WO2017063233A1 - Ionic group induced compound phase modified lithium-rich layered cathode material and preparation method - Google Patents

Ionic group induced compound phase modified lithium-rich layered cathode material and preparation method Download PDF

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WO2017063233A1
WO2017063233A1 PCT/CN2015/093105 CN2015093105W WO2017063233A1 WO 2017063233 A1 WO2017063233 A1 WO 2017063233A1 CN 2015093105 W CN2015093105 W CN 2015093105W WO 2017063233 A1 WO2017063233 A1 WO 2017063233A1
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lithium
cathode material
solution
layered cathode
rich layered
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赵乃勤
郭立超
师春生
刘恩佐
何春年
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天津大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 with reduced ionic group induced surface spinel transformation and a preparation method thereof, and belongs to the preparation technology of nano composite materials.
  • lithium-ion batteries are designed for large-scale energy storage equipment with their high energy density and flexible process design. Powered vehicle power supply system.
  • the endurance of lithium-ion electric vehicles is far from meeting the actual needs.
  • the lithium-rich material Compared with the conventional LiCoO 2 and LiFePO 4 , the lithium-rich material has a higher specific capacity, but its rate performance is poor, which cannot meet the requirements of high power density.
  • surface coating is the main means of surface modification.
  • electrochemically active phosphates FePO 4 , AlPO 4 , etc.
  • spinel-type lithium manganate carbon (graphene, carbon nanotubes, acetylene black, etc.) are the main coating materials for improving the rate performance; If a uniform coating structure is formed, it is often necessary to precisely control the reaction rate, and the controllability of the operation is weak. Therefore, it is necessary to find a surface modification technology with strong controllability, easy operation and surface modification originating from in-situ phase transition.
  • the invention aims to provide a lithium-rich layered cathode material with a surface modification of a composite phase induced by a reducing ionic group to induce surface spinel transformation, and a preparation method thereof, the method has the advantages that the amount of the modification material is small, the process operation is simple, and the structure can be The controllability is strong, and the composite modified lithium-rich layered cathode material has better electrochemical performance.
  • the present invention has been achieved by the following technical solutions.
  • a lithium-rich layered cathode material modified by an ionic group-inducing composite phase characterized in that the composition of the lithium-rich layered cathode material is that the inner layer is a lithium-rich layered cathode material having a particle diameter of 50 to 200 nm, and the outer layer is thin
  • the layer is a sulfate-substituted molybdenum oxide, and the spinel phase region formed by the in-situ reaction of the lithium-rich phase Li 2 MnO 3 on the surface of the thiomolybdate and the lithium-rich layered cathode material between the inner layer and the outer layer
  • an intermediate layer composed of a composite phase region the outer thin layer has a thickness of less than 5 nm, and the intermediate layer has a thickness of 10 to 30 nm.
  • the preparation method of the above composite phase modified lithium-rich layered cathode material comprises the following steps:
  • Ni(CH 3 COO) 2 ⁇ 4H 2 O, Co(CH 3 COO) 2 ⁇ 4H 2 O, Mn(CH 3 COO) 2 ⁇ 4H 2 O and LiCH 3 COO are metal ions.
  • the molar ratio is 0.13:0.13:0.54:(1.21 ⁇ 1.25) dissolved in deionized water, and the solution with the total metal ion concentration of 0.5-2.5mol/L is recorded as solution A; the citric acid is dissolved in deionized water.
  • solution B A solution prepared to a concentration of 0.5 to 2.0 mol/L is referred to as solution B, and the ratio of the amount of nickel ions in the citric acid to the solution A is (0.8 to 1.2): 0.13; the solution B is added dropwise to the solution.
  • solution A add ammonia water to adjust the pH value of the mixed solution to 7.1-7.8, and then put the mixed solution in a constant temperature water bath at 80 ° C for 4-7 hours to obtain a semi-gel, and dry the semi-gel at 100-120 ° C for 12 ⁇ After 24h, a dry gel was obtained, placed in a box furnace, heated to 450-500 ° C at a rate of 5 ⁇ 10 ° C / min, and kept for 3 ⁇ 5 h.
  • the powder obtained after cooling to room temperature was placed in a tube furnace. In an air atmosphere, the temperature is raised to 800 ° C at a rate of 5 to 10 ° C / min, and the temperature is maintained for 16 to 20 hours, and cooled to room temperature to obtain a lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 ;
  • step 3 a mass fraction of 40 ⁇ 48% aqueous solution of ammonium sulfide is added dropwise to the suspension obtained in step 2), wherein the volume ratio of ammonium sulfide solution to suspension is (0.8 ⁇ 1.2): 100, stirred for 12 ⁇ 24h; After suction filtration and drying, the obtained powder was placed in a tube furnace, kept at 300-400 ° C for 1 h, and cooled to room temperature to obtain a composite phase-modified Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 .
