CN107492630A - Sodium-ion battery flexible electrode material and preparation method thereof and sodium-ion battery - Google Patents

Sodium-ion battery flexible electrode material and preparation method thereof and sodium-ion battery Download PDF

Info

Publication number
CN107492630A
CN107492630A CN201710531495.4A CN201710531495A CN107492630A CN 107492630 A CN107492630 A CN 107492630A CN 201710531495 A CN201710531495 A CN 201710531495A CN 107492630 A CN107492630 A CN 107492630A
Authority
CN
China
Prior art keywords
electrode material
flexible electrode
sodium
ion battery
main part
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
Application number
CN201710531495.4A
Other languages
Chinese (zh)
Other versions
CN107492630B (en
Inventor
吴川
倪乔
吴锋
白莹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Institute of Technology BIT
Original Assignee
Beijing Institute of Technology BIT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing Institute of Technology BIT filed Critical Beijing Institute of Technology BIT
Priority to CN201710531495.4A priority Critical patent/CN107492630B/en
Publication of CN107492630A publication Critical patent/CN107492630A/en
Application granted granted Critical
Publication of CN107492630B publication Critical patent/CN107492630B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to field of batteries, discloses a kind of sodium-ion battery flexible electrode material and preparation method thereof and sodium-ion battery, and the electrode material includes：The carbon nanofiber networks skeleton of more carbon nano-fiber compositions, and the host material particles being distributed between more carbon nano-fibers.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 carry out electrostatic spinning, obtain spinning thing；(3) the spinning thing is pre-processed and is heat-treated successively, obtain sodium-ion battery flexible electrode material.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 sodium-ion battery.

