WO2019192171A1 - Nickel-manganese binary oxide-based potassium ion battery positive electrode material and preparation method therefor - Google Patents

Nickel-manganese binary oxide-based potassium ion battery positive electrode material and preparation method therefor Download PDF

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WO2019192171A1
WO2019192171A1 PCT/CN2018/112825 CN2018112825W WO2019192171A1 WO 2019192171 A1 WO2019192171 A1 WO 2019192171A1 CN 2018112825 W CN2018112825 W CN 2018112825W WO 2019192171 A1 WO2019192171 A1 WO 2019192171A1
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nickel
salt
manganese
potassium
organic acid
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廖世军
黄斌
刘燕晨
曾建皇
杜丽
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华南理工大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a cathode material for a potassium ion battery and a preparation method thereof, in particular to a cathode material for a potassium ion battery based on a nickel manganese binary oxide and a preparation method thereof.
  • New secondary batteries such as potassium ion batteries, sodium ion batteries, and magnesium ion batteries have the same chemical reaction principles as lithium ion batteries, and the advantages of rich resources and low prices have attracted the attention of researchers.
  • the potassium ion battery has the standard electrode potential closest to that of the lithium ion battery, and the potassium ion has a large ion migration rate in the electrolyte.
  • research on potassium ion batteries is mostly focused on the preparation of anode materials, and there are few studies on cathode materials.
  • Kuniko Chihara found that a high-temperature calcination method can obtain a KVPO 4 F potassium ion battery cathode material with a discharge platform up to 4V and excellent rate performance, but such materials have a shortage of specific capacity;
  • the present invention provides a novel high performance nickel-manganese binary oxide based potassium ion battery cathode material and a preparation method thereof.
  • the invention comprises the following contents:
  • a preparation method of a potassium ion battery cathode material based on nickel manganese binary oxide comprising the following steps:
  • Preparing a precursor powder containing nickel manganese potassium includes one of the following steps: heating the suspension under vacuum C The precursor powder containing nickel manganese potassium is obtained by evaporation of water; or the suspension C is filtered and dried to obtain a precursor powder;
  • the nickel salt is one or more of nickel nitrate, nickel acetate, nickel sulfate, and nickel chloride
  • the manganese salt is one or more of manganese nitrate, manganese acetate, manganese sulfate, and manganese chloride
  • the potassium salt is one or more of potassium hydroxide, potassium acetate, potassium carbonate, potassium chloride, and potassium citrate
  • the doping element salt is a soluble iron salt, a soluble aluminum salt, a soluble magnesium salt, and a soluble lithium salt.
  • the organic acid is one or more of acetic acid, oxalic acid, and citric acid
  • the organic solvent is one or more of ethanol, acetone, and ethylene glycol; In 1), the volume ratio of the organic solvent to deionized water is 1:1-4.
  • step (2) The organic acid salt is one or more of an acetate, an oxalate, and a citrate; the organic acid is one or more of acetic acid, oxalic acid, and citric acid; the organic solvent and deionized The volume ratio of water is 1:2-6.
  • the mixing method is to add the solution A to the solution B, and the dropping acceleration is 1 to 2 drops/s. Or add solution B to solution A, the drop acceleration is 1 ⁇ 2 drops / s; in step (3), the stirring speed is 200 ⁇ 500 rev / min, and the stirring time is 6 ⁇ 12h .
  • the heating temperature is 60 to 120 °C.
  • the specific operation of the step (5) is: grinding the dried precursor material in an air atmosphere at 300 ⁇ 500 ° C Pre-sintering for 3 ⁇ 6h, then cooling to room temperature for grinding, and finally heating to 700 ⁇ 1000 °C for 8 ⁇ 20h.
  • a preparation method of a potassium ion battery cathode material based on nickel manganese binary oxide comprising the steps of: adding an organic acid salt containing nickel manganese potassium according to a nickel manganese potassium molar ratio of 0.1-0.5: 0.5-0.9: 0.4-1.2
  • the ratio of the ball mill is mixed to obtain an organic acid salt precursor powder; the obtained organic acid salt precursor powder is ground, pre-sintered at 300-500 ° C for 3-6 hours in an air atmosphere, then cooled to room temperature for grinding, and finally heated to 700 ⁇
  • the positive electrode material is K a X m Ni b Mn c O 2 ( 0.4 ⁇ a ⁇ 1.2, 0 ⁇ m ⁇ 0.1
  • K a X m Ni b Mn c O 2 has the important advantages of high discharge capacity, high discharge platform voltage and good stability, and is a novel potassium ion battery cathode material with application value and prospect. .
  • the method of the invention has the advantages of simple preparation, low production cost, high controllability and large-scale application in industrial production, and has very important practical significance.
  • Figure 1 is an XRD diagram of the positive electrode material of the nickel-manganese binary potassium ion battery
  • FIG. 2 is a cycle performance diagram of the positive electrode material of the nickel-manganese binary potassium ion battery.
  • the obtained powder is pre-sintered at 300 ° C in an air atmosphere (heating rate is 3 ° C / min), then cooled to room temperature and then ground, and calcined at 700 ° C for 8 h (heating rate is 5 ° C / min) to obtain potassium ions.
  • Battery cathode material K 1.20 Ni 0.50 Mn 0.50 O 2 .
