CN104600269A - Method for preparing graphene/oxygen vacancy lithium titanate composite material - Google Patents

Method for preparing graphene/oxygen vacancy lithium titanate composite material Download PDF

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Publication number
CN104600269A
CN104600269A CN201510027552.6A CN201510027552A CN104600269A CN 104600269 A CN104600269 A CN 104600269A CN 201510027552 A CN201510027552 A CN 201510027552A CN 104600269 A CN104600269 A CN 104600269A
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parts
lithium titanate
lithium
graphene
oxygen vacancy
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常程康
史运伟
陈茜
邓玲
王永强
蔡元元
郭倩
石明明
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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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
    • H01M4/364Composites as mixtures
    • 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
    • H01M4/36Selection 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 method for preparing a graphene/oxygen vacancy lithium titanate composite material. The method comprises the following steps: mixing titanium dioxide and deionized water at a certain ratio while stirring, thereby obtaining a suspension; dissolving lithium hydroxide in the deionized water, thereby obtaining aqueous solution of the lithium hydroxide; mixing the aqueous solution of the lithium hydroxide with the titanium dioxide suspension; mixing the mixed solution with graphene oxide solution, performing ball milling in a stirring state to obtain a precursor solution, and performing spray drying; and calcining the dried product in vacuum at high temperature, thereby obtaining blue lithium titanate with oxygen vacancy. According to the method disclosed by the invention, graphene serves as a reducing agent and promotes production of oxygen vacancy in lithium titanate in the high-temperature calcining process, the conductivity of lithium titanate is effectively improved, the prepared product is uniform in particle size and unified in morphology and has stable charge and discharge performances, the process is simple, and large-scale production is easily realized.

Description

The preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material
Technical field
The invention belongs to technical field of material chemistry, particularly relate to a kind of Graphene/oxygen vacancy lithium titanate (Li4Ti5O12), specifically the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material.
Background technology
Along with the develop rapidly of global economy, also increasing to the consumption of resource, the crisis of energy field is day by day serious.Based on current serious energy crisis and pollution problem, countries in the world are all paid much attention to Development of EV, also development electric motor car are classified as important development direction in China's 863 Program.The main candidate of current driving force battery has Ni-MH battery, lithium ion battery and fuel cell.Based on the consideration of cost performance, lithium ion battery has larger advantage.
At present, commercial lithium ion battery negative material adopts various embedding lithium material with carbon element mostly.Reversible embedding can deviate from the key factor that lithium ion is the application of lithium ion battery success.In recent years, be exactly round the energy storage density how improving existing material substantially to the research of lithium ion battery negative material, reduce irreversible charge/discharge capacity first, improve cycle performance and reduce costs that these aspects carry out.The fairly perfect negative material of commercialization is various embedding lithium material with carbon element mainly, and for lithium metal, the fail safe of battery is greatly improved really.But the current potential of the current potential of Carbon anode and lithium is very close, during over-charging of battery, lithium metal may be separated out in carbon electrodes and cause safety problem; Easy and electrolyte is had an effect; There is obvious voltage delay.
1996, Canadian Studies person K.Zaghib proposes to adopt lithium titanate material to form lithium-ions battery as negative pole and high-voltage anode first, form army with carbon electrode claimed ultracapacitor.Afterwards, little bavin letter was fine waits people also to it can be used as ion cathode material lithium to carry out research.(Chen Jingbo, Hu Guorong, Peng Zhongdong etc. Oxide as Anode Material for Lithium Ion Batteries progress [J]. battery, 2003,33 (3): 183 ~ 186.) but until before and after 1999 years, people are just to Li 4ti 5o 12large quantifier elimination is started as lithium ion battery negative material.Compared with carbon negative pole material, lithium titanate has " zero strain " characteristic (T.ohzuku, A.Ueda, N.Yamamoto.Zero-strain insertion materials of Li [Li that skeleton structure in charge and discharge process changes hardly 1/3ti 5/3] O 4for rechargeable lithium cells [J] .Electrochemicals Society, 1995,140:1431-1435.), high (the 1.55V vs.Li/Li of intercalation potential +) and not easily cause that the precipitation of lithium, coulombic efficiency are high, lithium ion diffusion coefficient (is 2*10 -8cm 2/ s) good characteristic such as the order of magnitude higher than Carbon anode, possess the characteristic that charging times is more, charging process is faster, safer that lithium-ions battery of future generation is necessary.
Li 4ti 5o 12the embedding lithium capacity of theory be 175mAh/g, but the Li of at present preparation 4ti 5o 12negative material still also exists the shortcomings such as poorly conductive, density is low.Prepare pattern unified, particle diameter reaches nano-scale, and the lithium titanate with oxygen vacancy can reduce the migration path of lithium ion at lithium titanate intracell greatly, improves the ion mobility of lithium titanate.
