CN107204426A - A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property - Google Patents

A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property Download PDF

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CN107204426A
CN107204426A CN201710432855.5A CN201710432855A CN107204426A CN 107204426 A CN107204426 A CN 107204426A CN 201710432855 A CN201710432855 A CN 201710432855A CN 107204426 A CN107204426 A CN 107204426A
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lithium
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cobalt
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zirconium
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朱继平
王娟
严家伟
王杰
徐金鑫
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Xuancheng Yili Energy Amperex Technology Ltd
Hefei University of Technology
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Hefei University of Technology
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Abstract

本发明公开了一种锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料。该正极材料首先用共沉淀法合成锆掺杂的氧化镍钴锰锂正极材料，然后采用钛酸锂活性电极材料对三元材料进行包覆。一方面可以提高电子电导率和离子电导率，提高电池的输出功率密度，而且还可以提高三元材料的结构稳定性。另一方面，通过包覆可以综合两种材料的优点，从而得到循环性较好、容量较高、能量密度较大的复合正极材料。

The invention discloses a zirconium doped modified nickel oxide cobalt manganese lithium/lithium titanate composite cathode material. The positive electrode material first synthesizes zirconium-doped nickel-cobalt-manganese-manganese-lithium positive electrode material by co-precipitation method, and then uses lithium titanate active electrode material to coat the ternary material. On the one hand, it can improve the electronic conductivity and ion conductivity, increase the output power density of the battery, and also improve the structural stability of the ternary material. On the other hand, the advantages of the two materials can be combined by coating, so as to obtain a composite cathode material with better cycle performance, higher capacity, and higher energy density.

Description

一种锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料A zirconium-doped modified nickel-cobalt-manganese-lithium/lithium titanate composite cathode material

技术领域technical field

本发明属锂离子电池正极材料领域，尤其涉及一种锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料。The invention belongs to the field of positive electrode materials for lithium ion batteries, in particular to a zirconium-doped modified nickel oxide cobalt manganese lithium/lithium titanate composite positive electrode material.

背景技术Background technique

锂离子电池是20世纪90年代迅速发展起来的新一代二次电池，广泛用于小型便携式电子通讯产品和电动交通工具。目前已经产业化的锂离子电池正极材料主要有钴酸锂、改性锰酸锂、三元材料、磷酸铁锂等。钴酸锂主要应用于小型高能量密度锂离子电池领域，但钴毒性较大，资源稀缺，价格昂贵，且其过充安全性能较差。尖晶石型锰酸锂比容量低，且高温循环和存储性能差。磷酸铁锂导电性差、产品批次一次性差、低温性能差，并存在微量铁的溶解可能引起电池短路的问题。因此，研究发现，以LiNixMnyCo1-x-yO2 为代表的层状氧化镍钴锰系列材料（简称三元材料）较好的兼备了上述材料的优点，并在一定程度上弥补其不足，具有高比容量、循环性能稳定、成本相对较低、安全性能较好等特点，被认为是用于混合型动力电源的理想选择。但同时它也存在较低的电导率和容量衰减快、倍率性能不佳等缺点。Lithium-ion batteries are a new generation of secondary batteries developed rapidly in the 1990s, and are widely used in small portable electronic communication products and electric vehicles. At present, the anode materials of lithium-ion batteries that have been industrialized mainly include lithium cobalt oxide, modified lithium manganese oxide, ternary materials, and lithium iron phosphate. Lithium cobalt oxide is mainly used in the field of small-scale high-energy-density lithium-ion batteries, but cobalt is highly toxic, resources are scarce, expensive, and its overcharge safety performance is poor. Spinel-type lithium manganate has low specific capacity, and poor high-temperature cycle and storage performance. Lithium iron phosphate has poor conductivity, poor disposable product batches, poor low-temperature performance, and there is a problem that the dissolution of trace iron may cause short circuit of the battery. Therefore, the study found that the layered nickel-cobalt-manganese oxide series materials represented by LiNi x Mn y Co 1-xy O 2 (referred to as ternary materials) have both the advantages of the above materials and make up for them to a certain extent. Insufficient, with high specific capacity, stable cycle performance, relatively low cost, good safety performance, etc., it is considered to be an ideal choice for hybrid power sources. But at the same time, it also has disadvantages such as low conductivity, fast capacity decay, and poor rate performance.

目前LiNixMnyCo1-x-yO2的制备方法主要有高温固相法、共沉淀法、溶胶-凝胶法等。本课题使用共沉淀法来制备颗粒更细的镍钴锰酸锂材料，缩短锂离子的扩散路径，提高其电化学性能。共沉淀法制备的材料能够达到分子或原子级别的混合，解决了传统固相法混料不均和粒径过大的问题，制备出的材料纯度高、粒径小，分布较窄且烧结性能好。At present, the preparation methods of LiNi x Mn y Co 1-xy O 2 mainly include high-temperature solid-phase method, co-precipitation method, sol-gel method and so on. This topic uses the co-precipitation method to prepare nickel-cobalt-lithium manganese oxide materials with finer particles, shorten the diffusion path of lithium ions, and improve its electrochemical performance. The materials prepared by the co-precipitation method can achieve molecular or atomic level mixing, which solves the problems of uneven mixing and excessive particle size of the traditional solid-phase method. The prepared materials have high purity, small particle size, narrow distribution and excellent sintering performance. it is good.

LiNixMnyCo1-x-yO2正极材料集合了LiNiO2、LiCoO2、LiMnO2三种正极材料优点，拥有优异的性价比和电化学性能，在电子产品中得到广泛应用，有望取代LiCoO2正极材料，被认为是最有潜力广泛应用的正极材料之一。LiNixMnyCo1-x-yO2材料在镍钴锰酸锂三元材料体系中性能优异，得到国内外许多研究机构的关注，不仅在小型电子产品中被广泛使用，在大型汽车动力电池上也有较好的发展趋势，具有很好的应用前景。但同时它也存在较低的电导率和容量衰减快、倍率性能不佳等缺点，为了获得更加优异的三元正极材料，对镍钴锰酸锂进行掺杂和包覆。通过离子掺杂使晶格发生一定的畸变，产生一定的缺陷，提高电子电导率和离子扩散速率，以提高倍率性能和循环性能。LiNi x Mn y Co 1-xy O 2 positive electrode material combines the advantages of LiNiO 2 , LiCoO 2 , and LiMnO 2 positive electrode materials. It has excellent cost performance and electrochemical performance. It is widely used in electronic products and is expected to replace LiCoO 2 positive electrode material is considered to be one of the cathode materials with the most potential for wide application. The LiNi x Mn y Co 1-xy O 2 material has excellent performance in the nickel-cobalt lithium manganese oxide ternary material system, and has attracted the attention of many research institutions at home and abroad. It is not only widely used in small electronic products, but also in large-scale automotive power batteries. It also has a good development trend and has a good application prospect. But at the same time, it also has disadvantages such as low conductivity, fast capacity decay, and poor rate performance. In order to obtain a more excellent ternary cathode material, nickel-cobalt lithium manganese oxide is doped and coated. Through ion doping, the crystal lattice is distorted to a certain extent, and certain defects are generated, and the electronic conductivity and ion diffusion rate are improved to improve the rate performance and cycle performance.

