WO2017139982A1 - Procédé de préparation pour un matériau d'électrode positive de batterie au lithium-soufre ayant une structure tridimensionnelle, codopé au bore et à l'azote - Google Patents

Procédé de préparation pour un matériau d'électrode positive de batterie au lithium-soufre ayant une structure tridimensionnelle, codopé au bore et à l'azote Download PDF

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Publication number
WO2017139982A1
WO2017139982A1 PCT/CN2016/074171 CN2016074171W WO2017139982A1 WO 2017139982 A1 WO2017139982 A1 WO 2017139982A1 CN 2016074171 W CN2016074171 W CN 2016074171W WO 2017139982 A1 WO2017139982 A1 WO 2017139982A1
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suspension
sulfur
boron
nitrogen
graphene
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PCT/CN2016/074171
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English (en)
Chinese (zh)
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肖丽芳
钟玲珑
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肖丽芳
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Priority to PCT/CN2016/074171 priority Critical patent/WO2017139982A1/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 preparation method of a cathode material for 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 ionic insulator, and the room temperature conductivity is low (5 ⁇ 10 -30 S ⁇ cm -1 ). Since there is no ionic sulfur, it acts as a positive electrode.
  • Lithium polysulfide Li 2 S n (8>n ⁇ 4) produced during the electrode reaction is easily soluble in the electrolyte, forming a concentration difference between the positive and negative electrodes. The gradient 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; (3) the final product of the reaction, Li 2 S, is also an electronic insulator, which is deposited on the sulfur electrode, and lithium slow ion mobility in the solid state lithium sulfide, the slow electrochemical reaction kinetics; different density (4) sulfur and Li 2 S final product when sulfur is expanded to about 79% of the volume of lithium, Li 2 easily lead The powdering of S causes safety problems in lithium-sulfur batteries.
  • the above-mentioned shortcomings restrict the development of lithium-sulfur batteries, which is also the key issue that needs to be solved in the research of lithium-sulfur batteries.
  • the technical problem to be solved by the present invention is to provide a three-dimensional structure lithium-sulfur battery cathode material, and a three-dimensional structure of boron-nitroco-doped graphene, nano-sulfur particles and Ketjen black deposited on boron-nitroco-doped graphene are prepared by the method.
  • the design can improve the electrical conductivity of the sulfur motor and prevent the dissolution of the polysulfide of the discharge product.
  • the invention provides a preparation process of a three-dimensional lithium-sulfur battery cathode material as follows:
  • step (3) taking the three-dimensional boron-nitrogen co-doped graphene obtained in step (2) and adding Ketjen black to N-methylpyrrolidone to form a suspension;
  • the ultrasonic reaction time in the step (1) is 10-60 minutes, and the concentration of the graphene oxide suspension is 1-10 g/L;
  • the temperature of the hydrothermal reaction in the step (2) is 160-200 ° C, the reaction time is 1-6 hours, the ratio of graphite oxide to ammonia water is 1 g: 10-50 mL, and the mass ratio of graphite oxide to sodium borohydride is 1:10. -30;
  • the mass ratio of the three-dimensional boron-nitroco-doped graphene to the Ketjen black in the step (3) is 1:0.05-0.5, and the concentration of the suspension is 1-5 g/L;
  • step (4) the mass-to-mass ratio of elemental sulfur to three-dimensional boron-nitrogen co-doped graphene and Ketjen black is 10-20:1, the ultrasonic reaction temperature is 40-50 ° C, and the ultrasonic time is until sulfur is completely dissolved.
  • the concentration of the sulfur suspension is 10-15 g/L;
  • the invention has the following beneficial effects: (1) the preparation method reduces the graphite oxide and the boron-nitrogen co-doping with the hydrothermal reaction in one step to improve the reaction efficiency; (2) the high conductivity Ketchen black and graphene materials can be effective.
  • the three-dimensional structure is conducive to the lithium ion and electrons in the multi-dimensional conduction path to improve the ion and electron conductivity;
  • the Ketjen black further shortens the conduction distance between the nano-sulfur particles and the nano-sulfur and graphene sheets, which is beneficial to the improvement of electrical conductivity;
  • the nitrogen and boron atoms in the boron-nitrogen co-doped graphene The synergistic effect on the adsorption of sulfur can effectively reduce the shuttle effect and improve the cycle life of the lithium-sulfur battery.
  • 1 is an SEM image of a three-dimensional boron-nitrogen co-doped graphene sulfur composite prepared by 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, 1 mol/L LiNO 3 is an additive, assembled into a button-type battery in a filled glove box, and a constant current charge and discharge is performed using a Land battery test system. test. The charge and discharge voltage range is 1 to 3 V, and the current density is 0.01 C. The 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 positive electrode material has a large number of open three-dimensional pore-like structures, which can provide an ion transport channel and improve 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 pour un matériau d'électrode positive de batterie au lithium-soufre ayant une structure tridimensionnelle, codopé au bore et à l'azote, comprenant les différentes étapes suivantes : étape (1) : ajouter du graphite oxydé dans de l'eau pour un ultrason, former une suspension de graphène oxydé ; étape (2) : ajouter de l'ammoniaque aqueux dans la suspension de graphène oxydé, puis ajouter du borohydrure de sodium pour produire du graphène codopé au bore et à l'azote tridimensionnel ; étape (3) : ajouter le graphène codopé au bore et à l'azote tridimensionnel produit dans l'étape (2) et du noir de Ketjen dans de la N-méthyl-pyrrolidone pour une réaction ultrasonore afin de former une suspension ; étape (4) : ajouter du soufre dans la N-méthyl-pyrrolidone pour un ultrason jusqu'à ce que du soufre élémentaire soit dissous complètement pour former une suspension ; et étape (5) : mélanger les deux suspensions produites dans l'étape (4) et l'étape (3), puis ajouter de l'eau distillée pour produire le matériau d'électrode positive de batterie au lithium-soufre ayant une structure tridimensionnelle. Les atomes d'azote et les atomes de bore dans le graphène codopé au bore et à l'azote effectuent de manière synergique l'adsorption de soufre, réduisent un effet de mélange, et augmentent le cycle de vie d'une batterie au lithium-soufre.
PCT/CN2016/074171 2016-02-19 2016-02-19 Procédé de préparation pour un matériau d'électrode positive de batterie au lithium-soufre ayant une structure tridimensionnelle, codopé au bore et à l'azote WO2017139982A1 (fr)

