-600 ℃ for 1-6 h at a heating rate of 2-5 ℃/min in an air atmosphere, and naturally cooling the porcelain boat;
step 6, mixing the product obtained in the step 5 with aluminum powder or magnesium powder or a mixture of aluminum and magnesium powder according to a mass ratio of 1-6: 1-6, uniformly mixing, putting into a ball milling tank, ball milling for 10 min-10 h under inert gas, putting into a stainless steel closed reactor, reducing at the temperature of 650-750 ℃ for 2-6 h at the temperature rising rate of 2-15 ℃/min under the inert gas atmosphere, and naturally cooling;
step 7, soaking the product obtained in the step 6 in an acid solution with the concentration of 0.1-2 mol/L for reaction for 4-24 hours, filtering and washing to be neutral, and performing vacuum drying;
step 8, ultrasonically dispersing the product obtained in the step 7 in a graphene oxide solution with the concentration of 1-2 mg/mL for 1-2 h, performing hydrothermal reaction at 150-180 ℃ for 4-12 h, naturally cooling, filtering and washing with ultrapure water;
and 9, freeze-drying the product obtained in the step 8, placing the product in a tubular furnace, keeping the product in a hydrogen-argon mixed gas at a temperature rise rate of 2-5 ℃/min within a temperature range of 500-600 ℃ for 2-6 hours, and naturally cooling to obtain the rice hull silicon oxide/graphene aerogel composite negative electrode material.
3. The preparation method of the rice hull silicon oxide/graphene aerogel composite negative electrode material according to claim 2, characterized in that: the acid solution in the step 1 is any one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid or a mixed acid of a plurality of the hydrochloric acid, the sulfuric acid, the nitric acid, the acetic acid and the oxalic acid in any proportion.
4. The preparation method of the rice hull silicon oxide/graphene aerogel composite negative electrode material according to claim 2, characterized in that: the inert atmosphere in the step 2 is nitrogen or argon or nitrogen-argon mixed gas.
5. The preparation method of the rice hull silicon oxide/graphene aerogel composite negative electrode material according to claim 2, characterized in that: the acid solution in the step 4 is any one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and the concentration is 1-15 wt%.
6. The preparation method of the rice hull silicon oxide/graphene aerogel composite negative electrode material according to claim 2, characterized in that: the inert atmosphere in the step 6 is nitrogen or argon or nitrogen-argon mixed gas.
7. The preparation method of the rice hull silicon oxide/graphene aerogel composite negative electrode material according to claim 2, characterized in that: the acid solution in the step 7 is any one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid or a mixed acid of a plurality of the hydrochloric acid, the sulfuric acid, the nitric acid, the acetic acid and the oxalic acid in any proportion.
8. The application of the rice hull silicon oxide/graphene aerogel composite negative electrode material according to claim 1 is characterized in that: the material is applied as a negative electrode material of a lithium ion battery.
9. A method according to claim 8, characterized in that: the method is particularly used as a CR2032 button lithium ion battery and comprises the following steps:
(A) and mixing the rice hull silicon oxide/graphene aerogel composite material, Keqin black and polyvinylidene fluoride according to the mass ratio of 5-8: 4-1: 1, uniformly mixing to obtain a solid mixture;
(B) mixing the solid mixture obtained in the step (A) with N-methylpyrrolidone according to a mass ratio of 18-30: 70-82, and uniformly stirring to obtain slurry;
(C) coating the slurry obtained in the step (B) on copper foil, and drying and rolling to obtain an electrode plate of the lithium ion battery with the thickness of 11-25 mu m;
(D) and (C) taking the electrode plate of the lithium ion battery obtained in the step (C) as a working electrode, taking a lithium sheet as a counter electrode, adopting a microporous polypropylene-polyethylene film as a diaphragm, adopting 1mol/L LiPF6 as electrolyte, and assembling into the CR2032 button type lithium ion battery in a glove box filled with argon.
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