WO2022237110A1 - 氟掺杂锂正极材料及其制备方法和应用 - Google Patents

氟掺杂锂正极材料及其制备方法和应用 Download PDF

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WO2022237110A1
WO2022237110A1 PCT/CN2021/131509 CN2021131509W WO2022237110A1 WO 2022237110 A1 WO2022237110 A1 WO 2022237110A1 CN 2021131509 W CN2021131509 W CN 2021131509W WO 2022237110 A1 WO2022237110 A1 WO 2022237110A1
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fluorine
preparation
lithium
positive electrode
electrode material
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French (fr)
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王鹏飞
杨红新
李子郯
乔齐齐
施泽涛
郭丰
许鑫培
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蜂巢能源科技有限公司
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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
    • C01G53/40—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
    • 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
    • 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
    • H01M4/50—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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 the technical field of lithium ion batteries, in particular to a fluorine-doped lithium positive electrode material and a preparation method and application thereof.
  • Lithium-rich manganese-based layered oxides are attracting more and more attention from researchers because of their high specific capacity over 250mAhg -1 , high operating cost at 4.8V, and high safety.
  • LMROs lithium-rich manganese-based layered oxides
  • lithium-rich materials generally have three major problems: 1. The initial coulombic efficiency is low due to the precipitation of lattice oxygen during charge and discharge; 2. The voltage decay is serious; 3. The rate performance is poor.
  • the main purpose of the present invention is to provide a fluorine-doped lithium positive electrode material and its preparation method and application, so as to solve the problems of low first efficiency, poor cycle performance and rate performance of lithium-rich materials in the prior art.
  • step S1 includes: step S1, under the first stirring, mix and react the aqueous solution of NH 4 F and Li x Ni y Mnz O 2 to obtain an intermediate product system.
  • the mass ratio of NH 4 F to Li x Ni y Mnz O 2 in the aqueous solution of NH 4 F is 0.01 ⁇ 0.1:1, preferably 0.05 ⁇ 0.07:1.
  • the speed of the above-mentioned first stirring is 300-2000 rpm, and the time is 1-10 min.
  • the preparation method further includes: filtering the intermediate product system to obtain fluorine-modified Li x Ni y Mnz O 2 .
  • the temperature of the above-mentioned first calcination is 400-800° C., and the time is 4-8 hours.
  • volume content of oxygen in the first oxygen-containing gas is 10-100%.
  • the above-mentioned first oxygen-containing gas is air.
  • the flow rate of the first oxygen-containing gas is 5-10 L/min.
  • the ratio of the molar weight of lithium in the lithiated compound to the sum of the molar weights of nickel and manganese in the Ni a Mn b CO 3 precursor is 1.4-1.6.
  • the lithium compound is selected from one or more of lithium hydroxide, lithium carbonate, lithium chloride, and lithium acetate.
  • Ni a Mn b CO 3 precursor has a particle size of 5-10 ⁇ m, and preferably the specific surface area of the Ni a Mn b CO 3 precursor is 20-120 m 2 /g.
  • the bulk density of the above-mentioned Ni a Mn b CO 3 precursor is 1.4 ⁇ 2.5 g/cm 3 .
  • the temperature of the above-mentioned second calcination is 750-850° C., and the time is 8-12 hours.
  • volume content of oxygen in the second oxygen-containing gas is 10-100%.
  • the flow rate of the second oxygen-containing gas is 5-10 L/min.
  • the above-mentioned second oxygen-containing gas is air.
  • a fluorine-doped lithium positive electrode material is provided, and the fluorine-doped lithium positive electrode material is prepared by any one of the above preparation methods.
  • a lithium ion battery comprising an electrolyte, a positive electrode material and a negative electrode material, the positive electrode material includes a lithium positive electrode material, and the lithium positive electrode material is any one of the above-mentioned fluorine-doped lithium positive electrode materials.
  • the above fluorine-modified Li x Ni y Mnz O 2 is first calcined to further infiltrate fluorine into the material to obtain a fluorine-doped lithium positive electrode material doped with fluorine. Due to the protection of fluorine, the material reduces the amount of free oxygen that enters the electrolyte during the first charging and discharging process when it is used as the positive electrode of lithium-ion batteries, and reduces the amount of lithium ions that are solidified into Li 2 O by free oxygen, thereby effectively improving the lithium ion battery. The first effect of ion batteries. At the same time, the cycle performance and rate performance of the battery are also improved compared with the lithium cathode material without F doping.
  • Fig. 1 shows the SEM image of the fluorine-doped lithium cathode material prepared in Example 2.
  • FIG. 2 shows the SEM image of the fluorine-doped lithium cathode material prepared in Comparative Example 1.
