WO2018148979A1

WO2018148979A1 - Composite active material for lithium-ion battery and preparation method therefor, electrode paste of lithium-ion battery, positive electrode or negative electrode of lithium-ion battery, and lithium-ion battery

Info

Publication number: WO2018148979A1
Application number: PCT/CN2017/074514
Authority: WO
Inventors: 先雪峰
Original assignee: 先雪峰
Priority date: 2017-02-15
Filing date: 2017-02-23
Publication date: 2018-08-23
Also published as: CN106848191A

Abstract

A composite active material for a lithium-ion battery and a preparation method therefor, an electrode paste of the lithium-ion battery, a positive electrode or a negative electrode of the lithium-ion battery, and the lithium-ion battery. The composite active material for a lithium-ion battery is an additive-coated active material, and the additive is M(OH)a(PO4)b(CO3)c(OCOCH3)d•eH2O, M being at least one of an IIA family metal element, an IB family metal element, a IIB family metal element, a IIIB family metal element, a IVB family metal element, a VB family element, a VIB family metal element, a VIIB family metal element, a VIII family metal element, a IIIA family metal element, the IVA family metal element and the VA family metal element, a>0,b≥0,c≥0,d≥0 and b, c and d being not simultaneously equal to 0, e≥0. The addition of the additive in the preparation of the positive electrode or the negative electrode of the lithium-ion battery can significantly improves the safety of the prepared lithium-ion battery. As positive and negative active materials, the composite active material for a lithium-ion battery is used for preparing the positive electrode or the negative electrode of the lithium-ion battery, and accordingly, the safety of the prepared lithium-ion battery can be remarkably improved.

Description

锂离子电池复合活性物质及其制备方法、锂离子电池电极浆料、正极或负极以及锂离子电池Lithium ion battery composite active material and preparation method thereof, lithium ion battery electrode slurry, positive electrode or negative electrode, and lithium ion battery

技术领域Technical field

本发明涉及锂离子电池技术领域，具体地，涉及一种锂离子电池复合活性物质及其制备方法、一种锂离子电池电极浆料、一种正极或负极以及一种锂离子电池。The present invention relates to the field of lithium ion battery technology, and in particular to a lithium ion battery composite active material and a preparation method thereof, a lithium ion battery electrode slurry, a positive electrode or a negative electrode, and a lithium ion battery.

背景技术Background technique

锂离子电池是新一代的绿色高能电池，具有电压高、能量密度大、寿命长、自放电小、无记忆效应、工作温度范围宽等众多优点，在小型移动能源领域(例如手机、数码相机等)、大型移动能源领域(例如插电式混合动力车、纯电动车等)和固定能源领域(例如储能电站、UPS等)，都有着广泛的应用前景。Lithium-ion battery is a new generation of green high-energy battery, with many advantages such as high voltage, high energy density, long life, small self-discharge, no memory effect, wide operating temperature range, etc., in the field of small mobile energy (such as mobile phones, digital cameras, etc. ), large mobile energy fields (such as plug-in hybrid vehicles, pure electric vehicles, etc.) and fixed energy fields (such as energy storage power stations, UPS, etc.) have broad application prospects.

锂离子电池电压高也意味着在荷电状态下，电池的正、负极具有较大的电势差，也就意味着负极还原性更强，正极氧化性更强，热稳定性更差。特别是对于采用钴酸锂、锂镍钴铝氧、锂镍钴锰氧等高电压正极材料的电池而言，在过充、针刺、挤压等滥用情况下常常会因为热失控引起起火甚至***，存在着严重的安全隐患。The high voltage of the lithium ion battery also means that in the state of charge, the positive and negative electrodes of the battery have a large potential difference, which means that the negative electrode is more reductive, the positive electrode is more oxidized, and the thermal stability is worse. Especially for batteries using high-voltage positive electrode materials such as lithium cobaltate, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, etc., in the case of overcharging, acupuncture, extrusion, etc., it is often caused by heat runaway and even fire. Explosion, there are serious security risks.

