CN110197899A - A kind of preparation method of lithium foil - Google Patents
A kind of preparation method of lithium foil Download PDFInfo
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- CN110197899A CN110197899A CN201910535606.8A CN201910535606A CN110197899A CN 110197899 A CN110197899 A CN 110197899A CN 201910535606 A CN201910535606 A CN 201910535606A CN 110197899 A CN110197899 A CN 110197899A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to lithium foil technical fields, and in particular to a kind of preparation method of lithium foil includes the following steps: that (1) carbon nanotube is acidified；(2) preparation of spinning solution；(3) spinning forms a film；(4) it is carbonized；(5) electro-deposition.The present invention is using three-dimensional carbon nano-fiber film as matrix, lithium powder is deposited in carbon nano-fiber film by electro-deposition, the impedance of relatively conventional lithium foil, surface SEI film is significantly reduced, and has high-energy density and excellent cycle performance using the matrix as the lithium battery of cathode；Furthermore, the present invention has been mixed into carbon nanotube in carbon nano-fiber film, carbon nanotube is embedded in the network structure of carbon nano-fiber film, the current flow uniformity of carbon nano-fiber film is improved when electro-deposition, lithium is realized in the uniform deposition of carbon nano-fiber film, to can effectively inhibit the generation of Li dendrite and dead lithium as cathode of lithium battery.
Description
Technical field
The present invention relates to lithium foil technical fields, and in particular to a kind of preparation method of lithium foil.
Background technique
The rechargeable battery that lithium ion battery is made of positive plate, negative electrode tab, diaphragm and electrolyte or electrolyte,
Because having the characteristics that energy density height, having extended cycle life and environmental-friendly being widely used in mobile communication equipment, notebook
In the electronic products such as computer, digital camera, and gradually play a role in electric vehicle and energy storage field.Lithium ion at present
The negative electrode material of battery mostly uses graphite, since the theoretical specific capacity of graphite is limited, as battery energy density is wanted in market
Ask higher and higher, lithium anode is widely studied as a kind of cathode that theoretical specific capacity is high.
Although lithium anode has very high theoretical specific capacity (3861mAh/g), being used as cathode of lithium battery be can be improved
Battery energy density, but insertion and the process deviate from occur in graphite flake layer not with lithium ion when graphite cathode charge and discharge
Together, lithium anode is in charge and discharge happens is that the process of chemical deposition and the dissolution of lithium, this deposition and course of dissolution meeting
Sizable volume change is brought, and nonuniform deposition can occur, Li dendrite is generated and punctures diaphragm, lead to the safe thing of short circuit
Therefore.Therefore, although lithium anode has been widely studied, it yet there are no its commercial applications.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of preparations of lithium foil
Method, the lithium foil have the characteristics that high-specific surface area, effectively inhibit the generation of Li dendrite as negative current collector have high-energy
Density and excellent cycle performance.
The purpose of the invention is achieved by the following technical solution:
A kind of preparation method of lithium foil, includes the following steps:
(1) carbon nanotube is acidified: carbon nanotube is added in mixed acid, is heated to 60-80 DEG C, keeps the temperature 1-3h, be filtered, washed,
Carbon nanotube after being acidified after drying, the mixed acid are mixed by concentrated nitric acid and the concentrated sulfuric acid；
(2) preparation of spinning solution: the carbon nanotube after step (1) acidification is added in polyacrylonitrile solution, ultrasonic disperse
Afterwards, it is spare to obtain spinning solution；
(3) spinning forms a film: the spinning solution that step (2) is obtained carries out electrostatic spinning, obtains nano fibrous membrane；
(4) it is carbonized: the nano fibrous membrane being carbonized, carbon nano-fiber film is obtained；
(5) electro-deposition: using the carbon nano-fiber film as cathode, lithium metal piece is dipped in electrolyte and carries out electric sink as anode
Product reacts to arrive the lithium foil.
