CN103560231A - Lithium ion battery anode composite material and its preparation method - Google Patents

Lithium ion battery anode composite material and its preparation method Download PDF

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Publication number
CN103560231A
CN103560231A CN201310449844.XA CN201310449844A CN103560231A CN 103560231 A CN103560231 A CN 103560231A CN 201310449844 A CN201310449844 A CN 201310449844A CN 103560231 A CN103560231 A CN 103560231A
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composite material
solution
anode composite
fecl
tube
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张艳丽
王莉
何向明
赵鹏
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Priority to PCT/CN2014/085568 priority patent/WO2015043359A1/en
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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
    • H01M4/62—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/1397—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
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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

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  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a lithium ion battery anode composite material, which comprises a plurality of iron fluoride particles and a plurality of carbon nanotubes. The plurality of iron fluoride particles and the plurality of carbon nanotubes form a three-dimensional conductive network, wherein the plurality of carbon nanotubes are uniformly dispersed among the plurality of iron fluoride particles, and at least parts of the iron fluoride particles are connected through the carbon nanotubes. The invention also provides a preparation method of the anode composite material. The method comprises the steps of: providing a carbon nanotube raw material and an HF solution; dispersing the carbon nanotube raw material in the HF solution to form a first suspension solution; providing an FeCl3 solution, and mixing the FeCl3 solution with the first suspension solution to obtain a precipitate FeF3.3H2O-CNTs; and subjecting the precipitate to separation and purification, and carrying out heat treatment on the precipitate, thereby obtaining the lithium ion battery anode composite material.

Description

Anode composite material of lithium ion battery and preparation method thereof
Technical field
The present invention relates to a kind of anode composite material of lithium ion battery and preparation method thereof, relate in particular to a kind of anode composite material of lithium ion battery that comprises ferric flouride and preparation method thereof.
Background technology
At present, along with the continuous expansion in lithium ion battery applications field, as novel energy storage and Electric power car field, market is increasing to the demand of high power, high energy density cells.Ferric flouride (FeF 3) because it has very high theoretical energy density and excellent high high-temp stability, and be subject to extensive concern.
Yet, due to FeF 3conductivity lower, and it is very slow in charge and discharge process, to transform the non-conductive dynamic process of conversion reaction that makes of product LiF.Above effects limit FeF 3practical application in lithium ion battery.
At present, main employing reduces the particle size of ferric flouride and uses second-phase electric conducting material to support as it mode that carrier combines, and improves conductivity, the raising electrode kinetics reaction rate of ferric flouride.Particle size reduces to reduce electric transmission path, augmenting response area, thereby improves the electro-chemical activity of ferric flouride.With second-phase electric conducting material, as it, supporting carrier is that ferric flouride particle is combined to improve its chemical property with the good material of another conductivity.The second-phase material of having reported at present has: mesoporous carbon, active carbon ball, PEDOT, V 2o 5, MoS 2, Graphene or carbon nano-tube.In above-mentioned various second-phase materials, carbon nano-tube has electronic conductivity and heat conductivity and the low-density of unique one-dimensional nano structure, excellence, is considered to improve the ideal material of electrode material conductivity.At present Korea S researcher prepares flower-shaped ferric flouride particle and the compound structure of carbon nano-tube, in its preparation process, has used Surfactant CTAB.Wherein, the more difficult removal of surfactant, cause easily existing in end product remaining CTAB, and CTAB can have a negative impact to the chemical property of battery electrode material.
Summary of the invention
In view of this, the necessary preparation method who does not use the anode composite material of lithium ion battery of any surfactant in a kind of preparation process that provides, and the ferric flouride (FeF that uses the method to prepare 3)-carbon nano-tube (CNT) anode composite material.
