WO2015039490A1

WO2015039490A1 - Lithium-rich anode material and preparation method thereof

Info

Publication number: WO2015039490A1
Application number: PCT/CN2014/082357
Authority: WO
Inventors: 王先友; 杨秀康; 袁好; 王泽平; 李建邦; 舒洪波; 白艳松; 孙海龙
Original assignee: 中兴通讯股份有限公司
Priority date: 2013-09-22
Filing date: 2014-07-16
Publication date: 2015-03-26
Also published as: CN104466158A

Abstract

A lithium-rich anode material preparation method, and lithium-rich anode material prepared thereby, the method comprising the following steps: preparing a saline solution A by mixing at least cobalt salt and other metal salt; preparing a saline solution B via at least manganese salt, and making the concentration of manganese ions in the saline solution B higher than the concentration of the manganese ions in the saline solution A; gradually adding the saline solution B into the saline solution A, and correspondingly controlling the crystallization coprecipitation to prepare a spherical precursor so as to cause the proportion of manganese element in the precursor to gradually increase from an inner layer to an outer layer, and cause the proportion of cobalt element to gradually decrease from the inner layer to the outer layer; mixing the precursor with a lithium source to obtain a lithium-rich semi-finished product, and calcining the lithium-rich semi-finished product to prepare spherical lithium-rich anode material. The present invention has a simple process, controllable operation steps, rich sources of raw materials and low costs, and is environmentally friendly, easy to operate, and is also suitable for large-scale industrialization.

Description

富锂正极材料及其制备方法技术领域本发明涉及锂离子电池正极材料与电化学领域，具体涉及一种球形富锂正极材料及其制备方法。背景技术相对于传统电池，如铅酸电池、镍镉电池和镍氢电池，锂离子电池具有能量密度高、循环寿命长、自放电率小、无记忆效应和绿色环保等突出优势，自 90年代初由索尼公司开发出来后，已经在人们的生活中得到广泛的应用，如便携式电子产品、新能源交通工具及储能等领域。随着锂离子电池技术的发展，要求锂离子电池具有高能量密度、高功率、低成本等特点。锂离子电池的成分组成一般包括：正极材料、负极材料、电解液、隔膜，其中正极材料的性能是影响锂离子电池综合性能的关键因素。目前，商业化的锂离子电池正极材料主要有钴酸锂、锰酸锂、三元材料、磷酸铁锂。但是，上述正极材料都有各自的缺点： LiCo0₂具有成本高、环境污染等缺点，且截止电压超过 4.4 V以上，材料结构不稳定，循环、安全性能变差； Li₂Mn0₄的高温循环与储存性能欠佳；三元材料压实密度偏低，其倍率性能与安全性能有待提高；磷酸铁锂放电比容量不高，振实密度偏低，且产品存在较严重的一致性问题，阻碍其快速发展。因此，以上几种正极材料均难以同时满足高能量密度、高功率、低成本、安全性及循环性好等要求。富锂多元正极材料 xLi₂Mn0₃ l-x)LiM0₂ (M=Mn， Ni, Co、 Al、 Cr、 Fe、 Mg等， 0 < x < 1) 因其新的电化学充放电机制、较宽的充放电范围、成本低廉等特点，是近年来发展迅速的锂离子电池正极材料。富锂多元正极材料中的 Li₂Mn0₃组分具有重要的作用，不但可以起到稳定材料结构的作用，同时在高电压下可以提供额外的容量。但是，当截止电压 < 4.5 V时，富锂多元正极材料的放电容量较低；当截止电压 > 4.5 V 时，虽然可以获得 200 mAh/g以上的可逆容量，但是材料的倍率性能和循环性能欠佳。现有合成富锂多元正极材料的方法主要包括固相法、喷雾干燥法、溶胶-凝胶法和共沉淀法等。固相法工艺简单，但该方法难以保证混料均匀，易生产非计量比化合物，产品的一致性和重现性较差；喷雾干燥法操作复杂，成本高，大规模产业化困难；溶胶-凝胶法制备的产物纯度高、颗粒粒径小、化学计量比准确，材料倍率性能突出；共沉淀法合成材料形貌大小可控，产品一致性较好、振实密度高，是富锂多元正极材料较为理想的制备方法。发明内容本发明实施例的目的就是基于上述出发点，提供一种富锂正极材料的制备方法，其工艺简单，便于实现，操作过程可控，并且原材料来源丰富，成本低廉，环境友好，可进行大规模产业化，具有很好的应用前景；本发明实施例还提供一种由上述方法制备的富锂正极材料，从其内层到外层，锰元素的比例逐渐增加，钴元素的比例逐渐降低，其他金属元素的比例保持不变，因此具有高比容量，具有优异的循环寿命和倍率性能，可满足电动汽车等领域对动力电源的使用需求。为实现本发明实施例的上述目的，本发明的一个实施例提供一种富锂正极材料的制备方法，其包括如下步骤：制备至少由钴盐和其它金属盐混合而形成的盐溶液 A; 制备至少由锰盐形成的盐溶液 B，且使盐溶液 B中的锰离子浓度高于盐溶液 A中的锰离子浓度；通过逐步将盐溶液 B加入到盐溶液 A中，并进行相应的控制结晶共沉淀处理，生成球形前躯体，使前躯体的锰元素比例从内层到外层逐渐增加，并使钴元素比例从内层到外层逐渐减少；将前躯体与锂源混合得到富锂半成品，再对其进行煅烧处理，制得球形富锂正极材料。其中，所述其它金属盐中含有的金属离子为镍（M)、铝（Al)、镁（Mg)、钛（Ti)、铬（Cr) 和铜（Cu) 离子中的一种或多种。其中，所述进行相应的控制结晶共沉淀处理包括如下步骤：逐步将盐溶液 B加入到盐溶液 A中，同时将两者混合得到的混合盐溶液加入到反应釜内；将混合盐溶液加入到反应釜内的同时，将沉淀剂加入到反应釜内；混合盐溶液和沉淀剂发生沉淀反应而生成结晶沉淀产物，并且按照生成结晶沉淀产物的先后顺序，后结晶沉淀生成的产物逐步沉积在先结晶沉淀生成的产物的表面，从而得到球形前躯体。其中，所述后结晶沉淀生成产物中的锰元素的比例高于先结晶沉淀生成产物中的锰元素的比例；所述后结晶沉淀生成产物中的钴元素的比例低于先结晶沉淀生成产物中的钴元素的比例。其中，所述盐溶液 A中混合有锰盐。其中，所述盐溶液 B中混合有其它金属盐。进一步的，所述盐溶液 B中混合有钴盐，且盐溶液 B中的钴离子浓度低于所述盐溶液 A中的钴离子浓度。其中，制备所述盐溶液 A时，盐溶液 A中的锰离子浓度与总金属离子浓度的百分比不超过 40%; 制备所述盐溶液 B时，盐溶液 B中的锰离子浓度占总金属离子浓度的 50%-100%。其中，所述盐溶液 A的总金属离子浓度与所述盐溶液 B的总金属离子浓度相同，均为 1.0-3.0mol/L。其中，所述沉淀剂包括配位剂和络合剂；其中，配位剂为碱溶液，其浓度为 1.0-5.0 mol/L; 络合剂为氨水溶液，其浓度为 0.1-5.0 mol/L。其中，所述混合盐溶液和沉淀剂发生沉淀反应时，对混合盐溶液和沉淀剂形成的混合液的搅拌速度为 50-1500rpm，控制反应温度为 30-70°C，控制混合液的 pH值为 7-12。其中，所述的煅烧处理包括如下步骤：将富锂半成品在空气中进行预烧，预烧温度为 400-700°C，预烧时间为 l-12h; 对预烧后的富锂半成品进行升温煅烧，升温煅烧的温度为 750-1000°C，升温煅烧的时间为 4-3 Oh; 对升温煅烧后的富锂半成品进行退火处理，退火处理的温度为 400-700°C，时间为TECHNICAL FIELD The present invention relates to the field of lithium ion battery cathode materials and electrochemistry, and in particular to a spherical lithium-rich cathode material and a preparation method thereof. BACKGROUND OF THE INVENTION Compared with conventional batteries, such as lead-acid batteries, nickel-cadmium batteries, and nickel-hydrogen batteries, lithium-ion batteries have outstanding advantages such as high energy density, long cycle life, low self-discharge rate, no memory effect, and green environmental protection, since the 1990s. Developed by Sony, it has been widely used in people's lives, such as portable electronics, new energy vehicles and energy storage. With the development of lithium-ion battery technology, lithium-ion batteries are required to have high energy density, high power, and low cost. The composition of a lithium ion battery generally includes: a positive electrode material, a negative electrode material, an electrolyte, and a separator, wherein the performance of the positive electrode material is a key factor affecting the overall performance of the lithium ion battery. At present, commercial lithium ion battery cathode materials mainly include lithium cobaltate, lithium manganate, ternary materials, and lithium iron phosphate. However, the above positive electrode materials have their own disadvantages: LiCo0 ₂ has the disadvantages of high cost, environmental pollution, etc., and the cut-off voltage exceeds 4.4 V, the material structure is unstable, the cycle and safety performance are deteriorated; the high temperature cycle of Li ₂ Mn0 ₄ Poor storage performance; low compaction density of ternary materials, its rate performance and safety performance need to be improved; lithium iron phosphate discharge specific capacity is not high, tap density is low, and the product has serious consistency problems, hindering its Rapid development. Therefore, it is difficult for the above positive electrode materials to meet the requirements of high energy density, high power, low cost, safety, and good cycleability. Lithium-rich multi-element cathode material xLi ₂ Mn0 ₃ lx)LiM0 ₂ (M=Mn, Ni, Co, Al, Cr, Fe, Mg, etc., 0 < x < 1) due to its new electrochemical charge and discharge mechanism, wide The characteristics of charge and discharge range and low cost are the positive electrode materials for lithium ion batteries that have developed rapidly in recent years. The Li ₂ Mn0 ₃ component in the lithium-rich multi-element cathode material plays an important role, not only to stabilize the material structure, but also to provide additional capacity at high voltage. However, when the cut-off voltage is < 4.5 V, the discharge capacity of the lithium-rich multi-element cathode material is low; when the cut-off voltage is > 4.5 V, although the reversible capacity of 200 mAh/g or more can be obtained, the material's rate performance and cycle performance are not. good. The existing methods for synthesizing lithium-rich multi-element cathode materials mainly include a solid phase method, a spray drying method, a sol-gel method, and a coprecipitation method. The solid phase process is simple, but the method is difficult to ensure uniform mixing, easy to produce non-metering compounds, and the product consistency and reproducibility are poor; spray drying method is complicated, high cost, large-scale industrialization is difficult; The product prepared by the gel method has high purity, small particle size, accurate stoichiometric ratio, and outstanding material rate performance; The morphology of the synthetic material of the precipitation method is controllable, the product consistency is good, and the tap density is high. It is an ideal preparation method for the lithium-rich multi-component cathode material. SUMMARY OF THE INVENTION The object of the embodiments of the present invention is to provide a method for preparing a lithium-rich cathode material based on the above starting point, which is simple in process, easy to implement, controllable in operation, rich in raw materials, low in cost, environmentally friendly, and large in size. The industrialization of scale has a good application prospect; the embodiment of the invention also provides a lithium-rich cathode material prepared by the above method, from the inner layer to the outer layer, the proportion of manganese element is gradually increased, and the proportion of cobalt element is gradually decreased. The ratio of other metal elements remains unchanged, so it has a high specific capacity, excellent cycle life and rate performance, and can meet the demand for power supply in electric vehicles and other fields. In order to achieve the above object of the embodiments of the present invention, an embodiment of the present invention provides a method for preparing a lithium-rich cathode material, comprising the steps of: preparing a salt solution A formed by mixing at least a cobalt salt and another metal salt; a salt solution B formed of at least a manganese salt, and the manganese ion concentration in the salt solution B is higher than the manganese ion concentration in the salt solution A; by gradually adding the salt solution B to the salt solution A, and performing corresponding control crystallization Co-precipitation treatment produces a spherical precursor, which gradually increases the proportion of manganese in the precursor from the inner layer to the outer layer, and gradually reduces the proportion of cobalt from the inner layer to the outer layer; and mixes the precursor with the lithium source to obtain a lithium-rich semi-finished product. Then, it is calcined to obtain a spherical lithium-rich cathode material. Wherein the metal ions contained in the other metal salt are one or more of nickel (M), aluminum (Al), magnesium (Mg), titanium (Ti), chromium (Cr) and copper (Cu) ions. . Wherein, performing the corresponding controlled crystallization coprecipitation treatment comprises the steps of: gradually adding the salt solution B to the salt solution A, and simultaneously adding the mixed salt solution obtained by mixing the two into the reaction kettle; adding the mixed salt solution to the mixture While precipitating the reactor, the precipitant is added to the reaction vessel; The mixed salt solution and the precipitant are subjected to a precipitation reaction to form a crystalline precipitated product, and the product formed by the post-crystallization precipitation is gradually deposited on the surface of the product formed by the first crystal precipitation in order of formation of the crystal precipitated product, thereby obtaining a spherical precursor. Wherein the proportion of the manganese element in the product obtained by the post-crystallization precipitation is higher than the ratio of the manganese element in the product of the first crystal precipitation; the proportion of the cobalt element in the product of the post-crystallization precipitate is lower than that in the product of the first crystal precipitation The proportion of cobalt elements. Wherein, the salt solution A is mixed with a manganese salt. Wherein, the salt solution B is mixed with other metal salts. Further, the salt solution B is mixed with a cobalt salt, and the cobalt ion concentration in the salt solution B is lower than the cobalt ion concentration in the salt solution A. Wherein, when the salt solution A is prepared, the percentage of the manganese ion concentration in the salt solution A to the total metal ion concentration does not exceed 40%; when the salt solution B is prepared, the manganese ion concentration in the salt solution B accounts for the total metal ion. 50%-100% of the concentration. Wherein, the total metal ion concentration of the salt solution A is the same as the total metal ion concentration of the salt solution B, and both are 1.0-3.0 mol/L. Wherein, the precipitating agent comprises a complexing agent and a complexing agent; wherein the complexing agent is an alkali solution, the concentration is 1.0-5.0 mol/L; the complexing agent is an aqueous ammonia solution, and the concentration is 0.1-5.0 mol/L. . Wherein, when the mixed salt solution and the precipitating agent are subjected to a precipitation reaction, the stirring speed of the mixed solution of the mixed salt solution and the precipitating agent is 50-1500 rpm, the control reaction temperature is 30-70 ° C, and the pH of the mixed solution is controlled. For 7-12. Wherein, the calcination treatment comprises the following steps: pre-firing the lithium-rich semi-finished product in air, the calcination temperature is 400-700 ° C, the calcination time is l-12 h; and the pre-fired lithium-rich semi-finished product is heated. Calcination, temperature rising calcination temperature is 750-1000 ° C, heating calcination time is 4-3 Oh; annealing of the lithium-rich semi-finished product after heating and calcining, annealing temperature is 400-700 ° C, time is

