CN105914359B - A kind of foldable lithium battery flexibility anode preparation method - Google Patents
A kind of foldable lithium battery flexibility anode preparation method Download PDFInfo
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- CN105914359B CN105914359B CN201610485053.6A CN201610485053A CN105914359B CN 105914359 B CN105914359 B CN 105914359B CN 201610485053 A CN201610485053 A CN 201610485053A CN 105914359 B CN105914359 B CN 105914359B
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- ion battery
- lithium ion
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 36
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 24
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 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 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 229920002239 polyacrylonitrile Polymers 0.000 description 8
- 239000011149 active material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 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
- 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
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy 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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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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
- 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
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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
- 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
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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
-
- 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 kind of preparation method of foldable lithium ion battery flexibility positive electrode, carbon nano-fiber film is placed in the matrix of magnetron sputtering, argon gas and oxygen are passed through in the cavity of magnetron sputtering, using cobalt acid lithium as target, magnetron sputtering is opened and obtains composite and flexible membrane sample；Obtained composite and flexible membrane sample is placed in tube furnace, the lower heating of argon gas protection obtains required carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane.The beneficial effects of the invention are as follows carbon nano-fiber/cobalt acid lithium three-dimensional coaxial composite membrane to have good mechanical strength, pliability and elasticity, and the composite membrane is a kind of flexible membrane of self-supporting, can bend and fold；Satisfactory mechanical property.
Description
Technical field
The invention belongs to technical field of lithium ion, is related to a kind of system of foldable lithium ion battery flexibility positive electrode
Preparation Method.
Background technology
Lithium ion battery has high energy density and excellent cyclical stability, miniaturized electronics, electric automobile,
Mixed type electric automobile has a wide range of applications.At present, the preparation method of the both positive and negative polarity of commercialized lithium ion battery is mixed
The slurry for closing uniform active material particle, conductive agent and binding agent is coated in copper foil or aluminum foil current collector, dries compacting
After be assembled into lithium ion battery.The defects of this preparation method is the both positive and negative polarity during the transition of both positive and negative polarity pole piece is bent and is folded
Active material and collector depart from, the problems such as finally influenceing the combination property of lithium ion battery, or even cause short circuit.
With the development of folding type electronic product, the charging equipment that can be folded is its essential composition portion
Point, but flexible positive and negative pole material is one of main bottleneck prepared by folding lithium ion battery at present, traditional lithium-ion electric
The preparation method of pond both positive and negative polarity limits its application in flexible lithium ion battery.Currently reported lithium ion battery is flexible
The preparation method of negative pole, using carbon fiber, the three-dimensional order material such as graphene and nickel foam does conductive current collector, achieves
Greater advance.But anode active material of lithium ion battery typically all forms micron particles using high temperature solid-state method, how will
Positive electrode active materials original position is coated on three-dimensional collector, limits the development of flexible lithium ion battery positive pole.To solve this
Problem, researcher employs different three-dimensional collectors and painting method in situ is modified, but high temperature solid-state method is roasting
Three-dimensional conductive collector is destroyed during burning.
Therefore prepare high performance compliant conductive collector and select suitable method coating active material in situ to flexibility
Composite and flexible positive pole is formed on collector, is the research emphasis for preparing foldable lithium ion battery flexibility positive pole at present.
The content of the invention
It is an object of the invention to provide a kind of preparation method of foldable lithium ion battery flexibility positive electrode, solve
The preparation method of the both positive and negative polarity of lithium ion battery is the slurry well mixed active material particle, conductive agent and binding agent at present
Material is coated in copper foil or aluminum foil current collector, is assembled into lithium ion battery after drying compacting, so, both positive and negative polarity pole piece transition is curved
Both positive and negative polarity active material and collector depart from during bent and folding, the final combination property for influenceing lithium ion battery, even
The problem of causing short circuit.
The technical solution adopted in the present invention is that carbon nano-fiber film is placed in the matrix of magnetron sputtering, by argon gas and oxygen
It is passed through in the cavity of magnetron sputtering, using cobalt acid lithium as target, opens magnetron sputtering and obtain composite and flexible membrane sample；What is obtained
Composite and flexible membrane sample is placed in tube furnace, and the lower heating of argon gas protection obtains required carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial
Composite membrane.
