CN104183832A - Preparation method and application of FeF3 flexible electrode based on carbon nano tube-graphene composite three-dimensional network - Google Patents

Preparation method and application of FeF3 flexible electrode based on carbon nano tube-graphene composite three-dimensional network Download PDF

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CN104183832A
CN104183832A CN201410398206.4A CN201410398206A CN104183832A CN 104183832 A CN104183832 A CN 104183832A CN 201410398206 A CN201410398206 A CN 201410398206A CN 104183832 A CN104183832 A CN 104183832A
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graphene
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范奇
孙岳明
徐庆宇
王育乔
齐齐
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Southeast University
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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
    • 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
    • H01M4/58—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
    • H01M4/582—Halogenides
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 provides a preparation method of a FeF3 flexible electrode based on a carbon nano tube-graphene composite three-dimensional network. The preparation method comprises the steps of preparation of a FeF3-graphene electrode material, preparation of a water-soluble carbon nano tube and preparation of a FeF3-graphene-carbon nano tube flexible electrode. The method adopts a liquid phase self-assembling method to obtain the FeF3-graphene-carbon nano tube flexible electrode with a three-dimensional electrode. The process is simple, the operation is convenient, and the prepared electrode has good cycle performance, good rate capability, excellent mechanical property, good electrochemical performance and high safety and reliability, and has potential for use as a novel lithium ion secondary battery anode.

Description

A kind of FeF based on carbon nano-tube-Graphene complex three-dimensional network 3the preparation method of flexible electrode and application
Technical field
The invention belongs to electrochemical field, particularly a kind of FeF based on carbon nano-tube-Graphene complex three-dimensional network 3the preparation method of flexible electrode, also relates to this FeF based on carbon nano-tube-Graphene complex three-dimensional network 3flexible electrode is in the application of preparing in lithium rechargeable battery.
Background technology
Energy problem and environmental problem have become the two large problems that contemporary society urgently will solve.Adopt the new-energy automobile of clean electric energy to replace the fuel power automobile of original high pollution imperative.At present, the main development bottleneck of new-energy automobile is the exploitation of safe and reliable motive-power battery.Lithium ion battery has advantages of that the not available high-energy-density of traditional electrokinetic cell, Environmental compatibility are good, memory-less effect, stable work in work, safe and reliable, has become the developing direction of electrical source of power of new generation.
Electrode material is one of key factor determining lithium ion battery combination property quality.At present, the lithium ion anode material of extensive use has LiCoO 2, LiNiO 2, ternary material, rich lithium material, LiMn 2o 4and LiFePO 4, LiMnPO 4deng.But the theoretical capacity of these materials is all too low, and need high temperature sintering to obtain, waste time and energy and not environmental protection.Become the focus of research in recent years so explore the positive electrode of high power capacity, high efficiency, good cycle and novel environment friendly.
In numerous lithium ion secondary battery anode materials of studying, three ferric flouride (FeF 3) there is very high theoretical specific capacity (712mAh g -1), be about 3 times of current commercialization oxide material.Simultaneously FeF3 reduction potential is high, and electrochemical reversible capacity is high, and security performance is good and can synthesize by low temperature, is the study hotspot of power lithium-ion battery positive electrode of new generation.But the poorly conductive of three ferric flourides (FeF3), in the deintercalation process of lithium ion, is accompanied by serious polarization phenomena, cause in charge and discharge process capacity attenuation serious, reduce efficiency and the cycle performance of battery.
At present, improve FeF 3anodal method mainly contains: reduce FeF 1. 3particle size; 2. optimize FeF 3anodal electric conductivity.Reduce FeF 3the object of particle size is mainly to reduce lithium ion and electron diffusion path, increases electrochemical reaction area; Optimize FeF 3anodal electric conductivity can improve the efficiency of transmission of electronics in electrode interior, optimizes chemical property.Wherein, for realizing the object of optimizing electrodes conduct performance, the method for having reported has anode material doped modification; Coated with conductive polymer; Add carbon nano-tube, Graphene, V 2o 5, MoS 2deng.Result of study shows, the combination of conductive agent and positive electrode has appreciable impact to the chemical property of electrode.