  • the invention has the following advantages and effects: the preparation process is simple, and the thiomolybdate which induces the surface spinel phase transformation is an ionic group, and is sufficiently contacted with the surface of the primary particle of the lithium-rich material in the aqueous solution, thereby avoiding the heterogeneous reducing agent. The problem of spontaneously dispersing uniformly on the surface of lithium-rich material particles.
  • the prepared composite phase modified lithium-rich layered cathode material, the sulfate-doped molybdenum oxide layer is uniformly coated on the primary particle surface of the lithium-rich layered cathode material as a physical protective layer; the thiomolybdate and the primary particles are The surface reaction produces a spinel phase region and a transition phase region to form a good ion transport layer.
  • the composite phase structure of the double layer (physical protective layer and in-situ spinel phase transition layer) enables the material to exhibit excellent capacity retention while the rate performance is improved and the large current density charge and discharge cycle test.
  • Example 1 is a scanning electron micrograph of a lithium-rich layered cathode material prepared by a composite phase in Example 1 of the present invention.
  • Example 2 is a high resolution transmission electron micrograph of the surface of a composite phase-modified lithium-rich layered positive electrode material prepared in Example 1 of the present invention.
  • Example 3 is a diagram showing the element distribution of the surface of a composite phase-modified lithium-rich layered positive electrode material prepared in Example 1 of the present invention.
  • Example 4 is an X-ray diffraction contrast map of Example 1 and a blank sample of the present invention.
  • Fig. 5 is a graph showing the rate performance curve of the lithium-rich layered cathode material prepared by the composite phase in the first embodiment of the present invention.
  • Example 6 is a comparison diagram of cycle performance of a composite phase-modified lithium-rich layered cathode material and a blank sample at different current densities according to Example 1 of the present invention.
  • the liquid was transferred to the crucible. Dry at 120 ° C for 24 h, placed in a box furnace, heated to 480 ° C at a rate of 10 ° C / min, held for 2 h, pre-sintered powder was placed in a tube furnace, air atmosphere, at a rate of 10 ° C / min The temperature was raised to 800 ° C, and the temperature was kept for 20 hours. Immediately after the end of the heat preservation phase, it was taken out and rapidly cooled in room temperature air to obtain a lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 .
  • step 2 0.11g of ammonium molybdate tetrahydrate was dissolved in 60mL of deionized water, and the obtained Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 obtained in step 1) was weighed and added to the aqueous ammonium molybdate solution, and ultrasonicated for 10 minutes, and stirred;
  • step 3 0.05mL ammonium sulfide solution was added dropwise to the suspension obtained in step 2), stirred for 12h; suction filtration, drying, the obtained powder was placed in a tube furnace, at an air atmosphere, at a rate of 10 ° C / min The temperature was raised to 400 ° C, and the temperature was kept at 400 ° C for 1 h, and cooled to room temperature to obtain a composite phase-modified Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 .
  • the lithium-rich layered cathode material modified by the above-mentioned process, acetylene black, and polyvinylidene fluoride is dissolved in N-methylpyrrolidone at a mass ratio of 8:1:1, mechanically stirred.
  • the slurry was prepared in 3 to 5 hours, coated on an aluminum foil with a dough blade, and dried under vacuum at 80 ° C for 24 hours.
  • step 3 0.04mL ammonium sulfide solution was added dropwise to the suspension obtained in step 2), stirred for 12h; suction filtration, drying, the obtained powder was placed in a tube furnace, at an air atmosphere, at a rate of 10 ° C / min The temperature was raised to 350 ° C, and the temperature was kept at 350 ° C for 1 h, and cooled to room temperature to obtain a composite phase-modified Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 .
  • step 3 0.05mL ammonium sulfide solution was added dropwise to the suspension obtained in step 2), stirred for 12h; suction filtration, drying, the obtained powder was placed in a tube furnace, at an air atmosphere, at a rate of 10 ° C / min The temperature was raised to 350 ° C, and the temperature was kept at 350 ° C for 1 h, and cooled to room temperature to obtain a composite phase-modified Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 .

