WO2022188480A1 - 锂电池复合正极材料的前驱体及复合正极材料的制备方法 - Google Patents

锂电池复合正极材料的前驱体及复合正极材料的制备方法 Download PDF

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WO2022188480A1
WO2022188480A1 PCT/CN2021/135237 CN2021135237W WO2022188480A1 WO 2022188480 A1 WO2022188480 A1 WO 2022188480A1 CN 2021135237 W CN2021135237 W CN 2021135237W WO 2022188480 A1 WO2022188480 A1 WO 2022188480A1
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positive electrode
electrode material
precursor
composite positive
lithium
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French (fr)
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杨张萍
韩珽
陈英
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浙江美达瑞新材料科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/48—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of lithium batteries, in particular to a precursor of a lithium battery composite positive electrode material and a preparation method of the composite positive electrode material.
  • lithium batteries have become more and more widely used in the field of electric bicycles, electric vehicles, power tools, 3C digital products and other fields with the advantages of environmental protection, long service life and relatively light quality.
  • GGII Lithium Institute of High-tech Industrial Research Institute
  • the positive electrode material should also have similar or better electrochemical properties to those of the high-nickel ternary material.
  • nickel cobalt lithium manganate ternary material has higher energy density, but the increase of nickel content will adversely affect the cycle performance, rate capability and thermal stability of the battery. Therefore, in order to reduce these adverse effects, the commonly used method is to carry out coating modification or structural doping modification on the surface of the cathode material.
  • the relatively high cost of modification there is still a long way to go from large-scale production and final industrial application.
  • CN104218234B discloses a lithium ion battery composite positive electrode material with high cycle performance and a preparation method thereof. It mixes LiNi 1-mn Co m Al n O 2 and LiNi a Co 1-ab Mnl b O 2 two active materials uniformly in a certain proportion, and after calcining, cooling, pulverizing, sieving or calcining after surface treatment, The composite cathode material is obtained by cooling, crushing and sieving. Compared with lithium nickel cobalt manganate, the specific capacity of the composite material is greatly improved, and the cycle performance, thermal stability and safety performance are improved compared with lithium nickel cobalt aluminate.
  • the method of mixing the two active materials evenly and then sintering has low stability of the material structure, which may destroy the fusion between the materials during the battery manufacturing process, and there is the possibility of uneven mixing at one time, thus affecting the material. the overall electrical conductivity.
  • the present invention provides a precursor of a composite positive electrode material for a lithium battery and a preparation method for the composite positive electrode material to overcome the deficiencies of the prior art. Specifically, two or more precursors are used in a certain proportion.
  • the composite positive electrode material is obtained by mixing and sintering, and the composite positive electrode material is modified to improve the cycle performance, rate performance and thermal stability of the material.
  • the preparation method of the precursor of the lithium battery composite positive electrode material which comprises the following steps:
  • a soluble salt containing metal or non-metal element M and deionized water Provide a soluble salt containing metal or non-metal element M and deionized water, and dissolve the soluble salt containing metal or non-metal element M in a certain amount of deionized water according to a predetermined molar ratio, and configure a mixed salt solution;
  • M is any combination of five or less of metal elements, rare earth elements, and non-metal elements.
  • the metal elements are nickel, cobalt, aluminum, manganese, sodium, lithium, potassium, barium, iron, calcium, copper, zinc, titanium, magnesium, zirconium, strontium, chromium, tin, antimony, tungsten, niobium, One of molybdenum, vanadium, palladium, bismuth, cesium, hafnium, tantalum, polonium, gallium, indium, thallium.
  • the rare earth element is one of lanthanides, yttrium, and scandium.
  • the non-metal element is one of sulfur, boron, silicon, arsenic, phosphorus, selenium, tellurium, fluorine, iodine, and astatine.
  • the soluble salt containing metal or non-metal element M is one or more of nitrates, formates, acetates, sulfates, phosphates and chlorides.
  • the molar ratio of the soluble salt containing the metal or non-metal element M to the sum of the metal or non-metal element it contains is an arbitrary ratio.
  • the molar ratio of NaOH and ammonia water is 1:1.
  • the preparation method of composite positive electrode material it comprises the following steps:
  • each precursor is in phase with other precursors. than the composition of at least one element is different or the molar ratio of the composition of at least one element is different;
  • the chemical formula of the mixed precursor is: where 0 ⁇ n ⁇ 1, and 2 ⁇ x ⁇ 100, x is an integer;
  • the obtained mixed precursor powder and lithium source are uniformly mixed in a certain proportion, calcined at a high temperature in an oxygen or air atmosphere, cooled, ground and sieved to obtain a composite positive electrode material where 0 ⁇ n ⁇ 1, and 2 ⁇ x ⁇ 100, x is an integer, 0.9 ⁇ a ⁇ 1.8;
  • the content ratio of two or more of the precursors is any ratio.
  • the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride and lithium sulfate, and the lithium source is the sum of the lithium element and the mixed precursor and its content.
  • the molar ratio of the sum total of metals is 0.9 to 1.80:1.