Graphene, because having special construction and performance, becomes the focus of international scientific research.This typical Two-dimensional Carbon material has good chemical stability, wide electrochemical window and excellent mechanical property, and Graphene itself has storage lithium characteristic, can be with three ferric flouride (FeF 3) carry out compoundly, effectively overcome FeF 3the shortcoming such as poorly conductive and serious polarization in application process.It should be noted that especially because grapheme material often has high specific area the FeF being therefore prepared into 3/ graphene composite material has higher loading, is much better than other material with carbon elements such as carbon nano-tube.But compared with carbon nano-tube, the conductivity of the grapheme material of electronation is relatively poor, hinder the further performance of battery actual capacity and high rate performance.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, the first object of the present invention is to provide the FeF based on carbon nano-tube-Graphene complex three-dimensional network that a kind of mechanical property is good, chemical property is good, energy density is high 3the preparation method of flexible electrode.
The second object of the present invention is to provide above-mentioned electrode in the application of preparing in lithium rechargeable battery.
Technical scheme: a kind of FeF based on carbon nano-tube-Graphene complex three-dimensional network provided by the invention 3the preparation method of flexible electrode, comprises the following steps:
(1) FeF 3the preparation of-Graphene electrodes material: redox graphene adopts modification Hummer method to make; Redox graphene is dispersed in to ultrasonic processing 10-30min in absolute ethyl alcohol and obtains graphene dispersing solution; Add in graphene dispersing solution 60-100 DEG C to react 5-10h Fe(NO3)39H2O and ammonium acid fluoride, centrifugal, washing of precipitate, dry after, in argon gas atmosphere, be heated to 200-350 DEG C of insulation 3-5h, obtain FeF 3-Graphene electrodes material;
(2) preparation of water-soluble carbon nanometer tube: in the concentrated sulfuric acid, stirring at room temperature 36-60h, is heated to after 65-75 DEG C by carbon nanotube dispersed, add 5ml red fuming nitric acid (RFNA) insulation reaction 1-3h, reaction system is added in ultra-pure water, and filtration, freeze drying, obtain water-soluble carbon nanometer tube;
(3) FeF 3the preparation of-graphene-carbon nano tube flexible electrode: by FeF 3-Graphene electrodes material and water-soluble carbon nanometer tube are scattered in ultra-pure water, and ultrasonic 10-30min filters, is dried, and are heated to 200-350 DEG C of insulation 3-5h in argon gas atmosphere, to obtain final product.
In step (1), Fe(NO3)39H2O and ammonium acid fluoride mol ratio are 1:1.5, and the addition of redox graphene is FeF in the product of the Fe(NO3)39H2O that calculates and ammonium acid fluoride 3the 1:(5-40 of quality); In reaction system, the concentration of Fe(NO3)39H2O is 0.05-1mol/L, and the concentration of ammonium acid fluoride is 0.05-1mol/L.
In step (3), water-soluble carbon nanometer tube and FeF 3the mass ratio of-Graphene electrodes material is 1:(5-40).
In step (3), adopt ultrafiltration membrance filter, filter membrane aperture is 5-200nm.
The FeF based on carbon nano-tube-Graphene complex three-dimensional network that the present invention also provides above method to make 3flexible electrode is in the application of preparing in lithium rechargeable battery.
Beneficial effect: the present invention adopts the method for liquid phase self assembly to obtain the FeF with three-dimensional structure 3-graphene-carbon nano tube flexible electrode, technique is simple, easy and simple to handle, and the electrode making has good cycle performance and high rate performance, and its mechanical property is good, chemical property is good, safe and reliable, has the potentiality that become new type lithium ion anode of secondary battery.Be the compound skeleton structure of Graphene and carbon nano-tube due to what adopt, the conductivity of electrode integral can be significantly improved, and has in use given play to good chemical property thereby be conducive to electrode; Be the design of flexible electrode due to what adopt, the energy density of full electrode has obtained obvious lifting simultaneously.
The inventive method adopts two step synthetic technologys, first obtains FeF by liquid-phase synthesis process 3-grapheme composite positive electrode material, then under the effect of surfactant, the method by liquid phase self assembly obtains the FeF with three-dimensional structure 3-graphene-carbon nano tube flexible electrode, because above-mentioned material has again flexibility, therefore, can save conductive agent, and bonding and the collector as electrode material carrier, further promoted the energy density of electrode.
Brief description of the drawings
Fig. 1 is FeF 3the SEM photo (scale=1um) of-grapheme composite positive electrode material.
