WO2020259436A1 - Method for improving stability and processability of ternary positive electrode material - Google Patents

Method for improving stability and processability of ternary positive electrode material Download PDF

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WO2020259436A1
WO2020259436A1 PCT/CN2020/097428 CN2020097428W WO2020259436A1 WO 2020259436 A1 WO2020259436 A1 WO 2020259436A1 CN 2020097428 W CN2020097428 W CN 2020097428W WO 2020259436 A1 WO2020259436 A1 WO 2020259436A1
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positive electrode
electrode material
ternary positive
processability
ternary
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PCT/CN2020/097428
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French (fr)
Chinese (zh)
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夏阳
王坤
陈安琪
张文魁
吴海军
钱志挺
毛秦钟
黄辉
甘永平
张俊
梁初
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浙江工业大学
浙江美都海创锂电科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a modification method for improving the storage stability and processability of a ternary positive electrode material, and belongs to the technical field of lithium ion battery positive electrode materials.
  • ternary cathode materials have higher requirements for storage and processing environments, and ternary cathode materials are prone to a series of side reactions with the electrolyte during charge and discharge, such as electrolysis at high voltage at the end of charging.
  • the decomposition of the liquid, the acidic substance after the decomposition of the electrolyte corrodes the electrode, the dissolution of the electrode active material, etc.
  • researchers usually use surface coating to solve the above problems in order to improve the cycle stability of the material.
  • Stable lithium salt substances such as Li 3 PO 4 , LiFePO 4 , LiAlO 2, etc.
  • Materials that do not contain lithium ions such as SiO 2 , Al 2 O 3 , ZrO 2 etc.
  • solid-phase coating and liquid-phase coating sintering The coating layer obtained by the two coating methods is weakly bonded to the substrate, and the thickness is not uniform.
  • the present invention provides a supercritical carbon dioxide surface modification treatment method.
  • the method Compared with the traditional coating method, the method has the advantages of simple and convenient operation, fast and efficient, low cost, no "three wastes", etc., and has great potential for large-scale production.
  • the present invention provides a fast, high-efficiency, low-cost, no "three wastes" and other advantages to improve the storage stability and processability of lithium ion battery ternary cathode materials.
  • a modification method for improving the storage stability and processability of a ternary cathode material of a lithium ion battery comprising the following steps:
  • the reaction kettle is heated and reacted for a period of time and exhausted to obtain the modified ternary cathode material.
  • the chemical formula of the ternary cathode material is LiNi (1-xy) Co x M y O 2 , x+y ⁇ 0.7, and M is Mn or Al.
  • the chemical formula of the ternary cathode material is LiNi 0.83 Co 0.085 Mn 0.085 O 2 , LiNi 0.80 Co 0.15 Al 0.05 O 2 , LiNi 0.80 Co 0.10 Mn 0.10 O 2 or Li Ni 0.6 Co 0.2 Al 0.2 O 2 .
  • the pressure range of the carbon dioxide gas introduced in step S1 is 7.1 MPa-10 MPa.
  • the temperature of the heat preservation reaction in step S2 is 35-80° C., and the time is 0.1-48 h.
  • the temperature of the heat preservation reaction in step S2 is 35-45° C., and the time is 8-15 h.
  • the invention also discloses a lithium ion battery, which comprises the modified ternary positive electrode material prepared by the method of the invention.
  • the present invention uses supercritical carbon dioxide surface modification treatment to construct a dense metal carbonate coating layer on the surface of the ternary positive electrode material, and the coating layer is tightly combined with the ternary positive electrode material matrix; this surface coating treatment method
  • the ternary cathode material can be isolated from the humid environment to prevent it from reacting with water vapor to generate lithium hydroxide or metal hydroxide, destroying its surface and interface structure, improving its storage performance and subsequent processing performance, thereby greatly improving its cycle performance and increasing use Life:
  • the method is simple in process, easy to operate, fast and efficient, no "three wastes" are generated, carbon dioxide and recycled use, and economic benefits are significant.
  • Figure 1 is a SEM image of the modified ternary cathode material prepared in Example 1 of the present invention.
  • Example 2 is a graph of the first three charge and discharge curves of the battery prepared in Example 1 of the present invention at a current density of 20 mA g -1 ;
  • Fig. 3 is a charge-discharge cycle curve diagram of the battery prepared in Example 1 of the present invention activated for three cycles at a current density of 20 mA g -1 and then cycled 110 times at a current density of 100 mA g -1 .
  • Step 1 Preparation of surface-modified ternary cathode material
  • the reactor containing the ternary cathode material of the lithium ion battery and carbon dioxide is kept at 35° C. for reaction for 10 hours and exhausted to obtain the modified ternary cathode material.
