A kind of preparation method of negative electrode of lithium ion battery flexible compound nano material
Technical field
The invention belongs to novel lithium storage materials fields, it particularly relates to a kind of negative electrode of lithium ion battery flexible compound
The preparation method of nano material.
Background technique
As increasingly shortage and environmental problem continuously emerge traditional energy, people's environmental consciousness is increasingly enhanced, and exploitation is new
The energy becomes the task of top priority using renewable energy with reasonable.In recent years, wind energy, solar energy and tide energy etc. it is environmentally friendly,
Green regenerative energy sources receive significant attention, but there are insoluble difficulties for the continuity stable supplying of these energy, seriously
Limit their effective use.It is latent that the lithium ion battery of currently referred to as " Green Chemistry power supply " has become most development
One of energy storage mode of power.Lithium ion battery negative material is most important to the capacity and cycle life of battery.Commercialization at present
The cathode of lithium ion battery still mainly uses graphite type material at present, such material has low chemical potential and preferable circulation
Performance, but its actual capacity has basically reached theoretical capacity (372mAh/g), constrains lithium ion battery in New Energy Industry
Application.
Tin abundance on earth, because Theoretical Mass specific capacity with higher (Sn:992 mAh/g) becomes lithium ion
One of the hot spot negative electrode material of battery research.But tin electrode causes the volume of electrode acutely to become during charge and discharge cycles
Change, causes tin electrode active constituent to reunite or fall off, and then electrode cycle life and capacity is made sharply to fail.By active metal tin
Compound with carbon material is the main path for solving the problems, such as this.Currently, there are many complex method of metallic tin and carbon material, but it is big
The electric conductivity of multi-cathode material, capacity and cycle life is relatively low and electrode production process in need to be added conductive agent, binder
The electrode of material is increased, and preparation process is cumbersome.
Summary of the invention
The purpose of the present invention is to provide a kind of negative electrode of lithium ion battery preparation methods of flexible compound nano material, should
The composite nano materials of method preparation have good electric conductivity, capacity and cycle life.
To achieve the above object, the embodiment of the present invention uses a kind of negative electrode of lithium ion battery flexible compound nano material
Preparation method, this method comprises:
Step 10) prepares carbon nano tube dispersion liquid: by Dispersion of Solute Matter in methanol, ethyl alcohol, acetone, N,N-dimethylformamide
Or n,N-dimethylacetamide solvent, wherein the ratio of solute and solvent is 1mg:2 ~ 10ml;The solute is single wall carbon
The mixture of nanotube, multi-walled carbon nanotube or single-walled carbon nanotube and multi-walled carbon nanotube composition;
Step 20 prepares carbon nanotube paper: using electrostatic painting process, prepares carbon nanotube paper;Wherein, spray coating liquor is step
The carbon nano tube dispersion liquid of rapid 10) preparation, reception device is cylindric rotary drum, and rotary drum is connected with vacuum pump;
Step 30) prepares the carbon nanotube paper of nano nickel particles load: polyacrylonitrile and nickel salt being mixed, presoma is made
Solution, wherein the mass ratio of polyacrylonitrile and nickel salt is 1:0.1 ~ 0.5;In precursor solution, the mass fraction of polyacrylonitrile is
2-6%;
Using electrostatic painting process, precursor solution is sprayed on the carbon nanotube paper of step 20 preparation, forms spraying
There is the carbon nanotube paper of nickel salt;By the carbon nanotube paper for being coated with nickel salt with 1 ~ 2 DEG C/min be warming up to 250 ~ 280 DEG C keep 1 ~
3h, then 600 ~ 800 DEG C of 2 ~ 4h of holding are warming up to 5 ~ 10 DEG C/min, obtain the carbon nanotube paper of nano nickel particles load;
Step 40) prepares carbon nanotube paper, tin composite nano materials: by the nano nickel particles load of step 30) preparation
Carbon nanotube paper is placed in the tin-salt solution that molar concentration is 20 ~ 100mmol/L, temperature is 25 ~ 90 DEG C, is kept 2 ~ 12h, is obtained
Carbon nanotube paper, tin composite nano materials;
Step 50) prepares carbon nanotube paper, tin, graphene quantum dot composite nano materials: electrostatic painting process is used, it will
Spray coating liquor is sprayed on the carbon nanotube paper of step 40) preparation, tin composite nano materials surface, and dry, be made carbon nanotube paper,
Tin, graphene quantum dot composite nano materials;The spray coating liquor is the graphene quantum that mass concentration is 0.5 ~ 1.2 mg/mL
Point solution.
As preference, in the step 20), using the parameter of electrostatic painting process are as follows: voltage is 10 ~ 40 kV, stream
Speed is 0.5 ~ 5.0 mL/h, and the distance between spinning head and reception device are 10 ~ 40 cm, and spray time is 20 ~ 60min.
