CN106784684A - A kind of used as negative electrode of Li-ion battery flexible compound nano-fiber material and preparation method - Google Patents

A kind of used as negative electrode of Li-ion battery flexible compound nano-fiber material and preparation method Download PDF

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CN106784684A
CN106784684A CN201611189496.7A CN201611189496A CN106784684A CN 106784684 A CN106784684 A CN 106784684A CN 201611189496 A CN201611189496 A CN 201611189496A CN 106784684 A CN106784684 A CN 106784684A
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cortex
sandwich layer
electrostatic spinning
preparation
graphene
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CN106784684B (en
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高大伟
王丽丽
王春霞
陆振乾
宋晓蕾
贾高鹏
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JIANGSU ZHENZHONG FILTER MATERIAL TECHNOLOGY Co.,Ltd.
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Yangcheng Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 invention discloses a kind of used as negative electrode of Li-ion battery flexible compound nano-fiber material and preparation method, the composite nano-fiber material includes cortex and sandwich layer, and cortex is coated on the outer surface of sandwich layer, and cortex is made up of carbon and Graphene；Sandwich layer is voided layer, and hollow nanospheres particle is provided with sandwich layer, and the nanometer ball particle is made up of tin.The materials conductive rate is high, capacity big, good cycling stability.

Description

A kind of used as negative electrode of Li-ion battery flexible compound nano-fiber material and preparation method
Technical field
The invention belongs to nano material and field of chemical power source, it particularly relates to a kind of used as negative electrode of Li-ion battery is soft Property composite nano-fiber material and preparation method.
Background technology
Structural functionality nanofiber with the advantage such as its structure-controllable, specific surface area be big, easily modified, catalysis, energy storage, Filtering, organizational project etc. are received significant attention.In the method for numerous preparation nano materials, electrostatic spinning technique sets as one kind The advantages such as standby, process is simple, morphology controllable, can prepare special construction（Such as core-skin, hollow structure）Nanofiber and answered For field of lithium.
Tin (Sn) abundance, its theoretical specific capacity is up to 992mAhg-1, it is the 2.7 of conventional electrode materials graphite capacity Times.But, Sn never has realization commercialization, is primarily due to Sn electrodes and causes volume acutely swollen in de- lithium and process of intercalation It is swollen, cause the powdered of Sn, the globality of electrode is destroyed, and then cause cycle life and capacity sharp-decay.For in solution Problem is stated, Sn materials are mainly carried out nanosizing or are combined with carbon material by researcher.At present, metallic tin and carbon material are answered Conjunction method is a lot, but the electric conductivity of negative material, capacity and cycle life are relatively low mostly, and is needed in electrode production process Conductive agent, binder is added to increased the electrode of material, and preparation process is cumbersome, still can not meet commercialized demand.
The content of the invention
It is an object of the invention to provide a kind of used as negative electrode of Li-ion battery flexible compound nano-fiber material and preparation side Method, the materials conductive rate is high, capacity big, good cycling stability.
To achieve the above object, the embodiment of the present invention uses following technical scheme：
On the one hand, the embodiment of the present invention provides a kind of used as negative electrode of Li-ion battery flexible compound nano-fiber material, including cortex And sandwich layer, cortex is coated on the outer surface of sandwich layer, and cortex is made up of carbon and Graphene；Sandwich layer is voided layer, in being provided with sandwich layer Empty nanometer ball particle, the nanometer ball particle is made up of tin.
Used as preference, described hollow nanospheres particle is connected with the inner surface of cortex.