  • step S3 Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
  • conductive agent acetylene black
  • binder polyvinylidene fluoride
  • step S4 The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
  • the third step battery performance test
  • Figure 1 is an SEM chart of the LiNi 0.83 Co 0.085 Mn 0.085 O 2 ternary cathode material of this embodiment after treatment. The chart shows that the surface of the material is uniform after carbon dioxide supercritical treatment, and the morphology is unchanged;
  • Figure 2 is a graph of the first three charge and discharge curves of the battery prepared in this embodiment at a current density of 20 mA g -1 and a voltage range of 3 to 4.2V, and the first discharge capacity is 190 mA h g -1 ;
  • Figure 3 is a graph showing the cycle performance of the battery prepared in this example at a current density of 20 mA g -1 for 3 times, and then at a current density of 100 mA g -1 . After 110 cycles, the discharge capacity is still 157 mA. hg -1 , the capacity retention rate is 93.2% (relative to the fourth charge and discharge).
  • Step 1 Preparation of surface-modified ternary cathode material
  • the reactor containing the ternary cathode material of the lithium ion battery and carbon dioxide is kept at 38° C. for reaction for 12 hours and then exhausted to obtain the modified ternary cathode material.
  • step S3 Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
  • conductive agent acetylene black
  • binder polyvinylidene fluoride
  • step S4 The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
  • the third step battery performance test
  • the button battery assembled with this material is charged and discharged 3 times at a current density of 20mA g -1 within the voltage range of 3 to 4.2V, and the first discharge capacity is 207mA h g -1 , and then at a current density of 100mA g -1 After 110 cycles, the discharge capacity is still 163 mA hg -1 , and the capacity retention rate is 96% (relative to the fourth charge and discharge).
  • Step 1 Preparation of surface-modified ternary cathode material
  • the ternary positive electrode material containing the lithium ion battery and the carbon dioxide reactor are kept at 43° C. for 6 hours and then exhausted to obtain the modified ternary positive electrode material.
  • step S3 Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
  • conductive agent acetylene black
  • binder polyvinylidene fluoride
  • step S4 The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
  • the third step battery performance test
  • the button battery assembled with this material is charged and discharged 3 times at a current density of 20mA g -1 within the voltage range of 3 to 4.2V, and the first discharge capacity is 208mA h g -1 , and then at a current density of 100mA g -1 After 110 cycles, the discharge capacity is still 166 mA hg -1 , and the capacity retention rate is 95% (relative to the fourth charge and discharge).
  • Step 1 Preparation of surface-modified ternary cathode material
  • the ternary cathode material containing the lithium ion battery and the carbon dioxide reactor are kept at 40° C. for 8 hours and then exhausted to obtain the modified ternary cathode material.
  • step S3 Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
  • conductive agent acetylene black
  • binder polyvinylidene fluoride
  • step S4 The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
  • the third step battery performance test
  • the button cell assembled with this material is charged and discharged 3 times at a current density of 20mA g -1 within the voltage range of 3 to 4.2V, and the first discharge capacity is 197mA h g -1 , and then at a current density of 100mA g -1 After 110 cycles, the discharge capacity is still 156mA hg -1 , and the capacity retention rate is 93% (relative to the fourth charge and discharge).
  • the modified ternary cathode material obtained by the method of the present application is used in lithium ion batteries, which can significantly improve the cycle stability of lithium ion batteries, and the modification method is simple, easy to operate, fast and efficient, and has no "three wastes". The economic benefits are significant.

Abstract

The present invention relates to a modification method for improving storage stability and processability of a ternary positive electrode material of a lithium ion battery, and provides a ternary positive electrode material surface modification method for the purpose of solving the problems in the prior art that the storage requirements of the ternary positive electrode material of the lithium ion battery are high, the processability and the battery cycling stability are poor, and the like. Supercritical carbon dioxide reacts with metal hydroxide on the surface of the ternary positive electrode material, and a uniform and dense metal carbonate coating layer is generated on the surface of the ternary positive electrode material in situ. The coating layer is tightly combined with the ternary positive electrode material matrix, and can also effectively inhibit the reaction between the ternary positive electrode material and humid air, so that the requirements on the storage and use environments are reduced, and the subsequent electrode processing performance is improved; moreover, the in-situ construction coating layer can isolate the ternary positive electrode material from an electrolyte, so that the occurrence of side reactions on the surface of the electrode is reduced, the structure stability of the electrode material is enhanced, and the cycling performance of the battery is improved. In addition, the surface modification method is simple to operate and low in costs.