As preference, in the step 20), drum surface is made of the copper mesh of 200 ~ 500 mesh, and rotary drum revolving speed is
100 ~ 600 turns/min.
As preference, in the step 30), using the parameter of electrostatic painting process are as follows: voltage is 10 ~ 40 kV, stream
Speed is 0.5 ~ 4.0 mL/h, and the distance between spinning head and reception device are 10 ~ 30 cm, and spray time is 15 ~ 60min.
As preference, in the step 30), nickel salt is nickel chloride, nickel sulfate or nickel acetate.
As preference, in the step 40), tin-salt solution is will be in stannous chloride, stannous sulfate, stannous acetate
It is a kind of or any two are dissolved in water or ethanol solution, tin-salt solution is made.
As preference, in the step 40), the structure of carbon nanotube paper, tin composite nano materials are as follows: carbon nanotube
Area load hollow nanospheres particle;The hollow nanospheres particle is made of Sn.
As preference, in the step 50), using the parameter of electrostatic painting process are as follows: voltage is 10 ~ 30 kV, stream
Speed is 0.5 ~ 2.0 mL/h, and the distance between spinning head and reception device are 10 ~ 30 cm, and the time is 30 ~ 60min.
As preference, carbon nanotube paper, tin, graphene quantum dot composite nano materials made of the step 50)
In, the area load hollow nanospheres particle of carbon nanotube, the hollow nanospheres particle is made of Sn;Hollow nanospheres
The area load graphene quantum dot layer not covered by hollow nanospheres particle in grain surface and carbon nanotube paper.
As preference, in the step 50), carbon nanotube, tin, graphene quantum dot composite nano materials thickness
It is 20 ~ 50 μm.
Compared with prior art, carbon nanotube paper, the tin, graphene quantum dot composite Nano material of preparation of the embodiment of the present invention
Material has preferable flexibility, can use directly as negative electrode material, and preparation process is not necessarily to conductive agent and binder.The present invention
In, the CNTs orientations of carbon nanotube paper are constituted, the electric conductivity of material can be improved.In addition, GQDs is coated on CNTs and Sn
Surface can further improve electric conductivity.The composite nano materials capacity with higher of preparation of the embodiment of the present invention and circulation longevity
Life.CNTs, Sn and GQDs have preferable storage lithium performance, therefore capacity with higher.During hollow tin nanoparticles have
Hollow structure, in process of intercalation, when expansion can inwardly expansion and outward expansion simultaneously, thus hollow tin nanoparticles electrode is relatively swollen
Swollen volume will not sharply become larger.In addition, Sn particle outer layer also coats one layer of GQDs, these can buffer the volume expansion of Sn,
Improve the cyclical stability and cycle life of material.
Specific embodiment
The technical solution of the embodiment of the present invention is described in detail below.
The embodiment of the present invention provides a kind of preparation method of negative electrode of lithium ion battery flexible compound nano material, this method
Include:
Step 10) prepares carbon nanotube (text in referred to as: CNTs) dispersion liquid: by Dispersion of Solute Matter in methanol, ethyl alcohol, acetone,
N,N-Dimethylformamide or n,N-dimethylacetamide solvent, wherein the ratio of solute and solvent is 1mg:2 ~ 10ml;Institute
The solute stated is the mixing that single-walled carbon nanotube, multi-walled carbon nanotube or single-walled carbon nanotube and multi-walled carbon nanotube form
Object.
Wherein, the composition of solute single-walled carbon nanotube, multi-walled carbon nanotube or both, for example, single-walled carbon nanotube
Solute is formed according to mass ratio 1:1 with multi-walled carbon nanotube.Solvent be methanol, ethyl alcohol, acetone, N,N-dimethylformamide or
DMAC N,N' dimethyl acetamide.Solute is dissolved in solvent, and carbon nano tube dispersion liquid is made.
Step 20 prepares carbon nanotube paper: using electrostatic painting process, prepares carbon nanotube paper;Wherein, spray coating liquor is step
The carbon nano tube dispersion liquid of rapid 10) preparation, reception device is cylindric rotary drum, and rotary drum is connected with vacuum pump.
Wherein, using the parameter of electrostatic painting process are as follows: voltage is 10 ~ 40 kV, and flow velocity is 0.5 ~ 5.0 mL/h, spinneret
The distance between head and reception device are 10 ~ 40 cm, and spray time is 20 ~ 60min.
Using cylindric rotary drum, it is therefore an objective to make carbon nano tube oriented arranging, improve the electric conductivity of material.Rotary drum and vacuum pump
The purpose being connected: accelerate the volatilization of CNTs surface solvent, improve the structural stability of carbon nanotube paper.Preferably, rotary drum
Surface is made of the copper mesh of 200 ~ 500 mesh, and rotary drum revolving speed is 100 ~ 600 turns/min.Use copper mesh as reception device, works as copper mesh
When being connected with vacuum pump, solvent can be recycled quickly, improve the binding strength between carbon nanotube.Rotary drum keeps certain revolving speed, can
Keep carbon nanotube a degree of according to arrangement is turned to, improves its electric conductivity.
