WO2023060992A1 - 正极边角料回收合成高安全性正极材料的方法和应用 - Google Patents

正极边角料回收合成高安全性正极材料的方法和应用 Download PDF

Info

Publication number
WO2023060992A1
WO2023060992A1 PCT/CN2022/108665 CN2022108665W WO2023060992A1 WO 2023060992 A1 WO2023060992 A1 WO 2023060992A1 CN 2022108665 W CN2022108665 W CN 2022108665W WO 2023060992 A1 WO2023060992 A1 WO 2023060992A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
scrap
filtrate
safety
lithium
Prior art date
Application number
PCT/CN2022/108665
Other languages
English (en)
French (fr)
Inventor
余海军
陈江东
谢英豪
徐加雷
吴奔奔
张丛光
Original Assignee
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东邦普循环科技有限公司, 湖南邦普循环科技有限公司, 湖南邦普汽车循环有限公司 filed Critical 广东邦普循环科技有限公司
Publication of WO2023060992A1 publication Critical patent/WO2023060992A1/zh

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention belongs to the technical field of batteries, and in particular relates to a method and application of recycling and synthesizing high-safety positive electrode materials from positive electrode leftover materials.
  • lithium-ion batteries have become the mainstream product of secondary batteries at this stage, widely used in portable electronic devices such as smartphones and notebook computers, and promote the industrial upgrading and transformation of new energy vehicles and large-scale energy storage.
  • the most widely used positive electrode materials in lithium-ion batteries are the following: layered lithium cobaltate (LiCoO 2 ) and nickel cobalt manganese acid (LiCo x Ni y Mn z O 2 ), spinel lithium manganate (LiMn 2 O 4 ) and lithium iron phosphate (LiFePO 4 ).
  • LiCoO 2 layered lithium cobaltate
  • NiCo x Ni y Mn z O 2 nickel cobalt manganese acid
  • spinel lithium manganate LiMn 2 O 4
  • lithium iron phosphate LiFePO 4
  • positive electrode material for power batteries its safety is particularly important. Therefore, the development of positive electrode materials mainly focuses on seeking electrode materials with high energy density, high power density, environmental friendliness, low price and high safety performance.
  • the current process route of waste lithium-ion battery recycling is to refine and recycle the metal in the positive electrode material and the graphite in the negative electrode material, but the process line is complicated and the recovery rate is not high.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a method and application of recycling and synthesizing high-safety positive electrode materials from positive electrode scraps, which can synthesize the required positive electrode materials from waste materials in one step, can optimize the recovery rate, and can also save costs.
  • a method for recycling and synthesizing high-safety positive electrode materials from positive electrode scraps comprising the following steps:
  • the fluorine source is PVDF.
  • the fluorine source can be the solid phase obtained by the solid-liquid separation in step S1.
  • the solid phase obtained from the solid-liquid separation in step S1 should also contain conductive agent acetylene black, but in step S4, the conductive agent acetylene black (C) can be converted into CO 2 gas, has no effect on the material.
  • the positive electrode scrap is one of the positive scrap of the discarded lithium ion battery, the scrap of the positive electrode of the discarded sodium ion battery, or the scrap of the positive electrode of the lithium polymer battery. More preferably, it is waste lithium ion battery positive electrode scraps.
  • the waste lithium-ion battery positive electrode scrap is one of waste nickel-cobalt-manganese ternary positive electrode scrap, waste lithium iron phosphate scrap, waste lithium cobalt oxide scrap, or waste lithium manganese oxide scrap. More preferably, it is waste nickel-cobalt-manganese ternary positive electrode scraps.
  • the waste nickel-cobalt-manganese ternary positive electrode scrap is one of NCM811, NCM523, NCM622 or NCM334, more preferably NCM811.
  • the acid is one or more of hydrochloric acid, sulfuric acid or citric acid, more preferably sulfuric acid.
  • the reducing agent is one of glucose, hydrogen peroxide or formic acid. Hydrogen peroxide is more preferred.
  • step S2 the molar ratio of aluminum ions to other transition metals in the second filtrate is (0.01-0.03):(1-1.05).
  • the remaining amount of aluminum ions can be controlled by adjusting the pH value and precipitation time.
  • the alkali is one of potassium hydroxide, sodium hydroxide or lithium hydroxide, more preferably sodium hydroxide.
  • the specific process of the precipitation reaction in step S3 is: first add alkali and complexing agent, and then Add the second filtrate dropwise, control the pH and temperature to react for a period of time, then stop feeding, age, separate solid and liquid, wash the precipitate, and dry to obtain the precursor.
  • the alkali is one or more of potassium hydroxide, sodium hydroxide or lithium hydroxide, preferably sodium hydroxide; optionally, the reaction temperature is 30-70°C, preferably 50°C Optionally, the reaction time is 12-24h, preferably 20h; Optionally, the pH is 10-12, preferably 11; Optionally, the washing is sequentially washed with distilled water and ethanol solution , the concentration of the ethanol solution is preferably 30-99.5%; optionally, the drying is vacuum drying at 50-70°C for 6-18h, preferably at 60°C for 12h; optionally, the aging The time is 12-48h.
  • the specific process of the precipitation reaction in step S3 is: adding the second filtrate into the reactor, and controlling After reacting for a period of time, keep the temperature of the reactor and the stirring rate constant, and carry out aging, then separate the materials in the reactor, wash and dry the solids, and obtain the precursor.
