CN104409708A - Preparation method of carbon coated Sn-Co/graphene microsphere negative electrode material of lithium ion battery - Google Patents

Preparation method of carbon coated Sn-Co/graphene microsphere negative electrode material of lithium ion battery Download PDF

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CN104409708A
CN104409708A CN201410623977.9A CN201410623977A CN104409708A CN 104409708 A CN104409708 A CN 104409708A CN 201410623977 A CN201410623977 A CN 201410623977A CN 104409708 A CN104409708 A CN 104409708A
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graphene
preparation
lithium ion
salt
ion battery
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CN104409708B (en
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沈丁
杨绍斌
董伟
王晓亮
李思南
孟阳
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Jiangsu Jiaming Carbon New Materials Co., Ltd.
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Liaoning Technical 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

In the prior art, there is no a lithium ion cell negative electrode material, which is based on a Sn-Co alloy and can have the advantages of large lithium storage capacity, high coulomb efficiency, long cycle life, and large filling density at the same time. In order to solve the problem mentioned above, the invention provides a preparation method of a carbon coated Sn-Co alloy/graphene microsphere negative electrode material of a lithium ion battery, and belongs to the technical field of lithium ion battery negative electrode materials. The preparation method comprises the following steps: depositing nano Sn-Co alloy onto the graphene surface through a wet process, then granulating nano intermediates through a spray drying method, coating the composite microsphere intermediates by asphalt, and finally heating to carbonize the intermediates so as to obtain the carbon coated Sn-Co alloy/graphene microsphere negative electrode material. The technology of the preparation method is simple, and thus the preparation method is suitable for massive industrial production. The prepared carbon coated Sn-Co alloy/graphene microsphere negative electrode material has the advantages of large lithium storage capacity, high coulomb efficiency, long cycle life, and large filling density.

Description

The preparation method of a kind of lithium ion battery carbon coated Sn-Co/ Graphene microballoon negative material
Technical field
The invention belongs to a kind of lithium ion battery negative material field, particularly the preparation method of a kind of lithium ion battery carbon coated Sn-Co/ Graphene microballoon negative material.
Background technology
In recent years, along with electronic information technology development, multimedia function increases, and mobile phone 4G communication function is promoted and electric automobile single charge travels distance prolongation.Therefore, existing lithium ion battery more and more can not meet people's demand growing to capacity.Negative material is one of key factor affecting capacity of lithium ion battery.The graphite cathode material of current large-scale application has the advantages such as efficiency for charge-discharge is high, good cycle, but theoretical lithium storage content is low, and specific discharge capacity is 372mAh/g, and volume and capacity ratio is 800mAh/cm 3, actual capacity is close to theoretical capacity, and raising space is little.The Theoretical Mass specific capacity of metallic tin is 990mAh/g, and especially volume and capacity ratio reaches 7200mAh/cm 3, be the focus of cathode material for high capacity lithium ion battery research always.But the volumetric expansion in charge and discharge process of this kind of material reaches 3 ~ 4 times, crystal structure is easily destroyed and final efflorescence, cycle performance is deteriorated, seriously hinders the extensive industrialization of Sn base negative material.
For this reason, people mainly adopt the approach such as particle nanometer, alloying and Composite to reduce the volumetric expansion of Sn sill, improve cycle performance.The nanometer of metal Sn significantly can reduce particle volume and to expand the internal stress produced, and reduces volumetric expansion multiple, make cycle performance be improved significantly.But the packing density of nano material is little, specific area and surface energy greatly, cause volume and capacity ratio low low with coulombic efficiency.The alloying of metal Sn and active element or inert element can reduce volumetric expansion multiple, improves cycle performance, and wherein the inert alloy element such as Co is not as itself participated in reaction, and skeletal support effect is better.The Composite of Sn-Co alloy and carbon, boron and phosphorus etc. can cushion the volumetric expansion of alloy, and play compartmentation prevents Nanoalloy from reuniting simultaneously, improves the cycle performance of material.But, up to the present, people also do not invent a kind of based on Sn-Co alloy can have that lithium storage content is high simultaneously, coulombic efficiency is large, have extended cycle life and lithium ion battery negative material that packing density is large.
