WO2022143889A1 - 一种极片和锂离子电池 - Google Patents

一种极片和锂离子电池 Download PDF

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Publication number
WO2022143889A1
WO2022143889A1 PCT/CN2021/143038 CN2021143038W WO2022143889A1 WO 2022143889 A1 WO2022143889 A1 WO 2022143889A1 CN 2021143038 W CN2021143038 W CN 2021143038W WO 2022143889 A1 WO2022143889 A1 WO 2022143889A1
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WO
WIPO (PCT)
Prior art keywords
groove
pole piece
active layer
current collector
length
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PCT/CN2021/143038
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English (en)
French (fr)
Inventor
孙雷明
张健
张双虎
彭冲
Original Assignee
珠海冠宇电池股份有限公司
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Application filed by 珠海冠宇电池股份有限公司 filed Critical 珠海冠宇电池股份有限公司
Priority to EP21914620.6A priority Critical patent/EP4160722A4/en
Priority to JP2023500035A priority patent/JP2023533259A/ja
Priority to KR1020237000395A priority patent/KR20230019962A/ko
Publication of WO2022143889A1 publication Critical patent/WO2022143889A1/zh
Priority to US18/149,018 priority patent/US20230143216A1/en

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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on 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
    • H01M4/64—Carriers or collectors
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
    • 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
    • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
    • 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
    • H01M50/536—Electrode connections inside a battery casing characterised by the method of fixing the leads to the electrodes, e.g. by welding
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • 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
    • H01M2004/027—Negative 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 invention relates to a pole piece and a lithium ion battery, and relates to the technical field of lithium ion batteries.
  • the invention provides a pole piece for improving the cycle performance of a lithium ion battery under the condition of high rate charging.
  • a first aspect of the present invention provides a pole piece, comprising a current collector and a first active layer and a second active layer sequentially stacked on the surface of the current collector;
  • the first active layer is provided with a first groove
  • the second active layer is provided with a second groove
  • the vertical projection of the second groove on the current collector covers the first groove A vertical projection of a groove on the current collector
  • a tab is disposed at the first groove and is electrically connected to the current collector.
  • the length of the second groove is greater than the length of the first groove.
  • the width of the second groove is the same as the width of the current collector.
  • the difference between the length of the second groove and the length of the first groove is less than or equal to 500 mm.
  • the pole piece is a negative electrode piece, and the average particle size of the negative electrode active material in the second active layer is 10-18 ⁇ m, and the graphitization degree is 86-94%.
  • the average particle size and graphitization degree of the negative electrode active material in the first active layer are greater than the average particle size and graphitization degree of the negative electrode active material in the second active layer.
  • the area of the vertical projection of the first groove on the current collector is larger than the area of the upper tab connection area of the current collector.
  • the width of the first groove is 1-2 times the width of the tab connecting region.
  • the length of the first groove is 1-2 times the length of the tab connecting region.
  • a second aspect of the present invention provides a lithium ion battery, comprising any of the above-mentioned pole pieces.
  • the present invention provides a pole piece. By reducing the thickness of the active layer around the pole tab, the charging risk at the connection position of the pole tab is effectively improved, and the cycle retention rate of the lithium ion battery is improved under the condition of maintaining high-rate charging. .
  • the lithium ion battery provided by the present invention has better cycle performance under the condition of high rate charging.
  • 1a is a front view of a pole piece provided by an embodiment of the present invention.
  • FIG. 1b is a top view of a pole piece provided by an embodiment of the present invention.
  • 1c is a left side view of a pole piece provided by an embodiment of the present invention.
  • FIG. 2a is a front view of a pole piece provided by another embodiment of the present invention.
  • FIG. 2b is a top view of a pole piece provided by another embodiment of the present invention.
  • FIG. 3 is a top view of a pole piece provided by still another embodiment of the present invention.
  • a first aspect of the present invention provides a pole piece, comprising a current collector and a first active layer and a second active layer sequentially stacked on the surface of the current collector;
  • the first active layer is provided with a first groove
  • the second active layer is provided with a second groove
  • the vertical projection of the second groove on the current collector covers the first groove A vertical projection of a groove on the current collector
  • a tab is disposed at the first groove and is electrically connected to the current collector.
