WO2014134967A1 - Positive electrode film of lithium ion battery and preparation and application therefor - Google Patents

Positive electrode film of lithium ion battery and preparation and application therefor Download PDF

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Publication number
WO2014134967A1
WO2014134967A1 PCT/CN2013/091128 CN2013091128W WO2014134967A1 WO 2014134967 A1 WO2014134967 A1 WO 2014134967A1 CN 2013091128 W CN2013091128 W CN 2013091128W WO 2014134967 A1 WO2014134967 A1 WO 2014134967A1
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lithium
positive electrode
battery
lithium ion
electrode film
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PCT/CN2013/091128
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French (fr)
Chinese (zh)
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王辰云
刘现军
刘杨
方燕群
王德宇
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中国科学院宁波材料技术与工程研究所
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Publication of WO2014134967A1 publication Critical patent/WO2014134967A1/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0438Processes of manufacture in general by electrochemical processing
    • H01M4/044Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the invention belongs to the field of lithium ion batteries.
  • the present invention relates to a positive electrode film for a lithium ion battery and its preparation and use. Background technique
  • lithium-ion batteries Since its commercialization in the early 1980s, lithium-ion batteries have been widely used in portable electronic devices such as mobile phones, notebook computers, and compact cameras because of their high voltage, high specific energy, long cycle life, and no environmental pollution. Lithium-ion batteries can also replace traditional non-renewable resources such as oil and natural gas, and are more widely used in power tools, electric bicycles, electric vehicles, solar cells and wind energy storage, satellite and aerospace, etc. It plays an important role in saving non-renewable energy.
  • lithium ion cathode materials mainly include lithium cobaltate, lithium nickelate, lithium nickel cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate. Compounds and their modified complexes.
  • the commercial anode materials mainly include surface-modified natural graphite, mesocarbon microspheres, lithium titanate, a small amount of amorphous carbon, hard carbon, artificial graphite, and carbon silicon materials, silicon materials, and nitrogen-based materials under study. , bismuth based materials, metal alloys, etc.
  • the electrolyte is mainly a mixture of one or more of an organic solvent such as a carbonate, an ether or a nitrile and a solute such as lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate or lithium difluorooxalate borate. Solution.
  • an organic solvent such as a carbonate, an ether or a nitrile
  • a solute such as lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate or lithium difluorooxalate borate.
  • lithium ion batteries can provide energy transfer medium and an electrolyte solute material in only the positive electrode is a lithium ion Li + in the battery charging and discharging process. It has been proved that in the first charge-discharge cycle of a lithium ion battery, a solid electrolyte film (SEI) is formed on the surface of the negative electrode material of the lithium battery, and lithium ions in the lithium ion and the electrolyte are accompanied by the cycle of the lithium battery. It cannot be completely removed after being embedded in the negative electrode material. These two conditions lead to a decrease in the capacity of the lithium battery and a decrease in the cycle efficiency, especially in the first cycle.
  • SEI solid electrolyte film
  • the commonly used battery additives include three aspects of negative electrode additive, electrolyte additive and conductive agent additive, which are applied to negative electrode film formation, flame retardant and anti-overcharge functions.
  • a negative electrode additive is disclosed, wherein the negative electrode additive has the general formula F (CF2CF2) m* (CH2CH20) n-R.
  • the addition of the fluorine-containing ether compound can make the anode slurry mix more uniformly, increase the electrolyte retention, and improve the capacity and cycle performance of the battery to some extent, but the preparation method is complicated, and more toxic substances are produced. Therefore, there is an urgent need in the art to develop a method and product for solving the lithium ion battery field in the charge and discharge cycle of a lithium battery, reducing its capacity attenuation and improving its cycle efficiency. Summary of the invention
  • a positive electrode film for a lithium battery comprises:
  • the lithium intercalation transition metal oxide cathode material is selected from the group consisting of lithium cobaltate, lithium nickelate, lithium nickel cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, and manganic acid. Lithium, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof.
  • the conductive agent includes carbon black, graphite, carbon nanotubes, graphene, and the like.
  • the binder comprises polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), a copolymer of styrene and butadiene (SBR). ).
  • the positive electrode film further contains a current collector aluminum foil.
  • the lithium ion extender comprises: a lithium oxygen compound, a lithium salt, a ruthenium lithium compound, or a combination thereof.
  • the lithium oxygen compound comprises: lithium oxide, lithium peroxide, lithium superoxide, or a combination thereof;
  • the mercaptolithium compound comprises: lithium methoxide, lithium ethoxide, lithium isopropoxide, ethyl lithium, isopropyl lithium, butyl lithium or a combination thereof;
  • the lithium salt includes: lithium carbonate, lithium borohydride, lithium fluoride, lithium nitride, lithium sulfide, lithium persulfide, or a combination thereof.
  • the lithium ion extender is in a solid or liquid state.
  • the lithium ion-replenishing agent has a mass percentage of the lithium intercalated metal oxide positive electrode material of 0.5 to 10%, more preferably 1 to 3%.
  • a lithium battery positive electrode film according to the first aspect of the present invention is provided The method includes: (al) providing a positive electrode material slurry, the slurry comprising a lithium intercalation transition metal oxide positive electrode material, a lithium ion supplement, and a conductive agent and a binder; and the slurry a positive electrode film is formed by vacuum drying after coating the tablet; or
  • the method comprises: (a2) mixing a lithium ion supplement with a conductive agent, adding a lithium intercalation transition metal oxide positive electrode material and a binder, and forming a positive electrode film by vacuum drying after coating the tablet; or
  • the method comprises: (a3) applying a lithium ion extender to the surface of the positive electrode of the dried lithium ion battery, thereby forming a positive electrode film of the lithium battery containing the lithium ion extender.
  • a lithium ion battery comprising the battery positive electrode film of the first aspect of the invention.
  • the lithium ion battery further includes a negative electrode film, a separator, an electrolyte, a casing, and a battery assisting system.
  • the electrolyte is a liquid electrolyte (electrolyte) or a polymer electrolyte.
  • a method for preparing a positive electrode of a lithium ion battery comprising the steps of: bonding or coating a positive electrode film according to the first aspect of the present invention to a current collector, thereby preparing a positive electrode of a lithium ion battery .
  • the positive electrode film for a lithium battery according to the first aspect of the invention which is used for preparing a positive electrode of a lithium battery or for preparing a lithium battery.
  • a method for compensating for irreversible capacity loss of a negative electrode of a lithium ion battery or reducing lithium ion loss of a lithium ion battery comprising the steps of: adding a lithium ion supplement to a positive electrode of the lithium ion battery.
  • the lithium ion extender comprises: a lithium oxygen compound, a lithium salt, a mercaptolithium compound, or a combination thereof;
  • the adding comprises: preliminarily mixing the lithium ion supplement in the lithium intercalation transition metal oxide positive electrode material or the conductive agent, or coating the surface of the positive electrode of the lithium ion battery.
  • the method further includes compensating for the loss of lithium ions on the surface of the negative electrode of the lithium battery to form a loss of the SEI film, thereby compensating for the irreversible capacity loss of the negative electrode of the lithium ion battery or reducing the lithium ion loss of the lithium ion battery.
  • Figure 1 is the cyclic voltammogram of lithium battery 2 (half-cell), as shown in the figure, in the cycle of lithium battery 2
  • an oxidation peak appeared at about 4. 4V, indicating that lithium peroxide decomposes at 4. 4V, which decomposes to produce lithium ions, which can compensate for lithium ion loss in the cathode material and electrolyte.
  • Figure 2 shows the cyclic volt-ampere curve of a comparative lithium battery C2 (half-cell). As can be seen, at about 4. 4V, no oxidation peak appears.
  • Figure 3 is the first charge and discharge curve of the lithium battery 2, as shown in the figure, the lithium peroxide decomposition platform appears around 4. 4V, indicating that the lithium peroxide is decomposed at 4. 4V, and the lithium ion generated by the decomposition can make up the cathode material. And lithium ion loss in the electrolyte.
  • Figure 4 shows the first charge-discharge curve of the lithium battery C2. As can be seen, there is no lithium peroxide decomposition platform at around 4. 4V.
  • Fig. 5 shows the charge and discharge curves of the lithium battery 3 and the comparative lithium battery C3 (full battery). As can be seen, the discharge capacity of the lithium battery 3 is increased by about 10% compared to the lithium battery C3.
  • lithium ion battery means a secondary battery composed of two compounds capable of reversibly intercalating and deintercalating lithium ions as a positive and negative electrode, respectively.
  • lithium ions are deintercalated from the positive electrode and embedded in the negative electrode, and vice versa when discharging.
  • the positive electrode of the lithium ion battery is in a lithium intercalated state prior to assembly.
  • a lithium-intercalation transition metal oxide having good stability is selected as a positive electrode material.
  • the material of the negative electrode is not particularly limited, and may be various materials having a potential close to the lithium potential and intercalable with a lithium compound, and representative examples include, but are not limited to: natural graphite, synthetic graphite, carbon fiber, intermediate The phase ball carbon and the like and the metal oxide include Sn0, Sn0 2 , tin composite oxide and the like.
  • the electrolyte is not particularly limited and may be a liquid electrolyte (electrolyte) or a polymer electrolyte.
  • Representative examples include, but are not limited to, a mixed solvent system of sulfhydryl carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and low viscosity diethyl carbonate (DEC) using LiPF 6 .
