WO2020098768A1 - 一种电池 - Google Patents

一种电池 Download PDF

Info

Publication number
WO2020098768A1
WO2020098768A1 PCT/CN2019/118694 CN2019118694W WO2020098768A1 WO 2020098768 A1 WO2020098768 A1 WO 2020098768A1 CN 2019118694 W CN2019118694 W CN 2019118694W WO 2020098768 A1 WO2020098768 A1 WO 2020098768A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
active material
electrode active
battery
conductive
Prior art date
Application number
PCT/CN2019/118694
Other languages
English (en)
French (fr)
Inventor
李伟
史海浩
刘会会
靳超
高天一
徐建宝
李世松
郭超
Original Assignee
宁德时代新能源科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宁德时代新能源科技股份有限公司 filed Critical 宁德时代新能源科技股份有限公司
Publication of WO2020098768A1 publication Critical patent/WO2020098768A1/zh

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M2004/028—Positive electrodes

Definitions

  • This application belongs to the field of electrochemical technology. More specifically, this application relates to a battery.
  • Lithium ion batteries are widely used in electric vehicles and consumer electronic products due to their advantages such as high energy density, high output power, long cycle life, and low environmental pollution.
  • lithium-ion batteries are susceptible to fire and explosion when they are subject to abnormal conditions such as crushing, collision, or puncture, causing serious harm. Therefore, the safety of lithium-ion batteries greatly limits the application and popularization of lithium-ion batteries.
  • An object of the present application is to provide a battery with improved safety, especially with improved safety for nailing.
  • a further object of the present application is to provide a battery having excellent performances such as good safety, improved electrical performance, and ease of processing.
  • the present application provides a battery including a positive electrode tab, a separator, and a negative electrode tab, wherein the positive electrode tab includes a positive electrode current collector and at least two positive electrode active material layers coated on at least one surface of the positive electrode current collector, and the positive electrode
  • the lower positive electrode active material layer contacted by the current collector includes a first positive electrode active material, a first polymer material, and a first conductive material.
  • the weight percentage of the first positive electrode active material is A%
  • the weight percentage of the first polymer material is B%
  • the weight percentage of the first conductive material is C%
  • the upper positive electrode active material layer in contact with the lower positive electrode active material layer and away from the positive electrode current collector includes the second positive electrode
  • the active material, the second polymer material and the second conductive material are based on the total weight of the upper positive electrode active material layer
  • the weight percentage content of the second positive electrode active material is A ′%
  • the weight percentage content of the second polymer material is B ′%
  • the weight percentage content of the second conductive material is C ′%, where A% ⁇ A ′%, B%> B ′%, C% ⁇ C ′%, and the first polymer material is contained at 130 ° C 5.
  • An oily polymer material whose solubility in NMP within 5 minutes is less than 30% of the solubility of PVDF under the same conditions.
  • the battery of this application has good safety and improved electrical performance.
  • FIG. 1 is a schematic structural diagram of a positive electrode tab of a battery according to an embodiment of the present application, where 10—positive electrode current collector; 14—upper positive electrode active material layer; 12—lower positive electrode active material layer.
  • FIG. 2 is a perspective view of an embodiment of a lithium ion battery.
  • FIG. 3 is an exploded view of FIG. 2.
  • FIG. 4 is a perspective view of an embodiment of a battery module.
  • FIG. 5 is a perspective view of an embodiment of a battery pack.
  • Fig. 6 is an exploded view of Fig. 5.
  • FIG. 7 is a schematic diagram of an embodiment of a device using a lithium ion battery as a power source.
  • the short circuit in the battery is the root cause of the safety hazard of the lithium ion battery.
  • the root cause of the short circuit in the battery is the electrical connection between the positive pole piece and the negative pole piece in the battery.
  • the metal burrs usually Al metal burrs
  • the metal burr of the positive pole piece can be effectively covered (or wrapped) by designing the coating of the positive pole piece, thereby preventing the short circuit in the battery and the resulting thermal runaway of the battery.
  • the present application discloses a battery including a positive pole piece, a separator, and a negative pole piece.
  • the positive electrode tab in the battery includes a positive electrode current collector and at least two positive electrode active material layers coated on at least one surface of the positive electrode current collector. After the at least two positive electrode active material layers are respectively formed on the current collector, they are usually closely adhered together and the coating is peeled off from the current collector, and generally a whole coating is also obtained. Therefore, the at least two positive electrode active material layers are collectively referred to as a positive electrode membrane layer.
  • the lower positive electrode active material layer in contact with the positive electrode current collector includes the first positive electrode active material, the first polymer material, and the first conductive material. Based on the total weight of the lower positive electrode active material layer, the weight percentage of the first positive electrode active material is A%, the weight percentage of the first polymer material is B%, and the weight percentage of the first conductive material is C%.
  • the upper positive electrode active material layer in contact with the lower positive electrode active material layer and away from the positive electrode current collector contains the second positive electrode active material, the second polymer material, and the second conductive material. Based on the total weight of the upper positive electrode active material layer, the second positive electrode active material layer The weight percentage content of the material is A '%, the weight percentage content of the second polymer material is B'%, and the weight percentage content of the second conductive material is C '%.
  • the first polymer material includes an oily polymer material whose solubility in NMP at 130 ° C. within 5 minutes is 30% or less (ie, not more than 30%) of the solubility of PVDF under the same conditions.
  • the content of the polymer material and the content of the conductive material in the lower cathode active material layer are higher than those of the upper cathode active material layer. Since the lower positive electrode active material layer contains a higher content of the first polymer material, the lower positive electrode active material layer has the property of an adhesive layer compared to the upper positive electrode active material layer, so that it can be wrapped under abnormal conditions such as nail penetration Metal burrs may be generated in the current collector to effectively prevent the occurrence of short circuits in the battery.
  • the bonding force between the positive electrode membrane layer and the positive electrode current collector is greater than or equal to 10 N / m. If the binding force between the two is insufficient, the lower positive electrode active material layer may not effectively wrap the metal burrs that may be generated in the current collector.
  • the lower positive electrode active material layer is disposed between the current collector and the upper positive electrode active material layer, and serves as a primer layer, which functions as an adhesive layer, thereby greatly improving the safety performance of the battery for nail penetration.
  • the positive electrode active material layer is two layers, that is, only composed of an upper positive electrode active material layer and a lower active material layer. This is beneficial to simplify the manufacturing process.
  • FIG. 1 shows a schematic structural diagram of a positive electrode sheet according to some embodiments of the present application, in which 10-current collector, 14-upper positive electrode active material layer, and 12-lower positive electrode active material layer.
  • FIG. 1 shows that the positive electrode active material layer is provided only on one side of the positive electrode current collector 10, in other embodiments, the positive electrode current collector 10 may be provided with lower positive electrode active materials on both sides, respectively Layer 12 and upper positive electrode active material layer 14.
  • the at least two positive electrode active material layers are provided on both surfaces of the positive electrode current collector, so as to more effectively improve the safety problem of nail penetration of traditional lithium ion batteries.
  • the lower positive electrode active material layer provided between the current collector and the upper positive electrode active material layer has high ductility, it can play a role of wrapping the current collector and metal burrs generated in the current collector under abnormal conditions such as nail penetration to prevent Metal burrs or current collectors are in direct contact with the counter electrode, thereby improving the safety performance of the battery for nail penetration.
  • a glue layer composed of a conventional polymer material (such as PVDF) and a conductive material provided between the current collector and the upper positive electrode active material layer is used, although it may improve the safety performance of nail penetration, it will also come Side effects: First, there may be cracking problems of the upper positive electrode active material layer, second, it may worsen the DCR (DC internal resistance) of the battery, and third, after the upper positive electrode active material layer is compacted, etc., the adhesive layer (lower layer The positive electrode active material layer) may be easily deformed, and thus cannot effectively play a role in improving safety.
  • a glue layer composed of a conventional polymer material (such as PVDF) and a conductive material provided between the current collector and the upper positive electrode active material layer is used, although it may improve the safety performance of nail penetration, it will also come Side effects: First, there may be cracking problems of the upper positive electrode active material layer, second, it may worsen the DCR (DC internal resistance) of the battery, and third, after the upper positive electrode active material layer is compacted
  • the present application starts from various aspects and adopts a variety of technical means to coordinate processing to improve the performance and stability of the glue layer provided between the current collector and the positive electrode active material layer.
  • the lower cathode active material layer includes a first cathode active material, a first polymer material, and a first conductive material.
  • the gel layer base material in the lower positive electrode active material layer is an oily polymer material whose solubility in NMP at 130 ° C. for 5 minutes is 30% or less of the solubility of PVDF under the same conditions.
  • the organic solvent such as NMP, etc.
  • the organic solvent such as NMP, etc.
  • the polymer material dissolves and swells. Therefore, if the above-mentioned dissolution and swelling degree is large, when the coating speed is fast, it is easy to crack the upper positive electrode active material layer due to uneven stress, which will seriously affect production and production. effectiveness;
  • an oily polymer material with a solubility in NMP at 130 ° C. for 5 minutes of less than 30% of the solubility of PVDF under the same conditions is adopted as the substratum base material, and the substratum base material is regarded as “insoluble "Ingredients” can effectively hinder the dissolution and swelling of organic solvents (such as NMP, etc.) and electrolytes, which can solve the problems of cracking and the deterioration of battery DCR.
  • the adhesive layer base material is selected from at least one of polyacrylonitrile, polyacrylic acid, polyacrylate, polyacrylic acid-acrylate, polyacrylonitrile-acrylic acid, and polyacrylonitrile-acrylate.
  • the aqueous polymer material means that the polymer molecular chain is fully extended and dispersed in water
  • the oily polymer material means that the polymer molecular chain is fully extended and dispersed in the oily solvent.
  • the same type of polymer materials can be dispersed in water and oil by using suitable surfactants, that is, the same type of polymer materials can be made into high water Molecular materials and oily polymer materials.
  • a person skilled in the art can appropriately select oily polyacrylonitrile or oily polyacrylate as the base material (insoluble polymer material) of the first polymer material as needed.
  • the lower positive electrode active material layer may further include a polymer binder (that is, the first polymer material includes a glue layer matrix and an optional polymer Binder).
  • the weight percentage of the glue layer matrix material is preferably 20 wt% or more relative to the total weight of the lower positive electrode active material layer.
  • the mechanism of action of the lower positive electrode active material layer of the present application is to improve the safety performance of the positive electrode tab and the electrochemical device by encapsulating the current collector and metal burrs generated in the current collector under abnormal conditions such as nail penetration, the lower layer positive electrode
  • the binding force between the active material layer and the current collector cannot be too small, otherwise it may not be guaranteed to effectively and reliably wrap the current collector and metal burrs generated in the current collector under abnormal conditions such as nail penetration.
  • a polymer binder can be added to the lower positive electrode active material layer.
  • the binder may be fluorinated polyolefin and / or chlorinated polyolefin.
  • the fluorinated polyolefin and / or chlorinated polyolefin refers to polyvinylidene fluoride (PVDF), polyvinylidene chloride (PVDC), modified PVDF, and / or modified PVDC .
  • the fluorinated polyolefin and / or chlorinated polyolefin can be selected from PVDF, carboxylic acid modified PVDF, acrylic modified PVDF, PVDF copolymer, PVDC, carboxylic acid modified PVDC, acrylic modified PVDC, PVDC copolymer, or any mixture thereof (ie, at least one selected from them).
  • the addition of the above-mentioned binder has a significant improvement effect on improving the safety performance of battery nailing.
  • the weight percentage of the base material of the adhesive layer is 30wt% -100wt%
  • the weight percentage of the polymer binder is 0wt% -70wt%.
  • the content of the first conductive material and the first positive electrode active material is fixed, if the content of the binder is too large, the content of the adhesive layer matrix as the "insoluble component" will be too small, and it cannot be guaranteed that the coating can be completely solved. Cracking and deterioration of battery DCR.
  • the weight percent content of fluorinated polyolefin and / or chlorinated polyolefin is not less than 15% by weight based on the total weight of the underlying positive electrode active material layer being 100%. At this amount, the bonding force between the lower positive electrode active material layer and the current collector is greater, which has a significant improvement effect for improving the safety of nail penetration.
  • the fluorinated polyolefin and / or chlorinated polyolefin polymer material in the lower positive electrode active material layer is optionally cross-linked.
  • the lower positive electrode active material layer In order to make the lower positive electrode active material layer have better ductility, and have good conductivity and stability, relative to the total weight of the lower positive electrode active material layer (ie, the first polymer material, the first conductive The total weight of the material, the first positive electrode active material and optionally other auxiliary agents is regarded as 100%), and the weight percentage of the polymer material is usually 35wt% -75wt%, preferably 40wt% -75wt%, more preferably 50wt% -75wt%.
  • the solvent such as NMP, etc.
  • the electrolyte in the upper positive electrode active material layer above the lower positive electrode active material will affect the polymer in the lower positive electrode active material layer
  • the material has adverse effects such as dissolution and swelling, so that the lower positive electrode active material layer will be destroyed, affecting the stability of the lower positive electrode active material layer.
  • the inorganic filler is equivalent to a barrier substance, which is beneficial to eliminate the above-mentioned adverse effects of dissolution and swelling, and is conducive to stabilizing the underlying positive electrode active material layer.
  • the addition of inorganic fillers also helps to ensure that the lower positive electrode active material layer is not easily deformed during the compaction of the pole piece. Therefore, the addition of the inorganic filler can ensure that the glue layer is stable between the current collector and the upper positive electrode active material layer, and prevent the current collector from directly contacting the upper positive electrode active material layer, thereby improving the safety performance of the battery.
  • the first positive electrode active material contained in the lower positive electrode active material layer is equivalent to a barrier substance, which is beneficial to eliminate the solvent (such as NMP, etc.) or electrolyte in the upper positive electrode active material layer.
  • the adverse effects of dissolution and swelling of fluorinated polyolefin and / or chlorinated polyolefin in a polymer material are beneficial to stabilize the lower positive electrode active material layer.
