CN105914359A - Preparation method of flexible positive electrode of foldable lithium battery - Google Patents
Preparation method of flexible positive electrode of foldable lithium battery Download PDFInfo
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- CN105914359A CN105914359A CN201610485053.6A CN201610485053A CN105914359A CN 105914359 A CN105914359 A CN 105914359A CN 201610485053 A CN201610485053 A CN 201610485053A CN 105914359 A CN105914359 A CN 105914359A
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- magnetron sputtering
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- positive electrode
- ion battery
- lithium ion
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 41
- 229910052744 lithium Inorganic materials 0.000 title claims description 40
- 239000012528 membrane Substances 0.000 claims abstract description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 36
- 239000010941 cobalt Substances 0.000 claims description 35
- 229910017052 cobalt Inorganic materials 0.000 claims description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 35
- 239000011159 matrix material Substances 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 abstract 3
- 239000000758 substrate Substances 0.000 abstract 1
- 239000013077 target material Substances 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 15
- 239000004917 carbon fiber Substances 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 229920002239 polyacrylonitrile Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000011149 active material Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010041 electrostatic spinning Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a flexible positive electrode material of a foldable lithium-ion battery. The method comprises the following steps of: putting a carbon nanofiber membrane into a magnetron sputtering substrate; introducing argon and oxygen into a magnetron sputtering cavity; with lithium cobalt oxide as a target material, starting magnetron sputtering to obtain a composite flexible membrane sample; putting the obtained composite flexible membrane sample into a tube furnace, and heating the sample under argon protection to obtain required carbon nanofiber membrane/lithium cobalt oxide three-dimensional coaxial composite membrane. The method has the beneficial effects that the carbon nanofiber/lithium cobalt oxide three-dimensional coaxial composite membrane has good mechanical strength, flexibility and elasticity, is a self-supported flexible membrane, and can be bent and folded; and the mechanical property is good.
Description
Technical field
The invention belongs to technical field of lithium ion, relate to a kind of collapsible lithium ion battery soft
The preparation method of property positive electrode.
Background technology
Lithium ion battery has high energy density and excellent cyclical stability, at miniature electric
Equipment, electric automobile, mixed type electric automobile have a wide range of applications.At present, business-like
The preparation method of the both positive and negative polarity of lithium ion battery is the active material particle of mix homogeneously, conduction
The slurry of agent and binding agent is coated in Copper Foil or aluminum foil current collector, is assembled into after being dried compacting
Lithium ion battery.The defect of this preparation method is in both positive and negative polarity pole piece transition bending and the mistake of folding
In journey, both positive and negative polarity active material and collector depart from, and finally affect the comprehensive of lithium ion battery
Can, even cause the problems such as short circuit.
Development along with folding type electronic product, it is possible to the charger carrying out folding is that it must not
The ingredient that can lack, but the most flexible positive and negative pole material is prepared by folding lithium ion battery
One of Main Bottleneck, the preparation method of traditional lithium ion battery plus-negative plate limits it soft
Application in property lithium ion battery.The preparation side of currently reported lithium ion battery flexibility negative pole
Method, including utilizing carbon fiber, the three-dimensional order material such as Graphene and nickel foam does conductive current collector,
Achieve greater advance.But anode active material of lithium ion battery the most all uses high temperature solid-state
Method forms micron particles, how to be coated in situ on three-dimensional collector by positive electrode active materials,
Limit the development of flexible lithium ion battery positive pole.For solving this problem, researcher is adopted
It is modified with different three-dimensional collectors and original position painting method, but high temperature solid-state method is in roasting
Three-dimensional conductive collector is destroyed during burning.
Therefore prepare high performance compliant conductive collector and select the coating in situ of suitable method
Active material to forming composite and flexible positive pole on flexible current-collecting body, be prepare at present collapsible lithium from
The research emphasis of sub-cell flexible positive pole.
Summary of the invention
It is an object of the invention to provide a kind of collapsible lithium ion battery flexibility positive electrode
Preparation method, the preparation method of the both positive and negative polarity solving current lithium ion battery is mix homogeneously
The slurry of active material particle, conductive agent and binding agent be coated to Copper Foil or aluminum foil current collector
On, it is assembled into lithium ion battery after being dried compacting, so, both positive and negative polarity pole piece transition bending and folding
During Die, both positive and negative polarity active material and collector depart from, and finally affect combining of lithium ion battery
Close performance, the problem even causing short circuit.
The technical solution adopted in the present invention is that carbon nano-fiber film is placed in the base of magnetron sputtering
Body, is passed through argon and oxygen in the cavity of magnetron sputtering, using cobalt acid lithium as target, opens
Magnetron sputtering obtains composite and flexible membrane sample；The composite and flexible membrane sample obtained is placed in tube furnace
In, heat up under argon shield and obtain required carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane.