Summary of the invention
In order to solve the problem, the present invention proposes the preparation method of a kind of lithium ion battery carbon coated Sn-Co/ Graphene microballoon negative material.Sn-Co Nanoalloy is deposited on graphenic surface by wet method and forms nanostructure intermediate by the method, then adopt spray drying process to carry out granulation to nanostructure intermediate and form complex microsphere intermediate, again complex microsphere intermediate is carried out pitch-coating, the mode finally carrying out heating charing prepares charcoal coated Sn-Co/ Graphene microballoon negative material, simple, the applicable large-scale industrialized production of the method preparation technology; The obtained charcoal coated Sn-Co/ Graphene microballoon negative material lithium storage content of the method is high, coulombic efficiency large, have extended cycle life, packing density is large.
For achieving the above object, technical solution of the present invention is as follows:
A preparation method for lithium ion battery carbon coated Sn-Co/ Graphene microballoon negative material, comprises following steps:
(1) nanostructure intermediate is prepared: solubility Sn salt and solubility Co salt are added deionized water, after abundant dissolving, add Graphene and surface modifier solution, after ultrasonic disperse 5 ~ 10min, add reducing agent reaction 10 ~ 20min again, the Sn-Co Nanoalloy that reaction generates is deposited on graphenic surface, is filtered by reaction solution, again by solid matter washing, drying, obtains nanostructure intermediate;
Wherein, described Graphene by natural flake graphite through Hummer method be oxidized and hydrazine hydrate reduction obtain, have atomic structure of carbon defect and surface functional group individual layer or lower than few layer graphene of 10 layers;
Solubility Sn salt is SnCl 4, SnSO 4, Na 2snO 3or Sn 2p 2o 7, solubility Co salt is CoSO 4or Co (NO 3) 2; Reducing agent is the NaBH of 0.1 ~ 1mol/L 4ethanolic solution or KBH 4the aqueous solution; Surface modifier is lauryl sodium sulfate or dodecyl sodium sulfate;
The additional proportion of solubility Sn salt and solubility Co salt is: in Sn, Co atom in Sn salt and Co salt, Sn accounts for 65 ~ 80% of Sn, Co gross mass; The rate of charge of Sn salt and Co salt gross mass and deionized water is 1g:5 ~ 30mL; In Graphene quality and Sn salt and Co salt, the ratio of Sn, Co atom gross mass is (0.5 ~ 10): (60 ~ 98.5); Surface modifier quality is 2 ~ 5% of deionized water quality; The molal quantity of reducing agent is Co ion and the chemical valence sum of products 1.1 ~ 1.5 times in Sn ion and chemical valence sum of products Co salt in Sn salt;
(2) complex microsphere intermediate is prepared: add deionized water by the nanostructure intermediate of step (1) gained, after stirring, add binding agent, stir into slurry, then be 110 ~ 180 DEG C in inlet temperature, outlet temperature is 80 ~ 95 DEG C, and atomisation pressure is 0.5 ~ 2MPa, nozzle diameter is carry out spray drying granulation under the condition of 0.3 ~ 0.7mm, and obtaining particle diameter is micron-sized complex microsphere intermediate bulky grain;
Wherein, the solid-to-liquid ratio of nanostructure intermediate and deionized water is 10g:(5 ~ 15) mL, the mass ratio of nanostructure intermediate and binding agent is 10:(1 ~ 3);
Described binding agent is starch, polyvinyl alcohol or sodium carboxymethylcellulose;
(3) charcoal covered composite yarn microballoon is prepared: added by petroleum asphalt in kerosene, after abundant dissolving, add the complex microsphere intermediate of step (2) gained again, heating, drying at speed stirs 50 ~ 100rpm, temperature 200 ~ 280 DEG C, under the inert gas atmosphere such as nitrogen or argon gas, finally carry out heating charing, obtain charcoal coated Sn-Co/ Graphene microballoon;
Wherein, in the complex microsphere intermediate obtained in described petroleum asphalt addition and step (2), the mass ratio of Graphene is (1 ~ 30): (0.5 ~ 10);
Described charing heating cycle is: with the ramp of 2 ~ 10 DEG C/min to after 600-1500 DEG C, insulation 0.5 ~ 5h, then cools with stove.
After tested, charcoal prepared by the present invention coated Sn-Co/ Graphene microballoon negative material, embedding lithium capacity is 332 ~ 645mAh/g first, and efficiency for charge-discharge is 80.6 ~ 90.3%, and the discharge capacity after 50 times that circulates is 303 ~ 497mAh/g.
Through scanning electron microscopic observation, the granularity of microballoon negative material prepared by the present invention is 20 ~ 60 μm, microballoon top layer is the compound layer of charcoal that Graphene and pyrolytic carbon are formed, microballoon inside is the loose structure be separated to form by Graphene, deposits at the pore interior of loose structure the Sn-Co alloying pellet that particle diameter is 40 ~ 100nm.
