CN104319377A - Ternary multilevel multi-dimensional structure composite material and preparation method thereof - Google Patents

Ternary multilevel multi-dimensional structure composite material and preparation method thereof Download PDF

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CN104319377A
CN104319377A CN201410525275.7A CN201410525275A CN104319377A CN 104319377 A CN104319377 A CN 104319377A CN 201410525275 A CN201410525275 A CN 201410525275A CN 104319377 A CN104319377 A CN 104319377A
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tio
metal oxide
composite material
height ratio
simple graphene
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CN104319377B (en
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朱晓东
王可心
孙克宁
马汝甲
闫杜娟
乐士儒
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Harbin Institute of Technology
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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
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a ternary multilevel multi-dimensional structure composite material and a preparation method thereof. The excellent electrochemical comprehensive performance can be exerted by utilizing the remarkable synergistic effect and unique multilevel multi-dimensional structure. The composite material is formed by TiO2 of a low-dimensional nano structure and second-phase high-specific-capacity metal oxide as well as two-dimensional micrometer (x-y plane direction) high-conductivity plain graphene. Drive force for lowering the total surface free energy of the solution system is utilized to uniformly load and compactly combine TiO2 of the nano structure and high-specific-capacity metal oxide to an exposed surface of the plain graphene nanosheet by virtue of a tetrahydrofuran solution mixing method. The ternary multilevel multi-dimensional structure composite material effectively integrates the remarkable function of each ingredient, including excellent circulating property and outstanding safety of TiO2, high specific capacity of the second-phase metal oxide, and good conductivity of the plain graphene.

Description

Multistage multidimensional structure composite material of ternary and preparation method thereof
Technical field
The invention belongs to technical field of energy material, relate to the multistage multidimensional structure TiO of a kind of ternary 2-height ratio capacity metal oxide-simple graphene composite material and preparation method thereof.
Background technology
The exhaustive exploitation of the mankind to fossil resource brings serious energy crisis and environmental pollution, has caused the flourish of electric motor car thus, and this just requires that lithium ion battery is to more high-energy-density and power density development.But current lithium ion battery commercialization negative material---graphite, not only specific capacity is low, and lower intercalation potential easily causes serious safety problem, can not meet the demand of high performance lithium ion battery of future generation far away.So the negative pole substitution material seeking to have more high electrochemical performance has attracted the extensive concern of whole world scientific research person.
In numerous anode substitution material that researchers propose, the TiO of nanostructure (as nano particle, nanometer rods, nanotube etc.) 2, show one's talent because it has following advantage, such as low cost, environmentally friendly, Li +the evolving path is short, particularly the high structural stability brought of zero volume emergent property.In addition, its relatively high intercalation potential (1.6-1.8Vvs.Li +/ Li) (its reduction potential is at 1V (vs.Li effectively can to avoid the decomposition of electrolyte +/ Li) below) and the formation of Li dendrite, make the TiO of nanostructure 2become a kind of high security negative material.Although but there is above-mentioned many advantages, nanostructure TiO 2still because its practical application of drawbacks limit of following two aspects: theoretical specific capacity (~ 170mAh g that (1) is lower -1) even can not compete with graphite-phase; (2) lower electronic conductivity (~ 10 -12s cm-1) cause capacity during high-multiplying power discharge to reduce.
In order to make up the low defect of capacity, people attempt nanostructure TiO 2with there is height ratio capacity (750-1250mA h g -1) secondary phase metal oxide materials combine, such as Fe 2o 3, Fe 3o 4, SnO 2, Co 3o 4or MnO 2deng.These binary heterostructures are at reservation nano-TiO 2specific capacity is substantially increased while advantage.But the same TiO of these oxide materials 2identical, all belong to wide bandgap semiconductor materials material or even insulator, its intrinsic low conductivity causes poor transferring charge dynamics, makes capacity rapid decay.Low conductivity is also unfavorable for eliminating the Joule heat that electrode produces, and brings certain potential safety hazard.And nano level metal oxide increases resistance owing to adding crystal boundary, is degrading cycle performance further.
In general, the conductivity defect of active material can solve by introducing conductive agent, the Graphene (Chemically Converted Grephene, CCG) of such as chemical modification or title redox graphene (reduced-Grephene Oxide, r-GO).Matrix using CCG as metal oxide-loaded nano particle, can provide electron propagation ducts fast for electrode.Unfortunately, the poisonous Oxidizing and Reducing Agents that oxidation-reduction process need consumption during preparation CCG is a large amount of, causes inevitable destruction to environment.And in the process, the conductivity of CCG also can suffer slackening to a great extent.Therefore the simple Graphene (Pristine Graphene, PG) of the high-quality obtained with ultrasonic stripping direct from native graphite is compared, conductivity both inadequate also heterogeneities of CCG.And the preparation condition of simple Graphene is more gentle, than CCG more economy and environmental protection, therefore simple Graphene is more conducive to the high-effective conductive agent as electrode, with guarantee active material circulation and high rate performance in good reliability and reappearance.But by metal oxide supported on simple Graphene, be a huge challenge technically.Up to the present, rare report.Its difficult point is that simple Graphene has chemical inertness, lacks the oxygen-containing functional group that CCG has, is difficult to utilize Hydrothermal Synthesis or electrostatic interaction practical function.Tsing-Hua University Liu Yitao etc. adopt complexing successfully to achieve the assembling of simple Graphene and metal or metal oxide nanoparticles.But this method needs introducing organic ligand and metal ion as crosslinking agent, not only complex steps, complex process, and also cost is higher.