Lithium powder is deposited on carbon nano-fiber film by electro-deposition using three-dimensional carbon nano-fiber film as matrix by the present invention
On, the impedance of relatively conventional lithium foil, surface SEI film is significantly reduced, and the lithium battery using the matrix as cathode has
High-energy density and excellent cycle performance；In addition, the present invention has been mixed into carbon nanotube, carbon nanometer in carbon nano-fiber film
Pipe is embedded in the network structure of carbon nano-fiber film, and the current flow uniformity of carbon nano-fiber film is improved when electro-deposition, realizes lithium
In the uniform deposition of carbon nano-fiber film, to can effectively inhibit the generation of Li dendrite and dead lithium as cathode of lithium battery.
Wherein, in step (1), the mixed acid is mixed by concentrated nitric acid and the concentrated sulfuric acid ratio of 1:2-3 in mass ratio
It forms, the mass ratio of the carbon nanotube and mixed acid is 1:20-30.
The present invention makes carbon nano tube surface richness active group dough, in polypropylene by carrying out acidification to carbon nanotube
There is preferably dispersibility, so that carbon nanotube has preferably uniformly in nano fibrous membrane after spinning film forming in nitrile solution
Distributivity, the bending and electric conductivity of obtained lithium foil more preferably, meet industrial production demand.
Wherein, in step (2), the polyacrylonitrile solution is dissolved in n,N-Dimethylformamide by polyacrylonitrile and is made, institute
The mass ratio of carbon nanotube, polyacrylonitrile and N,N-dimethylformamide after stating acidification is 1:1-2:15-20.
Mass ratio of the present invention by carbon nanotube, polyacrylonitrile and n,N-Dimethylformamide after control acidification, benefit
In the progress of spinning film forming, carbon nanotube good dispersion on the tunica fibrosa that polyacrylonitrile is formed, the stable structure of tunica fibrosa.
Wherein, in step (2), the temperature of the ultrasonic disperse is 40-50 DEG C, and time 2-4h, carbon nanotube is poly- third
Alkene nitrile solution has preferable dispersity.
Wherein, in step (3), the spinning voltage of electrostatic spinning is 20-30kV, and spinning flow velocity is 0.5-0.7mL/h, is received
Distance is 8-16cm.
The fibre diameter of nano fibrous membrane produced by the present invention be 200-300nm, nano fibrous membrane with a thickness of 13.7-
18.5 μm, the surface of nano fibrous membrane is without cracking, conducive to the intensity for keeping structure after carbonization.
Wherein, in step (4), the concrete operations of carbonization are as follows: the nano fibrous membrane is placed in atmosphere of inert gases, with
The heating rate of 3-5 DEG C/min is warming up to 300-400 DEG C, keeps the temperature 0.5-1.5h, is warming up to the heating rate of 9-10 DEG C/min
900-1100 DEG C, keep the temperature 4-6h.
The present invention can control the surface topography of carbon nano-fiber film by the actual conditions of control high temperature cabonization, be carbonized
Process is less likely to occur the phenomenon that tunica fibrosa rupture volume contraction, and three-dimensional net structure is complete, has uniform conductive
Performance, conducive to uniform lithium metal sedimentary is formed.
Wherein, in step (5), the current density of electro-deposition is 20-30mA/cm3, the time of electro-deposition is 120-
200min。
Current density is too small, and deposition efficiency is too low, is unfavorable for the uniform deposition of lithium metal；Current density is excessive, deposits
Journey is easier to generate metal Li dendrite in defect area, is similarly unfavorable for the formation of uniform lithium metal layer, especially of the invention
Matrix is the non-uniform three dimensional matrix in surface, and unreasonable control current density is that showing for lithium foil surface irregularity more easily occurs
As.