Description

一种提高三元正极材料稳定性和加工性的方法A method for improving the stability and processability of ternary cathode materials 技术领域Technical field
本发明涉及一种提高三元正极材料储存稳定性和加工性的改性方法，属于锂离子电池正极材料技术领域。The invention relates to a modification method for improving the storage stability and processability of a ternary positive electrode material, and belongs to the technical field of lithium ion battery positive electrode materials.
背景技术Background technique
近年来，蓬勃发展的锂离子电池市场迅速从消费电子产品扩展到汽车行业。随着电动汽车行驶里程不断提高，新型高能量密度正极材料的研究成为人们广泛关注的焦点。镍基层状氧化物结构的三元正极材料(LiNi 1-xM xO 2，M＝Co、Mn、Al)具有高容量密度和价格低廉等优点，最有希望满足人们对高能量密度的需求。然而，高镍正极材料在空气中容易变质，特别是潮湿的空气，因为空气中的水分易与材料表面的锂反应生成不均匀的氢氧化锂，而氢氧化锂又进一步与空气中的二氧化碳反应生成不均匀的碳酸锂，从而造成材料表面变质，导致内部的金属元素分布不均匀引起过渡金属元素的外逸，引发后续正极浆料制备困难、正极容量衰减和循环稳定性变差等一系列问题。因此，未改性的三元正极材料对储存环境和加工环境的要求较高，而且三元正极材料在充放电过程中容易与电解液发生一系列的副反应，比如充电末期的高电压下电解液的分解、电解液分解后的酸性物质腐蚀电极、电极活性物质的溶解等。研究人员通常采用表面包覆的方式来解决上述问题，以提高材料的循环稳定性。 In recent years, the booming lithium-ion battery market has rapidly expanded from consumer electronics to the automotive industry. With the continuous improvement of the mileage of electric vehicles, the research of new high-energy density cathode materials has become the focus of widespread attention. The nickel-based layered oxide structure of the ternary cathode material (LiNi 1-x M x O 2 , M=Co, Mn, Al) has the advantages of high capacity density and low price, and it is most hopeful to meet people's demand for high energy density . However, high nickel cathode materials are prone to deterioration in the air, especially humid air, because the moisture in the air easily reacts with the lithium on the surface of the material to form uneven lithium hydroxide, and the lithium hydroxide further reacts with the carbon dioxide in the air Uneven formation of lithium carbonate, resulting in deterioration of the surface of the material, resulting in uneven distribution of internal metal elements, resulting in the escape of transition metal elements, and a series of problems such as difficulty in subsequent preparation of positive electrode slurry, degradation of positive electrode capacity, and poor cycle stability . Therefore, unmodified ternary cathode materials have higher requirements for storage and processing environments, and ternary cathode materials are prone to a series of side reactions with the electrolyte during charge and discharge, such as electrolysis at high voltage at the end of charging. The decomposition of the liquid, the acidic substance after the decomposition of the electrolyte corrodes the electrode, the dissolution of the electrode active material, etc. Researchers usually use surface coating to solve the above problems in order to improve the cycle stability of the material.
用于包覆的材料主要有两大类：1、稳定的锂盐类物质如Li 3PO 4、LiFePO 4、LiAlO 2等；2、不含锂离子的物质如SiO 2、Al 2O 3、ZrO 2等。对三元正极材料表面包覆改性方法目前主要有固相和液相包覆烧结两种。两种包覆方法所得到得包覆层与基体结合较弱，而且厚度不均一。在循环过程中，由于锂离子的嵌入和脱出引起体积变化所产生的应力，会使得包覆层破裂，活性物质暴露在电解液中，进而引起材料的恶化，循环稳定性变差。针对上述问题，本发明提供一种超临界二氧化碳表面改性处理方法，二氧化碳在超临界状态下快速均匀渗入二次晶粒之间，与三元正极材料表面的金属氢氧化物反应后生成一层均匀而致密的金属碳酸盐，且其与三元正极材料基体结合紧密，不仅能够有效分离活性物质与电解液的直接接触，防止副反应发生，提高活性物质的结构稳定性，同时还可大幅提高三元正极材料对潮湿环境的化学稳定性，有助于改善三元正极材料的存储性和后期加工性。该方法相对于传统包覆方法具有操作简单方便，快速高效，成本低廉，无“三废”等优势，极具规模化生产潜力。 There are two main types of materials used for coating: 1. Stable lithium salt substances such as Li 3 PO 4 , LiFePO 4 , LiAlO 2, etc.; 2. Materials that do not contain lithium ions such as SiO 2 , Al 2 O 3 , ZrO 2 etc. Currently, there are two main methods for surface coating modification of ternary cathode materials: solid-phase coating and liquid-phase coating sintering. The coating layer obtained by the two coating methods is weakly bonded to the substrate, and the thickness is not uniform. During the cycle, due to the stress generated by the volume change caused by the insertion and extraction of lithium ions, the coating layer will be broken and the active material will be exposed to the electrolyte, which will cause the deterioration of the material and the deterioration of the cycle stability. In view of the above problems, the present invention provides a supercritical carbon dioxide surface modification treatment method. The carbon dioxide penetrates into the secondary crystal grains quickly and uniformly in a supercritical state, and reacts with the metal hydroxide on the surface of the ternary cathode material to form a layer Uniform and dense metal carbonate, and it is tightly combined with the ternary cathode material matrix, not only can effectively separate the direct contact between the active material and the electrolyte, prevent side reactions, improve the structural stability of the active material, but also greatly Improving the chemical stability of the ternary cathode material to a humid environment will help improve the storage performance and later processability of the ternary cathode material. Compared with the traditional coating method, the method has the advantages of simple and convenient operation, fast and efficient, low cost, no "three wastes", etc., and has great potential for large-scale production.