除此之外，与采用不可燃且具有阻燃作用的水做电解液溶剂的传统的铅酸、碱性电池相比，商用锂离子电池通常采用可燃的碳酸酯类有机溶剂做电解液溶剂，或凝胶类聚合物做电解质，在滥用条件下，会进一步扩大安全事故的后果。In addition, compared with conventional lead-acid and alkaline batteries that use non-flammable and flame-retardant water as the electrolyte solvent, commercial lithium-ion batteries usually use a combustible carbonate-based organic solvent as the electrolyte solvent. Or gel-like polymers as electrolytes, under the abuse conditions, will further expand the consequences of safety accidents.

现有的锂离子电池的安全隐患阻碍了对锂离子电池的大规模应用，因此，研发一种安全性大幅提高的锂离子电池，具有重要的现实意义。The safety hazards of existing lithium-ion batteries hinder the large-scale application of lithium-ion batteries. Therefore, it is of great practical significance to develop a lithium-ion battery with greatly improved safety.

发明内容Summary of the invention

本发明的目的是为了克服现有技术中锂离子电池安全性低、存在严重安全隐患的缺陷，提供一种锂离子电池复合活性物质及其制备方法、一种锂离子电池电极浆料、一种正极或负极以及一种锂离子电池。The object of the present invention is to overcome the defects of low safety and serious safety hazards of the lithium ion battery in the prior art, and provide a lithium ion battery composite active material and a preparation method thereof, a lithium ion battery electrode slurry, and a A positive or negative electrode and a lithium ion battery.

为了实现上述目的，第一方面，本发明提供了一种锂离子电池复合活性物质，所述锂离子电池复合活性物质为添加剂包覆的活性物质，所述添加剂为M(OH)_a(PO₄)_b(CO₃)_c(OCOCH₃)_d·eH₂O，其中，M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素和VA族金属元素中的至少一种元素，a>0，b≥0，c≥0，d≥0，且b，c，d不同时为0，e≥0。In order to achieve the above object, in a first aspect, the present invention provides a lithium ion battery composite active material, wherein the lithium ion battery composite active material is an additive-coated active material, and the additive is M(OH) _a (PO ₄ _b (CO ₃ ) _c (OCOCH ₃ ) _d ·eH ₂ O, wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, a VB group metal element , at least one of a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IIIA metal element, a group IVA metal element, and a group VA metal element, a>0, b≥0, c≥0,d ≥ 0, and b, c, d are not 0 at the same time, and e ≥ 0.

第二方面，本发明提供了一种锂离子电池复合活性物质的制备方法，该方法包括：制备元素M的碱式盐，在分散剂存在下，将所述元素M的碱式盐与活性物质混合，然后将所得混合物进行热处理。In a second aspect, the present invention provides a method for preparing a lithium ion battery composite active material, which comprises: preparing a basic salt of element M, and using the basic salt of the element M and an active material in the presence of a dispersing agent Mixing and then subjecting the resulting mixture to heat treatment.

第三方面，本发明提供了一种锂离子电池电极浆料，所述电极浆料包括锂离子电池活性物质、粘结剂、导电剂、溶剂和任选的增稠剂，其中，所述锂离子电池活性物质为本发明所述的锂离子电池复合活性物质。In a third aspect, the present invention provides a lithium ion battery electrode slurry, the electrode paste comprising a lithium ion battery active material, a binder, a conductive agent, a solvent, and an optional thickener, wherein the lithium The ion battery active material is a lithium ion battery composite active material according to the present invention.

第四方面，本发明提供了一种锂离子电池正极或负极，所述锂离子电池正极或负极包括集流体及位于集流体上的电极敷料，所述电极敷料含有锂离子电池活性物质、粘结剂、导电剂和任选的增稠剂，其中，所述锂离子电池活性物质为本发明所述的锂离子电池复合活性物质。In a fourth aspect, the present invention provides a positive electrode or a negative electrode of a lithium ion battery, the positive electrode or the negative electrode of the lithium ion battery comprising a current collector and an electrode dressing on the current collector, the electrode dressing containing a lithium ion battery active material and bonding The agent, the conductive agent and the optional thickener, wherein the lithium ion battery active material is a lithium ion battery composite active material according to the invention.

第五方面，本发明提供了一种锂离子电池，所述锂离子电池包括电池壳体以及位于电池壳体内部的电芯组件和电解液，所述电芯组件包括正极、负极和隔膜，且所述正极为本发明所述的锂离子电池正极，和/或所述负极为本发明所述的锂离子电池负极。In a fifth aspect, the present invention provides a lithium ion battery including a battery case and a cell assembly and an electrolyte located inside the battery case, the cell assembly including a positive electrode, a negative electrode, and a diaphragm, and The positive electrode is the positive electrode of the lithium ion battery according to the present invention, and/or the negative electrode is the negative electrode of the lithium ion battery according to the present invention.