Through finding prior art retrieval, there is not yet relevant TiO both at home and abroad at present 2-height ratio capacity metal oxide (Fe 2o 3, Fe 3o 4, SnO 2, Co 3o 4or MnO 2deng) the open report of-simple graphene composite material, rarely seen several such as TiO 2-Fe 3o 4-Graphene (Lu Jin et al.Appl.Mater.Interfaces 2013,5,7330-7334), TiO 2-SnO 2-Graphene (Jiang Xin et al.New J.Chem.2013,37,3671-3678), G-TiO 2@Co 3o 4nBs (Luo Yongsong et al.J.Mater.Chem.A2013,1,273-281) is all TiO 2with the compound of metal oxide and CCG, even TiO 2-Fe 3o 4-Graphene (Min Qianhao et al.Chem.Commun.2011,47,11709-11711; Lin Yue et al.Eur.J.Inorg.Chem.2012,4439-4444; Tian Miaomiao et al.Anal.Methods 2013,5,3984-3991; Liang Yulu et al.RSCAdv.2014,4,18132-18135), TiO 2-SnO 2-Graphene (Tang Yanping et al.Energy Environ.Sci.2013,6,2447-2451) is TiO 2with the compound of metal oxide and graphene oxide (Graphene Oxide, GO).Graphene oxide (GO) conductivity is extremely low, and the conductivity of the Graphene of chemical modification (CCG) compares simple Graphene (PG) both inadequate also heterogeneities.
Summary of the invention
For nano-TiO 2the defect of specific capacity and conductivity aspect, the present invention passes through the codope of time phase height ratio capacity metal oxide and the simple Graphene component of high conductivity, provides the multistage multidimensional structure TiO of a kind of ternary 2-height ratio capacity metal oxide-simple graphene composite material and preparation method thereof, utilizes its outstanding cooperative effect and unique multistage multidimensional structure, has given play to excellent electrochemistry combination property.
The multistage multidimensional structure TiO of ternary of the present invention 2-height ratio capacity metal oxide-simple graphene composite material, its composition characteristic is composite material is by the TiO of low-dimensional nano structure 2, the simple Graphene of secondary phase height ratio capacity metal oxide and two-dimentional micron (x-y plane direction) high conductivity three kinds of components take mol ratio as the ternary heterojunction structure of the composition of proportions of 2 ~ 5: 1 ~ 4: 3 ~ 5, effectively combine the outstanding function of each component: TiO 2excellent cycle performance and outstanding fail safe, height ratio capacity (the 750-1250mAh g of secondary phase metal oxide -1) and the good electric conductivity of simple Graphene.
In the present invention, described height ratio capacity metal oxide is Fe 2o 3, Fe 3o 4, SnO 2, Co 3o 4or MnO 2deng any one of height ratio capacity metal oxide.
In the present invention, described TiO 2, height ratio capacity metal oxide and simple Graphene mol ratio can be a kind of ratio in 3: 3: 4,4: 2: 4,4: 3: 3,3: 4: 3,5: 2: 3,4: 1: 5,3: 2: 5,2: 3: 5, the actual electrical chemical property that this mol ratio goes out according to composite material exhibits is determined.
The multistage multidimensional structure TiO of ternary of the present invention 2-height ratio capacity metal oxide-simple graphene composite material, its architectural feature is the TiO of nanostructure 2with height ratio capacity metal oxide uniform load and the multistage multidimensional structure formed on the exposed surface of simple graphene nanometer sheet of combining closely, wherein simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO 2for zero-dimension nano particle, and height ratio capacity metal oxide is any one one-dimensional nano structure such as monodimension nano stick, nano wire, nanotube, nanoneedle or nanobelt; Or TiO 2for any one one-dimensional nano structures such as monodimension nano stick, nano wire, nanotube, nanoneedle or nanobelts, and height ratio capacity metal oxide is zero-dimension nano particle, the trielement composite material of such formation, not only there is zero dimension, the two-dimentional multidimensional structure coexisted of a peacekeeping, and possess nanometer simultaneously, multilevel hierarchy that micron combines, while this micro-nano multi-level structure increases reaction active region, also for charge transport provides express passway.The multistage multidimensional composite construction of this ternary can give full play to the architectural characteristic of each component: (1) zero/one dimension TiO 2with the nanoscale structures of height ratio capacity metal oxide, Li can be shortened +with the transmission path of electronics, improve the high rate capability of composite material; (2) micron order two dimension simple graphene nanometer sheet as conductive agent, can with TiO 2form 3 D stereo network with height ratio capacity metal oxide, form the 3 D stereo network configuration of Quick conductive; (3) TiO 2as a kind of zero structure strain gauge material, primary fail safe can be provided in charge and discharge process; (4) simple graphene nanometer sheet is as a kind of matrix, has good pliability and elasticity, can alleviate Li in height ratio capacity metal oxide +embed/deviate from the structural stress that process is brought, suppress the change in volume of composite material and the efflorescence of electrode; (5) zero/one dimension height ratio capacity metal oxide of simple graphenic surface and TiO 2as a kind of spacer, the again stacking of simple Graphene can be avoided, increase interlamellar spacing further, be conducive to Li +embedding/deviate from.
Above-mentioned one-dimensional nano structure can be any one one-dimensional nano structures such as nanometer rods, nano wire, nanotube, nanoneedle or nanobelt.
