WO2021121032A1 - Structure de bus d'électrode positive pour batterie permettant de générer du graphène au moyen d'un frottement, collecteur de courant et batterie - Google Patents

Structure de bus d'électrode positive pour batterie permettant de générer du graphène au moyen d'un frottement, collecteur de courant et batterie Download PDF

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Publication number
WO2021121032A1
WO2021121032A1 PCT/CN2020/133173 CN2020133173W WO2021121032A1 WO 2021121032 A1 WO2021121032 A1 WO 2021121032A1 CN 2020133173 W CN2020133173 W CN 2020133173W WO 2021121032 A1 WO2021121032 A1 WO 2021121032A1
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Prior art keywords
positive electrode
battery
current collector
present disclosure
electrode bus
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PCT/CN2020/133173
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English (en)
Chinese (zh)
Inventor
陈璞
刘正军
罗云峰
罗小松
李成钢
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瑞海泊有限公司
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Publication of WO2021121032A1 publication Critical patent/WO2021121032A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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

Definitions

  • the present disclosure relates to the field of electrochemical devices.
  • the present disclosure relates to a battery positive electrode bus structure, a current collector, and a battery that can generate graphene by friction.
  • the positive electrode current collector In water-based batteries, in addition to good electrical conductivity, the positive electrode current collector also needs to have strong oxidation resistance (the positive electrode material in the charged state has strong oxidation ability) and excellent resistance to electrolyte corrosion. Therefore, there are fewer metal materials suitable for use as a positive electrode current collector for water-based batteries.
  • metal materials suitable for use as a positive electrode current collector for water-based batteries.
  • nickel-metal hydride, nickel-zinc, nickel-cadmium and other water-based batteries foamed nickel is generally used as the cathode current collector for drainage. This material has complex processing techniques, scarce raw materials, and relatively expensive prices. Therefore, the cost of the positive electrode current collector limits the large-scale promotion and application of such batteries to a certain extent.
  • Graphite plates and graphite foils are both graphite products. They are inexpensive and have excellent properties such as electrical conductivity, oxidation resistance, and corrosion resistance. They are both ideal water-based battery cathode current collectors. However, their mechanical strength is weaker than that of metals, and they are more difficult to weld to metals. Therefore, in water-based batteries, for this type of current collector, if it is drawn out by conventional bolt fastening or metal welding, it is difficult to achieve, which greatly limits their application in water-based batteries. If conductive glue is used to connect the positive bus plate and the positive electrode tabs, since the conductive glue is generally made of a resin matrix with conductive fillers, there is a certain resistance, which will have obvious side effects on the aggregated current. If the ultrasonic welding technology is used to converge the battery, it is prone to corrosion.
  • an objective of the present disclosure is to propose a battery positive electrode bus structure and current collector that can generate graphene by friction, and a battery using the battery positive electrode bus structure or current collector.
  • the present disclosure proposes a battery cathode bus structure that can generate graphene by friction.
  • the battery positive electrode bus structure includes: a plurality of positive electrode current collectors, each side of the positive electrode current collector is provided with a positive electrode tab; a positive electrode bus plate, the positive electrode bus plate is arranged on the On the positive electrode tab, and suitable for friction with the positive electrode tab, so as to generate graphene.
  • the positive electrode bus plate is in direct friction contact with the cross section of the positive electrode tab of each positive electrode current collector, and no conductive glue is used for connection.
  • the positive electrode confluence structure capable of generating graphene by friction may also have the following additional technical features:
  • the positive electrode current collector and the positive electrode bus plate are formed of graphite.
  • the positive electrode current collector is graphite foil.
  • the positive bus plate is a graphite plate.
  • the positive electrode bus structure further includes: a positive electrode drain wire, and the positive electrode drain wire is electrically connected to the positive electrode bus plate.
  • the present disclosure proposes a battery.
  • the battery includes the positive electrode bus structure of the above-mentioned embodiment.
  • the battery can generate graphene through friction between the positive electrode bus plate in the positive electrode bus structure and the positive electrode tabs, thereby significantly improving electrochemical performance.
  • the present disclosure proposes a method for preparing a positive electrode current collector.
  • the method includes: providing a graphite foil; rubbing the surface of the graphite foil with a graphite plate to obtain the positive electrode current collector. Therefore, this method uses the graphite plate to rub the surface of the graphite foil. According to the principle of mechanical exfoliation of graphite, graphene can be produced on the surface of the graphite foil.
  • the graphite foil rubbed by the graphite plate is used as the positive electrode current collector, which can significantly improve The electrical conductivity of the positive electrode current collector, and the combination of the positive electrode current collector and the positive electrode active material to prepare a battery can significantly improve the electrochemical performance of the battery.
  • the method for preparing a positive electrode current collector according to the foregoing embodiments of the present disclosure may also have the following additional technical features:
  • the graphite plate in the friction, is used to apply a vertical pressure of 0.001 to 0.01 MPa to the graphite foil.
  • the present disclosure proposes a positive electrode current collector.
  • the positive electrode current collector is prepared by the method for preparing a positive electrode current collector of the foregoing embodiment.
  • the surface of the positive electrode current collector has graphene obtained by friction between the graphite plate and the graphite foil, so that the electrochemical performance is significantly improved.
  • the present disclosure proposes a battery.
  • the battery includes the positive electrode current collector of the above-mentioned embodiment. Therefore, the surface of the positive electrode current collector used in the battery has graphene obtained by friction between the graphite plate and the graphite foil, so that the electrochemical performance is significantly improved.
  • FIG. 1 is a schematic structural diagram of a positive electrode confluence structure capable of generating graphene by friction according to an embodiment of the present disclosure
  • FIG. 2 is a schematic structural diagram of a battery with a positive electrode bus structure capable of rubbing to generate graphene according to an embodiment of the present disclosure
  • FIG. 3 is a schematic diagram of a method for preparing a positive electrode current collector according to an embodiment of the present disclosure
  • Figure 5 is the battery cycle performance test results of Example 1 and Comparative Example 1;
  • Figure 6 is the battery rate performance test results of Example 1 and Comparative Example 1.
  • first”, “second”, “third”, “fourth”, etc. are used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features.
  • the features defined with “first”, “second”, “third”, and “fourth” may explicitly or implicitly include at least one of the features.
  • “plurality” means at least two, such as two, three, etc., unless otherwise specifically defined.
  • the first feature “on” or “under” the second feature may be in direct contact with the first and second features, or the first and second features may be indirectly through an intermediary. contact.
  • the "above”, “above” and “above” of the first feature on the second feature may mean that the first feature is directly above or diagonally above the second feature, or it simply means that the level of the first feature is higher than that of the second feature.
  • the “below”, “below” and “below” of the second feature of the first feature may mean that the first feature is directly below or obliquely below the second feature, or it simply means that the level of the first feature is smaller than the second feature.
  • the present disclosure proposes a battery cathode bus structure that can generate graphene by friction.
  • the battery positive electrode bus structure includes: a plurality of positive electrode current collectors 1 and a positive electrode bus plate 2, and a positive electrode tab 3 is provided on one side of each positive electrode current collector 1; 2 is arranged on the positive electrode tab 3 and is suitable for friction with the positive electrode tab 3 to generate graphene.
  • the positive electrode bus plate is in direct friction contact with the cross section of the positive electrode tab of each positive electrode current collector, and no conductive glue is used for connection.
  • graphene By rubbing the cross section of the positive electrode bus plate and the positive electrode tab, graphene can be generated on the cross section of the positive electrode tab (that is, the contact point between the positive electrode tab and the positive electrode bus plate) and both sides of the positive electrode tab according to the principle of mechanical peeling of graphite. Increase the electrical conductivity of the two, and significantly improve the electrochemical performance (such as cycle performance, rate performance, etc.) of the battery adopting the battery cathode bus structure.
  • the friction between the positive electrode bus plate 2 and the positive electrode tab 3 is performed by rotating the positive electrode bus plate 2, for example, the positive electrode bus plate 2 can be rotated in the direction of the curved arrow in FIG. 1.
  • the number of repeated rubbing between the positive electrode bus plate 2 and the positive electrode tab 3 is 1 to 5 times.
  • a vertical pressure of 0.001 to 0.01 MPa is applied to the positive electrode bus plate 2. Therefore, the friction effect between the positive electrode bus plate 2 and the positive electrode tab 3 can be further improved, which is further beneficial to the cross section of the positive electrode tab 3 (that is, the contact point between the positive electrode tab 3 and the positive electrode bus plate 2) and both sides of the surface.
  • the above-mentioned positive electrode current collector and positive electrode bus plate are formed of graphite. Therefore, it can further facilitate the friction between the cross section of the positive electrode bus plate and the positive electrode tab. According to the principle of mechanical peeling of graphite, the cross section of the positive electrode tab (that is, the contact point between the positive electrode tab and the positive electrode bus plate) and both sides of the surface Produce graphene.
  • the above-mentioned positive electrode current collector is graphite foil.
  • the above-mentioned positive busbar is a graphite plate.
  • the above-mentioned positive electrode bus structure further includes: a positive electrode drain wire 4.
  • the positive drain wire 4 is electrically connected to the positive bus plate 2.
  • the present disclosure proposes a battery.
  • the battery includes the positive electrode bus structure of the above-mentioned embodiment.
  • the battery can generate graphene through friction between the positive electrode bus plate in the positive electrode bus structure and the positive electrode tabs, thereby significantly improving electrochemical performance.
  • the battery includes the positive electrode bus structure of the above-mentioned embodiment and the positive and negative electrode clusters 6.
  • the positive and negative electrode cluster 6 includes a positive pole piece and a negative pole piece spaced apart from each other, wherein the negative pole piece includes a negative electrode tab 5.