本发明的发明人在研究中创造性发现，将本发明的锂离子电池复合活性物质(在活性物质的表面包覆本发明所述的添加剂，制备得到锂离子电池复合活性物质)作为正负极活性物质制备锂离子电池正极和/或负极，能够明显提高由此制备得到的锂离子电池的安全性,且几乎对锂离子电池的导电性能和循环性能等无不良影响。The inventors of the present invention have found in the research that the lithium ion battery composite active material of the present invention (the surface of the active material is coated with the additive of the present invention to prepare a lithium ion battery composite active material) is used as a positive and negative electrode activity. The preparation of the positive electrode and/or the negative electrode of the lithium ion battery can significantly improve the safety of the lithium ion battery thus prepared, and has almost no adverse effect on the conductivity and cycle performance of the lithium ion battery.

本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the invention will be described in detail in the detailed description which follows.

具体实施方式detailed description

以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are only used. The invention is illustrated and described, and is not intended to limit the invention.

在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to include values that are close to the ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and the individual point values, and the individual point values can be combined with one another to yield one or more new ranges of values. The scope should be considered as specifically disclosed herein.

第一方面，本发明提供了一种锂离子电池复合活性物质，所述锂离子电池复合活性物质为添加剂包覆的活性物质，所述添加剂为M(OH)_a(PO₄)_b(CO₃)_c(OCOCH₃)_d·eH₂O，其中，M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素和VA族金属元素中的至少一种元素，a>0，b≥0，c≥0，d≥0，且b，c，d不同时为0，e≥0。In a first aspect, the present invention provides a lithium ion battery composite active material, wherein the lithium ion battery composite active material is an additive coated active material, and the additive is M(OH) _a (PO ₄ ) _b (CO ₃ _c (OCOCH ₃ ) _d ·eH ₂ O, wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, a VB group metal element, a Group VIB metal element At least one of a Group VIIB metal element, a Group VIII metal element, a Group IIIA metal element, a Group IVA metal element, and a Group VA metal element, a>0, b≥0, c≥0, d≥0, and b , c, d are not 0 at the same time, e ≥ 0.

其中，本领域技术人员应该理解的是，本发明中，添加剂为碱式盐，其归一化通式为M(OH)_a(PO₄)_b(CO₃)_c(OCOCH₃)_d·eH₂O，且在M(OH)_a(PO₄)_b(CO₃)_c(OCOCH₃)_d·eH₂O中，a、b、c、d的选择符合相应物质的化学计量比原则。Among them, it should be understood by those skilled in the art that in the present invention, the additive is a basic salt, and its normalized formula is M(OH) _a (PO ₄ ) _b (CO ₃ ) _c (OCOCH ₃ ) _d ·eH ₂ O, and in M(OH) _a (PO ₄ ) _b (CO ₃ ) _c (OCOCH ₃ ) _d ·eH ₂ O, the choice of a, b, c, d is in accordance with the stoichiometric ratio principle of the corresponding substance.

本发明的锂离子电池复合活性物质中，优选情况下，添加剂中，所述IIA族金属元素为Mg、Ca和Sr中的至少一种，所述IB族金属元素为Cu，所述IIB族金属元素为Zn，所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种，所述IVB族金属元素为Ti和/或Zr，所述VB族金属元素为V和/或Nb，所述VIB族金属元素为Cr和/或Mo，所述VIIB族金属元素为Mn，所述VIII族金属元素为Fe、Co和Ni中的至少一种，所述IIIA族金属元素为Al，所述IVA族金属元素为Sn，所述VA族金属元素为Bi和/或Sb。In the lithium ion battery composite active material of the present invention, preferably, in the additive, the Group IIA metal element is at least one of Mg, Ca and Sr, the Group IB metal element is Cu, and the Group IIB metal The element is Zn, and the Group IIIB metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er, and the Group IVB metal element is Ti and/or Zr, the VB group metal The element is V and/or Nb, the group VIB metal element is Cr and/or Mo, the group VIIB metal element is Mn, and the group VIII metal element is at least one of Fe, Co and Ni, The Group IIIA metal element is Al, the Group IVA metal element is Sn, and the Group VA metal element is Bi and/or Sb.

