CN112086632B - Defect-state disordered-layer stacked graphene assembled battery material and preparation method thereof - Google Patents

Defect-state disordered-layer stacked graphene assembled battery material and preparation method thereof Download PDF

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CN112086632B
CN112086632B CN202010990142.2A CN202010990142A CN112086632B CN 112086632 B CN112086632 B CN 112086632B CN 202010990142 A CN202010990142 A CN 202010990142A CN 112086632 B CN112086632 B CN 112086632B
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graphene oxide
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graphene
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CN112086632A (en
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彭蠡
方文章
高超
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Hangzhou Gaoxi 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a defect-state disordered-layer stacked graphene assembled battery material and a preparation method thereof. The defect state structure provides a capacitor on one hand and an electrolyte access channel on the other hand, and improves the coulomb efficiency; the disordered-layer stacking structure is convenient for interlayer insertion of graphene layers, the intercalation proportion is improved, and the capacitance and the charge-discharge speed are further improved; the nano-silicon particles then act completely as capacitive carriers. The three structures are applied to battery materials, supplement each other, and greatly improve the battery capacity, so that the three structures can be used for preparing high-quality capacity batteries.

Description

Defect-state disordered-layer stacked graphene assembled battery material and preparation method thereof
Technical Field
The invention relates to a defect-state disordered-layer stacked graphene assembled battery material and a preparation method thereof.
Background
The capacity problem of the lithium battery is always the first problem in the field of lithium batteries and cannot be solved effectively.
High capacity silicon materials have been discovered in recent years and their use has also been of continued interest. However, silicon itself undergoes volume expansion during charging and discharging processes, which damages the material assembly structure and further affects the battery performance. The existing silicon nanoparticle packaging method needs polymer assistance, and the final result is a hollow sphere with relatively low density, so that the volume capacitance is reduced; therefore, a simple method for wrapping the close-packed silicon particles is urgently needed, and the conductive material assembly structure is not damaged in the charging and discharging expansion process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a defect-state disordered-layer stacked graphene assembled battery material and a preparation method thereof. The structure combines the defects, disordered layer structures and elasticity of the graphene assembly material, and lays a foundation for the application of the graphene high-capacity lithium battery material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a defect-state disordered-layer stacked graphene assembled battery material and a preparation method thereof have the structure that folded graphene spheres wrap nano silicon particles; wherein the thickness of the graphene is between 20 and 120 atomic layers. The defect degree of the graphene is I D /I G Between 0.2 and 0.04; the graphene layers are stacked in a completely disordered structure.
The material has a stacked structure with complete disordered layers, local defect states and controllable silicon filling volume of an internal space. The defect state structure provides a capacitor on one hand and an electrolyte access channel on the other hand, and improves the coulomb efficiency; the disordered-layer stacking structure is convenient for interlayer insertion of graphene layers, the intercalation proportion is improved, and the capacitance and the charge-discharge speed are further improved; the nano-silicon particles then act completely as capacitive carriers. The three structures are applied to battery materials, supplement each other, and greatly improve the battery capacity, so that the three structures can be used for preparing high-quality capacity batteries.
A preparation method of a defect-state disordered-layer stacked graphene assembled battery material comprises the following steps:
(1) Placing graphene oxide in 30-50% hydrogen peroxide by mass fraction, heating for 2-12h at 60-80 ℃ to obtain a high defect state graphene oxide solution with a rich cavity structure, wherein the hydrogen peroxide by mass fraction is 10% -20% in the high defect state graphene oxide solution.
(2) Uniformly mixing the silicon dioxide nano particles and the high-defect-state graphene oxide solution, wherein in the mixed solution, the concentration of the high-defect-state graphene oxide is less than 0.1mg/ml, and the mass ratio of the silicon dioxide nano particles to the high-defect-state graphene oxide is 1:6-1:20. and spraying to form a graphene oxide coated silicon dioxide structure, and carrying out chemical reduction to obtain a reduced graphene oxide microsphere coated silicon dioxide structure.