  • the temperature is 170-190° C.
  • the reaction time is 10-13 hours
  • the aging time is 12-48 hours. More preferably, the aging time is 24 hours.
  • the complexing agent is one of ammonia or urea. Ammonia water is more preferable.
  • the lithium salt is one or more of lithium hydroxide, lithium carbonate or lithium oxalate, more preferably lithium hydroxide.
  • step S4 the molar ratio of the precursor, lithium salt and PVDF is (1-2):1:(0.01-0.1). More preferably, it is 1.05:1:0.04.
  • step S4 the calcination is carried out in two stages: the temperature of the first stage of calcination is 400-500°C, the temperature of the second stage of calcination is 900-1200°C, and the temperature rise of the two stages of calcination
  • the rate is 2-7° C./min; preferably, the time for the first stage of calcination is 3-5 hours, and the time for the second stage of calcination is 8-24 hours.
  • the invention also provides the application of the high-safety cathode material prepared by the method in aerospace batteries.
  • the present invention uses waste positive electrode leftovers to recycle and synthesize high-performance and high-safety Al and F co-doped positive electrode materials.
  • the preparation method is simple to operate, the reaction conditions are mild, and it is suitable for industrial production.
  • F ions replace O ions, and the Al-F bond has a higher covalent bond than other metals with O.
  • the binding energy of the material stabilizes the crystal structure of the material, slows down the release of active oxygen at high temperature, improves the structural stability of the material at high temperature, effectively inhibits the structural damage caused by the reaction between the positive electrode and the electrolyte at high temperature, and improves the initial reaction time. temperature and slow down the release of heat, thereby improving safety. In addition, it also reduces cation mixing, enhances the ion migration kinetics of lithium ion deintercalation and intercalation, significantly improves the ion transport rate, and has excellent electrochemical performance.
  • the method provided by the present invention has no pollution to the environment, uses the aluminum foil of waste positive electrode scraps as the Al source and the recycled binder PVDF as the F source, can effectively recycle industrial waste, reduce production costs, and optimize the recycling industry.
  • Fig. 1 is the rate performance test chart of embodiment 1, 2, 3 and comparative example 1;
  • Fig. 2 is the rate performance test figure of embodiment 4, 5 and embodiment 1;
  • Fig. 3 is the 1C cycle performance test figure of embodiment 1 and comparative example 1;
  • Fig. 4 is the safety performance diagram of embodiment 1, 2, 3 and comparative example 1;
  • Fig. 5 is the safety performance figure of embodiment 1 and comparative example 1,2;
  • Fig. 6 is the safety performance figure of embodiment 1, 6 and comparative example 3;
  • Fig. 7 is the EDS diagram of the element content of the Al and F co-doped NCM ternary cathode material obtained in Example 1;
  • FIG. 8 is a SEM image of the Al and F co-doped NCM ternary cathode material obtained in Example 1.
  • FIG. 8 is a SEM image of the Al and F co-doped NCM ternary cathode material obtained in Example 1.
  • a method for recycling and synthesizing Al and F co-doped cathode materials from waste ternary scrap, the specific process is:
  • step (3) Mix the precursor, lithium hydroxide monohydrate and the filter residue collected in step (1) at a molar ratio of 1:1.05:0.03 using a ball mill to mix evenly, and place the ball-milled solid powder in a tube furnace under pure oxygen conditions ( 50sccm (50mL/min), heat up to 450°C at a heating rate of 5°C/min, burn at a constant temperature of 450°C for 4 hours, then raise the temperature to 900°C at a heating rate of 5°C/min, calcine at a constant temperature for 12 hours, and then cool with the furnace , grind, and finally obtain Al and F co-doped NCM ternary cathode material LiNi 0.8 Co 0.1 Mn 0.09 Al 0.01 O 1.94 F 0.06 .
  • Figure 7 is the EDS diagram of the element content of the Al and F co-doped NCM ternary cathode material obtained in this example. It can be seen that the material has been doped with Al and F, and due to sintering under pure oxygen conditions, all carbon is converted into CO 2 Gas, no C element exists in the material.
  • Figure 8 is the SEM image of the Al and F co-doped NCM ternary positive electrode material obtained in this example. It can be seen from the figure that the material is a spherical secondary particle with a diameter of about 4 ⁇ m composed of small nanometer primary particles. The spherical shape is composed of multiple nanoparticles closely connected, showing a porous structure with high porosity, which is conducive to the deintercalation reaction of Li + , and has better structural stability, thereby improving thermal stability.
  • a method for recovering and synthesizing Al and F co-doped positive electrode materials from waste ternary scrap the difference from Example 1 is the molar ratio of the precursor, lithium hydroxide monohydrate and the filter residue collected in step (1) The ratio is 1:1.05:0.01; during the calcination process, first raise the temperature to 450°C with a heating rate of 5°C/min, and then burn at a constant temperature of 450°C for 4 hours, then raise the temperature to 700°C, with a heating rate of 5°C/min, and calcine at a constant temperature for 8 hours.
