CN106784652A - Barium oxide/carbon nano tube flexible film and its preparation method and application - Google Patents

Barium oxide/carbon nano tube flexible film and its preparation method and application Download PDF

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CN106784652A
CN106784652A CN201611046722.6A CN201611046722A CN106784652A CN 106784652 A CN106784652 A CN 106784652A CN 201611046722 A CN201611046722 A CN 201611046722A CN 106784652 A CN106784652 A CN 106784652A
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barium oxide
carbon nano
nano tube
tube flexible
flexible film
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麦立强
魏湫龙
潘烨欣
谭双双
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Wuhan University of Technology WUT
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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
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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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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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Abstract

The present invention relates to a kind of powerful barium oxide/carbon nanometer flexible pipe film and its preparation method and application, it is stacked formed layer by layer by barium oxide nanobelt, barium oxide nanometer roll and CNT, wherein film thickness is 40~160 microns, barium oxide nanometer tape thickness is 6~10 nanometers, barium oxide nanometer roll is formed by the curling of barium oxide nanobelt, a diameter of 0.3~1 micron, and length is 0.8~2 micron, CNT external diameter is 8~15 nanometers, and length is 45~50 microns.The beneficial effects of the invention are as follows：Flexible Vanadium oxide/carbon nanometer tube composite materials are successfully synthesized by one step hydro thermal method, and using the method for simple suction filtration, prepares the controllable self-supporting barium oxide/carbon nano tube flexible thin-film electrode material of thickness.During as anode active material of lithium ion battery, the fexible film electrode shows excellent cyclical stability and high-rate characteristics.

Description

Barium oxide/carbon nano tube flexible film and its preparation method and application
Technical field
The invention belongs to nanometer material and electrochemical technology field, and in particular to a kind of powerful barium oxide/carbon is received Rice flexible pipe film and its preparation method and application, the material can be used as high-energy, high magnification, long-life flexible lithium ion battery Positive electrode active materials.
Background technology
Lithium ion battery is widely used to mobile phone, digital camera, notebook electricity as a kind of Green Chemistry memory device The portable equipments such as brain, and the progressively optimal selection as power mobile power supply.Therefore, research Large Copacity, high power, the long-life, The lithium ion battery of low cost is one of forward position and focus of current low-carbon economy epoch Study on Li-ion batteries.And with the modern times Science and technology development, increasing portable electronic products gradually to wearable, foldable, flexible development, this require for The characteristics of energy storage device of electronic product energy supply has light, thin, tough, more illustrates that the exploitation of flexible device would is that energy storage device not Come the inexorable trend for developing.And many electrode material quality is more crisp, the characteristics of do not possess flexibility.In order in flexible device Find application, the electrode material of lithium ion battery needs to realize pliability and mechanical strength higher.
Barium oxide as typical layered metal oxide, because the presence of its various oxidation state and coordination polyhedrom makes It possesses can reversibly be embedded in abjection lithium ion, and be considered as the lithium ion battery material of great potential.But common vanadium Oxide electrode material particle is larger, shape heterogeneity, it is difficult to realize flexible feature.Barium oxide nanobelt due to its compared with The when ultra-thin thickness of length and width high, it is possible to achieve certain pliability, can be used for the preparation of fexible film electrode.But it is general Ultrathin nanometer band easily occur from reuniting, it is difficult to realize orderly layer assembly, high rate performance and the circulation that have impact on material are steady It is qualitative.Nanobelt is carried out into three-dimensional porous gelation, nanobelt can be made to be interconnected and suppressed the unordered stacking between belt With the uniform compound and ordered fabrication for from reuniting, being conducive to subsequent thin film material.Meanwhile, the CNT of introducing forms height and leads Electric network, realize ion transported with the co-continuous of electronics it is unimpeded so that the high rate performance of barium oxide further improves, while Excellent cyclical stability is kept, and enhances the mechanical strength of film.In recent years, barium oxide/carbon nanotube composite Material is progressively studied as anode material for lithium-ion batteries, but barium oxide/carbon nano tube flexible membrane electrode is not reported yet Road.