  • the assembly process of the button battery mixing the positive electrode material with the binder polyvinylidene fluoride (PVDF) and the conductive agent acetylene black in a ratio of 8:1:1 by mass, and adding the solvent N-methylpyrrolidone (NMP) to stir 4- 6h, the slurry is spread on a clean aluminum foil and placed in a vacuum oven at 80 ° C for use; K 1.20 Ni 0.50 Mn 0.50 O 2 pole piece is used as the positive electrode, potassium plate or graphite is used as the negative electrode, and Whatman GF/D is used.
  • a button battery was assembled using 0.8 mol/L potassium hexafluorophosphate (KPF 6 ) / ethylene carbonate (EC ): dimethyl carbonate (DEC) as an electrolyte.
  • Electrochemical performance test The assembled button battery is subjected to constant current charge and discharge test to detect the first ring capacity and cycle performance of the battery.
  • the test voltage range is 2-4.5 V; Cyclic voltammetry on an electrochemical workstation with a potential sweep range of 2-4.5 V and a scan speed of 0.1 mV/s.
  • Figure 1 shows the XRD pattern of the material
  • Figure 2 shows the charge and discharge curve for the first cycle of the material.
  • the obtained powder is pre-sintered at 500 ° C in an air atmosphere (heating rate is 5 ° C / min), cooled to room temperature and then ground, and calcined at 1000 ° C for 20 h (heating rate is 3 ° C / min) to obtain a potassium ion battery.
  • the positive electrode material K 1.20 Li 0.01 Ni 0.10 Mn 0.90 O 2 was prepared except that an equimolar amount of potassium citrate, magnesium chloride was substituted for potassium hydroxide and ferrous nitrate, and other components were used and prepared in the same manner as in Example 2 .
  • Table 1 is the main performance table of each embodiment.

Abstract

Disclosed in the present invention are a nickel-manganese binary oxide-based potassium ion battery positive electrode material and a preparation method therefor. Said method comprises the following steps: dissolving a nickel salt, a manganese salt, a potassium salt and a doping element salt in deionized water to obtain a metal ion salt solution at a certain concentration; adding the metal ion salt solution to an organic acid or a salt solution and stirring them; heating an organic acid or an organic acid salt precursor suspension to evaporate water until the water is completely evaporated to obtain a precursor powder of organic acid salts; or directly mixing organic acid salts containing nickel/manganese/potassium to obtain a precursor of the organic acid salts; and milling, pre-sintering, and then milling the precursor powder, and calcining same at high temperature to obtain a positive electrode material. The preparation method has operation steps with high controllability, and has low production cost, and scale production is easily carried out.

Description

一种基于镍锰二元氧化物的钾离子电池正极材料及其制备方法 Potassium ion battery cathode material based on nickel manganese binary oxide and preparation method thereof
技术领域Technical field
本发明涉及钾离子电池正极材料及其制备方法，具体涉及一种基于镍锰二元氧化物的钾离子电池正极材料及其制备方法。  The invention relates to a cathode material for a potassium ion battery and a preparation method thereof, in particular to a cathode material for a potassium ion battery based on a nickel manganese binary oxide and a preparation method thereof.
背景技术Background technique
随着经济的快速发展以及工业的急剧扩张，以煤、石油、天然气三大主要能源为代表的化石燃料消耗量激增，这种对不可再生资源的过度开发及使用，加剧了能源短缺和全球环境恶化之间的矛盾，严重制约着人类经济和社会的发展。因此，开发清洁可再生的新能源是今后世界经济中最具决定性影响的技术领域之一。锂离子二次电池作为一种新型、清洁、可再生的能源，具有开路电压高、比能量高、安全性能优越以及环境友好等特点，因此广泛应用于便携式电子设备和电动汽车等领域。但由于锂资源稀缺的储量与高昂的价格严重制约了锂离子电池在大规模储能等方面的应用。因此有必要大力发展下一代综合效能优异的二次电池新体系。 With the rapid development of the economy and the rapid expansion of industry, the consumption of fossil fuels represented by the three main energy sources of coal, oil and natural gas has surged. This overexploitation and use of non-renewable resources has intensified energy shortage and the global environment. The contradiction between the deterioration has seriously restricted the economic and social development of mankind. Therefore, the development of clean and renewable new energy is one of the most decisive technical areas in the world economy in the future. As a new, clean and renewable energy source, lithium ion secondary batteries are widely used in portable electronic equipment and electric vehicles, such as high open circuit voltage, high specific energy, superior safety performance and environmental friendliness. However, the scarcity of lithium resources and high prices have severely restricted the application of lithium-ion batteries in large-scale energy storage. Therefore, it is necessary to vigorously develop a new system of secondary batteries with excellent comprehensive performance.
钾离子电池、钠离子电池、镁离子电池等新型二次电池与锂离子电池具有相同的化学反应原理以及资源丰富、价格便宜等优势备受研究者的关注。其中钾离子电池具有与锂离子电池最为接近的标准电极电势，同时钾离子在电解液中具有较大的离子迁移速率。目前关于钾离子电池的研究多关注于负极材料的制备，而关于正极材料方面的研究较少。 New secondary batteries such as potassium ion batteries, sodium ion batteries, and magnesium ion batteries have the same chemical reaction principles as lithium ion batteries, and the advantages of rich resources and low prices have attracted the attention of researchers. Among them, the potassium ion battery has the standard electrode potential closest to that of the lithium ion battery, and the potassium ion has a large ion migration rate in the electrolyte. At present, research on potassium ion batteries is mostly focused on the preparation of anode materials, and there are few studies on cathode materials.
