WO2020140941A1 - Lini0.69mn0.23co0.08o2 compound having a layered structure, synthesis method therefor and application thereof - Google Patents

Lini0.69mn0.23co0.08o2 compound having a layered structure, synthesis method therefor and application thereof Download PDF

Info

Publication number
WO2020140941A1
WO2020140941A1 PCT/CN2020/070098 CN2020070098W WO2020140941A1 WO 2020140941 A1 WO2020140941 A1 WO 2020140941A1 CN 2020070098 W CN2020070098 W CN 2020070098W WO 2020140941 A1 WO2020140941 A1 WO 2020140941A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
layered
lini
mixed
sodium carbonate
Prior art date
Application number
PCT/CN2020/070098
Other languages
French (fr)
Chinese (zh)
Inventor
简宏希
杨华
薄涛
王保田
黄允然
夏元华
孙光爱
童剑飞
梁天骄
Original Assignee
散裂中子源科学中心
中国科学院高能物理研究所
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
Priority to CN201910006756.X priority Critical
Priority to CN201910006756.XA priority patent/CN109704416B/en
Application filed by 散裂中子源科学中心, 中国科学院高能物理研究所 filed Critical 散裂中子源科学中心
Publication of WO2020140941A1 publication Critical patent/WO2020140941A1/en

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

Provided are a LiNi0.69Mn0.23Co0.08O2 compound, a synthesis method therefor, and an application thereof. The compound is a new compound having a layered crystal structure prepared under a new synthesis condition, having a unique shape, a uniform size, and a high tap density, capable of being used as a cathode material for lithium ion batteries, having a high energy density, Coulomb efficiency, and cycle performance, and therefore having an excellent industrial prospect.

