WO2022057666A1 - 一种正极片及电池 - Google Patents

一种正极片及电池 Download PDF

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Publication number
WO2022057666A1
WO2022057666A1 PCT/CN2021/116763 CN2021116763W WO2022057666A1 WO 2022057666 A1 WO2022057666 A1 WO 2022057666A1 CN 2021116763 W CN2021116763 W CN 2021116763W WO 2022057666 A1 WO2022057666 A1 WO 2022057666A1
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Prior art keywords
coating area
negative electrode
coating
positive electrode
material layer
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PCT/CN2021/116763
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English (en)
French (fr)
Inventor
李根宗
彭冲
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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 EP21868491.8A priority Critical patent/EP4071866A1/en
Publication of WO2022057666A1 publication Critical patent/WO2022057666A1/zh
Priority to US17/811,475 priority patent/US20220344645A1/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
    • H01M4/64—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
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application belongs to the technical field of lithium ion batteries, and in particular relates to a positive electrode sheet and a battery.
  • lithium-ion batteries are widely used in all walks of life as environmentally friendly green energy. Consumer electronic products have higher and higher requirements for the service life and fast charging capacity of lithium secondary batteries. In order to meet customer needs, the capacity of lithium ion batteries is getting larger and larger, and the charging rate is also increasing.
  • the pole piece of a lithium ion battery it is usually necessary to coat a layer of active material on the surface of the pole piece, and ion exchange between the positive and negative active materials of the positive electrode piece and the negative electrode piece realizes charging and discharging.
  • the battery capacity increases and the charging rate increases, it is easy to cause the temperature of the pole pieces of the lithium-ion battery to increase during the charging and discharging process, which will cause thermal runaway and cause safety problems. It can be seen that the safety of the battery in the prior art is relatively low.
  • the embodiments of the present application provide a positive electrode sheet and a battery to solve the problem of low safety of the battery in the prior art.
  • an embodiment of the present application provides a positive electrode sheet, including a positive electrode current collector, one side or both sides of the positive electrode current collector is coated with a first coating area, a second coating area and a third coating area area, the first coating area, the second coating area and the third coating area are distributed along a first direction, and the first direction is the length direction of the positive electrode current collector; in the width of the positive electrode current collector In the direction, the second coating area is located between the first coating area and the third coating area;
  • the first coating area and the third coating area are coated with a positive electrode active material layer, the second coating area is coated with a porous material layer, the pore size of the porous material layer is greater than 50 nm, and the porosity is greater than 30%. .
  • the porous material layer includes a porous insulating material and a binder; or, an inorganic ionic material and a binder; or, a porous insulating material, an inorganic ionic material and a binder.
  • the porous material layer includes ceramic powder, inorganic ionic material and binder, and the mass ratio of the ceramic powder, inorganic ionic material and binder is (70%-95%): (5%-20%) %): (0% to 10%).
  • the particle size of the ceramic powder is 0.5-50 ⁇ m.
  • the coating width of the first coating area is equal to the coating width of the third coating area, and the coating width of the second coating area is the same as the coating width of the first coating area.
  • the cloth width ratio is 1/40 ⁇ 3/8.
  • an embodiment of the present application further provides a battery, including a negative electrode sheet, a separator, and the positive electrode sheet described in any one of the above.
  • the negative electrode sheet includes a negative electrode current collector, and one side or both sides of the negative electrode current collector is coated with a fourth coating area, a fifth coating area and a sixth coating area, and the fourth coating area is coated.
  • the distribution area, the fifth coating area and the sixth coating area are distributed along a second direction, the second direction is the length direction of the negative electrode current collector, and the fifth coating area is located in the fourth coating area and the sixth coating zone;
  • the fourth coating area and the sixth coating area are coated with a first negative electrode active material layer, the fifth coating area is coated with a second negative electrode active material layer, and the second negative electrode active material layer
  • the mass ratio of the conductive agent in the first negative electrode active material layer is greater than the mass ratio of the conductive agent in the first negative electrode active material layer.
  • the second negative electrode active material layer includes a conductive agent, a negative electrode active material and a binder, and the mass ratio of the conductive agent, the negative electrode active material and the binder is (50% to 90%): (0 % ⁇ 20%): (5% ⁇ 15%).
  • the particle size of the conductive agent and the negative electrode active material is 15-50 ⁇ m.
  • the length of the positive electrode current collector is less than or equal to the length of the negative electrode current collector
  • the width of the positive electrode current collector is less than or equal to the width of the negative electrode current collector
  • the coating of the second coating area The width is less than or equal to the coating width of the fifth coating area; the second coating area and the fifth coating area are arranged opposite to each other.
