CN106784692B - Graphene array loads lithium titanate/carbon/carbon nano tube composite array electrode material and its preparation method and application - Google Patents
Graphene array loads lithium titanate/carbon/carbon nano tube composite array electrode material and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 72
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 65
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 45
- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000004744 fabric Substances 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 229910052786 argon Inorganic materials 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000005334 plasma enhanced chemical vapour deposition Methods 0.000 claims abstract 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 229910009866 Ti5O12 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910011229 Li7Ti5O12 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 235000010357 aspartame Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0428—Chemical vapour deposition
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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
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Abstract
The invention discloses a kind of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode materials and its preparation method and application, this method comprises: using microwave plasma enhanced chemical vapour deposition technique on carbon cloth vertical-growth graphene array；TiO is grown in resulting graphene array using technique for atomic layer deposition2；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 later, drying and calcination；Using chemical vapour deposition technique, using acetylene as carbon source, under the atmosphere of hydrogen and argon gas, carbon nanotube is grown on graphene array load lithium titanate composite array electrode, obtains 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, there is excellent high rate capability and cyclical stability.
Description
Technical field
The present invention relates to technical field of lithium ion battery electrode, and in particular to a kind of graphene array load metatitanic acid
Lithium/carbon nanotube composite array electrode material and its preparation method and application.
Background technique
Currently, the continuous consumption of the energy, the increasingly protrusion of environmental problem, green energy resource is with economic continuous development
Through becoming hot spot concerned by people.Electric energy is because its storage is convenient, and no pollution to the environment, it is considered to be the 21 century ideal energy
One of.And storage device of the lithium ion battery as electric energy, have that energy density is high, has extended cycle life and environmental-friendly etc. excellent
Point, and large-scale commercialization has been obtained.In recent years, with the development of technology, lithium ion battery electrode material is ground
Study carefully increasingly emphasis high rate capability.However, now commercialized graphite cathode because of low ion and electron-transport efficiency, and
It is not able to satisfy this demand.Therefore, it is badly in need of developing a kind of lithium ion battery negative material with super-quick charging discharge performance.
In lithium ion battery negative material, lithium titanate has fabulous cyclical stability as a kind of zero strain material
With high rate capability, theoretical capacity is 175mAh g-1.In addition, its charge and discharge platform with 1.55V, it is possible to prevente effectively from lithium
The formation of dendrite and SEI film (solid electrolyte interface, solid electrolyte interface film) improves safety
Energy.The storage lithium process of lithium titanate is to pass through Li4Ti5O12With Li7Ti5O12Between phase transition complete, cubical expansivity is only
0.2%.Therefore, it in de- lithium process of intercalation, is not likely to lead to material cracks because of volume expansion and make capacitance loss, to have
There is preferable cyclical stability.But lower electronic conductivity limits its application under high current charge-discharge.So
How to improve the electronic conductivity of lithium titanate is the key that it as lithium ion battery negative material using section's knowledge urgently to be resolved
Topic.
Currently, by by lithium titanate and other conductive materials it is compound and by its nanosizing be improve its electronic conductivity
A kind of effective way.Conductive material generally compound with it is carbon material, such as graphene, carbon nanotube, active carbon.Carbon materials
Material provides a conducting matrix grain for lithium titanate, entire electrodic electron conductivity is improved, so as to improve high rate capability.
Summary of the invention
The object of the present invention is to provide a kind of graphene arrays to 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, has excellent high rate capability
And cyclical stability.
A kind of preparation method of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material, including it is 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 step (1) resulting graphene array using atomic layer deposition (ALD) technology2, hung down
Straight graphene-supported titanium dioxide combination electrode material；
(3) lithium hydroxide is dissolved in water, forms solution A；
(4) the resulting vertical graphene-supported titanium dioxide combination electrode material of step (2) is placed in solution A, is carried out
Hydro-thermal reaction is washed, drying and calcination later, obtains the array-supported lithium titanate (Li of graphene (VG)4Ti5O12, LTO) and multiple
Close array electrode, i.e. VG/LTO composite array electrode；
(5) chemical vapor deposition (CVD) technology is utilized, using acetylene as carbon source, under the atmosphere of hydrogen and argon gas, in step
(4) carbon nanotube (CNTs) is grown on resulting graphene array load lithium titanate composite array electrode, obtains graphene array
Load lithium titanate/carbon/carbon nano tube composite array electrode material, i.e. VG/LTO-CNTs composite array electrode material.