The content of the invention
The technical problems to be solved by the invention are directed to above-mentioned prior art and propose a kind of barium oxide/CNT Fexible film and preparation method thereof, its process is simple, aboundresources, the barium oxide/carbon nano tube flexible membrane electrode of gained Positive electrode has excellent chemical property.
The present invention solves the technical scheme that is used of above-mentioned technical problem：Barium oxide/carbon nano tube flexible film, its Stacked formed layer by layer by barium oxide nanobelt, barium oxide nanometer roll and CNT, film thickness is 40~160 microns, Wherein barium oxide nanometer tape thickness is 6~10 nanometers, and barium oxide nanometer roll is formed by the curling of barium oxide nanobelt, diameter It it is 0.3~1 micron, length is 0.8~2 micron, CNT external diameter is 8~15 nanometers, length is 45~50 microns.
The preparation method of barium oxide/carbon nano tube flexible film, includes following steps：
1) polyvinylpyrrolidone (PVP, K30) and Li are weighed2CO3Dissolving is in deionized water；
2) in step 1) multi-walled carbon nano-tubes is added in resulting solution, ultrasonic disperse is uniform；
3) in step 2) vanadium pentoxide sol is added in resulting solution, continue to stir, and ultrasonic disperse；
4) by step 3) resulting solution is transferred in reactor, reacts in an oven；Reactor is taken out, room is naturally cooled to Temperature；
5) by step 4) after products therefrom is sufficiently stirred for breaing up, using cellulose mixture filter membrane as suction filtration paper, taken out Filter；
6) by step 5) gained film after natural drying on filter paper, is peeled off, and further dry film；
7) by step 6) gained film cutting i.e. acquisition barium oxide/carbon nano tube flexible membrane electrode.
By such scheme, the consumption of described polyvinylpyrrolidone is 17mg；Described Li2CO3Amount for 0.1~ 0.2mmol；The amount of described multi-walled carbon nano-tubes is 100~200mg；The consumption of described vanadium pentoxide sol is 1.5mmol。
By such scheme, step 4) described in reaction temperature be 160~200 DEG C；The described reaction time is 96~120 small When.
By such scheme, the aperture of cellulose mixture filter membrane is 0.10~0.45 μm.
By such scheme, step 5) described in suction filtration amount be 5~20mL.
Described barium oxide/carbon nano tube flexible film as anode active material of lithium ion battery application.
The present invention is interconnected to form using ultrathin nanometer band in barium oxide/carbon nano tube flexible film with CNT High connductivity nanometer network, be capable of achieving ion and transported with the co-continuous of electronics unimpeded, it is possessed excellent high rate performance.Simultaneously Nanometer roll clamps the dilation stress that Lithium-ion embeding abjection can be preferably buffered in belt structure, carbon nano tube network Its excellent cyclical stability can be realized as the structural framework of high intensity.
The beneficial effects of the invention are as follows：Unique advantage based on ultrathin nanometer band and carbon nano tube compound material, by one One-step hydrothermal successfully synthesizes Flexible Vanadium oxide/carbon nanometer tube composite materials, and using the method for simple suction filtration, prepares The controllable self-supporting barium oxide/carbon nano tube flexible thin-film electrode material of thickness.The present invention lives as lithium ion cell positive During property material, the fexible film electrode shows excellent cyclical stability and high-rate characteristics, is high-energy, high magnification, length The potential application material of life-span lithium ion battery.During as anode active material of lithium ion battery, in 100mA g-1Current density Under carry out constant current charge-discharge test, its specific discharge capacity is up to 310mAh g-1, 6000,8000,12000mA g-1High current Under density, its specific discharge capacity is up to 174,164,145mAh g-1.In 4000mA g-1Specific discharge capacity is under current density 194mAh g-1, capacity is 205mAh g after circulating 200 times-1, capacity is 162mAh g after circulating 1000 times-1, circulation guarantor Holdup is 83.5%.Present invention process is simple, and the simple hydro-thermal method for being used is low for equipment requirements, and obtained material purity High, good dispersion, it is easy to extension production, is very beneficial for market-oriented popularization.
