CN104319377B - Ternary multistage multidimensional structure composite and preparation method thereof - Google Patents
Ternary multistage multidimensional structure composite and preparation method thereof Download PDFInfo
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- CN104319377B CN104319377B CN201410525275.7A CN201410525275A CN104319377B CN 104319377 B CN104319377 B CN 104319377B CN 201410525275 A CN201410525275 A CN 201410525275A CN 104319377 B CN104319377 B CN 104319377B
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a kind of ternary multistage multidimensional structure composite and preparation method thereof, utilize its prominent cooperative effect and unique multistage multidimensional structure, given play to the electrochemistry combination property of excellence.Described composite is by the TiO of low-dimensional nano structure2Constitute with secondary phase height ratio capacity metal-oxide and two dimension micron (x y plane direction) high conductivity simpleness Graphene.The present invention pass through tetrahydrofuran solution mixing method, with reduce solution system total surface free energy as driving force, by the TiO of nanostructured2With height ratio capacity metal-oxide uniform load combining closely on the exposed surface of simple graphene nanometer sheet.The ternary multistage multidimensional structure composite of the present invention effectively combines the prominent function of each component: TiO2The electric conductivity that excellent cycle performance and prominent safety, the height ratio capacity of secondary phase metal-oxide and simple Graphene are good.
Description
Technical field
The invention belongs to technical field of energy material, relate to a kind of ternary multistage multidimensional structure TiO2
-height ratio capacity metal-oxide-simpleness graphene composite material and preparation method thereof.
Background technology
The mankind bring serious energy crisis and environmental pollution to the exhaustive exploitation of fossil resource,
Thus having caused the flourish of electric motor car, this just requires that lithium ion battery is to higher energy density
Develop with power density.But current lithium ion battery commercialization negative material graphite, no
Only specific capacity is low, and relatively low intercalation potential easily causes serious safety problem, far from
The demand of high performance lithium ion battery of future generation can be met.So seeking to have more high electrochemical
The negative pole substitution material of energy has attracted the extensive concern of whole world scientific research person.
Researchers propose numerous anode substitution material in, nanostructured (as nanoparticle,
Nanometer rods, nanotube etc.) TiO2, show one's talent owing to it has following advantage, than
Such as low cost, environmentally friendly, Li+The evolving path is short, particularly zero volume emergent property band
The high structural stability come.Additionally, its of a relatively high intercalation potential (1.6-1.8Vvs.
Li+/ Li) (its reduction potential is at 1V (vs.Li can be prevented effectively from the decomposition of electrolyte+/Li)
Below) and the formation of Li dendrite so that the TiO of nanostructured2Become a kind of high security to bear
Pole material.But despite the presence of above-mentioned many advantages, nanostructured TiO2Still because of as follows
Of both its actual application of drawbacks limit: (1) relatively low theoretical specific capacity (～170mA
h g-1) even can not compete with graphite-phase；(2) relatively low electronic conductivity (～10-12 S cm-1)
Capacity during high-multiplying power discharge is caused to reduce.
The defect low in order to make up capacity, is attempted to nanostructured TiO2Compare with having height
Capacity (750-1250 mAh g-1) secondary phase metal oxide materials combine, such as Fe2O3、
Fe3O4、SnO2、Co3O4Or MnO2Deng.These binary heterojunction structures are retaining nano-TiO2
Specific capacity is substantially increased while advantage.But the same TiO of these oxide materials2It is identical,
Broadly falling into wide bandgap semiconductor materials material even insulator, its intrinsic low conductivity causes relatively
The electric charge transmission kinetics of difference so that capacity rapid decay.Low conductivity is also unfavorable for eliminating electricity
The extremely upper Joule heat produced, brings certain potential safety hazard.And nano level metal-oxide
Increase resistance owing to adding crystal boundary, be degrading cycle performance further.
In general, the electrical conductivity defect of active material can solve by introducing conductive agent,
The Graphene (Chemically Converted Grephene, CCG) of such as chemical modification or
Claim redox graphene (reduced-Grephene Oxide, r-GO).Using CCG as
The matrix of metal oxide-loaded nanoparticle, can be that electrode provides quick electric transmission to lead to
Road.Unfortunately, oxidation-reduction process when preparing CCG needs to consume substantial amounts of poisonous
Oxidizing and Reducing Agents, causes inevitably destruction to environment.And in the process,
The electrical conductivity of CCG also can suffer slackening largely.Therefore straight with from native graphite
Connect the high-quality simpleness Graphene (Pristine Graphene, PG) that ultrasonic stripping obtains to compare,
The most inadequate also heterogeneity of electrical conductivity of CCG.And the preparation condition of simpleness Graphene is more
Gentleness, therefore simple Graphene is more conducive to as electrode than CCG more economical and environmentally friendly
High-effective conductive agent, with guarantee active material circulation and high rate performance in terms of good reliability and
Repeatability.But by metal oxide supported on simple Graphene, be technically one huge
Big challenge.Up to the present, rare report.Its difficult point is that simple Graphene has chemistry
Inertia, lacks the oxygen-containing functional group that CCG is had, it is difficult to utilize Hydrothermal Synthesis or electrostatic
Interaction realizes functionalization.Tsing-Hua University Liu Yitao etc. use complexing successfully real
Simple Graphene and metal or the assembling of metal oxide nanoparticles are showed.But this method
Need to introduce organic ligand and metal ion as cross-linking agent, not only complex steps, complex process,
And it is relatively costly.