Wherein, in step (5), the electrolyte is by LiPF6It is formed with solvent, the LiPF6Concentration be 0.8-
1.2mol/L, the solvent is by the vinylene carbonate of 1-2wt%, the cetyl benzenesulfonic acid sodium of 0.1-0.3wt%, 0.1-1wt%
Polyethylene glycol oxide, 40-60wt% EC and 37-57wt% EMC composition.
In order to which lithium metal has preferable surface deposition morphology on carbon nanofiber membrane, another core point of the invention exists
In the composition of electrolyte, vinylene carbonate, cetyl benzenesulfonic acid sodium and polyethylene glycol oxide are added in a solvent as function
Property additive, be conducive to the uniform deposition of lithium metal, obtained lithium foil surface does not have granular lithium metal to generate, surface topography
More smooth, the stability of lithium foil gets a promotion.
The beneficial effects of the present invention are: the present invention, will by electro-deposition using three-dimensional carbon nano-fiber film as matrix
Lithium powder is deposited in carbon nano-fiber film, and the impedance of relatively conventional lithium foil, surface SEI film is significantly reduced, with the base
Body has high-energy density and excellent cycle performance as the lithium battery of cathode；In addition, the present invention is in carbon nano-fiber film
In be mixed into carbon nanotube, carbon nanotube is embedded in the network structure of carbon nano-fiber film, and when electro-deposition improves Nano carbon fibers
The current flow uniformity of film is tieed up, realizes lithium in the uniform deposition of carbon nano-fiber film, to can effectively press down as cathode of lithium battery
The generation of Li dendrite processed and dead lithium.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of preparation method of lithium foil, includes the following steps:
(1) carbon nanotube is acidified: carbon nanotube being added in mixed acid, is heated to 70 DEG C, 2h is kept the temperature, after being filtered, washed, drying
Carbon nanotube after being acidified, the mixed acid are mixed by concentrated nitric acid and the concentrated sulfuric acid；
(2) preparation of spinning solution: the carbon nanotube after step (1) acidification is added in polyacrylonitrile solution, ultrasonic disperse
Afterwards, it is spare to obtain spinning solution；
(3) spinning forms a film: the spinning solution that step (2) is obtained carries out electrostatic spinning, obtains nano fibrous membrane；
(4) it is carbonized: the nano fibrous membrane being carbonized, carbon nano-fiber film is obtained；
(5) electro-deposition: using the carbon nano-fiber film as cathode, lithium metal piece is dipped in electrolyte and carries out electric sink as anode
Product reacts to arrive the lithium foil.
Wherein, in step (1), the mixed acid is mixed by concentrated nitric acid and the concentrated sulfuric acid ratio of 1:2.5 in mass ratio
It forms, the mass ratio of the carbon nanotube and mixed acid is 1:25.
Wherein, in step (2), the polyacrylonitrile solution is dissolved in n,N-Dimethylformamide by polyacrylonitrile and is made, institute
The mass ratio of carbon nanotube, polyacrylonitrile and N,N-dimethylformamide after stating acidification is 1:1.5:18.
Wherein, in step (2), the temperature of the ultrasonic disperse is 45 DEG C, time 3h.
Wherein, in step (3), the spinning voltage of electrostatic spinning is 25kV, and spinning flow velocity is 0.6mL/h, receives distance and is
12cm。
Wherein, in step (4), the concrete operations of carbonization are as follows: the nano fibrous membrane is placed in atmosphere of inert gases, with
The heating rate of 4 DEG C/min is warming up to 350 DEG C, keeps the temperature 1h, is warming up to 1000 DEG C with the heating rate of 9.5 DEG C/min, keeps the temperature 5h.
Wherein, in step (5), the current density of electro-deposition is 25mA/cm3, the time of electro-deposition is 160min.
Wherein, in step (5), the electrolyte is by LiPF6It is formed with solvent, the LiPF6Concentration be 1mol/L, institute
State solvent by the vinylene carbonate of 1.5wt%, the cetyl benzenesulfonic acid sodium of 0.2wt%, 0.5wt% polyethylene glycol oxide,
The EMC of the EC and 47.8wt% of 50wt% are formed.