  • the lithium-rich materials in the prior art have low first efficiency, poor cycle performance and rate performance.
  • the present application provides a fluorine-doped lithium positive electrode material and its preparation method and application.
  • the material Due to the protection of fluorine, the material reduces the amount of free oxygen that enters the electrolyte during the first charging and discharging process when it is used as the positive electrode of lithium-ion batteries, and reduces the amount of lithium ions that are solidified into Li 2 O by free oxygen, thereby effectively improving the lithium ion battery.
  • the first effect of ion batteries At the same time, the cycle performance and rate performance of the battery are also improved compared with the lithium cathode material without F doping.
  • the hydrolysis of NH 4 F will produce hydrofluoric acid.
  • the mass ratio of NH 4 F to Li x Ni y Mnz O 2 in the NH 4 F aqueous solution is preferably 0.01 ⁇ 0.1:1. Within the above raw material ratio range, it can further ensure that Li x Ni y Mnz O 2 is doped with more fluorine, and avoid the internal structure of the material from being corroded by HF acid, which will lead to performance degradation, especially when the ratio is 0.05-0.07:1 , the effect is particularly prominent.
  • the above step S1 includes: step S1, under the first stirring, mixing and reacting an aqueous solution of NH 4 F and Li x Ni y Mnz O 2 to obtain an intermediate product system.
  • step S1 under the first stirring, mixing and reacting an aqueous solution of NH 4 F and Li x Ni y Mnz O 2 to obtain an intermediate product system.
  • the speed of the above-mentioned first stirring can be selected by those skilled in the art according to the needs in actual operation.
  • the speed of the first stirring is preferably 300-2000 rpm and the time is 1-10 min.
  • the preparation method further includes: filtering the intermediate product system , to obtain fluorine-modified Li x Ni y Mnz O 2 .
  • the above-mentioned filtration methods can be selected from common filtration methods in the field, such as pressure filtration, suction filtration, centrifugal separation, etc., which will not be repeated here.
  • the purpose of the first calcination is to allow fluorine to further penetrate into Li x Ni y Mnz O 2 to achieve a better doping effect.
  • the temperature of the first calcination is 400-800°C, and the time is 4 ⁇ 8h.
  • the infiltration of fluorine can be achieved relatively quickly and at the same time, it is ensured that the structural stability of the material will not be reduced due to the high sintering temperature.
  • the volume content of oxygen in the first oxygen-containing gas is 10-100%, and preferably the first oxygen-containing gas is air.
  • the flow rate of the first oxygen-containing gas is 5-10 L/min.
  • the Li x Ni y MnzO used in the present application can be existing materials in the prior art or prepare the material by methods known in the prior art.
  • the above-mentioned preparation method also includes Li x Ni y
  • the content of nickel and manganese can be flexibly adjusted through the above preparation process.
  • the ratio of the molar weight of lithium in the lithiated compound to the sum of the molar weights of nickel and manganese in the Ni a Mn b CO 3 precursor is 1.4 to 1.6, thereby further ensuring that the Li content in Li x Ni y Mnz O 2 is optimal within range.
  • the lithium compound is selected from one or more of lithium hydroxide, lithium carbonate, lithium chloride, and lithium acetate.
  • the particle size of the Ni a Mn b CO 3 precursor is 5-10 ⁇ m
  • the specific surface area (BET) of the Ni a Mn b CO 3 precursor is preferably 20-120 m 2 /g
  • the Ni a Mn b CO 3 precursor is preferably Bulk density (TD) is 1.4 ⁇ 2.5g/cm 3 .
  • the Ni a Mn b CO 3 precursor within the above parameter range can prepare fluorine-doped lithium cathode materials with particle size and specific surface area that are easier to homogeneously coat.
  • the temperature of the second calcination is preferably 750-850° C., and the time is 8-12 hours.
  • the volume content of oxygen in the second oxygen-containing gas is preferably 10-100%, and the second oxygen-containing gas is preferably air.
  • the flow rate of the second oxygen-containing gas is 5-10 L/min, so as to further improve the production rate and effect of Li x Ni y Mnz O 2 .
  • a fluorine-doped lithium positive electrode material is provided, and the fluorine-doped lithium positive electrode material is prepared by any one of the above-mentioned preparation methods.
  • the fluorine-doped lithium positive electrode material of the present application is doped with fluorine, and the stability of the bond formed by fluorine and metal is higher than that of oxygen and metal. Therefore, by doping fluorine, the oxygen in the material can be made
  • the protection of fluorine reduces the free oxygen that leaves the material and enters the electrolyte during the charge and discharge process, especially reduces the amount of free oxygen that enters the electrolyte after the first charge and discharge. Less free oxygen will reduce the amount of lithium ions that are solidified by free oxygen and exist in the form of Li 2 O and cannot continue to participate in the electrochemical reaction, which will greatly increase the number of free lithium ions in the electrolyte, thereby effectively improving the performance of lithium-ion batteries. the first effect.
