CN105811049A - All-solid-state flexible and stretchable fibrous aluminum air battery and preparation method thereof - Google Patents

All-solid-state flexible and stretchable fibrous aluminum air battery and preparation method thereof Download PDF

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CN105811049A
CN105811049A CN201610275850.1A CN201610275850A CN105811049A CN 105811049 A CN105811049 A CN 105811049A CN 201610275850 A CN201610275850 A CN 201610275850A CN 105811049 A CN105811049 A CN 105811049A
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carbon nanotube
aluminium
peo
pva
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CN105811049B (en
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彭慧胜
徐帆
徐一帆
赵阳
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Fudan University
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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte

Abstract

The invention belongs to the technical field of aluminum air batteries, and particularly discloses an all-solid-state flexible and stretchable fibrous aluminum air battery and a preparation method thereof. According to the method, a hydrogel electrolyte is firstly prepared by a cyclic freezing method; the electrolyte coats an aluminum spring at a negative electrode and is crosslinked into a solid state; and staggered oriented carbon nanotube films evaporated with silver nanoparticles coat the outmost layer to obtain the fibrous aluminum air battery. The special air electrode structure does not need a metal current collector or a binder. Due to the structural design, the fibrous aluminum air battery has excellent electrochemical properties; the specific capacity can reach 935mAh/g; and the energy density can reach 1168Wh/kg. The battery also has flexibility and stretchability. The electrolyte is in the solid state, so that the risks of a short circuit and an electrolyte leakage in the bending and stretching process can be effectively prevented; the battery is easy to weave and integrate; and the battery can be woven into energy storage fabrics to provide energy for a wearable electronic device, and large-scale application is excepted to be achieved.

Description

A kind of fibrous aluminium-air cell of all solid state flexible extensible and preparation method thereof
Technical field
The invention belongs to aluminium-air cell technical field, be specifically related to a kind of threadiness aluminium-air cell and preparation side thereof Method.
Background technology
The demand of high-performance energy storage device is increased by the mankind day by day.[1-5]Excellent owing to having environmental protection, low cost high power capacity etc. Point, metal-air battery is widely studied as the function battery of a new generation.[6]Metal-air battery utilizes the oxygen in air As positive active material, this causes them to have than conventional batteries (such as lithium ion battery) higher theoretical energy density[7]。 Aluminium-air cell has the theoretical energy density of up to 2796Wh/kg, is the tens of commercial Li-ion batteries energy density Times[8-12].But, traditional aluminium-air cell is the most all the structure of rigidity,[13-14]This cannot meet flexibility of future generation and can wear The requirement to flexible extensible of the wearing electronic device.Therefore, we are badly in need of realizing the flexible and stretchable performance of aluminium-air cell, To meet flexibility and the energy supply requirement of wearable device.
Summary of the invention
It is an object of the invention to provide fibrous aluminium-air cell and the preparation thereof of a kind of all solid state flexible extensible Method.
The fibrous aluminium-air cell of all solid state flexible extensible that the present invention provides, is born as battery by aluminium bomb spring Pole, wraps up polyvinyl alcohol (PVA)/poly(ethylene oxide) (PEO)/zinc oxide (ZnO)/sodium stannate (Na on aluminium bomb spring2SnO3)/hydrogen Potassium oxide (KOH) hydrogel has, as electrolyte, outermost layer cladding evaporation, the aligned carbon nanotube (CNT) that Ag nano-particle is staggered Film is as anode air electrode.This threadiness aluminium-air cell specific capacity is 935 mAh/g, and energy density is 1168 Wh/ Kg, and open-circuit voltage is maintained at original 98% after bending 1000 times.
The preparation method of fibrous aluminium-air cell that the present invention provides, it concretely comprises the following steps:
(1) first, by PVA/PEO/ZnO/Na2SnO3/ KOH hydrogel electrolyte uniformly wraps up aluminium bomb spring, puts into refrigerator frost It is cross-linked into solid-state；
(2) then, the Ag nano-particle of different-thickness on orientation carbon nanotube film surface heat evaporation, as air electrode；
(3) last, evaporation have the orientation CNT film of silver nano-grain be wrapped in the outermost layer of the aluminium bomb spring that step (1) obtains, i.e. Obtain threadiness aluminium-air cell.