Description

层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物及其合成方法和应用 Layered LiNi 0.69Mn 0.23Co 0.08O 2 Compounds and their synthesis methods and applications 技术领域Technical field
本发明涉及一种新化合物,具体来说涉及一种层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物及其合成方法和应用,属于电池用阴极材料技术领域。 The invention relates to a new compound, in particular to a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound and its synthesis method and application, which belong to the technical field of cathode materials for batteries.
背景技术Background technique
锂电池(Lithium battery)是指电化学体系中含有锂(包括金属锂、锂合金和锂离子、锂聚合物)的电池。锂电池大致可分为两类:锂金属电池和锂离子电池。目前锂离子电池技术应用广泛,可作为移动电子设备及小型车辆的主要供电系统。在实现无人车应用方面,锂离子电池较汽油驱动系统在燃料补充系统上能提供更加安全可靠的保障,而锂离子电池较其他储能系统在能量密度方面提供数倍以上的优势。Lithium battery refers to a battery that contains lithium (including metal lithium, lithium alloy and lithium ion, lithium polymer) in the electrochemical system. Lithium batteries can be roughly divided into two categories: lithium metal batteries and lithium ion batteries. At present, lithium-ion battery technology is widely used, and can be used as the main power supply system for mobile electronic devices and small vehicles. In realizing the application of unmanned vehicles, lithium-ion batteries can provide a safer and more reliable guarantee on fuel replenishment systems than gasoline-driven systems, while lithium-ion batteries provide several times more advantages in energy density than other energy storage systems.
另外,锂离子电池在能源危机及负荷调平方面亦能提供有效方案,通过化学能方式储备各种再生能源。锂离子电池的新应用将为科技发展带来新的机遇,但同时也促使电池技术在容量、工作电压、功率、耐久性、安全性、环保、可回收性及生产成本方面有所改进。In addition, lithium-ion batteries can also provide effective solutions in terms of energy crisis and load leveling, and store various renewable energy through chemical energy. The new application of lithium-ion batteries will bring new opportunities for technological development, but at the same time also promote battery technology in terms of capacity, operating voltage, power, durability, safety, environmental protection, recyclability and production costs.
但是,锂离子电池的库仑效率和长期循环性能还有待优化,开发大容量/高功率的锂离子电池及其控制系统能进一步强化或拓展现有市场。However, the coulombic efficiency and long-term cycle performance of lithium-ion batteries need to be optimized. The development of large-capacity/high-power lithium-ion batteries and their control systems can further strengthen or expand the existing market.
发明内容Summary of the invention
为解决现有技术的不足,本发明的目的在于提供一种层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物及其合成方法和应用,该化合物能够作为锂离子电池的阴极材料使用,具有更高的振实密度和能量密度,库仑效率和循环性能更优。 In order to solve the deficiencies of the prior art, the object of the present invention is to provide a layered structure of LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound and its synthesis method and application. The compound can be used as a cathode material for lithium ion batteries With high tap density and energy density, Coulomb efficiency and cycle performance are better.
为了实现上述目标,本发明采用如下的技术方案:In order to achieve the above objectives, the present invention adopts the following technical solutions:
层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物,该化合物的晶体结构为层状,于混合碳酸钠/氢氧化钠溶液共沉淀法下合成。 The layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound, which has a layered crystal structure, was synthesized under a mixed sodium carbonate/sodium hydroxide solution co-precipitation method.
本发明还公布了制备前述的层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物的方法,包括步骤: The invention also discloses a method for preparing the aforementioned layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound, which includes the steps of:
S1、共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2:以醋酸钴、醋酸锰、醋酸镍及氢氧化铵为前驱体,向前驱体混合溶液中滴加混合碳酸钠/氢氧化钠溶液,通过共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2S1. Co-precipitation method to synthesize layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 : using cobalt acetate, manganese acetate, nickel acetate and ammonium hydroxide as precursors, and adding mixed sodium carbonate/hydroxide to the precursor mixed solution For sodium solution, layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 was synthesized by co-precipitation method;
制备原理如下:The preparation principle is as follows:
0.69Ni 2++0.23Mn 2++0.08Co 2++2OH -→Ni 0.69Mn 0.23Co 0.08(OH) 2 0.69Ni 2+ + 0.23Mn 2+ + 0.08Co 2+ + 2OH - → Ni 0.69 Mn 0.23 Co 0.08 (OH) 2
S2、制备层状LiNi 0.69Mn 0.23Co 0.08O 2化合物:将步骤S1制得的层状Ni 0.69Mn 0.23Co 0.08(OH) 2与LiOH·H 2O以1:1.05摩尔比预先混料均匀后,再以固态法烧结,制得层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物。 S2. Preparation of layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound: the layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 and LiOH·H 2 O prepared in step S1 are mixed in advance at a molar ratio of 1:1.05 , And then sintered by solid state method to obtain a layered structure of LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound.
优选地,前述步骤S1中,醋酸钴、醋酸锰、醋酸镍及氢氧化铵的摩尔比为:0.08:0.23:0.69:0.8。Preferably, in the foregoing step S1, the molar ratio of cobalt acetate, manganese acetate, nickel acetate and ammonium hydroxide is: 0.08:0.23:0.69:0.8.