0-12h; 将退火处理后的富锂半成品自然冷却至室温。其中，所述富锂半成品中，锂源中锂的摩尔数和前驱体的金属总摩尔数之比为 n: 1，其中， 1 <n <2。其中，所述其它金属盐包括硫酸盐、硝酸盐、氯化盐、乙酸盐中的一种或多种；所述钴盐包括硫酸盐、硝酸盐、氯化盐、乙酸盐中的一种或多种；所述锰盐包括硫酸盐、硝酸盐、氯化盐、乙酸盐中的一种或多种；所述碱溶液包括氢氧化钠、氢氧化钾、氢氧化锂、碳酸钠、碳酸氢钠、碳酸氢氨中的一种或多种。其中，所述共沉淀法是氢氧化物共沉淀法、碳酸盐共沉淀法或草酸盐共沉淀法。其中，所述锂源包括碳酸锂、氢氧化锂、硝酸锂中的一种或多种。本发明还提供一种由上述的制备方法制备的富锂正极材料，其由化学通式为0-12h; The annealed lithium-rich semi-finished product was naturally cooled to room temperature. Wherein, in the lithium-rich semi-finished product, the ratio of the number of moles of lithium in the lithium source to the total number of moles of metal of the precursor is n: 1, wherein 1 < n < 2. Wherein the other metal salt comprises one or more of a sulfate, a nitrate, a chloride, and an acetate; the cobalt salt comprises one of a sulfate, a nitrate, a chloride, and an acetate. One or more; the manganese salt includes one or more of a sulfate, a nitrate, a chloride, and an acetate; the alkali solution includes sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate One or more of sodium hydrogencarbonate and ammonia hydrogencarbonate. Wherein, the coprecipitation method is a hydroxide coprecipitation method, a carbonate coprecipitation method or an oxalate coprecipitation method. Wherein, the lithium source comprises one or more of lithium carbonate, lithium hydroxide and lithium nitrate. The present invention also provides a lithium-rich cathode material prepared by the above preparation method, which has a chemical formula of

Li_1+xM0₂化合物构成；其中， 0 < χ < 1， M包括锰（Mn)和钴（Co)，以及镍（M)、铝（Al)、镁（Mg)、钛（Ti)、铬（Cr)和铜（Cu) 元素中的一种或多种；其中，所述化合物为球形颗粒，且球形颗粒中的锰元素比例由内层到外层逐渐增加，钴元素比例由内层到外层逐渐减少。与现有技术相比，本发明实施例的富锂正极材料的制备方法具有如下突出优点： Composition of Li _1+x M0 ₂ compound; wherein, 0 < χ < 1, M includes manganese (Mn) and cobalt (Co), and nickel (M), aluminum (Al), magnesium (Mg), titanium (Ti), One or more of chromium (Cr) and copper (Cu) elements; wherein the compound is a spherical particle, and the proportion of manganese element in the spherical particle is gradually increased from the inner layer to the outer layer, and the proportion of the cobalt element is from the inner layer Gradually reduce to the outer layer. Compared with the prior art, the preparation method of the lithium-rich cathode material of the embodiment of the invention has the following outstanding advantages:

1 )本发明实施例的制备方法，通过控制结晶共沉淀处理方法生成前躯体，相比于现有技术的普通共沉淀法，生成的球形富锂正极材料具有由内层到外层，锰元素比例逐渐增加而钴元素比例逐渐减少的特点，因此使由本发明的富锂正极材料制成的电池具有优异的循环寿命和倍率性能，可以满足电动汽车等领域对动力电源的使用需求，适用范围更广； 1) The preparation method of the embodiment of the present invention, the precursor is formed by controlling the crystal coprecipitation treatment method, and the spherical lithium-rich cathode material is formed from the inner layer to the outer layer, manganese element, compared to the conventional coprecipitation method of the prior art. The ratio gradually increases and the proportion of cobalt element gradually decreases, so that the battery made of the lithium-rich positive electrode material of the invention has excellent cycle life and rate performance, and can meet the demand for power source in the field of electric vehicles and the like, and the scope of application is more applicable. Wide

2) 本发明实施例的制备方法中，通过配制两种锰离子浓度不同的盐溶液 B和盐溶液 A，再逐步将盐溶液 B加入到盐溶液 A中，并进行相应的控制结晶共沉淀处理而生成球形前躯体，其工艺简单，过程可控，便于实现； 2) In the preparation method of the embodiment of the present invention, by preparing two salt solutions B and a salt solution A having different manganese ion concentrations, the salt solution B is gradually added to the salt solution A, and the corresponding controlled crystal coprecipitation treatment is carried out. The spherical precursor is generated, the process is simple, the process is controllable, and the implementation is convenient;

3 )本发明实施例采用控制结晶共沉淀处理方法生成前躯体时，混合盐溶液和沉淀剂发生沉淀反应所生成的结晶沉淀产物中，按照生成结晶沉淀产物的先后顺序，后结晶沉淀生成的产物逐步沉积在先结晶沉淀生成的产物的表面，从而使得后结晶沉淀生成产物中的锰元素的含量大于先结晶沉淀生成产物中的锰元素的含量，并使后结晶沉淀生成产物中的钴元素的含量小于先结晶沉淀生成产物中的钴元素的含量，进而使由该前躯体制得的富锂正极材料比容量高，具有优异的循环寿命和倍率性能； 4) 本发明实施例的制备方法中，采用的原材料来源丰富，成本低廉，环境友好，可进行大规模产业化，具有很好的应用前景。下面结合附图对本发明进行详细说明。附图说明表 1为本发明第一实施例制得的富锂正极材料的剖面结构能量色散 X射线 (EDS) 数据；图 1为本发明第一实施例制得的富锂正极材料的扫描电镜（SEM) 图；图 2为本发明第一实施例制得的富锂正极材料的剖面结构扫描电镜（SEM) 图；图 3为本发明第一实施例制得的富锂正极材料的 XRD衍射图谱；图 4为本发明第一实施例制得的富锂正极材料的第 1、 2次充放电曲线；图 5为本发明第一实施例制得的富锂正极材料与对比例制得的富锂正极材料的循环寿命图；图 6为本发明第一实施例制得的富锂正极材料与对比例制得的富锂正极材料的倍率性能图。具体实施方式本发明实施例提供了一种富锂正极材料的制备方法，其包括如下步骤： 3) In the embodiment of the present invention, when the precursor is formed by the method of controlling the crystal coprecipitation, the product formed by the precipitation of the crystal precipitated product in the order of the crystal precipitation product is formed in the crystal precipitation product formed by the precipitation reaction of the mixed salt solution and the precipitating agent. Gradually depositing the surface of the product formed by the first crystal precipitation, so that the content of manganese element in the product of the post-crystallization precipitate is greater than the content of manganese element in the product of the first crystal precipitation, and the precipitated crystal precipitates to form cobalt in the product. The content is less than the content of the cobalt element in the product of the first crystal precipitation, and the lithium-rich cathode material obtained from the precursor system has a higher specific capacity, and has excellent cycle life and rate performance; 4) In the preparation method of the embodiment of the invention, the raw materials used are abundant, the cost is low, the environment is friendly, and the large-scale industrialization can be carried out, which has a good application prospect. The invention will be described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Table 1 is a cross-sectional structure energy dispersive X-ray (EDS) data of a lithium-rich cathode material prepared in accordance with a first embodiment of the present invention; FIG. 1 is a scanning electron microscope of a lithium-rich cathode material obtained in accordance with a first embodiment of the present invention. (SEM) FIG. 2 is a scanning electron microscope (SEM) diagram of a cross-sectional structure of a lithium-rich cathode material prepared in accordance with a first embodiment of the present invention; FIG. 3 is an XRD diffraction of a lithium-rich cathode material prepared according to a first embodiment of the present invention. Figure 4 is a first and second charge-discharge curve of the lithium-rich cathode material obtained in the first embodiment of the present invention; Figure 5 is a lithium-rich cathode material prepared according to the first embodiment of the present invention and a comparative example. Fig. 6 is a graph showing the rate performance of the lithium-rich cathode material prepared in the first embodiment of the present invention and the lithium-rich cathode material prepared in the comparative example. DETAILED DESCRIPTION OF THE INVENTION Embodiments of the present invention provide a method for preparing a lithium-rich cathode material, which includes the following steps:

1 ) 制备至少由钴盐和其它金属盐混合而形成的盐溶液 A，使得盐溶液 A的总金属离子浓度为 1.0-3.0mol/L，并将盐溶液 A置于第一容器中； 1) preparing a salt solution A formed by mixing at least a cobalt salt and another metal salt such that the total metal ion concentration of the salt solution A is 1.0-3.0 mol/L, and the salt solution A is placed in the first container;

2) 制备由锰盐形成的盐溶液 B，且盐溶液 B的总金属离子浓度与盐溶液 A的总金属离子浓度相同（即盐溶液 B的总金属离子浓度也为 1.0-3.0mol/L)，并使盐溶液 B 中的锰离子浓度占总金属离子浓度的 50%-100%，使得盐溶液 B中的锰离子浓度高于盐溶液 A中的锰离子浓度，然后将盐溶液 B置于第二容器中； 2) preparing a salt solution B formed of a manganese salt, and the total metal ion concentration of the salt solution B is the same as the total metal ion concentration of the salt solution A (ie, the total metal ion concentration of the salt solution B is also 1.0-3.0 mol/L) And the manganese ion concentration in the salt solution B is 50%-100% of the total metal ion concentration, so that the manganese ion concentration in the salt solution B is higher than the manganese ion concentration in the salt solution A, and then the salt solution B is placed In the second container;

3 ) 配制包括配位剂和络合剂的沉淀剂，其中，配位剂采用浓度为 1.0-5.0 mol/L 的碱溶液，络合剂采用浓度为 0.1-5.0 mol/L的氨水溶液； 4)通过逐步将盐溶液 B加入到盐溶液 A中，并进行相应的控制结晶共沉淀处理，生成球形前躯体，使前躯体的锰元素比例从内层到外层逐渐增加，并使钴元素比例从内层到外层逐渐减少； 3) preparing a precipitant comprising a complexing agent and a complexing agent, wherein the complexing agent is an alkali solution having a concentration of 1.0-5.0 mol/L, and the complexing agent is an aqueous ammonia solution having a concentration of 0.1-5.0 mol/L; 4) By gradually adding the salt solution B to the salt solution A, and performing corresponding controlled crystallization coprecipitation treatment to form a spherical precursor body, the manganese content of the precursor body is gradually increased from the inner layer to the outer layer, and the cobalt element is made. The proportion gradually decreases from the inner layer to the outer layer;

5 )将前躯体与锂源混合得到富锂半成品，再对其进行煅烧处理，制得球形富锂正极材料。其中，在配制上述的盐溶液 A时，盐溶液 A中还可以混合有锰盐，但需使盐溶液 A中的锰离子浓度低于盐溶液 B中的锰离子浓度。优选的，制备盐溶液 A时，盐溶液 A中的锰离子浓度与总金属离子浓度的百分比不超过 40%; 制备盐溶液 B 时，盐溶液 B 中的锰离子浓度占总金属离子浓度的 50%-100%。其中，本发明中的总金属离子浓度是指溶液中含有的所有金属离子的总量与溶液体积之比。其中，盐溶液 B中还可以混合有其它金属盐；进一步的，盐溶液 B中还可以混合有钴盐，且需使盐溶液 B中的钴离子浓度低于盐溶液 A中的钴离子浓度。其中，其它金属盐中含有的金属离子为镍（M)、铝（Al)、镁（Mg)、钛（Ti)、铬（Cr) 和铜（Cu) 离子中的一种或多种，且其它金属盐可以采用硫酸盐、硝酸盐、氯化盐、乙酸盐中的一种或多种。其中，在步骤 4) 中，进行相应的控制结晶共沉淀处理包括如下步骤： 5) mixing the precursor with the lithium source to obtain a lithium-rich semi-finished product, which is then calcined to obtain a spherical lithium-rich positive electrode material. Among them, in the preparation of the above salt solution A, the salt solution A may also be mixed with a manganese salt, but the manganese ion concentration in the salt solution A is required to be lower than the manganese ion concentration in the salt solution B. Preferably, when the salt solution A is prepared, the percentage of the manganese ion concentration in the salt solution A and the total metal ion concentration does not exceed 40%; when the salt solution B is prepared, the manganese ion concentration in the salt solution B accounts for 50% of the total metal ion concentration. %-100%. Here, the total metal ion concentration in the present invention means the ratio of the total amount of all metal ions contained in the solution to the volume of the solution. Among them, the salt solution B may be mixed with other metal salts; further, the salt solution B may be mixed with a cobalt salt, and the cobalt ion concentration in the salt solution B is required to be lower than the cobalt ion concentration in the salt solution A. Wherein, the metal ion contained in the other metal salt is one or more of nickel (M), aluminum (Al), magnesium (Mg), titanium (Ti), chromium (Cr), and copper (Cu) ions, and The other metal salt may be one or more selected from the group consisting of a sulfate, a nitrate, a chloride, and an acetate. Wherein, in step 4), performing the corresponding controlled crystallization coprecipitation treatment comprises the following steps:

41 )将第二容器中的盐溶液 B通过恒流泵逐渐加入到第一容器的盐溶液 A中，搅拌均匀，形成由盐溶液 A和盐溶液 B混合的、锰离子浓度逐渐增加的混合盐溶液，并随着盐溶液 B的逐渐加入，将混合盐溶液逐渐泵入到反应釜中； 41) The salt solution B in the second container is gradually added to the salt solution A of the first container by a constant flow pump, and stirred uniformly to form a mixed salt in which the concentration of manganese ions is gradually increased by mixing the salt solution A and the salt solution B. Solution, and with the gradual addition of the salt solution B, the mixed salt solution is gradually pumped into the reaction kettle;

42) 在将混合盐溶液逐渐泵入到反应釜中的同时，将沉淀剂（即碱溶液和氨水溶液）并流加入到反应釜内，与混合盐溶液形成混合液； 42) while gradually pumping the mixed salt solution into the reaction vessel, the precipitating agent (ie, the alkali solution and the aqueous ammonia solution) is simultaneously fed into the reaction vessel to form a mixed solution with the mixed salt solution;

43 ) 控制反应釜内混合液的搅拌速度，使搅拌速度为 50-1500rpm，反应温度为 30-70"C , 混合液的 pH值控制在 7-12之间，使得混合液中的混合盐溶液、碱溶液和氨水溶液发生沉淀反应而生成结晶沉淀产物，直至反应结束制得前躯体。其中，盐溶液 B加入到盐溶液 A的加料速度（即恒流泵的流速）与反应釜的大小、反应所需的温度、反应时间和搅拌速度等因素有关，其数值视反应时的具体情况而定。其中，按照生成结晶沉淀产物的先后顺序，后结晶沉淀生成的产物逐步沉积在先结晶沉淀生成的产物的表面。由于盐溶液 B中的锰离子浓度高于盐溶液 A中的锰离子浓度，且盐溶液 B通过恒流泵逐渐加入到盐溶液 A中，即由盐溶液 B和盐溶液 A形成的混合盐溶液中锰离子浓度逐渐增加，因此后结晶沉淀生成产物中的锰元素的比例高于先结晶沉淀生成产物中的锰元素的比例，并且，后结晶沉淀生成产物中的钴元素的比例低于先结晶沉淀生成产物中的钴元素的比例，直至沉淀反应结束，得到球形颗粒的前躯体，从而使得前躯体中，锰元素的比例由球的内心到外层逐渐增加，钴元素的比例由球的内心到外层逐渐降低。本发明实施例中，钴盐可以采用硫酸盐、硝酸盐、氯化盐、乙酸盐中的一种或多种，锰盐可以采用硫酸盐、硝酸盐、氯化盐、乙酸盐中的一种或多种，控制结晶共沉淀处理时，可以采用氢氧化物共沉淀法、碳酸盐共沉淀法或草酸盐共沉淀法，即采用的碱溶液可以为氢氧化钠、氢氧化钾、氢氧化锂、碳酸钠、碳酸氢钠、碳酸氢氨、草酸钠中的一种或多种。其中，步骤 5 ) 中，在将前躯体与锂源混合之前，需将步骤 4)制得的前躯体进行过滤、洗涤后，将前躯体置于 110 °C的温度下干燥 12 h，再与含锂的锂源按比例均合混合，以得到富锂半成品。其中，本发明实施例中所用的锂源可以为碳酸锂、氢氧化锂、硝酸锂中的一种或多种。当将前躯体与锂源混合时，按锂的摩尔数和前驱体的金属总摩尔数之比为 n: 1 的比例均匀混合（其中， 1 <n <2)，以得到富锂半成品，然后再对富锂半成品进行煅烧处理，制得球形富锂正极材料。在进行煅烧处理时，先将富锂半成品在空气中进行预烧，预烧温度为 400-700°C，预烧时间为 l-12h; 然后对预烧后的富锂半成品进行升温煅烧，升温煅烧的温度为 750-1000°C，升温煅烧的时间为 4-30h;接着对升温煅烧后的富锂半成品进行退火处理，退火处理的温度为 400-700°C，时间为 0-12h; 最后，将退火处理后的富锂半成品自然冷却至室温，或者，不经过退火处理，直接将升温煅烧后的富锂半成品自然冷却至室温，从而得到球形的富锂正极材料。本发明实施例的制备方法，工艺简单，过程可控，采用的原材料成本低廉且环境友好，可以进行大规模的产业化生产，具有良好的应用前景。本发明实施例还提供一种通过本发明的制备方法制得的富锂正极材料，其由化学通式为 Li_1+xM0₂的化合物构成，其中， 0 < χ < 1， M包括锰（Mn) 和钴（Co)，以及镍（Ni)、铝（Al)、镁（Mg)、钛（Ti)、铬（Cr) 和铜（Cu) 元素中的一种或多种；其中，所述化合物为球形颗粒，且球形颗粒中的锰元素比例由内层到外层逐渐增加，钴元素比例由内层到外层逐渐减少。本发明实施例制备的富锂正极材料呈球形，从球形的内层到外层，锰元素的比例逐渐增加，钴元素的比例逐渐降低，因此使得富锂正极材料具有优异的循环寿命和倍率性能，比容量高，可以满足电动汽车等领域对动力电源的使用需求。下面结合具体实施例，对本发明实施例的富锂正极材料的制备方法进行详细描述，需要指出的是，本发明中可以采用的其它金属盐、钴盐、锰盐、碱溶液、锂源并不仅限于以下实施例中采用的种类。实施例 1 43) Control the stirring speed of the mixed liquid in the reaction kettle so that the stirring speed is 50-1500 rpm, the reaction temperature is 30-70"C, and the pH of the mixed liquid is controlled between 7-12, so that the mixed salt solution in the mixed liquid The alkali solution and the aqueous ammonia solution are precipitated to form a crystalline precipitated product, and the precursor is obtained until the reaction is completed. The feed solution of the salt solution B is added to the salt solution A (that is, the flow rate of the constant flow pump) and the size of the reaction vessel. The temperature, reaction time and stirring speed required for the reaction are related, and the values are determined depending on the specific conditions of the reaction. Among them, the product formed by the post-crystallization precipitation is gradually deposited on the surface of the product formed by the crystal precipitation first, in the order in which the crystal precipitation product is formed. Since the concentration of manganese ions in the salt solution B is higher than the concentration of manganese ions in the salt solution A, the salt solution B is gradually added to the salt solution A by a constant flow pump, that is, a mixed salt solution formed by the salt solution B and the salt solution A. The concentration of manganese ions is gradually increased, so the proportion of manganese in the product of post-crystallization precipitation is higher than the ratio of manganese in the product of crystal precipitation, and the proportion of cobalt in the product of post-crystallization precipitation is lower than that of the first crystal. Precipitating the proportion of cobalt in the product until the end of the precipitation reaction, obtaining the precursor of the spherical particles, so that the proportion of manganese in the precursor increases gradually from the inner core to the outer layer of the sphere, and the proportion of cobalt is from the inner core of the sphere Gradually lower to the outer layer. In the embodiment of the present invention, the cobalt salt may be one or more of a sulfate, a nitrate, a chloride or an acetate, and the manganese salt may be used in a sulfate, a nitrate, a chloride or an acetate. One or more, when controlling the crystallization coprecipitation treatment, the hydroxide coprecipitation method, the carbonate coprecipitation method or the oxalate coprecipitation method may be used, that is, the alkali solution may be sodium hydroxide or potassium hydroxide. And one or more of lithium hydroxide, sodium carbonate, sodium hydrogencarbonate, ammonium hydrogencarbonate, and sodium oxalate. In the step 5), before mixing the precursor with the lithium source, the precursor prepared in the step 4) is filtered and washed, and the precursor is dried at 110 ° C for 12 h, and then Lithium-containing lithium sources are mixed in proportion to obtain a lithium-rich semi-finished product. The lithium source used in the embodiments of the present invention may be one or more of lithium carbonate, lithium hydroxide, and lithium nitrate. When the precursor is mixed with a lithium source, the ratio of the number of moles of lithium to the total number of moles of metal of the precursor is uniformly mixed (where 1 <n < 2) to obtain a lithium-rich semi-finished product, and then The lithium-rich semi-finished product is then calcined to obtain a spherical lithium-rich cathode material. In the calcination treatment, the lithium-rich semi-finished product is first calcined in air, the calcination temperature is 400-700 ° C, and the calcination time is l-12 h; then the calcined lithium-rich semi-finished product is heated and calcined, and the temperature is raised. The calcination temperature is 750-1000 ° C, and the heating and calcining time is 4-30 h; then the lithium-rich semi-finished product after heating and calcining is annealed, the annealing temperature is 400-700 ° C, and the time is 0-12 h; The annealed lithium-rich semi-finished product is naturally cooled to room temperature, or the lithium-rich semi-finished product after heating and calcination is directly cooled to room temperature without annealing, thereby obtaining a spherical lithium-rich positive electrode material. The preparation method of the embodiment of the invention has the advantages of simple process, controllable process, low cost of raw materials and environmental friendliness, large-scale industrial production, and good application prospect. The embodiment of the present invention further provides a lithium-rich cathode material obtained by the preparation method of the present invention, which is composed of a compound of the chemical formula Li _1+x M0 ₂ , wherein 0 < χ < 1, M includes manganese ( Mn) and cobalt (Co), and one or more of nickel (Ni), aluminum (Al), magnesium (Mg), titanium (Ti), chromium (Cr), and copper (Cu) elements; The compound is a spherical particle, and the proportion of the manganese element in the spherical particle gradually increases from the inner layer to the outer layer, and the proportion of the cobalt element gradually decreases from the inner layer to the outer layer. The lithium-rich cathode material prepared by the embodiment of the invention has a spherical shape. From the inner layer to the outer layer of the sphere, the proportion of the manganese element is gradually increased, and the proportion of the cobalt element is gradually decreased, thereby making the lithium-rich cathode material have excellent cycle life and rate performance. With high specific capacity, it can meet the demand for power supply in electric vehicles and other fields. Hereinafter, a method for preparing a lithium-rich cathode material according to an embodiment of the present invention will be described in detail with reference to specific embodiments. It should be noted that other metal salts, cobalt salts, manganese salts, alkali solutions, and lithium sources that can be used in the present invention are not only It is limited to the types used in the following embodiments. Example 1

1 ) 将硫酸锰（MnS0₄'H₂0)，硫酸镍（MS(V6H₂0)，硫酸钴（CoS0₄'7H₂0) 按 Mn:Ni:Co的摩尔比为 0.3:0.3:0.4比例混合，溶解在去离子水中，配制成总金属离子浓度为 2.0 mol/L的盐溶液 A，即盐溶液 A中锰离子浓度占总金属离子浓度的 30%。 1) a ratio of manganese sulfate (MnS0 ₄ 'H ₂ 0), nickel sulfate (MS (V6H ₂ 0), cobalt sulfate (CoS0 ₄ '7H ₂ 0) in a molar ratio of Mn:Ni:Co of 0.3:0.3:0.4 The mixture is dissolved in deionized water to prepare a salt solution A having a total metal ion concentration of 2.0 mol/L, that is, the concentration of manganese ions in the salt solution A is 30% of the total metal ion concentration.

2) 称取一定量的硫酸锰（MnS(VH₂0) 和硫酸镍（MS(V6H₂0) 溶解在去离子水中，配制成总金属离子浓度为 2.0 mol/L的盐溶液 B，其中 Mn: M的摩尔比为 0.7:0.3，即盐溶液 B中的锰离子浓度占总金属离子浓度的 70%。 2) Weigh a certain amount of manganese sulfate (MnS (VH ₂ 0) and nickel sulfate (MS (V6H ₂ 0) dissolved in deionized water to prepare a salt solution B with a total metal ion concentration of 2.0 mol/L, where Mn The molar ratio of M is 0.7:0.3, that is, the concentration of manganese ions in the salt solution B is 70% of the total metal ion concentration.

3 ) 配制浓度为 2.0 mol/L的 Na₂C0₃碱溶液作为配位剂，配制浓度为 0.4 mol/L的氨水作为络合剂。 3) Prepare a concentration of 2.0 mol/L Na ₂ CO ₃ alkali solution as a complexing agent to prepare ammonia water with a concentration of 0.4 mol/L as a complexing agent.