发明内容Summary of the invention
本发明是为了解决上述现有技术中的不足，而提供一种快速高效、成本低廉、无“三废”等优势的提高锂离子电池三元正极材料储存稳定性和加工性的改性方法。In order to solve the above-mentioned shortcomings in the prior art, the present invention provides a fast, high-efficiency, low-cost, no "three wastes" and other advantages to improve the storage stability and processability of lithium ion battery ternary cathode materials.
本发明解决其技术问题所采用的技术方案是：The technical solutions adopted by the present invention to solve its technical problems are:
一种提高锂离子电池三元正极材料储存稳定性和加工性的改性方法，所述方法包括如下步骤：A modification method for improving the storage stability and processability of a ternary cathode material of a lithium ion battery, the method comprising the following steps:
S1、先将锂离子电池三元正极材料放入反应釜中，再将反应釜抽真空后向其中通入二氧化碳气体；S1. Put the ternary cathode material of the lithium ion battery into the reaction kettle first, and then evacuate the reaction kettle and introduce carbon dioxide gas into it;
S2、将反应釜保温反应一段时间后排气，即得改性三元正极材料。S2. The reaction kettle is heated and reacted for a period of time and exhausted to obtain the modified ternary cathode material.
作为优选，所述三元正极材料的化学式为LiNi (1-x-y)Co xM yO 2，x+y≤0.7，M为Mn或Al。 Preferably, the chemical formula of the ternary cathode material is LiNi (1-xy) Co x M y O 2 , x+y≤0.7, and M is Mn or Al.
更优选的，所述三元正极材料的化学式为LiNi 0.83Co 0.085Mn 0.085O 2、LiNi 0.80Co 0.15Al 0.05O 2、LiNi 0.80Co 0.10Mn 0.10O 2或Li Ni 0.6Co 0.2Al 0.2O 2。 More preferably, the chemical formula of the ternary cathode material is LiNi 0.83 Co 0.085 Mn 0.085 O 2 , LiNi 0.80 Co 0.15 Al 0.05 O 2 , LiNi 0.80 Co 0.10 Mn 0.10 O 2 or Li Ni 0.6 Co 0.2 Al 0.2 O 2 .
作为优选，步骤S1中通入的二氧化碳气体的压力范围为7.1MPa～10MPa。Preferably, the pressure range of the carbon dioxide gas introduced in step S1 is 7.1 MPa-10 MPa.
作为优选，步骤S2中保温反应的温度为35～80℃，时间为0.1～48h。Preferably, the temperature of the heat preservation reaction in step S2 is 35-80° C., and the time is 0.1-48 h.
更优选的，步骤S2中保温反应的温度为35～45℃，时间为8～15h。More preferably, the temperature of the heat preservation reaction in step S2 is 35-45° C., and the time is 8-15 h.
本发明还公开了一种锂离子电池，该电池包括本发明所述的方法制备的改性三元正极材料。The invention also discloses a lithium ion battery, which comprises the modified ternary positive electrode material prepared by the method of the invention.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明采用超临界二氧化碳表面改性处理在三元正极材料表面构筑一层致密的金属碳酸盐包覆层，且该包覆层与三元正极材料基体紧密结合；这种表面包覆处理方法可将三元正极材料与潮湿环境隔离，避免其与水汽反应生成氢氧化锂或金属氢氧化物，破坏其表界面结构，提高其储存性能和后续加工性能，从而大幅改善其循环性能，提高使用寿命；该方法工艺简单，操作简便，快速高效，无“三废”产生，二氧化碳和循环使用，经济效益显著。The present invention uses supercritical carbon dioxide surface modification treatment to construct a dense metal carbonate coating layer on the surface of the ternary positive electrode material, and the coating layer is tightly combined with the ternary positive electrode material matrix; this surface coating treatment method The ternary cathode material can be isolated from the humid environment to prevent it from reacting with water vapor to generate lithium hydroxide or metal hydroxide, destroying its surface and interface structure, improving its storage performance and subsequent processing performance, thereby greatly improving its cycle performance and increasing use Life: The method is simple in process, easy to operate, fast and efficient, no "three wastes" are generated, carbon dioxide and recycled use, and economic benefits are significant.
