CN108649190A - Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application - Google Patents
Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- 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
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Abstract
The invention discloses the vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composites and its preparation method and application, this includes：Vertical and growth of entwining the graphene nanometer sheet on matrix；It is coated on the TiNb of the graphene nano on piece2O7, form VG/TiNb2O7Nanometer sheet；And it is coated on the VG/TiNb2O7Sulfur doping carbon-coating in nanometer sheet forms VG/TiNb2O7The three-dimensional porous arrays of@S C.The present invention is counter to have synthesized VG/TiNb2O7Nano-array prepares composite material of the present invention as carrier by constant current anodic deposition.Composite material of the present invention has the features such as high circulation stability, high rate capability and coulombic efficiency, when being matched with LiFePO4 or ternary material, is remarkably improved the energy density/power density and cyclical stability of full battery.The advanced composite material (ACM) of the present invention is suitable as lithium ion battery negative material, can be applied to various electronic equipments and electric vehicle and hybrid vehicle etc..
Description
Technical field
The present invention relates to the technical fields of ion secondary battery cathode material lithium, and in particular to one kind having three-dimensional porous battle array
The vertical graphene of array structure/titanium niobium oxygen/sulphur carbon composite and preparation method thereof and as lithium ion battery negative material
Using.
Background technology
Lithium ion battery is widely applied to communications and transportation, information electronics etc. as currently the most important ones electrical energy storage device
Field.The fast development of lithium ion battery depends primarily on the innovation of positive and negative pole material.And commercial applications are most commonly used negative
Pole Activated Graphite material easily forms dendrite, and silicon, tinbase compound have serious volume expansion again, moreover, easily forming SEI films
(solid electrolyte interface film, solid electrolyte interface), safety is poor.Though lithium titanate does not form SEI
Film, but theoretical capacity is relatively low, niobic acid titanium compound (TiNbxO2+2.5x) do not form SEI films in cyclic process, and it is theoretical
Capacity is relatively high, causes great concern.In niobic acid titanium compound, widely used is TiNb2O7With
Ti2Nb10O29, theoretical capacity is respectively 388 and 396mAh g-1.Wherein, TiNb2O7, carried first by the seminar of Goodenough
Go out, in its operating voltage range, without the formation of SEI films, and theoretical capacity is higher, slightly above the theoretical capacity of graphite.
But titanium niobate material native electronic/ionic conductivity is relatively low, limits high magnification chemical property.Therefore to by niobic acid
Titanium material is designed to high performance lithium ion cell electrode, it is necessary to is modified to it.
In view of the above problems, researcher usually optimizes its electrochemical lithium storage using following some modification modes both at home and abroad
Performance：Mainly have three ways, such as nanosizing, metal ion mixing and surface cladding etc..Electrode material design is synthesized into nanometer
The nanostructures such as pipe, nano wire, nano particle reduce electronics/lithium ion transport path, accelerate transmission speed, to improve electricity
Son/ion transmission efficiency；Using Ru4+, Cu2+, Mo6+Equal metal ions are doped, and are provided more vacancy and are passed convenient for ion
It is defeated, to improve its high magnification chemical property；It is highly conductive using Ag, CNTs (carbon nanotube), graphene (graphene) etc.
Property clad improve the contact interface between its electrode/electrolyte, reduce interfacial electrochemistry impedance, improve electron conductivity.But
It is that above-mentioned major part modification mode is based on dusty material.Powder electrode limits its electrochemistry there are binder and additive
The further improvement of energy.Film composite material does not need binder/additive, is suitable as the substitute of dusty material.Therefore,
Find a kind of high-specific surface area, the base material of high conductivity is very urgent, while being also structure high-performance niobic acid titanium-based
The preferred option of lithium ion battery.But in the array structure, electrode material TiNb2O7It will be in direct contact, lack with electrolyte
The quick transmission channel of electronics is lacked.Efficient surface conductance clad can provide channel for it and further increase electrochemistry
Energy.The VG/TiNb of above-mentioned synthesis2O7The compound porous array electrodes of@S-C have high rate capability, cyclical stability and coulombic efficiency
It is expected to become the energy high power density of commercial applications and the lithium ion battery negative material of energy density.
Invention content
For the problems in background technology, it is an object of the invention to the VG/TiNb of synthesizing high specific surface area2O7@S-C are multiple
Porous array electrode is closed, collaboration optimization is carried out by three-D nano-porous array substrate and coated with carbon bed, improves intrinsic electricity
The low problem of son/ionic mobility.
