CN106784692A - Graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material and its preparation method and application - Google Patents

Graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material and its preparation method and application Download PDF

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CN106784692A
CN106784692A CN201611205948.6A CN201611205948A CN106784692A CN 106784692 A CN106784692 A CN 106784692A CN 201611205948 A CN201611205948 A CN 201611205948A CN 106784692 A CN106784692 A CN 106784692A
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carbon
array
graphene
electrode
lithium titanate
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CN106784692B (en
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夏新辉
姚珠君
涂江平
王秀丽
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Zhejiang University ZJU
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0421Methods of deposition of the material involving vapour deposition
    • H01M4/0428Chemical vapour deposition
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material and its preparation method and application, the method includes:Using microwave plasma enhanced chemical vapour deposition technique on carbon cloth vertical-growth graphene array;Using technique for atomic layer deposition TiO is grown in the graphene array of gained2;Lithium hydroxide is dissolved in water, solution A is formed;Vertical graphene-supported titanium dioxide combination electrode material is placed in solution A, hydro-thermal reaction is carried out, is washed afterwards, drying and calcination;Using chemical vapour deposition technique, with acetylene as carbon source, under the atmosphere of hydrogen and argon gas, CNT is grown on graphene array load lithium titanate composite array electrode, obtain graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material.When the electrode material is used for lithium ion battery negative material, with excellent high rate capability and cyclical stability.

Description

Graphene array loads lithium titanate/carbon/carbon nano tube composite array electrode material and its system Preparation Method and application
Technical field
The present invention relates to technical field of lithium ion battery electrode, and in particular to a kind of graphene array loads metatitanic acid Lithium/CNT composite array electrode material and its preparation method and application.
Background technology
At present, as economic continues to develop, the continuous consumption of the energy, the increasingly protrusion of environmental problem, green energy resource is Through as focus of concern.Electric energy is convenient and environmentally safe because of its storage, it is considered to be the 21 century preferable energy One of.And lithium ion battery is used as the storage device of electric energy, with energy density it is high, have extended cycle life and environment-friendly etc. excellent Point, and have been obtained for large-scale commercialization.In recent years, with the development of technology, lithium ion battery electrode material grinds Study carefully and increasingly focus on high rate capability.However, present commercialized graphite cathode is because of low ion and electric transmission efficiency, and This demand can not be met.Therefore, it is badly in need of a kind of lithium ion battery negative material with super-quick charging discharge performance of exploitation.
In lithium ion battery negative material, lithium titanate as a kind of zero strain material, with fabulous cyclical stability With high rate capability, theoretical capacity is 175mAh g-1.In addition, it has the charge and discharge platform of 1.55V, it is possible to prevente effectively from lithium The formation of dendrite and SEI films (solid electrolyte interface, solid electrolyte interface film), improves security Energy.The storage lithium process of lithium titanate is by Li4Ti5O12With Li7Ti5O12Between phase in version complete, cubical expansivity is only 0.2%.Therefore, in de- lithium process of intercalation, less can cause material cracks because of volumetric expansion and make capacitance loss, so as to have There is preferable cyclical stability.But, relatively low electronic conductivity limits its application under high current charge-discharge.So, The electronic conductivity for how improving lithium titanate is it as lithium ion battery negative material application crucial section's knowledge urgently to be resolved hurrily Topic.
At present, by lithium titanate and other conductive materials are compound and be to improve its electronic conductivity by its nanosizing A kind of effective way.Conductive material typically compound with it is carbon material, such as Graphene, CNT, activated carbon.Carbon materials Expect to provide a conducting matrix grain for lithium titanate, whole electrodic electron conductance is improve, so as to improve high rate capability.
The content of the invention
Object of the present invention is to provide a kind of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material Material and its preparation method and application, when the electrode material is used for lithium ion battery negative material, with excellent high rate capability And cyclical stability.