  • a method for recovering and synthesizing Al and F co-doped positive electrode materials from waste ternary scrap the difference from Example 1 is the molar ratio of the precursor, lithium hydroxide monohydrate and the filter residue collected in step (1) The ratio is 1:1.05:0.02; during the calcination process, the temperature is first raised to 450°C at a heating rate of 5°C/min, and then fired at a constant temperature of 450°C for 4 hours, then heated to 1200°C at a heating rate of 5°C/min, and calcined at a constant temperature for 24 hours.
  • a method for recovering and synthesizing Al and F co-doped positive electrode materials from waste ternary scrap the difference from Example 1 is that the pH in the control reactor is 10 in step (2), the temperature in the reactor is 30°C, and the reaction time is At 12 hours, the aging time is 12 hours.
  • a method for recovering and synthesizing Al and F co-doped positive electrode materials from waste ternary scrap the difference from Example 1 is that the pH in the control reactor is 12 in step (2), the temperature in the reactor is 70°C, and the reaction time is At 24 hours, the aging time is 48 hours.
  • a method for recovering and synthesizing Al and F co-doped lithium iron phosphate cathode materials from waste lithium iron phosphate scrap, the specific process is:
  • step (1) The precursor, lithium hydroxide monohydrate, and the PVDF collected in step (1) are mixed uniformly by ball milling at a molar ratio of 1:1.05:0.04, and the solid powder that has been ball-milled is placed in a tube furnace under pure oxygen conditions (50 sccm That is, at 50mL/min), heat up to 450°C with a heating rate of 5°C/min, burn at a constant temperature of 450°C for 4 hours, then heat up to 850°C with a heating rate of 5°C/min, and calcine at a constant temperature for 12 hours, then cool with the furnace. Grinding finally obtains the target Al and F co-doped lithium iron phosphate positive electrode material.
  • step (3) does not add PVDF to obtain an Al-doped ternary positive electrode material.
  • step (1) completely precipitates Al ions without doping aluminum, and step (3) does not add PVDF to obtain an undoped ternary cathode material.
  • step (1) completely precipitates Al ions without doping aluminum, and step (3) does not add PVDF to obtain no Doped lithium iron phosphate cathode material.
  • the positive electrode materials obtained in Examples 1-6 and Comparative Examples 1-3 were made into button batteries in the following way: the positive electrode material was used as the positive electrode active material, and the mass ratio of the conductive agent acetylene black and the binder PVDF was 80:10 : 10 for weighing; then fully stir and mix the conductive agent acetylene black and the positive electrode material evenly, add the adhesive PVDF after dry mixing evenly, add N-methylpyrrolidone to form a slurry after dry mixing evenly, and control the slurry
  • the solid content of the material is 40%, the viscosity of the slurry is 4500cps, and the positive electrode slurry is obtained; the positive electrode slurry is coated on the aluminum foil, rolled on the rolling roller, and the electrode is obtained after punching; the above electrode is used as the positive electrode, Lithium metal was used as the negative electrode, and the electrolyte was 1.0mol/L LiPF 6 -EC+DMC (volume ratio 1:1), and a button cell was assembled in a dry
  • the coin cells were charged to 4.4V, then disassembled, each positive electrode and 0.10mL electrolyte were used for DSC testing, so that the DSC results could simulate the actual heat release.
  • FIG. 1 is a rate performance test diagram of Examples 1, 2, 3 and Comparative Example 1. It can be seen from the figure that compared to the Al-doped electrode (Comparative Example 1), the Al and F co-doped samples (Example 1, 2, 3) all provide higher Capacitance, and better rate performance, wherein embodiment 1 has the best rate performance.
  • FIG. 2 is a rate performance test diagram of Examples 4, 5 and Example 1. It can be seen from the figure that Example 1 has higher capacitance than Example 4 and 5 at rates of 0.1C and 10C, and also has better rate performance.
  • FIG. 3 is a 1C cycle performance test graph of Example 1 and Comparative Example 1. It can be seen from the figure that the Al-F co-doped sample (Example 1) exhibits higher cycle performance than the Al-doped sample (Comparative Example 1).
  • Fig. 4 is the safety performance diagram of embodiment 1, 2, 3 and comparative example 1. It can be seen from the figure that the samples (Example 1, 2, 3) co-doped with Al and F have higher initial exothermic temperature and lower heat release than the Al-doped samples, indicating that Al and F co-doped The safety performance of doping is better than that of Al doping, and Example 1 shows the best safety performance.
  • Fig. 5 is the safety performance diagram of embodiment 1 and comparative examples 1 and 2. It can be seen from the figure that Al and F co-doped (Example 1) and Al-doped samples (Comparative Example 1) exhibited higher initial exothermic temperature and released Lower heat means better safety performance.
  • Fig. 6 is the safety performance figure of embodiment 1, 6 and comparative example 3.
  • the safety performance of the lithium iron phosphate sample (Example 6, Comparative Example 3) is better than that of the ternary NCM sample (Example 1), and the Al and F co-doped lithium iron phosphate (Example 6) is more Undoped lithium iron phosphate (comparative example 3) shows better safety performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Secondary Cells (AREA)

