CN107611348A - Aluminium ion cell flexible electrode material and preparation method thereof and aluminium ion battery - Google Patents
Aluminium ion cell flexible electrode material and preparation method thereof and aluminium ion battery Download PDFInfo
- Publication number
- CN107611348A CN107611348A CN201710830723.8A CN201710830723A CN107611348A CN 107611348 A CN107611348 A CN 107611348A CN 201710830723 A CN201710830723 A CN 201710830723A CN 107611348 A CN107611348 A CN 107611348A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- flexible electrode
- aluminium ion
- main part
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to field of batteries, discloses a kind of aluminium ion cell flexible electrode material and preparation method thereof and aluminium ion battery, and the preparation method of aluminium ion cell flexible electrode material includes：(1) carbon polymer will be contained to be dissolved in solvent, and will obtain solution；(2) presoma of material of main part and/or material of main part is mixed with the solution, obtains spinning solution, then carry out electrostatic spinning, obtain spinning thing；(3) the spinning thing is optionally pre-processed, be then heat-treated, obtain aluminium ion cell flexible electrode material；The material of main part contains at least one of transition metal oxide and transient metal sulfide.Aluminium ion cell flexible electrode material preparation method provided by the invention is simple, universality is strong, cost is cheap, and flexible electrode material produced by the present invention is used for having higher charging and discharging capacity, cyclic reversibility in aluminium ion battery.
Description
Technical field
The present invention relates to field of batteries, in particular it relates to a kind of aluminium ion cell flexible electrode material and preparation method thereof
With aluminium ion battery.
Background technology
Flexible energy storage device is the more popular direction of current research, and flexible material is excellent because possessing bent, Portable belt etc.
Point is increasingly held in both hands by heat, and has huge applications prospect, such as in camber display screen, intelligent clothing, electronic skin, implantable
Medicine equipment etc..Chargeable aluminium ion battery is one of popular research device of high volume energy density of future generation.Make
For trivalent metal, Al can realize the redox reaction of three electronics, and its rich reserves, cheap, be great research and development
The system of prospect.Common electrode material has generally required copper foil or aluminium foil as collector, it is necessary to which binding agent is by active material
It is attached to above collector, such electrode material is under the infiltration of electrolyte, if bent again, electrode material is easy to
Split away off.And both positive and negative polarity, the barrier film of flexible electrode material require it is flexible, can be used directly to make electrode material.
Because without additionally addition collector, conductive additive and binding agent, the entirety that this largely reduces battery are heavy again
Amount and cost, and help to increase the energy density of battery.Therefore, the soft of high security, high-flexibility and practicality is developed
Property aluminium ion battery has important researching value.
In recent years, the country headed by the U.S., Japan, South Korea is laid out flexible energy storage device one after another, the direction bag studied
Include flexible lithium ion battery, flexible super capacitor, flexible sodium-ion battery and corresponding electrolyte system.In aluminium ion electricity
Research in terms of the flexible electrode of pond just starts to walk at present, finds the method for preparing aluminium ion cell flexible electrode of simple and efficient
It is very crucial for capturing the field.
In order to solve above-mentioned problem, a kind of electric conductivity that electrode material is effectively improved without using hard collector and can is found
Method it is particularly significant.Distinctive carbon nano-fiber skeleton is prepared by method of electrostatic spinning to provide well for material of main part
Conductive network, so as to serve as collector effect.Although it is related to prepare flexible electrode by method of electrostatic spinning both at home and abroad at present
Report, such as document Nano Lett.2016, Liu etc. prepares MnFe using method of electrostatic spinning in 16,3321-33282O4@C nanos are fine
Flexible electrode is tieed up, and is applied to anode material of lithium-ion battery, but the flexible material is synthesized using in-situ chemical route,
MnFe2O4Be present in nanofiber carbon pipe, be easy in high-temperature process destroy nanofibrous structures, and combined coefficient compared with
It is low, it is difficult to industrial applications.Xiong etc. is also using electrostatic spinning in document Scientific Reports.2015,5,9254
Method is prepared for MoS2/ C fexible films are used for anode material of lithium-ion battery, and the document is using polyacrylonitrile (PAN) as high
Polymers, the one-dimensional carbon nano-tube material of synthesis, used spin solvent PAN require that solvent is dimethylformamide, and PAN's is non-
The raw material that water-soluble then requirement prepares material of main part is soluble in dimethylformamide, and this is caused very to the selection of raw material
Big limitation, difficulty is also result in for mass industrialized production, and synthesized using in-situ chemical route, MoS2
It is present in nanofiber carbon pipe, equally with drawbacks described above.The method that Jiao Lifang seminars of Nankai University use electrostatic spinning
The N doped one-dimensionals CuCo of synthesis2O4Film, secondary battery cathode material is then used it for, it is in 1000mA g-1Electric current it is close
The lower circulation of degree still has 314mA h g in 1000 weeks-1Reversible capacity, even in 5000mA h g-1High current density under still
There are 296mA h g-1Reversible capacity.But the flexible material is synthesized using in-situ chemical route, CuCo2O4It is present in nanometer
In fibrous carbon pipe, equally with drawbacks described above.
Therefore, the preparation method for finding a kind of cheap and efficiently pervasive aluminium ion cell flexible electrode material of cost has
Important Research Significance.
The content of the invention
The invention aims to overcome the easily quilt of the nanofibrous structures in flexible electrode material existing for prior art
Destroy, the defects of fabricated in situ efficiency is low and condition is harsh, there is provided a kind of aluminium ion cell flexible electrode material and its preparation side
Method and aluminium ion battery, flexible electrode material preparation method provided by the invention is simple, universality is strong, cost is cheap, and this
Flexible electrode material made from invention is used for having higher charging and discharging capacity, cyclic reversibility in aluminium ion battery.