It is used as the preferred technical solution of the present invention below:
In step (1), vertically given birth on carbon cloth using microwave plasma enhanced chemical vapor deposition (MPECVD) technology
Long graphene array, actual conditions are as follows: reaction atmosphere is methane and hydrogen, and the flow of methane is 30-50sccm, the flow of hydrogen
For 40-60sccm, reaction temperature and time are 400-500 DEG C and 1-3 hour respectively.
In step (2), TiO is grown in step (1) resulting graphene array using atomic layer deposition (ALD) technology2,
Actual conditions are as follows: the source Ti is titanium tetrachloride, and the source O is water, and reaction temperature is 200-300 DEG C.
In step (3), lithium hydroxide concentration is 1-3molL in the solution A-1。
In step (4), 80-90 DEG C progress hydro-thermal reaction 1-2 hours.
Protective atmosphere is argon gas when 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 5-10sccm, the flow of argon gas is 50-100sccm,
Reaction temperature and time are respectively 600-700 DEG C and 1-10 minute.
The graphene array loads lithium titanate/carbon/carbon nano tube composite array electrode material, including carbon cloth, vertical-growth
On the carbon cloth graphene array, the lithium titanate nano particle that is coated in the graphene array and be interweaved ground
The carbon nanotube being grown on the lithium titanate nano particle.Lithium titanate nano particle is equably covered on vertical graphene array
On.Then, carbon nanotube 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 overall thickness is 0.4~0.8mm, is 0.5~0.65mm further preferably.
The 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, carbon nanotube
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 carbon nanotube 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, carbon nanotube
Load capacity be 0.5mg cm-2。
The present invention is by the way that with vertical graphene (VG), for conducting matrix grain, atomic layer deposition combines the embedding lithium method of chemistry resulting
Lithium titanate (Li4Ti5O12, LTO) and nano particle is equably covered on vertical graphene, and carbon nanotube (CNTs) is as cladding
Conductive network construct VG/LTO-CNTs nucleocapsid array electrode material, thus obtain overlength cycle life and excellent high magnification
Performance.
Graphene array loads lithium titanate/carbon/carbon nano tube composite array electrode material as lithium ion battery electrode material,
Obtained VG/LTO-CNTs film is cut into pieces as lithium ion cell electrode, i.e., to electrode, assembled battery.Diaphragm is micro-
Hole polypropylene screen, electrolyte is to 1molL-1LiPF6For solute, the ethylene carbonate (EC) and carbonic acid two that volume ratio is 1:1
Methyl esters (DMC) is solvent, is lithium piece to electrode, and battery is assembled in the glove box full of argon gas and completed.
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 negative electrode of lithium ion battery in 25 ± 1 DEG C of environment.
Compared with prior art, the present invention has the advantage that
(1) present invention prepares lithium titanate using technique for atomic layer deposition combination hydro-thermal lithiumation, ensure that lithium titanate equably
It is covered in substrate, and not easy to reunite in forming process, scale is controllable, to ensure that electrode performance is stablized.
(2) VG/LTO-CNTs prepared by is flexible nucleocapsid array interlayer structure, and in bottom, vertical graphene provides one
A conducting matrix grain, at top, carbon nanotube provides the conductive network that interweaves to obtain, so that the transmission for electronics provides quickly
Channel.
(3) the VG/LTO-CNTs composite material prepared by, vertical graphene have certain machinery strong as conducting matrix grain
Degree is conducive to the ion exchange between electrode and electrolyte with certain gap between graphene film and piece.In addition, graphene film
Bigger serface can provide more active sites, and very thin thickness is conducive to the quick transmission of electronic and ionic, to improve
The chemical property of entire electrode.
