CN106531969A - Preparation method of flexible composite nanomaterial for lithium ion battery anode - Google Patents
Preparation method of flexible composite nanomaterial for lithium ion battery anode Download PDFInfo
- Publication number
- CN106531969A CN106531969A CN201611189498.6A CN201611189498A CN106531969A CN 106531969 A CN106531969 A CN 106531969A CN 201611189498 A CN201611189498 A CN 201611189498A CN 106531969 A CN106531969 A CN 106531969A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- nanotube paper
- preparation
- stannum
- nickel
- 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.)
- Granted
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a flexible composite nanomaterial for a lithium ion battery anode. The preparation method comprises the following steps: step 10) dissolving a solute into a methyl alcohol, ethanol, acetone, N,N-dimethylformamide or N,N-dimethylacetamide solvent; step 20) preparing carbon nano tube paper; step 30) mixing polyacrylonitrile and a nickel salt to prepare a precursor solution; spraying the precursor solution onto the carbon nano tube paper to form carbon nano tube paper coated with the nickel salt; and raising the temperature of the carbon nano tube paper to obtain carbon nano tube paper loaded with nickel nano-particles; step 40) putting the carbon nano tube paper loaded with the nickel nano-particles into a tin salt solution so as to obtain a carbon nano tube paper and tin composite nanomaterial; and step 50) spraying a spraying solution onto the surface of the carbon nano tube paper and tin composite nanomaterial, and drying to obtain a carbon nano tube paper, tin and graphene quantum dot composite nanomaterial. The composite nanomaterial prepared by the invention has good electrical conductivity, capacity and cycle life.
Description
Technical field
The invention belongs to new lithium storage materials field, it particularly relates to a kind of used as negative electrode of Li-ion battery flexible compound
The preparation method of nano material.
Background technology
As traditional energy day by day shortage and environmental problem continuously emerge, the increasingly enhancing of people's environmental consciousness, exploitation are new
The energy and rationally become the task of top priority using regenerative resource.In recent years, wind energy, solar energy and tide energy etc. it is environmentally friendly,
Green regenerative energy sources are received significant attention, but the seriality stable supplying of these energy has insoluble difficulty, seriously
Limit their effectively utilizes.The lithium ion battery of currently referred to as " Green Chemistry power supply " has become most to develop and dives
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 negative pole of lithium ion battery still mainly adopts graphite type material, such material to have low chemical potential and preferably circulation at present
Performance, but its actual capacity has basically reached theoretical capacity（372mAh/g）, constrain lithium ion battery in New Energy Industry
Application.
Stannum abundance on earth, because with higher Theoretical Mass specific capacity（Sn：992 mAh/g）Become lithium ion
One of focus negative material of battery research.But, tin electrode causes the volume of electrode acutely to become during charge and discharge cycles
Change, cause tin electrode active component to reunite or come off, and then make electrode cycle life and capacity drastically fail.By active metal stannum
It is the main path for solving this problem to be combined with material with carbon element.At present, metallic tin is many with the complex method of material with carbon element, but greatly
The electric conductivity of multi-cathode material, capacity and cycle life are low, and need to add conductive agent, adhesive in electrode production process
The electrode of material is increased, and preparation process is cumbersome.
The content of the invention
It is an object of the invention to provide a kind of preparation method of used as negative electrode of Li-ion battery flexible compound nano material, should
Composite nano materials prepared by method have good electric conductivity, capacity and cycle life.
For achieving the above object, the embodiment of the present invention is using a kind of used as negative electrode of Li-ion battery flexible compound nano material
Preparation method, the method include：
Step 10）Prepare carbon nano tube dispersion liquid：By Dispersion of Solute Matter in methanol, ethanol, acetone, N,N-dimethylformamide or
N,N-dimethylacetamide solvent, wherein, the ratio of solute and solvent is 1mg:2~10ml；Described solute is single
The mixture of pipe, multi-walled carbon nano-tubes or SWCN and multi-walled carbon nano-tubes composition；
Step 20）Prepare carbon nanotube paper：Using electrostatic painting process, carbon nanotube paper is prepared；Wherein, spray coating liquor is step
10）The carbon nano tube dispersion liquid of preparation, reception device are cylindric rotary drum, and rotary drum is connected with vacuum pump；
Step 30）Prepare the carbon nanotube paper of nano nickel particles load：Polyacrylonitrile and nickel salt are mixed, presoma is made molten
Liquid, 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 into into step 20）On the carbon nanotube paper of preparation, formation is coated with nickel
The carbon nanotube paper of salt；The carbon nanotube paper for being coated with nickel salt is warming up to into 250 ~ 280 DEG C of 1 ~ 3h of holding with 1 ~ 2 DEG C/min, then
600 ~ 800 DEG C of 2 ~ 4h of holding are warming up to 5 ~ 10 DEG C/min, the carbon nanotube paper of nano nickel particles load is obtained；
Step 40）Prepare carbon nanotube paper, stannum composite nano materials：By step 30）The carbon of the nano nickel particles load of preparation is received
During mitron paper is placed in molar concentration for 20 ~ 100mmol/L, the tin-salt solution that temperature is 25 ~ 90 DEG C, 2 ~ 12h is kept, carbon is obtained and is received
Mitron paper, stannum composite nano materials；
Step 50）Prepare carbon nanotube paper, stannum, graphene quantum dot composite nano materials：Using electrostatic painting process, will spraying
Liquid is sprayed on step 40）The carbon nanotube paper of preparation, stannum composite nano materials surface, and be dried, make carbon nanotube paper, stannum,
Graphene quantum dot composite nano materials；Described spray coating liquor is the graphene quantum dot that mass concentration is 0.5 ~ 1.2 mg/mL
Solution.
As preference, described step 20）In, adopt the parameter of electrostatic painting process for：Voltage is 10 ~ 40 kV, is flowed
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, described step 20）In, drum surface is made up of the copper mesh of 200 ~ 500 mesh, and rotary drum rotating speed is
100 ~ 600 turns/min.
As preference, described step 30）In, adopt the parameter of electrostatic painting process for：Voltage is 10 ~ 40 kV, is flowed
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, described step 30）In, nickel salt is Nickel dichloride., nickel sulfate or nickel acetate.