  • the sides of the first active layer and the second active layer are provided with grooves, and the grooves communicate with the upper surface of the second active layer and the upper surface of the current collector, so that the tabs can be arranged in the grooves. It is electrically connected to the current collector exposed at the groove, and the pole piece provided by the application mainly reduces the thickness of the active layer around the tab to improve the charging risk at the connection position of the tab.
  • FIG. 1a is an implementation of the present invention.
  • the middle position of the side surface of the first active layer 2 is provided with a No.
  • the second active layer 3 is provided with a second groove
  • the tab 4 is arranged at the first groove and is electrically connected to the current collector 1 (the vertical projection of the tab on the current collector 1 is the same as the first groove).
  • the vertical projection of a groove on the current collector 1 overlaps), the vertical projection of the second groove on the current collector covers the vertical projection of the first groove on the current collector, so that the thickness of the active layer in the area around the tab Below the thickness of the active layer away from the tab area, the length of the pole piece is the same as the definition of the length of the pole piece in the art, that is, the longest side of the pole piece is the length of the pole piece, the shortest side is the height of the pole piece, and the intermediate The side of the longest side and the shortest side is the width of the pole piece, that is, the longer side in Figure 1a is the length of the pole piece, the shorter side is the height of the pole piece, and the shorter side in Figure 1b is the width of the pole piece, and the length is the length of the pole piece.
  • the value of the side is the length of the pole piece
  • the value of the high side is the thickness of the pole piece
  • the value of the wide side is the width of the pole piece
  • the length and width of the first groove and the second groove and the pole piece are same as the thickness direction.
  • the second active layer is provided with a second groove
  • blank coating needs to be performed on the position of the second groove, but the existing coating
  • the equipment and coating process cannot directly realize this coating method. Therefore, in order to improve the preparation efficiency of the second active layer, the width of the second groove can be increased to make it the same as the width of the current collector.
  • Some coating equipment performs jump coating to obtain a second active layer provided with a second groove.
  • FIG. 2a is a front view of a pole piece provided by another embodiment of the present invention
  • FIG. 2b is a top view of a pole piece provided by another embodiment of the present invention
  • the pole piece includes a current collector 1 and is arranged in sequence On the first active layer 2 and the second active layer 3 on the surface of the current collector 1, a first groove is provided in the middle of the side surface of the first active layer 1, and the first groove is connected to the tabs in the corresponding area on the current collector 1 4.
  • the second active layer 2 is provided with a second groove, and the width of the second groove is the same as that of the current collector 1 , that is, the second groove divides the second active layer into two independent parts left and right.
  • the length of the second groove is greater than the length of the first groove, and through the study of the length of the first groove and the second groove, it is found that with the second groove The length of the groove is continuously increased, and the cycle performance of the lithium ion battery will gradually improve.
  • the difference between the length of the second groove and the length of the first groove is less than or equal to 500mm .
  • the length and width of the first groove are specifically determined according to the pole lug, and those skilled in the art can determine the length and width of the first groove according to the actual pole piece design and needs.
  • the average particle size of the negative electrode active material in the second active layer is 10-18 ⁇ m, and the graphitization degree is 86-94%.
  • the average particle size and graphitization degree of the negative electrode active material in the first active layer are greater than the average particle size and graphitization degree of the negative electrode active material in the second active layer, for example, when the average particle size and graphitization degree of the negative electrode active material in the second active layer When the diameter is 10-18 ⁇ m and the graphitization degree is 86-94%, the average particle size of the negative electrode active material in the first active layer is 12-30 ⁇ m, and the graphitization degree is 90-98%.
  • the first negative electrode active layer slurry in the preparation process of the negative electrode piece, can be prepared by combining the negative electrode active material with the binder, the conductive agent and the thickener, and then coated on the surface of the current collector, Obtain the first active layer; then prepare the second negative electrode active layer slurry, and coat the second negative electrode active material on the surface of the first active layer away from the current collector.
  • the negative active material may include at least one of artificial graphite, natural graphite, and modified graphite
  • the binder may include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyvinylidene fluoride Acrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethylmethacrylate, polytetrafluoroethylene, polyhexafluoropropylene and styrene-butadiene rubber (SBR) at least one
  • the conductive agent may include at least one of conductive carbon black, carbon nanotubes,
  • the pole piece provided by the present invention is also suitable for the positive pole piece, and the specific preparation method can refer to the negative pole piece.