  • the presence of the first positive electrode active material contained in the lower positive electrode active material layer is also beneficial to ensure that the lower positive electrode active material layer is not easily deformed during the compaction of the pole piece. Therefore, it can be well ensured that the lower positive electrode active material layer is stable between the current collector and the upper positive electrode active material layer, and the direct current contact between the current collector and the upper positive electrode active material layer is prevented, thereby improving the safety performance of the battery.
  • the first positive electrode active material contained in the lower positive electrode active material layer can stabilize and improve the technical effect of the lower positive electrode active material layer functioning as a glue layer from the following two aspects:
  • the weight percentage A% of the first cathode active material generally satisfies 10wt% ⁇ A% ⁇ 60wt%. If the content is too small, it is insufficient to stabilize the lower positive electrode active material layer; if the content is too large, it will affect the PTC performance of the lower positive electrode active material layer.
  • the weight percentage of the first positive electrode active material is preferably 15% to 45% by weight.
  • inorganic fillers can also have similar technical effects.
  • at least one of metal oxides, non-metal oxides, metal carbides, non-metal carbides, inorganic salts, or conductive carbon coating modification, conductive metal coating modification or conductive polymer coating of the above materials At least one of the modified materials.
  • the other inorganic filler may be selected from magnesium oxide, alumina, titania, zirconia, silica, silicon carbide, boron carbide, calcium carbonate, aluminum silicate, calcium silicate, potassium titanate, barium sulfate At least one.
  • the inventors discovered that materials using a positive electrode electrochemically active material (ie, the first positive electrode active material) or a positive electrode electrochemically active material are coated with a conductive carbon, a conductive metal, or a conductive polymer. Replacing other inorganic fillers has particular advantages.
  • the first positive electrode active material can also play the following two roles: (1) improve the overcharge performance of the battery: because the electrochemically active material (ie, the first positive electrode active material) has the characteristics of intercalation and deintercalation of lithium ions, During the overcharging process, the electrochemically active material will be delithiated and it becomes more and more difficult to delithiate, and the impedance continues to increase.
  • the first positive electrode active material may be selected from lithium cobaltate, lithium nickel manganese cobaltate, lithium nickel manganese aluminate, lithium iron phosphate, lithium vanadium phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium manganese iron phosphate, lithium iron silicate, Lithium vanadium silicate, lithium cobalt silicate, lithium manganese silicate, spinel-type lithium manganate, spinel-type lithium nickel manganate, lithium titanate, or their conductive carbon coating modified materials, conductive metal packages At least one of the coating modified material or the conductive polymer coating modified material.
  • the first positive electrode active material is preferably lithium iron phosphate, lithium vanadium phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium manganese iron phosphate or their conductive carbon-coated modified material, conductive metal-coated modified material or conductive polymer package Covering at least one of the modified materials.
  • lithium iron phosphate, lithium vanadium phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium manganese iron phosphate and other substances have high safety performance and do not release oxygen when overcharged; the second is relative to lithium cobalt oxide and nickel
  • the resistance of the above materials increases more when overcharged, so that the undercoat layer (that is, the lower positive electrode active material layer) generates more heat, so that the lower positive electrode active material layer "executes" faster PTC effect.
  • the average particle diameter D of the first positive electrode active material in the lower positive electrode active material layer satisfies 100 nm ⁇ D ⁇ 10 ⁇ m, more preferably 1 ⁇ m ⁇ D ⁇ 6 ⁇ m.
  • the effect of blocking the conductive network at high temperature can also be improved, thereby improving its response speed as the lower positive electrode active material layer.
  • the specific surface area (BET) of the first positive electrode active material in the lower positive electrode active material layer is not more than 500 m 2 / g.
  • the specific surface area of the first positive electrode active material increases, side reactions will increase and affect battery performance; and when the specific surface area of the first positive electrode active material is too large, a higher proportion of binder needs to be consumed, which will cause the lower positive electrode active material layer and collection The adhesion between the fluid and the upper positive electrode active material layer is reduced, and the internal resistance growth rate is higher.
  • the specific surface area (BET) of the first positive electrode active material is not more than 500 m 2 / g, a better overall effect can be provided.
  • the conductivity ⁇ of the first positive electrode active material when the conductivity ⁇ of the first positive electrode active material satisfies 10 ⁇ 3 S / m ⁇ ⁇ ⁇ 10 2 S / m, it will bring additional benefits.
  • the conductivity ⁇ of the first positive electrode active material satisfies 10 ⁇ 3 S / m ⁇ ⁇ ⁇ 10 2 S / m, the conductivity of the lower positive electrode active material layer at the normal use temperature of the battery can be improved.
  • the conductivity ⁇ of the first positive electrode active material is too small, the initial internal resistance and internal resistance growth rate of the lower positive electrode active material layer will be very high; if the ⁇ is too high, the conductive network is not easy to be cut off, which is not conducive to improving overcharge safety and Safe to wear nails.
  • controlling the content of the first conductive material in the lower positive electrode active material layer helps to further optimize the safety performance of the lower positive electrode active material layer.
  • the lower positive electrode active material layer disposed between the current collector and the upper positive electrode active material layer further includes a first conductive material.
  • the lower positive electrode active material layer In order for the battery to normally carry out an electrochemical reaction under normal operating conditions, the lower positive electrode active material layer must contain a certain amount of conductive material. If the content of the conductive material is too low, it is not conducive to the electrochemical reaction of the battery under normal working conditions, and the internal resistance is too large; if the content of the conductive material is too high, the conductive network is not easily damaged, which is not conducive to the battery's overcharge safety performance Improvement.
  • the weight percentage C% of the first conductive material generally satisfies 5 wt% ⁇ C% ⁇ 25wt%, preferably 5wt% ⁇ C% ⁇ 20wt%.
  • the weight ratio of the first polymer material to the first conductive material is 2 or more, and more preferably the weight ratio is 3 or more and 8 or less.
  • the first conductive material may be selected from at least one of conductive carbon-based materials, conductive metal materials and conductive polymer materials, wherein the conductive carbon-based materials are selected from conductive carbon black, acetylene black, graphite, graphene, carbon nanotubes At least one of carbon nanofibers; conductive metal material is selected from at least one of Al powder, Ni powder, gold powder; conductive polymer material is selected from at least one of conductive polythiophene, conductive polypyrrole, conductive polyaniline .
  • the first conductive material may be used alone or in combination of two or more.
  • the first conductive material is usually used in the form of powder or granules. Depending on the specific application environment, its particle size may be 5nm-500nm, such as 10nm-300nm, 15nm-200nm, 15nm-100nm, 20nm-400nm, 20nm-150nm, etc.
  • the lower cathode active material layer of the present application can be formed by a conventional method.
  • a slurry is formed by dissolving a first polymer material, a first conductive material, a first positive electrode active material, and optionally other auxiliary agents in a solvent and stirring, and then applying the slurry onto a current collector and heating After drying, the required lower positive electrode active material layer can be obtained.
  • the lower positive electrode active material layer of the present application may be substantially composed of the first polymer material (including the glue layer matrix and the optional polymer binder), the first conductive
  • the material is composed of the first positive electrode active material, that is, does not contain a significant amount (for example, content ⁇ 3%, ⁇ 1%, or ⁇ 0.5%) of other components.
  • the lower positive electrode active material layer directly adheres to the current collector and is disposed between the current collector and the upper positive electrode active material layer.
  • the thickness H of the lower positive electrode active material layer can be reasonably determined according to actual needs.
  • the thickness H of the lower positive electrode active material layer is usually not more than 40 ⁇ m, preferably not more than 25 ⁇ m, and more preferably not more than 20 ⁇ m, 15 ⁇ m or 10 ⁇ m.
  • the coating thickness of the lower positive electrode active material layer is usually 1 ⁇ m or more, preferably 2 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • the thickness is too small, it is not enough to ensure the effect of the lower positive electrode active material layer to improve the safety performance of the battery; if it is too large, the internal resistance of the battery will increase seriously, which will affect the electrochemical performance of the battery during normal operation.
  • the lower positive electrode active material layer and the upper positive electrode active material layer are not easy to separate after coating and drying. Therefore, in this application, the lower positive electrode active material layer and the upper positive electrode active material layer are collectively referred to as a membrane layer. Therefore, the bonding force between the diaphragm layer and the current collector is equivalent to the bonding force between the lower positive electrode active material layer and the current collector.
  • the bonding force between the lower positive electrode active material layer and the current collector is preferably 10 N / m or more. The larger binding force can ensure that the lower positive electrode active material layer effectively and reliably wraps the current collector and metal burrs generated in the current collector under abnormal conditions such as nail penetration.
  • the inventor also found that, in the present application, the elongation rate of the membrane layer has a certain influence on the safety performance of the nailing of the pole piece.
  • the positive electrode active material layer of a conventional lithium ion battery that is, the membrane layer without the lower positive electrode active material layer
  • its elongation rate is generally not more than 1%, and it cannot play the role of wrapping metal burrs, so the bare metal Glitches can easily cause short circuits in the battery.
  • the positive electrode sheet of the present application due to the introduction of the lower positive electrode active material layer, the elongation rate of the membrane layer is greatly improved, which can wrap the metal burrs that may be generated in the current collector to prevent the occurrence of short circuits in the battery, thereby Greatly improve the safety of the battery through the nail.
  • the elongation of the membrane layer is greater than or equal to 30%, preferably greater than or equal to 80%.
  • the advantage of the larger elongation rate is that under abnormal conditions such as nail penetration, the membrane layer with greater elongation rate can wrap the metal burrs that may be generated in the current collector to prevent the occurrence of short circuits in the battery, thereby greatly improving the battery nailing safety Sex.
  • the elongation of the membrane layer can be adjusted by changing the type, relative dosage, molecular weight, degree of crosslinking, etc. of the first polymer material in the lower cathode active material layer. If the content of the first polymer material in the lower positive electrode active material layer is increased, it will inevitably contribute to the improvement of the elongation of the membrane layer. However, if the content of the first polymer material in the lower positive electrode active material layer is too large, the content of the conductive material will be relatively low, thereby causing a large increase in the DCR of the battery during normal operation. Therefore, it is preferable that the elongation of the membrane layer is 80% or more and 300% or less.
  • the upper positive electrode active material layer of the positive electrode sheet of the present application may be a positive electrode active material layer of a lithium ion battery commonly used in the art, and also includes a positive electrode active material (second positive electrode active material) and a binder (second polymer material) And conductive material (second conductive material).
  • the composition of the upper active material layer is the same as the conventional positive electrode active material layer used in the positive electrode tab in the prior art, and its composition and preparation method are also well known in the art. However, the present application has restrictions on the content of each component in the upper positive electrode active material layer.
  • the weight percentage content of the second cathode active material is A ′%
  • the weight percentage content of the second polymer material is B ′%
  • the weight percentage content of the second conductive material is C ′%, it needs to satisfy: A% ⁇ A ′%, B%> B ′%, C% ⁇ C ′%.
  • a person skilled in the art may reasonably determine the ranges of A ′%, B ′%, and C ′% according to A%, B%, and C% of the lower positive electrode active material layer.
  • Their range may be, for example, as follows: the second positive electrode active material satisfies 90wt% ⁇ A '% ⁇ 99wt%, the second polymer material satisfies 0.5wt% ⁇ B'% ⁇ 5wt%, and the second conductive material satisfies 0.5wt% ⁇ C '% ⁇ 5wt%.
  • the types of polymer materials, positive electrode active materials, and conductive materials used in the lower positive electrode active material layer and the upper positive electrode active material layer may be different or the same (or partially the same).
  • the positive electrode active material in the upper positive electrode active material layer various positive electrode active materials known to those skilled in the art for preparing a positive electrode of a lithium ion secondary battery can be used, for example, the positive electrode active material is a lithium-containing composite metal oxide, specific materials For example, one or more of LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiFePO 4 , lithium nickel cobalt manganese oxide (such as LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) and lithium nickel manganese oxide Or several.
  • LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiFePO 4 lithium nickel cobalt manganese oxide (such as LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) and lithium nickel manganese oxide Or several.
  • the second polymer material (binder) in the upper positive electrode active material layer may be, for example, PVDF, PVDC, SBR, CMC, polyacrylate, polycarbonate, polyethylene oxide, or other conventional binder.
  • the second conductive material in the upper positive electrode active material layer may be, for example, a conventional conductive agent such as at least one of conductive carbon black, acetylene black, graphite, graphene, carbon nanotubes, and carbon nanofibers.
  • the material of the current collector materials commonly used in the art may be used, and metal current collectors such as stainless steel, aluminum, copper, titanium and other metal sheets or metal foils are preferred.
  • the thickness of the metal current collector is usually 4 ⁇ m to 16 ⁇ m.
  • the current collector is an aluminum-containing porous current collector (porous aluminum foil).
  • porous aluminum foil Under abnormal conditions such as nail penetration, the use of porous aluminum foil can reduce the probability of occurrence of metal burrs, and thereby reduce the probability of occurrence of violent thermite reaction, so the safety of the battery can be further improved.
  • the use of porous aluminum foil can also improve the electrolyte infiltration pole piece, and thereby improve the kinetic performance of lithium ion batteries; and the lower positive electrode active material layer can cover the surface of the porous aluminum foil to prevent the upper active material layer during the coating process The phenomenon of missing coating.
  • the elongation at break of the current collector has a great influence on the safety of the battery. If the elongation at break of the current collector is too large, the metal burr is large, which is not conducive to improving the safety performance of the battery; if the elongation at break of the current collector is too small, the battery may be squeezed during processing such as pole piece compaction It is easy to break when pressed or collided, which reduces the quality or safety of the battery. Therefore, in order to further improve safety, especially nailing safety, the elongation at break ⁇ of the current collector should be no more than 4% and no less than 0.8%.
  • the elongation at break of the metal current collector can be adjusted by changing the purity, impurity content and additives of the metal current collector, billet production process, rolling speed, heat treatment process, etc.