  • the preparation method in which two or more precursors are mixed uniformly in a certain proportion and then sintered.
  • the preparation process is relatively simple and easy to operate. Compared with the commonly used cathode material modification treatment, the cost is lower, which is conducive to large-scale production. .
  • FIG. 1 is a flow chart of the preparation method of the precursor of the lithium ion composite positive electrode material provided by the present invention.
  • FIG. 2 is a flow chart of the preparation method of the composite positive electrode material provided by the present invention.
  • FIG. 3 is a specific capacity-voltage diagram of the composite positive electrode material of Example 1 provided by the present invention during charging and discharging.
  • FIG. 4 is a cycle performance diagram of the composite cathode material of Example 1 provided by the present invention.
  • FIG. 1 it is a flow chart of the preparation method of the precursor of the lithium ion composite positive electrode material provided by the present invention.
  • the preparation method of the precursor of the lithium ion composite positive electrode material comprises the following steps:
  • STEP101 Provide a soluble salt containing metal or non-metal element M and deionized water, and dissolve the soluble salt containing metal or non-metal element M in a certain amount of deionized water according to a predetermined molar ratio, and configure mixed salt solution;
  • STEP102 Provide NaOH, ammonia water, and deionized water, and dissolve the NaOH and ammonia water in the deionized water to configure a mixed alkali solution;
  • STEP103 Provide deionized water, add the mixed salt solution and mixed alkali solution into the deionized water at a certain speed, and adjust the pH value to 9 to 12. After reacting for a period of time, filter, wash and dry to obtain the precursor M. (OH) 2 , M is any combination of five or less of metal elements, rare earth elements, and non-metal elements.
  • the metal element M may be nickel, cobalt, aluminum, manganese, sodium, lithium, potassium, barium, iron, calcium, copper, zinc, titanium, magnesium, zirconium, strontium, chromium, tin, antimony, One of tungsten, niobium, molybdenum, vanadium, palladium, bismuth, cesium, hafnium, tantalum, polonium, gallium, indium, thallium.
  • the metal element M may also be a rare earth element, and the rare earth element is one of lanthanide elements, yttrium and scandium.
  • the non-metal element M may be one of sulfur, boron, silicon, arsenic, phosphorus, selenium, tellurium, fluorine, iodine, and astatine.
  • the elemental composition of M may be less than or equal to 5 kinds.
  • the elemental composition of the M may be 6 kinds, 7 kinds, or more.
  • the elements of M in this application are limited to five or less, because the combination range of five or less is already relatively wide.
  • the soluble salt containing metal or non-metal element M can be one or more of nitrates, formates, acetates, sulfates, phosphates and chlorides. The properties and preparation methods of these soluble salts should be in the prior art and will not be repeated here.
  • the molar ratio of the soluble salt containing the metal or non-metal element M based on the sum of the metal or non-metal element it contains is an arbitrary ratio.
  • step STEP102 the molar ratio of NaOH to ammonia water in the mixed alkali solution is 1:1 to 5, and preferably, the molar ratio of NaOH to ammonia water in the mixed alkali solution is 1:1.
  • NaOH and ammonia water itself, it should be the prior art, and will not be described in detail here.
  • step STEP103 the pH value of the mixed solution of the mixed salt solution and the mixed alkali solution is preferably 11.
  • the methods and equipment for filtering, washing and drying should be known to those skilled in the art, and will not be repeated here.
  • the precursor M(OH) 2 of the composite cathode material for lithium batteries can be prepared.
  • the composition of M is determined by the soluble salt added in STEP101.
  • FIG. 2 it is a flow chart of the preparation method of the composite positive electrode material provided by the present invention.
  • the preparation method of the composite positive electrode material which comprises the following steps:
  • Step 201 Provide two or more precursors M(OH) 2 of the above-mentioned composite cathode material for lithium batteries, each precursor has at least one element that is different in composition or has at least one element compared to other precursors The molar ratios of the ingredients are different;
  • Step STEP202 Mix all the precursors uniformly in a certain proportion to obtain the powder of the mixed precursor.
  • the general chemical formula of the mixed precursor is: where 0 ⁇ n ⁇ 1, and 2 ⁇ x ⁇ 100, x is an integer;
  • Step STEP203 Mix the obtained powder of the mixed precursor and the lithium source uniformly in a certain proportion, calcinate at high temperature in an oxygen or air atmosphere, and obtain a composite positive electrode material through cooling, grinding and sieving.
  • 0 ⁇ n ⁇ 1, and 2 ⁇ x ⁇ 100, x is an integer, 0.9 ⁇ a ⁇ 1.8;
  • Step STEP204 Combine the composite cathode material Modified.
  • the content ratio of two or more of the precursors is an arbitrary ratio, but the molar ratio of the M element in each precursor and the M element in the other precursors is different. Meanwhile, when the content ratio of two or more of the precursors is the same, the molar ratio of the M element in the precursors needs to be different.
  • the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride and lithium sulfate, and the lithium source is the sum of the lithium element and the mixed precursor with its
  • the molar ratio of the total sum of the metals contained is 0.9 to 1.80:1.