中国发明专利申请 CN 107226475 A 提出基于普鲁士蓝的钾离子电池正极材料，虽然其容量可达 90.7mAh/g ，循环 400 次，容量保持率在 90.37% ；然而，这种材料存在操作可控性差、难以大规模生产的问题。 Chinese invention patent application CN 107226475 A A Prussian blue based potassium ion battery cathode material is proposed, although its capacity is up to 90.7 mAh/g, cycled 400 times, the capacity retention rate was 90.37%; however, this material has the problem of poor controllability of operation and difficulty in mass production.
中国发明专利申请 CN 107093739 A 提出了基于钾锰氧化物的钾离子电池正极材料，其容量可达 83.9mAh/g ，但是这种材料存在循环性能差、无明显放电平台的不足。 Chinese invention patent application CN 107093739 A A cathode material of potassium ion battery based on potassium manganese oxide is proposed, and its capacity is up to 83.9 mAh / g, but this material has poor cycle performance, no obvious discharge platform.
中国发明专利申请 CN 105826521 A 提出了基于聚阴离子化合物的钾离子电池正极材料，在 1.6V 左右有明显的放电平台，但是这类材料存在能量密度低的问题； Chinese invention patent application CN 105826521 A A cathode material for potassium ion battery based on polyanion compound is proposed at 1.6V There are obvious discharge platforms on the left and right, but such materials have problems of low energy density;
Kuniko Chihara 发现，通过高温焙烧的方法可得到一种 KVPO4F 的钾离子电池正极材料，其具有可达 4V 的放电平台和优异的倍率性能，但是这类材料存在比容量低的不足；Kuniko Chihara found that a high-temperature calcination method can obtain a KVPO 4 F potassium ion battery cathode material with a discharge platform up to 4V and excellent rate performance, but such materials have a shortage of specific capacity;
由于钾离子电池正极材料的研究尚处于起步阶段，目前报道的正极材料的种类十分有限，且这些材料均存在这样或者那样的不足，严重阻碍了钾离子电池的商业化进程，因此，亟待开发新型高性能的钾离子电池正极材料。 Since the research on the cathode material of potassium ion battery is still in its infancy, the types of cathode materials reported so far are very limited, and these materials have such shortcomings, which seriously hinder the commercialization of potassium ion batteries. Therefore, it is urgent to develop new types. High performance potassium ion battery cathode material.
发明内容Summary of the invention
鉴于现有材料存在的不足，本发明提供一种新型高性能的基于镍锰二元氧化物的钾离子电池正极材料及其制备方法。 In view of the deficiencies of existing materials, the present invention provides a novel high performance nickel-manganese binary oxide based potassium ion battery cathode material and a preparation method thereof.
本发明包含如下内容： The invention comprises the following contents:
一种基于镍锰二元氧化物的钾离子电池正极材料，其化学式为： KaXmNibMncO 2 ；其中 0.4≤a≤1.2 ， 0≤m≤0.1 ， 0.1≤b≤0.5 ， 0.5≤c≤0.9 ， b+c=1 ；所述 X 包括 Fe 、 Al 、 Mg 或 Li 。A positive electrode material for potassium ion battery based on nickel manganese binary oxide, the chemical formula is: K a X m Ni b Mn c O 2 ; wherein 0.4 ≤ a ≤ 1.2, 0 ≤ m ≤ 0.1, 0.1 ≤ b ≤ 0.5, 0.5 ≤ c ≤ 0.9, b + c = 1; the X includes Fe, Al, Mg or Li.
一种基于镍锰二元氧化物的钾离子电池正极材料的制备方法，包括如下步骤： A preparation method of a potassium ion battery cathode material based on nickel manganese binary oxide, comprising the following steps:
（ 1 ）将可溶性的镍盐、锰盐、钾盐和掺杂元素盐溶解于有机溶剂与去离子水的混合溶剂中配成溶液 A ； (1) dissolving soluble nickel salt, manganese salt, potassium salt and doping element salt in a mixed solvent of organic solvent and deionized water to form a solution A ;
（ 2 ）将有机酸或者有机酸盐溶解于有机溶剂与去离子水形成的混合溶剂中得到溶液 B ； (2) dissolving an organic acid or an organic acid salt in a mixed solvent of an organic solvent and deionized water to obtain a solution B;
（ 3 ）在搅拌下将溶液 A 加入到溶液 B 中，混合均匀并连续搅拌，得到悬浊液 C ； (3) adding solution A to solution B under stirring, mixing uniformly and continuously stirring to obtain suspension C;
（ 4 ）制备含有镍锰钾的前驱体粉末包括如下步骤之一：真空下加热悬浊液 C 直至蒸干水分得到含有镍锰钾的前驱体粉末；或者将 悬浊液 C 过滤、干燥得到前驱体粉末； (4) Preparing a precursor powder containing nickel manganese potassium includes one of the following steps: heating the suspension under vacuum C The precursor powder containing nickel manganese potassium is obtained by evaporation of water; or the suspension C is filtered and dried to obtain a precursor powder;
（ 5 ）将步骤（ 4 ）得到的有机酸盐前驱体粉末进行研磨，预烧结，研磨，再高温焙烧，即得到化学式为 KaXmNibMncO 2 （ 0.4≤a≤1.2 ， 0≤m≤0.1 ， 0.1≤b≤0.5 ， 0.5≤c≤0.9 ， b+c=1 ）的正极材料。(5) grinding the organic acid salt precursor powder obtained in the step (4), pre-sintering, grinding, and then calcining at a high temperature to obtain a chemical formula of K a X m Ni b Mn c O 2 (0.4 ≤ a ≤ 1.2, 0) A positive electrode material of ≤ m ≤ 0.1, 0.1 ≤ b ≤ 0.5, 0.5 ≤ c ≤ 0.9, b + c = 1).
