CN107768659A - A kind of preparation method of the sulfur electrode material of loose structure - Google Patents

A kind of preparation method of the sulfur electrode material of loose structure Download PDF

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Publication number
CN107768659A
CN107768659A CN201610668836.8A CN201610668836A CN107768659A CN 107768659 A CN107768659 A CN 107768659A CN 201610668836 A CN201610668836 A CN 201610668836A CN 107768659 A CN107768659 A CN 107768659A
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China
Prior art keywords
sulphur
loose structure
electrode material
sulfur electrode
culture medium
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Pending
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CN201610668836.8A
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Chinese (zh)
Inventor
孙绍庆
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Fujian Xinfeng Two Mstar Technology Ltd
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Fujian Xinfeng Two Mstar Technology Ltd
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Priority to CN201610668836.8A priority Critical patent/CN107768659A/en
Priority to PCT/CN2017/095797 priority patent/WO2018032974A1/en
Publication of CN107768659A publication Critical patent/CN107768659A/en
Pending legal-status Critical Current

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    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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
    • H01M4/36—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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 preparation method of the sulfur electrode material of loose structure to comprise the following steps：Prepare sulphur bacteria culture fluid；Prepare sulphur and vulcanized ester mixed-culture medium；The sulfur electrode material of loose structure is prepared, including：Obtained sulphur and vulcanized ester mixed-culture medium are dried into 1 5h in vacuum drying chamber, then in full of protective gas ar gas environment, with 10 30 DEG C/min heating rate, and 1 5h that annealed at 600 800 DEG C, obtain the sulfur electrode material of loose structure.Loose structure of the present invention can make metal ion such as Li+, Na+And Mg2+Deng the duct of loose structure being freed in and out, so as to strengthen the cycle performance of battery；And sulphion is fixed in the biological plastid vulcanized ester being carbonized, it is impossible to is lost in easily, is increased the utilization rate of sulphur.