Abstract

The present invention relates to an ionic group induced compound phase modified lithium-rich layered cathode material. The lithium-rich layered cathode material is composed of an inner layer, which is a lithium-rich layered cathode material of which the particle diameter is 50-200 nm; an outer thin layer, which is molybdenum oxide partially replaced with sulfate radicals; and an intermediate layer, arranged between the inner layer and the outer thin film, formed by an in-situ reaction between sulfo-molybdate radicals and lithium-rich phase Li2MnO3 on the surface of the lithium-rich layered cathode material, and formed by a spinel phase zone and a compound phase zone. The thickness of the outer thin layer is less than 5 nm, and the thickness of the intermediate layer is 10-30 nm. The present invention further provides a preparation method for the cathode material. The present invention is less in using amount of modification materials, simple in technological operation, and strong in structure controllability, and the prepared lithium-rich layered cathode material in compound modification has better electrochemical performance.

Description

离子基团诱导复合相修饰的富锂层状正极材料及制备方法Lithium group-inducing composite phase modified lithium-rich layered cathode material and preparation method thereof 技术领域Technical field
本发明涉及一种还原性离子基团诱导表面尖晶石转变的富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2及制备方法，属于纳米复合材料的制备技术。The invention relates to a lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 with reduced ionic group induced surface spinel transformation and a preparation method thereof, and belongs to the preparation technology of nano composite materials.
背景技术Background technique
绿色清洁能源及其能量转换装置正在逐步取代不可再生能源及动力***，在这场能源变革中，锂离子电池以其较高的能量密度和灵活的工艺设计，被应用于大型电网储能设备、动力汽车供能***中。然而，锂离子电动汽车的续航能力，远远不能满足实际需要，主要制约因素之一是锂离子电池正极材料本身的比容量较低。因此，一种理论比容量较高的正极材料——富锂层状正极材料Li2MnO3·LiMO2(M＝Co、Ni、Mn、Fe、Ru…)——受到研究者的高度重视。相对于传统的LiCoO2和LiFePO4，富锂材料虽然比容量较高，然而其倍率性能较差，无法满足高功率密度的要求。为了解决这一问题，人们试图通过表面修饰来提高富锂材料的电导率，其中，表面包覆是表面修饰的主要手段。目前，具有电化学活性的磷酸盐(FePO4,AlPO4等)、尖晶石型锰酸锂、碳(石墨烯、碳管、乙炔黑等)成为提高倍率性能的主要包覆材料；上述材料若形成均匀包覆结构，往往需要精确地控制反应速率，操作的可控性较弱。所以，有必要寻找一种可控性强，操作简易且表面修饰相源于原位相转变的表面改性技术。Green clean energy and its energy conversion devices are gradually replacing non-renewable energy and power systems. In this energy revolution, lithium-ion batteries are designed for large-scale energy storage equipment with their high energy density and flexible process design. Powered vehicle power supply system. However, the endurance of lithium-ion electric vehicles is far from meeting the actual needs. One of the main constraints is that the specific capacity of lithium-ion battery cathode materials is low. Therefore, a cathode material with a higher specific capacity than the lithium-rich layered cathode material Li 2 MnO 3 ·LiMO 2 (M=Co, Ni, Mn, Fe, Ru...) has been highly valued by researchers. Compared with the conventional LiCoO 2 and LiFePO 4 , the lithium-rich material has a higher specific capacity, but its rate performance is poor, which cannot meet the requirements of high power density. In order to solve this problem, attempts have been made to improve the electrical conductivity of lithium-rich materials by surface modification, wherein surface coating is the main means of surface modification. At present, electrochemically active phosphates (FePO 4 , AlPO 4 , etc.), spinel-type lithium manganate, carbon (graphene, carbon nanotubes, acetylene black, etc.) are the main coating materials for improving the rate performance; If a uniform coating structure is formed, it is often necessary to precisely control the reaction rate, and the controllability of the operation is weak. Therefore, it is necessary to find a surface modification technology with strong controllability, easy operation and surface modification originating from in-situ phase transition.
发明内容Summary of the invention
本发明目的在于提供一种还原性离子基团诱导表面尖晶石转变的复合相表面修饰的富锂层状正极材料及制备方法，该方法优势在于修饰材料使用量少，工艺操作简单，结构可控性强，并且制得的复合修饰的富锂层状正极材料具有更好的电化学性能。The invention aims to provide a lithium-rich layered cathode material with a surface modification of a composite phase induced by a reducing ionic group to induce surface spinel transformation, and a preparation method thereof, the method has the advantages that the amount of the modification material is small, the process operation is simple, and the structure can be The controllability is strong, and the composite modified lithium-rich layered cathode material has better electrochemical performance.
本发明是通过以下技术方案实现的。The present invention has been achieved by the following technical solutions.