Through prior art retrieval is found, there is not yet relevant TiO the most both at home and abroad2-Fabrication of High Specific Capacitance
Amount metal-oxide (Fe2O3、Fe3O4、SnO2、Co3O4Or MnO2Deng)-simple stone
The open report of ink alkene composite, rarely seen several such as TiO2-Fe3O4-Graphene(Lu
Jin et al.Appl.Mater.Interfaces 2013,5,7330-7334),
TiO2-SnO2-Graphene (Jiang Xin et al.New J.Chem.2013,37,
3671-3678)、G-TiO2@Co3O4 NBs(Luo Yongsong et al.J.Mater.Chem.
A2013,1,273-281) it is all TiO2Compound, even with metal-oxide and CCG
TiO2-Fe3O4-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.
RSC Adv.2014,4,18132-18135), TiO2-SnO2-Graphene(Tang Yanping et
Al.Energy Environ.Sci.2013,6,2447-2451) it is TiO2With metal-oxide and oxygen
Being combined of functionalized graphene (Graphene Oxide, GO).Graphene oxide (GO) conductance
Rate is extremely low, and the electrical conductivity of the Graphene of chemical modification (CCG) compares simple Graphene (PG)
The most inadequate also heterogeneity.
Summary of the invention
For nano-TiO2Defect in terms of specific capacity and electrical conductivity, the present invention is by secondary mutually high
Specific capacity metal-oxide and the codope of high conductivity simpleness Graphene component, it is provided that a kind of
Ternary multistage multidimensional structure TiO2-height ratio capacity metal-oxide-simpleness Graphene composite wood
Material and preparation method thereof, utilizes its prominent cooperative effect and unique multistage multidimensional structure, sends out
Shoot the electrochemistry combination property of excellence.
The ternary multistage multidimensional structure TiO of the present invention2-height ratio capacity metal-oxide-simpleness
Graphene composite material, its composition characteristic be composite be by the TiO of low-dimensional nano structure2、
Secondary phase height ratio capacity metal-oxide and two dimension micron (x-y plane direction) high conductivity are simple
Three kinds of components of Graphene are with the ternary heterojunction of composition of proportions that mol ratio is 2～5: 1～4: 3～5
Structure, effectively combines the prominent function of each component: TiO2Excellent cycle performance is with prominent
Safety, height ratio capacity (the 750-1250mAh g of secondary phase metal-oxide-1) and simple
The electric conductivity that Graphene is good.
In the present invention, described height ratio capacity metal-oxide is Fe2O3、Fe3O4、SnO2、
Co3O4Or MnO2Deng any one of height ratio capacity metal-oxide.
In the present invention, described TiO2, height ratio capacity metal-oxide and simple Graphene mole
Ratio can be 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
A kind of ratio, the actual chemical property that this mol ratio goes out according to composite material exhibits is carried out really
Fixed.
The ternary multistage multidimensional structure TiO of the present invention2-height ratio capacity metal-oxide-simpleness
Graphene composite material, its architectural feature is the TiO of nanostructured2With height ratio capacity metal oxygen
Compound uniform load combining closely is constituted on the exposed surface of simple graphene nanometer sheet
Multistage multidimensional structure, wherein simple graphene nanometer sheet be that micron order is two-dimentional on the x-y plane
Structure, TiO2For zero-dimension nano particle, and height ratio capacity metal-oxide be monodimension nano stick,
Any one one-dimensional nano structure such as nano wire, nanotube, nanoneedle or nano belt；Or TiO2
For any one 1-dimention nanos such as monodimension nano stick, nano wire, nanotube, nanoneedle or nano belt
Structure, and height ratio capacity metal-oxide is zero-dimension nano particle, the tri compound so formed
Material, not only has zero dimension, a multidimensional structure that a peacekeeping two dimension coexists, and is provided simultaneously with receiving
The multilevel hierarchy that rice, micron combine, this micro-nano multi-level structure increases reaction active region
Meanwhile, also express passway is provided for charge transport.This ternary multistage multidimensional composite construction can
To give full play to the architectural characteristic of each component: (1) zero/one-dimensional TiO2With height ratio capacity gold
Belong to the nanoscale structures of oxide, Li can be shortened+With the transmission path of electronics, improve compound
The high rate capability of material；(2) micron order two dimension simpleness graphene nanometer sheet is as conductive agent,
Can be with TiO2Constitute 3 D stereo network with height ratio capacity metal-oxide, constitute and quickly lead
The 3 D stereo network structure of electricity；(3)TiO2As a kind of zero structure strain gauge material, Ke Yi
Charge and discharge process provides primary safety；(4) simple graphene nanometer sheet is as a kind of base
Body, has good pliability and elasticity, can alleviate Li in height ratio capacity metal-oxide+
The structural stress that intercalation/deintercalation process is brought, the suppression change in volume of composite and electrode
Efflorescence；(5) zero/one-dimensional height ratio capacity metal-oxide of simple graphenic surface and TiO2Make
For a kind of spacer, the stacking again of simple Graphene can be avoided, increase interlamellar spacing further,
Be conducive to Li+Intercalation/deintercalation.
Above-mentioned one-dimensional nano structure, can be nanometer rods, nano wire, nanotube, nanoneedle or
Any one one-dimensional nano structure such as nano belt.