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC low viscosity diethyl carbonate
  • lithium ion extender and “lithium ion additive” may be used interchangeably, and refer to a lithium battery additive for supplementing lithium ions applied to a positive electrode of a lithium battery.
  • the lithium ion replenishing agent which can be used in the present invention is not particularly limited, and may be any lithium ion replenishing agent having a decomposition potential lower than the oxidative decomposition potential of the electrolytic solution and higher than the discharge cutoff potential of the positive electrode of the battery.
  • the lithium ion content is the highest in lithium. While the stability of lithium is higher than that of the simple substance, the preferred lithium ion supplement is an oxidized lithium ion compound.
  • the decomposition potential of the lithium ion replenishing agent usable in the present invention should be lower than the oxidative decomposition potential of the electrolyte and higher than the discharge cutoff potential of the positive electrode of the battery.
  • lithium ion supplements are selected from:
  • Lithium-containing inorganics lithium oxide, lithium peroxide, lithium superoxide, lithium hydride, lithium fluoride, lithium nitride, lithium sulfide, aluminum lithium alloy;
  • Lithium-containing organics lithium methoxide, lithium ethoxide, lithium isopropoxide, ethyl lithium, isopropyl lithium, butyl lithium, lithium benzene hexaoxide.
  • the lithium ion extender which can be used in the present invention is preferably: lithium peroxide, lithium superoxide, lithium nitride, lithium sulfide, aluminum lithium alloy, lithium methoxide, lithium ethoxide, lithium isopropoxide, ethyl lithium, isopropyl Lithium, butyl lithium; more preferably, lithium peroxide, lithium superoxide, lithium nitride.
  • the lithium ion supplement is added to the positive electrode of the lithium ion battery by mixing the lithium ion supplement in advance in the positive electrode material or the conductive agent, or coating the surface of the dried positive electrode.
  • the lithium ion supplement will decompose and release lithium ions, which can compensate for the lithium ion loss of the SEI film formed on the surface of the negative electrode, compensate the lithium ion loss in the positive electrode material and the electrolyte, and the other decomposition products are basically not Affecting the performance of lithium ion batteries, thereby significantly improving the reversible charge and discharge capacity of lithium ion batteries, and improving the electrochemical performance of lithium ion batteries.
  • the lithium ion supplement used in the invention is chemically stable, is not easily decomposed in air, has low requirements on the process flow and environment, and has low production cost. Lithium battery positive film and preparation thereof
  • the invention provides a lithium battery positive film, comprising:
  • the lithium intercalation transition metal oxide cathode material is selected from the group consisting of lithium cobaltate, lithium nickelate, lithium nickel cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate, lithium iron phosphate, Lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof.
  • the lithium ion supplement includes: a lithium oxygen compound, a lithium salt, a mercapto lithium compound, or a combination thereof; wherein the lithium oxygen compound comprises: lithium oxide, lithium peroxide, lithium superoxide, or a combination thereof;
  • the mercaptolithium compound comprises: lithium methoxide, lithium ethoxide, lithium isopropoxide, ethyl lithium, isopropyl lithium, butyl lithium or a combination thereof;
  • the lithium salt includes: lithium carbonate, lithium borohydride, lithium fluoride, lithium nitride, lithium sulfide, lithium persulfide, or a combination thereof.
  • the lithium ion extender is in a solid state.
  • the conductive agent includes carbon black, graphite, carbon nanotubes, graphene, and the like.
  • the binder comprises PVDF, PTFE, CMC, SBR, etc., wherein PVDF is polyvinylidene fluoride, PTFE is polytetrafluoroethylene, CMC is carboxymethyl cellulose, and SBR is a copolymer of styrene and butadiene. (styrene-butadiene rubber).
  • the positive electrode film further contains a current collector aluminum foil.
  • the mass percentage of the lithium ion-containing transition metal oxide cathode material is 0.5 to 10%, more preferably 1 to 3%.
  • the lithium ion supplement provided by the present invention may be used in advance in a positive electrode material or a conductive agent, or may be applied to a surface of a dried lithium ion battery positive electrode.
  • the method of preparing the positive electrode film for a lithium battery of the present invention may be carried out by mixing a lithium ion extender into a positive electrode material or slurry of a lithium battery and/or applying it to the positive electrode of the battery after preparation of the positive electrode of the conventional lithium battery.
  • the preparation methods generally used include the following three types:
  • the positive electrode of the battery of the present invention contains the lithium ion supplement of the present invention
  • the battery positive electrode of the present invention further contains a conductive agent and a binder, wherein the conductive agent is carbon black, graphite, carbon nanotubes, graphene, etc.; the binder is PVDF, PTFE, CMC, SBR, etc.; The current collector is aluminum foil.
  • a preferred method of preparation comprises the steps of:
  • the cathode material is uniformly mixed with a lithium ion supplement, a conductive agent, and a binder in a solution (such as nitrogen methylpyrrolidone ( ⁇ P)) to adjust a mass ratio of a suitable lithium ion supplement and a cathode material, and a mass ratio of the positive electrode material, the acetylene black, and the binder, and then coating the tablet on the aluminum foil to prepare a positive electrode; or
  • a solution such as nitrogen methylpyrrolidone ( ⁇ P)
  • the positive electrode film of the present invention is bonded to a current collector to prepare a positive electrode of a lithium ion battery.
  • the lithium ion positive electrode of the lithium battery of the present invention is added with a lithium ion supplement, which can decompose and release lithium ions during the first charging of the lithium battery, and can compensate for the lithium ion forming the SEI film on the surface of the negative electrode. Loss, compensation for lithium ion loss in the positive electrode material and electrolyte, while other decomposition products do not substantially affect the performance of the lithium ion battery, thereby significantly improving the reversible charge and discharge capacity of the lithium ion battery, and improving the electrochemical performance of the lithium ion battery.
  • the lithium ion supplement is chemically stable, and the preparation cost of the positive electrode film is low: the lithium ion supplement used in the invention is a lithium-containing inorganic or organic compound in an oxidized state, which is more stable than the reduced state additive in the conventional technology, and the battery preparation process and The process environment requirements are low, thereby reducing the cost of preparation.
  • the invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are merely illustrative of the invention and are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer.
  • Example 1 Preparation of Battery Positive Electrode 1
  • lithium ion battery cathode material lithium iron phosphate and lithium ion supplement lithium peroxide, conductive agent acetylene black, and binder polyvinylidene fluoride (PVDF) in nitrogen methylpyrrolidone ( ⁇ P) solution Evenly mixed
  • the mass of the added lithium peroxide is 1% of the mass of the lithium iron phosphate of the positive electrode material, and the mass ratio of the positive electrode material, the acetylene black and the binder is 85:10:5, respectively, and then the tablet is coated on the aluminum foil to prepare the positive electrode of the battery. 1.
  • Example 2 Preparation of Lithium Battery 2 (Half Battery)
  • the positive electrode of the battery 1 was made of a lithium metal plate as a positive electrode, a solution of 1 mol/L of lithium hexafluorophosphate of ethylene carbonate and dimethyl carbonate was used as an electrolyte, and 20 ⁇ m of polyethylene was used as a separator to assemble a CR2032 type lithium coin battery.
  • Example 3 Preparation of Lithium Battery 3 (Full Battery)
  • the battery positive electrode 1 graphite as the negative electrode, lmol/L lithium hexafluorophosphate carbonate solution and dimethyl carbonate solution as the electrolyte, 20 micron thick polyethylene as the separator, assembled into a 18650 cylindrical lithium battery 3 o 1 Comparison of battery positive C1 preparation
  • the commercial lithium ion battery cathode material lithium iron phosphate is uniformly mixed with the conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) in the solution of nitrogen methylpyrrolidone ( ⁇ P), the positive electrode material, acetylene black and The mass ratio of the binder was 85:10:5, respectively, and then the tablet was coated on an aluminum foil to prepare a positive electrode Cl of the comparative battery.
  • Comparative Example 2 Preparation of comparative lithium battery C2 (half battery)
  • the preparation method was the same as in Example 2 except that the positive electrode C1 of the battery was replaced with the positive electrode C1 of the battery.
  • the preparation method was the same as in Example 3 except that the positive electrode C1 of the battery was replaced with the positive electrode C1 of the battery.
  • Example 4 Electrochemical performance of lithium battery 2 (half-cell) and comparative lithium battery C2 (half-cell) In this example, electrochemical performance tests were carried out by a conventional method using commercially available equipment, and the test methods were as follows:
  • a lithium battery 2 and a comparative lithium battery C2 are respectively on the electrochemical workstation, in the range of 2. 0-4. 75V, scanning from the positive electrode of the battery to the negative electrode of the battery at a speed of 0.01 mV / s; B.
  • the lithium battery 2 and the comparative lithium battery C2 were respectively subjected to a charge and discharge test on the charge and discharge test system, and the battery was charged and discharged with a constant current of 5 mA/g in a voltage range of 2. 0-4. 4V.
  • Example 5 Electrochemical performance of lithium battery 3 (full battery) and comparative lithium battery C3 (full battery)
  • the 18650 type lithium battery 3 and the comparative lithium battery C3 were subjected to charge and discharge tests on a charge and discharge test system.
  • the battery was subjected to a charge and discharge test with a constant current of 5 mA/g in a voltage range of 2.4-4. 4V.

