WO2018023325A1 - Procédé de préparation d'un matériau composite d'électrode positive de graphène comprenant du lithium à base d'alcool - Google Patents

Procédé de préparation d'un matériau composite d'électrode positive de graphène comprenant du lithium à base d'alcool Download PDF

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Publication number
WO2018023325A1
WO2018023325A1 PCT/CN2016/092658 CN2016092658W WO2018023325A1 WO 2018023325 A1 WO2018023325 A1 WO 2018023325A1 CN 2016092658 W CN2016092658 W CN 2016092658W WO 2018023325 A1 WO2018023325 A1 WO 2018023325A1
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WO
WIPO (PCT)
Prior art keywords
moo
lithium
graphene
reaction
alcohol
Prior art date
Application number
PCT/CN2016/092658
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English (en)
Chinese (zh)
Inventor
肖丽芳
钟玲珑
Original Assignee
肖丽芳
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Priority to PCT/CN2016/092658 priority Critical patent/WO2018023325A1/fr
Publication of WO2018023325A1 publication Critical patent/WO2018023325A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention belongs to the technical field of lithium ion supercapacitors, and relates to a method for preparing a lithium ion supercapacitor cathode material.
  • the battery negative electrode generally uses a carbon material such as graphite
  • the positive electrode uses a lithium-containing metal oxide such as lithium cobaltate or lithium manganate.
  • the charged negative electrode supplies lithium ions to the positive electrode, and the lithium ion of the positive electrode of the discharge positive electrode returns to the negative electrode, so it is called a "rocking chair type battery".
  • This battery is characterized by high safety and high cycle life compared to lithium batteries using metallic lithium.
  • Lithium-ion capacitors generally use carbon materials such as graphite and hard carbon for the anode material, and activated carbon materials with double-layer characteristics for the cathode material, and the lithium anode is pre-diffused to the anode material, so that the potential of the anode is greatly reduced, thereby improving Energy Density.
  • a lithium ion capacitor is disclosed in the special ljCN200580001498.2.
  • the positive current collector and the negative current collector used in the lithium ion capacitor have holes penetrating the front and back surfaces, and the electrode layer is formed by the positive electrode active material and the negative electrode active material respectively. Electrochemical contact is made to the negative electrode, and lithium ions are carried in the negative electrode in advance.
  • a pretreatment method for a negative electrode for an electrochemical capacitor is disclosed in the Japanese Patent Publication No. Hei. No. 1,200, 406, 9.6, a lithium layer is formed on a substrate by a vapor phase method or a liquid phase method, and then the lithium layer is transferred to an electrode layer of a negative electrode.
  • These pre-excessive methods involve complex processes and require special handling of the raw materials, which makes the manufacturing process difficult.
  • the technical problem to be solved by the present invention is to provide a method for preparing a lithium ion supercapacitor positive electrode material, and the positive electrode material prepared by the method can provide a lithium source in a lithium ion capacitor, thereby eliminating the need for complicated pre-processing of the negative electrode.
  • Lithium-intercalation or lithium-ion capacitors in lithium-ion capacitors simplify lithium-ion capacitors The preparation process reduces the cost of the process.
  • the preparation method of the lithium ion supercapacitor cathode material provided by the invention is:
  • Step (1) Mixing Li 2 CO 3 and MoO 3 in a ratio of 1-2:1, mixing uniformly, and placing in a muffle furnace at 500-700 ° C for 3-8 small inches, the reaction After completion, a Li 2 MoO 4 material was obtained.
  • Step (2) will result in Li 2 Mo0 4
  • the mixture was placed in a muffle furnace protected with a 5% hydrogen gas mixture atmosphere at 500-900 ° C for 5-10 hours, and after completion of the reaction, a Li 2 MoO 3 material was obtained.
  • Step (3) The graphite oxide and Li 2 CO 3 are mixed at a mass ratio of 50-10:1, uniformly mixed, and then placed in a nitrogen-protected muffle furnace at 200-600 ° C for 1-6 h to obtain A graphene material containing an alcohol-based lithium.
  • Step (4) The graphene material and the Li 2 MoO rf material are mixed at a ratio of 50 to 5:1 by mass ratio, and then ball milled to obtain a graphene-composite Li 2 MoO 3 material containing an alcohol-based lithium.
  • the present invention provides a process for preparing a lithium ion supercapacitor as follows:
  • the material, the conductive agent and the binder are added to the NMP in a ratio of 90:5:5 by mass to form a slurry, and then coated on the positive current collector aluminum foil, and dried to obtain a positive electrode sheet;
  • the process for preparing a lithium ion supercapacitor using the positive electrode material of the present invention is a general lithium ion battery preparation process, which greatly simplifies the preparation process of the lithium ion supercapacitor.
  • the graphene-composite Li 2 MoO 3 material containing the alcohol-based lithium prepared by the invention is used as a lithium ion supercapacitor cathode material, and the Li 2 MoO material and the alcohol-based lithium on the graphene provide a lithium source, which is charged for the first time.
  • Lithium ion deionized Li 2 MoO 3 material and lithium alcohol are inserted into the graphite negative electrode, thereby lowering the negative electrode potential and thus the negative electrode No need for lithium metal sheets or complex pre-intercalation lithium processes; Li 2 Mo0 3 in graphene composite Li 2 MoO 3 materials