In the present invention, staggered orientation CNT film air electrode is obtained by dry spinning by spinning CNT array.First First CNT array is glued on the glass sheet, be then pulled in PTFE plate from array edges pull-out continuous print CNT film with blade.By CNT Film successively interlocks with the angle of 0 °-180 ° (preferably 90 °) and is laid on rectangle PTFE plate, then utilizes hot vapour deposition method on its surface Evaporation 10-200 nm(preferably 50 nm) Ag nano-particle, obtain the orientation CNT film air electrode that porous is staggered.Monolayer CNT The surface density of film is 0.5-5 μ g/cm2.The staggered orientation CNT film of Ag is had for the gas in anode air electrode with evaporation Diffusion layer, Catalytic Layer and collector.Wherein, CNT film is the orderly loose and porous structure being made up of orientation CNT.
In the present invention, CNT array is prepared by chemical vapour deposition technique.CNT array height is in 200-300 μm.CNT takes To arrangement, there is no the deposition of agraphitic carbon.CNT is many wall constructions, and caliber is 10-50 nm.
In the present invention, hydrogel electrolyte is by PVA/PEO/ZnO/Na2SnO3/ KOH forms, by PVA Yu PEO in proportion PVA:PEO=(1-20): 1 is dissolved in deionized water 60-120 DEG C of oil bath, continuously stirred 1-4h, be subsequently added ZnO, Na2SnO3, KOH concentration be respectively 0.1 M-5 M, 0.01 M-0.5 M, the aqueous solution of 5 M-20 M, 60-100 DEG C of oil bath continues Stirring 0.5-1h, obtains PVA/PEO/ZnO/Na after cooling2SnO3/ KOH hydrogel electrolyte.
In the present invention, PVA/PEO/ZnO/Na2SnO3After/KOH hydrogel electrolyte parcel aluminium bomb spring, put into-10-20 DEG C Environment freezes 1-8h, then thaw at RT, repeats this frost course of defrosting and be physical crosslinking for 1-10 time；It is finally putting into 0-15 In DEG C environment, 1-10h further enhances physical crosslinking.
In the present invention, on orientation carbon nanotube film surface heat evaporation, the process of the Ag nano-particle of different-thickness is: First the CNT array that width is 0.1-10 cm is glued on the glass sheet, then pull out continuous print CNT with blade from array edges Film is pulled on PTFE plate.CNT film is successively interlocked with the angle of 0-180 ° and is tiled across a width of a length of 0.1-50 of 0.1-10 cm On the rectangle PTFE plate of cm, obtain the orientation CNT film that 2-20 layer porous is staggered.The surface density of monolayer CNT film is 0.5-5 μ g/ cm2.Then PTFE plate is put into the cavity of heat evaporation, puts into silver, be evacuated to 1 × 10-4Below Pa, regulation electric current is 150-200 A, now speed is 3-10/s, opens baffle plate, and on PTFE plate, evaporation thickness is the Ag nanometer of 10-200 nm Grain, closes electric current, takes out PEFE, obtain being deposited with the staggered orientation CNT film of Ag nano-particle, as air electrode after venting.
In the present invention, CNT array is prepared by chemical vapour deposition technique.CNT array height is in 200-300 μm.CNT is orientated row Row, do not have the deposition of agraphitic carbon.CNT is many wall constructions, and caliber is 10-50 nm.
The fibrous aluminium-air cell that the inventive method obtains has brand-new structure, special sky compared to conventional batteries Pneumoelectric electrode structure need not metal collector and binding agent, alleviates the weight and volume of battery, thus improves the energy of battery Metric density and power density.The design of such structure makes this threadiness aluminium-air cell have the chemical property of excellence, specific volume Amount up to 935 mAh/g, energy density reaches 1168 Wh/kg.This battery also has flexibility and tensility, and electrolyte is solid State can effectively prevent short circuit and the danger of electrolyte leakage during bend tension, and battery is prone to braiding with integrated, it is possible to quilt Being woven in energy storage fabric is wearable electronic device energy supply, is expected to realize large-scale application.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of this threadiness aluminium-air cell.
Fig. 2 is the structural characterization that evaporation has the staggered orientation carbon nanotube thin film air electrode of Ag nano-particle.Wherein, a-b, Ag Load capacity is 45.5 μ g/cm2The low power of staggered orientation carbon nanotube thin film and high power stereoscan photograph.C, Ag load capacity is 45.5 μg/cm2The transmission electron microscope photo of staggered orientation carbon nanotube thin film.D-f, Ag load capacity is respectively 23.3,45.5 and 66.9 μ g/cm2 The transmission electron microscope photo of staggered orientation carbon nanotube thin film.