Embodiment 2
A kind of preparation method of lithium foil, includes the following steps:
(1) carbon nanotube is acidified: carbon nanotube being added in mixed acid, is heated to 60 DEG C, 3h is kept the temperature, after being filtered, washed, drying
Carbon nanotube after being acidified, the mixed acid are mixed by concentrated nitric acid and the concentrated sulfuric acid；
(2) preparation of spinning solution: the carbon nanotube after step (1) acidification is added in polyacrylonitrile solution, ultrasonic disperse
Afterwards, it is spare to obtain spinning solution；
(3) spinning forms a film: the spinning solution that step (2) is obtained carries out electrostatic spinning, obtains nano fibrous membrane；
(4) it is carbonized: the nano fibrous membrane being carbonized, carbon nano-fiber film is obtained；
(5) electro-deposition: using the carbon nano-fiber film as cathode, lithium metal piece is dipped in electrolyte and carries out electric sink as anode
Product reacts to arrive the lithium foil.
Wherein, in step (1), the mixed acid mixed by concentrated nitric acid and the concentrated sulfuric acid ratio of 1:2 in mass ratio and
At the mass ratio of the carbon nanotube and mixed acid is 1:20.
Wherein, in step (2), the polyacrylonitrile solution is dissolved in n,N-Dimethylformamide by polyacrylonitrile and is made, institute
The mass ratio of carbon nanotube, polyacrylonitrile and N,N-dimethylformamide after stating acidification is 1:1:15.
Wherein, in step (2), the temperature of the ultrasonic disperse is 40 DEG C, time 4h, and carbon nanotube is molten in polyacrylonitrile
Liquid has preferable dispersity.
Wherein, in step (3), the spinning voltage of electrostatic spinning is 20kV, and spinning flow velocity is 0.5mL/h, receives distance and is
8cm。
Wherein, in step (4), the concrete operations of carbonization are as follows: the nano fibrous membrane is placed in atmosphere of inert gases, with
The heating rate of 3 DEG C/min is warming up to 300 DEG C, keeps the temperature 0.5h, is warming up to 900 DEG C with the heating rate of 9 DEG C/min, keeps the temperature 4h.
Wherein, in step (5), the current density of electro-deposition is 20mA/cm3, the time of electro-deposition is 120min.
Wherein, in step (5), the electrolyte is by LiPF6It is formed with solvent, the LiPF6Concentration be 0.8mol/L,
The solvent by the vinylene carbonate of 1wt%, the cetyl benzenesulfonic acid sodium of 0.1wt%, 0.1wt% polyethylene glycol oxide,
The EMC of the EC and 38.8wt% of 60wt% are formed.
Embodiment 3
A kind of preparation method of lithium foil, includes the following steps:
(1) carbon nanotube is acidified: carbon nanotube being added in mixed acid, is heated to 80 DEG C, 1h is kept the temperature, after being filtered, washed, drying
Carbon nanotube after being acidified, the mixed acid are mixed by concentrated nitric acid and the concentrated sulfuric acid；
(2) preparation of spinning solution: the carbon nanotube after step (1) acidification is added in polyacrylonitrile solution, ultrasonic disperse
Afterwards, it is spare to obtain spinning solution；
(3) spinning forms a film: the spinning solution that step (2) is obtained carries out electrostatic spinning, obtains nano fibrous membrane；
(4) it is carbonized: the nano fibrous membrane being carbonized, carbon nano-fiber film is obtained；
(5) electro-deposition: using the carbon nano-fiber film as cathode, lithium metal piece is dipped in electrolyte and carries out electric sink as anode
Product reacts to arrive the lithium foil.
Wherein, in step (1), the mixed acid mixed by concentrated nitric acid and the concentrated sulfuric acid ratio of 1:3 in mass ratio and
At the mass ratio of the carbon nanotube and mixed acid is 1:30.