  • the difference lies in the material.
  • the current collector can be aluminum foil
  • the positive electrode active material includes lithium cobaltate, lithium manganate, lithium nickelate , at least one of nickel-cobalt lithium manganate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadium phosphate, lithium-rich manganese-based materials, and lithium nickel-cobalt aluminate.
  • the area of the vertical projection of the first groove on the current collector may be larger than the area of the tab connection area on the current collector.
  • the tab connection area on the current collector refers to the vertical projection area of the tab on the current collector.
  • FIG. 3 is a top view of a pole piece provided by yet another embodiment of the present invention. As shown in FIG. 3 , the first groove The area of the vertical projection on the current collector is larger than the area of the tab connection area on the current collector.
  • the width of the first groove is 1-2 times the width of the tab connecting region.
  • the length of the first groove is 1-2 times the length of the tab connecting region.
  • the present invention provides a pole piece. By reducing the thickness of the active layer around the tab, the charging risk at the connection position of the tab is effectively improved, and the cycle retention of the lithium ion battery is improved under the condition of maintaining high-rate charging. Rate.
  • a second aspect of the present invention provides a lithium ion battery, comprising any one of the above-mentioned pole pieces.
  • the present invention provides a lithium ion battery, which can be prepared by those skilled in the art based on the pole piece provided by the present invention and in combination with the prior art.
  • the lithium ion battery provided by the invention has better cycle performance under the condition of high rate charging.
  • FIG 2a The front view of the pole piece provided by this embodiment is shown in Figure 2a, the top view is shown in Figure 3, and the left side view is shown in Figure 1c, wherein:
  • the current collector is copper foil with a width of 81mm;
  • the width of the first groove is 25mm and the length is 10mm;
  • the width of the second groove is 81 mm and the length is 30 mm.
  • the first active layer and the second active layer include 97 parts by mass of lithium cobalt oxide, 1.5 parts by mass of PVDF and 1.5 parts by mass of carbon black conductive agent 1.5% according to mass percentage;
  • both the first active layer and the second active layer include 97 parts by mass of graphite, 0.7 parts by mass of carbon black, 1.3 parts by mass of styrene-butadiene rubber and 1 part by mass of carboxymethyl cellulose sodium, wherein the average particle size of the negative electrode active material in the first active layer is 18 ⁇ m, and the graphitization degree is 96%; the average particle size of the negative electrode active material in the second active layer is 15 ⁇ m, and the graphitization degree is 92%.
  • FIG 2a The front view of the pole piece provided by this embodiment is shown in Figure 2a, the top view is shown in Figure 3, and the left side view is shown in Figure 1c, wherein:
  • the current collector is copper foil with a width of 81mm;
  • the width of the first groove is 25mm and the length is 10mm;
  • the width of the second groove is 81 mm and the length is 40 mm.
  • the materials of the first active layer and the second active layer are the same as those in Example 1.
  • FIG 2a The front view of the pole piece provided by this embodiment is shown in Figure 2a, the top view is shown in Figure 3, and the left side view is shown in Figure 1c, wherein:
  • the current collector is copper foil with a width of 81mm;
  • the width of the first groove is 25mm and the length is 10mm;
  • the width of the second groove is 81 mm and the length is 50 mm.
  • the materials of the first active layer and the second active layer are the same as those in Example 1.
  • FIG 2a The front view of the pole piece provided by this embodiment is shown in Figure 2a, the top view is shown in Figure 3, and the left side view is shown in Figure 1c, wherein:
  • the current collector is copper foil with a width of 81mm;
  • the width of the first groove is 25mm and the length is 10mm;
  • the width of the second groove is 81mm and the length is 60mm;
  • the materials of the first active layer and the second active layer are the same as those in Example 1.
  • FIG 2a The front view of the pole piece provided by this embodiment is shown in Figure 2a, the top view is shown in Figure 3, and the left side view is shown in Figure 1c, wherein:
  • the current collector is copper foil with a width of 81mm;
  • the width of the first groove is 25mm and the length is 10mm;
  • the width of the second groove is 81mm and the length is 70mm;
  • the materials of the first active layer and the second active layer are the same as those in Example 1.