Further, air pressure 10 in the magnetron sputtering matrix~3Pa-10~4Pa。
Further, argon gas and oxygen press 8 in the magnetron sputtering matrix:1-10:1 proportional arrangement.
Further, the power for sputtering being kept in the magnetron sputtering matrix is 200W-400W, the rotation of magnetron sputtering matrix
Speed is 100rpm-200rpm；The cobalt acid lithium target of magnetron sputtering and the distance on chassis are 30~100mm.
Further, the magnetron sputtering working gas flow is 150~300sccm.
Further, 20~2000nm of thickness of the cobalt acid lithium shell.
Further, the composite and flexible membrane sample is placed in tube furnace, is warming up to 1 DEG C/min-3 DEG C/min speed
500 DEG C -900 DEG C, 100min-120min is incubated at this temperature, is naturally cooling to room temperature.
The beneficial effects of the invention are as follows carbon nano-fiber/cobalt acid lithium three-dimensional coaxial composite membrane have good mechanical strength,
Pliability and elasticity, the composite membrane are a kind of flexible membranes of self-supporting, can bend and fold；Satisfactory mechanical property.
Brief description of the drawings
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 electron microscope of individual carbon fibers/cobalt acid lithium three-dimensional coaxial fiber；
Fig. 3 is the charge-discharge performance figure of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane positive pole.
Fig. 4 is the cycle performance figure of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane positive pole.
Embodiment
With reference to embodiment, the present invention is described in detail.
Polyacrylonitrile is dissolved completely in after dimethyl formamide solution and prepares flexible nano carbon fibre with electrostatic spinning apparatus
The mass ratio of dimension film, polyacrylonitrile and dimethyl formamide solution is 1:7-1:8, after vacuum drying in tube furnace, air gas
Under atmosphere, 1h-2h is pre-oxidized after being warming up to 200 DEG C -300 DEG C with 1 DEG C/min-2 DEG C/min speed.High-purity after the completion of pre-oxidation
Carbonization 30min obtains required soft after being warming up to 800 DEG C -1000 DEG C in argon gas atmosphere protection with 2 DEG C/min-3 DEG C/min speed
Property carbon nano-fiber film.The thickness of flexible nano carbon-fiber film is 20~200 μm, and porosity is 50-90%, and tensile strength exists
10-500mPa；The radius of carbon fiber is 50~1000nm, is controlled by the diameter of precursor polymer fiber.
It is prepared by foldable lithium battery flexibility positive pole：Electrostatic is used after polyacrylonitrile is dissolved completely in into dimethyl formamide solution
Device for spinning prepares flexible nano carbon-fiber film, and the flexible nano carbon-fiber film of preparation is placed in into the matrix of magnetron sputtering, passed through
Vavuum pump takes the air inside magnetron sputtering matrix away, air pressure is reached 10~3Pa-10~4Pa；Argon gas and oxygen are pressed 8:1-10:
1 ratio is passed through in the cavity of magnetron sputtering, keeps pressure in 2Pa-3Pa；Using cobalt acid lithium as target, magnetron sputtering is opened,
The power for keeping sputtering is 200W-400W, and the rotary speed of magnetron sputtering matrix is 100rpm-200rpm；The cobalt of magnetron sputtering
The distance on sour lithium target and chassis is 30~100mm.Working gas flow is 150~300sccm, the thickness 20 of cobalt acid lithium shell
~2000nm, obtain composite and flexible membrane sample；Obtained composite and flexible membrane sample is placed in tube furnace, under argon gas protection, with 1
DEG C/min-3 DEG C/min speed is warming up to 500 DEG C -900 DEG C, 100min-120min is incubated at this temperature, is naturally cooling to
Room temperature, obtain required carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane.Carbon nano-fiber and the shell of cobalt acid lithium are formed together
The fiber of axle.
It is also an advantage of the present invention that it is controllable to prepare a kind of thickness, high mechanical properties, high conductivity, lightweight is high
Porosity, there is certain flexible carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane, the composite membrane is a kind of self-supporting
Flexible membrane, can bend and fold；Satisfactory mechanical property；Preparation process does not need expensive equipment and exacting terms, behaviour
Make simply, cheap easy, short preparation period, experiment condition is simple, and industrialized production can be achieved.When as lithium ion battery just
During the material of pole, there is the cyclical stability that high charging and discharging capacity is become reconciled.This preparation method is simple, can be given birth on a large scale
Production.