The multistage multidimensional structure TiO of above-mentioned ternary 2the preparation method of-height ratio capacity metal oxide-simple graphene composite material, its concrete implementation step is as follows:
(1) be simple Graphene by the ultrasonic direct stripping in METHYLPYRROLIDONE (NMP) of native graphite powder, and simple Graphene transferred in its poor solvent oxolane (THF);
(2) synthesis of nano such as hydro-thermal reaction, hydrolysis structure Ti O is utilized 2, and by TiO 2transfer in its good solvent oxolane;
(3) hydro-thermal reaction, hydrolysis etc. is utilized to synthesize a kind of Fe 2o 3, Fe 3o 4, SnO 2, Co 3o 4or MnO 2nanostructure height ratio capacity metal oxide, and transfer in its good solvent oxolane;
(4) above-mentioned three kinds of solution are mixed with certain proportion, and stir 6 ~ 12 hours, under the actuating force of free energy reducing system, be assembled into the multistage multidimensional structure TiO of ternary 2nano particle-height ratio capacity metal oxide-simple graphene nanometer sheet composite material.
In the present invention, the poor solvent that oxolane (THF) described in step (1) is simple Graphene, in THF, between simple Graphene and oxolane, there is unmatched Hansen Solubility Parameter, thus there is strong again stacking tendency, thus THF can not reduce the huge surface free energy that simple Graphene has.
In the present invention, step (2) and the oxolane described in (3) (THF) are TiO 2with the good solvent of height ratio capacity metal oxide, these metal oxides can in oxolane stable existence.
In the present invention, the actuating force described in step (4) is reduce total free energy of solution system.In THF, simple Graphene has huge surface free energy, once the TiO of more stable nanostructure 2be introduced in THF with height ratio capacity metal oxide, will trend towards residing on the exposed surface of simple graphene nanometer sheet under van der Waals interacts, to reduce the total surface free energy of solution system, make the simple Graphene two-dimensional nano sheet stabilisation in THF, thus successfully assemble the multistage multidimensional structure TiO of ternary 2-height ratio capacity metal oxide-simple graphene composite material.
The ultrasonic direct stripping in METHYLPYRROLIDONE (NMP) of native graphite powder is simple Graphene by the present invention; Then simple Graphene is transferred in its poor solvent one oxolane (THF), the again stacking tendency that simple Graphene is strong because Hansen Solubility Parameter unmatched between solvent has in THF, this step is very crucial to successfully carrying out the collaborative assembling of classification later, because THF can not reduce the huge surface free energy that insoluble two-dimensional nano sheet has.The TiO of therefore more stable nanostructure 2with height ratio capacity metal oxide once be introduced in THF, will trend towards residing on the exposed surface of simple graphene nanometer sheet because van der Waals interacts, to reduce the total surface free energy of solution system, make the two-dimensional nano layer-stabilizing in THF.This self-assembling method, because do not introduce external crosslinking agent, compares the method utilizing complexing to prepare metal oxide-simple graphene composite material, has advantage that is gentle and low cost.
Accompanying drawing explanation
Fig. 1 is the multistage multidimensional structure TiO of ternary in embodiment 1 2-height ratio capacity metal oxide (Fe 3o 4the X-ray diffractogram of)-simple Graphene (PG) composite material;
Fig. 2 is the multistage multidimensional structure TiO of ternary in embodiment 1 2-height ratio capacity metal oxide (Fe 3o 4the transmission electron microscope picture of)-simple Graphene (PG) composite material;
Fig. 3 is the multistage multidimensional structure TiO of ternary in embodiment 1 2-height ratio capacity metal oxide (Fe 3o 4the high-resolution-ration transmission electric-lens figure of)-simple Graphene (PG) composite material;
Fig. 4 is the multistage multidimensional structure TiO of ternary in embodiment 1 2-height ratio capacity metal oxide (Fe 3o 4)-simple Graphene (PG) composite material is at 0.5A g -1cycle performance curve chart under current density.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but do not limit to so; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1
For nano-TiO 2the defect of low specific capacity and low conductivity aspect, by secondary phase height ratio capacity metal oxide Fe 3o 4(927mA h g -1) and the codope of the simple Graphene component of high conductivity, present embodiments provide the multistage multidimensional structure TiO of a kind of ternary 2nanometer rods-Fe 3o 4nano particle-simple graphene nanometer sheet composite material, utilizes its outstanding cooperative effect and unique multistage multidimensional structure, has given play to excellent electrochemistry combination property.
The multistage multidimensional structure TiO of the ternary that the present embodiment provides 2nanometer rods-Fe 3o 4nano particle-simple graphene nanometer sheet composite material is by TiO 2, Fe 3o 4with the simple Graphene of high conductivity three kinds of components with 4: 2: 4 the ternary heterojunction structure that formed of mol ratio, its preparation method is as follows:
(1) joined by native graphite powder in METHYLPYRROLIDONE (NMP), initial concentration is 10mg mL -1, then under 70W power ultrasonic 4 hours.By the suspension that obtains under the rotating speed of 2000 revs/min centrifugal 30 minutes, then collect supernatant and vacuum filtration.The pressed powder filtered to be joined in THF and ultrasonic, obtain the simple graphene dispersion solution of black.
(2) by 3mmol Fe (acac) 3, 30mL oleyl amine and 30mL octadecylene mixing, and nitrogen atmosphere protection under be heated to 280 DEG C insulation 1 hour, then naturally cool to room temperature.Sedimentation afterproduct ethanol is washed 2 ~ 3 times, and 40 DEG C of vacuumizes 12 hours, obtains Fe 3o 4nano particle.By above-mentioned dried Fe 3o 4nano particle is dissolved in THF, obtains the brown Fe of 1mg/mL 3o 4solution.