Fig. 3 is the Electrochemical Characterization of this threadiness aluminium-air cell.Wherein, the fiber under a-b, different Ag load capacity The polarization curve of shape aluminium-air cell and power density curve (sweeping speed is 2 mV/s).C, orientation carbon pipe are respectively staggered, parallel Polarization curve (sweeping speed is 2 mV/s) with the fibrous aluminium-air cell being perpendicular to fibre cell length direction.D, threadiness aluminum Air cell discharge curve under different electric current densities.
Fig. 4 is that the flexibility of this threadiness aluminium-air cell characterizes with tensility.Wherein, a, discharge current are under 1 mA, Bend to the discharge curve of the fibrous aluminium-air cell of various angle.B, discharge current are under 1 mA, stretch different weight percentage The discharge curve of fibrous aluminium-air cell.C, the polarization curve of the single fibrous aluminium-air cell connected with two (are swept Speed is 2 mV/s).D, the power density curve (sweeping speed is 2 mV/s) of the single fibrous aluminium-air cell connected with two.e- F, with two series connection fibrous aluminium-air cells be woven in fabric give a business LED watch power.Scale: 2 cm.
Detailed description of the invention
The invention is further illustrated by the following examples.
Embodiment 1
(1) chemical vapour deposition technique is used to prepare CNT array: to deposit one layer by electron beam evaporation deposition instrument on Si sheet respectively The film preparation of nano thickness obtains catalyst, consisting of silicon (Si)/silicon dioxide (SiO2)/aluminium oxide (Al2O3)/ferrum (Fe), Al2O3Being positioned in the middle of silicon chip and Fe as cushion, Fe is as catalyst.Wherein, SiO2Layer thickness is 400 μm, Al2O3 Layer thickness is 3 nm, and Fe layer thickness is 1.2 nm.By being coated with the Si substrate catalyst of catalyst towards upper, with a piece of bigger silicon Sheet, as substrate, is put in the quartz ampoule of tube furnace, near the middle body of tube furnace.Regulation breather line flow is: argon: 400sccm；Hydrogen: 30sccm；Ethylene gas: 90sccm.Connecting line.First open argon, close hydrogen and ethylene gas.In room Ventilate under temperature 10min, to guarantee to get rid of the oxygen among pipeline and steam.Opening hydrogen and ethylene, 15 min are from room temperature liter To 740 DEG C, stable 10 min at 740 DEG C, turn off ethylene and hydrogen when program starts to lower the temperature voluntarily.Temperature is down to 150 DEG C Time open stove, take out long at suprabasil height-oriented spun CNT array；
(2) preparation of the staggered orientation CNT film air electrode having Ag nano-particle it is deposited with: first the CNT that width is 1.5 cm Array is viscous on the glass sheet, is then pulled in PTFE plate from array edges pull-out continuous print CNT film with blade.By CNT film successively Interlock with the angle of 90 ° on the rectangle PTFE plate being tiled across a length of 5 cm of a width of 1.0 cm, obtain staggered the taking of 6 layers of porous To CNT film.The surface density of monolayer CNT film is 1.4 μ g/cm2.Then PTFE plate is put into the cavity of heat evaporation, puts into silver, take out Vacuum is to 1 × 10-4Below Pa, regulation electric current is 170 A, and now speed is 5/s, opens baffle plate, evaporation thickness on PTFE plate Degree is the Ag nano-particle of 50 nm, closes electric current, takes out PEFE, obtain being deposited with the staggered orientation of Ag nano-particle after venting CNT film air electrode；
(3) PVA/PEO/ZnO/Na2SnO3The preparation of/KOH hydrogel electrolyte: by 1 g PVA and 0.1g PEO at 95 DEG C of oil Bath is dissolved in 10 mL deionized waters, and continuously stirred 2h is subsequently added 1 mL and is dissolved with 0.1 g ZnO, 0.03 g Na2SnO3 With the aqueous solution of 1 g KOH, 95 DEG C of oil baths continue stirring 50 min, obtain PVA/PEO/ZnO/Na after cooling2SnO3/ KOH water-setting Glue electrolyte；
(4) assembling of threadiness aluminium-air cell: in heat-shrink tube, by above-mentioned PVA/PEO/ZnO/Na2SnO3/ KOH hydrogel Electrolyte packages length is on the aluminium bomb spring of 1.5 cm, puts into and freezes thaw at RT after 1 h in-20 DEG C of environment, repeats this frost Course of defrosting is physical crosslinking for 3 times.Put into 5 h in 4 DEG C of environment and further enhance physical crosslinking.Finally by spring along rectangle Length direction on PTFE plate rolls, and utilizes the stickiness of gel that evaporation has the orientation of the Ag CNT film that interlocks be coated on outermost layer, To all solid state flexible extensible stretchable threadiness aluminium-air cell.