On the other hand, the embodiment of the present invention also provides a kind of used as negative electrode of Li-ion battery flexible compound nano-fiber material Preparation method, the method includes：
Step 10）Graphene and polyacrylonitrile are dispersed in N,N-dimethylformamide solution or DMAC N,N' dimethyl acetamide solution In, cortex electrostatic spinning liquid is obtained；
During polyvinylpyrrolidone and nickel salt are scattered in into DMF solution or DMA solution, Sandwich layer electrostatic spinning liquid is obtained；
Step 20）By step 10）The cortex electrostatic spinning liquid and sandwich layer electrostatic spinning liquid of preparation, using coaxial electrostatic spinning method, Cortex electrostatic spinning liquid is located at sandwich layer electrostatic spinning liquid outside, spins nano fibrous membrane；
Step 30）By step 20）Obtained nano fibrous membrane is placed in tube furnace, and 250 ~ 280 DEG C of guarantors are warming up to 1 ~ 2 DEG C/min 1 ~ 3h is held, 5 ~ 10 DEG C/min is warming up to 600 ~ 800 DEG C of 1 ~ 4h of holding, obtain carbon, Graphene, the nickel composite Nano fibre of core shell structure Dimension；
Step 40）By step 30）The carbon of preparation, Graphene, nickel composite nano fiber be placed in molar concentration for 20 ~ 100mmol/L, During temperature is for 25 ~ 90 DEG C of tin-salt solution, 2 ~ 12h is kept, obtain carbon, Graphene, tin composite nano fiber.
As preference, described step 10）In, in obtained cortex electrostatic spinning liquid, the mass fraction of polyacrylonitrile It is 6 ~ 12%；The mass ratio of Graphene and polyacrylonitrile is 0.2 ~ 2:100.
As preference, described step 10）In, in obtained sandwich layer electrostatic spinning liquid, the matter of polyvinylpyrrolidone Amount fraction is 6 ~ 10%；The mass ratio of polyvinylpyrrolidone and nickel salt is 1: 1~10；
Used as preference, described nickel salt is nickel chloride, nickel sulfate or nickel acetate.
As preference, described step 20）In, during electrostatic spinning：Voltage is 10 ~ 30 kV, and spinning flow velocity is 0.5 ~ 3.0 mL/h, the distance between spinning head and reception device：10 ~ 40 cm, spray time is 15 ~ 60min.
As preference, described step 30）In, in carbon, Graphene, nickel composite nano fiber, cortex is by carbon and graphite Alkene is constituted, and sandwich layer is voided layer, and the solid sphere particle being made up of nickel is contained in sandwich layer.
As preference, described step 40）In, the preparation process of tin-salt solution is：By stannous chloride, stannous sulfate or One or two in stannous acetate are dissolved in water or ethanol solution, are made tin-salt solution.
Compared with prior art, the used as negative electrode of Li-ion battery flexible compound nano-fiber material of the embodiment of the present invention has It is preferably flexible, can be used directly as negative material, and preparation process is without conductive agent and binder.
In the present invention, carbon, Graphene, tin have electric conductivity higher, constitute the carbon and graphite of composite nano fiber cortex The metallic tin of alkene and sandwich layer is conducive to improving the electric conductivity of material.Composite nano-fiber material prepared by the embodiment of the present invention With capacity and cycle life higher.Nanofiber specific surface area higher and hollow structure, metallic tin can improve electricity The capacity in pond.Nanometer ball particle is located in hollow sandwich layer, and nanometer ball particle also has hollow structure in itself, so embedding lithium mistake When being expanded in journey, nanometer ball particle can inwardly expansion and outwards expansion, thus nanosphere mosaic electrode relative expansion simultaneously Volume will not drastically become big.In addition, containing carbon in the cortex on the outside of nanometer ball particle, the body of nanometer ball particle can be buffered Product expansion, improves the cyclical stability and cycle life of material.
Brief description of the drawings
Fig. 1 is the structural representation of the embodiment of the present invention.
Have in figure：Cortex 1, sandwich layer 2, nanometer ball particle 3.
Specific embodiment
Below in conjunction with the accompanying drawings, technical scheme is described in further detail.