The present inventor has found that prior art prepares flexible electrode using electrospinning process in research process
When, the predominantly in-situ chemical synthetic method of use (will prepare the raw material of flexible electrode material and spinning solution mixes common progress
Electrostatic spinning), the flexible electrode material of in-situ chemical synthetic method synthesis is primarily present in the carbon pipe of nanofiber, this kind of structure
Flexible electrode material be easy to destroy nanofibrous structures in high-temperature process, and combined coefficient is relatively low.The present invention's
Inventor has found in further research process, by aluminium ion battery electrode material of main part and/or aluminium ion battery electrode main body
The presoma of material carries out soft made from electrostatic spinning with the spinning solution that solution (containing containing carbon polymer and solvent) is mixed to get
Property electrode material, host material particles are distributed between more carbon nano-fibers, are not present in the carbon pipe of nanofiber.Should
Kind structure will not destroy nanofibrous structures in high-temperature process, and taken off using the electrode of this kind of electrode material assembling
Also the stability of carbon nano-fiber structure can be kept during embedding.
Based on this, the invention provides a kind of aluminium ion cell flexible electrode material, the electrode material includes：More carbon are received
The carbon nanofiber networks skeleton of rice fiber composition, and the host material particles being distributed between more carbon nano-fibers；It is described
Host material particles contain at least one of transition metal oxide and transient metal sulfide；
The transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2At least one of；
The transient metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of.
The invention provides a kind of preparation method of aluminium ion cell flexible electrode material, this method includes：
(1) carbon polymer will be contained to be dissolved in solvent, and will obtain solution；
(2) presoma of material of main part and/or material of main part is mixed with the solution, obtains spinning solution, then
Electrostatic spinning is carried out, obtains spinning thing；
(3) the spinning thing is optionally pre-processed, be then heat-treated, obtain aluminium ion cell flexible electrode
Material；
The material of main part contains at least one of transition metal oxide and transient metal sulfide；
The transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2At least one of；
The transient metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of.
Present invention also offers aluminium ion cell flexible electrode material made from a kind of above method.
Present invention also offers a kind of aluminium ion battery, the electrode material of the aluminium ion battery includes above-mentioned electrode material
Material.
Aluminium ion cell flexible electrode material provided by the invention has following advantage：
(1) flexible electrode material that the present invention is prepared using method of electrostatic spinning, host material particles are distributed in more carbon and received
Between rice fiber, the structure is advantageous to increase the electric conductivity of material of main part, is assembled into aluminium ion battery, is advantageous to aluminium
The transmission of ion and the infiltration of electrolyte；
(2) flexible electrode material provided by the invention does not need collector and binding agent, it is not necessary to conductive additive, can be with
It is directly used in assembling aluminium ion battery；
(3) flexible electrode material provided by the invention is due to that need not use collector, and then has the characteristics of light weight,
The weight of battery can be substantially reduced, improves the energy density of battery, great practical application foreground；
(4) present invention uses and first prepares the presoma of material of main part and/or material of main part, then is dispersed to molten
Liquid obtains spinning solution and then spinning, and this method is almost applicable to appoint because the dissolving of active material is not only restricted to spin solvent
The preparation of what aluminium ion battery plus-negative plate flexible material；
(5) compared with the synthesis aluminium ion battery electrode material of routine, the flexible aluminium that is prepared by the electrospinning process
Ion battery flexible electrode material can realize the high rate charge-discharge and long circulating of battery, have application value well.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Fig. 1 is the SEM figures of flexible electrode material S1 made from the embodiment of the present invention 1；
Fig. 2 is the SEM figures of flexible electrode material D1 made from comparative example 1 of the present invention.
Embodiment
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of aluminium ion cell flexible electrode material, and the electrode material includes：More carbon nano-fiber groups
Into carbon nanofiber networks skeleton, and host material particles being distributed between more carbon nano-fibers；The material of main part
Particle contains at least one of transition metal oxide and transient metal sulfide；
The transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2At least one of；
The transient metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of.
As shown in figure 1, the host material particles in aluminium ion cell flexible electrode material provided by the invention be distributed in it is more
Between root carbon nano-fiber, and the flexible electrode material that prior art provides, host material particles are located at a carbon nano-fiber
Inside, the particle diameter of host material particles are limited by carbon nano-fiber diameter, and particle diameter is smaller, flexible electrode provided by the invention
There is no particular limitation for size of the material to host material particles；The main body material for the flexible electrode material that other prior art provides
The deintercalation of material particle intermediate ion can damage to carbon nano-fiber structure, and then it is whole to influence aluminium ion cell flexible electrode material
The stability of body.
In order to further improve the chemical property of flexible electrode material provided by the invention, it is preferable that material of main part
The average grain diameter of particle is 20nm-0.5mm, more preferably 150nm-4 μm.
In the present invention, the average grain diameter is counted by field emission scanning electron microscope (SEM), is shone by measuring shooting Electronic Speculum
The longest diameter of host material particles in piece, the method for repeatedly measuring and then averaging measure.
According to flexible electrode material provided by the invention, it is preferable that a diameter of 50nm-500nm of carbon nano-fiber, enter one
Step is preferably 100nm-500nm, is still more preferably 100nm-250nm.
The diameter of carbon nano-fiber of the present invention can be counted by field emission scanning electron microscope (SEM), pass through survey
The maximum gauge of carbon nano-fiber in amount shooting electromicroscopic photograph, the method for repeatedly measuring and then averaging measure.
The present invention is wider to the range of choice of the carbon nano-fiber and the content of host material particles, in order to more enter one
Step improves the chemical property of flexible electrode material, it is preferable that the content of the host material particles is 40-90 weight %, institute
The content for stating carbon nano-fiber is 10-60 weight %, it is further preferred that the content of the host material particles is 40-80 weights
% is measured, the content of the carbon nano-fiber is 20-60 weight %, it is further preferred that the content of the host material particles
For 60-80 weight %, the content of the carbon nano-fiber is 20-40 weight %.
