CN104577126A - Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode - Google Patents

Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode Download PDF

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CN104577126A
CN104577126A CN201510044539.1A CN201510044539A CN104577126A CN 104577126 A CN104577126 A CN 104577126A CN 201510044539 A CN201510044539 A CN 201510044539A CN 104577126 A CN104577126 A CN 104577126A
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mwcnt
electrode material
preparation
ethylene glycol
water
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马小健
周艳丽
杨剑
钱逸泰
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Shandong University
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Shandong 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
    • H01M4/58—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
    • H01M4/13—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 relates to a method for preparing an MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and an application of the material in a lithium electrode. The preparation method comprises the following steps: performing amorphous carbon coating on multi-walled carbon nanotubes for 5-10 hours, thereby obtaining MWCNT@a-C; mixing the MWCNT@a-C, a transition metal cobalt salt and thiourea, adding the mixture into a mixed solvent, and sealing and reacting for 12-30 hours; and washing, separating and drying the obtained product, and calcining in an argon and hydrogen mixed atmosphere for 1-10 hours, thereby obtaining the final product. The method disclosed by the invention has the advantages of simple needed conditions, cheap and readily available raw materials, uniform morphology and high yield, and the industrial production is easily realized. A lithium storage electrode prepared by taking the MWCNT@a-C@Co9S8 composite material prepared by the method as an active material has high reversible specific capacity and stable cycle performance under high current density and has excellent rate capability, and the increasing energy demands of electric vehicle and other various electronic products in the future can be met.

Description

A kind of pattern uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material and the application in lithium electricity
Technical field
The present invention relates to a kind of high power capacity, the MWCNT@a-C@Co of long circulation life 9s 8the preparation method of combination electrode material, belongs to electrochemical nano material preparation technology and new energy materials field.
Background technology
Secondary cell represents the main direction of studying of energy storage technology.Existing secondary cell is because the factors such as life-span, power, capacity, cost can't meet the demand of Future Mobile Communication and electric automobile.The preparation of nano material is just becoming and is promoting conventional batteries performance, development of new battery, the crucial science and technology that reduces costs, be the inevitable choice of the existing secondary cell combination property of General Promotion and development of new battery, represent main flow and the leading edge developments direction of current cell materials and technical research.
Along with lithium battery is in the development in electric automobile field, people propose higher requirement to current business-like storage lithium electrode material, not only wish improve its energy density and power density further, also have great expectations of and can have better cycle performance and security performance.Current business-like storage lithium titanate cathode material mainly graphite material, but its theoretical specific capacity only has 372mAh/g.In addition due to its fail safe, cycle life and to negative issues such as limiting temperature tolerances, its widely used bottleneck in extensive energy storage and electric automobile is constrained.Therefore, it is high to seek a kind of specific capacity, the lithium storage materials of cycle performance and high rate performance excellence, has important practical significance for the storage lithium performance improving serondary lithium battery.
In recent years, transient metal sulfide is due to its higher theoretical specific capacity, and high conductivity, good thermal stability causes the extensive concern of people.In addition, our transition metal rich reserves is that one is very potential can business-like lithium storage materials.But its shortcoming is in cyclic process because large change in volume causes structural instability.In order to suppress this bulk effect, the method that current people adopt mainly contains two kinds: one, prepare various nanostructure.Such as, L.Jiao seminar is by the CoS of preparation 2tiny balloon is as negative material, and under the current density of 100mA/g, circulation 40 circle, obtains the reversible capacity (J.Phys.Chem.C, 2011,115,8300-8304.) of 320mAh/g.Two, by improving conductivity with material with carbon element compound, the bulk effect of inhibit activities electrode material, multiplying power and the cycle performance of material is improved to the greatest extent.The CoS that carbon prepared by Y.Xie et.al is coated 2core shell nanoparticles is at 0.2mA/cm 2current density under, circulation 50 circle, its reversible specific capacity still can remain on 440mAh/g.The CoS compound of the graphene coated that Y.Wang project team system is standby, when current density is 62.5mA/g, circulation 40 circle, reversible specific capacity is still up to 749mAh/g.Compared with simple nano material, these composite materials above-mentioned show the cycle performance of certain excellence, possess certain chemical property advantage.But the circulation under its high current density and high rate performance also need further improvement.The people such as W.Li adopt transmission electron microscope in-situ observation to arrive Co 9s 8lithiumation/de-lithium the process of/Co carbon pipe.