The method of current synthesis lithium titanate mainly contains high temperature solid-state method, hydro thermal method etc.
Li source compound, titanium source compound mainly mix according to certain ratio by lithium titanate high temperature process heat method, join in decentralized medium, stir, dry, cooling, then obtain product through vacuum at high temperatures calcining.As CN102009998 A describes a kind of method adopting high temperature solid-state method to synthesize lithium titanate, this invention adopts lithium source, the mixture in titanium source joins in polyacrylamide solution, strong stirring mixes, then dry cool to room temperature, material 600 DEG C of pre-burning constant temperature 12 hours, cooling, grinding, 750-950 DEG C of calcining again, obtained product.This technology path, although avoid complicated feed way to a certain extent, obtained lithium titanate of good performance, process is too loaded down with trivial details, and step is many, and energy resource consumption is serious, and calcining synthesis cycle is longer, is unfavorable for industrialized production.
Hydro thermal method preparation is a kind of (Li preparing lithium titanate generally adopted 4ti 5o 12) method.As CN 102064315 A describes a kind of method of Hydrothermal Synthesis lithium titanate.This invention adopts titanium dioxide to mix with lithium hydroxide finite concentration ratio, then through salt acid elution; Get said products again and mix hydro-thermal again with lithium hydroxide according to finite concentration ratio, eventually pass high-temperature heat treatment and obtain lithium titanate product.The advantage of the method is that obtained product purity is higher, and particle size is easy to control, but the intermediate water thermal process too loaded down with trivial details time is longer, and required operation is more, is unfavorable for large-scale industrial production.
Summary of the invention
For the defect existed in above-mentioned prior art, technical problem to be solved by this invention is to provide the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material, the preparation method of described this Graphene/oxygen vacancy lithium titanate composite material will solve in synthesis technique of the prior art that the production cycle is long, energy resource consumption is large, hydro-thermal synthesis process process is various, the technical problem that the hydro-thermal time is longer.
The preparation method of the present invention's a kind of Graphene/oxygen vacancy lithium titanate composite material, comprises the steps:
1), the titanium dioxide that takes 150 mass parts joins in the deionized water of 500 mass parts and is mixed with tio_2 suspension, under the state stirred, poured into by tio_2 suspension in ball mill and carries out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, is of a size of 100-350nm;
2), obtain lithium hydroxide aqueous solution in the deionized water that the lithium hydroxide of 63-69 mass parts is dissolved in 400-600 mass parts, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
3), be configured to graphene oxide solution in the deionized water that the graphene oxide of 0.05-18 mass parts is dispersed in 100-300 mass parts, gained graphene oxide solution joined ball milling in step (2) ball mill;
4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
5), under vacuum conditions by the temperature lower calcination of presoma powder at 750 DEG C-950 DEG C, obtain lithium ion battery negative material nano oxygen omission type lithium titanate, nano oxygen omission type lithium titanate particle is of a size of 110-190nm.
Further, described titanium dioxide is anatase titanium dioxide, one or more the combination in rutile titanium dioxide.
Further, in described step (3), the mass percentage content of graphene oxide is 0.05%-10%.
Further, in described step (5), high-temperature calcination temperature is 750 DEG C-950 DEG C.
Further, the mass fraction of described lithium hydroxide is 63 parts, and the mass fraction of described graphene oxide is 0.05 part, and the gross mass number of described deionized water is 1200 parts, and described calcining heat is 850 DEG C.
Further, the mass fraction of described lithium hydroxide is 63 parts, and the mass fraction of described graphene oxide is 9 parts, and the gross mass number of described deionized water is 1200 parts, and described calcining heat is 950 DEG C.
Further, the mass fraction of described lithium hydroxide is 63 parts, and the mass fraction of described graphene oxide is 18 parts, and the gross mass number of described deionized water is 1200 parts, and described calcining heat is 850 DEG C.
Further, the mass fraction of described lithium hydroxide is 66 parts, and the mass fraction of described graphene oxide is 0.05 part, and the gross mass number of described deionized water is 1200 parts, and described calcining heat is 950 DEG C.
Further, the mass fraction of described lithium hydroxide is 66 parts, and the mass fraction of described graphene oxide is 9 parts, and the gross mass number of described deionized water is 1200 parts, and described calcining heat is 850 DEG C.
Further, the mass fraction of described lithium hydroxide is 63 parts, and the mass fraction of described graphene oxide is 18 parts, and the gross mass number of described deionized water is 1200 parts, and described calcining heat is 750 DEG C.