本发明的锂离子电池复合活性物质中，本发明的发明人发现，在锂离子电池活性物质表面包覆特定的添加剂，能够得到安全性更好的锂离子电池活性物质，因此，为了进一步提高制备得到的锂离子电池的安全性，优选情况下，所述添加剂为碱式碳酸镁、碱式醋酸铜和碱式碳酸镍中的至少一种；进一步优选地，所述添加剂为Mg(OH)_0.40(CO₃)_0.80·H₂O、Cu(OH)_1.50(OCOCH₃)_0.50·0.50H₂O和Ni(OH)_4/3(CO₃)_1/3·4/3H₂O中的至少一种。In the lithium ion battery composite active material of the present invention, the inventors of the present invention have found that a lithium ion battery active material having a better safety can be obtained by coating a specific additive on the surface of a lithium ion battery active material, and therefore, in order to further improve the preparation The safety of the obtained lithium ion battery, preferably, the additive is at least one of basic magnesium carbonate, basic copper acetate and basic nickel carbonate; further preferably, the additive is Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O, Cu(OH) _1.50 (OCOCH ₃ ) _0.50 · 0.50H ₂ O and at least one of Ni(OH) _4/3 (CO ₃ ) _1/3 · 4/3H ₂ O Kind.

本发明的锂离子电池复合活性物质中，出于锂离子电池安全性提高和能量密度的综合考虑，优选情况下，以锂离子电池复合活性物质的重量为基准，添加剂的含量为0.05-33重量％，进一步优选为3-16重量％，更进一步优选为5.6-10.1重量％。In the lithium ion battery composite active material of the present invention, in order to improve the safety of the lithium ion battery and the energy density, the content of the additive is preferably 0.05-33 by weight based on the weight of the lithium ion battery composite active material. % is further preferably from 3 to 16% by weight, still more preferably from 5.6-1.1% by weight.

本发明的锂离子电池复合活性物质中，对于活性物质没有特别的限定，可以为本领域常规使用的各种活性物质，优选情况下，活性物质为正极活性物质或负极活性物质，所述正极活性物质为钴酸锂、锂镍氧、锂镍钴氧、锂镍钴铝氧、锂镍钴锰氧、锂镍锰氧、锰酸锂、钒酸锂、磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸锰铁镍锂、磷酸锰铁钴锂、磷酸锰铁镍钴锂、磷酸钒锂和硅酸铁锂中的至少一种，所述负极活性物质为石墨、钛酸锂、硅、硬碳、锡和氧化锡中的至少一种。In the lithium ion battery composite active material of the present invention, the active material is not particularly limited, and various active materials conventionally used in the art may be used. Preferably, the active material is a positive electrode active material or a negative electrode active material, and the positive electrode active material The substance is lithium cobaltate, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium manganate, lithium vanadate, lithium iron phosphate, lithium manganese phosphate, manganese phosphate At least one of iron lithium, lithium iron manganese phosphate, lithium manganese iron cobalt cobalt, lithium manganese iron nickel cobalt, lithium vanadium phosphate, and lithium iron silicate, the negative active material being graphite, lithium titanate, silicon, At least one of hard carbon, tin, and tin oxide.

第二方面，本发明提供了上述的锂离子电池复合活性物质的制备方法，该方法包括：制备元素M的碱式盐，在分散剂存在下，将所述元素M的碱式盐与活性物质混合，然后将所得混合物进行热处理。In a second aspect, the present invention provides a method for preparing a lithium ion battery composite active material, which comprises: preparing a basic salt of an element M, and using the basic salt of the element M and an active material in the presence of a dispersing agent Mixing and then subjecting the resulting mixture to heat treatment.

本发明的制备方法中，元素M的选择同上述添加剂中的元素M，可参见前述相应内容，在此不再重复赘述。In the preparation method of the present invention, the selection of the element M is the same as the element M in the above-mentioned additive, and the above-mentioned corresponding contents can be referred to, and the detailed description thereof will not be repeated here.