  • FIG 2a The front view of the pole piece provided by this embodiment is shown in Figure 2a, the top view is shown in Figure 3, and the left side view is shown in Figure 1c, wherein:
  • the current collector is copper foil with a width of 81mm;
  • the width of the first groove is 25mm and the length is 10mm;
  • the width of the second groove is 81mm and the length is 30mm;
  • the materials of the first active layer and the second active layer can refer to Example 1.
  • the difference is that the average particle size of the negative active material in the second active layer is 15 ⁇ m, and the graphitization degree was 94%.
  • FIG 2a The front view of the pole piece provided by this embodiment is shown in Figure 2a, the top view is shown in Figure 3, and the left side view is shown in Figure 1c, wherein:
  • the current collector is copper foil with a width of 81mm;
  • the width of the first groove is 25mm and the length is 10mm;
  • the width of the second groove is 81mm and the length is 30mm;
  • the materials of the first active layer and the second active layer can refer to Example 1.
  • the difference is that the average particle size of the negative active material in the second active layer is 15 ⁇ m, and the graphitization degree is 90%.
  • FIG 2a The front view of the pole piece provided by this embodiment is shown in Figure 2a, the top view is shown in Figure 3, and the left side view is shown in Figure 1c, wherein:
  • the current collector is copper foil with a width of 81mm;
  • the width of the first groove is 25mm and the length is 10mm;
  • the width of the second groove is 81mm and the length is 30mm;
  • the materials of the first active layer and the second active layer can refer to Example 1.
  • the difference is that the average particle size of the negative active material in the second active layer is 10 ⁇ m, and the graphitization degree is 90%.
  • the pole piece provided by this comparative example includes a current collector, a first active layer and a second active layer, and a groove is provided in the middle of the sides of the first active layer and the second active layer, wherein,
  • the current collector is copper foil with a width of 81mm;
  • the grooves are 25mm wide and 10mm long.
  • the materials of the first active layer and the second active layer are the same as those in Example 1.
  • the positive electrode sheet and the negative electrode sheet provided by the embodiments of the present invention 1-8 and comparative example 1 are matched with a separator and an electrolyte to prepare a lithium ion battery, and the cycle capacity retention rate of the lithium ion battery is tested.
  • the positive active material was purchased from Xiamen Xia Tungsten New Energy Materials Co., Ltd.
  • the negative active material was purchased from Shanghai Shanshan Technology Co., Ltd.
  • the diaphragm was purchased from Dongguan Zhuo Gao Electronic Technology Co., Ltd.
  • the electrolyte was purchased from Shenzhen Xinzhoubang Technology Co., Ltd. Ltd.
  • the performance test method of lithium-ion battery is:
  • the lithium ion batteries provided in Examples 1-8 and Comparative Example 1 were subjected to a 2C/0.7C charge-discharge cycle test at 25°C, and the cycle retention (%) was calculated after 500 cycles.
  • the test results are shown in Table 1.
  • Example 1 25°C cycle retention rate
  • Example 2 85.5%
  • Example 3 86.1%
  • Example 4 87.2%
  • Example 5 88.1%
  • Example 6 83.9%
  • Example 7 85.8%
  • Example 8 86.7% Comparative Example 1 82.5%
  • the lithium-ion batteries provided in Examples 1-8 all have good cycle capacity retention rates; according to the data provided in Examples 1-5, it can be seen that with the increase of the length of the second groove, the The cycle performance will be improved accordingly; according to the data provided in Examples 6-8, as the graphitization degree and average particle size of the active material in the second active layer decrease, the cycle retention rate of the lithium ion battery will increase.
  • the lithium ion battery provided by the present invention has good cycle performance under the condition of high rate charging.