In addition, at present also not about MWCNT@a-C@Co 9s 8the preparation of combination electrode material and the report as storage lithium electrode material.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of easy MWCNT@a-C@Co be easy to get 9s 8the preparation method of composite material, the MWCNT@a-C@Co that the inventive method prepares 9s 8composite material and MWCNT@Co 9s 8composite material and Co 9s 8compare, can improve to significant effective performance and the cyclical stability of high current charge-discharge.
Technical scheme of the present invention is as follows:
A kind of pattern uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material, comprises step as follows:
(1) adopted by multi-walled carbon nano-tubes hydro thermal method to carry out amorphous carbon coated, obtain MWCNT@a-C,
(2) by MWCNT a-C with transition metal cobalt salt, thiocarbamide by MWCNT a-C: transition metal cobalt salt: thiocarbamide=(0.5 ~ 1): (5 ~ 6): the mass ratio of (4 ~ 8) mixes, obtain mixed material, then mixed material is joined in water-ethylene glycol mixed solvent, obtain mixture; The mass volume ratio of described mixed material and water-ethylene glycol mixed solvent is (1.0 ~ 2.0): 100, unit: g/mL,
(3) mixture is reacted 12 ~ 30h under sealed environment, at 160 ~ 220 DEG C of temperature, products therefrom through washing, be separated, dry primary product, by primary product in an inert atmosphere in 350 ~ 750 DEG C of calcining 1 ~ 10h, after cooling, namely obtain pattern uniform MWCNT@a-C@Co 9s 8combination electrode material.
The present invention is preferred, amorphous carbon in step (1) is coated: be scattered in by multi-walled carbon nano-tubes 50 ~ 70mg in the glucose solution of concentration 0.03 ~ 0.06mol/L, be transferred in reactor, sealing, hydrothermal temperature is 160 ~ 220 DEG C, the coated time is 5 ~ 10h, obtains the coated many walls carbon pipe of amorphous carbon (MWCNT@a-C).
The present invention is preferred, described MWCNT a-C: transition metal cobalt salt: the mass ratio of thiocarbamide is: (0.6 ~ 0.8): (5.2 ~ 5.8): (6 ~ 7).
Preferred further, described transition metal cobalt salt is cobalt chloride, cobalt acetate, cobalt nitrate or cobaltous sulfate.
The present invention is preferred, and in described water-ethylene glycol mixed solvent, the volume ratio of water and ethylene glycol is: (1 ~ 2): (2 ~ 1), and further preferably, the volume ratio of water and ethylene glycol is: 1:2.
The present invention is preferred, and the mass volume ratio of mixed material and water-ethylene glycol mixed solvent is (1.5 ~ 1.8): 100, unit: g/mL.
The present invention is preferred, and in step (3), the reaction temperature of mixture is 180 ~ 210 DEG C, and the reaction time is 20 ~ 28h.
The present invention is preferred, and in step (3), the calcining heat of primary product is 500 ~ 700 DEG C, and calcination time is 2 ~ 8h.
The present invention is preferred, and described inert gas is argon hydrogen mixture, and the volume of hydrogen accounts for 5 ~ 7vol% of mist cumulative volume.