(3) Heating the reduced graphene oxide microsphere-coated silicon dioxide structure to 1000 ℃ at a heating rate of below 30 ℃/min under the protection of nitrogen, and keeping the temperature for 1-4h; introducing 5v/v% hydrogen, stably heating to 1400 ℃, maintaining for 2-6h, and completely reducing the silicon dioxide nano particles into silicon nano particles.
(4) And (3) placing the graphene-coated silicon nanoparticle material obtained in the step (3) in microwave equipment, heating at the highest speed of 2000-2300 ℃, keeping the heating speed at 500-1000 ℃/min for 1-30s, and developing the porous structure into a relatively close-packed wrinkle form.
Further, the chemical reduction condition is that HI is used as a reducing agent and is treated for 1-4h at the temperature of 60-120 ℃.
Further, the silica nanoparticles are mixed with the high defect state graphene oxide solution through a solution containing the silica nanoparticles, and the concentration of the silica nanoparticles in the solution containing the silica nanoparticles is lower than 0.1ml/g.
The invention has the beneficial effects that:
firstly, the existence of the disordered layer structure can improve the capacitance of the graphene assembly material by about one time.
Secondly, the existence of the defect state can continuously improve the capacity of the graphene assembled nano material by 0.5 to 1 time on the basis of the disordered layer structure.
Thirdly, the graphene spheres are rapidly shrunk in the extremely-fast heating process at 2000-2300 ℃, and then the silicon nanoparticles are densely packed and wrapped; meanwhile, the high-defect graphene cannot be repaired on a large scale in the heating process within an ultrashort time, so that the graphene layer has good elasticity due to the existence of a defect-state disordered layer structure, and can shrink and expand along with the charging and discharging processes of the silicon nano particles.
Drawings
Fig. 1 is a TEM image of defective graphene.
Fig. 2 is a TEM image of a graphene film/silicon wrapping structure, where a is a shrinkage state after preparation and b is an expansion state after charging.
FIG. 3 is a high resolution TEM image of silicon nanoparticles.
Fig. 4 is a TEM image of the graphene film/silicon-coated structure after discharge, and a and b are two forms after shrinkage respectively.
Fig. 5 is a raman spectrum of the graphene film/silicon composite microsphere.
Detailed Description
The present invention will be further described with reference to the following examples.
In the following examples, the defect content was tested in the following manner: raman I D /I G To determine how much material is defective.
Example 1:
(1) Adding 1mg/ml graphene oxide aqueous solution into 30% hydrogen peroxide, heating at 60 ℃ for 12h to obtain a high defect state graphene oxide solution with a rich cavity structure (figure 1), wherein the 30% hydrogen peroxide is diluted to 10%.
(2) Uniformly mixing the silicon dioxide nano particles and the high-defect-state graphene oxide solution, wherein in the mixed solution, the concentration of the high-defect-state graphene oxide is 0.1mg/ml, and the mass ratio of the silicon dioxide nano particles to the high-defect-state graphene oxide is 1:6. spraying to form a graphene coated silicon dioxide structure; and (4) carrying out chemical reduction (HI, treatment at 60 ℃ for 4 h) to obtain a reduced graphene oxide microsphere coated silicon dioxide structure.
(3) Heating the graphene oxide film to 1000 ℃ at a heating rate of below 30 ℃/min under the protection of nitrogen, and keeping the temperature for 4 hours; introducing 5v/v% hydrogen, stably heating to 1400 ℃, maintaining for 2h, and completely reducing the silicon dioxide nano particles into the silicon nano particles.
(4) The obtained graphene-coated silicon nanoparticle material is placed in a microwave device, the microwave device is heated at a maximum speed of 2000 ℃, the temperature rising speed is 1000 ℃/min, the porous structure is maintained for 25s, the porous structure is developed into a relatively close-packed wrinkle shape (figure 2 a), wherein silicon particles exist in a polycrystalline nanoscale (figure 3), after charging, the microparticles expand, the size stretch increases, and after discharge which shows a deeper color state under an electron microscope (figure 2 b), the microparticles shrink into a relatively close-packed wrinkle shape, as shown in figure 4. Fig. 5 shows the raman of the finally prepared graphene-silicon composite material. According to the figure, graphene and silicon have a good coexistence relationship; graphene materials have a large number of defect states to maintain capacity and elasticity.
