CN109768284A - A kind of lithium-sulfur cell standalone functionality interlayer and preparation method thereof - Google Patents
A kind of lithium-sulfur cell standalone functionality interlayer and preparation method thereof Download PDFInfo
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Abstract
A kind of lithium-sulfur cell standalone functionality interlayer and preparation method thereof, belongs to lithium-sulfur cell technical field.The standalone feature interlayer is directed to lithium sulfur battery anode material poorly conductive, the problems such as intermediate product solubility polysulfide shuttle effect of discharging, polyacrylonitrile nanofiber film is made by electrostatic spinning technique, and aluminum oxide nanoparticle is sputtered on the nano fibrous membrane with low temperature physical deposition technology, then independent porous functional interlayer is obtained using high temperature cabonization technique.Wherein, the porous structure of independent carbonization nanofiber interlayer promotes electronics transfer and provides physical barriers with lithium ion conduction and for the shuttle of polysulfide, while the electric conductivity of carbon compensates for the insulating properties defect of positive active material sulphur.Also, the addition of polar oxygenated aluminium improves lithium ion conductivity, and more reliable chemisorption is provided for polysulfide, by physics, chemical cooperated effect, further hinders the diffusion of polysulfide, to realize the high-capacity battery design of stable circulation.
Description
Technical field
The invention belongs to lithium-sulfur cell technical fields, more particularly to a kind of standalone functionality interlayer and preparation method thereof
Background technique
Compared to traditional lithium ion battery, lithium-sulfur cell system has relatively high energy density.Elemental sulfur anode
Theoretical specific capacity reach 1675mAhg-1, the theoretical energy density of battery pair is reachable when forming battery with lithium metal
2600Wh·kg-1.The numerical value is 3~5 times of lithium ion battery theoretical energy density, to assign it as next-generation high-energy
A possibility that densitybattery system.And sulphur is huge in the reserves of nature, toxicity is low, and environmental pollution is small.Thus, lithium-sulfur cell
The hot spot for having become current international research is the ideal chose of Future New Energy Source power battery.
The charge and discharge of lithium-sulfur cell are the processes of a multistep electron exchange, and polyelectron response feature brings Fabrication of High Specific Capacitance
The characteristics of amount, but also a series of problems is brought to lithium-sulfur cell system.The commercialization of developmental research lithium-sulfur cell is faced with sternly
High challenge.The practical application of lithium-sulfur cell is still poor by cycle life, and coulombic efficiency is low, the serious resistance such as self-discharge performance
Hinder.These problems are mainly due to the insulating properties of sulphur and its dissolution of discharging product polysulfide and between positive and negative anodes
Shuttle effect.Lithium-sulfur cell first is in charge and discharge process, the polysulfide ion meeting of the higher valence state for dissolving in electrolyte of generation
It is diffused into cathode of lithium, side reaction directly occurs with lithium metal, generates more lithium sulfides of lower valency, more lithium sulfides of these lower valencies
Sulphur anode is spread back, more lithium sulfides of high-valence state are generated, to generate shuttle effect.The generation of shuttle effect, directly results in
The loss of active material and the corrosion of cathode of lithium, make battery capacity decay rapidly, and coulombic efficiency reduces.In addition, sulphur simple substance
Conductivity it is extremely low (at 25 DEG C, Ω=5 × 10-30S/cm), cause lithium-sulfur cell dynamics of oxidation reduction slow.Sulphur anode is following
It can occur volume expansion during ring and fragmentation (76%), these can all cause lithium-sulfur cell cyclical stability to be deteriorated.
In order to solve the lithium-sulfur cell above problem, numerous studies are dedicated to developing effective layout strategy.Main stream approach packet
The inter-modification of sulphur cathode is included, such as various substrates such as conducting polymer and metal oxide of sulphur and carbon material etc. is combined into the phase
Diversified substrate is hoped to will increase conductivity, inhibiting to shuttle migrates and adapt to volume change.Although the tool of these sulfenyl composite materials
There is certain validity, but this method is related to complicated manufacturing process, and reduces the practical sulphur analysis of cathode.Therefore, in order to more
The shuttle of polysulfide is effectively limited, setting " barrier layer " is limited and caught to polysulfide between anode and diaphragm
It catches, improves the utilization rate of active material, become mentality of designing in one.