As preference, described step 40）In, tin-salt solution is by stannous chloride, stannous sulfate, stannous acetate
It is a kind of or any two be dissolved in water or ethanol solution, make tin-salt solution.
As preference, described step 40）In, carbon nanotube paper, the structure of stannum composite nano materials are：CNT
Area load hollow nanospheres granule；Described hollow nanospheres granule is made up of Sn.
As preference, described step 50）In, adopt the parameter of electrostatic painting process for：Voltage is 10 ~ 30 kV, is flowed
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, described step 50）Made by carbon nanotube paper, stannum, graphene quantum dot composite nano materials
In, the area load hollow nanospheres granule of CNT, described hollow nanospheres granule are made up of Sn；Hollow nanospheres
The area load graphene quantum dot layer not covered by hollow nanospheres granule in grain surface and carbon nanotube paper.
As preference, described step 50）In, CNT, stannum, the thickness of graphene quantum dot composite nano materials
For 20 ~ 50 μm.
Compared with prior art, the carbon nanotube paper of embodiment of the present invention preparation, stannum, graphene quantum dot composite Nano material
Material can be used directly as negative material, and preparation process is without the need for conductive agent and adhesive with preferably flexible.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.Composite nano materials prepared by the embodiment of the present invention have higher capacity and circulation longevity
Life.CNTs, Sn and GQDs have preferably storage lithium performance, therefore with higher capacity.During hollow tin nanoparticles have
Hollow structure, in process of intercalation, can inwardly expand simultaneously and outwards expansion during expansion, thus hollow tin nanoparticles electrode is relatively swollen
Swollen volume will not drastically become big.In addition, Sn granules outer layer also coats one layer of GQDs, these can buffer the volumetric expansion of Sn,
Improve the cyclical stability and cycle life of material.
Specific embodiment
Below the technical scheme of the embodiment of the present invention is described in detail.
The embodiment of the present invention provides a kind of preparation method of used as negative electrode of Li-ion battery flexible compound nano material, the method
Including：
Step 10）Prepare CNT（In text referred to as：CNTs）Dispersion liquid：By Dispersion of Solute Matter in methanol, ethanol, acetone, N, N-
Dimethylformamide or N,N-dimethylacetamide solvent, wherein, the ratio of solute and solvent is 1mg:2~10ml；Described
Solute is the mixture that SWCN, multi-walled carbon nano-tubes or SWCN and multi-walled carbon nano-tubes are constituted.
Wherein, the compositionss of solute SWCN, multi-walled carbon nano-tubes or both, for example, SWCN
With multi-walled carbon nano-tubes according to mass ratio 1:1 composition solute.Solvent be methanol, ethanol, acetone, N,N-dimethylformamide or
DMAC N,N' dimethyl acetamide.Solute is dissolved in solvent, makes carbon nano tube dispersion liquid.
Step 20）Prepare carbon nanotube paper：Using electrostatic painting process, carbon nanotube paper is prepared；Wherein, spray coating liquor is step
Rapid 10）The carbon nano tube dispersion liquid of preparation, reception device are cylindric rotary drum, and rotary drum is connected with vacuum pump.
Wherein, adopt the parameter of electrostatic painting process for：Voltage be 10 ~ 40 kV, flow velocity be 0.5 ~ 5.0 mL/h, spray webbing
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, the electric conductivity of material is improved.Rotary drum and vacuum pump
The purpose being connected：Accelerate the volatilization of CNTs surface solvents, improve the structural stability of carbon nanotube paper.Preferably, rotary drum
Surface is made up of the copper mesh of 200 ~ 500 mesh, and rotary drum rotating speed is 100 ~ 600 turns/min.Using copper mesh as reception device, work as copper mesh
When being connected with vacuum pump, solvent quickly can be reclaimed, and improve the binding strength between CNT.Rotary drum keeps certain rotating speed, can
Enable CNT a certain degree of according to arrangement is turned to, improve its electric conductivity.
Published to prepare carbon nanotube paper technology mainly using sucking filtration method, the arrangement of CNT has unordered
Property, electric conductivity is poor.The present embodiment prepares carbon nanotube paper using electrostatic painting process, can improve the degree of orientation of CNT,
And then improve electric conductivity.Copper mesh is connected as receiving device and with vacuum pump, can improve binding strength between CNT simultaneously
Improve efficiency.Copper mesh is connected with vacuum pump, and into negative pressure inside copper mesh rotary drum, CNT receives the dual work of electric field force and negative pressure
It is even closer with combine can CNT.Most solvents can be reclaimed by vacuum pump, improve efficiency.
Step 30）Prepare the carbon nanotube paper of nano nickel particles load：By polyacrylonitrile（Abbreviation PAN in text）It is mixed with nickel salt
Close, make precursor solution, 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 dichloride., nickel sulfate or nickel acetate.
Using electrostatic painting process, precursor solution is sprayed into into step 20）On the carbon nanotube paper of preparation, spraying is formed
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, adopt the parameter of electrostatic painting process for：Voltage is 10 ~ 40 kV, and flow velocity is 0.5 ~ 4.0
ML/h, the distance between spinning head and reception device are 10 ~ 30 cm, and spray time is 15 ~ 60min.
Step 30）In, PAN is mixed with nickel salt and sprays to carbon nanotube paper surface, and Jing high-temperature process, nickel are decomposed into the oxygen of nickel
Compound, PAN are converted into carbon, and nickel oxide is reduced to elemental nickel nanometer ball particle by carbon.
Step 40）Prepare carbon nanotube paper, stannum composite nano materials：By step 30）The nano nickel particles load of preparation
During carbon nanotube paper is placed in molar concentration for 20 ~ 100mmol/L, the tin-salt solution that temperature is 25 ~ 90 DEG C, 2 ~ 12h is kept, is obtained
Carbon nanotube paper, stannum composite nano materials；
Wherein, tin-salt solution is by the one kind in stannous chloride, stannous sulfate, stannous acetate or any two are dissolved in water or ethanol is molten
In liquid, tin-salt solution is made.Described step 40）In, carbon nanotube paper, the structure of stannum composite nano materials are：CNT
Contain hollow nanospheres granule in the cavity of paper, the volume of nanometer ball particle is less than the cavity volume of carbon nanotube paper；Described
Nanometer ball particle is made up of Sn.