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Abstract

Provided is a positive electrode film of a lithium battery, comprising: (i) a positive electrode material of a lithium intercalated transition metallic oxide; (ii) a lithium ion replenisher; and (iii) a conductive agent and an adhesive. The lithium ion replenisher in the positive electrode film decomposes during initial charging and then releases lithium ions, so as to make up for a loss of lithium ions forming an SEI film on a negative electrode surface, thereby improving the reversible charging and discharging capacity of the lithium ion battery. In the prepared positive electrode film, the lithium ion replenisher can be mixed in the positive electrode material or the conductive agent in advance, and can be coated on the surface of the positive electrode of the lithium ion battery as well.

Description

一种锂离子电池正极膜及其制备和应用  Positive electrode film of lithium ion battery and preparation and application thereof
技术领域  Technical field
本发明属于锂离子电池领域。 具体地, 本发明涉及一种锂离子电池正极膜及 其制备和应用。 背景技术  The invention belongs to the field of lithium ion batteries. In particular, the present invention relates to a positive electrode film for a lithium ion battery and its preparation and use. Background technique
锂离子电池于上世纪 80年代初商业化以来, 因其具有电压高、 比能量高、 循 环寿命长、 无环境污染等特点, 已广泛应用于移动电话、 笔记本电脑、 小型摄像 机等便携式电子设备中; 锂离子电池还可以代替传统的石油、 天然气等非再生资 源, 在电动工具、 电动自行车、 电动汽车、 太阳能电池和风能电池储能、 卫星及 航天等领域中得到更加广泛应用, 从而在保护环境、 节约非再生性能源等方面起 到重要作用。  Since its commercialization in the early 1980s, lithium-ion batteries have been widely used in portable electronic devices such as mobile phones, notebook computers, and compact cameras because of their high voltage, high specific energy, long cycle life, and no environmental pollution. Lithium-ion batteries can also replace traditional non-renewable resources such as oil and natural gas, and are more widely used in power tools, electric bicycles, electric vehicles, solar cells and wind energy storage, satellite and aerospace, etc. It plays an important role in saving non-renewable energy.
迄今为止, 锂离子的正极材料主要有钴酸锂、 镍酸锂、 镍钴酸锂、 镍钴锰酸 锂、 镍钴铝酸锂、 锰酸锂、 磷酸铁锂、 磷酸锰锂、 磷酸钒锂等化合物及其改性复 合物。 商业化的负极材料主要有表面改性的天然石墨、 中间相碳微球、 钛酸锂, 少量的无定形碳、 硬碳、 人造石墨, 以及正在研究的碳硅材料、 硅材料、 氮基材 料、 锗基材料、 金属合金等。 电解液主要为碳酸酯类、 醚类、 腈类等有机溶剂和 六氟磷酸锂、 四氟硼酸锂、 高氯酸锂、 二草酸硼酸锂、 二氟草酸硼酸锂等溶质中 的一种或几种的混合溶液。  So far, lithium ion cathode materials mainly include lithium cobaltate, lithium nickelate, lithium nickel cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate. Compounds and their modified complexes. The commercial anode materials mainly include surface-modified natural graphite, mesocarbon microspheres, lithium titanate, a small amount of amorphous carbon, hard carbon, artificial graphite, and carbon silicon materials, silicon materials, and nitrogen-based materials under study. , bismuth based materials, metal alloys, etc. The electrolyte is mainly a mixture of one or more of an organic solvent such as a carbonate, an ether or a nitrile and a solute such as lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate or lithium difluorooxalate borate. Solution.
在锂离子电池中,能为锂离子电池在充放电过程中提供能量传输介质 Li+的只 有正极材料和电解液中的溶质。 目前已经证明, 在锂离子电池首次充放电循环时, 在锂电池的负极材料表面会形成一种固体电解质薄膜(SEI ) , 同时随着锂电池的 循环过程, 锂离子和电解液中的锂离子在嵌入到负极材料后不能完全脱出, 这两 种情况会导致锂电池的容量衰减和循环效率的降低, 尤其是首次循环效率降低更 明显。 In lithium ion batteries, can provide energy transfer medium and an electrolyte solute material in only the positive electrode is a lithium ion Li + in the battery charging and discharging process. It has been proved that in the first charge-discharge cycle of a lithium ion battery, a solid electrolyte film (SEI) is formed on the surface of the negative electrode material of the lithium battery, and lithium ions in the lithium ion and the electrolyte are accompanied by the cycle of the lithium battery. It cannot be completely removed after being embedded in the negative electrode material. These two conditions lead to a decrease in the capacity of the lithium battery and a decrease in the cycle efficiency, especially in the first cycle.
目前常用的电池添加剂包括负极添加剂、 电解液添加剂、 导电剂添加剂三个 方面, 应用于负极成膜、 阻燃、 防过充等功能。 如中国专利 201010611339. 7中, 公开了一种负极添加剂, 其中负极添加剂具有通式 F (CF2CF2) m* (CH2CH20) n- R。 其中, 含氟醚化物的添加能使负极浆料混合更均匀, 提高电解液保有量, 一定程 度上提高了电池的容量和循环性能, 但制备方法复杂, 产生有毒物质多。 因此, 本领域迫切需要开发一种解决在锂电池的充放电循环过程中, 减少其容 衰减和提高其循环效率的锂离子电池领域的方法和产品。 发明内容 At present, the commonly used battery additives include three aspects of negative electrode additive, electrolyte additive and conductive agent additive, which are applied to negative electrode film formation, flame retardant and anti-overcharge functions. For example, in Chinese Patent No. 201010611339. 7, a negative electrode additive is disclosed, wherein the negative electrode additive has the general formula F (CF2CF2) m* (CH2CH20) n-R. Among them, the addition of the fluorine-containing ether compound can make the anode slurry mix more uniformly, increase the electrolyte retention, and improve the capacity and cycle performance of the battery to some extent, but the preparation method is complicated, and more toxic substances are produced. Therefore, there is an urgent need in the art to develop a method and product for solving the lithium ion battery field in the charge and discharge cycle of a lithium battery, reducing its capacity attenuation and improving its cycle efficiency. Summary of the invention
针对上述锂离子电池的容量衰减和循环效率降低这一问题, 本发明目的在于 提供一种含有锂离子补充剂的锂离子电池正极膜以及相应的电池。  In view of the above problems of capacity attenuation and cycle efficiency of a lithium ion battery, it is an object of the present invention to provide a lithium ion battery positive electrode film containing a lithium ion replenisher and a corresponding battery.
本发明的第一方面, 提供了一种锂电池正极膜, 所述的正极膜包括:  In a first aspect of the invention, a positive electrode film for a lithium battery is provided, and the positive electrode film comprises:
(i) 嵌锂过渡金属氧化物正极材料;  (i) a lithium intercalation transition metal oxide cathode material;
(ii) 掺于所述正极材料或导电剂之中的和 /或涂覆于锂离子电池正极表面的锂离 子补充剂; 以及  (ii) a lithium ion extender doped into the positive electrode material or the conductive agent and/or applied to the surface of the positive electrode of the lithium ion battery;
(iii) 导电剂和粘结剂。  (iii) Conductive agents and binders.
在另一优选例中, 所述的嵌锂过渡金属氧化物正极材料选自下组: 钴酸锂、 镍 酸锂、 镍钴酸锂、 镍钴锰酸锂、 镍钴铝酸锂、 锰酸锂、 磷酸铁锂、 磷酸锰锂、 磷 酸钒锂、 或其组合。  In another preferred embodiment, the lithium intercalation transition metal oxide cathode material is selected from the group consisting of lithium cobaltate, lithium nickelate, lithium nickel cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, and manganic acid. Lithium, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof.
在另一优选例中, 所述的导电剂包括碳黑、 石墨、 碳纳米管、 石墨烯等。 在另一优选例中,所述的粘结剂包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、 羧甲基纤维素 (CMC) 、 苯乙烯与丁二烯的共聚物 (SBR) 。  In another preferred embodiment, the conductive agent includes carbon black, graphite, carbon nanotubes, graphene, and the like. In another preferred embodiment, the binder comprises polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), a copolymer of styrene and butadiene (SBR). ).
在另一优选例中, 所述的正极膜还含有集流体铝箔。  In another preferred embodiment, the positive electrode film further contains a current collector aluminum foil.
在另一优选例中, 所述的锂离子补充剂包括: 锂氧化合物、 锂盐、 垸基锂化 合物、 或其组合。  In another preferred embodiment, the lithium ion extender comprises: a lithium oxygen compound, a lithium salt, a ruthenium lithium compound, or a combination thereof.
在另一优选例中, 所述的锂氧化合物包括: 氧化锂、 过氧化锂、 超氧化锂、 或其组合;  In another preferred embodiment, the lithium oxygen compound comprises: lithium oxide, lithium peroxide, lithium superoxide, or a combination thereof;
所述的垸基锂化合物包括: 甲醇锂、 乙醇锂、 异丙醇锂、 乙基锂、 异丙基锂、 丁基锂或其组合;  The mercaptolithium compound comprises: lithium methoxide, lithium ethoxide, lithium isopropoxide, ethyl lithium, isopropyl lithium, butyl lithium or a combination thereof;
所述的锂盐包括: 碳酸锂、 硼氢化锂、 氟化锂、 氮化锂、 硫化锂、 过硫化锂、 或其组合。  The lithium salt includes: lithium carbonate, lithium borohydride, lithium fluoride, lithium nitride, lithium sulfide, lithium persulfide, or a combination thereof.
在另一优选例中, 所述的锂离子补充剂为固态或液态。  In another preferred embodiment, the lithium ion extender is in a solid or liquid state.