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PCT/CN2016/074171 WO2017139982A1 (fr) 2016-02-19 2016-02-19 Procédé de préparation pour un matériau d'électrode positive de batterie au lithium-soufre ayant une structure tridimensionnelle, codopé au bore et à l'azote

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PCT/CN2016/074171 WO2017139982A1 (fr) 2016-02-19 2016-02-19 Procédé de préparation pour un matériau d'électrode positive de batterie au lithium-soufre ayant une structure tridimensionnelle, codopé au bore et à l'azote

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CN109148861A (zh) * 2018-08-30 2019-01-04 广东工业大学 硫/氧化铁/石墨烯电池正极材料、制备方法及锂硫电池
CN109485129A (zh) * 2018-12-16 2019-03-19 北京化工大学 一种pvc废旧塑料制备的多孔碳材料电吸附金属离子的方法
CN112934132A (zh) * 2021-03-10 2021-06-11 瓮福（集团）有限责任公司 一种硼氮共掺杂还原氧化石墨烯气凝胶及其制备方法和应用
CN114497602A (zh) * 2020-10-26 2022-05-13 中国石油化工股份有限公司 碳材料、铂碳催化剂及其制备方法和应用
CN115548339A (zh) * 2022-09-26 2022-12-30 陕西科技大学 一种锂硫电池夹层及其制备方法和锂硫电池

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CN105609733A (zh) * 2016-02-19 2016-05-25 钟玲珑 一种硼氮共掺杂三维结构锂硫电池正极材料的制备方法

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109148861A (zh) * 2018-08-30 2019-01-04 广东工业大学 硫/氧化铁/石墨烯电池正极材料、制备方法及锂硫电池
CN109485129A (zh) * 2018-12-16 2019-03-19 北京化工大学 一种pvc废旧塑料制备的多孔碳材料电吸附金属离子的方法
CN114497602A (zh) * 2020-10-26 2022-05-13 中国石油化工股份有限公司 碳材料、铂碳催化剂及其制备方法和应用
CN114497602B (zh) * 2020-10-26 2024-05-17 中国石油化工股份有限公司 碳材料、铂碳催化剂及其制备方法和应用
CN112934132A (zh) * 2021-03-10 2021-06-11 瓮福（集团）有限责任公司 一种硼氮共掺杂还原氧化石墨烯气凝胶及其制备方法和应用
CN115548339A (zh) * 2022-09-26 2022-12-30 陕西科技大学 一种锂硫电池夹层及其制备方法和锂硫电池
CN115548339B (zh) * 2022-09-26 2023-10-20 陕西科技大学 一种锂硫电池夹层及其制备方法和锂硫电池

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