The porous structure of carbon material can alleviate the volume change during circulating battery, and can mention to polysulfide
It, cannot be with polar polysulfide shape for the transmission of physical barriers and promotion electronics and lithium ion, but since it belongs to nonpolarity
At stable chemical bond, it is difficult to effectively inhibit shuttle effect for a long time；And polar oxide can then be formed very polysulfide
Good chemisorption, but the transmission of electronics and lithium ion can be hindered.So two kinds of materials are combined into one, learn from other's strong points to offset one's weaknesses, mention
The ionic conductivity and cyclical stability of high battery.
The exploration early period of low temperature physical deposition technology and electrostatic spinning technique, the theoretical research of magnetron sputtering and high temperature cabonization
The exploration practice of technique provides possibility for the realization of above-mentioned imagination.Polyacrylonitrile (PAN) is prepared using electrostatic spinning technique to receive
Rice tunica fibrosa, has 3D gap structure.By low temperature physical deposition technology, nanometer Al is sputtered in PAN film surface2O3Nanoparticle
Structure sheaf, not only has that uniform, stable, fine and close, deposition process is easily controllable using nano thin-film prepared by physical deposition techniques,
The problem of overcoming the increase of doctor blade process bring thickness, and whole process does not have the advantages that chemical contamination.By pyrocarbon chemical industry
The carbon nanofiber membrane that skill obtains has independent self supporting structure, and the network structure of interconnection provides certain stable structure
The characteristics of property and high porosity.
Summary of the invention
It is existing to solve present invention aims at proposing a kind of lithium-sulfur cell standalone functionality interlayer and preparation method thereof
On the one hand the above problem present in lithium-sulfur cell, the standalone functionality interlayer using this method preparation can improve positive electrode
The problem of poorly conductive, another aspect interlayer have the function of lithium ion selective penetrated property, are efficiently hindering polysulfide diffusion
Meanwhile allowing lithium ion quickly through to effectively improve the ionic conductivity and cyclical stability of battery.
The present invention to achieve the above object, adopts the following technical scheme that
A kind of lithium-sulfur cell standalone functionality interlayer, the interlayer using polyacrylonitrile (PAN) nano fibrous membrane as substrate,
Surface constructs Al2O3Al is made finally by high temperature cabonization in coating2O3/ carbon nano-fiber (Al2O3/ CNF) interlayer.
It is further characterized by: the Al2O3/ CNF interlayer is located between the anode and diaphragm of lithium-sulfur cell.
A kind of preparation method of lithium-sulfur cell standalone functionality interlayer, using magnetron sputtering technique, in PAN nanofiber
Film surface sputters polarity Al2O3Then Al is made by high temperature cabonization technique in nanoparticle2O3/ CNF interlayer.
The preparation method comprises the following steps:
(1) polyacrylonitrile (PAN) nano fibrous membrane is prepared using electrostatic spinning technique；
(2) aluminium target and PAN nanofiber membrane are put into magnetron sputtering vacuum chamber, are vacuumized to reach background vacuum
After carry out magnetron sputtering, obtain Al2O3/ nano fibrous membrane；By the Al after having sputtered2O3/ nano fibrous membrane vacuum at 60 DEG C is dry
It is dry, to remove moisture removal；
(3) Al for preparing step (2)2O3/ nano fibrous membrane is heat-treated, to obtain Al2O3/ CNF interlayer.
The electrostatic spinning voltage is 10~20kV, and receiving distance is 15~20cm, and spinning flow velocity is 0.8~1.2ml/
h。
The condition of the magnetron sputtering are as follows: background vacuum 6.6*10-4~8.8*10-4Pa, argon oxygen ratio are maintained at 10:
1, magnetron sputtering power is 30~40W, and magnetron sputtering pressure is 0.8~0.9Pa, and the magnetron sputtering time is 20~40min.
The process of the heat treatment is related in Muffle furnace rising to 120 DEG C by room temperature 30min, then heats up through 2 DEG C/min
To 170 DEG C, last 1 DEG C/min rises to 270 DEG C of heat preservation 3h, obtains Al2O3/ preoxidised polyacrylonitrile nano fibrous membrane.By Al2O3/
Preoxidised polyacrylonitrile nano fibrous membrane is in N2Under atmosphere, 700 DEG C of heat preservation 1h are risen to 3 DEG C/min heating rate.Obtain Al2O3/ carbon
Nanofiber interlayer.