钛酸锂是一个“零应变”材料，在锂离子嵌入脱出的过程中，能稳定材料的结构；其次，在Li-Ti-O中，Ti-O键的键能大于M-O(M=Mn、Ni、Go)键的键能，即Ti4+离子比Mx+离子对氧具有更强的束缚力，能稳定材料的层状结构；再者，Li-Ti-O中，锂是一个快速锂离子导体。该材料的引入可以扩大三元材料中的锂离子扩散系数高传输通道；最后，在镍钴锰层状结构中植入钛酸锂尖晶石组分，可以提高首次库伦效率，抑制不可逆容量损失，这主要是因为钛酸锂可以吸纳从镍钴锰材料中脱嵌的多余的锂离子。所以，通过钛酸锂包覆锆掺杂的镍钴锰三元材料，不仅可以提高材料的安全性，还可以提高材料的循环性能，提高活性物质利用率。Lithium titanate is a "zero strain" material, which can stabilize the structure of the material during the process of intercalation and extraction of lithium ions; secondly, in Li-Ti-O, the bond energy of the Ti-O bond is greater than that of MO (M=Mn, The bond energy of the Ni, Go) bond, that is, the Ti 4+ ion has a stronger binding force to oxygen than the M x+ ion, which can stabilize the layered structure of the material; moreover, in Li-Ti-O, lithium is a fast lithium ion conductor. The introduction of this material can expand the transmission channel with high lithium ion diffusion coefficient in the ternary material; finally, implanting lithium titanate spinel components in the nickel-cobalt-manganese layered structure can improve the first Coulombic efficiency and suppress irreversible capacity loss , this is mainly because lithium titanate can absorb excess lithium ions deintercalated from nickel-cobalt-manganese materials. Therefore, coating the zirconium-doped nickel-cobalt-manganese ternary material with lithium titanate can not only improve the safety of the material, but also improve the cycle performance of the material and improve the utilization rate of the active material.

发明内容Contents of the invention

本发明旨在提供一种用锆掺杂氧化镍钴锰锂正极材料，并在其基础上采用钛酸锂包覆，所要解决的技术问题是三元层状正极材料氧化镍钴锰锂重复性差和倍率性能，同时提供一种工艺过程简单、安全性高、稳定性好的钛酸锂包覆的锆掺杂的镍钴锰锂正极材料。The present invention aims to provide a zirconium-doped nickel-cobalt-manganese-manganese-lithium positive electrode material, on the basis of which is coated with lithium titanate. The technical problem to be solved is that the repeatability of the ternary layered positive electrode material nickel-cobalt-manganese-lithium oxide is poor and rate performance, while providing a zirconium-doped nickel-cobalt-manganese-lithium positive electrode material coated with lithium titanate with simple process, high safety and good stability.

本发明解决技术问题采用如下技术方案：The present invention solves technical problem and adopts following technical scheme:

一种锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料，其特征在于：制备包括如下步骤：A zirconium-doped modified nickel-cobalt-manganese-lithium/lithium titanate composite positive electrode material, characterized in that the preparation includes the following steps:

(1)将锂源、部分钴源、锰源、锆源按照一定摩尔比溶解在水和无水乙醇的混合溶液中，标记为溶液A，将镍源、剩余的钴源按照一定摩尔比溶解在水和乙醇的溶液中，标记为溶液B，将二水合草酸溶解在水和乙醇溶液中，标记为溶液C；首先将A溶液倒入溶液C中，反应10~12min后，再将B溶液倒入A和C的混合溶液中，反应5~6h，使之完全沉淀；将反应后的物质放在干燥箱中干燥后，得到粉末，再进行研磨，然后放入坩埚中，煅烧后，得到黑色粉末；将粉末进行研磨，并过400~500目筛，即可得到锆掺杂的氧化镍钴锰锂LiNixCoyMnl-x-y-zZrzO2正极材料，其中0<x<0.6，0<y<0.6，0<z<0.1；(1) Dissolve the lithium source, part of the cobalt source, manganese source, and zirconium source in a mixed solution of water and absolute ethanol according to a certain molar ratio, mark it as solution A, and dissolve the nickel source and the remaining cobalt source according to a certain molar ratio In the solution of water and ethanol, mark it as solution B, dissolve oxalic acid dihydrate in the solution of water and ethanol, mark it as solution C; first pour solution A into solution C, react for 10~12min, then dissolve solution B Pour into the mixed solution of A and C, and react for 5~6h to make it completely precipitated; put the reacted substance in a drying oven to dry to obtain a powder, then grind it, then put it into a crucible, and after calcining, get Black powder; grind the powder and pass through a 400-500 mesh sieve to obtain zirconium-doped nickel-cobalt-manganese-lithium LiNi x Co y Mn lxyz Zr z O 2 cathode material, where 0<x<0.6, 0<y<0.6,0<z<0.1;

(2)将钛酸锂和上述（1）制备的LiNixCoyMn1-x-y-zZrzO2正极材料置于无水乙醇/异丙醇溶液中，浓度为0.01~0.02mol/L，再在75~85℃下加热搅拌蒸干，并研磨过筛，得到前驱体，将该前驱体置于马弗炉中，以3~5℃/min的速度升温，在600~800℃下煅烧2~5h，然后冷却至室温，得到LiNixCoyMn1-x-y-zZrzO2/LTO正极材料。(2) Lithium titanate and the LiNi x Co y Mn 1-xyz Zr z O 2 cathode material prepared in (1) above were placed in absolute ethanol/isopropanol solution with a concentration of 0.01~0.02mol/L, and then Heat, stir and evaporate to dryness at 75-85°C, grind and sieve to obtain the precursor, place the precursor in a muffle furnace, heat up at a rate of 3-5°C/min, and calcinate at 600-800°C for 2 ~5h, and then cooled to room temperature to obtain LiNi x Co y Mn 1-xyz Zr z O 2 /LTO cathode material.