As shown in figure 1, a kind of used as negative electrode of Li-ion battery flexible compound nano-fiber material of the embodiment of the present invention, including Cortex 1 and sandwich layer 2, cortex 1 are coated on the outer surface of sandwich layer 2, and cortex 1 is made up of carbon and Graphene；Sandwich layer 2 is voided layer, core Hollow nanospheres particle 3 is provided with layer 2, the nanometer ball particle 3 is made up of tin.Preferably, described hollow nanospheres Grain 3 is connected with the inner surface of cortex 1.
The composite nano-fiber material of above-described embodiment is carbon, Graphene, tin composite nano-fiber material, with preferable Flexibility, can use directly as lithium ion battery negative material.Meanwhile, constitute carbon, Graphene, the tin of composite nano-fiber material With electric conductivity higher so that whole composite nano-fiber material has electric conductivity higher.In the present embodiment, it is combined and receives Rice fibrous material has capacity and cycle life higher.Nano-fiber material has specific surface area and hollow structure higher, The capacity of battery can be improved.Especially, the hollow nanospheres particle 3 being made up of tin because with hollow structure, and positioned at sandwich layer 3 In, when being expanded in process of intercalation, can inwardly expand simultaneously and outwards expansion, thus the electrode of hollow nanospheres particle 3 is relatively swollen Swollen volume will not drastically become big.In addition, the outer layer of hollow nanospheres particle 3 also coats a cortex 1.This can buffer hollow nanospheres Particle 3 outwards expands, and improves the cyclical stability and cycle life of material.
The preparation method of the used as negative electrode of Li-ion battery flexible compound nano-fiber material of said structure, including：
Step 10）By Graphene and polyacrylonitrile（In text referred to as： PAN）It is dispersed in N,N-dimethylformamide solution or N, N- In dimethylacetamide solution, cortex electrostatic spinning liquid is obtained；By polyvinylpyrrolidone（In text referred to as： PVP）With nickel salt point Dissipate in DMF solution or DMA solution, sandwich layer electrostatic spinning liquid is obtained.
Wherein, preferably, during cortex electrostatic spinning liquid is prepared, the mass ratio of Graphene and polyacrylonitrile is 0.2~2:100.In cortex electrostatic spinning liquid, the mass fraction of polyacrylonitrile is 6 ~ 12%.Preparing sandwich layer electrostatic spinning liquid mistake The mass ratio of Cheng Zhong, PVP and nickel salt is 1: 1~10.In sandwich layer electrostatic spinning liquid, the mass fraction of PVP is 6 ~ 10%.It is described Nickel salt be preferably nickel chloride, nickel sulfate or nickel acetate.
Step 20）By step 10）The cortex electrostatic spinning liquid and sandwich layer electrostatic spinning liquid of preparation, using coaxial electrostatic spinning Method, cortex electrostatic spinning liquid is located at sandwich layer electrostatic spinning liquid outside, spins nano fibrous membrane.
Wherein, during electrostatic spinning：Voltage be 10 ~ 30 kV, spinning flow velocity be 0.5 ~ 3.0 mL/h, spinning head and The distance between reception device：10 ~ 40 cm, spray time is 15 ~ 60min.The nano fibrous membrane being spun into is in film-form.
Step 30）By step 20）Obtained nano fibrous membrane is placed in tube furnace, and 250 ~ 280 are warming up to 1 ~ 2 DEG C/min DEG C keep 1 ~ 3h, 5 ~ 10 DEG C/min to be warming up to 600 ~ 800 DEG C of 1 ~ 4h of holding, obtain that the carbon of core shell structure, Graphene, nickel are compound to be received Rice fiber.
In step 30, by high-temperature process, PAN is converted into carbon；Nickel salt is decomposed into the oxide of nickel first, and then by carbon also Originally it was solid nickel nanometer ball particle；PVP belongs to small-molecular-weight high polymer, and PVP is decomposed completely after high-temperature process, therefore in sandwich layer shape Into hollow structure.So, in carbon, Graphene, nickel composite nano fiber, cortex is made up of carbon and Graphene, and sandwich layer is voided layer, Contain the solid sphere particle being made up of nickel in sandwich layer.