Abstract

本发明公开了一种正极边角料回收合成高安全性正极材料的方法和应用，包括向正极边角料中加入酸和还原剂溶解，固液分离得到第一滤液，向第一滤液中加入碱调节pH反应一段时间，使大部分铝离子沉淀，固液分离得到第二滤液，取第二滤液进行沉淀反应得到前驱体，将前驱体、锂盐和氟源混合，在氧气氛围下煅烧，得到高安全性正极材料，氟源为PVDF。本发明利用废弃正极边角料回收合成高性能和高安全性的Al与F共掺杂的正极材料，利用Al与F的协同作用，提高了材料在高温下的结构稳定性，有效抑制高温下正极与电解液反应时导致的结构破坏，提高安全性，还减少阳离子混排，增强锂离子脱嵌与嵌入的离子迁移动力学，具有优异的电化学性能。

Description

正极边角料回收合成高安全性正极材料的方法和应用 技术领域
本发明属于电池技术领域，具体涉及一种正极边角料回收合成高安全性正极材料的方法和应用。
背景技术
目前锂离子电池已成为现阶段二次电池中的主流产品，广泛应用于智能手机、笔记本电脑等便携电子设备中，并推动着新能源汽车和大规模储能等领域的产业升级与变革，从固定储能到混合电动汽车再到电动交通工具的各种应用中具有潜在优势。目前，在锂离子电池中使用量最多的正极材料有以下几种：层状的钻酸锂(LiCoO 2)和镍钴锰酸(LiCo xNi yMn zO 2)、尖晶石锰酸锂(LiMn 2O 4)以及磷酸铁锂(LiFePO 4)。但是，作为动力电池正极材料，其安全性尤为重要，因此正极材料的发展主要集中体现在寻求高能量密度、高功率密度、环境友好、价格便宜和高安全性能的电极材料。
目前常用正极材料的电子电导率和离子电导率较低、电极容量快速衰减、结构稳定性和倍率性能较差，以及材料的安全性能差，从而需要寻找提高正极材料电化学性能和安全性能的有效方法。在21世纪的太空中，对于航天器不可能时时面对着太阳。然而当航天器位于阴暗面时，太阳能电池也就不能正常工作，需要储能的蓄电池供电。目前锂离子电池虽然具有较高的能量密度，但因其较低的安全性能导致无法应用到航空航天电池。因此用于航天航空领域的锂离子电池必须具有安全性高、超长的循环寿命、能量密度高和体积更小等，应用该领域的电池均应具有高安全性能和电化学性能，用于太空探索。
结合废旧锂离子电池回收研究现状，目前废旧锂离子电池回收的工艺路线是分别把正极材料中的金属提炼回收和负极材料的石墨回收利用，但是工艺线复杂，且回收率不高。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种正极边角料回收合成高安全性正极材料的方法和应用，能够将废旧材料一步合成所需的正极材料，可以优化回收率，也可以节省成本。
根据本发明的一个方面，提出了一种正极边角料回收合成高安全性正极材料的方法，包括以下步骤：
S1：向正极边角料中加入酸和还原剂溶解，固液分离得到第一滤液；
S2：向所述第一滤液中加入碱调节pH反应一段时间，使大部分铝离子沉淀，固液分离得到第二滤液；
S3：取所述第二滤液进行沉淀反应得到前驱体；
S4：将所述前驱体、锂盐和氟源混合，在氧气氛围下煅烧，得到高安全性正极材料；其中，所述氟源为PVDF。在所述正极边角料的粘接剂为PVDF的情况下，所述氟源可采用步骤S1中所述固液分离所得的固相。
需要说明的是，步骤S1所述固液分离所得的固相除了PVDF，应该还含有导电剂乙炔黑，但在步骤S4中纯氧气的氛围高温煅烧，导电剂乙炔黑(C)可变成CO 2气体，对材料没有影响。
在本发明的一些实施方式中，所述正极边角料为废弃锂离子电池正极边角料、废弃钠离子电池正极边角料或锂聚合物电池正极边角料中的一种。进一步优选为废弃锂离子电池正极边角料。
在本发明的一些实施方式中，所述废弃锂离子电池正极边角料为废镍钴锰三元正极边角料、废磷酸铁锂边角料、废钴酸锂边角料或废锰酸锂边角料中的一种。进一步优选为废镍钴锰三元正极边角料。
在本发明的一些实施方式中，所述废镍钴锰三元正极边角料为NCM811、NCM523、NCM622或NCM334中的一种，进一步优选为NCM811。
在本发明的一些实施方式中，步骤S1中，所述酸为盐酸、硫酸或柠檬酸中的一种或几种，进一步优选为硫酸。
在本发明的一些实施方式中，步骤S1中，所述还原剂为葡萄糖、过氧化氢或甲酸中的一种。进一步优选为过氧化氢。
在本发明的一些实施方式中，步骤S2中，所述第二滤液中铝离子与其余过渡金属的摩尔比为(0.01-0.03)：(1-1.05)。可以通过调节pH值与沉淀时间进行控制铝离子的剩余量。
在本发明的一些实施方式中，步骤S2中，所述碱为氢氧化钾、氢氧化钠或氢氧化锂中的一种，进一步优选为氢氧化钠。