  • the positive pole pieces of the battery described in this application can be formed by conventional methods. For example, by dissolving the first positive electrode active material, the first polymer material, the first conductive material, and optionally other additives in a solvent and stirring to form a slurry, and then applying the slurry onto the current collector, heating After drying, the lower positive electrode active material layer can be obtained. Dissolve the second positive electrode active material, the second polymer material, the second conductive material, and optional other additives in the solvent and stir to form a slurry, and then apply the slurry to the lower positive electrode active material layer and heat After drying, the upper positive electrode active material layer can be obtained. Then, the current collector including the lower positive electrode active material layer and the upper positive electrode active material layer is subjected to post-processing such as cold pressing, trimming, and cutting to obtain a desired positive electrode sheet.
  • post-processing such as cold pressing, trimming, and cutting to obtain a desired positive electrode sheet.
  • the battery of the present application includes a separator and a negative electrode in addition to the positive electrode.
  • the negative pole piece used in conjunction with the positive pole piece according to the present application various conventional negative pole pieces commonly used in the art can be selected, and its composition and preparation method are well known in the art.
  • the negative electrode tab may include a negative electrode current collector and a negative electrode active material layer provided on the negative electrode current collector, and the negative electrode active material layer may include a negative electrode active material, a binder, a conductive material, and the like.
  • the negative electrode active material is, for example, a carbonaceous material such as graphite (artificial graphite or natural graphite), conductive carbon black, carbon fiber, etc., for example, metal or semi-metallic materials such as Si, Sn, Ge, Bi, Sn, In or their alloys, containing lithium Nitride or lithium-containing oxide, lithium metal or lithium aluminum alloy, etc.
  • a carbonaceous material such as graphite (artificial graphite or natural graphite), conductive carbon black, carbon fiber, etc.
  • metal or semi-metallic materials such as Si, Sn, Ge, Bi, Sn, In or their alloys, containing lithium Nitride or lithium-containing oxide, lithium metal or lithium aluminum alloy, etc.
  • separator used in the battery of the present application various separators commonly used in the art can be selected.
  • the battery of the present application usually also includes an electrolyte.
  • electrolytes commonly used in the art may be selected, for example, a solution of an electrolyte salt in a non-aqueous solvent.
  • a mixed solution of an electrolyte lithium salt and a non-aqueous solvent can be used.
  • the electrolyte lithium salt may be selected from one or more of lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium halide, lithium chloroaluminate, and lithium fluoroalkylsulfonate.
  • the organic solvent may be selected from chain carbonates, cyclic carbonates, or mixed solvents thereof.
  • the chain carbonate can be dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other At least one of fluorine, sulfur-containing or unsaturated bond-containing chain organic esters.
  • the cyclic carbonate can be ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), ⁇ -butyrolactone ( ⁇ -BL), sultone, and other fluorine-containing, containing One or more of sulfur or unsaturated bond-containing cyclic organic esters.
  • the battery of the present application may be a primary battery or a secondary battery.
  • the battery of the present application may be a lithium ion battery or a sodium ion battery, preferably a lithium ion battery, for example, a lithium ion primary battery or a lithium ion secondary battery.
  • the construction and manufacturing methods of these batteries are known per se. Due to the use of the above-mentioned positive pole pieces, the battery can have improved safety (such as nail safety) and electrical performance.
  • the positive electrode tab according to the present application is easy to process, so the manufacturing cost of the battery using the positive electrode tab according to the present application can be reduced.
  • FIG. 2 is a perspective view of an embodiment of a lithium ion battery 5.
  • FIG. 3 is an exploded view of FIG. 2. 2 to 3, the lithium ion battery 5 includes a case 51, an electrode assembly 52, a top cover assembly 53, and an electrolyte (not shown).
  • the electrode assembly 52 is accommodated in the case 51.
  • the number of electrode assemblies 52 is not limited, and may be one or more.
  • the electrode assembly 52 includes a positive pole piece, a negative pole piece, and a separator.
  • the separator separates the positive pole piece from the negative pole piece.
  • the electrolyte is injected into the case 51 and impregnates the electrode assembly 52, which includes, for example, a first pole piece, a second pole piece, and a separator.
  • the lithium-ion battery 5 shown in FIG. 2 is a can-type battery, but it is not limited thereto.
  • the lithium-ion battery 5 may be a pouch-type battery, that is, the case 51 is replaced by a metal plastic film and the top cover assembly 53 is eliminated.
  • FIG. 4 is a perspective view of an embodiment of the battery module 4.
  • the battery module 4 provided by the embodiment of the present application includes the lithium ion battery 5 of the present application.
  • the battery module 4 includes a plurality of batteries 5.
  • a plurality of lithium ion batteries 5 are arranged in the longitudinal direction.
  • the battery module 4 can serve as a power source or an energy storage device.
  • the number of lithium ion batteries 5 in the battery module 4 can be adjusted according to the application and capacity of the battery module 4.
  • FIG. 5 is a perspective view of an embodiment of the battery pack 1.
  • Fig. 6 is an exploded view of Fig. 5.
  • the battery pack 1 provided by the present application includes the battery module 4 according to an embodiment of the present application.
  • the battery pack 1 includes an upper case 2, a lower case 3 and a battery module 4.
  • the upper case 2 and the lower case 3 are assembled together and form a space for accommodating the battery module 4.
  • the battery module 4 is placed in the space of the upper case 2 and the lower case 3 assembled together.
  • the output pole of the battery module 4 passes through one or both of the upper case 2 and the lower case 3 to supply power to or charge from the outside.
  • the number and arrangement of battery modules 4 used in the battery pack 1 can be determined according to actual needs.
  • FIG. 7 is a schematic diagram of an embodiment of a device using a lithium ion battery as a power source.
  • the device provided by the present application includes the lithium ion battery 5 according to an embodiment of the present application, and the lithium ion battery 5 can be used as a power source of the device.
  • the device using the lithium ion battery 5 is an electric car.
  • the device using the lithium-ion battery 5 may be any electric vehicle (for example, electric bus, electric tram, electric bicycle, electric motorcycle, electric scooter, electric golf cart, electric truck) other than electric cars ), Electric ships, electric tools, electronic equipment and energy storage systems.
  • the electric vehicle may be an electric pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • the device provided in this application may include the battery module 4 described in this application.
  • the device provided in this application may also include the battery pack 1 described in this application.
  • the electrodes and batteries in the examples and comparative examples were prepared as follows.
  • the slurry was obtained in pyrrolidone (NMP), stirred uniformly, coated on both surfaces of the current collector, and dried at 85 ° C to obtain the lower positive electrode active material layer.
  • the second positive electrode active material 90% by weight of the second positive electrode active material, 5% by weight of SP (second conductive material) and 5% by weight of PVDF (second polymer material), using NMP as a solvent, evenly mixed and coated on the assembly prepared according to the above method On the lower positive electrode active material layer of the fluid; after drying at 85 ° C, the upper positive electrode active material layer is obtained.
  • SP second conductive material
  • PVDF second polymer material
  • the current collector with two positive electrode active material layers is cold pressed, then trimmed, cut, and slitted, and then dried under a vacuum condition of 85 ° C for 4 hours, and the welding lugs are made to meet the requirements of the secondary Positive pole piece of battery.
  • PVDF manufactured by Manufacturing "Solvay", model 5130
  • Substrate base material polyacrylonitrile, polyacrylic acid, polyacrylonitrile-acrylate;
  • the first conductive material (conductive agent): Super-P (Swiss TIMCAL company, referred to as SP);
  • the first positive electrode active material lithium iron phosphate (abbreviated as LFP), carbon-coated modified lithium iron phosphate (abbreviated as LFP / C), carbon-coated modified lithium titanate (abbreviated as Li 4 Ti 5 O 12 / C);
  • Inorganic filler alumina
  • Second positive electrode active material NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ).
  • the above materials are common and commonly used materials in the field of lithium battery industry, and can be easily obtained through corresponding suppliers through commercial channels.
  • Negative pole piece Add active material graphite, conductive agent Super-P, thickener CMC, adhesive SBR according to the mass ratio of 96.5: 1.0: 1.0: 1.5 to the solvent deionized water and mix to make anode slurry; The slurry is coated on the surface of the negative electrode current collector copper foil, and dried at 85 °C, then trimmed, cut, and slit, and then dried at 110 °C under vacuum for 4 hours, welding the pole ears, made to meet Required secondary battery negative pole piece.
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) are mixed in a volume ratio of 3: 5: 2 to obtain an EC / EMC / DEC mixed solvent, and then the fully dried lithium salt LiPF 6 is dissolved in a mixed solvent to obtain a solution with a concentration of 1M, that is, an electrolyte is obtained.
  • separator Using a 12 ⁇ m polypropylene film as the separator, stack the positive pole piece, the separator and the negative pole piece in order, so that the separator is in the middle of the positive pole piece and the negative pole piece to play the role of isolation, and then wound into a bare battery core.
  • Vacuum-bake at 75 ° C for 10 hours inject the electrolyte (prepared as described in "Preparation of Electrolyte” above), vacuum encapsulate and let stand for 24 hours, then charge to 4.2V with a constant current of 0.1C, and then Charge at a constant voltage of V until the current drops to 0.05C, then discharge to 3.0V at a constant current of 0.1C, repeat the charge and discharge twice, and finally charge to 3.8V at a constant current of 0.1C, that is, the preparation of the secondary battery is completed.
  • the powder sample of the material is dispersed in a dispersion medium (distilled water), and a Malvern laser particle size analyzer MS2000 is used, and the average value is measured 5 times and the unit is ⁇ m.
  • a dispersion medium distilled water
  • MS2000 Malvern laser particle size analyzer MS2000
  • the specific surface area of the powder sample of the material was tested with a Quadrasorb SI specific surface tester, and the average value was measured 5 times and the unit was m 2 / g.
  • Coating thickness, diaphragm layer thickness The thickness of the current collector is measured first, and then the total thickness is measured after the coating is applied. The difference between the two is taken as the coating thickness.
  • the thickness of the diaphragm layer adopts a similar method.
  • the absence of cracks in the 100 m 2 pole piece is defined as no cracking.
  • the polymer material is made into a film of about 7 ⁇ m, cut into 20mm * 50mm strips, weighed and recorded as M1;
  • NMP N-methylpyrrolidone
  • solubility of PVDF manufactured by manufactureurer "Solvay", model 5130
  • Solvay model 5130
  • the ratio of the solubility of other materials to the solubility of PVDF is recorded.
  • GBT31485-2015 Safety requirements and test methods for power batteries for electric vehicles was used to evaluate the safety of the secondary batteries of the examples and comparative examples, and the test results were recorded.
  • the high temperature resistant steel needle (the cone angle of the needle tip is 45 °), penetrates at a speed of 25mm / s from the direction perpendicular to the battery plate, the penetration position should be close to the geometric center of the puncture surface, the steel needle stays in the battery, Observe whether the battery is burning or exploding.
  • the test conditions for the number of cycles are: at 25 ° C, the secondary battery is subjected to a 1C / 1C cycle test, the charging and discharging voltage range is 2.8 to 4.2V, and the capacity is reduced to 80% of the first discharge specific capacity.
  • the secondary battery was adjusted to 50% SOC at a current of 1C, and the voltage U1 was recorded. Then discharge at a current of 4C for 30 seconds, and record the voltage U2.
  • DCR (U1-U2) / 4C.
  • the DCR of the battery cell containing only the non-crosslinked PVDF as the polymer matrix as the reference is recorded as 100%, and the DCR and its ratio of other battery cells are calculated and recorded.
  • polyacrylonitrile, polyacrylonitrile-acrylate, and polyacrylate are all oily polymer materials whose solubility in NMP at 130 ° C. within 5 minutes is less than 30% of the solubility of PVDF under the same conditions. It is used as the base material of the glue layer in the first polymer material in this application.
  • the corresponding lower positive electrode active material layer was prepared according to the methods and steps described in "1. Preparation Method”. Positive pole piece, negative pole piece and battery, and then test according to the method specified in "3. Battery Performance Test”. In order to ensure the accuracy of the data, 4 batteries of each type (20 batteries used for acupuncture test or overcharge test) are prepared and tested independently. The final test results are averaged and shown in Table 1-2.
  • the conventional pole piece P is basically prepared according to the method described in "1.1 Preparation of Positive Electrode Pieces", but the lower positive electrode active material layer is not provided, that is, the upper positive electrode active material layer is directly coated on the current collector, and the conventional pole piece N is prepared according to Prepared by the method described in "1.2 Preparation of Negative Electrode Sheets".
  • a polymer material such as PVDF
  • adheresive layer base a polymer material with relatively large dissolution and swelling
  • the polymer material with relatively small swelling is used as the base material of the lower positive electrode active material layer (substrate layer substrate), which obviously improves the above problems, and is composed of a polymer material such as polyacrylonitrile that dissolves and swells with relatively small swelling.
  • the active material layer further significantly improves the safety performance of the battery through nails;
  • the corresponding lower cathodes were prepared according to the methods and steps described in "1, Preparation Method” with the specific materials and dosages listed in Table 2-1 below The active material layer, the positive pole piece, the negative pole piece and the battery, and then perform the test according to the method specified in the "3. Battery Performance Test” section.
  • 4 batteries of each type (20 batteries used for acupuncture test or overcharge test) are prepared and tested independently. The final test results are averaged and summarized in Table 2-2.
  • the data in Table 2-1 and Table 2-2 show that: (1) If the content of the first positive electrode active material is too low, the lower positive electrode active material layer is easily deformed and the stability is not high, so the safety performance of the battery cannot be fully improved; If the content of the first positive electrode active material is too high, the content of the base material of the adhesive layer will be too low, and the ductility of the lower positive electrode active material layer will be reduced, which cannot guarantee the normal performance of the lower positive electrode active material layer to improve the safety of nail penetration; (2) First The conductive material has a greater influence on the internal resistance and polarization of the battery, and thus affects the cycle life of the battery. The higher the content of the first conductive material, the smaller the internal resistance and polarization of the battery, the better the cycle life.
  • the weight percentage of the first polymer material is 35wt% -75wt%
  • the weight percentage of the first conductive material is 5wt% -25wt%.
  • the weight percentage of the first positive electrode active material is 10wt% -60wt%.
  • the content of each component of the lower positive electrode active material layer is within the above range, the effect of improving the safety and electrical performance (such as cycle performance) of the battery can be achieved.
  • pole piece of the present application is only illustrated by a lithium battery, but the pole piece of the present application can also be applied to other types of batteries or electrochemical devices, and the application can still be obtained Good technical effect. Moreover, those skilled in the art can understand that the present application also discloses various embodiments of the positive electrode tab as described above.
  • 1, 2 weight percent relative to the total weight of the lower positive electrode active material layer; 3: relative to the total weight of the first polymer material (ie, gel layer matrix + high score