更优选地,前述步骤S1中,通过控制混合碳酸钠/氢氧化钠溶液的滴加速度调节反应液的pH值为7.5~8.5,更优选的pH值为8.3。pH值的控制对于产物的纯度和密度均有显著的影响,太高或太低的pH值均会导致不均匀结晶,形成杂质。More preferably, in the aforementioned step S1, the pH value of the reaction solution is adjusted by controlling the dripping rate of the mixed sodium carbonate/sodium hydroxide solution, and a more preferred pH value is 8.3. The control of pH value has a significant effect on the purity and density of the product. A too high or too low pH value will cause uneven crystallization and the formation of impurities.
再优选地,在前述步骤S1中,反应液温度为55℃。More preferably, in the aforementioned step S1, the temperature of the reaction liquid is 55°C.
进一步优选地,前述步骤S2中,固态法烧结温度600~1000℃,烧结时间为8~20h。更优选的烧结温度为800℃,烧结时间为15h。烧结温度过高或烧结时间过长会导致非常致密的微观结构,不利于锂离子插入或离开样品,锂离子也 会在高温下蒸发。烧结温度过低或烧结时间过短,则会导致结晶度低,也不利于锂离子插入或离开样品。Further preferably, in the foregoing step S2, the solid-state sintering temperature is 600 to 1000° C., and the sintering time is 8 to 20 h. A more preferred sintering temperature is 800°C and sintering time is 15h. If the sintering temperature is too high or the sintering time is too long, it will result in a very dense microstructure, which is not conducive to lithium ion insertion or leaving the sample. Lithium ions will also evaporate at high temperatures. If the sintering temperature is too low or the sintering time is too short, it will lead to low crystallinity, which is not conducive to lithium ion insertion or leaving the sample.
再进一步优选地,在前述混合碳酸钠/氢氧化钠溶液中,碳酸钠与氢氧化钠的摩尔比2:1~3:1。Still further preferably, in the aforementioned mixed sodium carbonate/sodium hydroxide solution, the molar ratio of sodium carbonate to sodium hydroxide is 2:1 to 3:1.
本发明还公布了前述的层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物,其可作为电池的阴极材料使用。 The present invention also discloses the aforementioned layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound, which can be used as a cathode material for batteries.
本发明的有益之处在于:本发明的LiNi 0.69Mn 0.23Co 0.08O 2是在一种新的合成条件下制得的晶体结构为层状的化合物,该化合物形貌独特、尺寸均匀、振实密度高,具有良好的库仑效率和循环性能,可作为电池上的阴极材料使用,具有极好的工业前景。 The benefit of the present invention is that the LiNi 0.69 Mn 0.23 Co 0.08 O 2 of the present invention is a compound with a layered crystal structure prepared under a new synthesis condition. The compound has a unique morphology, uniform size and vibration High density, good Coulomb efficiency and cycle performance, can be used as a cathode material on batteries, and has excellent industrial prospects.
附图说明BRIEF DESCRIPTION
图1为本发明的实施例1的产物的SEM图,其中a图为b图的局部放大图;1 is an SEM image of the product of Example 1 of the present invention, where a is a partially enlarged view of b;
图2为本发明的实施例2的产物的SEM图,其中a图为b图的局部放大图;2 is an SEM image of the product of Example 2 of the present invention, where a is a partially enlarged view of b;
图3为本发明的实施例1的Rietveld精修的样品相分量图;3 is a sample phase component diagram of the Rietveld refinement of Example 1 of the present invention;
图4为本发明的实施例2的Rietveld精修的样品相分量图;4 is a sample phase component diagram of Rietveld refinement of Example 2 of the present invention;
图5为本发明的应用例1的首周电化学循环图;5 is a first week electrochemical cycle diagram of Application Example 1 of the present invention;
图6为本发明的应用例2的首周电化学循环图;6 is a first week electrochemical cycle diagram of Application Example 2 of the present invention;
图7为本发明的应用例1的连续多个周期的电化学循环性能图;7 is a graph of the electrochemical cycle performance of successive multiple cycles of Application Example 1 of the present invention;
图8为本发明的应用例2的连续多个周期的电化学循环性能图;8 is a graph of the electrochemical cycle performance of consecutive multiple cycles of Application Example 2 of the present invention;
图9为本发明的对比例2的首周电化学循环图;9 is a first week electrochemical cycle diagram of Comparative Example 2 of the present invention;
图10为本发明的对比例2的连续多个周期的电化学循环性能图。FIG. 10 is a graph of the electrochemical cycle performance of Comparative Example 2 of the present invention for a plurality of consecutive cycles.
具体实施方式detailed description
以下结合附图和具体实施例对本发明作具体的介绍。The present invention will be described in detail below with reference to the drawings and specific embodiments.
本发明中若无特殊说明,所用原料均为市购。Unless otherwise specified in the present invention, all raw materials used are commercially available.
实施例1Example 1
S1、共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2:以醋酸钴、醋酸锰、醋酸镍及氢氧化铵为前驱体,四者的摩尔比为:0.08:0.23:0.69:0.8,向前驱体混合溶液中滴加混合碳酸钠/氢氧化钠溶液,通过控制混合碳酸钠/氢氧化钠溶液的滴加速度调节反应液的pH值为8.3,反应液温度为55℃,碳酸钠与氢氧化钠的摩尔比为2:1,这样,即可通过共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2S1, Co-precipitation method to synthesize layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 : using cobalt acetate, manganese acetate, nickel acetate and ammonium hydroxide as precursors, the molar ratio of the four is: 0.08:0.23:0.69:0.8 ,Add the mixed sodium carbonate/sodium hydroxide solution dropwise to the precursor mixed solution, adjust the pH value of the reaction solution by controlling the dropping speed of the mixed sodium carbonate/sodium hydroxide solution, the reaction solution temperature is 55℃, the sodium carbonate and The molar ratio of sodium hydroxide is 2:1, so that layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 can be synthesized by co-precipitation method;
