WO2009021379A1 - A current collector of lithium ion battery, a high-capacity cylindrical lithium ion battery and the preparation method of the same - Google Patents

A current collector of lithium ion battery, a high-capacity cylindrical lithium ion battery and the preparation method of the same Download PDF

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Publication number
WO2009021379A1
WO2009021379A1 PCT/CN2007/070457 CN2007070457W WO2009021379A1 WO 2009021379 A1 WO2009021379 A1 WO 2009021379A1 CN 2007070457 W CN2007070457 W CN 2007070457W WO 2009021379 A1 WO2009021379 A1 WO 2009021379A1
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WIPO (PCT)
Prior art keywords
current collector
lithium ion
ion battery
positive
electrode sheet
Prior art date
Application number
PCT/CN2007/070457
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French (fr)
Chinese (zh)
Inventor
Xin Li
Rongpeng Zheng
Rongguang Huang
Jianwen Zhang
Yongluan Zhang
Fang Liu
Chiwei Wang
Fuyong Liu
Wenwei Lin
Daotan Liu
Chuntai Guo
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Shenzhen Bak Battery Co., Ltd
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Application filed by Shenzhen Bak Battery Co., Ltd filed Critical Shenzhen Bak Battery Co., Ltd
Priority to PCT/CN2007/070457 priority Critical patent/WO2009021379A1/en
Publication of WO2009021379A1 publication Critical patent/WO2009021379A1/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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • 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
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/742—Meshes or woven material; Expanded metal perforated material
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of lithium ion batteries, and more particularly to a current collector for a lithium ion battery, a high capacity cylindrical lithium ion battery, and a method of preparing the battery.
  • the lithium ion secondary batteries currently on the market are mainly manufactured in two processes: laminated battery and wound battery.
  • the main features of the laminated battery manufacturing are: pre-forming the positive and negative electrodes of the battery with the lead-out electrode
  • the square sheet of the ear, in turn, the positive electrode sheet, the separator, the negative electrode sheet, the separator and the like are sequentially stacked, and then the lead tab and the lead electrode are connected together to be packaged in the shell
  • the main features of the wound battery manufacturing are: The soldering positions of the tabs on the positive and negative plates are intermittently coated. After welding the tabs, the positive and negative electrodes are separated by a separator and then wound into a pole group and then packaged into a package.
  • the laminated battery is generally square in shape, and each pole piece has a tab-out lead to share a large current, so it can be adapted to the requirements of large current discharge, and is mainly applied to a high-capacity, high-power lithium ion secondary battery, which is rolled.
  • the latter pole piece must first be cut into a plurality of square pieces.
  • the cross-cut edge of each piece is prone to defects such as burrs, dust, partial drops, etc. Process control is very difficult, and these are the main causes of internal short circuit of the cell.
  • the reason is also a safety hazard for the future use of the battery core; another disadvantage of using the lamination process is that the production efficiency is low and automation is not easy.
  • the small-capacity battery is fabricated by winding, which is easy to automate and greatly improves the production efficiency.
  • low-power lithium-ion secondary batteries with a capacity of less than 2 Ah, such as mobile phones and notebook computers.
  • the battery because the universal use of monopoles can meet the requirements of use, intermittent coating, with the ear winding process is currently a mainstream production process in the lithium ion secondary battery industry.
  • the object of the present invention is to provide a lithium ion battery current collector capable of improving the capacity and safety of a lithium ion battery in view of the deficiencies of current lithium ion secondary battery products and production processes.
  • Another object of the present invention is to provide a cylindrical lithium having a high capacity and containing the above-mentioned current collector An ion battery and a method of preparing the same.
  • the present invention adopts the following technical solutions:
  • the invention discloses a lithium ion battery current collector, wherein the current collector is provided with a stress dispersion hole.
  • the stress dispersion holes are arranged in a row, and an angle between a center line of each row of stress dispersion holes and a current collector edge line is a non-right angle.
  • the adjacent rows of stress dispersion holes are misaligned.
  • the misalignment distribution means that at most one stress dispersion hole is distributed on the same straight line perpendicular to the side of the current collector.
  • the diameter of the stress dispersion hole is preferably 0.02 to 0.20 mm, and the center line spacing of each row of the stress dispersion holes is 0.5 to 10 times the width of the current collector, and the hole spacing of the stress dispersion holes of the same row is 2 to 10 times the aperture. . .
  • the stress dispersion hole has a diameter of 0.04 to 0.08 mm.
  • the center line of each row of stress dispersion holes and the edge line of the current collector are at an angle of 30 to 60 degrees, preferably
  • the stress dispersion hole is preferably a circular hole.
  • Each row of stress dispersion holes is distributed parallel to each other or in a zigzag pattern.
  • the current collector is a positive electrode current collector, and the current collector is an aluminum foil.
  • the current collector is a negative current collector, and the current collector is a copper foil.
  • the invention also discloses a high-capacity cylindrical lithium ion battery, comprising a positive electrode sheet and a negative electrode sheet, wherein the current collector of the positive electrode sheet is the positive electrode current collector, and/or the current collector of the negative electrode sheet is the above-mentioned negative electrode Current collector.
  • the current collector of the positive electrode sheet and/or the negative electrode sheet is continuously coated with an active material coating, and the active material is reserved on both sides of the current collector.
  • the strip-shaped empty foil portions A and B, the positive electrode sheet, the negative electrode sheet and the separator are wound together to form a pole group, the strip-shaped empty foil portions B on the positive/negative electrode sheets are respectively located at both ends of the pole group, and the positive/negative electrode is taken out
  • the current collectors are respectively taken out from the strip-shaped empty foil portion B on the current collector of the positive/negative electrode sheets.
  • the width of the strip-shaped empty foil portion A is 0.20 to 2.0 mm, and the width of B is 5.0 to 30 mm.
  • the positive electrode active material of the lithium ion battery is a lithium iron phosphate active material, preferably a carbon coated LiFea ⁇ NbacnPO ⁇
  • the invention also discloses a preparation method of a high-capacity cylindrical lithium ion battery, the method comprising:
  • A has a width of 0.20 to 2.0 mm
  • B has a width of 5.0 to 30 mm
  • the current collector of the positive electrode sheet is the above positive electrode.
  • the current collector, and/or the current collector of the negative electrode sheet is the anode current collector described above;
  • the positive electrode sheet, the negative electrode sheet and the separator are wound together to form a pole group, so that the strip-shaped empty foil portions B on the positive/negative electrode sheet are respectively located at both ends of the pole group;
  • the positive/negative lead extraction current collectors are respectively taken out from the strip-shaped empty foil portion B on the current collector of the positive/negative electrode sheets.
  • the invention adopts a stress dispersion hole in the current collector, can disperse and reduce the stress during the expansion of the pole piece/foil, avoid the expansion of the pole piece and reduce the shear stress between the coating and the current collector foil substrate, and ensure the coating. Reliable contact with the current collector foil to reduce the battery capacity and safety hazards caused by partial peeling of the coating.
  • the stress dispersion holes are arranged in a row, and the angle between the center line of each row of stress dispersion holes and the edge line of the current collector is a non-right angle, in particular, a misalignment between adjacent rows of stress dispersion holes, the purpose of which is in the foil
  • the stress dispersion hole is provided on the material collecting fluid, and the tensile strength of the foil can be not excessively reduced, and the film can be cut in the steps of coating, rolling, winding, etc., and the battery can be efficiently produced with high efficiency.
  • the invention adopts a continuous coating process to manufacture a pole piece, and is easy to ensure a thickness tolerance of ⁇ 2 ⁇ m, which improves the uniformity of the coating thickness, enables the battery capacity to be fully exerted, and improves the uniformity of the battery.
  • the invention can avoid the occurrence of slitting burr and improve the safety of the battery while facilitating the high efficiency by leaving the strip-shaped empty foil portion which is not coated with the active material on both sides of the pole piece when coating the active material coating. Winding.
  • the invention adopts lithium iron phosphate-based positive electrode active material, can effectively avoid the explosion reaction, and has the potential to meet the performance requirements of current electric vehicles or electric toys for high-capacity, high-power power batteries.
  • Fig. 1 is a schematic view showing the arrangement of a dispersion stress hole in a positive current collector aluminum foil by a laser drilling process, and 1 is a stress dispersion hole.
  • Fig. 2 is a schematic view showing the strip-shaped empty foils A and B which are not coated with an active material on both sides of the pole piece when the active material coating is continuously applied on the current collector.
  • Fig. 3A is an SEM diagram of an example of a stress dispersion hole in which a positive electrode sheet aluminum foil is processed by a laser drilling process
  • Fig. 3B is an SEM image of a stress dispersion hole in which a negative electrode sheet copper foil is processed by a laser drilling process.
  • Figure 4 is a schematic view showing the surface of a pole group wound on a supporting plastic cylinder, wherein 4 is a positive pole piece, 5 is The diaphragm, 6 is the negative pole piece, and 7 is the PP supporting plastic cylinder.
  • Fig. 5 is a schematic view of the pole group after winding, and an insulating covering structure is designed at both ends of the pole group to prevent direct contact between the pole piece and the casing.
