CN104638256B - Nanocomposite, method for preparing nanocomposite, and lithium ion battery - Google Patents

Nanocomposite, method for preparing nanocomposite, and lithium ion battery Download PDF

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CN104638256B
CN104638256B CN201510056701.1A CN201510056701A CN104638256B CN 104638256 B CN104638256 B CN 104638256B CN 201510056701 A CN201510056701 A CN 201510056701A CN 104638256 B CN104638256 B CN 104638256B
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tio
nano
composite material
graphene oxide
polyaniline
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CN104638256A (en
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叶星
叶一星
王盼盼
刘俊
梁长浩
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Hefei Institutes of Physical Science of CAS
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Hefei Institutes of Physical Science of CAS
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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 nanocomposite, a method for preparing the nanocomposite, and a lithium ion battery. The nanocomposite is composed of a polyaniline nanolayer at the top, a TiO2/oxidized graphene composite layer at the centre and a polyaniline nanolayer at the bottom, wherein the polyaniline nanolayer is a nanometer-rod-shaped polyaniline array; the TiO2/oxidized graphene composite layer is formed in a manner that TiO2 nano-particles are distributed in the net structure of multi-layer oxidized graphene. The nanocomposite disclosed by the embodiment of he invention is good in cycling stability and high-rate discharge performance, nontoxic, environmentally friendly, and cheap in price; the preparation method of the nanocomposite is easy to operate, environmentally friendly and high-efficiency.

Description

A kind of nano composite material and preparation method thereof and lithium ion battery
Technical field
The present invention relates to field of nanometer material technology, more particularly, to a kind of nano composite material and preparation method thereof and use this receive The lithium ion battery that nano composite material is obtained.
Background technology
With the continuous progress of scientific and technological level, energy storage device just develops towards the direction of high-performance, miniaturization.Lithium-ion electric Pond not only has the advantages that self-discharge rate is little, has extended cycle life, memory-less effect, operating voltage are high, and has excellent height Low temperature performance, environmental protection, therefore lithium ion battery are the energy storage devices being widely recognized as by people at present.
In the prior art, the negative material of lithium ion battery mainly adopts material with carbon element, tin-based material, silica-base material, titanium The materials such as sill, nitride and transition metal oxide, but these materials all have the shortcomings that some are difficult to overcome, for example： 1. some materials, during forming SEI film, easily form Li dendrite, thus causing short circuit；2. some materials are de- in lithium During embedding, larger volumetric expansion being caused, thus causing the avalanche of material structure, and then leading to the cyclical stability of material Decline；Although 3. also have some Ti base negative material abundant raw material, nontoxic, cheaply stable, security good, specific capacity is not High, electronic conductivity is low, and surface cannot form effective electric field.In view of above some, people start to prepare quantum dot, alloy etc. Material, to reduce volumetric expansion, improves cyclical stability, but size is little and active high nano material is easily assembled, and inserts in lithium After entering alloy, mechanical stability is poor, easily makes material efflorescence.
Content of the invention
For above-mentioned weak point of the prior art, the invention provides a kind of nano composite material and preparation method thereof With the lithium ion battery being obtained using this nano composite material；This nano composite material not only have excellent cyclical stability and High-rate discharge ability, and material non-toxic, environmental friendliness, low price；And the preparation method operation of this nano composite material Simply, green high-efficient.
The purpose of the present invention is achieved through the following technical solutions：
A kind of nano composite material, by the polyaniline nano layer on top, middle TiO2/ graphene oxide composite bed, under The polyaniline nano layer in portion is constituted；
Wherein, described polyaniline nano layer is nano bar-shape polyaniline array；Described TiO2/ graphene oxide is combined Layer is TiO2Nano particle is distributed in the composite bed formed in the network structure of multilayer graphene oxide.
Preferably, described multilayer graphene oxide is 2～9 layers of graphene oxide.
Preferably, described TiO2/ graphene oxide composite bed is TiO2Nano particle is evenly distributed on multilayer graphite oxide Composite bed formed in the network structure of alkene.
Preferably, the thickness of the polyaniline nano layer of the polyaniline nano layer on top and bottom is 40～60nm.
A kind of preparation method of nano composite material, comprises the steps：
Step one, prepares the mixed solution of graphite oxide and hydrochloric acid using Hummers method, and in graphite oxide and hydrochloric acid Mixed solution in, using rotation TiO2Target carries out liquid laser corrode, thus amorphous TiO is obtained2The high activity of growth in situ TiO2/ graphene oxide composite material；
Step 2, to the high activity TiO being obtained in step one2/ graphene oxide composite material carries out ice bath stirring, is stirring Mix and add aniline monomer after half an hour, and carry out oxidation polymerization being stirring evenly and then adding into ammonium persulfate, thus obtain polyaniline/ TiO2/ graphene oxide ternary nano composite material.