  • the molar ratio of the sum of the lithium source in terms of lithium element and the sum of the mixed precursor in terms of metals contained therein is 1.2:1.
  • the modification treatment may be coating modification or structural doping modification, but the coating modification or structural doping modification itself is in the prior art, and details are not described herein again.
  • the above two mixed solutions were simultaneously added to the reactor at a certain speed, the pH value of the reaction was controlled to be 12, the reaction temperature was 60 °C, the reaction was 6 h after aging for 8 h, and the precursor Ni 0.85 Mn was obtained after filtration, washing and drying. 0.10 Mg 0.05 (OH) 2 .
  • the above two mixed solutions are simultaneously added to the reactor at a certain speed, the pH value of the reaction is controlled to be 12, the reaction temperature is 60 ° C, the reaction is 6h and then aged for 8h, and the precursor Ni 0.85 Fe is obtained after filtration, washing and drying. 0.10 Al 0.05 (OH) 2 .
  • the above two precursors are uniformly mixed according to the mass percentage of Ni 0.85 Mn 0.10 Mg 0.05 (OH) 2 : Ni 0.85 Fe 0.10 Al 0.05 (OH) 2 in a ratio of 6:4 to obtain a mixed precursor powder.
  • the above mixed precursor powder and lithium hydroxide are uniformly mixed according to the ratio of Li:(Ni+Mn+Mg+Fe+Al) to 1.05:1, then calcined at 800°C for 8h in an oxygen atmosphere, cooled, pulverized, and passed through. Sieve to obtain 60% LiNi 0.85 Mn 0.10 Mg 0.05 O 2 -40% LiNi 0.85 Fe 0.10 Al 0.05 O 2 composite positive electrode material.
  • the electrochemical performance test of the composite positive electrode material was tested at 25°C using a blue battery test system, and the test voltage range was 2.8V to 4.3V; the rate performance test condition: 0.1C (C is used to indicate the battery charge and discharge The ratio of the current size, that is, the rate.
  • C is used to indicate the battery charge and discharge
  • the ratio of the current size that is, the rate.
  • a 1200mAh battery 0.2C means 240mA (0.2 rate of 1200mAh), 1C means 1200mA (1 rate of 1200mAh)) charge and discharge once, 0.2C charge and discharge once, 0.2C charge and 1C discharge once ; Cyclic performance test conditions: charge and discharge at a rate of 1C, cycle for 100 cycles, and investigate the capacity retention rate.
  • the composite cathode material has a specific discharge capacity of 209.1mAh/g at a rate of 0.1C, a specific discharge capacity of 203.2mAh/g at a rate of 0.2C, and a specific discharge capacity of 192.7mAh/g at a rate of 1C.
  • the 0.1C discharge ratio is 92.1%, and it can be seen from Figure 3 that the composite cathode material has better rate performance.
  • the 100-cycle capacity retention rate of 1C charge-discharge cycle is greater than 98.2%, and its cycle performance is better, as shown in Figure 4.
  • the above three precursors are mixed according to the mass percentage Ni 0.85 Mn 0.10 Al 0.05 (OH) 2 : Ni 0.60 Co 0.20 Mn 0.20 (OH) 2 : Ni 0.80 Fe 0.15 Al 0.05 (OH) 2 in a ratio of 5:2:3
  • the mixed precursor powder is uniformly obtained.
  • the above mixed precursor powder and lithium hydroxide were uniformly mixed according to the ratio of Li:(Ni+Mn+Fe+Al+Co) to 1.05:1, then calcined at 800°C for 16h in an oxygen atmosphere, cooled, pulverized, and calcined. Sieve to obtain 50% LiNi 0.85 Mn 0.10 Al 0.05 O 2 -20% Ni 0.60 Co 0.20 Mn 0.20 (OH) 2 - 30% LiNi 0.80 Fe 0.15 Al 0.05 O 2 composite positive electrode material.
  • the above two precursors are uniformly mixed in a ratio of 5:5 by mass percentage Ni 0.90 Mn 0.05 Al 0.03 Cr 0.02 (OH) 2 : Ni 0.80 Mn 0.10 Al 0.07 Cr 0.03 (OH) 2 to obtain a mixed precursor powder.
  • the above mixed precursor powder and lithium hydroxide are uniformly mixed according to the ratio of Li:(Ni+Mn+Al+Cr) to 1.05:1, then calcined at a high temperature of 700 °C in an oxygen atmosphere for 20h, cooled, pulverized and sieved to obtain 50% LiNi 0.90 Mn 0.05 Al 0.03 Cr 0.02 O 2 -50% Li Ni 0.80 Mn 0.10 Al 0.07 Cr 0.03 O 2 composite positive electrode material.
  • the preparation method in which two or more precursors are mixed uniformly in a certain proportion and then sintered.
  • the preparation process is relatively simple and easy to operate. Compared with the commonly used cathode material modification treatment, the cost is lower, which is conducive to large-scale production. .