Description

A kind of preparation method of the sulfur electrode material of loose structure
Technical field
The present invention relates to electrode material preparation field, more particularly to a kind of preparation side of the sulfur electrode material of loose structure Method.
Background technology
In recent years, because the rise of electric automobile and intelligent grid, increasing researcher begin look for and ground Study carefully the electrode material of high-energy-density.Wherein, the theoretical specific capacity of sulphur is more than 1600 MAhs/g.Sulphur has and is produced into simultaneously The advantages that this is cheap, and toxicity is low, and capacity is high and energy density is high, causes the great research interest of battery workers.
But there is problems with sulphur as electrode：Sulphion electric conductivity is poor, causes the utilization rate of sulphur low.With metal from The polysulfide that son is formed is soluble in electrolyte solution, causes active material to reduce.The disadvantages described above of sulfur electrode to assemble Into after battery, the poor circulation of battery, performance degradation are fast.It is well known that the pattern of electrode material and surface area are to battery Chemical property has important influence.
Therefore exploring one kind can be fixed with sulphion, and metal ion is turned into by the passage or pore structure that pass in and out solves sulphur electricity The Main Basiss of pole problem of materials.
The content of the invention
In view of the above-mentioned problems, the invention provides a kind of preparation method of the sulfur electrode material of loose structure.
In order to solve the above technical problems, the technical solution adopted in the present invention is：A kind of sulfur electrode material of loose structure Preparation method comprise the following steps：Prepare sulphur bacteria culture fluid；Prepare sulphur and vulcanized ester mixed-culture medium；Prepare porous knot The sulfur electrode material of structure, including：Obtained sulphur and vulcanized ester mixed-culture medium are dried into 1-5h in vacuum drying chamber, then In full of protective gas ar gas environment, with 10-30 DEG C/min heating rate, and the 1-5h that annealed at 600-800 DEG C, Obtain the sulfur electrode material of loose structure.
Further, the step prepares sulphur bacteria culture fluid and is：The pH value of culture medium is first arranged to 3-8, temperature is 25-30 DEG C, then weigh corn flour 1-3g, peptone 0.5-1.5g, MgSO4.7H2O 0.05-0.15g, KH2PO40.1-0.3g It is added to and is placed with 50-150ml deionized waters with sulphur bacterium powder, is put into the constant temperature oscillation shaking table that rotating speed is 100-160r/min Middle shaken cultivation 5-7d, obtained sulphur bacteria culture fluid.
Further, the step prepares sulphur and vulcanized ester mixed-culture medium is:Cosan is weighed in the vulcanized ester In nutrient solution, and magnetic agitation 1-30min；Then 15-40h is placed；Then removed slag, will be suspended with slow-speed of revolution centrifugal method Liquid centrifuges at high speed, and washs 2-8 times repeatedly, obtains sulphur and vulcanized ester mixed-culture medium.
Further, the sulphur bacterium powder is bayesian sulfur bacteria, hair sulphur bacterium, sulphur dialister bacterium, sulfolobus solfataricus, purple sulfur bacteria and green Any one in sulphur bacterium.
From the above-mentioned description to structure of the present invention, compared to the prior art, the invention has the advantages that：The present invention The material activity surface of obtained loose structure is larger, can increase contact of the electrolyte with active material, it is more to provide material Electrochemical reaction position, improve electrode capacity；Cushion can be used as, reduces the structure change in cyclic process, improves electrode cycle Stability.Loose structure can make metal ion such as Li+, Na+And Mg2+Deng the duct of loose structure being freed in and out, so as to strengthen The cycle performance of battery.And sulphion is fixed in the biological plastid vulcanized ester being carbonized, it is impossible to is lost in easily, is made the utilization of sulphur Rate increases.
Brief description of the drawings
The accompanying drawing for forming the part of the application is used for providing a further understanding of the present invention, schematic reality of the invention Apply example and its illustrate to be used to explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is a kind of schematic flow sheet of the preparation method of the sulfur electrode material of loose structure of the present invention；
Fig. 2 is the structural representation of the sulfur electrode material of loose structure of the present invention.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
As shown in Figures 1 and 2, it is the present invention a kind of preparation method and structure chart of the sulfur electrode material of loose structure.
Embodiment 1
S101, prepare sulphur bacteria culture fluid；The pH value of culture medium is arranged to 5.0 first, temperature weighs corn at 27 DEG C Powder 3g, peptone 1.5g, MgSO4.7H2O (seven water manganese sulfates) 0.05g, KH2PO4(potassium dihydrogen phosphate) 0.2g and bacterium powder are added to It is placed with 100ml deionized waters, the solution of configuration is put into the constant temperature oscillation shaking table that rotating speed is 120r/m in and vibrated by more than 7d is cultivated, obtains sulphur bacteria culture fluid.
S102, prepare sulphur and vulcanized ester mixed-culture medium；The Cosan measured on a small quantity is weighed in sulphur bacteria culture fluid, and Magnetic agitation 15min；Then 20h is placed；Then removed slag with slow-speed of revolution centrifugal method, will obtain suspension at high speed from The heart, and wash 6 times repeatedly and obtain sulphur and vulcanized ester mixed-culture medium；
S103, the sulfur electrode material for preparing loose structure, obtained sulphur and vulcanized ester mixed-culture medium are done in vacuum 3h is dried in dry case and then in full of protective gas ar gas environment, with 20 DEG C/min heating rate, and at 700 DEG C Anneal 3h, obtains the sulfur electrode material of loose structure.
Embodiment 2
S101, prepare sulphur bacteria culture fluid；The pH value of culture medium is arranged to 8.0 first, temperature weighs corn at 28 DEG C Powder 3g, peptone 1.2g, MgSO4.7H2O (seven water manganese sulfates) 0.1g, KH2PO4(potassium dihydrogen phosphate) 0.3g and bacterium powder are added to It is placed with 100ml deionized waters, the solution of configuration is put into the constant temperature oscillation shaking table that rotating speed is 150r/m in and vibrated by more than 6d is cultivated, obtains sulphur bacteria culture fluid.
S102, prepare sulphur and vulcanized ester mixed-culture medium；The Cosan measured on a small quantity is weighed in sulphur bacteria culture fluid, and Magnetic agitation 20min；Then 25h is placed；Then removed slag with slow-speed of revolution centrifugal method, will obtain suspension at high speed from The heart, and wash 8 times repeatedly and obtain sulphur and vulcanized ester mixed-culture medium；
S103, the sulfur electrode material for preparing loose structure, obtained sulphur and vulcanized ester mixed-culture medium are done in vacuum 3h is dried in dry case and then in full of protective gas ar gas environment, with 25 DEG C/min heating rate, and at 600 DEG C Anneal 4h, obtains the sulfur electrode material of loose structure.
Loose structure produced by the present invention can make metal ion such as Li+, Na+And Mg2+Deng freeing in and out loose structure Duct, so as to strengthen the cycle performance of battery.And sulphion is fixed in the biological plastid vulcanized ester being carbonized, it is impossible to is flowed easily Lose, increase the utilization rate of sulphur.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.