所述的锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料，其特征在于，所述的镍源为碳酸镍、乙酸镍、硝酸镍中的一种或几种；The zirconium-doped modified nickel-cobalt-manganese-lithium oxide/lithium titanate composite positive electrode material is characterized in that the nickel source is one or more of nickel carbonate, nickel acetate, and nickel nitrate;

所述的钴源为碳酸钴、乙酸钴、硝酸钴中的一种或几种；Described cobalt source is one or more in cobalt carbonate, cobalt acetate, cobalt nitrate;

所述的锰源为碳酸锰、乙酸锰、硝酸锰中的一种或几种；Described manganese source is one or more in manganese carbonate, manganese acetate, manganese nitrate;

所述的锆源为硝酸锆、磷酸锆、氯化锆中的一种或几种；The zirconium source is one or more of zirconium nitrate, zirconium phosphate, and zirconium chloride;

所述的锂盐为碳酸锂、乙酸锂、硝酸锂、氢氧化锂中的一种或几种；Described lithium salt is one or more in lithium carbonate, lithium acetate, lithium nitrate, lithium hydroxide;

所述的水和无水乙醇的混合溶液中水和无水乙醇的体积比为1：0~10。The volume ratio of water and absolute ethanol in the mixed solution of water and absolute ethanol is 1:0-10.

所述的锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料，其特征在于，将锂源、部分钴源、锰源、锆源按照一定摩尔比溶解在水和无水乙醇的混合溶液中，浓度为0.1~0.15mol/L，标记为溶液A；将镍源、剩余的钴源按照一定摩尔比溶解在水和乙醇的溶液中，浓度为0.03~0.04mol/L，标记为溶液B,将二水合草酸溶解在水和乙醇溶液中，浓度为0.15~0.2mol/L，标记为溶液C。The zirconium-doped modified nickel-cobalt-manganese lithium/lithium titanate composite positive electrode material is characterized in that the lithium source, part of the cobalt source, the manganese source, and the zirconium source are dissolved in water and absolute ethanol according to a certain molar ratio. In the mixed solution, the concentration is 0.1~0.15mol/L, which is marked as solution A; the nickel source and the remaining cobalt source are dissolved in the solution of water and ethanol according to a certain molar ratio, and the concentration is 0.03~0.04mol/L, which is marked as For solution B, dissolve oxalic acid dihydrate in water and ethanol solution at a concentration of 0.15~0.2mol/L, and mark it as solution C.

所述的锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料，其特征在于：步骤（1）所述的干燥指的是在70~90℃干燥8~12h；所述煅烧过程是先升温至300~600℃煅烧4~10h，再升温至700~950℃煅烧10~24h。The zirconium-doped modified nickel-cobalt-manganese-lithium oxide/lithium titanate composite positive electrode material is characterized in that: the drying in step (1) refers to drying at 70-90°C for 8-12 hours; the calcination The process is to heat up to 300~600°C for 4~10 hours, and then heat up to 700~950°C for 10~24 hours.

所述的锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料，其特征在于：步骤（2）中将该前驱体置于马弗炉中，以4℃/min的速度升温。The zirconium-doped modified nickel-cobalt-manganese-lithium oxide/lithium titanate composite positive electrode material is characterized in that: in step (2), the precursor is placed in a muffle furnace, and the temperature is raised at a rate of 4°C/min .

所述的锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料，其特征在于，所述钛酸锂的用量占氧化镍钴锰锂质量的0.5%~15%。The zirconium-doped modified nickel-cobalt-manganese-lithium oxide/lithium titanate composite positive electrode material is characterized in that the amount of lithium titanate accounts for 0.5%-15% of the mass of nickel-cobalt-manganese-lithium oxide.

所述的锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料，其特征在于，所述的钛酸锂的制备方法包括以下步骤：The zirconium-doped modified nickel-cobalt-manganese lithium/lithium titanate composite positive electrode material is characterized in that the preparation method of the lithium titanate comprises the following steps:

(1)将钛源化合物溶于无水乙醇中，两者体积比为1:1~1.2形成溶液A；锂源化合物溶于去离子水中，配制成一定浓度的含Li+的溶液；(1) The titanium source compound is dissolved in absolute ethanol, and the volume ratio of the two is 1:1~1.2 to form a solution A; the lithium source compound is dissolved in deionized water, and a solution containing Li + with a certain concentration is prepared;

(2)在磁力搅拌下向溶液A中逐滴加入上述配制的一定浓度的含Li+的溶液，形成白色悬浮液B，继续大力搅拌1~1.5 h；(2) Under magnetic stirring, add the above-mentioned solution containing Li + at a certain concentration to the solution A dropwise to form a white suspension B, and continue vigorously stirring for 1-1.5 h;

(3)将所述白色悬浮液B转移至不锈钢高压反应釜中，放入鼓风电热干燥箱内在120~200℃下连续反应12~24h后自然冷却至室温，将所得物离心、洗涤、干燥得到前驱体粉末；(3) Transfer the white suspension B to a stainless steel high-pressure reaction kettle, put it into a blower electric drying oven, react continuously at 120-200°C for 12-24h, then cool it down to room temperature naturally, centrifuge, wash and dry the resultant Obtain precursor powder;

(4)将所述前驱体在马弗炉中、空气气氛下、500~800℃下煅烧2~12h后得到的白色粉末即为制得的钛酸锂。(4) The white powder obtained after calcining the precursor in a muffle furnace under an air atmosphere at 500-800° C. for 2-12 hours is the prepared lithium titanate.

