CN107910513A - Compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof - Google Patents

Compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof Download PDF

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CN107910513A
CN107910513A CN201711069504.9A CN201711069504A CN107910513A CN 107910513 A CN107910513 A CN 107910513A CN 201711069504 A CN201711069504 A CN 201711069504A CN 107910513 A CN107910513 A CN 107910513A
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graphene
silicon
ion battery
lithium ion
carbon nanotubes
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孟岩
丁古巧
梁勇
田素云
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Shanghai Sc Graphene Industrial Technology Co ltd
Shanghai Institute of Microsystem and Information Technology of CAS
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Shanghai Sc Graphene Industrial Technology Co ltd
Shanghai Institute of Microsystem and Information Technology of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
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    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
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    • Y02E60/10Energy storage using batteries

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Abstract

The present invention provides compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof.The compound negative electrode of lithium ion battery of the graphene/silicon, it is characterized in that, sandwich construction including copper foil and on copper foil, the sandwich construction includes the graphene layer and silicon/carbon nanotube layer of alternate setting, silicon/the carbon nanotube layer contains nano silicon particles and carbon nanotubes, and carbon nanotubes is coated on nano silicon particles.This laminar composite can be applied to lithium ion battery as negative material.With high specific capacity, the characteristic such as stable cycle performance.Graphene and carbon pipe nano silicon particles have successfully been wrapped up into this simple step, and bulk effect of the silicon materials in charge and discharge process is improved by the special construction of stratiform, the condition of graphene and carbon nanotubes also improves electrode conductivuty at the same time so that final electrode material specific capacity is high, coulombic efficiency is high, good cycle.

Description

Compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof
Technical field
The present invention relates to compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof.
Background technology
Lithium ion battery has capacity high, has extended cycle life, pollution-free, the characteristics such as security is good, more and more Applied to portable electronic products and power battery field.Under the promotion that electric car development and renewable resource are explored, chemical-electrical The research in source needs energy storage and the energy conversion of higher, while also to have high-energy-density, high-specific-power, long-life.And For the lithium ion battery of present commercialization also there are many deficiencies, the negative material of lithium ion battery is the key for influencing battery performance Factor, current commodity lithium ion battery are 372mAh/g more using carbonaceous anode, its theoretical capacities such as graphite, it is difficult to are met high The demand of capacity.And silicon materials rich reserves, and there is very high specific capacity (4200mAh/g), but silicon materials do electrode In use, as the carry out material volume of reaction changes greatly (4 times that about can reach original volume), it is broken that this make it that silicon electrode occurs Split and dusting, can not practical application.It is swollen presently mainly to alleviate the volume of silicon using nano silicon material and silicon compound It is swollen, so as to improve its cycle life.
Graphene is a kind of two-dimentional monolayer material, has high specific surface area, silicon materials are for composite with graphene Destruction of the silicon materials to electrode material in expansion and contraction process can be effectively reduced, so that the cycle performance of device is improved, The problem of high conductivity of graphene also contributes to improve silicon materials poorly conductive at the same time.By the way that graphene and silicon materials are made Layer structure, can make full use of the flexibility of graphene, and the stratiform clad structure that high surface area is brought is expanded and shunk to reduce silicon During electrode material powdered, layer structure be also beneficial to improve silicon materials conductive capability, patent CN 103579589 A elaborates graphene-silicon-graphene to prepare stratiform anode, although high performance can be obtained, its method is more complicated, Its raw material is gaseous carbon source and silicon source, and manufacturing cost is high, and security is poor, and equipment requirement is high, is unfavorable for the development of industrialization.And We use carbon nanotubes, graphene, and the compound system of silicon will reduce the difficulty and cost prepared, safe, can scale Prepare;In addition, also there are 105576203 A of patent CN to propose to prepare electrode using the compound mode of silicon/graphene/carbon nano-tube Material, due to it, directly mixing without being coated well in structure, causes its cycle performance poor, coulombic efficiency It is low.