  • the first coating area, the second coating area and the third coating area are coated along the length direction, and the first coating area and the third coating area are coated with positive electrode activity material, the second coating area is located between the first coating area and the third coating area, and is a porous material layer. Since the large porosity material of the porous material layer can effectively increase the heat dissipation area, at the same time, due to the reduction in the content of the positive active material, the internal resistance of the pole piece will also be reduced, which can effectively reduce the battery during the charge and discharge cycle during the charge and discharge process. The increased resistance heat due to the internal resistance can improve the heat dissipation efficiency, thereby avoiding the instability of the electrochemical system caused by the high temperature during the charge-discharge cycle, resulting in safety problems, thereby improving the safety of the battery.
  • FIG. 1 is a schematic structural diagram of a positive electrode sheet provided by an embodiment of the present application.
  • FIG. 2 is a schematic structural diagram of a negative electrode sheet provided in an embodiment of the present application.
  • an embodiment of the present application provides a positive electrode sheet, including a positive electrode current collector 100 , one side or both sides of the positive electrode current collector 100 is coated with a first coating area 110 , a second coating area 120 and The third coating area 130 , the first coating area 110 , the second coating area 120 and the third coating area 130 are distributed along a first direction, and the first direction is the length direction of the positive electrode current collector 100 ; In the width direction of the positive electrode current collector, the second coating area 120 is located between the first coating area 110 and the third coating area 130;
  • the first coating area 110 and the third coating area 130 are coated with a positive electrode active material layer, the second coating area 120 is coated with a porous material layer, and the pore size of the porous material layer is greater than 50 nm.
  • the porosity is greater than 30%.
  • the positive electrode current collector 100 may be an aluminum foil.
  • the positive electrode current collector 100 may be wound into a part of a battery core, and the length direction of the positive electrode current collector 100 may be the positive electrode current collector 100 described above. the winding direction or the direction opposite to the winding direction.
  • the first coating area 110 , the second coating area 120 and the third coating area 130 are all coated along the first direction.
  • the above-mentioned porous material layer may include insulating materials such as ceramic powder or resin material, may also be a large-porous positive electrode active material, etc., or may include porous ceramic insulating materials and/or inorganic ionic materials, so that both insulation and resistance can be achieved.
  • insulating materials such as ceramic powder or resin material
  • the effect of burning is not further limited here.
  • the pore size of the porous material layer can be greater than 50 nm and the porosity is greater than 30%.
  • the above-mentioned positive electrode active material layer may include one or more of lithium phosphate cobalt oxide, lithium nickel cobalt manganate, lithium iron phosphate, lithium nickel cobalt aluminate or lithium iron manganese phosphate.
  • Common cathode active materials for lithium ion batteries and may also include materials such as conductive agents and binders.
  • the above-mentioned binder can be polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyamide The group consisting of vinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, styrene-butadiene rubber, and combinations thereof.
  • the first coating area 110 , the second coating area 120 and the third coating area 130 , and the first coating area 110 and the third coating area are coated along the length direction.
  • 130 coats the positive electrode active material
  • the second coating area 120 is located between the first coating area 110 and the third coating area 130 and is a porous material layer. Since the large porosity material of the porous material layer can effectively increase the heat dissipation area, at the same time, due to the reduction in the content of the positive active material, the internal resistance of the pole piece will also be reduced, which can effectively reduce the battery during the charge and discharge cycle during the charge and discharge process. The increased resistance heat due to the internal resistance can improve the heat dissipation efficiency, thereby avoiding the instability of the electrochemical system caused by the high temperature during the charge-discharge cycle, resulting in safety problems, thereby improving the safety of the battery.
  • the porous material layer with large pores has more space capacity to store the electrolyte, so it is beneficial to improve the cycle life of the battery during use, that is, with the increase of the number of cycles, The capacity retention rate is reduced to a lesser extent.
  • the porous material layer may include a porous insulating material and a binder, or an inorganic ionic material and a binder.
  • the porous material layer may include a porous insulating material and a binder, so that an insulating tape is formed on the positive electrode active material in the first coating region 110 and the third coating region 130 .
  • the inorganic ionic material in the porous material layer can play a flame retardant effect, reduce the risk of thermal runaway, and further improve the safety of the battery.
  • the above-mentioned porous material layer may also include an inorganic ionic material and a binder.
  • the porous material layer includes ceramic powder, inorganic ionic material and binder, and the mass ratio of the ceramic powder, inorganic ionic material and binder is (70%-95%): (5%-20%) %): (0% to 10%).
  • the above-mentioned porous material layer may include two kinds of porous insulating materials, ceramic powder and inorganic ionic material, and the bonding between particles is realized by a binder.
  • the mass percentage of the ceramic powder may be 70% to 95%, preferably 85% to 90%.