所述的锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料，其特征在于，所述钛源化合物为钛酸丁酯、钛酸四异丙酯、四氯化钛、纳米级二氧化钛中的一种或几种；The zirconium-doped modified nickel-cobalt-manganese-lithium oxide/lithium titanate composite positive electrode material is characterized in that the titanium source compound is butyl titanate, tetraisopropyl titanate, titanium tetrachloride, nano One or more of high-grade titanium dioxide;

所述锂源化合物为氢氧化锂、醋酸锂、碳酸锂、氧化锂中的一种或几种；The lithium source compound is one or more of lithium hydroxide, lithium acetate, lithium carbonate, and lithium oxide;

所述锂源中的Li和钛源中的Ti之间的摩尔比为0.8~1；The molar ratio between the Li in the lithium source and the Ti in the titanium source is 0.8～1;

所述锂源化合物配制成的含Li+的溶液浓度为1~5mol/L；The Li + -containing solution prepared by the lithium source compound has a concentration of 1 to 5 mol/L;

钛酸锂的制备方法中所述煅烧时的升温速率为4℃/min。The heating rate during calcination in the preparation method of lithium titanate is 4° C./min.

与现有技术相比，本发明有益效果体现在：Compared with the prior art, the beneficial effects of the present invention are reflected in:

1、本发明复合正极材料是一种更高比容量、更好倍率性能的LiNixCoyMn1-x-y-zZrzO2/LTO复合正极材料。1. The composite cathode material of the present invention is a LiNix Co y Mn 1-xyz Zr z O 2 /LTO composite cathode material with higher specific capacity and better rate performance.

2、本发明简单易行，生产效率高，减少了生产工序，节省了生产成本，适宜规模化生产，与没有进行改性的材料相比，在电池容量、倍率性能和循环性能上得到了很大的提高。2. The present invention is simple and easy to implement, has high production efficiency, reduces production procedures, saves production costs, and is suitable for large-scale production. Compared with unmodified materials, the battery capacity, rate performance and cycle performance have been greatly improved. Big improvement.

3、本发明在锆掺杂的氧化镍钴锰锂结构中植入钛酸锂尖晶石组分，能稳定材料的层状结构，提高安全性；钛酸锂能吸纳从镍钴锰材料中脱出的多余的锂离子，可以提高首次库伦效率，抑制不可逆容量损失。3. The present invention implants lithium titanate spinel components in the zirconium-doped nickel-cobalt-manganese-lithium oxide structure, which can stabilize the layered structure of the material and improve safety; lithium titanate can be absorbed from the nickel-cobalt-manganese material The excess lithium ions released can improve the first Coulombic efficiency and suppress irreversible capacity loss.

附图说明Description of drawings

图1为LiNi1/3Co1/3Mn1/3O2和LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2的 XRD图谱。Figure 1 is the XRD patterns of LiNi 1/3 Co 1/3 Mn 1/3 O 2 and LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 .

图2为LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2和LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2/LTO的XRD图谱。Fig. 2 is the XRD patterns of LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 and LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 /LTO.

图3为 LiNi1/3Co1/3Mn1/3O2、LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2和LiNi1/3Co1/3Mn1/3- 0.02Zr0.02O2/LTO在 0.2C下首次充放电曲线。Figure 3 shows LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 and LiNi 1/3 Co 1/3 Mn 1/3- The first charge-discharge curve of 0.02 Zr 0.02 O 2 /LTO at 0.2C.

图4为LiNi1/3Co1/3Mn1/3O2和LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2复合正极材料的循环性能图。Figure 4 is a cycle performance diagram of LiNi 1/3 Co 1/3 Mn 1/3 O 2 and LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 composite cathode materials.

图5为实施例2制备的LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2的FE-SEM图。5 is a FE-SEM image of LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 prepared in Example 2.

具体实施方式detailed description

为了进一步了解本发明的内容特点和有益效果，下面通过具体的实例并结合附图对本发明作进一步详细的描述。In order to further understand the content, characteristics and beneficial effects of the present invention, the present invention will be further described in detail below through specific examples and in conjunction with the accompanying drawings.

实施例1：Example 1:

本实施例中锂离子电池氧化镍钴锰锂正极材料是按照以下步骤制备得到的：In this embodiment, the lithium-ion battery nickel-cobalt-manganese-lithium positive electrode material is prepared according to the following steps:

称取0.536g醋酸锂、0.409g醋酸锰、0.276g醋酸钴，溶解在10ml水和50ml乙醇的混合溶液中，记为A溶液，为了弥补煅烧过程中锂源的损失，醋酸锂过量5%；称取0.415g醋酸镍、0.138g醋酸钴溶解在10ml水和50ml乙醇的混合溶液中，记为B溶液；称取1.1649g二水合草酸，溶解在10ml水和50ml乙醇的混合溶液中，记为C溶液。将A溶液滴加到C溶液中，使之沉淀，10min后，将B溶液倒入C中，室温下反应5h。然后在烘箱中80℃下干燥12h，研磨得到前驱体粉末。将前驱体放在坩埚内置于马弗炉中，在空气气氛中以4℃/min的升温速率升温至500℃，煅烧6h，再继续升温至850℃，煅烧24h，然后随炉冷却至室温，取出样品再次研磨得到LiNi1/3Co1/3Mn1/3O2粉末。Take by weighing 0.536g lithium acetate, 0.409g manganese acetate, 0.276g cobalt acetate, be dissolved in the mixed solution of 10ml water and 50ml ethanol, be recorded as A solution, in order to make up for the loss of lithium source in the calcining process, lithium acetate is excessive 5%; Weigh 0.415g of nickel acetate and 0.138g of cobalt acetate and dissolve them in a mixed solution of 10ml of water and 50ml of ethanol, and record it as solution B; weigh 1.1649g of dihydrate oxalic acid, dissolve it in a mixed solution of 10ml of water and 50ml of ethanol, and record it as C solution. Add solution A to solution C dropwise to make it precipitate. After 10 minutes, pour solution B into solution C and react at room temperature for 5 hours. Then it was dried in an oven at 80°C for 12 hours, and ground to obtain the precursor powder. Put the precursor in a crucible in a muffle furnace, heat up to 500°C at a rate of 4°C/min in an air atmosphere, calcinate for 6 hours, then continue to heat up to 850°C, calcinate for 24 hours, and then cool to room temperature with the furnace. The sample was taken out and ground again to obtain LiNi 1/3 Co 1/3 Mn 1/3 O 2 powder.