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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)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

本发明提供了一种极片和锂离子电池。本发明第一方面提供了一种极片，包括集流体以及依次层叠设置在集流体表面的第一活性层和第二活性层；其中，第一活性层上设置有第一凹槽，第二活性层上设置有第二凹槽，第二凹槽在集流体上的竖直投影覆盖第一凹槽在集流体上的竖直投影；极耳设置于第一凹槽处并与集流体电连接。本发明提供的极片，有效改善了极耳连接位置的充电风险，在保持高倍率充电的条件下，提高了锂离子电池的循环保持率。

Description

一种极片和锂离子电池
本申请要求于2020年12月30日提交中国专利局、申请号为202011631163.1、申请名称为“一种极片和锂离子电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种极片和锂离子电池，涉及锂离子电池技术领域。
背景技术
随着5G时代的不断发展，锂离子电池的地位显得愈发重要，也促使锂离子电池向着能量密度高，快充倍率大的方向不断发展。目前，通过将极片上极耳的连接位置从边缘调整到侧面中间部分，降低锂离子电池的阻抗，提高锂离子电池的充电速度。
但是，当极耳的位置发生改变后，会使极耳周围电流密度增加，并且随着锂离子电池的循环，会析出锂离子，导致锂离子电池的循环性能变差。因此，如何在保持高倍率充电的情况下，提高锂离子电池的循环性能受到了越来越多的关注。
发明内容
本发明提供一种极片，用于提高锂离子电池在高倍率充电情况下的循环性能。
本发明第一方面提供了一种极片，包括集流体以及依次层叠设置在所述集流体表面的第一活性层和第二活性层；
其中，所述第一活性层上设置有第一凹槽，所述第二活性层上设置有第二凹槽，所述第二凹槽在所述集流体上的竖直投影覆盖所述第一凹槽在所述集流体上的竖直投影；
极耳设置于所述第一凹槽处并与所述集流体电连接。
进一步地，所述第二凹槽的长度大于所述第一凹槽的长度。
进一步地，所述第二凹槽的宽度与所述集流体的宽度相同。
进一步地，所述第二凹槽的长度与所述第一凹槽长度的差值小于等于500mm。
进一步地，所述极片为负极片，且所述第二活性层中负极活性物质的平均粒径为10-18μm，石墨化度为86-94％。
进一步地，所述第一活性层中负极活性物质的平均粒径和石墨化度大于第二活性层中负极活性物质的平均粒径和石墨化度。
进一步地，所述第一凹槽在集流体上竖直投影的面积大于集流体上极耳连接区的面积。
进一步地，所述第一凹槽的宽度为所述极耳连接区宽度的1-2倍。
进一步地，所述第一凹槽的长度为所述极耳连接区长度的1-2倍。
本发明第二方面提供了一种锂离子电池，包括上述任一所述的极片。
本发明的实施，至少具有以下优势：
1、本发明提供了一种极片，通过降低极耳周围活性层的厚度，有效改善了极耳连接位置的充电风险，在保持高倍率充电的条件下，提高了锂离子电池的循环保持率。
2、本发明提供的锂离子电池在高倍率充电情况下，具备较好的循环性能。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1a为本发明一实施例提供的极片的主视图；
图1b为本发明一实施例提供的极片的俯视图；
图1c为本发明一实施例提供的极片的左视图；
图2a为本发明又一实施例提供的极片的主视图；
图2b为本发明又一实施例提供的极片的俯视图；
图3为本发明再一实施例提供的极片的俯视图。
附图标记说明：
1：集流体；
2：第一活性层；
3：第二活性层；
4：极耳。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明第一方面提供了一种极片，包括集流体以及依次层叠设置在所述集流体表面的第一活性层和第二活性层；
其中，所述第一活性层上设置有第一凹槽，所述第二活性层上设置有第二凹槽，所述第二凹槽在所述集流体上的竖直投影覆盖所述第一凹槽在所述集流体上的竖直投影；