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

一种电池，包括正极极片、隔膜和负极极片，其中正极极片包括正极集流体(10)和涂覆在正极集流体(10)的至少一个表面上的至少两层正极活性材料层，与正极集流体(10)接触的下层正极活性材料层(12)包含第一正极活性材料、第一高分子材料和第一导电材料，基于下层正极活性材料层(12)的总重量，第一正极活性材料的重量百分含量为A％，第一高分子材料的重量百分含量为B％，第一导电材料的重量百分含量为C％，与下层正极活性材料层(12)接触而远离正极集流体(10)的上层正极活性材料层(14)包含第二正极活性材料、第二高分子材料和第二导电材料，基于上层正极活性材料层(14)的总重量，第二正极活性材料的重量百分含量为A'％，第二高分子材料的重量百分含量为B'％，第二导电材料的重量百分含量为C'％，其中A％<A'％，B％>B'％，C％≥C'％，且第一高分子材料包含在130℃、5min内于NMP中的溶解度为相同条件下PVDF的溶解度的30％以下的油性高分子材料；所述电池具有良好的安全性、改善的电性能。

Description

一种电池
相关申请的交叉引用
本申请要求享有于2018年11月16日提交的名称为“一种电池”的中国专利申请201811367724.4的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本申请属于电化学技术领域，更具体地说，本申请涉及一种电池。
背景技术
锂离子电池由于具备能量密度大、输出功率高、循环寿命长和环境污染小等优点而被广泛应用于电动汽车以及消费类电子产品中。然而锂离子电池在受到挤压、碰撞或穿刺等异常情况时很容易发生着火、爆炸，从而引起严重危害。因此锂离子电池的安全问题很大程度地限制了锂离子电池的应用和普及。
虽然研究人员提出了很多方法来提高电池的安全性，但是对于电池被穿刺所造成的安全隐患仍然缺乏非常有效的手段。有鉴于此，确有必要提供一种能够改善电池安全性、尤其是穿钉安全性的电池。
发明内容
本申请的一个目的在于：提供一种具有改善的安全性、尤其是具有改善的穿钉安全性的电池。
本申请的进一步目的在于：提供一种具有良好的安全性、改善的电性能、易加工性等优良性能的电池。
本申请提供了一种电池，包括正极极片、隔膜和负极极片，其中正极极片包括正极集流体和涂覆在正极集流体的至少一个表面上的至少两层正极活性材料层，与正极集流体接触的下层正极活性材料层包含第一正极活性材料、第一高分 子材料和第一导电材料，基于下层正极活性材料层的总重量，第一正极活性材料的重量百分含量为A％，第一高分子材料的重量百分含量为B％，第一导电材料的重量百分含量为C％，与下层正极活性材料层接触而远离正极集流体的上层正极活性材料层包含第二正极活性材料、第二高分子材料和第二导电材料，基于上层正极活性材料层的总重量，第二正极活性材料的重量百分含量为A′％，第二高分子材料的重量百分含量为B′％，第二导电材料的重量百分含量为C′％，其中A％<A′％，B％>B′％，C％≥C′％，且第一高分子材料包含在130℃、5min内于NMP中的溶解度为相同条件下PVDF的溶解度的30％以下的油性高分子材料。
本申请的电池具有良好的安全性、改善的电性能。
附图说明
下面结合附图和具体实施方式，对本申请的电池及其有益效果进行详细说明。
图1为根据本申请的一个实施方式所描述的电池的正极极片的结构示意图，其中10—正极集流体；14—上层正极活性材料层；12—下层正极活性材料层。
图2是锂离子电池的一实施方式的立体图。
图3是图2的分解图。
图4是电池模块的一实施方式的立体图。
图5是电池包的一实施方式的立体图。
图6是图5的分解图。
图7是锂离子电池作为电源的装置的一实施方式的示意图。
其中，附图标记说明如下：
1电池包
2上箱体
3下箱体
4电池模块
5电池
51壳体
52电极组件
53顶盖组件
具体实施方式
大量实验结果表明，电池内短路是造成锂离子电池安全隐患的根本所在。电池内短路的根本原因在于正极极片与负极极片在电池内部的电连接，在穿钉等异常情况下，在正极极片中产生的金属毛刺(通常为Al金属毛刺)与负极极片的直接接触会导致电池内短路。本申请的发明人发现，可以通过对正极极片的涂层设计来有效地掩盖(或包裹)正极极片的金属毛刺，从而防止电池内短路以及由此导致的电池热失控。
本申请公开了一种电池，包括正极极片、隔膜和负极极片。该电池中的正极极片包括正极集流体和涂覆在正极集流体的至少一个表面上的至少两层正极活性材料层。由于在所述至少两层正极活性材料层分别形成在集流体上之后，通常会紧密地粘结在一起，将涂层从集流体上剥离，一般也会得到一个涂层整体。因此，将所述至少两层正极活性材料层统称为正极膜片层。
与正极集流体接触的下层正极活性材料层包含第一正极活性材料、第一高分子材料和第一导电材料，基于下层正极活性材料层的总重量，第一正极活性材料的重量百分含量为A％，第一高分子材料的重量百分含量为B％，第一导电材料的重量百分含量为C％。
与下层正极活性材料层接触而远离正极集流体的上层正极活性材料层包含第二正极活性材料、第二高分子材料和第二导电材料，基于上层正极活性材料层的总重量，第二正极活性材料的重量百分含量为A′％，第二高分子材料的重量百分含量为B′％，第二导电材料的重量百分含量为C′％。
在本申请的实施方式中，A％<A′％，B％>B′％，C％≥C′％，
且第一高分子材料包含在130℃、5min内于NMP中的溶解度为相同条件下PVDF的溶解度的30％以下(即，不大于30％)的油性高分子材料。
即下层正极活性材料层中的高分子材料的含量和导电材料的含量均高于上层正极活性材料层。由于下层正极活性材料层包含较高含量的第一高分子材料，因此下层正极活性材料层相对于上层正极活性材料层来说，具有胶层的性质，从而可在穿钉等异常情况下，包裹集流体中可能产生的金属毛刺，以有效地防止电池内短路的发生。
优选地，所述正极膜片层与正极集流体之间的结合力大于等于10N/m。若两者之间的结合力不够，则下层正极活性材料层可能无法有效地包裹集流体中可能产生的金属毛刺。
所以，该下层正极活性材料层设置于集流体和上层正极活性材料层之间，作为底涂层，起到了胶层的作用，从而很大程度上改善了电池的穿钉安全性能。
在本申请的优选实施方式中，所述正极活性材料层是两层，即仅由上层正极活性材料层和下层活性材料层组成。这样有利于制造工艺的简化。
图1示出了根据本申请某些实施例的正极极片的结构示意图，其中10—集流体，14—上层正极活性材料层，12—下层正极活性材料层。
易于理解的是，虽然图1中示出的是仅在正极极集流体10的单面设置正极活性材料层，但在其他实施例中，正极集流体10可以在双面分别设置下层正极活性材料层12和上层正极活性材料层14。
优选的，在正极集流体的两个表面上均设置有所述至少两层正极活性材料层，以更有效地改善传统锂离子电池的穿钉安全问题。
由于设置于集流体与上层正极活性材料层之间的下层正极活性材料层延展性高，因此在穿钉等异常情况下可以起到包裹集流体以及集流体中产生的金属毛刺的作用，以防止金属毛刺或集流体与对电极直接接触，由此改善电池的穿钉 安全性能。
发明人发现，若采用由常规的高分子材料(例如PVDF)和导电材料组成设置于集流体与上层正极活性材料层之间的胶层的话，虽然可能改善穿钉安全性能，但是也会到来一些副作用：一来可能会存在上层正极活性材料层的开裂问题，二来可能会恶化电池的DCR(直流内阻)，三来在对上层正极活性材料层进行压实等处理后，胶层(下层正极活性材料层)可能易变形，由此无法有效地起到改善安全的作用。
为了克服以上缺陷，本申请从多个方面着手，采用多种技术手段协同处理来改善设置于集流体与正极活性材料层之间的胶层的性能和稳定性。
下面对本申请的电池中的正极极片的具体组成和结构进行更详细的描述。
(一)下层正极活性材料层
发明人发现，可以通过对下层正极活性材料层中第一高分子材料的选择来提高下层正极活性材料层的稳定性和作为胶层的性能。下层正极活性材料层包含第一正极活性材料、第一高分子材料和第一导电材料。
一)、关于本申请中下层正极活性材料层中基体材料的选择
本申请公开的正极极片中，其下层正极活性材料层中的胶层基体材料是在130℃、5min内于NMP中的溶解度为相同条件下PVDF的溶解度的30％以下的油性高分子材料。
若不对胶层基体的材料进行选择性采用，即采用常规的高分子材料(例如PVDF)，则易带来如下技术问题：
(1)在下层正极活性材料层的上方涂布上层正极活性材料层时，由于上层正极活性材料层的浆料中的有机溶剂(如NMP等)以及电解液会对下层正极活性材料层中的高分子材料产生溶解、溶胀，因此若上述溶解、溶胀程度较大，则在涂布速度较快时，则易于由于应力不均导致上层正极活性材料层的开裂，由此会严重影响生产和生产效率；
(2)若上述溶解、溶胀程度较大，则由于下层正极活性材料层的引入，会恶化电池DCR，不利于电池的动力学性能改善。
因此，在本申请中，采用在130℃、5min内于NMP中的溶解度为相同条件下PVDF的溶解度的30％以下的油性高分子材料作为胶层基体材料，该胶层基体材料作为“难溶成分”可有效阻碍有机溶剂(如NMP等)和电解液对其的溶解、溶胀，从而可解决开裂问题和电池DCR恶化的问题。
所述胶层基体材料选自聚丙烯腈、聚丙烯酸、聚丙烯酸酯、聚丙烯酸-丙烯酸酯、聚丙烯腈-丙烯酸、聚丙烯腈-丙烯酸酯中的至少一种。
在本申请中，水性高分子材料是指高分子分子链完全伸展开分散在水中，油性高分子材料是指高分子分子链完全伸展开分散在油性溶剂中。本领域技术人员理解，通过采用合适的表面活性剂可以将同一类的高分子材料分别分散在水中和油中，即通过采用合适的表面活性剂同一类的高分子材料可以为分别做成水性高分子材料和油性高分子材料。例如，本领域技术人员可以根据需要，适当选用油性聚丙烯腈或油性聚丙烯酸酯作为第一高分子材料中的胶层基体材料(难溶高分子材料)。
为了增强下层正极活性材料层与集流体之间的粘结力，所述下层正极活性材料层还可包含高分子粘结剂(即第一高分子材料包含胶层基体和任选存在的高分子粘结剂)。
为了使得上述胶层基体起到较明显的“阻碍溶解、溶胀”的作用，相对于所述下层正极活性材料层的总重量，所述胶层基体材料的重量百分比优选为大于等于20wt％。
二)、关于本申请中粘结剂的材料的选择
由于本申请下层正极活性材料层的作用机理是在穿钉等异常情况下通过包裹集流体以及集流体中产生的金属毛刺，来改善正极极片和电化学装置的穿钉安全性能，因此下层正极活性材料层与集流体之间的结合力不能过小，否则可能 无法保证有效地、可靠地在穿钉等异常情况下包裹集流体以及集流体中产生的金属毛刺。
为了提高下层正极活性材料层与集流体之间的结合力，发明人发现，可以在下层正极活性材料层中添加高分子粘结剂。所述粘结剂可以是氟化聚烯烃和/或氯化聚烯烃。在本申请中，所述氟化聚烯烃和/或氯化聚烯烃是指聚偏氟乙烯(PVDF)、聚偏氯乙烯(PVDC)、经改性的PVDF、和/或经改性的PVDC。例如，所述氟化聚烯烃和/或氯化聚烯烃可以选自PVDF、羧酸改性的PVDF、丙烯酸改性的PVDF、PVDF共聚物、PVDC、羧酸改性的PVDC、丙烯酸改性的PVDC、PVDC共聚物或它们的任意混合物(即，选自它们之中的至少一种)。
上述粘结剂的添加对于改善电池穿钉安全性能具有明显的改进作用。
当然基于胶层基体材料的选择，也可以选择不添加任何粘结剂。
基于所述第一高分子材料的重量为100％(即相对于第一高分子材料的总重量)，
所述胶层基体材料的重量百分比为30wt％-100wt％，且
所述高分子粘结剂的重量百分比为0wt％-70wt％。
第一导电材料和第一正极活性材料的含量一定的情况下，粘结剂的含量过大，则作为“难溶成分”的胶层基体的含量会过小，则无法保证可以完全解决涂层开裂和电池DCR恶化的问题。