一种离子基团诱导复合相修饰的富锂层状正极材料，其特征在于，该富锂层状正极材料的组成是，内层为粒径50～200nm的富锂层状正极材料，外薄层为硫酸根部分取代的氧化钼，在内层与外薄层之间为硫代钼酸根和富锂层状正极材料表面的富锂相Li2MnO3原位反应生成的尖晶石相区和复合相区组成的中间层；外薄层厚度小于5nm，中间层厚度为10～30nm。A lithium-rich layered cathode material modified by an ionic group-inducing composite phase, characterized in that the composition of the lithium-rich layered cathode material is that the inner layer is a lithium-rich layered cathode material having a particle diameter of 50 to 200 nm, and the outer layer is thin The layer is a sulfate-substituted molybdenum oxide, and the spinel phase region formed by the in-situ reaction of the lithium-rich phase Li 2 MnO 3 on the surface of the thiomolybdate and the lithium-rich layered cathode material between the inner layer and the outer layer And an intermediate layer composed of a composite phase region; the outer thin layer has a thickness of less than 5 nm, and the intermediate layer has a thickness of 10 to 30 nm.
上述复合相修饰的富锂层状正极材料的制备方法，包括以下步骤：The preparation method of the above composite phase modified lithium-rich layered cathode material comprises the following steps:
1)溶胶凝胶法制备富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2 1) Preparation of lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 by sol-gel method
在机械搅拌下，首先将Ni(CH3COO)2·4H2O、Co(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O和LiCH3COO按金属离子的摩尔比依次为0.13:0.13:0.54:(1.21～1.25)溶解于去离子水中，配成金属总离子浓度为0.5～2.5mol/L的溶液记作溶液A；将柠檬酸溶解于去离子水中，配制成 浓度为0.5～2.0mol/L的溶液记作溶液B，且柠檬酸与A溶液中镍离子的物质的量之比为(0.8～1.2):0.13；将溶液B逐滴逐滴加入到溶液A中，并滴加氨水调节混合溶液pH值为7.1～7.8，之后将混合溶液置于80℃恒温水浴反应4～7h，得到半凝胶，将半凝胶在100～120℃干燥12～24h，得到干凝胶，置于箱式炉中，以5～10℃/min的速率升温至450～500℃，保温3～5h，冷却至室温后得到的粉末再置于管式炉，在空气气氛中，以5～10℃/min的速率升温至800℃，保温16～20h，冷却至室温得到富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2；Under mechanical agitation, firstly, Ni(CH 3 COO) 2 · 4H 2 O, Co(CH 3 COO) 2 · 4H 2 O, Mn(CH 3 COO) 2 · 4H 2 O and LiCH 3 COO are metal ions. The molar ratio is 0.13:0.13:0.54:(1.21~1.25) dissolved in deionized water, and the solution with the total metal ion concentration of 0.5-2.5mol/L is recorded as solution A; the citric acid is dissolved in deionized water. A solution prepared to a concentration of 0.5 to 2.0 mol/L is referred to as solution B, and the ratio of the amount of nickel ions in the citric acid to the solution A is (0.8 to 1.2): 0.13; the solution B is added dropwise to the solution. In solution A, add ammonia water to adjust the pH value of the mixed solution to 7.1-7.8, and then put the mixed solution in a constant temperature water bath at 80 ° C for 4-7 hours to obtain a semi-gel, and dry the semi-gel at 100-120 ° C for 12~ After 24h, a dry gel was obtained, placed in a box furnace, heated to 450-500 ° C at a rate of 5 ~ 10 ° C / min, and kept for 3 ~ 5 h. The powder obtained after cooling to room temperature was placed in a tube furnace. In an air atmosphere, the temperature is raised to 800 ° C at a rate of 5 to 10 ° C / min, and the temperature is maintained for 16 to 20 hours, and cooled to room temperature to obtain a lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 ;
2)将四水合钼酸铵溶解在去离子水中，配制成2～2.5g·L-1的钼酸铵水溶液，按照Li1.2Co0.13Ni0.13Mn0.54O2与四水合钼酸铵的质量比为(4～6):1，将步骤1)所得Li1.2Co0.13Ni0.13Mn0.54O2加入到该钼酸铵水溶液中，充分超声5～10min，钼酸铵与Li1.2Co0.13Ni0.13Mn0.54O2一次颗粒表面充分接触；2) Dissolving ammonium molybdate tetrahydrate in deionized water to prepare an aqueous solution of ammonium molybdate of 2 to 2.5 g·L -1 according to the mass ratio of Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 to ammonium molybdate tetrahydrate For (4-6): 1, the Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 obtained in the step 1) is added to the aqueous ammonium molybdate solution, and fully ultrasonicated for 5 to 10 minutes, ammonium molybdate and Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 primary particle surface is in full contact;
3)将质量分数为40～48％硫化铵水溶液滴加到步骤2)所得的悬浊液中，其中硫化铵溶液与悬浊液体积比为(0.8～1.2):100，搅拌12～24h；抽滤，烘干，所得粉末置于管式炉中，在300～400℃保温1h，冷却至室温得到复合相修饰的Li1.2Co0.13Ni0.13Mn0.54O2。3) a mass fraction of 40 ~ 48% aqueous solution of ammonium sulfide is added dropwise to the suspension obtained in step 2), wherein the volume ratio of ammonium sulfide solution to suspension is (0.8 ~ 1.2): 100, stirred for 12 ~ 24h; After suction filtration and drying, the obtained powder was placed in a tube furnace, kept at 300-400 ° C for 1 h, and cooled to room temperature to obtain a composite phase-modified Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 .