Brief description of the drawings
Fig. 1 is the XRD of the barium oxide/carbon nano tube flexible film of present example 1；
Fig. 2 is the Raman spectrum of the barium oxide/carbon nano tube flexible film of present example 1；
Fig. 3 is the optical photograph of the barium oxide/carbon nano tube flexible film of present example 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of the barium oxide/carbon nano tube flexible film of the different-thickness of present example 1；
Fig. 5 is the scanning electron microscope (SEM) photograph of the barium oxide/carbon nano tube flexible film sections of present example 1；
Fig. 6 is the transmission electron microscope picture of the barium oxide/carbon nano tube flexible film of present example 1；
Fig. 7 is the high rate performance figure of the barium oxide/carbon nano tube flexible film of the different-thickness of present example 1；
Fig. 8 is the barium oxide/carbon nano tube flexible film of the different-thickness of present example 1 in 4000mA g-1Electric current Cycle performance of battery curve map under density.
Specific embodiment
For a better understanding of the present invention, it is with reference to the embodiment content that the present invention is furture elucidated but of the invention Content is not limited solely to the following examples.
Embodiment 1：
Barium oxide/carbon nano tube flexible method for manufacturing thin film, it is comprised the following steps：
1) polyvinylpyrrolidone (PVP, K30) and 0.1mmol LiCO of 17mg are weighed3It is dissolved in 30mL deionized waters In；
2) in step 1) 100mg multi-walled carbon nano-tubes, ultrasonic disperse 1 hour are added in resulting solution；
3) in step 2) to add volume be the 1.5mmol vanadium pentoxide sols of 30mL to resulting solution, continue to stir 1 small When, ultrasonic disperse 1 hour；
4) by step 3) resulting solution is transferred in 100mL reactors, reacted 96 hours in 160 DEG C of baking oven；Take out anti- Kettle is answered, room temperature is naturally cooled to；
5) by step 4) after products therefrom is sufficiently stirred for breaing up, cellulose mixture filter membrane using 0.45 μm of aperture is used as taking out Filter paper, taking 5mL hydrogels carries out suction filtration；
6) by step 5) filter membrane after natural drying on filter paper, peeled off, and film is further placed in 100 DEG C of bakings Carry out case drying；
7) by step 6) gained film cutting i.e. acquisition barium oxide/carbon nano tube flexible membrane electrode.
By taking this example product barium oxide/carbon nano tube flexible film as an example, its structure is determined by x-ray diffractometer.Such as Shown in Fig. 1, X-ray diffracting spectrum (XRD) shows, the barium oxide in barium oxide/carbon nano tube flexible film is orthorhombic phase H2V3O8(JCPDS card numbers are 01-085-2401), wherein the diffraction maximum at 26 ° comes from CNT.As shown in Fig. 2 Raman Test shows that the multi-walled carbon nano-tubes for adding has degree of graphitization very high, and electric conductivity is higher.As shown in figure 3, the flexible thin Film has pliability and mechanical strength higher, can carry out 180 degree bending.As shown in fig. 4 a, field emission scanning electron microscope (FESEM) test shows that the barium oxide/carbon nano tube flexible film thickness is 40 microns.As shown in figure 5, Flied emission is scanned Electronic Speculum (FESEM) test shows that the fexible film is to be stacked to form layer by layer by nanobelt, nanometer roll and CNT, and often Uniform CNT is all dispersed with individual subgrade.As shown in fig. 6, transmission electron microscope (TEM) test shows that barium oxide/carbon is received Mitron film is that ultrathin nanometer band and nanometer roll by connecting are constituted, wherein CNT be evenly dispersed in material surface with Inside, indicates the formation of continuous conduction carbon nano tube network.
Barium oxide/carbon nano tube flexible film prepared by this example is used as anode active material of lithium ion battery, and this is electric Pole directly as lithium ion battery positive plate, remaining step of the preparation method of lithium ion battery and common preparation method phase Together.With the LiPF of 1M6It is dissolved in vinyl carbonate (EC) and dimethyl carbonate (DMC) as electrolyte, lithium piece is negative pole, Celgard2400 is barrier film, and the type stainless steels of CR 2016 are assembled into fastening lithium ionic cell for battery case.