上述方法中，步骤（ 1 ）中，所述镍盐为硝酸镍、乙酸镍、硫酸镍、氯化镍中的一种以上；所述锰盐为硝酸锰、乙酸锰、硫酸锰、氯化锰中的一种以上；所述钾盐为氢氧化钾、乙酸钾、碳酸钾、氯化钾、柠檬酸钾中的一种以上；所述掺杂元素盐为可溶性铁盐、可溶性铝盐、可溶性镁盐、可溶性锂盐中的一种以上；所述有机酸为乙酸、草酸、柠檬酸中的一种以上；所述有机溶剂为乙醇、丙酮、乙二醇中的一种以上；步骤（ 1 ）中，所述有机溶剂与去离子水的体积比 1:1-4 。 In the above method, the step (1) The nickel salt is one or more of nickel nitrate, nickel acetate, nickel sulfate, and nickel chloride; the manganese salt is one or more of manganese nitrate, manganese acetate, manganese sulfate, and manganese chloride; The potassium salt is one or more of potassium hydroxide, potassium acetate, potassium carbonate, potassium chloride, and potassium citrate; the doping element salt is a soluble iron salt, a soluble aluminum salt, a soluble magnesium salt, and a soluble lithium salt. One or more; the organic acid is one or more of acetic acid, oxalic acid, and citric acid; and the organic solvent is one or more of ethanol, acetone, and ethylene glycol; In 1), the volume ratio of the organic solvent to deionized water is 1:1-4.
上述方法中，步骤（ 2 ）中，所述有机酸盐为乙酸盐、草酸盐、柠檬酸盐中的一种以上；所述有机酸为乙酸、草酸、柠檬酸中的一种以上；所述有机溶剂与去离子水的体积比为 1:2-6 。 In the above method, step (2) The organic acid salt is one or more of an acetate, an oxalate, and a citrate; the organic acid is one or more of acetic acid, oxalic acid, and citric acid; the organic solvent and deionized The volume ratio of water is 1:2-6.
上述方法中，步骤（ 3 ）中，所述混合方法为将溶液 A 滴加到溶液 B 中，滴加速度为 1~2 滴 /s 或者将溶液 B 滴加到溶液 A 中，滴加速度为 1~2 滴 /s ；步骤（ 3 ）中，所述搅拌的转速为 200~500 转 /min ，搅拌时间为 6~12h 。 In the above method, in the step (3), the mixing method is to add the solution A to the solution B, and the dropping acceleration is 1 to 2 drops/s. Or add solution B to solution A, the drop acceleration is 1~2 drops / s; in step (3), the stirring speed is 200~500 rev / min, and the stirring time is 6~12h .
上述方法中，步骤（ 4 ）中，所述加热的温度为 60~120℃ 。 In the above method, in the step (4), the heating temperature is 60 to 120 °C.
上述方法中，步骤（ 5 ）的具体操作为：将干燥后的前驱体材料进行研磨，在空气气氛中 300~500℃ 预烧结 3~6h ，然后冷却至室温进行研磨，最后升温到 700~1000℃ 焙烧 8~20h 。 In the above method, the specific operation of the step (5) is: grinding the dried precursor material in an air atmosphere at 300~500 ° C Pre-sintering for 3~6h, then cooling to room temperature for grinding, and finally heating to 700~1000 °C for 8~20h.
一种基于镍锰二元氧化物的钾离子电池正极材料的制备方法，包括如下步骤：将含有镍锰钾的有机酸盐按照镍锰钾摩尔比为 0.1-0.5:0.5-0.9:0.4-1.2 的比例球磨混合得到有机酸盐前驱体粉末；将所得的有机酸盐前驱体粉末进行研磨，在空气气氛中 300~500℃ 预烧结 3~6h ，然后冷却至室温进行研磨，最后升温到 700~1000℃ 焙烧 8~20h ，即得到化学式为 KaXmNibMncO 2 （ 0.4≤a≤1.2 ， 0≤m≤0.1 ， 0.1≤b≤0.5 ， 0.5≤c≤0.9 ， b+c=1 ）的正极材料。A preparation method of a potassium ion battery cathode material based on nickel manganese binary oxide, comprising the steps of: adding an organic acid salt containing nickel manganese potassium according to a nickel manganese potassium molar ratio of 0.1-0.5: 0.5-0.9: 0.4-1.2 The ratio of the ball mill is mixed to obtain an organic acid salt precursor powder; the obtained organic acid salt precursor powder is ground, pre-sintered at 300-500 ° C for 3-6 hours in an air atmosphere, then cooled to room temperature for grinding, and finally heated to 700~ When calcined at 1000 °C for 8~20h, the chemical formula is K a X m Ni b Mn c O 2 ( 0.4 ≤ a ≤ 1.2, 0 ≤ m ≤ 0.1, 0.1 ≤ b ≤ 0.5, 0.5 ≤ c ≤ 0.9, b+c= 1) The positive electrode material.
与现有技术相比，本发明的优点在于： The advantages of the present invention over the prior art are:
（ 1 ）本发明所制备的材料 KaXmNibMncO 2 具有放电容量高、放电平台电压高、稳定性好等重要优点，是一种具有应用价值和前景新型钾离子电池正极材料。(1) The material prepared by the invention K a X m Ni b Mn c O 2 has the important advantages of high discharge capacity, high discharge platform voltage and good stability, and is a novel potassium ion battery cathode material with application value and prospect. .