  • the mass percentage of the above-mentioned inorganic ionic material may be 5% to 20%, preferably 10% to 15%.
  • the mass percentage of the above-mentioned adhesive may be 0% to 10%, preferably 3% to 5%.
  • the above-mentioned inorganic ionic materials can be alumina, silica, magnesia, titania, hafnium dioxide, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconium dioxide, yttrium oxide, carbide
  • the particle size of the ceramic powder may be 0.5-50 ⁇ m, preferably 10-30 ⁇ m.
  • the coating width of the first coating area 110 is the same as that of all the first coating areas 110.
  • the coating widths of the third coating regions 130 are equal.
  • the coating widths of the first coating area 110 and the second coating area 120 can be set according to actual needs.
  • the ratio of the coating width of the second coating region 120 to the coating width of the first coating region 110 may be 1/40 ⁇ 3/8.
  • the positive electrode active material can be fully coated first, and then laser cleaning is performed along the middle of the coated electrode sheet to form an empty foil area.
  • the porous material layer is coated on the empty foil area, so that the above-mentioned second coating area 120 can be formed, and the original positive electrode active material can be divided into the above-mentioned first coating area 110 and the third coating area 130 .
  • an embodiment of the present application further provides a battery, including a negative electrode sheet, a separator, and the positive electrode sheet as described in any of the foregoing embodiments.
  • the negative electrode sheet includes a negative electrode current collector 200, and one or both sides of the negative electrode current collector 200 are coated with a fourth coating area 210, a fifth coating area 220 and a sixth coating area.
  • area 230, the fourth coating area 210, the fifth coating area 220 and the sixth coating area 230 are distributed along a second direction, and the second direction is the length direction of the negative electrode current collector 200;
  • the fifth coating region 220 is located between the fourth coating region 210 and the sixth coating region 230;
  • the fourth coating area 210 and the sixth coating area 230 are coated with a first negative electrode active material layer, the fifth coating area 220 is coated with a second negative electrode active material layer, and the second negative electrode active material layer is coated
  • the mass ratio of the conductive agent in the active material layer is greater than the mass ratio of the conductive agent in the first negative electrode active material layer.
  • the positive and negative electrode sheets in the battery are usually arranged opposite to each other, the reaction between the positive and negative electrode active materials is realized. Since the second coating region 120 of the positive electrode sheet is a porous material layer, the fifth coating region 220 at the corresponding position of the negative electrode sheet can also be uncoated or coated with less negative electrode active material, and will not be further reduced. battery capacity.
  • the positive electrode sheet and the negative electrode sheet are wound to form a battery core.
  • the second direction may be the winding direction of the negative electrode sheet or the direction opposite to the winding direction.
  • the fifth coating region 220 can be coated with more conductive agents, so that the kinetic performance of the negative electrode can be effectively improved, which is beneficial to meet the requirements of the fast charging system.
  • the second negative electrode active material layer may include a conductive agent, a negative electrode active material and a binder, and the mass ratio of the conductive agent, the negative electrode active material and the binder may be (50% to 90%): ( 0% to 20%): (5% to 15%).
  • the negative electrode current collector 200 may be the negative electrode active material such as copper foil, microporous copper foil, carbon-coated copper foil or material.
  • the above negative electrode active material may include one or more of graphite, hard carbon and artificial graphite.
  • the mass percentage of the conductive agent may be 50% to 90%, preferably 70% to 80%.
  • the mass percentage of the negative electrode active material may be 0-20%, preferably 10-15%.
  • the mass percentage of the above-mentioned binder is 5% to 15%, preferably 8% to 10%.
  • the conductive agent and the negative electrode active material may be large particle materials.
  • the particle size of the conductive agent may be 15-50 ⁇ m; and/or the particle size of the negative electrode active material may be 15-50 ⁇ m.
  • the negative electrode capacity of the negative electrode sheet needs to be slightly larger than the positive electrode capacity of the positive electrode sheet. Therefore, the length of the positive electrode current collector 100 is less than or equal to the length of the negative electrode current collector 200 , the width of the positive electrode current collector 100 is less than or equal to the width of the negative electrode current collector 200 , the second coating region 120 The coating width of 1 is less than or equal to the coating width of the fifth coating area 220 ; the second coating area 120 and the fifth coating area 220 are disposed opposite to each other.
  • the first negative electrode active material can also be completely coated, and then laser cleaning is performed along the middle of the coated electrode piece to form an empty foil area.
  • the second active material is coated on the empty foil area, so that the above-mentioned fifth coating area 220 can be formed, and the original negative electrode active material is divided into the above-mentioned fourth coating area 210 and sixth coating area 230.
  • the separator in the above-mentioned battery can be a lithium-ion battery separator such as a water-based separator, a macroporous oil separator, and a gravure oil-based separator.