  • Fig. 5A is a schematic view showing that the insulating covering structure is not used, and
  • Fig. 5B is an insulating layer installed.
  • Schematic diagram of the cladding structure 7 is a PP supporting plastic cylinder, 8 is an insulating coating structure, 9 is a positive electrode current collector for extraction, and 10 is a negative electrode current collector for extraction.
  • Figure 6 is a schematic diagram of a lithium ion battery fabricated using the present invention.
  • the high-capacity battery of the present invention specifically refers to a lithium ion secondary battery having a rated capacity (1C) of 4 Ah or more, particularly a lOAh or higher, and a high-capacity battery including a capacity type battery and a high-power type battery, the former having a maximum discharge rate of 2 C or less, large Power type batteries refer to high-power batteries with a maximum discharge rate of 3C or higher.
  • proper process adjustment can be made according to the method and design idea of the present invention, which can produce pure high-capacity batteries, and can also produce high-capacity, large-sized batteries.
  • the object of the present invention can be achieved by designing and manufacturing the following products:
  • the positive electrode material is made of lithium iron phosphate active material
  • the positive and negative electrode sheets are respectively made of aluminum foil and copper foil as a current collector
  • two of the pole pieces are continuously coated with the active material coating.
  • the strip-shaped empty foil parts A and B which are not coated with the active material are reserved on the side, the width of the part A is in the range of 0.20-2.0 mm, and the width of the part B is in the range of 5.0-30 mm, the purpose of leaving the A side is to avoid When the coiled pole piece is cut, the coating is cut to produce burrs and partial blanking.
  • the purpose of leaving the B edge is to connect the current collector to the current collector after continuous coating, the positive pole piece
  • the current collectors for the extraction of the negative electrode tabs are respectively located on both sides of the pole group, and are respectively taken out from the upper and lower cylindrical cover plates, and the cylindrical casing is not charged; 0.5-10 times per interval on the copper foil and/or the aluminum foil
  • the foil width is preliminarily produced with a stress-distributed pore having a diameter of 0.02 to 0.20 mm which is spaced apart before coating the active material.
  • the main function of the stress dispersion hole is to disperse and reduce the stress of the pole piece/foil expansion, avoid the expansion of the pole piece and reduce the shear stress between the coating and the current collector foil substrate, and ensure the coating and the current collector foil. Reliable contact, which reduces the battery capacity and safety hazards caused by partial peeling of the coating.
  • the stress dispersion holes are arranged in a row, and the angle between the center line of each row of stress dispersion holes and the edge line of the current collector is non-right angle, especially the displacement distribution between the adjacent rows of stress dispersion holes, the purpose of which is to avoid the foil material Excessive pores appear on the same straight line perpendicular to the side of the current collector, so that the tensile strength of the foil is excessively lowered, and the film is broken in the steps of coating, rolling, winding, etc., thereby reducing the battery production efficiency.
  • the purpose of the stress dispersion holes being spaced apart and being made into round holes instead of other shaped holes is also It does not excessively reduce the tensile strength of the foil, and avoids fragmentation in processes such as coating, rolling, and winding, and facilitates efficient production of the battery.
  • the stress dispersion hole can also be punched out after the pole piece is coated, but the present invention is not particularly recommended in view of the fact that the punching is likely to cause burrs and partial dropping at the hole, and the present invention will be further explained below.
  • Battery production facilitates a highly efficient winding process, although small square batteries can also be wound, but for high-capacity, high-power lithium
  • a multi-pole process must be used. If a conventional process is used to solder the tabs and then re-wrap in the production process, due to the thickness tolerance of the pole pieces, a plurality of tabs are present. The position after winding is difficult to overlap uniformly, which is inconvenient to connect and lead to the collector.
  • the rigidity and flatness of the ear are not easy to match with the pole piece during high-speed winding, and partial poles are prone to occur.
  • the defect of the ear is in the pole group, and the waste product appears;
  • another disadvantage of the square battery is that the four angular portions are not fully spaced due to the uneven spacing of the positive and negative electrodes, and the battery consistency needs to be improved.
  • the main purpose of the conventional intermittent coating manufacturing positive and negative electrode sheets is to facilitate the welding of the lead tabs.
  • the disadvantage is that the coating thickness precision is difficult to control, and the general thickness tolerance is ⁇ 4 micrometers.
  • the present invention uses a continuous coating process to manufacture the pole pieces, which is easy. The thickness tolerance is guaranteed to be ⁇ 2 microns.
  • the main design ideas for the strip-shaped empty foil parts A and B which are not coated with active materials on both sides of the pole piece when coating the active material coating are: First, reduce the cutting burr to improve battery safety, and second, it is easy to realize High efficiency winding.
  • One of the main causes of ignition of lithium-ion batteries is caused by internal short-circuits. Internal short-circuits are caused by burrs or conductive dust on the edges of the positive and negative electrodes, or lithium dendrites on the negative electrodes and other metal dendrites that break through the ruthenium film, causing positive and The negative electrode is physically short-circuited, and a large amount of Joule heat and chemical reaction heat are generated inside the battery.
  • the electrolyte used in the lithium ion battery is mainly composed of an organic solvent and a lithium salt.
  • the commonly used organic solvents include low boiling points such as EC, DEC, DMC, and PC.
  • Low flash point, low ignition point ester compounds under high temperature conditions, the electrolyte will vaporize or decompose.
  • the safety valve on the cell is opened due to internal pressure increase, the gaseous high temperature organic solvent contacts the oxygen in the air. An oxidative exothermic reaction occurs, which leads to the occurrence of ignition.
  • internal short-circuits must be controlled as much as possible, such as dust control in cell production workshops, high-quality diaphragms, and advanced system control measures such as pole piece cutting equipment.
  • the pole piece is divided into burrs.
  • the system still needs to be improved, and the formation of the slitting burr has a great relationship with the wear of the high-hardness inorganic active material in the pole piece coating.
  • the cutting of the pole piece is only cut to pure For the aluminum foil or copper foil, the grinding of the tool The damage is very slight, and the above burrs can be greatly reduced, so that the safety of the large-capacity battery can be improved.
  • the stress dispersion holes on the copper foil and/or the aluminum foil current collector are spaced apart, and the hole pitch is preferably 2 to 10 times the aperture diameter, and the hole center line is not perpendicular to the edge line of the foil in principle, preferably 30-60.
  • the angle between the angles of the center of each row of stress dispersion holes is 0.5-10 times the width of the foil.
  • the purpose of the design is to reduce and disperse the expansion stress of the high expansion coefficient of the foil without excessively reducing the longitudinal direction of the foil.
  • the stress dispersion hole diameter is designed to be 0.02-0.20mm, especially the control is 0.04-0.08mm.
  • the slurry is easy to contaminate the roll surface during coating; the stress dispersion hole can be processed by laser drilling process or by punching into hole process; the center line spacing of stress dispersion hole is too large, which is not conducive to reducing expansion stress, and the pitch is too small, affecting The strength of the current collector; the distribution pattern of the stress dispersion holes can be appropriately adjusted according to the specific battery size requirements, for example, it can also be distributed in a zigzag manner.
  • the battery positive electrode material of the present invention is made of a lithium iron phosphate-based active material is based on the following analysis:
  • positive electrode materials such as LiCo0 2 , LiNiCoMn0 2 , LiMn 2 0 4 , and LiFeP0 4 are used for research on high-capacity power batteries, but When overcharged, LiCo0 2 cathode material becomes very unstable with the excessive elution of lithium ions, and a hexagonal to monoclinic phase transition occurs. The cobalt ion of Li ⁇ CoO ⁇ will migrate from its plane to lithium.
  • the plane where the ions are located causes the structure to be unstable and releases highly active oxygen, which is prone to intense exothermic reaction with the organic electrolyte and lithium storage anode materials, forming a "thermal runaway” phenomenon, causing accidents such as combustion and explosion.
  • a battery of LiNiCoMnO 2 , LiMn 2 0 4 cathode material also undergoes a similar "thermal runaway” reaction, which presents a serious safety hazard.
  • Lithium iron phosphate (LiFe (M) P0 4 (M is doped Nb, Mn, Co, Mg, etc.) is a very stable P0 4 3 - tetrahedron in the positive electrode material, which plays a structural support role during charge and discharge, especially It does not release high-activity oxygen atoms under overcharge and overheat conditions, and there is no severe oxidation and explosion reaction like cathode materials such as LiCo0 2 , LiNiCoMn0 2 , and LiMn 2 0 4 ; and LiFeP0 during charge and discharge. 4 and FeP0 4 in the completely delithiated state are orthogonal structures, crystal The cell parameters have only minor changes, and the battery has excellent cycle performance. Therefore, the lithium ion battery using LiFeP0 4 as the positive electrode material can effectively avoid the explosion reaction, and has the potential to meet the performance requirements of current electric vehicles or electric toys for high-capacity, high-power power batteries.
  • LiFeP0 4 LiFeP
  • Cell size Housing diameter 50mm, total height 420mm, pole group height 363mm, nominal capacity: 50Ah.
  • the positive electrode active material is 5% carbon-coated LiFe a99 Nb aQ1 P0 4 , the binder is 4 parts of P VDF (brand: Solvay 7200), and the conductive agent is 3 parts of carbon black.