The content of the invention
It is an object of the invention to provide the negative material that capacity is high, a kind of good cycle graphene/silicon is compound and Its preparation method and application.The layer structure of the present invention, can make graphene coat silicon layer well, pass through between graphene and silicon The mutual unicom of carbon nanotubes, realizes the conductive system that point-line-surface is combined, while in short distance carbon nanotubes and long-range graphene To the parcel of nano silicon particles so that the volumetric expansion of silicon is limited, and solid electrolyte interface film becomes firm.
In order to achieve the above object, the present invention provides a kind of compound negative electrode of lithium ion battery of graphene/silicon, its feature Be, including copper foil and the sandwich construction on copper foil, the sandwich construction include alternate setting graphene layer and Silicon/carbon nanotube layer, the silicon/carbon nanotube layer contain nano silicon particles and carbon nanotubes, and carbon nanotubes is coated on silicon and receives In rice grain.
Present invention also offers the preparation method of the compound negative electrode of lithium ion battery of above-mentioned graphene/silicon, its feature exists In, including:
Step 1:Graphene is placed in water, PAA binding agents is added, is sheared in cutter, obtain finely dispersed stone Black alkene slurry;
Step 2:Copper foil is immersed in organic acid or hydrogen peroxide under room temperature, or copper foil is immersed in organic acid under room temperature In, then it is transferred in hydrogen peroxide and soaks, is then washed with deionized totally, naturally dry, obtains the copper that surface was modified Paper tinsel;
Step 3:Carbon nano tube paste is diluted and is stirred, it is dispersed in water, then adds nano silicon particles, point Dissipate uniformly, while add BYK dispersants, stir, obtain the dispersion liquid of silicon/carbon nanotubes;
Step 4:Graphene slurry obtained by step 1 is coated on the copper foil that surface was modified with coating machine, drying, shape Into graphene layer;The dispersion liquid of silicon/carbon nanotubes of gained in step 3 is sprayed onto to the graphene surface of drying with spray gun, then Drying, forms silicon/carbon nanotube layer, obtains drying pole piece;
Step 5:Graphene slurry obtained by step 1 is coated on the drying pole piece obtained by step 4, then spraying process The dispersion liquid of silicon/carbon nanotubes of gained in 3, is coated with the graphene slurry obtained by step 1, is rolled on roll squeezer, cut into slices, dried It is dry, obtain the compound negative electrode of lithium ion battery of graphene/silicon.
Preferably, the thickness of the graphene is 1-10 atomic layer.
Preferably, the adding proportion of the PAA in the step 1 is 1-5wt.%, and the additive amount of graphene is 5- 10wt.%.
Preferably, the shear time in the step 1 is 0.5-5h.
Preferably, the organic acid in the step 2 is acetic acid, oxalic acid or citric acid, soaking time 5-20h, double The soaking time of oxygen water is 6-15h.
Preferably, the size of the carbon nanotubes in the step 3 is 1-10 μm, and the size of nano silicon particles is 20- 500nm, carbon nanotubes, nano silicon particles, the addition mass ratio of BYK is 5-10: 80-100: 5-10.
Preferably, the mixing time in the step 3 is 0.5-6h.
Preferably, the thickness of the graphene layer in the step 4 is 0.2-1 μm, and the thickness of silicon/carbon nanotube layer is 1- 3μm。
Preferably, the drying temperature in the step 4 is 80-100 DEG C, and the time is not less than 5h.
Preferably, the step 4 is further included is put into glove box progress by the compound negative electrode of lithium ion battery of graphene/silicon The assembling of battery, electrolyte during assembling in electrolyte used is LiPF6、LiBF4, LiTFSI or LiFSI, in the electrolyte Solvent be dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate or acetonitrile, the electrolyte is in the electricity The concentration solved in liquid is 1mol/L.
The compound lithium ion battery of the graphene/silicon shows high capacity, stable cycle performance.
The compound lithium ion battery material of graphene/silicon obtained by the present invention combines graphene and silicon materials, carbon nanometer The various advantages of pipe, this laminar composite can be applied to lithium ion battery as negative material.So that gained battery has The characteristic such as capacity height, coulombic efficiency height, good cycling stability.