本发明具有以下优点和效果：制备工艺步骤简单，诱导表面尖晶石相转变的硫代钼酸根是离子基团，在水溶液中与富锂材料一次颗粒表面充分接触，避免了异质还原剂无法自发均匀分散在富锂材料颗粒表面的问题。所制备的复合相修饰的富锂层状正极材料，硫酸根掺杂的氧化钼层均匀包覆在富锂层状正极材料的一次颗粒表面，作为物理保护层；由硫代钼酸根和一次颗粒表面反应生成尖晶石相区和过渡相区构成良好的离子传输层。双层(物理保护层和原位尖晶石相转变层)的复合相结构，使得材料在倍率性能提升的同时，较大电流密度充放电循环测试表现出优良的容量保持率。The invention has the following advantages and effects: the preparation process is simple, and the thiomolybdate which induces the surface spinel phase transformation is an ionic group, and is sufficiently contacted with the surface of the primary particle of the lithium-rich material in the aqueous solution, thereby avoiding the heterogeneous reducing agent. The problem of spontaneously dispersing uniformly on the surface of lithium-rich material particles. The prepared composite phase modified lithium-rich layered cathode material, the sulfate-doped molybdenum oxide layer is uniformly coated on the primary particle surface of the lithium-rich layered cathode material as a physical protective layer; the thiomolybdate and the primary particles are The surface reaction produces a spinel phase region and a transition phase region to form a good ion transport layer. The composite phase structure of the double layer (physical protective layer and in-situ spinel phase transition layer) enables the material to exhibit excellent capacity retention while the rate performance is improved and the large current density charge and discharge cycle test.
附图说明DRAWINGS
图1为本发明实施例1制得复合相修饰的富锂层状正极材料的扫描电镜照片。1 is a scanning electron micrograph of a lithium-rich layered cathode material prepared by a composite phase in Example 1 of the present invention.
图2为本发明实施例1制得复合相修饰的富锂层状正极材料的表界面的高分辨透射电镜照片。2 is a high resolution transmission electron micrograph of the surface of a composite phase-modified lithium-rich layered positive electrode material prepared in Example 1 of the present invention.
图3为本发明实施例1制得复合相修饰的富锂层状正极材料的表界面的元素分布图。3 is a diagram showing the element distribution of the surface of a composite phase-modified lithium-rich layered positive electrode material prepared in Example 1 of the present invention.
图4为本发明实施例1和空白样品的X射线衍射对比图谱。4 is an X-ray diffraction contrast map of Example 1 and a blank sample of the present invention.
图5为本发明实施例1制得复合相修饰的富锂层状正极材料的倍率性能曲线。Fig. 5 is a graph showing the rate performance curve of the lithium-rich layered cathode material prepared by the composite phase in the first embodiment of the present invention.
图6为本发明实施例1制得复合相修饰的富锂层状正极材料与空白样品在不同电流密度下的循环性能对比图。6 is a comparison diagram of cycle performance of a composite phase-modified lithium-rich layered cathode material and a blank sample at different current densities according to Example 1 of the present invention.
具体实施方式detailed description
下面结合实施例对本发明作进一步描述，这些实施例只是用于说明本发明，并不限制本发明。 The invention is further described in the following examples, which are intended to illustrate the invention and not to limit the invention.
