WO2024036695A1 - Nano single-crystal type lithium-rich manganese-based positive electrode material, and preparation method therefor and use thereof - Google Patents

Nano single-crystal type lithium-rich manganese-based positive electrode material, and preparation method therefor and use thereof Download PDF

Info

Publication number
WO2024036695A1
WO2024036695A1 PCT/CN2022/120354 CN2022120354W WO2024036695A1 WO 2024036695 A1 WO2024036695 A1 WO 2024036695A1 CN 2022120354 W CN2022120354 W CN 2022120354W WO 2024036695 A1 WO2024036695 A1 WO 2024036695A1
Authority
WO
WIPO (PCT)
Prior art keywords
rich manganese
lithium
nano
single crystal
water
Prior art date
Application number
PCT/CN2022/120354
Other languages
French (fr)
Chinese (zh)
Inventor
李伟权
李长东
阮丁山
刘更好
蒋伟
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
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 filed Critical 广东邦普循环科技有限公司
Publication of WO2024036695A1 publication Critical patent/WO2024036695A1/en

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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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-ion battery cathode materials, and particularly relates to a nano single crystal lithium-rich manganese-based cathode material and its preparation method and application.
  • Lithium-rich manganese-based cathode materials have a high specific capacity of 250mAh/g, and they contain low amounts of expensive rare metals and are relatively low cost. Therefore it is considered to be one of the most promising next-generation lithium-ion battery materials. However, its cycle performance is poor due to severe voltage attenuation and irreversible anionic redox reactions during the cycle.
  • the present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a nano single crystal lithium-rich manganese-based positive electrode material and its preparation method and application.
  • the nano single crystal type lithium-rich manganese-based positive electrode material has excellent cycle performance.
  • a kind of nano single crystal lithium-rich manganese-based cathode material its chemical formula is: Li (1+x) Mn y Sn z M k O 2 , where 0 ⁇ x ⁇ 0.5, 0.5 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 0.5 , 0 ⁇ k ⁇ 0.2, M is at least one of Ti, Co, W, Ni, and Nb metal elements.
  • the chemical formulas are Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 , Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 , Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 and Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 at least one of them.
  • the particle size of the nano-single crystal lithium-rich manganese-based cathode material is 100-1000 nm.
  • solution A Dissolve soluble Li salt, soluble Mn salt, soluble Sn salt and soluble M salt in water to form solution A;
  • the precursor material is sintered, kept warm, and pulverized to obtain the nano-single crystal lithium-rich manganese-based cathode material.
  • the soluble Li salt in step (1) is at least one of lithium nitrate, lithium hydroxide or lithium acetate.
  • the soluble Mn salt in step (1) is at least one of manganese nitrate, manganese sulfate, manganese chloride or manganese acetate.
  • the soluble Sn salt in step (1) is at least one of tin tetrachloride, stannous chloride or stannous sulfate.
  • the soluble M salt in step (1) is titanium tetrachloride, butyl titanate, titanium nitrate, cobalt nitrate, cobalt sulfate, cobalt chloride, ammonium paratungstate, tungsten trioxide, nickel sulfate, nickel nitrate, At least one of niobyl nitrate or niobium pentachloride.
  • the total metal concentration of solution A in step (1) is ⁇ 1 mol/L.
  • adjusting the pH to alkaline means adjusting the pH to 7.0-9.0.
  • adjusting the pH to be alkaline means adjusting the pH to 7.0-8.0.
  • the water-absorbent material is a water-absorbent resin material containing carboxylic acid groups and/or carboxylate groups.
  • the water-absorbent resin material is at least one of starch cross-linked water-absorbent resin, polyacrylate-type water-absorbent resin or vinyl acetate copolymer water-absorbent resin.
  • the drying temperature is 100-200°C.
  • the drying temperature is 120-150°C.
  • the sintering temperature is 800-1200°C, and the holding time is 8-12 hours.
  • the sintering temperature is 900-1000°C, and the holding time is 10-12h.
  • step (4) the material obtained after the precursor material is sintered, kept warm, and pulverized is also screened.
  • the nano single crystal lithium-rich manganese-based cathode material of the present invention improves the voltage attenuation problem of lithium-rich manganese-based materials through the doping of M elements, and reduces the initial valence state of Mn through the introduction of high-valence elements, thereby suppressing Anionic irreversible redox reactions occur, thereby improving the material's cycle performance;
  • the preparation method of the nano single crystal lithium-rich manganese-based cathode material of the present invention uses a specific water-absorbing resin as a template agent and precursor carrier.
  • the specific water-absorbing resin contains carboxylic acid groups and carboxylate groups. Polymers are generally weakly acidic and have a stronger absorption effect on weakly alkaline solutions.
  • the present invention uses super absorbent resin as template agent and precursor carrier. The synthesis process is time-consuming, low-cost, simple operation and control, and easy for industrial production. .
  • Figure 1 is an SEM image of the nano single crystal lithium-rich manganese-based cathode material in Example 1 of the present invention
  • Figure 2 is the charge and discharge curve (0.1C) of the nano single crystal lithium-rich manganese-based cathode material in the first week at a voltage of 2.0-4.8V according to Embodiment 1 of the present invention
  • Figure 3 is a schematic diagram of the cycle performance of the nano single crystal lithium-rich manganese-based cathode material at 0.33C for 100 cycles after activation at 0.1C for 2 cycles in Example 1 of the present invention.
  • a kind of nano single crystal lithium-rich manganese-based cathode material its chemical formula is: Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 .
  • the preparation method of the above-mentioned nano single crystal lithium-rich manganese-based cathode material includes the following steps:
  • the obtained lithium-rich manganese-based material was examined by scanning electron microscopy (SEM). Its morphology is shown in Figure 1.
  • the morphology of the material is nanometer single crystal particles of 100 to 1000 nm.
  • the obtained nano single crystal lithium-rich manganese-based material Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 is made into a button battery positive electrode sheet through slurry mixing, coating and tableting. Lithium metal is used as the negative electrode sheet, and separators and The electrolyte was made into button cells to test their electrical properties.
  • the obtained nano-single crystal lithium-rich manganese-based material Li 1.15 Mn 0.58 Sn 0.25 Co 0.02 O 2 has a first-week discharge capacity of 254.4mAh ⁇ g -1 at a voltage of 2.0-4.8V.
  • the button battery after 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 216.2mAh ⁇ g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 92.2%, showing Outstanding capacity retention.
  • a kind of nano single crystal lithium-rich manganese-based cathode material its chemical formula is: Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 .
  • the preparation method of the above-mentioned nano single crystal lithium-rich manganese-based cathode material includes the following steps:
  • the obtained nano single crystal lithium-rich manganese-based material Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 is made into a button battery positive electrode sheet through slurry mixing, coating and tableting. Lithium metal is used as the negative electrode sheet, and separators and The electrolyte was made into button cells to test their electrical properties. At a voltage of 2.0-4.8V, its first-week discharge capacity is 255.1mAh ⁇ g -1 . After 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 213.5mAh ⁇ g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 91.6%.
  • a nanocrystalline lithium-rich manganese-based cathode material its chemical formula is: Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 .
  • the preparation method of the above-mentioned nano single crystal lithium-rich manganese-based cathode material includes the following steps:
  • the obtained nano single crystal lithium-rich manganese-based material Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 is made into a button battery positive electrode sheet through slurry mixing, coating and tableting. Lithium metal is used as the negative electrode sheet, and separators and The electrolyte was made into button cells to test their electrical properties. At a voltage of 2.0-4.8V, its first-week discharge capacity is 248.8mAh ⁇ g -1 . After 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 215.5mAh ⁇ g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 92.6%.
  • a kind of nano single crystal lithium-rich manganese-based cathode material its chemical formula is: Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 .
  • the preparation method of the above-mentioned nano single crystal lithium-rich manganese-based cathode material includes the following steps:
  • the obtained nano single crystal lithium-rich manganese-based material Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 is made into a button battery positive electrode sheet through slurry mixing, coating and tableting. Lithium metal is used as the negative electrode sheet, and separators and The electrolyte was made into button cells to test their electrical properties. At a voltage of 2.0-4.8V, its first-week discharge capacity is 255.4mAh ⁇ g -1 . After 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 218.5mAh ⁇ g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 91.2%.
  • Comparative Example 1 (Compared to Example 1, cobalt nitrate is not added during the preparation process)
  • a method for preparing nano-single crystal lithium-rich manganese-based cathode material including the following steps:
  • the obtained nano-single crystal lithium-rich manganese-based material is made into a button battery positive electrode sheet through slurry mixing, coating, and tableting. Lithium metal is used as the negative electrode sheet, and a separator and electrolyte are added to make a button battery to test its performance. electrical properties. At a voltage of 2.0-4.8V, its first-week discharge capacity is 250.8mAh ⁇ g -1 . After 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 214.3mAh ⁇ g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 82.5%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Disclosed in the present invention are a nano single-crystal type lithium-rich manganese-based positive electrode material, and a preparation method therefor and a use thereof. The chemical formula of the nano single-crystal type lithium-rich manganese-based positive electrode material is: Li(1+x)MnySnzMkO2, wherein 0<x≤0.5, 0.5≤y<1, 0<z<0.5, 0<k<0.2, and M is at least one of metal elements Ti, Co, W, Ni, and Nb. The nano single-crystal type lithium-rich manganese-based positive electrode material has excellent cycle performance.