It is as anode active material of lithium ion battery using barium oxide/carbon nano tube flexible film prepared by this example Example, as shown in fig. 7, in 100mA g-1Constant current charge-discharge test is carried out under current density, its specific discharge capacity is up to 310mAh g-1, 1000,2000,4000mA g-1Under current density, its specific discharge capacity is up to 234,213,193mAh g-1.6000, 8000、12000mA g-1Under high current density, its specific discharge capacity is up to 174,164,145mAh g-1.As shown in figure 8, 4000mA g-1Specific discharge capacity is 194mAh g under current density-1, capacity is 205mAh g after circulating 200 times-1, circulation Capacity is 162mAh g after 1000 times-1, circulation conservation rate is 83.5%.The result shows barium oxide/carbon nano tube flexible Film has excellent high-rate characteristics, is the potential application material of high-energy, high magnification, extended-life lithium ion battery.
Embodiment 2：
Barium oxide/carbon nano tube flexible method for manufacturing thin film, it is comprised the following steps：
1) polyvinylpyrrolidone (PVP, K30) and 0.2mmol LiCO of 17mg are weighed3It is dissolved in 30mL deionized waters In；
2) in step 1) 150mg multi-walled carbon nano-tubes, ultrasonic disperse 1 hour are added in resulting solution；
3) in step 2) to add volume be the 1.5mmol vanadium pentoxide sols of 30mL to resulting solution, continue to stir 1 small When, ultrasonic disperse 1 hour；
4) by step 3) resulting solution is transferred in 100mL reactors, reacted 120 hours in 200 DEG C of baking oven；Take out anti- Kettle is answered, room temperature is naturally cooled to；
5) by step 4) after products therefrom is sufficiently stirred for breaing up, cellulose mixture filter membrane using 0.10 μm of aperture is used as taking out Filter paper, taking 5mL hydrogels carries out suction filtration；
6) by step 5) filter membrane after natural drying on filter paper, peeled off, and film is further placed in 100 DEG C of bakings Case is dried；
7) by step 6) gained film cutting i.e. acquisition barium oxide/carbon nano tube flexible membrane electrode.
By taking this example product as an example, the membrane electrode is stacked layer by layer by barium oxide nanobelt, nanometer roll and CNT Form, wherein film thickness is 40 microns, barium oxide nanometer tape thickness is 6~10 nanometers, and nanometer roll is by nanobelt curling Into a diameter of 0.3~1 micron, length is 0.8~2 micron, and CNT external diameter is 8~15 nanometers, and length is about 50 microns.
It is as anode active material of lithium ion battery using barium oxide/carbon nano tube flexible film prepared by this example Example, in 100mA g-1Constant current charge-discharge test is carried out under current density, its specific discharge capacity is up to 308mAh g-1, 1000, 2000、4000mA g-1Under current density, its specific discharge capacity is up to 230,210,188mAh g-1。
Embodiment 3：
Barium oxide/carbon nano tube flexible method for manufacturing thin film, it is comprised the following steps：
1) polyvinylpyrrolidone (PVP, K30) and 0.1mmol LiCO of 17mg are weighed3It is dissolved in 30mL deionized waters In；
2) in step 1) 150mg multi-walled carbon nano-tubes, ultrasonic disperse 1 hour are added in resulting solution；
3) in step 2) to add volume be the 1.5mmol vanadium pentoxide sols of 30mL to resulting solution, continue to stir 1 small When, ultrasonic disperse 1 hour；
4) by step 3) resulting solution is transferred in 100mL reactors, reacted 108 hours in 180 DEG C of baking oven；Take out anti- Kettle is answered, room temperature is naturally cooled to；
5) by step 4) after products therefrom is sufficiently stirred for breaing up, cellulose mixture filter membrane using 0.45 μm of aperture is used as taking out Filter paper, taking 10mL hydrogels carries out suction filtration；
6) by step 5) filter membrane after natural drying on filter paper, peeled off, and film is further placed in 100 DEG C of bakings Case is dried；
7) by step 6) gained film cutting i.e. acquisition barium oxide/carbon nano tube flexible membrane electrode.