The content of carbon nano-fiber and host material particles can pass through heat in heretofore described flexible electrode material
Method of double differences heat (TG-DTA) method measures, and flexible electrode material is tested into thermogravimetric differential thermal curve under air atmosphere, then according to mistake
Weight curve calculates the content of material of main part and carbon nano-fiber.
The present invention is wider to the species range of choice of the host material particles, can be conventional in aluminium ion field of batteries
The various material of main parts used, can be positive pole material of main part or negative pole material of main part, and the present invention is not special to this
Restriction, those skilled in the art can suitably be selected as the case may be.On the basis of disclosed in the description of the invention,
Those skilled in the art are fully able to judge which aluminium ion battery electrode material of main part used.
A preferred embodiment of the invention, the host material particles contain V2O5、Mn3O4、MoO2、FeS2、
CuS and Ni3S2At least one of.
There is no particular limitation for thickness of the present invention to the aluminium ion cell flexible electrode material, in order to further carry
The chemical property of the high aluminium ion cell flexible electrode material, it is preferable that the aluminium ion cell flexible electrode material
Thickness is 0.01-5mm, more preferably 0.1-3mm, is still more preferably 0.5-1mm.
Present invention also offers a kind of preparation method of aluminium ion cell flexible electrode material, this method includes：
(1) carbon polymer will be contained to be dissolved in solvent, and will obtain solution；
(2) presoma of material of main part and/or material of main part is mixed with the solution, obtains spinning solution, then
Electrostatic spinning is carried out, obtains spinning thing；
(3) the spinning thing is optionally pre-processed, be then heat-treated, obtain aluminium ion cell flexible electrode
Material；
The material of main part contains at least one of transition metal oxide and transient metal sulfide；
The transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2At least one of；
The transient metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of.
It is of the invention that solvent in solution described in step (1) and the mass content containing carbon polymer are not required particularly,
As long as enable to the dissolving containing carbon polymer complete, it is preferable that described to contain carbon poly on the basis of the gross weight of the solution
The content of compound is preferably 5-20 weight %, more preferably 5-15 weight %, is still more preferably 7.1-11.5 weights
Measure %.
A preferred embodiment of the invention, described containing carbon polymer selected from number-average molecular weight is 10000-
1500000 high polymer, further preferably selected from the high polymer that number-average molecular weight is 16000-1300000.
In the present invention, as long as the high polymer that can act as electrostatic spinning is used equally for the present invention, and it is preferably described to contain carbon poly
Compound is selected from PEO, Kynoar, polymethacrylates, polyethylene glycol oxide, polyvinylpyrrolidone, polyethylene
Base carbazole, polybenzimidazoles, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyurethane, poly- second
At least one of enol, PLA, polyacrylonitrile and polyvinyl chloride, more preferably polyacrylonitrile, polyethylene glycol oxide, gather
At least one of vinylpyrrolidone and polyvinyl alcohol.
In accordance with the present invention it is preferred that the solvent is selected from dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), carbon
At least one of vinyl acetate and water.
As long as solvent of the present invention can dissolve the carbon compound, when the carbon compound is specific thing
During matter, those skilled in the art can select appropriate solvent according to description of the invention disclosure.The present invention is herein not
Another one illustrates.
According to method provided by the invention, it can be mixed, be obtained with the solution using material of main part in step (2)
Spinning solution, electrostatic spinning is then carried out, the presoma of material of main part can also be used to be mixed with the solution, obtain spinning
Liquid, electrostatic spinning is then carried out, can also be and mixed the presoma of material of main part and material of main part with the solution, obtain
To spinning solution, electrostatic spinning is then carried out, there is no particular limitation to this by the present invention.
It should be noted that the presoma of material of main part of the present invention does not refer to the raw material for synthesizing material of main part, and
It is that each raw material has produced certain interaction, material of main part can be converted under step (3) described heat treatment condition
Material.
According to method provided by the invention, the presoma of material of main part and/or material of main part and the dosage of the solution
Range of choice is wider, it is preferable that the quality of the presoma of the material of main part and/or the material of main part with containing carbon polymer
The mass ratio of the solution of meter is (0.1-2)：1, be preferably (0.25-0.6)：1.
When step (2) is to be mixed the presoma of material of main part and material of main part with the solution, the main body
The quality of the presoma of material and/or material of main part with the mass ratio of the solution of carbon containing polymer weight with referring to main body material
The quality and the mass ratio with the solution of carbon containing polymer weight of the summation of the presoma of material and material of main part.
There is no particular limitation for size of the present invention to the material of main part and the particle diameter of the presoma of material of main part, as long as
Being capable of electrostatic spinning.
According to method provided by the invention, it is preferable that the particle diameter of material of main part is not more than 1mm, more preferably little
In 0.5mm, more preferably 0.15-5 μm.
According to method provided by the invention, it is preferable that the particle diameter of the presoma of material of main part is not more than 1mm, further excellent
Elect as and be not more than 0.5mm, more preferably 0.15-5 μm.
The present invention is not limited particularly the method for obtaining the material of main part of above-mentioned particle diameter and the presoma of material of main part
It is fixed, at least one step that can be in preparation process be ground or be prepared material of main part and/or its before
It is ground after driving body.In addition, the particle diameter for the product that the presoma of some material of main parts and/or material of main part is prepared is direct
Meet that the present invention to the material of main part and/or the Particle size requirements of the presoma of material of main part, therefore, can not include ground
Journey.For whether needing to grind and be specifically ground depending on different material of main parts in which step, art technology
Personnel can suitably be selected.