  • the fluorine-doped lithium cathode material of the present application also improves the cycle performance and rate performance of the battery compared with the non-F-doped lithium cathode material.
  • the fluorine content in the fluorine-doped lithium cathode material within the above range can better ensure the structural integrity of the material, thereby ensuring its advantages of high first efficiency, good cycle performance and rate performance.
  • a lithium-ion battery including an electrolyte, a positive electrode material, and a negative electrode material
  • the positive electrode material includes a lithium positive electrode material
  • the lithium positive electrode material is any one of the above-mentioned fluorine-doped lithium positive electrodes
  • the material or the fluorine-doped lithium positive electrode material prepared by any one of the above preparation methods.
  • the material of this application reduces the amount of free oxygen that enters the electrolyte during the first charging and discharging process when it is used as the positive electrode of lithium-ion batteries, so that the amount of lithium ions that are solidified into Li 2 O by free oxygen decreases, thereby effectively improving the battery life.
  • the first effect of lithium-ion batteries At the same time, the cycle performance and rate performance of the battery are also improved compared with the lithium cathode material without F doping.
  • Example 1 The difference from Example 1 is that the calcination temperature in step 4) is 400°C.
  • Example 1 The difference from Example 1 is that the calcination temperature in step 4) is 800°C.
  • Example 1 The difference from Example 1 is that the calcination temperature in step 4) is 300°C.
  • Example 1 The difference from Example 1 is that the calcination temperature in step 4) is 900°C.
  • Example 1 The difference from Example 1 is that the calcination time in step 4) is 4h.
  • Example 1 The difference from Example 1 is that the calcination time in step 4) is 8h.
  • Example 1 The difference from Example 1 is that the calcination time in step 4) is 3h.
  • Example 1 The difference from Example 1 is that the calcination time in step 4) is 9h.
  • Example 1 The difference from Example 1 is that the air flow rate in step 4) is 5 L/min.
  • Example 1 The difference from Example 1 is that the air flow rate in step 4) is 10 L/min.
  • the prepared pole piece is assembled with CR2032 shell, the voltage window is 2-4.8V negative electrode material lithium metal, the electrolyte is conventional lithium-rich electrolyte: 1mol/L LiPF6, EC (ethylene carbonate): DEC (diethyl carbonate) volume ratio is 3:7.
  • Table 1 shows the 0.1C discharge capacity, 1C discharge capacity, first effect and 50-week capacity retention rate of the above-mentioned examples and comparative examples.
  • the SEM characterization of the fluorine-doped lithium cathode material prepared in Example 2 is shown in FIG. 1
  • the SEM characterization of the non-fluorine-doped lithium cathode material prepared in Comparative Example 1 is shown in FIG. 2 . It can be seen that the structure and surface physical properties of the lithium cathode material do not change significantly before and after fluorine doping, indicating that the method of the present application will not adversely affect the structure of the lithium cathode material.
  • the material Due to the protection of fluorine, the material reduces the amount of free oxygen that enters the electrolyte during the first charging and discharging process when it is used as the positive electrode of lithium-ion batteries, and reduces the amount of lithium ions that are solidified into Li 2 O by free oxygen, thereby effectively improving the lithium ion battery.
  • the first effect of ion batteries At the same time, the cycle performance and rate performance of the battery are also improved compared with the lithium cathode material without F doping.