Compared with the prior art, the advantage of the invention is that:Graphene, silicon materials and carbon are received with relatively simple step Mitron is compound, has coated silicon materials well by the flexibility and layer structure special construction of graphene, has utilized carbon nanotubes Connection relation between electric conductivity and carbon nanotubes and graphene, constitutes effective point-line-surface structure, improves silicon materials and is filling Bulk effect in discharge process, improves the electric conductivity of silicon materials so that final electrode material specific capacity is high, coulombic efficiency High, good cycle, makes composite material obtain the specific capacity of higher and more preferable cycle performance.
Brief description of the drawings
Fig. 1 is the schematic diagram of the compound negative electrode of lithium ion battery of graphene/silicon.
Fig. 2 is the scanning electron microscope diagram of the compound negative electrode of lithium ion battery of graphene/silicon.
Fig. 3 is the Raman collection of illustrative plates of the compound negative electrode of lithium ion battery of graphene/silicon.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Scope.
Unless otherwise specified, each percentage composition of the invention is mass percentage.
Each raw material used in the present invention is commercial product.
Embodiment 1
A kind of compound negative electrode of lithium ion battery of graphene/silicon, including copper foil and the five-layer structure on copper foil, such as Shown in Fig. 1, the five-layer structure includes 3 layer graphene layers and 2 layers of silicon/carbon nanotube layer, graphene layer and silicon/carbon nanotubes The alternate setting of layer, the silicon/carbon nanotube layer contain nano silicon particles and carbon nanotubes, and carbon nanotubes is coated on silicon nanometer On grain.Graphene layer can prevent silicon materials from reuniting together in charge and discharge process, and carbon nanotubes is coated on nano silicon particles The cladding of the first order can be achieved, while improve the conductive capability of nano silicon particles;π-π stackings connect between carbon nanotubes and graphene Connect, also so that structure is even closer firm, can effectively limit volumetric expansion of the silicon in charging process.
The preparation method of the compound negative electrode of lithium ion battery of above-mentioned graphene/silicon is:
Step (1), thickness is placed in 10ml water for the graphene 0.5g of 1-10 atomic layer, addition 0.1gPAA is bonded Agent, shears the finely dispersed graphene slurry of 5h acquisitions in cutter;
Step (2), is immersed in acetum 5h by copper foil under room temperature, is then transferred in hydrogen peroxide and soaks 15h, Ran Houyong Deionized water washes clean, naturally dry, obtains the copper foil that surface was modified;
Step (3), 1g carbon nanotubes (1 μm, 5wt.%) pulp dilution is stirred, it is dispersed in 20ml water, Then add 1g nano silicon particles (200nm) to be uniformly dispersed, while add 0.05gBYK dispersants, persistently stir 0.5h, obtain The dispersion liquid of silicon/carbon nanotubes;
Step (4), the copper foil that surface was modified in (2) is coated to by graphene slurry scattered in (1) with coating machine On, 5h is dried at 100 DEG C, forms graphene layer, it is 0.2 μm to control thickness;
The dispersion liquid of silicon/carbon nanotubes scattered in (3), is sprayed onto the graphene of drying by step (5) with spray gun Surface, then 5h is dried at 100 DEG C, silicon/carbon nanotube layer is formed, it is 1 μm to control thickness, obtains drying pole piece;
Step (6), graphene slurry scattered in (1) is coated on drying pole piece with coating machine, is dried at 100 DEG C Dry 5h, forms graphene layer, and it is 0.2 μm to control thickness;The dispersion liquid of silicon/carbon nanotubes scattered in (3) is sprayed Rifle is sprayed onto the graphene surface of drying, then dries 5h at 100 DEG C, forms silicon/carbon nanotube layer, and it is 1 μm to control thickness;By (1) In scattered graphene slurry be coated to coating machine on silicon/carbon nanotube layer, 5h is dried at 100 DEG C, forms graphene Layer, it is 0.2 μm to control thickness, forms alternate layer structure, and additional size retains spare;
Step (7), rolling on roll squeezer is so that the compacted density of electrode material is 1g/cm3, section, is put into 80 DEG C of baking ovens Middle drying 6h, obtains the compound negative electrode of lithium ion battery of graphene/silicon, its scanning electron microscope diagram is as shown in Fig. 2, Raman figure Spectrum is as shown in figure 3, be put into the assembling that glove box carries out battery, and electrolyte during assembling in electrolyte used is LiPF6, electrolyte Concentration in the electrolyte is 1mol/L, and the solvent in the electrolyte is dimethyl carbonate, the carbon using mass ratio as 1: 1 Diethyl phthalate mixed liquor.