Further, the mass fraction of described lithium hydroxide is 69 parts, and the mass fraction of described graphene oxide is 0.05 part, and the gross mass number of described deionized water is 1200 parts, and described calcining heat is 850 DEG C.
Further, the mass fraction of described lithium hydroxide is 69 parts, and the mass fraction of described graphene oxide is 9 parts, and the gross mass number of described deionized water is 1200 parts, and described calcining heat is 750 DEG C.
Further, the mass fraction of described lithium hydroxide is 69 parts, and the mass fraction of described graphene oxide is 18 parts, and the gross mass number of described deionized water is 1200 parts, and described calcining heat is 950 DEG C.
Concrete, the step 2 in preparation process) in, the molar ratio controlling lithium and titanium is 0.8-0.86;
The vacant lithium titanate of the lithium ion battery negative material nano oxygen of above-mentioned gained, mainly adopts and carries out size controlling to presoma, mutually control with high-temperature calcination, final synthesized high-performance, nano-scale Graphene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Above-mentioned gained Graphene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material has homogeneous nanotopology features, its particle size range is at 110-190nm.
A kind of Graphene of the present invention/oxygen vacancy lithium titanate (Li 4ti 5o 12) preparation method of composite material, owing to adopting the size controlling presoma particle diameter, obtain presoma there is higher activity, can synthesize lithium titanate at relatively low temperature, nano-scale reduces the path of lithium ion mobility, improves chemical property; On the other hand, dissociate the Graphene that as reducing agent under graphene oxide high temperature, at high temperature promote the formation of oxygen vacancy, simultaneously residual graphene oxide can be used as due to the good conductivity that it has the chemical property that conductive agent further improves material, is easy to realize suitability for industrialized production.The lithium titanate of final gained is the nanocrystal of 100-200 nm, reduces the distance of lithium ion mobility, thus improves the chemical property of lithium titanate material.
A kind of Graphene of the present invention/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material, the raw material used in building-up process is technical grade titanium dioxide, and cost is lower, does not adopt organic solvent to do dispersant, and adopt distilled water during wet ball grinding, using Graphene as reducing agent in lithium titanate generative process, and reduction part Ti + 4for Ti + 3, facilitate the generation of oxygen vacancy, improve intrinsic conductivity, therefore to have operation few for synthetic method of the present invention, and low production cost, safe and reliable, the product chemical property of synthesis is good, conductivity high feature.
A kind of Graphene of the present invention/oxygen vacancy lithium titanate (Li 4ti 5o 12) method of composite material, half-cell method is used to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.5C, the charge-discharge performance of this battery is tested, its averaged discharge specific capacity is its first discharge specific capacity of 177.6mAh/g is 176.3mAh/g-181.5mAh/g, initial charge specific capacity is 175.8 mAh/g-180.1mAh/g, coulombic efficiency is 98.8% first, and electric discharge mean voltage is 1.53V-1.6V.
The present invention compares with prior art, and its technological progress is significant.The present invention promotes the generation of oxygen vacancy in lithium titanate in high-temperature burning process using Graphene as reducing agent, effectively raise the conductivity of lithium titanate, obtained product cut size is even, pattern is unified, there is comparatively stable charge-discharge performance and cycle performance, and technique is simple, is easy to large-scale production, is expected to apply in electrokinetic cell field.
Accompanying drawing explanation
Fig. 1 is the graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li of embodiment 1 gained 4ti 5o 12) the XRD collection of illustrative plates of composite material;
Fig. 2 is the graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li of embodiment 1 gained 4ti 5o 12) composite material SEM figure;
Fig. 3 is the graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li of embodiment 1 gained 4ti 5o 12) the chemical property collection of illustrative plates of composite material.
Embodiment
Below by specific embodiment, also the present invention is described in detail by reference to the accompanying drawings, but do not limit the present invention.
The preparation of battery and electrochemical property test method
(1), the preparation of battery anode slice:
By the graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li obtained 4ti 5o 12) composite material, conductive agent, organic binder bond gather after inclined tetrafluoroethene (PVDF) mixes according to mass ratio 80:10:10 and obtain mixed powder, by this mixed powder 8 grams, add organic solvent 1-METHYLPYRROLIDONE 4 grams, slurry is formed after abundant stirring, coating and aluminium foil surface, after oven dry, repeatedly rolling, obtains battery cathode sheet;
(2), battery assembling and performance test
2016 type half-cell assessments are used to obtain the chemical property of lithium titanate.The battery pole piece that rolling is good is stamped into the disk of diameter 12mm, after its quality of precise, the quality of the lithium titanate in pole piece is calculated according to formula composition, use the barrier film of diameter 19mm, use the metal lithium sheet of diameter 15mm as positive pole, being assembled in German Braun glove box can test battery.