Step 40）By step 30）The carbon of preparation, Graphene, nickel composite nano fiber be placed in molar concentration for 20 ~ During 100mmol/L, temperature are for 25 ~ 90 DEG C of tin-salt solution, 2 ~ 12h is kept, obtain carbon, Graphene, tin composite nano fiber.
Wherein, the preparation process of tin-salt solution is：By one or two in stannous chloride, stannous sulfate or stannous acetate It is dissolved in water or ethanol solution, is made tin-salt solution.
In step 40）In, in tin-salt solution, elemental nickel is oxidized to Ni2+And enter in solution, corresponding Sn2+It is reduced The surface of nano nickel particles is deposited directly to after into simple substance tin.Each nickle atom produces two electronics, because metal has in itself Electric conductivity, the electrons of generation are transferred to the surface of nano particle, in nano grain surface Sn2+It is reduced, and gradually in nickel table Face forms tin shell, eventually forms hollow tin nanoparticles.
In above-mentioned preparation method, if being directly added into a certain amount of pink salt in sandwich layer spinning solution, through step 30）Treatment Afterwards, what is obtained is that tin particles are solid sphere structure.Compared with medicine ball, the hollow structure of tin can be in battery charge and discharge process Extra free volume is provided, can inwardly or outwardly be expanded simultaneously, be conducive to improving electrode cycle stability.
Meanwhile, in above-mentioned preparation process, without adding conductive agent and binder, the carbon that is finally made, Graphene, tin are combined Nanofiber has good electric conductivity.
Below by experiment, the carbon of checking embodiment of the present invention preparation, Graphene, tin composite nano fiber have superiority Energy.Wherein, the electric conductivity of material is tested using four probe method.
Carbon that each embodiment preparation method is made, Graphene, tin composite material are cut into the circular electrode of a diameter of 15mm, It is that, to electrode, barrier film is Celgrad2400 with metal lithium sheet in the glove box full of nitrogen, electrolyte is for molar concentration 1mol/L, volume ratio are 1:1:1 lithium hexafluoro phosphate/ethylene carbonate-methyl ethyl carbonate-dimethyl carbonate（In text referred to as： LiPF6/EC-EMC-DMC）Solution, is assembled into button cell, and stand more than 6h.Carried out with 0.5C on charge-discharge test instrument Constant current charge-discharge performance test, charging/discharging voltage scope is 0.01 ~ 1.5V, and current density is 50mAg-1.By constant current charge-discharge Performance test, evaluates the capacity and cyclical stability of material（Cycle life）.
Capability retention is represented after the cyclical stability or cycle life of material is circulated by 100 times, capability retention The cyclical stability of bigger material is better.
Subjects：
Comparative example 1
Using carbon nano-fiber as lithium ion battery negative.
Comparative example 2
Using the hollow sijna rice material that is made of spherical particles as lithium ion battery negative.
Embodiment 1
Using carbon, Graphene, tin composite nano-fiber material as lithium ion battery negative.The system of the composite nano-fiber material Preparation Method is as follows：
Step 10）It is 0.2 according to mass ratio by Graphene and polyacrylonitrile:100, be dispersed in DMF solution or In DMA solution, cortex electrostatic spinning liquid is obtained；In cortex electrostatic spinning liquid, the mass fraction of polyacrylonitrile It is 10%；
By PVP and nickel chloride according to mass ratio 1:8, it is scattered in DMF solution or DMA is molten In liquid, sandwich layer electrostatic spinning liquid is obtained；In sandwich layer electrostatic spinning liquid, the mass fraction of PVP is 7%；
Step 20）By step 10）The cortex electrostatic spinning liquid and sandwich layer electrostatic spinning liquid of preparation, using coaxial electrostatic spinning method, Cortex electrostatic spinning liquid is located at sandwich layer electrostatic spinning liquid outside, spins nano fibrous membrane；During electrostatic spinning：Voltage is 10 KV, spinning flow velocity is 3.0 mL/h, and the distance between spinning head and reception device are 40 cm, and spray time is 20min.