(3) 5mmol butyl titanate, 25mmol oleyl amine, 25mmol oleic acid and 100mL ethanol to be joined in 35mL polytetrafluoroethylene cup and to stir 10 minutes, then this polytetrafluoroethylene cup is put into a 130mL polytetrafluoroethyllining lining, and add the ethanolic solution of 20mL (96Vol%) within the liner.Stainless steel cauldron is incubated 18 hours at 180 DEG C.Naturally collect product after cooling and with ethanol washing 2 ~ 3 times, 40 DEG C of vacuumizes 12 hours, obtain TiO 2nanometer rods.By above-mentioned dried TiO 2nanometer rods is dissolved in THF, obtains the milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO 2: Fe 3o 4: the mixed in molar ratio of PG=4: 2: 4, and stir 10 hours.In whipping process, organically-modified Fe 3o 4nano particle and TiO 2nanometer rods can spontaneously be assembled on the exposed surface of simple Graphene, obtains the multistage multidimensional structure TiO of ternary 2nanometer rods-Fe 3o 4nano particle-simple graphene nanometer sheet composite material.
The multistage multidimensional structure TiO of ternary of the present embodiment 2nanometer rods-Fe 3o 4nano particle-simple graphene composite material, can effectively in conjunction with the outstanding function of each component: TiO 2excellent cycle performance and outstanding fail safe, Fe 3o 4height ratio capacity (927mA h g -1), low cost and the good electric conductivity of simple Graphene, thus show excellent electrochemistry combination property.Its architectural feature is: TiO 2nanometer rods and Fe 3o 4nano particle uniform load the multistage multidimensional structure formed on the exposed surface of simple graphene nanometer sheet of combining closely, wherein simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO 2for monodimension nano stick, and Fe 3o 4for zero-dimension nano particle, the trielement composite material formed so not only has zero dimension, the multidimensional structure that coexists of peacekeeping two dimension, and possess nanometer simultaneously, multilevel hierarchy that micron combines.The multistage multidimensional composite construction of this ternary can give full play to the architectural characteristic of each component: (1) low-dimensional TiO 2and Fe 3o 4nanoscale structures, can Li be shortened +with the transmission path of electronics, improve the high rate capability of composite material; (2) micron order two dimension simple graphene nanometer sheet as conductive agent, can with TiO 2and Fe 3o 4form 3 D stereo network, construct the 3 D stereo network configuration electrode of Quick conductive; (3) TiO 2as a kind of zero structure strain gauge material, primary fail safe can be provided in charge and discharge process; (4) simple graphene nanometer sheet is as a kind of matrix, has good pliability and elasticity, can alleviate Fe 3o 4at Li +embed/deviate from the structural stress that process is brought, suppress the change in volume of composite material and the efflorescence of electrode; (5) the zero dimension Fe of simple graphenic surface 3o 4with one dimension TiO 2as spacer, the again stacking of simple Graphene can be avoided, increase interlamellar spacing further, be conducive to Li +embedding/deviate from.
Embodiment 2
Unlike step (3): 35 grams of oleic acid are joined and is connected with in 50 milliliters of three-necked bottles of reflux cooler in the present embodiment and embodiment 1, and 120 DEG C of dryings 1 hour with vigorous stirring, in nitrogen stream, be cooled to 80 ~ 100 DEG C.Then 1mmol titanium tetraisopropylate to be joined in oleic acid and to stir 5 minutes, solution being become from white light yellow.10mmol hydroxylation tetrabutyl ammonia is dissolved in 2mL water, and in inhalation syringe, then injects mixed solution fast, solution is made to remain on 80 ~ 100 DEG C, and at the water stirred at reflux condition 8 hours of gentleness, then stop heating, under vacuum water removing is obtained clear solution.In above-mentioned solution, add 20mL ethanol, be precipitated, centrifugal rear ethanol purge 2 times, and 40 DEG C of vacuumizes 12 hours, obtain TiO 2nanometer rods.By above-mentioned dried TiO 2nano particle is dissolved in THF, obtains the milky white solution of 1mg/mL.Step (4): the mol ratio of three kinds of components is TiO 2: Fe 3o 4: PG=3: 3: 4.
Embodiment 3
For nano-TiO 2the defect of low specific capacity and low conductivity aspect, by secondary phase height ratio capacity metal oxide Co 3o 4(891mA h g -1) and the codope of the simple Graphene component of high conductivity, present embodiments provide the multistage multidimensional structure TiO of a kind of ternary 2nano particle-Co 3o 4nanobelt-simple graphene nanometer sheet composite material, utilizes its outstanding cooperative effect and unique multistage multidimensional structure, has given play to excellent electrochemistry combination property.
The multistage multidimensional structure TiO of ternary in the present embodiment 2nano particle-Co 3o 4nanobelt-simple graphene nanometer sheet composite material is by TiO 2, Co 3o 4with the simple Graphene of high conductivity three kinds of components with 3: 3: 4 the ternary heterojunction structure that formed of mol ratio, its preparation method is as follows:
(1) joined by native graphite powder in METHYLPYRROLIDONE (NMP), initial concentration is 10mg mL -1, then under 70W power ultrasonic 4 hours.By the suspension that obtains under the rotating speed of 2000 revs/min centrifugal 30 minutes, then collect supernatant and vacuum filtration.The pressed powder filtered to be joined in THF and ultrasonic, obtain the simple graphene dispersion solution of black.