Preferably, carry out rapidly the process of step 2 after step one end.
Preferably, in step 2, after adding aniline monomer, need to stir half an hour is stirred with reaching, then plus Enter ammonium persulfate and carry out oxidation polymerization.
A kind of lithium ion battery, the negative pole of this lithium ion battery adopts the nano composite material system described in such scheme Become.
As seen from the above technical solution provided by the invention, the nano composite material that the embodiment of the present invention is provided is One " sandwich structure ", in this " sandwich structure ", graphene oxide is prevented from the gathering of high-activity nano particle, and The nano bar-shape polyaniline array of outer layer provides easily passage for the transmission of ion and electronics, and hinders to a certain extent Stop the structural breakdown that internal layer active material causes because of volumetric expansion, give full play to internal layer TiO2The storage of/GO composite The nano composite material that lithium performance, the therefore embodiment of the present invention are provided presents excellent cyclical stability and high magnification is put Electrical property.And the preparation method of the nano composite material that the embodiment of the present invention is provided utilizes graphite oxide under liquid laser corrode The nano particle of alkene surface in situ growth has more Lacking oxygen and defect, and has high surface reaction activity, special thing The features such as Physicochemical property, so that aniline monomer can be in TiO2The upper and lower surface of/GO composite is with nano bar-shape array Form aggregation growth, and the embodiment of the present invention PANI/TiO that provided finally is obtained2/ GO ternary nano composite material.By This is visible, and the nano composite material that the embodiment of the present invention is provided not only has excellent cyclical stability and high-multiplying power discharge Can, and material non-toxic, environmental friendliness, low price；And the preparation method of this nano composite material is simple to operate, green is high Effect.
Brief description
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below will be to required use in embodiment description Accompanying drawing be briefly described it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this For the those of ordinary skill in field, on the premise of not paying creative work row, it can also be obtained according to these accompanying drawings His accompanying drawing.
The structural representation of the nano composite material that Fig. 1 a is provided by the embodiment of the present invention.
The nano composite material that Fig. 1 b is provided by the embodiment of the present invention is illustrated as principle during lithium ion battery negative Figure.
SEM (i.e. SEM) analysis chart of polyaniline in the prior art that Fig. 2 a provides for the present invention.
The sem analysis figure one of the nano composite material that Fig. 2 b is provided by the embodiment of the present invention.
The sem analysis figure two of the nano composite material that Fig. 2 c is provided by the embodiment of the present invention.
The nano composite material that Fig. 3 is provided by the embodiment of the present invention, TiO2/ GO and TiO2Raman spectrogram.
The TiO that Fig. 4 a is provided by the embodiment of the present invention2TEM (i.e. transmission electron microscope) analysis chart one of/GO.
The TiO that Fig. 4 b is provided by the embodiment of the present invention2The tem analysis figure two of/GO.
TEM, the HRTEM (i.e. high-resolution-ration transmission electric-lens) of the nano composite material that Fig. 4 c is provided by the embodiment of the present invention with And the analysis chart of SEAD (i.e. SEAD).
The performance schematic diagram one of the lithium ion battery that Fig. 5 a is provided by the embodiment of the present invention.
The performance schematic diagram two of the lithium ion battery that Fig. 5 b is provided by the embodiment of the present invention.
The performance schematic diagram three of the lithium ion battery that Fig. 5 c is provided by the embodiment of the present invention.
Specific embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Ground description is it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on this Inventive embodiment, the every other enforcement that those of ordinary skill in the art are obtained under the premise of not making creative work Example, broadly falls into protection scope of the present invention.
Separately below to nano composite material provided by the present invention and preparation method thereof with using this nano composite material Prepared lithium ion battery is described in detail.
(1) a kind of nano composite material
A kind of nano composite material, by polyaniline (i.e. PANI) nanometer layer on top, middle TiO2/ graphene oxide (i.e. Graphene oxide, GO) composite bed, the polyaniline nano layer of bottom are constituted.