Description

Sodium-ion battery flexible electrode material and preparation method thereof and sodium-ion battery
Technical field
The present invention relates to field of batteries, in particular it relates to a kind of sodium-ion battery flexible electrode material and preparation method thereof And sodium-ion battery.
Background technology
Flexible electrode material 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, has huge applications prospect, such as camber display screen, intelligent clothing, electronic skin, medicine equipment. And the development of matched flexible battery material also receives much concern.Common electrode material has generally required copper foil or aluminium foil As collector, it is necessary to which active material is attached to above collector by binding agent, infiltration of such electrode material in electrolyte Under, if bent again, electrode material is easy to split away off.And the both positive and negative polarity of flexible electrode material, barrier film requires is Flexible, it can be used directly to make electrode material.Because without additionally adding collector and binding agent again, this is largely On reduce the overall weight and cost of battery.But to reach same with current commodity electrochemical cell or can be practical effect Fruit, then need electrode material that there is good electric conductivity, it is necessary to the dependence for departing to collector, binding agent it is necessary to have higher Energy density.And the method for being presently used for making flexible electrode material is led using graphene or CNT as support more Body, its complex manufacturing technology, cost are higher, and larger to the selectivity of material of main part.
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.However, at present, make flexible electrode material using electrospinning process both at home and abroad Also it is rarely reported.Liu etc. prepares MnFe using method of electrostatic spinning in document Nano Lett.2016,16,3321-33282O4@C receive Rice fiber flexibility electrode, and it is applied to anode material of lithium-ion battery, but the flexible material is synthesized using in-situ chemical route , MnFe2O4It is present in nanofiber carbon pipe, is easy to destroy nanofibrous structures, and combined coefficient in high-temperature process It is relatively low, it is difficult to industrial applications.Xiong etc. also uses electrostatic spinning in document Scientific Reports.2015,5,9254 Method be prepared for MoS2/ C fexible films are used for anode material of lithium-ion battery, and the document uses polyacrylonitrile (PAN) conduct High polymer, the one-dimensional carbon nano-tube material of synthesis, used spin solvent PAN require that solvent is dimethylformamide, PAN's Water-insoluble, it is required that the raw material for preparing material of main part is soluble in dimethylformamide, this is caused to the selection of raw material Very big limitation, difficulty also result in for mass industrialized production, and synthesized using in-situ chemical route, MoS2It is present in nanofiber carbon pipe, equally with drawbacks described above.
Therefore, the preparation method for finding a kind of cheap and efficiently pervasive flexible electrode material of cost has important research Meaning.
The content of the invention
The invention aims to overcome flexible electrode material nanofibrous structures existing for prior art easily destroyed, Combined coefficient is low and the defects of condition is harsh, there is provided a kind of sodium-ion battery flexible electrode material and preparation method thereof and sodium ion Battery, flexible electrode material preparation method provided by the invention is simple, universality is strong, cost is cheap, and produced by the present invention Flexible electrode material is used to serve as electric specific capacity, cyclic reversibility with higher in sodium-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 sodium-ion battery electrode body material and/or sodium-ion battery electrode 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 sodium-ion battery 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.
The invention provides a kind of preparation method of sodium-ion battery 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 pre-processed and is heat-treated successively, obtain sodium-ion battery flexible electrode material.
Present invention also offers sodium-ion battery flexible electrode material made from a kind of above method.
Present invention also offers a kind of sodium-ion battery, the above-mentioned electrode material of the electrode material of the sodium-ion battery.
Sodium-ion battery flexible electrode material provided by the invention has following advantage：
(1) 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 sodium-ion battery；
(2) 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, great practical application foreground can be substantially reduced；
(3) flexible electrode material that the present invention is prepared using method of electrostatic spinning, its structure are that main body material outer wraps up carbon Nanofiber Network skeleton, the structure are advantageous to increase the electric conductivity of material of main part；
(4) 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, sodium-ion battery is assembled into, is advantageous to the transmission of sodium ion and the infiltration of electrolyte；
(5) 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 both positive and negative polarity flexible material；
(6) with the conventional sodium ion battery electrode material phase by synthesis such as solid phase method, sol-gal process, coprecipitations Than the flexible sodium-ion battery flexible electrode material prepared by the electrospinning process can realize the big multiplying power charge and discharge of battery Electricity and long circulating, there is 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；
Fig. 3 is the SEM figures of flexible electrode material S12 made from the embodiment of the present invention 12.
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 sodium-ion battery 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.
As shown in figure 1, the host material particles in sodium-ion battery 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 sodium-ion battery 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 100nm-5 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 50-900nm of carbon nano-fiber, further Preferably 100-500nm.The diameter of carbon nano-fiber of the present invention can be united by field emission scanning electron microscope (SEM) Meter, the maximum gauge of the carbon nano-fiber in electromicroscopic photograph is shot by measuring, the method for repeatedly measuring and then averaging is surveyed .
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 60-90 weight %, institute The content for stating carbon nano-fiber is 10-40 weight %, it is further preferred that the content of the host material particles is 60-80 weights % is measured, 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.
There is no particular limitation for species of the present invention to the host material particles, can be normal in sodium-ion battery field The various material of main parts used are advised, can be positive pole material of main part or negative pole material of main part, the present invention is to this without spy Other restriction, those skilled in the art can suitably be selected as the case may be.It is basic disclosed in description of the invention On, those skilled in the art are fully able to judge which electrode body material used.
According to a kind of embodiment of the present invention, the host material particles contain polyanion phosphoric acid salt thing At least one of matter, silicates material, pyrophosphoric acid salts substances, mixed phosphate salt material and transition metal oxide.
Preferably, the polyanion phosphoric acid salt material is selected from Na3MxV2-x(PO4)3And/or NaTi2(PO4)3, wherein, M is at least one of Mg, Ni and Ti, 0≤x≤2.
Preferably, the silicates material is selected from Na2FeSiO4And/or Na2MnSiO4；
Preferably, the pyrophosphoric acid salts substances are Na2FeP2O7；
Preferably, the mixed phosphate salt material is Na4Y3(PO4)2P2O7, wherein, in Y Fe, Co and Mn at least It is a kind of；
Preferably, the transition metal oxide is selected from Na2/3Fe1/2Mn1/2O2、NiCo2O4And TiO2In at least one Kind；
A preferred embodiment of the invention, the host material particles contain Na3Mg0.05V1.95(PO4)3、 Na3V2(PO4)3、Na3Ni0.03V1.97(PO4)3、NaTi2(PO4)3、Na2FeSiO4、Na2FeP2O7、Na4Mn3(PO4)2P2O7、Na2/ 3Fe1/2Mn1/2O2、NiCo2O4And TiO2At least one of.
There is no particular limitation for thickness of the present invention to the sodium-ion battery flexible electrode material, in order to further carry The chemical property of the high sodium-ion battery flexible electrode material, it is preferable that the sodium-ion battery 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 sodium-ion battery 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 pre-processed and is heat-treated successively, obtain sodium-ion battery flexible electrode material.