The present invention has following remarkable advantage relative to prior art:
1, by charcoal coated Sn-Co/ Graphene microballoon negative material prepared by the present invention, overcoming existing nanoscale Sn-Co alloy, to there is packing density low, the shortcoming that volume and capacity ratio is little.The present invention, using starch, polyvinyl alcohol or sodium carboxymethylcellulose as binding agent, adopts spray drying granulation method to obtain micron-size spherical particles, effectively can improve packing density, obtain high volume and capacity ratio.
2, by charcoal coated Sn-Co/ Graphene microballoon negative material prepared by the present invention, overcome the complex carriers such as existing graphite granule, organic matter pyrolysis charcoal, Carbon fibe effectively to separate and reserved expansion space Sn-Co alloy, cause cycle performance to point out the shortcoming of weak effect.Graphene is a kind of two-dimensional material by monolayer carbon atomic building, there is the intensity of superelevation, good pliability, excellent conductivity and self can store Li, the present invention take Graphene as carrier, Graphene effectively can be separated to form loose structure, for the elastic space that the expansion of Sn-Co Nanoalloy is reserved, and good supporting function is played to Sn-Co Nanoalloy, the capacity being not only conducive to Sn-Co alloy plays and the raising of cycle performance but also raising negative pole whole volume and electron conduction.
3, by charcoal coated Sn-Co/ Graphene microballoon negative material prepared by the present invention, overcome existing Sn-Co/C composite material and there is specific area comparatively greatly, irreversible capacity is high, the shortcoming that efficiency for charge-discharge is low.The present invention is using pitch as carbon precursor covered composite yarn microsphere particle, the compound layer of charcoal formed can play stable particle structure and reduce the double action that particle exposes surface area in the electrolytic solution, reduce irreversible capacity, improve first charge-discharge efficiency and cycle performance.
4, by charcoal coated Sn-Co/ Graphene microballoon negative material prepared by the present invention, Co-Sn Nanoalloy is by CoSn and CoSn 2phase composition, wherein CoSn 2have higher capacity, CoSn has good cycle performance, and the Sn-Co alloy of the two compound composition has had good capacity and cycle performance concurrently.
5, the present invention adopts the method that liquid deposition, granulation, surrounding phase combine, simple, the applicable large-scale industrialized production of technique.
Therefore, the preparation method of the charcoal coated Sn-Co/ Graphene microballoon negative material of a kind of lithium ion battery of the present invention, it is high that the microballoon negative material obtained has lithium storage content, coulombic efficiency is large, the advantage such as have extended cycle life and packing density is large, meets the requirement of high performance lithium ion battery anticathode material combination property.
Accompanying drawing explanation
Fig. 1 is the electron-microscope scanning figure of the charcoal coated Sn-Co/ Graphene microballoon negative material of lithium ion battery obtained in embodiment 1.
Embodiment
In embodiment, the preparation method of Graphene is: the dense H getting 18 ~ 25mL98% 2sO 4adding the reactor being placed in ice bath, is the natural flake graphite of 10 ~ 30 μm and the KMnO of 3 ~ 4g by 1 ~ 1.5g granularity 4add in reactor, stir 30 ~ 60min with 30 ~ 80rpm rotating speed; Again above-mentioned reactor is moved in the tepidarium of 40 ± 2 DEG C and continue stirring 30 ~ 60min; Again reacting liquid temperature is increased to 98 ± 2 DEG C, adds 70 ~ 100mL deionized water and continue stirring 30 ~ 60min; Then the H that 8 ~ 15mL mass fraction is 5% is added 2o 2mix, filter while hot, wash filter residue, until without SO in filtrate with the HCl that mass fraction is 5% 4 2-(use BaC1 2solution detects), more fully wash to neutrality with deionized water, filter, obtain graphite oxide; Then 400 ~ 500mL deionized water is added to graphite oxide, with the ultrasonic process 60 ~ 90min of 60kHz at 80 ~ 90 DEG C, then with the centrifugal 5 ~ 10min of 3000 ~ 4000rpm rotating speed; Get supernatant, then add the hydrazine hydrate aqueous solution of 0.5 ~ 1g50%, at 85 ~ 95 DEG C of reduction reaction 60 ~ 120min, filter, sediment is put into 50 ~ 70 DEG C of oven drying 60 ~ 80h.
Other reagent are commercial.
Be described in further detail below in conjunction with specific embodiment, but the present invention is not limited thereto.
