CN108878835A - A kind of preparation method of lithium sulfur battery anode material - Google Patents

A kind of preparation method of lithium sulfur battery anode material Download PDF

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Publication number
CN108878835A
CN108878835A CN201810688168.4A CN201810688168A CN108878835A CN 108878835 A CN108878835 A CN 108878835A CN 201810688168 A CN201810688168 A CN 201810688168A CN 108878835 A CN108878835 A CN 108878835A
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preparation
anode material
sulphur
graphite alkene
carbon
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张永光
王加义
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/028—Positive 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

The invention belongs to technical field of material chemistry, it is related to a kind of preparation method of lithium sulfur battery anode material, preparation of this method Jing Guo graphene oxide water solution, the preparation of foamy graphite alkene/carbon nano tube compound material and sulphur/foamy graphite alkene/carbon/carbon nano tube compound anode material three steps of preparation, a kind of payload amount for significantly improving sulphur is obtained, reduce the composite material of polysulfide " shuttle effect ", the material is used as anode material of lithium battery, the volume expansion of lithium-sulfur cell can be effectively reduced, improve the electrochemical stability of battery, discharge capacity is up to 1529mAh/g for the first time for it, discharge capacity still has 859mAh/g after 200 charge and discharge cycles.

Description

A kind of preparation method of lithium sulfur battery anode material
Technical field
The invention belongs to technical field of material chemistry, are related to a kind of preparation method of lithium sulfur battery anode material, more specifically, relating to And a kind of preparation method of foamy graphite alkene/carbon nano tube compound material.
Background technique
With the continuous development of science and technology, industrial level is continuously improved, and people increasingly increase the demand of the energy, changes Stone energy reserve is increasingly depleted in the case where people continually develop, tap a new source of energy have become people must not ametropia ask Topic, Optimization of Energy Structure greatly develop new and renewable energy, make a vital task of the current working energy in China. Become emphasis concerned by people by the secondary cell of representative of lithium ion battery, especially as electric car, portable electronic is set Standby continuous development, recyclable secondary cell have become essential a part in people's daily life.Currently, The lithium ion battery theoretical specific capacity having been commercialized is that 300 mAh/g are limited by itself theoretical specific capacity, has been unable to satisfy people Growing energy demand, therefore the secondary cell for developing new type is imperative, and the reason of novel lithium-sulfur cell By five times that specific capacity is about commercial Li-ion batteries theoretical specific capacity（Theoretical specific capacity is 1675mAh/g, specific energy 2500 Wh/kg）, it is considered to be most one of the high-energy battery of development potentiality.
Lithium-sulfur cell still have in current research it is several be difficult to overcome the problems, such as, be primarily due to that there are following sides Face：
1, elemental sulfur is electronics and ion insulator, and conductivity only has 5*10 at room temperature-30S/cm, using it as positive electrode Electro-chemical activity is not high.
2, elemental sulfur is different with the density of charge and discharge resulting sulfides, it may occur that serious volume expansion, cubical expansivity About 76%.And repeatedly volume change can finally destroy the physical structure of battery in charge and discharge process, collapse entire battery system It bursts.
3, the distinctive shuttle effect of lithium-sulfur cell, i.e., the polysulfide generated in battery charge and discharge process is between positive and negative anodes The phenomenon that shuttling, causing self-discharge of battery.The shuttle effect of lithium-sulfur cell will affect normal battery charge and discharge process, drop The specific capacity of low battery and the cyclical stability of battery.
4, the polysulfide generated in lithium-sulfur cell charge and discharge process can be dissolved in electrolyte solution used at present, be made It is lost at the active material of positive electrode, reduces the whole chemical property of battery.