Wherein, in step (2), the polyacrylonitrile solution is dissolved in n,N-Dimethylformamide by polyacrylonitrile and is made, institute
The mass ratio of carbon nanotube, polyacrylonitrile and N,N-dimethylformamide after stating acidification is 1:2:20.
Wherein, in step (2), the temperature of the ultrasonic disperse is 50 DEG C, time 4h, and carbon nanotube is molten in polyacrylonitrile
Liquid has preferable dispersity.
Wherein, in step (3), the spinning voltage of electrostatic spinning is 30kV, and spinning flow velocity is 0.7mL/h, receives distance and is
16cm。
Wherein, in step (4), the concrete operations of carbonization are as follows: the nano fibrous membrane is placed in atmosphere of inert gases, -5
DEG C/heating rate of min is warming up to 400 DEG C, 1.5h is kept the temperature, 1100 DEG C is warming up to the heating rate of 10 DEG C/min, keeps the temperature 6h.
Wherein, in step (5), the current density of electro-deposition is 30mA/cm3, the time of electro-deposition is 200min.
Wherein, in step (5), the electrolyte is by LiPF6It is formed with solvent, the LiPF6Concentration be 1.2mol/L,
The solvent by the vinylene carbonate of 2wt%, the cetyl benzenesulfonic acid sodium of 0.3wt%, 1wt% polyethylene glycol oxide, 40wt%
EC and 56.7wt% EMC composition.
Embodiment 4
The present embodiment the difference from embodiment 1 is that:
Wherein, in step (5), the electrolyte is by LiPF6It is formed with solvent, the LiPF6Concentration be 1mol/L, it is described molten
Agent is made of the EMC of the vinylene carbonate of 1.5wt%, the cetyl benzenesulfonic acid sodium of 0.2wt%, the EC of 50wt% and 48.3wt%.
Embodiment 5
The present embodiment the difference from embodiment 1 is that:
Wherein, in step (5), the electrolyte is by LiPF6It is formed with solvent, the LiPF6Concentration be 1mol/L, it is described molten
Agent is made of the EMC of the vinylene carbonate of 1.5wt%, the polyethylene glycol oxide of 0.5wt%, the EC of 50wt% and 48wt%.
Comparative example 1
This comparative example the difference from embodiment 1 is that:
Polyacrylonitrile solution is directly subjected to electrostatic spinning, obtains nano fibrous membrane, other steps and embodiment 1 are identical.
Battery is made as cathode in the lithium foil of embodiment 1-5 and comparative example 1, wherein plus plate current-collecting body is with nickle cobalt lithium manganate
As active material, for electrolyte using lithium hexafluoro phosphate as lithium salts, propene carbonate is organic solvent, in 3.0V-4.5V voltage model
In enclosing, charge and discharge cycles, the charge and discharge under 1C multiplying power are carried out to battery, record battery first discharge specific capacity is recycled through 400 times
Thickness swelling and capacity retention ratio.