The specific capacity test of battery uses Wuhan Lan electricity company cell tester (Land2000) to carry out.Repeatedly loop test is carried out under 0.5C condition.
In various embodiments of the present invention, the specification of each raw material used and lithium hydroxide are LITHIUM BATTERY, and titanium dioxide is technical grade.
Embodiment 1
A kind of Graphene/oxygen vacancy lithium titanate (Li 4ti 5o 12) method of composite material, the raw material used in building-up process, calculates by mass fraction, its composition and content as follows:
Titanium dioxide 150 parts
Lithium hydroxide 63 parts
Graphene oxide 0.05 part
Deionized water 1200 parts
Its synthetic method specifically comprises the steps:
(1), take 150 parts of titanium dioxide and add 500 parts of deionized waters and be mixed with tio_2 suspension, under the state of stirring, batch mixing is poured in ball mill and carry out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, average particle size 350nm.
(2), by 63 parts of lithium hydroxides be dissolved in 400 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in step (1) ball mill;
(3), by 0.005 part of graphene oxide be dispersed in 300 parts of deionized waters and be configured to graphene oxide solution, gained graphene oxide solution is joined ball milling in step (1) ball mill;
(4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
(5), last 750 DEG C of calcinings under vacuo, obtain graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material carries out XRD test by X-ray diffractometer (XRD, Rigaku Rigaku), Discriminating materials result is as shown in Figure 1.Diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of lithium titanate, does not have other peaks to occur, result shows above-mentioned graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) the final material of synthetic method of composite material is pure phase lithium titanate (Li 4ti 5o 12).
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material uses ESEM (SEM, NEC 6700F) to carry out SEM microexamination, as shown in Figure 2, as can be seen from Figure 2, the vacant lithium titanate of the lithium ion battery negative material nano oxygen of gained has uniform nanotopology features to result.Particle size range is at 180nm.
By above-mentioned graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material, half-cell method is used to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.2C, the charge-discharge performance of this battery is tested, its first discharge specific capacity is 178.6mAh/g, initial charge specific capacity is 176.5mAh/g, coulombic efficiency is 98.8% first, and electric discharge mean voltage is 1.53V.Good electrochemical properties and cycle performance, be expected to apply in electrokinetic cell field
Embodiment 2
The synthetic method of oxygen vacancy lithium titanate, the raw material used in building-up process are prepared in Graphene reduction, calculate by mass fraction, its composition and content as follows:
Titanium dioxide 150 parts
Lithium hydroxide 63 parts
Graphene oxide 9 parts
Deionized water 1200 parts
Its synthetic method specifically comprises the steps:
(1), take 150 parts of titanium dioxide and add 500 parts of deionized waters and be mixed with tio_2 suspension, under the state of stirring, batch mixing is poured in ball mill and carry out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, average particle size 310nm.
(2), by 63 parts of lithium hydroxides be dissolved in 400 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in step (1) ball mill;
(3), by 9 parts of graphene oxides be dispersed in 300 parts of deionized waters and be configured to graphene oxide solution, gained graphene oxide solution is joined ball milling in step (1) ball mill;
(4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
(5), last 750 DEG C of calcinings under vacuo, obtain graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, carry out XRD test by X-ray diffractometer (XRD, Rigaku Rigaku), Discriminating materials result and Fig. 1 similar.Diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of lithium titanate, does not have other peaks to occur, result shows that the final material of synthetic method of the vacant lithium titanate of above-mentioned lithium ion battery negative material nano oxygen is pure phase lithium titanate (Li 4ti 5o 12).
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, use ESEM (SEM, NEC 6700F) to carry out SEM microexamination, result is also similar to Fig. 2, and the vacant lithium titanate of lithium ion battery negative material nano oxygen of gained has uniform nanotopology features.Particle size range is at 170nm.
By above-mentioned graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material, half-cell method is used to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.2C, the charge-discharge performance of this battery is tested, its first discharge specific capacity is 179.3mAh/g, initial charge specific capacity is 177.4mAh/g, coulombic efficiency is 98.94% first, and electric discharge mean voltage is 1.56V.Good electrochemical properties and cycle performance, be expected to apply in electrokinetic cell field
Embodiment 3
The synthetic method of oxygen vacancy lithium titanate, the raw material used in building-up process are prepared in Graphene reduction, calculate by mass fraction, its composition and content as follows:
Titanium dioxide 150 parts
Lithium hydroxide 63 parts
Graphene oxide 18 parts
Deionized water 1200 parts
Its synthetic method specifically comprises the steps:
(1), take 150 parts of titanium dioxide and add 500 parts of deionized waters and be mixed with tio_2 suspension, under the state of stirring, batch mixing is poured in ball mill and carry out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, average particle size 200nm.