实施例1：Example 1:
1)称取1.6887g Ni(CH3COO)2·4H2O，1.6647g Co(CH3COO)2·4H2O，6.6100g Mn(CH3COO)2·4H2O和6.3067g LiCH3COO溶解在100mL去离子水中，记作溶液A；将10.5598g柠檬酸溶解在60mL去离子水中，记作溶液B。溶液B逐滴加入到溶液A中，持续搅拌15min，滴加氨水调节体系pH值为7.5，继续搅拌15min后，80℃恒温水浴4～5h，得到深紫色粘稠液，该液体转移至坩埚中，在120℃干燥24h，置于箱式炉中，以10℃/min的速率升温至480℃，保温2h，预烧结所得粉末置于在管式炉，空气气氛，以10℃/min的速率升温至800℃，保温20h，保温阶段结束后立即取出在室温空气中快速冷却，得到富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2。1) Weigh 1.6887g Ni(CH 3 COO) 2 ·4H 2 O, 1.6647g Co(CH 3 COO) 2 ·4H 2 O, 6.6100g Mn(CH 3 COO) 2 ·4H 2 O and 6.3067g LiCH 3 COO was dissolved in 100 mL of deionized water and designated as Solution A; 10.5598 g of citric acid was dissolved in 60 mL of deionized water and designated as Solution B. Solution B was added dropwise to Solution A, stirring was continued for 15 min, and the pH of the ammonia solution was adjusted to 7.5. After stirring for 15 minutes, the water bath was heated at 80 ° C for 4 to 5 hours to obtain a deep purple viscous liquid. The liquid was transferred to the crucible. Dry at 120 ° C for 24 h, placed in a box furnace, heated to 480 ° C at a rate of 10 ° C / min, held for 2 h, pre-sintered powder was placed in a tube furnace, air atmosphere, at a rate of 10 ° C / min The temperature was raised to 800 ° C, and the temperature was kept for 20 hours. Immediately after the end of the heat preservation phase, it was taken out and rapidly cooled in room temperature air to obtain a lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 .
2)将0.11g四水合钼酸铵溶解在60mL去离子水中，步骤1)所得Li1.2Co0.13Ni0.13Mn0.54O2称取0.5g加入到该钼酸铵水溶液中，超声10min，搅拌；2) 0.11g of ammonium molybdate tetrahydrate was dissolved in 60mL of deionized water, and the obtained Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 obtained in step 1) was weighed and added to the aqueous ammonium molybdate solution, and ultrasonicated for 10 minutes, and stirred;
3)将0.05mL硫化铵溶液滴加到步骤2)所得的悬浊液中，搅拌12h；抽滤，烘干，所得粉末置于管式炉中，空气气氛下，以10℃/min的速率升温至400℃，在400℃保温1h，冷却至室温得到复合相修饰的Li1.2Co0.13Ni0.13Mn0.54O2。3) 0.05mL ammonium sulfide solution was added dropwise to the suspension obtained in step 2), stirred for 12h; suction filtration, drying, the obtained powder was placed in a tube furnace, at an air atmosphere, at a rate of 10 ° C / min The temperature was raised to 400 ° C, and the temperature was kept at 400 ° C for 1 h, and cooled to room temperature to obtain a composite phase-modified Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 .
将上述过程制得的复合相表面修饰的富锂层状正极材料、乙炔黑、聚偏四氟乙烯，按照质量比为8:1:1的质量比溶解在N-甲基吡咯烷酮中，机械搅拌3～5h制成浆料，用工字刮刀涂敷于铝箔上，80℃真空干燥24h。将极片冲切成直径为12mm的圆片，以其为工作电极，以金属埋箔为对电极，隔膜采用Celgard 2325隔膜纸，电解液采用1mol/L的LiPF6的EC:EMC:DEC＝1:1:1(体积比)溶液，在手套箱组装电池。在LANDt电池测试***进行循环和倍率性能测试，性能曲线见图5和图6。The lithium-rich layered cathode material modified by the above-mentioned process, acetylene black, and polyvinylidene fluoride is dissolved in N-methylpyrrolidone at a mass ratio of 8:1:1, mechanically stirred. The slurry was prepared in 3 to 5 hours, coated on an aluminum foil with a dough blade, and dried under vacuum at 80 ° C for 24 hours. The pole piece was die-cut into a 12 mm diameter disc, which was used as the working electrode, with the metal buried foil as the counter electrode, the diaphragm using Celgard 2325 diaphragm paper, and the electrolyte using 1 mol/L LiPF 6 EC: EMC: DEC = 1:1:1 (volume ratio) solution, assemble the battery in the glove box. Cycle and rate performance tests were performed on the LANDt battery test system. The performance curves are shown in Figures 5 and 6.
实施例2：Example 2:
1)至2)步骤与实施例1相同。The steps 1) to 2) are the same as in the first embodiment.