附图说明Description of the drawings
图1为本发明实施例1制备的改性三元正极材料的SEM图谱；Figure 1 is a SEM image of the modified ternary cathode material prepared in Example 1 of the present invention;
图2为本发明实施例1制备的电池在20mA g -1的电流密度下的前三次充放电曲线图； 2 is a graph of the first three charge and discharge curves of the battery prepared in Example 1 of the present invention at a current density of 20 mA g -1 ;
图3为本发明实施例1制备的电池在20mA g -1的电流密度下活化三个循环，然后在100mA g -1电流密度下循环110次的充放电循环曲线图。 Fig. 3 is a charge-discharge cycle curve diagram of the battery prepared in Example 1 of the present invention activated for three cycles at a current density of 20 mA g -1 and then cycled 110 times at a current density of 100 mA g -1 .
具体实施方式Detailed ways
下面通过实施例，结合附图，对本发明的技术方案进一步阐述说明，但本发明的保护范围不限于此。The technical solutions of the present invention will be further elaborated and explained below through embodiments and drawings, but the protection scope of the present invention is not limited thereto.
实施例1：Example 1:
第一步：制备表面改性的三元正极材料Step 1: Preparation of surface-modified ternary cathode material
S1、先将10g LiNi 0.83Co 0.085Mn 0.085O 2放入反应釜中，再将反应釜抽真空后向其中通入压力为8MPa的二氧化碳气体； S1. Put 10g LiNi 0.83 Co 0.085 Mn 0.085 O 2 into the reaction kettle first, and then evacuate the reaction kettle and then pass carbon dioxide gas with a pressure of 8MPa into it;
S2、将装有锂离子电池三元正极材料和二氧化碳的反应釜在35℃下保温反应10h后排气，即得改性三元正极材料。S2. The reactor containing the ternary cathode material of the lithium ion battery and carbon dioxide is kept at 35° C. for reaction for 10 hours and exhausted to obtain the modified ternary cathode material.
第二步：锂离子电池的制备Step 2: Preparation of Li-ion battery
S3、按质量比为90:5:5称取步骤S2获得的三元正极材料、导电剂(乙炔黑)与粘结剂(聚偏氟乙烯)，混合均匀，再加入适量的1-甲基-2吡咯烷酮(NMP)作溶剂，机械搅拌3h，得到具有一定粘度的浆料；S3. Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
S4、将步骤S3获得的浆料均匀涂覆在干净平整的铝箔上，用空烘箱中干燥后，冲成极片，再压实；S4. The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
S5、在手套箱中按正极壳、正极极片、隔膜、电解液、锂片、泡沫镍、电解液、负极壳的顺序组装成CR2025型纽扣电池，其中，隔膜的型号为Celgard 2300，电解液是1molL -1LiPF 6/EC+DEC(体积比为1:1)； S5. Assemble CR2025 button battery in the order of positive shell, positive pole piece, separator, electrolyte, lithium sheet, foam nickel, electrolyte, and negative shell in the glove box. The separator model is Celgard 2300, electrolyte Is 1molL -1 LiPF 6 /EC+DEC (volume ratio is 1:1);
搁置12h后测试电化学性能；Test the electrochemical performance after being left for 12h;
第三步：电池性能测试The third step: battery performance test
S6、采用一定的电流密度对电池进行充放电测试(前3次用电流密度为20mAg -1的电流活化电池，随后用电流密度为100mA g -1的电流进行充放电循环)，电压区间为3～4.2V，充放电的时间间隔为5min。 S6. Use a certain current density to charge and discharge the battery (the first 3 times use a current density of 20mAg -1 to activate the battery, and then use a current density of 100mA g -1 for charge and discharge cycles), the voltage range is 3 ～4.2V, the time interval between charge and discharge is 5min.