Beneficial effects of the present invention:
Lightweight Al2O3/ CNF interlayer can effectively inhibit the shuttle effect of polysulfide, while improve the ion-conductance of lithium-sulfur cell
Conductance and cyclical stability.
On the one hand the porous structure of carbon can alleviate the volume change in positive electrode process recycling, be on the other hand more
Sulfide provides physical barriers.Polarity Al2O3Chemisorption can be realized to polysulfide, the two cooperates with so that efficiently inhibiting
The shuttle effect of polysulfide is achieved.
The electric conductivity of carbon compensates for the insulating properties defect of positive active material sulphur, the polarity feature of aluminium oxide be conducive to lithium from
The transmission of son.The synergistic effect of electronic conductive material and fast ion conducting material is so that lithium-sulfur cell improves electronic conductivity and lithium
The ability of ionic conductivity is achieved.
The setting of standalone feature interlayer avoids the practical sulphur analysis of cathode caused by changing because of lithium-sulfur cell cathode construction
Reduction problem.
The nano fibrous membrane of electrostatic spinning technique preparation has the 3D network structure of interconnection, porosity with higher.
Magnetron sputtering technique depositing Al2O3Nanoparticle, overcomes the increase of doctor blade process bring thickness, and the energy content of battery is close
The problem of degree reduces.
Electrostatic spinning technique, magnetron sputtering technique it is mature and easy to operate, be advantageously implemented large-scale production.
Detailed description of the invention
Fig. 1 is Al in the embodiment of the present invention2O3The structural schematic diagram in lithium-sulfur cell of/CNF interlayer.
Fig. 2 is the XRD spectra of CNF interlayer in comparative example of the present invention.
Fig. 3 is Al in the embodiment of the present invention2O3The scanning electron microscope and Mapping of/nano fibrous membrane are schemed.Wherein, (a) is to sweep
Retouch electron microscope；(b) scheme for the Mapping of C element；(c) scheme for the Mapping of O element；(d) scheme for the Mapping of Al element.
Fig. 4 is the interface impedance of lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example
Comparison diagram.
Fig. 5 is the cyclic voltammetric of lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example
Curve comparison figure.
Fig. 6 is that the charge and discharge of lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example is electrical
It can correlation curve.
Fig. 7 is the cycle performance of lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example
Correlation curve.
Fig. 8 is lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example in difference
High rate performance correlation curve under (0.2C, 0.5C, 1C, 2C, 5C, 0.2C) current density.
Specific embodiment
Embodiment
A kind of embodiment of preparation method of the lithium-sulfur cell with standalone functionality interlayer and the lithium-sulfur cell with the interlayer:
Electrostatic spinning prepares polyacrylonitrile (PAN) nano fibrous membrane.2.65gPAN is dissolved in 15.8ml's (0.948g/ml)
The solution of mass fraction 15% is made in n,N-Dimethylformamide (DMF), is stirred overnight, solution is formed by method of electrostatic spinning
Nano fibrous membrane, spinning voltage 19kV, receiving distance is 15cm, and spinning flow velocity is 1.0ml/h.Obtain PAN nanofiber
Film.
Magnetron sputtering prepares Al2O3/ nano fibrous membrane.Using metal Al target, using PAN nanofiber membrane as substrate, in superelevation
In vacuum magnetic-control sputtering system, the method sputtered using DC source carries out the spray of function nano layer in PAN nanofiber membrane
It splashes.The vacuum degree of sputter chamber is evacuated to lower than 8.8*10 before sputtering-4Pa, working gas when sputtering are high-purity Ar gas, reaction
Gas is high-purity O2Gas, argon oxygen ratio are maintained at 10:1, sputtering power 40W, sputtering pressure 0.8Pa, and target pole span is 12cm, splash
Penetrating the time is 20min.Obtain Al2O3/ nano fibrous membrane.
High temperature cabonization technique prepares Al2O3/ CNF interlayer.The Al that will be prepared2O3/ nano fibrous membrane is heat-treated, carbon
Change process is related to: rising to 120 DEG C by room temperature 30min, then is warming up to 170 DEG C through 2 DEG C/min, last 1 DEG C/min rises to 270 DEG C of guarantors
Warm 3h obtains pre-oxidation PAN film.By pre-oxidized fibers film in N2700 DEG C of heat preservations are risen to 3 DEG C/min heating rate under atmosphere
1h.Obtain Al2O3/ CNF interlayer.