  • the performance of one or several cathode materials is also improved, because by mixing two or more precursors and then sintering at high temperature, the crystal grains of various component materials in the composite cathode material are fused, thereby making the component materials A crystal with a good layered structure in the composite material, and the crystal with a good layered structure can be fused with other agglomerated crystals to improve the structural stability and conductivity of the composite cathode material, thereby improving the electrochemical performance of the battery. .

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Abstract

锂电池复合正极材料的前驱体及复合正极材料的制备方法，复合正极材料的制备方法，其包括如下步骤：提供两种或多种锂电池复合正极材料的前驱体M（OH）2，将所有前驱体按一定比例混合均匀，得到混合前驱体的粉体，该混合前驱体的化学通式为式（I），将所得的混合前驱体的粉体与锂源按一定比例混合均匀，在氧气或空气气氛中高温煅烧，经过冷却、研磨、过筛得到复合正极材料式（II），将复合正极材料式（II）进行改性处理。本发明的最大优点在于将两种或多种前驱体按照一定比例混合均匀后进行烧结的制备方式，制备工艺较为简单易操作，与常用的正极材料改性处理相比，成本较低，有利于规模化生产。本发明还提供所述锂电池复合正极材料的前驱体的制备方法。

Description

锂电池复合正极材料的前驱体及复合正极材料的制备方法 技术领域
本发明属于锂电池技术领域，特别是锂电池复合正极材料的前驱体及复合正极材料的制备方法。
背景技术
随着技术的进步以及新国标的推动下，锂电池凭借着环保、使用寿命长、质量相对较轻等优势，在电动自行车领域、电动汽车、电动工具、3C数码产品等领域的应用愈发广泛。高工产研锂电研究所(GGII)调研数据显示，2020年中国正极材料的出货量达到51万吨，镍钴锰酸锂三元材料与磷酸铁锂市场占比排名前二。
随着原材料钴价格的波动，镍钴锰酸锂三元材料锂电池对钴的依赖带来了恶劣的环境和可持续性问题。因此，开发新的无钴且具有成本效益的正极材料成为一种研发趋势。当然，可以理解的是，该正极材料还应具有与高镍三元材料类似或更好的电化学特性。另外，与磷酸铁锂相比，镍钴锰酸锂三元材料具有较高的能量密度，但镍含量的提高，会对电池的循环性能、倍率性以及热稳定性产生不利影响。因此，为了减少这些不利影响，常用的方法是对正极材料的表面进行包覆改性或结构掺杂改性等。但是由于改性成本比较高，目前离规模化生产与最终的工业化应用还有很远的距离。
CN104218234B公开了一种高循环性能的锂离子电池复合正极材料及其制备方法。其将LiNi 1-m-nCo mAl nO 2和LiNi aCo 1-a-bMnl bO 2两种活性物质按一定的比例混合均匀，经煅烧后冷却、粉碎、过筛或者经表面处理后煅烧、冷却、粉碎、过筛得到复合正极材料。该复合材料的比容量相对于镍钴锰酸锂有了大幅度的提高，同时循环性能、热稳定性及安全性能相对于镍钴铝酸锂有所提高。但是，将两种活性物质混合均匀后烧结的方式，材料结构稳定性较低，在电池制作工艺过程中可能会破坏材料之间的融合，且一次混合存在混合不均匀的可能性，从而影响材料的整体导电性能。
发明内容
有鉴于此，本发明提供了一种锂电池复合正极材料的前驱体及复合正极材料的制备方法，以克服现有技术的不足，具体地，其采用两种或多种前驱体按一定比例进行混合烧结得到复合正极材料，同时对复合正极材料进行改性处理以提高材料的循环性能、倍率性能及热稳定性。
锂电池复合正极材料的前驱体的制备方法，其包括如下步骤：
提供含有金属或非金属元素M的可溶性盐与去离子水，并将所述含有金属或非金属元素M的可溶性盐按照预定的摩尔比溶于一定量的所述去离子水中，配置得到混合盐溶液；
提供NaOH、氨水、以及去离子水，并将该NaOH和氨水溶解在所述去离子水中配置成混合碱溶液；