  • the positive current collector is made of aluminum foil with a thickness of 20 microns.
  • the aluminum foil current collector width is 354mm.
  • the aluminum foil is laser-punched for every 30mm interval.
  • a row of stress dispersion holes is used.
  • the hole spacing is 0.5mm
  • the stress dispersion hole diameter is 0.05-0.08mm
  • the stress is dispersed.
  • the center line of the hole is at an angle of 45 degrees to the edge of the foil.
  • the negative electrode active material is made of artificial graphite
  • the adhesive is made of PVDF 3 parts (brand: Solvay 7200)
  • the conductive agent is made of carbon black 2 parts
  • the negative electrode current collector is rolled copper foil with thickness of 12 microns, copper foil current collector width: 360mm
  • the copper foil is wound with a row of stress dispersion holes at intervals of 360mm, the hole spacing is 0.5mm, the stress dispersion hole diameter is 0.05-0.08mm, and the stress dispersion hole center line is at an angle of 45 degrees with the foil edge; when the negative electrode slurry is continuously coated, A strip of empty foil A of 2 mm width is reserved on one side of the copper foil, and a strip of empty foil B of 18 mm width is reserved on the other side, and B is ultrasonically welded to each of the two sides of the copper foil by a thickness of 6 mm and a thickness of 0.05 mm.
  • the copper tab, the positive electrode sheet, the negative electrode sheet and the biaxially oriented porous PE separator having a width of 350 mm and a thickness of 25 ⁇ m are wound together to form a pole group.
  • the basic principle of the winding alignment is the active material coating portion of the positive and negative pole pieces.
  • the longitudinal center line and the diaphragm are superposed on each other in the longitudinal center line, and the strip-shaped empty foil portions B on the positive/negative electrode sheets are respectively located at both ends of the pole group, and the copper tab current collector is bent and led out.
  • Hollow collector copper bolts are used together Ultrasonic welding or laser welding, the other end of the aluminum tab collector is bent and used with the solid collector aluminum bolt for ultrasonic welding or laser welding; hollow collector copper bolt and solid collector aluminum bolt
  • the aluminum cover plate is fastened to the aluminum cover plate through the PFA seal on both sides.
  • the aluminum cover plate and the housing are sealed by laser welding.
  • the battery case is made of aluminum shell, thickness 1mm, no charge, positive and negative
  • the collector current aluminum and copper bolts are respectively taken out from the end portions of the cover plates on both sides of the battery core; after drying, the electrolyte is injected into the battery from the center hole of the hollow collector copper bolt, and the liquid is prefilled/formed and then used.
  • the stainless steel ball is pressed into the center hole to seal, and further divided into 50Ah high capacity cylindrical aluminum shell lithium ion battery.
  • the positive current collector aluminum foil was not subjected to stress dispersion holes as in Example 1.
  • the positive active material was changed to LiMn 2 0 4 , and the rest was the same as in Example 1.
  • the positive active material was changed to LiNiCoMnO, and the rest was the same as in Example 1.
  • the positive active material was changed to LiCo0 2 , and the rest was the same as in Example 1.

Abstract

A current collector of lithium ion battery which is provided with stress distribution holes. A cylindrical lithium ion battery and the preparation method of the same, wherein the battery includes the said current collector.

Description

锂电池集流体、 高容量圆柱形锂离子电池及制备方法 技术领域  Lithium battery current collector, high capacity cylindrical lithium ion battery and preparation method
本发明涉及锂离子电池领域， 特别是涉及锂离子电池的集流体、 一种 高容量的圆柱形锂离子电池以及该电池的制备方法。  The present invention relates to the field of lithium ion batteries, and more particularly to a current collector for a lithium ion battery, a high capacity cylindrical lithium ion battery, and a method of preparing the battery.
背景技术 Background technique
当前市场上存在的锂离子二次电池主要有两种工艺制造： 叠片式电池 与卷绕式电池， 叠片式电池制造的主要特点为： 将电池的正、 负极片预先 做成带引出极耳的方形片材， 再依次将正极片、 隔膜、 负极片、 隔膜等顺 序叠加， 然后将引出极耳与引出电极连接在一起， 入壳封装； 卷绕式电池 制造的主要特点为： 预先在间歇涂布的正、 负极片上留出极耳的焊接位置， 焊接极耳后再用隔膜将正、 负极片分隔后一起卷绕成极组然后入壳封装。  The lithium ion secondary batteries currently on the market are mainly manufactured in two processes: laminated battery and wound battery. The main features of the laminated battery manufacturing are: pre-forming the positive and negative electrodes of the battery with the lead-out electrode The square sheet of the ear, in turn, the positive electrode sheet, the separator, the negative electrode sheet, the separator and the like are sequentially stacked, and then the lead tab and the lead electrode are connected together to be packaged in the shell; the main features of the wound battery manufacturing are: The soldering positions of the tabs on the positive and negative plates are intermittently coated. After welding the tabs, the positive and negative electrodes are separated by a separator and then wound into a pole group and then packaged into a package.
叠片式电池一般为方形构造， 每个极片都有极耳引出， 可以分担大电 流， 因此可以适应大电流放电的要求， 主要应用于高容量、 大功率型锂离 子二次电池， 辊压后的极片必须首先分切成多个方形小片， 每个小片的横 切边缘上容易存在毛刺、 粉尘、 局部掉料等缺陷， 工艺控制非常困难， 而 这些都是导致电芯内部短路的主要原因， 也为电芯的日后使用留下安全隐 患； 采用叠片式工艺的另一缺点是生产效率很低， 不易实现自动化。  The laminated battery is generally square in shape, and each pole piece has a tab-out lead to share a large current, so it can be adapted to the requirements of large current discharge, and is mainly applied to a high-capacity, high-power lithium ion secondary battery, which is rolled. The latter pole piece must first be cut into a plurality of square pieces. The cross-cut edge of each piece is prone to defects such as burrs, dust, partial drops, etc. Process control is very difficult, and these are the main causes of internal short circuit of the cell. The reason is also a safety hazard for the future use of the battery core; another disadvantage of using the lamination process is that the production efficiency is low and automation is not easy.
相比而言， 小容量电池采用卷绕的方法制作极组， 容易实现自动化， 在生产效率上大大提高， 对于容量 2Ah以下的小容量、 低功率锂离子二次 电池， 如手机、 笔记本电脑用电池， 由于普遍采用单极耳即可满足使用要 求， 间歇涂布、 带极耳卷绕工艺是目前锂离子二次电池行业的一个主流生 产工艺。  In contrast, the small-capacity battery is fabricated by winding, which is easy to automate and greatly improves the production efficiency. For small-capacity, low-power lithium-ion secondary batteries with a capacity of less than 2 Ah, such as mobile phones and notebook computers. The battery, because the universal use of monopoles can meet the requirements of use, intermittent coating, with the ear winding process is currently a mainstream production process in the lithium ion secondary battery industry.
由于高容量、 大功率型电池一般采用串联组成电池组的方式工作， 对 电池的安全性与一致性、 经济性要求更高， 因此需要开发新的工艺， 以进 一步满足高容量、 大功率的需要。  Since high-capacity, high-power batteries generally operate in a battery pack in series, the safety, consistency, and economic requirements of the battery are higher, so new processes need to be developed to further meet the needs of high-capacity and high-power. .
发明内容 Summary of the invention
本发明的目的是针对目前的锂离子二次电池产品和生产工艺所存在的 不足， 提出一种能提高锂离子电池容量发挥及使用安全性的锂离子电池集 流体。  SUMMARY OF THE INVENTION The object of the present invention is to provide a lithium ion battery current collector capable of improving the capacity and safety of a lithium ion battery in view of the deficiencies of current lithium ion secondary battery products and production processes.
本发明的另一目的在于提供含有上述集流体、 具有高容量的圆柱形锂 离子电池以及该电池的制备方法。 Another object of the present invention is to provide a cylindrical lithium having a high capacity and containing the above-mentioned current collector An ion battery and a method of preparing the same.
为实现上述目的， 本发明采用了以下技术方案：  To achieve the above object, the present invention adopts the following technical solutions:
本发明公开了一种锂离子电池集流体， 所述集流体上设置有应力分散 孔。  The invention discloses a lithium ion battery current collector, wherein the current collector is provided with a stress dispersion hole.
优选的， 所述应力分散孔成排分布， 并且每排应力分散孔的中心线与 集流体边缘线的夹角为非直角。  Preferably, the stress dispersion holes are arranged in a row, and an angle between a center line of each row of stress dispersion holes and a current collector edge line is a non-right angle.
更优选的， 相邻的各排应力分散孔之间错位分布。  More preferably, the adjacent rows of stress dispersion holes are misaligned.