(2) by 0.1g Co (NO 3) 26H 2o, 0.5g CO (NH 2) 2with 0.37g NH 4f joins in 40mL deionized water, and at room temperature stirs 10 minutes.Then transfer in 50mL stainless steel cauldron, 120 DEG C of reactions 4 hours, naturally cool to room temperature.Product ethanol is washed 3 times, and within 12 hours, obtains Co 40 DEG C of vacuumizes 3o 4nanobelt.By above-mentioned dried Co 3o 4nanobelt is dissolved in THF, obtains the Co of 1mg/mL 3o 4solution.
(3) 0.2mL butyl titanate and 25mL isopropyl alcohol mixed and stir 30 minutes, then dropwise add 1mL deionized water and stir 30 minutes.Then above-mentioned mixed solution is forwarded in the polytetrafluoroethyllining lining stainless steel autoclave of 50mL, 180 DEG C of reactions 6 hours, naturally cool to room temperature, product ethanol is washed 3 times, and 40 DEG C of vacuumizes 12 hours, obtain TiO 2nano particle.By above-mentioned dried TiO 2nano particle is dissolved in THF, obtains the milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO 2: Co 3o 4: the mixed in molar ratio of PG=3: 3: 4, and stir 10 hours.In whipping process, organically-modified Co 3o 4nanobelt and TiO 2nano particle can spontaneously be assembled on the exposed surface of simple Graphene, obtains the multistage multidimensional structure TiO of ternary 2nano particle-Co 3o 4nanobelt-simple graphene nanometer sheet composite material.
The multistage multidimensional structure TiO of ternary of the present embodiment 2nano particle-Co 3o 4nanobelt-simple graphene nanometer sheet composite material, having can effectively in conjunction with the outstanding function of each component: TiO 2excellent cycle performance and outstanding fail safe, Co 3o 4height ratio capacity (891mA h g -1) and the good electric conductivity of simple Graphene, thus show excellent electrochemistry combination property.Its architectural feature is: TiO 2nano particle and Co 3o 4nanobelt uniform load is also combined closely form multistage multidimensional structure on the exposed surface of simple graphene nanometer sheet, and wherein simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO 2for zero-dimension nano particle, and Co 3o 4for 1-dimention nano band, the trielement composite material formed like this, not only has zero dimension, the multidimensional structure that coexists of peacekeeping two dimension, and possess nanometer simultaneously, multilevel hierarchy that micron combines.The multistage multidimensional composite construction of this ternary can give full play to the architectural characteristic of each component: (1) low-dimensional TiO 2and Co 3o 4nanoscale structures, can Li be shortened +with the transmission path of electronics, improve the high rate capability of composite material; (2) micron order two dimension simple graphene nanometer sheet as conductive agent, can with TiO 2and Co 3o 4form 3 D stereo network, construct the 3 D stereo network configuration electrode of Quick conductive; (3) TiO 2as a kind of zero structure strain gauge material, primary fail safe can be provided in charge and discharge process; (4) simple graphene nanometer sheet is as a kind of matrix, has good pliability and elasticity, can alleviate Co 3o 4at Li +embed/deviate from the structural stress that process is brought, suppress the change in volume of composite material and the efflorescence of electrode; (5) the zero dimension TiO of simple graphenic surface 2with one dimension Co 3o 4as spacer, the again stacking of simple Graphene can be avoided, increase interlamellar spacing further, be conducive to Li +embedding/deviate from.
Embodiment 4
For nano-TiO 2the defect of low specific capacity and low conductivity aspect, by secondary phase height ratio capacity metal oxide SnO 2(782mA h g -1) and the codope of the simple Graphene component of high conductivity, present embodiments provide the multistage multidimensional structure TiO of a kind of ternary 2nanometer rods-SnO 2nano particle-simple graphene nanometer sheet composite material, utilizes its outstanding cooperative effect and unique multistage multidimensional structure, has given play to excellent electrochemistry combination property.
The multistage multidimensional structure TiO of ternary in the present embodiment 2nanometer rods-SnO 2nano particle-simple graphene nanometer sheet composite material is by TiO 2, SnO 2with the simple Graphene of high conductivity three kinds of components with 4: 2: 4 the ternary heterojunction structure that formed of mol ratio, its preparation method is as follows:
(1) joined by native graphite powder in METHYLPYRROLIDONE (NMP), initial concentration is 10mg mL -1, then under 70W power ultrasonic 4 hours.By the suspension that obtains under the rotating speed of 2000 revs/min centrifugal 30 minutes, then collect supernatant and vacuum filtration.The pressed powder filtered to be joined in THF and ultrasonic, obtain the simple graphene dispersion solution of black.
(2) 0.3g Sn (Cl) 45H 2o to be dissolved in 25mL deionized water and under the power of 240 watts ultrasonic 10 minutes, is then transferred in reactor, 180 DEG C of reactions 8 hours, product ethanol is washed 3 times, naturally cools to room temperature, and 40 DEG C of vacuumizes 12 hours, obtain SnO 2nano particle.By above-mentioned dried SnO 2nano particle is dissolved in THF, obtains the SnO of 1mg/mL 2solution.