提供去离子水，将所述混合盐溶液与混合碱溶液以一定速度加入该去离子水中，并调节pH值于9～12，反应一段时间后，经过过滤、洗涤和干燥得到前驱体M(OH) 2，M为金属元素、稀土元素、以及非金属元素中的五种及以下的任意组合。
进一步地，所述金属元素为镍、钴、铝、锰、钠、锂、钾、钡、铁、钙、铜、锌、钛、镁、锆、锶、铬、锡、锑、钨、铌、钼、钒、钯、铋、铯、铪、钽、钋、镓、铟、铊中的一种。
进一步地，所述稀土元素为镧系元素以及、钇、钪中的一种。
进一步地，所述非金属元素为硫、硼、硅、砷、磷、硒、碲、氟、碘、砹中的一种。
进一步地，含有金属或非金属元素M的可溶性盐为硝酸盐、甲酸盐、乙酸盐、硫酸盐、磷酸盐和氯化盐中的一种或几种。
进一步地，所述含有金属或非金属元素M的可溶性盐以其含有的金属或非金属元素计的总和的摩尔比为任意比。
进一步地，所述的混合碱溶液中NaOH与氨水的摩尔比为1:1。
复合正极材料的制备方法，其包括如下步骤：
提供两种或多种如权利要求1至7任一项所述的锂电池复合正极材料的前驱体的制备方法所制备的前驱体M(OH) 2，每一种前驱体与其他前驱体相比至少有一个元素的成分不同或者至少有一个元素成分的摩尔比例不同；
将所有前驱体按一定比例混合均匀，得到混合前驱体的粉体，该混合前驱 体的化学通式为
Figure PCTCN2021135237-appb-000001
其中0≤n≤1,且
Figure PCTCN2021135237-appb-000002
2≤x≤100，x为整数；
将所得的混合前驱体的粉体与锂源按一定比例混合均匀，在氧气或空气气氛中高温煅烧，经过冷却、研磨、过筛得到复合正极材料
Figure PCTCN2021135237-appb-000003
其中0≤n≤1,且
Figure PCTCN2021135237-appb-000004
2≤x≤100，x为整数，0.9≤a≤1.8；
将复合正极材料
Figure PCTCN2021135237-appb-000005
进行改性处理。
进一步地，两种或多种所述前驱体的含量比为任意比。
进一步地，所述锂源为碳酸锂、氢氧化锂、醋酸锂、氯化锂和硫酸锂中的一种或几种，所述锂源以锂元素计的总和与混合前驱体以其含有的金属计的总和的摩尔比为0.9～1.80:1。
与现有技术相比，本发明的最大优点和有益效果如下：
(1)将两种或多种前驱体按照一定比例混合均匀后进行烧结的制备方式，制备工艺较为简单易操作，与常用的正极材料改性处理相比，成本较低，有利于规模化生产。
(2)将两种或多种前驱体按照一定比例混合均匀后进行烧结的制备方式，形成的复合正极材料
Figure PCTCN2021135237-appb-000006
具有协同效应，即该复合正极材料包含的各种正极组分材料调配在一起形成的复合正极材料所表现出来的性能优于各种正极组分材料其单独存在时的性能。同时还改善了某种或几种正极材料的性能，因为通过将两种或多种前驱体混合后高温烧结，使复合正极材料中的各种组分材料晶粒产生融合，从而使得组份材料中具有良好层状结构的晶体，且该具有良好层状结构的晶体与其他团聚晶体融合即可改善复合正极材料的结构稳定性和导电性，从而提高电池的电化学性能。
附图说明
图1为本发明提供的锂离子复合正极材料的前驱体的制备方法的流程图。
图2为本发明提供的复合正极材料的制备方法的流程图。
图3为本发明提供的实施例一的复合正极材料的充放电时的比容量-电压图。
图4为本发明提供的实施例一的复合正极材料的循环性能图。
具体实施方式
以下对本发明的具体实施例进行进一步详细说明。应当理解的是，此处对本发明实施例的说明并不用于限定本发明的保护范围。
如图1所示，其为本发明提供的锂离子复合正极材料的前驱体的制备方法的流程图。所述锂离子复合正极材料的前驱体的制备方法包括如下步骤：
STEP101：提供含有金属或非金属元素M的可溶性盐与去离子水，并将所述含有金属或非金属元素M的可溶性盐按照预定的摩尔比溶于一定量的所述去离子水中，配置得到混合盐溶液；
STEP102：提供NaOH、氨水、以及去离子水，并将该NaOH和氨水溶解在所述去离子水中配置成混合碱溶液；
STEP103：提供去离子水，将所述混合盐溶液与混合碱溶液以一定速度加入该去离子水中，并调节pH值于9～12，反应一段时间后，经过过滤、洗涤和干燥得到前驱体M(OH) 2，M为金属元素、稀土元素、以及非金属元素中的五种及以下的任意组合。