Step 30）By step 20）Obtained nano fibrous membrane is placed in tube furnace, and 250 DEG C of holdings are warming up to 1 DEG C/min 2h, 5 DEG C/min are warming up to 800 DEG C of holding 2h, obtain carbon, Graphene, the nickel composite nano fiber of core shell structure；
Step 40）By step 30）The carbon of preparation, Graphene, nickel composite nano fiber are placed in molar concentration for 20mmol/L, temperature In 70 DEG C of tin-salt solutions, to keep 6h, carbon, Graphene, tin composite nano fiber are obtained.The preparation process of tin-salt solution is： Stannous chloride is soluble in water, it is made tin-salt solution.
Embodiment 2
Using carbon, Graphene, tin composite nano-fiber material as lithium ion battery negative.The system of the composite nano-fiber material Preparation Method is as follows：
Step 10）It is 1 according to mass ratio by Graphene and polyacrylonitrile:100, DMF solution or N are dispersed in, In N- dimethylacetamide solutions, cortex electrostatic spinning liquid is obtained；In cortex electrostatic spinning liquid, the mass fraction of polyacrylonitrile is 6%；
By PVP and nickel sulfate according to mass ratio 1:3, it is scattered in DMF solution or DMA is molten In liquid, sandwich layer electrostatic spinning liquid is obtained；In sandwich layer electrostatic spinning liquid, the mass fraction of PVP is 6%；
Step 20）By step 10）The cortex electrostatic spinning liquid and sandwich layer electrostatic spinning liquid of preparation, using coaxial electrostatic spinning method, Cortex electrostatic spinning liquid is located at sandwich layer electrostatic spinning liquid outside, spins nano fibrous membrane；During electrostatic spinning：Voltage is 30 KV, spinning flow velocity is 0.5mL/h, the distance between spinning head and reception device：10 cm, spray time is 30min.
Step 30）By step 20）Obtained nano fibrous membrane is placed in tube furnace, and 260 DEG C of holdings are warming up to 2 DEG C/min 3h, 10 DEG C/min are warming up to 700 DEG C of holding 3h, obtain carbon, Graphene, the nickel composite nano fiber of core shell structure；
Step 40）By step 30）The carbon of preparation, Graphene, nickel composite nano fiber are placed in molar concentration for 80mmol/L, temperature In 90 DEG C of tin-salt solutions, to keep 2h, carbon, Graphene, tin composite nano fiber are obtained.The preparation process of tin-salt solution is： Stannous sulfate is dissolved in ethanol solution, tin-salt solution is made.
Embodiment 3
Using carbon, Graphene, tin composite nano-fiber material as lithium ion battery negative.The system of the composite nano-fiber material Preparation Method is as follows：
Step 10）By Graphene and polyacrylonitrile（PAN）It is 2 according to mass ratio:100, it is dispersed in DMF molten In liquid or DMA solution, cortex electrostatic spinning liquid is obtained；In cortex electrostatic spinning liquid, the quality of polyacrylonitrile Fraction is 11%；
By PVP and nickel acetate according to mass ratio 1:5, it is scattered in DMF solution or DMA In solution, sandwich layer electrostatic spinning liquid is obtained；In sandwich layer electrostatic spinning liquid, the mass fraction of PVP is 10%；
Step 20）By step 10）The cortex electrostatic spinning liquid and sandwich layer electrostatic spinning liquid of preparation, using coaxial electrostatic spinning method, Cortex electrostatic spinning liquid is located at sandwich layer electrostatic spinning liquid outside, spins nano fibrous membrane；During electrostatic spinning：Voltage is 20 KV, spinning flow velocity is 2mL/h, the distance between spinning head and reception device：30cm, spray time is 40min.
