WO2017139990A1 - Procédé de préparation d'un matériau de cathode à sphères creuses d'alumine pour batterie lithium-soufre - Google Patents

Procédé de préparation d'un matériau de cathode à sphères creuses d'alumine pour batterie lithium-soufre Download PDF

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Publication number
WO2017139990A1
WO2017139990A1 PCT/CN2016/074186 CN2016074186W WO2017139990A1 WO 2017139990 A1 WO2017139990 A1 WO 2017139990A1 CN 2016074186 W CN2016074186 W CN 2016074186W WO 2017139990 A1 WO2017139990 A1 WO 2017139990A1
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WO
WIPO (PCT)
Prior art keywords
hollow
sulfur
graphene
alumina
lithium
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PCT/CN2016/074186
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English (en)
Chinese (zh)
Inventor
肖丽芳
钟玲珑
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肖丽芳
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Publication date
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Priority to PCT/CN2016/074186 priority Critical patent/WO2017139990A1/fr
Publication of WO2017139990A1 publication Critical patent/WO2017139990A1/fr

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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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Definitions

  • the invention relates to the synthesis of nano materials, in particular to a method for preparing a cathode material of a lithium sulfur battery.
  • the lithium-sulfur battery is a battery system in which lithium metal is used as a negative electrode and elemental sulfur is used as a positive electrode.
  • Lithium-sulfur batteries have two discharge platforms (about 2.4V and 2.1V), but their electrochemical reaction mechanism is complicated. Lithium-sulfur batteries have the advantages of high specific energy (2600Wh/kg), high specific capacity (1675mAh/g), low cost, etc., and are considered to be promising new generation batteries.
  • problems such as low utilization rate of active materials, low cycle life and poor safety, which seriously restricts the development of lithium-sulfur batteries.
  • Elemental sulfur is an electron and ion insulator, and the room temperature conductivity is low (5 ⁇ 10 -30 S ⁇ cm -1 ). Since there is no ionic sulfur, it is used as The activation of the positive electrode material is difficult; (2) the high polylithium polysulfide Li 2 S n (8>n ⁇ 4) generated during the electrode reaction is easily dissolved in the electrolyte, forming a concentration difference between the positive and negative electrodes. Under the action of the concentration gradient, it migrates to the negative electrode, and the high poly lithium polysulfide is reduced by the lithium metal to the oligomeric lithium polysulfide.
  • the oligomeric lithium polysulfide aggregates at the negative electrode, eventually forming a concentration difference between the two electrodes, and then migrating to the positive electrode to be oxidized to a highly polylithium polysulfide.
  • This phenomenon is known as the shuttle effect, which reduces the utilization of sulfur active substances.
  • insoluble Li 2 S and Li 2 S 2 are deposited on the surface of the lithium negative electrode, which further deteriorates the performance of the lithium-sulfur battery;
  • the final product of the reaction, Li 2 S is also an electronic insulator, which is deposited on the sulfur electrode, and lithium
  • the migration speed of ions in solid lithium sulfide is slow, which makes the electrochemical reaction kinetics slower.
  • the technical problem to be solved by the present invention is to provide a graphene/alumina hollow sphere/sulfur composite material, which has a simple preparation method, a conductive conductive graphene provides a conductive network, and a hollow structure alumina coated with a sulfur-based material, capable of Prevents the dissolution of polysulfide in the discharge product and relieves volume expansion, improving the electrochemical properties of the material performance.
  • the invention provides a preparation process of a graphene/alumina hollow sphere/sulfur composite material as follows:
  • the particle size of the aluminum powder in step (1) is 1-100 um, and the concentration of the aqueous solution of octahydrate aluminum silicate is 0.2-0.4 mol/L;
  • the temperature of the high temperature calcination in the step (2) is 900-1100 ° C, and the reaction time is 1-3 hours;
  • Step (3) The mass ratio of hollow alumina, sulfur elemental, graphene is 15-30:60-80:5-10; the ultrasonic dispersion time is 0.5-5 hours; and the temperature of the evaporated solvent is 40-60 °C.
  • the invention has the following beneficial effects: (1) graphene has ultra-high electrical conductivity, and the graphene/alumina hollow sphere/sulfur composite material prepared by the method can effectively improve the electronic conductivity of the cathode material of the lithium-sulfur battery and Ionic conductivity; (2) Graphene/alumina hollow sphere/sulfur composite material coated with sulfur-based material in alumina hollow sphere, can inhibit the dissolution of polysulfide of discharge products and relieve volume expansion, improve its electrochemical performance .
  • Figure 1 is an SEM image of a graphene/alumina hollow sphere/sulfur composite prepared in accordance with the present invention.
  • Electrode preparation and performance test electrode material, acetylene black and PVDF were mixed in NMP at a mass ratio of 80:10:10, coated on aluminum foil as electrode film, lithium metal plate as counter electrode, CELGARD 2400 as separator, 1 mol /L LiTFSI/DOL-DME (volume ratio 1:1) is an electrolyte, 1mol/L LiNO3 is an additive, assembled into a button-type battery in a filled glove box, and a constant current charge and discharge test is performed using a Land battery test system. .
  • the charge and discharge voltage range is 1-3V
  • the current density is 1C
  • performance is shown in Table 1.
  • FIG. 1 is an SEM image of a positive electrode material prepared by the present invention. It can be seen from the figure that the aluminum oxide coated lithium sulfide particles are uniformly distributed on the surface of the graphene, which is beneficial to improving the electrochemical performance of the material.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de préparation d'un matériau de cathode à sphères creuses d'alumine pour batterie lithium-soufre, le procédé comprenant les étapes suivantes : étape (1), dispersion d'une poudre d'aluminium dans une solution aqueuse d'octadécahydrate de silicate d'aluminium, agitation, puis ajout progressif d'urée et poursuite de l'agitation jusqu'à ce que le précipité cesse d'augmenter, et après réaction complète, filtrage du précipité, lavage à l'eau et séchage de manière à obtenir un matériau Al-Al(OH)3 ; étape (2), placement du matériau Al-Al(OH)3 obtenu dans un four à moufle en vue d'une calcination à haute température, afin d'obtenir des sphères d'oxyde d'aluminium creuses après réaction complète ; et étape (3), ajout des sphères d'oxyde d'aluminium creuses obtenues, de soufre élémentaire et de graphène dans du disulfure de carbone en vue d'une dispersion par ultrasons afin de former une suspension, et ensuite évaporation du solvant, de manière à obtenir un matériau composite. Dans le matériau composite graphène/sphères creuses d'oxyde d'aluminium/soufre, les sphères creuses d'oxyde d'aluminium recouvrent le matériau à base de soufre, ce qui permet de supprimer la dissolution du produit de décharge polysulfure, et de réduire la dilatation volumique, améliorant ses propriétés électrochimiques.
PCT/CN2016/074186 2016-02-21 2016-02-21 Procédé de préparation d'un matériau de cathode à sphères creuses d'alumine pour batterie lithium-soufre WO2017139990A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2016/074186 WO2017139990A1 (fr) 2016-02-21 2016-02-21 Procédé de préparation d'un matériau de cathode à sphères creuses d'alumine pour batterie lithium-soufre