（ 2 ）本发明的方法制备简单，生产成本低，操作可控性高，可大规模应用于工业生产中，具有十分重要的现实意义。 ( 2 The method of the invention has the advantages of simple preparation, low production cost, high controllability and large-scale application in industrial production, and has very important practical significance.
附图说明DRAWINGS
图 1 为所述镍锰二元钾离子电池正极材料 XRD 图； Figure 1 is an XRD diagram of the positive electrode material of the nickel-manganese binary potassium ion battery;
图 2 为所述镍锰二元钾离子电池正极材料循环性能图。 2 is a cycle performance diagram of the positive electrode material of the nickel-manganese binary potassium ion battery.
具体实施方式detailed description
下面结合具体实施例对本发明进一步地具体详细描述，但本发明的实施方式不限于此，对于未特别注明的工艺参数，可参照常规技术进行。 The present invention will be further specifically described in detail below with reference to the specific embodiments, but the embodiments of the present invention are not limited thereto, and the process parameters not specifically noted may be referred to conventional techniques.
实施例 1 Example 1
（ 1 ）将 0.005mol 乙酸镍、 0.005mol 乙酸锰和 0.013mol 乙酸钾（过量 5% ）溶解于 20mL 体积比为 1:1 的乙醇和去离子水中； (1) 0.005 mol of nickel acetate, 0.005 mol of manganese acetate, and 0.013 mol of potassium acetate (excess 5%) dissolved in 20 mL of ethanol and deionized water at a volume ratio of 1:1;
（ 2 ）将 1.299g 乙酸溶解于 10mL 体积比为 1:2 的乙醇和去离子水中； (2) Dissolve 1.299 g of acetic acid in 10 mL of ethanol and deionized water at a volume ratio of 1:2;
（ 3 ）将金属盐溶液以 1 ~ 2 滴 /s 的速度滴加到乙酸溶液中，再以 200 转 /min 的速度进行搅拌 6h ； (3) Add the metal salt solution to the acetic acid solution at a rate of 1 ~ 2 drops / s, then at 200 rpm The speed was stirred for 6 h;
（ 4 ）真空下将所得混合液 60℃ 加热至水分蒸干，得到粉末； (4) heating the resulting mixture to a temperature of 60 ° C under vacuum to evaporate to obtain a powder;
（ 5 ）将所得粉末在空气气氛下 300℃ 预烧结（升温速率为 3℃/min ），然后冷却到室温下再研磨， 700℃ 高温焙烧 8h( 升温速率为 5℃/min) ，得到钾离子电池正极材料 K1.20Ni0.50Mn0.50O 2 。(5) The obtained powder is pre-sintered at 300 ° C in an air atmosphere (heating rate is 3 ° C / min), then cooled to room temperature and then ground, and calcined at 700 ° C for 8 h (heating rate is 5 ° C / min) to obtain potassium ions. Battery cathode material K 1.20 Ni 0.50 Mn 0.50 O 2 .
纽扣电池的组装步骤：将正极材料与粘结剂聚偏氟乙烯（ PVDF ）、导电剂乙炔黑按照质量比 8:1:1 的比例混合，加入溶剂 N- 甲基吡咯烷酮（ NMP ）搅拌 4-6h ，将浆料涂抹在干净的铝箔上，放入 80℃ 真空烘箱烘干待用；以 K1.20Ni0.50Mn0.50O 2 极片作为正极，以钾片或者石墨作为负极，以 Whatman GF/D 作为隔膜，以 0.8 mol/L 六氟磷酸钾（ KPF6 ） / 碳酸乙烯酯（ EC ）：碳酸二甲酯（ DEC ）作为电解液组装纽扣电池。The assembly process of the button battery: mixing the positive electrode material with the binder polyvinylidene fluoride (PVDF) and the conductive agent acetylene black in a ratio of 8:1:1 by mass, and adding the solvent N-methylpyrrolidone (NMP) to stir 4- 6h, the slurry is spread on a clean aluminum foil and placed in a vacuum oven at 80 ° C for use; K 1.20 Ni 0.50 Mn 0.50 O 2 pole piece is used as the positive electrode, potassium plate or graphite is used as the negative electrode, and Whatman GF/D is used. As a separator, a button battery was assembled using 0.8 mol/L potassium hexafluorophosphate (KPF 6 ) / ethylene carbonate (EC ): dimethyl carbonate (DEC) as an electrolyte.
电化学性能检测：将组装好的纽扣电池进行恒电流充放电测试，检测电池的首圈容量和循环性能，测试电压范围在 2-4.5 V ；在电化学工作站上进行循环伏安测试，电位扫描范围为 2-4.5 V ，扫描速度为 0.1 mV/s 。 Electrochemical performance test: The assembled button battery is subjected to constant current charge and discharge test to detect the first ring capacity and cycle performance of the battery. The test voltage range is 2-4.5 V; Cyclic voltammetry on an electrochemical workstation with a potential sweep range of 2-4.5 V and a scan speed of 0.1 mV/s.
图 1 为该材料的 XRD 图；图 2 为该材料的首圈充放电曲线图。 Figure 1 shows the XRD pattern of the material; Figure 2 shows the charge and discharge curve for the first cycle of the material.
材料的基础性能见表 1 。 The basic properties of the materials are shown in Table 1.