(4) VG/LTO-CNTs prepared by is prepared into negative electrode of lithium ion battery, is the membrane electrode of self-supporting, directly cuts
It cuts 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 material that the present invention prepares has soft
Property support, ultra-high magnifications performance (100C still has 75% theoretical capacity) and overlength cyclical stability (still have after recycling for 10000 times
89.5% initial capacity) the advantages that, the composite material of the building 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.
Detailed description of the invention
Fig. 1 is the mistake that graphene array prepared by embodiment 1 loads lithium titanate/carbon/carbon nano tube composite array electrode material
Journey schematic diagram, wherein (a) is the vertical graphene (VG) being grown on carbon cloth in Fig. 1, (b) is VG/LTO array structure, (c)
For VG/LTO-CNTs array structure；
Fig. 2 (a), (b) are that the graphene array prepared in embodiment 1 loads lithium titanate/carbon/carbon nano tube composite array electrode
The photo in kind of material；
Fig. 3 is that the graphene array prepared in embodiment 1 loads lithium titanate/carbon/carbon nano tube composite array electrode material
XRD spectrum；
Fig. 4 is the different multiples SEM figure of the VG/LTO array prepared in embodiment 1, wherein (a) is high magnification in Fig. 4
SEM figure, (b) schemes for low range SEM；
Fig. 5 is the VG/LTO-CNTs array different multiples SEM figure prepared in embodiment 1, wherein (a) is high power in Fig. 5
Rate SEM figure, (b) schemes for low range SEM.
Fig. 6 is that the graphene array prepared in embodiment 1 loads the electricity of lithium titanate/carbon/carbon nano tube composite array electrode material
Pond high rate performance.
Fig. 7 is that the graphene array prepared in embodiment 1 loads the electricity of lithium titanate/carbon/carbon nano tube composite array electrode material
Pond cycle performance.
Specific embodiment
The present invention is made below by embodiment and further being illustrated, but the invention is not limited to 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 are passed through, reacts 1 at a temperature of 400 DEG C
Hour.
(2) TiO is grown on the resulting vertical graphene of step (1) using atomic layer deposition (ALD) technology2, the source Ti and O
Source is titanium tetrachloride and water respectively, and reaction temperature is 200 DEG C.
(3) 2.9372g lithium hydroxide is dissolved in 70mL water, forms solution A, concentration of the lithium hydroxide in solution A
For 1molL-1。
(4) the resulting vertical graphene-supported titanium dioxide combination electrode material of step (2) is placed in solution A, 80
Hydro-thermal reaction 1 hour, is washed later and is dried at DEG C, finally in argon atmosphere, is calcined 2 hours, is obtained at 500 DEG C
To VG/LTO composite array structure；
(5) chemical vapor deposition (CVD) technology is utilized, by Li obtained by step (4)4Ti5O12/ VG composite array is placed in tubular type
In furnace, it is passed through the acetylene of 2sccm, the hydrogen of 5sccm and 50sccm argon gas, 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 VG/LTO-CNTs composite material chip drying obtained by step (5) as electrode material, diaphragm is poly- for micropore
Propylene film, electrolyte is to 1mol L-1LiPF6For solute, volume ratio is the ethylene carbonate (EC) and dimethyl carbonate of 1:1
(DMC) it is solvent, is lithium piece to electrode, battery is assembled in the glove box full of argon gas and completed.
The method preparation graphene array load metatitanic acid combined in conjunction with chemical vapor deposition, atomic layer deposition and hydro-thermal
Lithium/carbon nanotube composite array electrode material preparation process 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 structure, (c) is VG/LTO-CNTs array structure.The pictorial diagram of this electrode is such as
Fig. 2 (a) and (b) are shown, and as seen from the figure, the present embodiment 1 prepares the spy that VG/LTO-CNTs combination electrode has flexible self-supporting
Point, with a thickness of 0.57mm.
