CN107785539A - Sodium-ion battery TiO2The preparation method of/graphene composite negative pole - Google Patents

Sodium-ion battery TiO2The preparation method of/graphene composite negative pole Download PDF

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Publication number
CN107785539A
CN107785539A CN201610718324.8A CN201610718324A CN107785539A CN 107785539 A CN107785539 A CN 107785539A CN 201610718324 A CN201610718324 A CN 201610718324A CN 107785539 A CN107785539 A CN 107785539A
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graphene
tio
negative pole
sodium
ion battery
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CN201610718324.8A
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Chinese (zh)
Inventor
肖伟
王红
赵丽娜
刘建国
严川伟
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Institute of Metal Research of CAS
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Institute of Metal Research 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
    • H01M4/362—Composites
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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 present invention relates to sodium-ion battery TiO2Base composite negative pole material field, specially a kind of sodium-ion battery TiO2The preparation method of/graphene composite negative pole.Using water as solvent, with TiCl4As titanium source, TiO is prepared for using hydrothermal synthesis method2Particle diameter is 5~15nm TiO2/ graphite composite material, and TiO2The evengranular surface for being grown in graphene.TiO prepared by the present invention2/ graphene composite negative pole is mainly made up of nano-titanium oxide and graphene, nano-titanium oxide can assign the higher discharge capacity of sodium-ion battery and preferable cycle life, graphene assigns electrode material higher electronic conduction characteristic, assigns electrode material good large current discharging capability.TiO prepared by the present invention2/ graphene composite negative pole has good physical and chemical stability and chemical property, and this method has the advantages that cost is cheap, easily large scale produces on a large scale.