  • the method of combining the above-mentioned negative electrode sheet, positive electrode sheet and separator into a battery may be as follows: the above-mentioned positive electrode and negative electrode are combined with winding-packaging-baking liquid injection-chemical formation-two sealing-sorting to obtain the above-mentioned battery.
  • the rolling-slitting-sheeting-winding-packaging-baking liquid injection-chemical formation-two sealing-sorting can all adopt conventional technical means in the art.
  • the "positive and negative active materials”, “binders”, “separators”, “conductive agents” and “current collectors” involved in the following specific embodiments are all conventional materials in lithium ion batteries; Rolling, slitting, and tableting” can all be conventional technical means for preparing lithium ion batteries in the art.
  • This embodiment provides a lithium-ion battery with reduced temperature rise and increased life cycle, the specific method is:
  • NMP N-methylpyrrolidone
  • a slurry PB made of 85% ceramic powder, 10% inorganic ionic material and 5% binder was applied to the empty foil area to obtain a positive electrode piece; 96.5% graphite, 0.5% conductive agent and A mixture consisting of 3% binder is uniformly dispersed in NMP solvent to make negative electrode slurry NA; the slurry NA is placed in a coating machine and coated, and the coating method includes extrusion coating, One of transfer coating and roller coating, the coated pole piece is laser cleaned to the empty foil area with a width of NW2, and the empty foil area is coated with a ratio of 80% conductive agent, 12% hard carbon and 8 % of the slurry NB made of the binder, to obtain a negative pole piece; after drying and rolling the positive pole piece and the negative pole piece, the required positive pole piece can be obtained.
  • the above-mentioned positive electrode and negative electrode are combined with winding-packaging-baking liquid injection-chemical formation-two sealing-sorting to obtain a lithium ion battery
  • the rolling-slitting-making-rolling Winding-encapsulation-baking liquid injection-chemical formation-two sealing-sorting can all use conventional technical means in the art.