Assemble lithium-sulfur cell.Using the sulfur-bearing pole piece previously prepared as positive electrode, lithium piece is as cathode, polypropylene (PP)
Film is battery diaphragm, Al2O3Modified carbon nano-fiber (Al2O3/ CNF) as the interlayer between diaphragm and anode, electrolyte is
Double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M are dissolved in 1,3-dioxolane (DOL)/glycol dimethyl ether (DME)=1:
1V%, and add 1% LiNO3.All batteries assembling full of Ar atmosphere glove box in carry out, with exclude air and
The influence of water.
Test the chemical property of lithium-sulfur cell: by carrying out electrochemical property test (electricity to assembled button cell
Chem workstation CHI66E Shanghai Chen Hua Instrument Ltd.；The Shenzhen high accuracy battery test macro CT-3008W-5VmA-S4
New Weir Electronics Co., Ltd.) etc. evaluation lithium-sulfur cell chemical property.Wherein the cyclical stability of battery should do emphasis and grind
Study carefully.
Comparative example
A kind of comparative example of preparation method of the lithium-sulfur cell with standalone functionality interlayer and the lithium-sulfur cell with the interlayer
Electrostatic spinning prepares polyacrylonitrile (PAN) nano fibrous membrane.2.65gPAN is dissolved in 15.8ml's (0.948g/ml)
The solution of mass fraction 15% is made in DMF, is stirred overnight, solution forms nano fibrous membrane, spinning electricity by method of electrostatic spinning
Pressure is 19kV, and receiving distance is 15cm, and spinning flow velocity is 1.0ml/h.Obtain PAN nanofiber membrane.
High temperature cabonization technique prepares carbon nano-fiber (CNF) interlayer.The nano fibrous membrane prepared is heat-treated, carbon
Change process is related to: rising to 120 DEG C by room temperature 30min, then is warming up to 170 DEG C through 2 DEG C/min, last 1 DEG C/min rises to 270 DEG C of guarantors
Warm 3h obtains pre-oxidation PAN film.By pre-oxidized fibers film in N2700 DEG C of heat preservations are risen to 3 DEG C/min heating rate under atmosphere
1h.Obtain CNF interlayer.
Assemble lithium-sulfur cell.Using the sulfur-bearing pole piece previously prepared as positive electrode, lithium piece is cathode, and diaphragm is polypropylene
(PP) film, electrolyte are that double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M are dissolved in 1,3-dioxolane (DOL)/ethylene glycol two
Methyl ether (DME)=1:1V%, and add 1% LiNO3.All batteries assembling full of Ar atmosphere glove box in into
Row, to exclude the influence of air and water.
Test the chemical property of lithium-sulfur cell: by carrying out electrochemical property test (electricity to assembled button cell
Chem workstation CHI66E Shanghai Chen Hua Instrument Ltd.)；Charge-discharge test (high accuracy battery test macro CT-3008W-
New Weir Electronics Co., Ltd., the Shenzhen 5VmA-S4) etc. evaluation lithium-sulfur cell chemical property.
Fig. 1 is Al in the embodiment of the present invention2O3The structural schematic diagram in lithium-sulfur cell of/CNF interlayer.Folder as shown in the figure
Layer be located at anode and diaphragm between, porous carbon nanofiber interlayer can provide physical barriers for polysulfide, without influence lithium from
Son passes through；Polar oxygenated aluminum nanoparticles can chemical anchoring polysulfide；Furthermore the electric conductivity of carbon can be relieved sulphur positive electrode and lead
Electrically poor problem.To realize that high-performance lithium-sulfur cell provides possibility.
Fig. 2 is the XRD spectra of CNF interlayer in comparative example of the present invention.The broad peak of 2 θ=25 ° or so and 2 θ=51 ° in figure
Broad peak respectively corresponds (002) and (101) crystal face of graphitic carbon diffraction, is the vibration peak of carbon atom.Prove PAN nanofiber membrane
Be carbonized success.
Fig. 3 is Al in the embodiment of the present invention2O3The scanning electron microscope and Mapping of/nano fibrous membrane are schemed.It can from figure
Out, aluminium oxide has been deposited in PAN nanofiber membrane.