A kind of anode composite material of lithium ion battery, it is characterized in that, comprise a plurality of ferric flouride particles and a plurality of carbon nano-tube, described a plurality of ferric flouride particle and a plurality of carbon nano-tube form a three-dimensional conductive network, wherein, described a plurality of carbon nanotube dispersed is between described a plurality of ferric flouride particles, and at least part of described ferric flouride particle connects by described carbon nano-tube.
A preparation method for anode composite material of lithium ion battery, comprises the steps: to provide a carbon nanometer tube material and a HF solution; Described carbon nanometer tube material is scattered in described HF solution, forms one first suspension-turbid liquid; One FeCl is provided 3solution, and by described FeCl 3solution mixes with described the first suspension-turbid liquid, obtains a sediment FeF 33H 2o-CNTs; And by described sediment separating-purifying, and sediment described in heat treatment, thereby obtain described anode composite material of lithium ion battery.
Compared to prior art, described compound by carbon nano-tube and ferric flouride are carried out, adopt the method for co-precipitation, and in course of reaction, do not use any surfactant, prepare FeF 3-CNTs anode composite material.Make carbon nano-tube and ferric flouride particle form a three-dimensional conductive network, in battery charge and discharge process, can provide electron propagation ducts, make FeF 3-CNTs anode composite material has higher conductance.Therefore, by FeF 3the battery that-CNTs anode composite material forms has higher discharge capacity and good circulation ability, and has obvious charge and discharge platform.
Accompanying drawing explanation
Fig. 1 is the anode composite material of lithium ion battery preparation method flow chart that the embodiment of the present invention provides.
Fig. 2 is the FeF of the embodiment of the present invention 1 3the stereoscan photograph of-CNTs anode composite material.
Fig. 3 is the embodiment of the present invention 1 intermediate product FeF 33H 2the XRD diffracting spectrum of O-CNTs.
Fig. 4 is the FeF of the embodiment of the present invention 1 3the XRD diffracting spectrum of-CNTs anode composite material.
Fig. 5 is the FeF of the embodiment of the present invention 1 3the first charge-discharge test curve of-CNTs anode composite material under 1.0V-4.5V voltage.
Fig. 6 is the FeF of comparative example 1 of the present invention 3the first charge-discharge test curve of positive electrode under 1.0V-4.5V voltage.
Fig. 7 is the FeF of the embodiment of the present invention 1 3the constant current charge-discharge test curve of-CNTs anode composite material.
Fig. 8 is the FeF of the embodiment of the present invention 1 3the multiplying power discharging curve of-CNTs anode composite material under different power densities.
Fig. 9 is the FeF of comparative example 1 of the present invention 3the multiplying power discharging curve of positive electrode under different current densities.
Figure 10 is the FeF of comparative example 1 of the present invention 3the FeF of positive electrode and embodiment 1 3the charge and discharge cycles test comparison diagram of-CNTs anode composite material.
Embodiment
Below with reference to accompanying drawing, describe anode composite material of lithium ion battery of the present invention and preparation method thereof in detail.
Refer to Fig. 1, the embodiment of the present invention provides a kind of preparation method of anode composite material of lithium ion battery, and it comprises the following steps:
S1 a: carbon nanometer tube material and a HF solution are provided;
S2: described carbon nanometer tube material is scattered in described HF solution, forms one first suspension-turbid liquid;
S3 a: FeCl is provided 3solution, and by described FeCl 3solution mixes with described the first suspension-turbid liquid, obtains a sediment FeF 33H 2o-CNTs; And
S4: by described sediment separating-purifying, and sediment described in heat treatment, thereby obtain described anode composite material of lithium ion battery.
In step S1, described carbon nanometer tube material can be one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes.The internal diameter of this carbon nano-tube is preferably 2 nanometer ~ 15 nanometers, and external diameter is 10 nanometer ~ 30 nanometers, and length is hundreds of micron left and right.This carbon nanometer tube material can be prepared by methods such as arc discharge method, chemical vapour deposition technique or laser evaporation methods.Described HF solution for to be prepared from HF gas dissolution in water, and in this HF solution, the mass fraction of HF is 30%-40%.