A kind of graphene array loads the preparation method of lithium titanate/carbon/carbon nano tube composite array electrode material, including following Step:
(1) microwave plasma enhanced chemical vapor deposition (MPECVD) technology vertical-growth Graphene on carbon cloth is utilized Array;
(2) TiO is grown in the graphene array obtained by step (1) using ald (ALD) technology2, hung down Straight graphene-supported titanium dioxide combination electrode material;
(3) lithium hydroxide is dissolved in water, forms solution A;
(4) the vertical graphene-supported titanium dioxide combination electrode material obtained by step (2) is placed in solution A, is carried out Hydro-thermal reaction, is washed, drying and calcination afterwards, obtains the array-supported lithium titanate (Li of Graphene (VG)4Ti5O12, LTO) and it is multiple Close array electrode, i.e. VG/LTO composite arrays electrode;
(5) chemical vapor deposition (CVD) technology is utilized, with acetylene as carbon source, under the atmosphere of hydrogen and argon gas, in step (4) CNT (CNTs) is grown on the graphene array load lithium titanate composite array electrode obtained by, graphene array is obtained Load lithium titanate/carbon/carbon nano tube composite array electrode material, i.e. VG/LTO-CNTs composite arrays electrode material.
It is following as the preferred technical solution of the present invention:
In step (1), vertically given birth on carbon cloth using microwave plasma enhanced chemical vapor deposition (MPECVD) technology Graphene array long, actual conditions is:Reaction atmosphere is methane and hydrogen, and the flow of methane is 30-50sccm, the flow of hydrogen It is 40-60sccm, reaction temperature and time are respectively 400-500 DEG C and 1-3 hour.
In step (2), TiO is grown in the graphene array obtained by step (1) using ald (ALD) technology2, Actual conditions is:Ti sources are titanium tetrachloride, and O sources are water, and reaction temperature is 200-300 DEG C.
In step (3), lithium hydroxide concentration is 1-3molL in described solution A-1
In step (4), carried out at 80-90 DEG C hydro-thermal reaction 1-2 hours.
Protective atmosphere is argon gas during calcining, and reaction temperature is 500-600 DEG C, and the reaction time is 2-3 hours.
In step (5), the flow of acetylene is 2-10sccm, and hydrogen is 5-10sccm, and the flow of argon gas is 50-100sccm, Reaction temperature is respectively 600-700 DEG C and 1-10 minute with the time.
Described graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material, including carbon cloth, vertical-growth Graphene array on the carbon cloth, the lithium titanate nano particle being coated in the graphene array and it is interweaved ground It is grown in the CNT on the lithium titanate nano particle.Lithium titanate nano particle is equably covered in vertical graphene array On.Then, CNT is grown on lithium titanate nano particle with being interweaved, and obtains graphene array load lithium titanate/carbon Nanometer tube combination electrode material, is sheet, and gross thickness is 0.4~0.8mm, is 0.5~0.65mm further preferably.
Described graphene array load lithium titanate/carbon/carbon nano tube composite electrode material is calculated with unit area, Graphene The load capacity of array is 0.3~0.7mg cm-2, the load capacity of lithium titanate nano particle is 0.5~1.5mg cm-2, CNT Load capacity be 0.3~0.7mg cm-2.Further preferably, the load capacity of graphene array is 0.4~0.6mg cm-2, metatitanic acid The load capacity of lithium nano particle is 0.8~1.2mg cm-2, the load capacity of CNT is 0.4~0.6mg cm-2.Further It is preferred that, the load capacity of graphene array is 0.5mg cm-2, the load capacity of lithium titanate nano particle is 1mg cm-2, CNT Load capacity be 0.5mg cm-2
The present invention is by the way that with vertical Graphene (VG), as conducting matrix grain, ald is combined obtained by chemical embedding lithium method Lithium titanate (Li4Ti5O12, LTO) and nano particle is equably covered on vertical Graphene, and CNT (CNTs) is used as cladding Conductive network builds VG/LTO-CNTs nucleocapsid array electrode materials, so as to obtain the cycle life and excellent high magnification of overlength Performance.
Graphene array loads lithium titanate/carbon/carbon nano tube composite array electrode material as lithium ion battery electrode material, The VG/LTO-CNTs films that will be obtained are cut into pieces as lithium ion cell electrode, i.e., to electrode, assembled battery.Barrier film is micro- Hole polypropylene screen, electrolyte is used to 1molL-1LiPF6It is solute, volume ratio is 1:1 ethylene carbonate (EC) and carbonic acid two Methyl esters (DMC) is solvent, is lithium piece to electrode, and battery assembles completion in the glove box full of argon gas.
The lithium ion battery that assembles carries out constant current charge-discharge test after placing 12 hours, charging/discharging voltage be 2.5V~ 1.0V, measures capacity, multiplying power property and the charge-discharge performance of lithium ion battery negative in 25 ± 1 DEG C of environment.