The present invention provides a kind of vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composites
And preparation method thereof and as lithium ion battery negative material application, with nucleocapsid VG/TiNb2O7@S-C are compound more
Hole array electrode, the material include VG nanometer porous array substrates, TiNb2O7Active material and S-C amorphous surfaces cladding
Carbon-coating.VG/TiNb2O7The compound porous array electrode using plasma chemical vapor depositions (PECVD) of@S-C, solvent-thermal method with
And prepared by constant current anodic deposition method, the VG/TiNb2O7Nanometer sheet thickness is 20-50nm, VG/TiNb2O7@S-C cores
Shell array thickness is 50-120nm.
Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite, including：
Vertical and growth of entwining graphene nanometer sheet (VG), forms three-D nano-porous structure on matrix；
It is coated on the TiNb of the graphene nano on piece2O7(i.e. TNO) forms VG/TiNb2O7Nanometer sheet；
And it is coated on the VG/TiNb2O7Sulfur doping carbon-coating (S-C) in nanometer sheet forms VG/TiNb2O7@S-C tri-
Tie up porous array.
The thickness of the graphene nanometer sheet is 5-8nm, the VG/TiNb2O7The thickness of nanometer sheet is 20-50nm,
The VG/TiNb finally obtained2O7Thickness (the i.e. VG/TiNb of the three-dimensional porous arrays of@S-C2O7@S-C nucleocapsid arrays nanometer sheet thickness)
For 50-120nm.
Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite, that is, be used for improve electronics/
The high-energy density of ionic conductivity/power density composite lithium ion battery cathode material, the material is by three-D nano-porous battle array
Row substrate and coated with carbon bed constitute and cooperate with optimization.
The compound VG/TiNb2O7The three-dimensional porous arrays of@S-C, by the vertical graphene nanoplatelets (VG for growth of entwining
~5-8nm) constitute nanometer porous array be conductive substrates, solvent thermal growth coat TNO, formed (VG/TiNb2O7) after core
Coat amorphous sulphur doping carbon-coating (S-C), the VG/TiNb2O7Nanometer sheet thickness is 20-50nm, VG/TiNb2O7@S-C nucleocapsids
Array nanometer sheet thickness is 50-120nm.
A kind of preparation method of the vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite, packet
Include that steps are as follows：
(1) preparation method of vertical graphene (VG)：By plasma enhanced chemical vapor deposition method (PECVD),
Graphene array is orderly deposited on carbon cloth, vertical graphene nanometer sheet (VG) is obtained；
(2)VG/TiNb2O7Preparation method：Vertical graphene nanometer sheet is dried, is made with the vertical graphene nanometer sheet
For growth substrate, isopropyl titanate (C is utilized12H28O4) and columbium pentachloride (NbCl Ti5) presoma is used as to carry out solvent thermal reaction,
Cleaning, drying after having reacted, heat treatment calcining obtain VG/TiNb2O7Nanometer sheet；
(3)VG/TiNb2O7The preparation method of@S-C：By 3,4- ethylenedioxy thiophenes (EDOT) and LiClO4It is dissolved in acetonitrile
In, by constant current anodic deposition, in the VG/TiNb of preparation2O7After depositing PEDOT (polymer of EDOT) in nanometer sheet, forge
It burns, obtains the vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite.
In step (1), in plasma enhanced chemical vapor deposition method, microwave frequency is 2.2~2.6GHz and microwave
Power 1.5kW~2.5kW, further preferably, microwave frequency are 2.45GHz and microwave power 2kW.
It specifically includes：
First, carbon cloth is placed in cavity and its air pressure is made to reach 10mTorr；
Secondly, after cavity temperature is increased to 400 DEG C, make to generate hydrogen plasma in cavity, hydrogen plasma passes through
H of the 500W microwave plasmas in 90sccm flow velocitys2It is generated in air-flow, while being passed through methane, in entire reaction process, hydrogen
Volume ratio with methane is 3:2, the reaction time remains 2h；
Finally, cooling, graphene nanometer sheet of the vertical-growth on carbon cloth is obtained, i.e., vertical graphene nanometer sheet (VG).
In step (2), the isopropyl titanate (C12H28O4Ti) with columbium pentachloride (NbCl5) mass ratio be 1：1.5
~2.5, further preferably, 0.5684g：1.08g.