在另一优选例中, 所述的锂离子补充剂占嵌锂过渡金属氧化物正极材料的质 量百分比为 0. 5〜10%, 更佳地为 1〜3%。  In a further preferred embodiment, the lithium ion-replenishing agent has a mass percentage of the lithium intercalated metal oxide positive electrode material of 0.5 to 10%, more preferably 1 to 3%.
本发明的第二方面, 提供了一种制备本发明第一方面所述的锂电池正极膜的 方法, 所述方法包括: (al)提供一正极材料浆料, 所述浆料含有嵌锂过渡金属氧 化物正极材料、 锂离子补充剂、 以及导电剂和粘结剂; 和将所述浆料通过涂覆压 片后真空干燥的方式制成正极膜; 或 According to a second aspect of the present invention, a lithium battery positive electrode film according to the first aspect of the present invention is provided The method includes: (al) providing a positive electrode material slurry, the slurry comprising a lithium intercalation transition metal oxide positive electrode material, a lithium ion supplement, and a conductive agent and a binder; and the slurry a positive electrode film is formed by vacuum drying after coating the tablet; or
所述方法包括: (a2)将锂离子补充剂与导电剂混匀之后加入嵌锂过渡金属氧 化物正极材料以及粘结剂, 通过涂覆压片后真空干燥的方式制成正极膜; 或  The method comprises: (a2) mixing a lithium ion supplement with a conductive agent, adding a lithium intercalation transition metal oxide positive electrode material and a binder, and forming a positive electrode film by vacuum drying after coating the tablet; or
所述方法包括: (a3)将锂离子补充剂涂覆于烘干的锂离子电池正极表面, 从 而形成含所述锂离子补充剂的锂电池正极膜。  The method comprises: (a3) applying a lithium ion extender to the surface of the positive electrode of the dried lithium ion battery, thereby forming a positive electrode film of the lithium battery containing the lithium ion extender.
本发明第三方面, 提供了一种锂离子电池, 包含本发明第一方面所述的电池 正极膜。  According to a third aspect of the invention, there is provided a lithium ion battery comprising the battery positive electrode film of the first aspect of the invention.
在另一优选例中, 所述的锂离子电池还包含负极膜、 隔膜、 电解质、 外壳及 电池辅助系统。  In another preferred embodiment, the lithium ion battery further includes a negative electrode film, a separator, an electrolyte, a casing, and a battery assisting system.
在另一优选例中, 所述的电解质为液体电解质(电解液)或聚合物电解质。 本发明的第四方面, 提供了一种锂离子电池正极的制备方法, 包括步骤: 将 本发明第一方面所述的正极膜粘合于或涂覆于集流体,从而制得锂离子电池正极。  In another preferred embodiment, the electrolyte is a liquid electrolyte (electrolyte) or a polymer electrolyte. According to a fourth aspect of the present invention, a method for preparing a positive electrode of a lithium ion battery, comprising the steps of: bonding or coating a positive electrode film according to the first aspect of the present invention to a current collector, thereby preparing a positive electrode of a lithium ion battery .
本发明第五方面, 提供了本发明第一方面所述的锂电池正极膜的应用, 用于 制备锂电池正极或用于制备锂电池。  According to a fifth aspect of the invention, there is provided the use of the positive electrode film for a lithium battery according to the first aspect of the invention, which is used for preparing a positive electrode of a lithium battery or for preparing a lithium battery.
本发明第六方面, 提供了一种补偿锂离子电池负极不可逆容量损失或减少锂 离子电池锂离子损耗的方法, 包括步骤: 向锂离子电池正极添加锂离子补充剂。  According to a sixth aspect of the present invention, a method for compensating for irreversible capacity loss of a negative electrode of a lithium ion battery or reducing lithium ion loss of a lithium ion battery is provided, comprising the steps of: adding a lithium ion supplement to a positive electrode of the lithium ion battery.
在另一优选例中, 所述的锂离子补充剂包括: 锂氧化合物、 锂盐、 垸基锂化 合物或其组合;  In another preferred embodiment, the lithium ion extender comprises: a lithium oxygen compound, a lithium salt, a mercaptolithium compound, or a combination thereof;
在另一优选例中, 所述的添加包括: 将锂离子补充剂提前混合在嵌锂过渡金 属氧化物正极材料或导电剂之中, 也可以涂覆在锂离子电池正极表面。  In another preferred embodiment, the adding comprises: preliminarily mixing the lithium ion supplement in the lithium intercalation transition metal oxide positive electrode material or the conductive agent, or coating the surface of the positive electrode of the lithium ion battery.
在另一优选例中, 所述的方法还包括补偿锂电池负极表面形成 SEI膜的损耗 的锂离子, 从而补偿锂离子电池负极不可逆容量损失或减少锂离子电池锂离子损 耗。  In another preferred embodiment, the method further includes compensating for the loss of lithium ions on the surface of the negative electrode of the lithium battery to form a loss of the SEI film, thereby compensating for the irreversible capacity loss of the negative electrode of the lithium ion battery or reducing the lithium ion loss of the lithium ion battery.
应理解, 在本发明范围内中, 本发明的上述各技术特征和在下文(如实施例) 中具体描述的各技术特征之间都可以互相组合,从而构成新的或优选的技术方案。 限于篇幅, 在此不再一一累述。 附图说明  It is to be understood that within the scope of the present invention, the various technical features of the present invention and the technical features specifically described hereinafter (as in the embodiments) may be combined with each other to constitute a new or preferred technical solution. Due to space limitations, we will not repeat them here. DRAWINGS
图 1为锂电池 2 (半电池) 的循环伏安曲线, 如图可见, 在锂电池 2的循环 伏安曲线上, 发现在 4. 4V左右出现氧化峰, 说明过氧化锂在 4. 4V发生分解, 其 分解产生了锂离子, 可以弥补正极材料和电解液中的锂离子损失。 Figure 1 is the cyclic voltammogram of lithium battery 2 (half-cell), as shown in the figure, in the cycle of lithium battery 2 On the volt-ampere curve, it was found that an oxidation peak appeared at about 4. 4V, indicating that lithium peroxide decomposes at 4. 4V, which decomposes to produce lithium ions, which can compensate for lithium ion loss in the cathode material and electrolyte.
图 2为对比锂电池 C2 (半电池) 的循环伏安曲线, 如图可见, 在 4. 4V左右, 并未出现氧化峰。  Figure 2 shows the cyclic volt-ampere curve of a comparative lithium battery C2 (half-cell). As can be seen, at about 4. 4V, no oxidation peak appears.
图 3为锂电池 2的首次充放电曲线, 如图可见, 在 4. 4V左右出现过氧化锂分 解平台, 说明过氧化锂在 4. 4V发生分解, 其分解产生的锂离子, 可以弥补正极材 料和电解液中的锂离子损失。  Figure 3 is the first charge and discharge curve of the lithium battery 2, as shown in the figure, the lithium peroxide decomposition platform appears around 4. 4V, indicating that the lithium peroxide is decomposed at 4. 4V, and the lithium ion generated by the decomposition can make up the cathode material. And lithium ion loss in the electrolyte.
图 4为对比锂电池 C2的首次充放电曲线, 如图可见, 在 4. 4V左右未出现过 氧化锂分解平台。  Figure 4 shows the first charge-discharge curve of the lithium battery C2. As can be seen, there is no lithium peroxide decomposition platform at around 4. 4V.
图 5为锂电池 3和对比锂电池 C3 (全电池) 的充放电曲线, 如图可见, 锂电 池 3的放电容量相较于锂电池 C3, 提高了约 10%。  Fig. 5 shows the charge and discharge curves of the lithium battery 3 and the comparative lithium battery C3 (full battery). As can be seen, the discharge capacity of the lithium battery 3 is increased by about 10% compared to the lithium battery C3.
具体实施方式  detailed description
本发明人经过广泛而深入的研究, 首次意外地发现向锂离子正极添加锂离子 补充剂, 可以弥补负极表面形成 SEI膜的锂离子损失, 其分解产物基本不影响锂 离子电池的性能, 从而明显提高锂离子电池的可逆充放电容量, 改善了锂离子电 池的电化学性能。 在此基础上完成了本发明。 锂离子电池  After extensive and intensive research, the inventors discovered for the first time that the addition of a lithium ion supplement to a lithium ion positive electrode can compensate for the lithium ion loss of the SEI film formed on the surface of the negative electrode, and the decomposition product thereof does not substantially affect the performance of the lithium ion battery. Improve the reversible charge and discharge capacity of lithium ion batteries and improve the electrochemical performance of lithium ion batteries. The present invention has been completed on this basis. Lithium Ion Battery
如本文所用, 术语 "锂离子电池"是指分别用二个能可逆地嵌入与脱嵌锂离子 的化合物作为正负极构成的二次电池。  As used herein, the term "lithium ion battery" means a secondary battery composed of two compounds capable of reversibly intercalating and deintercalating lithium ions as a positive and negative electrode, respectively.
当电池充电时, 锂离子从正极中脱嵌, 在负极中嵌入, 放电时反之。 在锂离子 电池的正极在组装前处于嵌锂状态。 通常, 选择稳定性好的嵌锂过渡金属氧化物 做正极材料。  When the battery is charged, lithium ions are deintercalated from the positive electrode and embedded in the negative electrode, and vice versa when discharging. The positive electrode of the lithium ion battery is in a lithium intercalated state prior to assembly. Usually, a lithium-intercalation transition metal oxide having good stability is selected as a positive electrode material.