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 7-11.5 weight %.
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.
The present invention is wider to the species range of choice of the solvent, it is preferable that the solvent is selected from dimethylformamide, two At least one of methylacetamide, dimethyl sulfoxide (DMSO), ethylene carbonate 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 that the presoma of material of main part and material of main part is carried out into second with the solution mixes Close, obtain spinning solution, then carry out electrostatic spinning, 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 presoma of material of main part and/or material of main part and the dosage with the solution of carbon containing polymer weight Mass ratio is 0.1-2：1, more preferably 0.2-1：1.
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 presoma of material and/or material of main part with the dosage mass ratio of the solution of carbon containing polymer weight refer to material of main part and The summation of the presoma of material of main part and the dosage mass ratio with the solution of carbon containing polymer weight.
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.
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.
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 sodium-ion battery 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 5-10h.
A preferred embodiment of the invention, the condition of the electrostatic spinning include：Voltage is 10kV-30kV, More preferably 15kV-20kV；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 Step is preferably 250-350 DEG C, time 30-300min, more preferably 120-300min.
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 500-800 DEG C, time 2-10h, more preferably 5-10h.
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 sodium-ion battery flexible electrode material as made from the above method.
Present invention also offers a kind of sodium-ion battery, wherein, the electrode material of the sodium-ion battery is including above-mentioned Electrode material.
According to the present invention, the sodium-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 metallic sodium piece 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 the glass fibres of Gelgard 2400 can be used.Wherein, the electrolyte can be electrolyte commonly used in the art, Such as NaPF6Or NaClO4Carbonic allyl ester solution.
The sodium-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 Sodium-ion battery, and collector 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 regards the ESEM up to the model QUANTA FEG250 of (China) Co., Ltd purchased from section；
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；
Fibreglass diaphragm is the glass fibres of Gelgard 2400；
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
Polyanion phosphoric acid salt Na3V2(PO4)3The preparation of flexible electrode material.
(1) by 1.32g NaOH, 2.3396g NH4VO3, 3.4506g NH4H2PO4Burnt with 6.3042g citric acids in 250mL In cup plus deionized water (80g) mixes, and is stirred at 80 DEG C, until forming colloidal sol, 12h, shape are then dried in vacuo at 80 DEG C Into dry glue, then the dry glue is ground, in 350 DEG C of Muffle furnace pre-burning 3h, obtains Na3V2(PO4)3(particle diameter is about for precursor powder For 3 μm)；
(2) 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 %；
(3) Na that 1g steps (1) obtain is weighed3V2(PO4)3Precursor powder, add in above-mentioned solution, stir, so Carry out ultrasonic disperse (40kHz, 2h), magnetic agitation (1000rpm, 20h) successively afterwards, obtain spinning solution, the spinning solution that will be obtained It is fitted into 10ml disposable syringes, is put into electrostatic spinning machine and carries out electrostatic spinning, twining a circle aluminium foil on roller is received connects The nanofiber obtained by spinning is received, the condition of electrostatic spinning includes：Fltting speed 0.08mm/min, filament mouth (syringe needle) is with receiving Device (reception roller) distance is 15cm, spinning voltage 15kV, and obtained spinning thing is taken off from aluminium foil, first in Muffle furnace 250 DEG C of pretreatment 2h, then 800 DEG C of heat treatment 6h under argon atmosphere, that is, obtain flexible electrode material S1.Prepared flexibility Electrode material S1 thickness is 1mm.
Sem analysis is carried out to flexible electrode material S1, obtained SEM figures are as shown in figure 1, as can be seen from the figure 1, Na3V2 (PO4)3Distribution of particles is between more carbon nano-fibers.
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
By 1.32g NaOH, 2.3396g NH4VO3, 3.4506g NH4H2PO4With 6.3042g citric acids in 250mL beakers In plus deionized water (80g) mixing, stirred at 80 DEG C, until be evaporated to 10ml solution, the solution be labeled as solution A.Claim 1g polyacrylonitrile (PAN, number-average molecular weight 150000) powder is taken to be dissolved in dimethylformamide (DMF), stirring forms matter The solution that content is 7.1 weight % is measured, the solution is labeled as solution B, solution A is added in solution B, stirred, will Then it carries out electrostatic spinning same as Example 1, pretreatment and heat treatment, obtains flexible electrode material as spinning solution D1。
Sem analysis is carried out to flexible electrode material D1, obtained SEM figures are as shown in figure 3, as can be seen from the figure 3, main body Material Na3V2(PO4)3Particle 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
Polyanion phosphoric acid salt Na3Mg0.05V1.95(PO4)3The preparation of flexible electrode material.
(1) by 1.32g NaOH, 2.2811g NH4VO3, 3.4506g NH4H2PO4, 0.1072g (CH3COO)2Mg·4H2O Add deionized water (70g) mixing in 250mL beakers with 6.3042g citric acids, stirred at 80 DEG C, until forming colloidal sol, so 12h is dried in vacuo at 80 DEG C afterwards, dry glue is formed, then the dry glue is ground, in 350 DEG C of Muffle furnace pre-burning 3h, obtained Na3Mg0.05V1.95(PO4)3Precursor powder (particle diameter is about 5 μm)；
(2) 2g polyethylene glycol oxides (PEO, number-average molecular weight 600000, similarly hereinafter) powder is weighed to be dissolved in distilled water, stir Mix the solution to form that mass content is 11.5 weight %；
(3) Na that 1.5g steps (1) obtain is weighed3Mg0.05V1.95(PO4)3Precursor powder, add in above-mentioned solution, stir Mix uniformly, then carry out ultrasonic disperse (100kHz, 2h), magnetic agitation (500rpm, 10h) successively, obtain spinning solution, will obtain Spinning solution be fitted into 10ml disposable syringes, be put into electrostatic spinning machine and carry out electrostatic spinning, receive roller on twine one The nanofiber obtained by aluminium foil reception spinning is enclosed, the condition of electrostatic spinning includes：Fltting speed 0.2mm/min, filament mouth (pin Head) with receiver (reception roller) distance be 20cm, spinning voltage 20kV, obtained spinning thing is taken off from aluminium foil, elder generation 350 DEG C of pretreatment 5h in Muffle furnace, then 800 DEG C of heat treatment 6h under argon atmosphere, that is, obtain flexible electrode material S2.Institute The flexible electrode material S2 of preparation thickness is 1mm.
Sem analysis is carried out to flexible electrode material S2, sem analysis result is shown, Na3Mg0.05V1.95(PO4)3Distribution of particles 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
Polyanion phosphoric acid salt Na3Ni0.03V1.97(PO4)3The preparation of flexible electrode material.
(1) by 1.32g NaOH, 2.3045g NH4VO3, 3.4506g NH4H2PO4, 0.0747g Ni (CH3COO)2With 6.3042g citric acids are in 250mL beakers plus deionized water (100g) mixes, and stirred at 80 DEG C, until forming colloidal sol, then 12h is dried in vacuo at 80 DEG C, forms dry glue.Then the dry glue is ground, in 350 DEG C of Muffle furnace pre-burning 3h, obtained Na3Ni0.03V1.97(PO4)3Precursor powder (particle diameter is about 2 μm)；
(2) 2g polyvinylpyrrolidones (PVP, number-average molecular weight 1300000) are weighed and polyacrylonitrile (PAN, is counted and divided equally Son amount is mixed-powder (wherein, PVP 150000)：PAN mol ratio is 1:3) it is dissolved in distilled water, stirring forms quality Content is 10 weight % solution；
(3) Na that 0.7g steps (1) obtain is weighed3Ni0.03V1.97(PO4)3Precursor powder, add in above-mentioned solution, stir Mix uniformly, then carry out ultrasonic disperse (80kHz, 6h), magnetic agitation (150rpm, 15h) successively, obtain spinning solution, will obtain Spinning solution be fitted into 10ml disposable syringes, be put into electrostatic spinning machine and carry out electrostatic spinning, receive roller on twine one The nanofiber obtained by aluminium foil reception spinning is enclosed, the condition of electrostatic spinning includes：Fltting speed 0.1mm/min, filament mouth (pin Head) with receiver (reception roller) distance be 18cm, spinning voltage 18kV, obtained spinning thing is taken off from aluminium foil, elder generation 280 DEG C of pretreatment 3h in Muffle furnace, then 750 DEG C of heat treatment 8h under argon atmosphere, that is, obtain flexible electrode material S3.Institute The flexible electrode material S3 of preparation thickness is 1mm.