Embodiment 2
(1) chemical vapour deposition technique is used to prepare CNT array: to deposit one layer by electron beam evaporation deposition instrument on Si sheet respectively The film preparation of nano thickness obtains catalyst, consisting of silicon (Si)/silicon dioxide (SiO2)/aluminium oxide (Al2O3)/ferrum (Fe), Al2O3Being positioned in the middle of silicon chip and Fe as cushion, Fe is as catalyst.Wherein, SiO2Layer thickness is 400 μm, Al2O3 Layer thickness is 3 nm, and Fe layer thickness is 1.2 nm.By being coated with the Si substrate catalyst of catalyst towards upper, with a piece of bigger silicon Sheet, as substrate, is put in the quartz ampoule of tube furnace, near the middle body of tube furnace.Regulation breather line flow is: argon: 400sccm；Hydrogen: 30sccm；Ethylene gas: 90sccm.Connecting line.First open argon, close hydrogen and ethylene gas.In room Ventilate under temperature 10min, to guarantee to get rid of the oxygen among pipeline and steam.Opening hydrogen and ethylene, 15 min are from room temperature liter To 740 DEG C, stable 10 min at 740 DEG C, turn off ethylene and hydrogen when program starts to lower the temperature voluntarily.Temperature is down to 200 DEG C Time open stove, take out long at suprabasil height-oriented spun CNT array；
(2) preparation of the staggered orientation CNT film air electrode having Ag nano-particle it is deposited with: first the CNT that width is 1.0 cm Array is viscous on the glass sheet, is then pulled in PTFE plate from array edges pull-out continuous print CNT film with blade.By CNT film successively Interlock with the angle of 90 ° on the rectangle PTFE plate being tiled across a length of 5 cm of a width of 2.0 cm, obtain staggered the taking of 6 layers of porous To CNT film.The surface density of monolayer CNT film is 1.4 μ g/cm2.Then PTFE plate is put into the cavity of heat evaporation, puts into silver, take out Vacuum is to 1 × 10-4Below Pa, regulation electric current is 170 A, and now speed is 5.5/s, opens baffle plate, is deposited with on PTFE plate Thickness is the Ag nano-particle of 25 nm, closes electric current, takes out PEFE, obtain being deposited with the staggered of Ag nano-particle and take after venting To CNT film air electrode；
(3) PVA/PEO/ZnO/Na2SnO3The preparation of/KOH hydrogel electrolyte: by 1 g PVA and 0.1g PEO at 95 DEG C of oil Bath is dissolved in 10 mL deionized waters, and continuously stirred 2h is subsequently added 1 mL and is dissolved with 0.1 g ZnO, 0.03 g Na2SnO3 With the aqueous solution of 1 g KOH, 95 DEG C of oil baths continue stirring 50 min, obtain PVA/PEO/ZnO/Na after cooling2SnO3/ KOH water-setting Glue electrolyte；
(4) assembling of threadiness aluminium-air cell: in heat-shrink tube, by above-mentioned PVA/PEO/ZnO/Na2SnO3/ KOH hydrogel Electrolyte packages length is on the aluminium bomb spring of 1.5 cm, puts into and freezes thaw at RT after 1 h in-20 DEG C of environment, repeats this frost Course of defrosting is physical crosslinking for 3 times.Put into 5 h in 4 DEG C of environment and further enhance physical crosslinking.Finally by spring along rectangle Length direction on PTFE plate rolls, and utilizes the stickiness of gel that evaporation has the orientation of the Ag CNT film that interlocks be coated on outermost layer, Fibrous aluminium-air cell to all solid state flexible extensible.