Embodiment 2
A kind of compound negative electrode of lithium ion battery of graphene/silicon, including copper foil and the five-layer structure on copper foil, such as Shown in Fig. 1, the five-layer structure includes 3 layer graphene layers and 2 layers of silicon/carbon nanotube layer, graphene layer and silicon/carbon nanotubes The alternate setting of layer, the silicon/carbon nanotube layer contain nano silicon particles and carbon nanotubes, and carbon nanotubes is coated on silicon nanometer On grain.Graphene layer can prevent silicon materials from reuniting together in charge and discharge process, and carbon nanotubes is coated on nano silicon particles The cladding of the first order can be achieved, while improve the conductive capability of nano silicon particles;π-π stackings connect between carbon nanotubes and graphene Connect, also so that structure is even closer firm, can effectively limit volumetric expansion of the silicon in charging process.
The preparation method of the compound negative electrode of lithium ion battery of above-mentioned graphene/silicon is:
Step (1), 1g thickness is placed in 10ml water for the graphene of 1-10 atomic layer, addition 0.5g PAA are bonded Agent, shears the finely dispersed graphene slurry of 5h acquisitions in cutter;
Step (2), is immersed in oxalic acid solution 10h by copper foil under room temperature, is then transferred in hydrogen peroxide and soaks 6h, Ran Houyong Deionized water washes clean, naturally dry, obtains the copper foil that surface was modified;
Step (3), 2g carbon nanotubes (10 μm, 5wt.%) pulp dilution is stirred, it is dispersed in 20ml water, Then add 0.8g nano silicon particles (200nm) to be uniformly dispersed, while add 0.1g BYK dispersants, persistently stir 6h, obtain The dispersion liquid of silicon/carbon nanotubes;
Step (4), the copper foil that surface was modified in (2) is coated to by graphene slurry scattered in (1) with coating machine On, 5h is dried at 80 DEG C, forms graphene layer, it is 1 μm to control thickness;
The dispersion liquid of silicon/carbon nanotubes scattered in (3), is sprayed onto the graphene of drying by step (5) with spray gun Surface, then 6h is dried at 80 DEG C, silicon/carbon nanotube layer is formed, it is 3 μm to control thickness, obtains drying pole piece;
Step (6), graphene slurry scattered in (1) is coated on drying pole piece with coating machine, is dried at 80 DEG C Dry 5h, forms graphene layer, and it is 1 μm to control thickness;By the dispersion liquid spray gun of silicon/carbon nanotubes scattered in (3) The graphene surface of drying is sprayed onto, then 6h is dried at 80 DEG C, forms silicon/carbon nanotube layer, it is 3 μm to control thickness;By in (1) points The graphene slurry dissipated is coated on silicon/carbon nanotube layer with coating machine, and 5h is dried at 80 DEG C, forms graphene layer, control Thickness processed is 1 μm, forms alternate layer structure, and additional size retains spare;
Step (7), the compacted density that rolling obtains electrode material on roll squeezer is 1g/cm3, section, is put into 80 DEG C of baking ovens Middle drying 6h, obtains the compound negative electrode of lithium ion battery of graphene/silicon, the assembling that glove box carries out battery is put into, in electrolyte Electrolyte be LiBF4, concentration of the electrolyte in the electrolyte is 1mol/L, and the solvent in the electrolyte is with quality Than the diethyl carbonate for 1: 1, propene carbonate mixed liquor.
Embodiment 3
A kind of compound negative electrode of lithium ion battery of graphene/silicon, including copper foil and the five-layer structure on copper foil, such as Shown in Fig. 1, the five-layer structure includes 3 layer graphene layers and 2 layers of silicon/carbon nanotube layer, graphene layer and silicon/carbon nanotubes The alternate setting of layer, the silicon/carbon nanotube layer contain nano silicon particles and carbon nanotubes, and carbon nanotubes is coated on silicon nanometer On grain.Graphene layer can prevent silicon materials from reuniting together in charge and discharge process, and carbon nanotubes is coated on nano silicon particles The cladding of the first order can be achieved, while improve the conductive capability of nano silicon particles;π-π stackings connect between carbon nanotubes and graphene Connect, also so that structure is even closer firm, can effectively limit volumetric expansion of the silicon in charging process.