优选地，基于下层正极活性材料层的总重量为100％，氟化聚烯烃和/或氯化聚烯烃的重量百分含量不小于15wt％。在这种用量下，下层正极活性材料层与集流体之间的粘结力较大，对于改善穿钉安全具有较明显的改善效果。
下层正极活性材料层中的氟化聚烯烃和/或氯化聚烯烃高分子材料任选地是经过交联处理的。
为了使得下层正极活性材料层具有较好的延展性，并兼具良好的导电性和稳定性，相对于所述下层正极活性材料层的总重量(即，将第一高分子材料、第 一导电材料、第一正极活性材料和任选存在的其他助剂的总重量视为100％)，所述高分子材料的重量百分比通常为35wt％-75wt％，优选为40wt％-75wt％，更优选为50wt％-75wt％。
其次，发明人发现，下层正极活性材料层中的第一正极活性材料可以作为无机填料起到稳定下层正极活性材料层的作用。
已发现当下层正极活性材料层中不含有无机填料时，处于下层正极活性材料之上的上层正极活性材料层中的溶剂(如NMP等)或电解液会对下层正极活性材料层中的高分子材料产生溶解、溶胀等不良影响，从而下层正极活性材料层会遭到破坏，影响下层正极活性材料层的稳定性。在添加了无机填料后，该无机填料相当于一种阻隔物质，从而有利于消除上述溶解、溶胀等不良影响，有利于稳定下层正极活性材料层。此外，还发现无机填料的添加还有利于保证在极片压实过程中，下层正极活性材料层不易变形。因此无机填料的添加可以很好地保证胶层稳定地处于集流体与上层正极活性材料层之间，防止集流体与上层正极活性材料层直接接触，从而可以改善电池的安全性能。
下层正极活性材料层中包含的第一正极活性材料相当于一种阻隔物质，从而有利于消除上层正极活性材料层中的溶剂(如NMP等)或电解液对下层正极活性材料层中包含的第一高分子材料中的氟化聚烯烃和/或氯化聚烯烃的溶解、溶胀等不良影响，有利于稳定下层正极活性材料层。
还发现下层正极活性材料层中包含的第一正极活性材料的存在还有利于保证在极片压实过程中，下层正极活性材料层不易变形。因此可以很好地保证下层正极活性材料层稳定地处于集流体与上层正极活性材料层之间，防止集流体与上层正极活性材料层直接接触，从而可以改善电池的安全性能。
概括而言，下层正极活性材料层中包含的第一正极活性材料可以从如下两个方面起到稳定和改善下层正极活性材料层作为胶层发挥作用的技术效果的作用：
(1)阻碍上层正极活性材料层中的溶剂(如NMP等)或电解液对下层正极活性材料层中的氟化聚烯烃和/或氯化聚烯烃高分子材料的溶解、溶胀等不良影响；(2)有利于保证在极片压实过程中，下层正极活性材料层不易变形，以避免集流体与上层正极活性材料层之间的直接接触。
基于下层正极活性材料层的总重量，所述第一正极活性材料的重量百分比A％通常满足10wt％≤A％≤60wt％。含量过小，不足以稳定下层正极活性材料层；含量过大，则会影响下层正极活性材料层的PTC性能。第一正极活性材料的重量百分比优选为15wt％-45wt％。
发明人发现，除了第一正极活性材料之外，许多其他无机填料也可具有类似的技术效果。例如金属氧化物、非金属氧化物、金属碳化物、非金属碳化物、无机盐中的至少一种，或上述材料的导电碳包覆改性、导电金属包覆改性或导电聚合物包覆改性的材料中的至少一种。
例如，所述其他无机填料可以选自氧化镁、氧化铝、二氧化钛、氧化锆、二氧化硅、碳化硅、碳化硼、碳酸钙、硅酸铝、硅酸钙、钛酸钾、硫酸钡中的至少一种。
但是，发明人发现，使用正极电化学活性材料(即第一正极活性材料)或正极电化学活性材料的导电碳包覆改性、导电金属包覆改性或导电聚合物包覆改性的材料替代其他无机填料具有特别的优势。这种情况下，第一正极活性材料还可以发挥如下两方面的作用：(1)改善电池的过充性能：由于电化学活性材料(即第一正极活性材料)具有嵌脱锂离子的特点，在过充过程中，电化学活性材料会脱锂且脱锂难度越来越大，阻抗不断增加，因此当电流通过时，产热功率增大，胶层的温度增加速度更快，从而造成下层活性材料层中的高分子材料体积增大，下层活性材料层中导电材料组成的导电网络遭到“破坏”，胶层中的电阻增大，从而可以改善电池的过充安全性能；(2)贡献充放电容量：由于电化学活性材料(即第一正极活性材料)可以在电池正常工作温度下贡献一定的充放电容量，因此可 使得在正常工作温度下下层活性材料层对电池的容量等电化学性能的影响降至最低。
第一正极活性材料可选自钴酸锂、镍锰钴酸锂、镍锰铝酸锂、磷酸铁锂、磷酸钒锂、磷酸钴锂、磷酸锰锂、磷酸锰铁锂、硅酸铁锂、硅酸钒锂、硅酸钴锂、硅酸锰锂、尖晶石型锰酸锂、尖晶石型镍锰酸锂、钛酸锂、或它们的导电碳包覆改性材料、导电金属包覆改性材料或导电聚合物包覆改性材料中的至少一种。第一正极活性材料优选为磷酸铁锂、磷酸钒锂、磷酸钴锂、磷酸锰锂、磷酸锰铁锂或它们的导电碳包覆改性材料、导电金属包覆改性材料或导电聚合物包覆改性材料中的至少一种。其一是由于磷酸铁锂、磷酸钒锂、磷酸钴锂、磷酸锰锂、磷酸锰铁锂等物质本身安全性能较高，在过充时不释氧；其二是相对于钴酸锂、镍锰钴酸锂等材料来说，上述材料在过充时电阻增加更大，使底涂层(即下层正极活性材料层)产热较多，从而使下层正极活性材料层更快地“执行”PTC效应。
当第一正极活性材料的颗粒粒径过小时，比表面积增大，副反应会增多；过大时，会造成下层正极活性材料层的涂布厚度过大且厚度易不均匀。优选地，下层正极活性材料层中的第一正极活性材料的平均粒径D满足100nm≤D≤10μm，更优选为1μm≤D≤6μm。第一正极活性材料的颗粒粒径处于上述范围时，还可以改善高温下阻隔导电网络的效果，从而改善其作为下层正极活性材料层的响应速度。
还优选地，下层正极活性材料层中的第一正极活性材料的比表面积(BET)为不大于500m 2/g。第一正极活性材料比表面积增大时，副反应会增多影响电池性能；而且第一正极活性材料比表面积过大时，需消耗更高比例的粘结剂，会造成下层正极活性材料层与集流体、上层正极活性材料层之间的粘结力降低，内阻增长率较高。当第一正极活性材料的比表面积(BET)为不大于500m 2/g时，可以提供更好的综合效果。
作为本申请的一种进一步改进，当第一正极活性材料的电导率σ满足10 -3 S/m≤σ≤10 2S/m时，会带来额外的好处。发明人发现第一正极活性材料的添加会影响胶层的导电性能，进而可能影响整个极片的导电性。当第一正极活性材料的电导率σ满足10 -3S/m≤σ≤10 2S/m时，可以使下层正极活性材料层在电池正常使用温度下的导电性能得以改善。若第一正极活性材料的电导率σ过小，则下层正极活性材料层的初始内阻和内阻增长率会很高；σ过高，则导电网络不易被切断，不利于改善过充安全和穿钉安全。
本领域技术人员可以理解：如果某些第一正极活性材料的电导率σ不满足10 -3S/m≤σ≤10 2S/m，则可以通过本领域常用的材料修饰或改性手段使得其电导率满足上述要求。
第三，发明人发现，控制下层正极活性材料层中第一导电材料的含量有助于进一步优化下层正极活性材料层的安全性能。
除了第一高分子材料和第一正极活性材料，设置于集流体与上层正极活性材料层之间的下层正极活性材料层还包含第一导电材料。
为了在正常的工作条件下，电池可正常地进行电化学反应，下层正极活性材料层中必须包含一定含量的导电材料。导电材料的含量过低，则不利于电池在正常的工作条件下的电化学反应，内阻过大；导电材料的含量过高，则导电网络不易被破坏，从而不利于电池的过充安全性能的改善。
在本申请中，相对于下层正极活性材料层的总重量，所述第一导电材料的重量百分比C％通常满足5wt％≤C％≤25wt％，优选为5wt％≤C％≤20wt％。
优选地，第一高分子材料与第一导电材料的重量比大于等于2，更优选地上述重量比大于等于3且小于等于8。
所述第一导电材料可以选自导电碳基材料、导电金属材料和导电聚合物材料中的至少一种，其中导电碳基材料选自导电炭黑、乙炔黑、石墨、石墨烯、碳纳米管、碳纳米纤维中的至少一种；导电金属材料选自Al粉、Ni粉、金粉中的至少一种；导电聚合物材料选自导电聚噻吩、导电聚吡咯、导电聚苯胺中的至少 一种。第一导电材料可单独使用一种或组合使用两种以上。
第一导电材料通常以粉末或颗粒的形式使用。取决于具体应用环境，其粒径可以是5nm-500nm，例如10nm-300nm、15nm-200nm、15nm-100nm、20nm-400nm、20nm-150nm等等。
本申请的下层正极活性材料层可以通过常规方法来形成。例如，通过将第一高分子材料、第一导电材料、第一正极活性材料和可选的其他助剂溶解在溶剂中并搅拌形成浆料，然后将浆料涂覆到集流体之上，加热烘干即可得到所需下层正极活性材料层。
在本申请的一些优选实施方式中，且本申请的下层正极活性材料层可以基本上由所述第一高分子材料(包括胶层基体和任选存在的高分子粘结剂)、第一导电材料和第一正极活性材料组成，即不含显著量(例如含量≤3％、≤1％、或≤0.5％)的其他组分。
在本申请的正极极片中，下层正极活性材料层直接粘附在集流体之上，设置于集流体和上层正极活性材料层之间。所述下层正极活性材料层的厚度H可以根据实际需要进行合理确定。所述下层正极活性材料层的厚度H通常为不大于40μm，优选的为不大于25μm，更优选的为不大于20μm、15μm或10μm。下层正极活性材料层的涂布厚度通常为大于或等于1μm，优选的为大于或等于2μm，更优选为大于或等于3μm。厚度过小，不足以保证下层正极活性材料层改善电池安全性能的效果；过大，会造成电池内阻增大严重，从而影响电池正常工作时的电化学性能。优选地1μm≤H≤20μm，更优选地3μm≤H≤10μm。
通常下层正极活性材料层和上层正极活性材料层在涂布并烘干之后，不易分离，因此在本申请中，将下层正极活性材料层与上层正极活性材料层统称为膜片层。因此膜片层与集流体之间的结合力与下层正极活性材料层与集流体之间的结合力相当。优选下层正极活性材料层与集流体之间的结合力优选大于等于10N/m。较大的结合力可以保证下层正极活性材料层有效地、可靠地在穿钉等异 常情况下包裹集流体以及集流体中产生的金属毛刺。
发明人还发现，本申请中，膜片层的延展率对于极片的穿钉安全性能有一定影响。
对于常规的锂离子电池的正极活性材料层来说(即不含下层正极活性材料层的膜片层)，其延展率一般不超过1％，无法起到包裹金属毛刺的作用，因此裸露的金属毛刺易于导致电池内短路。而根据本申请的正极极片，由于下层正极活性材料层的引入，膜片层的延展率得到了很大的提高，可以包裹集流体中可能产生的金属毛刺，防止电池内短路的发生，从而大大改善电池的穿钉安全性。
作为本申请的一种进一步改进，所述膜片层的延展率为大于等于30％，优选大于等于80％。较大延展率的好处是：在穿钉等异常情况下，延展率较大的膜片层可以包裹集流体中可能产生的金属毛刺，防止电池内短路的发生，从而大大改善电池的穿钉安全性。
膜片层的延展率可通过改变下层正极活性材料层中第一高分子材料的种类、相对用量、分子量、交联程度等来进行调整。若增大下层正极活性材料层中的第一高分子材料的含量，则必然会对膜片层的延展率的提高有益。然而若下层正极活性材料层中的第一高分子材料的含量过大，则会造成导电材料的含量相对较低，由此造成正常工作时电池的DCR增长较大。因此优选膜片层的延展率大于等于80％且小于等于300％。
(二)上层正极活性材料层
本申请的正极极片的上层正极活性材料层可以为本领域常用的锂离子电池的正极活性材料层，也包含正极活性材料(第二正极活性材料)、粘结剂(第二高分子材料)和导电材料(第二导电材料)。上层活性材料层的组成与现有技术中用于正极极片的常规正极活性材料层相同，其构成和制备方法也是本领域公知的。但是，本申请对于上层正极活性材料层中各组分含量有限制。基于上层正极活性材料层的总重量，第二正极活性材料的重量百分含量为A′％，第二高分 子材料的重量百分含量为B′％，第二导电材料的重量百分含量为C′％，则需满足：A％<A′％，B％>B′％，C％≥C′％。