  • a lithium-ion battery with reduced temperature rise and increased life cycle the difference from Example 1 is that the diameter of the ceramic particles is 25 microns.
  • a lithium-ion battery with reduced temperature rise and increased life cycle the difference from Example 1 is that the diameter of the ceramic particles is 30 microns.
  • a lithium-ion battery the difference from Example 1 is that there is no leakage foil coating area in the middle.
  • the above-mentioned battery was tested at room temperature: 100 and 300 cycles at 25°C, 1.5C/1C, and the temperature rise was tested.
  • the test method is as follows: at 25°C, the lithium-ion battery is fully charged at 1.5C to the rated voltage and then discharged at 1C, and the charge and discharge are both terminated at 0.05C.
  • Table 1 The specific results are shown in Table 1:

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Abstract

本申请提供一种正极片及电池，所述正极片包括正极集流体，所述正极集流体的一侧或两侧涂布有第一涂布区、第二涂布区和第三涂布区，所述第一涂布区、第二涂布区与第三涂布区沿第一方向分布，所述第一方向为所述正极集流体的长度方向；在所述正极集流体的宽度方向上，所述第二涂布区位于所述第一涂布区和所述第三涂布区之间；所述第一涂布区与所述第三涂布区涂布有正极活性材料层，所述第二涂布区涂布有多孔材料层，所述多孔材料层的孔径大于50nm，孔隙率大于30％。本申请实施例可以提升电池的安全性。

Description

一种正极片及电池
本申请要求于2020年09月21日提交中国专利局、申请号为202010995089.5、申请名称为“一种正极片及电池”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
本申请属于锂离子电池技术领域，具体涉及一种正极片及电池。
背景技术
当今，锂离子电池作为环保型绿色能源在各行各业广泛应用。消费类电子产品对于锂二次电池的使用寿命和快充能力要求越来越高，为了满足客户需求，锂离子电池容量越做越大，充电倍率也在不断提高。
现有技术中，对于锂离子电池的极片而言，通常需要在极片的表面涂布一层活性材料，正极片和负极片的正负极活性材料间的离子交换实现充放电。但当电池容量增大以及充电倍率增加时，容易导致锂离子电池的极片在充放电过程中温度升高，从而引发热失控，造成安全问题。可见现有技术中电池的安全性较低。
发明内容
本申请实施例提供一种正极片及电池，以解决现有技术中电池的安全性较低的问题。
第一方面，本申请实施例提供了一种正极片，包括正极集流体，所述正极集流体的一侧或两侧涂布有第一涂布区、第二涂布区和第三涂布区，所述第一涂布区、第二涂布区与第三涂布区沿第一方向分布，所述第一方向为所述正极集流体的长度方向；在所述正极集流体的宽度方向上，所述第二涂布区位于所述第一涂布区和所述第三涂布区之间；
所述第一涂布区与所述第三涂布区涂布有正极活性材料层，所述第二涂布区涂布有多孔材料层，所述多孔材料层的孔径大于50nm，孔隙率大于30％。。
可选的，所述多孔材料层包括多孔绝缘材料和粘结剂；或者，无机离子材料和粘结剂；或者，多孔绝缘材料、无机离子材料和粘结剂。
可选的，所述多孔材料层包括陶瓷粉、无机离子材料和粘结剂，所述陶瓷粉、无机离子材料和粘结剂的质量比为(70％～95％)：(5％～20％)：(0％～10％)。
可选的，所述陶瓷粉的粒径为0.5～50μm。
可选的，所述第一涂布区的涂布宽度与所述第三涂布区的涂布宽度相等，所述第二涂布区的涂布宽度与所述第一涂布区的涂布宽度比为1/40～3/8。
第二方面，本申请实施例还提供一种电池，包括负极片、隔膜和如上任一项所述的正极片。
可选的，所述负极片包括负极集流体，所述负极集流体的一侧或两侧涂布有第四涂布区、第五涂布区和第六涂布区，所述第四涂布区、第五涂布区和第六涂布区沿第二方向分布，所述第二方向为所述负极集流体的长度方向，所述第五涂布区位于所述第四涂布区和所述第六涂布区之间；
所述第四涂布区与所述第六涂布区涂布有第一负极活性材料层，所述第五涂布区涂布有第二负极活性材料层，所述第二负极活性材料层中导电剂所占的质量比大于所述第一负极活性材料层中导电剂所占的质量比。