S2、制备层状LiNi 0.69Mn 0.23Co 0.08O 2化合物:将步骤S1制得的层状Ni 0.69Mn 0.23Co 0.08(OH) 2与LiOH·H 2O以1:1.05摩尔比预先混料均匀后,再以固态法烧结,控制烧结温度为800℃,烧结时间为15h,制得层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物。 S2. Preparation of layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound: the layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 and LiOH·H 2 O prepared in step S1 are mixed in advance at a molar ratio of 1:1.05 Then, the solid-state sintering was carried out, the sintering temperature was controlled at 800°C, and the sintering time was 15h. A layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound was obtained.
实施例2Example 2
S1、共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2:以醋酸钴、醋酸锰、醋酸镍及氢氧化铵为前驱体,四者的摩尔比为:0.08:0.23:0.69:0.8,向前驱体混合溶液中滴加混合碳酸钠/氢氧化钠溶液,通过控制混合碳酸钠/氢氧化钠溶液的滴加速度调节反应液的pH值为8.3,反应液温度为55℃,碳酸钠与氢氧化钠的摩尔比为3:1,这样,即可通过共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2S1, Co-precipitation method to synthesize layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 : using cobalt acetate, manganese acetate, nickel acetate and ammonium hydroxide as precursors, the molar ratio of the four is: 0.08:0.23:0.69:0.8 ,Add the mixed sodium carbonate/sodium hydroxide solution dropwise to the precursor mixed solution, adjust the pH value of the reaction solution by controlling the dropping speed of the mixed sodium carbonate/sodium hydroxide solution, the reaction solution temperature is 55℃, the sodium carbonate and The molar ratio of sodium hydroxide is 3:1, so that layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 can be synthesized by co-precipitation method;
S2、制备层状LiNi 0.69Mn 0.23Co 0.08O 2化合物:将步骤S1制得的层状Ni 0.69Mn 0.23Co 0.08(OH) 2与LiOH·H 2O以1:1.05摩尔比预先混料均匀后,再以固态法烧结,控制烧结温度为800℃,烧结时间为15h,制得层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物。 S2. Preparation of layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound: the layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 and LiOH·H 2 O prepared in step S1 are mixed in advance at a molar ratio of 1:1.05 Then, the solid-state sintering was carried out, the sintering temperature was controlled at 800°C, and the sintering time was 15h. A layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound was obtained.
实施例3Example 3
S1、共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2:以醋酸钴、醋酸锰、醋酸镍 及氢氧化铵为前驱体,四者的摩尔比为:0.08:0.23:0.69:0.8,向前驱体混合溶液中滴加混合碳酸钠/氢氧化钠溶液,通过控制混合碳酸钠/氢氧化钠溶液的滴加速度调节反应液的pH值为7.5,反应液温度为55℃,碳酸钠与氢氧化钠的摩尔比为3:1,这样,即可通过共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2S1, Co-precipitation method to synthesize layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 : using cobalt acetate, manganese acetate, nickel acetate and ammonium hydroxide as precursors, the molar ratio of the four is: 0.08:0.23:0.69:0.8 ,Add the mixed sodium carbonate/sodium hydroxide solution dropwise to the precursor mixed solution, adjust the pH value of the reaction solution by controlling the dropping speed of the mixed sodium carbonate/sodium hydroxide solution, the reaction solution temperature is 55℃, the sodium carbonate and The molar ratio of sodium hydroxide is 3:1, so that layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 can be synthesized by co-precipitation method;
S2、制备层状LiNi 0.69Mn 0.23Co 0.08O 2化合物:将步骤S1制得的层状Ni 0.69Mn 0.23Co 0.08(OH) 2与LiOH·H 2O以1:1.05摩尔比预先混料均匀后,再以固态法烧结,控制烧结温度为600℃,烧结时间为20h,制得层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物。 S2. Preparation of layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound: the layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 and LiOH·H 2 O prepared in step S1 are mixed in advance at a molar ratio of 1:1.05 Then, the solid-state sintering was carried out, the sintering temperature was controlled at 600°C, and the sintering time was 20h, and a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound was prepared.
实施例4Example 4
S1、共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2:以醋酸钴、醋酸锰、醋酸镍及氢氧化铵为前驱体,四者的摩尔比为:0.08:0.23:0.69:0.8,向前驱体混合溶液中滴加混合碳酸钠/氢氧化钠溶液,通过控制混合碳酸钠/氢氧化钠溶液的滴加速度调节反应液的pH值为8.5,反应液温度为55℃,碳酸钠与氢氧化钠的摩尔比为2:1,这样,即可通过共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2S1, Co-precipitation method to synthesize layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 : using cobalt acetate, manganese acetate, nickel acetate and ammonium hydroxide as precursors, the molar ratio of the four is: 0.08:0.23:0.69:0.8 , Add the mixed sodium carbonate/sodium hydroxide solution dropwise to the precursor mixture solution, and adjust the pH value of the reaction solution to 8.5 by controlling the drop rate of the mixed sodium carbonate/sodium hydroxide solution. The temperature of the reaction solution is 55°C. The molar ratio of sodium hydroxide is 2:1, so that layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 can be synthesized by co-precipitation method;
S2、制备层状LiNi 0.69Mn 0.23Co 0.08O 2化合物:将步骤S1制得的层状Ni 0.69Mn 0.23Co 0.08(OH) 2与LiOH·H 2O以1:1.05摩尔比预先混料均匀后,再以固态法烧结,控制烧结温度为1000℃,烧结时间为8h,制得层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物。 S2. Preparation of layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound: the layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 and LiOH·H 2 O prepared in step S1 are mixed in advance at a molar ratio of 1:1.05 Then, sintering by solid state method, controlling the sintering temperature to 1000 ℃, sintering time to 8h, to prepare a layered structure of LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound.