Further, described magnetron sputtering matrix internal gas pressure 10～3Pa-10～4Pa。
Further, in described magnetron sputtering matrix, argon and oxygen press the proportional arrangement of 8:1-10:1.
Further, the power keeping sputtering in described magnetron sputtering matrix is 200W-400W,
The rotary speed of magnetron sputtering matrix is 100rpm-200rpm；The cobalt acid lithium target of magnetron sputtering
The distance on material and chassis is 30～100mm.
Further, described magnetron sputtering working gas flow is 150～300sccm.
Further, the thickness 20～2000nm of described cobalt acid lithium shell.
Further, described composite and flexible membrane sample is placed in tube furnace, with 1 DEG C/min-3 DEG C/min
Speed be warming up to 500 DEG C-900 DEG C, be incubated 100min-120min at this temperature, natural
It is cooled to room temperature.
The invention has the beneficial effects as follows that carbon nano-fiber/cobalt acid lithium three-dimensional coaxial composite membrane has very
Good mechanical strength, pliability and elasticity, this composite membrane is the flexible membrane of a kind of self-supporting, energy
Enough bendings and folding；Satisfactory mechanical property.
Accompanying drawing explanation
Fig. 1 is the photo of flexible nano carbon-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane；
Fig. 2 (a) is the microgram of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane；
Fig. 2 (b) is the scanning electron microscope (SEM) photograph of carbon nano-fiber/cobalt acid lithium three-dimensional coaxial composite membrane；
Fig. 2 (c) is the projection Electronic Speculum figure of individual carbon fibers/cobalt acid lithium three-dimensional coaxial fiber；
Fig. 3 is the charge-discharge performance of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane positive pole
Figure.
Fig. 4 is the cycle performance figure of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane positive pole.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
Electrostatic spinning apparatus system is used after polyacrylonitrile is dissolved completely in dimethyl formamide solution
Standby flexible nano carbon-fiber film, polyacrylonitrile with the mass ratio of dimethyl formamide solution is
1:7-1:8, after vacuum drying in tube furnace, under air atmosphere, with 1 DEG C/min-2 DEG C/min
Speed be warming up to 200 DEG C-300 DEG C after pre-oxidize 1h-2h.In high-purity argon after having pre-oxidized
Carbonization after being warming up to 800 DEG C-1000 DEG C with the speed of 2 DEG C/min-3 DEG C/min in gas atmosphere protection
30min obtains required flexible nano carbon-fiber film.The thickness of flexible nano carbon-fiber film is
20～200 μm, porosity is 50-90%, and hot strength is at 10-500mPa；Carbon fiber
Radius is 50～1000nm, is controlled by the diameter of precursor polymer fiber.
Prepared by collapsible lithium battery flexibility positive pole: polyacrylonitrile is dissolved completely in dimethyl formyl
Flexible nano carbon-fiber film is prepared with electrostatic spinning apparatus, by the flexible nano of preparation after amine aqueous solution
Carbon-fiber film is placed in the matrix of magnetron sputtering, is taken away inside magnetron sputtering matrix by vacuum pump
Air, makes air pressure reach 10～3Pa-10～4Pa；By argon and oxygen in the ratio of 8:1-10:1
It is passed through in the cavity of magnetron sputtering, keeps pressure at 2Pa-3Pa；Using cobalt acid lithium as target,
Opening magnetron sputtering, the power keeping sputtering is 200W-400W, the rotation of magnetron sputtering matrix
Rotary speed is 100rpm-200rpm；The cobalt acid lithium target of magnetron sputtering and the distance on chassis are
30～100mm.Working gas flow is 150～300sccm, the thickness of cobalt acid lithium shell
20～2000nm, obtain composite and flexible membrane sample；The composite and flexible membrane sample obtained is placed in pipe
In formula stove, under argon shield, it is warming up to 500 DEG C-900 DEG C with the speed of 1 DEG C/min-3 DEG C/min,
It is incubated 100min-120min at this temperature, is naturally cooling to room temperature, obtain required nanometer
Carbon-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane.The shell of carbon nano-fiber and cobalt acid lithium is formed
Coaxial fiber.