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Abstract

本发明提供了一种氟掺杂锂正极材料及其制备方法和应用。该制备方法包括：步骤S1，将NH 4F、Li xNi yMn zO 2和水混合反应，得到中间产物体系，中间产物体系包括氟改性的Li xNi yMn zO 2；步骤S2，在第一含氧气体中，对氟改性的Li xNi yMn zO 2进行第一煅烧，得到氟掺杂锂正极材料，其中x＝1～1.3，y＝0.1～0.9，z＝0.1～0.9，x:(y+z)＝1.4～1.6。在正极材料中掺杂氟，使材料内部的氧得到氟的保护有效提升了锂离子电池的首效。同时，此外，氟掺杂锂正极材料中的氟含量在上述范围内可以更好地保证材料的结构完整性，进而保证其首效高、循环性能和倍率性能良好的优势。

Description

氟掺杂锂正极材料及其制备方法和应用 技术领域
本发明涉及锂离子电池技术领域，具体而言，涉及一种氟掺杂锂正极材料及其制备方法和应用。
背景技术
在当前节能减排和环境保护的背景下，发展高能量密度和高功率密度化学电源体系的任务迫在眉睫。富锂锰基层状氧化物(LMROs)因有超过250mAhg -1的高比容量、4.8V的高工作低成本以及高安全性等特点，正越来越受到研究者的广泛关注。但是富锂材料普遍存三大问题：1、由于充放电过程中晶格氧的析出导致其首次库伦效率低；2、电压衰减严重；3、倍率性能差。
发明内容
本发明的主要目的在于提供一种氟掺杂锂正极材料及其制备方法和应用，以解决现有技术中富锂材料首效低、循环性能和倍率性能差的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种氟掺杂锂正极材料的制备方法，该制备方法包括：步骤S1，将NH 4F、Li xNi yMn zO 2和水混合反应，得到中间产物体系，中间产物体系包括氟改性的Li xNi yMn zO 2；步骤S2，在第一含氧气体中，对氟改性的Li xNi yMn zO 2进行第一煅烧，得到氟掺杂锂正极材料，其中x＝1～1.3，y＝0.1～0.9，z＝0.1～0.9，x:(y+z)＝1.4～1.6。
进一步地，上述步骤S1包括：步骤S1，在第一搅拌下，将NH 4F的水溶液和Li xNi yMn zO 2混合并发生反应，得到中间产物体系。
进一步地，上述NH 4F的水溶液中NH 4F与Li xNi yMn zO 2质量比为0.01～0.1:1，优选为0.05～0.07:1。
进一步地，上述第一搅拌的速度为300～2000rpm，时间为1～10min。
进一步地，在上述步骤S2之前，制备方法还包括：对中间产物体系进行过滤，得到氟改性的Li xNi yMn zO 2。
进一步地，上述第一煅烧的温度为400～800℃，时间为4～8h。
进一步地，上述第一含氧气体中氧气的体积含量为10～100％。
进一步地，上述第一含氧气体为空气。
进一步地，上述第一含氧气体的流量为5～10L/min。
进一步地，上述制备方法还包括Li xNi yMn zO 2的制备过程，制备过程包括：在第二含氧气体中，对包含Ni aMn bCO 3前驱体和锂化物的原料体系进行第二煅烧，得到Li xNi yMn zO 2，其中a＝0.1～0.9，b＝0.1～0.9，a+b＝1。
进一步地，上述锂化物中的锂的摩尔量和Ni aMn bCO 3前驱体中的镍和锰摩尔量总和的比值为1.4～1.6。
进一步地，上述锂化物选自氢氧化锂、碳酸锂和氯化锂、醋酸锂中的一种或多种。
进一步地，上述Ni aMn bCO 3前驱体粒径为5～10μm，优选Ni aMn bCO 3前驱体的比表面积为20～120m 2/g。
进一步地，上述Ni aMn bCO 3前驱体的堆密度为1.4～2.5g/cm 3。
进一步地，上述第二煅烧的温度为750～850℃，时间为8～12h。
进一步地，上述第二含氧气体中氧气的体积含量为10～100％。
进一步地，上述第二含氧气体的流量为5～10L/min。
进一步地，上述第二含氧气体为空气。
根据本发明的另一方面，提供了一种氟掺杂锂正极材料，该氟掺杂锂正极材料由上述任一种制备方法制备得到。
根据本发明的又一方面，提供了一种锂离子电池，包含电解液、正极材料和负极材料，正极材料包含锂正极材料，该锂正极材料为上述任一种氟掺杂锂正极材料。