By step 40）Solid nickel nanometer ball particle is converted into into hollow tin nanoparticles.In tin-salt solution, elemental nickel
It is oxidized to Ni2+And enter in solution, corresponding Sn2+The surface of nano nickel particles is deposited directly to after being reduced into simple substance stannum.Often
Individual nickle atom produces two electronics, and as metal itself has electric conductivity, the electrons of generation are transferred to the surface of nano-particle,
In nano grain surface Sn2+Be reduced, and gradually stannum shell formed in nickel surface, eventually form hollow structure.
Step 50）Prepare carbon nanotube paper, stannum, graphene quantum dot composite nano materials：Using electrostatic painting process, will
Spray coating liquor is sprayed on step 40）The carbon nanotube paper of preparation, stannum composite nano materials surface, and be dried, make carbon nanotube paper,
Stannum, graphene quantum dot composite nano materials；Described spray coating liquor is the Graphene quantum that mass concentration is 0.5 ~ 1.2 mg/mL
Point（In text referred to as：GQDs）Solution.
Wherein, preferably, adopt the parameter of electrostatic painting process for：Voltage is 10 ~ 30 kV, and flow velocity is 0.5 ~ 2.0
ML/h, the distance between spinning head and reception device are 10 ~ 30 cm, and the time is 30 ~ 60min.Step 50）Made by carbon nanometer
In pipe paper, stannum, graphene quantum dot composite nano materials, the area load hollow nanospheres granule of CNT, it is described in
Empty nanometer ball particle is made up of Sn；Do not covered by hollow nanospheres granule in hollow nanospheres particle surface and carbon nanotube paper
Area load graphene quantum dot layer.Preferably, CNT, stannum, the thickness of graphene quantum dot composite nano materials
For 20 ~ 50 μm.
Step 50）, during graphene quantum dot layer is loaded to carbon nanotube paper, stannum composite nano materials surface,
Graphene quantum dot more uniform and stable is loaded to sijna rice ball particle and carbon nanotube paper surface by electrostatic painting process.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, and
Improve the capacity of material.Electric conductivity and cyclical stability based on grapheme material, graphene quantum dot are played and can slow down charge and discharge
In electric cyclic process, the crushing and reunion of stannum, so as to improve the cycle performance of electrode.
CNT has preferable electric conductivity, a pliability, thus make after carbon nanotube paper can as electrode from
Backing material, and there is preferable pliability, electrode required form can be processed into, conductive agent and adhesive need not be added.Xi Ben
Body has high theoretical specific capacity, and in the present embodiment, stannum is in hollow nanospheres body granule, can alleviate charge and discharge to a certain extent
In electric process, because volumetric expansion causes capacity and cyclical stability to decline.Compared with Graphene, graphene quantum dot size is more
It is little, can be more uniform and stable load to hollow nanospheres body granule and carbon nano tube surface.Graphene quantum dot is loaded to
Hollow nanospheres body granule and carbon nanotube paper surface, not only can further improve the electric conductivity of material and can improve material
The capacity of material.Electric conductivity and cyclical stability based on grapheme material, graphene quantum dot are played and can slow down charge and discharge cycles
During stannum crushing and reunion, so as to improve the cycle performance of electrode.
Below by test, the carbon nanotube paper of checking embodiment of the present invention preparation, stannum, graphene quantum dot composite Nano
Material has excellent properties.Wherein, the electric conductivity of material is tested using four probe method.
The carbon nanotube paper of each embodiment preparation, stannum, graphene quantum dot composite nano materials are cut into into a diameter of 15mm
Circular electrode, in the glove box full of nitrogen, be that, to electrode, barrier film is Celgrad2400 with metal lithium sheet, electrolyte is
Lithium hexafluoro phosphate/ethylene carbonate-Ethyl methyl carbonate-dimethyl carbonate of the molar concentration for 1mol/L（Abbreviation LiPF6/ in text
EC-EMC-DMC）Solution, the volume ratio between LiPF6/EC-EMC-DMC are 1:1:1, button cell is assembled into, and stands 7h.
Constant current charge-discharge performance test is carried out with 0.5C on charge-discharge test instrument, charging/discharging voltage scope is 0.01 ~ 1.5V, electric current is close
Spend for 50mAg-1。
The capacity and cyclical stability of material are evaluated by constant current charge-discharge performance test（Cycle life）.The circulation of material
Stability or cycle life circulated by 100 times after capability retention representing, the stable circulation of the bigger material of capability retention
Property is better.
Subjects：
Comparative example 1
Using carbon nanotube paper as lithium ion battery negative.
Comparative example 2
Using material made by hollow sijna rice spherical particles as lithium ion battery negative.
Embodiment 1
Using carbon nanotube paper, stannum, graphene quantum dot composite nano materials as lithium ion battery negative.The composite Nano material
The preparation method of material is as follows：
Step 10）Prepare CNT（CNTs）Dispersion liquid：SWCN is scattered in into methanol solvate, wherein, solute with
The ratio of solvent is 1mg:2ml；
Step 20）Prepare carbon nanotube paper：Using electrostatic painting process, carbon nanotube paper is prepared.Wherein, spray coating liquor is step
10）The carbon nano tube dispersion liquid of preparation.Adopt the parameter of electrostatic painting process for：Voltage is 40 kV, and flow velocity is 5mL/h, spray webbing
The distance between head and reception device are 30 cm, and spray time is 30min.Reception device be cylindric rotary drum, drum surface by
The copper mesh composition of 260 mesh, rotary drum rotating speed is 400 turns/min.Rotary drum is connected with vacuum pump.
Step 30）Prepare the carbon nanotube paper of nano nickel particles load：PAN and nickel salt are 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 dichloride..
Using electrostatic painting process, precursor solution is sprayed into into step 20）On the carbon nanotube paper of preparation, spraying is formed
There is the carbon nanotube paper of nickel salt.Adopt the parameter of electrostatic painting process for：Voltage is 20kV, and flow velocity is 2mL/h, spinning head and is connect
The distance between receiving apparatus are 30 cm, and spray time is 20min.The carbon nanotube paper for being coated with nickel salt is heated up with 2 DEG C/min
To 250 DEG C of holding 3h, then 800 DEG C of holding 4h are warming up to 10 DEG C/min, obtain the carbon nanotube paper of nano nickel particles load.