本领域技术人员可以根据下层正极活性材料层的A％、B％、C％来合理确定A′％、B′％、C′％的范围。它们的范围可以例如如下：第二正极活性材料满足90wt％≤A′％≤99wt％，第二高分子材料满足0.5wt％≤B′％≤5wt％，第二导电材料满足0.5wt％≤C′％≤5wt％。
本申请中，下层正极活性材料层和上层正极活性材料层中所使用的高分子材料、正极活性材料和导电材料种类可以不同，也可以相同(或是部分相同)。
上层正极活性材料层中的正极活性材料，可以使用本领域技术人员公知的各种用于制备锂离子二次电池正极的正极活性物质，例如该正极活性物质为含锂复合金属氧化物，具体材料例如是LiCoO 2、LiNiO 2、LiMn 2O 4、LiFePO 4、锂镍钴锰氧化物中的一种或几种(如LiNi 0.8Co 0.1Mn 0.1O 2)和锂镍锰氧化物中的一种或几种。
上层正极活性材料层中的第二高分子材料(粘结剂)例如可以是PVDF、PVDC、SBR、CMC、聚丙烯酸酯、聚碳酸酯、聚环氧乙烷等常规粘合剂。
上层正极活性材料层中的第二导电材料例如可以是导电炭黑、乙炔黑、石墨、石墨烯、碳纳米管、碳纳米纤维中的至少一种等常规导电剂。
(三)集流体
对于集流体的材料，可以使用本领域常用的材料，优选金属集流体，例如不锈钢、铝、铜、钛等金属薄片或金属箔。金属集流体的厚度通常为4μm～16μm。
优选地，所述集流体为含铝多孔集流体(多孔铝箔)。由于在穿钉等异常情况下，多孔铝箔的使用可以降低金属毛刺的产生概率，并进而降低发生剧烈铝热反应的概率，因此可以进一步改善电池的安全性。此外，多孔铝箔的使用还可以改善电解液浸润极片，并进而改善锂离子电池的动力学性能；而下层正极活性材 料层则可以覆盖在多孔铝箔的表面，防止上层活性材料层在涂布过程中的漏涂现象。
另外考虑到穿钉安全性，集流体的断裂伸长率对于电池安全性有很大影响。如果集流体的断裂伸长率过大，则金属毛刺较大，不利于改善电池的安全性能；如果集流体的断裂伸长率过小，则在极片压实等加工过程中或电池受到挤压或碰撞时容易出现断裂，降低电池质量或安全性。因此，为了进一步改善安全性，尤其是穿钉安全性，集流体的断裂伸长率δ应该不大于4％且不小于0.8％。金属集流体的断裂伸长率可通过改变金属集流体的纯度、杂质含量和添加剂、坯料生产工艺、轧制速度、热处理工艺等进行调整。
(四)正极极片
本申请中所述电池的正极极片可以通过常规方法来形成。例如，通过将第一正极活性材料、第一高分子材料、第一导电材料和可选的其他助剂溶解在溶剂中并搅拌形成浆料，然后将浆料涂覆到集流体之上，加热烘干即可得到下层正极活性材料层。通过将第二正极活性材料、第二高分子材料、第二导电材料和可选的其他助剂溶解在溶剂中并搅拌形成浆料，然后将浆料涂覆到下层正极活性材料层上，加热烘干即可得到上层正极活性材料层。然后对包含下层正极活性材料层和上层正极活性材料层的集流体进行冷压、切边、裁片等后处理即可得到所需正极极片。
本领域技术人员可以理解：以上提到的本申请的不同实施方式中对于各组分选择、组分含量和材料理化性能参数(厚度、粒径、比表面积、断裂伸长率等)的各种限定或优选范围可以任意组合，其组合而得到的各种实施方式仍然在本申请范围内，且视为本说明书公开内容的一部分。
(五)本申请的电池
本申请的电池除了如上所述的正极极片还包括隔膜和负极极片。用于与根据本申请的正极极片配合使用的负极极片可以选用本领域常用的各种常规负极 极片，其构成和制备方法是本领域公知的。例如，负极极片可以包括负极集流体和设置于负极集流体上负极活性材料层，所述负极活性材料层可以包括负极活性材料、粘结剂和导电材料等。负极活性材料例如为诸如石墨(人造石墨或天然石墨)、导电炭黑、碳纤维等的碳质材料，例如Si、Sn、Ge、Bi、Sn、In等金属或半金属材料或其合金，含锂氮化物或含锂氧化物，锂金属或锂铝合金等。
用于本申请的电池的隔膜可以选用本领域常用的各种隔膜。
本申请的电池通常还包括电解液。可以选用本领域常用的各种电解液，例如电解质盐在非水溶剂中的溶液。例如，对于锂电池，可以使用电解质锂盐和非水溶剂的混合溶液。电解质锂盐可选自六氟磷酸锂(LiPF 6)、高氯酸锂、四氟硼酸锂、六氟砷酸锂、卤化锂、氯铝酸锂、氟烃基磺酸锂中的一种或几种。有机溶剂可以选自链状碳酸酯、环状碳酸酯或它们组成的混合溶剂。其中，链状碳酸酯可以为碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)以及其他含氟、含硫或含不饱和键的链状有机酯类中的至少一种。环状碳酸酯可以为碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚乙烯酯(VC)、γ-丁内酯(γ-BL)、磺内酯以及其他含氟、含硫或含不饱和键的环状有机酯类中的一种或多种。
本申请的电池可以为一次电池或二次电池。本申请的电池可以是锂离子电池或钠离子电池，优选锂离子电池，例如可以为锂离子一次电池或锂离子二次电池。除了使用了如上所述的正极极片外，这些电池的构造和制备方法本身是公知的。由于使用了上述的正极极片，所述电池可以具有改善的安全性(如穿钉安全性)和电性能。并且根据本申请的正极极片容易加工，因此可以降低使用了根据本申请的正极极片的电池的制造成本。
图2是锂离子电池5的一实施方式的立体图。图3是图2的分解图。参照图2至图3，锂离子电池5包括壳体51、电极组件52、顶盖组件53以及电解液(未示出)。
电极组件52收容于壳体51内。电极组件52的数量不受限制，可以为一个或多个。电极组件52包括正极极片、负极极片、隔离膜。隔离膜将正极极片和负极极片隔开。电解液注入在壳体51内并浸渍电极组件52，所述电极组件包括例如第一极片、第二极片以及隔离膜。
注意的是图2所示的锂离子电池5为罐型电池，但不限于此，锂离子电池5可以是袋型电池，即壳体51由金属塑膜替代且取消顶盖组件53。
接下来说明本申请又一方面的电池模块。
图4是电池模块4的一实施方式的立体图。
本申请的实施方式提供的电池模块4包括本申请的锂离子电池5。
参照图4，电池模块4包括多个电池5。多个锂离子电池5沿纵向排列。电池模块4可以作为电源或储能装置。电池模块4中的锂离子电池5的数量可以根据电池模块4的应用和容量进行调节。
接下来说明本申请又一方面的电池包。
图5是电池包1的一实施方式的立体图。图6是图5的分解图。
本申请提供的电池包1包括本申请的一实施方式所述的电池模块4。
具体地，参照图5和图6，电池包1包括上箱体2、下箱体3以及电池模块4。上箱体2和下箱体3组装在一起并形成收容电池模块4的空间。电池模块4置于组装在一起的上箱体2和下箱体3的空间内。电池模块4的输出极从上箱体2和下箱体3的其中之一或二者之间穿出，以向外部供电或从外部充电。电池包1采用的电池模块4的数量和排列可以依据实际需要来确定。
接下来说明本申请又一方面的装置。
图7是锂离子电池作为电源的装置的一实施方式的示意图。
本申请提供的装置包括本申请的一实施方式所述的锂离子电池5，所述锂离子电池5可以用作所述装置的电源。在图7中，采用锂离子电池5的装置为电动汽车。当然不限于此，采用锂离子电池5的装置可以为除电动汽车外的任何电动车辆(例如电动大巴、电动有轨电车、电动自行车、电动摩托车、电动踏板车、电动高尔夫球车、电动卡车)、电动船舶、电动工具、电子设备及储能系统。电动汽车可以为电动纯电动车、混合动力电动车、插电式混合动力电动车。当然，依据实际使用形式，本申请提供的装置可包括本申请所述的电池模块4，当然，本申请提供的装置也可包括本申请的所述的电池包1。
实施例
为了使本申请的发明目的、技术方案和有益技术效果更加清晰，以下结合实施例进一步详细描述本申请。但是，应当理解的是，本申请的实施例仅仅是为了解释本申请，并非为了限制本申请，且本申请的实施例并不局限于说明书中给出的实施例。实施例中未注明实验条件采用常规条件，或采用材料供应商或设备供应商推荐的条件。
1、制备方法
如无特殊指明，各实施例和对比例中的电极和电池均按照如下方法进行制备。
1.1 正极极片的制备
1)下层活性材料层的涂覆
采用一定配比的第一高分子材料(包括胶层基体材料和任选的粘结剂)、第一导电材料、第一正极活性材料(或无机填料)，加入到N-甲基-2-吡咯烷酮(NMP)中得到浆料，搅拌均匀后涂布在集流体的两个表面上，在85℃下烘干后得下层正极活性材料层。
2)上层活性材料层的涂覆
然后再将90wt％第二正极活性材料、5wt％SP(第二导电材料)和5wt％PVDF(第二高分子材料)，以NMP为溶剂，搅拌均匀后涂布在按照上述方法所制备的集流体的下层正极活性材料层上；在85℃下烘干后得到上层正极活性材料层。
3)极片的制备
然后对带有两层正极活性材料层的集流体进行冷压，然后切边、裁片、分条，再在85℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池正极极片。
在各具体实施例中使用的主要材料如下：
下层活性材料层中的粘结剂：PVDF(厂家“苏威”，型号5130)；
胶层基体材料：聚丙烯腈、聚丙烯酸、聚丙烯腈-丙烯酸酯；
第一导电材料(导电剂)：Super-P(瑞士TIMCAL公司，简称SP)；
第一正极活性材料：磷酸铁锂(简写为LFP)，碳包覆改性的磷酸铁锂(简写为LFP/C),碳包覆改性的钛酸锂(简写为Li 4Ti 5O 12/C)；
无机填料：氧化铝；
第二正极活性材料：NCM811(LiNi 0.8Co 0.1Mn 0.1O 2)。
以上所用材料均为锂电池工业领域常见和常用材料，可以通过相应的供应商通过商业途径方便地得到。
1.2 负极极片的制备
负极极片：将活性物质石墨、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5加入到溶剂去离子水中混合均匀制成阳极浆料；将阳极浆料涂布负极集流体铜箔表面上，并在85℃下烘干，然后进行切边、裁片、分条，再在110℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池负极极片。
1.3 电解液的配制
将碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3∶5∶2体积比进行混合得EC/EMC/DEC混合溶剂，接着将充分干燥的锂盐LiPF 6溶解于混合溶剂中得浓度为1M的溶液，即得电解液。
1.4 电池的制备
以12μm的聚丙烯薄膜作为隔离膜，将正极极片、隔离膜和负极极片按顺序叠好，使隔离膜处于正极极片和负极极片中间起到隔离的作用，然后卷绕成裸电芯。在75℃下真空烘烤10h，注入(按照上面“电解液的配制”所述配制的)电解液，经过真空封装、静置24h，之后用0.1C的恒定电流充电至4.2V，然后以4.2V恒压充电至电流下降到0.05C，再以0.1C的恒定电流放电至3.0V，重复2次充放电，最后以0.1C的恒定电流充电至3.8V，即完成二次电池的制备。
2、材料性能的测试
在各实施例和对比例中，除非另有指明，对于材料的物理性能参数均采用本领域的常用公知方法进行测量。
一些具体参数采用以下方法进行测试。
2.1 粒径
将材料的粉末样品分散于分散介质(蒸馏水)中，使用马尔文激光粒度仪MS2000，测量5次取平均值，单位μm。
2.2 BET(比表面积)
使用Quadrasorb SI比表面测试仪测试材料的粉末样品的比表面积，测量5次取平均值，单位m 2/g。
2.3 膜片层与集流体之间的结合力
将含集流体的双面具有膜片层的极片裁切为宽度为2cm，长度15cm的待测样品，将待测样品的一面在25℃、常压条件下，使用3M双面胶均匀贴于不锈 钢板上，将待测样品的一端固定在高铁拉力机上，使用高铁拉力机将待测样品的膜片层与集流体剥离，根据拉力和位移的数据图，读取最大拉力，将读取的值(单位N)除以样品的宽度(0.02m)，计算得到结合力(N/m)。