According to method provided by the invention, the selection of the material of main part species will not be repeated here as described above.
There is no particular limitation for embodiment of the present invention to step (2) described mixing, it is preferable that the mixing bag
Include：The presoma of material of main part and/or material of main part is contacted with the solution, then carries out ultrasonic disperse successively, magnetic force stirs
Mix.By the way of ultrasonic disperse and magnetic agitation combine, be more beneficial for material of main part and/or material of main part presoma it is molten
Solution, and then it is more beneficial for improving the chemical property of aluminium ion cell flexible electrode material.
According to method provided by the invention, the ultrasonic disperse can be carried out according to this area conventional technical means, preferably
Ground, the frequency of the ultrasonic disperse is 40kHz-100kHz, time 0.5-6h.
According to method provided by the invention, the magnetic agitation can be carried out according to this area conventional technical means, preferably
Ground, the rotating speed of the magnetic agitation are 150rpm-1000rpm, time 1-20h, it is further preferred that the magnetic agitation
Rotating speed is 400rpm-600rpm, time 4-10h.
A preferred embodiment of the invention, the condition of the electrostatic spinning include：Voltage is 10kV-30kV,
More preferably 15kV-22kV；The distance of filament mouth and receiver is 10cm-25cm, more preferably 15cm-20cm；
Fltting speed is 0.01mm/min-0.5mm/min, more preferably 0.08mm/min-0.2mm/min.
According to method provided by the invention, can by by the product that step (2) obtains from receiver (can be aluminium foil)
On take off, and then obtain the spinning thing.
According to method provided by the invention, it is preferable that the condition of the pretreatment includes：Temperature is 100-500 DEG C, enters one
Preferably 250-350 DEG C of step, more preferably 250-300 DEG C, more preferably time 30-300min, 120-300min, more
Preferably 120-180min.
According to method provided by the invention, it is preferable that the condition of the heat treatment includes：Carried out under inert atmosphere, temperature
For 300-1600 DEG C, more preferably 450-900 DEG C, more preferably 450-600 DEG C, time 1-12h, more preferably
4-10h。
There is no particular limitation to the inert atmosphere by the present invention, such as can be by nitrogen, helium, argon gas and neon
One or more provide, and are preferably provided by argon gas.
Present invention also offers the aluminium ion cell flexible electrode material as made from the above method.
Present invention also offers a kind of aluminium ion battery, wherein, the electrode material of the aluminium ion battery is including above-mentioned
Electrode material.
According to the present invention, the aluminium ion battery can be full battery or refer to half-cell.Wherein, for testing
During the electrical property of battery electrode material, then tested using half-cell.The half-cell can also include to electrode, barrier film and
Electrolyte.Wherein, it is metal aluminium flake to electrode.Wherein, the effect of barrier film is to avoid both positive and negative polarity from directly contacting to cause battery short circuit,
Such as glass fibre Whatman GF/C NO.1822-047 can be used.Wherein, the electrolyte can be that this area is conventional
The il electrolyte used, such as (preferably, aluminium chloride and imidazolium halide molar ratio are for aluminium chloride and imidazolium halide
1.1-1.5：1) ionic liquid is electrolyte.
The aluminium ion battery can be assembled into the form of button cell in the glove box full of inert gas.
By using the flexible electrode material of the present invention, it can obtain that reversible discharge specific capacity is higher, stability is preferable
Aluminium ion battery, and collector, conductive additive and binding agent need not be used.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, electrostatic spinning machine is worked in peace and contentment development in science and technology Co., Ltd purchased from Beijing Yongkang, type
Number for Elite series；
Sem analysis uses the field emission scanning electron microscope of the model S-4800 purchased from FDAC Co., Ltd.；
Using meter Kai Luo, that argon gas gloves for protection case carries out battery assembling；
Magnetic stirring apparatus is German IKA topolino magnetic stirring apparatus；
Barrier film is glass fibre Whatman GF/C NO.1822-047；
The diameter of carbon nano-fiber is counted using field emission scanning electron microscope (SEM), is shot by measuring in electromicroscopic photograph
Carbon nano-fiber maximum gauge, the method for repeatedly measuring and then averaging measures.
The average grain diameter of host material particles is counted using field emission scanning electron microscope (SEM), and Electronic Speculum is shot by measuring
The longest diameter of host material particles in photo, the method for repeatedly measuring and then averaging measure；
In flexible electrode material, the content of carbon nano-fiber and host material particles uses thermogravimetric differential thermal (TG-DTA) method
Measure, flexible electrode material is tested into thermogravimetric differential thermal curve under air atmosphere, material of main part is then calculated according to weight-loss curve
With the content of carbon nano-fiber.
Embodiment 1
Transition metal oxide MoO2The preparation of flexible electrode material.
(1) 6.5g Ammonium Molybdate Tetrahydrate (NH is weighed4)6Mo7O24·4H2(commercially available from acros companies, the trade mark is O
205851000) 30min is ground in agate mortar, obtained powder is calcined into 30min for 300 DEG C in air atmosphere Muffle furnace,
Then 600 DEG C of calcining 5h in the tube furnace of argon atmosphere, obtain MoO2Powder (particle diameter is about 4.3 μm)；
(2) 2g polyethylene glycol oxides (PEO, number-average molecular weight 600000, similarly hereinafter) are weighed to be dissolved in deionized water, are stirred
Form the solution that mass content is 11.5 weight %；
(3) MoO that 0.5g steps (1) obtain is weighed2Powder, add in the solution of step (2), stir, Ran Houyi
Secondary progress ultrasonic disperse (100kHz, 2h), magnetic agitation (700rpm, 8h), obtain spinning solution, and obtained spinning solution is loaded
In 10ml disposable syringes, it is put into electrostatic spinning machine and carries out electrostatic spinning, a circle aluminium foil is twined on roller is received and receives spinning
The nanofiber of silk gained, the condition of electrostatic spinning include：Fltting speed 0.08mm/min, filament mouth (syringe needle) and receiver
(reception roller) distance is 18cm, spinning voltage 20kV, and obtained spinning thing is taken off from aluminium foil, first in Muffle furnace
300 DEG C of pretreatment 2h, then 600 DEG C of heat treatment 5h under tube furnace argon atmosphere, that is, obtain flexible electrode material S1.It is prepared
Flexible electrode material S1 thickness be 1.5mm.