By taking this example product as an example, the film is stacked and formed layer by layer by barium oxide nanobelt, nanometer roll and CNT, Wherein film thickness is 80 microns as shown in Figure 4 b, and barium oxide nanometer tape thickness is 6~10 nanometers, and nanometer roll is by nanobelt Curling is formed, a diameter of 0.3~1 micron, and length is 0.8~2 micron, and CNT external diameter is 8~15 nanometers, and length is about 50 Micron.
It is as anode active material of lithium ion battery using barium oxide/carbon nano tube flexible film prepared by this example Example, in 100mA g-1Constant current charge-discharge test is carried out under current density, its first discharge specific capacity is up to 304mAh g-1, 1000、2000、4000mA g-1Under current density, its specific discharge capacity is up to 230,200,163mAh g-1。
Embodiment 4：
Barium oxide/carbon nano tube flexible method for manufacturing thin film, it is comprised the following steps：
1) polyvinylpyrrolidone (PVP, K30) and 0.1mmol LiCO of 17mg are weighed3It is dissolved in 30mL deionized waters In；
2) in step 1) 120mg multi-walled carbon nano-tubes, ultrasonic disperse 1 hour are added in resulting solution；
3) in step 2) to add volume be the 1.5mmol vanadium pentoxide sols of 30mL to resulting solution, continue to stir 1 small When, ultrasonic disperse 1 hour；
4) by step 3) resulting solution is transferred in 100mL reactors, reacted 120 hours in 180 DEG C of baking oven；Take out anti- Kettle is answered, room temperature is naturally cooled to；
5) by step 4) after products therefrom is sufficiently stirred for breaing up, cellulose mixture filter membrane using 0.45 μm of aperture is used as taking out Filter paper, taking 15mL hydrogels carries out suction filtration；
6) by step 5) filter membrane after natural drying on filter paper, peeled off, and film is further placed in 100 DEG C of bakings Case is dried；
7) by step 6) gained film cutting i.e. acquisition barium oxide/carbon nano tube flexible membrane electrode.
By taking this example product as an example, the film is stacked and formed layer by layer by barium oxide nanobelt, nanometer roll and CNT, Wherein film thickness is 120 microns as illustrated in fig. 4 c, and barium oxide nanometer tape thickness is 6~10 nanometers, and nanometer roll is by nanobelt Curling is formed, a diameter of 0.3~1 micron, and length is 0.8~2 micron, and CNT external diameter is 8~15 nanometers, and length is about 50 Micron.
It is as anode active material of lithium ion battery using barium oxide/carbon nano tube flexible film prepared by this example Example, in 100mA g-1Constant current charge-discharge test is carried out under current density, its first discharge specific capacity is up to 300mAh g-1, 1000、2000、4000mA g-1Under current density, its specific discharge capacity is up to 210,150,80mAh g-1。
Embodiment 5：
Barium oxide/carbon nano tube flexible method for manufacturing thin film, it is comprised the following steps：
1) polyvinylpyrrolidone (PVP, K30) and 0.2mmol LiCO of 17mg are weighed3It is dissolved in 30mL deionized waters In；
2) in step 1) 200mg multi-walled carbon nano-tubes, ultrasonic disperse 1 hour are added in resulting solution；
3) in step 2) to add volume be the 1.5mmol vanadium pentoxide sols of 30mL to resulting solution, continue to stir 1 small When, ultrasonic disperse 1 hour；
4) by step 3) resulting solution is transferred in 100mL reactors, reacted 120 hours in 200 DEG C of baking oven；Take out anti- Kettle is answered, room temperature is naturally cooled to；
5) by step 4) after products therefrom is sufficiently stirred for breaing up, taking 20mL hydrogels carries out suction filtration, using 0.45 μm of aperture Cellulose mixture filter membrane as suction filtration paper；
6) by step 5) filter membrane after natural drying on filter paper, peeled off, and film is further placed in 100 DEG C of bakings Case is dried；
7) by step 6) gained film cutting i.e. acquisition barium oxide/carbon nano tube flexible membrane electrode.Produced with this example As a example by thing, the film is stacked and formed layer by layer by barium oxide nanobelt, nanometer roll and CNT, wherein film thickness such as Fig. 4 d It is shown, it is 160 microns, barium oxide nanometer tape thickness is 6~10 nanometers, and nanometer roll is formed by nanobelt curling, a diameter of 0.3 ~1 micron, length is 0.8~2 micron, and CNT external diameter is 8~15 nanometers, and length is about 50 microns.