The optimum preferred embodiment of the present invention, a kind of pattern uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material, comprises step as follows:
(1) multi-walled carbon nano-tubes be scattered in glucose solution adopt hydro thermal method to carry out the coated 5 ~ 10h of amorphous carbon in 160 ~ 220 DEG C, obtain MWCNT@a-C,
(2) by 30 ~ 100mg MWCNT a-C, 0.3736g transition metal cobalt salt, 0.34254g thiocarbamide mixes, and obtains mixed material, is joined by mixed material in water-ethylene glycol mixed solvent, obtain mixture; The mass volume ratio of mixed material and mixed solvent is 1.5:100, and unit is g/mL, and in water-ethylene glycol mixed solvent, the volume ratio of water and ethylene glycol is: 1:2;
(3) mixture is placed in reactor to seal, in temperature 180 ~ 210 DEG C reaction 20 ~ 28h, products therefrom through deionized water with absolute ethanol washing, be separated and be drying to obtain primary product at 60 DEG C, finally in argon hydrogen mixture, calcine 2 ~ 8h in 500 ~ 700 DEG C, after cooling, namely obtain pattern uniform MWCNT@a-C@Co 9s 8combination electrode material.
Gained MWCNT@a-C@Co of the present invention 9s 8composite material is the powder-product of black.Compared with prior art, the invention provides one and prepare MWCNT@a-C@Co 9s 8the new method of composite material, reaction temperature is lower, and easy control simple to operate, products therefrom pattern is even.Described composite material is by Co 9s 8the surface that nano particle is assembled in MWCNT@a-C at random uniformly formed, and pattern is even, Co 9s 8the size of nano particle is approximately 10 ~ 30nm (as Fig. 2).
The pattern uniform MWCNT@a-C@Co that the present invention also provides said method obtained 9s 8the application of combination electrode material,
The pattern that the present invention obtains uniform MWCNT@a-C@Co 9s 8the application of composite material, as storage lithium electrode material activity substance migration, prepare electrode by the following method:
By conductive agent: binding agent: active material presses the quality of 20:10:70 than mixed slurry, conductive agent adopts acetylene black, and binding agent adopts carboxymethyl cellulose (CMC), the MWCNT a-C Co that active material adopts the present invention to obtain 9s 8composite material; Be coated on by mixed slurry in copper foil current collector, be cut into electrode slice, in vacuum, 80 DEG C are dried 12 hours, and by prior art composition button cell, lithium sheet is as to electrode, and battery operated interval is 0.01V-3.0V.
By MWCNT@a-C@Co of the present invention 9s 8the battery of composite material composition carries out the electrochemical property test of electrode, and test result shows: be used as electroactive substance MWCNT a-C Co 9s 8electrode prepared by composite material, at 1A g -1current density under, initial electrochemistry is embedding/reversible capacity of de-Li ion reaches 988mAh/g, and circulate after 120 times, its reversible capacity still can maintain 662mAh/g.
The method that the present invention is combined with heat treatment phase by employing solvent heat is prepared with MWCNT@a-C@Co 9s 8for the composite materials of representative, its method is simple, with low cost, goes for the preparation of other materials equally, significant to possible commercial applications.In addition, research is carried out to its chemical property and find that this compound demonstrates relative to single transient metal sulfide and MWCNT@Co 9s 8compound, have the multiplying power and cycle performance that obviously strengthen, the study on the modification for sulfide provides a kind of effective way, for the application of its possible high current charge-discharge is laid a good foundation.
The composite material prepared by the inventive method improves high current charge-discharge multiplying power and cycle performance effectively as lithium storage materials, may further be big current on electric automobile and long-time discharge and recharge provides application product.The inventive method is workable, favorable reproducibility, and products obtained therefrom output is high, steady quality.
Accompanying drawing explanation
Fig. 1 is MWCNT@a-C@Co prepared by the embodiment of the present invention 1 9s 8the XRD spectra of composite material.
Fig. 2 is the MWCNT@a-C@Co that the embodiment of the present invention 1 obtains 9s 8the ESEM (a) of composite material and transmission electron microscope photo (b).