Description

一种纳米单晶型富锂锰基正极材料及其制备方法和应用A kind of nano single crystal lithium-rich manganese-based cathode material and its preparation method and application 技术领域Technical field
本发明属于锂离子电池正极材料技术领域，特别涉及一种纳米单晶型富锂锰基正极材料及其制备方法和应用。The invention belongs to the technical field of lithium-ion battery cathode materials, and particularly relates to a nano single crystal lithium-rich manganese-based cathode material and its preparation method and application.
背景技术Background technique
自上个世纪末期锂离子电池被成功商业化生产以来，由于其具有比容量高、循环性能好、无记忆效应等的优点，其应用越来越广泛。特别是近年来新能源汽车的大力发展，对锂离子电池的需求量越来越大，同时对锂离子电池的性能也提出了越来越高的要求。Since the successful commercial production of lithium-ion batteries at the end of the last century, their applications have become more and more widespread due to their advantages such as high specific capacity, good cycle performance, and no memory effect. Especially in recent years, with the vigorous development of new energy vehicles, the demand for lithium-ion batteries is increasing, and at the same time, higher and higher requirements have been placed on the performance of lithium-ion batteries.
目前新能源汽车应用的主流的动力型电池有两种，一种是能量密度约为150～180Wh/kg的磷酸铁锂型锂离子电池，其能量密度较低但安全性能好，成本较低。另一种是能量密度约200～250Wh/kg的三元锂离子电池，其容量及循环性能较好，但成本较高。即使是装载能量密度较高的三元锂离子电池，市场上主流的纯电动汽车的续航里程也大多在400～600km左右，加上充电设施的不完善，充电速度较慢等问题，人们依然对纯电动汽车存在里程焦虑。为了提高电池的能量密度，增加纯电动汽车的续航里程，需要开发新的电池材料与结构体系。There are currently two mainstream power batteries used in new energy vehicle applications. One is a lithium iron phosphate lithium-ion battery with an energy density of about 150-180Wh/kg. It has a low energy density but good safety performance and low cost. The other is a ternary lithium-ion battery with an energy density of about 200 to 250Wh/kg. It has better capacity and cycle performance, but the cost is higher. Even if they are equipped with ternary lithium-ion batteries with higher energy density, the cruising range of mainstream pure electric vehicles on the market is mostly around 400 to 600km. In addition, due to imperfect charging facilities and slow charging speeds, people are still concerned about Pure electric vehicles suffer from range anxiety. In order to improve the energy density of batteries and increase the cruising range of pure electric vehicles, new battery materials and structural systems need to be developed.
富锂锰基正极材料具有250mAh/g的高比容量，且其含昂贵的稀有金属含量低，成本相对较低。因此它被认为是最有潜力的下一代锂离子电池材料之一。但由于其循环过程中电压衰减严重和不可逆的阴离子的氧化还原反应，导致其循环性能较差。Lithium-rich manganese-based cathode materials have a high specific capacity of 250mAh/g, and they contain low amounts of expensive rare metals and are relatively low cost. Therefore it is considered to be one of the most promising next-generation lithium-ion battery materials. However, its cycle performance is poor due to severe voltage attenuation and irreversible anionic redox reactions during the cycle.
发明内容Contents of the invention
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出一种纳米单晶型富锂锰基正极材料及其制备方法和应用，该纳米单晶型富锂锰基正极材料具有优异的循环性能。The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a nano single crystal lithium-rich manganese-based positive electrode material and its preparation method and application. The nano single crystal type lithium-rich manganese-based positive electrode material has excellent cycle performance.
本发明的上述技术目的是通过以下技术方案得以实现的：The above technical objectives of the present invention are achieved through the following technical solutions:
一种纳米单晶型富锂锰基正极材料，其化学式为：Li (1+x)Mn ySn zM kO 2，其中0<x≤0.5，0.5≤y<1，0<z<0.5，0<k<0.2，M为Ti、Co、W、Ni、Nb金属元素中的至少一种。 A kind of nano single crystal lithium-rich manganese-based cathode material, its chemical formula is: Li (1+x) Mn y Sn z M k O 2 , where 0<x≤0.5, 0.5≤y<1, 0<z<0.5 , 0<k<0.2, M is at least one of Ti, Co, W, Ni, and Nb metal elements.
优选的，所述化学式中0.1≤x≤0.3，0.55≤y≤0.7，0.1≤z≤0.3。Preferably, in the chemical formula, 0.1≤x≤0.3, 0.55≤y≤0.7, 0.1≤z≤0.3.
优选的，所述化学式为Li 1.15Mn 0.58Sn 0.15Co 0.07O 2、Li 1.21Mn 0.55Sn 0.20Ti 0.02O 2、Li 1.18Mn 0.60Sn 0.12Nb 0.05O 2及Li 1.20Mn 0.58Sn 0.15Ni 0.06O 2中的至少一种。 Preferably, the chemical formulas are Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 , Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 , Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 and Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 at least one of them.
优选的，所述纳米单晶型富锂锰基正极材料的粒径为100-1000nm。Preferably, the particle size of the nano-single crystal lithium-rich manganese-based cathode material is 100-1000 nm.
一种如上所述纳米单晶型富锂锰基正极材料的制备方法，包括以下步骤：A method for preparing the nano-single crystal lithium-rich manganese-based cathode material as described above, including the following steps:
(1)将可溶性Li盐、可溶性Mn盐、可溶性Sn盐及可溶性M盐溶解于水中形成溶液A；(1) Dissolve soluble Li salt, soluble Mn salt, soluble Sn salt and soluble M salt in water to form solution A;
(2)向所述溶液A中加入氨水溶液，调节pH为碱性，形成溶液B；(2) Add ammonia solution to solution A to adjust the pH to alkaline to form solution B;
(3)向所述溶液B中加入吸水材料，所述吸水材料吸收所述溶液B形成溶胀材料，将所述溶胀材料烘干得到含Li、Mn、Sn及M金属的前驱体材料；(3) Add a water-absorbing material to the solution B, the water-absorbing material absorbs the solution B to form a swelling material, and dry the swelling material to obtain a precursor material containing Li, Mn, Sn and M metals;
(4)将所述前驱体材料烧结并保温、粉碎得到所述纳米单晶型富锂锰基正极材料。(4) The precursor material is sintered, kept warm, and pulverized to obtain the nano-single crystal lithium-rich manganese-based cathode material.
优选的，步骤(1)中的所述可溶性Li盐为硝酸锂、氢氧化锂或乙酸锂中的至少一种。Preferably, the soluble Li salt in step (1) is at least one of lithium nitrate, lithium hydroxide or lithium acetate.
优选的，步骤(1)中的所述可溶性Mn盐为硝酸锰、硫酸锰、氯化锰或乙酸锰中的至少一种。Preferably, the soluble Mn salt in step (1) is at least one of manganese nitrate, manganese sulfate, manganese chloride or manganese acetate.
优选的，步骤(1)中的所述可溶性Sn盐为四氯化锡、氯化亚锡或硫酸亚锡中的至少一种。Preferably, the soluble Sn salt in step (1) is at least one of tin tetrachloride, stannous chloride or stannous sulfate.
优选的，步骤(1)中的所述可溶性M盐为四氯化钛、钛酸丁酯、硝酸钛、硝酸钴、硫酸钴、氯化钴、仲钨酸铵、三氧化钨、硫酸镍、硝酸镍、硝酸铌酰或五氯化铌中的至少一种。Preferably, the soluble M salt in step (1) is titanium tetrachloride, butyl titanate, titanium nitrate, cobalt nitrate, cobalt sulfate, cobalt chloride, ammonium paratungstate, tungsten trioxide, nickel sulfate, nickel nitrate, At least one of niobyl nitrate or niobium pentachloride.
优选的，步骤(1)中所述溶液A的总金属浓度≤1mol/L。Preferably, the total metal concentration of solution A in step (1) is ≤1 mol/L.
优选的，步骤(2)中，所述调节pH为碱性是指将pH调至7.0-9.0。Preferably, in step (2), adjusting the pH to alkaline means adjusting the pH to 7.0-9.0.
进一步优选的，步骤(2)中，所述调节pH为碱性是指将pH调至7.0-8.0。Further preferably, in step (2), adjusting the pH to be alkaline means adjusting the pH to 7.0-8.0.
优选的，步骤(3)中，所述吸水材料为含有羧酸基团和/或羧酸盐基团的吸水性树脂材料。Preferably, in step (3), the water-absorbent material is a water-absorbent resin material containing carboxylic acid groups and/or carboxylate groups.
优选的，所述吸水性树脂材料为淀粉交联型吸水树脂、聚丙烯酸盐型吸水树脂或醋酸乙烯脂共聚物吸水树脂中的至少一种。Preferably, the water-absorbent resin material is at least one of starch cross-linked water-absorbent resin, polyacrylate-type water-absorbent resin or vinyl acetate copolymer water-absorbent resin.
优选的，步骤(3)中，所述烘干的温度为100-200℃。Preferably, in step (3), the drying temperature is 100-200°C.
进一步优选的，步骤(3)中，所述烘干的温度为120-150℃。Further preferably, in step (3), the drying temperature is 120-150°C.
优选的，步骤(3)中，所述烧结的温度为800-1200℃，保温时间为8-12h。Preferably, in step (3), the sintering temperature is 800-1200°C, and the holding time is 8-12 hours.
进一步优选的，步骤(3)中，所述烧结的温度为900-1000℃，保温时间为10-12h。Further preferably, in step (3), the sintering temperature is 900-1000°C, and the holding time is 10-12h.
优选的，步骤(4)中，所述前驱体材料烧结并保温、粉碎后得到的物料还经过过筛处理。Preferably, in step (4), the material obtained after the precursor material is sintered, kept warm, and pulverized is also screened.
如上所述的纳米单晶型富锂锰基正极材料在锂离子电池中的应用。The application of the nanocrystalline lithium-rich manganese-based cathode material as mentioned above in lithium-ion batteries.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明的纳米单晶型富锂锰基正极材料通过M元素的掺杂，改善了富锂锰基材料的电压衰减问题，通过高价态元素的引入降低Mn的初始价态，抑制了阴离子不可逆氧化还原反应的发生，从而提高材料的循环性能；(1) The nano single crystal lithium-rich manganese-based cathode material of the present invention improves the voltage attenuation problem of lithium-rich manganese-based materials through the doping of M elements, and reduces the initial valence state of Mn through the introduction of high-valence elements, thereby suppressing Anionic irreversible redox reactions occur, thereby improving the material's cycle performance;
(2)本发明的纳米单晶型富锂锰基正极材料在制备方法上采用特定的吸水树脂作为模板 剂和前驱体载体，该特定的吸水树脂为含有羧酸基团和羧酸盐基团的高分子，一般呈弱酸性，对弱碱性溶液有更强烈的吸收作用，本发明采用高吸水树脂作为模板剂和前驱体载体，合成过程时间段、成本低，操作控制简单，易于工业化生产。(2) The preparation method of the nano single crystal lithium-rich manganese-based cathode material of the present invention uses a specific water-absorbing resin as a template agent and precursor carrier. The specific water-absorbing resin contains carboxylic acid groups and carboxylate groups. Polymers are generally weakly acidic and have a stronger absorption effect on weakly alkaline solutions. The present invention uses super absorbent resin as template agent and precursor carrier. The synthesis process is time-consuming, low-cost, simple operation and control, and easy for industrial production. .