4)一边将配制好的盐溶液 B ( 1400mL)通过恒流泵（恒流泵的流速为 1.0mL/min) 逐步加入处于搅拌状态下的混合盐溶液 A (600mL) 中，一边将盐溶液 A和盐溶液 B 形成的混合盐溶液逐步泵入到反应釜内，同时将 Na₂C0₃碱溶液和氨水分别通过恒流泵并流加入到反应釜中形成混合液（Na₂C0₃碱溶液和氨水的流速也为 1.0mL/min)，控制对混合液的搅拌速度为 800 rpm，反应温度为 60°C，pH值为 8.0，反应时间为 33.3h，通过控制结晶共沉淀反应得到球形前躯体 (M_{n 58}Ni _3QCo_Q.₁₂)C0₃。 4) While preparing the prepared salt solution B (1400 mL) through a constant flow pump (flow rate of the constant flow pump is 1.0 mL/min), gradually add the mixed salt solution A (600 mL) under stirring, and then the salt solution A The mixed salt solution formed with the salt solution B is gradually pumped into the reaction kettle, and the Na ₂ CO ₃ alkali solution and the ammonia water are separately fed into the reaction vessel through a constant flow pump to form a mixed liquid (Na ₂ CO ₃ alkali solution and The flow rate of ammonia water is also 1.0 mL/min. The stirring speed of the mixture is controlled to 800 rpm, the reaction temperature is 60 ° C, the pH is 8.0, and the reaction time is 33.3 h. The spherical precursor is obtained by controlling the crystal coprecipitation reaction. (M _{n 58} Ni _3Q Co _Q . ₁₂ ) C0 ₃ .

5 ) 将步骤 4) 中得到的前躯体进行过滤、洗涤，然后置于 110 °C的温度下干燥 12 h, 再与 Li₂C0₃按锂的摩尔数与^^、 Mn、 Co三种金属元素的总摩尔数之比为 1.35： 1的比例均匀混合，得到富锂半成品。之后，对富锂半成品进行煅烧处理，即：首先，在空气气氛下进行预烧，预烧温度为 500 °C , 预烧时间为 6 h; 然后对预烧后的富锂半成品进行升温煅烧，煅烧温度为 900 °C , 煅烧时间为 14 h; 再对升温煅烧后的富锂半成品进行退火处理，退火处理的温度为 400 °C，退火时间为 12 h; 最后，将退火处理后的富锂半成品自然冷却至室温，从而得到球形富锂正极材料 Li_L35(Mn₀.₅₈M ₃₀Co _i2)O₂。对本实施例的制备方法所制得的富锂正极材料进行相应分析，发现其结构具有如下特点： 5) The precursor obtained in step 4) is filtered, washed, and then dried at 110 ° C for 12 h, and then with Li ₂ C0 _{3 in} terms of the molar number of lithium and ^^, Mn, Co three metals The ratio of the total number of moles of the elements is 1.35:1, and the ratio is uniformly mixed to obtain a lithium-rich semi-finished product. After that, the lithium-rich semi-finished product is calcined, that is: First, The pre-firing is carried out in an air atmosphere, the pre-firing temperature is 500 ° C, and the calcination time is 6 h; then the pre-fired lithium-rich semi-finished product is subjected to temperature-raising calcination, the calcination temperature is 900 ° C, and the calcination time is 14 h; Annealing the lithium-rich semi-finished product after heating and calcining, the annealing temperature is 400 °C, and the annealing time is 12 h. Finally, the annealed lithium-rich semi-finished product is naturally cooled to room temperature to obtain a spherical lithium-rich cathode material Li. _L35 (Mn ₀ . ₅₈ M ₃₀ Co _i 2)O ₂ . Corresponding analysis was carried out on the lithium-rich cathode material prepared by the preparation method of the present example, and the structure was found to have the following characteristics:

1 )如图 1所示，为本实施例制备的材料的扫描电镜（SEM) 图，从扫描电镜图片可以看出，本实施例所得到的材料为微米级的球形颗粒，该球形颗粒由许多纳米级的一次粒子团聚而成，且球形颗粒为多孔网状结构，有利于锂离子的嵌入与脱出。 1) As shown in FIG. 1 , a scanning electron microscope (SEM) image of the material prepared in the present embodiment, as can be seen from the scanning electron microscope image, the material obtained in this embodiment is a micron-sized spherical particle, and the spherical particle is composed of many Nano-sized primary particles are agglomerated, and the spherical particles are porous network structures, which facilitate the insertion and extraction of lithium ions.

2) 如图 3所示，为本实施例制备材料的 X射线衍射图谱，从图中可以看出，本实施例制得的材料为层状 α-NaF_e0₂结构，空间群为 R-3m，各衍射峰尖锐，结晶度高，并且在 20°-25°之间出现明显的 Li₂Mn0₃特征峰。 2) As shown in Fig. 3, the X-ray diffraction pattern of the material prepared in the present example, as can be seen from the figure, the material obtained in this example is a layered α-NaF _e 0 ₂ structure, and the space group is R- 3m, each diffraction peak is sharp, the crystallinity is high, and a distinct Li ₂ Mn0 ₃ characteristic peak appears between 20°-25°.

3 )如图 2所示，为本实施例制备材料的剖面扫描电镜图，由图可知，材料的球形颗粒内部没有明显裂缝。 3) As shown in Fig. 2, a cross-sectional scanning electron micrograph of the material prepared in the present example, as shown in the figure, shows that there is no obvious crack inside the spherical particles of the material.

4)对如图 2所示的材料的剖面结构由内至外取 5点进行 EDXS分析，得出如表 1 所示的结果。由表 1 可知，本实施例制得的球形颗粒材料中，由其内层到外层， Mn 的摩尔比分别为 28.77%， 37.30%, 45.18%, 50.76%, 59.93%, Co的摩尔比分别为 41.02%， 32.12%, 24.12%, 18.12%, 10.05%, 而 M的摩尔比基本保持不变，即：从材料的内层到外层，锰元素的比例逐渐增加，钴元素的比例逐渐降低，其它金属元素的比例保持不变。利用本实施例制得的富锂正极材料制成测试电池，并对其进行电化学测试，得到如下数据： 4) The EDXS analysis was performed on the cross-sectional structure of the material shown in Fig. 2 from the inside to the outside, and the results shown in Table 1 were obtained. It can be seen from Table 1 that the molar ratio of Mn from the inner layer to the outer layer of the spherical granular material obtained in this example is 28.77%, 37.30%, 45.18%, 50.76%, 59.93%, respectively. It is 41.02%, 32.12%, 24.12%, 18.12%, 10.05%, and the molar ratio of M remains basically the same, that is: from the inner layer to the outer layer of the material, the proportion of manganese element gradually increases, and the proportion of cobalt element gradually decreases. The proportion of other metal elements remains unchanged. A test battery was fabricated using the lithium-rich positive electrode material prepared in this example, and electrochemically tested to obtain the following data:

1 ) 如图 4所示，为在电流密度为 0.1 C，充放电电压范围为 2.0-4.6 V的条件下，测试电池的第 1、 2次充放电曲线图（其中， 1st表示第 1次， 2nd表示第 2次），由图可知，第 1次充电比容量为 330 mAh/g，第 1次放电比容量为 232mAh/g，库伦效率为 70.3%；第 2次充电比容量为 258 mAh/g，第 2次放电比容量为 232mAh/g; 并且，在第 1次充电曲线中出现一个较长的 4.5 V平台，而在第 2次充电曲线中此平台消失，说明本实施例制得的富锂正极材料与常规富锂正极材料的充电特征相符，符合富锂正极材料的充放电特点。 2) 如图 5所示，曲线为在电流密度为 0.5 C，充放电电压范围为 2.0-4.6 V的条件下，本实施例测试电池和对比例测试电池经过 200次循环的循环寿命图，由图可知，经过 200次循环后，本实施例材料制成的测试电池的容量保持率为 92.6 %，显示优越的电化学性能。 3 ) 如图 6所示，为本实施例测试电池和对比例测试电池在 0.1 C、 0.2 C、 0.5 C、1) As shown in Figure 4, the first and second charge and discharge curves of the battery are tested under the conditions of a current density of 0.1 C and a charge and discharge voltage range of 2.0-4.6 V (where 1st represents the first time, 2nd indicates the second time. As can be seen from the figure, the first charge specific capacity is 330 mAh/g, the first discharge specific capacity is 232 mAh/g, the Coulomb efficiency is 70.3%, and the second charge specific capacity is 258 mAh/ g, the second discharge specific capacity is 232 mAh / g; and, a longer 4.5 V platform appears in the first charging curve, and the platform disappears in the second charging curve, indicating that the system is made in this embodiment The lithium-rich cathode material is consistent with the charging characteristics of the conventional lithium-rich cathode material, and meets the charging and discharging characteristics of the lithium-rich cathode material. 2) As shown in Fig. 5, the curve is a cycle life diagram of 200 cycles of the test battery and the comparative test battery under the conditions of a current density of 0.5 C and a charge and discharge voltage range of 2.0-4.6 V. As can be seen, after 200 cycles, the test cell made of the material of this example had a capacity retention ratio of 92.6%, showing superior electrochemical performance. 3) As shown in Figure 6, the test battery and the comparative test battery of this example are at 0.1 C, 0.2 C, 0.5 C,

1 C、 2C、 5 C、 IO C倍率下的倍率性能对比图，由图可知，本实施例测试电池在 0.1 C 倍率下的放电比容量为 232 mAh /g，在 10C倍率下的放电比容量为 142 mAh /g，可见本实施例材料制成的测试电池具有优异的倍率性能。实施例 2 1 ) 将硫酸锰（MnS0₄'H₂0)，硫酸镍（MS0₄'6H₂0)，硫酸钴（CoS0₄'7H₂0) 按1 C, 2C, 5 C, IO C rate ratio performance comparison chart, as can be seen from the figure, the discharge specific capacity of the test battery at 0.1 C rate is 232 mAh / g, the discharge specific capacity at 10 C rate At 142 mAh / g, it can be seen that the test battery made of the material of this example has excellent rate performance. Example 2 1) Manganese sulfate (MnS0 ₄ 'H ₂ 0), nickel sulfate (MS0 ₄ '6H ₂ 0), cobalt sulfate (CoS0 ₄ '7H ₂ 0)

Ni： Mn： Co (摩尔比） = 0.333： 0.333： 0.333比例混合，溶解在去离子水中，配制成总金属离子浓度为 1.0 mol/L的混合盐溶液 A，即盐溶液 A中锰离子浓度占总金属离子浓度的 33.3%。 Ni: Mn: Co (molar ratio) = 0.333: 0.333: 0.333 ratio mixed, dissolved in deionized water, formulated into a mixed salt solution A with a total metal ion concentration of 1.0 mol / L, that is, the concentration of manganese ions in the salt solution A The total metal ion concentration was 33.3%.

2 ) 称取一定量的硫酸锰（MnS(VH₂0 ) 和硫酸镍（MS(V6H₂0) 溶解在去离子水中，配制成总金属离子浓度为 1.0 mol/L的盐溶液 B，其中 Mn: Ni (摩尔比） = 0.667:2) Weigh a certain amount of manganese sulfate (MnS (VH ₂ 0 ) and nickel sulfate (MS (V6H ₂ 0) dissolved in deionized water to prepare a salt solution B with a total metal ion concentration of 1.0 mol/L, where Mn : Ni (molar ratio) = 0.667:

0.333 , 即盐溶液 B中锰离子浓度占总金属离子浓度的 66.7%。 0.333, that is, the concentration of manganese ions in the salt solution B accounts for 66.7% of the total metal ion concentration.

3 ) 分别配制浓度为 1.0 mol/L的 Na₂C0₃碱溶液和浓度为 0.1 mol/L的氨水。 3) Prepare a Na ₂ C0 ₃ alkaline solution with a concentration of 1.0 mol/L and a concentration of 0.1 mol/L ammonia water.

4)一边将配制好的盐溶液 B ( 700mL)通过恒流泵（流速与实施例 1相同，以下各实施例相同，）逐步加入处于搅拌状态下的混合盐溶液 A OOOmL) 中，一边将盐溶液 A和盐溶液 B形成的混合盐溶液逐步泵入到反应釜内，同时将 Na₂C0₃碱溶液和氨水分别通过恒流泵并流加入到反应釜中形成混合液，控制对混合液的搅拌速度为 1000 rpm, 反应温度为 55 °C， pH值为 7.5，反应时间为 24h，通过控制结晶共沉淀反应得到球形前躯体（Mn ₅₆₇M_a333Co _i(x))C0₃。 4) While the prepared salt solution B (700 mL) was passed through a constant flow pump (the flow rate was the same as in Example 1, the following examples are the same), the mixed salt solution A OOOmL under stirring was gradually added, and the salt was added while The mixed salt solution formed by the solution A and the salt solution B is gradually pumped into the reaction kettle, and the Na ₂ CO ₃ alkali solution and the ammonia water are separately fed into the reaction kettle through a constant flow pump to form a mixed liquid, and the mixed liquid is controlled. The stirring speed was 1000 rpm, the reaction temperature was 55 ° C, the pH was 7.5, and the reaction time was 24 h. The spherical precursor (Mn ₅₆₇ M _a333 Co _i( x)) C0 ₃ was obtained by controlling the crystal coprecipitation reaction.