优选的， 所述错位分布是指在垂直于集流体侧边的同一直线上最多分 布有 1个应力分散孔。 所述应力分散孔的直径优选为 0.02〜0.20mm， 并且 每排应力分散孔的中心线间距为集流体宽度的 0.5〜10倍，同一排的应力分 散孔的孔间距为孔径的 2〜10倍。。  Preferably, the misalignment distribution means that at most one stress dispersion hole is distributed on the same straight line perpendicular to the side of the current collector. The diameter of the stress dispersion hole is preferably 0.02 to 0.20 mm, and the center line spacing of each row of the stress dispersion holes is 0.5 to 10 times the width of the current collector, and the hole spacing of the stress dispersion holes of the same row is 2 to 10 times the aperture. . .
更优选的， 所述应力分散孔的直径为 0.04〜0.08mm。  More preferably, the stress dispersion hole has a diameter of 0.04 to 0.08 mm.
每排应力分散孔的中心线与集流体的边缘线呈 30〜60度夹角， 优选为 The center line of each row of stress dispersion holes and the edge line of the current collector are at an angle of 30 to 60 degrees, preferably
45度， 并且所述应力分散孔优选为圆孔。 45 degrees, and the stress dispersion hole is preferably a circular hole.
每排应力分散孔相互平行分布或者呈锯齿状分布。  Each row of stress dispersion holes is distributed parallel to each other or in a zigzag pattern.
所述集流体为正极集流体， 且所述集流体为铝箔。  The current collector is a positive electrode current collector, and the current collector is an aluminum foil.
或者所述集流体为负极集流体， 且所述集流体为铜箔。  Or the current collector is a negative current collector, and the current collector is a copper foil.
本发明还公开了一种高容量圆柱形锂离子电池， 包括正极片与负极片， 所述正极片的集流体为上述的正极集流体， 和 /或所述负极片的集流体为上 述的负极集流体。  The invention also discloses a high-capacity cylindrical lithium ion battery, comprising a positive electrode sheet and a negative electrode sheet, wherein the current collector of the positive electrode sheet is the positive electrode current collector, and/or the current collector of the negative electrode sheet is the above-mentioned negative electrode Current collector.
所述高容量圆柱形锂离子电池中， 所述正极片和 /或负极片的集流体上 连续涂布有活性材料涂层， 并且在集流体的两侧边分别预留有不涂活性材 料的条形空箔部位 A和 B, 正极片、 负极片及隔膜一起卷绕形成极组后， 正 /负极片上的条形空箔部位 B分别位于极组的两端，且正 /负极的引出用集 电体分别从正 /负极片的集流体上的条形空箔部位 B引出。  In the high-capacity cylindrical lithium ion battery, the current collector of the positive electrode sheet and/or the negative electrode sheet is continuously coated with an active material coating, and the active material is reserved on both sides of the current collector. After the strip-shaped empty foil portions A and B, the positive electrode sheet, the negative electrode sheet and the separator are wound together to form a pole group, the strip-shaped empty foil portions B on the positive/negative electrode sheets are respectively located at both ends of the pole group, and the positive/negative electrode is taken out The current collectors are respectively taken out from the strip-shaped empty foil portion B on the current collector of the positive/negative electrode sheets.
所述条形空箔部位 A的宽度为 0.20〜2.0mm， B的宽度为 5.0〜30mm。 所述锂离子电池的正极活性材料为磷酸亚铁锂系活性材料， 优选为炭 包覆的 LiFea^NbacnPO^  The width of the strip-shaped empty foil portion A is 0.20 to 2.0 mm, and the width of B is 5.0 to 30 mm. The positive electrode active material of the lithium ion battery is a lithium iron phosphate active material, preferably a carbon coated LiFea^NbacnPO^
本发明还公开了一种高容量圆柱形锂离子电池的制备方法， 所述方法 包括：  The invention also discloses a preparation method of a high-capacity cylindrical lithium ion battery, the method comprising:
a、在正极集流体和 /或负极集流体上连续涂布活性材料涂层， 并在集流 体的两侧分别预留有不涂活性材料的条形空箔部位 A 和 B， A 的宽度为 0.20〜2.0mm， B的宽度为 5.0〜30mm， 所述正极片的集流体为上述的正极 集流体， 和 /或所述负极片的集流体为上述的负极集流体； a. Continuously coating the active material coating on the positive current collector and/or the negative current collector, and collecting at the current Stripe-shaped empty foil portions A and B which are not coated with active material are respectively reserved on both sides of the body, A has a width of 0.20 to 2.0 mm, B has a width of 5.0 to 30 mm, and the current collector of the positive electrode sheet is the above positive electrode. The current collector, and/or the current collector of the negative electrode sheet is the anode current collector described above;
b、将正极片、 负极片及隔膜一起卷绕形成极组， 使正 /负极片上的条形 空箔部位 B分别位于极组的两端；  b. The positive electrode sheet, the negative electrode sheet and the separator are wound together to form a pole group, so that the strip-shaped empty foil portions B on the positive/negative electrode sheet are respectively located at both ends of the pole group;
c、 将正 /负极引出用集电体分别从正 /负极片的集流体上的条形空箔部 位 B引出。  c. The positive/negative lead extraction current collectors are respectively taken out from the strip-shaped empty foil portion B on the current collector of the positive/negative electrode sheets.
本发明在集流体中采用应力分散孔， 能够分散、 降低极片 /箔材膨胀时 的应力， 避免极片胀断和减小涂层与集流体箔材基体之间的剪应力， 保证 涂层与集流体箔材可靠接触， 降低因涂层局部剥离而影响电池容量发挥和 产生安全隐患。 其中， 应力分散孔成排分布， 并且每排应力分散孔的中心 线与集流体边缘线的夹角为非直角， 特别是相邻的各排应力分散孔之间错 位分布， 其目的是在箔材集流体上设置应力分散孔的同时能够不过分降低 箔材的抗拉强度， 避免在涂布、 辊压、 卷绕等工序断片， 便于电池高效率 生产。 本发明采用连续涂布工艺制造极片， 易于保证厚度公差在 ±2微米， 提高了涂布厚度的均一性， 是电池容量能充分发挥， 并改善了电池的一致 性。  The invention adopts a stress dispersion hole in the current collector, can disperse and reduce the stress during the expansion of the pole piece/foil, avoid the expansion of the pole piece and reduce the shear stress between the coating and the current collector foil substrate, and ensure the coating. Reliable contact with the current collector foil to reduce the battery capacity and safety hazards caused by partial peeling of the coating. Wherein, the stress dispersion holes are arranged in a row, and the angle between the center line of each row of stress dispersion holes and the edge line of the current collector is a non-right angle, in particular, a misalignment between adjacent rows of stress dispersion holes, the purpose of which is in the foil The stress dispersion hole is provided on the material collecting fluid, and the tensile strength of the foil can be not excessively reduced, and the film can be cut in the steps of coating, rolling, winding, etc., and the battery can be efficiently produced with high efficiency. The invention adopts a continuous coating process to manufacture a pole piece, and is easy to ensure a thickness tolerance of ±2 μm, which improves the uniformity of the coating thickness, enables the battery capacity to be fully exerted, and improves the uniformity of the battery.
本发明通过在在涂布活性材料涂层时在极片的两侧预留不涂活性材料 的条形空箔部位， 极大避免出现分切毛刺， 并提高电池安全性， 同时便于 实现高效率卷绕。  The invention can avoid the occurrence of slitting burr and improve the safety of the battery while facilitating the high efficiency by leaving the strip-shaped empty foil portion which is not coated with the active material on both sides of the pole piece when coating the active material coating. Winding.
本发明采用磷酸亚铁锂系正极活性材料， 能够有效避免***反应， 有 潜力满足目前电动汽车或电动玩具对高容量、 大功率动力电池的性能需求。 附图说明  The invention adopts lithium iron phosphate-based positive electrode active material, can effectively avoid the explosion reaction, and has the potential to meet the performance requirements of current electric vehicles or electric toys for high-capacity, high-power power batteries. DRAWINGS
图 1为正极集流体铝箔采用激光打孔工艺加工分散应力孔排布示意图， 1为应力分散孔。  Fig. 1 is a schematic view showing the arrangement of a dispersion stress hole in a positive current collector aluminum foil by a laser drilling process, and 1 is a stress dispersion hole.
图 2为在集流体上连续涂布活性材料涂层时在极片的两侧预留不涂活 性材料的条形空箔 A与 B示意图。  Fig. 2 is a schematic view showing the strip-shaped empty foils A and B which are not coated with an active material on both sides of the pole piece when the active material coating is continuously applied on the current collector.
图 3A为正极片铝箔采用激光打孔工艺加工的应力分散孔的实例 SEM 图， 图 3B为负极片铜箔采用激光打孔工艺加工的应力分散孔的实例 SEM 图。  Fig. 3A is an SEM diagram of an example of a stress dispersion hole in which a positive electrode sheet aluminum foil is processed by a laser drilling process, and Fig. 3B is an SEM image of a stress dispersion hole in which a negative electrode sheet copper foil is processed by a laser drilling process.
图 4为极组卷绕在支撑塑料圆筒表面示意图， 其中 4为正极极片， 5为 隔膜， 6为负极极片， 7为 PP支撑塑料圆筒。 Figure 4 is a schematic view showing the surface of a pole group wound on a supporting plastic cylinder, wherein 4 is a positive pole piece, 5 is The diaphragm, 6 is the negative pole piece, and 7 is the PP supporting plastic cylinder.
