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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- graphene
- silicon
- ion battery
- lithium ion
- carbon nanotubes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- 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
- H01M4/38—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
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
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。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711069504.9A CN107910513A (en) | 2017-11-03 | 2017-11-03 | Compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711069504.9A CN107910513A (en) | 2017-11-03 | 2017-11-03 | Compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107910513A true CN107910513A (en) | 2018-04-13 |
Family
ID=61842531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711069504.9A Pending CN107910513A (en) | 2017-11-03 | 2017-11-03 | Compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107910513A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108807842A (en) * | 2018-07-04 | 2018-11-13 | 西南石油大学 | Silicon@carbon-graphite alkenyl flexible composites and preparation method thereof, lithium battery |
| CN108987666A (en) * | 2018-06-29 | 2018-12-11 | 成都三乙医疗科技有限公司 | A kind of battery electrode piece preparation method |
| CN109596597A (en) * | 2018-12-28 | 2019-04-09 | 中兴高能技术有限责任公司 | A kind of method of evaluating graphite surface coating modification |
| 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 |
| WO2020103965A1 (en) * | 2018-11-21 | 2020-05-28 | Neutrino Deutschland Gmbh | Film made of metal or a metal alloy |
| 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 |
| CN114447284A (en) * | 2022-01-13 | 2022-05-06 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
| CN115084479A (en) * | 2022-07-05 | 2022-09-20 | 浙江吉利控股集团有限公司 | Lithium battery cathode composite material and preparation method thereof |
| CN117205795A (en) * | 2023-10-07 | 2023-12-12 | 博路天成新能源科技有限公司 | Homogeneous mixing process for anisotropic micro-nano particles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269515A (en) * | 2014-09-19 | 2015-01-07 | 清华大学深圳研究生院 | Negative electrode piece of lithium ion battery, preparation method of negative electrode piece and lithium ion battery |
| CN104617280A (en) * | 2015-01-28 | 2015-05-13 | 哈尔滨工业大学 | Adhesive-free graphene/silicon electrode for lithium ion battery and preparation method thereof |
| CN106505200A (en) * | 2016-12-27 | 2017-03-15 | 电子科技大学 | Carbon nano tube/graphene/silicon composite lithium ion battery negative material and preparation method thereof |
-
2017
- 2017-11-03 CN CN201711069504.9A patent/CN107910513A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269515A (en) * | 2014-09-19 | 2015-01-07 | 清华大学深圳研究生院 | Negative electrode piece of lithium ion battery, preparation method of negative electrode piece and lithium ion battery |
| CN104617280A (en) * | 2015-01-28 | 2015-05-13 | 哈尔滨工业大学 | Adhesive-free graphene/silicon electrode for lithium ion battery and preparation method thereof |
| CN106505200A (en) * | 2016-12-27 | 2017-03-15 | 电子科技大学 | Carbon nano tube/graphene/silicon composite lithium ion battery negative material and preparation method thereof |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987666A (en) * | 2018-06-29 | 2018-12-11 | 成都三乙医疗科技有限公司 | A kind of battery electrode piece preparation method |
| CN108807842B (en) * | 2018-07-04 | 2020-12-04 | 西南石油大学 | Silicon @ carbon-graphene-based flexible composite material, preparation method thereof and lithium battery |
| CN108807842A (en) * | 2018-07-04 | 2018-11-13 | 西南石油大学 | Silicon@carbon-graphite alkenyl flexible composites and preparation method thereof, lithium battery |
| US20210383945A1 (en) * | 2018-11-21 | 2021-12-09 | Neutrino Deutschland Gmbh | Film made of metal or a metal alloy |
| WO2020103965A1 (en) * | 2018-11-21 | 2020-05-28 | Neutrino Deutschland Gmbh | Film made of metal or a metal alloy |
| CN113167911A (en) * | 2018-11-21 | 2021-07-23 | 德国中微子有限公司 | Foil made of metal or metal alloy |
| CN109596597A (en) * | 2018-12-28 | 2019-04-09 | 中兴高能技术有限责任公司 | A kind of method of evaluating graphite surface coating modification |
| 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 |
| CN114335477B (en) * | 2021-12-31 | 2024-04-26 | 珠海冠宇电池股份有限公司 | Silicon-based material and battery containing same |
| CN114447284A (en) * | 2022-01-13 | 2022-05-06 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
| CN114447284B (en) * | 2022-01-13 | 2024-04-05 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
| CN115084479A (en) * | 2022-07-05 | 2022-09-20 | 浙江吉利控股集团有限公司 | Lithium battery cathode composite material and preparation method thereof |
| CN117205795A (en) * | 2023-10-07 | 2023-12-12 | 博路天成新能源科技有限公司 | Homogeneous mixing process for anisotropic micro-nano particles |
| CN117205795B (en) * | 2023-10-07 | 2024-03-12 | 博路天成新能源科技有限公司 | Homogeneous mixing process for anisotropic micro-nano particles |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107910513A (en) | Compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof | |
| CN100492721C (en) | Lithium ion battery pole piece with high multiplying power and production thereof | |
| CN103682327B (en) | Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel | |
| CN105576185A (en) | Silicon-carbon composite cathode pole piece of lithium ion battery and preparation method of silicon-carbon composite cathode pole piece | |
| CN103400964B (en) | A kind of preparation method of iron phosphate lithium electrode | |
| CN106532045B (en) | Graphite negative material of lithium ion battery and preparation method thereof | |
| CN105047427B (en) | Ultracapacitor combination electrode material and preparation method thereof and ultracapacitor | |
| CN103199258A (en) | Cathode material of lithium ion battery, preparation method of cathode, and lithium ion battery | |
| CN106207177B (en) | Silicon-carbon cathode material containing artificial SEI layers of high-volume and capacity ratio and cycle performance | |
| CN105024044A (en) | Preparation method of high-capacity silica-powder-doped lithium battery anode slurry | |
| CN109616645B (en) | Flexible silicon negative electrode material for lithium ion battery and preparation method thereof | |
| CN107611411A (en) | A kind of preparation method and application of the classifying porous nitrogen-doped carbon bag silicon composite of three-dimensional | |
| CN105206790A (en) | Preparation method for lithium battery anode slurry doped with tin powder | |
| CN108682813A (en) | A kind of preparation method and application of Si-C composite material | |
| Jin et al. | Pomegranate-like Li3VO4/3D graphene networks nanocomposite as lithium ion battery anode with long cycle life and high-rate capability | |
| CN114400309A (en) | Sodium ion positive electrode material and preparation method and application thereof | |
| CN110078053A (en) | A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating | |
| CN103137942B (en) | The preparation method of a kind of ferric phosphate lithium cell collector and positive plate | |
| CN102969509A (en) | Preparation method of lithium ion battery silicon carbon composite material | |
| CN103682277B (en) | Hollow porous nickel oxide composite material of N doping carbon-coating parcel and preparation method thereof | |
| US20220052342A1 (en) | Prelithiated negative electrode, preparation method thereof, and lithium ion battery and supercapacitor comprising the same | |
| CN104577126A (en) | Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode | |
| CN115513415A (en) | Low cost positive prefabricated lithium and high specific energy electrode, manufacturing method and quasi-solid battery | |
| CN109428079A (en) | A kind of preparation method of lithium sulfur battery anode material | |
| Han et al. | Hollow tremella-like graphene sphere/SnO2 composite for high performance Li-ion battery anodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180413 |