Description

Sodium-ion battery TiO2The preparation method of/graphene composite negative pole
Technical field
The present invention relates to sodium-ion battery TiO2Base composite negative pole material field, specially a kind of sodium-ion battery are used TiO2The preparation method of/graphene composite negative pole.
Background technology
In current various technologies, lithium ion battery is due to operating voltage is high, capacity is high, self discharge is small and the circulation longevity Order the advantages that long and conquered portable electronic market, and turn into electric automobile (including EV and HEV etc.) and extensive energy storage system The primary selection of system electrical source of power.But with electric automobile, the real arrival in intelligent grid epoch, global lithium resource The great demand for effectively meeting power lithium-ion battery is will be unable to, so as to will further raise price with lithium associated materials, is increased Big battery cost, the final development for hindering New Energy Industry.Therefore, the related storage of other cheap alternative lithium ion batteries is developed Energy technology is very crucial.
At present, sodium-ion battery most possibly replaces because the reasons such as the inexpensive, environment-friendly of its sodium source, security turn into For the secondary cell of lithium ion battery.Anode material of lithium-ion battery is mainly carbon based negative electrodes material, and carbon-based material mainly includes Graphitic carbon, the major class of agraphitic carbon two.Wherein, graphite (including native graphite and Delanium) has been widely used for lithium-ion electric Pond, it is that research is also commercialized degree highest negative material earliest.In view of in the experience of field of lithium ion battery, carbon-based material Also it is widely studied as potential anode material of lithium-ion battery.But when being used for sodium-ion battery negative pole, sodium poor-performing is stored up, Because sodium ion radius ratio lithium ion is big so that sodium ion is difficult in graphite layers deintercalation, therefore the storage sodium capacity of graphite It is relatively low.In the research to negative material, TiO2Due to high storage sodium capacity, the extensive concern of battery material circle is caused.
Research shows, by with carbon is compound can be greatly enhanced TiO2The cyclical stability of electrode material, but it is conventional Method is more complicated, significantly limit its production in enormous quantities.Therefore it is simple to develop a kind of preparation process, and can be with Effective Regulation TiO2The method of/graphene-structured has great importance.
The content of the invention
It is an object of the invention to provide a kind of sodium-ion battery TiO2The preparation side of/graphene composite negative pole Method, prepared TiO2/ graphene combination electrode material, its TiO2The evengranular surface for being grown in graphene of nano.
To reach above-mentioned purpose, present invention employs following technical scheme：
A kind of sodium-ion battery TiO2The preparation method of/graphene composite negative pole, comprises the following steps：
1) 20~100mg graphenes are added in 30~300mL deionized waters, is ultrasonically treated 30~180min, obtained equal Even graphene dispersing solution；0.1~2.5g TiCl are added dropwise into above-mentioned solution again4, continue under ultrasonic wave added stirring 30~ 120min obtains electrode material precursor liquid；
2) above-mentioned precursor liquid is transferred in hydrothermal synthesis reaction kettle, hydrothermal synthesis reaction kettle is then placed in constant temperature oven In, and 3~40h is reacted at 120~260 DEG C, reaction end is chilled to room temperature, then will react obtained powder by centrifuging Separation, isolated powder freezing is dried, obtains TiO2/ graphene combination electrode material.
In the step 1), TiCl4Mass ratio with graphene is 1~125:1.
In the step 1), the concentration of graphene is 0.2~15mgmL in graphene dispersing solution-1。
In the step 2), the compactedness of the hydrothermal synthesis reaction kettle is controlled 30~70%.
The graphene is selected from the graphene of carboxylated, and graphene is individual layer, lacks layer or multi-layer graphene, and a diameter of 0.5 ~5 μm.
The TiO2In/graphene composite negative pole, TiO2Particle diameter be 5~15nm, TiO2It is spherical in shape to be grown in graphite The surface of alkene.
The composite negative pole material has good electronic conductivity and excellent battery capacity performance, discharges first Capacity is 300~500mAhg-1。
The present invention design philosophy be：
TiO of the present invention2/ graphene composite negative pole is mainly made up of nano-titanium oxide and graphene, nano-titanium oxide The higher discharge capacity of sodium-ion battery and preferable cycle life can be assigned, graphene assigns electrode material higher electricity Subconductivity characteristic, assign electrode material good large current discharging capability.So as to TiO prepared by the present invention2/ graphene is compound Negative material has good a physical and chemical stability and chemical property, and this method has that cost is cheap, easily extensive large scale life The advantages that production.
The advantages of the present invention are：
1st, the preparation method based on conventional lithium ion battery negative material, the present invention propose following idea：It is thin in graphene Piece surface in situ grows TiO2, obtain combination electrode material.The electrode material has good electric conductivity, while can play Go out higher battery capacity and longer battery life.
2nd, the preparation method of multi-functional composite diaphragm of the present invention, makes conductive material and electrode using hydrothermal synthesis method Active material direct combination, the charge and discharge battery performance of sodium-ion battery is improved, have technique simple, energy-conserving and environment-protective, be adapted to scale The characteristics of metaplasia is produced.
Embodiment
In specific implementation process, the present invention is using water as solvent, with TiCl4As titanium source, using Hydrothermal Synthesiss legal system For TiO2Particle diameter is 5~15nm TiO2/ graphite composite material, and TiO2The evengranular surface for being grown in graphene.This It is simple to invent the preparation method used, repeatability is high, reaction temperature is low, the cycle is short, energy consumption is low, is adapted to prepared by large-scale production Need, there is significant scientific meaning in sodium-ion battery application aspect.
In order that technical scheme and advantage are clearer, retouched in detail below in conjunction with specific embodiment State.
Embodiment 1
In the present embodiment, sodium-ion battery TiO2The preparation method of/graphene composite negative pole, specific steps are such as Under：
1) 50mg graphenes are added in 100mL deionized waters, 120min is persistently stirred under ultrasonic wave added and is obtained uniformly Graphene dispersing solution, the concentration of graphene is 0.5mgmL in dispersion liquid-1；Then 0.2g is added into graphene dispersing solution again TiCl4, 60min, which is persistently stirred, under ultrasonic wave added obtains electrode material precursor liquid.
2) above-mentioned precursor liquid is transferred in hydrothermal synthesis reaction kettle, reactor compactedness is 60%, then by reactor It is placed in constant temperature oven, and 12h is reacted at 180 DEG C, reaction end is chilled to room temperature, then by centrifuge at 12000 turns Obtained powder separation will be reacted under speed, powder freezing obtains TiO after drying2/ graphene combination electrode material.
3) by above-mentioned electrode material, acetylene black and Kynoar according to 90:4:6 mass ratio is prepared into pole piece, according to Existing process is assembled into button sodium-ion battery and tested.
Volume test result：In 20mAg-1Current density under, discharge capacity reaches 385mAhg to electrode first-1。
Loop test result：In 100mAg-1Current density under, after 100 cycle charge discharge electrical testings, electrode activity The capacity density 105mAhg of materials serve-1。
Embodiment 2
In the present embodiment, sodium-ion battery TiO2The preparation method of/graphene composite negative pole, specific steps are such as Under：
1) 30mg graphenes are added in 150mL deionized waters, 60min is persistently stirred under ultrasonic wave added and obtains uniform stone Black alkene dispersion liquid, the concentration of graphene is 0.2mgmL in dispersion liquid-1；Then 0.1g is added into graphene dispersing solution again TiCl4, 100min, which is persistently stirred, under ultrasonic wave added obtains electrode material precursor liquid.
2) above-mentioned precursor liquid is transferred in hydrothermal synthesis reaction kettle, reactor compactedness is 75%, then by reactor It is placed in constant temperature oven, and 6h is reacted at 150 DEG C, reaction end is chilled to room temperature, then by centrifuge in 16000 rotating speeds Lower to react obtained powder separation, powder freezing obtains TiO after drying2/ graphene combination electrode material.
3) by above-mentioned electrode material, acetylene black and Kynoar according to 90:4:6 mass ratio is prepared into pole piece, according to Existing process is assembled into button sodium-ion battery and tested.
Volume test result：In 20mAg-1Current density under, discharge capacity reaches 452mAhg to electrode first-1。
Loop test result：In 100mAg-1Current density under, after 100 cycle charge discharge electrical testings, electrode activity The capacity density 94mAhg of materials serve-1。
Embodiment 3
In the present embodiment, sodium-ion battery TiO2The preparation method of/graphene composite negative pole, specific steps are such as Under：
1) 100mg graphenes are added in 100mL deionized waters, 150min is persistently stirred under ultrasonic wave added and is obtained uniformly Graphene dispersing solution, the concentration of graphene is 1.0mgmL in dispersion liquid-1；Then 0.8g is added into graphene dispersing solution again TiCl4, 90min, which is persistently stirred, under ultrasonic wave added obtains electrode material precursor liquid.
2) above-mentioned precursor liquid is transferred in hydrothermal synthesis reaction kettle, reactor compactedness is 45%, then by reactor It is placed in constant temperature oven, and 32h is reacted at 220 DEG C, reaction end is chilled to room temperature, then by centrifuge at 10000 turns Obtained powder separation will be reacted under speed, powder freezing obtains TiO after drying2/ graphene combination electrode material.
3) by above-mentioned electrode material, acetylene black and Kynoar according to 90:4:6 mass ratio is prepared into pole piece, according to Existing process is assembled into button sodium-ion battery and tested.
Volume test result：In 20mAg-1Current density under, discharge capacity reaches 328mAhg to electrode first-1。
Loop test result：In 100mAg-1Current density under, after 100 cycle charge discharge electrical testings, electrode activity The capacity density 120mAhg of materials serve-1。
Embodiment 4
In the present embodiment, sodium-ion battery TiO2The preparation method of/graphene composite negative pole, specific steps are such as Under：
1) 25mg graphenes are added in 300mL deionized waters, 180min is persistently stirred under ultrasonic wave added and is obtained uniformly Graphene dispersing solution, the concentration of graphene is 0.5mgmL in dispersion liquid-1；Then 2.2g is added into graphene dispersing solution again TiCl4, 30min, which is persistently stirred, under ultrasonic wave added obtains electrode material precursor liquid.
2) above-mentioned precursor liquid is transferred in hydrothermal synthesis reaction kettle, reactor compactedness is 80%, then by reactor It is placed in constant temperature oven, and 20h is reacted at 200 DEG C, reaction end is chilled to room temperature, then by centrifuge in 8000 rotating speeds Lower to react obtained powder separation, powder freezing obtains TiO after drying2/ graphene combination electrode material.
3) by above-mentioned electrode material, acetylene black and Kynoar according to 90:4:6 mass ratio is prepared into pole piece, according to Existing process is assembled into button sodium-ion battery and tested.
Volume test result：In 20mAg-1Current density under, discharge capacity reaches 361mAhg to electrode first-1。
Loop test result：In 100mAg-1Current density under, after 100 cycle charge discharge electrical testings, electrode activity The capacity density 88mAhg of materials serve-1。
Embodiment result shows that the present invention is prepared for TiO using water as solvent using one step hydro thermal method2/ graphene is compound Electrode material, because graphene has preferable electric conductivity and mechanical stability, and TiO in the composite2For nanoscale Grain.Therefore, using it as anode material of lithium-ion battery, have excellent chemical property (such as：Higher capacity, has Preferable cyclical stability and high rate performance).The preparation method that the present invention uses have technique it is simple, without expensive device and effect Fruit significantly etc., can be achieved large-scale industrial production.

Claims (7)

  1. A kind of 1. sodium-ion battery TiO2The preparation method of/graphene composite negative pole, it is characterised in that including following step Suddenly：
    1) 20~100mg graphenes are added in 30~300mL deionized waters, is ultrasonically treated 30~180min, obtained uniform Graphene dispersing solution；0.1~2.5g TiCl are added dropwise into above-mentioned solution again4, continue to stir 30~120min under ultrasonic wave added Obtain electrode material precursor liquid；
    2) above-mentioned precursor liquid is transferred in hydrothermal synthesis reaction kettle, then hydrothermal synthesis reaction kettle is placed in constant temperature oven, And 3~40h is reacted at 120~260 DEG C, reaction end is chilled to room temperature, then will react obtained powder point by centrifuging From isolated powder freezing is dried, obtains TiO2/ graphene combination electrode material.
  2. 2. sodium-ion battery TiO according to claim 12The preparation method of/graphene composite negative pole, its feature It is, in the step 1), TiCl4Mass ratio with graphene is 1~125:1.
  3. 3. sodium-ion battery TiO according to claim 12The preparation method of/graphene composite negative pole, its feature It is, in the step 1), the concentration of graphene is 0.2~15mgmL in graphene dispersing solution-1。
  4. 4. sodium-ion battery TiO according to claim 12The preparation method of/graphene composite negative pole, its feature It is, in the step 2), the compactedness of the hydrothermal synthesis reaction kettle is controlled 30~70%.
  5. 5. sodium-ion battery TiO according to claim 12The preparation method of/graphene composite negative pole, its feature It is, the graphene is selected from the graphene of carboxylated, and graphene is individual layer, lacks layer or multi-layer graphene, a diameter of 0.5~5 μ m。
  6. 6. sodium-ion battery TiO according to claim 12The preparation method of/graphene composite negative pole, its feature It is, the TiO2In/graphene composite negative pole, TiO2Particle diameter be 5~15nm, TiO2It is spherical in shape to be grown in graphene Surface.
  7. 7. sodium-ion battery TiO according to claim 12The preparation method of/graphene composite negative pole, its feature It is, composite negative pole material has good electronic conductivity and excellent battery capacity performance, and discharge capacity is first 300~500mAhg-1。
CN201610718324.8A 2016-08-25 2016-08-25 Sodium-ion battery TiO2The preparation method of/graphene composite negative pole Pending CN107785539A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807923A (en) * 2018-06-21 2018-11-13 清远佳致新材料研究院有限公司 The preparation method of sodium-ion battery modifying titanium dioxide-graphene negative material
CN109088064A (en) * 2018-08-17 2018-12-25 北京师范大学 A kind of preparation method and application of the graphene-based metal oxide of electrochemical stripping
CN111446429A (en) * 2020-03-27 2020-07-24 珠海冠宇电池股份有限公司 Poly-polyanion cathode material and preparation method and application thereof
CN112520722A (en) * 2020-12-02 2021-03-19 深圳大学 Titanium dioxide coated biomass charcoal composite anode material and preparation method and application thereof

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CN101890344A (en) * 2010-07-27 2010-11-24 华东理工大学 Preparation method of graphene/titanium dioxide composite photocatalyst
CN103545491A (en) * 2013-09-25 2014-01-29 东莞市翔丰华电池材料有限公司 Preparation method of graphene/titanium dioxide composite material for lithium ion battery cathode material
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807923A (en) * 2018-06-21 2018-11-13 清远佳致新材料研究院有限公司 The preparation method of sodium-ion battery modifying titanium dioxide-graphene negative material
CN109088064A (en) * 2018-08-17 2018-12-25 北京师范大学 A kind of preparation method and application of the graphene-based metal oxide of electrochemical stripping
CN111446429A (en) * 2020-03-27 2020-07-24 珠海冠宇电池股份有限公司 Poly-polyanion cathode material and preparation method and application thereof
CN112520722A (en) * 2020-12-02 2021-03-19 深圳大学 Titanium dioxide coated biomass charcoal composite anode material and preparation method and application thereof

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