Fig. 3 is the MWCNT@Co that reference examples 1 obtains 9s 8the ESEM (a) of composite material and transmission electron microscope photo (b).
Fig. 4 is the Co that reference examples 2 obtains 9s 8the transmission electron microscope photo of nano particle.
Fig. 5 is the MWCNT@a-C@Co of the embodiment of the present invention 1 gained 9s 8the MWCNT@Co obtained with reference examples 1 9s 8, and the Co that reference examples 2 is obtained 9s 8the cycle performance comparison diagram of nano particle under the high current density of 1A/g.
Fig. 6 is the MWCNT@a-C@Co of the embodiment of the present invention 1 gained 9s 8the MWCNT@Co obtained with reference examples 1 9s 8, and the Co that reference examples 2 is obtained 9s 8the high rate performance comparison diagram of nano particle.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described, but protection scope of the present invention is not limited thereto.
The carbon nano-tube used in embodiment buy innanometer Port Co., Ltd., Shenzhen.
Cobalt chloride, cobalt acetate, cobalt nitrate and thiocarbamide are conventional commercial products.
Embodiment 1:MWCNT@a-C@Co 9s 8the preparation of composite material
(1) multi-walled carbon nano-tubes 60mg is scattered in the glucose solution of concentration 0.05mol/L, is transferred in reactor, sealing, hydrothermal temperature is 200 DEG C, the coated time is 8h, obtains the coated many walls carbon pipe of amorphous carbon (MWCNT@a-C)
(2) by 60mg MWCNT@a-C, 0.3736g cobalt chloride (CoCl 2), 0.34254g thiocarbamide mixes, and obtains mixed material, is joined by mixed material in water-ethylene glycol mixed solvent, obtain mixture; The mass volume ratio of mixed material and mixed solvent is 1.5:100, and unit is g/mL, and in water-ethylene glycol mixed solvent, the volume ratio of water and ethylene glycol is: 1:2;
(3) mixture is placed in reactor to seal, in temperature 200 DEG C reaction 24h, products therefrom through deionized water with absolute ethanol washing, be separated and be drying to obtain primary product at 60 DEG C, finally in argon hydrogen mixture, calcine 5h in 650 DEG C, after cooling, namely obtain pattern uniform MWCNT@a-C@Co 9s 8combination electrode material.
The MWCNT@a-C@Co of the present embodiment gained 9s 8the XRD spectra of composite material as shown in Figure 1; The ESEM of this composite material of gained and transmission electron microscope photo are as shown in Figure 2.
Reference examples 1:MWCNT@Co 9s 8the preparation of composite material
Then by the MWCNT of 60mg acidifying, 0.3736g cobalt chloride, 0.34254g thiocarbamide, joins in water-ethylene glycol mixed solvent (volume ratio 1:2), and the mass volume ratio of raw material and mixed solvent is 1.5/100, and unit is g/mL; Be placed in reactor to seal, in 200 DEG C reaction 24h, products therefrom through deionized water with absolute ethanol washing, be separated and be drying to obtain preliminary product at 60 DEG C.Last in an inert atmosphere in 650 DEG C of calcining 5h, obtain end product.
Gained MWCNT@Co 9s 8the ESEM of composite material and transmission electron microscope photo are as shown in Figure 3.
Reference examples 2:Co 9s 8the preparation of nano particle
0.3736g cobalt chloride, 0.34254g thiocarbamide joins in water-ethylene glycol mixed solvent (volume ratio 1:2), and the mass volume ratio of raw material and mixed solvent is 1.5/100, and unit is g/mL; Be placed in reactor to seal, in 200 DEG C reaction 24h, products therefrom through deionized water with absolute ethanol washing, be separated and be drying to obtain preliminary product at 60 DEG C.Last in an inert atmosphere in 650 DEG C of calcining 5h, obtain end product.