Step 30）By step 20）Obtained nano fibrous membrane is placed in tube furnace, and 280 DEG C of guarantors are warming up to 1.5 DEG C/min 1h is held, 9 DEG C/min is warming up to 600 DEG C of holding 1h, obtains carbon, Graphene, the nickel composite nano fiber of core shell structure；
Step 40）By step 30）The carbon of preparation, Graphene, nickel composite nano fiber are placed in molar concentration for 100mmol/L, temperature Spend in the tin-salt solution for 50 DEG C, keep 5h, obtain carbon, Graphene, tin composite nano fiber.The preparation process of tin-salt solution For：Stannous acetate is dissolved in ethanol solution, tin-salt solution is made.
Embodiment 4
Using carbon, Graphene, tin composite nano-fiber material as lithium ion battery negative.The system of the composite nano-fiber material Preparation Method is as follows：
Step 10）By Graphene and polyacrylonitrile（PAN）It is 1.5 according to mass ratio:100, it is dispersed in DMF In solution or DMA solution, cortex electrostatic spinning liquid is obtained；In cortex electrostatic spinning liquid, the matter of polyacrylonitrile Amount fraction is 12%；
By PVP and nickel chloride according to mass ratio 1:10, it is scattered in DMF solution or DMA In solution, sandwich layer electrostatic spinning liquid is obtained；In sandwich layer electrostatic spinning liquid, the mass fraction of PVP is 9%；
Step 20）By step 10）The cortex electrostatic spinning liquid and sandwich layer electrostatic spinning liquid of preparation, using coaxial electrostatic spinning method, Cortex electrostatic spinning liquid is located at sandwich layer electrostatic spinning liquid outside, spins nano fibrous membrane；During electrostatic spinning：Voltage is 15 KV, spinning flow velocity is 1mL/h, the distance between spinning head and reception device：26cm, spray time is 15min.
Step 30）By step 20）Obtained nano fibrous membrane is placed in tube furnace, and 270 DEG C of guarantors are warming up to 1.8 DEG C/min 1.5h is held, 8 DEG C/min is warming up to 650 DEG C of holding 4h, obtains carbon, Graphene, the nickel composite nano fiber of core shell structure；
Step 40）By step 30）The carbon of preparation, Graphene, nickel composite nano fiber are placed in molar concentration for 60mmol/L, temperature In 25 DEG C of tin-salt solutions, to keep 12h, carbon, Graphene, tin composite nano fiber are obtained.The preparation process of tin-salt solution is： By stannous chloride and stannous acetate according to mass ratio 1:1 is dissolved in ethanol solution, is made tin-salt solution.
Embodiment 5
Using carbon, Graphene, tin composite nano-fiber material as lithium ion battery negative.The system of the composite nano-fiber material Preparation Method is as follows：
Step 10）It is 0.8 according to mass ratio by Graphene and polyacrylonitrile:100, be dispersed in DMF solution or In DMA solution, cortex electrostatic spinning liquid is obtained；In cortex electrostatic spinning liquid, the mass fraction of polyacrylonitrile It is 8%；
By PVP and nickel acetate according to mass ratio 1:1, it is scattered in DMF solution or DMA In solution, sandwich layer electrostatic spinning liquid is obtained；In sandwich layer electrostatic spinning liquid, the mass fraction of PVP is 8%；
Step 20）By step 10）The cortex electrostatic spinning liquid and sandwich layer electrostatic spinning liquid of preparation, using coaxial electrostatic spinning method, Cortex electrostatic spinning liquid is located at sandwich layer electrostatic spinning liquid outside, spins nano fibrous membrane；During electrostatic spinning：Voltage is 27kV, spinning flow velocity is 2.6mL/h, the distance between spinning head and reception device：15cm, spray time is 60min.