在步骤STEP101中，所述金属元素M可以为镍、钴、铝、锰、钠、锂、钾、钡、铁、钙、铜、锌、钛、镁、锆、锶、铬、锡、锑、钨、铌、钼、钒、钯、铋、铯、铪、钽、钋、镓、铟、铊中的一种。所述金属元素M也可以为稀土元素，该稀土元素为镧系元素以及、钇、钪中的一种。所述非金属元素M可以为硫、硼、硅、砷、磷、硒、碲、氟、碘、砹中的一种。但是需要注意的是，在所述含有金属或非金属元素M的可溶性盐，M的元素组成可以小于或等于5种。当然可以想到的是，所述M的元素组成可以为6种、7种、或更多。本申请中M的元素限定了五种及以下，是由于五种及以下的组合范围已经比较广。含有金属或非金属元素M的可溶性盐可以为硝酸盐、甲酸盐、乙酸盐、硫酸盐、磷酸盐和氯化盐中的一种或几种。这些可溶性盐的性质、制备方法应当为现有技术，在此不再赘述。在添加所述含有金属或非金属元素M的可溶性盐时，所述含有金属或非金属元素M的可溶性盐以其含有的金属或非金属元素计的总和的摩尔比为任意比。
在步骤STEP102中，所述混合碱溶液中NaOH与氨水的摩尔比为1:1～5， 优选的是，所述混合碱溶液中NaOH与氨水的摩尔比为1:1。对于NaOH与氨水本身，其应当为现有技术，在此不再详细说明。
在步骤STEP103中，所述混合盐溶液与混合碱溶液的混合溶液的pH值优选的是11。对于过滤、洗涤和干燥的方法及设备应当本领域技术人员所习知的技术，在此不再赘述。在干燥后，即可以制得锂电池复合正极材料的前驱体M(OH) 2。M的成份由步骤STEP101所加入的可溶性盐来决定。
如图2所示，为本发明提供的复合正极材料的制备方法的流程图。所述复合正极材料的制备方法，其包括如下步骤：
步骤STEP201：提供两种或多种如上所述的锂电池复合正极材料的前驱体M(OH) 2，每一种前驱体与其他前驱体相比至少有一个元素的成分不同或者至少有一个元素成分的摩尔比例不同；
步骤STEP202：将所有的前驱体按一定比例混合均匀，得到混合前驱体的粉体，该混合前驱体的化学通式为
Figure PCTCN2021135237-appb-000007
其中0≤n≤1,且
Figure PCTCN2021135237-appb-000008
2≤x≤100，x为整数；
步骤STEP203：将所得的混合前驱体的粉体与锂源按一定比例混合均匀，在氧气或空气气氛中高温煅烧，经过冷却、研磨、过筛得到复合正极材料
Figure PCTCN2021135237-appb-000009
其中0≤n≤1,且
Figure PCTCN2021135237-appb-000010
2≤x≤100，x为整数，0.9≤a≤1.8；
步骤STEP204：将复合正极材料
Figure PCTCN2021135237-appb-000011
进行改性处理。
在步骤STEP201中，两种或多种所述前驱体的含量比为任意比，但是每一种前驱体中的M元素与其他前驱体中的中M元素的摩尔比不同。同时，两种或多种所述前驱体的含量比相同时，则前驱体中的M元素的摩尔比需不同。
在步骤STEP203中，所述锂源为碳酸锂、氢氧化锂、醋酸锂、氯化锂和硫酸锂中的一种或几种，所述锂源以锂元素计的总和与混合前驱体以其含有的金属计的总和的摩尔比为0.9～1.80:1。优选的是，所述锂源以锂元素计的总和与混合前驱体以其含有的金属计的总和的摩尔比为1.2:1。
在步骤STEP204中，所述改性处理可以为包覆改性或结构掺杂改性，但所述包覆改性或结构掺杂改性本身为现有技术，在此不再赘述。
实施例一
将硫酸镍、硫酸锰和硫酸镁按照金属离子摩尔比Ni:Mn:Mg＝0.85:0.10:0.05加入去离子水中得到混合盐溶液，其中金属离子总浓度为1mol/L，配置总浓度为10mol/L的NaOH和氨水的混合溶液，其中NaOH和氨水的摩尔比为1:1。将上述两种混合溶液以一定速度同时加入到反应器，控制反应的pH值为12，反应温度为60℃，反应6h后陈化8h，经过过滤、洗涤、烘干后得到前驱体Ni 0.85Mn 0.10Mg 0.05(OH) 2。
将硫酸镍、硫酸亚铁和十六水硫酸铝按照金属离子摩尔比Ni:Fe:Al＝0.85:0.10:0.05加入去离子水中得到混合盐溶液，其中金属离子总浓度为1mol/L，配置总浓度为10mol/L的NaOH和氨水的混合溶液，其中NaOH和氨水的摩尔比为1:1。将上述两种混合溶液以一定速度同时加入到反应器，控制反应的pH值为12，反应温度为60℃，反应6h后陈化8h，经过过滤、洗涤、烘干后得到前驱体Ni 0.85Fe 0.10Al 0.05(OH) 2。
将上述两种前驱体按照质量百分比Ni 0.85Mn 0.10Mg 0.05(OH) 2:Ni 0.85Fe 0.10Al 0.05(OH) 2为6:4的比例混合均匀得到混合前驱体粉体。
将上述混合前驱体粉体与氢氧化锂按照Li：(Ni+Mn+Mg+Fe+Al)为1.05:1的比例混合均匀后，在氧气气氛下800℃高温煅烧8h,冷却、粉碎、过筛得到60％LiNi 0.85Mn 0.10Mg 0.05O 2-40％LiNi 0.85Fe 0.10Al 0.05O 2复合正极材料。