It is as anode active material of lithium ion battery using barium oxide/carbon nano tube flexible film prepared by this example Example, in 100mA g-1Constant current charge-discharge test is carried out under current density, its first discharge specific capacity is up to 296mAh g-1, 1000、2000、4000mA g-1Under current density, its specific discharge capacity is up to 181,120,70mAh g-1。

Claims (7)

1. barium oxide/carbon nano tube flexible film, it is by barium oxide nanobelt, barium oxide nanometer roll and carbon nanotube layer Layer stacking is formed, and film thickness is 40~160 microns, and wherein barium oxide nanometer tape thickness is 6~10 nanometers, and barium oxide is received Rice volume is formed by the curling of barium oxide nanobelt, a diameter of 0.3~1 micron, and length is 0.8~2 micron, and CNT external diameter is 8~15 nanometers, length is 45~50 microns.
2. the preparation method of barium oxide/carbon nano tube flexible film, includes following steps：
1) polyvinylpyrrolidone and Li are weighed2CO3Dissolving is in deionized water；
2) in step 1) multi-walled carbon nano-tubes is added in resulting solution, ultrasonic disperse is uniform；
3) in step 2) vanadium pentoxide sol is added in resulting solution, continue to stir, and ultrasonic disperse；
4) by step 3) resulting solution is transferred in reactor, reacts in an oven；Reactor is taken out, room temperature is naturally cooled to；
5) by step 4) after products therefrom is sufficiently stirred for breaing up, using cellulose mixture filter membrane as suction filtration paper, carry out suction filtration；
6) by step 5) gained film after natural drying on filter paper, is peeled off, and further dry film；
7) by step 6) gained film cutting i.e. acquisition barium oxide/carbon nano tube flexible membrane electrode.
3. the preparation method of barium oxide/carbon nano tube flexible film according to claim 2, it is characterised in that described is poly- The consumption of vinylpyrrolidone is 17mg；Described Li2CO3Amount be 0.1~0.2mmol；The amount of described multi-walled carbon nano-tubes It is 100~200mg；The consumption of described vanadium pentoxide sol is 1.5mmol.
4. the preparation method of barium oxide/carbon nano tube flexible film according to claim 2, it is characterised in that step 4) institute The reaction temperature stated is 160~200 DEG C；The described reaction time is 96~120 hours.
5. the preparation method of barium oxide/carbon nano tube flexible film according to claim 2, it is characterised in that composite fibre The aperture of plain filter membrane is 0.10~0.45 μm.
6. the preparation method of barium oxide/carbon nano tube flexible film according to claim 2, it is characterised in that step 5) institute The amount of the suction filtration stated is 5~20mL.
7. the barium oxide described in claim 1/carbon nano tube flexible film as anode active material of lithium ion battery should With.
CN201611046722.6A 2016-11-23 2016-11-23 Barium oxide/carbon nano tube flexible film and its preparation method and application Pending CN106784652A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108335770A (en) * 2018-02-08 2018-07-27 哈尔滨工业大学 A kind of multi-functional gradient-structure flexible protective film
CN110048094A (en) * 2019-03-22 2019-07-23 湘潭大学 A kind of self-supporting laminated film and preparation method thereof for liquid phase Zinc ion battery
CN110289452A (en) * 2019-07-25 2019-09-27 安徽大学 Flexible zinc ion micro battery and preparation method thereof

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CN110289452B (en) * 2019-07-25 2021-06-25 安徽大学 Flexible zinc ion micro battery and preparation method thereof

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