In step S2, described carbon nanometer tube material can be scattered in by the mode of mechanical agitation or ultrasonic agitation in described HF solution.Described carbon nanometer tube material is uniformly distributed in described HF solution, thereby forms described the first suspension-turbid liquid.
In step S3, described FeCl 3solution can pass through FeCl 36H 2o grain dissolution is prepared from a solvent, or obtains by other means.Described solvent can be one or more in deionized water, methyl alcohol, ethanol, acetone, ether.Described FeCl 3the concentration of solution is not limit, can be according to the selection of solvent and actual needs configuration.Because a small amount of loss can occur fluorine in course of reaction, therefore, add excessive HF can be used for the loss of fluorine in compensatory reactionBu Changfanying process.Particularly, described the first suspension-turbid liquid and described FeCl 3solution is according to HF and FeCl 3molar concentration rate be greater than 3:1, described carbon nanometer tube material and described FeCl 3feCl in solution 3mass ratio be that 0.007:1～0.08:1 mixes.Preferably, described the first suspension-turbid liquid and described FeCl 3solution is according to HF and FeCl 3molar concentration rate be that 3.1:1～3.2:1 mixes.Thereby making the mass percent of described carbon nano-tube in the anode composite material of lithium ion battery of final preparation is 1-10%.
Described FeCl 3solution can dropwise be splashed in described the first suspension-turbid liquid and be reacted by the mode dripping, particularly, rate of addition preferably 5 seconds every.Thereby make in whole course of reaction fluorine in excessive state, thereby obtain the FeF of pure phase 3.Described FeCl 3solution also can splash in another reactor simultaneously and react with described the first suspension-turbid liquid.In course of reaction, described FeCl 3fe in solution 3+with the F in described the first suspension-turbid liquid -water generation reaction compound FeF 33H 2o precipitation.Meanwhile, described carbon nanometer tube material can be wrapped in described FeF 33H 2on O particle, or be dispersed in FeF 33H 2between O particle, thereby form a plurality of conductive channels.In addition, in course of reaction, can make by the mode of mechanical agitation, ultrasonic agitation or magnetic agitation described the first suspension-turbid liquid, FeCl 3solution fully reacts.Further, after completion of the reaction, can continue to be uniformly mixed liquid 10-12 hour, make described sediment and described carbon nanometer tube material dispersed.
In step S4, described sediment can pass through method and the liquid phase separation of filtering, thereby obtains described sediment.Described filter method can be that normal pressure filters or vacuum filtration.The method that described normal pressure filters specifically comprises, pour described mixed solution into one and be placed with in the funnel of filter paper, thereby standing a period of time obtains described sediment.The method of described vacuum filtration specifically comprises provides an a miillpore filter and funnel of bleeding, through this miillpore filter, pour described mixed solution into this and bleed in funnel, suction filtration and obtain one described in sediment.In addition, may further include with deionized water and wash this sedimentary step and described sediment is carried out to dry step.Described drying steps preferably proceeds to described sediment in air dry oven, and dries 8-10 hour under 60 ℃ of left and right conditions.
Described heat treatment FeF 33H 2o-CNTs is at N 2, carry out in the inert atmosphere such as Ar, heat treated temperature is 120 ℃-170 ℃, thereby is conducive to avoid the generation of dephasign in anode composite material, obtains the FeF of pure phase 3-CNTs anode composite material.Preferably, this heat treatment temperature is about 125 ℃-140 ℃.Particularly, the temperature curve of sintering can be set as: by room temperature, be warming up to 120 ℃-170 ℃; Heating rate can be 3～5 ℃/min; Temperature retention time is set as 8～12 hours.