可选的，所述第二负极活性材料层包括导电剂、负极活性材料和粘结剂，所述导电剂、负极活性材料和粘结剂的质量比为(50％～90％)：(0％～20％)：(5％～15％)。
可选的，所述导电剂和所述负极活性材料的粒径为15～50μm。
可选的，所述正极集流体的长度小于或等于所述负极集流体的长度，所述正极集流体的宽度小于或等于所述负极集流体的宽度，所述第二涂布区的涂布宽度小于或等于所述第五涂布区的涂布宽度；所述第二涂布区所述第五涂布区相对设置。
本申请实施例在正极片的集流体上，沿长度方向涂布第一涂布区、第二涂布区和第三涂布区，第一涂布区和第三涂布区涂布正极活性材料，第二涂布区位于第一涂布区和第三涂布区之间，且为多孔材料层。由于多孔材料层的大孔隙率材料能够有效的增加散热面积，同时，由于正极活性材料的含量减少，极片内阻也会减小，在充放电循环过程中能够有效的降低充放电过程中电池本身由于内阻而增加的阻抗热以及能够提升散热效率，从而避免在充 放电循环过程中由于温度过高而引发的电化学体系不稳定，导致的安全问题，进而提升电池的安全性。
附图说明
图1为本申请实施例提供的正极片的结构示意图；
图2为本申请实施例提供的负极片的结构示意图。
具体实施方式
下面将结合本申请实施例中的附图，对本申请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申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获取的所有其他实施例，都属于本申请保护的范围。
参照图1，本申请实施例提供了一种正极片，包括正极集流体100，所述正极集流体100的一侧或两侧涂布有第一涂布区110、第二涂布区120和第三涂布区130，所述第一涂布区110、第二涂布区120与第三涂布区130沿第一方向分布，所述第一方向为所述正极集流体100的长度方向；在所述正极集流体的宽度方向上，所述第二涂布区120位于所述第一涂布区110和所述第三涂布区130之间；
所述第一涂布区110与所述第三涂布区130涂布有正极活性材料层，所述第二涂布区120涂布有多孔材料层，所述多孔材料层的孔径大于50nm，孔隙率大于30％。
在本申请实施例中，上述正极集流体100可以为铝箔，在电池中，上述正极集流体100卷绕成电池卷芯的一部分，上述正极集流体100的长度方向，可以为上述正极集流体100的卷绕方向或者与卷绕方向相反的方向。上述第一涂布区110、第二涂布区120和第三涂布区130均沿上述第一方向涂布。
其中，上述多孔材料层可以包括陶瓷粉或树脂材料等绝缘材料，也可以为大孔隙的正极活性材料等，也可以包括多孔陶瓷绝缘材料和/或无机离子材料，从而可以同时起到绝缘和阻燃的效果，在此不作进一步的限定。
为了提升上述多孔材料层储存电解液的能力，并同时增加散热面积，上述多孔材料层的孔径可以大于50nm，孔隙率大于30％。
具体的，上述正极活性材料层中可以包括磷钴酸锂、镍钴锰酸锂、磷酸铁锂、镍钴铝酸锂或磷酸铁锰锂的一种或几种的锂离子电池常见正极活性材料，还可以包括导电剂和粘结剂等材料。
其中，上述粘结剂可以为聚偏氟乙烯、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、羧甲基纤维素钠、聚乙烯吡咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯、聚六氟丙烯、丁苯橡胶及其组合所组成的群组。
本申请实施例在正极片的集流体上，沿长度方向涂布第一涂布区110、第二涂布区120和第三涂布区130，第一涂布区110和第三涂布区130涂布正极活性材料，第二涂布区120位于第一涂布区110和第三涂布区130之间，且为多孔材料层。由于多孔材料层的大孔隙率材料能够有效的增加散热面积，同时，由于正极活性材料的含量减少，极片内阻也会减小，在充放电循环过程中能够有效的降低充放电过程中电池本身由于内阻而增加的阻抗热以及能够提升散热效率，从而避免在充放电循环过程中由于温度过高而引发的电化学体系不稳定，导致的安全问题，进而提升电池的安全性。
需要说明的是，由于大孔隙的多孔材料层与正极活性材料层相比，具有更多的空间容量储存电解液，因此有利于提升电池使用过程中的循环寿命，即随着循环次数的增加，容量保持率减小的程度有所降低。
进一步的，所述多孔材料层可以包括多孔绝缘材料和粘结剂，或者，无机离子材料和粘结剂。
由于正极片在发生短路时，可能引发局部的热失控，进而导致极片燃烧。在本申请实施例中，上述多孔材料层可以包括多孔绝缘材料和粘接剂，从而在上述第一涂布区110和上述第三涂布区130的正极活性材料形成了绝缘带。当发生短路时，多孔材料层中的无机离子材料可以起到阻燃的效果，降低热失控带来的风险，进一步提升了电池的安全性。
可以理解的是，为了实现上述的阻燃效果，上述多孔材料层也可以包括无机离子材料和粘结剂。
可选的，所述多孔材料层包括陶瓷粉、无机离子材料和粘结剂，所述陶瓷粉、无机离子材料和粘结剂的质量比为(70％～95％)：(5％～20％)：(0％～10％)。
在本申请实施例中，上述多孔材料层可以包括陶瓷粉和无机离子材料这 两种多孔绝缘材料，并通过粘结剂实现颗粒间的粘接。上述陶瓷粉的质量百分比可以为70％～95％，优选为85％～90％。相应的，上述无机离子材料的质量百分比可以为5％～20％，优选为10％～15％。上述粘接剂的质量百分比可以为0％～10％，优选为3％～5％。