Above-mentioned ternary multistage multidimensional structure TiO2-height ratio capacity metal-oxide-simpleness graphite
The preparation method of alkene composite, it is as follows that it is embodied as step:
(1) by native graphite powder body in METHYLPYRROLIDONE (NMP) ultrasonic directly
Peeling off is simple Graphene, and simpleness Graphene is transferred to its poor solvent oxolane
(THF) in；
(2) hydro-thermal reaction, hydrolysis etc. is utilized to synthesize nanostructured TiO2, and by TiO2
Transfer in its good solvent oxolane；
(3) a kind of Fe of the synthesis such as hydro-thermal reaction, hydrolysis is utilized2O3、Fe3O4、SnO2、
Co3O4Or MnO2Nanostructured height ratio capacity metal-oxide, and transfer to its good solvent four
In hydrogen furan；
(4) above-mentioned three kinds of solution are mixed with certain proportion, and stir 6～12 hours, in fall
Under the driving force of the free energy of low system, it is assembled into ternary multistage multidimensional structure TiO2Nanoparticle
Son-height ratio capacity metal-oxide-simpleness graphene nanometer sheet composite.
In the present invention, the oxolane (THF) described in step (1) is simple Graphene
Poor solvent, has unmatched Hansen between simple Graphene and oxolane molten in THF
Solution degree parameter, thus there is the strong tendency again stacked, thus THF can not reduce matter
The huge surface free energy that Piao's Graphene is had.
In the present invention, the oxolane (THF) described in step (2) and (3) is TiO2
With the good solvent of height ratio capacity metal-oxide, these metal-oxides can be in oxolane
Stable existence.
In the present invention, the driving force described in step (4) is the total free energy reducing solution system.
In THF, simple Graphene has huge surface free energy, the most more stable nano junction
The TiO of structure2It is introduced in THF with height ratio capacity metal-oxide, will be at van der
Waals trends towards under interacting residing on the exposed surface of simple graphene nanometer sheet, with
Reduce the total surface free energy of solution system, make the simple Graphene two-dimensional nano sheet in THF
Stabilisation, thus successfully assemble ternary multistage multidimensional structure TiO2The burning of-height ratio capacity
Thing-simpleness graphene composite material.
The present invention by native graphite powder body in METHYLPYRROLIDONE (NMP) ultrasonic directly
Connect stripping for simple Graphene；Then simpleness Graphene is transferred to its poor solvent-tetrahydrochysene furan
Mutter in (THF), in THF simple Graphene due to Hansen unmatched between solvent molten
Solution degree parameter has a strong tendency again stacked, the step for the most successfully carrying out classification
Collaborative assembling is the most crucial, because THF can not reduce what insoluble two-dimensional nano sheet was had
Huge surface free energy.The TiO of the most more stable nanostructured2With height ratio capacity metal oxygen
Compound is once introduced in THF, will tend to because van der Waals interacts
On the exposed surface residing in simple graphene nanometer sheet, to reduce the total surface of solution system
Free energy, makes the two-dimensional nano layer-stabilizing in THF.This self-assembling method is not because drawing
Enter external cross-linking agent, compare and utilize complexing to prepare metal-oxide-simpleness Graphene again
The method of condensation material, has the gentle and advantage of low cost.
Accompanying drawing explanation
Fig. 1 is ternary multistage multidimensional structure TiO in embodiment 12-height ratio capacity metal-oxide
(Fe3O4The X-ray diffractogram of)-simple Graphene (PG) composite；
Fig. 2 is ternary multistage multidimensional structure TiO in embodiment 12-height ratio capacity metal-oxide
(Fe3O4The transmission electron microscope picture of)-simple Graphene (PG) composite；
Fig. 3 is ternary multistage multidimensional structure TiO in embodiment 12-height ratio capacity metal-oxide
(Fe3O4The high-resolution-ration transmission electric-lens figure of)-simple Graphene (PG) composite；
Fig. 4 is ternary multistage multidimensional structure TiO in embodiment 12-height ratio capacity metal-oxide
(Fe3O4)-simple Graphene (PG) composite is at 0.5Ag-1Following under electric current density
Ring performance chart.
Detailed description of the invention
Below in conjunction with the accompanying drawings technical scheme is further described, but does not limit to
So, every technical solution of the present invention is modified or equivalent, without deviating from this
The spirit and scope of bright technical scheme, all should contain in protection scope of the present invention.
Embodiment 1
For nano-TiO2Defect in terms of low specific capacity and low conductivity, by secondary mutually high ratio
Capacitance metal oxide Fe3O4(927mA h g-1) and high conductivity simpleness Graphene component
Codope, present embodiments provides a kind of ternary multistage multidimensional structure TiO2Nanometer rods-Fe3O4
Nanoparticle-simpleness graphene nanometer sheet composite, utilizes its prominent cooperative effect with only
Special multistage multidimensional structure, has given play to the electrochemistry combination property of excellence.
The ternary multistage multidimensional structure TiO that the present embodiment provides2Nanometer rods-Fe3O4Nanoparticle
-simple graphene nanometer sheet composite is by TiO2、Fe3O4With high conductivity simpleness graphite
The ternary heterojunction structure that three kinds of components of alkene are constituted with the mol ratio of 4: 2: 4, its preparation method is as follows:
(1) native graphite powder body is joined in METHYLPYRROLIDONE (NMP), just
Beginning concentration is 10mg mL-1, then under 70W power ultrasonic 4 hours.Outstanding by obtain
Supernatant liquid is centrifuged 30 minutes under the rotating speed of 2000 revs/min, then collects supernatant vacuum
Sucking filtration.The pressed powder filtered is joined in THF and ultrasonic, obtain black simpleness graphite
Alkene dispersion soln.
(2) by 3mmol Fe (acac)3, 30mL oleyl amine and 30mL octadecylene mixing, and
It is heated to 280 DEG C under nitrogen atmosphere protection and is incubated 1 hour, then naturally cool to room temperature.Will
Sedimentation afterproduct ethanol is washed 2～3 times, and is vacuum dried 12 hours at 40 DEG C, obtains
Fe3O4Nanoparticle.By above-mentioned dried Fe3O4Nanoparticle is dissolved in THF, obtains
Brown Fe of 1mg/mL3O4Solution.