在本发明的一些实施方式中，步骤S2中，所述pH为3.0-6.0，进一步优选为pH＝4.5。
在本发明的一些实施方式中，当所述废弃锂离子电池正极边角料为废镍钴锰三元正极边角料时，步骤S3中所述沉淀反应的具体过程为：先加入碱和络合剂，再滴加所述第二滤液，控制pH和温度反应一段时间，然后停止进料，陈化，固液分离，洗涤沉淀物，干燥，得到所述前躯体。其中，所述碱为氢氧化钾、氢氧化钠或氢氧化锂中的一种或几种，优选为氢氧化钠；可选地，所述反应的温度为30-70℃，优选为50℃；可选地，所述反应的时间为12-24h，优选为20h；可选地，所述pH为10-12，优选为11；可选地，所述洗涤为使用蒸馏水和乙醇溶液依次洗涤，乙醇溶液的浓度优选为30-99.5％；可选地，所述干燥是在50-70℃下真空干燥6-18h，优选为在60℃下真空干燥12h；可选地，所述陈化的时间为12-48h。
在本发明的一些实施方式中，当所述废弃锂离子电池正极边角料为废磷酸铁锂边角料时，步骤S3中所述沉淀反应的具体过程为：将所述第二滤液加入反应釜中，控制反应釜内温度，反应一段时间后，保持反应釜温度、搅拌速率不变，进行陈化，然后将反应釜内物料分离，固体进行洗涤和干燥，得到前躯体。优选的，所述温度为170-190℃，反应的时间为10-13h，陈化的时间为12-48h，进一步优选的，陈化的时间为24h。
在本发明的一些实施方式中，所述络合剂为氨水或尿素中的一种。进一步优选为氨水。
在本发明的一些实施方式中，步骤S4中，所述锂盐为氢氧化锂、碳酸锂或草酸锂中的一种或几种，进一步优选为氢氧化锂。
在本发明的一些实施方式中，步骤S4中，所述前躯体、锂盐和PVDF的摩尔比为(1-2)：1：(0.01-0.1)。进一步优选为1.05：1：0.04。
在本发明的一些实施方式中，步骤S4中，所述煅烧分两段进行：第一段煅烧的温度为400-500℃，第二段煅烧的温度为900-1200℃，两段煅烧的升温速率为2-7℃/min；优选的，所述第一段煅烧的时间为3-5h，第二段煅烧的时间为8-24h。
本发明还提供所述的方法制得的高安全性正极材料在航空航天电池中的应用。
根据本发明的一种优选的实施方式，至少具有以下有益效果：
1、本发明利用废弃正极边角料回收合成高性能和高安全性的Al与F共掺杂的正极材料，制备方法操作简单，反应条件温和，适合工业化生产。而且利用Al与F的协同作用，减轻层状到尖晶石的相变并增强电子和离子电导率，F离子取代O离子，而Al-F键比其他金属与O的共价键具备更高的结合能，稳定了材料晶体结构，减缓了在高温下活性氧的释放，提高了材料在高温下的结构稳定性，有效抑制高温下正极与电解液反应时导致的结构破坏，提高反应的初始温度和减缓热量的释放，进而提高安全性。另外，还减少阳离子混排，增强锂离子脱嵌与嵌入的离子迁移动力学，显著提高离子传输速率，具有优异的电化学性能。
2、本发明提供的方法对环境无污染，利用废旧正极边角料的铝箔作为Al源和回收的粘结剂PVDF作为F源，能有效的将工业废料回收利用，降低制作成本，优化回收工业。
附图说明
下面结合附图和实施例对本发明做进一步的说明，其中：
图1为实施例1、2、3与对比例1的倍率性能测试图；
图2为实施例4、5与实施例1的倍率性能测试图；
图3为实施例1与对比例1的1C循环性能测试图；
图4为实施例1、2、3与对比例1的安全性能图；
图5为实施例1与对比例1、2的安全性能图；
图6为实施例1、6与对比例3的安全性能图；
图7为实施例1所得Al与F共掺杂NCM三元正极材料的元素含量EDS图；
图8为实施例1所得Al与F共掺杂NCM三元正极材料的SEM图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1
一种废三元边角料回收合成Al与F共掺杂正极材料的方法，具体过程为：
(1)用6mol/L硫酸和过氧化氢溶液将废三元边角料溶解，直到不再溶解，过滤得到滤渣(含粘结剂PVDF和导电剂乙炔黑)和滤液A，滤渣干燥收集，往滤液A中加入适量的NaOH溶液，调节pH＝4.5搅拌2h，使大部分Al离子沉淀，然后过滤分离得到滤液B，滤渣Al(OH) 3回收利用，滤液B中铝离子与过渡金属Ni、Co、Mn的摩尔比为0.01:0.79:0.10:0.11；
(2)配置一定浓度的氢氧化钠作为沉淀剂加入反应釜中，再加入一定量的氨水，控制反应釜内的pH为11，釜内温度为55℃，接着使用蠕动泵向反应釜内滴加滤液B，蠕动泵进料速度设定为500μL/min，反应时间为20h时，停止进料，保持反应釜温度、pH、搅拌速率等参数不变，陈化24h，陈化过程结束后，将反应釜内物料分离，分离后溶液加入Na 2CO 3得到Li 2CO 3回收利用，分离后固体进行反复洗涤，最终将固体在80℃下干燥24h得到前躯体；