2.4 集流体断裂伸长率
在集流体上取2个长度为200mm，宽度为15mm的样片，用万分尺量取样品的厚度h(μm)。然后将样片固定于拉力机(型号AI7000)上，以50mm/min速度进行拉伸。2次测试的算数平均值为测试结果。记录初始长度L0，启动拉力机测试，直至样片断裂，从拉力机上读取断裂时样片的位移L1。断裂伸长率＝(L1-L0)/L0*100％。
2.5 集流体厚度、涂层厚度、膜片层厚度
集流体厚度：采用万分尺测量，测量5处取平均值。
涂层厚度、膜片层厚度：先测量集流体厚度，涂覆涂层后再测量总厚度，以两者之差作为涂层厚度。膜片层厚度采用类似的方法。
2.6 涂层开裂状况
在烘干并得到正极活性材料层之后，100m 2极片不出现裂纹定义为不开裂。100m 2极片裂纹出现次数≤3，定义为轻度开裂。100m 2极片裂纹出现次数＞3，定义为严重开裂。
2.7 高分子材料在油性溶剂中的溶解度
将高分子材料制成约7μm胶膜，裁剪成20mm*50mm长条，称重并记为M1；
将胶膜置于NMP(N-甲基吡咯烷酮)溶剂中，130℃下放置5min，取出，100℃下真空烘干；真空烘干后称量重量并记为M2；
则溶解度＝(M1-M2)/M1*100％
本申请中，为方便比较，以PVDF(厂家“苏威”，型号5130)的溶解度作为参比，记为100％，记录其它材料溶解度相对于PVDF溶解度的比值。
2.8 膜片层的延展率
取极片并去除集流体：将正极极片从电芯中取出，加入电解液，使极片完全浸泡于电解液中，置于90℃下存储48h以上，然后取出极片，正极极片的膜片层即可从集流体上剥落。
将去除集流体后的膜片层，制成宽度20mm、长度50mm的试样，用万分尺量取样品的厚度h(μm)。然后将试样固定于拉力机(型号AI7000)上，记录初始长度L0。启动拉力机测试，以50mm/min速度进行拉伸，直至试样断裂。从拉力机上读取断裂时试样的位移L1。延展率＝(L1-L0)/L0*100％。
3、电池的性能测试
采用GBT31485-2015《电动汽车用动力蓄电池安全要求及试验方法》对各实施例和对比例的二次电池的安全性进行评估，并记录测试结果。
3.1 针刺测试：
将二次电池以1C电流满充至充电截止电压，再恒压充电至电流降至0.05C，停止充电。用
Figure PCTCN2019118694-appb-000001
的耐高温钢针(针尖的圆锥角度为45°)，以25mm/s的速度，从垂直于电池极板的方向贯穿，贯穿位置宜靠近所刺面的几何中心，钢针停留在电池中，观察电池是否有燃烧、爆炸现象。
针对20个电池样品进行测试。
3.2 过充测试：
将二次电池以1C电流满充至充电截止电压，再恒压充电至电流降至0.05C，停止充电。然后，以1C电流恒流至充电终止电压的1.5倍或充电1h后停止充电。
针对20个电池样品进行测试。
3.3 循环性能测试：
循环次数测试条件为：在25℃下，将二次电池进行1C/1C循环测试，充放 电电压范围2.8～4.2V，容量衰减至首次放电比容量的80％时停止测试，并记录循环次数。
3.4 直流电阻增长率测试
将二次电池以1C电流满充至充电截止电压，再恒压充电至电流降至0.05C，停止充电，测试电芯直流电阻(4C电流放电10s)。然后将电芯放置于130℃下恒温1h，测试直流电阻，计算直流电阻增长率；然后将电芯放置于130℃下恒温2h，测试直流电阻，计算直流电阻增长率。
3.5 DCR测试
在25℃下，以1C电流将二次电池调整至50％SOC，记录电压U1。然后以4C电流放电30秒，记录电压U2。DCR＝(U1-U2)/4C。
本申请中，为方便比较，以第一高分子材料仅含非交联PVDF作为高分子基体的电芯的DCR作为参比，记为100％，计算和记录其它电芯的DCR和其比值。
4、性能测试结果
4.0 胶层基体材料的溶解度
选择不同的高分子材料，按照上述“2.7 130℃、5min内于NMP中的溶解度”中所述方法测量溶解度，结果如下：
130℃、5min内于NMP中的溶解度：
材料 溶解度
PVDF 100％
聚丙烯腈 8％
聚丙烯腈-丙烯酸酯 12％
聚丙烯酸酯 15％
上述结果表明，聚丙烯腈、聚丙烯腈-丙烯酸酯、聚丙烯酸酯均为在130℃、 5min内于NMP中的溶解度为相同条件下PVDF的溶解度的30％以下的油性高分子材料，因此适于作为本申请中的第一高分子材料中的胶层基体材料使用。
4.1 下层正极活性材料层的防护效果和对电池性能的影响
为了验证下层正极活性材料层的防护效果，以下面表1-1中所列出的具体材料和用量，按照“1、制备方法”所描述的方法和步骤制备出相应的下层正极活性材料层、正极极片、负极极片和电池，然后按照“3、电池的性能测试”部分规定方法进行测试。为了保证数据准确，每种电池制备4个(用于针刺测试或过充测试的电池制备20个)并独立测试，最终测试结果取平均值，示于表1-2。
其中，常规极片P基本按照“1.1正极极片的制备”所述方法进行制备，但是不设置下层正极活性材料层，即上层正极活性材料层直接涂覆在集流体上，常规极片N按照“1.2负极极片的制备”所述方法制备。
表1-1：极片组成
Figure PCTCN2019118694-appb-000002
表1-2：锂离子电池的性能测试结果
Figure PCTCN2019118694-appb-000003
表1-1和表1-2的数据表明：
(1)若采用溶解、溶胀比较大的高分子材料(例如PVDF)作为下层正极活性材料层基体材料(胶层基体)，则会产生开裂、电池DCR恶化的问题，而采用聚丙烯腈等溶解、溶胀相对较小的高分子材料作为下层正极活性材料层基体材料(胶层基体)，则明显改善了上述问题，且由聚丙烯腈等溶解、溶胀相对较小的高分子材料组成的下层正极活性材料层相对于常规正极极片而言，也进一步明显改善了电池的穿钉安全性能；
(2)下层正极活性材料层中不添加第一正极活性材料(LFP/C)的极片，由于下层正极活性材料层会发生变形或被破坏，因而抗穿钉改善效果无法保证；而添加了第一正极活性材料的下层正极活性材料层则有效改善了电池的穿钉安全性能。
综合考虑穿钉性能、涂层开裂情况和电池电阻DCR等因素，上述电池中以使用了极片1、2、3的电池3、4、5的性能最为均衡，既具有相对较好的穿钉安全性能，在涂布时也不会造成涂层开裂，另外DCR也可以接受。
4.2 下层正极活性材料层中组分含量的影响
为了进一步研究下层正极活性材料层中组分含量的影响，以下面表2-1中所列出的具体材料和用量，按照“1、制备方法”所描述的方法和步骤制备出相应的下层正极活性材料层、正极极片、负极极片和电池，然后按照“3、电池的性能测试”部分规定方法进行测试。为了保证数据准确，每种电池制备4个(用于针刺测试或过充测试的电池制备20个)并独立测试，最终测试结果取平均值，总结于表2-2。
表2-1：极片组成
Figure PCTCN2019118694-appb-000004
表2-2：锂离子电池的性能测试结果
电池 正极 负极 针刺测试(20个电池) 循环寿命(cycle)
电池3 极片1 常规极片N 10个通过 1600
电池3-1 对比极片1-1 常规极片N 5个通过 1880
电池3-2 对比极片1-2 常规极片N 15个通过 1170
电池3-3 对比极片1-3 常规极片N 12个通过 1060
电池3-4 极片1-4 常规极片N 13个通过 1300
电池3-5 极片1-5 常规极片N 14个通过 1200
电池3-6 极片1-6 常规极片N 12个通过 1250
电池3-7 极片1-7 常规极片N 10个通过 1900
电池3-8 极片1-8 常规极片N 9个通过 1890
电池3-9 极片1-9 常规极片N 8个通过 1300
表2-1和表2-2的数据表明：(1)第一正极活性材料含量过低，则下层正极活性材料层的易于变形、稳定性不高，因此电池的安全性能不能得到充分改善；第一正极活性材料含量过高，则胶层基体材料含量会过低，则下层正极活性材料层延展性降低，无法保证下层正极活性材料层正常发挥改善穿钉安全的效果；(2)第一导电材料对电池的内阻、极化的影响较大，因此会影响电池的循环寿命，第一导电材料含量越高，则电池的内阻、极化越小，则循环寿命越好。
经实验发现下层正极活性材料层的各组分的适当含量范围如下：
第一高分子材料的重量百分比为35wt％-75wt％；
第一导电材料的重量百分比为5wt％-25wt％；且
第一正极活性材料的重量百分比为10wt％-60wt％。
只要下层正极活性材料层的各组分含量在以上范围内，就可以实现改善电池的安全性和电性能(如循环性能)的效果。
4.3 第一正极活性材料种类对电池性能的影响
为了进一步研究下层正极活性材料层中材料选择对极片和电池性能的影响，以下面表3-1中所列出的具体材料和用量，按照“1、制备方法”所描述的方法和步骤制备出相应的下层正极活性材料层、正极极片、负极极片和电池，然后按照“3、电池的性能测试”部分规定方法进行测试。为了保证数据准确，每种电池制备4个(用于针刺测试或过充测试的电池制备20个)并独立测试，最终测试结果取平均值，总结于表3-2。
表3-1：极片组成
Figure PCTCN2019118694-appb-000005
表3-2：锂离子电池的性能测试结果
电池 正极 负极 针刺测试 过充测试
电池3 极片1 常规极片N 10个通过 全部通过
电池3-11 极片1-11 常规极片N 9个通过 全部不通过
电池3-12 极片1-12 常规极片N 10个通过 全部通过
表3-1和表3-2的数据表明，(1)以氧化铝作为无机填料的话，也改善了电池的穿钉安全性能；(2)然而相对于其他材料(例如氧化铝)来说，电化学活性材料(即第一正极活性材料)进一步明显改善了电池的过充安全性能。
4.4 加入粘结剂对电池性能的影响
为了进一步研究下层正极活性材料层中粘结剂的选择对极片和电池性能的影响，以下面表表4-1中所列出的具体材料和用量，按照“1、制备方法”所描述的方法和步骤制备出相应的下层正极活性材料层、正极极片、负极极片和电池，然后按照“3、电池的性能测试”部分规定方法进行测试。为了保证数据准确，每种电池制备4个(用于针刺测试或过充测试的电池制备20个)并独立测试，最终测试结果取平均值，总结于表4-2。
表4-1和表4-2的数据表明，当下层正极活性材料层中添加了高分子粘结剂PVDF之后，电池的穿钉安全性能得到了进一步改善，尤其是PVDF的含量在 15wt％以上的时候；然而由于PVDF在NMP中的溶解溶胀较大，因此会恶化电池DCR并在聚丙烯腈的含量过小时带来涂层开裂问题。
本领域技术人员可以理解：以上仅以锂电池为例示出了本申请的极片的应用实例，但是本申请的极片同样可以应用于其它类型的电池或电化学装置，而仍然可以获得本申请的良好技术效果。而且，本领域技术人员可以理解，本申请还公开了如上所述的正极极片的各种实施方式。
根据上述说明书的揭示和教导，本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此，本申请并不局限于上面揭示和描述的具体实施方式，对本申请的一些修改和变更也应当落入本申请的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本申请构成任何限制。
表4-1：极片组成
Figure PCTCN2019118694-appb-000006
1，2:相对于下层正极活性材料层总重量的重量百分百；3:相对于第一高分子材料总重量(即胶层基体+高分
表4-2：锂离子电池的性能测试结果
Figure PCTCN2019118694-appb-000007