Step 40）Prepare carbon nanotube paper, stannum composite nano materials：By step 30）The nano nickel particles load of preparation
During carbon nanotube paper is placed in molar concentration for 20mmol/L, the tin-salt solution that temperature is 70 DEG C, 5h is kept, CNT is obtained
Paper, stannum composite nano materials.Wherein, tin-salt solution is that stannous chloride is dissolved in water to be obtained.
Step 50）Prepare carbon nanotube paper, stannum, graphene quantum dot composite nano materials：Using electrostatic painting process, will
Spray coating liquor is sprayed on step 40）The carbon nanotube paper of preparation, stannum composite nano materials surface, and be dried, make carbon nanotube paper,
Stannum, graphene quantum dot composite nano materials.Adopt the parameter of electrostatic painting process for：Voltage is 20 kV, and flow velocity is 1mL/h,
The distance between spinning head and reception device are 25cm, and the time is 45min.Spray coating liquor is stone that mass concentration is 0.5 mg/mL
Black alkene quantum dot solution.
Made by carbon nanotube paper, stannum, in graphene quantum dot composite nano materials, made by carbon nanotube paper, stannum, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres granule of CNT, described hollow nanospheres
Grain is made up of Sn；The area load not covered by hollow nanospheres granule in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.CNT, stannum, the thickness of graphene quantum dot composite nano materials are 20 μm.
Embodiment 2
Using carbon nanotube paper, stannum, graphene quantum dot composite nano materials as lithium ion battery negative.The composite Nano material
The preparation method of material is as follows：
Step 10）Prepare CNT（CNTs）Dispersion liquid：By multi-walled carbon nano-tubes Dispersion of Solute Matter in alcohol solvent, wherein, it is molten
The ratio of matter and solvent is 1mg:5ml；
Step 20）Prepare carbon nanotube paper：Using electrostatic painting process, carbon nanotube paper is prepared.Wherein, spray coating liquor is step
10）The carbon nano tube dispersion liquid of preparation.Adopt the parameter of electrostatic painting process for：Voltage is 10 kV, and flow velocity is 0.5 mL/h,
The distance between spinning head and reception device are 10cm, and spray time is 60min.Reception device be cylindric rotary drum, rotary drum table
Face is made up of the copper mesh of 200 mesh, and rotary drum rotating speed is 600 turns/min.Rotary drum is connected with vacuum pump.
Step 30）Prepare the carbon nanotube paper of nano nickel particles load：PAN and nickel salt are 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 into into step 20）On the carbon nanotube paper of preparation, spraying is formed
There is the carbon nanotube paper of nickel salt.Adopt the parameter of electrostatic painting process for：Voltage is 10kV, and flow velocity is 3mL/h, spinning head and is connect
The distance between receiving apparatus are 20 cm, and spray time is 60min.The carbon nanotube paper for being coated with nickel salt is heated up with 1 DEG C/min
To 280 DEG C of holding 2.5h, then 700 DEG C of holding 3h are warming up to 8 DEG C/min, obtain the carbon nanotube paper of nano nickel particles load.
Step 40）Prepare carbon nanotube paper, stannum composite nano materials：By step 30）The nano nickel particles load of preparation
During carbon nanotube paper is placed in molar concentration for 50mmol/L, the tin-salt solution that temperature is 85 DEG C, 10h is kept, CNT is obtained
Paper, stannum composite nano materials.Wherein, tin-salt solution is to be obtained stannous sulfate soluble in water.
Step 50）Prepare carbon nanotube paper, stannum, graphene quantum dot composite nano materials：Using electrostatic painting process, will
Spray coating liquor is sprayed on step 40）The carbon nanotube paper of preparation, stannum composite nano materials surface, and be dried, make carbon nanotube paper,
Stannum, graphene quantum dot composite nano materials.Adopt the parameter of electrostatic painting process for：Voltage is 30 kV, and flow velocity is 1.5mL/
H, the distance between spinning head and reception device are 15cm, and the time is 30min.Spray coating liquor is the stone that mass concentration is 0.8mg/mL
Black alkene quantum dot solution.
Made by carbon nanotube paper, stannum, in graphene quantum dot composite nano materials, made by carbon nanotube paper, stannum, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres granule of CNT, described hollow nanospheres
Grain is made up of Sn；The area load not covered by hollow nanospheres granule in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.CNT, stannum, the thickness of graphene quantum dot composite nano materials are 40 μm.
Embodiment 3
Using carbon nanotube paper, stannum, graphene quantum dot composite nano materials as lithium ion battery negative.The composite Nano material
The preparation method of material is as follows：
Step 10）Prepare CNT（CNTs）Dispersion liquid：By SWCN and multi-walled carbon nano-tubes according to mass ratio 1:1
Acetone solvent is scattered in, wherein, the ratio of solute and solvent is 1mg: 10ml；
Step 20）Prepare carbon nanotube paper：Using electrostatic painting process, carbon nanotube paper is prepared.Wherein, spray coating liquor is step
10）The carbon nano tube dispersion liquid of preparation.Adopt the parameter of electrostatic painting process for：Voltage is 30 kV, and flow velocity is 4mL/h, spray webbing
The distance between head and reception device are 40 cm, and spray time is 40min.Reception device be cylindric rotary drum, drum surface by
The copper mesh composition of 400 mesh, rotary drum rotating speed is 100 turns/min.Rotary drum is connected with vacuum pump.
Step 30）Prepare the carbon nanotube paper of nano nickel particles load：PAN and nickel salt are 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 into into step 20）On the carbon nanotube paper of preparation, spraying is formed
There is the carbon nanotube paper of nickel salt.Adopt the parameter of electrostatic painting process for：Voltage is 30 kV, and flow velocity is 3.5mL/h, spinning head
It is 10 cm with the distance between reception device, spray time is 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）Prepare carbon nanotube paper, stannum composite nano materials：By step 30）The nano nickel particles load of preparation
During carbon nanotube paper is placed in molar concentration for 100mmol/L, the tin-salt solution that temperature is 30 DEG C, 4h is kept, CNT is obtained
Paper, stannum composite nano materials.Wherein, tin-salt solution is according to mass ratio 1 by stannous chloride and stannous sulfate:1 to be dissolved in ethanol molten
It is obtained in liquid.