The reaction condition of the solvent thermal reaction is：180 DEG C~220 DEG C reaction 4h~8h, further preferably, 200 DEG C
React 6h.
The condition of the described heat treatment calcining is：600 DEG C~800 DEG C heat treatment calcining 1h~3h, further preferably, 700
DEG C heat treatment calcining 2h.
The heat treatment calcining carries out under argon atmosphere.
In step (3), the 3,4-ethylene dioxythiophene (EDOT), LiClO4With the proportioning of acetonitrile be 0.3mL~
0.7mL：0.5g~1.5g：80mL~120mL, further preferably 0.5mL：1g：100ml.
The condition of the calcining is：600 DEG C~800 DEG C calcining 1h~3h, further preferably, 700 DEG C of calcining 2h.
The calcining carries out under argon atmosphere.
Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite has three-dimensional porous array
Structure is highly suitable as lithium ion battery negative material.
The present invention has the following advantages that and protrudes compared with the prior art effect：
In the present invention, VG/TiNb2O7The compound porous arrays of@S-C are thin-film material, and additive-free and binder has excellent
Cyclical stability more and high rate capability；VG porous, electrically conductive substrates have three-D nano-porous structure, increase electrode/electro solution
Liquid contact area shortens lithium ion transport path；The carbon-coating of sulfur doping coats the electron-transport between electrolyte and electrode
Express passway is provided, interface is improved, reduces interfacial migration resistance, to improve electron conductivity, reduce the intrinsic low electronics of material/
The influence of ionic conductivity.The composite negative pole improves the security performance and cycle performance of lithium ion battery, helps to promote high
The development of the lithium metal secondary cell of energy density, high stability.
Description of the drawings
Fig. 1 is VG/TiNb obtained in embodiment 22O7The scanning electron microscope (SEM) photograph of array；
Fig. 2 is VG/TiNb obtained in embodiment 22O7The transmission electron microscope picture of array；
A is VG/TiNb obtained in embodiment 2 in Fig. 32O7The scanning electron microscope (SEM) photograph of@S-C, b is to be made in embodiment 2 in Fig. 3
The VG/TiNb obtained2O7The Ti Elemental redistribution spectrograms of@S-C, c is VG/TiNb obtained in embodiment 2 in Fig. 32O7The Nb members of@S-C
Element is distributed spectrogram, and d is VG/TiNb obtained in embodiment 2 in Fig. 32O7The O Elemental redistribution spectrograms of@S-C, e is embodiment in Fig. 3
VG/TiNb obtained in 22O7The C element of@S-C is distributed spectrogram, and f is VG/TiNb obtained in embodiment 2 in Fig. 32O7@S-C's
S Elemental redistribution spectrograms；
Fig. 4 is VG/TiNb obtained in embodiment 22O7The scanning electron microscope (SEM) photograph of@S-C composite Nano porous arrays.
Specific implementation mode
With reference to embodiment, the present invention will be described in detail, but the present invention is not limited to this.
(1) preparation method of vertical graphene (VG)：By plasma enhanced chemical vapor deposition method (PECVD),
VG arrays are orderly deposited on carbon cloth (microwave frequency is 2.45GHz and microwave power 2kW).First, carbon cloth is placed in cavity
In and so that its air pressure is reached 10mTorr, secondly, after cavity temperature is increased to 400 DEG C, make to generate hydrogen plasma in cavity,
Hydrogen plasma by 500W microwave plasmas 90sccm flow velocitys H2It is generated in air-flow, while being passed through methane.Entire
In reaction process, the ratio of hydrogen and methane is 3:2, the reaction time remains 2h, finally, is cooled to room temperature 25 DEG C, VG samples
It prepares and completes.
(2)VG/TiNb2O7Preparation method：By VG substrates, 12h is dried and is weighed in an oven, with the vertical stone after having claimed
Black alkene (VG) is used as growth substrate, utilizes isopropyl titanate (C12H28O4) and columbium pentachloride (NbCl Ti5) carried out as presoma
Solvent thermal reaction.Take 0.5684g C12H28O4Ti and 1.08g NbCl5Stirred 15 minutes in beaker, after be transferred in water heating kettle
200 DEG C of reaction 6h, furnace cooling.Then sample deionized water and washes of absolute alcohol for several times and are dried, is protected in argon gas
Under atmosphere, it is heat-treated to calcining 2h in tube furnace at 700 DEG C, heating rate is 5 DEG C/min, obtains VG/TiNb2O7Film
Sample.