  • the battery has all the features and advantages described above for the positive electrode bus structure of the battery, which will not be repeated here.
  • the present disclosure proposes a method of preparing a positive electrode current collector.
  • the method includes: providing a graphite foil 10; rubbing the surface of the graphite foil 10 with a graphite plate 20 to obtain the positive electrode current collector. Therefore, this method uses the graphite plate to rub the surface of the graphite foil. According to the principle of mechanical exfoliation of graphite, graphene can be produced on the surface of the graphite foil.
  • the graphite foil rubbed by the graphite plate is used as the positive electrode current collector, which can significantly improve
  • the electrical conductivity of the positive electrode current collector, and the combination of the positive electrode current collector and the positive electrode active material to prepare a battery can significantly improve the electrochemical performance of the battery (such as cycle performance, rate performance, etc.).
  • the graphite plate in the process of horizontally rubbing the graphite foil by the graphite plate, may be used to apply a vertical pressure of 0.001 to 0.01 MPa to the graphite foil.
  • the number of repeated rubbing between the graphite plate and the graphite foil is 1 to 5 times.
  • the present disclosure proposes a positive electrode current collector.
  • the positive electrode current collector is prepared by the method for preparing the positive electrode current collector of the above-mentioned embodiment.
  • the surface of the positive electrode current collector has graphene obtained by friction between the graphite plate and the graphite foil, so that the electrochemical performance is significantly improved.
  • the present disclosure proposes a battery.
  • the battery includes the positive electrode current collector of the above-mentioned embodiment. Therefore, the surface of the positive electrode current collector used in the battery has graphene obtained by friction between the graphite plate and the graphite foil, thereby significantly improving electrochemical performance (such as cycle performance, rate performance, etc.).
  • the battery has all the features and advantages described above for the positive electrode current collector, which will not be repeated here.
  • the positive electrode active material is LiMn 2 O 4 , the current collector is graphite foil, the graphite foil is reserved for the positive electrode tab 3; the negative electrode active material is metal Zn, the current collector is a copper mesh, and the copper mesh is reserved for the negative electrode tab 5; electrolyte It is an aqueous solution of 1mol/L Li 2 SO 4 + 2mol/L ZnSO 4.
  • electrolyte It is an aqueous solution of 1mol/L Li 2 SO 4 + 2mol/L ZnSO 4.
  • the contact between the positive electrode bus plate 2 and the positive electrode tab 3 is frictional contact. After rotating and rubbing for 5 times, the positive electrode bus plate is aligned to make the positive electrode tab 3 evenly contact the surface of the positive electrode bus plate 2.
  • the SEM image of graphene produced by friction at the cross section of the tab is shown in Figure 4.
  • the material of the negative electrode tab 5 is copper mesh, and each negative electrode tab is connected together by soldering to converge.
  • Electrochemical performance test charge and discharge voltage range is 1.4 ⁇ 2.1V, 25 °C environment.
  • the battery was manufactured and tested in the same manner as in Example 1, except that the contact between the positive electrode bus plate and the positive electrode tabs was direct and vertical contact, and no mutual friction was performed.
  • the cycle curve generated by rotating friction contact is relatively stable, the capacity is stable at 108 ⁇ 110mAh ⁇ /g, and the capacity retention rate of 30 cycles is 98.3% at a rate of 0.2C.
  • the specific capacity of the discharge generated by direct vertical contact is significantly reduced. After 15 cycles of charge and discharge, the capacity decreases significantly. At a rate of 0.2C, the capacity retention rate of 30 cycles is 96.7%.
  • the average specific capacity of the battery of Example 1 at 0.1C, 0.2C, 0.5C, 1C and back to 0.1C is 108.3mAh ⁇ /g, 106.7mAh ⁇ /g, 103.1mAh ⁇ /g, 98.9mAh ⁇ /g, respectively , 107.1mA ⁇ h/g.
  • the capacity retention rate back to 0.1C was 98.9%.
  • the average specific capacity of the battery of Comparative Example 1 at 0.1C, 0.2C, 0.5C, 1C and back to 0.1C is 108.3mAh ⁇ /g, 106.6mAh ⁇ /g, 102.3mAh ⁇ /g, 97.2mAh ⁇ /g, respectively , 106.3mA ⁇ h/g.
  • the capacity retention rate back to 0.1C was 98.2%.
  • magnification performance produced by rotating friction contact is significantly better than direct vertical contact. Especially under the higher magnification of 0.5C and 1C, the capacity gap is more obvious.
  • the battery was manufactured and tested in the same manner as in Example 1, except that the positive electrode bus plate and the positive electrode tab were combined by conductive glue.
  • the 0.1 ⁇ 1C rate performance was tested, and the capacity retention rate was 95.8% when it returned to 0.1C.
  • the specific capacity at 1C is 93.6mA ⁇ h/g.
  • the battery was fabricated and tested in the same manner as in Example 1, except that the number of rotational friction between the positive electrode bus plate and the positive electrode tab was 2 times. Test the 0.1-C rate performance, and the capacity retention rate is 98.3% when it returns to 0.1C.
  • the specific capacity at 1C is 97.7mA ⁇ h/g.
  • the battery was fabricated and tested in the same manner as in Example 1, except that the surface of the graphite foil current collector was repeatedly rubbed with a graphite plate for 5 times before the positive electrode active material was combined with the graphite foil current collector.
  • the 0.1 ⁇ 1C rate performance was tested, and the capacity retention rate was 99.1% when it returned to 0.1C.
  • the specific capacity at 1C is 99.3mA ⁇ h/g.
  • the surface is subjected to friction treatment to also produce graphene, which makes the conductive performance of the graphite foil better and the rate performance further improved.