附图1为本实施例的LiNi 0.83Co 0.085Mn 0.085O 2三元正极材料处理后的SEM图谱，图谱显示在二氧化碳超临界处理后材料表面均匀，形貌未改变； Figure 1 is an SEM chart of the LiNi 0.83 Co 0.085 Mn 0.085 O 2 ternary cathode material of this embodiment after treatment. The chart shows that the surface of the material is uniform after carbon dioxide supercritical treatment, and the morphology is unchanged;
附图2为本实施例制备的电池在20mA g -1的电流密度下，电压区间为3～4.2V的前三次充放电曲线图，首次放电容量为190mA h g -1； Figure 2 is a graph of the first three charge and discharge curves of the battery prepared in this embodiment at a current density of 20 mA g -1 and a voltage range of 3 to 4.2V, and the first discharge capacity is 190 mA h g -1 ;
附图3为本实施例制备的电池先在20mA g -1的电流密度下活化3次，然后在100mA g -1的电流密度下的循环性能图，在110次循环后，放电容量仍有157mA h g -1，容量保持率为93.2％(相对第4次充放电)。 Figure 3 is a graph showing the cycle performance of the battery prepared in this example at a current density of 20 mA g -1 for 3 times, and then at a current density of 100 mA g -1 . After 110 cycles, the discharge capacity is still 157 mA. hg -1 , the capacity retention rate is 93.2% (relative to the fourth charge and discharge).
实施例2：Example 2:
第一步：制备表面改性的三元正极材料Step 1: Preparation of surface-modified ternary cathode material
S1、先将8g LiNi 0.80Co 0.15Al 0.05O 2放入反应釜中，再将反应釜抽真空后向其中通入压力为8.5MPa的二氧化碳气体； S1. Put 8g LiNi 0.80 Co 0.15 Al 0.05 O 2 into the reaction kettle first, and then evacuate the reaction kettle and introduce carbon dioxide gas with a pressure of 8.5MPa into it;
S2、将装有锂离子电池三元正极材料和二氧化碳的反应釜在38℃下保温反应12h后排气，即得改性三元正极材料。S2. The reactor containing the ternary cathode material of the lithium ion battery and carbon dioxide is kept at 38° C. for reaction for 12 hours and then exhausted to obtain the modified ternary cathode material.
第二步：锂离子电池的制备Step 2: Preparation of Li-ion battery
S3、按质量比为90:5:5称取步骤S2获得的三元正极材料、导电剂(乙炔黑)与粘结剂(聚偏氟乙烯)，混合均匀，再加入适量的1-甲基-2吡咯烷酮(NMP)作溶剂，机械搅拌3h，得到具有一定粘度的浆料；S3. Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
S4、将步骤S3获得的浆料均匀涂覆在干净平整的铝箔上，用空烘箱中干燥后，冲成极片，再压实；S4. The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
S5、在手套箱中按正极壳、正极极片、隔膜、电解液、锂片、泡沫镍、电解液、负极壳的顺序组装成CR2025型纽扣电池，其中，隔膜的型号为Celgard 2300，电解液是1mol L -1LiPF 6/EC+DEC(体积比为1:1)； S5. Assemble CR2025 button battery in the order of positive shell, positive pole piece, separator, electrolyte, lithium sheet, foam nickel, electrolyte, and negative shell in the glove box. The separator model is Celgard 2300, electrolyte Is 1mol L -1 LiPF 6 /EC+DEC (volume ratio is 1:1);
搁置12h后测试电化学性能；Test the electrochemical performance after being left for 12h;
第三步：电池性能测试The third step: battery performance test
S6、该材料组装的扣式电池在3～4.2V电压范围内，先在20mA g -1的电流密度下充放电3次，首次放电容量207mA h g -1，再在100mA g -1电流密度下循环110次后，放电容量仍有163mA h g -1，容量保持率为96％(相对第4次充放电)。 S6. The button battery assembled with this material is charged and discharged 3 times at a current density of 20mA g -1 within the voltage range of 3 to 4.2V, and the first discharge capacity is 207mA h g -1 , and then at a current density of 100mA g -1 After 110 cycles, the discharge capacity is still 163 mA hg -1 , and the capacity retention rate is 96% (relative to the fourth charge and discharge).
实施例3：Example 3:
第一步：制备表面改性的三元正极材料Step 1: Preparation of surface-modified ternary cathode material
S1、先将12g LiNi 0.80Co 0.10Mn 0.10O 2放入反应釜中，再将反应釜抽真空后向其中通入压力为7.8MPa的二氧化碳气体； S1. Put 12g LiNi 0.80 Co 0.10 Mn 0.10 O 2 into the reaction kettle first, and then evacuate the reaction kettle and introduce carbon dioxide gas with a pressure of 7.8MPa into it;
S2、将装有锂离子电池三元正极材料和二氧化碳反应釜在43℃下保温反应6h后排气，即得改性三元正极材料。S2. The ternary positive electrode material containing the lithium ion battery and the carbon dioxide reactor are kept at 43° C. for 6 hours and then exhausted to obtain the modified ternary positive electrode material.