附图说明Description of drawings
图1为本发明实施例1纳米单晶型富锂锰基正极材料的SEM图；Figure 1 is an SEM image of the nano single crystal lithium-rich manganese-based cathode material in Example 1 of the present invention;
图2为本发明实施例1纳米单晶型富锂锰基正极材料在首周2.0-4.8V电压下充放电曲线(0.1C)；Figure 2 is the charge and discharge curve (0.1C) of the nano single crystal lithium-rich manganese-based cathode material in the first week at a voltage of 2.0-4.8V according to Embodiment 1 of the present invention;
图3为本发明实施例1纳米单晶型富锂锰基正极材料在0.1C下激活2圈后，在0.33C下100周循环性能示意图。Figure 3 is a schematic diagram of the cycle performance of the nano single crystal lithium-rich manganese-based cathode material at 0.33C for 100 cycles after activation at 0.1C for 2 cycles in Example 1 of the present invention.
具体实施方式Detailed ways
下面结合具体实施例对本发明做进一步的说明。The present invention will be further described below in conjunction with specific embodiments.
实施例1：Example 1:
一种纳米单晶型富锂锰基正极材料，其化学式为：Li 1.15Mn 0.58Sn 0.15Co 0.07O 2。 A kind of nano single crystal lithium-rich manganese-based cathode material, its chemical formula is: Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 .
上述纳米单晶型富锂锰基正极材料的制备方法，包括以下步骤：The preparation method of the above-mentioned nano single crystal lithium-rich manganese-based cathode material includes the following steps:
(1)称取1.15mol的硝酸锂，0.58mol的硝酸锰，0.15mol的硫酸亚锡，0.07mol的硝酸钴，溶解于5L去离子水中，搅拌使其充分溶解，形成溶液A；(1) Weigh 1.15 mol of lithium nitrate, 0.58 mol of manganese nitrate, 0.15 mol of stannous sulfate, and 0.07 mol of cobalt nitrate, dissolve them in 5 L of deionized water, and stir to fully dissolve to form solution A;
(2)边搅拌边向溶液A中滴加氨水溶液，调节pH为8.0，形成溶液B；(2) Add ammonia solution dropwise to solution A while stirring to adjust the pH to 8.0 to form solution B;
(3)向溶液B中加入500g聚丙烯酸高吸水树脂，高吸水性树脂完全吸收溶液B形成溶胀树脂颗粒，将溶胀颗粒在150℃烘干10小时，得到含Li、Mn、Sn、Co金属的前驱体材料；(3) Add 500g polyacrylic acid super absorbent resin to solution B. The super absorbent resin completely absorbs solution B to form swollen resin particles. Dry the swollen particles at 150°C for 10 hours to obtain Li, Mn, Sn, and Co metals. Precursor materials;
(4)将所得的前驱体材料置于马弗炉中高温烧结，烧结温度为900℃，保温时间10小时，将烧结后的物料经过粉碎、过筛得到纳米单晶型富锂锰基材料Li 1.15Mn 0.58Sn 0.15Co 0.07O 2。 (4) Place the obtained precursor material in a muffle furnace for high-temperature sintering at a sintering temperature of 900°C and a holding time of 10 hours. The sintered material is crushed and sieved to obtain nano single crystal lithium-rich manganese-based material Li. 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 .
所得到的富锂锰基材料经过扫描电子显微镜(SEM)检测，其形貌如图1所示，材料形貌呈100～1000nm的纳米单晶颗粒。The obtained lithium-rich manganese-based material was examined by scanning electron microscopy (SEM). Its morphology is shown in Figure 1. The morphology of the material is nanometer single crystal particles of 100 to 1000 nm.
将所得到的纳米单晶型富锂锰基材料Li 1.15Mn 0.58Sn 0.15Co 0.07O 2经过调浆、涂布、压片制成扣式电池正极片，以锂金属为负极片，加入隔膜和电解液制成扣式电池以测试其电性能。如图2所示，所得到的纳米单晶型富锂锰基材料Li 1.15Mn 0.58Sn 0.25Co 0.02O 2在2.0-4.8V电压下，首周放电容量为254.4mAh·g -1。如图3所示，扣式电池在0.1C下激活2圈后，在0.33C下循环100周放电容量为216.2mAh·g -1，去除激活圈数后，其容量保持率为92.2％，展现出优异的容量保持率。 The obtained nano single crystal lithium-rich manganese-based material Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 is made into a button battery positive electrode sheet through slurry mixing, coating and tableting. Lithium metal is used as the negative electrode sheet, and separators and The electrolyte was made into button cells to test their electrical properties. As shown in Figure 2, the obtained nano-single crystal lithium-rich manganese-based material Li 1.15 Mn 0.58 Sn 0.25 Co 0.02 O 2 has a first-week discharge capacity of 254.4mAh·g -1 at a voltage of 2.0-4.8V. As shown in Figure 3, after 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 216.2mAh·g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 92.2%, showing Outstanding capacity retention.
实施例2：Example 2:
一种纳米单晶型富锂锰基正极材料，其化学式为：Li 1.21Mn 0.55Sn 0.20Ti 0.02O 2。 A kind of nano single crystal lithium-rich manganese-based cathode material, its chemical formula is: Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 .
上述纳米单晶型富锂锰基正极材料的制备方法，包括以下步骤：The preparation method of the above-mentioned nano single crystal lithium-rich manganese-based cathode material includes the following steps:
(1)称取1.21mol的乙酸锂，0.55mol的硝酸锰，0.20mol的硫酸亚锡，0.02mol的四氯化钛，溶解于6L冷的去离子水中，搅拌使其充分溶解，形成溶液A；(1) Weigh 1.21 mol of lithium acetate, 0.55 mol of manganese nitrate, 0.20 mol of stannous sulfate, and 0.02 mol of titanium tetrachloride, dissolve them in 6 L of cold deionized water, and stir to fully dissolve to form solution A. ;