( 3 )将步骤 4) 中得到的前躯体进行过滤、洗漆，然后置于 110 °C的温度下干燥 12 h, 再与 Li₂C0₃按锂的摩尔数与M、 Mn、 Co三种金属元素的总摩尔数之比为 1.30： 1的比例均匀混合，得到富锂半成品。之后，对富锂半成品进行煅烧处理，即：首先，在空气气氛下进行预烧，预烧温度为 500 °C , 预烧时间为 8 h_; 然后对预烧后的富锂半成品进行升温煅烧，煅烧温度为 850°C，煅烧时间为 14 h_; 最后，将升温煅烧后的富锂半成品自然冷却至室温，从而得到球形富锂正极材料

利用本实施例制得的富锂正极材料制成测试电池，并对其进行电化学测试（图中未示出）。其中，电化学测试表明，在 0.1 C、 2.0-4.6 V电压范围内，本实施例的测试电池首次放电比容量为 227 mAh/g; 而在 0.2 C、 2.0-4.6 V条件下经过 100次循环后，本实施例的材料制成的测试电池的容量保持率为 98.2 %，显示优越的电化学性能。实施例 3 (3) The precursor obtained in step 4) is filtered, washed, and then dried at 110 ° C for 12 h, and then with Li ₂ C0 ₃ according to the number of moles of lithium and M, Mn, Co The ratio of the total number of moles of metal elements is 1.30:1, and the ratio is uniformly mixed to obtain a lithium-rich semi-finished product. Thereafter, the lithium-rich semi-finished product is subjected to calcination treatment, that is, first, pre-baking is performed in an air atmosphere, the calcination temperature is 500 ° C, and the calcination time is 8 h _; then the calcined lithium-rich semi-finished product is subjected to temperature-raising calcination. The calcination temperature is 850 ° C, and the calcination time is 14 h _. Finally, the lithium-rich semi-finished product after heating and calcination is naturally cooled to room temperature to obtain a spherical lithium-rich cathode material.

A test battery was fabricated using the lithium-rich positive electrode material prepared in this example, and electrochemically tested (not shown). Among them, electrochemical tests show that the test cell of the present embodiment has a first discharge specific capacity of 227 mAh/g in a voltage range of 0.1 C, 2.0-4.6 V; and 100 cycles under 0.2 C, 2.0-4.6 V conditions. Thereafter, the test cell made of the material of this example had a capacity retention ratio of 98.2%, showing superior electrochemical performance. Example 3

1 ) 将硫酸镍（MS0₄'7H₂0)，硫酸钴（CoS0₄'7H₂0) 按 ^^: 0) (摩尔比）= 1： 1比例混合，溶解在去离子水中，配制成总金属离子浓度为 3.0 mol/L的盐溶液 A，即盐溶液 A中锰离子浓度占总金属离子浓度的 0%。 1) Mix nickel sulfate (MS0 ₄ '7H ₂ 0), cobalt sulfate (CoS0 ₄ '7H ₂ 0) in a ratio of ^^: 0) (molar ratio) = 1: 1 and dissolve in deionized water to make a total The salt solution A having a metal ion concentration of 3.0 mol/L, that is, the concentration of manganese ions in the salt solution A accounts for 0% of the total metal ion concentration.

2)称取一定量的硫酸锰（MnS(VH₂0)溶解在去离子水中，配制成总金属离子浓度为 3.0 mol/L的盐溶液 B，即盐溶液 B中锰离子浓度占总金属离子浓度的 100%。 2) Weigh a certain amount of manganese sulfate (MnS (VH ₂ 0) dissolved in deionized water to prepare a salt solution B with a total metal ion concentration of 3.0 mol/L, that is, the concentration of manganese ions in the salt solution B accounts for the total metal ions. 100% concentration.

3 ) 分别配制浓度为 5.0 mol/L的 NaOH碱溶液和浓度为 5.0 mol/L的氨水。 3) Prepare NaOH alkali solution with a concentration of 5.0 mol/L and ammonia water with a concentration of 5.0 mol/L.

4) 一边将配制好的盐溶液 B ( 1200mL) 通过恒流泵逐步加入处于搅拌状态下的混合盐溶液 A ( 800mL) 中，一边将盐溶液 A和盐溶液 B形成的混合盐溶液逐步泵入到反应釜内，同时将 NaOH碱溶液和氨水分别通过恒流泵并流加入到反应釜中形成混合液，控制对混合液的搅拌速度为 800 rpm，反应温度为 50°C， pH值为 11.0，反应时间为 48h，通过控制结晶共沉淀反应得到球形前躯体 (Mn ₆Ni _2QCo _2Q)(OH)₂。 4) While gradually adding the prepared salt solution B (1200 mL) to the mixed salt solution A (800 mL) under stirring through a constant flow pump, the mixed salt solution formed by the salt solution A and the salt solution B is gradually pumped. Into the reaction kettle, the NaOH alkali solution and the ammonia water were separately fed into the reaction vessel through a constant flow pump to form a mixed liquid, and the stirring speed of the mixed liquid was controlled to be 800 rpm, the reaction temperature was 50 ° C, and the pH was 11.0. The reaction time was 48 h, and a spherical precursor (Mn ₆ Ni _2Q Co _2Q )(OH) ₂ was obtained by controlling the crystal coprecipitation reaction.

5 ) 将步骤 4) 中得到的前躯体进行过滤、洗涤，然后置于 110 °C的温度下干燥 12 h, 再与 Li₂C0₃按锂的摩尔数与^^、 Mn、 Co三种金属元素的总摩尔数之比为 1.42: 1的比例均匀混合，得到富锂半成品。之后，对富锂半成品进行煅烧处理，即：首先，在空气气氛下进行预烧，预烧温度为 500 °C , 预烧时间为 5 h_; 然后对预烧后的富锂半成品进行升温煅烧，煅烧温度为 900 °C , 煅烧时间为 12 h; 最后，将富锂半成品自然冷却至室温，从而得到球形富锂正极材料

利用本实施例制得的富锂正极材料制成测试电池，并对其进行电化学测试（图中未示出）。其中，在 0.1 C、 2.0-4.6 V电压范围内，本实施例的测试电池首次放电比容量为 235 mAh/g; 在 0.2 C、 2.0-4.6 V条件下经过 100次循环后，本实施例的测试电池的容量保持率为 95.7 %; 在 0.5 C、 1 C、 2 C、 5 C、 10 C倍率下，其可逆容量分别为 212mAh/g、 196 mAh/g 182 mAh/g, 156 mAh/g, 133 mAh/g, 显示本实施例材料制得的测试电池具有良好的电化学性能。实施例 4 1 ) 将硫酸锰 (MnS0₄-¾0), 硫酸钴 ( CoS0₄-7H₂0) 和硫酸镍 (NiS04-6H₂0) 按 Mn： Co： M (摩尔比） = 0.4： 0.4: 0.2比例混合，溶解在去离子水中，配制成总金属离子浓度为 1.8 mol/L的盐溶液 A，即盐溶液 A中锰离子浓度占总金属离子浓度的 40%。 5) The precursor obtained in step 4) is filtered, washed, and then dried at 110 ° C for 12 h, and then with Li ₂ C0 _{3 in} terms of the molar number of lithium and ^^, Mn, Co three metals The ratio of the total number of moles of the elements is 1.42: The ratio of 1 is uniformly mixed to obtain a lithium-rich semi-finished product. Thereafter, the lithium-rich semi-finished product is calcined, that is, firstly, calcination is carried out in an air atmosphere, the calcination temperature is 500 ° C, and the calcination time is 5 h _; then the calcined lithium-rich semi-finished product is heated and calcined. The calcination temperature is 900 °C and the calcination time is 12 h. Finally, the lithium-rich semi-finished product is naturally cooled to room temperature to obtain a spherical lithium-rich cathode material.

A test battery was fabricated using the lithium-rich positive electrode material prepared in this example, and electrochemically tested (not shown). Wherein, in the voltage range of 0.1 C, 2.0-4.6 V, the first discharge specific capacity of the test battery of the embodiment is 235 mAh/g; after 100 cycles of 0.2 C, 2.0-4.6 V, the embodiment The capacity retention rate of the test cell was 95.7 %; at 0.5 C, 1 C, 2 C, 5 C, 10 C rate, the reversible capacity was 212 mAh/g, 196 mAh/g 182 mAh/g, 156 mAh/g. 133 mAh/g, the test cell prepared by the material of this example was shown to have good electrochemical performance. Example 4 1) Mix manganese sulfate (MnS0 ₄ -3⁄40), cobalt sulfate (CoS0 ₄ -7H ₂ 0) and nickel sulfate (NiS04-6H ₂ 0) in a ratio of Mn: Co: M (molar ratio) = 0.4: 0.4: 0.2 Dissolved in deionized water to prepare a salt solution A with a total metal ion concentration of 1.8 mol/L, that is, the concentration of manganese ions in the salt solution A accounts for 40% of the total metal ion concentration.

2) 称取一定量的硫酸锰（MnS(VH₂0) 和硫酸镍（MS(V6H₂0) 溶解在去离子水中，配制成总金属离子浓度为 1.8 mol/L的盐溶液 B，其中 Mn: Ni (摩尔比） = 0.8：2) Weigh a certain amount of manganese sulfate (MnS (VH ₂ 0) and nickel sulfate (MS (V6H ₂ 0) dissolved in deionized water to prepare a salt solution B with a total metal ion concentration of 1.8 mol/L, where Mn : Ni (molar ratio) = 0.8:

0.2，即盐溶液 B中锰离子浓度占总金属离子浓度的 80%。 0.2, that is, the concentration of manganese ions in the salt solution B accounts for 80% of the total metal ion concentration.

3 ) 分别配制浓度为 3.6 mol/L的 NaOH碱溶液和浓度为 3.6 mol/L的氨水。 3) Prepare NaOH alkaline solution with a concentration of 3.6 mol/L and ammonia water with a concentration of 3.6 mol/L.

4)一边将配制好的盐溶液 B ( 800 mL)通过恒流泵逐步加入处于搅拌状态下的混合盐溶液 A ( 1200 mL) 中，一边将盐溶液 A和盐溶液 B形成的混合盐溶液逐步泵入到反应釜内，同时将 NaOH碱溶液和氨水分别通过恒流泵并流加入到反应釜中形成混合液，控制对混合液的搅拌速度为 1000 rpm，反应温度为 50°C， pH值为 11.0，反应时间为 60 h，通过控制结晶共沉淀反应得到球形前躯体 (Mn_Q.₆₄Ni _2QCo _i6)(OH)₂。 4) Gradually add the prepared salt solution B (800 mL) to the mixed salt solution A (1200 mL) under stirring through a constant flow pump, and gradually mix the salt solution formed by the salt solution A and the salt solution B. It is pumped into the reaction kettle, and the NaOH alkali solution and the ammonia water are respectively fed into the reaction kettle through a constant flow pump to form a mixed liquid, and the stirring speed of the mixed liquid is controlled to be 1000 rpm, the reaction temperature is 50 ° C, and the pH value is The reaction time was 60 h, and the spherical precursor (Mn _Q . ₆₄ Ni _2Q Co _i6 )(OH) ₂ was obtained by controlling the crystal coprecipitation reaction.

5 ) 将步骤 4) 中得到的前躯体进行过滤、洗涤，然后置于 110 °C的温度下干燥 12 h, 再与 Li₂C0₃按锂的摩尔数与^^、 Mn、 Co三种金属元素的总摩尔数之比为 1.45： 1的比例均匀混合，得到富锂半成品。之后，对富锂半成品进行煅烧处理，即：首先，在空气气氛下进行预烧，预烧温度为 500 °C , 预烧时间为 6 h; 然后对预烧后的富锂半成品进行升温煅烧，煅烧温度为 900 °C , 煅烧时间为 14 h; 最后自然冷却，从而得到球形富锂正极材料

利用本实施例制得的富锂正极材料制成测试电池，并对其进行电化学测试（图中未示出）。其中，在 0.1 C、 2.0-4.6 V电压范围内，本实施例的测试电池首次放电比容量为 243 mAh/g; 在 0.5 C、 2.0-4.6 V条件下经过 100次循环后，本实施例的测试电池的容量保持率为 96.4 %; 在 0.2C、 0.5 C、 1 C、 2 C、 5 C、 10 C倍率下，其可逆容量分别为 232mAh/g、 214 mAh/g、 198 mAh/g， 179 mAh/g， 163 mAh/g, 137 mAh/g, 显示本实施例材料制得的测试电池具有良好的电化学性能。实施例 5 5) The precursor obtained in step 4) is filtered, washed, and then dried at 110 ° C for 12 h, and then with Li ₂ C0 _{3 in} terms of the molar number of lithium and ^^, Mn, Co three metals The ratio of the total number of moles of the elements is 1.45:1, and the ratio is uniformly mixed to obtain a lithium-rich semi-finished product. Thereafter, the lithium-rich semi-finished product is subjected to calcination treatment, that is, first, calcination is carried out in an air atmosphere, the calcination temperature is 500 ° C, and the calcination time is 6 h; and then the calcined lithium-rich semi-finished product is subjected to temperature-raising calcination. The calcination temperature is 900 °C, the calcination time is 14 h; finally, it is naturally cooled to obtain a spherical lithium-rich cathode material.