第二步：锂离子电池的制备Step 2: Preparation of Li-ion battery
S3、按质量比为90:5:5称取步骤S2获得的三元正极材料、导电剂(乙炔黑)与粘结剂(聚偏氟乙烯)，混合均匀，再加入适量的1-甲基-2吡咯烷酮(NMP)作溶剂，机械搅拌3h，得到具有一定粘度的浆料；S3. Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
S4、将步骤S3获得的浆料均匀涂覆在干净平整的铝箔上，用空烘箱中干燥后，冲成极片，再压实；S4. The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
S5、在手套箱中按正极壳、正极极片、隔膜、电解液、锂片、泡沫镍、电解液、负极壳的顺序组装成CR2025型纽扣电池，其中，隔膜的型号为Celgard 2300，电解液是1mol L -1LiPF 6/EC+DEC(体积比为1:1)； S5. Assemble CR2025 button battery in the order of positive shell, positive pole piece, separator, electrolyte, lithium sheet, foam nickel, electrolyte, and negative shell in the glove box. The separator model is Celgard 2300, electrolyte Is 1mol L -1 LiPF 6 /EC+DEC (volume ratio is 1:1);
搁置12h后测试电化学性能；Test the electrochemical performance after being left for 12h;
第三步：电池性能测试The third step: battery performance test
S6、该材料组装的扣式电池在3～4.2V电压范围内，先在20mA g -1的电流密度下充放电3次，首次放电容量208mA h g -1，再在100mA g -1电流密度下循环110次后，放电容量仍有166mA h g -1，容量保持率为95％(相对第4次充放电)。 S6. The button battery assembled with this material is charged and discharged 3 times at a current density of 20mA g -1 within the voltage range of 3 to 4.2V, and the first discharge capacity is 208mA h g -1 , and then at a current density of 100mA g -1 After 110 cycles, the discharge capacity is still 166 mA hg -1 , and the capacity retention rate is 95% (relative to the fourth charge and discharge).
实施例4：Example 4:
第一步：制备表面改性的三元正极材料Step 1: Preparation of surface-modified ternary cathode material
S1、先将12g Li Ni 0.6Co 0.2Al 0.2O 2放入反应釜中，再将反应釜抽真空后向其中通入压力为7.5MPa的二氧化碳气体； S1. Put 12g Li Ni 0.6 Co 0.2 Al 0.2 O 2 into the reaction kettle first, and then evacuate the reaction kettle and then pass carbon dioxide gas with a pressure of 7.5 MPa into it;
S2、将装有锂离子电池三元正极材料和二氧化碳反应釜在40℃下保温反应8h后排气，即得改性三元正极材料。S2. The ternary cathode material containing the lithium ion battery and the carbon dioxide reactor are kept at 40° C. for 8 hours and then exhausted to obtain the modified ternary cathode material.
第二步：锂离子电池的制备Step 2: Preparation of Li-ion battery
S3、按质量比为90:5:5称取步骤S2获得的三元正极材料、导电剂(乙炔黑)与粘结剂(聚偏氟乙烯)，混合均匀，再加入适量的1-甲基-2吡咯烷酮(NMP)作溶剂，机械搅拌3h，得到具有一定粘度的浆料；S3. Weigh the ternary positive electrode material, conductive agent (acetylene black) and binder (polyvinylidene fluoride) obtained in step S2 at a mass ratio of 90:5:5, mix them evenly, and then add an appropriate amount of 1-methyl -2 Pyrrolidone (NMP) is used as a solvent and mechanically stirred for 3 hours to obtain a slurry with a certain viscosity;
S4、将步骤S3获得的浆料均匀涂覆在干净平整的铝箔上，用空烘箱中干燥后，冲成极片，再压实；S4. The slurry obtained in step S3 is evenly coated on clean and flat aluminum foil, dried in an empty oven, washed into pole pieces, and then compacted;
S5、在手套箱中按正极壳、正极极片、隔膜、电解液、锂片、泡沫镍、电解液、负极壳的顺序组装成CR2025型纽扣电池，其中，隔膜的型号为Celgard 2300，电解液是1mol L -1LiPF 6/EC+DEC(体积比为1:1)； S5. Assemble CR2025 button battery in the order of positive shell, positive pole piece, separator, electrolyte, lithium sheet, foam nickel, electrolyte, and negative shell in the glove box. The separator model is Celgard 2300, electrolyte Is 1mol L -1 LiPF 6 /EC+DEC (volume ratio is 1:1);
搁置12h后测试电化学性能；Test the electrochemical performance after being left for 12h;
第三步：电池性能测试The third step: battery performance test
S6、该材料组装的扣式电池在3～4.2V电压范围内，先在20mA g -1的电流密度下充放电3次，首次放电容量197mA h g -1，再在100mA g -1电流密度下循环110次后，放电容量仍有156mA h g -1，容量保持率为93％(相对第4次充放电)。 S6. The button cell assembled with this material is charged and discharged 3 times at a current density of 20mA g -1 within the voltage range of 3 to 4.2V, and the first discharge capacity is 197mA h g -1 , and then at a current density of 100mA g -1 After 110 cycles, the discharge capacity is still 156mA hg -1 , and the capacity retention rate is 93% (relative to the fourth charge and discharge).