Step 50）Prepare carbon nanotube paper, stannum, graphene quantum dot composite nano materials：Using electrostatic painting process, will
Spray coating liquor is sprayed on step 40）The carbon nanotube paper of preparation, stannum composite nano materials surface, and be dried, make carbon nanotube paper,
Stannum, graphene quantum dot composite nano materials.Adopt the parameter of electrostatic painting process for：Voltage is 15kV, and flow velocity is 0.8 mL/
H, the distance between spinning head and reception device are 30cm, and the time is 50min.Spray coating liquor is stone that mass concentration is 1 mg/mL
Black alkene quantum dot solution.
Made by carbon nanotube paper, stannum, in graphene quantum dot composite nano materials, made by carbon nanotube paper, stannum, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres granule of CNT, described hollow nanospheres
Grain is made up of Sn；The area load not covered by hollow nanospheres granule in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.CNT, stannum, the thickness of graphene quantum dot composite nano materials are 50 μm.
Embodiment 4
Using carbon nanotube paper, stannum, graphene quantum dot composite nano materials as lithium ion battery negative.The composite Nano material
The preparation method of material is as follows：
Step 10）Prepare CNT（CNTs）Dispersion liquid：By SWCN Dispersion of Solute Matter in N,N-dimethylformamide
Solvent, wherein, the ratio of solute and solvent is 1mg:8ml；
Step 20）Prepare carbon nanotube paper：Using electrostatic painting process, carbon nanotube paper is prepared.Wherein, spray coating liquor is step
10）The carbon nano tube dispersion liquid of preparation.Adopt the parameter of electrostatic painting process for：Voltage is 20kV, and flow velocity is 1 mL/h, spray webbing
The distance between head and reception device are 20cm, and spray time is 50min.Reception device be cylindric rotary drum, drum surface by
The copper mesh composition of 500 mesh, rotary drum rotating speed is 200 turns/min.Rotary drum is connected with vacuum pump.
Step 30）Prepare the carbon nanotube paper of nano nickel particles load：PAN and nickel salt are 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 dichloride..
Using electrostatic painting process, precursor solution is sprayed into into step 20）On the carbon nanotube paper of preparation, spraying is formed
There is the carbon nanotube paper of nickel salt.Adopt the parameter of electrostatic painting process for：Voltage is 40kV, and flow velocity is 4mL/h, spinning head and is connect
The distance between receiving apparatus are 15cm, and spray time is 50min.The carbon nanotube paper for being coated with nickel salt is heated up with 2 DEG C/min
To 270 DEG C of holding 1.5h, then 650 DEG C of holding 3.5h are warming up to 5 DEG C/min, obtain the CNT of nano nickel particles load
Paper.
Step 40）Prepare carbon nanotube paper, stannum composite nano materials：By step 30）The nano nickel particles load of preparation
During carbon nanotube paper is placed in molar concentration for 80mmol/L, the tin-salt solution that temperature is 25 DEG C, 8h is kept, CNT is obtained
Paper, stannum composite nano materials.Wherein, tin-salt solution is to be obtained stannous acetate soluble in water.
Step 50）Prepare carbon nanotube paper, stannum, graphene quantum dot composite nano materials：Using electrostatic painting process, will
Spray coating liquor is sprayed on step 40）The carbon nanotube paper of preparation, stannum composite nano materials surface, and be dried, make carbon nanotube paper,
Stannum, graphene quantum dot composite nano materials.Adopt the parameter of electrostatic painting process for：Voltage is 10 kV, and flow velocity is 2mL/h,
The distance between spinning head and reception device are 10cm, and the time is 55min.Spray coating liquor is the graphite that mass concentration is 0.9mg/mL
Alkene quantum dot solution.
Made by carbon nanotube paper, stannum, in graphene quantum dot composite nano materials, made by carbon nanotube paper, stannum, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres granule of CNT, described hollow nanospheres
Grain is made up of Sn；The area load not covered by hollow nanospheres granule in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.CNT, stannum, the thickness of graphene quantum dot composite nano materials are 30 μm.
Embodiment 5
Using carbon nanotube paper, stannum, graphene quantum dot composite nano materials as lithium ion battery negative.The composite Nano material
The preparation method of material is as follows：
Step 10）Prepare CNT（CNTs）Dispersion liquid：By multi-walled carbon nano-tubes Dispersion of Solute Matter in DMAC N,N' dimethyl acetamide
Solvent, wherein, the ratio of solute and solvent is 1mg:9ml；
Step 20）Prepare carbon nanotube paper：Using electrostatic painting process, carbon nanotube paper is prepared.Wherein, spray coating liquor is step
10）The carbon nano tube dispersion liquid of preparation.Adopt the parameter of electrostatic painting process for：Voltage is 35 kV, and flow velocity is 2mL/h, spray webbing
The distance between head and reception device are 35cm, and spray time is 20min.Reception device be cylindric rotary drum, drum surface by
The copper mesh composition of 350 mesh, rotary drum rotating speed is 300 turns/min.Rotary drum is connected with vacuum pump.
Step 30）Prepare the carbon nanotube paper of nano nickel particles load：PAN and nickel salt are 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 into into step 20）On the carbon nanotube paper of preparation, spraying is formed
There is the carbon nanotube paper of nickel salt.Adopt the parameter of electrostatic painting process for：Voltage is 18 kV, and flow velocity is 0.5mL/h, spinning head
It is 28cm with the distance between reception device, spray time is 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 CNT of nano nickel particles load
Paper.
Step 40）Prepare carbon nanotube paper, stannum composite nano materials：By step 30）The nano nickel particles load of preparation
During carbon nanotube paper is placed in molar concentration for 35mmol/L, the tin-salt solution that temperature is 60 DEG C, 12h is kept, CNT is obtained
Paper, stannum composite nano materials.Wherein, tin-salt solution is that stannous sulfate is dissolved in ethanol solution to be obtained.