The preparation method of the compound negative electrode of lithium ion battery of above-mentioned graphene/silicon is:
Step (1), 1g thickness is placed in 10ml water for the graphene of 1-10 atomic layer, addition 0.5g PAA are bonded Agent, shears the finely dispersed graphene slurry of 2h acquisitions in cutter;
Step (2), is immersed in citric acid solution 20h by copper foil under room temperature, is then transferred in hydrogen peroxide and soaks 15h, so After be washed with deionized clean, naturally dry, obtains the copper foil that surface was modified;
Step (3), 2g carbon nanotubes (5 μm, 5wt.%) pulp dilution is stirred, it is dispersed in 20ml water, Then add 0.8g nano silicon particles (20nm) to be uniformly dispersed, while add 0.1g BYK dispersants, persistently stir 6h, obtain The dispersion liquid of silicon/carbon nanotubes;
Step (4), the copper foil that surface was modified in (2) is coated to by graphene slurry scattered in (1) with coating machine On, 5h is dried at 90 DEG C, forms graphene layer, it is 1 μm to control thickness;
The dispersion liquid of silicon/carbon nanotubes scattered in (3), is sprayed onto the graphene of drying by step (5) with spray gun Surface, then 6h is dried at 90 DEG C, silicon/carbon nanotube layer is formed, it is 1 μm to control thickness, obtains drying pole piece;
Step (6), graphene slurry scattered in (1) is coated on drying pole piece with coating machine, is dried at 90 DEG C Dry 5h, forms graphene layer, and it is 1 μm to control thickness;By the dispersion liquid spray gun of silicon/carbon nanotubes scattered in (3) The graphene surface of drying is sprayed onto, then 6h is dried at 90 DEG C, forms silicon/carbon nanotube layer, it is 1 μm to control thickness;By in (1) points The graphene slurry dissipated is coated on silicon/carbon nanotube layer with coating machine, and 5h is dried at 90 DEG C, forms graphene layer, control Thickness processed is 1 μm, forms alternate layer structure, and additional size retains spare;
Step (7), the compacted density that rolling obtains electrode material on roll squeezer is 1g/cm3, section, is put into 80 DEG C of baking ovens Middle drying 6h, obtains the compound negative electrode of lithium ion battery of graphene/silicon, the assembling that glove box carries out battery is put into, in electrolyte Electrolyte be LiTFSI, concentration of the electrolyte in the electrolyte is 1mol/L, and the solvent in the electrolyte is with matter Amount is than the propene carbonate for 1: 1, ethylene carbonate mixed liquor.
Embodiment 4
A kind of compound negative electrode of lithium ion battery of graphene/silicon, including copper foil and the five-layer structure on copper foil, such as Shown in Fig. 1, the five-layer structure includes 3 layer graphene layers and 2 layers of silicon/carbon nanotube layer, graphene layer and silicon/carbon nanotubes The alternate setting of layer, the silicon/carbon nanotube layer contain nano silicon particles and carbon nanotubes, and carbon nanotubes is coated on silicon nanometer On grain.Graphene layer can prevent silicon materials from reuniting together in charge and discharge process, and carbon nanotubes is coated on nano silicon particles The cladding of the first order can be achieved, while improve the conductive capability of nano silicon particles;π-π stackings connect between carbon nanotubes and graphene Connect, also so that structure is even closer firm, can effectively limit volumetric expansion of the silicon in charging process.