(3) 5mmol butyl titanate, 25mmol oleyl amine, 25mmol oleic acid and 100mL ethanol to be joined in 35mL polytetrafluoroethylene cup and to stir 10 minutes, then this polytetrafluoroethylene cup is put into a 130mL polytetrafluoroethyllining lining, and add the ethanolic solution of 20mL (96Vol%) within the liner.Stainless steel cauldron is incubated 18 hours at 180 DEG C.Naturally collect product after cooling and with ethanol washing 2 ~ 3 times, 40 DEG C of vacuumizes 12 hours, obtain TiO 2nanometer rods.By above-mentioned dried TiO 2nanometer rods is dissolved in THF, obtains the milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO 2: SnO 2: the mixed in molar ratio of PG=4: 2: 4, and stir 10 hours.In whipping process, organically-modified SnO 2nano particle and TiO 2nanometer rods can spontaneously be assembled on the exposed surface of simple Graphene, obtains the multistage multidimensional structure TiO of ternary 2nanometer rods-SnO 2nano particle-simple graphene nanometer sheet composite material.
The multistage multidimensional structure TiO of ternary of the present embodiment 2nanometer rods-SnO 2nano particle-simple graphene composite material, can effectively in conjunction with the outstanding function of each component: TiO 2excellent cycle performance and outstanding fail safe, SnO 2height ratio capacity (782mA h g -1) and the good electric conductivity of simple Graphene, thus show excellent electrochemistry combination property.Its architectural feature is: TiO 2nanometer rods and SnO 2nano particle uniform load is also combined closely form multistage multidimensional structure on the exposed surface of simple graphene nanometer sheet, and wherein simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO 2for monodimension nano stick, and SnO 2for zero-dimension nano particle, the trielement composite material formed like this, not only has zero dimension, the multidimensional structure that coexists of peacekeeping two dimension, and possess nanometer simultaneously, multilevel hierarchy that micron combines.The multistage multidimensional composite construction of this ternary can give full play to the architectural characteristic of each component: (1) low-dimensional SnO 2and TiO 2nanoscale structures, can Li be shortened +with the transmission path of electronics, improve the high rate capability of composite material; (2) micron order two dimension simple graphene nanometer sheet as conductive agent, can with TiO 2and SnO 2form 3 D stereo network, construct the 3 D stereo network configuration electrode of Quick conductive; (3) TiO 2as a kind of zero structure strain gauge material, primary fail safe can be provided in charge and discharge process; (4) simple graphene nanometer sheet is as a kind of matrix, has good pliability and elasticity, can alleviate SnO 2middle Li +embed/deviate from the structural stress that process is brought, suppress the change in volume of composite material and the efflorescence of electrode; (5) the zero dimension SnO of simple graphenic surface 2with one dimension TiO 2as spacer, the again stacking of simple Graphene can be avoided, increase interlamellar spacing further, be conducive to Li +embedding/deviate from.
Embodiment 5
For nano-TiO 2the defect of low specific capacity and low conductivity aspect, by secondary phase height ratio capacity metal oxide MnO 2(1233mA h g -1) and the codope of the simple Graphene component of high conductivity, present embodiments provide the multistage multidimensional structure TiO of a kind of ternary 2nano particle-MnO 2nano wire-simple graphene nanometer sheet composite material, utilizes its outstanding cooperative effect and unique multistage multidimensional structure, has given play to excellent electrochemistry combination property.
The multistage multidimensional structure TiO of ternary in the present embodiment 2nano particle-MnO 2nano wire-simple graphene nanometer sheet composite material is by TiO 2, MnO 2with the simple Graphene of high conductivity three kinds of components with 3: 2: 5 the ternary heterojunction structure that formed of mol ratio, its preparation method is as follows:
(1) joined by native graphite powder in METHYLPYRROLIDONE (NMP), initial concentration is 10mg mL -1, then under 70W power ultrasonic 4 hours.By the suspension that obtains under the rotating speed of 2000 revs/min centrifugal 30 minutes, then collect supernatant and vacuum filtration.The pressed powder filtered to be joined in THF and ultrasonic, obtain the simple graphene dispersion solution of black.
(2) by 0.008mol MnSO 4h 2o and 0.008mol (NH 4) 2s 2o 8to join in 50mL deionized water and to stir 10 minutes, then above-mentioned mixed solution is forwarded in the polytetrafluoroethyllining lining stainless steel autoclave of 50mL, 120 DEG C of reactions 6 hours, naturally cool to room temperature, black solid product ethanol is washed 3 times, and 40 DEG C of vacuumizes 12 hours, obtain MnO 2nano wire.By above-mentioned dried MnO 2nano wire is dissolved in THF, obtains the black MnO of 1mg/mL 2solution.
(3) 0.2mL butyl titanate and 25mL isopropyl alcohol mixed and stir 30 minutes, then dropwise add 1mL deionized water and stir 30 minutes.Then above-mentioned mixed solution is forwarded in the polytetrafluoroethyllining lining stainless steel autoclave of 50mL, 180 DEG C of reactions 6 hours, naturally cool to room temperature, product ethanol is washed 3 times, and 40 DEG C of vacuumizes 12 hours, obtain TiO 2nano particle.By above-mentioned dried TiO 2nano particle is dissolved in THF, obtains the milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO 2: MnO 2: the mixed in molar ratio of PG=3: 2: 5, and stir 10 hours.In whipping process, organically-modified MnO 2nano wire and TiO 2nano particle can spontaneously be assembled on the exposed surface of simple Graphene, obtains the multistage multidimensional structure TiO of ternary 2nano particle-MnO 2nano wire-simple graphene nanometer sheet composite material.