在本发明中, 作为负极的材料没有特别限制, 可为电位接近锂电位并可嵌入锂 化合物的各种不同材料, 代表性例子包括 (但并不限于): 天然石墨、 合成石墨、 碳纤维、 中间相小球碳素等和金属氧化物, 包括 Sn0、 Sn02、 锡复合氧化物等。 In the present invention, the material of the negative electrode is not particularly limited, and may be various materials having a potential close to the lithium potential and intercalable with a lithium compound, and representative examples include, but are not limited to: natural graphite, synthetic graphite, carbon fiber, intermediate The phase ball carbon and the like and the metal oxide include Sn0, Sn0 2 , tin composite oxide and the like.
在本发明中, 电解质没有特别限制, 可以是液体电解质(电解液)或聚合物电解 质。 代表性的例子包括 (但并不限于): 采用 LiPF6的乙烯碳酸脂 (EC ) 、 丙烯碳 酸脂 (PC ) 和低粘度二乙基碳酸脂 (DEC ) 等垸基碳酸脂搭配的混合溶剂体系。 锂离子补充剂 In the present invention, the electrolyte is not particularly limited and may be a liquid electrolyte (electrolyte) or a polymer electrolyte. Representative examples include, but are not limited to, a mixed solvent system of sulfhydryl carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and low viscosity diethyl carbonate (DEC) using LiPF 6 . Lithium ion supplement
如本文所用, 术语 "锂离子补充剂" 、 "锂离子添加剂"可以替换使用, 均指 施用于锂电池正极的用于补充锂离子的锂电池添加剂。  As used herein, the terms "lithium ion extender" and "lithium ion additive" may be used interchangeably, and refer to a lithium battery additive for supplementing lithium ions applied to a positive electrode of a lithium battery.
可用于本发明的锂离子补充剂没有特别限制, 可以为任何分解电位低于电解 液的氧化分解电位, 且高于电池正极的放电截止电位的锂离子补充剂。  The lithium ion replenishing agent which can be used in the present invention is not particularly limited, and may be any lithium ion replenishing agent having a decomposition potential lower than the oxidative decomposition potential of the electrolytic solution and higher than the discharge cutoff potential of the positive electrode of the battery.
在可分解提供 Li+作为锂离子补充剂的含锂物质中,锂离子含量最高的为锂单 质。 而相对锂单质稳定性更高, 优选的锂离子补充剂为氧化态锂离子化合物。 Among the lithium-containing substances that can decompose and provide Li + as a lithium ion supplement, the lithium ion content is the highest in lithium. While the stability of lithium is higher than that of the simple substance, the preferred lithium ion supplement is an oxidized lithium ion compound.
可用于本发明的锂离子补充剂的分解电位应低于电解液的氧化分解电位, 且 高于电池正极的放电截止电位。  The decomposition potential of the lithium ion replenishing agent usable in the present invention should be lower than the oxidative decomposition potential of the electrolyte and higher than the discharge cutoff potential of the positive electrode of the battery.
常用的锂离子补充剂选自:  Commonly used lithium ion supplements are selected from:
含锂无机类: 氧化锂、 过氧化锂、 超氧化锂、 氢化锂、 氟化锂、 氮化锂、 硫 化锂、 铝锂合金;  Lithium-containing inorganics: lithium oxide, lithium peroxide, lithium superoxide, lithium hydride, lithium fluoride, lithium nitride, lithium sulfide, aluminum lithium alloy;
含锂有机类: 甲醇锂、 乙醇锂、 异丙醇锂、 乙基锂、 异丙基锂、 丁基锂、 苯 六酚锂、 。  Lithium-containing organics: lithium methoxide, lithium ethoxide, lithium isopropoxide, ethyl lithium, isopropyl lithium, butyl lithium, lithium benzene hexaoxide.
可用于本发明的锂离子补充剂优选地为: 过氧化锂、 超氧化锂、 氮化锂、 硫 化锂、 铝锂合金、 甲醇锂、 乙醇锂、 异丙醇锂、 乙基锂、 异丙基锂、 丁基锂; 更佳地, 为过氧化锂、 超氧化锂、 氮化锂。  The lithium ion extender which can be used in the present invention is preferably: lithium peroxide, lithium superoxide, lithium nitride, lithium sulfide, aluminum lithium alloy, lithium methoxide, lithium ethoxide, lithium isopropoxide, ethyl lithium, isopropyl Lithium, butyl lithium; more preferably, lithium peroxide, lithium superoxide, lithium nitride.
通过将锂离子补充剂提前混合在正极材料或导电剂之中、 或涂覆在已烘干正 极表面等手段, 将其中一种或多种添加于锂离子电池正极。 在锂电池首次充电过 程中, 锂离子补充剂会发生分解, 释放锂离子, 可以弥补负极表面形成 SEI膜的 锂离子损失, 补偿正极材料和电解液中的锂离子损失, 同时其他分解产物基本不 影响锂离子电池的性能, 从而明显提高锂离子电池的可逆充放电容量, 改善了锂 离子电池的电化学性能。 且本发明所用锂离子补充剂化学态稳定, 在空气中不易 分解, 对工艺流程及环境要求低, 生产成本低。 锂电池正极膜及其制备  One or more of them are added to the positive electrode of the lithium ion battery by mixing the lithium ion supplement in advance in the positive electrode material or the conductive agent, or coating the surface of the dried positive electrode. During the first charging of the lithium battery, the lithium ion supplement will decompose and release lithium ions, which can compensate for the lithium ion loss of the SEI film formed on the surface of the negative electrode, compensate the lithium ion loss in the positive electrode material and the electrolyte, and the other decomposition products are basically not Affecting the performance of lithium ion batteries, thereby significantly improving the reversible charge and discharge capacity of lithium ion batteries, and improving the electrochemical performance of lithium ion batteries. Moreover, the lithium ion supplement used in the invention is chemically stable, is not easily decomposed in air, has low requirements on the process flow and environment, and has low production cost. Lithium battery positive film and preparation thereof
锂电池正极膜  Lithium battery positive film
本发明提供的一种锂电池正极膜, 包括:  The invention provides a lithium battery positive film, comprising:
(i) 嵌锂过渡金属氧化物正极材料;  (i) a lithium intercalation transition metal oxide cathode material;
(ii) 掺于所述正极材料或导电剂之中的和 /或涂覆于锂离子电池正极表面的锂离 子补充剂; 以及 (iii) 导电剂和粘结剂。 (ii) a lithium ion extender doped into the positive electrode material or the conductive agent and/or applied to the surface of the positive electrode of the lithium ion battery; (iii) Conductive agents and binders.
其中所述的嵌锂过渡金属氧化物正极材料选自下组: 钴酸锂、 镍酸锂、 镍钴酸 锂、 镍钴锰酸锂、 镍钴铝酸锂、 锰酸锂、 磷酸铁锂、 磷酸锰锂、 磷酸钒锂、 或其 组合。  The lithium intercalation transition metal oxide cathode material is selected from the group consisting of lithium cobaltate, lithium nickelate, lithium nickel cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate, lithium iron phosphate, Lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof.
所述的锂离子补充剂包括: 锂氧化合物、 锂盐、 垸基锂化合物、 或其组合; 其中, 所述的锂氧化合物包括: 氧化锂、 过氧化锂、 超氧化锂、 或其组合; 所述的垸基锂化合物包括: 甲醇锂、 乙醇锂、 异丙醇锂、 乙基锂、 异丙基锂、 丁基锂或其组合;  The lithium ion supplement includes: a lithium oxygen compound, a lithium salt, a mercapto lithium compound, or a combination thereof; wherein the lithium oxygen compound comprises: lithium oxide, lithium peroxide, lithium superoxide, or a combination thereof; The mercaptolithium compound comprises: lithium methoxide, lithium ethoxide, lithium isopropoxide, ethyl lithium, isopropyl lithium, butyl lithium or a combination thereof;
所述的锂盐包括: 碳酸锂、 硼氢化锂、 氟化锂、 氮化锂、 硫化锂、 过硫化锂、 或其组合。  The lithium salt includes: lithium carbonate, lithium borohydride, lithium fluoride, lithium nitride, lithium sulfide, lithium persulfide, or a combination thereof.
所述的锂离子补充剂为固态。  The lithium ion extender is in a solid state.
所述的导电剂包括碳黑、 石墨、 碳纳米管、 石墨烯等。  The conductive agent includes carbon black, graphite, carbon nanotubes, graphene, and the like.
所述的粘结剂包括 PVDF、 PTFE、 CMC, SBR等, 其中 PVDF为聚偏氟乙烯, PTFE 为聚四氟乙烯, CMC为羧甲基纤维素, SBR为苯乙烯与丁二烯的共聚物(丁苯橡胶)。  The binder comprises PVDF, PTFE, CMC, SBR, etc., wherein PVDF is polyvinylidene fluoride, PTFE is polytetrafluoroethylene, CMC is carboxymethyl cellulose, and SBR is a copolymer of styrene and butadiene. (styrene-butadiene rubber).
所述的正极膜还含有集流体铝箔。  The positive electrode film further contains a current collector aluminum foil.
所述的锂离子补充剂占嵌锂过渡金属氧化物正极材料的质量百分比为 0. 5〜 10%, 更佳地为 1〜3%。  The mass percentage of the lithium ion-containing transition metal oxide cathode material is 0.5 to 10%, more preferably 1 to 3%.