The published carbon nanotube paper technology for preparing mainly uses suction filtration method, and the arrangement of carbon nanotube has unordered
Property, electric conductivity is poor.The present embodiment prepares carbon nanotube paper using electrostatic painting process, and the degree of orientation of carbon nanotube can be improved,
And then improve electric conductivity.Copper mesh is connected as receiving device and with vacuum pump, and binding strength between carbon nanotube can be improved simultaneously
It improves efficiency.Copper mesh is connected with vacuum pump, at negative pressure, dual work of the carbon nanotube by electric field force and negative pressure inside copper mesh rotary drum
It is even closer with carbon nanotube can be made to combine.Most solvents can be recycled by vacuum pump, improve efficiency.
Step 30) prepares the carbon nanotube paper of nano nickel particles load: polyacrylonitrile (abbreviation PAN in text) and nickel salt is mixed
It closes, precursor solution is made, wherein the mass ratio of PAN and nickel salt is 1:0.1 ~ 0.5;In precursor solution, the quality point of PAN
Number is 2-6%.Preferably, nickel salt is nickel chloride, nickel sulfate or nickel acetate.
Using electrostatic painting process, precursor solution is sprayed on the carbon nanotube paper of step 20 preparation, forms spraying
There is the carbon nanotube paper of nickel salt;By the carbon nanotube paper for being coated with nickel salt with 1 ~ 2 DEG C/min be warming up to 250 ~ 280 DEG C keep 1 ~
3h, then 600 ~ 800 DEG C of 2 ~ 4h of holding are warming up to 5 ~ 10 DEG C/min, obtain the carbon nanotube paper of nano nickel particles load.
Wherein, preferably, using electrostatic painting process parameter are as follows: voltage be 10 ~ 40 kV, flow velocity be 0.5 ~ 4.0
ML/h, the distance between spinning head and reception device are 10 ~ 30 cm, and spray time is 15 ~ 60min.
In step 30), PAN is mixed with nickel salt sprays to carbon nanotube paper surface, and through high-temperature process, nickel is decomposed into the oxygen of nickel
Compound, PAN is converted into carbon, and nickel oxide is reduced to elemental nickel nanometer ball particle by carbon.
Step 40) prepares carbon nanotube paper, tin composite nano materials: by the nano nickel particles load of step 30) preparation
Carbon nanotube paper is placed in the tin-salt solution that molar concentration is 20 ~ 100mmol/L, temperature is 25 ~ 90 DEG C, is kept 2 ~ 12h, is obtained
Carbon nanotube paper, tin composite nano materials;
Wherein, tin-salt solution be by one of stannous chloride, stannous sulfate, stannous acetate or any two be dissolved in water or second
In alcoholic solution, tin-salt solution is made.In the step 40), carbon nanotube paper, tin composite nano materials structure be: carbon is received
Contain hollow nanospheres particle in the cavity of mitron paper, the volume of nanometer ball particle is less than the cavity volume of carbon nanotube paper;Institute
The nanometer ball particle stated is made of Sn.
Hollow tin nanoparticles are converted by solid nickel nanometer ball particle by step 40).In tin-salt solution, elemental nickel
It is oxidized to Ni2+And enter in solution, corresponding Sn2+It is reduced into the surface that nano nickel particles are deposited directly to after simple substance tin.Often
A nickle atom generates two electronics, and since metal itself is conductive, the electrons of generation are transferred to the surface of nano particle,
In nano grain surface Sn2+It is reduced, and gradually forms tin shell in nickel surface, eventually form hollow structure.
Step 50) prepares carbon nanotube paper, tin, graphene quantum dot composite nano materials: electrostatic painting process is used, it will
Spray coating liquor is sprayed on the carbon nanotube paper of step 40) preparation, tin composite nano materials surface, and dry, be made carbon nanotube paper,
Tin, graphene quantum dot composite nano materials;The spray coating liquor is the graphene quantum that mass concentration is 0.5 ~ 1.2 mg/mL
Point is (in text referred to as: GQDs) solution.
Wherein, preferably, using electrostatic painting process parameter are as follows: voltage be 10 ~ 30 kV, flow velocity be 0.5 ~ 2.0
ML/h, the distance between spinning head and reception device are 10 ~ 30 cm, and the time is 30 ~ 60min.Carbon nanometer made of step 50)
Pipe paper, tin, in graphene quantum dot composite nano materials, the area load hollow nanospheres particle of carbon nanotube, it is described in
Empty nanometer ball particle is made of Sn;It is not covered by hollow nanospheres particle in hollow nanospheres particle surface and carbon nanotube paper
Area load graphene quantum dot layer.Preferably, the thickness of carbon nanotube, tin, graphene quantum dot composite nano materials
It is 20 ~ 50 μm.