Step 50）Prepare carbon nanotube paper, stannum, graphene quantum dot composite nano materials：Using electrostatic painting process, will
Spray coating liquor is sprayed on step 40）The carbon nanotube paper of preparation, stannum composite nano materials surface, and be dried, make carbon nanotube paper,
Stannum, graphene quantum dot composite nano materials.Adopt the parameter of electrostatic painting process for：Voltage is 26kV, and flow velocity is 0.5mL/
H, the distance between spinning head and reception device are 28cm, and the time is 60min.Spray coating liquor is the stone that mass concentration is 1.2mg/mL
Black alkene quantum dot solution.
Made by carbon nanotube paper, stannum, in graphene quantum dot composite nano materials, made by carbon nanotube paper, stannum, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres granule of CNT, described hollow nanospheres
Grain is made up of Sn；The area load not covered by hollow nanospheres granule in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.CNT, stannum, the thickness of graphene quantum dot composite nano materials are 35 μm.
Embodiment 6
Using carbon nanotube paper, stannum, graphene quantum dot composite nano materials as lithium ion battery negative.The composite Nano material
The preparation method of material is as follows：
Step 10）Prepare CNT（CNTs）Dispersion liquid：By SWCN Dispersion of Solute Matter in methanol solvate, wherein, it is molten
The ratio of matter and solvent is 1mg:3ml；
Step 20）Prepare carbon nanotube paper：Using electrostatic painting process, carbon nanotube paper is prepared.Wherein, spray coating liquor is step
10）The carbon nano tube dispersion liquid of preparation.Adopt the parameter of electrostatic painting process for：Voltage is 15 kV, and flow velocity is 3mL/h, spray webbing
The distance between head and reception device are 18cm, and spray time is 45min.Reception device be cylindric rotary drum, drum surface by
The copper mesh composition of 450 mesh, rotary drum rotating speed is 350 turns/min.Rotary drum is connected with vacuum pump.
Step 30）Prepare the carbon nanotube paper of nano nickel particles load：PAN and nickel salt are 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 into into step 20）On the carbon nanotube paper of preparation, spraying is formed
There is the carbon nanotube paper of nickel salt.Adopt the parameter of electrostatic painting process for：Voltage is 26kV, and flow velocity is 1mL/h, spinning head and is connect
The distance between receiving apparatus are 22cm, and spray time is 35min.The carbon nanotube paper for being coated with nickel salt is heated up with 1 DEG C/min
To 275 DEG C of holding 2.8h, then 680 DEG C of holding 2.6h are warming up to 5 DEG C/min, obtain the CNT of nano nickel particles load
Paper.
Step 40）Prepare carbon nanotube paper, stannum composite nano materials：By step 30）The nano nickel particles load of preparation
During carbon nanotube paper is placed in molar concentration for 65mmol/L, the tin-salt solution that temperature is 90 DEG C, 2h is kept, CNT is obtained
Paper, stannum composite nano materials.Wherein, tin-salt solution is according to mass ratio 1 by stannous chloride and stannous acetate:1 system soluble in water
.
Step 50）Prepare carbon nanotube paper, stannum, graphene quantum dot composite nano materials：Using electrostatic painting process, will
Spray coating liquor is sprayed on step 40）The carbon nanotube paper of preparation, stannum composite nano materials surface, and be dried, make carbon nanotube paper,
Stannum, graphene quantum dot composite nano materials.Adopt the parameter of electrostatic painting process for：Voltage is 18kV, and flow velocity is 1.8 mL/
H, the distance between spinning head and reception device are 12cm, and the time is 40min.Spray coating liquor is the stone that mass concentration is 0.7mg/mL
Black alkene quantum dot solution.
Made by carbon nanotube paper, stannum, in graphene quantum dot composite nano materials, made by carbon nanotube paper, stannum, stone
In black alkene quantum dot composite nano materials, the area load hollow nanospheres granule of CNT, described hollow nanospheres
Grain is made up of Sn；The area load not covered by hollow nanospheres granule in hollow nanospheres particle surface and carbon nanotube paper
Graphene quantum dot layer.CNT, stannum, the thickness of graphene quantum dot composite nano materials are 45 μm.
To above-mentioned 2 comparative examples and 6 embodiments, the test of electric conductivity, capacity and cyclical stability is carried out respectively.Test result
As shown in table 1.
Table 1
As can be seen from Table 1：Carbon nanotube paper prepared by the embodiment of the present invention, stannum, graphene quantum dot composite nano materials
Electric conductivity 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.Embodiment 4
Electric conductivity be far superior to comparative example 1.Meanwhile, the capacity of composite nano materials prepared by the embodiment of the present invention is significantly larger than contrasted
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 comparative example 1
3 times.The capability retention of composite nano materials prepared by the embodiment of the present invention is also significantly larger than comparative example.After 100 circulations,
The capability retention of embodiment 4 is 96%, and comparative example 1 only 45%.
The basic principles, principal features and advantages of the present 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 description be intended merely to into
One step explanation the present invention principle, without departing from the spirit and scope of the present invention, the present invention also have various change and
Improve, these changes and improvements are both fallen within scope of the claimed invention.The scope of protection of present invention will by right
Ask book and its equivalent thereof.