Compared with prior art, the invention has the advantages that:
(1) present invention prepares lithium titanate using technique for atomic layer deposition combination hydro-thermal lithiumation, it is ensured that lithium titanate is equably It is covered in substrate, and is difficult to reunite in forming process, yardstick is controllable, so as to ensure that electrode performance stabilization.
(2) VG/LTO-CNTs prepared by is flexible nucleocapsid array interlayer structure, and in bottom, vertical Graphene provides one Individual conducting matrix grain, at top, CNT is there is provided the conductive network that interweaves to obtain, so that for the transmission of electronics is provided quickly Passage.
(3) the VG/LTO-CNTs composites prepared by, vertical Graphene has certain machinery strong as conducting matrix grain Degree, has certain space beneficial to the ion exchange between electrode and electrolyte between graphene film and piece.In addition, graphene film Bigger serface can provide more avtive spots, and very thin thickness is conducive to the quick transmission of electronic and ionic, so as to improve The chemical property of whole electrode.
(4) VG/LTO-CNTs prepared by is prepared into lithium ion battery negative, is the membrane electrode of self-supporting, directly cuts Cut and can be used as electrode, eliminate the tedious steps of slurry preparation.
(5) the sandwich nucleocapsid array structure VG/LTO-CNTs lithium ion battery negative materials that the present invention is prepared have soft Property support, ultra-high magnifications performance (100C still has 75% theoretical capacity) and overlength cyclical stability (still have after circulating for 10000 times 89.5% initial capacity) the advantages of, the composite of the structure has excellent high power as lithium ion battery negative material The cycle life of rate performance and overlength, has superior application prospect in fast charging and discharging field.
Brief description of the drawings
Fig. 1 is the mistake of the graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material prepared by embodiment 1 Journey schematic diagram, wherein, (a) is the vertical Graphene (VG) being grown on carbon cloth in Fig. 1, and (b) is VG/LTO array structures, (c) It is VG/LTO-CNTs array structures;
Fig. 2 (a), (b) are the graphene array load lithium titanate/carbon/carbon nano tube composite array electrode of preparation in embodiment 1 The photo in kind of material;
Fig. 3 is the graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material of preparation in embodiment 1 XRD spectrum;
Fig. 4 is the different multiples SEM figures of the VG/LTO arrays of preparation in embodiment 1, wherein, (a) is high magnification in Fig. 4 SEM schemes, and (b) schemes for low range SEM;
Fig. 5 is the VG/LTO-CNTs array different multiples SEM figures of preparation in embodiment 1, wherein, (a) is high power in Fig. 5 Rate SEM schemes, and (b) schemes for low range SEM.
Fig. 6 is the electricity of the graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material of preparation in embodiment 1 Pond high rate performance.
Fig. 7 is the electricity of the graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material of preparation in embodiment 1 Pond cycle performance.
Specific embodiment
The present invention is made below by embodiment further being illustrated, but the invention is not limited in following realities Example.
Embodiment 1
(1) microwave plasma enhanced chemical vapor deposition (MPECVD) technology growth of vertical Graphene on carbon cloth is utilized (VG) array.Carbon cloth is placed in tube furnace, the methane of 30sccm and the hydrogen of 40sccm is passed through, 1 is reacted at a temperature of 400 DEG C Hour.
(2) TiO is grown on the vertical Graphene obtained by step (1) using ald (ALD) technology2, Ti sources and O Source is respectively titanium tetrachloride and water, and reaction temperature is 200 DEG C.
(3) 2.9372g lithium hydroxides are dissolved in 70mL water, form solution A, concentration of the lithium hydroxide in solution A It is 1molL-1
(4) the vertical graphene-supported titanium dioxide combination electrode material obtained by step (2) is placed in solution A, 80 Hydro-thermal reaction 1 hour, is washed and is dried afterwards at DEG C, finally in argon atmosphere, is calcined 2 hours at 500 DEG C, is obtained To VG/LTO composite array structures;
(5) chemical vapor deposition (CVD) technology is utilized, by step (4) gained Li4Ti5O12/ VG composite arrays are placed in tubular type In stove, the acetylene of 2sccm, the hydrogen of 5sccm and 50sccm argon gas are passed through, 1 minute growth carbon nanometer is reacted at a temperature of 600 DEG C Pipe, finally obtains graphene array load lithium titanate/carbon/carbon nano tube composite array electrode, i.e. VG/LTO-CNTs.