(3) by 5mmol butyl titanate, 25mmol oleyl amine, 25mmol oleic acid and 100mL
Ethanol joins in 35mL politef cup and stirs 10 minutes, then by this polytetrafluoro
Ethylene cup is put in a 130mL polytetrafluoroethyllining lining, and adds 20mL within the liner
(96Vol%) ethanol solution.Stainless steel cauldron is incubated 18 hours at 180 DEG C.
Product is collected and with washing with alcohol 2～3 times after natural cooling, 40 DEG C of vacuum drying 12 hours,
Obtain TiO2Nanometer rods.By above-mentioned dried TiO2Nanometer rods is dissolved in THF, obtains
The milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO2∶Fe3O4: the mixed in molar ratio of PG=4: 2: 4, and
Stir 10 hours.In whipping process, organically-modified Fe3O4Nanoparticle and TiO2Receive
Rice rod can spontaneously be assembled on the exposed surface of simple Graphene, obtains ternary multistage multidimensional knot
Structure TiO2Nanometer rods-Fe3O4Nanoparticle-simpleness graphene nanometer sheet composite.
The ternary multistage multidimensional structure TiO of the present embodiment2Nanometer rods-Fe3O4Nanoparticle-matter
Piao's graphene composite material, can effectively combine the prominent function of each component: TiO2Excellent
Cycle performance and prominent safety, Fe3O4Height ratio capacity (927mA h g-1), low
The electric conductivity that cost is good with simple Graphene, thus the electrochemistry showing excellence is comprehensive
Energy.Its architectural feature is: TiO2Nanometer rods and Fe3O4Nanoparticle uniform load is also closely tied
It is combined on the exposed surface of simple graphene nanometer sheet the multistage multidimensional structure constituted, Qi Zhongzhi
Piao's graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO2For monodimension nano stick,
And Fe3O4For zero-dimension nano particle, the trielement composite material so formed not only have zero dimension,
The multidimensional structure that one peacekeeping two dimension coexists, and be provided simultaneously with nanometer, that micron combines is multistage
Structure.The structure that this ternary multistage multidimensional composite construction can give full play to each component is special
Property: (1) low-dimensional TiO2And Fe3O4Nanoscale structures, Li can be shortened+Biography with electronics
Defeated path, improves the high rate capability of composite；(2) micron order two dimension simpleness Graphene is received
Rice sheet, can be with TiO as conductive agent2And Fe3O4Form 3 D stereo network, construct quickly
The 3 D stereo network structure electrode of conduction；(3)TiO2As a kind of zero structure strain gauge material,
Primary safety can be provided in charge and discharge process；(4) simple graphene nanometer sheet conduct
A kind of matrix, has good pliability and elasticity, can alleviate Fe3O4At Li+Embed/de-
Go out the structural stress that process is brought, the change in volume of suppression composite and the efflorescence of electrode；(5)
Zero dimension Fe of simple graphenic surface3O4With one-dimensional TiO2As spacer, simpleness can be avoided
Again the stacking of Graphene, increases interlamellar spacing, beneficially Li further+Intercalation/deintercalation.
Embodiment 2
The present embodiment is unlike embodiment 1: step (3): added by 35 grams of oleic acid
In the 50 milliliters of three-necked bottles being connected with reflux cooler, and 120 DEG C dry 1 with vigorous stirring
Hour, nitrogen stream is cooled to 80～100 DEG C.Then 1mmol titanium tetraisopropylate is added
In oleic acid and stir 5 minutes, solution is made to become light yellow from white.10mmol is hydroxylated
Tetrabutyl ammonia is dissolved in 2mL water, and in inhalation syringe, is then rapidly injected mixed solution
In, make solution be maintained at 80～100 DEG C, and gentle water stirred at reflux condition 8 hours,
Then stop heating, water is removed obtain clear solution under vacuum.In above-mentioned solution
Add 20mL ethanol, be precipitated, after being centrifuged, use ethanol purge 2 times, and in 40 DEG C of vacuum
It is dried 12 hours, obtains TiO2Nanometer rods.By above-mentioned dried TiO2Nanoparticle is dissolved in
In THF, obtain the milky white solution of 1mg/mL.Step (4): three kinds of components mole
Ratio is TiO2∶Fe3O4: PG=3: 3: 4.
Embodiment 3
For nano-TiO2Defect in terms of low specific capacity and low conductivity, by secondary mutually high ratio
Capacitance metal oxide Co3O4(891mA h g-1) and high conductivity simpleness Graphene component
Codope, present embodiments provides a kind of ternary multistage multidimensional structure TiO2Nanoparticle-
Co3O4Nano belt-simpleness graphene nanometer sheet composite, utilizes its prominent cooperative effect
With unique multistage multidimensional structure, give play to the electrochemistry combination property of excellence.
Ternary multistage multidimensional structure TiO in the present embodiment2Nanoparticle-Co3O4Nano belt
-simple graphene nanometer sheet composite is by TiO2、Co3O4With high conductivity simpleness graphite
The ternary heterojunction structure that three kinds of components of alkene are constituted with the mol ratio of 3: 3: 4, its preparation method is as follows:
(1) native graphite powder body is joined in METHYLPYRROLIDONE (NMP), just
Beginning concentration is 10mg mL-1, then under 70W power ultrasonic 4 hours.Outstanding by obtain
Supernatant liquid is centrifuged 30 minutes under the rotating speed of 2000 revs/min, then collects supernatant vacuum
Sucking filtration.The pressed powder filtered is joined in THF and ultrasonic, obtain black simpleness graphite
Alkene dispersion soln.