应用本发明的技术方案，首先将NH 4F、Li xNi yMn zO 2和水混合，NH 4F会在水中双水解，使溶液呈弱酸性，并且水解得到的HF酸会吸附到Li xNi yMn zO 2表面并与Li xNi yMn zO 2发生反应，使氟掺杂于Li xNi yMn zO 2中，得到氟改性的Li xNi yMn zO 2。之后，对上述氟改性的Li xNi yMn zO 2进行第一煅烧，使氟进一步向材料内部渗入，得到掺杂有氟的氟掺杂锂正极材料。该材料由于氟的保护，使得作为锂离子电池正极时首次充放电过程中进入到电解液中的游离氧数量下降，使被游离氧固化为Li 2O的锂离子量下降，进而有效提升了锂离子电池的首效。与此同时，电池的循环性能和倍率性能也较无F掺杂的锂正极材料得到了提升。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1示出了实施例2制备得到的氟掺杂锂正极材料的SEM图；以及
图2示出了对比例1制备得到的氟掺杂锂正极材料的SEM图。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
如本申请背景技术中所描述的，现有技术中的富锂材料首效低、循环性能和倍率性能差。为了解决上述问题，本申请提供了一种氟掺杂锂正极材料及其制备方法和应用。
根据本申请一种典型的实施方式，提供了一种氟掺杂锂正极材料的制备方法，该制备方法包括：步骤S1，将NH 4F、Li xNi yMn zO 2和水混合反应，得到中间产物体系，中间产物体系包括氟改性的Li xNi yMn zO 2，NH 4F与Li xNi yMn zO 2质量比为0.05～0.07:1；步骤S2，在第一含氧气体中，对氟改性的Li xNi yMn zO 2进行第一煅烧，得到氟掺杂锂正极材料，第一含氧气体中氧气的体积含量为10～100％，其中x＝1～1.3，y＝0.1～0.9，z＝0.1～0.9，x:(y+z)＝1.4～1.6。
本申请首先将NH 4F、Li xNi yMn zO 2和水混合，NH 4F会在水中双水解，使溶液呈弱酸性，并且水解得到的HF酸会吸附到Li xNi yMn zO 2表面并与Li xNi yMn zO 2发生反应，使氟掺杂于Li xNi yMn zO 2中，得到氟改性的Li xNi yMn zO 2。之后，对上述氟改性的Li xNi yMn zO 2进行第一煅烧，使氟进一步向材料内部渗入，得到掺杂有氟的氟掺杂锂正极材料。该材料由于氟的保护，使得作为锂离子电池正极时首次充放电过程中进入到电解液中的游离氧数量下降，使被游离氧固化为Li 2O的锂离子量下降，进而有效提升了锂离子电池的首效。与此同时，电池的循环性能和倍率性能也较无F掺杂的锂正极材料得到了提升。
如前所述，NH 4F水解会产生氢氟酸，为了使溶液的酸性更适于进行反应，优选NH 4F的水溶液中NH 4F与Li xNi yMn zO 2质量比为0.01～0.1:1。在上述原料配比范围内，可以进一步保证Li xNi yMn zO 2掺杂更多的氟，并且避免材料内部结构不被HF酸腐蚀导致性能有所降低，尤其在0.05～0.07:1时，效果尤为突出。
在一些实施例中，上述步骤S1包括：步骤S1，在第一搅拌下，将NH 4F的水溶液和Li xNi yMn zO 2混合并发生反应，得到中间产物体系。通过先制备NH 4F的水溶液，再将水溶液与Li xNi yMn zO 2混合并发生反应，不仅使NH 4F可以充分水解，而且使Li xNi yMn zO 2可以更好地分散在NH 4F的水溶液中，使氢氟酸和Li xNi yMn zO 2颗粒可以更快、更均匀地反应。
上述第一搅拌的速度可以由本领域技术人员在实际操作中根据需要进行选择，为了进一步提升反应速率和反应效果，优选第一搅拌的速度为300～2000rpm，时间为1～10min。
为了在进入第一煅烧步骤之前使更多的氟保留在Li xNi yMn zO 2中并且减少杂质对煅烧效果的影响，优选在步骤S2之前，制备方法还包括：对中间产物体系进行过滤，得到氟改性的Li xNi yMn zO 2。上述过滤方法可以选自本领域常用的过滤方法，如压滤、抽滤、离心分离等方式，在此不再一一赘述。
如前所述，第一煅烧的目的是为了使氟可以进一步渗入至Li xNi yMn zO 2中，达到更好的掺杂效果，优选第一煅烧的温度为400～800℃，时间为4～8h。在上述参数范围内，可以较为快速地实现氟的渗入且同时保证了材料不会因为烧结温度过高而使结构稳定性下降。优选第一 含氧气体中氧气的体积含量为10～100％，优选第一含氧气气体为空气。优选第一含氧气体的流量为5～10L/min，通过使用含氧气体进行烧结，避免Ni抢占Li的位置，造成材料稳定性下降。