Finally, the material is subjected to a specific mass capacity test, and data shows that the specific mass capacity of the material is 700mAh/g; the specific mass capacity of the comparative silicon-free composite is 540mAh/g; the specific capacity of the carbon material after the defects are removed is 360mAh/g; and after the stacked structure is restored to be an AB structure, the specific mass capacity of the carbon material is 170mAh/g.
Example 2:
(1) Adding 1mg/ml graphene oxide aqueous solution into 50% hydrogen peroxide, heating for 2h at 80 ℃, and obtaining the high defect state graphene oxide solution with abundant cavity structures, wherein the 50% hydrogen peroxide is diluted to 15%.
(2) Uniformly mixing silicon dioxide nano particles and a high defect state graphene oxide solution, wherein in the mixed solution, the concentration of the high defect state graphene oxide is 0.05mg/ml, and the mass ratio of the silicon dioxide nano particles to the high defect state graphene oxide is 1:20. spraying to form a graphene coated silicon dioxide structure; and (5) carrying out chemical reduction (HI, treatment at 80 ℃ for 2 h) to obtain a reduced graphene oxide microsphere coated silicon dioxide structure.
(3) Heating the graphene oxide film to 1000 ℃ at a heating rate of below 30 ℃/min under the protection of nitrogen, and keeping the temperature for 1h; introducing 5v/v% hydrogen, stably heating to 1400 ℃, maintaining for 6h, and completely reducing the silicon dioxide nano particles into the silicon nano particles.
(4) And placing the obtained graphene-coated silicon nanoparticle material into microwave equipment, heating at a maximum speed of 2300 ℃, heating at a heating speed of 800 ℃/min, maintaining for 20s, and developing a porous structure into a relatively close-packed wrinkle form, wherein silicon particles exist in a polycrystalline nanoscale, and after charging, the particles expand and the size is expanded and increased.
In the material prepared by the method, graphene and silicon have good coexistence relationship; graphene materials have a large number of defect states to maintain capacity and elasticity.
Finally, the material is subjected to a specific mass capacity test, and data shows that the material has excellent energy storage performance.
Example 3:
(1) Adding 2mg/ml graphene oxide aqueous solution into 35% hydrogen peroxide, and heating at 75 ℃ for 5h to obtain a high defect state graphene oxide solution with a rich cavity structure, wherein the hydrogen peroxide with the concentration of 50% is diluted to 20%.
(2) Uniformly mixing the silicon dioxide nano particles and the high-defect-state graphene oxide solution, wherein in the mixed solution, the concentration of the high-defect-state graphene oxide is 0.04mg/ml, and the mass ratio of the silicon dioxide nano particles to the high-defect-state graphene oxide is 1:15. spraying to form a graphene coated silicon dioxide structure; and (5) carrying out chemical reduction (HI, processing at 120 ℃ for 1 h) to obtain a reduced graphene oxide microsphere coated silicon dioxide structure.
(3) Heating the graphene oxide film to 1000 ℃ at a heating rate of below 30 ℃/min under the protection of nitrogen, and keeping the temperature for 1h; introducing 5v/v% hydrogen, stably heating to 1400 ℃, maintaining for 3h, and completely reducing the silicon dioxide nano particles into the silicon nano particles.
(4) And placing the obtained graphene-coated silicon nanoparticle material into microwave equipment, heating at the highest speed of 2250 ℃, heating at the speed of 500 ℃/min, maintaining for 5s, and developing the porous structure into a relatively close-packed wrinkle form, wherein silicon particles exist in a polycrystalline nanoscale, and after charging, the particles expand and the size is expanded and increased.
In the material prepared by the method, graphene and silicon have a good coexistence relationship; graphene materials have a large number of defect states to maintain capacity and elasticity.
Finally, the material is subjected to a specific mass capacity test, and data shows that the material has excellent energy storage performance.
Example 4:
(1) Adding 2mg/ml graphene oxide aqueous solution into 45% hydrogen peroxide, heating for 6h at 70 ℃, and obtaining the high defect state graphene oxide solution with abundant cavity structures, wherein the 45% hydrogen peroxide is diluted to 16%.