The multistage multidimensional structure TiO of ternary of the present invention 2nano particle-MnO 2nano wire-simple graphene nanometer sheet composite material, can effectively in conjunction with the outstanding function of each component: TiO 2excellent cycle performance and outstanding fail safe, MnO 2height ratio capacity (1233mA h g -1) and low cost and the good electric conductivity of simple Graphene, thus show excellent electrochemistry combination property.Its architectural feature is: TiO 2nano particle and MnO 2nano wire uniform load is also combined closely form multistage multidimensional structure on the exposed surface of simple graphene nanometer sheet, and wherein simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO 2for zero-dimension nano particle, and MnO 2for one-dimensional nano line, the trielement composite material formed like this, not only has zero dimension, the multidimensional structure that coexists of peacekeeping two dimension, and possess nanometer simultaneously, multilevel hierarchy that micron combines.The multistage multidimensional composite construction of this ternary can give full play to the architectural characteristic of each component: (1) low-dimensional TiO 2and MnO 2nanoscale structures, can Li be shortened +with the transmission path of electronics, improve the high rate capability of composite material; (2) micron order two dimension simple graphene nanometer sheet as conductive agent, can with TiO 2and MnO 2form 3 D stereo network, construct the 3 D stereo network configuration electrode of Quick conductive; (3) TiO 2as a kind of zero structure strain gauge material, primary fail safe can be provided in charge and discharge process; (4) simple graphene nanometer sheet is as a kind of matrix, has good pliability and elasticity, can alleviate MnO 2middle Li +embed/deviate from the structural stress that process is brought, suppress the change in volume of composite material and the efflorescence of electrode; (5) the zero dimension TiO of simple graphenic surface 2with one dimension MnO 2as spacer, the again stacking of simple Graphene can be avoided, increase interlamellar spacing further, be conducive to Li +embedding/deviate from.
Embodiment 6
For nano-TiO 2the defect of low specific capacity and low conductivity aspect, by secondary phase height ratio capacity metal oxide Fe 2o 3(1007mA h g -1) and the codope of the simple Graphene component of high conductivity, present embodiments provide the multistage multidimensional structure TiO of a kind of ternary 2nano particle-Fe 2o 3nanotube-simple graphene nanometer sheet composite material, utilizes its outstanding cooperative effect and unique multistage multidimensional structure, has given play to excellent electrochemistry combination property.
The multistage multidimensional structure TiO of ternary in the present embodiment 2nano particle-Fe 2o 3nanotube-simple graphene nanometer sheet composite material is by TiO 2, Fe 2o 3with the simple Graphene of high conductivity three kinds of components with 4: 2: 4 the ternary heterojunction structure that formed of mol ratio, its preparation method is as follows:
(1) joined by native graphite powder in METHYLPYRROLIDONE (NMP), initial concentration is 10mg mL -1, then under 70W power ultrasonic 4 hours.By the suspension that obtains under the rotating speed of 2000 revs/min centrifugal 30 minutes, then collect supernatant and vacuum filtration.The pressed powder filtered to be joined in THF and ultrasonic, obtain the simple graphene dispersion solution of black.
(2) be the FeCl of 0.5mol/L by 3.2mL concentration 3solution, 2.88mL concentration are the NH of 0.02mol/L 4h 2pO 4solution mixes under vigorous stirring, then adds deionized water to cumulative volume and is 80mL and stirs 30 minutes.Then above-mentioned mixed solution is forwarded in the polytetrafluoroethyllining lining stainless steel autoclave of 100mL, 220 DEG C of reactions 16 hours, naturally cool to room temperature, solid product ethanol and deionized water are respectively washed 3 times, and 80 DEG C of vacuumizes 6 hours, obtain Fe 2o 3nanotube.By above-mentioned dried Fe 2o 3nanotube is dissolved in THF, obtains the Fe of 1mg/mL 2o 3solution.
(3) 0.2mL butyl titanate and 25mL isopropyl alcohol mixed and stir 30 minutes, then dropwise add 1mL deionized water and stir 30 minutes.Then above-mentioned mixed solution is forwarded in the polytetrafluoroethyllining lining stainless steel autoclave of 50mL, 180 DEG C of reactions 6 hours, naturally cool to room temperature, product ethanol is washed 3 times, and 40 DEG C of vacuumizes 12 hours, obtain TiO 2nano particle.By above-mentioned dried TiO 2nano particle is dissolved in THF, obtains the milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO 2: Fe 2o 3: the mixed in molar ratio of PG=4: 2: 4, and stir 10 hours.In whipping process, organically-modified Fe 2o 3nanotube and TiO 2nano particle can spontaneously be assembled on the exposed surface of simple Graphene, obtains the multistage multidimensional structure TiO of ternary 2nano particle-Fe 2o 3nanotube-simple graphene nanometer sheet composite material.
The multistage multidimensional structure TiO of ternary of the present embodiment 2nano particle-Fe 2o 3nanotube-simple graphene nanometer sheet composite material, can effectively in conjunction with the outstanding function of each component: TiO 2excellent cycle performance and outstanding fail safe, Fe 2o 3height ratio capacity (1007mA h g -1) and low cost and the good electric conductivity of simple Graphene, thus show excellent electrochemistry combination property.Its architectural feature is: TiO 2nano particle and Fe 2o 3nanotube uniform load the multistage multidimensional structure formed on the exposed surface of simple graphene nanometer sheet of combining closely, wherein simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO 2for zero-dimension nano particle, and Fe 2o 3for 1-dimention nano pipe, the trielement composite material formed like this, not only has zero dimension, the multidimensional structure that coexists of peacekeeping two dimension, and possess nanometer simultaneously, multilevel hierarchy that micron combines.The multistage multidimensional composite construction of this ternary can give full play to the architectural characteristic of each component: (1) low-dimensional TiO 2and Fe 2o 3nanoscale structures, can Li be shortened +with the transmission path of electronics, improve the high rate capability of composite material; (2) micron order two dimension simple graphene nanometer sheet as conductive agent, can with TiO 2and Fe 2o 3form 3 D stereo network, construct the 3 D stereo network configuration electrode of Quick conductive; (3) TiO 2as a kind of zero structure strain gauge material, primary fail safe can be provided in charge and discharge process; (4) simple graphene nanometer sheet is as a kind of matrix, has good pliability and elasticity, can alleviate Fe 2o 3middle Li +embed/deviate from the structural stress that process is brought, suppress the change in volume of composite material and the efflorescence of electrode; (5) the zero dimension TiO of simple graphenic surface 2with one dimension Fe 2o 3as spacer, the again stacking of simple Graphene can be avoided, increase interlamellar spacing further, be conducive to Li +embedding/deviate from.