(6) using step (5) gained VG/LTO-CNTs composites chip drying as electrode material, barrier film is poly- for micropore Propylene film, electrolyte is used to 1mol L-1LiPF6It is solute, volume ratio is 1:1 ethylene carbonate (EC) and dimethyl carbonate (DMC) it is solvent, is lithium piece to electrode, battery assembles completion in the glove box full of argon gas.
The method being combined with reference to chemical vapor deposition, ald and hydro-thermal prepares graphene array load metatitanic acid The preparation process of lithium/CNT composite array electrode material is as shown in figure 1, wherein, (a) is to be grown on carbon cloth in Fig. 1 Vertical Graphene (VG), (b) is VG/LTO array structures, and (c) is VG/LTO-CNTs array structures.The pictorial diagram of this electrode is such as Shown in Fig. 2 (a) and (b), as seen from the figure, the present embodiment 1 prepares VG/LTO-CNTs combination electrodes has the spy of flexible self-supporting Point, thickness is 0.57mm.
Fig. 3 is the XRD spectrum that the present embodiment 1 prepares VG/LTO-CNTs composites.As seen from Figure 3 prepared by the present embodiment 1 VG/LTO-CNTs composites there is the characteristic peak and Graphene (JCPDS 65-6212) of lithium titanate (JCPDS 49-0207) Characteristic peak.Fig. 4 schemes for the SEM of VG/LTO nucleocapsid arrays, and the lithium titanate particle of diameter about 10-20nm is equably covered in vertically On Graphene, thickness is about 30-40nm.Fig. 5 is the SEM figures for having grown the VG/LTO-CNTs composites after CNT, carbon Nanotube is covered in VG/LTO nanometer sheets with interweaving, and forms network structure.In VG/LTO-CNTs combination electrodes, vertical graphite The load capacity of alkene is 0.5mg cm-2, the load capacity of metatitanic acid lithium layer is 1mg cm-2, the load capacity of CNT is 0.5mg cm-2
The lithium ion battery that will be assembled carries out constant current charge-discharge test, and it is 2.5V~1.0V that charging/discharging voltage is interval. Fig. 6 is the multiplying power figure of lithium ion battery, it can be seen that electric current of the lithium ion battery in 1C, 10C, 20C, 50C and 100C Capacity is respectively 171mA h g under density-1、151mA h g-1、150mA h g-1、146mA h g-1With 131mAh g-1, performance Go out excellent high rate performance.Lithium ion battery is can be seen that from the cycle performance figure of Fig. 7 to be circulated under the high current density of 20C Still there is 89.5% capability retention after 10000 times, coulombic efficiency maintains more than 99%, shows the cyclical stability of superelevation With the cycle life of overlength.
Embodiment 2
(1) microwave plasma enhanced chemical vapor deposition (MPECVD) technology growth of vertical Graphene on carbon cloth is utilized Array.Carbon cloth is placed in tube furnace, the methane of 40sccm and the hydrogen of 50sccm is passed through, 2 is reacted at a temperature of 450 DEG C small When.
(2) TiO is grown on the vertical Graphene obtained by step (1) using ald (ALD) technology2, Ti sources and O Source is respectively titanium tetrachloride and water, and reaction temperature is 250 DEG C.
(3) 5.8744g lithium hydroxides are dissolved in 70mL water, form solution A, concentration of the lithium hydroxide in solution A It is 2molL-1
(4) the vertical graphene-supported titanium dioxide combination electrode material obtained by step (2) is placed in solution A, 85 Hydro-thermal reaction 1.5 hours, are washed and are dried afterwards at DEG C, finally in argon atmosphere, 2.5 are calcined at 550 DEG C small When, obtain VG/LTO composite array structures;
(5) chemical vapor deposition (CVD) technology is utilized, by step (4) gained Li4Ti5O12/ VG composite arrays are placed in tubular type In stove, the acetylene of 5sccm, the hydrogen of 7sccm and 80sccm argon gas are passed through, 5 minutes growth carbon nanometers are reacted at a temperature of 650 DEG C Pipe, finally obtains graphene array load lithium titanate/carbon/carbon nano tube composite array electrode, i.e. VG/LTO-CNTs.
(6) using step (5) gained VG/LTO-CNTs composites chip drying as electrode material, barrier film is poly- for micropore Propylene film, electrolyte is used to 1mol L-1LiPF6It is solute, volume ratio is 1:1 ethylene carbonate (EC) and dimethyl carbonate (DMC) it is solvent, is lithium piece to electrode, battery assembles completion in the glove box full of argon gas.