(2), by 63 parts of lithium hydroxides be dissolved in 400 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in step (1) ball mill;
(3), by 18 parts of graphene oxides be dispersed in 300 parts of deionized waters and be configured to graphene oxide solution, gained graphene oxide solution is joined ball milling in step (1) ball mill;
(4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
(5), last 850 DEG C of calcinings under vacuo, obtain graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, carry out XRD test by X-ray diffractometer (XRD, Rigaku Rigaku), Discriminating materials result and Fig. 1 similar.Diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of lithium titanate, does not have other peaks to occur, result shows that the final material of synthetic method of the vacant lithium titanate of above-mentioned lithium ion battery negative material nano oxygen is pure phase lithium titanate (Li 4ti 5o 12).
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, use ESEM (SEM, NEC 6700F) to carry out SEM microexamination, result is also similar to Fig. 2, and the vacant lithium titanate of lithium ion battery negative material nano oxygen of gained has uniform nanotopology features.Particle size range is at 160nm.
By above-mentioned graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material, half-cell method is used to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.2C, test its first discharge specific capacity to the charge-discharge performance of this battery is 181.7mAh/g, initial charge specific capacity is 180.8 mAh/g, coulombic efficiency is 99.5% first, and electric discharge mean voltage is 1.59V.Good electrochemical properties and cycle performance, be expected to apply in electrokinetic cell field
Embodiment 4
The synthetic method of oxygen vacancy lithium titanate, the raw material used in building-up process are prepared in Graphene reduction, calculate by mass fraction, its composition and content as follows:
Titanium dioxide 150 parts
Lithium hydroxide 66 parts
Graphene oxide 9 parts
Deionized water 1200 parts
Its synthetic method specifically comprises the steps:
(1), take 150 parts of titanium dioxide and add 500 parts of deionized waters and be mixed with tio_2 suspension, under the state of stirring, batch mixing is poured in ball mill and carry out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, average particle size 160nm.
(2), by 66 parts of lithium hydroxides be dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in step (1) ball mill;
(3), by 0.005 part of graphene oxide be dispersed in 200 parts of deionized waters and be configured to graphene oxide solution, gained graphene oxide solution is joined ball milling in step (1) ball mill;
(4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
(5), last 750 DEG C of calcinings under vacuo, obtain graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, carry out XRD test by X-ray diffractometer (XRD, Rigaku Rigaku), Discriminating materials result and Fig. 1 similar.Diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of lithium titanate, does not have other peaks to occur, result shows that the final material of synthetic method of the vacant lithium titanate of above-mentioned lithium ion battery negative material nano oxygen is pure phase lithium titanate (Li 4ti 5o 12).
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, use ESEM (SEM, NEC 6700F) to carry out SEM microexamination, result is also similar to Fig. 2, and the vacant lithium titanate of lithium ion battery negative material nano oxygen of gained has uniform nanotopology features.Particle size range is at 115nm.
By above-mentioned graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material, half-cell method is used to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.2C, the charge-discharge performance of this battery is tested, its first discharge specific capacity is 178.2mAh/g, initial charge specific capacity is 175.5mAh/g, coulombic efficiency is 98.48% first, and electric discharge mean voltage is 1.56V.Good electrochemical properties and cycle performance, be expected to apply in electrokinetic cell field
Embodiment 5
The synthetic method of oxygen vacancy lithium titanate, the raw material used in building-up process are prepared in Graphene reduction, calculate by mass fraction, its composition and content as follows:
Titanium dioxide 150 parts
Lithium hydroxide 66 parts
Graphene oxide 9 parts
Deionized water 1100 parts
Its synthetic method specifically comprises the steps:
(1), take 150 parts of titanium dioxide and add 500 parts of deionized waters and be mixed with tio_2 suspension, under the state of stirring, batch mixing is poured in ball mill and carry out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, average particle size 120nm.
(2), by 66 parts of lithium hydroxides be dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in step (1) ball mill;
(3), by 9 parts of graphene oxides be dispersed in 200 parts of deionized waters and be configured to graphene oxide solution, gained graphene oxide solution is joined ball milling in step (1) ball mill;
(4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
(5), last 850 DEG C of calcinings under vacuo, obtain graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, carry out XRD test by X-ray diffractometer (XRD, Rigaku Rigaku), Discriminating materials result and Fig. 1 similar.Diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of lithium titanate, does not have other peaks to occur, result shows that the final material of synthetic method of the vacant lithium titanate of above-mentioned lithium ion battery negative material nano oxygen is pure phase lithium titanate (Li 4ti 5o 12).