(3)将前驱体、一水合氢氧化锂和步骤(1)收集的滤渣按摩尔比1：1.05：0.03使用球磨混合均匀，将球磨完的固体粉末放置在管式炉中，纯氧条件(50sccm即50mL/min)下，升温至450℃，升温速率为5℃/min，在450℃恒温烧4h，再升温到900℃，升温速率为5℃/min，恒温煅烧12h后，随炉冷却，研磨，最终得到Al与F共掺杂NCM 三元正极材料LiNi 0.8Co 0.1Mn 0.09Al 0.01O 1.94F 0.06。
图7为本实施例所得Al与F共掺杂NCM三元正极材料的元素含量EDS图，可见材料中已掺杂了Al和F，且由于纯氧条件下烧结，将碳全部变成CO 2气体，材料中无C元素存在。
图8为本实施例所得Al与F共掺杂NCM三元正极材料的SEM图，从图中可见材料是由小的纳米一级粒子组成的直径约为4μm的球形二级颗粒，材料表面的球状是由多个纳米颗粒紧密相连组成，表现出多孔的结构，孔隙率高，有利于Li +的脱嵌反应，具有较好的结构稳定型，进而提高热稳定性。
实施例2
一种废三元边角料回收合成Al与F共掺杂正极材料的方法，与实施例1的区别在于步骤(3)中前驱体、一水合氢氧化锂和步骤(1)收集的滤渣的摩尔比为1:1.05:0.01；煅烧过程先升温至450℃，升温速率为5℃/min，在450℃恒温烧4h，再升温到700℃，升温速率为5℃/min，恒温煅烧8h。
实施例3
一种废三元边角料回收合成Al与F共掺杂正极材料的方法，与实施例1的区别在于步骤(3)中前驱体、一水合氢氧化锂和步骤(1)收集的滤渣的摩尔比为1:1.05:0.02；煅烧过程先升温至450℃，升温速率为5℃/min，在450℃恒温烧4h，再升温到1200℃，升温速率为5℃/min，恒温煅烧24h。
实施例4
一种废三元边角料回收合成Al与F共掺杂正极材料的方法，与实施例1的区别在于步骤(2)中控制反应釜内的pH为10，釜内温度为30℃，反应时间为12h时，陈化的时间为12h。
实施例5
一种废三元边角料回收合成Al与F共掺杂正极材料的方法，与实施例1的区别在于步骤(2)中控制反应釜内的pH为12，釜内温度为70℃，反应时间为24h时，陈化 的时间为48h。
实施例6
一种废磷酸铁锂边角料回收合成Al与F共掺杂磷酸铁锂正极材料的方法，具体过程为：
(1)用6mol/L硫酸和过氧化氢溶液将废磷酸铁锂边角料溶解，直到不再溶解，过滤得到滤渣(粘结剂PVDF)和滤液A，滤渣干燥收集，往滤液A中加入适量的NaOH溶液，调节pH＝4.5搅拌2h，使大部分Al离子沉淀，然后过滤分离的滤液B，滤渣Al(OH) 3回收利用，滤液B中铝离子与过渡金属Fe的摩尔比为0.01:1.02；
(2)将滤液B加入反应釜中，控制反应釜内温度升温至180℃，反应时间为12h时，保持反应釜温度、搅拌速率等参数不变，陈化24h，陈化过程结束后，将反应釜内物料分离，固体进行反复洗涤，最终将固体在80℃下干燥24h得到前躯体；
(3)前驱体、一水合氢氧化锂和步骤(1)收集的PVDF按摩尔比1:1.05:0.04使用球磨混合均匀，将球磨完的固体粉末放置在管式炉中，纯氧条件(50sccm即50mL/min)下，升温至450℃，升温速率为5℃/min，在450℃恒温烧4h，再升温到850℃，升温速率为5℃/min，恒温煅烧12h后，随炉冷却，研磨最终得到目标Al与F共掺杂磷酸铁锂正极材料。
对比例1
一种废三元边角料回收合成三元正极材料的方法，与实施例1的区别在于步骤(3)不加入PVDF，得到Al掺杂的三元正极材料。
对比例2
一种废三元边角料回收合成三元正极材料的方法，与实施例1的区别在于步骤(1)使Al离子完全沉淀，不掺杂铝，且步骤(3)不加入PVDF，得到不掺杂的三元正极材料。
对比例3
一种废磷酸铁锂边角料回收合成磷酸铁锂正极材料的方法，与实施例6的区别在于 步骤(1)使Al离子完全沉淀，不掺杂铝，且步骤(3)不加入PVDF，得到不掺杂的磷酸铁锂正极材料。
试验例
将实施例1-6和对比例1-3获得的正极材料按以下方法制成扣式电池：将正极材料作为正极活性物质，与导电剂乙炔黑、粘结剂PVDF按质量比为80：10：10进行称量；然后将导电剂乙炔黑、正极材料充分搅拌混合均匀，在干混搅拌均匀后加入粘接剂PVDF，干混搅拌均匀后再加入N-甲基吡咯烷酮形成浆料，控制浆料的固含量为40％，浆料黏度为4500cps，得正极浆料；将正极浆料涂布在铝箔上，在碾压辊上进行碾压，冲切后获得电极；将上述电极作为正极，金属锂作为负极，电解液采用1.0mol/L LiPF 6-EC+DMC(体积比为1:1)，在充满氩气的干燥手套箱中组装成扣式电池。