Graphene it is conductive it is excellent, chemical stability is high, large specific surface area, the strong and unique two dimension of mechanical performance are more The feature of the brilliance such as pore network geometry, what can simply and easily be carried out forms nucleocapsid clad structure with sulphur, utilizes graphene Modified lithium-sulfur cell, can be improved the electro-chemical activity of sulphur simple substance, shortens electronics and ion transmission path, limits polysulfide Dissolution, and then improve lithium-sulfur cell overall performance.It is had been reported that about application of the graphene in lithium-sulfur cell more, but existing skill Application of the art to graphene in lithium-sulfur cell, it is existing total although improving the performance of lithium-sulfur cell to a certain extent It is with defect：The payload amount of sulphur is low in positive electrode, polysulfide " shuttle effect " obviously, the volume expansion of lithium-sulfur cell Effect is significant, and the chemical property of battery is unstable.
Summary of the invention
The purpose of the present invention is to the deficiencies of above-mentioned sulphur positive electrode, provide a kind of sulphur/foamy graphite alkene/carbon nanometer Pipe composite material, the composite material significantly improve the payload amount of sulphur, reduce polysulfide " shuttle effect ", reduce The volume expansion of lithium-sulfur cell improves the electrochemical stability of battery.
The technical solution adopted by the present invention includes the following steps：
（1）The preparation of graphene oxide water solution：
It takes graphene oxide to be placed in deionized water, is configured to the graphene oxide water solution of 1~10mg/mL, ultrasonic disperse 5~ 10min；
（2）The preparation of foamy graphite alkene/carbon nano tube compound material：
To step（1）In add carbon nanotube in graphene oxide water solution obtained, so that carbon nanotube concentration is reached 2%~5%, 5~10min of ultrasonic disperse obtains graphene oxide/carbon nanotube compound aqueous solution, will be cut into a thickness of the nickel foam of 1mm Side length is the square of 2cm, is dipped in graphene oxide/carbon nanotube compound aqueous solution of 5~10mL, ultrasonic disperse 20 ~30min is sufficiently submerged in graphene oxide and carbon nanotube in nickel foam porous structure, obtains graphene oxide/carbon nanometer Pipe/foam nickel composite, is then drawn off, then immerses in the sodium ascorbate solution of 10~20mg/ml, and immersion 12~for 24 hours, It restores graphene oxide sufficiently, obtains presoma, the presoma that preparation is completed immerses in dimethyl silicone polymer, impregnates 30 ~60min, so that dimethyl silicone polymer forms support frame, sample is placed it in baking oven after preparing and is done for 50~80 DEG C Dry 12~for 24 hours, then place it in 98% concentrated hydrochloric acid solution, nickel foam erosion removal is multiple up to foamy graphite alkene/carbon nanotube Condensation material sample；
（3）Sulphur/foamy graphite alkene/carbon/carbon nano tube compound anode material preparation：
By step（2）In prepared foamy graphite alkene be placed in reaction kettle, while adding nanometer sulphur powder for foamy graphite alkene/carbon Nanometer tube composite materials covering, then reaction kettle is placed in the glove box full of nitrogen and carries out ventilation processing, after will be anti- Answer kettle to be placed in Muffle furnace, at 100~200 DEG C keep the temperature 12~for 24 hours, obtain sulphur/foamy graphite alkene/carbon nano tube compound material.
A kind of preparation method of above-mentioned lithium sulfur battery anode material, related raw material are commercially available, as The nickel foam of mould material is commercially available.
Beneficial effects of the present invention are as follows：
（1）In design process of the invention, graphene and carbon nanotube are attached to foam nickel surface simultaneously, recycle poly- diformazan Radical siloxane forms after support frame nickel foam template utilizing concentrated hydrochloric acid erosion removal, obtains graphene doped carbon nanometer pipe Tubular structure, overall structure is similar to sponge, the i.e. original foam nickel skeleton of obtained tubular structure, and structure is obvious and mutually interconnects It is logical, there is stronger suction-operated to the intermediate product generated in active material and charge and discharge process, lithium can be significantly reduced Shuttle effect in sulphur battery actual application, can be obviously improved lithium-sulfur cell entirety chemical property.
（2）It is few in order to solve active material load capacity in existing lithium sulfur battery anode material in design process of the invention And the problem that active material utilization is low, it designs and obtains the tubular structure of graphene doped carbon nanometer pipe, not only integral tubular Structure can promote the load sulphur rate of positive electrode, and the carbon nanotube adulterated can also play certain captured sulfur result, secondly, The tubular structure of graphene doped carbon nanometer pipe of the invention common synusia stacked graphene-structured than in the prior art There is higher specific surface area, ensure that sulphur can be completely into tubular structure inside, so that its true sulfur content that carries is substantially better than The payload amount of the graphene of traditional general layer shape structure, sulphur is up to 73%, significantly improves the electricity of lithium sulfur battery anode material Chemical property, discharge capacity decays very little in cyclic process, and cyclical stability significantly improves.