Sem analysis is carried out to flexible electrode material S3, sem analysis result is shown, Na3Ni0.03V1.97(PO4)3Distribution of particles Between more carbon nano-fibers.
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
Polyanion phosphoric acid salt NaTi2(PO4)3The preparation of flexible electrode material.
(1) by 1g NaH2PO4·2H2O, 1mL volumetric concentration are 85% H3PO4Solution and 1g TiO2It is dissolved in deionization In water (70g), the hydro-thermal reaction 6h at 150 DEG C, after temperature drops to room temperature (25 DEG C), washed respectively with ethanol and deionized water Three times, by reaction products therefrom under vacuum, 12h is dried at 70 DEG C, obtains NaTi2(PO4)3(particle diameter is about for precursor powder For 250nm)；
(2) weigh 1.5g PAN powder to be dissolved in DMF solution, it is the molten of 11.5 weight % that stirring, which forms mass content, Liquid；
(3) NaTi that 0.5g steps (1) obtain is weighed2(PO4)3Precursor powder, add in above-mentioned solution, stir, Then ultrasonic disperse (100Hz, 2h), magnetic agitation (700rpm, 8h) are carried out successively, obtain spinning solution, the spinning solution that will be obtained It is fitted into 10ml disposable syringes, is put into electrostatic spinning machine and carries out electrostatic spinning, twining a circle aluminium foil on roller is received connects The nanofiber obtained by spinning is received, the condition of electrostatic spinning includes：Fltting speed 0.08mm/min, filament mouth (syringe needle) is with receiving Device (reception roller) distance is 18cm, spinning voltage 20kV, and obtained spinning thing is taken off from aluminium foil, first in Muffle furnace 280 DEG C of pretreatment 2h, then 600 DEG C of heat treatment 4h under argon atmosphere, that is, obtain flexible electrode material S4.Prepared flexibility Electrode material S4 thickness is 1.5mm.
Sem analysis is carried out to flexible electrode material S4, sem analysis result is shown, NaTi2(PO4)3Distribution of particles is at more Between carbon nano-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
According to the method for embodiment 4, the difference is that, in step (2), 1.5g PAN are replaced with to 2g PVP, DMF is replaced Distilled water is changed to, the solution that mass content is 9 weight % is obtained, obtains flexible electrode material S5.Prepared flexible electrode material The thickness for expecting S5 is 0.5mm.
Sem analysis is carried out to flexible electrode material S5, sem analysis result is shown, NaTi2(PO4)3Distribution of particles is at more Between carbon nano-fiber.
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
According to the method for embodiment 4, the difference is that, in step (2), 1.5g PAN are replaced with into 2.5g polyvinyl alcohol (PVA, number-average molecular weight 20000, similarly hereinafter), DMF is replaced with into distilled water, obtains the solution that mass content is 8.6 weight %, The condition of electrostatic spinning includes in step (3)：Fltting speed 0.05mm/min, filament mouth (syringe needle) and receiver (reception roller) Distance is 20cm, spinning voltage 20kV, obtains flexible electrode material S6.Prepared flexible electrode material S6 thickness is 2mm。
Sem analysis is carried out to flexible electrode material S6, sem analysis result is shown, NaTi2(PO4)3Distribution of particles is at more Between carbon nano-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.
Embodiment 7
Polyanion pyrophosphoric acid salt Na2FeP2O7The preparation of flexible electrode material.
(1) it is 1 by mol ratio:2:1 Na2CO3、(NH4)2HPO4And FeC2O4·2H2O mixes (wherein, Na2CO3With Na Meter, (NH4)2HPO4In terms of P, FeC2O4·2H2O is in terms of Fe), then under argon atmosphere, in 350 DEG C of pre-burning 3h, obtain Na2FeP2O7Precursor powder (particle diameter is about 1 μm)；
(2) weigh 0.5g PAN powder to be dissolved in DMF, stirring forms the solution that mass content is 10 weight %；
(3) Na that 0.8g steps (1) obtain is weighed2FeP2O7Precursor powder, add in above-mentioned solution, 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, and obtained spinning thing is taken off from aluminium foil, first in Muffle furnace 280 DEG C of pretreatment 3h, then 600 DEG C of heat treatment 6h under argon atmosphere, that is, obtain flexible electrode material S7.Prepared flexibility Electrode material S7 thickness is 1.5mm.
Sem analysis is carried out to flexible electrode material S7, sem analysis result is shown, Na2FeP2O7Distribution of particles is in more carbon Between nanofiber.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material S7 carbon nano-fiber The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1.
Embodiment 8
Polyanion mixed phosphate salt Na4Mn3(PO4)2P2O7The preparation of flexible electrode material.
(1) by 1.33g Na4P2O7, 1.15g NH4H2PO4, after the acetate hydrate manganese of 3.68g tetra- is well mixed, made with acetone Solvent, at 300 rpm ball milling 12h obtain slurries, slurry is dried in vacuo 12h at 70 DEG C, then the air atmosphere at 300 DEG C Pre-burning 6h in lower Muffle furnace is enclosed, reheating processing 6h obtains Na in Muffle furnace under 600 DEG C of air atmospheres after grinding4Mn3(PO4)2P2O7Powder (particle diameter is about 500nm)；
(2) weigh 1g PAN powder to be dissolved in DMF solution, stirring forms the solution that mass content is 8.3 weight %；
(3) Na that 1.5g steps (1) obtain is weighed4Mn3(PO4)2P2O7Powder, add in above-mentioned solution, stir, so Carry out ultrasonic disperse (100kHz, 2h), magnetic agitation (600rpm, 10h) successively afterwards, obtain spinning solution, the spinning solution that will be obtained It is fitted into 10ml disposable syringes, is put into electrostatic spinning machine and carries out electrostatic spinning, twining a circle aluminium foil on roller is received connects The nanofiber obtained by spinning is received, the condition of electrostatic spinning includes：Fltting speed 0.1mm/min, filament mouth (syringe needle) is with receiving Device (reception roller) distance is 15cm, spinning voltage 22kV, and obtained spinning thing is taken off from aluminium foil, first in Muffle furnace 280 DEG C of pretreatment 2h, then 800 DEG C of heat treatment 8h under argon atmosphere, that is, obtain flexible electrode material S8.Prepared flexibility Electrode material S8 thickness is 2mm.
Sem analysis is carried out to flexible electrode material S8, sem analysis result is shown, Na4Mn3(PO4)2P2O7Distribution of particles exists Between more carbon nano-fibers.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material S8 carbon nano-fiber The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1.
Embodiment 9
Polyanion mixed phosphate salt Na4Fe3(PO4)2P2O7The preparation of flexible electrode material.
According to the method for embodiment 8, the difference is that, replace the acetate hydrates of 3.68g tetra- using the oxalic acid hydrates of 2.7g bis- are ferrous Manganese, DMF in step (2) is replaced with into dimethyl acetamide, stirring forms the solution that mass content is 15 weight %, step (3) The condition of middle electrostatic spinning includes：Fltting speed 0.2mm/min, filament mouth (syringe needle) are with receiver (reception roller) distance 20cm, spinning voltage 18kV, obtain flexible electrode material S9.Prepared flexible electrode material S9 thickness is 1mm.
Sem analysis is carried out to flexible electrode material S9, sem analysis result is shown, Na4Fe3(PO4)2P2O7Distribution of particles exists Between more carbon nano-fibers.
The average grain diameter and carbon Nanowire of diameter, host material particles to flexible electrode material S9 carbon nano-fiber The content of peacekeeping host material particles is analyzed, and is as a result listed in table 1.
Embodiment 10
Polyanion mixed phosphate salt Na4Co3(PO4)2P2O7The preparation of flexible electrode material.
According to the method for embodiment 8, the difference is that, the acetate hydrate manganese of 3.68g tetra- is replaced using 3.74g cobalt acetates, obtained Flexible electrode material S10.Prepared flexible electrode material S10 thickness is 0.5mm.
Sem analysis is carried out to flexible electrode material S10, sem analysis result is shown, Na4Co3(PO4)2P2O7Distribution of particles exists Between more carbon nano-fibers.
The average grain diameter and carbon nanometer of diameter, host material particles to flexible electrode material S10 carbon nano-fiber The content of fiber and host material particles is analyzed, and is as a result listed in table 1.
Embodiment 11