The lithium ion battery that will be assembled carries out constant current charge-discharge test, and it is 2.5V~1.0V that charging/discharging voltage is interval. Lithium ion battery capacity under the current density of 1C, 10C, 20C, 50C and 100C is respectively 171mA h g-1、150mA h g-1、 149mA h g-1、145mA h g-1With 129mA h g-1, show excellent high rate performance.Height electricity of the lithium ion battery in 20C The capability retention for still having 88% after 10000 times is circulated under current density, coulombic efficiency maintains more than 99%, shows superelevation The cycle life of cyclical stability and overlength.
Embodiment 3
(1) microwave plasma enhanced chemical vapor deposition (MPECVD) technology growth of vertical Graphene on carbon cloth is utilized Array.Carbon cloth is placed in tube furnace, the methane of 50sccm and the hydrogen of 60sccm is passed through, 3 is reacted at a temperature of 500 DEG C small When.
(2) TiO is grown on the vertical Graphene obtained by step (1) using ald (ALD) technology2, Ti sources and O Source is respectively titanium tetrachloride and water, and reaction temperature is 300 DEG C.
(3) 8.8116g lithium hydroxides are dissolved in 70mL water, form solution A, concentration of the lithium hydroxide in solution A It is 3molL-1
(4) the vertical graphene-supported titanium dioxide combination electrode material obtained by step (2) is placed in solution A, 90 Hydro-thermal reaction 2 hours, are washed and are dried afterwards at DEG C, finally in argon atmosphere, are calcined 3 hours at 600 DEG C, are obtained To VG/LTO composite array structures;
(5) chemical vapor deposition (CVD) technology is utilized, by step (4) gained Li4Ti5O12/ VG composite arrays are placed in tubular type In stove, the acetylene of 10sccm, the hydrogen of 10sccm and 100sccm argon gas are passed through, 10 minutes growth carbon is reacted at a temperature of 700 DEG C Nanotube, finally obtains graphene array load lithium titanate/carbon/carbon nano tube composite array electrode, i.e. VG/LTO-CNTs.
(6) using step (5) gained VG/LTO-CNTs composites chip drying as electrode material, barrier film is poly- for micropore Propylene film, electrolyte is used to 1mol L-1LiPF6It is solute, volume ratio is 1:1 ethylene carbonate (EC) and dimethyl carbonate (DMC) it is solvent, is lithium piece to electrode, battery assembles completion in the glove box full of argon gas.
The lithium ion battery that will be assembled carries out constant current charge-discharge test, and it is 2.5V~1.0V that charging/discharging voltage is interval. Fig. 6 is the multiplying power figure of lithium ion battery, it can be seen that electric current of the lithium ion battery in 1C, 10C, 20C, 50C and 100C Capacity is respectively 170mA h g under density-1、149mA h g-1、145mA h g-1、140mA h g-1With 123mA h g-1, table Reveal excellent high rate performance.Lithium ion battery is can be seen that from the cycle performance figure of Fig. 7 to be followed under the high current density of 20C Still there is 86% capability retention after ring 10000 times, coulombic efficiency maintains more than 99%, shows the cyclical stability of superelevation With the cycle life of overlength.
A kind of graphene array in embodiment 1~3 loads lithium titanate/carbon/carbon nano tube composite array as li-ion electrode Its maximum discharge capacity in difference under current density is as shown in table 1 after material is assembled into lithium ion battery:
Table 1

Claims (10)

1. a kind of graphene array loads the preparation method of lithium titanate/carbon/carbon nano tube composite array electrode material, it is characterised in that Comprise the following steps:
(1) microwave plasma enhanced chemical vapour deposition technique vertical-growth graphene array on carbon cloth is utilized;
(2) TiO is grown in the graphene array obtained by step (1) using technique for atomic layer deposition2, obtain vertical Graphene and bear Carrying of titanium dioxide combination electrode material;
(3) lithium hydroxide is dissolved in water, forms solution A;
(4) the vertical graphene-supported titanium dioxide combination electrode material obtained by step (2) is placed in solution A, carries out hydro-thermal Reaction, is washed, drying and calcination afterwards, obtains graphene array load lithium titanate composite array electrode;
(5) chemical vapour deposition technique is utilized, with acetylene as carbon source, under the atmosphere of hydrogen and argon gas, obtained by step (4) CNT is grown on graphene array load lithium titanate composite array electrode, graphene array load lithium titanate/carbon is obtained and is received Mitron composite array electrode material.