将制得的LiNi1/3Co1/3Mn1/3O2与乙炔黑和聚偏氟乙烯（PVDF）按8:1:1 的质量比混合均匀，碾压成厚120μm的膜，在120 ℃真空干燥10h后，作为实验半电池的正极；采用lmol/L LiPF6 /碳酸乙烯酯（EC）-二甲基碳酸酯（DMC）(EC与DMC的体积比1:1）电解液，在干燥的充满氩气的手套箱中，以金属锂片作为负极、组装成电池。以本实施例所制备的LiNi1/ 3Co1/3Mn1/3O2为正极，以锂片为负极的扣式电池，在2.5~4.3V电压范围，以0.1C倍率下恒流-恒压充电，0.2C倍率下恒流放电时首次放电比容量为166.3mAh/g，但经过50次循环后容量仅为125.32mAh/g。Mix the prepared LiNi 1/3 Co 1/3 Mn 1/3 O 2 with acetylene black and polyvinylidene fluoride (PVDF) at a mass ratio of 8:1:1, and roll it into a film with a thickness of 120 μm. After vacuum drying at 120 °C for 10 h, it was used as the positive electrode of the experimental half-cell; using lmol/L LiPF 6 /ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio of EC to DMC was 1:1) electrolyte, In a dry argon-filled glove box, lithium metal sheets were used as negative electrodes to assemble batteries. With the LiNi 1/ 3 Co 1/3 Mn 1/3 O 2 prepared in this example as the positive electrode and the lithium sheet as the negative electrode, the button battery is in the voltage range of 2.5 ~ 4.3V, with a constant current of 0.1C rate - Constant voltage charging, constant current discharge at 0.2C rate, the first discharge specific capacity is 166.3mAh/g, but the capacity after 50 cycles is only 125.32mAh/g.

实施例2：Example 2:

本实施例中锂离子电池用锆掺杂改性的氧化镍钴锰锂正极材料是按照以下步骤制备得到的：In this example, the nickel oxide cobalt manganese lithium positive electrode material modified by zirconium doping for lithium ion battery is prepared according to the following steps:

a、称取0.536g醋酸锂、0.409g醋酸锰、0.276g醋酸钴，溶解在10ml水和50ml乙醇的混合溶液中，记为A溶液，为了弥补煅烧过程中锂源的损失，醋酸锂过量5%；称取0.415g醋酸镍、0.138g醋酸钴溶解在10ml水和50ml乙醇的混合溶液中，记为B溶液；称取1.1649g二水合草酸，溶解在10ml水和50ml乙醇的混合溶液中，记为C溶液。将A溶液滴加到C溶液中，使之沉淀，10min后，将B溶液倒入C中，室温下反应5h。然后在烘箱中80℃下干燥12h，研磨得到前驱体粉末。将前驱体放在坩埚内置于马弗炉中，在空气气氛中以4℃/min的升温速率升温至500℃，煅烧6h，再继续升温至850℃，煅烧24h，然后随炉冷却至室温，取出样品再次研磨得到LiNi1/3Co1/3Mn1/3O2粉末。a, take by weighing 0.536g lithium acetate, 0.409g manganese acetate, 0.276g cobalt acetate, dissolve in the mixed solution of 10ml water and 50ml ethanol, record as A solution, in order to make up for the loss of lithium source in the calcining process, lithium acetate is excessive 5 %; Weigh 0.415g of nickel acetate, 0.138g of cobalt acetate and dissolve in a mixed solution of 10ml of water and 50ml of ethanol, which is referred to as solution B; weigh 1.1649g of dihydrate oxalic acid, dissolve in a mixed solution of 10ml of water and 50ml of ethanol, Recorded as C solution. Add solution A to solution C dropwise to make it precipitate. After 10 minutes, pour solution B into solution C and react at room temperature for 5 hours. Then it was dried in an oven at 80°C for 12 hours, and ground to obtain the precursor powder. Put the precursor in a crucible in a muffle furnace, heat up to 500°C at a rate of 4°C/min in an air atmosphere, calcinate for 6 hours, then continue to heat up to 850°C, calcinate for 24 hours, and then cool to room temperature with the furnace. The sample was taken out and ground again to obtain LiNi 1/3 Co 1/3 Mn 1/3 O 2 powder.

b、称取0.536g醋酸锂、0.407g醋酸锰、0.276g醋酸钴、0.045g硝酸锆，溶解在10ml水和50ml乙醇的混合溶液中，记为A溶液，为了弥补煅烧过程中锂源的损失，醋酸锂过量5%；称取0.415g醋酸镍、0.138g醋酸钴溶解在10ml水和50ml乙醇的混合溶液中，记为B溶液；称取1.1649g二水合草酸，溶解在10ml水和50ml乙醇的混合溶液中，记为C溶液。将A溶液滴加到C溶液中，使之沉淀，10min后，将B溶液倒入C中，室温下反应5h。然后在烘箱中80℃下干燥12h，研磨得到前驱体粉末。将前驱体放在坩埚内置于马弗炉中，在空气气氛中以4℃/min的升温速率升温至500℃，煅烧6h，再继续升温至850℃，煅烧24h，然后随炉冷却至室温，取出样品再次研磨得到LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2粉末。b. Weigh 0.536g of lithium acetate, 0.407g of manganese acetate, 0.276g of cobalt acetate, and 0.045g of zirconium nitrate, dissolve them in a mixed solution of 10ml of water and 50ml of ethanol, and record it as solution A, in order to make up for the loss of lithium source during the calcination process , Lithium acetate excess 5%; Weigh 0.415g nickel acetate, 0.138g cobalt acetate and dissolve in the mixed solution of 10ml water and 50ml ethanol, record as B solution; Weigh 1.1649g dihydrate oxalic acid, dissolve in 10ml water and 50ml ethanol In the mixed solution of , denoted as C solution. Add solution A to solution C dropwise to make it precipitate. After 10 minutes, pour solution B into solution C and react at room temperature for 5 hours. Then it was dried in an oven at 80°C for 12 hours, and ground to obtain the precursor powder. Put the precursor in a crucible in a muffle furnace, heat up to 500°C at a rate of 4°C/min in an air atmosphere, calcinate for 6 hours, then continue to heat up to 850°C, calcinate for 24 hours, and then cool to room temperature with the furnace. The sample was taken out and ground again to obtain LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 powder.