（3）In design process of the invention, carbon in lithium sulfur battery anode material-sulphur composite material structure has been fully considered Problem, structurally-modified to graphene progress before mixing sulphur, using nickel foam as template, design obtains graphene doped carbon nanometer The tubular structure of pipe realizes the regulating microstructure to sulfur-donor material.Using hydro-thermal method mix sulphur make sulphur even into Preset micro-nano duct, effectively forms carbon-sulphur core-shell structure, and graphene doped carbon nanometer pipe structure obtained can be effective Sulphur is coated, while significantly improving positive electrode electric conductivity, efficiently solves the Volumetric expansion of lithium-sulfur cell. Therefore, the lithium sulfur battery anode material prepared by the present invention effectively inhibits the Volumetric expansion in charge and discharge process, conductive Property is significantly improved.
Detailed description of the invention
Fig. 1 is foamy graphite alkene/carbon nano tube compound material scanning electron microscope (SEM) photograph obtained by embodiment 1.
Fig. 2 is sulphur/foamy graphite alkene/carbon nano tube compound material hot weight curve obtained by embodiment 1.
Fig. 3 is the lithium sulphur electricity being prepared using sulphur described in embodiment 1/foamy graphite alkene/carbon nano tube compound material Electrochemical specific capacity curve of pond under the conditions of 0.1C charge and discharge.
Specific embodiment
The invention will be further described with specific embodiment with reference to the accompanying drawings of the specification.
Embodiment 1
The technical scheme comprises the following steps for the present embodiment use：
The first step, the preparation of graphene oxide water solution：
It takes graphene oxide to be placed in deionized water, is configured to the graphene oxide water solution of 10mg/mL, ultrasonic disperse 10min；
Second step, the preparation of foamy graphite alkene/carbon nano tube compound material：
Carbon nanotube is added in 10mg/mL graphene oxide water solution obtained into the first step, reaches carbon nanotube concentration 2%, ultrasonic disperse 10min obtain graphene oxide/carbon nanotube compound aqueous solution.It will will be cut with a thickness of the nickel foam of 1mm The square for being 2cm at side length, it is dipped in graphene oxide/carbon nanotube compound aqueous solution of 10mL, ultrasonic disperse 30min is sufficiently submerged in graphene oxide and carbon nanotube in nickel foam porous structure, and the nickel foam after the completion of immersion is taken Out, it then immerses in the sodium ascorbate solution of 20mg/ml, impregnates for 24 hours, restore graphene oxide sufficiently, obtain presoma.It will The presoma that preparation is completed immerses in dimethyl silicone polymer, impregnates 60min, so that dimethyl silicone polymer forms support rib Frame.Sample places it in baking oven 80 DEG C of dryings for 24 hours after preparing.It is placed it in 98% concentrated hydrochloric acid solution again, by nickel foam For erosion removal up to foamy graphite alkene/carbon nano tube compound material sample, Fig. 1 is the Flied emission electron-microscope scanning of the composite material Figure, it can be seen from the figure that foamy graphite alkene/carbon nanotube has abnormal pore structure abundant, this has sulphur storage huge Big help, sulphur are difficult to be lost after entering pore structure, so that lithium sulfur battery anode material prepared by the present invention is with excellent Cycle performance.
Third step, sulphur/foamy graphite alkene/carbon/carbon nano tube compound anode material preparation：
Foamy graphite alkene/carbon nano tube compound material prepared in second step is placed in reaction kettle, while adding nano-sulfur Powder covers foamy graphite alkene, and then reaction kettle is placed in the glove box full of nitrogen and carries out ventilation processing.After will be anti- It answers kettle to be placed in Muffle furnace, is kept the temperature at 200 DEG C for 24 hours, obtain sulphur/foamy graphite alkene/carbon nano tube compound material.It is examined through thermogravimetric It surveys, the mass percentage about 73% of sulphur in sulphur/foamy graphite alkene/carbon/carbon nano tube compound anode material, as shown in Fig. 2, showing this Composite material has excellent three-dimensional structure, and specific surface area is very big, and structure is obvious, fine to the covered effect of sulphur.This is compound Material is applied in lithium-sulfur cell, its electrochemical specific capacity curve is measured under the conditions of 0.1C charge and discharge, the results show that the material Discharge capacity for the first time be up to 1529mAh/g, discharge capacity still has 859mAh/g after 200 charge and discharge cycles, sees attached drawing 3。