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Application Number Priority Date Filing Date Title
PCT/CN2016/074186 WO2017139990A1 (fr) 2016-02-21 2016-02-21 Procédé de préparation d'un matériau de cathode à sphères creuses d'alumine pour batterie lithium-soufre

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WO2017139990A1 true WO2017139990A1 (fr) 2017-08-24

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110364684A (zh) * 2019-06-04 2019-10-22 江西力能新能源科技有限公司 一种陶瓷涂层极片制备方法及在锂电池中的应用
CN110775960A (zh) * 2019-11-05 2020-02-11 武汉华科三维科技有限公司 一种Al2O3包覆的石墨烯及其制备方法和在铝合金中的应用
CN112864375A (zh) * 2021-01-08 2021-05-28 中南大学 一种以冶炼渣为原料制备锂硫电池正极材料的方法
CN115172924A (zh) * 2022-07-22 2022-10-11 浙江大学 一种锂离子电池正极材料的回收修复方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1673085A (zh) * 2005-01-26 2005-09-28 中国科学院上海硅酸盐研究所 一种以湿化学法为基础的氧化铝空心球的制备方法
CN102280614A (zh) * 2011-07-07 2011-12-14 天津大学 一种锂硫电池的硫正极的制备方法
CN103280601A (zh) * 2013-05-27 2013-09-04 浙江大学 一种锂硫电池的制造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1673085A (zh) * 2005-01-26 2005-09-28 中国科学院上海硅酸盐研究所 一种以湿化学法为基础的氧化铝空心球的制备方法
CN102280614A (zh) * 2011-07-07 2011-12-14 天津大学 一种锂硫电池的硫正极的制备方法
CN103280601A (zh) * 2013-05-27 2013-09-04 浙江大学 一种锂硫电池的制造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110364684A (zh) * 2019-06-04 2019-10-22 江西力能新能源科技有限公司 一种陶瓷涂层极片制备方法及在锂电池中的应用
CN110775960A (zh) * 2019-11-05 2020-02-11 武汉华科三维科技有限公司 一种Al2O3包覆的石墨烯及其制备方法和在铝合金中的应用
CN110775960B (zh) * 2019-11-05 2022-12-09 武汉华科三维科技有限公司 一种Al2O3包覆的石墨烯及其制备方法和在铝合金中的应用
CN112864375A (zh) * 2021-01-08 2021-05-28 中南大学 一种以冶炼渣为原料制备锂硫电池正极材料的方法
CN115172924A (zh) * 2022-07-22 2022-10-11 浙江大学 一种锂离子电池正极材料的回收修复方法
CN115172924B (zh) * 2022-07-22 2023-12-15 浙江大学 一种锂离子电池正极材料的回收修复方法

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