A test battery was fabricated using the lithium-rich positive electrode material prepared in this example, and electrochemically tested (not shown). Wherein, in the voltage range of 0.1 C, 2.0-4.6 V, the first discharge specific capacity of the test battery of the embodiment is 243 mAh/g; after 100 cycles of 0.5 C, 2.0-4.6 V, the embodiment The capacity retention rate of the test cell was 96.4%; at 0.2C, 0.5 C, 1 C, 2 C, 5 C, 10 C rate, the reversible capacities were 232 mAh/g, 214 mAh/g, 198 mAh/g, respectively. 179 mAh/g, 163 mAh/g, 137 mAh/g, the test cell prepared by the material of this example showed good electrochemical performance. Example 5

1 )将硫酸钴 (CoS0₄-7H₂0)和硫酸镍 (NiS04-6H₂0)按 Co： M (摩尔比) = 0.75： 0.25比例混合，溶解在去离子水中，配制成总金属离子浓度为 1.0 mol/L的盐溶液 A，即盐溶液 A中锰离子浓度占总金属离子浓度的 0%。 2 ) 称取一定量的硫酸锰（MnS(VH₂0 )、硫酸镍（MS(V6H₂0 ) 和硫酸钴 ( CoS0₄-7H₂0)溶解在去离子水中，配制成总金属离子浓度为 l .O mol/L的盐溶液 B，其中 Mn： M： Co (摩尔比） = 0.5： 0.25： 0.25，即盐溶液 B中锰离子浓度占总金属离子浓度的 50%。 3 ) 分别配制浓度为 2.0 mol/L的 NaOH碱溶液和浓度为 4.0 mol/L的氨水。 1) Cobalt sulfate (CoS0 ₄ -7H ₂ 0) and nickel sulfate (NiS04-6H ₂ 0) are mixed in a ratio of Co: M (molar ratio) = 0.75: 0.25, dissolved in deionized water to prepare a total metal ion concentration. The salt solution A of 1.0 mol/L, that is, the concentration of manganese ions in the salt solution A accounts for 0% of the total metal ion concentration. 2) Weigh a certain amount of manganese sulfate (MnS (VH ₂ 0 ), nickel sulfate (MS (V6H ₂ 0 ) and cobalt sulfate (CoS0 ₄ -7H ₂ 0) dissolved in deionized water to make the total metal ion concentration l .O mol / L salt solution B, where Mn: M: Co (molar ratio) = 0.5: 0.25: 0.25, that is, the concentration of manganese ions in the salt solution B accounts for 50% of the total metal ion concentration. It is a 2.0 mol/L NaOH alkaline solution and a concentration of 4.0 mol/L ammonia water.

4)一边将配制好的盐溶液 B (400 mL)通过恒流泵逐步加入处于搅拌状态下的混合盐溶液 A ( 1600 mL ) 中，一边将盐溶液 A和盐溶液 B形成的混合盐溶液逐步泵入到反应釜内，同时将 NaOH碱溶液和氨水分别通过恒流泵并流加入到反应釜中形成混合液，控制对混合液的搅拌速度为 1000 rpm，反应温度为 50°C， pH值为 10.85，反应时间为 66 h，通过控制结晶共沉淀反应得到球形前躯体 (Mn _4QNi ₂₅Co ₃₅)(OH)₂。 4) While gradually adding the prepared salt solution B (400 mL) to the mixed salt solution A (1600 mL) under stirring through a constant flow pump, gradually mix the salt solution formed by the salt solution A and the salt solution B. It is pumped into the reaction kettle, and the NaOH alkali solution and the ammonia water are respectively fed into the reaction kettle through a constant flow pump to form a mixed liquid, and the stirring speed of the mixed liquid is controlled to be 1000 rpm, the reaction temperature is 50 ° C, and the pH value is The reaction time was 66 h, and the spherical precursor (Mn _4Q Ni ₂₅ Co ₃₅ )(OH) ₂ was obtained by controlling the crystal coprecipitation reaction.

5 ) 将步骤 4) 中得到的前躯体进行过滤、洗涤，然后置于 110 °C的温度下干燥 12 h, 再与 Li₂C0₃按锂的摩尔数与^^、 Mn、 Co三种金属元素的总摩尔数之比为 1.20： 1的比例均匀混合，得到富锂半成品。之后，对富锂半成品进行煅烧处理，即：首先，在空气气氛下进行预烧，预烧温度为 500 °C , 预烧时间为 6 h; 然后对预烧后的富锂半成品进行升温煅烧，煅烧温度为 900 °C , 煅烧时间为 16 h; 最后自然冷却，从而得到球形富锂正极材料

利用本实施例制得的富锂正极材料制成测试电池，并对其进行电化学测试（图中未示出）。其中，在 0.1 C、 2.0-4.6 V电压范围内，本实施例的测试电池首次放电比容量为 205 mAh/g; 在 0.5 C、 2.0-4.6 V条件下经过 100次循环后，本实施例的测试电池的容量保持率为 97.4 %; 在 0.2C、 0.5 C、 1 C、 2 C、 5 C、 10 C倍率下，其可逆容量分别为 195mAh/g、 186 mAh/g 175 mAh/g， 170 mAh/g， 156 mAh/g, 128 mAh/g, 显示本实施例材料制得的测试电池具有良好的电化学性能。实施例 6 5) The precursor obtained in step 4) is filtered, washed, and then dried at 110 ° C for 12 h, and then with Li ₂ C0 _{3 in} terms of the molar number of lithium and ^^, Mn, Co three metals The ratio of the total number of moles of the elements is 1.20: 1 ratio is uniformly mixed to obtain a lithium-rich semi-finished product. Thereafter, the lithium-rich semi-finished product is subjected to calcination treatment, that is, first, calcination is carried out in an air atmosphere, the calcination temperature is 500 ° C, and the calcination time is 6 h; and then the calcined lithium-rich semi-finished product is subjected to temperature-raising calcination. The calcination temperature is 900 °C, the calcination time is 16 h; finally, it is naturally cooled to obtain a spherical lithium-rich cathode material.

A test battery was fabricated using the lithium-rich positive electrode material prepared in this example, and electrochemically tested (not shown). Wherein, in the voltage range of 0.1 C, 2.0-4.6 V, the first discharge specific capacity of the test battery of the embodiment is 205 mAh/g; after 100 cycles of 0.5 C, 2.0-4.6 V, the embodiment The capacity retention rate of the test cell was 97.4%; at 0.2C, 0.5 C, 1 C, 2 C, 5 C, 10 C rate, the reversible capacity was 195 mAh/g, 186 mAh/g 175 mAh/g, 170 mAh/g, 156 mAh/g, 128 mAh/g, the test cell prepared by the material of this example showed good electrochemical performance. Example 6

1 )将硫酸钴（CoS0₄'7H₂0)和硫酸铝（A1₂S0₃ )按 Co： A1 (摩尔比） = 0.95： 0.05 比例混合，溶解在去离子水中，配制成总金属离子浓度为 1.0 mol/L的盐溶液 A，即盐溶液 A中锰离子浓度占总金属离子浓度的 0%，钴离子浓度占总金属离子浓度的 95%。 1) Cobalt sulfate (CoS0 ₄ '7H ₂ 0) and aluminum sulfate (A1 ₂ S0 ₃ ) are mixed in a ratio of Co: A1 (molar ratio) = 0.95: 0.05, dissolved in deionized water, and the total metal ion concentration is set to The 1.0 mol/L salt solution A, that is, the manganese ion concentration in the salt solution A accounts for 0% of the total metal ion concentration, and the cobalt ion concentration accounts for 95% of the total metal ion concentration.

2)称取一定量的硫酸锰（MnS(VH₂0)和硫酸铝（A1₂S0₃) 按 Mn： A1 (摩尔比） = 0.95： 0.05比例混合，溶解在去离子水中，配制成总金属离子浓度为 1.0 mol/L的盐溶液 B，即盐溶液 B中锰离子浓度占总金属离子浓度的 95%，钴离子浓度占总金属离子浓度的 0%。 3 ) 分别配制浓度为 2.0 mol/L的 NaOH碱溶液和浓度为 2.0 mol/L的氨水。 2) Weigh a certain amount of manganese sulfate (MnS (VH ₂ 0) and aluminum sulfate (A1 ₂ S0 ₃ ) according to Mn: A1 (molar ratio) = 0.95: 0.05 ratio, dissolved in deionized water, formulated into total metal The salt solution B having an ion concentration of 1.0 mol/L, that is, the concentration of manganese ions in the salt solution B accounts for 95% of the total metal ion concentration, and the cobalt ion concentration accounts for 0% of the total metal ion concentration. 3) Prepare NaOH alkali solution with a concentration of 2.0 mol/L and ammonia water with a concentration of 2.0 mol/L.

4)一边将配制好的盐溶液 B ( 600 mL)通过恒流泵逐步加入处于搅拌状态下的混合盐溶液 A ( 1400 mL ) 中，一边将盐溶液 A和盐溶液 B形成的混合盐溶液逐步泵入到反应釜内，同时将 NaOH碱溶液和氨水分别通过恒流泵并流加入到反应釜中形成混合液，控制对混合液的搅拌速度为 1000 rpm，反应温度为 55 °C， pH值为 10.85，反应时间为 50 h，通过控制结晶共沉淀反应得到球形前躯体 (Mn ₆₆₅Co ₂₈₅Al _Q5)(OH)₂。 4) While gradually adding the prepared salt solution B (600 mL) to the mixed salt solution A (1400 mL) under stirring through a constant flow pump, gradually mix the salt solution formed by the salt solution A and the salt solution B. The pump is pumped into the reaction kettle, and the NaOH alkali solution and the ammonia water are respectively fed into the reaction vessel through a constant flow pump to form a mixed liquid, and the stirring speed of the mixed liquid is controlled to be 1000 rpm, the reaction temperature is 55 ° C, and the pH value is The reaction time was 50 h, and the spherical precursor (Mn ₆₆₅ Co ₂₈₅ Al _Q5 ) (OH) ₂ was obtained by controlling the crystal coprecipitation reaction.

5 ) 将步骤 4) 中得到的前躯体进行过滤、洗涤，然后置于 110 °C的温度下干燥 12 h, 再与 Li₂C0₃按锂的摩尔数与^^、 Mn、 Co三种金属元素的总摩尔数之比为 1.50： 1的比例均匀混合，得到富锂半成品。之后，对富锂半成品进行煅烧处理，即：首先，在空气气氛下进行预烧，预烧温度为 600 °C , 预烧时间为 6 h_; 然后对预烧后的富锂半成品进行升温煅烧，煅烧温度为 900 °C , 煅烧时间为 12 h; 自然冷却，从而得到球形富锂正极材料

利用本实施例制得的富锂正极材料制成测试电池，并对其进行电化学测试（图中未示出）。其中，在 0.1 C、 2.0-4.6 V电压范围内，本实施例的测试电池首次放电比容量为 233 mAh/g; 在 0.5 C、 2.0-4.6 V条件下经过 100次循环后，本实施例的测试电池的容量保持率为 96.6 %; 在 0.2C、 0.5 C、 1 C、 2 C、 5 C、 10 C倍率下，其可逆容量分别为 223mAh/g、 206 mAh/g、 195 mAh/g， 181 mAh/g， 163 mAh/g, 135 mAh/g, 显示本实施例材料制得的测试电池具有良好的电化学性能。实施例 7 1 )将硫酸钴（CoS0₄'7H₂0)、硫酸锰（MnS0₄'H₂0)和硝酸镁（Mg(N0₃)₂'6H₂0) 按 Co： Mn： Mg (摩尔比） = 0.65： 0.25： 0.10比例混合，溶解在去离子水中，配制成总金属离子浓度为 1.0 mol/L的盐溶液 A，即盐溶液 A中锰离子浓度占总金属离子浓度的 25%，钴离子浓度站金属离子浓度的 65%。 5) The precursor obtained in step 4) is filtered, washed, and then dried at 110 ° C for 12 h, and then with Li ₂ C0 _{3 in} terms of the molar number of lithium and ^^, Mn, Co three metals The ratio of the total number of moles of the elements is 1.50:1, and the ratio is uniformly mixed to obtain a lithium-rich semi-finished product. Thereafter, the lithium-rich semi-finished product is subjected to calcination treatment, that is, first, calcination is carried out in an air atmosphere, the calcination temperature is 600 ° C, and the calcination time is 6 h _; then the calcined lithium-rich semi-finished product is subjected to temperature-raising calcination. Calcination temperature is 900 °C, calcination time is 12 h; natural cooling, thus obtaining spherical lithium-rich cathode material

A test battery was fabricated using the lithium-rich positive electrode material prepared in this example, and electrochemically tested (not shown). Wherein, in the voltage range of 0.1 C, 2.0-4.6 V, the first discharge specific capacity of the test battery of the embodiment is 233 mAh/g; after 100 cycles of 0.5 C, 2.0-4.6 V, the embodiment The capacity retention rate of the test cell was 96.6 %; at 0.2C, 0.5 C, 1 C, 2 C, 5 C, 10 C rate, the reversible capacities were 223 mAh/g, 206 mAh/g, 195 mAh/g, respectively. 181 mAh/g, 163 mAh/g, 135 mAh/g, the test cell prepared by the material of this example showed good electrochemical performance. Example 7 1) Cobalt sulfate (CoS0 ₄ '7H ₂ 0), manganese sulfate (MnS0 ₄ 'H ₂ 0) and magnesium nitrate (Mg(N0 ₃ ) ₂ '6H ₂ 0) as Co: Mn: Mg (molar) Ratio = 0.65: 0.25: 0.10 ratio mixing, dissolved in deionized water, formulated into a total metal ion concentration of 1.0 mol / L of salt solution A, that is, the concentration of manganese ions in the salt solution A accounted for 25% of the total metal ion concentration, The cobalt ion concentration station has a metal ion concentration of 65%.

2 ) 将硫酸钴 ( CoS0₄-7H₂0)、硫酸锰 (MnS0₄-H₂0 ) 和硝酸镁 (Mg(N0₃)₂ ) 按 Co： Mn： Mg (摩尔比） = 0.25： 0.65： 0.10比例混合，溶解在去离子水中，配制成总金属离子浓度为 1.0 mol/L的盐溶液 B，即盐溶液 B中锰离子浓度占总金属离子浓度的 65%, 钴离子浓度占总金属离子浓度的 25%。 2) Cobalt sulfate (CoS0 ₄ -7H ₂ 0), manganese sulfate (MnS0 ₄ -H ₂ 0 ) and magnesium nitrate (Mg(N0 ₃ ) ₂ ) as Co: Mn: Mg (molar ratio) = 0.25: 0.65: 0.10 proportion mixing, dissolved in deionized water, formulated into a total metal ion concentration of 1.0 mol / L of salt solution B, that is, salt solution B manganese ion concentration of 65% of the total metal ion concentration, cobalt ion concentration of total metal ions 25% of the concentration.