Sem analysis is carried out to flexible electrode material S1, as shown in figure 1, MoO2Distribution of particles more carbon nano-fibers it
Between.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material S1 carbon nano-fiber
The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1.
Comparative example 1
Weigh 6.5g Ammonium Molybdate Tetrahydrates (NH4)6Mo7O24·4H2O grinds 30min in agate mortar, weighs 2g PEO,
Then both are mixed and be dissolved in deionized water, the spinning solution that the mass content that stirring forms PEO is 11.5 weight %.Then
Electrostatic spinning same as Example 1, pretreatment and heat treatment are carried out, obtains flexible electrode material D1.
Sem analysis is carried out to flexible electrode material D1, obtained SEM figures are as shown in Fig. 2 as can be seen from the figure 2, main body
Material MoO2Particle is located inside the carbon pipe of carbon nano-fiber, and one-dimentional structure is presented.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material D1 carbon nano-fiber
The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1, because the particle diameter of host material particles is limited to carbon nanometer
Fiber, host material particles particle diameter are significantly less than the flexible electrode material S1 that embodiment 1 obtains.
Embodiment 2
Transition metal oxide V2O5The preparation of flexible electrode material.
(1) by 1.456g V2O5Powder (being purchased from Sigma) and 60mL deionized waters mix, at room temperature magnetic agitation
(400rpm) 30min, the hydrogen peroxide for adding that 10mL volume fractions are 30% in solution is stated then up, continue to stir 30min, obtain
To the orange solution of homogeneous transparent；
(2) orange solution that step (1) obtains is transferred in 100mL reactors, then the Heat preservation at 200 DEG C
96h, after being cooled to room temperature (25 DEG C), obtained precipitation is respectively washed 3 times with deionized water and ethanol, the vacuum at 90 DEG C
Dry 12h and obtain V2O5Precursor powder (particle diameter is about 180nm)；
(3) weigh 1g polyacrylonitrile (PAN, number-average molecular weight 150000, similarly hereinafter) powder and be dissolved in dimethylformamide
(DMF) in, stirring forms the solution that mass content is 7.1 weight %；
(4) V that 0.6g steps (2) obtain is weighed2O5Precursor powder, add in the solution that step (3) obtains, stirring is equal
It is even, ultrasonic disperse (40kHz, 2h), magnetic agitation (1000rpm, 20h) are then carried out successively, obtain spinning solution, the spinning that will be obtained
Silk liquid is fitted into 10ml disposable syringes, is put into electrostatic spinning machine and carries out electrostatic spinning, and a circle aluminium is twined on roller is received
Paper tinsel receives the nanofiber obtained by spinning, and the condition of electrostatic spinning includes：Fltting speed 0.08mm/min, filament mouth (syringe needle) with
Receiver (reception roller) distance is 15cm, spinning voltage 15kV, and obtained spinning thing is taken off from aluminium foil, first in Muffle
280 DEG C of pretreatment 2h in stove, then 500 DEG C of heat treatment 4h under argon atmosphere, that is, obtain flexible electrode material S2.Prepared
Flexible electrode material S2 thickness is 1mm.
Sem analysis is carried out to flexible electrode material S2, as a result shown, V2O5Distribution of particles is between more carbon nano-fibers.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material S2 carbon nano-fiber
The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1.
Embodiment 3
Transition metal oxide Mn3O4The preparation of flexible electrode material.
(1) weigh the acetate hydrate manganese of 4.41g tetra- and be dissolved in 150mL deionized waters and be evenly stirred until that manganese acetate is completely molten
Solution, obtains solution A；
(2) hydrazine hydrate that the mass content for taking 2mL is 98%, which is dissolved in 120mL deionized waters, is uniformly mixing to obtain hydration
Hydrazine solution B；Then, solution A and B solution are pumped into same reactor using peristaltic pump, at room temperature, using magnetic stirring apparatus with
400rpm mixing speed stirs 12h, then the still aging 12h at 25 DEG C；Gained mixed material after ageing is filtered,
Make precipitation to be washed with deionized 3 times, be then deposited at 80 DEG C under air atmosphere in baking oven dry 24h by what is obtained, obtain
Mn3O4Precursor powder (particle diameter is about 3 μm)；
(3) weigh 2g polyvinylpyrrolidones (PVP, number-average molecular weight 1300000, similarly hereinafter) powder and be dissolved in distilled water
In, stirring forms the solution that mass content is 10 weight %；
(4) Mn that 1g steps (2) obtain is weighed3O4Precursor powder, add in step (3) described solution, stir,
Then ultrasonic disperse (100kHz, 2h), magnetic agitation (500rpm, 10h) are carried out successively, obtain spinning solution, the spinning that will be obtained
Liquid is fitted into 10ml disposable syringes, is put into electrostatic spinning machine and carries out electrostatic spinning, and a circle aluminium foil is twined on roller is received
The nanofiber obtained by spinning is received, the condition of electrostatic spinning includes：Fltting speed 0.2mm/min, filament mouth (syringe needle) is with connecing
It is 20cm, spinning voltage 20kV to receive device (reception roller) distance, and obtained spinning thing is taken off from aluminium foil, first in Muffle furnace
In 250 DEG C pretreatment 3h, then under argon atmosphere 450 DEG C heat treatment 10h, that is, obtain flexible electrode material S3.Prepared
Flexible electrode material S3 thickness is 1mm.