将实验制备得到的LiNi1/3Co1/3Mn1/3O2和LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2的X-射线衍射谱图见图1中。从图1中可以看出，制备的LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2正极材料与未掺杂的LiNi1/3Co1/3Mn1/3O2材料的XRD图峰形相同，没有出现杂峰，这可能是Zr进入LiNi1/3Col/3Mnl/ 3O2晶格内，取代部分位置上的Mn4+，这说明掺杂并不影响主体层状结构。The X-ray diffraction patterns of LiNi 1/3 Co 1/3 Mn 1/3 O 2 and LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 prepared in the experiment are shown in FIG. 1 . It can be seen from Fig. 1 that the as-prepared LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 cathode material is comparable to the undoped LiNi 1/3 Co 1/3 Mn 1/3 O 2 material The peak shape of the XRD pattern is the same, and no miscellaneous peaks appear, which may be that Zr enters the LiNi 1/3 Co l/3 Mn l/ 3 O 2 lattice to replace Mn 4+ on some positions, which shows that the doping is not Affects the main layered structure.

将制得的LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2与乙炔黑和聚偏氟乙烯（PVDF）按8:1:1 的质量比混合均匀，碾压成厚120μm的膜，在120 ℃真空干燥10h后，作为实验半电池的正极；采用l mol/L LiPF6 /碳酸乙烯酯（EC）-二甲基碳酸酯（DMC）(EC与DMC的体积比1:1）电解液，在干燥的充满氩气的手套箱中，以金属锂片作为负极、组装成电池。以本实施例所制备的LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2为正极，以锂片为负极的扣式电池，在2.5~4.3V电压范围，以0.1C倍率下恒流-恒压充电，0.2C倍率下恒流放电时首次放电比容量为180.5mAh/g，但经过50次循环后容量仅为137.54mAh/g。Mix the prepared LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 with acetylene black and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1, and roll it into a thickness of 120 μm The membrane was dried in vacuum at 120 ℃ for 10h, and used as the positive electrode of the experimental half-cell; using l mol/L LiPF 6 /ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio of EC to DMC was 1: 1) Electrolyte, in a dry glove box filled with argon, use metal lithium sheet as negative electrode, and assemble into a battery. With the LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 prepared in this example as the positive electrode and the lithium sheet as the negative electrode, in the voltage range of 2.5~4.3V, at a rate of 0.1C Under constant current-constant voltage charging, the first discharge specific capacity is 180.5mAh/g when the constant current is discharged at a rate of 0.2C, but the capacity after 50 cycles is only 137.54mAh/g.

实施例3：Example 3:

本实施例中锂离子电池用锆掺杂改性的氧化镍钴锰锂正极材料是按照以下步骤制备得到的：In this example, the nickel oxide cobalt manganese lithium positive electrode material modified by zirconium doping for lithium ion battery is prepared according to the following steps:

称取0.536g醋酸锂、0.381g醋酸锰、0.276g醋酸钴、0.091g硝酸锆，溶解在10ml水和50ml乙醇的混合溶液中，记为A溶液，为了弥补煅烧过程中锂源的损失，醋酸锂过量5%；称取0.415g醋酸镍、0.138g醋酸钴溶解在10ml水和50ml乙醇的混合溶液中，记为B溶液；称取1.1649g二水合草酸，溶解在10ml水和50ml乙醇的混合溶液中，记为C溶液。将A溶液滴加到C溶液中，使之沉淀，10min中后，将B溶液倒入C中，室温下反应5h。然后在烘箱中80℃下干燥12h，研磨得到前驱体粉末。将前驱体放在坩埚内置于马弗炉中，在空气气氛中以4℃/min的升温速率升温至500℃，煅烧6h，再继续升温至850℃，煅烧24h，然后随炉冷却至室温，取出样品再次研磨得到LiNi1/3Co1/3Mn1/3-0.04Zr0.04O2粉末。Weigh 0.536g lithium acetate, 0.381g manganese acetate, 0.276g cobalt acetate, 0.091g zirconium nitrate, dissolve in the mixed solution of 10ml water and 50ml ethanol, and record it as solution A. In order to make up for the loss of lithium source in the calcining process, acetic acid Lithium excess 5%; Weigh 0.415g of nickel acetate and 0.138g of cobalt acetate and dissolve in a mixed solution of 10ml of water and 50ml of ethanol, and record it as solution B; Weigh out 1.1649g of dihydrate oxalic acid, dissolve in a mixture of 10ml of water and 50ml of ethanol solution, denoted as C solution. Add solution A to solution C dropwise to make it precipitate. After 10 minutes, pour solution B into solution C and react at room temperature for 5 hours. Then it was dried in an oven at 80°C for 12 hours, and ground to obtain the precursor powder. Put the precursor in a crucible in a muffle furnace, heat up to 500°C at a rate of 4°C/min in an air atmosphere, calcinate for 6 hours, then continue to heat up to 850°C, calcinate for 24 hours, and then cool to room temperature with the furnace. The sample was taken out and ground again to obtain LiNi 1/3 Co 1/3 Mn 1/3-0.04 Zr 0.04 O 2 powder.

将本实施例制备的复合正极材料组装成电池，具体方法同实施例1，在2.5~4.3V电压范围，以0.1C倍率下恒流-恒压充电，0.2C倍率下恒流放电时首次放电比容量为177.3mAh/g，且经50次循环后容量保持在135.24mAh/g。The composite cathode material prepared in this example is assembled into a battery, the specific method is the same as in Example 1, in the voltage range of 2.5~4.3V, charge at a constant current-constant voltage at a rate of 0.1C, and discharge at a constant current at a rate of 0.2C for the first time The specific capacity is 177.3mAh/g, and the capacity remains at 135.24mAh/g after 50 cycles.