所述复合正极材料的电化学性能测试采用蓝电电池测试系统在25℃下进行测试，测试电压范围为,2.8V～4.3V；倍率性能测试条件：0.1C(C用来表示电池充放电时电流大小的比率,即倍率。如1200mAh的电池,0.2C表示240mA(1200mAh的0.2倍率),1C表示1200mA(1200mAh的1倍率))充放电一次，0.2C充放电一次，0.2C充电1C放电一次；循环性能测试条件：以1C倍率进行充放电，循环100周，考察容量保持率。经检测，所述复合正极材料在0.1C倍率下放电比容量为209.1mAh/g，0.2C倍率下放电比容量为203.2mAh/g，1C倍率下的放电比容量为192.7mAh/g，1C/0.1C放电比率为92.1％，从图3可以看出，该复合正极材料的倍率性能较好。同时，1C充放电循环100周容量保持率大于98.2％，其循环性能较好，如图4所示。
实施例二
将硫酸镍、硫酸锰和十六水硫酸铝按照金属离子摩尔比Ni:Mn:Al＝0.85:0.10:0.05加入去离子水中得到混合盐溶液，其中金属离子总浓度为1mol/L，配置总浓度为10mol/L的NaOH和氨水的混合溶液，其中NaOH和氨水的摩尔比为1:1。将上述两种混合溶液以一定速度同时加入到反应器，控制反应的pH值为12，反应温度为60℃，反应6h后陈化8h，经过过滤、洗涤、烘干后得到前驱体Ni 0.85Mn 0.10Al 0.05(OH) 2。
将硫酸镍、硫酸锰和硫酸钴按照金属离子摩尔比Ni:Mn:Co＝0.60:0.2:0.2加入去离子水中得到混合盐溶液，其中金属离子总浓度为1mol/L，配置总浓度为10mol/L的NaOH和氨水的混合溶液，其中NaOH和氨水的摩尔比为1:1。将上述两种混合溶液以一定速度同时加入到反应器，控制反应的pH值为11，反应温度为60℃，反应6h后陈化8h，经过过滤、洗涤、烘干后得到前驱体Ni 0.60Co 0.20Mn 0.20(OH) 2。
将硫酸镍、硫酸亚铁和十六水硫酸铝按照金属离子摩尔比Ni:Fe:Al＝0.80:0.15:0.05加入去离子水中得到混合盐溶液，其中金属离子总浓度为1mol/L，配置总浓度为10mol/L的NaOH和氨水的混合溶液，其中NaOH和氨水的摩尔比为1:1。将上述两种混合溶液以一定速度同时加入到反应器，控制反应的pH值为12，反应温度为60℃，反应6h后陈化8h，经过过滤、洗涤、烘干后得到前驱体Ni 0.80Fe 0.15Al 0.05(OH) 2。
将上述三种前驱体按照质量百分比Ni 0.85Mn 0.10Al 0.05(OH) 2:Ni 0.60Co 0.20Mn 0.20(OH) 2:Ni 0.80Fe 0.15Al 0.05(OH) 2为5:2:3的比例混合均匀得到混合前驱体粉体。
将上述混合前驱体粉体与氢氧化锂按照Li：(Ni+Mn+Fe+Al+Co)为1.05:1的比例混合均匀后，在氧气气氛下800℃高温煅烧16h,冷却、粉碎、过筛得到50％LiNi 0.85Mn 0.10Al 0.05O 2-20％Ni 0.60Co 0.20Mn 0.20(OH) 2-30％LiNi 0.80Fe 0.15Al 0.05O 2复合正极材料。
按照与实施例一相同的检测方法进行测试。
实施例三
将硫酸镍、硫酸锰、十六水硫酸铝和硫酸铬按照金属离子摩尔比 Ni:Mn:Al:Cr＝0.90:0.05:0.03:0.02加入去离子水中得到混合盐溶液，其中金属离子总浓度为1mol/L，配置总浓度为10mol/L的NaOH和氨水的混合溶液，其中NaOH和氨水的摩尔比为1:1。将上述两种混合溶液以一定速度同时加入到反应器，控制反应的pH值为12，反应温度为60℃，反应6h后陈化8h，经过过滤、洗涤、烘干后得到前驱体Ni 0.90Mn 0.05Al 0.03Cr 0.02(OH) 2。
将硫酸镍、硫酸锰、十六水硫酸铝和硫酸铬按照金属离子摩尔比Ni:Mn:Al:Cr＝0.80:0.10:0.07:0.03加入去离子水中得到混合盐溶液，其中金属离子总浓度为1mol/L，配置总浓度为10mol/L的NaOH和氨水的混合溶液，其中NaOH和氨水的摩尔比为1:1。将上述两种混合溶液以一定速度同时加入到反应器，控制反应的pH值为12，反应温度为60℃，反应6h后陈化8h，经过过滤、洗涤、烘干后得到前驱体Ni 0.80Mn 0.10Al 0.07Cr 0.03(OH) 2。
将上述两种前驱体按照质量百分比Ni 0.90Mn 0.05Al 0.03Cr 0.02(OH) 2:Ni 0.80Mn 0.10Al 0.07Cr 0.03(OH) 2为5:5的比例混合均匀得到混合前驱体粉体。
将上述混合前驱体粉体与氢氧化锂按照Li：(Ni+Mn+Al+Cr)为1.05:1的比例混合均匀后，在氧气气氛下700℃高温煅烧20h,冷却、粉碎、过筛得到50％LiNi 0.90Mn 0.05Al 0.03Cr 0.02O 2-50％Li Ni 0.80Mn 0.10Al 0.07Cr 0.03O 2复合正极材料。