Fig. 3 is the XRD spectrum that the present embodiment 1 prepares VG/LTO-CNTs composite material.As seen from Figure 3 prepared by the present embodiment 1
VG/LTO-CNTs composite material have lithium titanate (JCPDS 49-0207) characteristic peak and graphene (JCPDS 65-6212)
Characteristic peak.Fig. 4 is that the SEM of VG/LTO nucleocapsid array schemes, and the lithium titanate particle of diameter about 10-20nm is equably covered on vertically
On graphene, thickness is about 30-40nm.Fig. 5 is the SEM figure for having grown the VG/LTO-CNTs composite material after carbon nanotube, carbon
Nanotube is covered in VG/LTO nanometer sheet with interweaving, and forms network structure.In VG/LTO-CNTs combination electrode, 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 carbon nanotube is 0.5mg cm-2。
Assembled lithium ion battery is subjected to constant current charge-discharge test, charging/discharging voltage section is 2.5V~1.0V.
Fig. 6 is the multiplying power figure of lithium ion battery, it can be seen from the figure 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
Excellent high rate performance out.It can be seen that lithium ion battery under the high current density of 20C from the cycle performance figure of Fig. 7 to recycle
Still there is 89.5% capacity retention ratio after 10000 times, coulombic efficiency maintains 99% or more, 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 are passed through, it is small that 2 are reacted at a temperature of 450 DEG C
When.
(2) TiO is grown on the resulting vertical graphene of step (1) using atomic layer deposition (ALD) technology2, the source Ti and O
Source is titanium tetrachloride and water respectively, and reaction temperature is 250 DEG C.
(3) 5.8744g lithium hydroxide is dissolved in 70mL water, forms solution A, concentration of the lithium hydroxide in solution A
For 2molL-1。
(4) the resulting vertical graphene-supported titanium dioxide combination electrode material of step (2) is placed in solution A, 85
Hydro-thermal reaction 1.5 hours, are washed later and are dried at DEG C, and finally in argon atmosphere, it is small that 2.5 are calcined at 550 DEG C
When, obtain VG/LTO composite array structure；
(5) chemical vapor deposition (CVD) technology is utilized, by Li obtained by step (4)4Ti5O12/ VG composite array is placed in tubular type
In furnace, it is passed through the acetylene of 5sccm, the hydrogen of 7sccm and 80sccm argon gas, 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 VG/LTO-CNTs composite material chip drying obtained by step (5) as electrode material, diaphragm is poly- for micropore
Propylene film, electrolyte is to 1mol L-1LiPF6For solute, volume ratio is the ethylene carbonate (EC) and dimethyl carbonate of 1:1
(DMC) it is solvent, is lithium piece to electrode, battery is assembled in the glove box full of argon gas and completed.
Assembled lithium ion battery is subjected to constant current charge-discharge test, charging/discharging voltage section is 2.5V~1.0V.
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
Still there is 88% capacity retention ratio after recycling 10000 times under current density, coulombic efficiency maintains 99% or more, 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 are passed through, it is small that 3 are reacted at a temperature of 500 DEG C
When.
(2) TiO is grown on the resulting vertical graphene of step (1) using atomic layer deposition (ALD) technology2, the source Ti and O
Source is titanium tetrachloride and water respectively, and reaction temperature is 300 DEG C.
(3) 8.8116g lithium hydroxide is dissolved in 70mL water, forms solution A, concentration of the lithium hydroxide in solution A
For 3molL-1。
(4) the resulting vertical graphene-supported titanium dioxide combination electrode material of step (2) is placed in solution A, 90
Hydro-thermal reaction 2 hours, are washed later and are dried at DEG C, finally in argon atmosphere, are calcined 3 hours, are obtained at 600 DEG C
To VG/LTO composite array structure；
(5) chemical vapor deposition (CVD) technology is utilized, by Li obtained by step (4)4Ti5O12/ VG composite array is placed in tubular type
In furnace, it is passed through the acetylene of 10sccm, the hydrogen of 10sccm and 100sccm argon gas, 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 VG/LTO-CNTs composite material chip drying obtained by step (5) as electrode material, diaphragm is poly- for micropore
Propylene film, electrolyte is to 1mol L-1LiPF6For solute, volume ratio is the ethylene carbonate (EC) and dimethyl carbonate of 1:1
(DMC) it is solvent, is lithium piece to electrode, battery is assembled in the glove box full of argon gas and completed.