本发明提供的锂离子补充剂, 所述补充剂可以提前混合在正极材料或导电剂 中使用, 也可以涂覆在烘干的锂离子电池正极表面使用。 制备  The lithium ion supplement provided by the present invention may be used in advance in a positive electrode material or a conductive agent, or may be applied to a surface of a dried lithium ion battery positive electrode. Preparation
制备本发明所述锂电池正极膜的方法可将锂离子补充剂混入锂电池正极材料 或浆料中和 /或在常规锂电池正极制备后涂覆于电池正极上。具体地, 通常所用的 制备方法包括以下三种:  The method of preparing the positive electrode film for a lithium battery of the present invention may be carried out by mixing a lithium ion extender into a positive electrode material or slurry of a lithium battery and/or applying it to the positive electrode of the battery after preparation of the positive electrode of the conventional lithium battery. Specifically, the preparation methods generally used include the following three types:
(al) 提供一正极材料浆料, 所述浆料含有嵌锂过渡金属氧化物正极材料、 锂离子补充剂、 以及导电剂和粘结剂; 和将所述浆料通过涂覆压片后真空干燥的 方式制成正极膜; 或  (al) providing a positive electrode material slurry containing a lithium intercalation transition metal oxide positive electrode material, a lithium ion replenishing agent, and a conductive agent and a binder; and vacuuming the slurry after coating the tablet Dry film is made into a positive film; or
(a2) 将锂离子补充剂与导电剂提前球磨混匀之后加入嵌锂过渡金属氧化物 正极材料以及粘结剂, 也通过涂覆压片后真空干燥的方式制成正极膜; 或  (a2) adding a lithium ion extender and a conductive agent in advance by ball milling, adding a lithium intercalation transition metal oxide positive electrode material and a binder, and also forming a positive electrode film by vacuum drying after coating the tablet; or
(a3)将锂离子补充剂涂覆于烘干的锂离子电池正极表面, 从而形成含所述锂 离子补充剂的锂电池正极膜。 电池正极 (a3) A lithium ion supplement is applied to the surface of the positive electrode of the dried lithium ion battery to form a lithium battery positive film containing the lithium ion replenisher. Battery positive
本发明所述的电池正极含有本发明的锂离子补充剂;  The positive electrode of the battery of the present invention contains the lithium ion supplement of the present invention;
本发明所述的电池正极还含有导电剂和粘结剂, 其中所述导电剂为碳黑、 石 墨、 碳纳米管、 石墨烯等; 所述粘结剂为 PVDF、 PTFE、 CMC, SBR等; 集流体为铝 箔。  The battery positive electrode of the present invention further contains a conductive agent and a binder, wherein the conductive agent is carbon black, graphite, carbon nanotubes, graphene, etc.; the binder is PVDF, PTFE, CMC, SBR, etc.; The current collector is aluminum foil.
优选的制备方法包括步骤:  A preferred method of preparation comprises the steps of:
将正极材料分别与锂离子补充剂、 导电剂、粘结剂在溶液(如氮甲基吡咯垸酮 (匪 P) )中均匀混合, 调节合适的锂离子补充剂和正极材料的质量比, 以及正极材 料、 乙炔黑和粘结剂的质量比, 然后涂覆压片在铝箔上, 制得正极; 或  The cathode material is uniformly mixed with a lithium ion supplement, a conductive agent, and a binder in a solution (such as nitrogen methylpyrrolidone (匪P)) to adjust a mass ratio of a suitable lithium ion supplement and a cathode material, and a mass ratio of the positive electrode material, the acetylene black, and the binder, and then coating the tablet on the aluminum foil to prepare a positive electrode; or
将本发明所述的正极膜粘合于集流体, 从而制得锂离子电池正极。  The positive electrode film of the present invention is bonded to a current collector to prepare a positive electrode of a lithium ion battery.
通常, 一种合适的锂离子补充剂占正极材料的质量百分比为 0. 5〜10%。 本发明的有益效果:  5〜10%。 The mass percentage of the positive electrode material is 0. 5~10%. The beneficial effects of the invention:
1.提高锂电池的可逆充放电容量: 本发明的锂电池正极膜中添加了锂离子补 充剂, 能够在锂电池首次充电过程中发生分解释放锂离子, 可以弥补负极表面形 成 SEI膜的锂离子损失, 补偿正极材料和电解液中的锂离子损失, 同时其他分解 产物基本不影响锂离子电池的性能,从而明显提高锂离子电池的可逆充放电容量, 改善了锂离子电池的电化学性能。  1. Increasing the reversible charge and discharge capacity of a lithium battery: The lithium ion positive electrode of the lithium battery of the present invention is added with a lithium ion supplement, which can decompose and release lithium ions during the first charging of the lithium battery, and can compensate for the lithium ion forming the SEI film on the surface of the negative electrode. Loss, compensation for lithium ion loss in the positive electrode material and electrolyte, while other decomposition products do not substantially affect the performance of the lithium ion battery, thereby significantly improving the reversible charge and discharge capacity of the lithium ion battery, and improving the electrochemical performance of the lithium ion battery.
2.锂离子补充剂化学态稳定, 正极膜制备成本低: 本发明所用的锂离子补充 剂为氧化态的含锂无机或有机化合物, 较传统技术中还原态添加剂更稳定, 对电 池制备流程及工艺环境要求低, 从而降低制备成本。 下面结合具体实施例, 进一步阐述本发明。 应理解, 这些实施例仅用于说明 本发明而不用于限制本发明的范围。 下列实施例中未注明具体条件的实验方法, 通常按照常规条件或按照制造厂商所建议的条件。 实施例 1 电池正极 1的制备  2. The lithium ion supplement is chemically stable, and the preparation cost of the positive electrode film is low: the lithium ion supplement used in the invention is a lithium-containing inorganic or organic compound in an oxidized state, which is more stable than the reduced state additive in the conventional technology, and the battery preparation process and The process environment requirements are low, thereby reducing the cost of preparation. The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are merely illustrative of the invention and are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer. Example 1 Preparation of Battery Positive Electrode 1
将商业化锂离子电池正极材料磷酸铁锂分别与锂离子补充剂过氧化锂、 导电 剂乙炔黑、 以及粘结剂聚偏氟乙烯(PVDF)在氮甲基吡咯垸酮(匪 P)溶液中均匀混 添加过氧化锂的质量为正极材料磷酸铁锂质量的 1%, 正极材料、 乙炔黑和粘 结剂的质量比分别为 85 : 10 : 5, 然后涂覆压片在铝箔上, 制得电池正极 1。 实施例 2 锂电池 2 (半电池) 的制备 Commercially available lithium ion battery cathode material lithium iron phosphate and lithium ion supplement lithium peroxide, conductive agent acetylene black, and binder polyvinylidene fluoride (PVDF) in nitrogen methylpyrrolidone (匪P) solution Evenly mixed The mass of the added lithium peroxide is 1% of the mass of the lithium iron phosphate of the positive electrode material, and the mass ratio of the positive electrode material, the acetylene black and the binder is 85:10:5, respectively, and then the tablet is coated on the aluminum foil to prepare the positive electrode of the battery. 1. Example 2 Preparation of Lithium Battery 2 (Half Battery)
将电池正极 1, 以金属锂片为正极, lmol/L六氟磷酸锂的碳酸乙烯酯和碳酸 二甲酯的溶液作为电解液, 20微米厚的聚乙烯为隔膜, 组装成 CR2032型纽扣锂 电池 2。 实施例 3 锂电池 3 (全电池) 的制备  The positive electrode of the battery 1 was made of a lithium metal plate as a positive electrode, a solution of 1 mol/L of lithium hexafluorophosphate of ethylene carbonate and dimethyl carbonate was used as an electrolyte, and 20 μm of polyethylene was used as a separator to assemble a CR2032 type lithium coin battery. Example 3 Preparation of Lithium Battery 3 (Full Battery)
将电池正极 1, 以石墨为负极, lmol/L六氟磷酸锂的碳酸乙烯酯和碳酸二甲 酯的溶液作为电解液, 20微米厚的聚乙烯为隔膜, 组装成 18650型圆柱型锂电池 3 o 对比例 1 对比电池正极 C1的制备  The battery positive electrode 1, graphite as the negative electrode, lmol/L lithium hexafluorophosphate carbonate solution and dimethyl carbonate solution as the electrolyte, 20 micron thick polyethylene as the separator, assembled into a 18650 cylindrical lithium battery 3 o 1 Comparison of battery positive C1 preparation
将商业化锂离子电池正极材料磷酸铁锂分别与导电剂乙炔黑、 粘结剂聚偏氟 乙烯(PVDF)在氮甲基吡咯垸酮(匪 P)溶液中均匀混合, 正极材料、 乙炔黑和粘结剂 的质量比分别为 85 : 10 : 5, 然后涂覆压片在铝箔上, 制得对比电池正极 Cl。 对比例 2 对比锂电池 C2 (半电池) 的制备  The commercial lithium ion battery cathode material lithium iron phosphate is uniformly mixed with the conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) in the solution of nitrogen methylpyrrolidone (匪P), the positive electrode material, acetylene black and The mass ratio of the binder was 85:10:5, respectively, and then the tablet was coated on an aluminum foil to prepare a positive electrode Cl of the comparative battery. Comparative Example 2 Preparation of comparative lithium battery C2 (half battery)
制备方法同实施例 2, 不同的是以对比电池正极 C1代替电池正极 1。  The preparation method was the same as in Example 2 except that the positive electrode C1 of the battery was replaced with the positive electrode C1 of the battery.