极耳设置于所述第一凹槽处并与所述集流体电连接。
依据现有的极片设计，第一活性层和第二活性层侧面设置有凹槽，该凹槽连通第二活性层的上表面和集流体的上表面，使得极耳可以设置在该凹槽处并与凹槽处暴露出的集流体电连接，本申请提供的极片主要降低了极耳周围活性层的厚度来改善极耳连接位置的充电风险，具体地，图1a为本发明一实施例提供的极片的主视图，图1b为本发明一实施例提供的极片的俯视图，图1c为本发明一实施例提供的极片的左视图，如图1a-1c所示，极片包括集流体1、设置在集流体1上表面的第一活性层2以及设置在第一活性层2远离集流体1上表面的第二活性层3，第一活性层2侧面中间位置设置有第一凹槽，第二活性层3上设置有第二凹槽，极耳4设置在所述第一凹槽处并与集流体1电连接(极耳在集流体1上的竖直投影与第一凹槽在集流体1上的竖直投影重叠)，第二凹槽在集流体上的竖直投影覆盖第一凹槽在集流体上的竖直投 影，使得极耳周围区域的活性层厚度低于远离极耳区域的活性层厚度，其中，极片的长度与本领域对极片长度的定义相同，即极片的最长边为极片的长，最短边为极片的高，介于最长边和最短边的边为极片的宽，即图1a中较长边为极片的长，较短边为极片的高，图1b中较短边为极片的宽，长边的值即为极片的长度，高边的值即为极片的厚度，宽边的值即为极片的宽度，并且，第一凹槽和第二凹槽与极片的长度、宽度和厚度方向相同。本发明提供的极片，通过降低极耳周围活性层的厚度，有效改善了极耳连接位置的充电风险，在保持高倍率充电的条件下，提高了锂离子电池的循环保持率。
在图1a-1c所示的极片结构中，由于第二活性层设置有第二凹槽，在实际制备过程中，需要对第二凹槽所在位置进行空白涂布，但现有的涂布设备和涂布工艺无法直接实现该种涂布方式，因此，为了提高第二活性层的制备效率，可将第二凹槽的宽度变大，使其与集流体的宽度相同，即可使用现有的涂布设备进行跳涂得到设置有第二凹槽的第二活性层。
图2a为本发明又一实施例提供的极片的主视图，图2b为本发明又一实施例提供的极片的俯视图，如图2a-2b所示，极片包括集流体1和依次设置在集流体1表面的第一活性层2和第二活性层3，第一活性层1侧面中间位置设置有第一凹槽，且第一凹槽在集流体1上的对应区域内连接极耳4，第二活性层2设置有第二凹槽，且第二凹槽的宽度与集流体1的宽度相同，即第二凹槽将第二活性层分为左右两个独立的部分。
为了进一步提高锂离子电池的循环性能，所述第二凹槽的长度大于所述第一凹槽的长度，并通过对第一凹槽和第二凹槽长度的研究发现，随着第二凹槽的长度不断提高，锂离子电池的循环性能会逐渐提高，为了兼顾锂离子电池的能量密度和循环性能，所述第二凹槽的长度与所述第一凹槽长度的差值小于等于500mm。
第一凹槽的长度和宽度具体依据极耳来确定，本领域技术人员可依据实际极片设计和需要确定第一凹槽的长度和宽度。
为了使锂离子电池具备快充性能，当所述极片为负极片时，所述第二活性层中负极活性物质的平均粒径为10-18μm，石墨化度为86-94％。
此外，由于快充型石墨的压实密度有限，会导致锂离子电池的能量密度下降，为了兼顾锂离子电池的能量密度和快充性能，第一活性层中负极活性物质选用常规石墨，具体地，第一活性层中负极活性物质的平均粒径和石墨 化度大于第二活性层中负极活性物质的平均粒径和石墨化度，例如，当第二层活性层中负极活性物质的平均粒径为10-18μm，石墨化度为86-94％时，第一层活性层中负极活性物质的平均粒径为12-30μm，石墨化度为90-98％。
根据上述极片的结构，在负极片的制备过程中，可将负极活性物质搭配粘结剂、导电剂和增稠剂制备得到第一负极活性层浆液，并将其涂布在集流体表面，得到第一活性层；接着制备得到第二负极活性层浆液，将第二负极活性物质涂布在第一活性层远离集流体的表面，涂布过程中，需对第二凹槽对应区域进行空白涂布，得到包括第二凹槽的第二活性层；最后，对第一活性层侧面中间区域进行清洗，得到第一凹槽，并将极耳设置于第一凹槽内得到该负极片，其中，负极活性物质可以包括人造石墨、天然石墨、改性石墨中的至少一种；粘结剂可以包括聚偏氟乙烯(PVDF)、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯、聚六氟丙烯和丁苯橡胶(SBR)中的至少一种；导电剂可以包括导电炭黑、碳纳米管、导电石墨、石墨烯中的至少一种；增稠剂可以包括羧甲基纤维素钠。