实施例 2 Example 2
（ 1 ）将 0.001mol 硝酸镍、 0.009mol 硝酸锰、 0.004mol 氢氧化钾（过量 5% ）和 0.001mol 硝酸亚铁溶解于 50mL 体积比为 1:4 的乙二醇和去离子水中； (1) 0.001 mol of nickel nitrate, 0.009 mol of manganese nitrate, 0.004 mol of potassium hydroxide (excess 5%) and 0.001 mol of ferrous nitrate are dissolved in 50 mL of ethylene glycol and deionized water at a volume ratio of 1:4;
（ 2 ）将 1.458g 草酸溶解于 40mL 体积比为 1:6 的乙二醇和去离子水中； (2) Dissolving 1.458 g of oxalic acid in 40 mL of ethylene glycol and deionized water at a volume ratio of 1:6;
（ 3 ）将草酸溶液以 1 ~ 2 滴 /s 的速度滴加到金属盐溶液中，再以 500 转 /min 的速度进行搅拌 12h ； (3) Add the oxalic acid solution to the metal salt solution at a rate of 1 ~ 2 drops / s, then at 500 rpm Stirring at a speed of 12 h;
（ 4 ）将所得混合液 120℃ 加热至水分蒸干，得到粉末； (4) heating the resulting mixture to 120 ° C until the water is evaporated to dryness to obtain a powder;
（ 5 ）将所得粉末在空气气氛下 500℃ 预烧结（升温速率为 5℃/min ），冷却到室温后再研磨， 1000℃ 焙烧 20 h( 升温速率为 3℃/min) ，得到钾离子电池正极材料 K0.40Fe0.10Ni0.10Mn 0.90O2 。(5) The obtained powder is pre-sintered at 500 ° C in an air atmosphere (heating rate is 5 ° C / min), cooled to room temperature and then ground, and calcined at 1000 ° C for 20 h (heating rate is 3 ° C / min) to obtain a potassium ion battery. Positive electrode material K 0.40 Fe 0.10 Ni 0.10 Mn 0.90 O 2 .
材料的基础性能见表 1 。 The basic properties of the materials are shown in Table 1.
实施例 3 Example 3
除采用 0.004mol 碳酸钾取代 0.013mol 乙酸钾， 0.0005mol 氯化铝取代硝酸亚铁，等摩尔数的硫酸镍、硫酸锰取代硝酸镍、硝酸锰，丙酮取代乙醇，柠檬酸取代乙酸外，其他成分使用和制备方法完全与实例 2 相同，制备得到正极材料 K0.40Al0.01Ni0.50Mn 0.50O2 。In addition to 0.004mol potassium carbonate instead of 0.013mol potassium acetate, 0.0005mol aluminum chloride instead of ferrous nitrate, equivalent moles of nickel sulfate, manganese sulfate instead of nickel nitrate, manganese nitrate, acetone instead of ethanol, citric acid substituted acetic acid, other components The use and preparation methods were the same as in Example 2, and a positive electrode material K 0.40 Al 0.01 Ni 0.50 Mn 0.50 O 2 was prepared .
材料的基础性能见表 1 。 The basic properties of the materials are shown in Table 1.
实施例 4 Example 4
除采用 0.001mol 氯化镍取代 0.005mol 乙酸镍， 0.009mol 氯化锰取代 0.005mol 乙酸锰， 0.012mol 氯化钾取代 0.013mol 乙酸钾，等摩尔数的氯化镁取代硝酸亚铁外，其他成分使用和制备方法完全与实例 2 相同，制备得到正极材料 K1.20Mg0.05Ni0.10Mn 0.90O2 。In addition to 0.001 mol of nickel chloride instead of 0.005 mol of nickel acetate, 0.009 mol of manganese chloride instead of 0.005 mol of manganese acetate, 0.012 mol of potassium chloride instead of 0.013 mol of potassium acetate, and an equivalent molar amount of magnesium chloride instead of ferrous nitrate, other components used and The preparation method was the same as in Example 2, and a positive electrode material K 1.20 Mg 0.05 Ni 0.10 Mn 0.90 O 2 was prepared .
材料的基础性能见表 1 。 The basic properties of the materials are shown in Table 1.
实施例 5 Example 5
除采用等摩尔数的柠檬酸钾、氯化镁取代氢氧化钾、硝酸亚铁外，其他成分使用和制备方法完全与实例 2 相同，制备得到正极材料 K1.20Li0.01Ni0.10Mn 0.90O2 。The positive electrode material K 1.20 Li 0.01 Ni 0.10 Mn 0.90 O 2 was prepared except that an equimolar amount of potassium citrate, magnesium chloride was substituted for potassium hydroxide and ferrous nitrate, and other components were used and prepared in the same manner as in Example 2 .
材料的基础性能见表 1 。 The basic properties of the materials are shown in Table 1.
表 1 为各实施例主要性能表
实施例 材料组成 20mA·g-1 的容量 库伦
效率 /%		 50 循环后的容量保持率 /%
1 K1.20Ni0.50Mn0.50O 2 87.07 54.0 81.7
2 K0.40Fe0.10Ni0.10Mn 0.90O2 83.15 73.1 79.4
3 K0.40Al0.01Ni0.50Mn 0.50O2 85.32 83.2 85.1
4 K1.20Mg0.05Ni0.10Mn 0.90O2 84.12 75.7 84.3
5 K1.20Li0.01Ni0.10Mn 0.90O2 93.38 86.2 83.5
Table 1 is the main performance table of each embodiment.