图 5 为极组卷绕后的示意图， 在极组两端设计有绝缘包覆结构以防止 极片与壳体直接接触， 图 5A为未采用绝缘包覆结构的示意图， 图 5B为安 装了绝缘包覆结构的示意图， 7为 PP支撑塑料圆筒， 8为绝缘包覆结构， 9 为引出用正极集电体， 10为引出用负极集电体。  Fig. 5 is a schematic view of the pole group after winding, and an insulating covering structure is designed at both ends of the pole group to prevent direct contact between the pole piece and the casing. Fig. 5A is a schematic view showing that the insulating covering structure is not used, and Fig. 5B is an insulating layer installed. Schematic diagram of the cladding structure, 7 is a PP supporting plastic cylinder, 8 is an insulating coating structure, 9 is a positive electrode current collector for extraction, and 10 is a negative electrode current collector for extraction.
图 6为采用本发明做出的锂离子电池示意图。  Figure 6 is a schematic diagram of a lithium ion battery fabricated using the present invention.
具体实施方式 detailed description
本发明的高容量电池特指额定容量 （1C) 在 4Ah 以上， 尤其是 lOAh 以上的锂离子二次电池， 高容量电池包括容量型电池和大功率型电池， 前 者最大放电倍率在 2C以下， 大功率型电池特指最大放电倍率在 3C以上的 大功率型电池， 根据具体使用要求， 做适当工艺调整按本发明的方法和设 计思路既可以生产纯粹高容量的电池， 也可以生产高容量、 大功率兼而有 之的电池。  The high-capacity battery of the present invention specifically refers to a lithium ion secondary battery having a rated capacity (1C) of 4 Ah or more, particularly a lOAh or higher, and a high-capacity battery including a capacity type battery and a high-power type battery, the former having a maximum discharge rate of 2 C or less, large Power type batteries refer to high-power batteries with a maximum discharge rate of 3C or higher. According to the specific application requirements, proper process adjustment can be made according to the method and design idea of the present invention, which can produce pure high-capacity batteries, and can also produce high-capacity, large-sized batteries. A battery with both power and power.
本发明的目的可以通过下述产品设计、 制造得以实现：  The object of the present invention can be achieved by designing and manufacturing the following products:
一种高容量圆柱形锂离子电池， 正极材料采用磷酸亚铁锂系活性材料 制造， 正、 负极片分别采用铝箔和铜箔做集流体， 在连续涂布活性材料涂 层时在极片的两侧预留不涂活性材料的条形空箔部位 A和 B, 部位 A的宽 度在 0.20-2.0mm范围内， 部位 B的宽度在 5.0-30mm范围内， 预留 A空边 的目的是为了避免成卷极片分切时切到涂层而产生毛刺和局部掉料，预留 B 空边的目的是为了采用连续涂布后在此空箔部位与引出用集电体相连接， 正极极片与负极极片的引出用集电体分别位于极组的两侧， 从上、 下圆柱 形盖板分别引出， 圆柱形壳体不带电； 在铜箔和、 或铝箔上每间隔 0.5-10 倍箔材宽度在涂布活性材料前预先制造出间隔分布的直径 0.02-0.20mm 的 应力分散孔。应力分散孔的主要作用是分散、 降低极片 /箔材膨胀时的应力， 避免极片胀断和减小涂层与集流体箔材基体之间的剪应力， 保证涂层与集 流体箔材可靠接触， 降低因涂层局部剥离而影响电池容量发挥和产生安全 隐患。 应力分散孔成排分布， 并且每排应力分散孔的中心线与集流体边缘 线的夹角为非直角， 特别是相邻各排应力分散孔之间错位分布， 其目的是 为了避免在箔材集流体垂直于侧边的同一直线上出现过多的孔而使箔材的 抗拉强度过分降低， 进而在涂布、 辊压、 卷绕等工序断片， 降低电池生产 效率。 应力分散孔呈间隔分布和做成圆孔而非其他异形孔的目的同样是为 了不过分降低箔材的抗拉强度， 避免在涂布、 辊压、 卷绕等工序断片， 便 于电池高效率生产。 应力分散孔也可以在极片涂布后再冲压出来， 但是考 虑到冲压成孔处易产生毛刺和局部掉料现象， 因此本发明不特别推荐使用， 以下对本发明做进一步解释。 A high-capacity cylindrical lithium ion battery, the positive electrode material is made of lithium iron phosphate active material, and the positive and negative electrode sheets are respectively made of aluminum foil and copper foil as a current collector, and two of the pole pieces are continuously coated with the active material coating. The strip-shaped empty foil parts A and B which are not coated with the active material are reserved on the side, the width of the part A is in the range of 0.20-2.0 mm, and the width of the part B is in the range of 5.0-30 mm, the purpose of leaving the A side is to avoid When the coiled pole piece is cut, the coating is cut to produce burrs and partial blanking. The purpose of leaving the B edge is to connect the current collector to the current collector after continuous coating, the positive pole piece The current collectors for the extraction of the negative electrode tabs are respectively located on both sides of the pole group, and are respectively taken out from the upper and lower cylindrical cover plates, and the cylindrical casing is not charged; 0.5-10 times per interval on the copper foil and/or the aluminum foil The foil width is preliminarily produced with a stress-distributed pore having a diameter of 0.02 to 0.20 mm which is spaced apart before coating the active material. The main function of the stress dispersion hole is to disperse and reduce the stress of the pole piece/foil expansion, avoid the expansion of the pole piece and reduce the shear stress between the coating and the current collector foil substrate, and ensure the coating and the current collector foil. Reliable contact, which reduces the battery capacity and safety hazards caused by partial peeling of the coating. The stress dispersion holes are arranged in a row, and the angle between the center line of each row of stress dispersion holes and the edge line of the current collector is non-right angle, especially the displacement distribution between the adjacent rows of stress dispersion holes, the purpose of which is to avoid the foil material Excessive pores appear on the same straight line perpendicular to the side of the current collector, so that the tensile strength of the foil is excessively lowered, and the film is broken in the steps of coating, rolling, winding, etc., thereby reducing the battery production efficiency. The purpose of the stress dispersion holes being spaced apart and being made into round holes instead of other shaped holes is also It does not excessively reduce the tensile strength of the foil, and avoids fragmentation in processes such as coating, rolling, and winding, and facilitates efficient production of the battery. The stress dispersion hole can also be punched out after the pole piece is coated, but the present invention is not particularly recommended in view of the fact that the punching is likely to cause burrs and partial dropping at the hole, and the present invention will be further explained below.
对于高容量或大功率电池， 设计成圆柱形而非方形的目的是： 电池生 产利于采用高效率的卷绕工艺， 虽然方形小电池也可以采用卷绕工艺， 但 是对于大容量、 高功率型锂离子二次电池而言， 由于工作电流较大， 必须 采用多极耳工艺， 如果采用常规工艺在制片时先焊接极耳然后再卷绕， 由 于极片厚度公差的存在， 多个极耳在卷绕后的位置很难一致重叠， 不便于 和集电体连接、 引出； 另外对于采用多极耳分布的电池， 高速卷绕时极耳 刚性和平整度不易和极片一致， 易出现部分极耳卷入极组的缺陷， 出现废 品； 方形电池的另一个缺点是四个角形部位由于正、 负极片间距不均， 容 量发挥不充分， 电池一致性有待改善。 传统间歇涂布制造正、 负极片的主 要目的就是为了方便焊接引出极耳， 其缺点是涂布厚度精度难以控制， 一 般厚度公差在 ±4微米， 本发明采用连续涂布工艺制造极片， 易于保证厚度 公差在 ±2微米。  For high-capacity or high-power batteries, the purpose of designing a cylinder instead of a square is: Battery production facilitates a highly efficient winding process, although small square batteries can also be wound, but for high-capacity, high-power lithium In the case of an ion secondary battery, since the operating current is large, a multi-pole process must be used. If a conventional process is used to solder the tabs and then re-wrap in the production process, due to the thickness tolerance of the pole pieces, a plurality of tabs are present. The position after winding is difficult to overlap uniformly, which is inconvenient to connect and lead to the collector. In addition, for batteries with multi-pole distribution, the rigidity and flatness of the ear are not easy to match with the pole piece during high-speed winding, and partial poles are prone to occur. The defect of the ear is in the pole group, and the waste product appears; another disadvantage of the square battery is that the four angular portions are not fully spaced due to the uneven spacing of the positive and negative electrodes, and the battery consistency needs to be improved. The main purpose of the conventional intermittent coating manufacturing positive and negative electrode sheets is to facilitate the welding of the lead tabs. The disadvantage is that the coating thickness precision is difficult to control, and the general thickness tolerance is ±4 micrometers. The present invention uses a continuous coating process to manufacture the pole pieces, which is easy. The thickness tolerance is guaranteed to be ±2 microns.