3 ) 分别配制浓度为 2.0 mol/L的 NaOH碱溶液和浓度为 2.0 mol/L的氨水。 4)一边将配制好的盐溶液 B ( 600 mL)通过恒流泵逐步加入处于搅拌状态下的混合盐溶液 A ( 1400 mL ) 中，一边将盐溶液 A和盐溶液 B形成的混合盐溶液逐步泵入到反应釜内，同时将 NaOH碱溶液和氨水分别通过恒流泵并流加入到反应釜中形成混合液，控制对混合液的搅拌速度为 1000 rpm，反应温度为 55 °C， pH值为 10.80，反应时间为 60 h，通过控制结晶共沉淀反应得到球形前躯体 (Mn_Q.₅₃Co ₃₇Mg _i)(OH)₂。 3) Prepare NaOH alkali solution with a concentration of 2.0 mol/L and ammonia water with a concentration of 2.0 mol/L. 4) While gradually adding the prepared salt solution B (600 mL) to the mixed salt solution A (1400 mL) under stirring through a constant flow pump, gradually mix the salt solution formed by the salt solution A and the salt solution B. The pump is pumped into the reaction kettle, and the NaOH alkali solution and the ammonia water are respectively fed into the reaction vessel through a constant flow pump to form a mixed liquid, and the stirring speed of the mixed liquid is controlled to be 1000 rpm, the reaction temperature is 55 ° C, and the pH value is The reaction time was 60 h, and the spherical precursor (Mn _Q . ₅₃ Co ₃₇ Mg _i )(OH) ₂ was obtained by controlling the crystal coprecipitation reaction.

5 ) 将步骤 4) 中得到的前躯体进行过滤、洗涤，然后置于 110 °C的温度下干燥 12 h, 再与 Li₂C0₃按锂的摩尔数与^^、 Mn、 Co三种金属元素的总摩尔数之比为 1.20： 1的比例均匀混合，得到富锂半成品。之后，对富锂半成品进行煅烧处理，即：首先，在空气气氛下进行预烧，预烧温度为 600 °C , 预烧时间为 6 h; 然后对预烧后的富锂半成品进行升温煅烧，煅烧温度为 900 °C , 煅烧时间为 14 h; 自然冷却，从而得到球形富锂正极材料

利用本实施例制得的富锂正极材料制成测试电池，并对其进行电化学测试（图中未示出）。其中，在 0.1 C、 2.0-4.6 V电压范围内，本实施例的测试电池首次放电比容量为 213 mAh/g; 在 0.5 C、 2.0-4.6 V条件下经过 100次循环后，本实施例的测试电池的容量保持率为 97.4%; 在 0.2C、 0.5 C、 1 C、 2 C、 5 C、 10 C倍率下，其可逆容量分别为 201mAh/g、 193 mAh/g 185 mAh/g， 174 mAh/g， 165 mAh/g， 125 mAh/g, 显示本实施例材料制得的测试电池具有良好的电化学性能。实施例 8 5) The precursor obtained in step 4) is filtered, washed, and then dried at 110 ° C for 12 h, and then with Li ₂ C0 _{3 in} terms of the molar number of lithium and ^^, Mn, Co three metals The ratio of the total number of moles of the elements is 1.20: 1 ratio is uniformly mixed to obtain a lithium-rich semi-finished product. Thereafter, the lithium-rich semi-finished product is subjected to calcination treatment, that is, first, pre-baking is performed in an air atmosphere, the calcination temperature is 600 ° C, and the calcination time is 6 h; then the calcined lithium-rich semi-finished product is subjected to temperature-raising calcination. Calcination temperature is 900 °C, calcination time is 14 h; natural cooling, thus obtaining spherical lithium-rich cathode material

A test battery was fabricated using the lithium-rich positive electrode material prepared in this example, and electrochemically tested (not shown). Wherein, in the voltage range of 0.1 C, 2.0-4.6 V, the first discharge specific capacity of the test battery of the embodiment is 213 mAh/g; after 100 cycles of 0.5 C, 2.0-4.6 V, the embodiment The capacity retention rate of the test cell was 97.4%; at 0.2C, 0.5 C, 1 C, 2 C, 5 C, 10 C rate, the reversible capacity was 201 mAh/g, 193 mAh/g 185 mAh/g, 174 mAh/g, 165 mAh/g, 125 mAh/g, the test cell prepared by the material of this example showed good electrochemical performance. Example 8

1 )将硫酸钴（CoS0₄'7H₂0)、硫酸锰（MnS0₄'H₂0)和硝酸镁（Mg(N0₃)₂'6H₂0) 按 Co： Mn： Mg (摩尔比） = 0.6： 0.20： 0.20比例混合，溶解在去离子水中，配制成总金属离子浓度为 1.0 mol/L的盐溶液 A，即盐溶液 A中锰离子浓度占总金属离子浓度的 20%，钴离子浓度站金属离子浓度的 60%。 1) Cobalt sulfate (CoS0 ₄ '7H ₂ 0), manganese sulfate (MnS0 ₄ 'H ₂ 0) and magnesium nitrate (Mg(N0 ₃ ) ₂ '6H ₂ 0) as Co: Mn: Mg (molar ratio) = 0.6: 0.20: 0.20 ratio mixed, dissolved in deionized water, formulated into a total metal ion concentration of 1.0 mol / L of salt solution A, that is, the concentration of manganese ions in the salt solution A accounted for 20% of the total metal ion concentration, cobalt ion concentration Standing at 60% of the metal ion concentration.

2)将硫酸锰（MnS(VH₂0)溶解在去离子水中，配制成总金属离子浓度为 1.0 mol/L 的盐溶液 B，即盐溶液 B中锰离子浓度占总金属离子浓度的 100%，钴离子浓度站金属离子浓度的 0%。 2) Dissolving manganese sulfate (MnS (VH ₂ 0) in deionized water to prepare a salt solution B with a total metal ion concentration of 1.0 mol/L, that is, the concentration of manganese ions in the salt solution B is 100% of the total metal ion concentration. , 0% of the metal ion concentration of the cobalt ion concentration station.

3 ) 分别配制浓度为 2.0 mol/L的 NaOH碱溶液和浓度为 2.0 mol/L的氨水。 3) Prepare NaOH alkali solution with a concentration of 2.0 mol/L and ammonia water with a concentration of 2.0 mol/L.

4) 一边将配制好的盐溶液 B ( 1000 mL) 通过恒流泵逐步加入处于搅拌状态下的混合盐溶液 A ( 1000 mL) 中，一边将盐溶液 A和盐溶液 B形成的混合盐溶液逐步泵入到反应釜内，同时将 NaOH碱溶液和氨水分别通过恒流泵并流加入到反应釜中形成混合液，控制对混合液的搅拌速度为 1000 rpm，反应温度为 60 V， pH值为 11.00，反应时间为 60 h，通过控制结晶共沉淀反应得到球形前躯体 (Mn_Q._6QCo _3QMg_Q._1Q)(OH)₂。 4) Gradually add the prepared salt solution B (1000 mL) to the mixed salt solution A (1000 mL) under stirring through a constant flow pump, and gradually mix the salt solution formed by the salt solution A and the salt solution B. Pumped into the reaction kettle, and simultaneously add NaOH alkali solution and ammonia water through a constant flow pump and flow into the reaction kettle to form The mixed solution was controlled to have a stirring speed of 1000 rpm, a reaction temperature of 60 V, a pH of 11.00, and a reaction time of 60 h. A spherical precursor was obtained by controlling the crystal coprecipitation reaction (Mn _Q . _6Q Co _3Q Mg _Q . _1Q )(OH) ₂ .

5 ) 将步骤 4) 中得到的前躯体进行过滤、洗涤，然后置于 110 °C的温度下干燥 12 h, 再与 Li₂C0₃按锂的摩尔数与^^、 Mn、 Co三种金属元素的总摩尔数之比为 1.40： 1的比例均匀混合，得到富锂半成品。之后，对富锂半成品进行煅烧处理，即：首先，在空气气氛下进行预烧，预烧温度为 600 °C , 预烧时间为 6 h; 然后对预烧后的富锂半成品进行升温煅烧，煅烧温度为 900 °C , 煅烧时间为 12 h; 自然冷却，从而得到球形富锂正极材料

利用本实施例制得的富锂正极材料制成测试电池，并对其进行电化学测试（图中未示出）。其中，在 0.1 C、 2.0-4.6 V电压范围内，本实施例的测试电池首次放电比容量为 228 mAh/g; 在 0.5 C、 2.0-4.6 V条件下经过 100次循环后，本实施例的测试电池的容量保持率为 97.2%; 在 0.2C、 0.5 C、 1 C、 2 C、 5 C、 10 C倍率下，其可逆容量分别为 214mAh/g、 201 mAh/g 192 mAh/g, 174 mAh/g, 158 mAh/g, 136mAh/g, 显示本实施例材料制得的测试电池具有良好的电化学性能。由实施例 2-8所示的制备方法所制得的富锂正极材料与实施例 1制得的富锂正极材料的结构类似，均呈球形颗粒状，且球形颗粒中，锰元素的比例由内层至外层逐渐增加，钴元素的比例由内层至外层逐渐减少，并且，实施例 2-8所制得的富锂正极材料与实施例 1制得的材料具有类似的电化学性能。由于锰在材料中以 +4价态存在，很难被还原，稳定性好，制得的富锂正极材料中的锰元素由内到外逐渐增加，即富锂正极材料的外层富锰，因此可以缓解电解液对材料的侵蚀，起到稳定材料结构的作用，从而提高富锂正极材料的循环稳定性。而钴元素可以提高材料的电子电导率，同时可以抑制材料的阳离子混排，制得的富锂正极材料中的钴元素由内到外逐渐减少，即富锂正极材料的外层贫钴，从而可以提高材料的倍率性能。对比例采用碳酸盐共沉淀法制备普通球形富锂正极材料

5) The precursor obtained in step 4) is filtered, washed, and then dried at 110 ° C for 12 h, and then with Li ₂ C0 _{3 in} terms of the molar number of lithium and ^^, Mn, Co three metals The ratio of the total number of moles of the elements is 1.40: 1 ratio is uniformly mixed to obtain a lithium-rich semi-finished product. Thereafter, the lithium-rich semi-finished product is subjected to calcination treatment, that is, first, pre-baking is performed in an air atmosphere, the calcination temperature is 600 ° C, and the calcination time is 6 h; then the calcined lithium-rich semi-finished product is subjected to temperature-raising calcination. Calcination temperature is 900 °C, calcination time is 12 h; natural cooling, thus obtaining spherical lithium-rich cathode material

A test battery was fabricated using the lithium-rich positive electrode material prepared in this example, and electrochemically tested (not shown). Wherein, in the voltage range of 0.1 C, 2.0-4.6 V, the first discharge specific capacity of the test battery of the embodiment is 228 mAh/g; after 100 cycles of 0.5 C, 2.0-4.6 V, the embodiment The capacity retention rate of the test cell was 97.2%; at 0.2C, 0.5 C, 1 C, 2 C, 5 C, 10 C rate, the reversible capacity was 214 mAh/g, 201 mAh/g 192 mAh/g, 174 mAh/g, 158 mAh/g, 136 mAh/g, the test cell prepared by the material of this example showed good electrochemical performance. The lithium-rich cathode material prepared by the preparation methods shown in Examples 2-8 has a structure similar to that of the lithium-rich cathode material prepared in Example 1, and all of them have spherical particles, and the proportion of manganese elements in the spherical particles is determined by The inner layer to the outer layer gradually increased, the proportion of the cobalt element gradually decreased from the inner layer to the outer layer, and the lithium-rich cathode material prepared in Examples 2-8 had similar electrochemical properties as the material obtained in Example 1. . Since manganese exists in the material in the +4 valence state, it is difficult to be reduced and has good stability. The manganese element in the obtained lithium-rich cathode material gradually increases from the inside to the outside, that is, the outer layer of the lithium-rich cathode material is rich in manganese. Therefore, the erosion of the material by the electrolyte can be alleviated, and the structure of the material can be stabilized, thereby improving the cycle stability of the lithium-rich cathode material. Cobalt element can improve the electronic conductivity of the material, and at the same time inhibit the cation mixing of the material. The cobalt element in the lithium-rich cathode material is gradually reduced from the inside to the outside, that is, the outer layer of the lithium-rich cathode material is cobalt-depleted. Can improve the rate performance of the material. Preparation of ordinary spherical lithium-rich cathode materials by carbonate co-precipitation method

1 )将硫酸锰、硫酸镍、硫酸钴按 Mn： M： Co (摩尔比） = 0.58: 0.30: 0.12比例混合，溶解在去离子水中，配制成总金属离子浓度为 2.0 mol/L的混合盐溶液； 1) Mixing manganese sulfate, nickel sulfate and cobalt sulfate in a ratio of Mn: M: Co (molar ratio) = 0.58: 0.30: 0.12, dissolving in deionized water to prepare a mixed salt with a total metal ion concentration of 2.0 mol/L. Solution

2) 分别配制浓度为 2.0 mol/L的 Na₂C0₃碱溶液和浓度为 0.4 mol/L的氨水。 3 ) 将步骤 1 ) 中配制的混合盐溶液和步骤 2) 中配制的 Na₂C0₃碱溶液、氨水通过恒流泵并流加入到反应釜中，控制搅拌速度为 1000 rpm，反应温度为 55 °C， pH值为 7.5，反应时间为 24 h，通过共沉淀反应得到球形前躯体^_¾.₅₈ ^¾.₃。0)。.₁₂]。0₃。 2) Prepare a Na ₂ C0 ₃ alkaline solution with a concentration of 2.0 mol/L and a concentration of 0.4 mol/L ammonia water. 3) The mixed salt solution prepared in the step 1) and the Na ₂ C0 ₃ alkali solution prepared in the step 2) and the ammonia water are fed into the reaction vessel through a constant flow pump, and the stirring speed is controlled at 1000 rpm, and the reaction temperature is 55. ° C, pH = 7.5, reaction time 24 h, to give a spherical body before ^ _¾. ₅₈ ^ _¾. ₃ by co-precipitation reaction. 0). . ₁₂ ]. 0 ₃ .