Claims (4)

  1. A kind of 1. preparation method of the sulfur electrode material of loose structure, it is characterised in that：The preparation method comprises the following steps：
    Prepare sulphur bacteria culture fluid；
    Prepare sulphur and vulcanized ester mixed-culture medium；
    The sulfur electrode material of loose structure is prepared, including：By obtained sulphur and vulcanized ester mixed-culture medium in vacuum drying chamber Middle dry 1-5h, then in full of protective gas ar gas environment, with 10-30 DEG C/min heating rate, and in 600- Anneal 1-5h at 800 DEG C, obtains the sulfur electrode material of loose structure.
  2. A kind of 2. preparation method of the sulfur electrode material of loose structure according to claim 1, it is characterised in that：The step Preparing sulphur bacteria culture fluid is：The pH value of culture medium is first arranged to 3-8, temperature is 25-30 DEG C, then weighs corn flour 1- 3g, peptone 0.5-1.5g, MgSO4.7H2O 0.05-0.15g, KH2PO40.1-0.3g and sulphur bacterium powder are added to and are placed with In 50-150ml deionized waters, shaken cultivation 5-7d in the constant temperature oscillation shaking table that rotating speed is 100-160r/min is put into, is obtained Sulphur bacteria culture fluid.
  3. A kind of 3. preparation method of the sulfur electrode material of loose structure according to claim 2, it is characterised in that：The step Prepare sulphur and vulcanized ester mixed-culture medium is：Cosan is weighed in the sulphur bacteria culture fluid, and magnetic agitation 1- 30min；Then 15-40h is placed；Then removed slag with slow-speed of revolution centrifugal method, suspension will be obtained and centrifuged at high speed, and instead After backwashing is washed 2-8 times, obtains sulphur and vulcanized ester mixed-culture medium.
  4. A kind of 4. preparation method of the sulfur electrode material of loose structure according to claim 1, it is characterised in that：The sulphur Bacterium powder is any one in bayesian sulfur bacteria, hair sulphur bacterium, sulphur dialister bacterium, sulfolobus solfataricus, purple sulfur bacteria and chloracea.
CN201610668836.8A 2016-08-15 2016-08-15 A kind of preparation method of the sulfur electrode material of loose structure Pending CN107768659A (en)

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CN201610668836.8A CN107768659A (en) 2016-08-15 2016-08-15 A kind of preparation method of the sulfur electrode material of loose structure
PCT/CN2017/095797 WO2018032974A1 (en) 2016-08-15 2017-08-03 Method of preparing material of negative electrode of lithium ion battery

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CN109671926A (en) * 2018-12-04 2019-04-23 昆明理工大学 A kind of biomass silicon based composite material and preparation method thereof
CN110729460B (en) * 2019-09-30 2023-06-30 山东玉皇新能源科技有限公司 Nano silicon composite lithium supplementing negative electrode material of lithium ion battery and preparation method and application thereof
CN111081981A (en) * 2019-12-20 2020-04-28 中国电子科技集团公司第十八研究所 Preparation method of self-supporting double-sided silicon-graphene composite cathode
CN112467123B (en) * 2020-08-14 2022-06-10 珠海中科兆盈丰新材料科技有限公司 High-capacity lithium ion battery cathode material and preparation method thereof
CN112331838B (en) * 2020-12-01 2022-02-08 郑州中科新兴产业技术研究院 High-capacity silicon monoxide composite negative electrode material of lithium ion battery and preparation method thereof
CN113184858A (en) * 2021-04-27 2021-07-30 郑州市博卓科技有限公司 Silicon-oxygen negative electrode material composition and preparation method thereof
CN114105133B (en) * 2021-10-19 2023-09-05 湖南金硅科技有限公司 Graphite-silicon/silicon oxide-carbon composite material and preparation method and application thereof
CN114361412A (en) * 2021-12-16 2022-04-15 江苏大学 Multi-walled carbon nanotube negative electrode material and preparation method and application thereof
CN114497518A (en) * 2022-01-20 2022-05-13 上海兰钧新能源科技有限公司 Negative active material, preparation method thereof and negative pole piece
CN115394973B (en) * 2022-07-20 2023-05-16 晖阳(贵州)新能源材料有限公司 High-first-efficiency high-energy-density negative electrode material and preparation method thereof

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CN105762337B (en) * 2016-01-22 2017-11-14 三峡大学 A kind of silicon/graphene/carbon fiber composite negative material and preparation method thereof

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CN102565159A (en) * 2010-12-20 2012-07-11 北京有色金属研究总院 Method for manufacturing bacterium-modified sulfide ore microelectrode
US20150155549A1 (en) * 2013-10-18 2015-06-04 NOHMs Technologies, Inc. Functionalized carbons for lithium-sulfur batteries
CN105375001A (en) * 2015-10-16 2016-03-02 广东烛光新能源科技有限公司 Preparation method of sulfur-containing electrode material

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Application publication date: 20180306