Embodiment 1
1, nanostructure intermediate is prepared: by the SnCl of 26.07g 4with the CoSO of 16.79g 4add 1286mL deionized water, after fully dissolving, then add 92.7mg Graphene and 25.7g lauryl sodium sulfate, after ultrasonic disperse 5min, then add the NaBH of 1mol/L 4ethanolic solution 925mL, reaction 20min, at graphenic surface deposition Sn-Co Nanoalloy, reaction solution washs after filtration, by solid matter, drying, obtains nanostructure intermediate;
2, complex microsphere intermediate is prepared: in the nanostructure intermediate that step 1 is obtained, in every 10g, add 15mL deionized water, after stirring, 3g starch is added again in every 10g nanostructure intermediate, stir into slurry, adopt spray drying granulation method to carry out granulation, inlet temperature is 110 DEG C, outlet temperature is 80 DEG C, atomisation pressure is 0.5MPa, and nozzle diameter is 0.7mm, obtains complex microsphere intermediate;
3, prepare charcoal covered composite yarn microballoon: added by 185.4mg pitch in 10mL kerosene solvent, after fully dissolving, then add the complex microsphere intermediate of step 2 gained, stir post-drying, finally at N 2under atmosphere, be warming up to 600 DEG C from room temperature by 2 DEG C/min, insulation 0.5h carbonizes, and obtains charcoal coated Sn-Co/ Graphene microballoon.
By coated for gained charcoal Sn-Co/ Graphene microballoon, conductive agent acetylene black and binding agent PVDF according to mass percent 85:5:10 mixing, making electrode slice, is to electrode by metal lithium sheet, the LiPF of 1mol/L 6/ EC+DMC+DEC is that electrolyte is assembled into half-cell.Adopt the new Weir battery test system in Shenzhen at room temperature to carry out constant current charge-discharge test to half-cell, charging or discharging current is 0.05mA/cm 2, voltage range is 0.01-1.5V.The embedding first lithium capacity of charcoal coated Sn-Co/ Graphene microballoon negative material of preparation is 320mAh/g, and efficiency for charge-discharge is 80.6%, and the discharge capacity after 50 times that circulates is 303mAh/g.
Through scanning electron microscopic observation, the granularity of this microballoon negative material is 20 ~ 60 μm, microballoon top layer is the compound layer of charcoal that Graphene and pyrolytic carbon are formed, microballoon inside is the loose structure be separated to form by Graphene, deposits at the pore interior of loose structure the Sn-Co alloying pellet that particle diameter is 40 ~ 100nm.Shown in Fig. 1 is the outward appearance scanning electron microscope (SEM) photograph of this negative material.
Embodiment 2
1, nanostructure intermediate is prepared: by the SnSO of 42.94g 4with the CoSO of 33.58g 4add 1377mL deionized water, after fully dissolving, then add 6.09g Graphene and 48.2g lauryl sodium sulfate, after ultrasonic disperse 10min, then add the KBH of 0.5mol/L 4aqueous solution 2467mL, reaction 10min, at graphenic surface deposition Sn-Co Nanoalloy, reaction solution washs after filtration, by solid matter, drying, obtains nanostructure intermediate;
2, complex microsphere intermediate is prepared: in the nanostructure intermediate that step 1 is obtained, in every 10g, add 5mL deionized water, after stirring, 1g polyvinyl alcohol is added again in every 10g nanostructure intermediate, stir into slurry, adopt spray drying granulation method to carry out granulation, inlet temperature is 140 DEG C, outlet temperature is 87 DEG C, atomisation pressure is 1.5MPa, and nozzle diameter is 0.5mm, obtains complex microsphere intermediate;
3, charcoal covered composite yarn microballoon is prepared: added by 18.26g pitch in 200mL kerosene solvent, after abundant dissolving, add the complex microsphere intermediate of step 2 gained again, stirring and drying, under an argon atmosphere finally, be warming up to 1500 DEG C from room temperature by 10 DEG C/min, insulation 5h carbonizes, and obtains charcoal coated Sn-Co/ Graphene microballoon.
The embedding first lithium capacity recording the charcoal coated Sn-Co/ Graphene microballoon negative material of preparation by the method for embodiment 1 is 620mAh/g, and efficiency for charge-discharge is 86.6%, and the discharge capacity after 50 times that circulates is 453mAh/g.
Through scanning electron microscopic observation, the granularity of this microballoon negative material is 20 ~ 60 μm, microballoon top layer is the compound layer of charcoal that Graphene and pyrolytic carbon are formed, microballoon inside is the loose structure be separated to form by Graphene, deposits at the pore interior of loose structure the Sn-Co alloying pellet that particle diameter is 40 ~ 100nm.