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, use ESEM (SEM, NEC 6700F) to carry out SEM microexamination, the vacant lithium titanate of lithium ion battery negative material nano oxygen of result also gained similar to Fig. 2 has uniform nanotopology features.Particle size range is at 100nm.
By above-mentioned graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material, lithium uses half-cell method to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.2C, the charge-discharge performance of this battery is tested, its averaged discharge specific discharge capacity is its first discharge specific capacity of 178.3 mAh/g is 179.4mAh/g, initial charge specific capacity is 178.5mAh/g, coulombic efficiency is 99.4% first, and electric discharge mean voltage is 1.54V.Good electrochemical properties and cycle performance, be expected to apply in electrokinetic cell field
Embodiment 6
The synthetic method of oxygen vacancy lithium titanate, the raw material used in building-up process are prepared in Graphene reduction, calculate by mass fraction, its composition and content as follows:
Titanium dioxide 150 parts
Lithium hydroxide 66 parts
Graphene oxide 18 parts
Deionized water 1150 parts
Its synthetic method specifically comprises the steps:
(1), take 150 parts of titanium dioxide and add 500 parts of deionized waters and be mixed with tio_2 suspension, under the state of stirring, batch mixing is poured in ball mill and carry out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, average particle size 170nm.
(2), by 66 parts of lithium hydroxides be dissolved in 500 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in step (1) ball mill;
(3), by 18 parts of graphene oxides be dispersed in 200 parts of deionized waters and be configured to graphene oxide solution, gained graphene oxide solution is joined ball milling in step (1) ball mill;
(4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
(5), last 750 DEG C of calcinings under vacuo, obtain graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, carry out XRD test by X-ray diffractometer (XRD, Rigaku Rigaku), Discriminating materials result and Fig. 1 similar.Diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of lithium titanate, does not have other peaks to occur, result shows that the final material of synthetic method of the vacant lithium titanate of above-mentioned lithium ion battery negative material nano oxygen is pure phase lithium titanate (Li 4ti 5o 12).
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, use ESEM (SEM, NEC 6700F) to carry out SEM microexamination, result is also similar to Fig. 2, and the vacant lithium titanate of lithium ion battery negative material nano oxygen of gained has uniform nanotopology features.Particle size range is at 130nm.
Half-cell method is used to be assembled into button-shaped 2016 batteries vacant for above-mentioned lithium ion battery negative material nano oxygen lithium titanate, under the multiplying power of 0.2C, the charge-discharge performance of this battery is tested, its averaged discharge specific discharge capacity is its first discharge specific capacity of 179.2mAh/g is 180.9mAh/g, initial charge specific capacity is 179.7mAh/g, coulombic efficiency is 99.3% first, and electric discharge mean voltage is 1.52V.Good electrochemical properties and cycle performance, be expected to apply in electrokinetic cell field
Embodiment 7
The synthetic method of oxygen vacancy lithium titanate, the raw material used in building-up process are prepared in Graphene reduction, calculate by mass fraction, its composition and content as follows:
Titanium dioxide 150 parts
Lithium hydroxide 69 parts
Graphene oxide 0.05 part
Deionized water 1200 parts
Its synthetic method specifically comprises the steps:
(1), take 150 parts of titanium dioxide and add 500 parts of deionized waters and be mixed with tio_2 suspension, under the state of stirring, batch mixing is poured in ball mill and carry out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, average particle size 350nm.
(2), by 69 parts of lithium hydroxides be dissolved in 600 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in step (1) ball mill;
(3), by 0.05 part of graphene oxide be dispersed in 100 parts of deionized waters and be configured to graphene oxide solution, gained graphene oxide solution is joined ball milling in step (1) ball mill;
(4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
(5), last 850 DEG C of calcinings under vacuo, obtain graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, carry out XRD test by X-ray diffractometer (XRD, Rigaku Rigaku), Discriminating materials result and Fig. 1 similar.Diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of lithium titanate, does not have other peaks to occur, result shows that the final material of synthetic method of the vacant lithium titanate of above-mentioned lithium ion battery negative material nano oxygen is pure phase lithium titanate (Li 4ti 5o 12).
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, use ESEM (SEM, NEC 6700F) to carry out SEM microexamination, the vacant lithium titanate of lithium ion battery negative material nano oxygen of result also gained similar to Fig. 2 has uniform nanotopology features.Particle size range is at 150nm.