Sem analysis is carried out to flexible electrode material S3, sem analysis result is shown, Mn3O4Distribution of particles is in more carbon nanometers
Between fiber.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material S3 carbon nano-fiber
The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1.
Embodiment 4
Transient metal sulfide FeS2The preparation of flexible electrode material.
(1) 2g FeS is weighed2Powder (99.9%, purchased from Alfa Aesar) is put into appropriate mill ball in ball grinder
(it is 10 to keep the weight ratio of ball and powder：1) full argon gas, is rushed in ball grinder, and is lower ball milling 24h in 500rpm rotating speeds, is obtained
FeS2Powder (particle diameter is about 200nm)；
(2) weigh 1.5g PAN to be dissolved in DMF solution, stirring forms the solution that mass content is 10 weight %；
(3) FeS that 0.8g steps (1) obtain is weighed2Powder, add in the solution described in step (2), stir, so
Carry out ultrasonic disperse (50kHz, 2h), magnetic agitation (400rpm, 10h) successively afterwards, obtain spinning solution, obtained spinning solution is filled
Enter in 10ml disposable syringes, be put into electrostatic spinning machine and carry out electrostatic spinning, a circle aluminium foil is twined on roller is received and is received
Nanofiber obtained by spinning, the condition of electrostatic spinning include：Fltting speed 0.05mm/min, filament mouth (syringe needle) and receiver
(reception roller) distance is 20cm, spinning voltage 16kV, obtained spinning thing is taken off from aluminium foil, then in argon atmosphere
Lower 500 DEG C of heat treatment 4h, that is, obtain flexible electrode material S4.Prepared flexible electrode material S4 thickness is 1.5mm.
Sem analysis is carried out to flexible electrode material S4, sem analysis result is shown, FeS2Distribution of particles is in more carbon nanometers
Between fiber.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material S4 carbon nano-fiber
The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1.
Embodiment 5
The preparation of transient metal sulfide CuS flexible electrode materials.
(1) 2g CuCl is weighed2·2H2O mixes with 40mL ethylene glycol, is then heated to 120 DEG C under agitation,
It is designated as solution A；Weigh 3.6g (NH2)2CS mixes with 40mL ethylene glycol, labeled as solution B；Solution A and solution B are mixed,
It is transferred to after magnetic agitation (400rmp) 30min in 100mL reactor, obtained mixed solution is heated at 140 DEG C
90min, after being cooled to room temperature, obtained precipitation is cleaned three times with deionized water and ethanol respectively, it is then true at 60 DEG C
Sky dries 12h, obtains CuS powder (particle diameter is about 3.2 μm)；
(2) weigh 1g PAN powder to be dissolved in DMF solution, stirring forms the solution that mass content is 8.3 weight %；
(3) the CuS powder that 0.5g steps (1) obtain is weighed, adds in the solution described in step (2), stirs, then
Ultrasonic disperse (100kHz, 2h), magnetic agitation (600rpm, 10h) are carried out successively, obtains spinning solution, and obtained spinning solution is filled
Enter in 10ml disposable syringes, be put into electrostatic spinning machine and carry out electrostatic spinning, a circle aluminium foil is twined on roller is received and is received
Nanofiber obtained by spinning, the condition of electrostatic spinning include：Fltting speed 0.1mm/min, filament mouth (syringe needle) and receiver
(reception roller) distance is 15cm, spinning voltage 22kV, obtained spinning thing is taken off from aluminium foil, 250 in Muffle furnace
DEG C pretreatment 2h, then in argon atmosphere tube furnace 500 DEG C heat treatment 5h, that is, obtain flexible electrode material S5.Prepared
Flexible electrode material S5 thickness is 2mm.
Sem analysis is carried out to flexible electrode material S5, sem analysis result shows that CuS distribution of particles is in more carbon Nanowires
Between dimension.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material S5 carbon nano-fiber
The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1.
Embodiment 6
Transient metal sulfide Ni3S2The preparation of flexible electrode material.
(1) 1.5g Ni is weighed3S2Powder (being purchased from alfa companies, the trade mark 035661) is put into appropriate grind in ball grinder
(it is 10 to keep the weight ratio of ball and powder to abrading-ball：1) argon gas, is full of in ball grinder, and is lower ball milling 24h in 500rpm rotating speeds,
Obtain Ni3S2Powder (particle diameter is about 1.3 μm)；
(2) polyvinyl alcohol (PVA, number-average molecular weight 20000) for weighing 2g is dissolved in deionized water, and stirring forms matter
Measure the solution that content is 10 weight %；
(3) the micron order Ni that 1g steps (1) obtain is weighed3S2Powder, add in the solution described in step (2), stirring is equal
It is even, ultrasonic disperse (100kHz, 2h), magnetic agitation (600rpm, 10h) are then carried out successively, obtain spinning solution, the spinning that will be obtained
Silk liquid is fitted into 10ml disposable syringes, is put into electrostatic spinning machine and carries out electrostatic spinning, and a circle aluminium is twined on roller is received
Paper tinsel receives the nanofiber obtained by spinning, and the condition of electrostatic spinning includes：Fltting speed 0.1mm/min, filament mouth (syringe needle) with
Receiver (reception roller) distance is 15cm, spinning voltage 22kV, obtained spinning thing is taken off from aluminium foil, in Muffle furnace
After 280 DEG C of pretreatment 2h, then 500 DEG C of heat treatment 4h in argon atmosphere tube furnace, that is, obtain flexible electrode material S6.It is made
Standby flexible electrode material S6 thickness is 2mm.