用于本申请的Li xNi yMn zO 2可以为现有技术中已有材料或者采用现有技术中已知方法制备该材料，在一些实施例中，上述制备方法还包括Li xNi yMn zO 2的制备过程，该制备过程包括：在第二含氧气体中，对包含Ni aMn bCO 3前驱体和锂化物的原料体系进行第二煅烧，得到Li xNi yMn zO 2，其中a＝0.1～0.9，b＝0.1～0.9，a+b＝1。通过上述制备过程可以灵活调整其中的镍锰含量。优选锂化物中的锂的摩尔量和Ni aMn bCO 3前驱体中的镍和锰摩尔量总和的比值为1.4～1.6，进而进一步保证Li xNi yMn zO 2中Li的含量在优选范围内。为了尽量避免向反应体系中引入杂质，优选锂化物选自氢氧化锂、碳酸锂和氯化锂、醋酸锂中的一种或多种。上述锂化物均成碱性，因此，在使用本申请的制备方法时，由于NH 4F水解后呈酸性，因此可以在对Li xNi yMn zO 2进行氟改性的同时，将其未反应的锂化物去除，避免其对后续反应造成影响。
进一步优选Ni aMn bCO 3前驱体粒径为5～10μm，优选Ni aMn bCO 3前驱体的比表面积(BET)为20～120m 2/g，优选Ni aMn bCO 3前驱体的堆密度(TD)为1.4～2.5g/cm 3。在上述参数范围内的Ni aMn bCO 3前驱体可以制备出粒径、比表面积更易于进行匀浆涂布的氟掺杂锂正极材料。优选第二煅烧的温度为750～850℃，时间为8～12h，优选第二含氧气体中氧气的体积含量为10～100％，优选第二含氧气气体为空气。优选第二含氧气体的流量为5～10L/min，以进一步提升Li xNi yMn zO 2的制备速率和效果。
根据本申请另一种典型的实施方式，提供了一种氟掺杂锂正极材料，该氟掺杂锂正极材料由上述任一种制备方法制备得到。
本申请的氟掺杂锂正极材料掺杂有氟，氟和金属形成的键的稳定性要高于氧和金属形成的键的稳定性，因此，通过在掺杂氟，可以使材料内部的氧得到氟的保护，减少了充放电过程中脱离材料进入电解液中的游离氧，尤其减少了首次充放电后进入电解液的游离氧的数量。更少的游离氧会降低被游离氧固化从而以Li 2O形态存在的不能继续参与电化学反应的锂离子的量，使电解液中游离锂离子的数量大幅提升，进而有效提升了锂离子电池的首效。与此同时，本申请的氟掺杂锂正极材料也使得电池的循环性能和倍率性能也较无F掺杂的锂正极材料得到了提升。此外，氟掺杂锂正极材料中的氟含量在上述范围内可以更好地保证材料的结构完整性，进而保证其首效高、循环性能和倍率性能良好的优势。
根据本申请又一种典型的实施方式，提供了一种锂离子电池，包含电解液、正极材料和负极材料，正极材料包含锂正极材料，该锂正极材料为上述任一种氟掺杂锂正极材料或者为上述任一种制备方法制备得到的氟掺杂锂正极材料。
本申请材料由于氟的保护，使得作为锂离子电池正极时首次充放电过程中进入到电解液中的游离氧数量下降，使被游离氧固化为Li 2O的锂离子量下降，进而有效提升了锂离子电池的首效。与此同时，电池的循环性能和倍率性能也较无F掺杂的锂正极材料得到了提升。
下结合实施例和对比例，进一步说明本申请的有益效果。
实施例1
1)以Ni 0.25Mn 0.75CO 3作为前驱体(粒度分布5～10μm，BET＝20m 2/g，TD＝1.6g/cm 3)，称量26.96g LiOH·H 2O与50gNi 0.25Mn 0.75CO 3(按n Li/(n Ni+n Mn)＝1.5)，采用手持式搅拌机以2000rpm的搅拌速度搅拌15min使Ni 0.25Mn 0.75CO 3前驱体和锂盐混合均匀，在800℃条件下煅烧10h，煅烧氛围为空气，气流量为10L/min，得到Li 1.20Ni 0.20Mn 0.60O 2材料。
2)配置浓度为15g/L的NH 4F的水溶液，以NH 4F：Li 1.20Ni 0.20Mn 0.60O 2＝0.03:1的质量比称量500g Li 1.20Ni 0.20Mn 0.60O 2。在第一搅拌条件下(速度为2000rpm，时间为10min)向NH 4F的水溶水中加入Li 1.20Ni 0.20Mn 0.60O 2粉末，得到中间产物体系。
3)对中间产物体系进行抽滤，得到氟改性的Li 1.20Ni 0.20Mn 0.60O 2。
4)在空气中(空气流量6.5L/min)，对氟改性的Li 1.20Ni 0.20Mn 0.60O 2进行煅烧(温度为550℃，时间为6h)，得到氟掺杂锂正极材料。
实施例2
与实施例1的区别在于，以NH 4F：Li 1.20Ni 0.20Mn 0.60O 2＝0.05:1的质量比称量500g Li 1.20Ni 0.20Mn 0.60O 2。配置浓度为25g/L的NH 4F的水溶液。