Embodiment 1
38g polyacrylonitrile and 290g dimethyl formamide solutions accurately are weighed, electrostatic spinning apparatus is placed in after being completely dissolved
In, setting spinning voltage is 20kv, receives distance 18cm, and spinning flow velocity is 1.5mL/min.Obtain a diameter of 600nm or so
Polyacrylonitrile fibre membrane.After vacuum drying in tube furnace, in air atmosphere, heated up, passed through with 1 DEG C/min speed
220min is warming up to 250 DEG C, and 1h is pre-oxidized at a temperature of 250 DEG C.With 2 in high-purity argon gas atmosphere protection after the completion of pre-oxidation
DEG C/min speed is warming up to 850 DEG C, the 30min that is carbonized at this temperature obtain needed for compliant conductive carbon nano-fiber film, carbon is fine
The radius of dimension is 500nm or so.
Second step is the preparation of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane, is comprised the concrete steps that：
The flexible nano carbon-fiber film of preparation is placed in the matrix of magnetron sputtering by step (1), and magnetic control is taken away by vavuum pump
Air inside sputtered substrate, makes air pressure reach 10~3Pa；
Argon gas and oxygen are pressed 9 by step (2):1 ratio is passed through in the cavity of magnetron sputtering, keeps pressure in 2Pa；
Step (3) opens magnetron sputtering using cobalt acid lithium as target, and the power for keeping sputtering is 300W, magnetron sputtering base
The rotary speed of body is 100rpm；Working gas flow is 150~300sccm.
It is 20 minutes that step (4) keeps the time of sputtering between this condition, obtains composite and flexible membrane sample；
Step (5) is placed in obtained composite and flexible membrane sample in tube furnace, under argon gas protection, with 2 DEG C/min speed
850 DEG C are warming up to, is incubated 100min at this temperature, is naturally cooling to room temperature, obtains required carbon nano-fiber film/cobalt acid lithium three
Tie up 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 the figure, it can be seen that
When being folded to it, composite cellulosic membrane maintains the pattern of principle, phenomena such as rupture does not occur.Utilize ESEM and throwing
The microstructure of radio sem observation composite, shown in obtained microstructure such as Fig. 2 (a).It can be seen that, lead to from Fig. 2 (b)
Cross the method for magnetron sputtering and cobalt acid lithium can be uniformly coated to the surface of carbon nano-fiber and form homogeneous coaxial core shell structure.
Fig. 2 (c) shows that the thickness of the cobalt acid lithium of coating is 100nm.
The charge-discharge test of folded battery：The carbon nano-fiber film of preparation/cobalt acid lithium three-dimensional coaxial composite membrane is cut to
A diameter of 2*4cm rectangle is as positive pole, and lithium piece is as negative pole, and Celgard films (model 2400) are used as barrier film, with 1mol/
LLiPF6It is immersed in ethylene carbonate (EC) and diethyl carbonate (DEC) volume ratio (1:1) solution is as electrolyte, full of argon
Flexible-packed battery is prepared in the glove box of gas, after the flexible-packed battery of preparation is folded completely, at room temperature, 0.5C discharge and recharge
Speed, tested under the conditions of 3.0~4.0V discharge and recharge, obtained charging and discharging curve is as shown in Figures 3 and 4.Can be with from Fig. 3
See, carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane positive discharge platform of preparation appears in 3.85V, and discharge specific volume
Amount is 126.5mAh/g, it was demonstrated that in situ can coat cobalt acid lithium to the surface of carbon nano-fiber by magnetically controlled sputter method.Fig. 4 tables
The composite cellulosic membrane of bright preparation is just having excellent cyclical stability.