Step 50), during graphene quantum dot layer is loaded to carbon nanotube paper, tin composite nano materials surface,
Electrostatic painting process stable loads to sijna rice ball particle and carbon nanotube paper surface for graphene quantum dot is more uniform.Stone
Black alkene quantum dot loads to sijna rice ball particle and carbon nano tube surface, not only can further improve the electric conductivity of material, but also
Improve the capacity of material.Electric conductivity and cyclical stability based on grapheme material, graphene quantum dot, which plays, can slow down charge and discharge
In electric cyclic process, the crushing and reunion of tin, to improve the cycle performance of electrode.
Carbon nanotube has preferable electric conductivity, flexibility, thus be made can be used as after carbon nanotube paper electrode from
Backing material, and there is preferable flexibility, it can be processed into shape needed for electrode, without adding conductive agent and binder.Xi Ben
Body has high theoretical specific capacity, and in the present embodiment, and tin is in hollow nanospheres body particle, can alleviate charge and discharge to a certain extent
In electric process, because volume expansion causes capacity and cyclical stability to decline.Compared with graphene, graphene quantum spot size is more
It is small, stable hollow nanospheres body particle and carbon nano tube surface can be loaded to more uniform.Graphene quantum dot loads to
Hollow nanospheres body particle and carbon nanotube paper surface not only can be further improved the electric conductivity of material but also material can be improved
The capacity of material.Electric conductivity and cyclical stability based on grapheme material, graphene quantum dot, which plays, can slow down charge and discharge cycles
The crushing and reunion of tin in the process, to improve the cycle performance of electrode.
Below by test, carbon nanotube paper, the tin, graphene quantum dot composite Nano of preparation of the embodiment of the present invention are verified
Material has excellent properties.Wherein, the electric conductivity of material is tested using four probe method.
It is 15mm that carbon nanotube paper, tin, graphene quantum dot composite nano materials prepared by each embodiment, which are cut into diameter,
Circular electrode be the diaphragm Celgrad2400 to electrode with metal lithium sheet in the glove box full of nitrogen, electrolyte is
Molar concentration be 1mol/L lithium hexafluoro phosphate/ethylene carbonate-methyl ethyl carbonate-dimethyl carbonate (text in abbreviation LiPF6/
EC-EMC-DMC) solution, the volume ratio between LiPF6/EC-EMC-DMC is 1:1:1, is assembled into button cell, and stand 7h.
Constant current charge-discharge performance test is carried out with 0.5C on charge-discharge test instrument, charging/discharging voltage range is 0.01 ~ 1.5V, and electric current is close
Degree is 50mAg-1。
The capacity and cyclical stability (cycle life) of material are evaluated by constant current charge-discharge performance test.The circulation of material
Stability or cycle life indicated by capacity retention ratio after 100 circulations, the stable circulation of the bigger material of capacity retention ratio
Property is better.
Subjects:
Comparative example 1
Using carbon nanotube paper as negative electrode of lithium ion battery.
Comparative example 2
Using material made of hollow sijna rice spherical particles as negative electrode of lithium ion battery.
Embodiment 1
Using carbon nanotube paper, tin, graphene quantum dot composite nano materials as negative electrode of lithium ion battery.This is compound to receive
Rice material the preparation method is as follows:
Step 10) prepares carbon nanotube (CNTs) dispersion liquid: dispersing methanol solvate for single-walled carbon nanotube, wherein molten
Matter and the ratio of solvent are 1mg:2ml;
Step 20 prepares carbon nanotube paper: using electrostatic painting process, prepares carbon nanotube paper.Wherein, spray coating liquor is step
The carbon nano tube dispersion liquid of rapid 10) preparation.Using the parameter of electrostatic painting process are as follows: voltage is 40 kV, flow velocity 5mL/h, spray
Silk the distance between head and reception device are 30 cm, spray time 30min.Reception device is cylindric rotary drum, drum surface
It is made of the copper mesh of 260 mesh, rotary drum revolving speed is 400 turns/min.Rotary drum is connected with vacuum pump.
Step 30) prepares the carbon nanotube paper of nano nickel particles load: PAN and nickel salt mixed, precursor solution is made,
Wherein, the mass ratio of PAN and nickel salt is 1:0.1;In precursor solution, the mass fraction of PAN is 2%.Nickel salt is nickel chloride.
Using electrostatic painting process, precursor solution is sprayed on the carbon nanotube paper of step 20 preparation, forms spraying
There is the carbon nanotube paper of nickel salt.Using the parameter of electrostatic painting process are as follows: voltage 20kV, flow velocity 2mL/h and connect spinning head
The distance between receiving apparatus is 30 cm, spray time 20min.By the carbon nanotube paper for being coated with nickel salt with 2 DEG C/min heating
800 DEG C of holding 4h are warming up to 250 DEG C of holding 3h, then with 10 DEG C/min, obtain the carbon nanotube paper of nano nickel particles load.