Polyanion silicates Na2FeSiO4The preparation of flexible electrode material.
(1) it is 2 by mol ratio:1:2 CH3COONa、FeC2O4·2H2O and citric acid (wherein, CH3COONa in terms of Na, FeC2O4·2H2O is in terms of Fe) in 60mL ethanol, 3h is stirred at 50 DEG C, the 0.02mol silicic acid then added in terms of Si elements Tetra-ethyl ester, 5h is stirred, be then heated to 80 DEG C until forming colloidal sol, being then dried in vacuo 12h at 60 DEG C forms Na2FeSiO4It is dry Glue, it is 100nm to be ground to particle diameter；
(2) weigh 1.5g PEO powder to be dissolved in distilled water, stirring forms the solution that mass content is 10 weight %；
(3) Na that 1.5g steps (1) obtain is weighed2FeSiO4Powder, add in above-mentioned solution, stir, then successively Ultrasonic disperse (300kHz, 3h), magnetic agitation (500rpm, 10h) are carried out, obtains spinning solution, 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 0.1mm/min, filament mouth (syringe needle) (connect with receiver Receive roller) apart from being 15cm, spinning voltage 22kV, obtained spinning thing is taken off from aluminium foil, first 280 DEG C in tube furnace 2h is pre-processed, then 8h is heat-treated at 600 DEG C, that is, obtains flexible electrode material S11.Prepared flexible electrode material S11's Thickness is 2mm.
Sem analysis is carried out to flexible electrode material S11, sem analysis result is shown, Na2FeSiO4Distribution of particles is in more carbon Between nanofiber.
The average grain diameter and carbon nanometer of diameter, host material particles to flexible electrode material S11 carbon nano-fiber The content of fiber and host material particles is analyzed, and is as a result listed in table 1.
Embodiment 12
Transition metal oxide electrode material Na2/3Fe1/2Mn1/2O2The preparation of flexible electrode material.
(1) it is 4 by mol ratio:3:3 NaNO3、Mn(AC)2·4H2O and Fe (NO3)3·9H2O (wherein, NaNO3With Na Meter, Mn (AC)2·4H2O is in terms of Mn, Fe (NO3)3·9H2O is in terms of Fe) it is dissolved separately in deionized water, then add citric acid (NaNO3、Mn(AC)2·4H2O and Fe (NO3)3·9H2O total amount and the mol ratio of citric acid are 1:1, wherein, NaNO3、Mn (AC)2·4H2O and Fe (NO3)3·9H2O molal quantity sum is with elemental metal) stirring 1h, then add NH3·H2O is adjusted PH to 7,60 DEG C is heated to until forming colloidal sol, then vacuum drying is up to forming dry glue at 120 DEG C, in 450 DEG C of Muffle furnaces Middle pre-burning 6h, obtains Na2/3Fe1/2Mn1/2O2Precursor powder (particle diameter is about 5 μm)；
(2) weigh 1g PAN powder to be dissolved in DMF, stirring forms the solution that mass content is 7.1 weight %；
(3) Na that 0.5g steps (1) obtain is weighed2/3Fe1/2Mn1/2O2Precursor powder is added in above-mentioned solution, and stirring is equal It is even, ultrasonic disperse (40kHz, 2h), magnetic agitation (500rpm, 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 0.05mm/min, filament mouth (syringe needle) with Receiver (reception roller) distance is 18cm, spinning voltage 18kV, and obtained spinning thing is taken off from aluminium foil, first in Muffle 280 DEG C of pretreatment 2h in stove, then 900 DEG C of heat treatment 15h under argon atmosphere, that is, obtain flexible electrode material S12.It is prepared Flexible electrode material S12 thickness be 0.5mm.
Sem analysis is carried out to flexible electrode material S12, obtained SEM is schemed as shown in figure 3, Na2/3Fe1/2Mn1/2O2Particle It is distributed between more carbon nano-fibers.
The average grain diameter and carbon nanometer of diameter, host material particles to flexible electrode material S12 carbon nano-fiber The content of fiber and host material particles is analyzed, and is as a result listed in table 1.
Embodiment 13
Transiton metal binary oxides electrode material NiCo2O4The preparation of flexible electrode material.
(1) use solvent-thermal method by mol ratio for 1:2 Ni (NO3)2·6H2O and Co (NO3)2·6H2O (wherein, Ni (NO3)2·6H2O is in terms of Ni, Co (NO3)2·6H2O is in terms of Co) it is dissolved in 60mL dimethylformamides (DMF) and 10mL deionizations In water, after being stirred in 100mL reactors, 20h is heat-treated at 180 DEG C, treats that temperature is down to room temperature (25 DEG C), uses ethanol With deionized water washing three times, NiCo is obtained2O4Precursor powder (particle diameter is about 6 μm)；
(2) weigh 1.5g PAN powder to be dissolved in DMF solution, stirring forms the solution that mass content is 10 weight %；
(3) NiCo that 1g steps (1) obtain is weighed2O4Precursor powder, add in above-mentioned solution, stir, Ran Houyi Secondary progress ultrasonic disperse (100kHz, 3h), magnetic agitation (400rpm, 10h), 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 0.1mm/min, filament mouth (syringe needle) (connect with receiver Receive roller) distance be 20cm, spinning voltage 19kV, obtained spinning thing three taken off from aluminium foil, elder generation is 280 in Muffle furnace DEG C pretreatment 2h, then in argon atmosphere pipe type stove 450 DEG C heat treatment 2h, that is, obtain flexible electrode material S13.It is prepared Flexible electrode material S13 thickness be 1mm.
Sem analysis is carried out to flexible electrode material S13, sem analysis result is shown, NiCo2O4Distribution of particles is received in more carbon Between rice fiber.
The average grain diameter and carbon nanometer of diameter, host material particles to flexible electrode material S13 carbon nano-fiber The content of fiber and host material particles is analyzed, and is as a result listed in table 1.
Embodiment 14
Metal oxide electrode material TiO2The preparation of flexible electrode material.
(1) 0.2g polyethylene glycol oxides (PVA) are dissolved in 70mL acetic acid, after stirring is homogeneous, add the fourth of 2mol metatitanic acids four Ester (TBOT, in terms of titanium elements), it is transferred in 100mL reactors after stirring 20min at 40 DEG C, is heat-treated at 180 DEG C 24h, treat that temperature is down to room temperature (25 DEG C), washed three times with ethanol and deionized water, then by obtained solid product in vacuum Under the conditions of, 12h is dried at 70 DEG C, obtains TiO2Precursor powder (particle diameter is about 300nm)；
(2) weigh 1g PAN powder to be dissolved in dimethyl sulfoxide (DMSO) (DMSO), it is 6.67 weights that stirring, which forms mass content, Measure % solution；
(3) TiO that 1g steps (1) obtain is weighed2Precursor powder, add in above-mentioned solution, stir, then successively Ultrasonic disperse (100kHz, 3h), magnetic agitation (500rpm, 10h) are carried out, obtains spinning solution, 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 0.1mm/min, filament mouth (syringe needle) (connect with receiver Receive roller) distance be 20cm, spinning voltage 19kV, obtained spinning thing three taken off from aluminium foil, elder generation is 280 in Muffle furnace DEG C pretreatment 2h, then in argon atmosphere pipe type stove 450 DEG C heat treatment 4h, that is, obtain flexible electrode material S14.It is prepared Flexible electrode material S14 thickness be 1mm.
Sem analysis is carried out to flexible electrode material S14, sem analysis result is shown, TiO2Distribution of particles is in more carbon nanometers Between fiber.
The average grain diameter and carbon nanometer of diameter, host material particles to flexible electrode material S14 carbon nano-fiber The content of fiber and 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 1-14 and comparative example 1 carries out electrochemical property test.Specifically：
The obtained flexible battery material of embodiment 1-14 and comparative example 1 is assembled into sodium-ion battery, metallic sodium piece is pair Electrode, using the glass fibres of Gelgard 2400 as barrier film, with 1mol/L NaClO4With 2 volume %'s (in terms of propene carbonate) The carbonic allyl ester solution of fluorinated ethylene carbonate (FEC) is electrolyte, and button cell is assembled in argon gas glove box (CR2025) charge-discharge test is carried out after, standing 24h 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 sodium ion assembled using flexible electrode material made from embodiment 1-14 can realize height The reversible discharge and recharge of specific capacity, and cyclical stability is preferable.In addition, flexible electrode material provided by the invention does not need collector And binding agent, it is not necessary to conductive additive, be used directly for assembling sodium-ion battery, and flexible electrode provided by the invention The preparation method of material is not only restricted to spin solvent, is almost applicable to the preparation of any both positive and negative polarity flexible material.By embodiment 1 Understand that flexible electrode material particle size provided by the invention is not only restricted to carbon nano-fiber with the results contrast of comparative example 1, and More excellent electrochemical cycle stability can be shown.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (11)