Assembled lithium ion battery is subjected to constant current charge-discharge test, charging/discharging voltage section is 2.5V~1.0V.
Fig. 6 is the multiplying power figure of lithium ion battery, it can be seen from the figure 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.It can be seen that lithium ion battery under the high current density of 20C from the cycle performance figure of Fig. 7 to follow
Still there is 86% capacity retention ratio after ring 10000 times, coulombic efficiency maintains 99% or more, shows the cyclical stability of superelevation
With the cycle life of overlength.
One of Examples 1 to 3 graphene array loads lithium titanate/carbon/carbon nano tube composite array as li-ion electrode
It is as shown in table 1 in maximum discharge capacity of the difference under current density after material is assembled into lithium ion battery:
Table 1
Claims (9)
1. a kind of preparation method of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material, which is characterized in that
The following steps are included:
(1) microwave plasma enhanced chemical vapour deposition technique vertical-growth graphene array on carbon cloth is utilized；
(2) TiO is grown in step (1) resulting graphene array using technique for atomic layer deposition2, it is negative to obtain vertical graphene
Carrying of titanium dioxide combination electrode material；Actual conditions are as follows: the source Ti is titanium tetrachloride, and the source O is water, and reaction temperature is 200-300 DEG C；
(3) lithium hydroxide is dissolved in water, forms solution A；
(4) the resulting vertical graphene-supported titanium dioxide combination electrode material of step (2) is placed in solution A, carries out hydro-thermal
Reaction, is washed, drying and calcination later, obtains graphene array load lithium titanate composite array electrode；
(5) chemical vapour deposition technique is utilized, it is resulting in step (4) under the atmosphere of hydrogen and argon gas using acetylene as carbon source
Carbon nanotube is grown on graphene array load lithium titanate composite array electrode, graphene array load lithium titanate/carbon is obtained and receives
Mitron composite array electrode material.
2. the preparation of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material according to claim 1
Method, which is characterized in that in step (1), vertically given birth on carbon cloth using microwave plasma enhanced chemical vapour deposition technique
Long graphene array, actual conditions are as follows: reaction atmosphere is methane and hydrogen, and the flow of methane is 30-50sccm, the flow of hydrogen
For 40-60sccm, reaction temperature and time are 400-500 DEG C and 1-3 hour respectively.
3. the preparation of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material according to claim 1
Method, which is characterized in that in step (3), lithium hydroxide concentration is 1-3molL in the solution A-1。
4. the preparation of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material according to claim 1
Method, which is characterized in that in step (4), 80-90 DEG C progress hydro-thermal reaction 1-2 hours.
5. the preparation of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material according to claim 1
Method, which is characterized in that in step (4), protective atmosphere is argon gas when calcining, and reaction temperature is 500-600 DEG C, and the reaction time is
2-3 hours.
6. the preparation of graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material according to claim 1
Method, which is characterized in that in step (5), the flow of acetylene is 2-10sccm, and hydrogen 5-10sccm, the flow of argon gas is 50-
100sccm, reaction temperature and time are respectively 600-700 DEG C and 1-10 minute.
7. the graphene array of described in any item preparation method preparations loads lithium titanate/carbon/carbon nano tube according to claim 1~6
Composite array electrode material.
8. graphene array according to claim 7 loads lithium titanate/carbon/carbon nano tube composite array electrode material, feature
It is, including carbon cloth, vertical-growth in the graphene array on the carbon cloth, the lithium titanate that is coated in the graphene array
Nano particle and the carbon nanotube being grown in being interweaved on the lithium titanate nano particle.
9. graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material according to claim 7 or 8 is being made
For the application of lithium ion battery electrode material.
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