按照与实施例一相同的检测方法进行测试。
与现有技术相比，本发明的最大优点和有益效果如下：
(1)将两种或多种前驱体按照一定比例混合均匀后进行烧结的制备方式，制备工艺较为简单易操作，与常用的正极材料改性处理相比，成本较低，有利于规模化生产。
(2)将两种或多种前驱体按照一定比例混合均匀后进行烧结的制备方式，形成的复合正极材料
Figure PCTCN2021135237-appb-000012
具有协同效应，即该复合正极材料包含的各种正极组分材料调配在一起形成的复合正极材料所表现出来的性能优于各种正极组分材料其单独存在时的性能。同时还改善了某种或几种正极材料的性能，因为通过将两种或多种前驱体混合后高温烧结，使复合正极材料中的各种组分材料晶粒产生融合，从而使得组份材料中具有良好层状结构的晶体，且该具有良好层状结构的晶体与其他团聚晶体融合即可改善复合正极材料的结构稳定性 和导电性，从而提高电池的电化学性能。。
以上仅为本发明的较佳实施例，并不用于局限本发明的保护范围，任何在本发明精神内的修改、等同替换或改进等，都涵盖在本发明的权利要求范围内。

Claims (10)

  1. 锂电池复合正极材料的前驱体的制备方法，其包括如下步骤：
    提供含有金属或非金属元素M的可溶性盐与去离子水，并将所述含有金属或非金属元素M的可溶性盐按照预定的摩尔比溶于一定量的所述去离子水中，配置得到混合盐溶液；
    提供NaOH、氨水、以及去离子水，并将该NaOH和氨水溶解在所述去离子水中配置成混合碱溶液；
    提供去离子水，将所述混合盐溶液与混合碱溶液以一定速度加入该去离子水中，并调节pH值于9～12，反应一段时间后，经过过滤、洗涤和干燥得到前驱体M(OH) 2，M为金属元素、稀土元素、以及非金属元素中的五种及以下的任意组合。
  2. 如权利要求1所述的锂电池复合正极材料的前驱体的制备方法，其特征在于：所述金属元素为镍、钴、铝、锰、钠、锂、钾、钡、铁、钙、铜、锌、钛、镁、锆、锶、铬、锡、锑、钨、铌、钼、钒、钯、铋、铯、铪、钽、钋、镓、铟、铊中的一种。
  3. 如权利要求1所述的锂电池复合正极材料的前驱体的制备方法，其特征在于：所述稀土元素为镧系元素以及、钇、钪中的一种。
  4. 如权利要求1所述的锂电池复合正极材料的前驱体的制备方法，其特征在于：所述非金属元素为硫、硼、硅、砷、磷、硒、碲、氟、碘、砹中的一种。
  5. 如权利要求1所述的锂电池复合正极材料的前驱体的制备方法，其特征在于：含有金属或非金属元素M的可溶性盐为硝酸盐、甲酸盐、乙酸盐、硫酸盐、磷酸盐和氯化盐中的一种或几种。
  6. 如权利要求1所述的锂电池复合正极材料的前驱体的制备方法，其特征在于：所述含有金属或非金属元素M的可溶性盐以其含有的金属或非金属元素计的总和的摩尔比为任意比。
  7. 如权利要求1所述的锂电池复合正极材料的前驱体的制备方法，其特征在于：所述的混合碱溶液中NaOH与氨水的摩尔比为1:1。
  8. 复合正极材料的制备方法，其包括如下步骤：
    提供两种或多种如权利要求1至7任一项所述的锂电池复合正极材料的前驱 体的制备方法所制备的前驱体M(OH) 2，每一种前驱体与其他前驱体相比至少有一个元素的成分不同或者至少有一个元素成分的摩尔比例不同；
    将所有前驱体按一定比例混合均匀，得到混合前驱体的粉体，该混合前驱体的化学通式为
    Figure PCTCN2021135237-appb-100001
    其中0≤n≤1,且
    Figure PCTCN2021135237-appb-100002
    2≤x≤100，x为整数；
    将所得的混合前驱体的粉体与锂源按一定比例混合均匀，在氧气或空气气氛中高温煅烧，经过冷却、研磨、过筛得到复合正极材料
    Figure PCTCN2021135237-appb-100003
    其中0≤n≤1,且
    Figure PCTCN2021135237-appb-100004
    2≤x≤100，x为整数，0.9≤a≤1.8；
    将复合正极材料
    Figure PCTCN2021135237-appb-100005
    进行改性处理。
  9. 如权利要求8所述的复合正极材料的制备方法，其特征在于：两种或多种所述前驱体的含量比为任意比。
  10. 如权利要求8所述的复合正极材料的制备方法，其特征在于：所述锂源为碳酸锂、氢氧化锂、醋酸锂、氯化锂和硫酸锂中的一种或几种，所述锂源以锂元素计的总和与混合前驱体以其含有的金属计的总和的摩尔比为0.9～1.80:1。
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