Gained Co 9s 8the transmission electron microscope photo of nano material as shown in Figure 4.
Experimental example:
Respectively with the MWCNT a-C Co of above-described embodiment 1 gained 9s 8the MWCNT@Co obtained with reference examples 1 9s 8, and the Co that reference examples 2 is obtained 9s 8nano particle is the active material in electrode material, characterizes chemical property.
Electrode preparation method is as follows: by conductive agent: binding agent: active material compares mixed slurry with the quality of 10:20:70, conductive agent adopts acetylene black, binding agent adopts carboxymethyl cellulose (CMC), controls certain thickness and is coated on uniformly in copper foil current collector.The electrode slice of the suitable size of cutting, in vacuum, 80 DEG C are dried 12 hours, button cell is formed in glove box, lithium sheet is to electrode, 1M LiPF6-EC/DMC/DMC (V/V/V=1:1:1) is electrolyte, barrier film is Celgard2400 (PP monofilm), composition button cell (CR2032).Battery operated interval is 0.01V ~ 3.0V.
Fig. 5 is the MWCNT@a-C@Co of embodiment 1 gained 9s 8the MWCNT@Co obtained with reference examples 1 9s 8, and the Co that reference examples 2 is obtained 9s 8the cycle performance contrast of nano particle under the high current density of 1A/g, under the high current density of 1A/g, MWCNT@a-C@Co 9s 8composite material is after circulation 120 is enclosed, and its reversible specific capacity still can reach 662mAh/g, demonstrates the electrochemical stability obviously strengthened.Fig. 6 is the high rate performance contrasts of above-mentioned three kinds of products under different current density, MWCNT@a-C@Co 9s 8under the high current density of 5A/g, average reversible specific capacity still can up to ~ 500mAh/g, and when returning low current density 100mA/g, still can obtain the specific capacity of 938mAh/g, compare MWCNT@Co 9s 8and Co 9s 8nano particle is greatly improved.
Embodiment 2:MWCNT@a-C@Co 9s 8the preparation of composite material
(1) multi-walled carbon nano-tubes 60mg is scattered in the glucose solution of concentration 0.05mol/L, is transferred in reactor, sealing, hydrothermal temperature is 180 DEG C, the coated time is 10h, obtains the coated many walls carbon pipe of amorphous carbon (MWCNT@a-C)
(2) by 80mg MWCNT@a-C, 0.3736g cobalt acetate, 0.34254g thiocarbamide mixes, and obtains mixed material, is joined by mixed material in water-ethylene glycol mixed solvent, obtain mixture; The mass volume ratio of mixed material and mixed solvent is 1.7:100, and unit is g/mL, and in water-ethylene glycol mixed solvent, the volume ratio of water and ethylene glycol is: 1:2;
(3) mixture is placed in reactor to seal, in temperature 210 DEG C reaction 22h, products therefrom through deionized water with absolute ethanol washing, be separated and be drying to obtain primary product at 60 DEG C, finally in argon hydrogen mixture, calcine 4h in 700 DEG C, after cooling, namely obtain pattern uniform MWCNT@a-C@Co 9s 8combination electrode material.
Embodiment 3:
With the MWCNT@a-C@Co described in embodiment 1 9s 8the preparation method of composite material, difference is:
In step (1), be scattered in the glucose solution of concentration 0.05mol/L by multi-walled carbon nano-tubes 70mg, be transferred in reactor, sealing, hydrothermal temperature is 190 DEG C, and the coated time is 9h.
Embodiment 4:
With the MWCNT@a-C@Co described in embodiment 1 9s 8the preparation method of composite material, difference is:
In step (2), by 100mg MWCNT@a-C, 0.3736g cobalt nitrate, 0.34254g thiocarbamide mixes, and obtains mixed material, is joined by mixed material in water-ethylene glycol mixed solvent, obtain mixture; The mass volume ratio of mixed material and mixed solvent is 1.7:100, and unit is g/mL, and in water-ethylene glycol mixed solvent, the volume ratio of water and ethylene glycol is: 1:1.