Wherein, described polyaniline nano layer is nano bar-shape polyaniline array；Described TiO2/ graphene oxide is combined Layer is TiO2Nano particle is distributed in the composite bed formed in the network structure of multilayer graphene oxide.As Fig. 1 a and Fig. 1 b institute Show, this nano composite material is by TiO2/ graphene oxide composite bed and this TiO2The upper and lower table of/graphene oxide composite bed The nano bar-shape polyaniline array looking unfamiliar long is constituted, i.e. usually said " sandwich structure "；The polyaniline nano layer 1 on top Constituting 3 with the polyaniline nano layer of bottom is all the array being made up of nano bar-shape polyaniline a；In TiO2/ graphene oxide On composite bed 2, TiO2Nano particle c is distributed in the network structure of multilayer graphene oxide b.
Specifically, the specific embodiments of each layer of this nano composite material include：
(1) graphene oxide that preferably 2～9 layers of the multilayer graphene oxide described in；If the number of plies of graphene oxide More than 9 layers, then lose the pliability of graphene oxide structure script, and be unfavorable for a large amount of Li+Embedded and electronics quick Transmission；If the number of plies of graphene oxide is less than 2 layers, the acid environment in preparation process can make graphene oxide easily decompose With damaged it is impossible to form " sandwich structure ".
(2) TiO described in2/ graphene oxide composite bed is preferably TiO2Nano particle is evenly distributed on multilayer graphite oxide Composite bed formed in the network structure of alkene；TiO2Nano particle is evenly distributed in the network structure of multilayer graphene oxide Benefit be to increased TiO to greatest extent2Nano particle and the contact area of electrolyte, are prevented from TiO2Nano particle gathers Collect the loss of the lithium storage content bringing.
(3) thickness of the polyaniline nano layer of the polyaniline nano layer on top and bottom is 40～60nm, preferably all exists 50nm, the benefit of this thickness is that the transmission for ion and electronics provides easily passage, can not only effectively prevent The blocked up caused ion of polyaniline nano layer conveys not in time, and can effectively prevent polyaniline nano layer excessively thin caused The structural breakdown causing because of volumetric expansion.
Further, as illustrated in figs. ia and ib, the nano composite material that the embodiment of the present invention is provided is " a Sanming City Control structure ", in this " sandwich structure ", graphene oxide b is prevented from the gathering of high-activity nano particle, and the receiving of outer layer The bar-shaped polyaniline a array of rice provides easily passage for the transmission of ion and electronics, and prevents interior to a certain extent The structural breakdown that layer active material causes because of volumetric expansion, has given full play to internal layer TiO2The storage lithium performance of/GO composite, The nano composite material that therefore embodiment of the present invention is provided presents excellent cyclical stability and high-rate discharge ability.
As can be seen here, the embodiment of the present invention make use of graphene oxide excellent to the peptizaiton of nano particle and polyaniline Electric conductivity solve the problems, such as that liquid laser corrode technology volume production is low, remain obtained TiO2The high of/GO composite is lived Property, so that the nano composite material that the embodiment of the present invention is provided has excellent cyclical stability and high-multiplying power discharge Energy；And this nano composite material only relates to polyaniline, TiO2, these three materials of graphene oxide, therefore embodiment of the present invention institute The nanocomposites providing are nontoxic, environmental friendliness, low price.
(2) preparation method of this nano composite material
The preparation method of nano composite material described in technique scheme, comprises the steps：
Step one, prepares the mixed solution of graphite oxide and hydrochloric acid using Hummers method, and in graphite oxide and hydrochloric acid Mixed solution in, using rotation TiO2Target carries out liquid laser corrode, thus amorphous TiO is obtained2The high activity of growth in situ TiO2/ GO composite.
Step 2, to the high activity TiO being obtained in step one2/ GO composite carries out ice bath stirring, in stirring half an hour Add aniline monomer afterwards, and (typically require stirring half an hour can reach the state of stirring) added after stirring Ammonium sulfate carries out oxidation polymerization, thus obtaining PANI/TiO2/ GO ternary nano composite material.
Specifically, preferably carry out rapidly the process of step 2 after step one end, this is due to just making in step one The fresh TiO obtaining2/ GO composite has high activity, and surface has more Lacking oxygen and defect；If do not walked rapidly Rapid two process, then TiO2/ GO composite can be spontaneous the stable crystal structure of formation, activity runs off, thus can not be Aniline monomer provides avtive spot aggregation growth, leads to not form composite.
Further, the preparation method of this nano composite material utilizes surface of graphene oxide original position under liquid laser corrode The nano particle of growth has more Lacking oxygen and defect, and has high surface reaction activity, special physicochemical properties The features such as, so that aniline monomer can be in TiO2The upper and lower surface of/GO composite is polymerized in the form of nano bar-shape array Growth, and PANI/TiO that the embodiment of the present invention provided finally is obtained2/ GO ternary nano composite material.