Embodiment 1:
200 mg carbon nano-tube are added to 80 mL HF(38% mass percents) in the aqueous solution, ultrasonic dispersion 2h obtains the first suspension-turbid liquid; By 27.027 g FeCl 3.6H 2o is dissolved in 20mL deionized water and obtains FeCl 3solution; Under magnetic agitation condition, by described FeCl 3solution dropwise splashes in described the first suspension-turbid liquid, continues magnetic agitation 10h, obtains one containing sedimentary mixed liquor; Filter described mixed liquor, described sediment, at 60 ℃ of dry 10h, by described sediment heat treatment 10h in the Ar atmosphere of 125 ℃, is obtained to FeF 3-CNTs anode composite material.
Embodiment 2:
300 mg carbon nano-tube are added to 40 mL HF(38% mass percents) in the aqueous solution, ultrasonic dispersion 1h obtains the first suspension-turbid liquid; By 40.54 g FeCl 3.6H 2o is dissolved in 40 mL deionized waters and obtains FeCl 3solution; Under magnetic agitation condition, by described FeCl 3solution dropwise splashes in described the first suspension-turbid liquid, continues magnetic agitation 10 h, obtains one containing sedimentary mixed liquor; Filter described mixed liquor, by described sediment at 60 ℃ of dry 10h, the N by described sediment at 130 ℃ 2in atmosphere, heat treatment 10h, obtains FeF 3-CNTs anode composite material.
Embodiment 3:
500 mg carbon nano-tube are added to 100 mL HF(38% mass percents) in the aqueous solution, ultrasonic dispersion 3h obtains the first suspension-turbid liquid; By 54.058 g FeCl 3.6H 2o is dissolved in 100 mL deionized waters and obtains FeCl 3solution; Under magnetic agitation condition, by described FeCl 3solution dropwise splashes in described the first suspension-turbid liquid, continues magnetic agitation 10 h, obtains one containing sedimentary mixed liquor; Filter described mixed liquor, by described sediment at 60 ℃ of dry 10h, the N by described sediment at 140 ℃ 2in atmosphere, heat treatment 10h, obtains FeF 3-CNTs anode composite material.
Comparative example 1:
Comparative example 1 is substantially the same manner as Example 1, and its difference is only not add carbon nano-tube.
Refer to Fig. 2, described FeF 3-CNTs anode composite material comprises a plurality of ferric flouride particles and a plurality of carbon nano-tube, described even carbon nanotube is scattered between described ferric flouride particle or is wound in and on described ferric flouride particle, forms a three-dimensional conductive network, a plurality of ferric flouride particles connect by a plurality of carbon nano-tube, and a plurality of carbon nano-tube form a plurality of conductive channels.Described ferric flouride particle is bar-shaped, and its length is 2 microns to 6 microns, diameter be 100 nanometers to 300 nanometers, and the nanometer ferric flouride particle that each bar-shaped ferric flouride is about 30nm by a plurality of diameters forms.
See also Fig. 3-4, as can be seen from the figure, the FeF that embodiment 1 obtains 3the diffraction maximum position of-CNTs anode composite material is completely corresponding with PDF standard diagram, and each diffraction peak intensity is higher, and peak shape is more sharp-pointed, and the FeF obtaining is described 3-CNTs anode composite material is pure phase, without other dephasigns, exists.
The FeF that embodiment 1, embodiment 2, embodiment 3 are obtained 3-CNTs anode composite material, and the FeF that obtains of comparative example 1 3positive electrode, forms battery as positive electrode respectively and carries out battery performance test.
The positive pole of this test battery comprises following component:
Material Component Mass percent
Positive electrode Embodiment 1 sample or embodiment 2 samples or embodiment 3 samples or comparative example 1 sample 80%
Conductive agent Graphite 10%
Binding agent Polyvinylidene fluoride (PVDF) is dissolved in 1-METHYLPYRROLIDONE (NMP) solvent 10%
Described each component is fully uniformly mixed and forms a slurry, and be coated on aluminum foil current collector surface, then 120 ℃ of vacuumizes 24 hours.Take metal lithium sheet as negative pole, and Celgard 2400 microporous polypropylene membranes are barrier film, with 1mol/L LiPF 6/ EC+DMC+DEC(1:1:1 volume ratio) be electrolyte, in argon gas atmosphere glove box, form button cell.