Step 30）By step 20）Obtained nano fibrous membrane is placed in tube furnace, and 275 DEG C of guarantors are warming up to 1.3 DEG C/min 2.8h is held, 6 DEG C/min is warming up to 750 DEG C of holding 3.5h, obtains carbon, Graphene, the nickel composite nano fiber of core shell structure；
Step 40）By step 30）The carbon of preparation, Graphene, nickel composite nano fiber are placed in molar concentration for 40mmol/L, temperature In 80 DEG C of tin-salt solutions, to keep 10h, carbon, Graphene, tin composite nano fiber are obtained.The preparation process of tin-salt solution is： By stannous sulfate and stannous acetate according to mass ratio 1:2 are dissolved in ethanol solution, are made tin-salt solution.
Embodiment 6
Using carbon, Graphene, tin composite nano-fiber material as lithium ion battery negative.The system of the composite nano-fiber material Preparation Method is as follows：
Step 10）It is 1.2 according to mass ratio by Graphene and polyacrylonitrile:100, be dispersed in DMF solution or In DMA solution, cortex electrostatic spinning liquid is obtained；In cortex electrostatic spinning liquid, the mass fraction of polyacrylonitrile It is 7%；
By PVP and nickel chloride according to mass ratio 1:6, it is scattered in DMF solution or DMA is molten In liquid, sandwich layer electrostatic spinning liquid is obtained；In sandwich layer electrostatic spinning liquid, the mass fraction of PVP is 8.6%；
Step 20）By step 10）The cortex electrostatic spinning liquid and sandwich layer electrostatic spinning liquid of preparation, using coaxial electrostatic spinning method, Cortex electrostatic spinning liquid is located at sandwich layer electrostatic spinning liquid outside, spins nano fibrous membrane；During electrostatic spinning：Voltage is 15 KV, spinning flow velocity is 1.6 mL/h, and the distance between spinning head and reception device are 32 cm, and spray time is 55min.
Step 30）By step 20）Obtained nano fibrous membrane is placed in tube furnace, and 255 DEG C of guarantors are warming up to 1.2 DEG C/min 2.2h is held, 7 DEG C/min is warming up to 750 DEG C of holding 3.5h, obtains carbon, Graphene, the nickel composite nano fiber of core shell structure；
Step 40）By step 30）The carbon of preparation, Graphene, nickel composite nano fiber are placed in molar concentration for 50mmol/L, temperature In 45 DEG C of tin-salt solutions, to keep 8h, carbon, Graphene, tin composite nano fiber are obtained.The preparation process of tin-salt solution is： Stannous chloride is soluble in water, it is made tin-salt solution.
To above-mentioned 2 comparative examples and 6 embodiments, the test of electric conductivity, capacity and cyclical stability is carried out respectively.Test Result is as shown in table 1.
Table 1
As can be seen from Table 1：Carbon, Graphene, the electric conductivity of tin composite nano fiber prepared by the embodiment of the present invention is better than contrast Example.The electric conductivity of comparative example 1 is 36 Ω/cm, and the electric conductivity of embodiment 4 is 8 Ω/cm.The electric conductivity of embodiment 4 is far superior to Comparative example 1.Meanwhile, the capacity of composite nano fiber prepared by the embodiment of the present invention is significantly larger than comparative example.The capacity of embodiment 4 It is 1648 mAhg-1, the capacity of comparative example 1 is 320 mAhg-1.The capacity of embodiment 4 is 5 times of comparative example 1.The present invention is implemented The capability retention of composite nano fiber prepared by example is also significantly larger than comparative example.After 100 circulations, the capacity of embodiment 4 is protected Holdup is 99%, and comparative example 2 only 43%.
The basic principles, principal features and advantages of the present invention have been shown and described above.Those skilled in the art should Understand, the present invention do not limited by above-mentioned specific embodiment, the description in above-mentioned specific embodiment and specification be intended merely into One step illustrates principle of the invention, without departing from the spirit and scope of the present invention, the present invention also have various change and Improve, these changes and improvements all fall within the protetion scope of the claimed invention.The scope of protection of present invention will by right Ask book and its equivalent thereof.