1. a kind of sodium-ion battery 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.
2. sodium-ion battery flexible electrode material according to claim 1, wherein, the content of the host material particles is 60-90 weight %, the content of the carbon nano-fiber is 10-40 weight %.
3. sodium-ion battery flexible electrode material according to claim 1, wherein,
The average grain diameter of the host material particles is 20nm-0.5mm, preferably 100nm-5 μm；
A diameter of 50nm-900nm of the carbon nano-fiber, preferably 100-500nm.
4. sodium-ion battery flexible electrode material according to claim 1, wherein, the host material particles contain poly- the moon Iron phosphate class material, silicates material, pyrophosphoric acid salts substances, mixed phosphate salt material and transition metal oxide At least one of；
Preferably, the polyanion phosphoric acid salt material is selected from Na3MxV2-x(PO4)3And/or NaTi2(PO4)3, wherein, M is At least one of Mg, Ni and Ti, 0≤x≤2；The silicates material is selected from Na2FeSiO4And/or Na2MnSiO4；It is described Pyrophosphoric acid salts substances are Na2FeP2O7；The mixed phosphate salt material is Na4Y3(PO4)2P2O7, wherein, Y Fe, Co and At least one of Mn；The transition metal oxide is selected from Na2/3Fe1/2Mn1/2O2、NiCo2O4And TiO2In at least one Kind；
It is further preferred that the host material particles contain Na3Mg0.05V1.95(PO4)3、Na3V2(PO4)3、Na3Ni0.03V1.97 (PO4)3、NaTi2(PO4)3、Na2FeSiO4、Na2FeP2O7、Na4Mn3(PO4)2P2O7、Na2/3Fe1/2Mn1/2O2、NiCo2O4And TiO2 At least one of.
5. a kind of preparation method of sodium-ion battery 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 pre-processed and is heat-treated successively, obtain sodium-ion battery flexible electrode material.
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 %, 7-11.5 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 Body with using the dosage mass ratio of the solution of carbon containing polymer weight as 0.1-2：1, preferably 0.2-1：1.
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；
The material of main part contains polyanion phosphoric acid salt material, silicates material, pyrophosphoric acid salts substances, mixed phosphate At least one of salts substances and transition metal oxide；
Preferably, the polyanion phosphoric acid salt material is selected from Na3MxV2-x(PO4)3And/or NaTi2(PO4)3, wherein, M is At least one of Mg, Ni and Ti, 0≤x≤2；The silicates material is selected from Na2FeSiO4And/or Na2MnSiO4；It is described Pyrophosphoric acid salts substances are Na2FeP2O7；The mixed phosphate salt material is Na4Y3(PO4)2P2O7, wherein, Y Fe, Co and At least one of Mn；The transition metal oxide is selected from Na2/3Fe1/2Mn1/2O2、NiCo2O4And TiO2In at least one Kind；
It is further preferred that the host material particles contain Na3Mg0.05V1.95(PO4)3、Na3V2(PO4)3、Na3Ni0.03V1.97 (PO4)3、NaTi2(PO4)3、Na2FeSiO4、Na2FeP2O7、Na4Mn3(PO4)2P2O7、Na2/3Fe1/2Mn1/2O2、NiCo2O4And TiO2 At 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-20kV；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 500-800 DEG C, the time For 2-10h, preferably 5-10h.
11. a kind of sodium-ion battery, wherein, the electrode material of the sodium-ion battery includes any one in claim 1-4 Sodium ion electricity made from method in described sodium-ion battery flexible electrode material or claim 5-10 described in any one Pond flexible electrode material.
CN201710531495.4A 2017-07-03 2017-07-03 Flexible electrode material of sodium ion battery, preparation method of flexible electrode material and sodium ion battery Active CN107492630B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710531495.4A CN107492630B (en) 2017-07-03 2017-07-03 Flexible electrode material of sodium ion battery, preparation method of flexible electrode material and sodium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710531495.4A CN107492630B (en) 2017-07-03 2017-07-03 Flexible electrode material of sodium ion battery, preparation method of flexible electrode material and sodium ion battery