By above-mentioned graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material, half-cell method is used to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.2C, the charge-discharge performance of this battery is tested, its first discharge specific capacity is 178.6mAh/g, initial charge specific capacity is 176.5mAh/g, coulombic efficiency is 98.82% first, and electric discharge mean voltage is 1.55V.Good electrochemical properties and cycle performance, be expected to apply in electrokinetic cell field
Embodiment 8
The synthetic method of oxygen vacancy lithium titanate, the raw material used in building-up process are prepared in Graphene reduction, calculate by mass fraction, its composition and content as follows:
Titanium dioxide 150 parts
Lithium hydroxide 69 parts
Graphene oxide 9 parts
Deionized water 1200 parts
Its synthetic method specifically comprises the steps:
(1), take 150 parts of titanium dioxide and add 500 parts of deionized waters and be mixed with tio_2 suspension, under the state of stirring, batch mixing is poured in ball mill and carry out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, average particle size 260nm.
(2), by 69 parts of lithium hydroxides be dissolved in 600 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in step (1) ball mill;
(3), by 9 parts of graphene oxides be dispersed in 100 parts of deionized waters and be configured to graphene oxide solution, gained graphene oxide solution is joined ball milling in step (1) ball mill;
(4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
(5), last 750 DEG C of calcinings under vacuo, obtain graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, carry out XRD test by X-ray diffractometer (XRD, Rigaku Rigaku), Discriminating materials result and Fig. 1 similar.Diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of lithium titanate, does not have other peaks to occur, result shows that the final material of synthetic method of the vacant lithium titanate of above-mentioned lithium ion battery negative material nano oxygen is pure phase lithium titanate (Li 4ti 5o 12).
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, use ESEM (SEM, NEC 6700F) to carry out SEM microexamination, result is also similar to Fig. 2, and the vacant lithium titanate of lithium ion battery negative material nano oxygen of gained has uniform nanotopology features.Particle size range is at 170nm.
By above-mentioned graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material, half-cell method is used to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.2C, the charge-discharge performance of this battery is tested, its first discharge specific capacity is 178.5mAh/g, initial charge specific capacity is 176.5 mAh/g, coulombic efficiency 98.87% first, electric discharge mean voltage is 1.54V.Good electrochemical properties and cycle performance, be expected to apply in electrokinetic cell field
Embodiment 9
The synthetic method of oxygen vacancy lithium titanate, the raw material used in building-up process are prepared in Graphene reduction, calculate by mass fraction, its composition and content as follows:
Titanium dioxide 150 parts
Lithium hydroxide 69 parts
Graphene oxide 18 parts
Deionized water 1200 parts
Its synthetic method specifically comprises the steps:
(1), take 150 parts of titanium dioxide and add 500 parts of deionized waters and be mixed with tio_2 suspension, under the state of stirring, batch mixing is poured in ball mill and carry out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, average particle size 300nm.
(2), by 69 parts of lithium hydroxides be dissolved in 600 parts of deionized waters and obtain lithium hydroxide aqueous solution, gained lithium hydroxide aqueous solution is joined in step (1) ball mill;
(3), by 18 parts of graphene oxides be dispersed in 100 parts of deionized waters and be configured to graphene oxide solution, gained graphene oxide solution is joined ball milling in step (1) ball mill;
(4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
(5), last 950 DEG C of calcinings under vacuo, obtain graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material.
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, carry out XRD test by X-ray diffractometer (XRD, Rigaku Rigaku), Discriminating materials result and Fig. 1 similar.Diffraction maximums all in this collection of illustrative plates can be demarcated as the diffraction maximum of lithium titanate, does not have other peaks to occur, result shows that the final material of synthetic method of the vacant lithium titanate of above-mentioned lithium ion battery negative material nano oxygen is pure phase lithium titanate (Li 4ti 5o 12).
Graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (the Li of above-mentioned gained 4ti 5o 12) composite material, use ESEM (SEM, NEC 6700F) to carry out SEM microexamination, result is also similar to Fig. 2, and the vacant lithium titanate of lithium ion battery negative material nano oxygen of gained has uniform nanotopology features.Particle size range is at 180nm.
By above-mentioned graphite as anode material for lithium-ion battery alkene/oxygen vacancy lithium titanate (Li 4ti 5o 12) composite material, half-cell method is used to be assembled into button-shaped 2016 batteries, under the multiplying power of 0.2C, the charge-discharge performance of this battery is tested, its first discharge specific capacity is 182.1mAh/g, initial charge specific capacity is 180.1mAh/g, coulombic efficiency is 98.9% first, and electric discharge mean voltage is 1.54V.Good electrochemical properties and cycle performance, be expected to apply in electrokinetic cell field.