Example Material composition 20mA·g -1 capacity Coulomb efficiency /% Capacity retention after 50 cycles /%
1 K 1.20 Ni 0.50 Mn 0.50 O 2 87.07 54.0 81.7
2 K 0.40 Fe 0.10 Ni 0.10 Mn 0.90 O 2 83.15 73.1 79.4
3 K 0.40 Al 0.01 Ni 0.50 Mn 0.50 O 2 85.32 83.2 85.1
4 K 1.20 Mg 0.05 Ni 0.10 Mn 0.90 O 2 84.12 75.7 84.3
5 K 1.20 Li 0.01 Ni 0.10 Mn 0.90 O 2 93.38 86.2 83.5
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。 The above-described embodiments of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. There is no need and no way to exhaust all of the implementations. Any modifications, equivalent substitutions and improvements made within the spirit and scope of the invention are intended to be included within the scope of the appended claims.

Claims (8)

  1. 一种基于镍锰二元氧化物的钾离子电池正极材料，其化学式为： KaXmNibMncO 2 ；其中 0.4≤a≤1.2 ， 0≤m≤0.1 ， 0.1≤b≤0.5 ， 0.5≤c≤0.9 ， b+c=1 ；所述 X 包括 Fe 、 Al 、 Mg 或 Li 。A positive electrode material for potassium ion battery based on nickel manganese binary oxide, the chemical formula is: K a X m Ni b Mn c O 2 ; wherein 0.4 ≤ a ≤ 1.2, 0 ≤ m ≤ 0.1, 0.1 ≤ b ≤ 0.5, 0.5 ≤ c ≤ 0.9, b + c = 1; the X includes Fe, Al, Mg or Li.
  2. 权利要求 1 所述基于镍锰二元氧化物的钾离子电池正极材料的制备方法，其特征在于，包括如下步骤： The method for preparing a nickel-manganese binary oxide-based potassium ion battery cathode material according to claim 1, comprising the steps of:
    （ 1 ）将可溶性的镍盐、锰盐、钾盐和掺杂元素盐溶解于有机溶剂与去离子水的混合溶剂中配成溶液 A ；(1) dissolving soluble nickel salt, manganese salt, potassium salt and doping element salt in a mixed solvent of organic solvent and deionized water to form a solution A ;
    （ 2 ）将有机酸或者有机酸盐溶解于有机溶剂与去离子水形成的混合溶剂中得到溶液 B ；(2) dissolving an organic acid or an organic acid salt in a mixed solvent of an organic solvent and deionized water to obtain a solution B;
    （ 3 ）在搅拌下将溶液 A 加入到溶液 B 中，混合均匀并连续搅拌，得到悬浊液 C ；(3) adding solution A to solution B under stirring, mixing uniformly and continuously stirring to obtain suspension C;
    （ 4 ）制备含有镍锰钾的前驱体粉末包括如下步骤之一：真空下加热悬浊液 C 直至蒸干水分得到含有镍锰钾的前驱体粉末；或者将 悬浊液 C 过滤、干燥得到前驱体粉末；(4) preparing a precursor powder containing nickel manganese potassium comprises one of the following steps: heating the suspension C under vacuum until the water is evaporated to obtain a precursor powder containing nickel manganese potassium; or Suspending liquid C is filtered and dried to obtain a precursor powder;
    （ 5 ）将步骤（ 4 ）得到的有机酸盐前驱体粉末进行研磨，预烧结，研磨，再高温焙烧，即得到化学式为 KaXmNibMncO 2 （ 0.4≤a≤1.2 ， 0≤m≤0.1 ， 0.1≤b≤0.5 ， 0.5≤c≤0.9 ， b+c=1 ）的正极材料。(5) grinding the organic acid salt precursor powder obtained in the step (4), pre-sintering, grinding, and then calcining at a high temperature to obtain a chemical formula of K a X m Ni b Mn c O 2 (0.4 ≤ a ≤ 1.2, 0) A positive electrode material of ≤ m ≤ 0.1, 0.1 ≤ b ≤ 0.5, 0.5 ≤ c ≤ 0.9, b + c = 1).
  3. 根据权利要求 2 所述基于镍锰二元氧化物的钾离子电池正极材料的制备方法，其特征为：步骤（ 1 ）中，所述镍盐为硝酸镍、乙酸镍、硫酸镍、氯化镍中的一种以上；所述锰盐为硝酸锰、乙酸锰、硫酸锰、氯化锰中的一种以上；所述钾盐为氢氧化钾、乙酸钾、碳酸钾、氯化钾、柠檬酸钾中的一种以上；所述掺杂元素盐为可溶性铁盐、可溶性铝盐、可溶性镁盐、可溶性锂盐中的一种以上；所述有机酸为乙酸、草酸、柠檬酸中的一种以上；所述有机溶剂为乙醇、丙酮、乙二醇中的一种以上；步骤（ 1 ）中，所述有机溶剂与去离子水的体积比 1:1-4 。The method for preparing a nickel-manganese binary oxide-based potassium ion battery cathode material according to claim 2, wherein the step (1) The nickel salt is one or more of nickel nitrate, nickel acetate, nickel sulfate, and nickel chloride; the manganese salt is one or more of manganese nitrate, manganese acetate, manganese sulfate, and manganese chloride; The potassium salt is one or more of potassium hydroxide, potassium acetate, potassium carbonate, potassium chloride, and potassium citrate; the doping element salt is a soluble iron salt, a soluble aluminum salt, a soluble magnesium salt, and a soluble lithium salt. One or more; the organic acid is one or more of acetic acid, oxalic acid, and citric acid; and the organic solvent is one or more of ethanol, acetone, and ethylene glycol; In 1), the volume ratio of the organic solvent to deionized water is 1:1-4.