Sem analysis is carried out to flexible electrode material S6, sem analysis result is shown, Ni3S2Distribution of particles is in more carbon nanometers
Between fiber.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material S6 carbon nano-fiber
The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1.
Table 1
Test example 1
The flexible battery material obtained to embodiment 1-6 and comparative example 1 carries out electrochemical property test.Specifically：
The obtained flexible battery material of embodiment 1-6 and comparative example 1 is assembled into aluminium ion battery, metal aluminium flake is to electricity
Pole, using glass fibre Whatman GF/C NO.1822-047 as barrier film, with aluminium chloride and imidazolium halide (aluminium chloride and halogenation miaow
Azoles molar ratio is 1.3：1) ionic liquid is electrolyte, and button cell (CR2025) is assembled in argon gas glove box, is stood
After 24h charge-discharge test is carried out on LAND CT2001A testers.As a result it is as shown in table 2.
Table 2
It can be seen from Table 2 that the aluminium ion assembled using flexible electrode material made from embodiment 1-6 can realize high ratio
The reversible discharge and recharge of capacity, and cyclical stability is preferable.In addition, flexible electrode material provided by the invention do not need collector and
Binding agent, it is not necessary to conductive additive, be used directly for assembling aluminium ion battery, and flexible electrode material provided by the invention
The preparation method of material is not only restricted to spin solvent, is almost applicable to the preparation of any aluminium ion battery plus-negative plate flexible material.
From the results contrast of embodiment 1 and comparative example 1, flexible electrode material particle size provided by the invention is not only restricted to carbon and received
Rice fiber, and more excellent electrochemical cycle stability can be shown.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited thereto.At this
In the range of the technology design of invention, a variety of simple variants, including each technical characteristic can be carried out to technical scheme
It is combined with any other suitable method, these simple variants and combination should equally be considered as in disclosed in this invention
Hold, belong to protection scope of the present invention.
Claims (11)
1. a kind of aluminium ion cell flexible electrode material, the electrode material include：The carbon Nanowire of more carbon nano-fiber compositions
Tie up network skeleton, and the host material particles being distributed between more carbon nano-fibers；The host material particles contain transition
At least one of metal oxide and transient metal sulfide；
The transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2At least one of；
The transient metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of.
2. aluminium ion cell flexible electrode material according to claim 1, wherein, the content of the host material particles is
40-80 weight %, the content of the carbon nano-fiber is 20-60 weight %.
3. aluminium ion cell flexible electrode material according to claim 1, wherein,
The average grain diameter of the host material particles is 20nm-0.5mm, preferably 150nm-4 μm；
A diameter of 50nm-500nm of the carbon nano-fiber, preferably 100nm-250nm.
4. aluminium ion cell flexible electrode material according to claim 1, wherein,
The host material particles contain V2O5、Mn3O4、MoO2、FeS2, CuS and Ni3S2At least one of.
5. a kind of preparation method of aluminium ion cell flexible electrode material, this method include：
(1) carbon polymer will be contained to be dissolved in solvent, and will obtain solution；
(2) presoma of material of main part and/or material of main part is mixed with the solution, obtains spinning solution, then carry out
Electrostatic spinning, obtain spinning thing；
(3) the spinning thing is optionally pre-processed, be then heat-treated, obtain aluminium ion cell flexible electrode material
Material；
The material of main part contains at least one of transition metal oxide and transient metal sulfide；
The transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2At least one of；
The transient metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of.
6. preparation method according to claim 5, wherein, on the basis of the gross weight of the solution, the carbon containing polymerization
The content of thing is 5-20 weight %, more preferably preferably 5-15 weight %, 7.1-11.5 weight %；
Preferably, it is described containing carbon polymer be selected from PEO, Kynoar, polymethacrylates, polyethylene glycol oxide,
Polyvinylpyrrolidone, PVK, polybenzimidazoles, polyethylene terephthalate, polymethyl methacrylate,
At least one of polystyrene, polyurethane, polyvinyl alcohol, PLA, polyacrylonitrile and polyvinyl chloride, it is more preferably poly-
At least one of acrylonitrile, polyethylene glycol oxide, polyvinylpyrrolidone and polyvinyl alcohol；
Preferably, the solvent is in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), ethylene carbonate and water
At least one.
7. the preparation method according to claim 5 or 6, wherein, the forerunner of the material of main part and/or the material of main part
The quality of body with using the mass ratio of the solution of carbon containing polymer weight as (0.1-2)：1, be preferably (0.25-0.6)：1.
8. the preparation method according to claim 5 or 6, wherein,
The particle diameter of the material of main part is not more than 1mm, preferably not greater than 0.5mm；
The particle diameter of the presoma of the material of main part is not more than 1mm, preferably not greater than 0.5mm；
Preferably, the material of main part contains V2O5、Mn3O4、MoO2、FeS2, CuS and Ni3S2At least one of.
9. according to the preparation method described in any one in claim 5-8, wherein, in step (2), the process of the mixing
Including：The presoma of the material of main part and/or the material of main part is contacted with the solution, then carries out ultrasound point successively
Dissipate, magnetic agitation；
Preferably, the frequency of the ultrasonic disperse is 40kHz-100kHz, time 0.5-6h；
Preferably, the rotating speed of the magnetic agitation is 150rpm-1000rpm, time 1-20h；
Preferably, the condition of the electrostatic spinning includes：Voltage is 10kV-30kV, preferably 15kV-22kV；Filament mouth is with connecing
The distance for receiving device is 10cm-25cm, preferably 15cm-20cm；Fltting speed is 0.01mm/min-0.5mm/min, is preferably
0.08mm/min-0.2mm/min。
10. according to the preparation method described in any one in claim 5-9, wherein,
The condition of the pretreatment includes：Temperature be 100-500 DEG C, preferably 250-350 DEG C, time 30-300min, preferably
For 120-300min；
The condition of the heat treatment includes：Carried out under inert atmosphere, temperature be 300-1600 DEG C, preferably 450-900 DEG C, the time
For 1-12h, preferably 2-12h.