It is also an advantage of the present invention that to prepare a kind of thickness controlled, high mechanical properties is high
Electric conductivity, lightweight, high porosity, there is certain flexible carbon nano-fiber film/cobalt acid lithium
Three-dimensional coaxial composite membrane, this composite membrane is the flexible membrane of a kind of self-supporting, it is possible to bends and folds；
Satisfactory mechanical property；Preparation process need not equipment and the exacting terms of costliness, simple to operate,
The most easy, manufacturing cycle is short, and experiment condition is simple, can realize industrialized production.When being used as
During the positive electrode of lithium ion battery, there is the stable circulation that high charging and discharging capacity is become reconciled
Property.This preparation method is simple, can carry out large-scale production.
Embodiment 1
Accurately weigh 38g polyacrylonitrile and 290g dimethyl formamide solution, after being completely dissolved
Being placed in electrostatic spinning apparatus, arranging spinning voltage is 20kv, receiving range 18cm, spinning
Flow velocity is 1.5mL/min.Obtain the polyacrylonitrile fibre membrane of a diameter of about 600nm.Very
Empty dried in tube furnace, in air atmosphere, heat up with the speed of 1 DEG C/min, pass through
220min is warming up to 250 DEG C, pre-oxidizes 1h at a temperature of 250 DEG C.After having pre-oxidized
It is warming up to 850 DEG C with the speed of 2 DEG C/min, at this temperature in high-purity argon gas atmosphere protection
Carbonization 30min obtains required compliant conductive carbon nano-fiber film, and the radius of carbon fiber is 500nm
Left and right.
Second step is the preparation of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane, specifically walks
Suddenly:
Step (1). the flexible nano carbon-fiber film of preparation is placed in the matrix of magnetron sputtering, passes through
Vacuum pump takes the air inside magnetron sputtering matrix away, makes air pressure reach 10～3Pa；
Step (2). argon and oxygen are passed through in the cavity of magnetron sputtering in the ratio of 9:1, protect
Hold pressure at 2Pa；
Step (3). using cobalt acid lithium as target, opening magnetron sputtering, the power of holding sputtering is
300W, the rotary speed of magnetron sputtering matrix is 100rpm；Working gas flow is 150～300
sccm。
Step (4). the time keeping sputtering between this condition is 20 minutes, obtains composite and flexible film
Sample；
Step (5). the composite and flexible membrane sample obtained is placed in tube furnace, under argon shield,
It is warming up to 850 DEG C with the speed of 2 DEG C/min, is incubated 100min, Temperature fall at this temperature
To room temperature, obtain required carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite films.
Micro-Structure Analysis:
Fig. 1 is the macro morphology figure of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane.From
It will be seen that when folding it, composite cellulosic membrane maintains the pattern of principle in figure,
Phenomenons such as rupturing does not occurs.Utilize scanning electron microscope and the microcosmic of projection electron microscopic observation composite
Structure, shown in the microstructure obtained such as Fig. 2 (a).From Fig. 2 (b) it will be seen that
Cobalt acid lithium uniformly can be coated to the surface shape of carbon nano-fiber by the method for magnetron sputtering
Become homogeneous coaxial nucleocapsid structure.Fig. 2 (c) shows that the thickness of the cobalt acid lithium of coating is 100nm.
The charge-discharge test of folded battery: by three-dimensional for carbon nano-fiber film/cobalt acid lithium of preparation same
Axle composite membrane is cut to the rectangle of a diameter of 2*4cm as positive pole, lithium sheet as negative pole,
Celgard film (model 2400) is as barrier film, with 1mol/LLiPF6It is immersed in ethylene carbonate
(EC) and the solution of diethyl carbonate (DEC) volume ratio (1:1) is as electrolyte, exist
It is full of in the glove box of argon and prepares flexible-packed battery, the flexible-packed battery of preparation is folded completely
After, at room temperature, the charge-discharge velocity of 0.5C, carry out under the conditions of the discharge and recharge of 3.0～4.0V
Test, the charging and discharging curve obtained is as shown in Figures 3 and 4.It can be seen in figure 3 that preparation
Carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane positive discharge platform occur in 3.85V,
Specific discharge capacity is 126.5mAh/g, it was demonstrated that can original position cobalt-coating by magnetically controlled sputter method
Acid lithium is to the surface of carbon nano-fiber.Fig. 4 shows that the composite cellulosic membrane of preparation is just having excellent
Cyclical stability.
Embodiment 2
The first step is the preparation of flexible nano carbon-fiber film, comprises the concrete steps that:
Electronic balance accurately weighs the short fibre of 15g polyacrylonitrile and 95g DMF (dimethyl
Methanamide) solution, magnetic agitation at 50 DEG C is until the short fibre of polyacrylonitrile is completely dissolved, so
Being placed in electrostatic spinning apparatus, arranging spinning voltage is 20kv, and receiving range 18cm spins
Silk flow velocity is 2mL/min.Obtain the polyacrylonitrile fibre membrane of a diameter of about 300nm.