The preparation method of the compound negative electrode of lithium ion battery of above-mentioned graphene/silicon is:
Step (1), 0.5g thickness is placed in 10ml water for the graphene of 1-10 atomic layer, addition 0.5g PAA are bonded Agent, shears the finely dispersed graphene slurry of 0.5h acquisitions in cutter;
Step (2), is immersed in oxalic acid solution 10h by copper foil under room temperature, is then transferred in hydrogen peroxide and soaks 6h, Ran Houyong Deionized water washes clean, naturally dry, obtains the copper foil that surface was modified;
Step (3), 2g carbon nanotubes (3 μm, 5wt.%) pulp dilution is stirred, it is dispersed in 20ml water, Then add 1g nano silicon particles (500nm) to be uniformly dispersed, while add 0.1g BYK dispersants, persistently stir 6h, obtain silicon/ The dispersion liquid of carbon nanotubes;
Step (4), the copper foil that surface was modified in (2) is coated to by graphene slurry scattered in (1) with coating machine On, 5h is dried at 80 DEG C, forms graphene layer, it is 1 μm to control thickness;
The dispersion liquid of silicon/carbon nanotubes scattered in (3), is sprayed onto the graphene of drying by step (5) with spray gun Surface, then 6h is dried at 80 DEG C, silicon/carbon nanotube layer is formed, it is 1 μm to control thickness, obtains drying pole piece;
Step (6), graphene slurry scattered in (1) is coated on drying pole piece with coating machine, is dried at 80 DEG C Dry 5h, forms graphene layer, and it is 1 μm to control thickness;By the dispersion liquid spray gun of silicon/carbon nanotubes scattered in (3) The graphene surface of drying is sprayed onto, then 6h is dried at 80 DEG C, forms silicon/carbon nanotube layer, it is 1 μm to control thickness;By in (1) points The graphene slurry dissipated is coated on silicon/carbon nanotube layer with coating machine, and 5h is dried at 80 DEG C, forms graphene layer, control Thickness processed is 1 μm, forms alternate layer structure, and additional size retains spare;
Step (7), the compacted density that rolling obtains electrode material on roll squeezer is 1g/cm3, section, is put into 80 DEG C of baking ovens Middle drying 6h, obtains the compound negative electrode of lithium ion battery of graphene/silicon, the assembling that glove box carries out battery is put into, in electrolyte Electrolyte be LiFSI, concentration of the electrolyte in the electrolyte is 1mol/L, and the solvent in the electrolyte is with quality Than the dimethyl carbonate for 1: 1, acetonitrile mixture.
Embodiment 5
A kind of compound negative electrode of lithium ion battery of graphene/silicon, including copper foil and the five-layer structure on copper foil, such as Shown in Fig. 1, the five-layer structure includes 3 layer graphene layers and 2 layers of silicon/carbon nanotube layer, graphene layer and silicon/carbon nanotubes The alternate setting of layer, the silicon/carbon nanotube layer contain nano silicon particles and carbon nanotubes, and carbon nanotubes is coated on silicon nanometer On grain.Graphene layer can prevent silicon materials from reuniting together in charge and discharge process, and carbon nanotubes is coated on nano silicon particles The cladding of the first order can be achieved, while improve the conductive capability of nano silicon particles;π-π stackings connect between carbon nanotubes and graphene Connect, also so that structure is even closer firm, can effectively limit volumetric expansion of the silicon in charging process.
The preparation method of the compound negative electrode of lithium ion battery of above-mentioned graphene/silicon is:
Step (1), 1g thickness is placed in 10ml water for the graphene of 1-10 atomic layer, addition 0.5g PAA are bonded Agent, shears the finely dispersed graphene slurry of 5h acquisitions in cutter;
Step (2), is immersed in oxalic acid solution 10h by copper foil under room temperature, is then transferred in hydrogen peroxide and soaks 15h, then It is washed with deionized totally, naturally dry, obtains the copper foil that surface was modified;
Step (3), 2g carbon nanotubes (3 μm, 5wt.%) pulp dilution is stirred, it is dispersed in 20ml water, Then add 1g nano silicon particles (500nm) to be uniformly dispersed, while add 0.1g BYK dispersants, persistently stir 6h, obtain silicon/ The dispersion liquid of carbon nanotubes;
Step (4), the copper foil that surface was modified in (2) is coated to by graphene slurry scattered in (1) with coating machine On, 5h is dried at 80 DEG C, forms graphene layer, it is 0.5 μm to control thickness;
The dispersion liquid of silicon/carbon nanotubes scattered in (3), is sprayed onto the graphene of drying by step (5) with spray gun Surface, then 6h is dried at 80 DEG C, silicon/carbon nanotube layer is formed, it is 1 μm to control thickness, obtains drying pole piece;
Step (6), graphene slurry scattered in (1) is coated on drying pole piece with coating machine, is dried at 80 DEG C Dry 5h, forms graphene layer, and it is 0.5 μm to control thickness;The dispersion liquid of silicon/carbon nanotubes scattered in (3) is sprayed Rifle is sprayed onto the graphene surface of drying, then dries 6h at 80 DEG C, forms silicon/carbon nanotube layer, and it is 1 μm to control thickness;By in (1) Scattered graphene slurry is coated on silicon/carbon nanotube layer with coating machine, and 5h is dried at 80 DEG C, forms graphene layer, It is 0.5 μm to control thickness, forms alternate layer structure, and additional size retains spare;
Step (7), the compacted density that rolling obtains electrode material on roll squeezer is 1g/cm3, section, is put into 80 DEG C of baking ovens Middle drying 6h, obtains the compound negative electrode of lithium ion battery of graphene/silicon, the assembling that glove box carries out battery is put into, in electrolyte Electrolyte be LiPF6, concentration of the electrolyte in the electrolyte is 1mol/L, and the solvent in the electrolyte is with quality Than the ethylene carbonate or acetonitrile mixture for 1: 1.