As can be seen here, the preparation method of this nano composite material that the embodiment of the present invention is provided is not only simple to operate, and And environmental protection, production efficiency height.
(3) a kind of lithium ion battery
A kind of lithium ion battery, its negative pole is made using the nano composite material described in technique scheme.By above-mentioned Content understands, the nano composite material that the embodiment of the present invention is provided, when the negative pole as lithium ion battery uses, shows Excellent cyclical stability and high-rate discharge ability, the lithium ion battery that therefore embodiment of the present invention is provided has excellent Cyclical stability and high-rate discharge ability.
In order to more clearly from show technical scheme provided by the present invention and produced technique effect, below by Test and combine nano composite material that accompanying drawing is provided to the embodiment of the present invention and preparation method thereof and lithium ion battery is carried out Describe in detail.
Experiment 1
In order to preferably characterize the PANI/TiO that the embodiment of the present invention is provided2The pattern of/GO ternary nano composite material, Obtain this PANI/TiO2The sem analysis figure of/GO ternary nano composite material, as shown in Fig. 2 b and Fig. 2 c；Meanwhile, using existing The prepared polyaniline of method in technology, and obtain the sem analysis figure of polyaniline, as shown in Figure 2 a.From Fig. 2 a, prior art In polyaniline be a diameter of 50nm about nano wire, and uniform free from admixture；From Fig. 2 b and Fig. 2 c, implement in the present invention The PANI/TiO that example is provided2In/GO ternary nano composite material, polyaniline is in the form of nanometer stub in TiO2/ GO composite wood The upper and lower surface of material assembles and grows and form array structure, and the thickness of this ternary structural composite is 115nm, single PANI/TiO2/ GO ternary nano composite material pattern is micron-sized.
Experiment 2
Obtain TiO respectively2TiO obtained by colloid, embodiment of the present invention step one2/ GO composite and the present invention The PANI/TiO that embodiment is finally obtained2The Raman spectrogram of/GO ternary nano composite material, concrete outcome can be as Fig. 3 institute Show.In figure 3, the PANI/TiO that curve a is finally obtained for the embodiment of the present invention2The Raman light of/GO ternary nano composite material Spectral curve, curve b is the TiO obtained by embodiment of the present invention step one2The Raman spectrum curve of/GO composite, curve c is TiO2The Raman spectrum curve of colloid；Understand by contrast：Curve a not only has D peak and the G peak of graphite oxide presence, Er Qiezeng Add this two characteristic peaks of 1175.8cm-1 and 1465.3cm-1, such characteristic peak belongs to the C-H vibration of quinonyl and phenyl, this Turn out the generation that there is polyaniline in the nano composite material that the embodiment of the present invention is finally obtained.
Experiment 3
In order to further determine that the Nomenclature Composition and Structure of Complexes of nano composite material that the embodiment of the present invention is finally obtained, respectively to this TiO obtained by inventive embodiments step one2/ GO composite, and the nano combined material that the embodiment of the present invention is finally obtained Material carries out tem analysis.Fig. 4 a and Fig. 4 b is the TiO obtained by embodiment of the present invention step one2The tem analysis of/GO composite Figure；TEM, HRTEM and SEAD analysis chart of the nano composite material that Fig. 4 c is finally obtained for the embodiment of the present invention；By Fig. 4 a, figure 4b and 4c can be seen that：Either TiO2Nano particle on/GO composite, or the embodiment of the present invention finally be obtained receive In nano composite material parcel nano particle all present unordered amorphous state, and diameter be less than or equal to 50nm, and they SEAD figure is also rendered as amorphous ring.Take the square frame 1 in Fig. 4 c to do mapping elementary analysis, find the very equal of Cl Elemental redistribution Even, illustrate that doped hydrochloride is good, this also implys that polyaniline in the nano composite material that the embodiment of the present invention is finally obtained accordingly Superior electric conductivity.Observe the distribution of Ti element and O element, can affirm that nano particle is made up of Ti and O.In conjunction with SEM figure and Raman analysis understands, the nano composite material that the embodiment of the present invention is finally obtained is the PANI/ amorphous TiO of sandwich structure2/ GO ternary nano composite material.