(2)边搅拌边向溶液A中滴加氨水溶液，调节pH为7.5，形成溶液B；(2) Add ammonia solution dropwise to solution A while stirring to adjust the pH to 7.5 to form solution B;
(3)向溶液B中加入550g醋酸乙烯酯共聚物高吸水树脂，高吸水性树脂完全吸收溶液B形成溶胀树脂颗粒，将溶胀颗粒在150℃烘干10小时，得到含Li、Mn、Sn、Ti金属的前驱体材料；(3) Add 550g of vinyl acetate copolymer super absorbent resin to solution B. The super absorbent resin completely absorbs solution B to form swollen resin particles. Dry the swollen particles at 150°C for 10 hours to obtain Li, Mn, Sn, Precursor material for Ti metal;
(4)将所得的前驱体材料置于马弗炉中高温烧结，烧结温度为950℃，保温时间10.5小时，将烧结后的物料经过粉碎、过筛得到纳米单晶型富锂锰基材料Li 1.21Mn 0.55Sn 0.20Ti 0.02O 2。 (4) Place the obtained precursor material in a muffle furnace for high-temperature sintering, with a sintering temperature of 950°C and a holding time of 10.5 hours. The sintered material is crushed and sieved to obtain nano single crystal lithium-rich manganese-based material Li. 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 .
将所得到的纳米单晶型富锂锰基材料Li 1.21Mn 0.55Sn 0.20Ti 0.02O 2经过调浆、涂布、压片制成扣式电池正极片，以锂金属为负极片，加入隔膜和电解液制成扣式电池以测试其电性能。在2.0-4.8V电压下，其首周放电容量为255.1mAh·g -1。扣式电池在0.1C下激活2圈后，在0.33C下循环100周放电容量为213.5mAh·g -1，去除激活圈数后，其容量保持率为91.6％。 The obtained nano single crystal lithium-rich manganese-based material Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 is made into a button battery positive electrode sheet through slurry mixing, coating and tableting. Lithium metal is used as the negative electrode sheet, and separators and The electrolyte was made into button cells to test their electrical properties. At a voltage of 2.0-4.8V, its first-week discharge capacity is 255.1mAh·g -1 . After 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 213.5mAh·g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 91.6%.
实施例3：Example 3:
一种纳米单晶型富锂锰基正极材料，其化学式为：Li 1.18Mn 0.60Sn 0.12Nb 0.05O 2。 A nanocrystalline lithium-rich manganese-based cathode material, its chemical formula is: Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 .
上述纳米单晶型富锂锰基正极材料的制备方法，包括以下步骤：The preparation method of the above-mentioned nano single crystal lithium-rich manganese-based cathode material includes the following steps:
(1)称取1.18mol的硝酸锂，0.60mol的硫酸锰，0.12mol的硫酸亚锡，0.05mol的硝酸铌酰，溶解于4L冷的去离子水中，搅拌使其充分溶解，形成溶液A；(1) Weigh 1.18 mol of lithium nitrate, 0.60 mol of manganese sulfate, 0.12 mol of stannous sulfate, and 0.05 mol of niobyl nitrate, dissolve them in 4L of cold deionized water, and stir to fully dissolve to form solution A;
(2)边搅拌边向溶液A中滴加氨水溶液，调节pH为7.7，形成溶液B；(2) Add ammonia solution dropwise to solution A while stirring to adjust the pH to 7.7 to form solution B;
(3)向溶液B中加入450g淀粉交联型高吸水树脂，高吸水性树脂完全吸收溶液B形成溶胀树脂颗粒，将溶胀颗粒在150℃烘干10小时，得到含Li、Mn、Sn、Nb金属的前驱体材料；(3) Add 450g of starch cross-linked super absorbent resin to solution B. The super absorbent resin completely absorbs solution B to form swollen resin particles. Dry the swollen particles at 150°C for 10 hours to obtain Li, Mn, Sn, and Nb. Precursor materials for metals;
(4)将所得的前驱体材料置于马弗炉中高温烧结，烧结温度为950℃，保温时间10.5小时，将烧结后的物料经过粉碎、过筛得到纳米单晶型富锂锰基材料Li 1.18Mn 0.60Sn 0.12Nb 0.05O 2。 (4) Place the obtained precursor material in a muffle furnace for high-temperature sintering, with a sintering temperature of 950°C and a holding time of 10.5 hours. The sintered material is crushed and sieved to obtain nano single crystal lithium-rich manganese-based material Li. 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 .
将所得到的纳米单晶型富锂锰基材料Li 1.18Mn 0.60Sn 0.12Nb 0.05O 2经过调浆、涂布、压片制成扣式电池正极片，以锂金属为负极片，加入隔膜和电解液制成扣式电池以测试其电性能。在2.0-4.8V电压下，其首周放电容量为248.8mAh·g -1。扣式电池在0.1C下激活2圈后，在0.33C下循环100周放电容量为215.5mAh·g -1，去除激活圈数后，其容量保持率为92.6％。 The obtained nano single crystal lithium-rich manganese-based material Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 is made into a button battery positive electrode sheet through slurry mixing, coating and tableting. Lithium metal is used as the negative electrode sheet, and separators and The electrolyte was made into button cells to test their electrical properties. At a voltage of 2.0-4.8V, its first-week discharge capacity is 248.8mAh·g -1 . After 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 215.5mAh·g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 92.6%.
实施例4：Example 4:
一种纳米单晶型富锂锰基正极材料，其化学式为：Li 1.20Mn 0.58Sn 0.15Ni 0.06O 2。 A kind of nano single crystal lithium-rich manganese-based cathode material, its chemical formula is: Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 .
上述纳米单晶型富锂锰基正极材料的制备方法，包括以下步骤：The preparation method of the above-mentioned nano single crystal lithium-rich manganese-based cathode material includes the following steps:
(1)称取1.20mol的氢氧化锂，0.58mol的硝酸锰，0.15mol的氯化亚锡，0.06mol的硝酸镍，溶解于8L冷的去离子水中，搅拌使其充分溶解，形成溶液A；(1) Weigh 1.20 mol of lithium hydroxide, 0.58 mol of manganese nitrate, 0.15 mol of stannous chloride, and 0.06 mol of nickel nitrate, dissolve them in 8 L of cold deionized water, and stir to fully dissolve to form solution A. ;
(2)边搅拌边向溶液A中滴加氨水溶液，调节pH为8.0，形成溶液B；(2) Add ammonia solution dropwise to solution A while stirring to adjust the pH to 8.0 to form solution B;
(3)向溶液B中加入750g醋酸乙烯酯共聚物高吸水树脂，高吸水性树脂完全吸收溶液B形成溶胀树脂颗粒，将溶胀颗粒在120℃烘干12小时，得到含Li、Mn、Sn、Ni金属的前驱体材料；(3) Add 750g of vinyl acetate copolymer super absorbent resin to solution B. The super absorbent resin completely absorbs solution B to form swollen resin particles. Dry the swollen particles at 120°C for 12 hours to obtain Li, Mn, Sn, Ni metal precursor material;
(4)将所得的前驱体材料置于马弗炉中高温烧结，烧结温度为940℃，保温时间12小时，将烧结后的物料经过粉碎、过筛得到纳米单晶型富锂锰基材料Li 1.20Mn 0.58Sn 0.15Ni 0.06O 2。 (4) Place the obtained precursor material in a muffle furnace for high-temperature sintering at a sintering temperature of 940°C and a holding time of 12 hours. The sintered material is crushed and sieved to obtain nano single crystal lithium-rich manganese-based material Li. 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 .
将所得到的纳米单晶型富锂锰基材料Li 1.20Mn 0.58Sn 0.15Ni 0.06O 2经过调浆、涂布、压片制成扣式电池正极片，以锂金属为负极片，加入隔膜和电解液制成扣式电池以测试其电性能。在2.0-4.8V电压下，其首周放电容量为255.4mAh·g -1。扣式电池在0.1C下激活2圈后，在0.33C下循环100周放电容量为218.5mAh·g -1，去除激活圈数后，其容量保持率为91.2％。 The obtained nano single crystal lithium-rich manganese-based material Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 is made into a button battery positive electrode sheet through slurry mixing, coating and tableting. Lithium metal is used as the negative electrode sheet, and separators and The electrolyte was made into button cells to test their electrical properties. At a voltage of 2.0-4.8V, its first-week discharge capacity is 255.4mAh·g -1 . After 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 218.5mAh·g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 91.2%.
对比例1：(相比实施例1在制备过程中不加入硝酸钴)Comparative Example 1: (Compared to Example 1, cobalt nitrate is not added during the preparation process)
一种纳米单晶型富锂锰基正极材料的制备方法，包括以下步骤：A method for preparing nano-single crystal lithium-rich manganese-based cathode material, including the following steps:
(1)称取1.15mol的硝酸锂，0.58mol的硝酸锰，0.25mol的硫酸亚锡，溶解于5L去离子水中，搅拌使其充分溶解，形成溶液A；(1) Weigh 1.15 mol of lithium nitrate, 0.58 mol of manganese nitrate, and 0.25 mol of stannous sulfate, dissolve them in 5 L of deionized water, and stir to fully dissolve to form solution A;
(2)边搅拌边向溶液A中滴加氨水溶液，调节pH为8.0，形成溶液B；(2) Add ammonia solution dropwise to solution A while stirring to adjust the pH to 8.0 to form solution B;
(3)向溶液B中加入500g聚丙烯酸高吸水树脂，高吸水性树脂完全吸收溶液B形成溶胀树脂颗粒，将溶胀颗粒在150℃烘干10小时，得到含Li、Mn、Sn、Co金属的前驱体材料；(3) Add 500g polyacrylic acid super absorbent resin to solution B. The super absorbent resin completely absorbs solution B to form swollen resin particles. Dry the swollen particles at 150°C for 10 hours to obtain Li, Mn, Sn, and Co metals. Precursor materials;
(4)将所得的前驱体材料置于马弗炉中高温烧结，烧结温度为900℃，保温时间10小时，将烧结后的物料经过粉碎、过筛得到纳米单晶型富锂锰基材料。(4) Place the obtained precursor material in a muffle furnace for high-temperature sintering at a sintering temperature of 900°C and a holding time of 10 hours. The sintered material is crushed and sieved to obtain a nano-single crystal lithium-rich manganese-based material.
将所得到的纳米单晶型富锂锰基材料经过调浆、涂布、压片制成扣式电池正极片，以锂金属为负极片，加入隔膜和电解液制成扣式电池以测试其电性能。在2.0-4.8V电压下，其首周放电容量为250.8mAh·g -1。扣式电池在0.1C下激活2圈后，在0.33C下循环100周放电容量为214.3mAh·g -1，去除激活圈数后，其容量保持率为82.5％。 The obtained nano-single crystal lithium-rich manganese-based material is made into a button battery positive electrode sheet through slurry mixing, coating, and tableting. Lithium metal is used as the negative electrode sheet, and a separator and electrolyte are added to make a button battery to test its performance. electrical properties. At a voltage of 2.0-4.8V, its first-week discharge capacity is 250.8mAh·g -1 . After 2 cycles of activation at 0.1C, the button battery has a discharge capacity of 214.3mAh·g -1 after 100 cycles at 0.33C. After removing the number of activation cycles, its capacity retention rate is 82.5%.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, etc. may be made without departing from the spirit and principles of the present invention. All simplifications should be equivalent substitutions, and are all included in the protection scope of the present invention.