(2) by 0.1g Co (NO3)2·6H2O、0.5g CO(NH2)2With 0.37g NH4F adds
In 40mL deionized water, and it is stirred at room temperature 10 minutes.It is then transferred into 50mL
In stainless steel cauldron, react 4 hours at 120 DEG C, naturally cool to room temperature.Product is used
Washing with alcohol 3 times, and within 12 hours, obtain Co 40 DEG C of vacuum drying3O4Nano belt.By upper
State dried Co3O4Nano belt is dissolved in THF, obtains the Co of 1mg/mL3O4Solution.
(3) 0.2mL butyl titanate and 25mL isopropanol are mixed and stirred for 30 minutes,
Then it is added dropwise over 1mL deionized water and stirs 30 minutes.Then above-mentioned mixed solution is turned
In the polytetrafluoroethyllining lining stainless steel autoclave of 50mL, react 6 hours at 180 DEG C,
Naturally cool to room temperature, by product washing with alcohol 3 times and little 40 DEG C of vacuum drying 12
Time, obtain TiO2Nanoparticle.By above-mentioned dried TiO2Nanoparticle is dissolved in THF,
Obtain the milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO2∶Co3O4: the mixed in molar ratio of PG=3: 3: 4, and
Stir 10 hours.In whipping process, organically-modified Co3O4Nano belt and TiO2Nanometer
Particle can spontaneously be assembled on the exposed surface of simple Graphene, obtains ternary multistage multidimensional knot
Structure TiO2Nanoparticle-Co3O4Nano belt-simpleness graphene nanometer sheet composite.
The ternary multistage multidimensional structure TiO of the present embodiment2Nanoparticle-Co3O4Nano belt-
Simple graphene nanometer sheet composite, has the prominent merit that can effectively combine each component
Can: TiO2Excellent cycle performance and prominent safety, Co3O4Height ratio capacity (891mA
h g-1) and the good electric conductivity of simple Graphene, thus the electrochemistry showing excellence is comprehensive
Performance.Its architectural feature is: TiO2Nanoparticle and Co3O4Nano belt uniform load is the tightst
It is combined on the exposed surface of simple graphene nanometer sheet and constitutes multistage multidimensional structure, wherein simple
Graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO2For zero-dimension nano particle,
And Co3O4For 1-dimention nano band, the trielement composite material so formed, not only have zero dimension,
The multidimensional structure that one peacekeeping two dimension coexists, and be provided simultaneously with nanometer, that micron combines is multistage
Structure.The structure that this ternary multistage multidimensional composite construction can give full play to each component is special
Property: (1) low-dimensional TiO2And Co3O4Nanoscale structures, Li can be shortened+Biography with electronics
Defeated path, improves the high rate capability of composite；(2) micron order two dimension simpleness Graphene is received
Rice sheet, can be with TiO as conductive agent2And Co3O4Form 3 D stereo network, construct fast
The 3 D stereo network structure electrode of speed conduction；(3)TiO2As a kind of zero structure strain gauge material,
Primary safety can be provided in charge and discharge process；(4) simple graphene nanometer sheet conduct
A kind of matrix, has good pliability and elasticity, can alleviate Co3O4At Li+Embed/de-
Go out the structural stress that process is brought, the change in volume of suppression composite and the efflorescence of electrode；(5)
Zero dimension TiO of simple graphenic surface2With one-dimensional Co3O4As spacer, matter can be avoided
Again the stacking of Piao's Graphene, increases interlamellar spacing, beneficially Li further+Intercalation/deintercalation.
Embodiment 4
For nano-TiO2Defect in terms of low specific capacity and low conductivity, by secondary mutually high ratio
Capacitance metal oxide S nO2(782mA h g-1) and high conductivity simpleness Graphene component
Codope, present embodiments provides a kind of ternary multistage multidimensional structure TiO2Nanometer rods-SnO2
Nanoparticle-simpleness graphene nanometer sheet composite, utilizes its prominent cooperative effect with only
Special multistage multidimensional structure, has given play to the electrochemistry combination property of excellence.
Ternary multistage multidimensional structure TiO in the present embodiment2Nanometer rods-SnO2Nanoparticle-
Simple graphene nanometer sheet composite is by TiO2、SnO2With high conductivity simpleness Graphene
The ternary heterojunction structure that three kinds of components are constituted with the mol ratio of 4: 2: 4, its preparation method is as follows:
(1) native graphite powder body is joined in METHYLPYRROLIDONE (NMP), just
Beginning concentration is 10mg mL-1, then under 70W power ultrasonic 4 hours.Outstanding by obtain
Supernatant liquid is centrifuged 30 minutes under the rotating speed of 2000 revs/min, then collects supernatant vacuum
Sucking filtration.The pressed powder filtered is joined in THF and ultrasonic, obtain black simpleness graphite
Alkene dispersion soln.
(2)0.3g Sn(Cl)4·5H2O is dissolved in 25mL deionized water and at the power of 240 watts
Under ultrasonic 10 minutes, be then transferred in reactor, 180 DEG C react 8 hours, will produce
Thing washing with alcohol 3 times, naturally cools to room temperature, and is vacuum dried 12 hours at 40 DEG C,
Obtain SnO2Nanoparticle.By above-mentioned dried SnO2Nanoparticle is dissolved in THF,
Obtain the SnO of 1mg/mL2Solution.