Step 40) prepares carbon nanotube paper, tin composite nano materials: by the nano nickel particles load of step 30) preparation
Carbon nanotube paper is placed in the tin-salt solution that molar concentration is 20mmol/L, temperature is 70 DEG C, is kept 5h, is obtained carbon nanotube
Paper, tin composite nano materials.Wherein, tin-salt solution is that stannous chloride is dissolved in water to be made.
Step 50) prepares carbon nanotube paper, tin, graphene quantum dot composite nano materials: electrostatic painting process is used, it will
Spray coating liquor is sprayed on the carbon nanotube paper of step 40) preparation, tin composite nano materials surface, and dry, be made carbon nanotube paper,
Tin, graphene quantum dot composite nano materials.Using the parameter of electrostatic painting process are as follows: voltage be 20 kV, flow velocity 1mL/h,
The distance between spinning head and reception device are 25cm, time 45min.Spray coating liquor is the stone that mass concentration is 0.5 mg/mL
Black alkene quantum dot solution.
Manufactured carbon nanotube paper, tin, in graphene quantum dot composite nano materials, manufactured carbon nanotube paper, tin, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres particle of carbon nanotube, the hollow nanospheres
Grain is made of Sn;The area load not covered by hollow nanospheres particle in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.Carbon nanotube, tin, graphene quantum dot composite nano materials with a thickness of 20 μm.
Embodiment 2
Using carbon nanotube paper, tin, graphene quantum dot composite nano materials as negative electrode of lithium ion battery.This is compound to receive
Rice material the preparation method is as follows:
Step 10) prepares carbon nanotube (CNTs) dispersion liquid: by multi-walled carbon nanotube Dispersion of Solute Matter in alcohol solvent,
In, the ratio of solute and solvent is 1mg:5ml;
Step 20 prepares carbon nanotube paper: using electrostatic painting process, prepares carbon nanotube paper.Wherein, spray coating liquor is step
The carbon nano tube dispersion liquid of rapid 10) preparation.Using the parameter of electrostatic painting process are as follows: voltage is 10 kV, and flow velocity is 0.5 mL/
H, the distance between spinning head and reception device are 10cm, spray time 60min.Reception device is cylindric rotary drum, rotary drum
Surface is made of the copper mesh of 200 mesh, and rotary drum revolving speed is 600 turns/min.Rotary drum is connected with vacuum pump.
Step 30) prepares the carbon nanotube paper of nano nickel particles load: PAN and nickel salt mixed, precursor solution is made,
Wherein, the mass ratio of PAN and nickel salt is 1:0.3;In precursor solution, the mass fraction of PAN is 4%.Nickel salt is nickel sulfate.
Using electrostatic painting process, precursor solution is sprayed on the carbon nanotube paper of step 20 preparation, forms spraying
There is the carbon nanotube paper of nickel salt.Using the parameter of electrostatic painting process are as follows: voltage 10kV, flow velocity 3mL/h and connect spinning head
The distance between receiving apparatus is 20 cm, spray time 60min.By the carbon nanotube paper for being coated with nickel salt with 1 DEG C/min heating
700 DEG C of holding 3h are warming up to 280 DEG C of holding 2.5h, then with 8 DEG C/min, obtain the carbon nanotube paper of nano nickel particles load.
Step 40) prepares carbon nanotube paper, tin composite nano materials: by the nano nickel particles load of step 30) preparation
Carbon nanotube paper is placed in the tin-salt solution that molar concentration is 50mmol/L, temperature is 85 DEG C, is kept 10h, is obtained carbon nanotube
Paper, tin composite nano materials.Wherein, tin-salt solution is that stannous sulfate is soluble in water obtained.
Step 50) prepares carbon nanotube paper, tin, graphene quantum dot composite nano materials: electrostatic painting process is used, it will
Spray coating liquor is sprayed on the carbon nanotube paper of step 40) preparation, tin composite nano materials surface, and dry, be made carbon nanotube paper,
Tin, graphene quantum dot composite nano materials.Using the parameter of electrostatic painting process are as follows: voltage is 30 kV, flow velocity 1.5mL/
H, the distance between spinning head and reception device are 15cm, time 30min.Spray coating liquor is the stone that mass concentration is 0.8mg/mL
Black alkene quantum dot solution.
Manufactured carbon nanotube paper, tin, in graphene quantum dot composite nano materials, manufactured carbon nanotube paper, tin, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres particle of carbon nanotube, the hollow nanospheres
Grain is made of Sn;The area load not covered by hollow nanospheres particle in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.Carbon nanotube, tin, graphene quantum dot composite nano materials with a thickness of 40 μm.