By the FeF of embodiment 1 3the FeF of-CNTs anode composite material and comparative example 1 3the battery that positive electrode forms is respectively at 100 mAg -1current density under, and within the scope of 1.0V～4.5V, carry out the test of charge-discharge test and constant current charge-discharge.Refer to Fig. 5-6, can find out, the FeF of embodiment 1 3-CNTs anode composite material has more obvious three electronics charge and discharge platform, and has higher discharge capacity, and discharge capacity can reach 600 mAhg first -1left and right; And the FeF of comparative example 1 3three electronics charge and discharge platform of positive electrode are not obvious, and its first discharge capacity only reach 350 mAhg -1left and right.
See also Fig. 7, after 10 charge and discharge cycles, the FeF of embodiment 1 3the specific discharge capacity of-CNTs anode composite material is by 600 mAhg of initial capacity -1be down to 300 mAhg -1, capability retention is 50%.And the FeF of comparative example 1 3positive electrode, under identical test condition, after 10 charge and discharge cycles, the specific discharge capacity of battery is by the 350mAhg of initial capacity -1be down to 100 mAhg -1, capability retention is only 28.5%.FeF is described 3-CNTs anode composite material compares FeF 3positive electrode has higher capacity and capability retention.
By the FeF of embodiment 1 3the FeF of-CNTs anode composite material and comparative example 1 3the battery that positive electrode forms is within the scope of 2.0V～4.5V, respectively at 50 mAg -1, 100 mAg -1and 500 mAg -1current density under carry out charge-discharge test.Refer to Fig. 8-9, can find out, the FeF of embodiment 1 3-CNTs anode composite material is at 50 mAg -1, 100 mAg -1, 500 mAg -1under current density discharge capacity be respectively 175 mAhg -1, 170 mAhg -1, 100 mAg -1.And the ferric fluoride anode material of comparative example 1 is at 50mAg -1, 100 mAg -1, 500 mAg -1under electric current discharge capacity be respectively 110 mAhg -1, 100 mAhg -1, 70 mAhg -1, illustrate within the scope of 2.0V～4.5V, and at 50 mAg -1, 100 mAg -1and 500 mAg -1current density under, FeF 3-CNTs anode composite material has higher discharge capacity than ferric flouride material.
See also Figure 10, can find out, in the voltage range of 2.0V～4.5V, at 50mAg -1, 100mAg -1, and 500mAg -1under electric current respectively after cycle charge-discharge 5 times.With FeF 3positive electrode is compared, FeF 3the discharge capacity of-CNTs anode composite material is higher, and battery capacity attenuation ratio is less.
FeF in embodiment 2 3the battery that-CNTs anode composite material forms is at 50 mAg -1current density under, and in the voltage range of 2.0V～4.5V, carry out constant current cycle charge discharge electrical testing.After electric discharge, the discharge capacity of battery is 173.9mAhg first -1, after 20 circulations, battery capacity decay is lower than 5%.FeF in embodiment 3 3the battery that-CNTs anode composite material forms is at 100 mAg -1current density under, and in the voltage range of 2.0V～4.5V, carry out constant current cycle charge discharge electrical testing.After electric discharge, the discharge capacity of battery is 170mAhg first -1, after 20 circulations, battery capacity decay is lower than 5%.This FeF is described 3-CNTs anode composite material has higher discharge capacity and good circulation ability.