  4. 根据权利要求 2 所述基于镍锰二元氧化物的钾离子电池正极材料的制备方法，其特征为：步骤（ 2 ）中，所述有机酸盐为乙酸盐、草酸盐、柠檬酸盐中的一种以上；所述有机酸为乙酸、草酸、柠檬酸中的一种以上；所述有机溶剂与去离子水的体积比为 1:2-6 。The method for preparing a nickel-manganese binary oxide-based potassium ion battery cathode material according to claim 2, wherein: step (2) The organic acid salt is one or more of an acetate, an oxalate, and a citrate; the organic acid is one or more of acetic acid, oxalic acid, and citric acid; the organic solvent and deionized The volume ratio of water is 1:2-6 .
  5. 根据权利要求 2 所述基于镍锰二元氧化物的钾离子电池正极材料的制备方法，其特征为：步骤（ 3 ）中，所述混合方法为将溶液 A 滴加到溶液 B 中，滴加速度为 1~2 滴 /s 或者将溶液 B 滴加到溶液 A 中，滴加速度为 1~2 滴 /s ；步骤（ 3 ）中，所述搅拌的转速为 200~500 转 /min ，搅拌时间为 6~12h 。The method for preparing a nickel-manganese binary oxide-based potassium ion battery cathode material according to claim 2, wherein in the step (3), the mixing method is a solution A is added to the solution B, the dropping rate is 1~2 drops / s or the solution B is added dropwise to the solution A, the dropping acceleration is 1~2 drops / s; in the step (3), the stirring speed is 200~500 rpm, the mixing time is 6~12h.
  6. 根据权利要求 2 所述基于镍锰二元氧化物的钾离子电池正极材料的制备方法，其特征为：步骤（ 4 ）中，所述加热的温度为 60~120℃ 。The method for preparing a nickel-manganese binary oxide-based potassium ion battery cathode material according to claim 2, wherein in the step (4), the heating temperature is 60~120°C.
  7. 根据权利要求 2 所述基于镍锰二元氧化物的钾离子电池正极材料的制备方法，其特征为：步骤（ 5 ）的具体操作为：将干燥后的前驱体材料进行研磨，在空气气氛中 300~500℃ 预烧结 3~6h ，然后冷却至室温进行研磨，最后升温到 700~1000℃ 焙烧 8~20h 。The method for preparing a nickel-manganese binary oxide-based potassium ion battery cathode material according to claim 2, wherein: step (5) The specific operation is as follows: the dried precursor material is ground, pre-sintered at 300-500 ° C for 3-6 h in an air atmosphere, then cooled to room temperature for grinding, and finally heated to 700-1000 ° C for roasting. 8~20h.
  8. 权利要求 1 所述基于镍锰二元氧化物的钾离子电池正极材料的制备方法，包括如下步骤：将含有镍锰钾的有机酸盐按照镍锰钾摩尔比为 0.1-0.5:0.5-0.9:0.4-1.2 的比例球磨混合得到有机酸盐前驱体粉末；将所得的有机酸盐前驱体粉末进行研磨，在空气气氛中 300~500℃ 预烧结The method for preparing a nickel-manganese binary oxide-based potassium ion battery cathode material according to claim 1, comprising the steps of: using a nickel manganese potassium-containing organic acid salt according to a nickel manganese potassium molar ratio 0.1-0.5: 0.5-0.9: 0.4-1.2 ratio by ball milling to obtain an organic acid salt precursor powder; the obtained organic acid salt precursor powder is ground in an air atmosphere at 300 to 500 ° C Presintering
    3~6h ，然后冷却至室温进行研磨，最后升温到 700~1000℃ 焙烧 8~20h ，即得到化学式为 KaXmNibMncO 2 的正极材料，其中 0.4≤a≤1.2 ， 0≤m≤0.13~6h, then cooled to room temperature for grinding, and finally heated to 700~1000 °C for 8~20h, then get the positive electrode material with chemical formula K a X m Ni b Mn c O 2 , where 0.4≤a≤1.2, 0≤ M≤0.1
    ， 0.1≤b≤0.5 ， 0.5≤c≤0.9 ， b+c=1 。, 0.1 ≤ b ≤ 0.5, 0.5 ≤ c ≤ 0.9, b + c = 1.
PCT/CN2018/112825 2018-04-03 2018-10-30 Nickel-manganese binary oxide-based potassium ion battery positive electrode material and preparation method therefor WO2019192171A1 (en)

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CN108615874B (en) * 2018-04-03 2019-08-20 华南理工大学 A kind of kalium ion battery positive electrode and preparation method thereof based on nickel manganese binary oxide
WO2020124507A1 (en) * 2018-12-20 2020-06-25 深圳先进技术研究院 Crystalline material, preparation method therefor and application thereof, positive electrode active material of battery, positive electrode material of battery, battery and electrical equipment
CN111354943A (en) * 2018-12-20 2020-06-30 中国科学院深圳先进技术研究院 Use of fluorinated oxalate materials and products comprising fluorinated oxalate materials, methods of making and uses thereof
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CN113270581A (en) * 2021-04-23 2021-08-17 佛山市天劲新能源科技有限公司 Potassium ion battery electrode material and preparation method and application thereof
CN113871586A (en) * 2021-09-07 2021-12-31 武汉理工大学 Controllable manganese-based layered oxide electrode material and preparation method and application thereof
CN115286049A (en) * 2022-07-26 2022-11-04 青岛大学 Preparation method of lithium-doped potassium nickel manganate material, positive electrode material and battery
CN115745030B (en) * 2023-01-09 2023-05-12 浙江帕瓦新能源股份有限公司 Potassium ion battery anode material, precursor thereof and preparation method
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