Publications (2)

Publication Number Publication Date
CN107492630A true CN107492630A (en) 2017-12-19
CN107492630B CN107492630B (en) 2019-12-13

Family

ID=60644262

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710531495.4A Active CN107492630B (en) 2017-07-03 2017-07-03 Flexible electrode material of sodium ion battery, preparation method of flexible electrode material and sodium ion battery

Country Status (1)

Country Link
CN (1) CN107492630B (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108461734A (en) * 2018-03-20 2018-08-28 华中科技大学 A kind of preparation method and application of titanium phosphate sodium/carbon composite
CN109921021A (en) * 2019-03-13 2019-06-21 欧格尼材料科技江苏有限公司 A kind of high potential high capacity organic polymer positive electrode and its preparation method and application
CN109950536A (en) * 2017-12-20 2019-06-28 苏州大学 A method of preparing vanadium phosphate sodium nanofiber positive electrode
CN110085849A (en) * 2019-05-17 2019-08-02 中南大学 A kind of carbon coating phosphoric acid manganese pyrophosphate sodium@SWCNT composite material and its preparation and application with reticular structure
CN110289389A (en) * 2019-05-09 2019-09-27 广东工业大学 A kind of molybdenum disulfide/carbon nano-fiber composite material and the preparation method and application thereof
CN111525122A (en) * 2020-05-12 2020-08-11 喻明兵 NaTi2(PO4)3Negative electrode material of-porous carbon nanofiber sodium ion battery and preparation method thereof
CN112981553A (en) * 2021-02-03 2021-06-18 国际竹藤中心 Iron-doped lignin-based flexible carbon fiber material and preparation method and application thereof
CN113437275A (en) * 2021-06-26 2021-09-24 宁德时代新能源科技股份有限公司 Positive electrode active material, electrochemical device, and electronic device
CN113437276A (en) * 2021-06-26 2021-09-24 宁德时代新能源科技股份有限公司 Positive electrode active material, electrochemical device, and electronic device
CN113584620A (en) * 2021-06-29 2021-11-02 中南大学 Na3M2XO6Particle-assembled hollow fiber and preparation method and application thereof
CN114530573A (en) * 2022-02-23 2022-05-24 广东工业大学 Flexible self-supporting anode for sodium ion battery and preparation method and application thereof
CN114538403A (en) * 2022-01-27 2022-05-27 上海交通大学 Preparation method and application of sodium ion battery positive electrode material ferric sodium phosphate pyrophosphate
CN114622347A (en) * 2022-02-28 2022-06-14 五邑大学 Fiber membrane and preparation method and application thereof
WO2023169136A1 (en) * 2022-03-09 2023-09-14 武汉理工大学 Manganese phosphate-titanium-chromium-sodium self-supported electrode material, preparation method therefor, and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103305965A (en) * 2013-06-04 2013-09-18 清华大学深圳研究生院 Silicon-carbon composite material with nano micropores and preparation method as well as application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103305965A (en) * 2013-06-04 2013-09-18 清华大学深圳研究生院 Silicon-carbon composite material with nano micropores and preparation method as well as application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BINGKUN GUO等: "Electrospun Li4Ti5O12/C composites for lithium-ion batteries with high rate performance", 《SOLID STATE IONICS》 *
JIANG CUI等: "Recent progress in rational design of anode materials for high-performance Na-ion batteries", 《ENERGY STORAGE MATERIALS》 *