Embodiment 3
(1) chemical vapour deposition technique is used to prepare CNT array: to deposit one layer by electron beam evaporation deposition instrument on Si sheet respectively The film preparation of nano thickness obtains catalyst, consisting of silicon (Si)/silicon dioxide (SiO2)/aluminium oxide (Al2O3)/ferrum (Fe), Al2O3Being positioned in the middle of silicon chip and Fe as cushion, Fe is as catalyst.Wherein, SiO2Layer thickness is 400 μm, Al2O3 Layer thickness is 3 nm, and Fe layer thickness is 1.2 nm.By being coated with the Si substrate catalyst of catalyst towards upper, with a piece of bigger silicon Sheet, as substrate, is put in the quartz ampoule of tube furnace, near the middle body of tube furnace.Regulation breather line flow is: argon: 400sccm；Hydrogen: 30sccm；Ethylene gas: 90sccm.Connecting line.First open argon, close hydrogen and ethylene gas.In room Ventilate under temperature 10min, to guarantee to get rid of the oxygen among pipeline and steam.Opening hydrogen and ethylene, 15 min are from room temperature liter To 740 DEG C, stable 10 min at 740 DEG C, turn off ethylene and hydrogen when program starts to lower the temperature voluntarily.Temperature is down to 220 DEG C Time open stove, take out long at suprabasil height-oriented spun CNT array；
(2) preparation of the staggered orientation CNT film air electrode having Ag nano-particle it is deposited with: first the CNT that width is 1.2 cm Array is viscous on the glass sheet, is then pulled in PTFE plate from array edges pull-out continuous print CNT film with blade.By CNT film successively Interlock with the angle of 0 ° on the rectangle PTFE plate being tiled across a length of 5 cm of a width of 5 cm, obtain the orientation that 6 layers of porous are staggered CNT film.The surface density of monolayer CNT film is 1.4 μ g/cm2.Then PTFE plate is put into the cavity of heat evaporation, puts into silver, take out true Empty to 1 × 10-4Below Pa, regulation electric current is 170 A, and now speed is 4.5/s, opens baffle plate, evaporation thickness on PTFE plate Degree is the Ag nano-particle of 75 nm, closes electric current, takes out PEFE, obtain being deposited with the staggered orientation of Ag nano-particle after venting CNT film air electrode；
(3) PVA/PEO/ZnO/Na2SnO3The preparation of/KOH hydrogel electrolyte: by 1 g PVA and 0.1g PEO at 95 DEG C of oil Bath is dissolved in 10 mL deionized waters, and continuously stirred 2h is subsequently added 1 mL and is dissolved with 0.1 g ZnO, 0.03 g Na2SnO3 With the aqueous solution of 1 g KOH, 95 DEG C of oil baths continue stirring 50 min, obtain PVA/PEO/ZnO/Na after cooling2SnO3/ KOH water-setting Glue electrolyte；
(4) assembling of threadiness aluminium-air cell: in heat-shrink tube, by above-mentioned PVA/PEO/ZnO/Na2SnO3/ KOH hydrogel Electrolyte packages length is on the aluminium bomb spring of 1.5 cm, puts into and freezes thaw at RT after 1 h in-20 DEG C of environment, repeats this frost Course of defrosting is physical crosslinking for 3 times.Put into 5 h in 4 DEG C of environment and further enhance physical crosslinking.Finally by spring along rectangle Length direction on PTFE plate rolls, and utilizes the stickiness of gel that evaporation has the orientation of the Ag CNT film that interlocks be coated on outermost layer, Fibrous aluminium-air cell to all solid state flexible extensible.
The structural characterization of the fibrous aluminium-air cell of all solid state flexible extensible prepared by above-described embodiment, electrochemistry Performances etc. see shown in Fig. 2-Fig. 4.
List of references
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Claims (6)

1. the fibrous aluminium-air cell of an all solid state flexible extensible, it is characterised in that: its structure consists of: by aluminium bomb Spring, as battery cathode, wraps up PVA/PEO/ZnO/Na on aluminium bomb spring2SnO3/ KOH hydrogel is as electrolyte, outermost layer bag Cover orientation carbon nanotube film as anode air electrode.
2. the preparation method of the fibrous aluminium-air cell of an all solid state flexible extensible, it is characterised in that concrete steps are such as Under:
(1) first, by PVA/PEO/ZnO/Na2SnO3/ KOH hydrogel electrolyte uniformly wraps up aluminium bomb spring, puts into refrigerator circulation cold Freeze and be cross-linked into solid-state；
(2) then, silver nano-grain on orientation carbon nanotube film surface heat evaporation；
(3) last, evaporation have the orientation carbon nanotube film of silver nano-grain be wrapped in the aluminium bomb spring that obtained by step (1) Outermost layer, i.e. obtains threadiness aluminium-air cell.