图1和图2所示的分别是实施例1和实施例2的SEM图,从图中可见,本发明的产品为微米级的颗粒状产物且尺寸均匀,结合图3和图4的Rietveld精修图分析可知,实施例1和实施例2制得的样品的晶体结构为非常相似的层状结构,样品的各晶体参数大致相同,其结构式为LiNi 0.69Mn 0.23Co 0.08O 2Figures 1 and 2 are SEM images of Example 1 and Example 2, respectively. It can be seen from the figure that the product of the present invention is a micron-level granular product with uniform size, combined with Rietveld fines of Figures 3 and 4 It can be seen from the retouching analysis that the crystal structures of the samples prepared in Example 1 and Example 2 are very similar layered structures. The crystal parameters of the samples are approximately the same, and the structural formula is LiNi 0.69 Mn 0.23 Co 0.08 O 2 .
对比例1Comparative Example 1
本对比例采用碳酸钠溶液代替实施例2中的碳酸钠/氢氧化钠溶液,其余制备参数和条件均与实施例2相同。In this comparative example, sodium carbonate solution is used instead of the sodium carbonate/sodium hydroxide solution in Example 2. The remaining preparation parameters and conditions are the same as in Example 2.
应用例1Application example 1
将实施例1的产物LiNi 0.69Mn 0.23Co 0.08O 2化合物作为阴极材料应用于锂电池上,以石墨或锂金属为阳极,以浓度为1M的LiPF 6/EC:DEC为电解质。对该锂电池进行充放电检测,检测结果见图5和图7。 The product LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound of Example 1 was used as a cathode material in a lithium battery, with graphite or lithium metal as the anode, and LiPF 6 /EC:DEC with a concentration of 1M as the electrolyte. The lithium battery was charged and discharged, and the test results are shown in Figure 5 and Figure 7.
应用例2Application example 2
将实施例2的产物LiNi 0.69Mn 0.23Co 0.08O 2化合物作为阴极材料应用于锂电池上,以石墨或锂金属为阳极,以浓度为1M的LiPF 6/EC:DEC为电解质。对该锂电池进行充放电检测,检测结果见图6和图8。 The LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound of Example 2 was used as a cathode material in a lithium battery, with graphite or lithium metal as the anode, and LiPF 6 /EC:DEC with a concentration of 1M as the electrolyte. Carry out charge and discharge tests on the lithium battery. The test results are shown in Figure 6 and Figure 8.
对比例2Comparative Example 2
将对比例1的产物作为阴极材料LiNi 0.69Mn 0.23Co 0.08O 2化合物应用于锂电池上,以石墨或锂金属为阳极,以浓度为1M的LiPF 6/EC:DEC为电解质。对该锂电池进行充放电检测,检测结果见图9和图10。 The product of Comparative Example 1 was used as a cathode material LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound in a lithium battery, with graphite or lithium metal as the anode, and LiPF 6 /EC:DEC with a concentration of 1M as the electrolyte. The charge and discharge test of the lithium battery is performed, and the test results are shown in Figure 9 and Figure 10.
对应用例1、应用例2及对比例2的锂电池进行性能检测,检测结果见图5至图10。The performance tests were performed on the lithium batteries of Application Example 1, Application Example 2 and Comparative Example 2. The test results are shown in Figures 5 to 10.
从图中可见,应用例1的首次充电容量为225mAh/g,放电容量为168mAh/g;应用例2的首次充电容量为213mAh/g,放电容量为165mAh/g;而对比例2的首次充电容量为204mAh/g,放电容量为140mAh/g。可见,本发明的制备方法得到的LiNi 0.69Mn 0.23Co 0.08O 2化合物能够获得更高的电学容量,电学性能更稳定,库仑效率更优。另外,本发明的各实施例产物和对比例2的容量退化率基本相似,实施例1为最优实施例。这是因为:碳酸钠与氢氧化钠的摩尔比2:1时有利于形成球形颗粒的样品,而且具有高振实密度;但过多的碳酸钠(碳酸钠与氢氧 化钠摩尔比为3:1)则会减少完整球形颗粒样品的形成,导致振实密度减少,产品性能变劣。 It can be seen from the figure that the first charge capacity of Application Example 1 is 225mAh/g and the discharge capacity is 168mAh/g; the first charge capacity of Application Example 2 is 213mAh/g and the discharge capacity is 165mAh/g; while the first charge of Comparative Example 2 The capacity is 204 mAh/g, and the discharge capacity is 140 mAh/g. It can be seen that the LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound obtained by the preparation method of the present invention can obtain higher electrical capacity, more stable electrical performance, and better Coulomb efficiency. In addition, the capacity degradation rates of the products of the examples of the present invention and Comparative Example 2 are basically similar, and Example 1 is the best example. This is because: the molar ratio of sodium carbonate to sodium hydroxide of 2:1 is favorable for the formation of samples with spherical particles, and has a high tap density; but too much sodium carbonate (the molar ratio of sodium carbonate to sodium hydroxide is 3:1) It will reduce the formation of intact spherical particle samples, resulting in reduced tap density and poor product performance.
综上,本发明的LiNi 0.69Mn 0.23Co 0.08O 2是在一种新的合成条件下制得的晶体结构为层状的化合物,该化合物形貌独特、尺寸均匀、振实密度高,其特殊的晶体结构赋予其更优的库仑效率和循环性能,其可作为电池上的阴极材料使用,具有极好的工业前景。 In summary, the LiNi 0.69 Mn 0.23 Co 0.08 O 2 of the present invention is a compound with a layered crystal structure prepared under a new synthesis condition. The compound has a unique morphology, uniform size, high tap density, and its special Its crystal structure gives it better coulombic efficiency and cycle performance. It can be used as a cathode material on batteries and has excellent industrial prospects.
以上显示和描述了本发明的基本原理、主要特征和优点。本行业的技术人员应该了解,上述实施例不以任何形式限制本发明,凡采用等同替换或等效变换的方式所获得的技术方案,均落在本发明的保护范围内。The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the above embodiments do not limit the present invention in any form, and any technical solution obtained by equivalent replacement or equivalent transformation falls within the protection scope of the present invention.