Fig. 2 is the FeF based on carbon nano-tube-Graphene complex three-dimensional network 3the SEM photo (scale=1um) of flexible electrode.
Fig. 3 is the FeF based on carbon nano-tube-Graphene complex three-dimensional network 3flexible electrode and FeF 3the high rate performance of the flexible electrode of-Graphene; As seen from the figure, carbon nano-tube-FeF 3-Graphene flexible electrode has better performance.
Embodiment
The mass percent of the concentrated sulfuric acid used in the present invention is 98%, the mass percent of red fuming nitric acid (RFNA) is 69%; , but the mass percent of the concentrated sulfuric acid is that the mass percent of 70-98%, red fuming nitric acid (RFNA) is that 40-69% all can realize object of the present invention.Reference examples
FeF 3the preparation method of-grapheme composite positive electrode material and chemical property, comprise the following steps:
(1) acquisition of graphene dispersing solution: redox graphene adopts modification Hummer method to make; Redox graphene is dispersed in to ultrasonic processing 20min in ethanol solution and obtains graphene dispersing solution;
(2) FeF 3the preparation of-graphene combination electrode material: the ammonium acid fluoride of the Fe(NO3)39H2O of 0.02mol and 0.03mol is put in polytetrafluoroethylcontainer container reactor, add the graphene dispersing solution that contains 100mg Graphene, add again 80% the absolute ethyl alcohol that is no more than reactor volume, at 60 DEG C, react 10h, naturally centrifugal after cooling, precipitation is used absolute ethanol washing 3 times, be put in dry 10h left and right in 80 DEG C of vacuum drying chambers, through be heated to 200-350 DEG C of insulation 4h in argon gas atmosphere, obtain FeF 3(Fig. 1 is FeF to-graphene combination electrode material 3the SEM photo of-grapheme composite positive electrode material).
(3) FeF 3the preparation of-Graphene composite and flexible electrode: the combination electrode material obtaining is used to absolute ethanol washing 3 times, be 100nm ultrafiltration membrance filter with aperture again, be put in 80 DEG C of vacuum drying chambers and be dried about 10 hours, within 4 hours, can obtain FeF through be heated to 350 DEG C of insulations in argon gas atmosphere 3-Graphene flexible electrode.
Embodiment 1
Based on the FeF of carbon nano-tube-Graphene complex three-dimensional network 3flexible electrode (FeF 3-graphene-carbon nano tube flexible electrode) preparation method and chemical property, comprise the following steps:
(1) FeF 3the preparation of-Graphene electrodes material: redox graphene adopts modification Hummer method to make; Redox graphene is dispersed in to ultrasonic processing 20min in ethanol solution and obtains graphene dispersing solution;
(2) FeF 3the preparation of-graphene combination electrode material: the ammonium acid fluoride of the Fe(NO3)39H2O of 0.02mol and 0.03mol is put in polytetrafluoroethylcontainer container reactor, add the graphene dispersing solution that contains 57mg Graphene, add again 80% the absolute ethyl alcohol that is no more than reactor volume, at 80 DEG C, react 8h, naturally centrifugal after cooling, precipitation is used absolute ethanol washing 3 times, is put in dry 10h in 80 DEG C of vacuum drying chambers, in argon gas atmosphere, be heated to 280 DEG C of insulation 4h, obtain FeF 3-graphene combination electrode material;
(3) preparation of water-soluble carbon nanometer tube: also at room temperature continue to stir 48h in the concentrated sulfuric acid that is 70% in mass percent by carbon nanotube dispersed, be heated to 70 DEG C, slowly adding 5ml mass percent is 70% red fuming nitric acid (RFNA) insulation reaction 2h again, and mixed liquor is cooling; After reaction system is cooling, slowly join in ultra-pure water, filter, freeze drying, can arrive water-soluble carbon nanometer tube;
(4) FeF 3the preparation of-graphene-carbon nano tube flexible electrode: by carbon nanotube dispersed in ultra-pure water, and FeF 3-Graphene electrodes material suspension is sneaked in a vial, water-soluble carbon nanometer tube and FeF 3the mass ratio of-Graphene electrodes material is 1:20, ultrasonic 20min after mixing, and aperture is 5nm ultrafiltration membrance filter, is heated to 280 DEG C of insulation 4h after dry in argon gas atmosphere, obtains that (Fig. 2 is carbon nano-tube-FeF 3the SEM photo of-graphene composite structure).