(3)VG/TiNb2O7The preparation method of@S-C：By 0.5mlEDOT and 1gLiClO4It is dissolved in 100ml acetonitriles, leads to
Cross constant current anodic deposition (1mA cm-2), in the VG/TiNb of preparation2O7On film deposit PEDOT after, under 700 DEG C of high temperature in
2h (Ar atmosphere) is calcined in tube furnace, heating rate is 5 DEG C/min, obtains VG/TiNb2O7The three-dimensional porous arrays of@S-C.
Embodiment 1
VG substrates is dry in vacuum drying oven.Utilize isopropyl titanate (C12H28O4) and columbium pentachloride (NbCl Ti5) make
200 DEG C of solvent thermal reaction 6h, furnace cooling are carried out for presoma.Gained sample deionized water and washes of absolute alcohol are for several times simultaneously
Drying calcines 2h under argon atmosphere at 700 DEG C, heating rate is 5 DEG C/min, obtains VG/TiNb2O7Film sample.
With VG/TiNb2O7For core, in EDOT and LiClO4Acetonitrile solution in, carry out constant current anodic deposition.After about 10s, PEDOT
Polymer will uniform deposition in VG/TiNb2O7Array forms nucleocapsid, is then forged in tube furnace under 700 DEG C of high temperature
2h (Ar atmosphere) is burnt, VG/TiNb is obtained2O7The three-dimensional porous arrays of@S-C.
Embodiment 2
VG substrates is dry in vacuum drying oven.Utilize isopropyl titanate (C12H28O4) and columbium pentachloride (NbCl Ti5) make
200 DEG C of solvent thermal reaction 6h, furnace cooling are carried out for presoma.Gained sample deionized water and washes of absolute alcohol are for several times simultaneously
Drying calcines 2h under argon atmosphere at 700 DEG C, heating rate is 5 DEG C/min, obtains VG/TiNb2O7Film sample.
With VG/TiNb2O7For core, in EDOT and LiClO4Acetonitrile solution in, carry out constant current anodic deposition.After about 20s,
PEDOT polymer will uniform deposition in VG/TiNb2O7Array forms nucleocapsid, then under 700 DEG C of high temperature
2h (Ar atmosphere) is calcined in tube furnace, obtains VG/TiNb2O7The three-dimensional porous arrays of@S-C.
VG/TiNb obtained in embodiment 22O7The scanning electron microscope (SEM) photograph of array is as shown in Figure 1；VG/ obtained in embodiment 2
TiNb2O7The transmission electron microscope picture of array is as shown in Figure 2；A is VG/TiNb obtained in embodiment 2 in Fig. 32O7The scanning electricity of@S-C
Mirror figure, b is VG/TiNb obtained in embodiment 2 in Fig. 32O7The Ti Elemental redistribution spectrograms of@S-C, c is to be made in embodiment 2 in Fig. 3
The VG/TiNb obtained2O7The Nb Elemental redistribution spectrograms of@S-C, d is VG/TiNb obtained in embodiment 2 in Fig. 32O7The O members of@S-C
Element is distributed spectrogram, and e is VG/TiNb obtained in embodiment 2 in Fig. 32O7The C element of@S-C is distributed spectrogram, and f is embodiment in Fig. 3
VG/TiNb obtained in 22O7The S Elemental redistribution spectrograms of@S-C；Fig. 4 is VG/TiNb obtained in embodiment 22O7@S-C are compound
The scanning electron microscope (SEM) photograph of nanometer porous array.
As seen from the figure, the present invention has vertical graphene/titanium niobium oxygen/sulphur carbon composite of three-dimensional porous array structure,
Including：Vertical and growth of entwining graphene nanometer sheet (VG), forms three-D nano-porous structure on matrix；It is coated on described
The TiNb of graphene nano on piece2O7(i.e. TNO) forms VG/TiNb2O7Nanometer sheet；And it is coated on the VG/TiNb2O7It receives
The sulfur doping carbon-coating (S-C) of rice on piece, forms VG/TiNb2O7The three-dimensional porous arrays [email protected] thickness of the graphene nanometer sheet
Degree is 5-8nm, the VG/TiNb2O7The thickness of nanometer sheet is 20-50nm, the VG/TiNb finally obtained2O7@S-C are three-dimensional more
Thickness (the i.e. VG/TiNb of hole array2O7@S-C nucleocapsid arrays nanometer sheet thickness) it is 50-120nm.