Fig. 4 is the interface impedance of lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example
Comparison diagram.As seen from the figure, contain Al in embodiment2O3It is 28.75 Ω that the lithium-sulfur cell of/CNF interlayer, which has minimum impedance,
The impedance of the lithium-sulfur cell containing CNF interlayer in comparative example and Al2O3The lithium-sulfur cell impedance of/CNF interlayer is similar, the two with
About 55% rate is reduced compared to impedance without lithium-sulfur cell with dissection.This is because the electric conductivity of porous carbon nanofiber and good
Good electrolyte, which retains, promotes electron-transport.Polar oxygenated aluminum nanoparticles increase electrolyte wetability to a certain extent.
Lesser impedance is conducive to the raising of the specific capacity of battery.
Fig. 5 is the cyclic voltammetric of lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example
Curve comparison figure.It can be seen that containing Al compared with the lithium-sulfur cell without interlayer2O3The volt-ampere of/CNF interlayer and CNF interlayer
Curve has biggish peak point current and lesser peak area and higher reduction potential and lower oxidizing potential, card
The lithium-sulfur cell of the bright interlayer containing Functional carbon has biggish lithium ion diffusion coefficient, lesser polarization.With the electricity for being free of interlayer
Pond is compared, and Al is contained in the embodiment of the present invention2O3The lithium-sulfur cell of/CNF interlayer has preferable electrochemical stability.
Fig. 6 is that the charge and discharge of lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example is electrical
It can correlation curve.As seen from the figure, what is prepared in the embodiment of the present invention contains Al2O3The lithium-sulfur cell of/CNF interlayer has highest first
Beginning specific discharge capacity is 1200.51mAhg-1, higher than the lithium-sulfur cell 393.42mAhg for being free of interlayer-1.Contain CNF in comparative example
The lithium-sulfur cell of interlayer takes second place, and is 1136.74mAhg-1.The higher initial discharge of the lithium-sulfur cell prepared in the embodiment of the present invention
Specific capacity due to the good electric conductivity of porous carbon nanofiber interlayer can promote electronics and ion transmission, and is polysulfide
Physical barriers are provided, on the one hand wetability that polar oxygenated aluminum nanoparticles increase electrolyte improves ionic conductivity, another party
Face chemical anchoring polysulfide.
Fig. 7 is the cycle performance of lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example
Correlation curve.It can be seen that containing Al in the embodiment of the present invention2O3The lithium-sulfur cell of/CNF interlayer is initially put with highest
There is 91.48% capacity retention rate, the capacity attenuation rate of every circle only has 0.084% after electric specific capacity and 200 circulations.
The lithium-sulfur cell of the interlayer containing CNF in comparative example is compared to the lithium-sulfur cell in embodiment, initial discharge specific capacity and capacity
Retention rate is reduced, but still much higher than the common lithium-sulfur cell without interlayer.
Fig. 8 be lithium-sulfur cell prepared by lithium-sulfur cell without dissection and the embodiment of the present invention, comparative example (0.2C,
0.5C, 1C, 2C, 5C, 0.2C) high rate performance correlation curve under current density.As seen from the figure, under different current densities, this
Lithium-sulfur cell in inventive embodiments all has highest specific discharge capacity.
It should be added that the lithium-sulfur cell of the interlayer containing CNF in comparative example is relative to the lithium-sulfur cell for being free of interlayer
For chemical property, be the conductance that on the one hand improves due to the excellent electric conductivity of carbon nano-fiber and preferable gap structure
Rate compensates for the defect of positive electrode poorly conductive, and on the other hand, porous structure provides physical barriers for polysulfide,
And alleviate the volume change in charge and discharge process.But carbon material be it is nonpolar, it is weaker with polarity polysulfide binding force.
Metal oxide is polar material, but its poorly conductive.The advantages of both present invention combination carbon material and metal oxide, implements
Contain Al in example2O3The lithium-sulfur cell of/CNF interlayer possesses best chemical property.
Claims (10)
1. a kind of lithium-sulfur cell standalone functionality interlayer, which is characterized in that the interlayer is with polyacrylonitrile nanofiber film
Substrate, surface construct Al2O3Al is made finally by high temperature cabonization in coating2O3/ carbon nano-fiber interlayer.
2. a kind of lithium-sulfur cell standalone functionality interlayer according to claim 1, which is characterized in that Al2O3/ carbon nanometer
Fibrous interlayer is located between the anode and diaphragm of lithium-sulfur cell.
3. a kind of lithium-sulfur cell preparation method of standalone functionality interlayer, which is characterized in that magnetron sputtering technique is used, poly-
Acrylonitrile nanofiber film surface sputters polarity Al2O3Then Al is made by high temperature cabonization technique in nanoparticle2O3/ carbon nanometer
Fibrous interlayer.