Embodiment 3
Using carbon nanotube paper, tin, graphene quantum dot composite nano materials as negative electrode of lithium ion battery.This is compound to receive
Rice material the preparation method is as follows:
Step 10) prepares carbon nanotube (CNTs) dispersion liquid: by single-walled carbon nanotube and multi-walled carbon nanotube according to quality
Acetone solvent is scattered in than 1:1, wherein the ratio of solute and solvent is 1mg:10ml;
Step 20 prepares carbon nanotube paper: using electrostatic painting process, prepares carbon nanotube paper.Wherein, spray coating liquor is step
The carbon nano tube dispersion liquid of rapid 10) preparation.Using the parameter of electrostatic painting process are as follows: voltage is 30 kV, flow velocity 4mL/h, spray
Silk the distance between head and reception device are 40 cm, spray time 40min.Reception device is cylindric rotary drum, drum surface
It is made of the copper mesh of 400 mesh, rotary drum revolving speed is 100 turns/min.Rotary drum is connected with vacuum pump.
Step 30) prepares the carbon nanotube paper of nano nickel particles load: PAN and nickel salt mixed, precursor solution is made,
Wherein, the mass ratio of PAN and nickel salt is 1:0.5;In precursor solution, the mass fraction of PAN is 6%.Nickel salt is nickel acetate.
Using electrostatic painting process, precursor solution is sprayed on the carbon nanotube paper of step 20 preparation, forms spraying
There is the carbon nanotube paper of nickel salt.Using the parameter of electrostatic painting process are as follows: voltage is 30 kV, flow velocity 3.5mL/h, spinning head
The distance between reception device is 10 cm, spray time 40min.By the carbon nanotube paper for being coated with nickel salt with 1.5 DEG C/
Min is warming up to 260 DEG C of holding 1h, then is warming up to 600 DEG C of holding 2h with 9 DEG C/min, obtains the carbon nanometer of nano nickel particles load
Pipe paper.
Step 40) prepares carbon nanotube paper, tin composite nano materials: by the nano nickel particles load of step 30) preparation
Carbon nanotube paper is placed in the tin-salt solution that molar concentration is 100mmol/L, temperature is 30 DEG C, is kept 4h, is obtained carbon nanotube
Paper, tin composite nano materials.Wherein, tin-salt solution is molten for stannous chloride and stannous sulfate are dissolved in ethyl alcohol according to mass ratio 1:1
It is made in liquid.
Step 50) prepares carbon nanotube paper, tin, graphene quantum dot composite nano materials: electrostatic painting process is used, it will
Spray coating liquor is sprayed on the carbon nanotube paper of step 40) preparation, tin composite nano materials surface, and dry, be made carbon nanotube paper,
Tin, graphene quantum dot composite nano materials.Using the parameter of electrostatic painting process are as follows: voltage 15kV, flow velocity are 0.8 mL/
H, the distance between spinning head and reception device are 30cm, time 50min.Spray coating liquor is the stone that mass concentration is 1 mg/mL
Black alkene quantum dot solution.
Manufactured carbon nanotube paper, tin, in graphene quantum dot composite nano materials, manufactured carbon nanotube paper, tin, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres particle of carbon nanotube, the hollow nanospheres
Grain is made of Sn;The area load not covered by hollow nanospheres particle in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.Carbon nanotube, tin, graphene quantum dot composite nano materials with a thickness of 50 μm.
Embodiment 4
Using carbon nanotube paper, tin, graphene quantum dot composite nano materials as negative electrode of lithium ion battery.This is compound to receive
Rice material the preparation method is as follows:
Step 10) prepares carbon nanotube (CNTs) dispersion liquid: by single-walled carbon nanotube Dispersion of Solute Matter in N, N- dimethyl methyl
Amide solvent, wherein the ratio of solute and solvent is 1mg:8ml;
Step 20 prepares carbon nanotube paper: using electrostatic painting process, prepares carbon nanotube paper.Wherein, spray coating liquor is step
The carbon nano tube dispersion liquid of rapid 10) preparation.Using the parameter of electrostatic painting process are as follows: voltage 20kV, flow velocity are 1 mL/h, spray
Silk the distance between head and reception device are 20cm, spray time 50min.Reception device is cylindric rotary drum, drum surface
It is made of the copper mesh of 500 mesh, rotary drum revolving speed is 200 turns/min.Rotary drum is connected with vacuum pump.
Step 30) prepares the carbon nanotube paper of nano nickel particles load: PAN and nickel salt mixed, precursor solution is made,
Wherein, the mass ratio of PAN and nickel salt is 1:0.2;In precursor solution, the mass fraction of PAN is 5%.Nickel salt is nickel chloride.