在涂布活性材料涂层时在极片的两侧预留不涂活性材料的条形空箔部 位 A和 B的主要设计思路是： 一是减少分切毛刺提高电池安全性， 二是便 于实现高效率卷绕。锂离子电池着火的一个主要原因是由内部短路引起的， 内部短路是因为正负极片边缘存在毛刺或导电粉尘、 或负极上的锂枝晶及 其他金属枝晶穿破膈膜， 造成正、 负极发生物理短路， 电芯内部产生大量 焦耳热及化学反应热量， 由于锂离子电池采用的电解液主要由有机溶剂和 锂盐组成， 常用的有机溶剂包括 EC、 DEC, DMC、 PC等低沸点、 低闪点、 低燃点的酯类化合物， 在高温条件下， 电解液会产生汽化或分解， 当电芯 上的安全阀因内部压力增大打开后， 气态的高温有机溶剂和空气中的氧气 接触发生氧化放热反应， 导致着火现象的发生， 为此必须尽量控制内部短 路的发生， 比如电芯生产车间的粉尘控制、 高品质的隔膜以及先进的极片 分切设备等***控制措施， 这些技术方法虽然在一定程度上可以降低电芯 发生内部短路的概率， 极片分切毛刺的控制仍需重点改善， 而分切毛刺的 形成与极片涂层里的高硬度无机活性材料对刀具的磨损有很大关系， 当采 用本发明的方法， 分切极片时仅仅分切到纯的铝箔或铜箔时， 对刀具的磨 损很轻微， 上述毛刺可大大降低， 因此可以提高大容量电池的安全性。 在铜箔和、 或铝箔集流体上的应力分散孔呈间隔分布， 孔间距设计为 孔径的 2-10倍为佳， 孔中心线原则上不与箔材边缘线垂直， 最好成 30-60 度夹角， 每排应力分散孔中心线间距 0.5-10倍箔材宽度， 这样设计的目的 是在降低、 分散高膨胀系数的箔材的膨胀应力的同时， 又不致于过分降低 箔材的纵向抗拉强度； 应力分散孔直径设计在 0.02-0.20mm， 尤其是控制在 0.04-0.08mm为佳， 其原因是： 应力分散孔直径过小工业上实现困难， 直径 过大容易影响涂布工艺， 涂布时料浆易污染辊面； 应力分散孔可以采用激 光打孔工艺加工， 也可以采用冲压成孔工艺加工； 应力分散孔中心线间距 过大， 不利于降低膨胀应力， 间距过小， 影响集流体的强度； 根据具体电 池尺寸要求可以适当调整应力分散孔的分布形式， 比如也可以呈锯齿状分 布。 The main design ideas for the strip-shaped empty foil parts A and B which are not coated with active materials on both sides of the pole piece when coating the active material coating are: First, reduce the cutting burr to improve battery safety, and second, it is easy to realize High efficiency winding. One of the main causes of ignition of lithium-ion batteries is caused by internal short-circuits. Internal short-circuits are caused by burrs or conductive dust on the edges of the positive and negative electrodes, or lithium dendrites on the negative electrodes and other metal dendrites that break through the ruthenium film, causing positive and The negative electrode is physically short-circuited, and a large amount of Joule heat and chemical reaction heat are generated inside the battery. The electrolyte used in the lithium ion battery is mainly composed of an organic solvent and a lithium salt. The commonly used organic solvents include low boiling points such as EC, DEC, DMC, and PC. Low flash point, low ignition point ester compounds, under high temperature conditions, the electrolyte will vaporize or decompose. When the safety valve on the cell is opened due to internal pressure increase, the gaseous high temperature organic solvent contacts the oxygen in the air. An oxidative exothermic reaction occurs, which leads to the occurrence of ignition. To this end, internal short-circuits must be controlled as much as possible, such as dust control in cell production workshops, high-quality diaphragms, and advanced system control measures such as pole piece cutting equipment. Although the method can reduce the probability of internal short circuit of the cell to a certain extent, the pole piece is divided into burrs. The system still needs to be improved, and the formation of the slitting burr has a great relationship with the wear of the high-hardness inorganic active material in the pole piece coating. When the method of the invention is used, the cutting of the pole piece is only cut to pure For the aluminum foil or copper foil, the grinding of the tool The damage is very slight, and the above burrs can be greatly reduced, so that the safety of the large-capacity battery can be improved. The stress dispersion holes on the copper foil and/or the aluminum foil current collector are spaced apart, and the hole pitch is preferably 2 to 10 times the aperture diameter, and the hole center line is not perpendicular to the edge line of the foil in principle, preferably 30-60. The angle between the angles of the center of each row of stress dispersion holes is 0.5-10 times the width of the foil. The purpose of the design is to reduce and disperse the expansion stress of the high expansion coefficient of the foil without excessively reducing the longitudinal direction of the foil. Tensile strength; The stress dispersion hole diameter is designed to be 0.02-0.20mm, especially the control is 0.04-0.08mm. The reason is: The stress dispersion hole diameter is too small to achieve industrial difficulties, and the diameter is too large to easily affect the coating process. The slurry is easy to contaminate the roll surface during coating; the stress dispersion hole can be processed by laser drilling process or by punching into hole process; the center line spacing of stress dispersion hole is too large, which is not conducive to reducing expansion stress, and the pitch is too small, affecting The strength of the current collector; the distribution pattern of the stress dispersion holes can be appropriately adjusted according to the specific battery size requirements, for example, it can also be distributed in a zigzag manner.
本发明的电池正极材料采用磷酸亚铁锂系活性材料制造的主要原因基 于如下分析： 目前 LiCo02、 LiNiCoMn02、 LiMn204、 LiFeP04等正极材料都 有用于高容量动力电池的研究， 但在过充时， 随着锂离子的过度脱出， LiCo02正极材料变得很不稳定，会发生六方到单斜的结构相变， Li^CoO^ 的钴离子将从其所在的平面迁移到锂离子所在的平面， 导致结构不稳定而 释放出高活性的氧， 容易与有机电解液、 储锂的负极材料等发生剧烈的放 热反应，形成"热失控"现象，引起燃烧、***等事故。同样地， LiNiCoMn02, LiMn204正极材料的电池也会发生类似的 "热失控"反应， 存在严重的安全 隐患。 即使电池不处于过充状态， 而是电芯受到挤压、 高温等场合， 上述 正极材料的热稳定性也不够， 在 200-250°C同样会发生释放氧的可能， 同样 会形成 "热失控"现象， 引起燃烧、 ***等事故。 另外， LiMn204正极材料 的电池虽然热稳定性在 280°C左右，但是该尖晶石材料在充放电循环中存在 Janh-Teller畸变和 Mn的溶解， 导致电池循环性能较差， 使用寿命不足， 用于 2Ah以上的高容量电池仍然不安全、 不经济。 The main reason why the battery positive electrode material of the present invention is made of a lithium iron phosphate-based active material is based on the following analysis: At present, positive electrode materials such as LiCo0 2 , LiNiCoMn0 2 , LiMn 2 0 4 , and LiFeP0 4 are used for research on high-capacity power batteries, but When overcharged, LiCo0 2 cathode material becomes very unstable with the excessive elution of lithium ions, and a hexagonal to monoclinic phase transition occurs. The cobalt ion of Li^CoO^ will migrate from its plane to lithium. The plane where the ions are located causes the structure to be unstable and releases highly active oxygen, which is prone to intense exothermic reaction with the organic electrolyte and lithium storage anode materials, forming a "thermal runaway" phenomenon, causing accidents such as combustion and explosion. Similarly, a battery of LiNiCoMnO 2 , LiMn 2 0 4 cathode material also undergoes a similar "thermal runaway" reaction, which presents a serious safety hazard. Even if the battery is not overcharged, but the battery is squeezed, high temperature, etc., the thermal stability of the above positive electrode material is not enough, and the possibility of releasing oxygen will also occur at 200-250 °C, which will also form "thermal runaway.""Phenomenon, causing accidents such as burning and explosion. In addition, although the thermal stability of the LiMn 2 0 4 cathode material is about 280 ° C, the spinel material has Janh-Teller distortion and Mn dissolution in the charge and discharge cycle, resulting in poor cycle performance and service life of the battery. Insufficient, high-capacity batteries for 2Ah or more are still unsafe and uneconomical.
而磷酸亚铁锂 LiFe (M) P04 (M为搀杂的 Nb、 Mn、 Co、 Mg等） 系正 极材料中 P04 3—四面体非常稳定， 在充放电过程中起到结构支撑作用， 尤其 是在过充、 过热情况下不会释放高活性的氧原子， 不存在像 LiCo02， LiNiCoMn02， LiMn204等正极材料那样的剧烈氧化、 ***反应； 同时由于 在充放电过程中， LiFeP04和完全脱锂状态下的 FeP04的都为正交结构， 晶 胞参数只有微小变化， 电池具有优异的循环性能。 因此采用 LiFeP04为正极 材料的锂离子电池可以有效避免***反应， 有潜力满足目前电动汽车或电 动玩具对高容量、 大功率动力电池的性能需求。 实 施 例 Lithium iron phosphate (LiFe (M) P0 4 (M is doped Nb, Mn, Co, Mg, etc.) is a very stable P0 4 3 - tetrahedron in the positive electrode material, which plays a structural support role during charge and discharge, especially It does not release high-activity oxygen atoms under overcharge and overheat conditions, and there is no severe oxidation and explosion reaction like cathode materials such as LiCo0 2 , LiNiCoMn0 2 , and LiMn 2 0 4 ; and LiFeP0 during charge and discharge. 4 and FeP0 4 in the completely delithiated state are orthogonal structures, crystal The cell parameters have only minor changes, and the battery has excellent cycle performance. Therefore, the lithium ion battery using LiFeP0 4 as the positive electrode material can effectively avoid the explosion reaction, and has the potential to meet the performance requirements of current electric vehicles or electric toys for high-capacity, high-power power batteries. Example
实施例 1：  Example 1:
电芯尺寸： 壳体直径 50mm， 总高 420mm， 极组高度 363mm， 标称容 量： 50Ah。  Cell size: Housing diameter 50mm, total height 420mm, pole group height 363mm, nominal capacity: 50Ah.