具体的，上述无机离子材料可以为氧化铝、二氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、二氧化锆、氧化钇、碳化硅、勃姆石、氢氧化镁、氢氧化钙、氢氧化铝、硫酸坝及其组合所组成的群组。
进一步的，所述陶瓷粉的粒径可以为0.5～50μm，优选为10～30μm。
进一步的，为了确保上述第一涂布区110和上述第三涂布区130的散热均匀，即保证上述正极片整体的温度分布较为均匀，所述第一涂布区110的涂布宽度与所述第三涂布区130的涂布宽度相等。
具体的，由于第二涂布区120的涂布宽度越宽，散热能力越好，但第一涂布区110和第三涂布区130的涂布宽度会相应变窄，正极活性材料减少，电池容量会相应减小。因此，上述第一涂布区110和第二涂布区120的涂布宽度可以根据实际需要进行设置。在本申请实施例中，所述第二涂布区120的涂布宽度与所述第一涂布区110的涂布宽度比可以为1/40～3/8。
需要说明的是，上述正极片中，可以先全部涂布正极活性材料，而后对于涂后的极片沿中部进行激光清洗，形成空箔区域。在空箔区域涂布多孔材料层，从而可以形成上述第二涂布区120，并将原来的正极活性材料分隔为上述第一涂布区110和第三涂布区130。
第二方面，本申请实施例还提供一种电池，包括负极片、隔膜和如上述任一实施例所述的正极片。
进一步的，参照图2，所述负极片包括负极集流体200，所述负极集流体200的一侧或两侧涂布有第四涂布区210、第五涂布区220和第六涂布区230，所述第四涂布区210、第五涂布区220和第六涂布区230沿第二方向分布，所述第二方向为所述负极集流体200的长度方向；在所述负极集流体的宽度方向上，所述第五涂布区220位于所述第四涂布区210和所述第六涂布区230之间；
所述第四涂布区210与所述第六涂布区230涂布有第一负极活性材料层， 所述第五涂布区220涂布有第二负极活性材料层，所述第二负极活性材料层中导电剂所占的质量比大于所述第一负极活性材料层中导电剂所占的质量比。
在本申请实施例中，由于电池中的正负极片通常为相对设置，从而实现正负极活性材料间的反应。由于上述正极片的第二涂布区120为多孔材料层，因此，负极片相应位置的第五涂布区220也可以不涂布或者涂布较少的负极活性材料，而不会因此进一步降低电池容量。
与上述正极片类似，在电池中，正极片和负极片卷绕形成电池卷芯。上述第二方向，即可以为上述负极片的卷绕方向或者与卷绕方向相反的方向。
具体的，上述第五涂布区220可以涂布有更多的导电剂，从而可以有效提升负极动力学性能，有利于满足快充体系的需求。
进一步的，所述第二负极活性材料层可以包括导电剂、负极活性材料和粘结剂，所述导电剂、负极活性材料和粘结剂的质量比可以为(50％～90％)：(0％～20％)：(5％～15％)。
其中，上述负极集流体200可以为上述负极活性材料可以铜箔、微孔铜箔、涂炭铜箔或者材料。上述负极活性材料可以包括石墨、硬碳和人工石墨中的一种或几种。上述导电剂的质量百分比可以为50％～90％，优选为70％～80％。上述负极活性材料的质量百分比可以为0～20％，优选为10％～15％。上述粘结剂的质量百分比为5％～15％，优选为8％～10％。
进一步的，为了提升负极片对于电解液的容量，所述导电剂和所述负极活性材料可以为大颗粒材料。具体的，上述导电剂的粒径可以为15～50μm；和/或，上述负极活性材料的粒径可以为15～50μm。
进一步的，为了减少电池的析锂风险，上述负极片的负极容量需要略大于上述正极片的正极容量。因此，所述正极集流体100的长度小于或等于所述负极集流体200的长度，所述正极集流体100的宽度小于或等于所述负极集流体200的宽度，所述第二涂布区120的涂布宽度小于或等于所述第五涂布区220的涂布宽度；所述第二涂布区120所述第五涂布区220相对设置。
上述负极片中，也可以先全部涂布第一负极活性材料，而后对于涂后的极片沿中部进行激光清洗，形成空箔区域。在空箔区域涂布第二活性材料，从而可以形成上述第五涂布区220，并将原来的负极活性材料分隔为上述第四 涂布区210和第六涂布区230。
进一步的，上述电池中的隔膜可以为水系隔膜、大孔油析和凹版油系等锂离子电池隔膜。将上述负极片、正极片和隔膜组合制成电池的方法，可以为：将上述正极和负极配合卷绕-封装-烘烤注液-化成-二封-分选得到上述电池。所述辊压-分切-制片-卷绕-封装-烘烤注液-化成-二封-分选，均可以采用本领域常规技术手段。
下面将以具体的实施例，详细阐述本申请的实现方式。
以下具体实施方式中涉及到的“正负极活性物质”“粘结剂”、“隔膜”“导电剂”、“集流体”均为锂离子电池中的常规材料；所涉及到的“干燥、辊压、分切、制片”均可以为本领域制备锂离子电池常规的技术手段。
实施例1
本实施例提供了一种降低温升和增加寿命循环的锂离子电池，具体方法为：