Embodiment 2
The first step is the preparation of flexible nano carbon-fiber film, is comprised the concrete steps that：
Short fine and 95g DMF (dimethylformamide) solution of 15g polyacrylonitrile is accurately weighed on electronic balance, at 50 DEG C
Lower magnetic agitation is completely dissolved up to the short fibre of polyacrylonitrile, is subsequently placed in electrostatic spinning apparatus, and setting spinning voltage is 20kv,
Distance 18cm is received, spinning flow velocity is 2mL/min.Obtain a diameter of 300nm or so polyacrylonitrile fibre membrane.Vacuum drying
Afterwards in tube furnace, in air atmosphere, heated up with 1 DEG C/min speed, 250 DEG C are warming up to by 220min, at 250 DEG C
At a temperature of pre-oxidize 1h.820 DEG C are warming up to 2 DEG C/min speed in high-purity argon gas atmosphere protection after the completion of pre-oxidation,
The 150min that is carbonized at a temperature of this obtains required super compliant conductive carbon nano-fiber film, and the radius of carbon fiber is 300 rans.
Second step is the preparation of carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane, is comprised the concrete steps that：
The flexible nano carbon-fiber film of preparation is placed in the matrix of magnetron sputtering by step (1), and magnetic control is taken away by vavuum pump
The air of the inside is sputtered, air pressure is reached 10-3Pa；
Argon gas and oxygen are pressed 9 by step (2):1 ratio is passed through in the cavity of magnetron sputtering, keeps pressure in 2Pa；
Step (3) opens magnetron sputtering using cobalt acid lithium as target, and the power for keeping sputtering is 200W, magnetron sputtering base
The rotary speed of body is 50rpm；Working gas flow is 150~300sccm.
It is 80 minutes that step (4) keeps the time of sputtering between this condition, obtains composite and flexible membrane sample；
Step (5) is placed in obtained composite and flexible membrane sample in tube furnace, under argon gas protection, with 2 DEG C/min speed
800 DEG C are warming up to, is incubated 30min at this temperature, is naturally cooling to room temperature, obtains required carbon nano-fiber film/cobalt acid lithium three
Tie up coaxial composite films.The thickness of cobalt acid lithium coating is about 50nm.
Carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane Micro-Structure Analysis and chemical property in this embodiment
The method of test is identical with embodiment 1, and obtained result is similar, therefore does not enumerate herein.
Described above is only the better embodiment to the present invention, not makees any formal limit to the present invention
System, any simple modification that every technical spirit according to the present invention is made to embodiment of above, equivalent variations and modification,
Belong in the range of technical solution of the present invention.
Claims (7)
- A kind of 1. preparation method of foldable lithium ion battery flexibility positive electrode, it is characterised in that：Carbon nano-fiber film is placed in the matrix of magnetron sputtering, argon gas and oxygen are passed through in the cavity of magnetron sputtering, with cobalt acid Lithium opens magnetron sputtering and obtains composite and flexible membrane sample as target；Obtained composite and flexible membrane sample is placed in tube furnace, The lower heating of argon gas protection obtains required carbon nano-fiber film/cobalt acid lithium three-dimensional coaxial composite membrane, Nano carbon fibers peacekeeping cobalt acid lithium Shell forms coaxial fiber.
- 2. according to a kind of preparation method of foldable lithium ion battery flexibility positive electrode described in claim 1, it is characterised in that： Air pressure 10 in the magnetron sputtering matrix~3Pa-10~4Pa。
- 3. according to a kind of preparation method of foldable lithium ion battery flexibility positive electrode described in claim 1, it is characterised in that： Argon gas and oxygen press 8 in the magnetron sputtering matrix:1-10:1 proportional arrangement.
- 4. according to a kind of preparation method of foldable lithium ion battery flexibility positive electrode described in claim 1, it is characterised in that： The power that sputtering is kept in the 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 a kind of preparation method of foldable lithium ion battery flexibility positive electrode described in claim 1, it is characterised in that： The magnetron sputtering working gas flow is 150~300sccm.
- 6. according to a kind of preparation method of foldable lithium ion battery flexibility positive electrode described in claim 1, it is characterised in that： 20~2000nm of thickness of the cobalt acid lithium shell.
- 7. according to a kind of preparation method of foldable lithium ion battery flexibility positive electrode described in claim 1, it is characterised in that： The composite and flexible membrane sample is placed in tube furnace, is warming up to 500 DEG C -900 DEG C with 1 DEG C/min-3 DEG C/min speed, herein At a temperature of be incubated 100min-120min, be naturally cooling to room temperature.
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| US11211606B2 (en) | 2017-12-28 | 2021-12-28 | The Hong Kong Polytechnic University | Electrode for battery and fabrication method thereof |
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