Claims (10)

  1. 一种纳米单晶型富锂锰基正极材料，其特征在于，其化学式为：Li (1+x)Mn ySn zM kO 2，其中0<x≤0.5，0.5≤y<1，0<z<0.5，0<k<0.2，M为Ti、Co、W、Ni、Nb金属元素中的至少一种。 A nano single crystal lithium-rich manganese-based cathode material, characterized in that its chemical formula is: Li (1+x) Mn y Sn z M k O 2 , where 0<x≤0.5, 0.5≤y<1,0 <z<0.5, 0<k<0.2, M is at least one of Ti, Co, W, Ni and Nb metal elements.
  2. 根据权利要求1所述的一种纳米单晶型富锂锰基正极材料，其特征在于，所述化学式中0.1≤x≤0.3，0.55≤y≤0.7，0.1≤z≤0.3，0<k<0.2。A nano-single crystal lithium-rich manganese-based cathode material according to claim 1, characterized in that in the chemical formula, 0.1≤x≤0.3, 0.55≤y≤0.7, 0.1≤z≤0.3, 0<k< 0.2.
  3. 根据权利要求2所述的一种纳米单晶型富锂锰基正极材料，其特征在于，所述化学式为Li 1.15Mn 0.58Sn 0.15Co 0.07O 2、Li 1.21Mn 0.55Sn 0.20Ti 0.02O 2、Li 1.18Mn 0.60Sn 0.12Nb 0.05O 2及Li 1.20Mn 0.58Sn 0.15Ni 0.06O 2中的至少一种。 A nanocrystalline lithium-rich manganese-based cathode material according to claim 2, characterized in that the chemical formula is Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 , Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 , At least one of Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 and Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 .
  4. 根据权利要求1所述的一种纳米单晶型富锂锰基正极材料，其特征在于，所述纳米单晶型富锂锰基正极材料的粒径为100-1000nm。A nano-single-crystal lithium-rich manganese-based positive electrode material according to claim 1, characterized in that the particle size of the nano-single-crystal lithium-rich manganese-based positive electrode material is 100-1000 nm.
  5. 一种如权利要求1-4任一项所述纳米单晶型富锂锰基正极材料的制备方法，其特征在于，包括以下步骤：A method for preparing nano-single crystal lithium-rich manganese-based cathode material according to any one of claims 1 to 4, characterized in that it includes the following steps:
    (1)将可溶性Li盐、可溶性Mn盐、可溶性Sn盐及可溶性M盐溶解于水中形成溶液A；(1) Dissolve soluble Li salt, soluble Mn salt, soluble Sn salt and soluble M salt in water to form solution A;
    (2)向所述溶液A中加入氨水溶液，调节pH为碱性，形成溶液B；(2) Add ammonia solution to solution A to adjust the pH to alkaline to form solution B;
    (3)向所述溶液B中加入吸水材料，所述吸水材料吸收所述溶液B形成溶胀材料，将所述溶胀材料烘干得到含Li、Mn、Sn及M金属的前驱体材料；(3) Add a water-absorbing material to the solution B, the water-absorbing material absorbs the solution B to form a swelling material, and dry the swelling material to obtain a precursor material containing Li, Mn, Sn and M metals;
    (4)将所述前驱体材料烧结并保温、粉碎得到所述纳米单晶型富锂锰基正极材料。(4) The precursor material is sintered, kept warm, and pulverized to obtain the nano-single crystal lithium-rich manganese-based cathode material.
  6. 根据权利要求5所述的一种纳米单晶型富锂锰基正极材料的制备方法，其特征在于，步骤(1)中所述溶液A的总金属浓度≤1mol/L。The method for preparing a nano-single crystal lithium-rich manganese-based cathode material according to claim 5, characterized in that the total metal concentration of solution A in step (1) is ≤1 mol/L.
  7. 根据权利要求5所述的一种纳米单晶型富锂锰基正极材料的制备方法，其特征在于，步骤(2)中，所述调节pH为碱性是指将pH调至7.0-9.0。The method for preparing a nano single crystal lithium-rich manganese-based positive electrode material according to claim 5, characterized in that in step (2), adjusting the pH to be alkaline means adjusting the pH to 7.0-9.0.
  8. 根据权利要求5所述的一种纳米单晶型富锂锰基正极材料的制备方法，其特征在于，步骤(3)中，所述吸水材料为含有羧酸基团和/或羧酸盐基团的吸水性树脂材料。The method for preparing a nano single crystal lithium-rich manganese-based cathode material according to claim 5, characterized in that in step (3), the water-absorbing material contains carboxylic acid groups and/or carboxylate groups. A group of water-absorbent resin materials.
  9. 根据权利要求8所述的一种纳米单晶型富锂锰基正极材料的制备方法，其特征在于，所述吸水性树脂材料为淀粉交联型吸水树脂、聚丙烯酸盐型吸水树脂或醋酸乙烯脂共聚物吸水树脂中的至少一种。The method for preparing a nano-single crystal lithium-rich manganese-based cathode material according to claim 8, wherein the water-absorbent resin material is starch cross-linked water-absorbent resin, polyacrylate-type water-absorbent resin or vinyl acetate. At least one type of lipid copolymer water-absorbing resin.
  10. 权利要求1-4任一项所述的纳米单晶型富锂锰基正极材料在锂离子电池中的应用。Application of the nanocrystalline lithium-rich manganese-based cathode material according to any one of claims 1 to 4 in lithium-ion batteries.
PCT/CN2022/120354 2022-08-18 2022-09-21 Nano single-crystal type lithium-rich manganese-based positive electrode material, and preparation method therefor and use thereof WO2024036695A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210991039.9A CN115411261A (en) 2022-08-18 2022-08-18 Nano single crystal type lithium-rich manganese-based positive electrode material and preparation method and application thereof
CN202210991039.9 2022-08-18