Claims (6)

1. a kind of preparation method of lithium sulfur battery anode material, which is characterized in that including（1）The system of graphene oxide water solution Standby,（2）The preparation of foamy graphite alkene/carbon nano tube compound material and（3）Sulphur/foamy graphite alkene/carbon/carbon nano tube compound anode material Three steps of preparation of material.
2. the preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that described（1）Oxidation The concentration of graphene aqueous solution is 1~10mg/mL.
3. the preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that described（2）Foam The preparation method of Graphene/carbon nanotube composite material is：To step（1）In add carbon in graphene oxide water solution obtained Nanotube, 5~10min of ultrasonic disperse obtain graphene oxide/carbon nanotube compound aqueous solution, will be with a thickness of the nickel foam of 1mm It is cut into the square that side length is 2cm, is dipped in graphene oxide/carbon nanotube compound aqueous solution of 5~10mL, ultrasound 20~30min of dispersion is sufficiently submerged in graphene oxide and carbon nanotube in nickel foam porous structure, obtains graphene oxide/carbon Nanotube/foam nickel composite, is then drawn off, then immerse in sodium ascorbate solution, and immersion 12~for 24 hours, make to aoxidize stone Black alkene sufficiently restores, and obtains presoma, and the presoma that preparation is completed immerses in dimethyl silicone polymer, impregnates 30~60min, So as to dimethyl silicone polymer formed support frame, sample placed it in after preparing 50~80 DEG C of dryings 12 in baking oven~ For 24 hours, it then places it in 98% concentrated hydrochloric acid solution, by nickel foam erosion removal up to foamy graphite alkene/carbon nano tube compound material Sample.
4. the preparation method of lithium sulfur battery anode material according to claim 3, which is characterized in that the carbon nanotube Concentration is 2%~5%.
5. the preparation method of lithium sulfur battery anode material according to claim 3, which is characterized in that the ascorbic acid Sodium solution concentration is 10~20mg/ml.
6. the preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that described（3）Sulphur/bubble The preparation method of foam graphene/carbon nano-tube composite positive pole is：By step（2）In prepared foamy graphite alkene be placed in instead It answers in kettle, while adding nanometer sulphur powder and covering foamy graphite alkene/carbon nano tube compound material, then reaction kettle is placed in and is full of Ventilation processing is carried out in the glove box of nitrogen, after reaction kettle is placed in Muffle furnace, at 100~200 DEG C keep the temperature 12~ For 24 hours, sulphur/foamy graphite alkene/carbon nano tube compound material is obtained.
CN201810688168.4A 2018-06-28 2018-06-28 A kind of preparation method of lithium sulfur battery anode material Pending CN108878835A (en)

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Cited By (9)