Embodiment 3
1, nanostructure intermediate is prepared: by the Na of 21.27g 2snO 3with the Co (NO of 19.82g 3) 2join 205mL deionized water, after fully dissolving, then add 1.14g Graphene and 10.3g dodecyl sodium sulfate, after ultrasonic disperse 8min, then add the NaBH of 0.1mol/L 4ethanolic solution 8016mL, reaction 15min, at graphenic surface deposition Sn-Co Nanoalloy, reaction solution washs after filtration, by solid matter, drying, obtains nanostructure intermediate;
2, complex microsphere intermediate is prepared: in the nanostructure intermediate that step 1 is obtained, in every 10g, add 10mL deionized water, after stirring, 2g sodium cellulose glycolate is added again in every 10g nanostructure intermediate, stir into slurry, adopt spray drying granulation method to carry out granulation, inlet temperature is 180 DEG C, outlet temperature is 95 DEG C, atomisation pressure is 2MPa, and nozzle diameter is 0.3mm, obtains complex microsphere intermediate;
3, prepare charcoal covered composite yarn microballoon: added by 3.4g pitch in 50mL kerosene solvent, after fully dissolving, then add the complex microsphere intermediate of 10g step 2 gained, stirring and drying, finally at N 2under atmosphere, be warming up to 1050 DEG C from room temperature by 6 DEG C/min, insulation 3h carbonizes, and obtains charcoal coated Sn-Co/ Graphene microballoon.
The embedding first lithium capacity recording the charcoal coated Sn-Co/ Graphene microballoon negative material of preparation by the method for embodiment 1 is 401mAh/g, and efficiency for charge-discharge is 83.6%, and the discharge capacity after 50 times that circulates is 356mAh/g.
Through scanning electron microscopic observation, the granularity of this microballoon negative material is 20 ~ 60 μm, microballoon top layer is the compound layer of charcoal that Graphene and pyrolytic carbon are formed, microballoon inside is the loose structure be separated to form by Graphene, deposits at the pore interior of loose structure the Sn-Co alloying pellet that particle diameter is 40 ~ 100nm.
Embodiment 4
1, nanostructure intermediate is prepared: by the Sn of 20.57g 2p 2o 7with the Co (NO of 9.20g 3) 2add 893mL deionized water, after fully dissolving, then add 75.3mg Graphene and 17.9g dodecyl sodium sulfate, after ultrasonic disperse 5min, then add the KBH of 1mol/L 4aqueous solution 451mL, reaction 20min, at graphenic surface deposition Sn-Co Nanoalloy, reaction solution washs after filtration, by solid matter, drying, obtains nanostructure intermediate;
2, complex microsphere intermediate is prepared: in the nanostructure intermediate that step 1 is obtained, in every 10g, add 15mL deionized water, after stirring, 3g sodium cellulose glycolate is added again in every 10g nanostructure intermediate, stir into slurry, adopt spray drying granulation method to carry out granulation, inlet temperature is 160 DEG C, outlet temperature is 85 DEG C, atomisation pressure is 1MPa, and nozzle diameter is 0.6mm, obtains complex microsphere intermediate;
3, prepare charcoal covered composite yarn microballoon: added by 150.6mg pitch in 10mL kerosene solvent, after fully dissolving, then add the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N 2under atmosphere, be warming up to 600 DEG C from room temperature by 2 DEG C/min, insulation 0.5h carbonizes, and obtains charcoal coated Sn-Co/ Graphene microballoon.
The embedding first lithium capacity recording the charcoal coated Sn-Co/ Graphene microballoon negative material of preparation by the method for embodiment 1 is 645mAh/g, and efficiency for charge-discharge is 84.3%, and the discharge capacity after 50 times that circulates is 497mAh/g.
Through scanning electron microscopic observation, the granularity of this microballoon negative material is 20 ~ 60 μm, microballoon top layer is the compound layer of charcoal that Graphene and pyrolytic carbon are formed, microballoon inside is the loose structure be separated to form by Graphene, deposits at the pore interior of loose structure the Sn-Co alloying pellet that particle diameter is 40 ~ 100nm.