Claims (10)

  1. 层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物,其特征在于,化合物的晶体结构为层状,于混合碳酸钠/氢氧化钠溶液共沉淀法下合成。 The layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound is characterized in that the crystal structure of the compound is layered and synthesized under the mixed precipitation method of mixed sodium carbonate/sodium hydroxide solution.
  2. 制备权利要求1所述的层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物的方法,其特征在于,包括步骤: The method for preparing the layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound according to claim 1, characterized in that it comprises the steps of:
    S1、共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2:以醋酸钴、醋酸锰、醋酸镍及氢氧化铵为前驱体,向前驱体混合溶液中滴加混合碳酸钠/氢氧化钠溶液,通过共沉淀法合成层状Ni 0.69Mn 0.23Co 0.08(OH) 2S1. Co-precipitation method to synthesize layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 : using cobalt acetate, manganese acetate, nickel acetate and ammonium hydroxide as precursors, and adding mixed sodium carbonate/hydroxide to the precursor mixed solution For sodium solution, layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 was synthesized by co-precipitation method;
    S2、制备层状LiNi 0.69Mn 0.23Co 0.08O 2化合物:将步骤S1制得的层状Ni 0.69Mn 0.23Co 0.08(OH) 2与LiOH·H 2O以摩尔比为1:1.05预先混料均匀后,再以固态法烧结,制得层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物。 S2. Preparation of layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound: the layered Ni 0.69 Mn 0.23 Co 0.08 (OH) 2 and LiOH·H 2 O prepared in step S1 are pre-mixed in a molar ratio of 1:1.05 After that, it was sintered in a solid state method to obtain a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound.
  3. 根据权利要求2所述的制备层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物的方法,其特征在于,所述步骤S1中,醋酸钴、醋酸锰、醋酸镍及氢氧化铵的摩尔比为:0.08:0.23:0.69:0.8。 The method for preparing a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound according to claim 2, wherein in step S1, the molar ratio of cobalt acetate, manganese acetate, nickel acetate and ammonium hydroxide is : 0.08:0.23:0.69:0.8.
  4. 根据权利要求2所述的制备层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物的方法,其特征在于,所述步骤S1中,通过控制混合碳酸钠/氢氧化钠溶液的滴加速度调节反应液的pH值为7.5~8.5。 The method for preparing a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound according to claim 2, wherein in step S1, the reaction solution is adjusted by controlling the dripping acceleration of the mixed sodium carbonate/sodium hydroxide solution The pH value is 7.5 ~ 8.5.
  5. 根据权利要求4所述的制备层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物的方法,其特征在于,反应液的pH值为8.3。 The method for preparing a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound according to claim 4, wherein the pH of the reaction solution is 8.3.
  6. 根据权利要求2所述的制备层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物的方法,其特征在于,所述步骤S1中,反应液温度为55℃。 The method for preparing a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound according to claim 2, wherein in step S1, the temperature of the reaction solution is 55°C.
  7. 根据权利要求2所述的制备层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物的方法,其特征在于,所述步骤S2中,固态法烧结温度为600~1000℃,烧结时间为8~20h。 The method for preparing a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound according to claim 2, wherein in the step S2, the solid-state sintering temperature is 600-1000°C and the sintering time is 8-20h .
  8. 根据权利要求7所述的制备层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物的方法,其特征在于,所述步骤S2中,固态法烧结温度为800℃,烧结时间为15h。 The method for preparing a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound according to claim 7, wherein in step S2, the solid-state sintering temperature is 800°C and the sintering time is 15h.
  9. 根据权利要求2所述的制备层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物的方法,其特征在于,混合碳酸钠/氢氧化钠溶液中,碳酸钠与氢氧化钠的摩尔比为2:1~3:1。 The method for preparing a layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound according to claim 2, characterized in that, in the mixed sodium carbonate/sodium hydroxide solution, the molar ratio of sodium carbonate to sodium hydroxide is 2: 1~3:1.
  10. 权利要求1所述的层状结构的LiNi 0.69Mn 0.23Co 0.08O 2化合物作为电池的阴极材料使用。 The layered LiNi 0.69 Mn 0.23 Co 0.08 O 2 compound according to claim 1 is used as a cathode material of a battery.
PCT/CN2020/070098 2019-01-04 2020-01-02 Lini0.69mn0.23co0.08o2 compound having a layered structure, synthesis method therefor and application thereof WO2020140941A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201910006756.X 2019-01-04
CN201910006756.XA CN109704416B (en) 2019-01-04 2019-01-04 Layered structured LiNi0.69Mn0.23Co0.08O2Compound and preparation method and application thereof