4) 将步骤 3 ) 中得到的前躯体进行过滤、洗涤、干燥，与 Li₂C0₃按锂的摩尔数与^^、 Mn、 Co总摩尔数之比为 1.35： 1的比例均匀混合后，在空气气氛下进行预烧，预烧温度为 500°C，预烧时间为 6 h，再进行升温煅烧，升温煅烧的温度为 900 °C , 煅烧时间为 14 h，然后再退火处理，退火处理的温度为 400 °C，冷却时间为 12 h; 最后，将退火处理后的半成品自然冷却至室温，从而得到普通球形富锂正极材料 Li_L35(Mn₀.₅₈M ₃₀Co _i2)O₂。对普通球形富锂正极材料进行相应分析，发现其具有如下特点：采用普通共沉淀法制得的富锂正极材料虽为球形颗粒，但从球形颗粒的内层到外层，各金属元素的比例相同，没有形成如实施例 1-3 的制备方法所制得的富锂正极材料那样的由内层到外层的锰元素的比例逐渐增加、钴元素的比例逐渐降低的结构。采用该普通球形富锂正极材料制作测试电池，对测试电池进行电化学分析，得出如下数据： 4) The precursor obtained in the step 3) is filtered, washed, and dried, and uniformly mixed with Li ₂ C0 _{3 in a} ratio of the molar number of lithium to the total number of moles of ^^, Mn, and Co of 1.35:1. Pre-burning in an air atmosphere, calcination temperature is 500 ° C, calcination time is 6 h, and then calcination is carried out, the temperature of calcination is 900 ° C, the calcination time is 14 h, and then annealing, annealing treatment The temperature was 400 ° C and the cooling time was 12 h. Finally, the annealed semi-finished product was naturally cooled to room temperature to obtain a general spherical lithium-rich cathode material Li _L35 (Mn ₀ . ₅₈ M ₃₀ Co _i 2)O ₂ . The ordinary spherical lithium-rich cathode material was analyzed and found to have the following characteristics: The lithium-rich cathode material prepared by the common co-precipitation method is spherical particles, but the ratio of each metal element is the same from the inner layer to the outer layer of the spherical particles. There is no structure in which the ratio of the manganese element from the inner layer to the outer layer is gradually increased and the proportion of the cobalt element is gradually decreased as in the lithium-rich cathode material obtained by the production method of the embodiment 1-3. The test cell was fabricated using the ordinary spherical lithium-rich positive electrode material, and the test battery was subjected to electrochemical analysis to obtain the following data:

1 ) 如图 5所示，在 0.1 C、 2.0-4.6 V电压范围内首次放电比容量达 238 mAh/g，而在 0.5 C、 2.0-4.6 V条件下经过 200次循环后容量保持率为 63.1 %； 1) As shown in Figure 5, the first discharge specific capacity is 238 mAh/g in the 0.1 C, 2.0-4.6 V voltage range, and the capacity retention rate is 63.1 after 200 cycles at 0.5 C, 2.0-4.6 V. %;

2) 如图 6所示，在 10 C倍率下，测试电池的放电比容量只有 95.2 mAh /g。如图 5、图 6所示，通过将对比例与实施例 1制备方法制得的测试电池进行电化学特性比较，可知： 2) As shown in Figure 6, at 10 C, the test battery has a specific discharge capacity of only 95.2 mAh / g. As shown in Fig. 5 and Fig. 6, by comparing the electrochemical characteristics of the test cells prepared in the comparative example with the preparation method of the first embodiment, it is known that:

1 ) 由本发明实施例的通过控制结晶共沉淀处理制备的富锂正极材料制成的电池，其高倍率下的比容量高，并且循环寿命大大高于由普通共沉淀法制备的富锂正极材料的循环寿命； 1) A battery made of a lithium-rich cathode material prepared by controlling a crystallization coprecipitation treatment according to an embodiment of the present invention has a high specific capacity at a high rate and a cycle life much higher than that of a lithium-rich cathode material prepared by a common coprecipitation method. Cycle life

2 ) 由本发明实施例的通过控制结晶共沉淀处理制备的富锂正极材料所制成的电池，在高倍率下具有良好的倍率性能，可满足电动汽车等领域对动力电源的使用需求; 2) The battery made of the lithium-rich cathode material prepared by controlling the crystal coprecipitation treatment according to the embodiment of the present invention has good rate performance at a high rate, and can meet the demand for power source in the field of electric vehicles and the like;

3 )本发明实施例的制备方法，工艺简单，过程可控，使用的原材料成本低廉且环境友好，可以应用于大规模的工业化生产，因此具有良好的应用前景。尽管上文对本发明作了详细说明，但本发明不限于此，本技术领域的技术人员可以根据本发明的原理进行修改，因此，凡按照本发明的原理进行的各种修改都应当理解为落入本发明的保护范围。 3) The preparation method of the embodiment of the invention has the advantages of simple process, controllable process, low cost of raw materials and environmental friendliness, and can be applied to large-scale industrial production, so it has a good application prospect. Although the present invention has been described in detail above, the present invention is not limited thereto, and those skilled in the art can make modifications according to the principles of the present invention. Therefore, various modifications in accordance with the principles of the present invention should be understood as falling. It is within the scope of protection of the present invention.

Claims

权利要求书、一种富锂正极材料的制备方法，包括如下步骤：制备至少由钴盐和其它金属盐混合而形成的盐溶液 A; a method for preparing a lithium-rich positive electrode material, comprising the steps of: preparing a salt solution A formed by mixing at least a cobalt salt and another metal salt;

制备至少由锰盐形成的盐溶液 B，且使盐溶液 B中的锰离子浓度高于盐溶液 A中的锰离子浓度；通过逐步将盐溶液 B加入到盐溶液 A中，并进行相应的控制结晶共沉淀处理，生成球形前躯体，使前躯体的锰元素比例从内层到外层逐渐增加，并使钴元素比例从内层到外层逐渐减少；将前躯体与锂源混合得到富锂半成品，再对其进行煅烧处理，制得球形富锂正极材料。、根据权利要求 1所述的制备方法，其中，所述进行相应的控制结晶共沉淀处理包括如下步骤： Preparing a salt solution B formed of at least a manganese salt, and making the manganese ion concentration in the salt solution B higher than the manganese ion concentration in the salt solution A; by gradually adding the salt solution B to the salt solution A, and performing corresponding control Crystallization coprecipitation treatment produces a spherical precursor, which gradually increases the proportion of manganese in the precursor from the inner layer to the outer layer, and gradually reduces the proportion of cobalt from the inner layer to the outer layer; mixing the precursor with the lithium source to obtain lithium rich The semi-finished product is then calcined to obtain a spherical lithium-rich cathode material. The preparation method according to claim 1, wherein the performing the corresponding controlled crystallization coprecipitation treatment comprises the following steps:

逐步将盐溶液 B加入到盐溶液 A中，同时将两者混合得到的混合盐溶液加入到反应釜内； The salt solution B is gradually added to the salt solution A, and the mixed salt solution obtained by mixing the two is added to the reaction vessel;

将混合盐溶液加入到反应釜内的同时，将沉淀剂加入到反应釜内；混合盐溶液和沉淀剂发生沉淀反应而生成结晶沉淀产物，并且按照生成结晶沉淀产物的先后顺序，后结晶沉淀生成的产物逐步沉积在先结晶沉淀生成的产物的表面，从而得到球形前躯体。、根据权利要求 2所述的制备方法，其中：所述后结晶沉淀生成产物中的锰元素的比例高于先结晶沉淀生成产物中的锰元素的比例；所述后结晶沉淀生成产物中的钴元素的比例低于先结晶沉淀生成产物中的钴元素的比例。、根据权利要求 1所述的制备方法，其中，所述盐溶液 A中混合有锰盐。、根据权利要求 1或 4所述的制备方法，其中，所述盐溶液 B中混合有其它金属、根据权利要求 5所述的制备方法，其中，所述盐溶液 B中混合有钴盐，且盐溶液 B中的钴离子浓度低于所述盐溶液 A中的钴离子浓度。、根据权利要求 5所述的制备方法，其中：制备所述盐溶液 A时，盐溶液 A中的锰离子浓度与总金属离子浓度的百分比不超过 40%; 制备所述盐溶液 B 时，盐溶液 B 中的锰离子浓度占总金属离子浓度的 50%-100%。、根据权利要求 1所述的制备方法，其中，所述盐溶液 A的总金属离子浓度与所述盐溶液 B的总金属离子浓度相同，均为 1.0-3.0mol/L。、根据权利要求 2所述的制备方法，其中，所述沉淀剂包括配位剂和络合剂；其中，配位剂为碱溶液，其浓度为 1.0-5.0 mol/L; 络合剂为氨水溶液，其浓度为 0.1-5.0 mol/L o 0、根据权利要求 2所述的制备方法，其中，所述混合盐溶液和沉淀剂发生沉淀反应时，对混合盐溶液和沉淀剂形成的混合液的搅拌速度为 50-1500rpm，控制反应温度为 30-70°C，控制混合液的 pH值为 7-12。 1、根据权利要求 1所述的制备方法，其中，所述富锂半成品中，锂源中锂的摩尔数和前驱体的金属总摩尔数之比为 n: 1，其中， 1 < η <2。 While the mixed salt solution is added to the reaction vessel, the precipitating agent is added to the reaction vessel; the mixed salt solution and the precipitant are precipitated to form a crystal precipitated product, and the crystal precipitate is formed according to the order of the crystal precipitation product. The product is gradually deposited on the surface of the product formed by the first crystal precipitation to obtain a spherical precursor. The preparation method according to claim 2, wherein: the ratio of the manganese element in the product obtained by the post-crystallization precipitation is higher than the ratio of the manganese element in the product of the crystallized precipitate; the cobalt in the product formed by the post-crystallization precipitate The proportion of the elements is lower than the proportion of the cobalt element in the product of the first crystal precipitation. The preparation method according to claim 1, wherein the salt solution A is mixed with a manganese salt. The preparation method according to claim 1 or 4, wherein the salt solution B is mixed with other metals The preparation method according to claim 5, wherein the salt solution B is mixed with a cobalt salt, and the cobalt ion concentration in the salt solution B is lower than the cobalt ion concentration in the salt solution A. The preparation method according to claim 5, wherein: when the salt solution A is prepared, the percentage of the manganese ion concentration in the salt solution A to the total metal ion concentration does not exceed 40%; when the salt solution B is prepared, the salt The concentration of manganese ions in solution B is from 50% to 100% of the total metal ion concentration. The preparation method according to claim 1, wherein the total metal ion concentration of the salt solution A is the same as the total metal ion concentration of the salt solution B, and both are 1.0 to 3.0 mol/L. The preparation method according to claim 2, wherein the precipitating agent comprises a complexing agent and a complexing agent; wherein the complexing agent is an alkali solution having a concentration of 1.0-5.0 mol/L; the complexing agent is ammonia An aqueous solution having a concentration of 0.1 to 5.0 mol/L o 0. The preparation method according to claim 2, wherein a mixed solution of the mixed salt solution and the precipitating agent is formed when the mixed salt solution and the precipitating agent are subjected to a precipitation reaction. The stirring speed is 50-1500 rpm, the reaction temperature is controlled to 30-70 ° C, and the pH of the mixed liquor is controlled to be 7-12. 1. The preparation method according to claim 1, wherein a ratio of the number of moles of lithium in the lithium source to the total number of moles of metal of the precursor in the lithium-rich semi-finished product is n: 1, wherein 1 < η <2 .

、一种如权利要求 1-11任一项所述的制备方法制备的富锂正极材料， A lithium-rich cathode material prepared by the preparation method according to any one of claims 1 to 11,

所述富锂正极材料由化学通式为 Li_1+xM0₂化合物构成； The lithium-rich cathode material is composed of a compound of the general formula Li _1+x M0 ₂ ;

其中， 0 < χ < 1， M包括锰（Mn) 和钴（Co)，以及镍（Ni)、铝（Al)、镁（Mg)、钛（Ti)、铬（Cr) 和铜（Cu) 元素中的一种或多种；其中，所述化合物为球形颗粒，且球形颗粒中的锰元素比例由内层到外层逐渐增加，钴元素比例由内层到外层逐渐减少。 Where 0 < χ < 1, M includes manganese (Mn) and cobalt (Co), and nickel (Ni), aluminum (Al), magnesium (Mg), titanium (Ti), chromium (Cr), and copper (Cu) One or more of the elements; wherein the compound is a spherical particle, and the proportion of the manganese element in the spherical particle gradually increases from the inner layer to the outer layer, and the proportion of the cobalt element gradually decreases from the inner layer to the outer layer.