Embodiment 5
1, nanostructure intermediate is prepared: by the SnSO of 21.47g 4with the CoSO of 7.80g 4add 526.8mL deionized water, after fully dissolving, then add 2.47g Graphene and 18.4g lauryl sodium sulfate, after ultrasonic disperse 10min, then add the KBH of 0.5mol/L 4aqueous solution 661mL, reaction 10min, at graphenic surface deposition Sn-Co Nanoalloy, reaction solution washs after filtration, by solid matter, drying, obtains nanostructure intermediate;
2, complex microsphere intermediate is prepared: in the nanostructure intermediate that step 1 is obtained, in every 10g, add 5mL deionized water, after stirring, 1g polyvinyl alcohol is added again in every 10g nanostructure intermediate, stir into slurry, adopt spray drying granulation method to carry out granulation, inlet temperature is 160 DEG C, outlet temperature is 85 DEG C, atomisation pressure is 1MPa, and nozzle diameter is 0.6mm, obtains complex microsphere intermediate;
3, prepare charcoal covered composite yarn microballoon: added by 7.42g pitch in 100mL kerosene solvent, after fully dissolving, then add the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N 2under atmosphere, be warming up to 1500 DEG C from room temperature by 10 DEG C/min, insulation 5h carbonizes, and obtains charcoal coated Sn-Co/ Graphene microballoon.
The embedding first lithium capacity recording the charcoal coated Sn-Co/ Graphene microballoon negative material of preparation by the method for embodiment 1 is 332mAh/g, and efficiency for charge-discharge is 87.6%, and the discharge capacity after 50 times that circulates is 301mAh/g.
Through scanning electron microscopic observation, the granularity of this microballoon negative material is 20 ~ 60 μm, microballoon top layer is the compound layer of charcoal that Graphene and pyrolytic carbon are formed, microballoon inside is the loose structure be separated to form by Graphene, deposits at the pore interior of loose structure the Sn-Co alloying pellet that particle diameter is 40 ~ 100nm.
Embodiment 6
1, nanostructure intermediate is prepared: by the SnCl of 26.07g 4with the Co (NO of 9.20g 3) 2add 176mL deionized water, after fully dissolving, then add 927.3mg Graphene and 8.8g dodecyl sodium sulfate, after ultrasonic disperse 8min, then add the NaBH of 0.1mol/L 4ethanolic solution 6508mL, reaction 15min, at graphenic surface deposition Sn-Co Nanoalloy, reaction solution washs after filtration, by solid matter, drying, obtains nanostructure intermediate;
2, complex microsphere intermediate is prepared: in the nanostructure intermediate that step 1 is obtained, in every 10g, add 10mL deionized water, after stirring, 2g starch is added again in every 10g nanostructure intermediate, stir into slurry, adopt spray drying granulation method to carry out granulation, inlet temperature is 180 DEG C, outlet temperature is 95 DEG C, atomisation pressure is 2MPa, and nozzle diameter is 0.3mm, obtains complex microsphere intermediate;
3, prepare charcoal covered composite yarn microballoon: added by 2.78g pitch in 50mL kerosene solvent, after fully dissolving, then add the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N 2under atmosphere, be warming up to 1050 DEG C from room temperature by 6 DEG C/min, insulation 3h carbonizes, and obtains charcoal coated Sn-Co/ Graphene microballoon.
The embedding first lithium capacity recording the charcoal coated Sn-Co/ Graphene microballoon negative material of preparation by the method for embodiment 1 is 353mAh/g, and efficiency for charge-discharge is 90.3%, and the discharge capacity after 50 times that circulates is 311mAh/g.
Through scanning electron microscopic observation, the granularity of this microballoon negative material is 20 ~ 60 μm, microballoon top layer is the compound layer of charcoal that Graphene and pyrolytic carbon are formed, microballoon inside is the loose structure be separated to form by Graphene, deposits at the pore interior of loose structure the Sn-Co alloying pellet that particle diameter is 40 ~ 100nm.
Embodiment 7
1, nanostructure intermediate is prepared: by the Na of 42.54g 2snO 3with the CoSO of 24.25g 4add 1670mL deionized water, after fully dissolving, then add 167.4mg Graphene and 66.8g dodecyl sodium sulfate, after ultrasonic disperse 6min, then add the NaBH of 0.8mol/L 4ethanolic solution 2087mL, reaction 18min, at graphenic surface deposition Sn-Co Nanoalloy, reaction solution washs after filtration, by solid matter, drying, obtains nanostructure intermediate;
2, complex microsphere intermediate is prepared: in the nanostructure intermediate that step 1 is obtained, in every 10g, add 13mL deionized water, after stirring, 2.5g polyvinyl alcohol is added again in every 10g nanostructure intermediate, stir into slurry, adopt spray drying granulation method to carry out granulation, inlet temperature is 140 DEG C, outlet temperature is 87 DEG C, atomisation pressure is 1.5MPa, and nozzle diameter is 0.5mm, obtains complex microsphere intermediate;
3, prepare charcoal covered composite yarn microballoon: added by 334.7mg pitch in 10mL kerosene solvent, after fully dissolving, then add the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N 2under atmosphere, be warming up to 800 DEG C from room temperature by 3 DEG C/min, insulation 1h carbonizes, and obtains charcoal coated Sn-Co/ Graphene microballoon.