实施例4：Example 4:

本实施例中锂离子电池用锆掺杂改性的氧化镍钴锰锂正极材料是按照以下步骤制备得到的：In this example, the nickel oxide cobalt manganese lithium positive electrode material modified by zirconium doping for lithium ion battery is prepared according to the following steps:

称取0.536g醋酸锂、0.343g醋酸锰、0.276g醋酸钴、0.1314g硝酸锆，溶解在10ml水和50ml乙醇的混合溶液中，记为A溶液，为了弥补煅烧过程中锂源的损失，醋酸锂过量5%；称取0.415g醋酸镍、0.138g醋酸钴溶解在10ml水和50ml乙醇的混合溶液中，记为B溶液；称取1.1649g二水合草酸，溶解在10ml水和50ml乙醇的混合溶液中，记为C溶液。将A溶液滴加到C溶液中，使之沉淀，10min中后，将B溶液倒入C中，室温下反应5h。然后在烘箱中80℃下干燥12h，研磨得到前驱体粉末。将前驱体放在坩埚内置于马弗炉中，在空气气氛中以4℃/min的升温速率升温至500℃，煅烧6h，再继续升温至850℃，煅烧24h，然后随炉冷却至室温，取出样品再次研磨得到LiNi1/3Co1/3Mn1/3-0.06Zr0.06O2粉末。Weigh 0.536g lithium acetate, 0.343g manganese acetate, 0.276g cobalt acetate, 0.1314g zirconium nitrate, dissolve in the mixed solution of 10ml water and 50ml ethanol, and record it as solution A. In order to make up for the loss of lithium source in the calcining process, acetic acid Lithium excess 5%; Weigh 0.415g of nickel acetate and 0.138g of cobalt acetate and dissolve in a mixed solution of 10ml of water and 50ml of ethanol, and record it as solution B; Weigh out 1.1649g of dihydrate oxalic acid, dissolve in a mixture of 10ml of water and 50ml of ethanol solution, denoted as C solution. Add solution A to solution C dropwise to make it precipitate. After 10 minutes, pour solution B into solution C and react at room temperature for 5 hours. Then it was dried in an oven at 80°C for 12 hours, and ground to obtain the precursor powder. Put the precursor in a crucible in a muffle furnace, heat up to 500°C at a rate of 4°C/min in an air atmosphere, calcinate for 6 hours, then continue to heat up to 850°C, calcinate for 24 hours, and then cool to room temperature with the furnace. The sample was taken out and ground again to obtain LiNi 1/3 Co 1/3 Mn 1/3-0.06 Zr 0.06 O 2 powder.

将本实施例制备的复合正极材料组装成电池，具体方法同实施例1，在2.5~4.3V电压范围，以0.1C倍率下恒流-恒压充电，0.2C倍率下恒流放电时首次放电比容量为168.7mAh/g，且经50次循环后容量保持在133.26mAh/g。The composite cathode material prepared in this example is assembled into a battery, the specific method is the same as in Example 1, in the voltage range of 2.5~4.3V, charge at a constant current-constant voltage at a rate of 0.1C, and discharge at a constant current at a rate of 0.2C for the first time The specific capacity is 168.7mAh/g, and the capacity remains at 133.26mAh/g after 50 cycles.

实施例5：Example 5:

本实施例中锆掺杂改性的氧化镍钴锰锂/钛酸锂复合正极材料是按照以下步骤制备得到的：In this example, the nickel-cobalt-manganese-lithium oxide/lithium titanate composite cathode material modified by zirconium doping was prepared according to the following steps:

a、称取0.536g醋酸锂、0.407g醋酸锰、0.276g醋酸钴、0.045g硝酸锆，溶解在10ml水和50ml乙醇的混合溶液中，记为A溶液，为了弥补煅烧过程中锂源的损失，醋酸锂过量5%；称取0.415g醋酸镍、0.138g醋酸钴溶解在10ml水和50ml乙醇的混合溶液中，记为B溶液；称取1.1649g二水合草酸，溶解在10ml水和50ml乙醇的混合溶液中，记为C溶液。将A溶液滴加到C溶液中，使之沉淀，10min后，将B溶液倒入C中，室温下反应5h。然后在烘箱中80℃下干燥12h，研磨得到前驱体粉末。将前驱体放在坩埚内置于马弗炉中，在空气气氛中以4℃/min的升温速率升温至500℃，煅烧6h，再继续升温至850℃，煅烧24h，然后随炉冷却至室温，取出样品再次研磨得到LiNi1/3Co1/3Mn1/3O2粉末。a. Weigh 0.536g lithium acetate, 0.407g manganese acetate, 0.276g cobalt acetate, 0.045g zirconium nitrate, dissolve in the mixed solution of 10ml water and 50ml ethanol, record it as solution A, in order to make up for the loss of lithium source during the calcination process , Lithium acetate excess 5%; Weigh 0.415g nickel acetate, 0.138g cobalt acetate and dissolve in the mixed solution of 10ml water and 50ml ethanol, record as B solution; Weigh 1.1649g dihydrate oxalic acid, dissolve in 10ml water and 50ml ethanol In the mixed solution of , denoted as C solution. Add solution A to solution C dropwise to make it precipitate. After 10 minutes, pour solution B into solution C and react at room temperature for 5 hours. Then it was dried in an oven at 80°C for 12 hours, and ground to obtain the precursor powder. Put the precursor in a crucible in a muffle furnace, heat up to 500°C at a rate of 4°C/min in an air atmosphere, calcinate for 6 hours, then continue to heat up to 850°C, calcinate for 24 hours, and then cool to room temperature with the furnace. The sample was taken out and ground again to obtain LiNi 1/3 Co 1/3 Mn 1/3 O 2 powder.

b、将上述制得的LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2称取1.00g，溶于20ml无水乙醇中磁力搅拌，加入质量比为1%的钛酸锂粉末0.01g，将其混合溶液在80℃下搅拌蒸干得到粉末。再将所得粉末在500℃下煅烧3h，即可得到LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2/LTO粉末。b. Weigh 1.00g of LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 prepared above, dissolve it in 20ml of absolute ethanol with magnetic stirring, and add lithium titanate with a mass ratio of 1%. The powder is 0.01 g, and the mixed solution thereof is stirred and evaporated to dryness at 80° C. to obtain a powder. Calcining the obtained powder at 500° C. for 3 hours to obtain LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 /LTO powder.

将实验制备得到的LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2和LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2/LTO的X-射线衍射谱图见图1中。从图1中可以看出，制备的LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2/LTO复合正极材料与LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2材料的XRD图峰形相同，没有出现杂峰，这可能是Zr进入LiNi1/3Col/3Mnl/3O2晶格内，取代部分位置上的Mn4+，且钛酸锂的加入并不影响主体层状结构。X-ray diffraction spectra of LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 and LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 /LTO prepared by experiment The picture is shown in Figure 1. It can be seen from Figure 1 that the prepared LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 /LTO composite cathode material and LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 The peak shape of the XRD pattern of the O 2 material is the same, and no miscellaneous peaks appear, which may be that Zr enters the LiNi 1/3 Co l/3 Mn l/3 O 2 lattice to replace Mn 4+ on some positions, and the titanate The addition of lithium does not affect the host layered structure.