将扣式电池搁置12h后对其进行0.1C、0.5C、1C、2C、3C、5C、10C的倍率性能测试以及2C循环性能测试。
将扣式电池充电至4.4V，然后拆开，每个正极和0.10mL电解液用于DSC测试，以便DSC结果可以模拟实际的放热。
图1为实施例1、2、3与对比例1的倍率性能测试图。从图中可以看出相比于Al掺杂的电极(对比例1)，Al与F共掺杂的样品(实施例1、2、3)都在0.1C和10C的倍率下提供更高的电容量，以及更好的倍率性能，其中实施例1具有最好的倍率性能。
图2为实施例4、5与实施例1的倍率性能测试图。从图中可以看出实施例1比实施例4和5在0.1C和10C的倍率下具有更高的电容量，也具有更好的倍率性能。
图3为实施例1与对比例1的1C循环性能测试图。从图中可以看出Al与F共掺杂的样品(实施例1)比Al掺杂的样品(对比例1)表现出更高的循环性能。
图4为实施例1、2、3与对比例1的安全性能图。从图中可以看出实Al与F共掺杂的样品(实施例1、2、3)比Al掺杂的样品具有更高的初始放热温度和释放更低的热量，表明Al与F共掺杂的安全性能比Al掺杂更好，实施例1表现出最优的安全性能。
图5为实施例1与对比例1、2的安全性能图。从图中可以看出Al与F共掺杂(实 施例1)和Al掺杂的样品(对比例1)表现出比不掺杂的样品(对比例2)更高的初始放热温度和释放更低的热量，即更好的安全性能。
图6为实施例1、6与对比例3的安全性能图。从图中可以看出磷酸铁锂样品(实施例6、对比例3)的安全性能优于三元NCM样品(实施例1)，Al与F共掺杂的磷酸铁锂(实施例6)比不掺杂的磷酸铁锂(对比例3)表现出更优的安全性能。
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种正极边角料回收合成高安全性正极材料的方法，其特征在于，包括以下步骤：
    S1：向正极边角料中加入酸和还原剂溶解，固液分离得到第一滤液；
    S2：向所述第一滤液中加入碱调节pH反应一段时间，使大部分铝离子沉淀，固液分离得到第二滤液；
    S3：取所述第二滤液进行沉淀反应得到前驱体；
    S4：将所述前驱体、锂盐和氟源混合，在氧气氛围下煅烧，得到高安全性正极材料；其中，所述氟源为PVDF。
  2. 根据权利要求1所述的方法，其特征在于，所述正极边角料为废弃锂离子电池正极边角料、废弃钠离子电池正极边角料或锂聚合物电池正极边角料中的一种。
  3. 根据权利要求2所述的方法，其特征在于，所述废弃锂离子电池正极边角料为废镍钴锰三元正极边角料、废磷酸铁锂边角料、废钴酸锂边角料或废锰酸锂边角料中的一种。
  4. 根据权利要求3所述的方法，其特征在于，当所述废弃锂离子电池正极边角料为废镍钴锰三元正极边角料时，步骤S3中所述沉淀反应的具体过程为：先加入碱和络合剂，再滴加所述第二滤液，控制pH和温度反应一段时间，然后停止进料，陈化，固液分离，洗涤沉淀物，干燥，得到所述前躯体。
  5. 根据权利要求4所述的方法，其特征在于，所述络合剂为氨水或尿素中的一种。
  6. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述还原剂为葡萄糖、过氧化氢或甲酸中的一种。
  7. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述第二滤液中铝离子与其余过渡金属的摩尔比为(0.01-0.03)：(1-1.05)。
  8. 根据权利要求1所述的方法，其特征在于，步骤S4中，所述前躯体、锂盐和PVDF的摩尔比为(1-2)：1：(0.01-0.1)。
  9. 根据权利要求1所述的方法，其特征在于，步骤S4中，所述煅烧分两段进行： 第一段煅烧的温度为400-500℃，第二段煅烧的温度为900-1200℃，两段煅烧的升温速率为2-7℃/min；优选的，所述第一段煅烧的时间为3-5h，第二段煅烧的时间为8-24h。
  10. 权利要求1-9任一项所述的方法制得的高安全性正极材料在航空航天电池中的应用。
PCT/CN2022/108665 2021-10-12 2022-07-28 正极边角料回收合成高安全性正极材料的方法和应用 WO2023060992A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111186036.X 2021-10-12
CN202111186036.XA CN114069083A (zh) 2021-10-12 2021-10-12 正极边角料回收合成高安全性正极材料的方法和应用