采用97.8％的钴酸锂，1.1％的导电剂和1.1％的粘结剂组成的混合物，均匀分散在N-甲基吡咯烷酮(NMP)溶剂中制成正极浆料P-A；将浆料P-A置于涂布机中，进行涂布，所述涂布方式包括挤压式涂布、转移式涂布、辊涂式涂布的一种，对于涂后的极片进行激光清洗宽度为PW2的空箔区域，对空箔区域涂覆采用比例85％陶瓷粉、10％无机离子材料和5％粘结剂制成的浆料P-B，得到正极极片；采用96.5％的石墨，0.5％的导电剂和3％的粘结剂组成的混合物，均匀分散在NMP溶剂中制成负极浆料N-A；将浆料N-A置于涂布机中，进行涂布，所述涂布方式包括挤压式涂布、转移式涂布、辊涂式涂布的一种，对于涂后的极片进行激光清洗宽度为NW2的空箔区域，对空箔区域涂覆采用比例80％导电剂、12％硬碳和8％粘结剂制成的浆料N-B，得到负极极片；将所述正极片和负极片进行烘干、辊压后，即可得到要求的正极极片。在本实施例中，PW2/PW1＝1/8，NW2/NW1＝3/20，陶瓷颗粒直径为20微米，大颗粒物质直径为30微米。
进一步的，使用行业内常见的方法，将上述正极和负极配合卷绕-封装-烘烤注液-化成-二封-分选得到锂离子电池，所述辊压-分切-制片-卷绕-封装-烘烤注液-化成-二封-分选，均可以采用本领域常规技术手段。
实施例2
一种降低温升和增加寿命循环的锂离子电池，与实施例1的区别在于，陶瓷颗粒直径为25微米。
实施例3
一种降低温升和增加寿命循环的锂离子电池，与实施例1的区别在于，陶瓷颗粒直径为30微米。
对比例1
一种锂离子电池，与实施例1的区别在于，中间没有漏空箔涂覆区域。
采用最常规的方法，对上述电池进行常温循环测试：25℃，1.5C/1C循环100次和300次，测试温升。所述测试方法为：在25℃下，将锂离子电池以1.5C充满至额定电压后1C放电，充放电均以0.05C截止。具体结果如表一：
表一
Figure PCTCN2021116763-appb-000001
由上表可以看出，与对比例1相比，实施例1、2、3的100次和300次循环保持率更好，这表明通过极片中间留空箔涂覆多孔物质的方法，可以有效的提高电池的循环性能。通过测试循环1次和100次电池的温升，发现实施例1、2、3的温升明显低于对比例1，这表明通过极片中间留空箔涂覆多孔物质的方法，可以有效降低电池的温升。
以上，仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应以权利要求的保护范围为准。

Claims (13)

  1. 一种正极片，包括正极集流体，其中，所述正极集流体的一侧或两侧涂布有第一涂布区、第二涂布区和第三涂布区，所述第一涂布区、第二涂布区与第三涂布区沿第一方向分布，所述第一方向为所述正极集流体的长度方向；在所述正极集流体的宽度方向上，所述第二涂布区位于所述第一涂布区和所述第三涂布区之间；
    所述第一涂布区与所述第三涂布区涂布有正极活性材料层，所述第二涂布区涂布有多孔材料层，所述多孔材料层的孔径大于50nm，孔隙率大于30％。
  2. 根据权利要求1所述的正极片，其中，所述多孔材料层包括多孔绝缘材料和粘结剂；或者，无机离子材料和粘结剂；或者，多孔绝缘材料、无机离子材料和粘结剂。
  3. 根据权利要求1或2所述的正极片，其中，所述多孔材料层包括陶瓷粉、无机离子材料和粘结剂，所述陶瓷粉、无机离子材料和粘结剂的质量比为(70％～95％)：(5％～20％)：(0％～10％)。
  4. 根据权利要求3所述的正极片，其中，所述多孔材料层包括陶瓷粉、无机离子材料和粘结剂，所述陶瓷粉、无机离子材料和粘结剂的质量比为(85％～90％)：(10％～15％)：(3％～5％)。
  5. 根据权利要求3或4所述的正极片，其中，所述陶瓷粉的粒径为0.5～50μm。
  6. 根据权利要求5所述的正极片，其中，所述陶瓷粉的粒径为10～30μm。
  7. 根据权利要求1-6任一项所述的正极片，其中，所述第一涂布区的涂布宽度与所述第三涂布区的涂布宽度相等，所述第二涂布区的涂布宽度与所述第一涂布区的涂布宽度比为1/40～3/8。
  8. 一种电池，其中，包括负极片、隔膜和如权利要求1～7中任一项所述的正极片。
  9. 根据权利要求8所述的电池，其中，所述负极片包括负极集流体，所述负极集流体的一侧或两侧涂布有第四涂布区、第五涂布区和第六涂布区，所述第四涂布区、第五涂布区和第六涂布区沿第二方向分布，所述第二方向为所述负极集流体的长度方向；在所述负极集流体的宽度方向上，所述第五涂布区位于所述第四涂布区和所述第六涂布区之间；
    所述第四涂布区与所述第六涂布区涂布有第一负极活性材料层，所述第五涂布区涂布有第二负极活性材料层，所述第二负极活性材料层中导电剂所占的质量比大于所述第一负极活性材料层中导电剂所占的质量比。
  10. 根据权利要求9所述的电池，其中，所述第二负极活性材料层包括导电剂、负极活性材料和粘结剂，所述导电剂、负极活性材料和粘结剂的质量比为(50％～90％)：(0％～20％)：(5％～15％)。
  11. 根据权利要求10所述的电池，其中，所述第二负极活性材料层包括导电剂、负极活性材料和粘结剂，所述导电剂、负极活性材料和粘结剂的质量比为(70％～80％)：(10％～15％)：(8％～10％)。
  12. 根据权利要求10或11所述的电池，其中，所述导电剂的粒径为15～50μm；和/或，所述负极活性材料的粒径为15～50μm。
  13. 根据权利要求9-12任一项所述的电池，其中，所述正极集流体的长度小于或等于所述负极集流体的长度，所述正极集流体的宽度小于或等于所述负极集流体的宽度，所述第二涂布区的涂布宽度小于或等于所述第五涂布区的涂布宽度；所述第二涂布区所述第五涂布区相对设置。
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