以本实施例所制备LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2/LTO为正极，以锂片为负极的扣式电池，在2.5~4.3V电压范围，以0.1C倍率下恒流-恒压充电，0.2C倍率下恒流放电时首次放电比容量为182.7mAh/g，但经过50次循环后容量为138.8mAh/g。A button battery with LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 /LTO prepared in this example as the positive electrode and a lithium sheet as the negative electrode, in the voltage range of 2.5~4.3V, at 0.1C Constant current-constant voltage charging at a rate of 0.2C, the first discharge specific capacity is 182.7mAh/g at a constant current discharge at a rate of 0.2C, but the capacity after 50 cycles is 138.8mAh/g.

通过实施例1-4可以看出，锆元素的掺杂并没有影响物质的晶体结构，不同掺杂量的锆元素能够改善LiNi1/3Col/3Mnl/3O2三元材料的充放电性能和循环性能。并且，掺杂量为2%的LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2性能最好。通过掺杂得到性能最佳的掺杂量，并在其基础上进行钛酸锂包覆。通过XRD，可以看出包覆也并没有改变物质的晶体结构，并且充放电测试显示，物质的充放电性能和循环性能均得到了进一步的提高。由此可见，不仅掺杂提高了三元材料的性能，并且在其基础上进行包覆也能提高它的性能。It can be seen from Examples 1-4 that the doping of zirconium element does not affect the crystal structure of the material, and different doping amounts of zirconium element can improve the properties of LiNi 1/3 Co l/3 Mn l/3 O 2 ternary materials. Charge and discharge performance and cycle performance. Moreover, LiNi 1/3 Co 1/3 Mn 1/3-0.02 Zr 0.02 O 2 with a doping amount of 2% has the best performance. The doping amount with the best performance is obtained by doping, and lithium titanate coating is carried out on the basis of it. Through XRD, it can be seen that the coating does not change the crystal structure of the material, and the charge and discharge test shows that the charge and discharge performance and cycle performance of the material have been further improved. It can be seen that not only doping improves the performance of the ternary material, but also coating on its basis can also improve its performance.

Claims (6)

1. a kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property, it is characterised in that：Prepare including as follows Step：
(1) lithium source, part cobalt source, manganese source, zirconium source are dissolved according to certain mol proportion in the mixed solution of water and absolute ethyl alcohol, Labeled as solution A, nickel source, remaining cobalt source are dissolved according to certain mol proportion in the solution of water and ethanol, labeled as solution B, two oxalic acid hydrates is dissolved in water and ethanol solution, labeled as solution C；Solution A is poured into solution C first, reaction 10 ~ After 12min, then B solution poured into A and C mixed solution, react 5 ~ 6h, be allowed to precipitation completely；Reacted material is put After being dried in drying box, powder is obtained, then is ground, is then placed in crucible, after calcining, obtains black powder；By powder End is ground, and crosses 400 ~ 500 mesh sieves, you can obtain the cobalt nickel oxide manganses lithium LiNi of zirconium dopingxCoyMnl-x-y-zZrzO2Positive pole Material, wherein 0<x<0.6,0<y<0.6,0<z<0.1；
(2) by lithium titanate and above-mentioned（1）The LiNi of preparationxCoyMn1-x-y-zZrzO2It is molten that positive electrode is placed in absolute ethyl alcohol/isopropanol In liquid, concentration is 0.01 ~ 0.02mol/L, then heating stirring is evaporated at 75 ~ 85 DEG C, and grinds sieving, obtains presoma, will The presoma is placed in Muffle furnace, is heated up with 3 ~ 5 DEG C/min speed, and 2 ~ 5h is calcined at 600 ~ 800 DEG C, room is subsequently cooled to Temperature, obtains LiNixCoyMn1-x-y-zZrzO2/ LTO positive electrodes.
2. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists In described nickel source is the one or more in nickelous carbonate, nickel acetate, nickel nitrate；
Described cobalt source is the one or more in cobalt carbonate, cobalt acetate, cobalt nitrate；
Described manganese source is the one or more in manganese carbonate, manganese acetate, manganese nitrate；
Described zirconium source is the one or more in zirconium nitrate, basic zirconium phosphate, zirconium chloride；
Described lithium salts is the one or more in lithium carbonate, lithium acetate, lithium nitrate, lithium hydroxide；
Described water and the mixed solution reclaimed water of absolute ethyl alcohol and the volume ratio of absolute ethyl alcohol are 1：0~10.
3. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists In lithium source, part cobalt source, manganese source, zirconium source being dissolved according to certain mol proportion in the mixed solution of water and absolute ethyl alcohol, concentration For 0.1 ~ 0.15mol/L, labeled as solution A；Nickel source, remaining cobalt source are dissolved in the molten of water and ethanol according to certain mol proportion In liquid, concentration is 0.03 ~ 0.04mol/L, labeled as solution B, two oxalic acid hydrates is dissolved in water and ethanol solution, concentration is 0.15 ~ 0.2mol/L, labeled as solution C.
4. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists In：Step（1）Described drying is referred in 70 ~ 90 DEG C of dry 8 ~ 12h；The calcination process is first to be warming up to 300 ~ 600 DEG C 4 ~ 10h is calcined, then is warming up to 700 ~ 950 DEG C of 10 ~ 24h of calcining.
5. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists In：Step（2）It is middle that the presoma is placed in Muffle furnace, heated up with 4 DEG C/min speed.
6. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists In the consumption of the lithium titanate accounts for the 0.5% ~ 15% of cobalt nickel oxide manganses lithium quality.
CN201710432855.5A 2017-06-09 2017-06-09 A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property Pending CN107204426A (en)

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CN112928253A (en) * 2021-01-22 2021-06-08 厦门厦钨新能源材料股份有限公司 Nickel-manganese-titanium composite material and preparation method and application thereof
CN113651373A (en) * 2021-10-19 2021-11-16 河南科隆新能源股份有限公司 Anode material with uniform porous structure and preparation method thereof
CN116043418A (en) * 2023-01-13 2023-05-02 天津巴莫科技有限责任公司 Zirconium-titanium co-doped fibrous high-nickel ternary cathode material and preparation method and application thereof

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