Embodiment 3
VG substrates is dry in vacuum drying oven.Utilize isopropyl titanate (C12H28O4) and columbium pentachloride (NbCl Ti5) make
200 DEG C of solvent thermal reaction 6h, furnace cooling are carried out for presoma.Gained sample deionized water and washes of absolute alcohol are for several times simultaneously
Drying calcines 2h under argon atmosphere at 700 DEG C, heating rate is 5 DEG C/min, obtains VG/TiNb2O7Film sample.
With VG/TiNb2O7For core, in EDOT and LiClO4Acetonitrile solution in, carry out constant current anodic deposition.After about 40s, PEDOT
Polymer will uniform deposition in VG/TiNb2O7Array forms nucleocapsid, is then forged in tube furnace under 700 DEG C of high temperature
2h (Ar atmosphere) is burnt, VG/TiNb is obtained2O7The three-dimensional porous arrays of@S-C.
Performance test
By VG/TiNb made of above-described embodiment 1~32O7The three-dimensional porous electrode materials of@S-C are respectively as button cell
To electrode and working electrode, lithium metal disk is to electrode, the LiPF of 1M6+EC/DMC(1:1) it is electrolyte.By negative plate, electricity
Solution liquid, diaphragm sequentially add progress battery assembling in battery case to electrode plates, by battery in full-automatic sealing machine after assembling
Middle compression sealing, electro-chemical test is carried out after standing 12h or more.Charge-discharge test is carried out in room temperature, and instrument is that blue electric battery is surveyed
Test system, test is mainly using constant current charge-discharge test and cyclic voltammetry.Constant current charge-discharge test is very important
Electro-chemical test means, index mainly have：Specific capacity, high rate performance, cycle performance, coulombic efficiency.Test voltage is ranging from
Relative to Li/Li+1.0-2.5V, Rate test currents 1C, 2C, 5C, 10C, 20C, 40C, 80C, 160C, loop test electric current
For 10C.
The performance test results are as follows：
The VG/TiNb of embodiment 1, embodiment 2 and embodiment 32O7The three-dimensional porous electrodes of@S-C are transferred in 10C current densities
Electric specific capacitance is respectively 134mAh/g, 182mAh/g and 165mAh/g.In addition, after 10000 circle cycle of cycle, specific discharge capacity is protected
For holdup up to 65% or more, coulombic efficiency is up to 95% or more.As it can be seen that VG/TiNb obtained above2O7The three-dimensional porous electrodes of@S-C
Good cycling stability after assembled battery, coulombic efficiency are high.The VG/TiNb of embodiment 1, embodiment 2 and embodiment 32O7@S-C are three-dimensional
Porous electrode specific capacitance of discharging under 160C current densities is respectively 145mAh/g, 225mAh/g and 180mAh/g.As it can be seen that above-mentioned
VG/TiNb obtained2O7The three-dimensional porous electrode material high rate capabilities of@S-C are preferable.
VG conductive substrates have three-D nano-porous structure, and nanometer turns to electronics and lithium ion increases electrode/electrolyte
Contact area shortens lithium ion transport path；On the other hand, the carbon-coating of three-dimensional porous VG substrates and sulfur doping all have compared with
High electron conductivity can promote the electronics between particle and particle to conduct, to improve its electrons/ions conductivity.
Therefore, VG/TiNb of the present invention2O7The three-dimensional porous electrodes of@S-C have high circulation stability, high rate capability and coulomb
The features such as efficiency, makes it be expected to become the energy high power density of commercial applications and the negative electrode of lithium ion battery material of energy density
Material.
Claims (10)
1. a kind of vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite, which is characterized in that packet
It includes：
Vertical and growth of entwining the graphene nanometer sheet on matrix；
It is coated on the TiNb of the graphene nano on piece2O7, form VG/TiNb2O7Nanometer sheet；
And it is coated on the VG/TiNb2O7Sulfur doping carbon-coating in nanometer sheet forms VG/TiNb2O7The three-dimensional porous battle arrays of@S-C
Row.
2. the vertical graphene according to claim 1 with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite wood
Material, which is characterized in that the thickness of the graphene nanometer sheet is 5-8nm, the VG/TiNb2O7The thickness of nanometer sheet is
20-50nm, the VG/TiNb finally obtained2O7The thickness of the three-dimensional porous arrays of@S-C is 50-120nm.