实施例3
与实施例1的区别在于，以NH 4F：Li 1.20Ni 0.20Mn 0.60O 2＝0.07:1的质量比称量500g Li 1.20Ni 0.20Mn 0.60O 2。配置浓度为35g/L的NH 4F的水溶液。
实施例4
与实施例1的区别在于，以NH 4F：Li 1.20Ni 0.20Mn 0.60O 2＝0.1:1的质量比称量500g Li 1.20Ni 0.20Mn 0.60O 2。配置浓度为50g/L的NH 4F的水溶液。
实施例5
与实施例1的区别在于，以NH 4F：Li 1.20Ni 0.20Mn 0.60O 2＝0.01:1的质量比称量500g Li 1.20Ni 0.20Mn 0.60O 2。配置浓度为5g/L的NH 4F的水溶液。
实施例6
与实施例1的区别在于，以NH 4F：Li 1.20Ni 0.20Mn 0.60O 2＝0.12:1的质量比称量500g Li 1.20Ni 0.20Mn 0.60O 2。配置浓度为60g/L的NH 4F的水溶液。
实施例7
与实施例1的区别在于，步骤4)中煅烧温度为400℃。
实施例8
与实施例1的区别在于，步骤4)中煅烧温度为800℃。
实施例9
与实施例1的区别在于，步骤4)中煅烧温度为300℃。
实施例10
与实施例1的区别在于，步骤4)中煅烧温度为900℃。
实施例11
与实施例1的区别在于，步骤4)中煅烧时间为4h。
实施例12
与实施例1的区别在于，步骤4)中煅烧时间为8h。
实施例13
与实施例1的区别在于，步骤4)中煅烧时间为3h。
实施例14
与实施例1的区别在于，步骤4)中煅烧时间为9h。
实施例15
与实施例1的区别在于，步骤4)中空气流量为5L/min。
实施例16
与实施例1的区别在于，步骤4)中空气流量为10L/min。
实施例17
与实施例1的区别在于，
1)中以Ni 0.25Mn 0.75CO 3作为前驱体(粒度分布5～10μm，BET＝20m 2/g，TD＝1.4g/cm 3)，称量25.16gLiOH·H 2O与50g Ni 0.25Mn 0.75CO 3(按n Li/(n Ni+n Mn)＝1.4)，采用手持式搅拌机以2000rpm的搅拌速度搅拌1min使Ni 0.25Mn 0.75CO 3前驱体和锂盐混合均匀，在750℃条件下煅烧8h，煅烧氛围为氧气，气流量为5L/min，得到Li 1.2Ni 0.2Mn 0.6O 2材料。
实施例18
与实施例1的区别在于，
1)中以Ni 0.75Mn 0.25CO 3作为前驱体(粒度分布5～10μm，BET＝120m 2/g，TD＝2.5g/cm 3)，称量28.76gLiOH·H 2O与50g Ni 0.75Mn 0.25CO 3(按n Li/(n Ni+n Mn)＝1.6)，采用手持式搅拌机以300rpm的搅拌速度搅拌10min使Ni 0.75Mn 0.25CO 3前驱体和锂盐混合均匀，在850℃条件下煅烧12h，煅烧氛围为空气，气流量为10L/min，得到Li 1.28Ni 0.6Mn 0.2O 2材料。
对比例1
以Ni 0.25Mn 0.75CO 3作为前驱体(粒度分布5～10μm，BET＝20m 2/g，TD＝1.6g/cm 3)，称量25.16gLiOH·H 2O与50gNi 0.25Mn 0.75CO 3(按n Li/(n Ni+n Mn)＝1.4)，采用手持式搅拌机以300rpm的搅拌速度搅拌1min使Ni 0.25Mn 0.75CO 3前驱体和锂盐混合均匀，在750℃条件下煅烧8h，煅烧氛围为空气，气流量为5L/min，得到Li 1.20Ni 0.20Mn 0.60O 2材料。
匀浆涂布扣电组装
以氟掺杂锂正极材料：Super p乙炔黑：PVDF胶液＝92：4：4配比，并进行匀浆涂布，其中PVDF胶液固含量为6.05％。对制得的极片采用CR2032壳体进行扣电组装，电压窗口为2～4.8V负极材料金属锂，电解液采用常规富锂电解液：1mol/L的LiPF6，EC(碳酸乙烯酯)：DEC(碳酸二乙酯)体积比为3:7。
扣电性能测试
在室温条件下，将组装好的模拟电池静置12小时，使电解液充分浸润电极材料。然后将其在LAND CT-2001A测试***上进行测试。上述实施例和对比例的0.1C放电容量、1C放电容量、首效和50周容量保持率如表1所示。
SEM表征
对实施例2制备得到的氟掺杂锂正极材料进行SEM表征，见图1，对比例1制备得到的没有氟掺杂的锂正极材料的SEM表征见图2。可以看出，在氟掺杂前后，锂正极材料的结构和表面物理特性没有明显变化，说明本申请的方法不会对锂正极材料的结构产生不利影响。