Publications (1)

Publication Number Publication Date
WO2020140941A1 true WO2020140941A1 (en) 2020-07-09

Family

ID=66260730

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/070098 WO2020140941A1 (en) 2019-01-04 2020-01-02 Lini0.69mn0.23co0.08o2 compound having a layered structure, synthesis method therefor and application thereof

Country Status (2)

Country Link
CN (1) CN109704416B (en)
WO (1) WO2020140941A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109704416B (en) * 2019-01-04 2021-04-06 散裂中子源科学中心 Layered structured LiNi0.69Mn0.23Co0.08O2Compound and preparation method and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1960039A (en) * 2005-10-31 2007-05-09 深圳市天骄科技开发有限公司 Anode material Li1+x(CoyMnzNi1-y-z)1-xO2 of lithium ion battery, and preparation method
CN103456933A (en) * 2012-06-01 2013-12-18 私立辅仁大学 Lithium nickel cobalt manganese composite oxide cathode material
CN104577096A (en) * 2013-10-17 2015-04-29 奇瑞汽车股份有限公司 Cathode material for lithium-ion battery, preparation method of cathode material and battery
CN104852038A (en) * 2015-04-08 2015-08-19 中国科学院长春应用化学研究所 Preparation method of high-capacity quickly-chargeable/dischargeable lithium ion battery ternary anode material
CN108172822A (en) * 2017-12-29 2018-06-15 昶联金属材料应用制品(广州)有限公司 Nickel-cobalt lithium manganate cathode material and preparation method thereof
CN108550791A (en) * 2018-04-20 2018-09-18 中国科学院化学研究所 A kind of layered cathode material and its preparation method and application of spinelle cladding
JP2018181487A (en) * 2017-04-06 2018-11-15 東洋インキScホールディングス株式会社 Aqueous coating liquid for electrode, and utilization thereof
CN109704416A (en) * 2019-01-04 2019-05-03 东莞中子科学中心 The LiNi of layer structure0.69Mn0.23Co0.08O2Compound and its preparation method and application