(2) Uniformly mixing the silicon dioxide nano particles and the high-defect-state graphene oxide solution, wherein in the mixed solution, the concentration of the high-defect-state graphene oxide is 0.03mg/ml, and the mass ratio of the silicon dioxide nano particles to the high-defect-state graphene oxide is 1:10. spraying to form a graphene coated silicon dioxide structure; and (5) carrying out chemical reduction (HI, treatment at 100 ℃ for 2.5 h) to obtain a reduced graphene oxide microsphere coated silicon dioxide structure.
(3) Heating the graphene oxide film to 1000 ℃ at a heating rate of below 30 ℃/min under the protection of nitrogen, and keeping the temperature for 2.5 hours; introducing 5v/v% hydrogen, stably heating to 1400 ℃, maintaining for 4h, and completely reducing the silicon dioxide nano particles into the silicon nano particles.
(4) Placing the obtained graphene-coated silicon nanoparticle material into microwave equipment, heating at the highest speed of 2250 ℃, heating at the speed of 600 ℃/min, maintaining for 1s, and developing the porous structure into a relatively close-packed wrinkle form, wherein the silicon particles exist in a polycrystalline nanoscale, and after charging, the particles expand and the size is expanded and increased.
In the material prepared by the method, graphene and silicon have good coexistence relationship; graphene materials have a large number of defect states to maintain capacity and elasticity.
Finally, the material is subjected to a specific mass capacity test, and data shows that the material has excellent energy storage performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should all embodiments be exhaustive. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.

Claims (3)

1. A preparation method of a defect-state disordered-layer stacked graphene assembled battery material is characterized in that the defect-state disordered-layer stacked graphene assembled battery material is in a structure that nano silicon particles are wrapped by folded graphene spheres; the method comprises the following steps:
(1) Placing graphene oxide in 30-50% by mass of hydrogen peroxide, heating for 2-12h at 60-80 ℃ to obtain a high-defect-state graphene oxide solution with a rich cavity structure, wherein the mass fraction of the hydrogen peroxide in the high-defect-state graphene oxide solution is 10% -20%;
(2) Uniformly mixing the silicon dioxide nano particles and the high-defect-state graphene oxide solution, wherein in the mixed solution, the concentration of the high-defect-state graphene oxide is less than 0.1mg/ml, and the mass ratio of the silicon dioxide nano particles to the high-defect-state graphene oxide is 1:6-1:20; spraying to form a graphene oxide coated silicon dioxide structure, and carrying out chemical reduction to obtain a reduced graphene oxide microsphere coated silicon dioxide structure;
(3) Heating the reduced graphene oxide microsphere wrapped silicon dioxide structure to 1000 ℃ at a heating rate of below 30 ℃/min under the protection of nitrogen, and keeping the temperature for 1-4h; introducing 5v/v% hydrogen, stably heating to 1400 ℃, maintaining for 2-6h, and completely reducing the silicon dioxide nano particles into silicon nano particles;
(4) And (3) placing the graphene-coated silicon nanoparticle material obtained in the step (3) in microwave equipment, heating at the highest speed of 2000-2300 ℃, keeping the heating speed at 500-1000 ℃/min for 1-30s, and developing the porous structure into a relatively close-packed wrinkle form.
2. The preparation method of claim 1, wherein the chemical reduction condition is that HI is used as a reducing agent and the HI is treated at 60-120 ℃ for 1-4h.
3. The preparation method according to claim 1, wherein the silica nanoparticles are mixed with the high defect state graphene oxide solution through a solution containing the silica nanoparticles, and the concentration of the silica nanoparticles in the solution containing the silica nanoparticles is lower than 0.1ml/g.
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US9450239B1 (en) * 2012-03-15 2016-09-20 Erik K. Koep Methods for fabrication of intercalated lithium batteries
CN107394135B (en) * 2017-06-26 2020-04-10 中航锂电（洛阳）有限公司 Graphene-based composite negative electrode material and preparation method thereof
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CN109309222A (en) * 2018-09-29 2019-02-05 盐城师范学院 A kind of preparation method of nano-silicon/fold graphene core-shell structure
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