Claims (14)

  1. 一种电池，包括正极极片、隔膜和负极极片，其中所述正极极片包括正极集流体和涂覆在所述正极集流体的至少一个表面上的至少两层正极活性材料层，
    与所述正极集流体接触的下层正极活性材料层包含第一正极活性材料、第一高分子材料和第一导电材料，基于所述下层正极活性材料层的总重量，所述第一正极活性材料的重量百分含量为A％，所述第一高分子材料的重量百分含量为B％，所述第一导电材料的重量百分含量为C％，
    与所述下层正极活性材料层接触而远离所述正极集流体的上层正极活性材料层包含第二正极活性材料、第二高分子材料和第二导电材料，基于所述上层正极活性材料层的总重量，所述第二正极活性材料的重量百分含量为A′％，所述第二高分子材料的重量百分含量为B′％，所述第二导电材料的重量百分含量为C′％，
    其中：
    A％<A′％，B％>B′％，C％≥C′％，
    所述第一高分子材料包含在130℃、5min内于NMP中的溶解度为相同条件下PVDF的溶解度的30％以下的油性高分子材料。
  2. 根据权利要求1所述的电池，其中，所述第一正极活性材料满足10wt％≤A％≤60wt％，所述第一高分子材料满足35wt％≤B％≤75wt％，且所述第一导电材料满足5wt％≤C％≤25wt％；和/或，
    所述第二正极活性材料满足90wt％≤A′％≤99wt％，所述第二高分子材料满足0.5wt％≤B′％≤5wt％，所述第二导电材料满足0.5wt％≤C′％≤5wt％。
  3. 根据权利要求1或2所述的电池，其中所述第一高分子材料全部为所述油性高分子材料或为所述油性高分子材料与高分子粘结剂组成的混合材料，
    优选地，所述高分子粘结剂为氟化聚烯烃和/或氯化聚烯烃高分子材料，且相对于所述第一高分子材料，
    所述油性高分子材料的重量百分比为30wt％-100wt％，且
    所述高分子粘结剂的重量百分比为0wt％-70wt％。
  4. 根据权利要求1至3任一项所述的电池，其中所述第一高分子材料中的所述油性高分子材料相对于所述下层正极活性材料层总重量的重量百分比为大于等于20wt％。
  5. 根据权利要求1至4任一项所述的电池，其中所述油性高分子材料选自油性聚丙烯腈、油性聚丙烯酸、油性聚丙烯酸酯、油性聚丙烯酸-丙烯酸酯、油性聚丙烯腈-丙烯酸、油性聚丙烯腈-丙烯酸酯中的至少一种。
  6. 根据权利要求3所述的电池，其中所述氟化聚烯烃和/或氯化聚烯烃高分子材料选自聚偏氟乙烯(PVDF)、羧酸改性的PVDF、丙烯酸改性的PVDF、聚偏氯乙烯(PVDC)、羧酸改性的PVDC、丙烯酸改性的PVDC、PVDF共聚物、PVDC共聚物中的至少一种。
  7. 根据权利要求1至6任一项所述的电池，其中所述第一导电材料选自导电碳基材料、导电金属材料和导电聚合物材料中的至少一种，优选地，
    所述导电碳基材料选自导电炭黑、乙炔黑、石墨、石墨烯、碳纳米管、碳纳米纤维中的至少一种；
    所述导电金属材料选自Al粉、Ni粉、金粉中的至少一种；
    所述导电聚合物材料选自导电聚噻吩、导电聚吡咯、导电聚苯胺中的至少一种。
  8. 根据权利要求1至7任一项所述的电池，其中所述第一正极活性材料选自钴酸锂、镍锰钴酸锂、镍锰铝酸锂、磷酸铁锂、磷酸钒锂、磷酸钴锂、磷酸锰锂、磷酸锰铁锂、硅酸铁锂、硅酸钒锂、硅酸钴锂、硅酸锰锂、尖晶石型锰酸锂、尖晶石型镍锰酸锂、钛酸锂、或上述材料的导电碳包覆改性材料、导电金属包覆 改性材料或导电聚合物包覆改性材料中的至少一种；
    优选地，所述第一正极活性材料为磷酸铁锂、磷酸钒锂、磷酸钴锂、磷酸锰锂、磷酸锰铁锂或上述材料的导电碳包覆改性材料、导电金属包覆改性材料或导电聚合物包覆改性材料中的至少一种；和/或
    优选地，所述第一正极活性材料的比表面积(BET)为不大于500m 2/g。
  9. 根据权利要求1至8任一项所述的电池，其中所述正极集流体的厚度为4μm至16μm。
  10. 根据权利要求1至9任一项所述的电池，其中当将所述至少两层正极活性材料层统称为正极膜片层时，所述正极膜片层与所述正极集流体之间的结合力大于等于10N/m，或者所述正极膜片层的延展率为大于等于30％。
  11. 一种如权利要求1-10中任意一项所定义的正极极片。
  12. 一种电池模块，其特征在于，包括根据权利要求1-10中任意一项所述的电池。
  13. 一种电池包，其特征在于，包括根据权利要求12所述的电池模块。
  14. 一种装置，其特征在于，包括根据权利要求1-10中任意一项所述的电池，所述电池作为所述装置的电源；优选地，所述装置包括电动车辆、混合动力电动车辆、插电式混合动力电动车辆、电动自行车、电动踏板车、电动高尔夫球车、电动卡车、电动船舶、储能系统。
PCT/CN2019/118694 2018-11-16 2019-11-15 一种电池 WO2020098768A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811367724.4 2018-11-16
CN201811367724.4A CN111200108B (zh) 2018-11-16 2018-11-16 一种电池

Publications (1)

Publication Number Publication Date
WO2020098768A1 true WO2020098768A1 (zh) 2020-05-22

Family

ID=66677045

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/118694 WO2020098768A1 (zh) 2018-11-16 2019-11-15 一种电池

Country Status (6)

Country Link
US (1) US11050053B2 (zh)
EP (1) EP3654417B1 (zh)
CN (1) CN111200108B (zh)
ES (1) ES2925641T3 (zh)
PL (1) PL3654417T3 (zh)
WO (1) WO2020098768A1 (zh)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111200159B (zh) * 2018-11-16 2021-03-23 宁德时代新能源科技股份有限公司 一种电池
CN111200103B (zh) * 2018-11-16 2021-01-08 宁德时代新能源科技股份有限公司 一种电池
CN111403749B (zh) * 2020-06-03 2020-09-01 江苏时代新能源科技有限公司 锂离子电池及其装置
CN111785923B (zh) * 2020-07-31 2023-05-05 蜂巢能源科技有限公司 锂离子电池阳极及其制备方法和应用与锂离子电池
KR20220066625A (ko) * 2020-11-16 2022-05-24 주식회사 엘지에너지솔루션 리튬 이차전지용 양극 및 리튬 이차전지
CN113422063B (zh) * 2021-06-15 2024-03-12 宁德新能源科技有限公司 电化学装置和电子装置
CN114122314A (zh) * 2021-11-05 2022-03-01 惠州锂威新能源科技有限公司 一种二次电池
EP4213246A4 (en) * 2021-11-30 2023-08-23 Contemporary Amperex Technology Co., Limited POSITIVE ELECTRODE PLATE, SECONDARY BATTERY, BATTERY MODULE, BATTERY PACK AND POWER DEVICE

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105703010A (zh) * 2014-11-28 2016-06-22 宁德时代新能源科技股份有限公司 电极片及电化学储能装置
CN106941149A (zh) * 2016-01-04 2017-07-11 宁德新能源科技有限公司 锂离子电池及其正极极片
KR20170142024A (ko) * 2016-06-16 2017-12-27 주식회사 엘지화학 용량 및 안전성이 개선된 리튬 이차전지용 양극 및 이를 포함하는 리튬 이차전지

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101740747B (zh) * 2008-11-27 2012-09-05 比亚迪股份有限公司 一种硅负极和含有该硅负极的锂离子电池
JP2013120736A (ja) * 2011-12-08 2013-06-17 Sony Corp 電極、電池、電池パック、電子機器、電動車両、蓄電装置および電力システム
EP3101716B1 (en) * 2014-01-27 2018-07-04 Sumitomo Chemical Company, Limited Positive electrode active material for lithium secondary batteries, positive electrode for lithium secondary batteries, and lithium secondary battery
JP6311670B2 (ja) * 2015-07-13 2018-04-18 トヨタ自動車株式会社 リチウムイオン二次電池用正極板の製造方法、及び、リチウムイオン二次電池用正極板
CN105098193A (zh) * 2015-09-24 2015-11-25 宁德时代新能源科技有限公司 正极片以及包括该正极片的锂离子电池
JP7074284B2 (ja) * 2017-02-10 2022-05-24 三井化学株式会社 正極及び非水電解質二次電池
CN109755468B (zh) 2017-11-08 2021-01-12 宁德时代新能源科技股份有限公司 一种电极极片、电化学装置及安全涂层

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105703010A (zh) * 2014-11-28 2016-06-22 宁德时代新能源科技股份有限公司 电极片及电化学储能装置
CN106941149A (zh) * 2016-01-04 2017-07-11 宁德新能源科技有限公司 锂离子电池及其正极极片
KR20170142024A (ko) * 2016-06-16 2017-12-27 주식회사 엘지화학 용량 및 안전성이 개선된 리튬 이차전지용 양극 및 이를 포함하는 리튬 이차전지

Also Published As

Publication number Publication date
CN111200108B (zh) 2021-03-19
US20200161640A1 (en) 2020-05-21
US11050053B2 (en) 2021-06-29
EP3654417B1 (en) 2022-08-03
CN111200108A (zh) 2020-05-26
EP3654417A1 (en) 2020-05-20
PL3654417T3 (pl) 2022-11-14
ES2925641T3 (es) 2022-10-19

Similar Documents

Publication Publication Date Title
WO2020098768A1 (zh) 一种电池
WO2020098765A1 (zh) 一种正极极片及电化学装置
WO2020098671A1 (zh) 一种正极极片及电化学装置
WO2020098743A1 (zh) 一种电池
WO2020098769A1 (zh) 一种正极极片及电化学装置
WO2020098787A1 (zh) 一种正极极片及电化学装置
WO2020098783A1 (zh) 一种电池
WO2020098784A1 (zh) 一种电池
WO2020098789A1 (zh) 一种电化学装置
WO2020098792A1 (zh) 一种正极极片及电化学装置
WO2020098797A1 (zh) 一种正极极片及电化学装置
WO2020098791A1 (zh) 一种正极极片及电化学装置
WO2020098742A1 (zh) 一种电池
WO2020098778A1 (zh) 一种电池
WO2020098745A1 (zh) 一种电池
WO2020098788A1 (zh) 一种正极极片及电化学装置
WO2020098770A1 (zh) 一种正极极片及电化学装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19883900

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19883900

Country of ref document: EP

Kind code of ref document: A1