  • the present invention has the following beneficial effects: (1) Graphene-composite Li 2 MoO 3 material containing lithium alcohol as a positive electrode of a lithium ion supercapacitor, so that the negative electrode does not need to be added with a lithium sheet or a complicated pre-lithium process, simplifying The preparation process reduces the cost; (2) The graphene composite Li 2 Mo0 3 material has high conductivity and high specific surface area, which can effectively replace the conventional activated carbon cathode material, and realize high energy density and high power density.
  • FIG. 1 is a cycle life diagram of a lithium ion supercapacitor of the present invention.
  • the mixture was mixed at a molar ratio of 1:1, uniformly mixed, and placed in a muffle furnace at 500 ° C for 3 hours, and after the reaction was completed, Li 2 MoO 4 was obtained.
  • the graphene-composite Li 2 MoO 3 material containing the alcohol-based lithium, the conductive agent Ketjen black, and the binder PVDF are added to the NMP in a ratio of 90:5:5 by mass to form a slurry. Then, it was coated on a positive electrode current collector aluminum foil, and dried to obtain a positive electrode sheet.
  • the negative electrode sheet, the separator and the positive electrode sheet are formed into a battery core by laminating according to a preparation process of a usual lithium ion battery, and then an electrolyte is injected into the battery case, and the injected electrolyte is 1 mol/L LiPF 6 DOL-DME solution (DOL and DME volume ratio is 1:1), sealed, to get lithium ion supercapacitor
  • the mixture was mixed at a molar ratio of 2:1, uniformly mixed, and placed in a muffle furnace at 700 ° C for 8 hours, and after the reaction was completed, Li 2 MoO 4 was obtained.
  • the mixture was mixed at a molar ratio of 1.3:1, uniformly mixed, and placed in a muffle furnace at 600 ° C for 7 hours, and after the reaction was completed, Li 2 MoO 4 was obtained.
  • the graphene-composite Li 2 MoO 3 material containing the alcohol-based lithium, the conductive agent Ketjen black, and the binder PVDF are added to the NMP in a ratio of 90:5:5 by mass to form a slurry. Then, it was coated on a positive electrode current collector aluminum foil, and dried to obtain a positive electrode sheet.
  • Example 4 Li 2 C0 3 and Mo0 3
  • the mixture was mixed at a molar ratio of 1.5:1, uniformly mixed, and placed in a muffle furnace at 650 ° C for 5 hours, and after the reaction was completed, Li 2 MoO 4 was obtained.
  • a graphene-composite Li 2 MoO 3 material containing lithium alcohol, a conductive agent Ketchen black, and a binder PVDF are added to NMP in a ratio of 90:5:5 by mass to form a slurry. Then, it was coated on a positive electrode current collector aluminum foil, and dried to obtain a positive electrode sheet.
  • the negative electrode sheet, the separator and the positive electrode sheet are assembled into a battery cell by laminating according to a usual preparation process of a lithium ion battery, and then an electrolyte is injected into the battery case, and the injected electrolyte is 1 mol/L LiPF 6 .
  • DOL-DME solution (DOL and DME volume ratio is 1:1), sealed, to get lithium ion supercapacitor
  • the mixture was mixed at a molar ratio of 1.7:1, uniformly mixed, and placed in a muffle furnace at 600 ° C for 6 hours, and after completion of the reaction, Li 2 MoO 4 was obtained.
  • the graphene-composite Li 2 MoO 3 material containing the alcohol-based lithium, the conductive agent Ketjen black, and the binder PVDF are added to the NMP in a ratio of 90:5:5 by mass to form a slurry. Then, it was coated on a positive electrode current collector aluminum foil, and dried to obtain a positive electrode sheet.
  • the negative electrode sheet, the separator and the positive electrode sheet are assembled into a cell according to a preparation process of a usual lithium ion battery, and then an electrolyte is injected into the battery case, and the injected electrolyte is 1 mol/L LiPF 6 .
  • DOL-DME solution (DOL and DME volume ratio is 1:1), sealed, to get lithium ion supercapacitor
  • the lithium ion supercapacitor prepared by the invention has an energy density of 57.5-62.4 wh/kg, which achieves the energy density level of the commonly used lithium ion supercapacitor.
  • the lithium ion supercapacitor prepared by the present invention is charged and discharged 1000 times, and the energy is not significantly attenuated.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un procédé de préparation d'un matériau composite d'électrode positive de graphène comprenant du lithium à base d'alcool, comprenant les étapes suivantes consistant à : (1) mélanger uniformément du Li2CO3 et du MoO3, puis placer le mélange dans un four à moufle à des fins de réaction, et obtenir un matériau de Li2MoO4 une fois la réaction achevée ; (2) placer le Li2MoO4 obtenu dans le four à moufle sous protection d'atmosphère de gaz mixte hydrogène-azote à des fins de réaction, et obtenir un matériau de Li2MoO3 une fois la réaction achevée ; (3) mélanger uniformément de l'oxyde de graphite avec le Li2CO3, et placer ensuite le mélange dans le four à moufle sous protection de gaz d'azote à des fins de réaction en vue d'obtenir un matériau de graphène comprenant du lithium à base d'alcool ; et (4) mélanger le matériau de graphène avec le matériau de Li2MoO3 selon un rapport de masse de 50-5:1, et exécuter ensuite un broyage à boulets du mélange en vue d'obtenir un matériau composite de graphène Li2MoO3 comprenant du lithium à base d'alcool. Le matériau est utilisé en tant qu'électrode positive pour un supercondensateur lithium-ion, de sorte que l'ajout d'une feuille de lithium ou la mise en œuvre d'un procédé complexe d'intercalation préalable de lithium ne soit plus nécessaire, simplifiant par conséquent le procédé de préparation et réduisant les coûts.
PCT/CN2016/092658 2016-07-31 2016-07-31 Procédé de préparation d'un matériau composite d'électrode positive de graphène comprenant du lithium à base d'alcool WO2018023325A1 (fr)