正极活性材料采用 5 %炭包覆的 LiFea99NbaQ1P04, 粘接剂采用 P VDF (牌号： 苏威 7200) 4份， 导电剂采用炭黑 3份。 The positive electrode active material is 5% carbon-coated LiFe a99 Nb aQ1 P0 4 , the binder is 4 parts of P VDF (brand: Solvay 7200), and the conductive agent is 3 parts of carbon black.
正极集流体采用厚度为 20微米的铝箔， 铝箔集流体宽度： 354mm, 铝 箔每间隔 360mm采用激光打孔技术打上一排应力分散孔， 孔间距 0.5mm， 应力分散孔直径 0.05-0.08mm，应力分散孔中心线与箔材边缘成 45度夹角， 连续涂布正极料浆时， 控制铝箔一侧预留 2mm宽度的条形空箔 A, 另一侧 预留 18mm宽度的条形空箔 B，B在正极极片辊压处理后分别超声波焊接两 个宽 6mm厚 0.10mm的引出用铝极耳集电体。  The positive current collector is made of aluminum foil with a thickness of 20 microns. The aluminum foil current collector width is 354mm. The aluminum foil is laser-punched for every 30mm interval. A row of stress dispersion holes is used. The hole spacing is 0.5mm, the stress dispersion hole diameter is 0.05-0.08mm, and the stress is dispersed. The center line of the hole is at an angle of 45 degrees to the edge of the foil. When the positive electrode slurry is continuously applied, the strip-shaped empty foil A of 2 mm width is reserved on one side of the control aluminum foil, and the strip-shaped empty foil B of 18 mm width is reserved on the other side. B. After the positive electrode sheet rolling treatment, ultrasonically welded two aluminum tab collectors with a width of 6 mm and a thickness of 0.10 mm.
负极活性材料采用人造石墨，粘接剂采用 PVDF 3份 (牌号：苏威 7200)， 导电剂采用炭黑 2份； 负极集流体采用厚度为 12微米的压延铜箔， 铜箔集 流体宽度： 360mm, 铜箔每间隔 360mm 打上一排应力分散孔， 孔间距 0.5mm, 应力分散孔直径 0.05-0.08mm， 应力分散孔中心线与箔材边缘成 45 度夹角；连续涂布负极料浆时，控制铜箔一侧预留 2mm宽度的条形空箔 A, 另一侧预留 18mm宽度的条形空箔 B，B在负极极片辊压处理后分别超声波 焊接两个宽 6mm 厚 0.05mm 的引出用铜极耳， 正极片、 负极片及宽度 350mm, 厚度 25微米的双向拉伸多孔 PE隔膜一起卷绕形成极组， 卷绕对 中的基本原则是正、 负极极片的活性材料涂层部分在纵向的中心线和隔膜 在纵向的中心线相重合后一起卷绕， 正 /负极片上的条形空箔部位 B分别位 于极组的两端， 铜极耳集电体折弯后与引出用空心集电体铜螺栓一起采用 超声波焊接或采用激光焊接， 另一端的铝极耳集电体折弯后与引出用实心 集电体铝螺栓一起采用超声波焊接或采用激光焊接； 空心集电体铜螺栓和 实心集电体铝螺栓在两侧分别与铝盖板通过 PFA密封垫紧固连接， 铝盖板 与壳体采用激光焊接密封， 电池壳体为铝壳， 厚度 1mm, 不带电， 正、 负 极集电体铝、 铜螺栓分别从电芯两侧盖板端部引出； 经干燥后从空心集电 体铜螺栓的中心孔向电池内注入电解液， 注液后经预充 /化成然后采用不锈 钢球压入中心孔密封，经进一步分容等制成 50Ah高容量型圆柱形铝壳锂离 子电池。 The negative electrode active material is made of artificial graphite, the adhesive is made of PVDF 3 parts (brand: Solvay 7200), the conductive agent is made of carbon black 2 parts; the negative electrode current collector is rolled copper foil with thickness of 12 microns, copper foil current collector width: 360mm The copper foil is wound with a row of stress dispersion holes at intervals of 360mm, the hole spacing is 0.5mm, the stress dispersion hole diameter is 0.05-0.08mm, and the stress dispersion hole center line is at an angle of 45 degrees with the foil edge; when the negative electrode slurry is continuously coated, A strip of empty foil A of 2 mm width is reserved on one side of the copper foil, and a strip of empty foil B of 18 mm width is reserved on the other side, and B is ultrasonically welded to each of the two sides of the copper foil by a thickness of 6 mm and a thickness of 0.05 mm. The copper tab, the positive electrode sheet, the negative electrode sheet and the biaxially oriented porous PE separator having a width of 350 mm and a thickness of 25 μm are wound together to form a pole group. The basic principle of the winding alignment is the active material coating portion of the positive and negative pole pieces. The longitudinal center line and the diaphragm are superposed on each other in the longitudinal center line, and the strip-shaped empty foil portions B on the positive/negative electrode sheets are respectively located at both ends of the pole group, and the copper tab current collector is bent and led out. Hollow collector copper bolts are used together Ultrasonic welding or laser welding, the other end of the aluminum tab collector is bent and used with the solid collector aluminum bolt for ultrasonic welding or laser welding; hollow collector copper bolt and solid collector aluminum bolt The aluminum cover plate is fastened to the aluminum cover plate through the PFA seal on both sides. The aluminum cover plate and the housing are sealed by laser welding. The battery case is made of aluminum shell, thickness 1mm, no charge, positive and negative The collector current aluminum and copper bolts are respectively taken out from the end portions of the cover plates on both sides of the battery core; after drying, the electrolyte is injected into the battery from the center hole of the hollow collector copper bolt, and the liquid is prefilled/formed and then used. The stainless steel ball is pressed into the center hole to seal, and further divided into 50Ah high capacity cylindrical aluminum shell lithium ion battery.
经 1C充 /2C放 100次循环后， 容量衰减为初始容量的 97%, 600次循 环后容量衰减为初始容量的 93%。  After 100 cycles of 1C charge / 2C, the capacity decays to 97% of the initial capacity, and the capacity decay after 600 cycles is 93% of the initial capacity.
1C/18V过充试验， 电池不着火、 不***。 对比例 1:  1C/18V overcharge test, the battery does not catch fire, does not explode. Comparative 1:
正极集流体铝箔不打应力分散孔其余同实施例 1。  The positive current collector aluminum foil was not subjected to stress dispersion holes as in Example 1.
经 1C充 /2C放 100次循环后， 容量衰减为初始容量的 70%, 600次循 环后容量衰减为初始容量的 50%。  After 100 cycles of 1C charge / 2C, the capacity decays to 70% of the initial capacity, and the capacity decay after 600 cycles is 50% of the initial capacity.
1C/18V过充不着火、 不***。 对比例 2:  1C/18V overcharge does not catch fire, does not explode. Comparative example 2:
正极活性材料改为 LiMn204， 其余同实施例 1 。 The positive active material was changed to LiMn 2 0 4 , and the rest was the same as in Example 1.
经 1C充 /2C放 100次循环后， 容量衰减为初始容量的 80%, 400次循 环后容量衰减为初始容量的 50%;  After 100 cycles of 1C charge / 2C, the capacity decays to 80% of the initial capacity, and the capacity decay after 400 cycles is 50% of the initial capacity;
1C/18V过充试验， 电池***。 对比例 3:  1C/18V overcharge test, battery explosion. Comparative example 3:
正极活性材料改为 LiNiCoMnO ， 其余同实施例 1 。  The positive active material was changed to LiNiCoMnO, and the rest was the same as in Example 1.
经 1C充 /2C放 100次循环后， 容量衰减为初始容量的 94%, 600次循 后容量衰减为初始容量的 88%;  After 100 cycles of 1C charge / 2C, the capacity decays to 94% of the initial capacity, and the capacity decay after 600 cycles is 88% of the initial capacity;
1C/18V过充试验， 电池***。 对比例 4:  1C/18V overcharge test, battery explosion. Comparative example 4:
正极活性材料改为 LiCo02， 其余同实施例 1 。 The positive active material was changed to LiCo0 2 , and the rest was the same as in Example 1.