11. a kind of aluminium ion battery, wherein, the electrode material of the aluminium ion battery includes any one in claim 1-4
Aluminium ion electricity made from method in described aluminium ion cell flexible electrode material or claim 5-10 described in any one
Pond flexible electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710830723.8A CN107611348B (en) | 2017-09-15 | 2017-09-15 | flexible electrode material of aluminum ion battery, preparation method of flexible electrode material and aluminum ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710830723.8A CN107611348B (en) | 2017-09-15 | 2017-09-15 | flexible electrode material of aluminum ion battery, preparation method of flexible electrode material and aluminum ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107611348A true CN107611348A (en) | 2018-01-19 |
| CN107611348B CN107611348B (en) | 2019-12-13 |
Family
ID=61063395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710830723.8A Active CN107611348B (en) | 2017-09-15 | 2017-09-15 | flexible electrode material of aluminum ion battery, preparation method of flexible electrode material and aluminum ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107611348B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931268A (en) * | 2019-11-22 | 2020-03-27 | 浙江工业大学 | Oxygen-sulfur doped Ni-Mo bimetallic material for super capacitor and preparation method thereof |
| CN111682265A (en) * | 2020-06-04 | 2020-09-18 | 北京理工大学 | Aluminum secondary battery |
| CN114335427A (en) * | 2021-11-18 | 2022-04-12 | 南京航空航天大学 | Three-dimensional V2O3@ carbon nanofiber composite flexible electrode and preparation method and application thereof |
-
2017
- 2017-09-15 CN CN201710830723.8A patent/CN107611348B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| XIAOXIAO LIU等: "Direct planting of ultrafine MoO2+δ nanoparticles in carbon nanofibers by electrospinning: self-supported mats as binder-free and long-life anodes for lithium-ion batteries", 《PHYS. CHEM. CHEM. PHYS.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931268A (en) * | 2019-11-22 | 2020-03-27 | 浙江工业大学 | Oxygen-sulfur doped Ni-Mo bimetallic material for super capacitor and preparation method thereof |
| CN111682265A (en) * | 2020-06-04 | 2020-09-18 | 北京理工大学 | Aluminum secondary battery |
| CN114335427A (en) * | 2021-11-18 | 2022-04-12 | 南京航空航天大学 | Three-dimensional V2O3@ carbon nanofiber composite flexible electrode and preparation method and application thereof |
| CN114335427B (en) * | 2021-11-18 | 2023-06-06 | 南京航空航天大学 | Three-dimensional V 2 O 3 Carbon nanofiber composite flexible electrode and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107611348B (en) | 2019-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107611346A (en) | Lithium ion battery flexible electrode material and preparation method thereof and lithium ion battery | |
| CN107492630A (en) | Sodium-ion battery flexible electrode material and preparation method thereof and sodium-ion battery | |
| Liu et al. | Advanced rechargeable lithium-ion batteries based on bendable ZnCo 2 O 4-urchins-on-carbon-fibers electrodes | |
| CN105118972B (en) | Metal hydroxide coated carbon and sulfur lithium-sulfur battery positive electrode material, and preparation method and application thereof | |
| CN102154739B (en) | Method for preparing lithium ion battery cathode material ZnFe2O4/C nano fibers | |
| CN104466134B (en) | The preparation method of self-supporting graphene/carbon nano-tube hybrid foam support amino anthraquinones base polymer | |
| CN109755534B (en) | Electrode material based on organic covalent framework material and preparation and application thereof | |
| CN104466168A (en) | Preparation method of cobaltosic oxide-carbon porous nanofiber and application of cobaltosic oxide-carbon porous nanofiber to preparation of lithium ion battery | |
| CN102399339B (en) | Preparation method of sulfurized polyacrylonitrile | |
| CN106784615A (en) | A kind of flexible lithium ion battery negative pole and preparation method thereof and flexible lithium ion battery | |
| CN104638252A (en) | Silicon composited negative electrode material, preparation method of silicon composited negative electrode material and lithium ion battery | |
| CN104538635A (en) | High-performance binder for silicon materials for lithium ion batteries and preparation method thereof | |
| CN104934610A (en) | Preparation method of self-supporting flexible composite electrode material used by lithium ion battery | |
| CN108615865A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| Yan et al. | Conducting polyaniline-wrapped lithium vanadium phosphate nanocomposite as high-rate and cycling stability cathode for lithium-ion batteries | |
| CN105226267B (en) | Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application | |
| CN102306774B (en) | Lithium iron phosphate nano array serving as cathode material of lithium ion battery and preparation method of lithium iron phosphate nano array | |
| CN107611348A (en) | Aluminium ion cell flexible electrode material and preparation method thereof and aluminium ion battery | |
| CN102399338A (en) | Sulfurized polyacrylonitrile and lithium ion batteries cathode material with application of sulfurized polyacrylonitrile | |
| CN102683712A (en) | Lithium ferric phosphate battery adopting compound conductive agent and manufacturing method thereof | |
| CN104979542A (en) | Modified lithium titanate composite material, preparation method and application thereof | |
| CN106711410A (en) | Battery negative electrode material and preparation method thereof as well as sodium-ion battery | |
| CN106450474A (en) | Gelled polymer electrolyte membrane and preparation method thereof | |
| CN105702938B (en) | A kind of iron-based oxide lithium ion battery negative material and preparation method and application | |
| Lu et al. | One-step synthesis of an urchin-like sulfur/polyaniline nano-composite as a promising cathode material for high-capacity rechargeable lithium–sulfur batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |