CN107799748A - A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application - Google Patents

A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application Download PDF

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CN107799748A
CN107799748A CN201710989580.5A CN201710989580A CN107799748A CN 107799748 A CN107799748 A CN 107799748A CN 201710989580 A CN201710989580 A CN 201710989580A CN 107799748 A CN107799748 A CN 107799748A
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cosno
cube
nanoscale
composite material
graphene composite
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李喜飞
窦树明
李德军
孙学良
范林林
颜波
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Tianjin University
Tianjin Normal University
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Tianjin Normal University
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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
    • 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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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 invention discloses a kind of nanoscale cube CoSnO3And graphene composite material, it is characterised in that nanoscale cube CoSnO3Clad structure is formed with the graphene of gauze-like.The present invention is prepared for a kind of nanoscale cube CoSnO with easy method3And graphene composite material, wherein graphene are by nanoscale cube CoSnO3Equably coat, because the cladding of graphene drastically increases CoSnO3The electric conductivity of material, meanwhile, also alleviate CoSnO3The volumetric expansion of material, effectively inhibit the efflorescence of electrode material and come off, thus nanoscale cube CoSnO prepared by the present invention3During with graphene composite material as anode material of lithium-ion battery, excellent specific discharge capacity and stable cycle performance are shown.

Description

A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method thereof with Using
Technical field
The present invention relates to sodium-ion battery Material Field, and in particular to a kind of nanoscale cube cobaltous stannate CoSnO3And stone Black alkene composite and preparation method and application.
Background technology
In recent decades, a large amount of consumption due to fossil fuel in the world, fossil fuel resource exhaustion and environment The problem of polluting getting worse causes significant impact to human survival and development.In order to reduce the dependence to fossil fuel And the regenerative resource such as the problem of alleviating environmental degradation, wind energy, solar energy, biomass energy, tide energy and geothermal energy and cleaning energy Greatly developed in source.Because these intermittent regenerative resources can be integrated into power network by extensive energy storage network system In, so the construction of energy storage network system is indispensable.In different energy storage technologies, rechargeable secondary cell technology is Realize the most potential technological means of large-scale energy storage system because it have high-energy conversion efficiency, environment friendly and The advantages that Substantial evaluation.
Past 20 years, people witnessed the successful commercialization of lithium ion battery and its in portable electronic device markets Popularization and application.However, limited lithium resource and high cost limit lithium ion battery large-scale application and large-scale energy storage The construction of system.It is intended to solve the above problems, human needs seeks and developed the material of alternative lithium ion battery.Due to sodium element It is located at same main group with elemental lithium, physico-chemical property is approximate, and sodium resource reserve enriches, and widely distributed, cost is relatively low, therefore, The research of sodium-ion battery gets most of the attention with application, it is often more important that sodium-ion battery is considered as that most have in future development can Can substitute lithium ion battery and most promising rechargeable secondary cell.
Electrode material is the passes that the important component of sodium-ion battery, particularly negative material are sodium-ion battery technology Key.At present, lithium ion battery negative material development than anode material of lithium-ion battery mature much, however, by Basically identical in the Mechanism of electrochemical behaviors of anhydrous of sodium-ion battery and the Mechanism of electrochemical behaviors of anhydrous of lithium ion battery, this causes sodium ion electricity in recent years The research of pond negative material has obtained fast development.Graphite is to be applied to the widest negative material of lithium ion battery, and it has The hierarchy of one long-range range order, lithium ion can relatively easily intercalation and the abjections between graphite linings.In lithium ion In battery system, graphite has higher theoretical reversible capacity（372mAh/g）Longer cycle life.However, should by graphite For in sodium ion battery system, its capacity to be only 35mAh/g.Therefore, seek high power capacity and the sodium ion of excellent cycling performance Cell negative electrode material has outstanding strategic importance for the large-scale application of sodium-ion battery.In numerous sodium cell negative pole materials In, very big concern of the ternary transition metal oxide because receiving researcher with high theoretical specific capacity.However, ternary transition Metal oxide, along with larger volumetric expansion, is easily caused electrode efflorescence and come off, so as to make during charge and discharge cycles Decline rapidly into battery capacity；Meanwhile ternary transition metal oxide it is conductive poor the characteristics of, this further restricts it Development in sodium ion battery electrode material.In order to improve the electric conductivity of material, suppress the efflorescence of material and come off, improve material The chemical property of material, it is a kind of effective design that ternary transition metal oxide and the carbon material of high conductivity, which are carried out compound, Strategy.
Chinese patent CN201510860848.6, disclose entitled：A kind of porous cube for sodium-ion battery ZnSnO3The patent document of@graphene negative materials and preparation method thereof, the solution containing zinc salt, pink salt is mixed one by it After the section time, filtering, dry, calcining obtain porous three-dimensional shape ZnSnO3；By ZnSnO3Ultrasonic disperse in the solution and adds surface Inorganic agent is stirred, then is mixed with graphene oxide water solution, filtering, is dried, is thermally treated resulting in graphene coated Porous cubic ZnSnO3.Surfactant is used in the preparation method, surfactant is that one kind can make surface tension The organic compound of reduction, there is the performances such as scattered, wetting and infiltration.In use, the waste liquid containing surfactant The environment such as water body, soil are inevitably discharged into, the presence of surfactant can cause environmental problem increasingly severe, even Entail dangers to is entirely ecological.Meanwhile its existing weak point also resides in preparation method and has used churned mechanically method to mix Close, the churned mechanically method inevitably makes graphene coated ZnSnO3There is uneven phenomenon.And in the present invention, Prepare nanoscale cube CoSnO3Surfactant is not used with the method for graphene composite material, efficiently avoid ring The problem of border is polluted.Meanwhile the preparation method uses solvent-thermal method, this method causes the nanoscale cube CoSnO prepared3With The pattern of graphene composite material is more uniform.
The content of the invention
The defects of in order to overcome anode material of lithium-ion battery, it is an object of the invention to provide a kind of nanoscale cube CoSnO3With graphene composite material and preparation method and application, the preparation method has that technological process is simple and easy to control, the cycle The features such as short energy consumption is low, the present invention have synthesized nanoscale cube CoSnO using easy method3And graphene composite material, Wherein graphene is by nanoscale cube CoSnO3Equably coat, because the cladding of graphene drastically increases composite Electric conductivity, meanwhile, also alleviate the volumetric expansion of material, effectively inhibit the efflorescence of electrode material and come off so that The chemical property of material significantly improves.Meanwhile by nanoscale cube CoSnO3With the nanoscale in graphene composite material Cube CoSnO3Applied in sodium-ion battery, nanoscale cube CoSnO3Anode material of lithium-ion battery has preferable Chemical property.
The purpose of the present invention is to be achieved through the following technical solutions：
A kind of nanoscale cube CoSnO3With the preparation method of graphene composite material, carried out by the steps:
（1）Grinding graphite oxide obtains the powder of brown color；
（2）20~60mg graphite oxide powder is dispersed in 4~60ml ethylene glycol using ultrasonic cell disruptor, prepared The concentration of graphite oxide-ethylene glycol dispersion liquid is 1~5mg/ml；
（3）30~200mg presomas are weighed, while measure 20~80ml butanol, add graphite oxide-second that step 2) obtains In glycol dispersion liquid, and stirring at normal temperature 0.5h；
（4）The presoma mixed liquor that step 3) obtains is transferred in polytetrafluoroethyllining lining, and it is close using stainless steel cauldron It is honored as a queen, is heated to 100~200 DEG C, is incubated 4~24h；
（5）After reaction terminates, normal temperature is cooled at room temperature, takes out product, is washed 2-3 times using deionized water and ethanol respectively, And freeze-drying process is carried out, obtain dried product；
（6）The product that step 5) is obtained is incubated 4h in argon gas atmosphere under conditions of 300 DEG C, you can obtains nanoscale and stands Cube CoSnO3And graphene composite material；Described presoma refers to CoSn (OH)6。
The present invention is on nanoscale cube CoSnO3With the preparation method of graphene anode material of lithium-ion battery more Add detailed be described as follows：
First, on presoma CoSn (OH)6Preparation and nanoscale cube pattern CoSnO3Formation：
（1）By 1mmolNa2SnO3It is dissolved in deionized water, obtains solution A；
（2）By 1mmolCoSO4It is dissolved in deionized water, obtains solution B；
（3）Solution A is added dropwise to solution B, stirring at normal temperature 0.5h；
（4）Product distilled water and absolute ethyl alcohol centrifuge washing 2-3 times, then place it in and 12h dried in 80 DEG C of baking oven, Obtain the cubical precursor CoSn (OH) of nanoscale6；·
（5）By presoma CoSn (OH)6It is placed in atmosphere tube type stove, under conditions of 300 DEG C, is incubated 4h, you can obtain nanometer The CoSnO of level cube pattern3。
2nd, on nanoscale cube CoSnO3With the preparation method of graphene composite material, carried out by the steps：
（1）Grinding graphite oxide obtains the powder of brown color；
（2）20mg graphite oxide powder is dispersed in 4ml ethylene glycol using ultrasonic cell disruptor, with oxygenerating stone The concentration of ink-ethylene glycol dispersion liquid is 5mg/ml；
（3）Weigh 50mg presomas CoSn (OH)6, while 30ml butanol is measured, add graphite oxide-second that step 2) obtains In glycol dispersion liquid, and stirring at normal temperature 0.5h；
（4）The presoma mixed liquor that step 3) obtains is transferred in polytetrafluoroethyllining lining, and it is close using stainless steel cauldron It is honored as a queen, is heated to 200 DEG C, is incubated 6h；
（5）After reaction terminates, normal temperature is cooled at room temperature, takes out product, is washed 2-3 times using deionized water and ethanol respectively, And freeze-drying process is carried out, obtain dried product；
（6）The product that step 5) is obtained is placed in atmosphere tube type stove, is incubated 4h under conditions of 300 DEG C, you can obtain nanometer Level cube CoSnO3And graphene composite material；Nanoscale cube CoSnO3Will with the graphene in graphene composite material Nanoscale cube CoSnO3Equably coat so that nanoscale cube CoSnO3Electric conductivity obtain larger raising, and Sanming City Control structure active material is bonded on graphene with coarse mode, it is impossible to ensure the conduction of all active materials Property can increase.In the present invention, the preparation of test sodium-ion battery electrode slice：By negative electrode active material, natural carbon black With binding agent CMC（Carboxymethyl cellulose）In certain proportion（8:1:1）Mixed pulp, sodium ion is obtained after drying, cut-parts GND tests pole piece.
The nanoscale cube CoSnO of the invention for further disclosing preparation3With graphene composite material for making Application in terms of standby anode material of lithium-ion battery.Experimental result is shown：Graphene is by nanoscale cube CoSnO3Equably Cladding, nanoscale cube CoSnO3Want excellent in nanoscale cube with the chemical property of the composite of graphene CoSnO3Chemical property, i.e., under the test condition of same current density, by 50 times circulation after, nanoscale cube CoSnO3Specific discharge capacity with graphene composite material is still 300 mAh/g.Nanoscale cube CoSnO prepared by the present invention3 Clad structure with graphene composite material be than more uniform, and sandwich structure disclosed in prior art exist it is uneven existing As, it may appear that particle stacking phenomenon.
Inventor has surprisingly observed that nanoscale cube CoSnO3It can be used for preparing anode material of lithium-ion battery.It is real Result is tested to show：Nanoscale cube CoSnO3Anode material of lithium-ion battery is in cube pattern, and is shown more excellent Chemical property.The CoSnO3Material is used to show higher specific capacity when sodium-ion battery is tested, its ratio that discharges first Capacity is 634mAh/g, at room temperature, charge-discharge test is carried out with 50mA/g current density, and its cycle performance is relatively stable, Its combination property is higher than commercialized graphitic carbon material.The CoSnO3Material is because having the small characteristic of particle size, certain The problem of volumetric expansion in charge and discharge process has been repaired in degree and has caused cyclical stability to reduce.The achievement is sodium ion The practical of battery provides a kind of feasible negative material solution.
Data above illustrates that the cladding of graphene drastically increases CoSnO3The electric conductivity of material, while also alleviate CoSnO3The volumetric expansion of material, effectively inhibit the efflorescence of electrode material and come off, thus nanoscale prepared by the present invention is stood Cube CoSnO3During with graphene composite material as anode material of lithium-ion battery, show excellent specific discharge capacity and Stable cycle performance.
Nanoscale cube CoSnO disclosed by the invention3It is relative with graphene composite material and preparation method and application Had the advantages that in prior art：
（1）Nanoscale cube CoSnO provided by the invention3With the preparation method of graphene composite material, there is technological process Simple and easy to control, preparation cost is low, short preparation period, and repeatability is high, is adapted to extensive the characteristics of synthesizing.
（2）CoSnO prepared by the present invention3Anode material of lithium-ion battery is in cube pattern, and the cubical length of side is about 80nm.The chemical property of material and the pattern of sample have close relationship, and particle is smaller, and specific surface area is bigger, then material Contact with electrolyte is better, Na+Migration distance can also shorten, be so more beneficial for anode material of lithium-ion battery electrochemistry The lifting of performance.Cube CoSnO prepared by the present invention3It is by numerous CoSnO3Nano particle composition, its larger ratio table Area causes the contact area of electrode/electrolyte to increase, and so as to improve the transmission rate of ion, accelerates electrochemical reaction Speed, therefore the nanoscale cube CoSnO that the present invention synthesizes3During as anode material of lithium-ion battery, show more excellent Chemical property.
（3）The present invention is prepared for a kind of nanoscale cube CoSnO with easy method3And graphene composite material, its Middle graphene is by nanoscale cube CoSnO3Equably coat, because the cladding of graphene drastically increases CoSnO3Material Electric conductivity, meanwhile, also alleviate CoSnO3The volumetric expansion of material, effectively inhibit the efflorescence of electrode material and come off, because And nanoscale cube CoSnO prepared by the present invention3During with graphene composite material as anode material of lithium-ion battery, performance Excellent specific discharge capacity and stable cycle performance are gone out.
Brief description of the drawings
Fig. 1 is nanoscale cube CoSnO prepared in embodiment 13X-ray diffraction（XRD）Collection of illustrative plates；
Fig. 2 is nanoscale cube CoSnO prepared in embodiment 23With the X-ray diffraction of graphene composite material（XRD） Collection of illustrative plates；
Fig. 3 is nanoscale cube CoSnO prepared in embodiment 13ESEM (SEM) photo and nanoscale cube Body CoSnO3Transmission electron microscope（TEM）Photo；
Fig. 4 is nanoscale cube CoSnO prepared in embodiment 23Shone with the ESEM (SEM) of graphene composite material Piece and nanoscale cube CoSnO3With the transmission electron microscope of graphene composite material（TEM）Photo；
Fig. 5 is nanoscale cube CoSnO prepared in embodiment 13Cycle performance figure；
Fig. 6 is nanoscale cube CoSnO prepared in embodiment 23With the cycle performance figure of graphene composite material.
Embodiment
Following embodiment facilitates a better understanding of the present invention, but does not limit the present invention.Experiment in following embodiments Method, it is conventional method unless otherwise specified.The natural carbon black of test material used, binding agent CMC in following embodiments （Carboxymethyl cellulose）It is commercially available, others are that reagent shop is commercially available unless otherwise specified.
Embodiment 1
The first step, by 1mmol Na2SnO3It is dissolved in 20ml deionized waters, obtains solution A；By 1mmol CoSO420ml is dissolved in go In ionized water, solution B is obtained；Solution A is added dropwise to solution B, stirring at normal temperature 0.5h；Product distilled water and absolute ethyl alcohol Centrifuge washing 2-3 times, then place it in and 12h is dried in 80 DEG C of baking oven, that is, obtain the cubical precursor of nanoscale CoSn(OH)6。
Second step, by presoma CoSn (OH)6It is placed in atmosphere tube type stove, under conditions of 300 DEG C, is incubated 4h, you can Obtain nanoscale cube pattern CoSnO3。
3rd step, the preparation of test sodium-ion battery electrode slice.By nanoscale cube CoSnO3With natural carbon black, viscous Tie agent CMC（Carboxymethyl cellulose）In certain proportion（8:1:1）It is prepared into sodium-ion battery negative pole test pole piece, detailed side Method is：
（1）According to 8:1:1 ratio weighs negative electrode active material nanoscale cube CoSnO respectively30.040g, natural carbon black 0.005g, binding agent CMC（Carboxymethyl cellulose）0.005g, add a small amount of solvent deionized water and mixed and be fully ground （Time 3h）；
（2）Above-mentioned pasty mixture is coated on copper foil, 12h is dried in vacuo at 80 DEG C；
（3）The above-mentioned copper foil for being loaded with electrode material is cut into the electrode slice of required size, button is assembled into glove box Battery, wherein comparison electrode are metallic sodium piece.
4th step, button cell prepared by upper three step is placed in blue electric battery test system and tested, wherein discharge and recharge Section is set to 0.01V~3V, and current density is set to 50mA/g；
Fig. 1 is nanoscale cube CoSnO prepared in embodiment 13X-ray diffraction（XRD）Collection of illustrative plates, can be with from collection of illustrative plates Find out nanoscale cube CoSnO3It is undefined structure.
Fig. 3 is nanoscale cube CoSnO prepared in embodiment 13ESEM (SEM) photo and nanoscale Cube CoSnO3Transmission electron microscope（TEM）Photo, it is from ESEM (SEM) photo it can be seen that prepared in embodiment 1 CoSnO3Pattern be nanoscale cube, its length of side is about 80nm, and even size distribution；From transmission electron microscope（TEM）According to Piece understands prepared nanoscale cube CoSnO3Surface be coarse, be inferred to accordingly embodiment 1 preparation nanoscale Cube CoSnO3It is by numerous CoSnO3What nano particle formed, meanwhile, from high power transmission electron microscope（TEM）In photo, see Examine less than obvious lattice fringe, this and nanoscale cube CoSnO3X-ray diffraction（XRD）The test result phase one of collection of illustrative plates Cause, this further demonstrates the nanoscale cube CoSnO of the preparation of embodiment 13It is unformed shape.
Fig. 5 is nanoscale cube CoSnO prepared in embodiment 13Cycle performance figure, can from cycle performance figure To find out prepared nanoscale cube CoSnO3The first discharge specific capacity of anode material of lithium-ion battery is 634mAh/g, At room temperature, charge-discharge test is carried out with 50mA/g current density, it shows preferable chemical property.
Embodiment 2
The first step is the same as the first step of embodiment 1.
Second step, grinding graphite oxide obtain the powder of brown color；20mg is aoxidized into stone using ultrasonic cell disruptor Ink powder is dispersed in 4ml ethylene glycol, prepares 5mg/ml graphite oxide-ethylene glycol dispersion liquid；Weigh 50mg presomas CoSn(OH)6, while 30ml butanol is measured, add in the graphite oxide-ethylene glycol dispersion liquid prepared, and stirring at normal temperature 0.5h；Obtained presoma mixed liquor is transferred in polytetrafluoroethyllining lining, and after use stainless steel cauldron sealing, heating To 200 DEG C, 6h is incubated；After reaction terminates, normal temperature is cooled at room temperature, is taken out product, is washed respectively using deionized water and ethanol Wash 2-3 times, and carry out freeze-drying process；Obtained desciccate is incubated 4h under conditions of 300 DEG C, through natural cooling Afterwards, nanoscale cube CoSnO is obtained3And graphene composite material.
3rd step, the preparation of test sodium-ion battery electrode slice.By nanoscale cube CoSnO3It is compound with graphene Material and natural carbon black, binding agent CMC（Carboxymethyl cellulose）In certain proportion（8:1:1）It is prepared into sodium-ion battery negative pole Pole piece is tested, detailed method is：
（1）According to 8:1:1 ratio weighs negative electrode active material nanoscale cube CoSnO respectively3And graphene composite material 0.040g, natural carbon black 0.005g, binding agent CMC（Carboxymethyl cellulose）0.005g, add a small amount of solvent deionized water and carry out Mix and be fully ground（Time 3h）；
（2）Above-mentioned pasty mixture is coated on copper foil, 12h is dried in vacuo at 80 DEG C；
（3）The above-mentioned copper foil for being loaded with electrode material is cut into the electrode slice of required size, button is assembled into glove box Battery, wherein comparison electrode are metallic sodium piece.
4th step, button cell prepared by upper three step is placed in blue electric battery test system and tested, wherein discharge and recharge Section is set to 0.01V~3V, and current density is set to 50mA/g；
There is nanoscale cube CoSnO prepared in embodiment 2 in Fig. 23With the X-ray diffraction of graphene composite material （XRD）Collection of illustrative plates, because the content of graphene is less, nanoscale cube CoSnO3With the X-ray diffraction of graphene composite material （XRD）Collection of illustrative plates and nanoscale cube CoSnO3X-ray diffraction（XRD）Collection of illustrative plates is almost consistent, but can be with 40 ° to 42 ° Find out the Bao Feng of graphene, further demonstrate the nanoscale cube CoSnO of preparation3With graphene in graphene composite material Presence.
Fig. 4 is nanoscale cube CoSnO prepared in embodiment 23With the ESEM of graphene composite material (SEM) photo and nanoscale cube CoSnO3With the transmission electron microscope of graphene composite material（TEM）Photo, stood from nanoscale Cube CoSnO3It can be seen that graphene by nanoscale cube with ESEM (SEM) photo of graphene composite material CoSnO3Equably coat, and transmission electron microscope（TEM）Photo further demonstrates that nanoscale cube CoSnO3With the stone of gauze-like Black alkene forms a kind of good clad structure.
Fig. 6 is nanoscale cube CoSnO prepared in embodiment 23With the cycle performance figure of graphene composite material, It will be apparent from this figure that under 50mA/g current densities, constant current charge-discharge test is carried out to the material, second of circulation is put Electric specific capacity is up to 405mAh/g, and after 50 circulations, its specific discharge capacity is still 300 mAh/g, and the material shows excellent Different specific discharge capacity and stable cycle performance, illustrate that graphene coated causes CoSnO3As anode material of lithium-ion battery Chemical property further improve.
Embodiment 3
The first step is the same as the first step of embodiment 1.
Second step, grinding graphite oxide obtain the powder of brown color；60mg is aoxidized into stone using ultrasonic cell disruptor Ink powder is dispersed in 60ml ethylene glycol, prepares 1mg/ml graphite oxide-ethylene glycol dispersion liquid；Weigh 200mg presomas CoSn(OH)6, while 50ml butanol is measured, add in the graphite oxide-ethylene glycol dispersion liquid prepared, and stirring at normal temperature 0.5h；Obtained presoma mixed liquor is transferred in polytetrafluoroethyllining lining, and after use stainless steel cauldron sealing, heating To 120 DEG C, 6h is incubated；After reaction terminates, normal temperature is cooled at room temperature, is taken out product, is washed respectively using deionized water and ethanol Wash 2-3 times, and carry out freeze-drying process；Obtained desciccate is incubated 4h under conditions of 300 DEG C, through natural cooling Afterwards, nanoscale cube CoSnO is obtained3And graphene composite material.
3rd step, the preparation of test sodium-ion battery electrode slice.By nanoscale cube CoSnO3It is compound with graphene Material and natural carbon black, binding agent CMC（Carboxymethyl cellulose）In certain proportion（8:1:1）It is prepared into sodium-ion battery negative pole Pole piece is tested, detailed method is：
（1）According to 8:1:1 ratio weighs negative electrode active material nanoscale cube CoSnO respectively3And graphene composite material 0.040g, natural carbon black 0.005g, binding agent CMC（Carboxymethyl cellulose）0.005g, add a small amount of solvent deionized water and carry out Mix and be fully ground（Time 3h）；
（2）Above-mentioned pasty mixture is coated on copper foil, 12h is dried in vacuo at 80 DEG C；
（3）The above-mentioned copper foil for being loaded with electrode material is cut into the electrode slice of required size, button is assembled into glove box Battery, wherein comparison electrode are metallic sodium piece.
4th step, button cell prepared by upper three step is placed in blue electric battery test system and tested, wherein discharge and recharge Section is set to 0.01V~3V, and current density is set to 50mA/g.

Claims (4)

  1. A kind of 1. nanoscale cube CoSnO3With the preparation method of graphene composite material, carried out by the steps：
    （1）Grinding graphite oxide obtains the powder of brown color；
    （2）20~60mg graphite oxide powder is dispersed in 4~60ml ethylene glycol using ultrasonic cell disruptor, prepared The concentration of graphite oxide-ethylene glycol dispersion liquid is 1~5mg/ml；
    （3）30~200mg presomas are weighed, while measure 20~80ml butanol, add graphite oxide-second that step 2) obtains In glycol dispersion liquid, and stirring at normal temperature 0.5h；
    （4）The presoma mixed liquor that step 3) obtains is transferred in polytetrafluoroethyllining lining, and it is close using stainless steel cauldron It is honored as a queen, is heated to 100~200 DEG C, is incubated 4~24h；
    （5）After reaction terminates, normal temperature is cooled at room temperature, takes out product, is washed 2-3 times using deionized water and ethanol respectively, And freeze-drying process is carried out, obtain dried product；
    （6）The product that step 5) is obtained is incubated 4h in argon gas atmosphere under conditions of 300 DEG C, you can obtains nanoscale and stands Cube CoSnO3And graphene composite material；Described presoma refers to CoSn (OH)6。
  2. 2. the preparation method described in 1 is required, wherein presoma CoSn (OH)6It is by 1mmol Na2SnO3With 1mmol CoSO4It is mixed Close and obtain.
  3. 3. the nanoscale cube CoSnO prepared using claim 1 methods described3With graphene composite material for preparing Application in terms of anode material of lithium-ion battery.
  4. 4. the CoSnO of prepared nanoscale cube pattern in claim 23For preparing anode material of lithium-ion battery The application of aspect.
CN201710989580.5A 2017-10-23 2017-10-23 A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application Pending CN107799748A (en)

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Application publication date: 20180313