Claims (9)

1. a kind of used as negative electrode of Li-ion battery flexible compound nano-fiber material, it is characterised in that described composite nano fiber Material includes cortex（1）And sandwich layer（2）, cortex（1）It is coated on sandwich layer（2）Outer surface, cortex（1）By carbon and Graphene structure Into；Sandwich layer（2）It is voided layer, sandwich layer（2）In be provided with hollow nanospheres particle（3）, the nanometer ball particle（3）It is made up of tin.
2. according to the used as negative electrode of Li-ion battery flexible compound nano-fiber material described in claim 1, it is characterised in that described Hollow nanospheres particle（3）With cortex（1）Inner surface connection.
3. the preparation method of the used as negative electrode of Li-ion battery flexible compound nano-fiber material described in a kind of claim 1, it is special Levy and be, the method includes：
Step 10）Graphene and polyacrylonitrile are dispersed in N,N-dimethylformamide solution or DMAC N,N' dimethyl acetamide solution In, cortex electrostatic spinning liquid is obtained；
During polyvinylpyrrolidone and nickel salt are scattered in into DMF solution or DMA solution, Sandwich layer electrostatic spinning liquid is obtained；
Step 20）By step 10）The cortex electrostatic spinning liquid and sandwich layer electrostatic spinning liquid of preparation, using coaxial electrostatic spinning method, Cortex electrostatic spinning liquid is located at sandwich layer electrostatic spinning liquid outside, spins nano fibrous membrane；
Step 30）By step 20）Obtained nano fibrous membrane is placed in tube furnace, and 250 ~ 280 DEG C of guarantors are warming up to 1 ~ 2 DEG C/min 1 ~ 3h is held, 5 ~ 10 DEG C/min is warming up to 600 ~ 800 DEG C of 1 ~ 4h of holding, obtain carbon, Graphene, the nickel composite Nano fibre of core shell structure Dimension；
Step 40）By step 30）The carbon of preparation, Graphene, nickel composite nano fiber be placed in molar concentration for 20 ~ 100mmol/L, During temperature is for 25 ~ 90 DEG C of tin-salt solution, 2 ~ 12h is kept, obtain carbon, Graphene, tin composite nano fiber.
4. according to the preparation method described in claim 3, it is characterised in that described step 10）In, obtained cortex Static Spinning In silk liquid, the mass fraction of polyacrylonitrile is 6 ~ 12%；The mass ratio of Graphene and polyacrylonitrile is 0.2 ~ 2:100.
5. according to the preparation method described in claim 3 or 4, it is characterised in that described step 10）In, obtained sandwich layer is quiet In Electrospun liquid, the mass fraction of polyvinylpyrrolidone is 6 ~ 10%；The mass ratio of polyvinylpyrrolidone and nickel salt is 1: 1 ~10。
6. according to the preparation method described in claim 5, it is characterised in that described nickel salt is nickel chloride, nickel sulfate or second Sour nickel.
7. according to the preparation method described in claim 3, it is characterised in that described step 20）In, during electrostatic spinning： Voltage is 10 ~ 30 kV, and spinning flow velocity is 0.5 ~ 3.0 mL/h, the distance between spinning head and reception device：10 ~ 40 cm, Spray time is 15 ~ 60min.
8. according to the preparation method described in claim 3, it is characterised in that described step 30）In, carbon, Graphene, nickel are combined In nanofiber, cortex is made up of carbon and Graphene, and sandwich layer is voided layer, and the solid sphere being made up of nickel is contained in sandwich layer Grain.
9. according to the preparation method described in claim 3, it is characterised in that described step 40）In, the preparation of tin-salt solution Cheng Wei：During one or two in stannous chloride, stannous sulfate or stannous acetate are dissolved in into water or ethanol solution, pink salt is made molten Liquid.
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