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CN110272625A (en) * 2018-10-09 2019-09-24 杭州师范大学 A kind of multi-level hole structural conductive polymer composite and preparation method thereof, application
CN110581276A (en) * 2018-06-11 2019-12-17 中国科学院宁波材料技术与工程研究所 interface protection structure, preparation method thereof and battery with interface protection structure
CN111342009A (en) * 2020-03-02 2020-06-26 肇庆市华师大光电产业研究院 Novel high-performance lithium-sulfur battery positive electrode material and preparation method thereof
CN111509226A (en) * 2020-04-24 2020-08-07 北京石墨烯研究院有限公司 Graphene foam compound, preparation method thereof, and composite electrode and lithium-sulfur battery comprising graphene foam compound
CN111864190A (en) * 2019-04-26 2020-10-30 河南师范大学 Preparation method of flexible sulfur positive electrode of lithium-sulfur battery
CN112436114A (en) * 2020-11-16 2021-03-02 扬州大学 Three-dimensional graphene/carbon nanotube/phosphotungstic acid/sulfur composite material, preparation method and application thereof
CN112993204A (en) * 2021-03-24 2021-06-18 肇庆市华师大光电产业研究院 Preparation method of high-specific-surface-area positive electrode material of lithium-sulfur battery
CN113451562A (en) * 2021-07-02 2021-09-28 辽宁工程技术大学 Flexible positive electrode material of lithium-sulfur battery and preparation method thereof
CN114735710A (en) * 2022-05-15 2022-07-12 连云港福东正佑照明电器有限公司 Method for purifying quartz sand by high-temperature acid mist

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CN106159209A (en) * 2016-08-16 2016-11-23 肖丽芳 A kind of preparation method of foamy graphite alkene lithium-sulphur cell positive electrode sheet
CN107768637A (en) * 2017-10-16 2018-03-06 河源广工大协同创新研究院 A kind of preparation method of porous graphene/carbon nanotube lithium sulphur positive electrode

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CN104291324A (en) * 2014-09-09 2015-01-21 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of graphene foams
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CN110581276B (en) * 2018-06-11 2022-01-04 中国科学院宁波材料技术与工程研究所 Interface protection structure, preparation method thereof and battery with interface protection structure
CN110581276A (en) * 2018-06-11 2019-12-17 中国科学院宁波材料技术与工程研究所 interface protection structure, preparation method thereof and battery with interface protection structure
CN110272625A (en) * 2018-10-09 2019-09-24 杭州师范大学 A kind of multi-level hole structural conductive polymer composite and preparation method thereof, application
CN111864190A (en) * 2019-04-26 2020-10-30 河南师范大学 Preparation method of flexible sulfur positive electrode of lithium-sulfur battery
CN111864190B (en) * 2019-04-26 2022-07-01 河南师范大学 Preparation method of flexible sulfur positive electrode of lithium-sulfur battery
CN111342009A (en) * 2020-03-02 2020-06-26 肇庆市华师大光电产业研究院 Novel high-performance lithium-sulfur battery positive electrode material and preparation method thereof
CN111509226A (en) * 2020-04-24 2020-08-07 北京石墨烯研究院有限公司 Graphene foam compound, preparation method thereof, and composite electrode and lithium-sulfur battery comprising graphene foam compound
CN111509226B (en) * 2020-04-24 2021-09-10 北京石墨烯研究院有限公司 Graphene foam compound, preparation method thereof, and composite electrode and lithium-sulfur battery comprising graphene foam compound
CN112436114A (en) * 2020-11-16 2021-03-02 扬州大学 Three-dimensional graphene/carbon nanotube/phosphotungstic acid/sulfur composite material, preparation method and application thereof
CN112993204A (en) * 2021-03-24 2021-06-18 肇庆市华师大光电产业研究院 Preparation method of high-specific-surface-area positive electrode material of lithium-sulfur battery
CN113451562A (en) * 2021-07-02 2021-09-28 辽宁工程技术大学 Flexible positive electrode material of lithium-sulfur battery and preparation method thereof
CN113451562B (en) * 2021-07-02 2023-06-20 辽宁工程技术大学 Flexible positive electrode material of lithium-sulfur battery and preparation method thereof
CN114735710A (en) * 2022-05-15 2022-07-12 连云港福东正佑照明电器有限公司 Method for purifying quartz sand by high-temperature acid mist
CN114735710B (en) * 2022-05-15 2022-12-20 连云港福东正佑照明电器有限公司 Method for purifying quartz sand by high-temperature acid mist

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