3)将0.04mL硫化铵溶液滴加到步骤2)所得的悬浊液中，搅拌12h；抽滤，烘干，所得粉末置于管式炉中，空气气氛下，以10℃/min的速率升温至350℃，在350℃保温1h，冷却至室温得到复合相修饰的Li1.2Co0.13Ni0.13Mn0.54O2。3) 0.04mL ammonium sulfide solution was added dropwise to the suspension obtained in step 2), stirred for 12h; suction filtration, drying, the obtained powder was placed in a tube furnace, at an air atmosphere, at a rate of 10 ° C / min The temperature was raised to 350 ° C, and the temperature was kept at 350 ° C for 1 h, and cooled to room temperature to obtain a composite phase-modified Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 .
实施例3：Example 3:
1)至2)步骤与实施例1相同。The steps 1) to 2) are the same as in the first embodiment.
3)将0.05mL硫化铵溶液滴加到步骤2)所得的悬浊液中，搅拌12h；抽滤，烘干，所得粉末置于管式炉中，空气气氛下，以10℃/min的速率升温至350℃，在350℃保温1h，冷却至室温得到复合相修饰的Li1.2Co0.13Ni0.13Mn0.54O2。3) 0.05mL ammonium sulfide solution was added dropwise to the suspension obtained in step 2), stirred for 12h; suction filtration, drying, the obtained powder was placed in a tube furnace, at an air atmosphere, at a rate of 10 ° C / min The temperature was raised to 350 ° C, and the temperature was kept at 350 ° C for 1 h, and cooled to room temperature to obtain a composite phase-modified Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 .
空白样品：Blank sample:
称取1.6887g Ni(CH3COO)2·4H2O，1.6647g Co(CH3COO)2·4H2O，6.6100g  Mn(CH3COO)2·4H2O和6.3067g LiCH3COO溶解在100mL去离子水中，记作溶液A；将10.5598g柠檬酸溶解在60mL去离子水中，记作溶液B。溶液B逐滴加入到溶液A中，持续搅拌15min，滴加氨水调节体系pH值为7.5，继续搅拌15min后，80℃恒温水浴4～5h，得到深紫色粘稠液，该液体转移至坩埚中，在120℃干燥24h，置于箱式炉中，以10℃/min的速率升温至480℃，保温2h，预烧结所得粉末置于在管式炉，空气气氛，以10℃/min的速率升温至800℃，保温20h，保温阶段结束后立即取出在室温空气中快速冷却，得到富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2，即为空白样品。 1.6887g Ni(CH 3 COO) 2 ·4H 2 O, 1.6647g Co(CH 3 COO) 2 ·4H 2 O, 6.6100g Mn(CH 3 COO) 2 ·4H 2 O and 6.3067g LiCH 3 COO were dissolved In 100 mL of deionized water, it was recorded as solution A; 10.5598 g of citric acid was dissolved in 60 mL of deionized water and recorded as solution B. Solution B was added dropwise to Solution A, stirring was continued for 15 min, and the pH of the ammonia solution was adjusted to 7.5. After stirring for 15 minutes, the water bath was heated at 80 ° C for 4 to 5 hours to obtain a deep purple viscous liquid. The liquid was transferred to the crucible. Dry at 120 ° C for 24 h, placed in a box furnace, heated to 480 ° C at a rate of 10 ° C / min, held for 2 h, pre-sintered powder was placed in a tube furnace, air atmosphere, at a rate of 10 ° C / min The temperature was raised to 800 ° C, and the temperature was kept for 20 hours. Immediately after the end of the heat preservation phase, it was taken out and rapidly cooled in room temperature air to obtain a lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 , which was a blank sample.

Claims (2)

  1. 一种离子基团诱导复合相修饰的富锂层状正极材料，其特征在于，该富锂层状正极材料的组成是，内层为粒径50～200nm的富锂层状正极材料，外薄层为硫酸根部分取代的氧化钼，在内层与外薄层之间为硫代钼酸根和富锂层状正极材料表面的富锂相Li2MnO3原位反应生成的尖晶石相区和复合相区组成的中间层；外薄层厚度小于5nm，中间层厚度为10～30nm。A lithium-rich layered cathode material modified by an ionic group-inducing composite phase, characterized in that the composition of the lithium-rich layered cathode material is that the inner layer is a lithium-rich layered cathode material having a particle diameter of 50 to 200 nm, and the outer layer is thin The layer is a sulfate-substituted molybdenum oxide, and the spinel phase region formed by the in-situ reaction of the lithium-rich phase Li 2 MnO 3 on the surface of the thiomolybdate and the lithium-rich layered cathode material between the inner layer and the outer layer And an intermediate layer composed of a composite phase region; the outer thin layer has a thickness of less than 5 nm, and the intermediate layer has a thickness of 10 to 30 nm.