(3) by 5mmol butyl titanate, 25mmol oleyl amine, 25mmol oleic acid and 100mL
Ethanol joins in 35mL politef cup and stirs 10 minutes, then by this polytetrafluoro
Ethylene cup is put in-130mL polytetrafluoroethyllining lining, and adds 20mL within the liner
(96Vol%) ethanol solution.Stainless steel cauldron is incubated 18 hours at 180 DEG C.
Product is collected and with washing with alcohol 2～3 times after natural cooling, 40 DEG C of vacuum drying 12 hours,
Obtain TiO2Nanometer rods.By above-mentioned dried TiO2Nanometer rods is dissolved in THF, obtains
The milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO2∶SnO2: the mixed in molar ratio of PG=4: 2: 4, and
Stir 10 hours.In whipping process, organically-modified SnO2Nanoparticle and TiO2Receive
Rice rod can spontaneously be assembled on the exposed surface of simple Graphene, obtains ternary multistage multidimensional knot
Structure TiO2Nanometer rods-SnO2Nanoparticle-simpleness graphene nanometer sheet composite.
The ternary multistage multidimensional structure TiO of the present embodiment2Nanometer rods-SnO2Nanoparticle-matter
Piao's graphene composite material, can effectively combine the prominent function of each component: TiO2Excellent
Cycle performance and prominent safety, SnO2Height ratio capacity (782mA h g-1) and matter
The electric conductivity that Piao's Graphene is good, thus show the electrochemistry combination property of excellence.Its knot
Structure is characterized as: TiO2Nanometer rods and SnO2Nanoparticle uniform load is also combined closely in simpleness
Multistage multidimensional structure, wherein simple graphene nano is constituted on the exposed surface of graphene nanometer sheet
Sheet is micron order two-dimensional structure on the x-y plane, TiO2For monodimension nano stick, and SnO2For
Zero-dimension nano particle, the trielement composite material so formed, not only there is zero dimension, a peacekeeping two
The multidimensional structure that coexists of dimension, and be provided simultaneously with nanometer, multilevel hierarchy that micron combines.This
Kind of ternary multistage multidimensional composite construction can give full play to the architectural characteristic of each component: (1)
Low-dimensional SnO2And TiO2Nanoscale structures, Li can be shortened+With the transmission path of electronics,
Improve the high rate capability of composite；(2) micron order two dimension simpleness graphene nanometer sheet conduct
Conductive agent, can be with TiO2And SnO2Form 3 D stereo network, construct the three of Quick conductive
Dimension dimensional network structure electrode；(3)TiO2As a kind of zero structure strain gauge material, can fill
Discharge process provides primary safety；(4) simple graphene nanometer sheet is as a kind of matrix,
There is good pliability and elasticity, SnO can be alleviated2Middle Li+Intercalation/deintercalation process is brought
Structural stress, the suppression change in volume of composite and the efflorescence of electrode；(5) simple graphite
Zero dimension SnO on alkene surface2With one-dimensional TiO2As spacer, simple Graphene can be avoided
Again stack, increase interlamellar spacing, beneficially Li further+Intercalation/deintercalation.
Embodiment 5
For nano-TiO2Defect in terms of low specific capacity and low conductivity, by secondary mutually high ratio
Capacitance metal oxide M nO2(1233mA h g-1) and high conductivity simpleness Graphene component
Codope, present embodiments provide a kind of ternary multistage multidimensional structure TiO2Nanoparticle-
MnO2Nano wire-simpleness graphene nanometer sheet composite, utilizes its prominent cooperative effect
With unique multistage multidimensional structure, give play to the electrochemistry combination property of excellence.
Ternary multistage multidimensional structure TiO in the present embodiment2Nanoparticle-MnO2Nano wire-
Simple graphene nanometer sheet composite is by TiO2、MnO2With high conductivity simpleness Graphene
The ternary heterojunction structure that three kinds of components are constituted with the mol ratio of 3: 2: 5, its preparation method is as follows:
(1) native graphite powder body is joined in METHYLPYRROLIDONE (NMP), just
Beginning concentration is 10mg mL-1, then under 70W power ultrasonic 4 hours.Outstanding by obtain
Supernatant liquid is centrifuged 30 minutes under the rotating speed of 2000 revs/min, then collects supernatant vacuum
Sucking filtration.The pressed powder filtered is joined in THF and ultrasonic, obtain black simpleness graphite
Alkene dispersion soln.
(2) by 0.008mol MnSO4·H2O and 0.008mol (NH4)2S2O8Join
In 50mL deionized water and stir 10 minutes, then forward above-mentioned mixed solution to 50mL
In polytetrafluoroethyllining lining stainless steel autoclave, react 6 hours at 120 DEG C, naturally cool to
Room temperature, by black solid product washing with alcohol 3 times, and is vacuum dried 12 hours at 40 DEG C,
Obtain MnO2Nano wire.By above-mentioned dried MnO2Nano wire is dissolved in THF, obtains
The black MnO of 1mg/mL2Solution.
(3) 0.2mL butyl titanate and 25mL isopropanol are mixed and stirred for 30 minutes,
Then it is added dropwise over 1mL deionized water and stirs 30 minutes.Then above-mentioned mixed solution is turned
In the polytetrafluoroethyllining lining stainless steel autoclave of 50mL, react 6 hours at 180 DEG C,
Naturally cool to room temperature, by product washing with alcohol 3 times and little 40 DEG C of vacuum drying 12
Time, obtain TiO2Nanoparticle.By above-mentioned dried TiO2Nanoparticle is dissolved in THF,
Obtain the milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO2∶MnO2: the mixed in molar ratio of PG=3: 2: 5, and
Stir 10 hours.In whipping process, organically-modified MnO2Nano wire and TiO2Nanometer
Particle can spontaneously be assembled on the exposed surface of simple Graphene, obtains ternary multistage multidimensional knot
Structure TiO2Nanoparticle-MnO2Nano wire-simpleness graphene nanometer sheet composite.