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109950536A (en) * 2017-12-20 2019-06-28 苏州大学 A method of preparing vanadium phosphate sodium nanofiber positive electrode
CN108461734A (en) * 2018-03-20 2018-08-28 华中科技大学 A kind of preparation method and application of titanium phosphate sodium/carbon composite
CN109921021A (en) * 2019-03-13 2019-06-21 欧格尼材料科技江苏有限公司 A kind of high potential high capacity organic polymer positive electrode and its preparation method and application
CN110289389A (en) * 2019-05-09 2019-09-27 广东工业大学 A kind of molybdenum disulfide/carbon nano-fiber composite material and the preparation method and application thereof
CN110085849A (en) * 2019-05-17 2019-08-02 中南大学 A kind of carbon coating phosphoric acid manganese pyrophosphate sodium@SWCNT composite material and its preparation and application with reticular structure
CN110085849B (en) * 2019-05-17 2021-02-02 中南大学 Carbon-coated sodium manganese pyrophosphate phosphate @ SWCNT composite material with network structure and preparation and application thereof
CN111525122A (en) * 2020-05-12 2020-08-11 喻明兵 NaTi2(PO4)3Negative electrode material of-porous carbon nanofiber sodium ion battery and preparation method thereof
CN111525122B (en) * 2020-05-12 2021-07-27 苗珍录 NaTi2(PO4)3Negative electrode material of-porous carbon nanofiber sodium ion battery and preparation method thereof
CN112981553A (en) * 2021-02-03 2021-06-18 国际竹藤中心 Iron-doped lignin-based flexible carbon fiber material and preparation method and application thereof
WO2022267550A1 (en) * 2021-06-26 2022-12-29 宁德时代新能源科技股份有限公司 Positive electrode active material, electrochemical apparatus and electronic device
CN113437276A (en) * 2021-06-26 2021-09-24 宁德时代新能源科技股份有限公司 Positive electrode active material, electrochemical device, and electronic device
CN114725341B (en) * 2021-06-26 2024-05-03 宁德时代新能源科技股份有限公司 Positive electrode active material, electrochemical device, and electronic device
WO2022267529A1 (en) * 2021-06-26 2022-12-29 宁德时代新能源科技股份有限公司 Positive electrode active material, electrochemical device, and electronic apparatus
CN113437275A (en) * 2021-06-26 2021-09-24 宁德时代新能源科技股份有限公司 Positive electrode active material, electrochemical device, and electronic device
CN114613954A (en) * 2021-06-26 2022-06-10 宁德时代新能源科技股份有限公司 Positive electrode active material, electrochemical device, and electronic device
CN114725341A (en) * 2021-06-26 2022-07-08 宁德时代新能源科技股份有限公司 Positive electrode active material, electrochemical device, and electronic device
CN113584620B (en) * 2021-06-29 2022-06-14 中南大学 Na3M2XO6Particle-assembled hollow fiber and preparation method and application thereof
CN113584620A (en) * 2021-06-29 2021-11-02 中南大学 Na3M2XO6Particle-assembled hollow fiber and preparation method and application thereof
CN114538403A (en) * 2022-01-27 2022-05-27 上海交通大学 Preparation method and application of sodium ion battery positive electrode material ferric sodium phosphate pyrophosphate
CN114538403B (en) * 2022-01-27 2023-08-22 廖小珍 Preparation method and application of sodium ion battery anode material sodium ferric pyrophosphate phosphate
CN114530573A (en) * 2022-02-23 2022-05-24 广东工业大学 Flexible self-supporting anode for sodium ion battery and preparation method and application thereof
CN114530573B (en) * 2022-02-23 2023-12-12 广东工业大学 Flexible self-supporting positive electrode for sodium ion battery and preparation method and application thereof
CN114622347A (en) * 2022-02-28 2022-06-14 五邑大学 Fiber membrane and preparation method and application thereof
WO2023169136A1 (en) * 2022-03-09 2023-09-14 武汉理工大学 Manganese phosphate-titanium-chromium-sodium self-supported electrode material, preparation method therefor, and application thereof

Also Published As

Publication number Publication date
CN107492630B (en) 2019-12-13

Similar Documents

Publication Publication Date Title
CN107492630A (en) Sodium-ion battery flexible electrode material and preparation method thereof and sodium-ion battery
CN107611346A (en) Lithium ion battery flexible electrode material and preparation method thereof and lithium ion battery
Chen et al. Tetsubo-like α-Fe2O3/C nanoarrays on carbon cloth as negative electrode for high-performance asymmetric supercapacitors
CN105098179B (en) A kind of preparation method of sodium-ion battery positive material Na3V2 (PO4) 3
CN105355877B (en) A kind of graphene metal oxide composite cathode material and preparation method thereof
CN101335347B (en) Preparing method of highly conductive lithium iron phosphate anode material of lithium ionic cell
CN101425576B (en) Preparing method of highly conductive lithium iron anode material of lithium ionic cell
CN108232139A (en) A kind of graphene composite material and preparation method thereof
CN104466134B (en) The preparation method of self-supporting graphene/carbon nano-tube hybrid foam support amino anthraquinones base polymer
CN101714627A (en) Carbon nanotube/lithium iron phosphate composite positive electrode material and in situ preparation method thereof
CN105226267B (en) Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application
CN104638252A (en) Silicon composited negative electrode material, preparation method of silicon composited negative electrode material and lithium ion battery
CN105226254B (en) A kind of silicon nanoparticle graphite nano plate carbon fibre composite and preparation method and application
Yan et al. Conducting polyaniline-wrapped lithium vanadium phosphate nanocomposite as high-rate and cycling stability cathode for lithium-ion batteries
CN108288711A (en) A kind of quaternary lithium-ion battery positive electrode material and preparation method
CN107256956A (en) A kind of nitrogen-doped carbon cladding vanadium nitride electrode material and preparation method and application
CN102637847A (en) Method for preparing high-dispersity lithium battery anode and cathode slurry
CN101188293A (en) Fe base lithium sale compound anode materials and its making method
CN109411713A (en) The machinery of the modified composite material of siliceous substrates material is total to method for coating, modified composite material and lithium ion battery
CN108539140A (en) A kind of preparation method of nitrogen doped silicon/carbon nucleocapsid structure lithium ion battery negative material
CN106784758A (en) Carbon nano tube modified Prussian blue sodium-ion battery positive material and its method
CN102683712A (en) Lithium ferric phosphate battery adopting compound conductive agent and manufacturing method thereof
CN104993116B (en) A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method
CN104979541A (en) Lithium titanate composite material and preparation method thereof
CN106711410A (en) Battery negative electrode material and preparation method thereof as well as sodium-ion battery

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