Because carbon nano-tube has unique one-dimensional nano structure, excellent characteristics such as electronic conductivity, high-specific surface area and low-density, it is the ideal material that improves electrode material conductivity.The present invention is compound by carbon nano-tube and ferric flouride are carried out, and obtains FeF 3-CNTs anode composite material.Make carbon nano-tube and ferric flouride particle form a three-dimensional conductive network, in battery charge and discharge process, can provide electron propagation ducts, make FeF 3-CNTs anode composite material has higher conductance.Therefore, by FeF 3the battery that-CNTs anode composite material forms has higher discharge capacity and good circulation ability, and has obvious charge and discharge platform.In addition, the present invention adopts the method for co-precipitation to prepare FeF 3-CNTs anode composite material, can not destroy ferric flouride structure, makes FeF 3-CNTs anode composite material can effectively utilize the advantage of the high-energy-density of ferric flouride and the high high-temp stability of excellence.And in preparation process, do not use any surfactant, preparation process is simple.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and these variations of doing according to spirit of the present invention certainly, all should be included in the present invention's scope required for protection.

Claims (10)

1. an anode composite material of lithium ion battery, it is characterized in that, comprise a plurality of ferric flouride particles and a plurality of carbon nano-tube, described a plurality of ferric flouride particle and a plurality of carbon nano-tube form a three-dimensional conductive network, wherein, described a plurality of carbon nanotube dispersed is between described a plurality of ferric flouride particles, and at least part of described ferric flouride particle connects by described carbon nano-tube.
2. anode composite material of lithium ion battery as claimed in claim 1, is characterized in that, described a plurality of carbon nano-tube are wrapped on described ferric flouride particle.
3. anode composite material of lithium ion battery as claimed in claim 1, it is characterized in that, described ferric flouride particle is bar-shaped, and its length is 2 microns to 6 microns, diameter be 100 nanometers to 300 nanometers, and the nanometer ferric flouride particle that each bar-shaped ferric flouride is 30 nm by a plurality of diameters forms.
4. anode composite material of lithium ion battery as claimed in claim 1, it is characterized in that, described anode composite material of lithium ion battery is comprised of a plurality of ferric flouride particles and a plurality of carbon nano-tube, and the mass percent of described carbon nano-tube in described anode composite material of lithium ion battery is 1-10%.
5. a preparation method for anode composite material of lithium ion battery, comprising:
One carbon nanometer tube material and a HF solution are provided;
Described carbon nanometer tube material is scattered in described HF solution, forms one first suspension-turbid liquid;
One FeCl is provided 3solution, and by described FeCl 3solution mixes with described the first suspension-turbid liquid, obtains a sediment FeF 33H 2o-CNTs; And
By described sediment separating-purifying, and sediment described in heat treatment, thereby described anode composite material of lithium ion battery obtained.
6. the preparation method of anode material for lithium-ion batteries as claimed in claim 5, is characterized in that, described FeCl 3solution is for passing through FeCl 3.6H 2o grain dissolution is prepared from a solvent, and described solvent is one or more in deionized water, methyl alcohol, ethanol, acetone, ether.
7. the preparation method of anode material for lithium-ion batteries as claimed in claim 5, is characterized in that, described FeCl 3solution is dropwise splashed in described the first suspension-turbid liquid and is mixed with described the first suspension-turbid liquid by the mode dripping.
8. the preparation method of anode material for lithium-ion batteries as claimed in claim 5, is characterized in that, described the first suspension-turbid liquid and described FeCl 3solution is according to HF and FeCl 3molar concentration rate be greater than 3:1 and mix.
9. the preparation method of anode material for lithium-ion batteries as claimed in claim 5, is characterized in that, described carbon nano-tube and described FeCl 3feCl in solution 3mass ratio be 0.007:1～0.08:1.
10. the preparation method of anode material for lithium-ion batteries as claimed in claim 5, is characterized in that, described heat treated temperature is 120 ℃-170 ℃, heat treated time 8-10 hour.