2. graphene array according to claim 1 loads the preparation of lithium titanate/carbon/carbon nano tube composite array electrode material Method, it is characterised in that in step (1), vertically given birth on carbon cloth using microwave plasma enhanced chemical vapour deposition technique Graphene array long, actual conditions is:Reaction atmosphere is methane and hydrogen, and the flow of methane is 30-50sccm, the flow of hydrogen It is 40-60sccm, reaction temperature and time are respectively 400-500 DEG C and 1-3 hour.
3. graphene array according to claim 1 loads the preparation of lithium titanate/carbon/carbon nano tube composite array electrode material Method, it is characterised in that in step (2), is grown using technique for atomic layer deposition in the graphene array obtained by step (1) TiO2, actual conditions is:Ti sources are titanium tetrachloride, and O sources are water, and reaction temperature is 200-300 DEG C.
4. graphene array according to claim 1 loads the preparation of lithium titanate/carbon/carbon nano tube composite array electrode material Method, it is characterised in that in step (3), lithium hydroxide concentration is 1-3molL in described solution A-1
5. graphene array according to claim 1 loads the preparation of lithium titanate/carbon/carbon nano tube composite array electrode material Method, it is characterised in that in step (4), is carried out hydro-thermal reaction 1-2 hours at 80-90 DEG C.
6. graphene array according to claim 1 loads the preparation of lithium titanate/carbon/carbon nano tube composite array electrode material Method, it is characterised in that in step (4), protective atmosphere is argon gas during calcining, and reaction temperature is 500-600 DEG C, and the reaction time is 2-3 hours.
7. graphene array according to claim 1 loads the preparation of lithium titanate/carbon/carbon nano tube composite array electrode material Method, it is characterised in that in step (5), the flow of acetylene is 2-10sccm, and hydrogen is 5-10sccm, and the flow of argon gas is 50- 100sccm, reaction temperature is respectively 600-700 DEG C and 1-10 minute with the time.
8. the graphene array load lithium titanate/carbon/carbon nano tube that prepared by the preparation method according to any one of claim 1~7 Composite array electrode material.
9. graphene array according to claim 8 loads lithium titanate/carbon/carbon nano tube composite array electrode material, its feature It is, including graphene array on the carbon cloth of carbon cloth, vertical-growth, the lithium titanate that is coated in the graphene array Nano particle and the CNT being grown in being interweaved on the lithium titanate nano particle.
10. graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material according to claim 8 or claim 9 exists As the application of lithium ion battery electrode material.
CN201611205948.6A 2016-12-23 2016-12-23 Graphene array loads lithium titanate/carbon/carbon nano tube composite array electrode material and its preparation method and application Active CN106784692B (en)

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CN107732205A (en) * 2017-10-18 2018-02-23 常州大学 A kind of method for preparing the flower-shaped lithium titanate composite anode material of sulfur and nitrogen co-doped carbon-coated nano
CN107785559A (en) * 2017-11-02 2018-03-09 徐军红 A kind of graphene lithium titanate composite material and preparation method thereof, mend lithium graphene lithium titanate thin film, lithium battery
CN107785559B (en) * 2017-11-02 2020-06-30 徐军红 Graphene-lithium titanate composite material, preparation method thereof, lithium-supplementing graphene-lithium titanate film and lithium battery
CN108335916A (en) * 2017-12-20 2018-07-27 肇庆市华师大光电产业研究院 A kind of multi-walled carbon nanotube@X combination electrodes and its preparation method and application
CN108649190A (en) * 2018-03-28 2018-10-12 浙江大学 Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application
CN108649190B (en) * 2018-03-28 2020-12-08 浙江大学 Vertical graphene/titanium niobium oxide/sulfur carbon composite material with three-dimensional porous array structure and preparation method and application thereof
CN109437290A (en) * 2018-10-09 2019-03-08 深圳大学 A kind of preparation method and lithium ion super capacitor of a lithium titanate nanobelt ball of string
CN109437290B (en) * 2018-10-09 2021-03-23 深圳大学 Preparation method of lithium titanate nanoribbon coil and lithium ion supercapacitor
CN109888229A (en) * 2019-03-01 2019-06-14 中山市华舜科技有限责任公司 A kind of preparation method of the lithium ion battery negative material based on lithium titanate coated graphite composite material
CN109888233A (en) * 2019-03-06 2019-06-14 广东轻工职业技术学院 It is a kind of can charge and discharge Grazing condition kalium ion battery, preparation method and application

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