Priority Applications (1)

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PCT/CN2016/092658 WO2018023325A1 (fr) 2016-07-31 2016-07-31 Procédé de préparation d'un matériau composite d'électrode positive de graphène comprenant du lithium à base d'alcool

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109545575A (zh) * 2018-11-21 2019-03-29 江苏大学 一种还原氧化石墨烯/氮掺杂碳点超级电容器负极材料的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102201275A (zh) * 2010-03-25 2011-09-28 海洋王照明科技股份有限公司 锂盐-石墨烯复合材料及其制备方法与应用
WO2013005737A1 (fr) * 2011-07-04 2013-01-10 日産自動車株式会社 Matière active d'électrode positive pour un dispositif électrique, électrode positive pour un dispositif électrique et dispositif électrique
CN103367708A (zh) * 2012-03-29 2013-10-23 海洋王照明科技股份有限公司 电池正极及其制备方法、电池负极及其制备方法、电容电池
CN103515110A (zh) * 2012-06-26 2014-01-15 海洋王照明科技股份有限公司 Li2MoO3/石墨烯复合材料及其制备方法和锂离子电容器
CN104241642A (zh) * 2013-06-17 2014-12-24 华南理工大学 锂离子电池的钼酸锂负极材料及其制备方法
US20150044556A1 (en) * 2013-08-08 2015-02-12 Yanbo Wang Cathode active material-coated discrete graphene sheets for lithium batteries and process for producing same
CN106128792A (zh) * 2016-07-31 2016-11-16 肖丽芳 一种含有醇基锂的石墨烯复合正极材料的制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102201275A (zh) * 2010-03-25 2011-09-28 海洋王照明科技股份有限公司 锂盐-石墨烯复合材料及其制备方法与应用
WO2013005737A1 (fr) * 2011-07-04 2013-01-10 日産自動車株式会社 Matière active d'électrode positive pour un dispositif électrique, électrode positive pour un dispositif électrique et dispositif électrique
CN103367708A (zh) * 2012-03-29 2013-10-23 海洋王照明科技股份有限公司 电池正极及其制备方法、电池负极及其制备方法、电容电池
CN103515110A (zh) * 2012-06-26 2014-01-15 海洋王照明科技股份有限公司 Li2MoO3/石墨烯复合材料及其制备方法和锂离子电容器
CN104241642A (zh) * 2013-06-17 2014-12-24 华南理工大学 锂离子电池的钼酸锂负极材料及其制备方法
US20150044556A1 (en) * 2013-08-08 2015-02-12 Yanbo Wang Cathode active material-coated discrete graphene sheets for lithium batteries and process for producing same
CN106128792A (zh) * 2016-07-31 2016-11-16 肖丽芳 一种含有醇基锂的石墨烯复合正极材料的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109545575A (zh) * 2018-11-21 2019-03-29 江苏大学 一种还原氧化石墨烯/氮掺杂碳点超级电容器负极材料的制备方法

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