综上所述，本申请的方法得到的改性三元正极材料用于锂离子电池，可显著提高锂离子电池的循环稳定性，并且改性方法简单，操作简便，快速高效，无“三废”产生，经济效益显著。In summary, the modified ternary cathode material obtained by the method of the present application is used in lithium ion batteries, which can significantly improve the cycle stability of lithium ion batteries, and the modification method is simple, easy to operate, fast and efficient, and has no "three wastes". The economic benefits are significant.
以上所述的实施例只是本发明的较佳方案，并非对本发明作任何形式上的限制，在不超出权利要求所记载的技术方案的前提下还有其他的变体及改型。The above-mentioned embodiments are only preferred solutions of the present invention, and do not limit the present invention in any form. There are other variations and modifications under the premise of not exceeding the technical solutions described in the claims.

Claims (7)

  1. 一种提高三元正极材料稳定性和加工性的方法，其特征在于，所述方法包括如下步骤：A method for improving the stability and processability of a ternary cathode material, characterized in that the method includes the following steps:
    S1、先将锂离子电池三元正极材料放入反应釜中，再将反应釜抽真空后向其中通入二氧化碳气体；S1. Put the ternary cathode material of the lithium ion battery into the reaction kettle first, and then evacuate the reaction kettle and introduce carbon dioxide gas into it;
    S2、将反应釜保温反应一段时间后排气，即得改性三元正极材料。S2. The reaction kettle is heated and reacted for a period of time and exhausted to obtain the modified ternary cathode material.
  2. 根据权利要求1所述的提高三元正极材料储存稳定性和加工性的改性方法，其特征在于，所述三元正极材料的化学式为LiNi (1-x-y)Co xM yO 2，x+y≤0.7，M为Mn或Al。 The modification method for improving the storage stability and processability of the ternary cathode material according to claim 1, wherein the chemical formula of the ternary cathode material is LiNi (1-xy) Co x M y O 2 , x +y≤0.7, M is Mn or Al.
  3. 根据权利要求1所述的提高三元正极材料储存稳定性和加工性的改性方法，其特征在于，所述三元正极材料的化学式为LiNi 0.83Co 0.085Mn 0.085O 2、LiNi 0.80Co 0.15Al 0.05O 2、LiNi 0.80Co 0.10Mn 0.10O 2或Li Ni 0.6Co 0.2Al 0.2O 2。 The modification method for improving storage stability and processability of a ternary cathode material according to claim 1, wherein the chemical formula of the ternary cathode material is LiNi 0.83 Co 0.085 Mn 0.085 O 2 , LiNi 0.80 Co 0.15 Al 0.05 O 2 , LiNi 0.80 Co 0.10 Mn 0.10 O 2 or Li Ni 0.6 Co 0.2 Al 0.2 O 2 .
  4. 根据权利要求1所述的提高三元正极材料储存稳定性和加工性的改性方法，其特征在于，步骤S1中通入的二氧化碳气体的压力范围为7.1MPa～10MPa。The modification method for improving the storage stability and processability of the ternary positive electrode material according to claim 1, wherein the pressure range of the carbon dioxide gas introduced in step S1 is 7.1 MPa-10 MPa.
  5. 根据权利要求1所述的提高三元正极材料储存稳定性和加工性的改性方法，其特征在于，步骤S2中保温反应的温度为35～80℃，时间为0.1～48h。The modification method for improving the storage stability and processability of the ternary cathode material according to claim 1, wherein the temperature of the heat preservation reaction in step S2 is 35-80°C, and the time is 0.1-48 h.
  6. 根据权利要求5所述的提高三元正极材料储存稳定性和加工性的改性方法，其特征在于，步骤S2中保温反应的温度为35～45℃，时间为8～15h。The modification method for improving the storage stability and processability of the ternary positive electrode material according to claim 5, wherein the temperature of the heat preservation reaction in step S2 is 35-45° C., and the time is 8-15 h.
  7. 一种锂离子电池，其特征在于，所述锂离子电池包括权利要求1～6任意一项所述的方法制备的改性三元正极材料。A lithium ion battery, wherein the lithium ion battery comprises a modified ternary positive electrode material prepared by the method of any one of claims 1 to 6.
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