Using electrostatic painting process, precursor solution is sprayed on the carbon nanotube paper of step 20 preparation, forms spraying
There is the carbon nanotube paper of nickel salt.Using the parameter of electrostatic painting process are as follows: voltage 40kV, flow velocity 4mL/h and connect spinning head
The distance between receiving apparatus is 15cm, spray time 50min.By the carbon nanotube paper for being coated with nickel salt with 2 DEG C/min heating
650 DEG C of holding 3.5h are warming up to 270 DEG C of holding 1.5h, then with 5 DEG C/min, obtain the carbon nanotube of nano nickel particles load
Paper.
Step 40) prepares carbon nanotube paper, tin composite nano materials: by the nano nickel particles load of step 30) preparation
Carbon nanotube paper is placed in the tin-salt solution that molar concentration is 80mmol/L, temperature is 25 DEG C, is kept 8h, is obtained carbon nanotube
Paper, tin composite nano materials.Wherein, tin-salt solution is that stannous acetate is soluble in water obtained.
Step 50) prepares carbon nanotube paper, tin, graphene quantum dot composite nano materials: electrostatic painting process is used, it will
Spray coating liquor is sprayed on the carbon nanotube paper of step 40) preparation, tin composite nano materials surface, and dry, be made carbon nanotube paper,
Tin, graphene quantum dot composite nano materials.Using the parameter of electrostatic painting process are as follows: voltage be 10 kV, flow velocity 2mL/h,
The distance between spinning head and reception device are 10cm, time 55min.Spray coating liquor is the graphite that mass concentration is 0.9mg/mL
Alkene quantum dot solution.
Manufactured carbon nanotube paper, tin, in graphene quantum dot composite nano materials, manufactured carbon nanotube paper, tin, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres particle of carbon nanotube, the hollow nanospheres
Grain is made of Sn;The area load not covered by hollow nanospheres particle in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.Carbon nanotube, tin, graphene quantum dot composite nano materials with a thickness of 30 μm.
Embodiment 5
Using carbon nanotube paper, tin, graphene quantum dot composite nano materials as negative electrode of lithium ion battery.This is compound to receive
Rice material the preparation method is as follows:
Step 10) prepares carbon nanotube (CNTs) dispersion liquid: by multi-walled carbon nanotube Dispersion of Solute Matter in N, N- dimethyl second
Amide solvent, wherein the ratio of solute and solvent is 1mg:9ml;
Step 20 prepares carbon nanotube paper: using electrostatic painting process, prepares carbon nanotube paper.Wherein, spray coating liquor is step
The carbon nano tube dispersion liquid of rapid 10) preparation.Using the parameter of electrostatic painting process are as follows: voltage is 35 kV, flow velocity 2mL/h, spray
Silk the distance between head and reception device are 35cm, spray time 20min.Reception device is cylindric rotary drum, drum surface
It is made of the copper mesh of 350 mesh, rotary drum revolving speed is 300 turns/min.Rotary drum is connected with vacuum pump.
Step 30) prepares the carbon nanotube paper of nano nickel particles load: PAN and nickel salt mixed, precursor solution is made,
Wherein, the mass ratio of PAN and nickel salt is 1:0.4;In precursor solution, the mass fraction of PAN is 4.5%.Nickel salt is nickel acetate.
Using electrostatic painting process, precursor solution is sprayed on the carbon nanotube paper of step 20 preparation, forms spraying
There is the carbon nanotube paper of nickel salt.Using the parameter of electrostatic painting process are as follows: voltage is 18 kV, flow velocity 0.5mL/h, spinning head
The distance between reception device is 28cm, spray time 15min.By the carbon nanotube paper for being coated with nickel salt with 2 DEG C/min
264 DEG C of holding 3h are warming up to, then 780 DEG C of holding 2h are warming up to 10 DEG C/min, obtain the carbon nanotube of nano nickel particles load
Paper.
Step 40) prepares carbon nanotube paper, tin composite nano materials: by the nano nickel particles load of step 30) preparation
Carbon nanotube paper is placed in the tin-salt solution that molar concentration is 35mmol/L, temperature is 60 DEG C, is kept 12h, is obtained carbon nanotube
Paper, tin composite nano materials.Wherein, tin-salt solution is to be dissolved in stannous sulfate in ethanol solution being made.
Step 50) prepares carbon nanotube paper, tin, graphene quantum dot composite nano materials: electrostatic painting process is used, it will
Spray coating liquor is sprayed on the carbon nanotube paper of step 40) preparation, tin composite nano materials surface, and dry, be made carbon nanotube paper,
Tin, graphene quantum dot composite nano materials.Using the parameter of electrostatic painting process are as follows: voltage 26kV, flow velocity 0.5mL/
H, the distance between spinning head and reception device are 28cm, time 60min.Spray coating liquor is the stone that mass concentration is 1.2mg/mL
Black alkene quantum dot solution.
Manufactured carbon nanotube paper, tin, in graphene quantum dot composite nano materials, manufactured carbon nanotube paper, tin, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres particle of carbon nanotube, the hollow nanospheres
Grain is made of Sn;The area load not covered by hollow nanospheres particle in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.Carbon nanotube, tin, graphene quantum dot composite nano materials with a thickness of 35 μm.