The embedding first lithium capacity recording the charcoal coated Sn-Co/ Graphene microballoon negative material of preparation by the method for embodiment 1 is 344mAh/g, and efficiency for charge-discharge is 89.1%, and the discharge capacity after 50 times that circulates is 308mAh/g.
Through scanning electron microscopic observation, the granularity of this microballoon negative material is 20 ~ 60 μm, microballoon top layer is the compound layer of charcoal that Graphene and pyrolytic carbon are formed, microballoon inside is the loose structure be separated to form by Graphene, deposits at the pore interior of loose structure the Sn-Co alloying pellet that particle diameter is 40 ~ 100nm.
Embodiment 8
1, nanostructure intermediate is prepared: by the Sn of 41.14g 2p 2o 7with the Co (NO of 28.64g 3) 2add 1396mL deionized water, after fully dissolving, then add 5.50g Graphene and 41.9g lauryl sodium sulfate, after ultrasonic disperse 9min, then add the KBH of 0.2mol/L 4aqueous solution 4278mL, reaction 11min, at graphenic surface deposition Sn-Co Nanoalloy, reaction solution washs after filtration, by solid matter, drying, obtains nanostructure intermediate;
2, complex microsphere intermediate is prepared: in the nanostructure intermediate that step 1 is obtained, in every 10g, add 6mL deionized water, after stirring, 1.5g starch is added again in every 10g nanostructure intermediate, stir into slurry, adopt spray drying granulation method to carry out granulation, inlet temperature is 110 DEG C, outlet temperature is 80 DEG C, atomisation pressure is 0.5MPa, and nozzle diameter is 0.7mm, obtains complex microsphere intermediate;
3, prepare charcoal covered composite yarn microballoon: added by 16.49g pitch in 200mL kerosene solvent, after fully dissolving, then add the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N 2under atmosphere, be warming up to 1300 DEG C from room temperature by 8 DEG C/min, insulation 4h carbonizes, and obtains charcoal coated Sn-Co/ Graphene microballoon.
The embedding first lithium capacity recording the charcoal coated Sn-Co/ Graphene microballoon negative material of preparation by the method for embodiment 1 is 332mAh/g, and efficiency for charge-discharge is 87.6%, and the discharge capacity after 50 times that circulates is 301mAh/g.
Through scanning electron microscopic observation, the granularity of this microballoon negative material is 20 ~ 60 μm, microballoon top layer is the compound layer of charcoal that Graphene and pyrolytic carbon are formed, microballoon inside is the loose structure be separated to form by Graphene, deposits at the pore interior of loose structure the Sn-Co alloying pellet that particle diameter is 40 ~ 100nm.

Claims (9)

1. a preparation method for lithium ion battery carbon coated Sn-Co/ Graphene microballoon negative material, is characterized in that, comprise following steps:
(1) nanostructure intermediate is prepared
Solubility Sn salt and solubility Co salt are added deionized water, after abundant dissolving, add Graphene and surface modifier solution, after ultrasonic disperse 5 ~ 10min, add reducing agent reaction 10 ~ 20min again, the Sn-Co Nanoalloy that reaction generates is deposited on graphenic surface, is filtered by reaction solution, again by solid matter washing, drying, obtains nanostructure intermediate;
Wherein, described Graphene by natural flake graphite through Hummer method be oxidized and hydrazine hydrate reduction obtain, have atomic structure of carbon defect and surface functional group individual layer or lower than few layer graphene of 10 layers; Solubility Sn salt is SnCl 4, SnSO 4, Na 2snO 3or Sn 2p 2o 7; Solubility Co salt is CoSO 4or Co (NO 3) 2; Reducing agent is the NaBH of 0.1 ~ 1mol/L 4ethanolic solution or KBH 4the aqueous solution; Surface modifier is lauryl sodium sulfate or dodecyl sodium sulfate;
(2) complex microsphere intermediate is prepared
Add deionized water by the nanostructure intermediate of step (1) gained, after stirring, add binding agent, stir into slurry, then carry out spray drying granulation, obtaining particle diameter is micron-sized complex microsphere intermediate bulky grain;
(3) charcoal covered composite yarn microballoon is prepared
Petroleum asphalt is added in kerosene, after fully dissolving, then add the complex microsphere intermediate of step (2) gained, heating, drying, finally carry out heating charing under an inert atmosphere, obtain charcoal coated Sn-Co/ Graphene microballoon.