Claims (10)
1. a kind of preparation method of used as negative electrode of Li-ion battery flexible compound nano material, it is characterised in that the method includes：
Step 10）Prepare carbon nano tube dispersion liquid：By Dispersion of Solute Matter in methanol, ethanol, acetone, N,N-dimethylformamide or
N,N-dimethylacetamide solvent, wherein, the ratio of solute and solvent is 1mg:2~10ml；Described solute is single
The mixture of pipe, multi-walled carbon nano-tubes or SWCN and multi-walled carbon nano-tubes composition；
Step 20）Prepare carbon nanotube paper：Using electrostatic painting process, carbon nanotube paper is prepared；Wherein, spray coating liquor is step
10）The carbon nano tube dispersion liquid of preparation, reception device are cylindric rotary drum, and rotary drum is connected with vacuum pump；
Step 30）Prepare the carbon nanotube paper of nano nickel particles load：Polyacrylonitrile and nickel salt are mixed, presoma is made molten
Liquid, 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 into into step 20）On the carbon nanotube paper of preparation, formation is coated with nickel
The carbon nanotube paper of salt；The carbon nanotube paper for being coated with nickel salt is warming up to into 250 ~ 280 DEG C of 1 ~ 3h of holding with 1 ~ 2 DEG C/min, then
600 ~ 800 DEG C of 2 ~ 4h of holding are warming up to 5 ~ 10 DEG C/min, the carbon nanotube paper of nano nickel particles load is obtained；
Step 40）Prepare carbon nanotube paper, stannum composite nano materials：By step 30）The carbon of the nano nickel particles load of preparation is received
During mitron paper is placed in molar concentration for 20 ~ 100mmol/L, the tin-salt solution that temperature is 25 ~ 90 DEG C, 2 ~ 12h is kept, carbon is obtained and is received
Mitron paper, stannum composite nano materials；
Step 50）Prepare carbon nanotube paper, stannum, graphene quantum dot composite nano materials：Using electrostatic painting process, will spraying
Liquid is sprayed on step 40）The carbon nanotube paper of preparation, stannum composite nano materials surface, and be dried, make carbon nanotube paper, stannum,
Graphene quantum dot composite nano materials；Described spray coating liquor is the graphene quantum dot that mass concentration is 0.5 ~ 1.2 mg/mL
Solution.
2., according to the preparation method of the used as negative electrode of Li-ion battery flexible compound nano material described in claim 1, its feature exists
In described step 20）In, adopt the parameter of electrostatic painting process for：Voltage is 10 ~ 40 kV, and flow velocity is 0.5 ~ 5.0 mL/
H, the distance between spinning head and reception device are 10 ~ 40 cm, and spray time is 20 ~ 60min.
3., according to the preparation method of the used as negative electrode of Li-ion battery flexible compound nano material described in claim 1, its feature exists
In described step 20）In, drum surface is made up of the copper mesh of 200 ~ 500 mesh, and rotary drum rotating speed is 100 ~ 600 turns/min.
4., according to the preparation method of the used as negative electrode of Li-ion battery flexible compound nano material described in claim 1, its feature exists
In described step 30）In, adopt the parameter of electrostatic painting process for：Voltage is 10 ~ 40 kV, and flow velocity is 0.5 ~ 4.0 mL/
H, the distance between spinning head and reception device are 10 ~ 30 cm, and spray time is 15 ~ 60min.
5., according to the preparation method of the used as negative electrode of Li-ion battery flexible compound nano material described in claim 1, its feature exists
In described step 30）In, nickel salt is Nickel dichloride., nickel sulfate or nickel acetate.
6., according to the preparation method of the used as negative electrode of Li-ion battery flexible compound nano material described in claim 1, its feature exists
In described step 40）In, tin-salt solution be by the one kind in stannous chloride, stannous sulfate, stannous acetate or any two be dissolved in
In water or ethanol solution, tin-salt solution is made.
7., according to the preparation method of the used as negative electrode of Li-ion battery flexible compound nano material described in claim 1, its feature exists
In described step 40）In, carbon nanotube paper, the structure of stannum composite nano materials are：The area load of CNT is hollow to be received
Rice ball particle；Described hollow nanospheres granule is made up of Sn.
8., according to the preparation method of the used as negative electrode of Li-ion battery flexible compound nano material described in claim 1, its feature exists
In described step 50）In, adopt the parameter of electrostatic painting process for：Voltage is 10 ~ 30 kV, and flow velocity is 0.5 ~ 2.0 mL/
H, the distance between spinning head and reception device are 10 ~ 30 cm, and the time is 30 ~ 60min.
9., according to the preparation method of the used as negative electrode of Li-ion battery flexible compound nano material described in claim 1, its feature exists
In described step 50）Made by carbon nanotube paper, stannum, in graphene quantum dot composite nano materials, the surface of CNT
Load hollow nanospheres granule, described hollow nanospheres granule are made up of Sn；Hollow nanospheres particle surface and carbon nanometer
The area load graphene quantum dot layer not covered by hollow nanospheres granule in pipe paper.
10., according to the preparation method of the used as negative electrode of Li-ion battery flexible compound nano material described in claim 9, its feature exists
In described step 50）In, CNT, stannum, graphene quantum dot composite nano materials
Thickness be 20 ~ 50 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611189498.6A CN106531969B (en) | 2016-12-21 | 2016-12-21 | A kind of preparation method of negative electrode of lithium ion battery flexible compound nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611189498.6A CN106531969B (en) | 2016-12-21 | 2016-12-21 | A kind of preparation method of negative electrode of lithium ion battery flexible compound nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106531969A true CN106531969A (en) | 2017-03-22 |
| CN106531969B CN106531969B (en) | 2019-07-30 |
Family
ID=58340561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611189498.6A Active CN106531969B (en) | 2016-12-21 | 2016-12-21 | A kind of preparation method of negative electrode of lithium ion battery flexible compound nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106531969B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109524709A (en) * | 2017-09-20 | 2019-03-26 | 成功大学 | Lithium battery |
| CN109546112A (en) * | 2018-11-15 | 2019-03-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin nanosphere and the compound preparation method of electrode material of carbon nanotube and products thereof and application |
| CN110444767A (en) * | 2018-05-03 | 2019-11-12 | 中国科学技术大学 | It is a kind of for the three-dimensional collector of primary/secondary cell lithium anode, lithium anode and primary/secondary cell |
| CN110504451A (en) * | 2019-08-09 | 2019-11-26 | 电子科技大学 | A kind of preparation method of ultra-thin lithium an- ode |