4. preparation method according to claim 3, which comprises the following steps:
(1) polyacrylonitrile nanofiber film is prepared using electrostatic spinning technique；
(2) aluminium target and polyacrylonitrile nanofiber film are put into magnetron sputtering vacuum chamber, are vacuumized to reach base vacuum
Magnetron sputtering is carried out after degree, obtains Al2O3/ nano fibrous membrane；By the Al after having sputtered2O3/ nano fibrous membrane vacuum at 60 DEG C
It is dry, to remove moisture removal；
(3) Al for preparing step (2)2O3/ nano fibrous membrane is heat-treated, to obtain Al2O3/ carbon nano-fiber interlayer.
5. preparation method according to claim 3 or 4, which is characterized in that in the step (1), electrostatic spinning voltage is
10~20kV, receiving distance is 15~20cm, and spinning flow velocity is 0.8~1.2ml/h.
6. preparation method according to claim 3 or 4, which is characterized in that in the step (2), the condition of magnetron sputtering
Are as follows: background vacuum 6.6*10-4~8.8*10-4Pa, argon oxygen ratio are maintained at 10:1, and magnetron sputtering power is 30~40W, magnetic
Control sputtering pressure is 0.8~0.9Pa, and the magnetron sputtering time is 20~40min.
7. preparation method according to claim 5, which is characterized in that in the step (2), the condition of magnetron sputtering are as follows:
Background vacuum is 6.6*10-4~8.8*10-4Pa, argon oxygen ratio are maintained at 10:1, and magnetron sputtering power is 30~40W, and magnetic control splashes
Penetrating pressure is 0.8~0.9Pa, and the magnetron sputtering time is 20~40min.
8. according to preparation method described in claim 3,4 or 7, which is characterized in that in the step (3), the heat treatment
Process are as follows: rise to 120 DEG C by room temperature 30min in Muffle furnace, then be warming up to 170 DEG C through 2 DEG C/min, last 1 DEG C/min rises to
270 DEG C of heat preservation 3h, obtain Al2O3/ preoxidised polyacrylonitrile nano fibrous membrane；By Al2O3/ preoxidised polyacrylonitrile nanofiber
Film is in N2Under atmosphere, 700 DEG C of heat preservation 1h are risen to 3 DEG C/min heating rate, obtain Al2O3/ carbon nano-fiber interlayer.
9. preparation method according to claim 5, which is characterized in that in the step (3), the process of the heat treatment
Are as follows: 120 DEG C are risen to by room temperature 30min in Muffle furnace, then is warming up to 170 DEG C through 2 DEG C/min, last 1 DEG C/min rises to 270 DEG C
3h is kept the temperature, Al is obtained2O3/ preoxidised polyacrylonitrile nano fibrous membrane；By Al2O3/ preoxidised polyacrylonitrile nano fibrous membrane is in N2
700 DEG C of heat preservation 1h are risen to 3 DEG C/min heating rate under atmosphere, obtain Al2O3/ carbon nano-fiber interlayer.
10. preparation method according to claim 6, which is characterized in that in the step (3), the process of the heat treatment
Are as follows: 120 DEG C are risen to by room temperature 30min in Muffle furnace, then is warming up to 170 DEG C through 2 DEG C/min, last 1 DEG C/min rises to 270 DEG C
3h is kept the temperature, Al is obtained2O3/ preoxidised polyacrylonitrile nano fibrous membrane；By Al2O3/ preoxidised polyacrylonitrile nano fibrous membrane is in N2
Under atmosphere, 700 DEG C of heat preservation 1h are risen to 3 DEG C/min heating rate, obtain Al2O3/ carbon nano-fiber interlayer.
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| CN113871625A (en) * | 2021-12-02 | 2021-12-31 | 中科南京绿色制造产业创新研究院 | Composite layer, preparation method thereof and lithium-sulfur battery |
| CN115020914A (en) * | 2022-05-19 | 2022-09-06 | 江南大学 | Spike-structured ceramic composite diaphragm interlayer for lithium/sodium-sulfur battery and preparation method thereof |
| CN115548339A (en) * | 2022-09-26 | 2022-12-30 | 陕西科技大学 | Lithium-sulfur battery interlayer, preparation method thereof and lithium-sulfur battery |
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