CN201310449844.XA 2013-09-27 2013-09-27 Lithium ion battery anode composite material and its preparation method Pending CN103560231A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015043359A1 (en) * 2013-09-27 2015-04-02 江苏华东锂电技术研究院有限公司 Lithium ion battery anode composite material and preparing method thereof
CN105098137A (en) * 2014-05-09 2015-11-25 宁德时代新能源科技有限公司 Lithium ion battery, and anode material and preparation method thereof
WO2016045558A1 (en) * 2014-09-26 2016-03-31 江苏华东锂电技术研究院有限公司 Composite positive electrode material and preparation method therefor
CN107275604A (en) * 2017-06-12 2017-10-20 四川大学 A kind of N doping porous carbon load iron-based fluoride three-dimensional manometer anode material for lithium-ion batteries and preparation method thereof
CN108615884A (en) * 2018-04-25 2018-10-02 国家纳米科学中心 A kind of KFeF of hollow structure3Nano material and its preparation method and application
CN114447291A (en) * 2021-12-22 2022-05-06 西安理工大学 Self-supporting ferric trifluoride-carbon nanofiber cathode material and preparation method thereof

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL3134932T3 (en) 2014-04-25 2022-01-17 South Dakota Board Of Regents High capacity electrodes
US10468674B2 (en) 2018-01-09 2019-11-05 South Dakota Board Of Regents Layered high capacity electrodes
CN110817958B (en) * 2019-10-11 2022-07-29 攀钢集团攀枝花钢铁研究院有限公司 Carbon-coated nano vanadium pentoxide lithium battery positive electrode material and liquid-phase in-situ preparation method thereof
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CN115954465B (en) * 2023-03-13 2023-06-09 河北坤天新能源股份有限公司 High-power hard carbon composite material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102315482A (en) * 2011-08-31 2012-01-11 北京理工大学 Lithium secondary battery with metal fluoride as positive electrode material
CN103165888A (en) * 2013-03-02 2013-06-19 合肥国轩高科动力能源股份公司 Preparation method of ferric three fluoride (FeF3) nanorod with embedded lithium activity

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9705124B2 (en) * 2012-02-27 2017-07-11 The Johns Hopkins University High energy density Li-ion battery electrode materials and cells
CN103151523B (en) * 2013-02-28 2015-07-22 湘潭大学 Preparation method of cuboid-shaped positive-pole FeF3(H2O)0.33 material
CN103560231A (en) * 2013-09-27 2014-02-05 江苏华东锂电技术研究院有限公司 Lithium ion battery anode composite material and its preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102315482A (en) * 2011-08-31 2012-01-11 北京理工大学 Lithium secondary battery with metal fluoride as positive electrode material
CN103165888A (en) * 2013-03-02 2013-06-19 合肥国轩高科动力能源股份公司 Preparation method of ferric three fluoride (FeF3) nanorod with embedded lithium activity

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SUNG-WOOK KIM ET AL.: "《Fabrication of FeF3 Nanoflowers on CNT Branches and Their Application to High Power Lithium Rechargeable Batteries》", 《ADVANCED MATERIALS》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015043359A1 (en) * 2013-09-27 2015-04-02 江苏华东锂电技术研究院有限公司 Lithium ion battery anode composite material and preparing method thereof
CN105098137A (en) * 2014-05-09 2015-11-25 宁德时代新能源科技有限公司 Lithium ion battery, and anode material and preparation method thereof
WO2016045558A1 (en) * 2014-09-26 2016-03-31 江苏华东锂电技术研究院有限公司 Composite positive electrode material and preparation method therefor
CN107275604A (en) * 2017-06-12 2017-10-20 四川大学 A kind of N doping porous carbon load iron-based fluoride three-dimensional manometer anode material for lithium-ion batteries and preparation method thereof
CN108615884A (en) * 2018-04-25 2018-10-02 国家纳米科学中心 A kind of KFeF of hollow structure3Nano material and its preparation method and application
CN114447291A (en) * 2021-12-22 2022-05-06 西安理工大学 Self-supporting ferric trifluoride-carbon nanofiber cathode material and preparation method thereof

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