Table 1 carries out the energy storage that the circle of charge-discharge test the 2nd and the 301st circle obtain by embodiment 1-5 under 0.2C electric currents to be held Amount and capacity retention ratio.
Embodiment Specific capacity (the 2nd circle) Specific capacity (100 circle) 100 circulation volume conservation rates
1 2543mAh/g 2111mAh/g 83%
2 2724mAh/g 2138mAh/g 78.5%
3 2436mAh/g 2073mAh/g 85.1%
4 2559mAh/g 2062mAh/g 80.6%
5 2678mAh/g 2180mAh/g 81.4%
It can be seen from upper table 1 using the capacity that is obtained of graphene/silicon complex layered materials prepared by this method compared with Height, all in more than 2000mAh/g, the capacity retention ratio all 80% or so particularly after the circle of circulation 100, up to 85.1% with On, cyclical stability is preferable.

Claims (10)

1. the compound negative electrode of lithium ion battery of a kind of graphene/silicon, it is characterised in that more including copper foil and on copper foil Rotating fields, the sandwich construction include the graphene layer and silicon/carbon nanotube layer of alternate setting, the silicon/carbon nanotubes Layer contains nano silicon particles and carbon nanotubes, and carbon nanotubes is coated on nano silicon particles;Its preparation method includes:Step 1:Will Graphene is placed in water, and is added PAA binding agents, is sheared in cutter, obtain finely dispersed graphene slurry;Step 2:Often Copper foil is immersed in organic acid or hydrogen peroxide under temperature, or copper foil is immersed in organic acid under room temperature, is then transferred to dioxygen Soak, be then washed with deionized totally, naturally dry, obtains the copper foil that surface was modified in water;Step 3:By carbon nanometer Pipe pulp dilution stirs, and it is dispersed in water, then adds nano silicon particles, be uniformly dispersed, while adds BYK and disperse Agent, stirring, obtains the dispersion liquid of silicon/carbon nanotubes;Step 4:Graphene slurry obtained by step 1 is coated to table with coating machine On the copper foil that face was modified, drying, forms graphene layer;By the dispersion liquid spray gun of silicon/carbon nanotubes of gained in step 3 The graphene surface of drying is sprayed onto, then is dried, forms silicon/carbon nanotube layer, obtains drying pole piece;Step 5:By obtained by step 1 Graphene slurry be coated on the drying pole piece obtained by step 4, then in spraying process 3 silicon/carbon nanotubes of gained point Dispersion liquid, is coated with the graphene slurry obtained by step 1, is rolled on roll squeezer, cut into slices, drying, obtains the compound lithium of graphene/silicon Ion battery anode.