本发明提供的极片同样适用于正极片，具体制备方法可参考负极片，区别在于材料的不同，具体地，集流体可以为铝箔，正极活性物质包括钴酸锂、锰酸锂、镍酸锂、镍钴锰酸锂、磷酸铁锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、富锂锰基材料、镍钴铝酸锂中的至少一种。
在实际制备过程中，为了便于极耳与集流体的连接，可将第一凹槽在集流体上的竖直投影的面积大于集流体上的极耳连接区的面积。
其中，集流体上的极耳连接区是指极耳在集流体上的竖直投影区域，图3为本发明再一实施例提供的极片的俯视图，如图3所示，第一凹槽在所述集流体上的竖直投影的面积大于所述集流体上极耳连接区的面积。
进一步地，所述第一凹槽的宽度为所述极耳连接区宽度的1-2倍。
进一步地，所述第一凹槽的长度为所述极耳连接区长度的1-2倍。
综上，本发明提供了一种极片，通过降低极耳周围活性层的厚度，有效改善了极耳连接位置的充电风险，在保持高倍率充电的条件下，提高了锂离子电池的循环保持率。
本发明第二方面提供了一种锂离子电池，包括上述任一一种极片。
本发明提供了一种锂离子电池，本领域技术人员在本发明提供的极片的 基础上，结合现有技术制备得到锂离子电池。本发明提供的锂离子电池在高倍率充电情况下，具备较好的循环性能。
以下结合具体实施例进行阐述：
实施例1
本实施例提供的极片的主视图如图2a所示，俯视图如图3所示，左视图如图1c所示，其中：
集流体为铜箔，宽度为81mm；
第一凹槽的宽度为25mm，长度为10mm；
第二凹槽的宽度为81mm，长度为30mm。
当极片为正极片时，第一活性层和第二活性层按照质量百分含量包括97质量份的钴酸锂、1.5质量份的PVDF和1.5质量份的炭黑导电剂1.5％；
当极片为负极片时，第一活性层和第二活性层中均包括97质量份的石墨、0.7质量份的炭黑、1.3质量份的丁苯橡胶和1质量份的羧甲基纤维素钠，其中，第一活性层中负极活性物质的平均粒径为18μm，石墨化度为96％；第二活性层中负极活性物质的平均粒径为15μm，石墨化度为92％。
实施例2
本实施例提供的极片的主视图如图2a所示，俯视图如图3所示，左视图如图1c所示，其中：
集流体为铜箔，宽度为81mm；
第一凹槽的宽度为25mm，长度为10mm；
第二凹槽的宽度为81mm，长度为40mm。
当极片为正极片或负极片时，第一活性层和第二活性层的材料与实施例1相同。
实施例3
本实施例提供的极片的主视图如图2a所示，俯视图如图3所示，左视图如图1c所示，其中：
集流体为铜箔，宽度为81mm；
第一凹槽的宽度为25mm，长度为10mm；
第二凹槽的宽度为81mm，长度为50mm。
当极片为正极片或负极片时，第一活性层和第二活性层的材料与实施例1相同。
实施例4
本实施例提供的极片的主视图如图2a所示，俯视图如图3所示，左视图如图1c所示，其中：
集流体为铜箔，宽度为81mm；
第一凹槽的宽度为25mm，长度为10mm；
第二凹槽的宽度为81mm，长度为60mm；
当极片为正极片或负极片时，第一活性层和第二活性层的材料与实施例1相同。
实施例5
本实施例提供的极片的主视图如图2a所示，俯视图如图3所示，左视图如图1c所示，其中：
集流体为铜箔，宽度为81mm；
第一凹槽的宽度为25mm，长度为10mm；
第二凹槽的宽度为81mm，长度为70mm；
当极片为正极片或负极片时，第一活性层和第二活性层的材料与实施例1相同。
实施例6
本实施例提供的极片的主视图如图2a所示，俯视图如图3所示，左视图如图1c所示，其中：
集流体为铜箔，宽度为81mm；
第一凹槽的宽度为25mm，长度为10mm；
第二凹槽的宽度为81mm，长度为30mm；
当极片为正极片或负极片时，第一活性层和第二活性层的材料可参考实施例1，不同的是，第二活性层中负极活性物质的平均粒径为15μm，石墨化 度为94％。
实施例7
本实施例提供的极片的主视图如图2a所示，俯视图如图3所示，左视图如图1c所示，其中：
集流体为铜箔，宽度为81mm；
第一凹槽的宽度为25mm，长度为10mm；