Embodiment 5:
With the MWCNT@a-C@Co described in embodiment 1 9s 8the preparation method of composite material, difference is:
In step (3), mixture reaction temperature is 160 DEG C, the reaction time: 30h, and primary product calcines 5h in 600 DEG C in argon hydrogen mixture.

Claims (10)

1. a pattern uniform MWCNT a-C Co 9s 8the preparation method of combination electrode material, comprises step as follows:
(1) adopted by multi-walled carbon nano-tubes hydro thermal method to carry out amorphous carbon coated, obtain MWCNT@a-C,
(2) by MWCNT a-C with transition metal cobalt salt, thiocarbamide by MWCNT a-C: transition metal cobalt salt: thiocarbamide=(0.5 ~ 1): (5 ~ 6): the mass ratio of (4 ~ 8) mixes, obtain mixed material, then mixed material is joined in water-ethylene glycol mixed solvent, obtain mixture; The mass volume ratio of described mixed material and water-ethylene glycol mixed solvent is (1.0 ~ 2.0): 100, unit: g/mL,
(3) mixture is reacted 12 ~ 30h under sealed environment, at 160 ~ 220 DEG C of temperature, products therefrom through washing, be separated, dry primary product, by primary product in an inert atmosphere in 350 ~ 750 DEG C of calcining 1 ~ 10h, after cooling, namely obtain pattern uniform MWCNT@a-C@Co 9s 8combination electrode material.
2. pattern according to claim 1 uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material, it is characterized in that, amorphous carbon in step (1) is coated: be scattered in by multi-walled carbon nano-tubes 50 ~ 70mg in the glucose solution of concentration 0.03 ~ 0.06mol/L, be transferred in reactor, sealing, hydrothermal temperature is 160 ~ 220 DEG C, and the coated time is 5 ~ 10h, obtains the coated many walls carbon pipe of amorphous carbon (MWCNT@a-C).
3. pattern according to claim 1 uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material, is characterized in that, described MWCNT a-C: transition metal cobalt salt: the mass ratio of thiocarbamide is: (0.6 ~ 0.8): (5.2 ~ 5.8): (6 ~ 7).
4. pattern according to claim 1 uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material, is characterized in that, described transition metal cobalt salt is cobalt chloride, cobalt acetate, cobalt nitrate or cobaltous sulfate.
5. pattern according to claim 1 uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material, is characterized in that, in described water-ethylene glycol mixed solvent, the volume ratio of water and ethylene glycol is: (1 ~ 2): (2 ~ 1), and further preferably, the volume ratio of water and ethylene glycol is: 1:2.
6. pattern according to claim 1 uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material, is characterized in that, the mass volume ratio of mixed material and water-ethylene glycol mixed solvent is (1.5 ~ 1.8): 100, unit: g/mL.
7. pattern according to claim 1 uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material, it is characterized in that, in step (3), the reaction temperature of mixture is 180 ~ 210 DEG C, and the reaction time is 20 ~ 28h, in step (3), the calcining heat of primary product is 500 ~ 600 DEG C, and calcination time is 2 ~ 8h.
8. pattern according to claim 1 uniform MWCNT@a-C@Co 9s 8the preparation method of combination electrode material, is characterized in that, described inert gas is argon hydrogen mixture, and the volume of hydrogen accounts for 5 ~ 7vol% of mist cumulative volume.