Publications (1)

Publication Number Publication Date
WO2023060992A1 true WO2023060992A1 (zh) 2023-04-20

Family

ID=80234503

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/108665 WO2023060992A1 (zh) 2021-10-12 2022-07-28 正极边角料回收合成高安全性正极材料的方法和应用

Country Status (2)

Country Link
CN (1) CN114069083A (zh)
WO (1) WO2023060992A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114069083A (zh) * 2021-10-12 2022-02-18 广东邦普循环科技有限公司 正极边角料回收合成高安全性正极材料的方法和应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868190A (zh) * 2015-05-13 2015-08-26 中国科学院过程工程研究所 一种锂离子电池正极废料中金属的浸出及回收方法
CN105633500A (zh) * 2016-02-22 2016-06-01 四川天齐锂业股份有限公司 利用回收锂离子电池材料制备三元正极材料前驱体的方法
CN105895879A (zh) * 2016-05-20 2016-08-24 中国科学院青岛生物能源与过程研究所 一种氟掺杂碳包覆正极复合材料及其制备方法及应用
CN105990577A (zh) * 2016-06-15 2016-10-05 电子科技大学 一种锂离子电池正极材料LiNi0.6-xCo0.2Mn0.2AlxO2-yFy及其制备方法
CN107653378A (zh) * 2017-08-25 2018-02-02 金川集团股份有限公司 一种废旧镍钴锰锂离子电池中有价金属的回收方法
CN107994223A (zh) * 2017-12-11 2018-05-04 广东工业大学 一种铝氟共掺杂改性的复合材料及其制备方法和应用
WO2018209164A1 (en) * 2017-05-11 2018-11-15 Worcester Polytechnic Institute Method and apparatus for recycling lithium iron phosphate batteries
CN109721043A (zh) * 2018-12-29 2019-05-07 宁德时代新能源科技股份有限公司 一种回收制备磷酸铁锂正极材料的方法
CN112591737A (zh) * 2020-12-16 2021-04-02 昆明理工大学 一种回收废旧锂离子电池负极石墨制备碳纳米角的方法
CN114069083A (zh) * 2021-10-12 2022-02-18 广东邦普循环科技有限公司 正极边角料回收合成高安全性正极材料的方法和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102347521A (zh) * 2011-10-08 2012-02-08 佛山市邦普循环科技有限公司 一种电动汽车用动力型锰酸锂电池中锰和锂的回收方法
CN103199320B (zh) * 2013-03-28 2015-05-27 四川天齐锂业股份有限公司 镍钴锰三元正极材料回收利用的方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868190A (zh) * 2015-05-13 2015-08-26 中国科学院过程工程研究所 一种锂离子电池正极废料中金属的浸出及回收方法
CN105633500A (zh) * 2016-02-22 2016-06-01 四川天齐锂业股份有限公司 利用回收锂离子电池材料制备三元正极材料前驱体的方法
CN105895879A (zh) * 2016-05-20 2016-08-24 中国科学院青岛生物能源与过程研究所 一种氟掺杂碳包覆正极复合材料及其制备方法及应用
CN105990577A (zh) * 2016-06-15 2016-10-05 电子科技大学 一种锂离子电池正极材料LiNi0.6-xCo0.2Mn0.2AlxO2-yFy及其制备方法
WO2018209164A1 (en) * 2017-05-11 2018-11-15 Worcester Polytechnic Institute Method and apparatus for recycling lithium iron phosphate batteries
CN107653378A (zh) * 2017-08-25 2018-02-02 金川集团股份有限公司 一种废旧镍钴锰锂离子电池中有价金属的回收方法
CN107994223A (zh) * 2017-12-11 2018-05-04 广东工业大学 一种铝氟共掺杂改性的复合材料及其制备方法和应用
CN109721043A (zh) * 2018-12-29 2019-05-07 宁德时代新能源科技股份有限公司 一种回收制备磷酸铁锂正极材料的方法
CN112591737A (zh) * 2020-12-16 2021-04-02 昆明理工大学 一种回收废旧锂离子电池负极石墨制备碳纳米角的方法
CN114069083A (zh) * 2021-10-12 2022-02-18 广东邦普循环科技有限公司 正极边角料回收合成高安全性正极材料的方法和应用

Also Published As

Publication number Publication date
CN114069083A (zh) 2022-02-18

Similar Documents

Publication Publication Date Title
US11855285B2 (en) Full-gradient nickel cobalt manganese positive electrode material, ruthenium oxide coated material and preparation method thereof
Tang et al. Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2
CN102983326B (zh) 一种球形锂镍钴复合氧化物正极材料的制备方法
CN102694166B (zh) 一种锂镍钴铝复合金属氧化物的制备方法
CN104241626B (zh) 锂离子电池钒酸锂负极材料的溶胶-凝胶制备方法
Gao et al. Recycling LiNi0. 5Co0. 2Mn0. 3O2 material from spent lithium-ion batteries by oxalate co-precipitation
CN103904321B (zh) 锂离子电池负极材料锰酸锂的高温固相制备方法
CN107069001B (zh) 一种蜂窝状硫化锌/碳复合负极材料及其制备方法
CN102386381A (zh) 一种锂离子电池纳米级正极材料的制备方法
CN109119624B (zh) 一种磷酸钛锂包覆富锂锰基正极材料的制备方法
CN109873140B (zh) 一种锂离子电池石墨烯复合三元正极材料及其制备方法
CN110233261B (zh) 一种单晶三元锂电池正极材料的制备方法及锂离子电池
CN105070970A (zh) 混合废碱性电池制备锂离子电池正极材料的方法
WO2024055519A1 (zh) 一种磷酸锰铁锂的制备方法及其应用
CN113772718B (zh) 一种SnS-SnS2@GO异质结构复合材料及其制备方法和应用
CN109802127B (zh) 一种银掺杂四氧化三铁纳米复合材料的制备方法
CN114804235A (zh) 一种高电压镍钴锰酸锂正极材料及其制备方法和应用
CN111342008A (zh) 一种氟化钾掺杂富锂锰基材料及其制备方法和应用
WO2023060992A1 (zh) 正极边角料回收合成高安全性正极材料的方法和应用
WO2019104948A1 (zh) 一种钼掺杂改性的锰酸锂复合材料、其制备方法及锂离子电池
CN110620217A (zh) 一种锌掺杂磷酸铁锂/碳复合材料及制备方法
CN114094089A (zh) 一种正极补锂添加剂及其制备和在锂离子电池正极补锂中的应用
TWI550938B (zh) 鋰離子電池正極材料及其製備方法
CN113735196A (zh) 废旧三元前驱体的回收利用方法及回收得到的三元正极材料
CN103219509B (zh) 一种尖晶石锰酸锂正极材料的制备方法

Legal Events

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

Ref document number: 22879939

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2022879939

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2022879939

Country of ref document: EP

Effective date: 20240423