组装成 CR2032型纽扣锂电池 C2。 对比例 3 对比锂电池 C3 (全电池) 的制备  Assembled into a CR2032 button lithium battery C2. Comparative Example 3 Preparation of comparative lithium battery C3 (full battery)
制备方法同实施例 3, 不同的是以对比电池正极 C1代替电池正极 1。  The preparation method was the same as in Example 3 except that the positive electrode C1 of the battery was replaced with the positive electrode C1 of the battery.
组装成 18650型锂电池 C3。 实施例 4 锂电池 2 (半电池) 和对比锂电池 C2 (半电池) 的电化学性能 在本实施例中, 用常规方法, 采用市售设备进行电化学性能测试, 测试方法 如下:  Assembled into a 18650 lithium battery C3. Example 4 Electrochemical performance of lithium battery 2 (half-cell) and comparative lithium battery C2 (half-cell) In this example, electrochemical performance tests were carried out by a conventional method using commercially available equipment, and the test methods were as follows:
A将锂电池 2和对比锂电池 C2分别在电化学工作站上, 在 2. 0-4. 75V电压范 围, 以 0. 01mV/s速度从电池正极扫描到电池负极; B将锂电池 2和对比锂电池 C2分别在充放电测试系统上进行充放电测试, 在 2. 0-4. 4V电压范围内, 用 5mA/g的恒定电流对电池充放电测试。 实施例 5 锂电池 3 (全电池) 和对比锂电池 C3 (全电池) 的电化学性能 将 18650型锂电池 3和对比锂电池 C3在充放电测试系统上进行充放电测试。 在 2. 4-4. 4V电压范围内, 用 5mA/g的恒定电流对电池进行充放电测试。 A lithium battery 2 and a comparative lithium battery C2 are respectively on the electrochemical workstation, in the range of 2. 0-4. 75V, scanning from the positive electrode of the battery to the negative electrode of the battery at a speed of 0.01 mV / s; B. The lithium battery 2 and the comparative lithium battery C2 were respectively subjected to a charge and discharge test on the charge and discharge test system, and the battery was charged and discharged with a constant current of 5 mA/g in a voltage range of 2. 0-4. 4V. Example 5 Electrochemical performance of lithium battery 3 (full battery) and comparative lithium battery C3 (full battery) The 18650 type lithium battery 3 and the comparative lithium battery C3 were subjected to charge and discharge tests on a charge and discharge test system. The battery was subjected to a charge and discharge test with a constant current of 5 mA/g in a voltage range of 2.4-4. 4V.
结果:  Result:
锂电池 2和对比锂电池 C2 (半电池) 的测试结果如图 1、 2、 3和 4所示, 锂 电池 3和对比锂电池 C3 (全电池) 的测试结果如图 5所示:  The test results of lithium battery 2 and comparative lithium battery C2 (half battery) are shown in Figures 1, 2, 3 and 4. The test results of lithium battery 3 and comparative lithium battery C3 (full battery) are shown in Figure 5:
( 1) 如图 1所示, 在添加了特定的锂离子补充剂之后, 锂电池 1的循环伏安 曲线中呈现了锂离子补充剂的分解峰, 从而说明过氧化锂在 4. 4V发生了分解。  (1) The decomposition peak of the lithium ion supplement is shown in the cyclic voltammetry curve of the lithium battery 1 after the addition of a specific lithium ion supplement, indicating that the lithium peroxide occurred at 4. 4V. break down.
在对比锂电池 C2的循环伏安曲线上, 并未在 4. 4V左右出现氧化峰(见图 2), 说明没有锂离子分解产生; 结果表明: 添加的锂离子补充剂过氧化锂能分解产生 锂离子, 可以弥补正极材料和电解液中的锂离子损失。  On the cyclic voltammetry curve of the lithium battery C2, there is no oxidation peak at about 4. 4V (see Figure 2), indicating that no lithium ion decomposition occurs; the results show that: the added lithium ion supplement lithium peroxide can be decomposed Lithium ions can compensate for lithium ion loss in the cathode material and electrolyte.
(2)在锂电池 2的首次充放电曲线上, 发现在 4. 4V左右出现过氧化锂分解平 台。 (见图 3) ; 在对比锂电池 C2的首次充放电曲线上, 则没有发现过氧化锂分解 平台(见图 4) ; 结果表明: 过氧化锂在 4. 4V发生分解, 其分解产生的锂离子, 可 以弥补正极材料和电解液中的锂离子损失。  (2) On the first charge and discharge curve of the lithium battery 2, it was found that a lithium peroxide decomposition platform appeared around 4. 4V. (See Figure 3); On the first charge-discharge curve of the lithium battery C2, no lithium peroxide decomposition platform was found (see Figure 4); the results showed that: lithium peroxide decomposed at 4. 4V, and the lithium produced by its decomposition Ions can compensate for lithium ion loss in the cathode material and electrolyte.
(3) 比较 18650型锂电池 3和对比锂电池 C3 (全电池) 的充放电曲线 (见图 5 ) , 发现添加了锂离子补充剂后, 锂电池 3的放电容量为 1426 mAh , 相较于未 添加锂离子补充剂的对比锂电池 C3提高了约 10%。 结果表明, 锂离子补充剂在首 次充电时能够发生分解释放锂离子,可以弥补负极表面形成 SEI膜的锂离子损失, 补偿正极材料和电解液中的锂离子损失, 从而明显提高锂离子电池的可逆充放电  (3) Comparing the charge and discharge curves of the 18650 lithium battery 3 and the comparative lithium battery C3 (full battery) (see Figure 5), it is found that the lithium battery 3 has a discharge capacity of 1426 mAh after the addition of the lithium ion supplement. The comparative lithium battery C3 without the lithium ion supplement was increased by about 10%. The results show that the lithium ion supplement can decompose and release lithium ions during the first charge, which can compensate for the lithium ion loss of the SEI film formed on the surface of the negative electrode, compensate the lithium ion loss in the positive electrode material and the electrolyte, and thus significantly improve the reversibility of the lithium ion battery. Discharge
实施例 6 Example 6
按照实施例 1-3的方法制备锂电池 (全电池) 4、 5、 6, 按照对比例 1-3的方 法制备不含锂离子补充剂的锂电池 (全电池) C4、 C5、 C6, 并按照实施例 5进行 充放电容量测试。 制备参数及测试结果请见表 1。 表 1 Preparation of lithium battery (full battery) according to the method of Examples 1-3 4, 5, 6, Preparation of lithium batteries (full battery) without lithium ion supplements C4, C5, C6 according to the method of Comparative Examples 1-3, and The charge and discharge capacity test was carried out in accordance with Example 5. The preparation parameters and test results are shown in Table 1. Table 1
Figure imgf000011_0001
由表 1可见, 在向锂电池正极添加了锂离子补充剂之后, 所有电池的充放电 容量都较未添加锂离子补充剂的锂电池增加了 10%以上。 在本发明提及的所有文献都在本申请中引用作为参考, 就如同每一篇文献被 单独引用作为参考那样。 此外应理解, 在阅读了本发明的上述讲授内容之后, 本 领域技术人员可以对本发明作各种改动或修改, 这些等价形式同样落于本申请所 附权利要求书所限定的范围。
Figure imgf000011_0001
As can be seen from Table 1, after the lithium ion supplement was added to the positive electrode of the lithium battery, the charge and discharge capacity of all the batteries was increased by more than 10% compared with the lithium battery without the lithium ion supplement. All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the the In addition, it is to be understood that various modifications and changes may be made by those skilled in the art in the form of the appended claims.

Claims

权 利 要 求 Rights request
1. 一种锂电池正极膜, 其特征在于, 所述的正极膜包括:  A positive electrode film for a lithium battery, characterized in that: the positive electrode film comprises:
(i) 嵌锂过渡金属氧化物正极材料;  (i) a lithium intercalation transition metal oxide cathode material;
(ii) 掺于所述正极材料或导电剂之中的和 /或涂覆于锂离子电池正极表面的锂离 子补充剂; 以及  (ii) a lithium ion extender doped into the positive electrode material or the conductive agent and/or applied to the surface of the positive electrode of the lithium ion battery;
(iii) 导电剂和粘结剂。  (iii) Conductive agents and binders.
2. 如权利要求 1所述的锂电池正极膜, 其特征在于, 所述的锂离子补充剂包 括: 锂氧化合物、 锂盐、 垸基锂化合物、 或其组合。  The lithium battery positive electrode film according to claim 1, wherein the lithium ion replenishing agent comprises: a lithium oxygen compound, a lithium salt, a mercapto lithium compound, or a combination thereof.
3. 如权利要求 2所述的锂离子补充剂, 其特征在于,  3. The lithium ion extender according to claim 2, wherein
所述的锂氧化合物包括: 氧化锂、 过氧化锂、 超氧化锂、 或其组合; 所述的垸基锂化合物包括: 甲醇锂、 乙醇锂、 异丙醇锂、 乙基锂、 异丙基锂、 丁基锂或其组合;  The lithium oxygen compound comprises: lithium oxide, lithium peroxide, lithium superoxide, or a combination thereof; the lithium-based lithium compound comprises: lithium methoxide, lithium ethoxide, lithium isopropoxide, ethyl lithium, isopropyl Lithium, butyl lithium or a combination thereof;
所述的锂盐包括: 碳酸锂、 硼氢化锂、 氟化锂、 氮化锂、 硫化锂、 过硫化锂、 或其组合。  The lithium salt includes: lithium carbonate, lithium borohydride, lithium fluoride, lithium nitride, lithium sulfide, lithium persulfide, or a combination thereof.