  2. 一种离子基团诱导复合相修饰的富锂层状正极材料的制备方法，包括以下步骤：A method for preparing a lithium-rich layered cathode material modified by an ionic group-inducing composite phase comprises the following steps:
    1)溶胶凝胶法制备富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2 1) Preparation of lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 by sol-gel method
    在机械搅拌下，首先将Ni(CH3COO)2·4H2O、Co(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O和LiCH3COO按金属离子的摩尔比依次为0.13:0.13:0.54:(1.21～1.25)溶解于去离子水中，配成金属总离子浓度为0.5～2.5mol/L的溶液记作溶液A；将柠檬酸溶解于去离子水中，配制成浓度为0.5～2.0mol/L的溶液记作溶液B，且柠檬酸与A溶液中镍离子的物质的量之比为(0.8～1.2):0.13；将溶液B逐滴逐滴加入到溶液A中，并滴加氨水调节混合溶液pH值为7.1～7.8，之后将混合溶液置于80℃恒温水浴反应4～7h，得到半凝胶，将半凝胶在100～120℃干燥12～24h，得到干凝胶，置于箱式炉中，以5～10℃/min的速率升温至450～500℃，保温3～5h，冷却至室温后得到的粉末再置于管式炉，在空气气氛中，以5～10℃/min的速率升温至800℃，保温16～20h，冷却至室温得到富锂层状正极材料Li1.2Mn0.54Ni0.13Co0.13O2；Under mechanical agitation, firstly, Ni(CH 3 COO) 2 · 4H 2 O, Co(CH 3 COO) 2 · 4H 2 O, Mn(CH 3 COO) 2 · 4H 2 O and LiCH 3 COO are metal ions. The molar ratio is 0.13:0.13:0.54:(1.21~1.25) dissolved in deionized water, and the solution with the total metal ion concentration of 0.5-2.5mol/L is recorded as solution A; the citric acid is dissolved in deionized water. A solution prepared to a concentration of 0.5 to 2.0 mol/L is referred to as solution B, and the ratio of the amount of nickel ions in the citric acid to the solution A is (0.8 to 1.2): 0.13; the solution B is added dropwise to the solution. In solution A, add ammonia water to adjust the pH value of the mixed solution to 7.1-7.8, and then put the mixed solution in a constant temperature water bath at 80 ° C for 4-7 hours to obtain a semi-gel, and dry the semi-gel at 100-120 ° C for 12~ After 24h, a dry gel was obtained, placed in a box furnace, heated to 450-500 ° C at a rate of 5 ~ 10 ° C / min, and kept for 3 ~ 5 h. The powder obtained after cooling to room temperature was placed in a tube furnace. In an air atmosphere, the temperature is raised to 800 ° C at a rate of 5 to 10 ° C / min, and the temperature is maintained for 16 to 20 hours, and cooled to room temperature to obtain a lithium-rich layered cathode material Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 ;
    2)将四水合钼酸铵溶解在去离子水中，配制成2～2.5g·L-1的钼酸铵水溶液，按照Li1.2Co0.13Ni0.13Mn0.54O2与四水合钼酸铵的质量比为(4～6):1，将步骤1)所得Li1.2Co0.13Ni0.13Mn0.54O2加入到该钼酸铵水溶液中，充分超声5～10min，钼酸铵与Li1.2Co0.13Ni0.13Mn0.54O2一次颗粒表面充分接触；2) Dissolving ammonium molybdate tetrahydrate in deionized water to prepare an aqueous solution of ammonium molybdate of 2 to 2.5 g·L -1 according to the mass ratio of Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 to ammonium molybdate tetrahydrate For (4-6): 1, the Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 obtained in the step 1) is added to the aqueous ammonium molybdate solution, and fully ultrasonicated for 5 to 10 minutes, ammonium molybdate and Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 primary particle surface is in full contact;
    3)将质量分数为40～48％硫化铵水溶液滴加到步骤2)所得的悬浊液中，其中硫化铵溶液与悬浊液体积比为(0.8～1.2):100，搅拌12～24h；抽滤，烘干，所得粉末置于管式炉中，在300～400℃保温1h，冷却至室温得到复合相修饰的Li1.2Co0.13Ni0.13Mn0.54O2。 3) a mass fraction of 40 ~ 48% aqueous solution of ammonium sulfide is added dropwise to the suspension obtained in step 2), wherein the volume ratio of ammonium sulfide solution to suspension is (0.8 ~ 1.2): 100, stirred for 12 ~ 24h; After suction filtration and drying, the obtained powder was placed in a tube furnace, kept at 300-400 ° C for 1 h, and cooled to room temperature to obtain a composite phase-modified Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 .
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