表1
Figure PCTCN2021131509-appb-000001
Figure PCTCN2021131509-appb-000002
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：
本申请首先将NH 4F、Li xNi yMn zO 2和水混合，NH 4F会在水中双水解，使溶液呈弱酸性，并且水解得到的HF酸会吸附到Li xNi yMn zO 2表面并与Li xNi yMn zO 2发生反应，使氟掺杂于Li xNi yMn zO 2中，得到氟改性的Li xNi yMn zO 2。之后，对上述氟改性的Li xNi yMn zO 2进行第一煅烧，使氟进一步向材料内部渗入，得到掺杂有氟的氟掺杂锂正极材料。该材料由于氟的保护，使得作为锂离子电池正极时首次充放电过程中进入到电解液中的游离氧数量下降，使被游离氧固化为Li 2O的锂离子量下降，进而有效提升了锂离子电池的首效。与此同时，电池的循环性能和倍率性能也较无F掺杂的锂正极材料得到了提升。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (14)

  1. 一种氟掺杂锂正极材料的制备方法，其特征在于，所述制备方法包括：
    步骤S1，将NH 4F、Li xNi yMn zO 2和水混合反应，得到中间产物体系，所述中间产物体系包括氟改性的所述Li xNi yMn zO 2，所述NH 4F与所述Li xNi yMn zO 2质量比为0.05～0.07:1；
    步骤S2，在第一含氧气体中，对所述氟改性的所述Li xNi yMn zO 2进行第一煅烧，得到所述氟掺杂锂正极材料，所述第一含氧气体中氧气的体积含量为10～100％，
    其中x＝1～1.3，y＝0.1～0.9，z＝0.1～0.9，x:(y+z)＝1.4～1.6。
  2. 根据权利要求1所述的制备方法，其特征在于，所述步骤S1包括：
    步骤S1，在第一搅拌下，将NH 4F的水溶液和所述Li xNi yMn zO 2混合并发生所述反应，得到所述中间产物体系。
  3. 根据权利要求1所述的制备方法，其特征在于，在所述步骤S2之前，所述制备方法还包括：
    对所述中间产物体系进行过滤，得到所述氟改性的所述Li xNi yMn zO 2。
  4. 根据权利要求1所述的制备方法，其特征在于，所述第一煅烧的温度为400～800℃，时间为4～8h。
  5. 根据权利要求1至4中任一项所述的制备方法，其特征在于，所述第一含氧气体的流量为5～10L/min。
  6. 根据权利要求1所述的制备方法，其特征在于，所述第一含氧气体为空气。
  7. 根据权利要求1所述的制备方法，其特征在于，所述制备方法还包括所述Li xNi yMn zO 2的制备过程，所述制备过程包括：
    在第二含氧气体中，对包含Ni aMn bCO 3前驱体和锂化物的原料体系进行第二煅烧，得到所述Li xNi yMn zO 2，其中a＝0.1～0.9，b＝0.1～0.9，a+b＝1。
  8. 根据权利要求7所述的制备方法，其特征在于，所述锂化物中的锂的摩尔量和所述Ni aMn bCO 3前驱体中的镍和锰摩尔量总和的比值为1.4～1.6。
  9. 根据权利要求7所述的制备方法，其特征在于，所述锂化物选自氢氧化锂、碳酸锂和氯化锂、醋酸锂中的一种或多种。
  10. 根据权利要求7至9中任一项所述的制备方法，其特征在于，所述Ni aMn bCO 3前驱体粒径为5～10μm，优选所述Ni aMn bCO 3前驱体的比表面积为20～120m 2/g，优选所述Ni aMn bCO 3前驱体的堆密度为1.4～2.5g/cm 3。
  11. 根据权利要求7所述的制备方法，其特征在于，所述第二煅烧的温度为750～850℃、时间为8～12h。
  12. 根据权利要求7或11所述的制备方法，其特征在于，所述第二含氧气体中氧气的体积含量为10～100％，优选所述第二含氧气体为空气，优选所述第二含氧气体的流量为5～10L/min。
  13. 一种氟掺杂锂正极材料，其特征在于，所述氟掺杂锂正极材料由权利要求1至12中任一项所述的制备方法制备得到。
  14. 一种锂离子电池，包含电解液、正极材料和负极材料，所述正极材料包含锂正极材料，其特征在于，所述锂正极材料为权利要求13所述的氟掺杂锂正极材料。
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