4. 如权利要求 1所述的锂电池正极膜, 其特征在于, 所述的锂离子补充剂占 嵌锂过渡金属氧化物正极材料的质量百分比为 0. 5〜10%, 更佳地为 1〜3%。  5〜10%更优选为1。 The lithium ion-filled metal oxide cathode material is 0. 5~10%, more preferably 1 ~3%.
5.一种制备如权利要求 1所述的锂电池正极膜的方法, 其特征在于, 所述方法包括: (al)提供一正极材料浆料, 所述浆料含有嵌锂过渡金属氧化 物正极材料、 锂离子补充剂、 以及导电剂和粘结剂; 和将所述浆料通过涂覆压片 后真空干燥的方式制成正极膜; 或  A method of preparing a positive electrode film for a lithium battery according to claim 1, wherein the method comprises: (al) providing a slurry of a positive electrode material, the slurry containing a lithium intercalation transition metal oxide positive electrode a material, a lithium ion extender, and a conductive agent and a binder; and preparing the positive electrode film by vacuum drying the coated slurry; or
所述方法包括: (a2)将锂离子补充剂与导电剂混匀之后加入嵌锂过渡金属氧 化物正极材料以及粘结剂, 通过涂覆压片后真空干燥的方式制成正极膜; 或  The method comprises: (a2) mixing a lithium ion supplement with a conductive agent, adding a lithium intercalation transition metal oxide positive electrode material and a binder, and forming a positive electrode film by vacuum drying after coating the tablet; or
所述方法包括: (a3)将锂离子补充剂涂覆于烘干的锂离子电池正极表面, 从 而形成含所述锂离子补充剂的锂电池正极膜。  The method comprises: (a3) applying a lithium ion extender to the surface of the positive electrode of the dried lithium ion battery, thereby forming a positive electrode film of the lithium battery containing the lithium ion extender.
6.—种锂离子电池, 其特征在于, 包含如权利要求 1所述的电池正极膜。  A lithium ion battery comprising the battery positive electrode membrane according to claim 1.
7. 一种锂离子电池正极的制备方法, 其特征在于, 包括步骤: 将权利要求 1 所述的正极膜粘合于或涂覆于集流体, 从而制得锂离子电池正极。  A method of producing a positive electrode of a lithium ion battery, comprising the steps of: bonding or coating a positive electrode film according to claim 1 to a current collector, thereby producing a positive electrode of a lithium ion battery.
8. 一种权利要求 1所述的锂电池正极膜的应用, 其特征在于, 用于制备锂电 池正极或用于制备锂电池。  A use of a positive electrode film for a lithium battery according to claim 1, which is used for preparing a lithium battery positive electrode or for preparing a lithium battery.
9.一种补偿锂离子电池负极不可逆容量损失或减少锂离子电池锂离子损耗的 方法, 其特征在于, 包括步骤: 向锂离子电池正极添加锂离子补充剂。 A method for compensating for irreversible capacity loss of a negative electrode of a lithium ion battery or for reducing lithium ion loss of a lithium ion battery, comprising the steps of: adding a lithium ion supplement to a positive electrode of the lithium ion battery.
10. 如权利要求 9所述的方法, 其特征在于, 所述的方法还包括补偿锂电池 负极表面形成固体电解质薄膜 (SEI膜) 的损耗的锂离子, 从而补偿锂离子电池 负极不可逆容量损失或减少锂离子电池锂离子损耗。 10. The method according to claim 9, wherein the method further comprises compensating for the loss of lithium ions on the surface of the negative electrode of the lithium battery to form a solid electrolyte film (SEI film), thereby compensating for the irreversible capacity loss of the negative electrode of the lithium ion battery or Reduce lithium ion loss in lithium-ion batteries.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11107639B2 (en) 2016-01-22 2021-08-31 Asahi Kasei Kabushiki Kaisha Positive electrode precursor
CN114552125A (en) * 2022-04-26 2022-05-27 华中科技大学 Nondestructive lithium supplement composite diaphragm and preparation method and application thereof

Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103441236B (en) * 2013-09-11 2017-10-13 东莞新能源科技有限公司 Cathode plate of lithium ion battery, lithium ion battery and preparation method thereof
CN105702913A (en) * 2014-11-27 2016-06-22 比亚迪股份有限公司 Positive electrode and preparation method therefor, and lithium secondary battery
FR3042914B1 (en) * 2015-10-21 2017-11-17 Renault PROCESS FOR MANUFACTURING A LITHIUM-ION TYPE BATTERY
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CN111415821B (en) * 2016-01-22 2022-06-07 旭化成株式会社 Method for manufacturing nonaqueous lithium storage device
WO2017126691A1 (en) 2016-01-22 2017-07-27 旭化成株式会社 Nonaqueous lithium-type power storage element
CN106058168A (en) * 2016-02-03 2016-10-26 万向A二三系统有限公司 Prelithiated positive electrode material for lithium ion secondary battery
US20170309914A1 (en) * 2016-04-20 2017-10-26 Ford Global Technologies, Llc Pre-lithiated lithium ion battery cell
FR3052597B1 (en) * 2016-06-08 2018-06-15 Commissariat A L'energie Atomique Et Aux Energies Alternatives METHOD OF MANUFACTURING AN ELECTRODE FOR ACCUMULATOR OPERATING ON THE PRINCIPLE OF INSERTION AND IONIC INSULATION OR ALLOY FORMATION
CN107808978B (en) * 2016-09-08 2020-07-28 中国科学院物理研究所 Liquid active lithium supplement, preparation method and application thereof
WO2018112801A1 (en) * 2016-12-21 2018-06-28 Robert Bosch Gmbh Lithium ion battery and preparation method thereof
CN109428138B (en) * 2017-08-24 2020-12-01 上海交通大学 Preparation method of lithium-air battery and lithium-air battery
CN107863567A (en) * 2017-09-22 2018-03-30 深圳市比克动力电池有限公司 It is a kind of for the benefit lithium additive of lithium ion cell positive and its application
CN109859959A (en) * 2017-11-30 2019-06-07 中国科学院大连化学物理研究所 A kind of lithium ion super capacitor cathode pre-embedding lithium method
CN110350194A (en) * 2018-04-02 2019-10-18 中国科学院物理研究所 A kind of benefit lithium slurry and its preparation method and application
US20210125791A1 (en) * 2018-04-20 2021-04-29 GM Global Technology Operations LLC Incorporation of lithium-ion source material into an activated carbon electrode for a capacitor-assisted battery
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CN109585844B (en) * 2018-11-26 2020-09-29 中南大学 Sodium-supplementing positive electrode active material, positive electrode material, sodium ion battery, and preparation and application thereof
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CN112151765A (en) * 2020-10-10 2020-12-29 惠州亿纬锂能股份有限公司 Lithium ion battery anode lithium supplementing method, product and product application thereof
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CN112885985B (en) * 2021-02-01 2022-08-30 中南大学 Positive pole piece and preparation method thereof, electrochemical energy storage device and pre-metallization method of electrochemical energy storage device
WO2023070287A1 (en) 2021-10-25 2023-05-04 宁德新能源科技有限公司 Positive electrode plate, electrochemical device, and electronic device
CN114665063B (en) * 2022-03-28 2023-08-15 中国矿业大学(北京) Lithium supplementing composite film, lithium ion battery positive electrode, lithium ion battery and preparation method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102054986A (en) * 2010-11-16 2011-05-11 中国科学院宁波材料技术与工程研究所 Ultrahigh-capacity lithium ion battery anode material prepared by microwave method and preparation method thereof
CN102201597A (en) * 2010-03-26 2011-09-28 中大工业集团公司 Production method for polymer lithium ion batteries of high performance and long service life

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100416893C (en) * 2004-11-17 2008-09-03 比亚迪股份有限公司 Anode of lithium ion cell and lithium ion cell
JP2010541166A (en) * 2007-09-28 2010-12-24 スリーエム イノベイティブ プロパティズ カンパニー Method for producing cathode composition
JP4715830B2 (en) * 2007-10-19 2011-07-06 ソニー株式会社 Positive electrode active material, positive electrode and non-aqueous electrolyte secondary battery
JP4636341B2 (en) * 2008-04-17 2011-02-23 トヨタ自動車株式会社 Lithium secondary battery and manufacturing method thereof
US8852452B2 (en) * 2009-11-05 2014-10-07 Umicore Core-shell lithium transition metal oxides
DE102010024479A1 (en) * 2010-06-21 2011-12-22 Li-Tec Battery Gmbh Lithium-ion battery with amorphous electrode materials
CN102386374A (en) * 2011-10-21 2012-03-21 超威电源有限公司 Lithium-ion power cell aqueous sizing agent and manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102201597A (en) * 2010-03-26 2011-09-28 中大工业集团公司 Production method for polymer lithium ion batteries of high performance and long service life
CN102054986A (en) * 2010-11-16 2011-05-11 中国科学院宁波材料技术与工程研究所 Ultrahigh-capacity lithium ion battery anode material prepared by microwave method and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11107639B2 (en) 2016-01-22 2021-08-31 Asahi Kasei Kabushiki Kaisha Positive electrode precursor
CN114552125A (en) * 2022-04-26 2022-05-27 华中科技大学 Nondestructive lithium supplement composite diaphragm and preparation method and application thereof

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