Claims (13)

1. a preparation method for Graphene/oxygen vacancy lithium titanate composite material, is characterized in that comprising the steps:
1), the titanium dioxide that takes 150 mass parts joins in the deionized water of 500 mass parts and is mixed with tio_2 suspension, under the state stirred, poured into by tio_2 suspension in ball mill and carries out ball milling, obtain nano-scale Detitanium-ore-type TiO 2slurry, is of a size of 100-350nm;
2), obtain lithium hydroxide aqueous solution in the deionized water that the lithium hydroxide of 63-69 mass parts is dissolved in 400-600 mass parts, gained lithium hydroxide aqueous solution is joined in the ball mill of step (1);
3), be configured to graphene oxide solution in the deionized water that the graphene oxide of 0.05-18 mass parts is dispersed in 100-300 mass parts, gained graphene oxide solution joined ball milling in step (2) ball mill;
4), by the slurry of step (3) gained under the state stirred, spraying dry is carried out, obtained presoma powder;
5), under vacuum conditions by the temperature lower calcination of presoma powder at 750 DEG C-950 DEG C, obtain lithium ion battery negative material nano oxygen omission type lithium titanate, nano oxygen omission type lithium titanate particle is of a size of 110-190nm.
2. the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material as claimed in claim 1, is characterized in that: described titanium dioxide is anatase titanium dioxide, one or more the combination in rutile titanium dioxide.
3. the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material as claimed in claim 1, is characterized in that: in described step (3), the mass percentage content of graphene oxide is 0.05%-10%.
4. the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material as claimed in claim 1, is characterized in that: in described step (5), high-temperature calcination temperature is 750 DEG C-950 DEG C.
5. the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material as described in claim 1, it is characterized in that: the mass fraction of described lithium hydroxide is 63 parts, the mass fraction of described graphene oxide is 0.05 part, the gross mass number of described deionized water is 1200 parts, and described calcining heat is 850 DEG C.
6. the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material as described in claim 1, it is characterized in that: the mass fraction of described lithium hydroxide is 63 parts, the mass fraction of described graphene oxide is 9 parts, the gross mass number of described deionized water is 1200 parts, and described calcining heat is 950 DEG C.
7. the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material as described in claim 1, it is characterized in that: the mass fraction of described lithium hydroxide is 63 parts, the mass fraction of described graphene oxide is 18 parts, the gross mass number of described deionized water is 1200 parts, and described calcining heat is 850 DEG C.
8. the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material as described in claim 1, it is characterized in that: the mass fraction of described lithium hydroxide is 66 parts, the mass fraction of described graphene oxide is 0.05 part, the gross mass number of described deionized water is 1200 parts, and described calcining heat is 950 DEG C.
9. the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material as described in claim 1, it is characterized in that: the mass fraction of described lithium hydroxide is 66 parts, the mass fraction of described graphene oxide is 9 parts, the gross mass number of described deionized water is 1200 parts, and described calcining heat is 850 DEG C.
10. the preparation method of a kind of Graphene/oxygen vacancy lithium titanate composite material as described in claim 1, it is characterized in that: the mass fraction of described lithium hydroxide is 63 parts, the mass fraction of described graphene oxide is 18 parts, the gross mass number of described deionized water is 1200 parts, and described calcining heat is 750 DEG C.
The preparation method of 11. a kind of Graphene/oxygen vacancy lithium titanate composite materials as described in claim 1, it is characterized in that: the mass fraction of described lithium hydroxide is 69 parts, the mass fraction of described graphene oxide is 0.05 part, the gross mass number of described deionized water is 1200 parts, and described calcining heat is 850 DEG C.
The preparation method of 12. a kind of Graphene/oxygen vacancy lithium titanate composite materials as described in claim 1, it is characterized in that: the mass fraction of described lithium hydroxide is 69 parts, the mass fraction of described graphene oxide is 9 parts, the gross mass number of described deionized water is 1200 parts, and described calcining heat is 750 DEG C.
The preparation method of 13. a kind of Graphene/oxygen vacancy lithium titanate composite materials as described in claim 1, it is characterized in that: the mass fraction of described lithium hydroxide is 69 parts, the mass fraction of described graphene oxide is 18 parts, the gross mass number of described deionized water is 1200 parts, and described calcining heat is 950 DEG C.
CN201510027552.6A 2014-04-25 2015-01-20 Method for preparing graphene/oxygen vacancy lithium titanate composite material Pending CN104600269A (en)

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CN108134068A (en) * 2017-12-25 2018-06-08 吉林大学 Titanium dioxide-graphene oxide composite material, preparation method and application
CN111392766A (en) * 2019-11-13 2020-07-10 中国人民解放军军事科学院防化研究院 Method for preparing nano lithium titanate/graphene porous composite electrode material

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CN106966387A (en) * 2017-04-26 2017-07-21 华南师范大学 A kind of preparation method of carbon point modified lithium titanate/graphene nanocomposite material
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