2. the preparation method of a kind of lithium ion battery carbon according to claim 1 coated Sn-Co/ Graphene microballoon negative material, it is characterized in that, in described step (1), the additional proportion of solubility Sn salt and solubility Co salt is: in Sn, Co atom in Sn salt and Co salt, Sn accounts for 65 ~ 80% of Sn, Co gross mass; The rate of charge of Sn salt and Co salt gross mass and deionized water is 1g:5 ~ 30mL; In Graphene quality and Sn salt and Co salt, the ratio of Sn, Co atom gross mass is (0.5 ~ 10): (60 ~ 98.5); Surface modifier quality is 2 ~ 5% of deionized water quality; The molal quantity of reducing agent is Co ion and the chemical valence sum of products 1.1 ~ 1.5 times in Sn ion and chemical valence sum of products Co salt in Sn salt.
3. the preparation method of a kind of lithium ion battery carbon according to claim 1 coated Sn-Co/ Graphene microballoon negative material, is characterized in that, in step (2), described binding agent is starch, polyvinyl alcohol or sodium carboxymethylcellulose.
4. the preparation method of a kind of lithium ion battery carbon according to claim 1 coated Sn-Co/ Graphene microballoon negative material, it is characterized in that, in step (2), described nanostructure intermediate and the solid-to-liquid ratio of deionized water are 10g:(5 ~ 15) mL, the mass ratio of nanostructure intermediate and binding agent is 10:(1 ~ 3).
5. the preparation method of a kind of lithium ion battery carbon according to claim 1 coated Sn-Co/ Graphene microballoon negative material, it is characterized in that, spray drying granulation condition described in step (2) is: inlet temperature is 110 ~ 180 DEG C, outlet temperature is 80 ~ 95 DEG C, atomisation pressure is 0.5 ~ 2MPa, and nozzle diameter is 0.3 ~ 0.7mm.
6. the preparation method of a kind of lithium ion battery carbon according to claim 1 coated Sn-Co/ Graphene microballoon negative material, it is characterized in that, in step (3), in the complex microsphere intermediate obtained in described petroleum asphalt addition and step (2), the mass ratio of Graphene is (1 ~ 30): (0.5 ~ 10).
7. the preparation method of a kind of lithium ion battery carbon according to claim 1 coated Sn-Co/ Graphene microballoon negative material, it is characterized in that, in step (3), described heating, drying condition is: speed stirs 50 ~ 100rpm, bake out temperature 200 ~ 280 DEG C.
8. the preparation method of a kind of lithium ion battery carbon according to claim 1 coated Sn-Co/ Graphene microballoon negative material, it is characterized in that, in step (3), described charing heating cycle is: with behind ramp to 600 ~ 1500 of 2 ~ 10 DEG C/min DEG C, insulation 0.5 ~ 5h, then cool with stove; Described inert gas is nitrogen or argon gas.
9. the preparation method of a kind of lithium ion battery carbon according to claim 1 coated Sn-Co/ Graphene microballoon negative material, is characterized in that, according to the lithium ion battery carbon coated Sn-Co/ Graphene microballoon negative material that the method is obtained.
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CN103715406A (en) * 2014-01-13 2014-04-09 中国科学院宁波材料技术与工程研究所 Preparation and applications of tin based alloy-carbon composite anode active material
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CN105565394A (en) * 2015-12-14 2016-05-11 大连理工大学 Preparation method of graphene hollow microspheres loaded with magnetic nanoparticles
CN105719848A (en) * 2016-01-29 2016-06-29 佛山市聚成生化技术研发有限公司 Preparation method for long-cycling-life supercapacitor and supercapacitor prepared by same
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CN114566623A (en) * 2022-03-02 2022-05-31 辽宁工程技术大学 Battery negative electrode material and preparation method thereof
CN114566623B (en) * 2022-03-02 2023-06-27 辽宁工程技术大学 Battery negative electrode material and preparation method thereof
CN114583142A (en) * 2022-03-08 2022-06-03 辽宁工程技术大学 Double-effect catalytic lithium-air battery electrode material and preparation method thereof
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