Embodiment 2
Based on the FeF of carbon nano-tube-Graphene complex three-dimensional network 3flexible electrode (FeF 3-graphene-carbon nano tube flexible electrode) preparation method and chemical property, comprise the following steps:
(1) FeF 3the preparation of-Graphene electrodes material: redox graphene adopts modification Hummer method to make; Redox graphene is dispersed in to ultrasonic processing 10min in ethanol solution and obtains graphene dispersing solution;
(2) FeF 3the preparation of-graphene combination electrode material: the ammonium acid fluoride of the Fe(NO3)39H2O of 0.02mol and 0.03mol is put in polytetrafluoroethylcontainer container reactor, add the graphene dispersing solution that contains 452mg Graphene, add again 80% the absolute ethyl alcohol that is no more than reactor volume, make in reaction system, the concentration of Fe(NO3)39H2O is 0.05-1mol/L, the concentration of ammonium acid fluoride is 0.05-1mol/L, at 60 DEG C, react 10h, naturally centrifugal after cooling, precipitation is used absolute ethanol washing 3 times, be put in dry 10h in 80 DEG C of vacuum drying chambers, in argon gas atmosphere, be heated to 200 DEG C of insulation 5h, obtain FeF 3-graphene combination electrode material,
(3) preparation of water-soluble carbon nanometer tube: also at room temperature continue to stir 36h in the concentrated sulfuric acid that is 70% in mass percent by carbon nanotube dispersed, be heated to 65 DEG C, slowly adding 5ml mass percent is 70% red fuming nitric acid (RFNA) insulation reaction 1h again, and mixed liquor is cooling; After reaction system is cooling, slowly join in ultra-pure water, filter, freeze drying, can arrive water-soluble carbon nanometer tube;
(4) FeF 3the preparation of-graphene-carbon nano tube flexible electrode: by carbon nanotube dispersed in ultra-pure water, and FeF 3-Graphene electrodes material suspension is sneaked in a vial, water-soluble carbon nanometer tube and FeF 3the mass ratio of-Graphene electrodes material is 1:5, ultrasonic 10min after mixing, and ultrafiltration membrance filter is heated to 200 DEG C of insulation 5h in argon gas atmosphere after being dried, obtain (SEM photo is consistent with Fig. 2).
Embodiment 3
Based on the FeF of carbon nano-tube-Graphene complex three-dimensional network 3flexible electrode (FeF 3-graphene-carbon nano tube flexible electrode) preparation method and chemical property, comprise the following steps:
(1) FeF 3the preparation of-Graphene electrodes material: redox graphene adopts modification Hummer method to make; Redox graphene is dispersed in to ultrasonic processing 30min in ethanol solution and obtains graphene dispersing solution;
(2) FeF 3the preparation of-graphene combination electrode material: the ammonium acid fluoride of the Fe(NO3)39H2O of 0.002mol and 0.003mol is put in polytetrafluoroethylcontainer container reactor, add the graphene dispersing solution that contains 0.1g Graphene, add again 80% the absolute ethyl alcohol that is no more than reactor volume, at 100 DEG C, react 5h, naturally centrifugal after cooling, precipitation is used absolute ethanol washing 3 times, is put in dry 10h in 80 DEG C of vacuum drying chambers, in argon gas atmosphere, be heated to 350 DEG C of insulation 3h, obtain FeF 3-graphene combination electrode material;
(3) preparation of water-soluble carbon nanometer tube: also at room temperature continue to stir 60h in the concentrated sulfuric acid that is 70% in mass percent by carbon nanotube dispersed, be heated to 75 DEG C, slowly adding 5ml mass percent is 70% red fuming nitric acid (RFNA) insulation reaction 3h again, and mixed liquor is cooling; After reaction system is cooling, slowly join in ultra-pure water, filter, freeze drying, can arrive water-soluble carbon nanometer tube;
(4) FeF 3the preparation of-graphene-carbon nano tube flexible electrode: by carbon nanotube dispersed in ultra-pure water, and FeF 3-Graphene electrodes material suspension is sneaked in a vial, water-soluble carbon nanometer tube and FeF 3the mass ratio of-Graphene electrodes material is 1:40, ultrasonic 30min after mixing, and aperture is 200nm ultrafiltration membrance filter, is heated to 350 DEG C of insulation 3h after being dried in argon gas atmosphere, obtains (SEM photo is consistent with Fig. 2).