Embodiment 6
Using carbon nanotube paper, tin, graphene quantum dot composite nano materials as negative electrode of lithium ion battery.This is compound to receive
Rice material the preparation method is as follows:
Step 10) prepares carbon nanotube (CNTs) dispersion liquid: by single-walled carbon nanotube Dispersion of Solute Matter in methanol solvate,
In, the ratio of solute and solvent is 1mg:3ml;
Step 20 prepares carbon nanotube paper: using electrostatic painting process, prepares carbon nanotube paper.Wherein, spray coating liquor is step
The carbon nano tube dispersion liquid of rapid 10) preparation.Using the parameter of electrostatic painting process are as follows: voltage is 15 kV, flow velocity 3mL/h, spray
Silk the distance between head and reception device are 18cm, spray time 45min.Reception device is cylindric rotary drum, drum surface
It is made of the copper mesh of 450 mesh, rotary drum revolving speed is 350 turns/min.Rotary drum is connected with vacuum pump.
Step 30) prepares the carbon nanotube paper of nano nickel particles load: PAN and nickel salt mixed, precursor solution is made,
Wherein, the mass ratio of PAN and nickel salt is 1:0.15;In precursor solution, the mass fraction of PAN is 3%.Nickel salt is nickel sulfate.
Using electrostatic painting process, precursor solution is sprayed on the carbon nanotube paper of step 20 preparation, forms spraying
There is the carbon nanotube paper of nickel salt.Using the parameter of electrostatic painting process are as follows: voltage 26kV, flow velocity 1mL/h and connect spinning head
The distance between receiving apparatus is 22cm, spray time 35min.By the carbon nanotube paper for being coated with nickel salt with 1 DEG C/min heating
680 DEG C of holding 2.6h are warming up to 275 DEG C of holding 2.8h, then with 5 DEG C/min, obtain the carbon nanotube of nano nickel particles load
Paper.
Step 40) prepares carbon nanotube paper, tin composite nano materials: by the nano nickel particles load of step 30) preparation
It is 65mmol/L, in tin-salt solution at a temperature of 90 °C that carbon nanotube paper, which is placed in molar concentration, keeps 2h, obtains carbon nanotube
Paper, tin composite nano materials.Wherein, tin-salt solution is by stannous chloride and stannous acetate according to mass ratio 1:1 system soluble in water
?.
Step 50) prepares carbon nanotube paper, tin, graphene quantum dot composite nano materials: electrostatic painting process is used, it will
Spray coating liquor is sprayed on the carbon nanotube paper of step 40) preparation, tin composite nano materials surface, and dry, be made carbon nanotube paper,
Tin, graphene quantum dot composite nano materials.Using the parameter of electrostatic painting process are as follows: voltage 18kV, flow velocity are 1.8 mL/
H, the distance between spinning head and reception device are 12cm, time 40min.Spray coating liquor is the stone that mass concentration is 0.7mg/mL
Black alkene quantum dot solution.
Manufactured carbon nanotube paper, tin, in graphene quantum dot composite nano materials, manufactured carbon nanotube paper, tin, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres particle of carbon nanotube, the hollow nanospheres
Grain is made of Sn;The area load not covered by hollow nanospheres particle in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.Carbon nanotube, tin, graphene quantum dot composite nano materials with a thickness of 45 μm.
To above-mentioned 2 comparative examples and 6 embodiments, electric conductivity, capacity and cyclical stability test are carried out respectively.Test
The results are shown in Table 1.
Table 1
As can be seen from Table 1: carbon nanotube paper, the tin, graphene quantum dot composite Nano material of preparation of the embodiment of the present invention
The electric conductivity of material is better than comparative example.The electric conductivity of comparative example 1 is 32 Ω/cm, and the electric conductivity of embodiment 4 is 11 Ω/cm.Implement
The electric conductivity of example 4 is far superior to comparative example 1.Meanwhile the capacity of the composite nano materials of preparation of the embodiment of the present invention is significantly larger than
Comparative example.The capacity of embodiment 4 is 1536 mAhg-1, the capacity of comparative example 1 is 580mAhg-1.The capacity of embodiment 4 is comparison
3 times of example 1.The capacity retention ratio of the composite nano materials of preparation of the embodiment of the present invention is also significantly larger than comparative example.100 circulations
Afterwards, the capacity retention ratio of embodiment 4 is 96%, and comparative example 1 only has 45%.
The basic principles, main features and advantages of the invention have been shown and described above.Those skilled in the art should
Understand, the present invention do not limited by above-mentioned specific embodiment, the description in above-mentioned specific embodiment and specification be intended merely into
One step illustrates the principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also have various change and
It improves, these changes and improvements all fall within the protetion scope of the claimed invention.The scope of protection of present invention is wanted by right
Ask book and its equivalent thereof.