The data of record are as follows:
| Specific discharge capacity mAh/g | Thickness swelling (%) | Through 400 circulation volume conservation rates (%) | |
| Embodiment 1 | 329.6 | 74.4 | 86.8 |
| Embodiment 2 | 301.5 | 80.3 | 83.7 |
| Embodiment 3 | 303.4 | 79.1 | 84.1 |
| Embodiment 4 | 285.8 | 82.6 | 80.2 |
| Embodiment 5 | 287.7 | 83.7 | 78.5 |
| Comparative example 1 | 265.1 | 105.7 | 71.1 |
As seen from the above table, lithium foil of the invention can effectively improve the capacity and cycle performance of lithium battery as cathode, from implementation
It is found that electrolyte composition when electro-deposition influences the deposition morphology of lithium, embodiment 1 has for the comparison of example 1, embodiment 4 and embodiment 5
There is preferable deposition uniformity, therefore capacity and cycle performance are all preferable；From the comparison of embodiment 1 and comparative example 1 it is found that lithium exists
The deposition uniformity for not having the carbon nano-fiber film of doped carbon nanometer pipe is also poor, thus capacity and cycle performance are also corresponding
Ground reduces.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (8)
1. a kind of preparation method of lithium foil, characterized by the following steps:
(1) carbon nanotube is acidified: carbon nanotube is added in mixed acid, is heated to 60-80 DEG C, keeps the temperature 1-3h, be filtered, washed,
Carbon nanotube after being acidified after drying, the mixed acid are mixed by concentrated nitric acid and the concentrated sulfuric acid；
(2) preparation of spinning solution: the carbon nanotube after step (1) acidification is added in polyacrylonitrile solution, ultrasonic disperse
Afterwards, it is spare to obtain spinning solution；
(3) spinning forms a film: the spinning solution that step (2) is obtained carries out electrostatic spinning, obtains nano fibrous membrane；
(4) it is carbonized: the nano fibrous membrane being carbonized, carbon nano-fiber film is obtained；
(5) electro-deposition: using the carbon nano-fiber film as cathode, lithium metal piece is dipped in electrolyte and carries out electric sink as anode
Product reacts to arrive the lithium foil.
2. a kind of preparation method of lithium foil according to claim 1, it is characterised in that: in step (1), the mixed acid by
Concentrated nitric acid and the concentrated sulfuric acid ratio of 1:2-3 in mass ratio are mixed, and the mass ratio of the carbon nanotube and mixed acid is
1:20-30。
3. a kind of preparation method of lithium foil according to claim 1, it is characterised in that: in step (2), the polyacrylonitrile
Solution is dissolved in n,N-Dimethylformamide by polyacrylonitrile and is made, carbon nanotube, polyacrylonitrile and N, N- bis- after the acidification
The mass ratio of methylformamide is 1:1-2:15-20.
4. a kind of preparation method of lithium foil according to claim 1, it is characterised in that: in step (2), the ultrasonic disperse
Temperature be 40-50 DEG C, time 2-4h.
5. a kind of preparation method of lithium foil according to claim 1, it is characterised in that: in step (3), the spinning of electrostatic spinning
Filament voltage is 20-30kV, and spinning flow velocity is 0.5-0.7mL/h, and receiving distance is 8-16cm.
6. a kind of preparation method of lithium foil according to claim 1, it is characterised in that: in step (4), the specific behaviour of carbonization
As: the nano fibrous membrane is placed in atmosphere of inert gases, is warming up to 300-400 DEG C with the heating rate of 3-5 DEG C/min,
0.5-1.5h is kept the temperature, 900-1100 DEG C is warming up to the heating rate of 9-10 DEG C/min, keeps the temperature 4-6h.
7. a kind of preparation method of lithium foil according to claim 1, it is characterised in that: in step (5), the electric current of electro-deposition
Density is 20-30mA/cm3, the time of electro-deposition is 120-200min.
8. a kind of preparation method of lithium foil according to claim 1, it is characterised in that: in step (5), the electrolyte by
LiPF6It is formed with solvent, the LiPF6Concentration be 0.8-1.2mol/L, the solvent by 1-2wt% vinylene carbonate,
The cetyl benzenesulfonic acid sodium of 0.1-0.3wt%, the polyethylene glycol oxide of 0.1-1wt%, the EC of 40-60wt% and the EMC of 37-57wt%
Composition.
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| CN110656391A (en) * | 2019-09-25 | 2020-01-07 | 翁菀蕾 | Composite conductive fabric and manufacturing method thereof |
| CN111900373A (en) * | 2020-08-04 | 2020-11-06 | 大连理工大学 | Preparation method of lithium dendrite-resistant lithium metal battery cathode side separator material |
| CN113921768A (en) * | 2021-10-08 | 2022-01-11 | 北京化工大学 | Preparation method of flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material |
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