3. the vertical graphene according to claim 1 or 2 with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon is compound
The preparation method of material, which is characterized in that including steps are as follows：
(1) by plasma enhanced chemical vapor deposition method, graphene array is orderly deposited on carbon cloth, is obtained vertical
Graphene nanometer sheet；
(2) vertical graphene nanometer sheet is dried, using the vertical graphene nanometer sheet as growth substrate, utilizes isopropyl titanate
Solvent thermal reaction is carried out as presoma with columbium pentachloride, cleaning, drying after having reacted, heat treatment calcining obtain VG/
TiNb2O7Nanometer sheet；
(3) by 3,4- ethylenedioxy thiophenes and LiClO4It is dissolved in acetonitrile, by constant current anodic deposition, in the VG/ of preparation
TiNb2O7After depositing PEDOT in nanometer sheet, calcining obtains the vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur
Carbon composite.
4. preparation method according to claim 3, which is characterized in that in step (1), plasma enhanced chemical vapor is heavy
In product method, microwave frequency is 2.2~2.6GHz and microwave power 1.5kW~2.5kW.
5. preparation method according to claim 3, which is characterized in that in step (2), the isopropyl titanate and pentachloro-
The mass ratio for changing niobium is 1：1.5~2.5.
6. preparation method according to claim 3, which is characterized in that in step (2), the reaction of the solvent thermal reaction
Condition is：180 DEG C~220 DEG C reaction 4h~8h.
7. preparation method according to claim 3, which is characterized in that in step (2), the condition of the heat treatment calcining
For：600 DEG C~800 DEG C heat treatment calcining 1h~3h；
The heat treatment calcining carries out under argon atmosphere.
8. preparation method according to claim 3, which is characterized in that in step (3), 3, the 4- enedioxy thiophenes
Pheno, LiClO4Proportioning with acetonitrile is 0.3mL~0.7mL：0.5g~1.5g：80mL~120mL.
9. preparation method according to claim 3, which is characterized in that in step (3), the condition of the calcining is：600
DEG C~800 DEG C of calcining 1h~3h；
The calcining carries out under argon atmosphere.
10. the vertical graphene according to claim 1 with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite wood
Expect the application as lithium ion battery negative material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810263754.4A CN108649190B (en) | 2018-03-28 | 2018-03-28 | Vertical graphene/titanium niobium oxide/sulfur carbon composite material with three-dimensional porous array structure and preparation method and application thereof |
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| CN109950489A (en) * | 2019-03-21 | 2019-06-28 | 浙江大学 | Carbon cloth/carbon fiber array supported titanium niobium O compoiste material and its preparation method and application |
| CN110277554A (en) * | 2019-03-22 | 2019-09-24 | 北方奥钛纳米技术有限公司 | Positive electrode and positive plate and preparation method thereof, lithium ion battery |
| CN110518251A (en) * | 2019-09-19 | 2019-11-29 | 哈尔滨工业大学（深圳） | A kind of three-dimensional grapheme powder body material and preparation method thereof |
| CN110993908A (en) * | 2019-11-27 | 2020-04-10 | 浙江大学 | Vertical graphene/manganese dioxide composite material and preparation method and application thereof |
| CN111403718A (en) * | 2020-03-31 | 2020-07-10 | 浙江大学 | Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof |
| CN112038629A (en) * | 2020-09-30 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | Integrated high-rate lithium iron phosphate positive electrode material and preparation method and application thereof |
| CN112151762A (en) * | 2019-06-26 | 2020-12-29 | 重庆大学 | Lithium-sulfur battery positive electrode material and preparation method thereof, lithium-sulfur battery positive electrode and preparation method thereof, and lithium-sulfur battery |
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| CN111403718B (en) * | 2020-03-31 | 2021-06-15 | 浙江大学 | Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof |
| CN111403718A (en) * | 2020-03-31 | 2020-07-10 | 浙江大学 | Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof |
| US11855278B2 (en) | 2020-06-25 | 2023-12-26 | 6K, Inc. | Microcomposite alloy structure |
| CN112038629B (en) * | 2020-09-30 | 2022-07-05 | 合肥国轩高科动力能源有限公司 | Integrated high-rate lithium iron phosphate positive electrode material and preparation method and application thereof |
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| CN113921826B (en) * | 2021-10-09 | 2023-08-04 | 深圳石墨烯创新中心有限公司 | Upright graphene/nano silver composite material and preparation method and application thereof |
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