Experiment 4
The PANI/TiO that inventive embodiments are finally obtained2/ GO ternary nano composite material is centrifuged drying, and It is assembled into according to prior art with this PANI/TiO2/ GO ternary nano composite material is the lithium ion button shape cell of negative pole, more right The performance of this lithium ion button shape cell is tested, and its result is as shown in Fig. 5 a, Fig. 5 b and Fig. 5 c.Fig. 5 a is this lithium ion button The different cycle charge-discharge comparison diagrams of battery；Fig. 5 b is the cycle performance figure of this lithium ion button shape cell；Fig. 5 c is this lithium ion The high rate performance figure of button cell.Can be seen that in the case that current density is for 100mA/g by Fig. 5 a, this lithium ion button Battery discharges first and has just reached 591.3mAhg-1Even if, after having carried out 250 charge and discharge cycles, this lithium ion button shape cell according to So remain 443.6mAhg-1Electric discharge.Be can be seen that and button cell with PANI/GO as negative pole in prior art by Fig. 5 b Compare, the PANI/TiO being provided with the embodiment of the present invention2/ GO ternary nano composite material is the lithium ion button shape cell of negative pole Present more superior specific capacity.Be can be seen that by Fig. 5 c and carry out discharge and recharge under different multiplying powers, with embodiment of the present invention institute The PANI/TiO providing2/ GO ternary nano composite material be negative pole lithium ion button shape cell present one highly stable State；After carrying out 120 circulations, under the high current density of 10A/g, the PANI/TiO that provided with the embodiment of the present invention2/ GO ternary nano composite material is that the lithium ion button shape cell of negative pole still possesses 140.9mAhg-1Specific capacity.Due to the present invention The PANI/TiO that embodiment is provided2In/GO ternary nano composite material, three materials have different embedding lithium speed, thus leading Cause the process having individual capacity to rise in 50 initial circulations, but this has had no effect on what the embodiment of the present invention was provided PANI/TiO2/ GO ternary nano composite material has excellent cyclical stability and high rate performance.
As fully visible, the nano composite material that the embodiment of the present invention is provided not only has excellent cyclical stability and height Multiplying power discharging property, and material non-toxic, environmental friendliness, low price；And the preparation method operation letter of this nano composite material Single, green high-efficient.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto, Any those familiar with the art the invention discloses technical scope in, the change or replacement that can readily occur in, All should be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims Enclose and be defined.

Claims (8)

1. a kind of nano composite material is it is characterised in that by the polyaniline nano layer on top, middle TiO2/ graphene oxide is multiple Close layer, the polyaniline nano layer of bottom is constituted；
Wherein, described polyaniline nano layer is nano bar-shape polyaniline array；Described TiO2/ graphene oxide composite bed is TiO2Nano particle is distributed in the composite bed formed in the network structure of multilayer graphene oxide.
2. nano composite material according to claim 1 is it is characterised in that described multilayer graphene oxide is 2～9 layers Graphene oxide.
3. nano composite material according to claim 1 and 2 is it is characterised in that described TiO2/ graphene oxide is combined Layer is TiO2Nano particle is evenly distributed on the composite bed formed in the network structure of multilayer graphene oxide.
4. nano composite material according to claim 1 and 2 is it is characterised in that the polyaniline nano layer on top and bottom The thickness of polyaniline nano layer be 40～60nm.
5. a kind of preparation method of nano composite material is it is characterised in that comprise the steps：
Step one, prepares the mixed solution of graphite oxide and hydrochloric acid using Hummers method, and mixed in graphite oxide and hydrochloric acid Close in solution, using rotation TiO2Target carries out liquid laser corrode, thus amorphous TiO is obtained2The high activity of growth in situ TiO2/ graphene oxide composite material；
Step 2, to the high activity TiO being obtained in step one2/ graphene oxide composite material carries out ice bath stirring, in stirring half Add aniline monomer after hour, and carry out oxidation polymerization being stirring evenly and then adding into ammonium persulfate, thus obtain aforesaid right will Seek the nano composite material any one of 1 to 4.
6. preparation method according to claim 5 is it is characterised in that carry out rapidly the place of step 2 after step one terminates Reason.
7. the preparation method according to claim 5 or 6 is it is characterised in that in step 2, after adding aniline monomer, Need to stir half an hour is stirred with reaching, and adds ammonium persulfate and carries out oxidation polymerization.
8. a kind of lithium ion battery is it is characterised in that the negative pole of this lithium ion battery is using arbitrary in the claims 1 to 4 Nano composite material described in is made.
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CN104157833A (en) * 2014-08-25 2014-11-19 厦门大学 Graphene/titanium dioxide composite porous material, preparation method and application thereof

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