The lithium ion battery that test comparison example and embodiment make, method is as follows:
By the FeF obtaining 3-Graphene composite and flexible electrode (reference examples) and FeF 3-graphene-carbon nano tube composite and flexible electrode (embodiment 1) is as anode.Simultaneously, taking lithium sheet as to electrode, micropore shaped polyethylene is barrier film, 1.0mol/LLiPF 6+ DMC is electrolyte, in the glove box that is full of argon gas, is assembled into button cell with tablet press machine, digestion time 8 hours.
In 2.0V～4.0V voltage range, battery is carried out to constant current charge-discharge loop test.Probe temperature is 25 DEG C ± 2 DEG C.Under 0.5C to 5C multiplying power, discharge and recharge, measure charge-discharge performance and the high-rate charge-discharge capability of the lithium ion battery of composition.
Fig. 1 is FeF 3the SEM photo (scale=1um) of-grapheme composite positive electrode material; Fig. 2 is carbon nano-tube-FeF 3the SEM photo (scale=1um) of-graphene composite structure; Fig. 3 is carbon nano-tube-FeF 3-Graphene flexible electrode and FeF 3the high rate performance of the flexible electrode of-Graphene, as seen from the figure, carbon nano-tube-FeF 3-Graphene flexible electrode has better performance.Can find out that by Fig. 1 to 3 above-mentioned battery has shown that in whole charge and discharge process comparatively stable specific capacity and high rate performance are good, can meet the needs of portable power source well.

Claims (5)

1. the FeF based on carbon nano-tube-Graphene complex three-dimensional network 3the preparation method of flexible electrode, is characterized in that: comprise the following steps:
(1) FeF 3the preparation of-Graphene electrodes material: redox graphene adopts modification Hummer method to make; Redox graphene is dispersed in to ultrasonic processing 10-30min in absolute ethyl alcohol and obtains graphene dispersing solution; Add in graphene dispersing solution 60-100 DEG C to react 5-10h Fe(NO3)39H2O and ammonium acid fluoride, centrifugal, washing of precipitate, dry after, in argon gas atmosphere, be heated to 200-350 DEG C of insulation 3-5h, obtain FeF 3-Graphene electrodes material;
(2) preparation of water-soluble carbon nanometer tube: in the concentrated sulfuric acid, stirring at room temperature 36-60h, is heated to after 65-75 DEG C by carbon nanotube dispersed, add 5ml red fuming nitric acid (RFNA) insulation reaction 1-3h, reaction system is added in ultra-pure water, and filtration, freeze drying, obtain water-soluble carbon nanometer tube;
(3) FeF 3the preparation of-graphene-carbon nano tube flexible electrode: by FeF 3-Graphene electrodes material and water-soluble carbon nanometer tube are scattered in ultra-pure water, and ultrasonic 10-30min filters, is dried, and are heated to 200-350 DEG C of insulation 3-5h in argon gas atmosphere, to obtain final product.
2. a kind of FeF based on carbon nano-tube-Graphene complex three-dimensional network according to claim 1 3the preparation method of flexible electrode, is characterized in that: in step (1), Fe(NO3)39H2O and ammonium acid fluoride mol ratio are 1:1.5, and the addition of redox graphene is FeF in the product of the Fe(NO3)39H2O that calculates and ammonium acid fluoride 3the 1:(5-40 of quality).
3. a kind of FeF based on carbon nano-tube-Graphene complex three-dimensional network according to claim 1 3the preparation method of flexible electrode, is characterized in that: in step (3), and water-soluble carbon nanometer tube and FeF 3the mass ratio of-Graphene electrodes material is 1:(5-40).
4. a kind of FeF based on carbon nano-tube-Graphene complex three-dimensional network according to claim 1 3the preparation method of flexible electrode, is characterized in that: in step (3), adopt ultrafiltration membrance filter, filter membrane aperture is 5-200nm.
5. the FeF based on carbon nano-tube-Graphene complex three-dimensional network that claim 1 to 4 any one makes 3flexible electrode is in the application of preparing in lithium rechargeable battery.
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CN108270003A (en) * 2018-01-05 2018-07-10 昆明理工大学 A kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes
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