The ternary multistage multidimensional structure TiO of the present invention2Nanoparticle-MnO2Nano wire-simpleness
Graphene nanometer sheet composite, can effectively combine the prominent function of each component: TiO2
Excellent cycle performance and prominent safety, MnO2Height ratio capacity (1233mA h g-1)
The electric conductivity good with low cost and simple Graphene, thus the electrochemistry showing excellence is combined
Close performance.Its architectural feature is: TiO2Nanoparticle and MnO2Nano wire uniform load is the tightest
Multistage multidimensional structure, Qi Zhongzhi is constituted on the close exposed surface being combined in simple graphene nanometer sheet
Piao's graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO2For zero-dimension nano grain
Son, and MnO2For one-dimensional nano line, the trielement composite material so formed, not only have zero
Dimension, the multidimensional structure that coexists of a peacekeeping two dimension, and be provided simultaneously with nanometer, micron combines
Multilevel hierarchy.This ternary multistage multidimensional composite construction can give full play to the knot of each component
Structure characteristic: (1) low-dimensional TiO2And MnO2Nanoscale structures, Li can be shortened+And electronics
Transmission path, improve composite high rate capability；(2) micron order two dimension simpleness graphite
Alkene nanometer sheet, can be with TiO as conductive agent2And MnO2Form 3 D stereo network, construct
The 3 D stereo network structure electrode of Quick conductive；(3)TiO2As a kind of zero structure strain material
Material, can provide primary safety in charge and discharge process；(4) simple graphene nanometer sheet
As a kind of matrix, there is good pliability and elasticity, MnO can be alleviated2Middle Li+Embedding
Enter/the structural stress that brings of abjection process, the change in volume of suppression composite and the powder of electrode
Change；(5) zero dimension TiO of simple graphenic surface2With one-dimensional MnO2As spacer, permissible
Avoid the stacking again of simple Graphene, increase interlamellar spacing, beneficially Li further+Embedding/
Abjection.
Embodiment 6
For nano-TiO2Defect in terms of low specific capacity and low conductivity, by secondary mutually high ratio
Capacitance metal oxide Fe2O3(1007mA h g-1) and high conductivity simpleness Graphene component
Codope, present embodiments provide a kind of ternary multistage multidimensional structure TiO2Nanoparticle-
Fe2O3Nanotube-simpleness graphene nanometer sheet composite, utilizes its prominent cooperative effect
With unique multistage multidimensional structure, give play to the electrochemistry combination property of excellence.
Ternary multistage multidimensional structure TiO in the present embodiment2Nanoparticle-Fe2O3Nanotube-
Simple graphene nanometer sheet composite is by TiO2、Fe2O3With high conductivity simpleness Graphene
The ternary heterojunction structure that three kinds of components are constituted with the mol ratio of 4: 2: 4, its preparation method is as follows:
(1) native graphite powder body is joined in METHYLPYRROLIDONE (NMP), just
Beginning concentration is 10mg mL-1, then under 70W power ultrasonic 4 hours.Outstanding by obtain
Supernatant liquid is centrifuged 30 minutes under the rotating speed of 2000 revs/min, then collects supernatant vacuum
Sucking filtration.The pressed powder filtered is joined in THF and ultrasonic, obtain black simpleness graphite
Alkene dispersion soln.
(2) it is the FeCl of 0.5mol/L by 3.2mL concentration3Solution, 2.88mL concentration are
The NH of 0.02mol/L4H2PO4Solution mixes under vigorous stirring, is subsequently adding deionized water
It is 80mL to cumulative volume and stirs 30 minutes.Then above-mentioned mixed solution is forwarded to 100mL
Polytetrafluoroethyllining lining stainless steel autoclave in, 220 DEG C react 16 hours, the coldest
But to room temperature, solid product ethanol and deionized water are respectively washed 3 times, and true at 80 DEG C
Empty dry 6 hours, obtain Fe2O3Nanotube.By above-mentioned dried Fe2O3Nanotube is molten
In THF, obtain the Fe of 1mg/mL2O3Solution.
(3) 0.2mL butyl titanate and 25mL isopropanol are mixed and stirred for 30 minutes,
Then it is added dropwise over 1mL deionized water and stirs 30 minutes.Then above-mentioned mixed solution is turned
In the polytetrafluoroethyllining lining stainless steel autoclave of 50mL, react 6 hours at 180 DEG C,
Naturally cool to room temperature, by product washing with alcohol 3 times and little 40 DEG C of vacuum drying 12
Time, obtain TiO2Nanoparticle.By above-mentioned dried TiO2Nanoparticle is dissolved in THF,
Obtain the milky white solution of 1mg/mL.
(4) by above-mentioned three kinds of components with TiO2∶Fe2O3: the mixed in molar ratio of PG=4: 2: 4, and
Stir 10 hours.In whipping process, organically-modified Fe2O3Nanotube and TiO2Nanometer
Particle can spontaneously be assembled on the exposed surface of simple Graphene, obtains ternary multistage multidimensional knot
Structure TiO2Nanoparticle-Fe2O3Nanotube-simpleness graphene nanometer sheet composite.