2. the preparation method of the compound negative electrode of lithium ion battery of graphene/silicon described in claim 1, it is characterised in that including:
Step 1:Graphene is placed in water, PAA binding agents is added, is sheared in cutter, obtain finely dispersed graphene Slurry;
Step 2:Copper foil is immersed in organic acid or hydrogen peroxide under room temperature, or copper foil is immersed in organic acid under room temperature, and After be transferred in hydrogen peroxide and soak, be then washed with deionized clean, naturally dry, obtains the copper foil that surface was modified;
Step 3:Carbon nano tube paste is diluted and is stirred, it is dispersed in water, then adds nano silicon particles, is disperseed equal It is even, while BYK dispersants are added, stir, obtain the dispersion liquid of silicon/carbon nanotubes;
Step 4:Graphene slurry obtained by step 1 is coated on the copper foil that surface was modified with coating machine, drying, forms stone Black alkene layer;The dispersion liquid of silicon/carbon nanotubes of gained in step 3 is sprayed onto to the graphene surface of drying with spray gun, then is dried, Silicon/carbon nanotube layer is formed, obtains drying pole piece;
Step 5:Graphene slurry obtained by step 1 is coated on the drying pole piece obtained by step 4, then in spraying process 3 The dispersion liquid of silicon/carbon nanotubes of gained, is coated with the graphene slurry obtained by step 1, is rolled on roll squeezer, cut into slices, drying, Obtain the compound negative electrode of lithium ion battery of graphene/silicon.
3. the preparation method of the compound negative electrode of lithium ion battery of graphene/silicon as claimed in claim 2, it is characterised in that institute The thickness for the graphene stated is 1-10 atomic layer.
4. the preparation method of the compound negative electrode of lithium ion battery of graphene/silicon as claimed in claim 2, it is characterised in that institute The adding proportion of PAA in the step 1 stated is 1-5wt.%, and the additive amount of graphene is 5-10wt.%.
5. the preparation method of the compound negative electrode of lithium ion battery of graphene/silicon as claimed in claim 2, it is characterised in that institute Shear time in the step 1 stated is 0.5-5h.
6. the preparation method of the compound negative electrode of lithium ion battery of graphene/silicon as claimed in claim 2, it is characterised in that institute Organic acid in the step 2 stated is acetic acid, oxalic acid or citric acid, and soaking time 5-20h, the soaking time of hydrogen peroxide is 6- 15h。
7. the preparation method of the compound negative electrode of lithium ion battery of graphene/silicon as claimed in claim 2, it is characterised in that institute The size of carbon nanotubes in the step 3 stated is 1-10 μm, and the sizes of nano silicon particles is 20-500nm, carbon nanotubes, and silicon is received Rice grain, the addition mass ratio of BYK is 5-10: 80-100: 5-10.
8. the preparation method of the compound negative electrode of lithium ion battery of graphene/silicon as claimed in claim 2, it is characterised in that institute The thickness of graphene layer in the step 4 stated is 0.2-1 μm, and the thickness of silicon/carbon nanotube layer is 1-3 μm.
9. the preparation method of the compound negative electrode of lithium ion battery of graphene/silicon as claimed in claim 2, it is characterised in that institute Drying temperature in the step 4 stated is 80-100 DEG C, and the time is not less than 5h.
10. the preparation method of the compound negative electrode of lithium ion battery of graphene/silicon as claimed in claim 2, it is characterised in that institute The step 4 stated further includes the assembling for being put into glove box and carry out battery the compound negative electrode of lithium ion battery of graphene/silicon, during assembling Electrolyte in electrolyte used is LiPF6、LiBF4, LiTFSI or LiFSI, the solvent in the electrolyte is carbonic acid diformazan Ester, diethyl carbonate, propene carbonate, ethylene carbonate or acetonitrile, concentration of the electrolyte in the electrolyte are 1mol/L。
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CN109888194A (en) * 2019-04-03 2019-06-14 山东星火科学技术研究院 The preparation method of graphene/silicon/carbon composite sandwich electrode
CN111596008A (en) * 2020-05-14 2020-08-28 上海超碳石墨烯产业技术有限公司 Quantitative analysis method for components of graphene mixture
CN113394386A (en) * 2021-06-09 2021-09-14 江苏载驰科技股份有限公司 Silicon-carbon negative electrode material and preparation method thereof
CN114335477A (en) * 2021-12-31 2022-04-12 珠海冠宇电池股份有限公司 Silicon-based material and battery containing same
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Application publication date: 20180413