By multistage for the ternary described in above-described embodiment multidimensional structure TiO 2-height ratio capacity metal oxide-simple graphene composite material is assembled into button cell, and in button cell, material proportion is composite material: acetylene black: PVDF=70: 20: 10, and adopt Clgard2300 type barrier film, be that metal buries sheet to electrode, electrolyte is by LiPF 6, ethylene carbonate and carbonic acid diethyl ester composition (LiPF in electrolyte 6concentration is 1mol/L, and the volume ratio of ethylene carbonate and carbonic acid diethyl ester is 1: 1), in the glove box being full of hydrogen, be assembled into 2025 type button cells, charging/discharging voltage scope is 2.5 ~ 1.0V.
Fig. 1 is TiO 2-Fe 3o 4the X-ray diffractogram of-PG composite material, result shows that this composite material is TiO 2, Fe 3o 4with the compound of PG, there is no other dephasigns; Fig. 2 is TiO 2-Fe 3o 4the transmission electron microscope picture of-PG composite material, can find out larger TiO 2nanometer rods and less Fe 3o 4nano particle uniform load at planar dimension on micron-sized simple graphene nanometer sheet; Fig. 3 is TiO 2-Fe 3o 4the high-resolution-ration transmission electric-lens figure of-PG composite material, result shows TiO 2(101), Fe 3o 4(311), the interplanar distance of PG (002) is respectively 0350 ~ 0.354nm, 0.255nm, 0.35nm, matches with document; Fig. 4 is TiO 2-Fe 3o 4-PG composite material is at 0.5A g -1cycle performance curve chart under current density, can find out that this electrode shows good chemical property under the multiplying power being equivalent to 1C, and after 100 circulations, specific discharge capacity is still higher than 500mAh g -1.

Claims (8)

1. the multistage multidimensional structure TiO of ternary 2-height ratio capacity metal oxide-simple graphene composite material, is characterized in that described composite material is by TiO 2, the ternary heterojunction structure that forms of the simple Graphene of secondary phase height ratio capacity metal oxide and high conductivity, wherein TiO 2, height ratio capacity metal oxide and simple Graphene mol ratio be 2 ~ 5:1 ~ 4:3 ~ 5.
2. the multistage multidimensional structure TiO of ternary according to claim 1 2-height ratio capacity metal oxide-simple graphene composite material, is characterized in that described ternary heterojunction structure is the TiO of nanostructure 2combine closely form multistage multidimensional structure with height ratio capacity metal oxide uniform load on the exposed surface of simple graphene nanometer sheet.
3. the multistage multidimensional structure TiO of ternary according to claim 2 2-height ratio capacity metal oxide-simple graphene composite material, is characterized in that described simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO 2for zero-dimension nano particle, height ratio capacity metal oxide is one-dimensional nano structure.
4. the multistage multidimensional structure TiO of ternary according to claim 2 2-height ratio capacity metal oxide-simple graphene composite material, is characterized in that described simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO 2for one-dimensional nano structure, height ratio capacity metal oxide is zero-dimension nano particle.
5. the multistage multidimensional structure TiO of ternary according to claim 1 2-height ratio capacity metal oxide-simple graphene composite material, is characterized in that described TiO 2, height ratio capacity metal oxide and simple Graphene mol ratio be 3:3:4,4:2:4,4:3:3,3:4:3,5:2:3,4:1:5,3:2:5 or 2:3:5.
6. the multistage multidimensional structure TiO of the ternary according to claim 1,2,3,4 or 5 2-height ratio capacity metal oxide-simple graphene composite material, is characterized in that described height ratio capacity metal oxide is Fe 2o 3, Fe 3o 4, SnO 2, Co 3o 4or MnO 2.
7. the multistage multidimensional structure TiO of the ternary according to claim 3 or 4 2-height ratio capacity metal oxide-simple graphene composite material, is characterized in that described one-dimensional nano structure is nanometer rods, nano wire, nanotube, nanoneedle or nanobelt.
8. the multistage multidimensional structure TiO of ternary described in the arbitrary claim of claim 1-7 2the preparation method of-height ratio capacity metal oxide-simple graphene composite material, is characterized in that described preparation method's step is as follows:
(1) simple Graphene is joined in oxolane, obtain the simple graphene dispersion solution of black;
(2) by TiO 2join in oxolane, obtain milky white solution;
(3) height ratio capacity metal oxide is joined in oxolane, obtain metal oxide solution;
(4) by above-mentioned three kinds of solution mixing, and stir 6 ~ 12 hours, be assembled into the multistage multidimensional structure TiO of ternary 2nano particle-height ratio capacity metal oxide-simple graphene nanometer sheet composite material.
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