The ternary multistage multidimensional structure TiO of the present embodiment2Nanoparticle-Fe2O3Nanotube-matter
Piao's graphene nanometer sheet composite, can effectively combine the prominent function of each component:
TiO2Excellent cycle performance and prominent safety, Fe2O3Height ratio capacity (1007mA h
g-1) and low cost and the good electric conductivity of simple Graphene, thus show the electricity of excellence
Chemical synthesis performance.Its architectural feature is: TiO2Nanoparticle and Fe2O3Nanotube is uniformly born
Carry and combine closely the multistage multidimensional constituted on the exposed surface of simple graphene nanometer sheet
Structure, wherein simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO2
For zero-dimension nano particle, and Fe2O3For 1-dimention nano pipe, the trielement composite material so formed,
Not only there is zero dimension, multidimensional structure that a peacekeeping two dimension coexists, and be provided simultaneously with nanometer, micro-
The multilevel hierarchy that rice combines.This ternary multistage multidimensional composite construction can give full play to each
The architectural characteristic of kind component: (1) low-dimensional TiO2And Fe2O3Nanoscale structures, can shorten
Li+With the transmission path of electronics, improve the high rate capability of composite；(2) micron order two
The simple graphene nanometer sheet of dimension, can be with TiO as conductive agent2And Fe2O3Form 3 D stereo
Network, constructs the 3 D stereo network structure electrode of Quick conductive；(3)TiO2As a kind of zero
Structural strain material, can provide primary safety in charge and discharge process；(4) simple stone
Ink alkene nanometer sheet, as a kind of matrix, has good pliability and elasticity, can alleviate Fe2O3
Middle Li+The structural stress that intercalation/deintercalation process is brought, the change in volume of suppression composite and electricity
The efflorescence of pole；(5) zero dimension TiO of simple graphenic surface2With one-dimensional Fe2O3As spacer,
The stacking again of simple Graphene can be avoided, increase interlamellar spacing, beneficially Li further+'s
Intercalation/deintercalation.
By multistage for the ternary described in above-described embodiment multidimensional structure TiO2-height ratio capacity metal
Oxide-simpleness graphene composite material is assembled into button cell, material proportion in button cell
For composite: acetylene black: PVDF=70: 20: 10, use Clgard2300 type barrier film, to electricity
Extremely metal buries sheet, and electrolyte is by LiPF6, ethylene carbonate and carbonic acid diethyl ester composition (electricity
Solve LiPF in liquid6Concentration is 1mol/L, and ethylene carbonate with the volume ratio of carbonic acid diethyl ester is
1: 1), the glove box of full hydrogen is assembled into 2025 type button cells, charging/discharging voltage
Scope is 2.5～1.0V.
Fig. 1 is TiO2-Fe3O4The X-ray diffractogram of-PG composite, result shows
This composite is TiO2、Fe3O4With the complex of PG, there is no other dephasigns；Figure
2 is TiO2-Fe3O4The transmission electron microscope picture of-PG composite, it can be seen that bigger TiO2
Nanometer rods and less Fe3O4Nanoparticle uniform load at planar dimension in micron-sized simpleness
On graphene nanometer sheet；Fig. 3 is TiO2-Fe3O4The high-resolution transmission electricity of-PG composite
Mirror figure, result shows TiO2(101)、Fe3O4(311), the interplanar distance of PG (002) is respectively
0350～0.354nm, 0.255nm, 0.35nm, match with document；Fig. 4 is TiO2-Fe3O4
-PG composite is at 0.5Ag-1Cycle performance curve chart under electric current density, it can be seen that
This electrode shows good chemical property under the multiplying power being equivalent to 1C, follows for 100 times
After ring, specific discharge capacity remains above 500mAh g-1。
Claims (3)
1. a ternary multistage multidimensional structure TiO2The preparation method of height ratio capacity metal-oxide simpleness graphene composite material, it is characterised in that described preparation method step is as follows:
(1) simpleness Graphene is joined in oxolane, obtain black simpleness graphene dispersion solution；
(2) by TiO2Join in oxolane, obtain milky white solution；
(3) joining in oxolane by height ratio capacity metal-oxide, obtain metal oxide solution, described height ratio capacity metal-oxide is Fe2O3、Fe3O4、SnO2、Co3O4Or MnO2；
(4) by above-mentioned three kinds of solution mixing, and stir 6 ~ 12 hours, be assembled into ternary multistage multidimensional structure TiO2Nanoparticle height ratio capacity metal-oxide simpleness graphene nanometer sheet composite, wherein: TiO2, the mol ratio of height ratio capacity metal-oxide and simple Graphene be 2 ~ 5:1 ~ 4:3 ~ 5, the multistage multidimensional structure of described ternary is the TiO of nanostructured2With height ratio capacity metal-oxide uniform load the multistage multidimensional structure constituted on the exposed surface of simple graphene nanometer sheet of combining closely, described simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO2For zero-dimension nano particle, height ratio capacity metal-oxide is one-dimensional nano structure, or simple graphene nanometer sheet is micron order two-dimensional structure on the x-y plane, TiO2For one-dimensional nano structure, height ratio capacity metal-oxide is zero-dimension nano particle.
Ternary the most according to claim 1 multistage multidimensional structure TiO2The preparation method of height ratio capacity metal-oxide simpleness graphene composite material, it is characterised in that described TiO2, the mol ratio of height ratio capacity metal-oxide and simple Graphene 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.
Ternary the most according to claim 1 multistage multidimensional structure TiO2The preparation method of height ratio capacity metal-oxide simpleness graphene composite material, it is characterised in that described one-dimensional nano structure is nanometer rods, nano wire, nanotube, nanoneedle or nano belt.
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