Publications (1)

Publication Number Publication Date
WO2024036695A1 true WO2024036695A1 (en) 2024-02-22

Family

ID=84159684

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/120354 WO2024036695A1 (en) 2022-08-18 2022-09-21 Nano single-crystal type lithium-rich manganese-based positive electrode material, and preparation method therefor and use thereof

Country Status (3)

Country Link
CN (1) CN115411261A (en)
FR (1) FR3138967A1 (en)
WO (1) WO2024036695A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110226985A1 (en) * 2010-03-19 2011-09-22 Samsung Electronics Co., Ltd. Cathode active material, cathode including the same, and lithium battery including cathode
CN107834063A (en) * 2017-12-15 2018-03-23 哈尔滨工业大学 A kind of monocrystalline type one-dimentional structure lithium-rich manganese-based anode material and preparation method thereof
CN108493446A (en) * 2018-04-24 2018-09-04 中国矿业大学 A kind of preparation method of lithium ion battery lithium-rich manganese base material
CN109244444A (en) * 2018-08-29 2019-01-18 湘潭大学 A kind of lithium-rich manganese-based layered oxide positive electrode and preparation method thereof of niobium doping
CN109437332A (en) * 2018-10-22 2019-03-08 成都新柯力化工科技有限公司 A kind of preparation method of the positive electrode of lithium ion battery size tunable
CN110492095A (en) * 2019-08-14 2019-11-22 中国科学院青岛生物能源与过程研究所 A kind of lithium-rich manganese-based anode material of tin dope and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110226985A1 (en) * 2010-03-19 2011-09-22 Samsung Electronics Co., Ltd. Cathode active material, cathode including the same, and lithium battery including cathode
CN107834063A (en) * 2017-12-15 2018-03-23 哈尔滨工业大学 A kind of monocrystalline type one-dimentional structure lithium-rich manganese-based anode material and preparation method thereof
CN108493446A (en) * 2018-04-24 2018-09-04 中国矿业大学 A kind of preparation method of lithium ion battery lithium-rich manganese base material
CN109244444A (en) * 2018-08-29 2019-01-18 湘潭大学 A kind of lithium-rich manganese-based layered oxide positive electrode and preparation method thereof of niobium doping
CN109437332A (en) * 2018-10-22 2019-03-08 成都新柯力化工科技有限公司 A kind of preparation method of the positive electrode of lithium ion battery size tunable
CN110492095A (en) * 2019-08-14 2019-11-22 中国科学院青岛生物能源与过程研究所 A kind of lithium-rich manganese-based anode material of tin dope and preparation method thereof

Also Published As

Publication number Publication date
FR3138967A1 (en) 2024-02-23
CN115411261A (en) 2022-11-29

Similar Documents

Publication Publication Date Title
US20190386293A1 (en) Ternary material and preparation method thereof, battery slurry, positive electrode and lithium battery
KR102477330B1 (en) Lithium-manganese-rich material, manufacturing method and application thereof
WO2022048346A1 (en) Vanadium pentoxide/rgo-coated lithium nickel cobalt manganese oxide positive electrode material and preparation method therefor
WO2020134048A1 (en) Cobalt-free, lithium-rich ternary positive electrode material nma and preparation method thereof
EP3965188A1 (en) Composite positive electrode material for lithium ion battery, lithium ion battery, and vehicle
WO2023130779A1 (en) High-voltage ternary positive electrode material with core-shell structure and preparation method therefor
CN106910887B (en) Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material
CN108493435B (en) Lithium ion battery anode material Li (Ni)0.8Co0.1Mn0.1)1-xYxO2And preparation method
WO2022089205A1 (en) Doped high-nickel ternary material and preparation method therefor
WO2024104240A1 (en) Medium- and high-entropy layered lithium-rich positive electrode oxide and preparation method therefor
CN111082059A (en) V-doped P2 type sodium ion battery positive electrode material and preparation method thereof
WO2019113870A1 (en) Lithium-rich manganese-based material and preparation and application thereof
CN110459764B (en) Lithium ion battery positive electrode material and preparation method and application thereof
CN104953109B (en) A kind of nucleocapsid LiMn2O4 and its synthetic method for promoting high temperature resistance
WO2024212632A1 (en) Pure-phase polyanionic sulfate sodium ion battery positive electrode material and preparation method therefor
WO2023184996A1 (en) Modified high-nickel ternary positive electrode material and preparation method therefor
CN111082042A (en) Ternary positive electrode material micron single crystal structure for lithium ion battery and preparation method thereof
CN111362318B (en) Nickel-cobalt-manganese carbonate and preparation method and application thereof
CN113629229A (en) Phosphate-coated wet-method-doped ternary cathode material and preparation method thereof
CN116014104A (en) Lithium-rich nickel positive electrode material, preparation method thereof, positive electrode sheet and secondary battery
CN114804235A (en) High-voltage nickel cobalt lithium manganate positive electrode material and preparation method and application thereof
CN108878873A (en) Lithium iron phosphate positive material modified surface structure and its preparation method and application
CN112952056B (en) Lithium-rich manganese-based composite cathode material and preparation method and application thereof
WO2024037261A1 (en) Preparation method for double-layer coated lithium-sodium composite lithium-rich manganese-based positive electrode material
WO2024066173A1 (en) Lithium-rich manganese-based positive electrode material with a double-layer coated surface, and preparation method therefor and use thereof

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: 22955471

Country of ref document: EP

Kind code of ref document: A1