第二凹槽的宽度为81mm，长度为30mm；
当极片为正极片或负极片时，第一活性层和第二活性层的材料可参考实施例1，不同的是，第二活性层中负极活性物质的平均粒径为15μm，石墨化度为90％。
实施例8
本实施例提供的极片的主视图如图2a所示，俯视图如图3所示，左视图如图1c所示，其中：
集流体为铜箔，宽度为81mm；
第一凹槽的宽度为25mm，长度为10mm；
第二凹槽的宽度为81mm，长度为30mm；
当极片为正极片或负极片时，第一活性层和第二活性层的材料可参考实施例1，不同的是，第二活性层中负极活性物质的平均粒径为10μm，石墨化度为90％。
对比例1
本对比例提供的极片包括集流体、第一活性层和第二活性层，第一活性层和第二活性层侧面中间位置设置有凹槽，其中，
集流体为铜箔，宽度为81mm；
凹槽的宽度为25mm，长度为10mm。
当极片为正极片或负极片时，第一活性层和第二活性层的材料与实施例1相同。
将本发明实施例1-8以及对比例1提供的正极片和负极片搭配隔膜和电解 液制备得到锂离子电池，并对锂离子电池的循环容量保持率进行测试。
其中，正极活性物质购自厦门厦钨新能源材料有限公司，负极活性物质购自上海杉杉科技有限公司；隔膜购自东莞市卓高电子科技有限公司，电解液购自深圳新宙邦科技股份有限公司。
锂离子电池的性能测试方法为：
将实施例1-8以及对比例1提供的锂离子电池在25℃条件下进行2C/0.7C的充放电循环测试，循环500次后计算其循环保持率(％)，测试结果见表1。
表1实施例1-8以及对比例1提供的锂离子电池的性能测试结果
  25℃循环保持率
实施例1 84.8％
实施例2 85.5％
实施例3 86.1％
实施例4 87.2％
实施例5 88.1％
实施例6 83.9％
实施例7 85.8％
实施例8 86.7％
对比例1 82.5％
由表1可知，实施例1-8提供的锂离子电池均具有较好的循环容量保持率；根据实施例1-5提供的数据可知，随着第二凹槽长度的增加，锂离子电池的循环性能会相应提高；根据实施例6-8提供的数据可知，随着第二活性层中活性物质的石墨化度和平均粒径的降低，锂离子电池的循环保持率会提高。综上，本发明提供的锂离子电池在高倍率充电情况下，具备较好的循环性能。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种极片，其特征在于，包括集流体以及依次层叠设置在所述集流体表面的第一活性层和第二活性层；
    其中，所述第一活性层上设置有第一凹槽，所述第二活性层上设置有第二凹槽，所述第二凹槽在所述集流体上的竖直投影覆盖所述第一凹槽在所述集流体上的竖直投影；
    极耳设置于所述第一凹槽处并与所述集流体电连接。
  2. 根据权利要求1所述的极片，其特征在于，所述第二凹槽的长度大于所述第一凹槽的长度。
  3. 根据权利要求1或2所述的极片，其特征在于，所述第二凹槽的宽度与所述集流体的宽度相同。
  4. 根据权利要求1-3任一项所述的极片，其特征在于，所述第二凹槽的长度与所述第一凹槽长度的差值小于等于500mm。
  5. 根据权利要求1-4任一项所述的极片，其特征在于，所述极片为负极片，且所述第二活性层中负极活性物质的平均粒径为10-18μm，石墨化度为86-94％。
  6. 根据权利要求5所述的极片，其特征在于，所述第一活性层中负极活性物质的平均粒径和石墨化度大于第二活性层中负极活性物质的平均粒径和石墨化度。
  7. 根据权利要求1-6任一项所述的极片，其特征在于，所述第一凹槽在集流体上竖直投影的面积大于集流体上极耳连接区的面积。
  8. 根据权利要求7所述的极片，其特征在于，所述第一凹槽的宽度为所述极耳连接区宽度的1-2倍。
  9. 根据权利要求7所述的极片，其特征在于，所述第一凹槽的长度为所述极耳连接区长度的1-2倍。
  10. 一种锂离子电池，其特征在于，包括权利要求1-9任一项所述的极片。
PCT/CN2021/143038 2020-12-30 2021-12-30 一种极片和锂离子电池 WO2022143889A1 (zh)

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