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103956479B (en) * 2014-05-20 2016-04-06 天津理工大学 The preparation method of the spherical lithium-rich anode material of a kind of high power capacity
CN107123793A (en) * 2017-04-26 2017-09-01 江苏大学 A kind of stratiform lithium-rich manganese base material Li1.2Ni0.13Co0.13Mn0.54O2Preparation method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1960039A (en) * 2005-10-31 2007-05-09 深圳市天骄科技开发有限公司 Anode material Li1+x(CoyMnzNi1-y-z)1-xO2 of lithium ion battery, and preparation method
CN103456933A (en) * 2012-06-01 2013-12-18 私立辅仁大学 Lithium nickel cobalt manganese composite oxide cathode material
CN104577096A (en) * 2013-10-17 2015-04-29 奇瑞汽车股份有限公司 Cathode material for lithium-ion battery, preparation method of cathode material and battery
CN104852038A (en) * 2015-04-08 2015-08-19 中国科学院长春应用化学研究所 Preparation method of high-capacity quickly-chargeable/dischargeable lithium ion battery ternary anode material
JP2018181487A (en) * 2017-04-06 2018-11-15 東洋インキScホールディングス株式会社 Aqueous coating liquid for electrode, and utilization thereof
CN108172822A (en) * 2017-12-29 2018-06-15 昶联金属材料应用制品(广州)有限公司 Nickel-cobalt lithium manganate cathode material and preparation method thereof
CN108550791A (en) * 2018-04-20 2018-09-18 中国科学院化学研究所 A kind of layered cathode material and its preparation method and application of spinelle cladding
CN109704416A (en) * 2019-01-04 2019-05-03 东莞中子科学中心 The LiNi of layer structure0.69Mn0.23Co0.08O2Compound and its preparation method and application

Also Published As

Publication number Publication date
CN109704416B (en) 2021-04-06
CN109704416A (en) 2019-05-03

Similar Documents

Publication Publication Date Title
CN109686938B (en) Magnesium ion doped gradient nickel cobalt lithium manganate positive electrode material and preparation method thereof
CN104241626B (en) The process for preparing sol-gel of lithium ion battery lithium vanadate negative material
CN107403913B (en) Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof
CN106410157B (en) High-magnification long-life cathode material and preparation method thereof
CN109721109B (en) Nickel-cobalt-manganese ternary positive electrode material precursor for lithium battery, preparation method of precursor and prepared positive electrode material
CN102891309B (en) Preparation method of spherical lithium-enriched anode material with gradient concentration
KR20170102293A (en) Multicomponent materials having a classification structure for lithium ion batteries, a method for manufacturing the same, an anode of a lithium ion battery and a lithium ion battery
CN108767216B (en) Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof
CN109119624B (en) Preparation method of lithium titanium phosphate coated lithium-rich manganese-based positive electrode material
CN103904321B (en) The high-temperature solid phase preparation method of lithium ion battery negative material LiMn2O4
CN102916171B (en) Concentration-gradually-changed spherical lithium nickel manganese oxide cathode material and preparation method thereof
CN101941685A (en) Preparation of spherical lithium iron phosphate material and lithium ion battery using spherical lithium iron phosphate material
KR20140119621A (en) Precusor for lithium rich active material and lithium rich active material made by the same
US20190386293A1 (en) Ternary material and preparation method thereof, battery slurry, positive electrode and lithium battery
WO2015039490A1 (en) Lithium-rich anode material and preparation method thereof
CN111785960B (en) Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof
CN105514373A (en) Positive electrode material of high-capacity lithium ion battery and preparation method of positive electrode material
CN106910887B (en) Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material
CN102832381A (en) Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life
WO2020140941A1 (en) Lini0.69mn0.23co0.08o2 compound having a layered structure, synthesis method therefor and application thereof
CN103413928B (en) High-capacity high-compaction metal oxide anode material and preparation method thereof
CN109004195B (en) Lithium supplement additive and preparation method thereof
WO2019104948A1 (en) Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery
KR20150080219A (en) Cathode active material and lithium secondary batteries comprising the same
CN110233261B (en) Preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery

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: 20735891

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20735891

Country of ref document: EP

Kind code of ref document: A1