| CN117174914A (en) * | 2023-09-20 | 2023-12-05 | 中能鑫储(北京)科技有限公司 | Three-dimensional current collector applied to aluminum ion battery and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857191A (en) * | 2010-04-16 | 2010-10-13 | 华侨大学 | Flexible transduction/energy-storage nanodevice and preparation method |
| CN102945947A (en) * | 2012-12-04 | 2013-02-27 | 中国科学院上海硅酸盐研究所 | Preparation method of flexible binding agent-free self-support combination electrode |
| US20150349307A1 (en) * | 2014-05-27 | 2015-12-03 | GM Global Technology Operations LLC | Method for preparing a coated lithium battery component |
| CN105870448A (en) * | 2016-06-08 | 2016-08-17 | 常熟理工学院 | High-capacity metallic oxide and carbon nanofiber composite flexible electrode film |
| CN106207118A (en) * | 2016-07-26 | 2016-12-07 | 中南大学 | A kind of regulate and control the method for nano titanium oxide pattern of graphene coated and the product of preparation thereof and application |
-
2016
- 2016-12-21 CN CN201611189498.6A patent/CN106531969B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857191A (en) * | 2010-04-16 | 2010-10-13 | 华侨大学 | Flexible transduction/energy-storage nanodevice and preparation method |
| CN102945947A (en) * | 2012-12-04 | 2013-02-27 | 中国科学院上海硅酸盐研究所 | Preparation method of flexible binding agent-free self-support combination electrode |
| US20150349307A1 (en) * | 2014-05-27 | 2015-12-03 | GM Global Technology Operations LLC | Method for preparing a coated lithium battery component |
| CN105870448A (en) * | 2016-06-08 | 2016-08-17 | 常熟理工学院 | High-capacity metallic oxide and carbon nanofiber composite flexible electrode film |
| CN106207118A (en) * | 2016-07-26 | 2016-12-07 | 中南大学 | A kind of regulate and control the method for nano titanium oxide pattern of graphene coated and the product of preparation thereof and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109524709A (en) * | 2017-09-20 | 2019-03-26 | 成功大学 | Lithium battery |
| CN110444767A (en) * | 2018-05-03 | 2019-11-12 | 中国科学技术大学 | It is a kind of for the three-dimensional collector of primary/secondary cell lithium anode, lithium anode and primary/secondary cell |
| CN109546112A (en) * | 2018-11-15 | 2019-03-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin nanosphere and the compound preparation method of electrode material of carbon nanotube and products thereof and application |
| CN109546112B (en) * | 2018-11-15 | 2021-07-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tin nanosphere and carbon nanotube composite electrode material, product and application thereof |
| CN110504451A (en) * | 2019-08-09 | 2019-11-26 | 电子科技大学 | A kind of preparation method of ultra-thin lithium an- ode |
| CN117174914A (en) * | 2023-09-20 | 2023-12-05 | 中能鑫储(北京)科技有限公司 | Three-dimensional current collector applied to aluminum ion battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106531969B (en) | 2019-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Self-healing liquid metal nanoparticles encapsulated in hollow carbon fibers as a free-standing anode for lithium-ion batteries | |
| CN105098160B (en) | The hollow porous carbon of a kind of doped graphene/silicon nanofiber lithium cell cathode material and preparation method thereof | |
| JP6445585B2 (en) | Porous carbon nanotube microspheres and production method and use thereof, metallic lithium-skeleton carbon composite material and production method thereof, negative electrode, and battery | |
| CN106531969B (en) | A kind of preparation method of negative electrode of lithium ion battery flexible compound nano material | |
| CN106784819B (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| Xu et al. | Tri-functionalized polypropylene separator by rGO/MoO 2 composite for high-performance lithium–sulfur batteries | |
| CN100576610C (en) | A kind of silicon composite and preparation method thereof that contains | |
| CN102832379A (en) | Preparation method of positive material for lithium-sulfur battery | |
| CN108448080A (en) | A kind of graphene coated silicon/metal composite negative pole material and preparation method thereof | |
| CN106654215A (en) | Small biological molecule and graphene composite material functional film and preparation method thereof | |
| CN108682813A (en) | A kind of preparation method and application of Si-C composite material | |
| CN106554004B (en) | A kind of porous carbon materials and its preparation method and application prepared based on aromatic compound monomer | |
| CN106450246A (en) | Porous silicon-carbon composite material for lithium ion battery and preparation method of material | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN107317011A (en) | A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping | |
| CN103682413A (en) | High-rate long-cycle-life lithium iron phosphate battery and preparation method thereof | |
| CN104362293A (en) | Sulfur-containing positive electrode material with multi-grade structure as well as preparation method and application of sulfur-containing positive electrode material | |
| CN113097478A (en) | Double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery cathode material and preparation method thereof | |
| CN107093709A (en) | A kind of porous carbon ball loads the preparation method of sulfide composite | |
| CN110391400B (en) | Preparation method of flexible self-supporting silicon/ultra-long titanium dioxide nanotube electrode | |
| Wei et al. | One-dimensional core-shell composite of AgNWs@ Si@ GO for high-specific capacity and high-safety anode materials of lithium-ion batteries | |
| Yan et al. | Hierarchical MnO2@ NiCo2O4@ Ti3SiC2/carbon cloth core-shell structure with superior electrochemical performance for all solid-state supercapacitors | |
| Wang et al. | ZnCo2O4 nanoflakes loaded on a Cu-supported Fe2O3-C network as an integrated lithium-ion battery anode | |
| CN113809286B (en) | Metal Organic Framework (MOF) catalyzed growth carbon nanotube coated nickel-tin alloy electrode material and preparation method and application thereof | |
| CN104600265B (en) | A kind of carbon sulphur composite positive pole and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200107 Address after: Room 501, No. 85, Xiaguang Dongli, Haicang District, Xiamen City, Fujian Province Patentee after: Xiamen reliable intellectual property service Co., Ltd Address before: 224051 No. 1166 Century Avenue, Jiangsu, Yancheng City Patentee before: Yangcheng Institute of Technology |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201030 Address after: 274000 No. 1633, Lanzhou Road, hi tech Zone, Shandong, Heze Patentee after: SHANDONG ODA COMPOSITE MATERIALS Co.,Ltd. Address before: Room 501, No. 85, Xiaguang Dongli, Haicang District, Xiamen City, Fujian Province Patentee before: Xiamen reliable intellectual property service Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210727 Address after: 274000 No. 1666, Caozhou West Road, high tech Zone, Heze City, Shandong Province Patentee after: SHANDONG PINGAN ELECTRIC EQUIPMENT Co.,Ltd. Address before: 1633 Lanzhou Road, hi tech Zone, Heze City, Shandong Province Patentee before: SHANDONG ODA COMPOSITE MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right |