After vacuum drying in tube furnace, in air atmosphere, heat up with the speed of 1 DEG C/min, warp
Cross 220min and be warming up to 250 DEG C, at a temperature of 250 DEG C, pre-oxidize 1h.Pre-oxidation completes
After in high-purity argon gas atmosphere protection, be warming up to 820 DEG C with the speed of 2 DEG C/min, in this temperature
Lower carbonization 150min obtains required super compliant conductive carbon nano-fiber film, and the radius of carbon fiber is
300 ran.
Second step is the preparation of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane, specifically walks
Suddenly:
Step (1). the flexible nano carbon-fiber film of preparation is placed in the matrix of magnetron sputtering, passes through
Vacuum pump takes the air inside magnetron sputtering away, makes air pressure reach 10-3Pa；
Step (2). argon and oxygen are passed through in the cavity of magnetron sputtering in the ratio of 9:1, protect
Hold pressure at 2Pa；
Step (3). using cobalt acid lithium as target, opening magnetron sputtering, the power of holding sputtering is
200W, the rotary speed of magnetron sputtering matrix is 50rpm；Working gas flow is 150～300
sccm。
Step (4). the time keeping sputtering between this condition is 80 minutes, obtains composite and flexible film
Sample；
Step (5). the composite and flexible membrane sample obtained is placed in tube furnace, under argon shield,
It is warming up to 800 DEG C with the speed of 2 DEG C/min, is incubated 30min, Temperature fall at this temperature
To room temperature, obtain required carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite films.Cobalt acid
The thickness of lithium coating is about 50nm.
In this embodiment, carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane microstructure divides
Analysing identical with embodiment 1 with the method for electrochemical property test, the result obtained is similar to, therefore
Do not enumerate at this.
The above is only the better embodiment to the present invention, not appoints the present invention
What pro forma restriction, embodiment of above is done by the technical spirit of every foundation present invention
Any simple modification, equivalent variations and modification, belong in the range of technical solution of the present invention.
Claims (7)
1. the preparation method of a collapsible lithium ion battery flexibility positive electrode, it is characterised in that:
Carbon nano-fiber film is placed in the matrix of magnetron sputtering, argon and oxygen are passed through in the cavity of magnetron sputtering, using cobalt acid lithium as target, open magnetron sputtering and obtain composite and flexible membrane sample；The composite and flexible membrane sample obtained is placed in tube furnace, and heating up under argon shield obtains required carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane.The shell of carbon nano-fiber and cobalt acid lithium forms coaxial fiber.
2. according to the preparation method of collapsible lithium ion battery flexibility positive electrode a kind of described in claim 1, it is characterised in that: described magnetron sputtering matrix internal gas pressure 10~ 3Pa-10~ 4Pa。
3. according to the preparation method of collapsible lithium ion battery flexibility positive electrode a kind of described in claim 1, it is characterised in that: in described magnetron sputtering matrix, argon and oxygen press the proportional arrangement of 8:1-10:1.
4. according to the preparation method of collapsible lithium ion battery flexibility positive electrode a kind of described in claim 1, it is characterised in that: the power keeping sputtering in described magnetron sputtering matrix is 200W-400W, and the rotary speed of magnetron sputtering matrix is 100rpm-200rpm；The cobalt acid lithium target of magnetron sputtering and the distance on chassis are 30～100mm.
5. according to the preparation method of collapsible lithium ion battery flexibility positive electrode a kind of described in claim 1, it is characterised in that: described magnetron sputtering working gas flow is 150～300sccm.
6. according to the preparation method of collapsible lithium ion battery flexibility positive electrode a kind of described in claim 1, it is characterised in that: the thickness 20～2000nm of described cobalt acid lithium shell.
7. according to the preparation method of collapsible lithium ion battery flexibility positive electrode a kind of described in claim 1, it is characterized in that: described composite and flexible membrane sample is placed in tube furnace, it is warming up to 500 DEG C-900 DEG C with the speed of 1 DEG C/min-3 DEG C/min, it is incubated 100min-120min at this temperature, is naturally cooling to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610485053.6A CN105914359B (en) | 2016-06-28 | 2016-06-28 | A kind of foldable lithium battery flexibility anode preparation method |
Applications Claiming Priority (1)
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| CN109659539A (en) * | 2018-12-20 | 2019-04-19 | 电子科技大学 | A method of based on In-situ reaction and being prepared by recombinant anode material of lithium battery |
| US11211606B2 (en) | 2017-12-28 | 2021-12-28 | The Hong Kong Polytechnic University | Electrode for battery and fabrication method thereof |
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