Preparation method the most according to claim 2, it is characterised in that hydrogel PVA/PEO/ZnO/ described in step (1) Na2SnO3/ KOH is by PVA, PEO, ZnO, Na2SnO3, KOH composition, its preparation process is: by PVA Yu PEO PVA:PEO=in proportion (1-20): 1 is dissolved in deionized water 60-120 DEG C of oil bath, continuously stirred 1-4h is subsequently added ZnO, Na2SnO3, KOH dense Degree is respectively 0.1 M-5 M, 0.01 M-0.5 M, the aqueous solution of 5 M-20 M, and 60-100 DEG C of oil bath continues stirring 0.5-1h, cold Obtain PVA/PEO/ZnO/Na the most afterwards2SnO3/ KOH hydrogel electrolyte.
Preparation method the most according to claim 3, it is characterised in that described in step (1), circulating frozen is cross-linked into solid-state, Its process is: PVA/PEO/ZnO/Na2SnO3After/KOH hydrogel electrolyte parcel aluminium bomb spring, put into ice in-10-20 DEG C of environment Freeze 1-8h, then thaw at RT, repeat this frost course of defrosting 1-10 time, be physical crosslinking；It is finally putting into 0-15 DEG C of environment Middle 1-10h further enhances physical crosslinking.
Preparation method the most according to claim 4, it is characterised in that described at orientation carbon nanotube film surface heat evaporation The process of upper silver nano-grain is: first the orientation carbon nanotube film array that width is 0.1-10 cm is glued on the glass sheet, Then it is pulled in PTFE plate from array edges pull-out continuous print orientation carbon nanotube film with blade；By orientation carbon nanotube film Successively interlock with the angle of 0-180 ° on the rectangle PTFE plate being tiled across a width of 0.1-10 cm a length of 0.1-50 cm, obtain The orientation orientation carbon nanotube film that 2-20 layer porous is staggered；The surface density of monolayer orientation carbon nanotube film is 0.5-5 μ g/ cm2；Then PTFE plate is put into the cavity of heat evaporation, puts into silver, be evacuated to 1 × 10-4Below Pa, regulation electric current is 150-200 A, now speed is 3-10/s, opens baffle plate, and on PTFE plate, evaporation thickness is the silver nanoparticle of 10-200 nm Grain, closes electric current, takes out PEFE, obtain being deposited with the staggered orientation carbon nanotube film of silver nano-grain after venting.
Preparation method the most according to claim 5, it is characterised in that described aligned carbon nanotube array is sunk by chemical gaseous phase Area method prepares, and aligned carbon nanotube array heights is in 200-300 μm；For many wall constructions, caliber is 10-50 nm.
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CN106129536A (en) * 2016-08-12 2016-11-16 复旦大学 A kind of stretchable lithium-air battery and preparation method thereof
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CN113178646A (en) * 2021-04-29 2021-07-27 南京大学 Magnesium air fiber battery and preparation method thereof
CN113517499A (en) * 2021-05-25 2021-10-19 西北大学 Flexible aluminum air battery based on PVA/KC-KOH composite gel electrolyte

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Publication number Priority date Publication date Assignee Title
CN106129536A (en) * 2016-08-12 2016-11-16 复旦大学 A kind of stretchable lithium-air battery and preparation method thereof
CN106129536B (en) * 2016-08-12 2019-07-05 复旦大学 A kind of stretchable lithium-air battery and preparation method thereof
CN111263991A (en) * 2017-10-23 2020-06-09 诺基亚技术有限公司 Method, device and computer program for producing a device
CN108597649A (en) * 2018-03-27 2018-09-28 佛山市飞程信息技术有限公司 A kind of high-strength flexible transparent electrode structure
CN109494431A (en) * 2018-11-12 2019-03-19 西安鸿钧睿泽新材料科技有限公司 Flexible aluminium air battery of flexible
CN109494431B (en) * 2018-11-12 2021-11-02 廖湘标 Flexible aluminium air battery of flexible
CN110600835A (en) * 2019-09-24 2019-12-20 中国科学技术大学 Stretchable flexible metal-air battery
CN112164828A (en) * 2020-09-22 2021-01-01 同济大学 Fibrous flexible aluminum ion battery and preparation method thereof
CN112259832A (en) * 2020-09-24 2021-01-22 江苏理工学院 Preparation method and application of graphene-modified all-solid-state electrolysis
CN113178646A (en) * 2021-04-29 2021-07-27 南京大学 Magnesium air fiber battery and preparation method thereof
CN113178646B (en) * 2021-04-29 2022-07-22 南京大学 Magnesium air fiber battery and preparation method thereof
CN113517499A (en) * 2021-05-25 2021-10-19 西北大学 Flexible aluminum air battery based on PVA/KC-KOH composite gel electrolyte

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