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

Abstract

Il est prévu une structure de bus d'électrode positive pour une batterie permettant de générer du graphène au moyen d'un frottement, un collecteur de courant et une batterie. La structure de bus d'électrode positive pour une batterie comprend : une pluralité de collecteurs de courant d'électrode positive, un côté de chacun des collecteurs de courant d'électrode positive étant doté d'une languette d'électrode positive ; une plaque de bus d'électrode positive, la plaque de bus d'électrode positive étant placée sur la languette d'électrode positive et pouvant se frotter contre la languette d'électrode positive, de manière à générer du graphène, ce qui permet d'augmenter la capacité conductrice des deux, réduisant efficacement la résistance interne d'une surface de contact, et augmentant un trajet de transmission électronique, améliorant ainsi significativement les performances électrochimiques d'une batterie à l'aide de la structure de bus d'électrode positive pour une batterie.
PCT/CN2020/133173 2019-12-18 2020-12-01 Structure de bus d'électrode positive pour batterie permettant de générer du graphène au moyen d'un frottement, collecteur de courant et batterie WO2021121032A1 (fr)

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CN201911307413.3A CN111129415B (zh) 2019-12-18 2019-12-18 可摩擦生成石墨烯的电池正极汇流结构和集流体
CN201911307413.3 2019-12-18

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CN111129415B (zh) * 2019-12-18 2022-02-01 瑞海泊有限公司 可摩擦生成石墨烯的电池正极汇流结构和集流体

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WO2019099650A1 (fr) * 2017-11-15 2019-05-23 Enovix Corporation Ensemble d'électrodes et batterie secondaire
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JP6069821B2 (ja) * 2011-09-28 2017-02-01 ソニー株式会社 リチウムイオン二次電池
US9484160B2 (en) * 2013-09-23 2016-11-01 Nanotek Instruments, Inc. Large-grain graphene thin film current collector and secondary batteries containing same
US9728786B2 (en) * 2015-12-21 2017-08-08 Nissan North America, Inc. Electrode having active material encased in conductive net
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Publication number Priority date Publication date Assignee Title
CN103779576A (zh) * 2012-10-24 2014-05-07 清华大学 电化学电池集流体的制备方法及电化学电池电极的制备方法
WO2019099650A1 (fr) * 2017-11-15 2019-05-23 Enovix Corporation Ensemble d'électrodes et batterie secondaire
CN110526235A (zh) * 2018-05-23 2019-12-03 浙江大学 一种通过电化学剥离制备原位氧掺杂三维石墨烯的方法
CN108847471A (zh) * 2018-05-28 2018-11-20 池州精研新能源科技有限公司 一种水系电池正极极耳结构及其制作方法
CN111129415A (zh) * 2019-12-18 2020-05-08 瑞海泊(青岛)能源科技有限公司 可摩擦生成石墨烯的电池正极汇流结构和集流体

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