9. a pattern uniform MWCNT a-C Co 9s 8the preparation method of combination electrode material, comprises step as follows:
(1) multi-walled carbon nano-tubes is scattered in glucose solution adopts hydro thermal method to carry out the coated 5 ~ 10h of amorphous carbon in 160 ~ 220 DEG C, obtain MWCNT@a-C;
(2) by 60mg MWCNT a-C, 0.3736g transition metal cobalt salt, 0.34254g thiocarbamide mixes, and obtains mixed material, is joined by mixed material in water-ethylene glycol mixed solvent, obtain mixture; The mass volume ratio of mixed material and mixed solvent is 1.5:100, and unit is g/mL, and in water-ethylene glycol mixed solvent, the volume ratio of water and ethylene glycol is: 1:2;
(3) mixture is placed in reactor to seal, in temperature 180 ~ 210 DEG C reaction 20 ~ 28h, products therefrom through deionized water with absolute ethanol washing, be separated and be drying to obtain primary product at 60 DEG C, finally in argon hydrogen mixture, calcine 2 ~ 8h in 500 ~ 600 DEG C, after cooling, namely obtain pattern uniform MWCNT@a-C@Co 9s 8combination electrode material.
10. pattern according to claim 1 uniform MWCNT@a-C@Co 9s 8the pattern uniform MWCNT@a-C@Co that the preparation method of combination electrode material obtains 9s 8the application of composite material, as storage lithium electrode material activity substance migration, prepare electrode by the following method:
By conductive agent: binding agent: active material presses the quality of 20:10:70 than mixed slurry, conductive agent adopts acetylene black, and binding agent adopts carboxymethyl cellulose (CMC), the MWCNT a-C Co that active material adopts the present invention to obtain 9s 8composite material; Be coated on by mixed slurry in copper foil current collector, be cut into electrode slice, in vacuum, 80 DEG C are dried 12 hours, and by prior art composition button cell, lithium sheet is as to electrode, and battery operated interval is 0.01V-3.0V.
CN201510044539.1A 2015-01-28 2015-01-28 Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode Pending CN104577126A (en)

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CN108301017A (en) * 2018-03-12 2018-07-20 郑州大学 A kind of water electrolysis hydrogen production catalyst Co9S8@CNT and preparation method thereof
CN109411239A (en) * 2018-08-22 2019-03-01 浙江师范大学 A kind of Cu doping Co for supercapacitor9S8Nano-tube array simple and convenient process for preparing
CN111682180A (en) * 2020-06-19 2020-09-18 西安建筑科技大学 Preparation and application of porous foamy graphene oxide coated Co9S8@ S composite material
CN113381030A (en) * 2021-05-13 2021-09-10 三峡大学 Co9S8Preparation method of-Co @ NCNTs composite electrode
CN114758903A (en) * 2022-04-14 2022-07-15 南京信息工程大学 Preparation method of supercapacitor electrode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANLI ZHOU等: ""Multiwalled carbon nanotube@a-C@Co9S8 nanocomposites: a high-capacity and long-life anode material for advanced lithium ion batteries"", 《NANOSCALE》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105789584A (en) * 2016-03-27 2016-07-20 华南理工大学 Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material
CN108301017A (en) * 2018-03-12 2018-07-20 郑州大学 A kind of water electrolysis hydrogen production catalyst Co9S8@CNT and preparation method thereof
CN109411239A (en) * 2018-08-22 2019-03-01 浙江师范大学 A kind of Cu doping Co for supercapacitor9S8Nano-tube array simple and convenient process for preparing
CN109411239B (en) * 2018-08-22 2023-10-03 浙江师范大学 Cu doped Co for super capacitor 9 S 8 Simple preparation method of nanotube array
CN111682180A (en) * 2020-06-19 2020-09-18 西安建筑科技大学 Preparation and application of porous foamy graphene oxide coated Co9S8@ S composite material
CN113381030A (en) * 2021-05-13 2021-09-10 三峡大学 Co9S8Preparation method of-Co @ NCNTs composite electrode
CN113381030B (en) * 2021-05-13 2022-08-05 三峡大学 Co 9 S 8 Preparation method of-Co @ NCNTs composite electrode
CN114758903A (en) * 2022-04-14 2022-07-15 南京信息工程大学 Preparation method of supercapacitor electrode material

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