经 1C充 /2C放 100次循环后， 容量衰减为初始容量的 93%, 600次循 环后容量衰减为初始容量的 78%;  After 100 cycles of 1C charge / 2C, the capacity decays to 93% of the initial capacity, and the capacity decay after 600 cycles is 78% of the initial capacity;
1C/18V过充试验， 电池***。 以上内容是结合具体的优选实施方式对本发明所作的进一步详细说 明， 不能认定本发明的具体实施只局限于这些说明。 对于本发明所属技术 领域的普通技术人员来说， 在不脱离本发明构思的前提下， 还可以做出若 干简单推演或替换， 都应当视为属于本发明的保护范围。 1C/18V overcharge test, battery explosion. The above is a further detailed description of the present invention in connection with the specific preferred embodiments, and the specific embodiments of the present invention are not limited to the description. It will be apparent to those skilled in the art that the present invention may be made without departing from the spirit and scope of the invention.

Claims

权 利 要 求 Rights request
1、 一种锂离子电池集流体， 其特征在于： 所述集流体上设置有应力分 散孔。 A lithium ion battery current collector, characterized in that: the current collector is provided with a stress dispersion hole.
2、 根据权利要求 1所述的一种锂离子电池集流体， 其特征在于： 所述 应力分散孔成排分布， 并且每排应力分散孔的中心线与集流体边缘线的夹 角为非直角。  2. A lithium ion battery current collector according to claim 1, wherein: said stress dispersion holes are arranged in a row, and an angle between a center line of each row of stress dispersion holes and a current collector edge line is a non-right angle .
3、 根据权利要求 2所述的一种锂离子电池集流体， 其特征在于： 相邻 的各排应力分散孔之间错位分布。  3. A lithium ion battery current collector according to claim 2, wherein: adjacent rows of stress dispersion holes are misaligned.
4、 根据权利要求 3所述的一种锂离子电池集流体， 其特征在于： 所述 错位分布是指在垂直于集流体侧边的同一直线上最多分布有 1 个应力分散 孔。  4. A lithium ion battery current collector according to claim 3, wherein: said misalignment distribution means that at most one stress dispersion hole is distributed on the same straight line perpendicular to the side of the current collector.
5、 根据权利要求 4所述的一种锂离子电池集流体， 其特征在于： 所述 应力分散孔的直径为 0.02〜0.20mm， 并且每排应力分散孔的中心线间距为 集流体宽度的 0.5〜10倍，同一排的应力分散孔的孔间距为孔径的 2〜10倍。  5. The lithium ion battery current collector according to claim 4, wherein: the stress dispersion hole has a diameter of 0.02 to 0.20 mm, and a center line pitch of each of the stress dispersion holes is 0.5 of a current collector width. ~10 times, the hole spacing of the stress relief holes of the same row is 2 to 10 times the pore diameter.
6、 根据权利要求 5所述的一种锂离子电池集流体， 其特征在于： 所述 应力分散孔的直径为 0.04〜0.08mm。  6. A lithium ion battery current collector according to claim 5, wherein: said stress dispersion hole has a diameter of 0.04 to 0.08 mm.
7、 根据权利要求 5所述的一种锂离子电池集流体， 其特征在于： 每排 应力分散孔的中心线与集流体的边缘线呈 30〜60度夹角， 且所述应力分散 孔为圆孔。  7. The lithium ion battery current collector according to claim 5, wherein: the center line of each row of stress dispersion holes and the edge line of the current collector are at an angle of 30 to 60 degrees, and the stress dispersion hole is Round hole.
8、 根据权利要求 4所述的一种锂离子电池集流体， 其特征在于： 每排 应力分散孔相互平行分布或者呈锯齿状分布。  8. A lithium ion battery current collector according to claim 4, wherein each of the stress dispersion holes is distributed in parallel or in a zigzag pattern.
9、 根据权利要求 1〜8任意一项所述的一种锂离子电池集流体， 其特 征在于： 所述集流体为正极集流体， 且所述集流体为铝箔。  A lithium ion battery current collector according to any one of claims 1 to 8, wherein the current collector is a positive electrode current collector, and the current collector is an aluminum foil.
10、 根据权利要求 1〜8任意一项所述的一种锂离子电池集流体， 其特 征在于： 所述集流体为负极集流体， 且所述集流体为铜箔。  The lithium ion battery current collector according to any one of claims 1 to 8, wherein the current collector is a negative electrode current collector, and the current collector is a copper foil.
11、 一种高容量圆柱形锂离子电池， 包括正极片与负极片， 其特征在 于： 所述正极片的集流体为权利要求 9所述的集流体， 和 /或所述负极片的 集流体为权利要求 10所述的集流体。 A high-capacity cylindrical lithium ion battery comprising a positive electrode sheet and a negative electrode sheet, characterized in that: the current collector of the positive electrode sheet is the current collector according to claim 9, and/or the current collector of the negative electrode sheet The current collector of claim 10.
12、 根据权利要求 11所述的一种高容量圆柱形锂离子电池， 其特征在 于： 所述正极片和 /或负极片的集流体上连续涂布有活性材料涂层， 并且在 集流体的两侧边分别预留有不涂活性材料的条形空箔部位 A和 B,正极片、 负极片及隔膜一起卷绕形成极组后， 正 /负极片上的条形空箔部位 B分别位 于极组的两端， 且正 /负极的引出用集电体分别从正 /负极片的集流体上的条 形空箔部位 B引出。 12. The high capacity cylindrical lithium ion battery according to claim 11, wherein: the current collector of the positive electrode sheet and/or the negative electrode sheet is continuously coated with an active material coating, and is in a current collector. The strip-shaped empty foil portions A and B which are not coated with the active material are reserved on both sides, and the positive electrode sheet, the negative electrode sheet and the separator are wound together to form a pole group, and the strip-shaped empty foil portions B on the positive/negative electrode sheets are respectively located at the poles The collectors for the extraction of the positive/negative electrodes at both ends of the group are respectively taken out from the strip-shaped empty foil portion B on the current collector of the positive/negative electrode sheets.
13、 根据权利要求 12所述的一种高容量圆柱形锂离子电池， 其特征在 于： 所述条形空箔部位 A的宽度为 0.20〜2.0mm， B的宽度为 5.0〜30mm。  A high-capacity cylindrical lithium ion battery according to claim 12, wherein: said strip-shaped empty foil portion A has a width of 0.20 to 2.0 mm, and B has a width of 5.0 to 30 mm.
14、 根据权利要求 12所述的一种高容量圆柱形锂离子电池， 其特征在 于： 所述锂离子电池的正极活性材料为磷酸亚铁锂系活性材料。  A high-capacity cylindrical lithium ion battery according to claim 12, wherein the positive electrode active material of the lithium ion battery is a lithium iron phosphate-based active material.
15、 根据权利要求 14所述的一种高容量圆柱形锂离子电池， 其特征在 于： 所述锂离子电池的正极活性材料为炭包覆的 LiFea99NbaQ1P04。 15. A high capacity cylindrical lithium ion battery according to claim 14, wherein: the positive active material of the lithium ion battery is carbon coated LiFe a99 Nb aQ1 P0 4 .
16、 一种高容量圆柱形锂离子电池的制备方法， 所述方法包括： a、在正极集流体和 /或负极集流体上连续涂布活性材料涂层， 并在集流 体的两侧分别预留有不涂活性材料的条形空箔部位 A 和 B， A 的宽度为 0.20〜2.0mm， B的宽度为 5.0〜30mm， 所述正极片的集流体为权利要求 8 所述的集流体， 和 /或所述负极片的集流体为权利要求 9所述的集流体； b、将正极片、 负极片及隔膜一起卷绕形成极组， 使正 /负极片上的条形 空箔部位 B分别位于极组的两端；  16. A method of preparing a high capacity cylindrical lithium ion battery, the method comprising: a. continuously coating an active material coating on a positive current collector and/or a negative current collector, and pre-preserving each side of the current collector The strip-shaped empty foil portions A and B which are not coated with the active material, the width of A is 0.20 to 2.0 mm, the width of B is 5.0 to 30 mm, and the current collector of the positive electrode sheet is the current collector according to claim 8. And/or the current collector of the negative electrode sheet is the current collector according to claim 9; b, the positive electrode sheet, the negative electrode sheet and the separator are wound together to form a pole group, and the strip-shaped empty foil portion B on the positive/negative electrode sheet is respectively Located at both ends of the pole group;
c、 将正 /负极引出用集电体分别从正 /负极片的集流体上的条形空箔部 位 B引出。  c. The positive/negative lead extraction current collectors are respectively taken out from the strip-shaped empty foil portion B on the current collector of the positive/negative electrode sheets.
17、 根据权利要求 16所述的制备方法， 其特征在于： 所述锂离子电池 的正极活性材料为磷酸亚铁锂系活性材料。  The method according to claim 16, wherein the positive electrode active material of the lithium ion battery is a lithium iron phosphate active material.
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CN113725475B (en) * 2020-05-26 2023-05-30 深圳格林德能源集团有限公司 Method for improving powder falling phenomenon at first crease of lithium ion battery negative plate
CN113488617A (en) * 2021-05-08 2021-10-08 上海兰钧新能源科技有限公司 Preparation method of lithium ion battery pole piece
CN114597332A (en) * 2021-12-02 2022-06-07 万向一二三股份公司 High-energy-density pole piece structure for increasing tensile strength of pole piece

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