本发明的制备方法中，对于前述不同的元素M的碱式盐的制备方法没有特别的限定，可以为本领域常用的各种方法，此为本领域技术人员所熟知，在此不再赘述。In the preparation method of the present invention, the preparation method of the basic salt of the different element M is not particularly limited, and various methods commonly used in the art can be used, which are well known to those skilled in the art and will not be described herein.

本发明的制备方法中，本领域技术人员应该理解的是，在将元素M的碱式盐与活性物质混合之前，先将制备得到的元素M的碱式盐中残留的杂质除去，对于除去其中杂质的方法没有特别的限定，可以为本领域常用的各种方法，例如可以用去离子水洗涤以除去其中的杂质。In the preparation method of the present invention, it should be understood by those skilled in the art that the impurities remaining in the basic salt of the prepared element M are removed before the basic salt of the element M is mixed with the active material. The method of the impurities is not particularly limited and may be various methods commonly used in the art, for example, washing with deionized water to remove impurities therein.

本发明的制备方法中，对于分散剂的种类没有特别的限定，可以为在制备元素M的碱式盐沉淀的过程所用的溶剂，优选情况下，分散剂为异丙醇、去离子水、乙醇、丁醇和丙酮中的至少一种，进一步优选为异丙醇或去离子水。In the production method of the present invention, the kind of the dispersant is not particularly limited, and may be a solvent used in the process of preparing a basic salt for the precipitation of the element M. Preferably, the dispersant is isopropanol, deionized water, ethanol. At least one of butanol and acetone is further preferably isopropanol or deionized water.

本发明的制备方法中，优选情况下，将元素M的碱式盐与活性物质混合的方式为强力搅拌，搅拌的条件优选包括：转速为100-400rpm，时间为1-10h。In the production method of the present invention, preferably, the manner in which the basic salt of the element M is mixed with the active material is vigorous stirring, and the stirring condition preferably includes a rotation speed of 100 to 400 rpm and a time of 1 to 10 hours.

本发明的制备方法中，对于热处理的方式没有特别的限定，可以为本领域常用的各种方式，优选情况下，热处理的方式为喷雾干燥、微波干燥、流化床干燥或烘箱干燥，为了提高效率，进一步优选为喷雾干燥。热处理的条件可以包括：温度为65-200℃，时间为1s-12h。其中，喷雾干燥的条件包括：温度为65-200℃，时间为1-100s，优选为1-10s。对于具体的温度和时间，可以根据不同的干燥方式进行选择，此为本领域技术人员所熟知，在此不再赘述。In the preparation method of the present invention, the manner of the heat treatment is not particularly limited, and may be various methods commonly used in the art. Preferably, the heat treatment is spray drying, microwave drying, fluidized bed drying or oven drying, in order to improve The efficiency is further preferably spray drying. The conditions of the heat treatment may include a temperature of 65 to 200 ° C and a time of 1 s to 12 h. The conditions for spray drying include a temperature of 65-200 ° C and a time of 1-100 s, preferably 1-10 s. For specific temperatures and times, depending on the The drying mode is selected, which is well known to those skilled in the art and will not be described herein.

根据本发明前述的制备方法，可以制备得到表面包覆有前述添加剂的活性物质，即得到锂离子电池复合活性物质，通过控制元素M的碱式盐沉淀与活性物质的用量，可以制备得到特定添加剂含量的锂离子电池复合活性物质，优选情况下，控制元素M的碱式盐沉淀与活性物质的用量，使得以锂离子电池复合活性物质的重量为基准，添加剂的含量为0.05-33重量％，进一步优选为3-16重量％，更进一步优选为5.6-10.1重量％。According to the preparation method of the present invention, an active material having a surface coated with the foregoing additive can be prepared, that is, a lithium ion battery composite active material can be obtained, and a specific additive can be prepared by controlling the basic salt precipitation of the element M and the amount of the active material. a lithium ion battery composite active material, preferably, the base salt of the control element M is precipitated and the amount of the active material is such that the content of the additive is 0.05-33 wt% based on the weight of the lithium ion battery composite active material. It is more preferably from 3 to 16% by weight, still more preferably from 5.6-10.1% by weight.

其中，本领域技术人员应该理解的是，本发明所述的锂离子电池电极浆料可以为锂离子电池正极浆料，也可以为锂离子电池负极浆料。在锂离子电池正极浆料或锂离子电池负极浆料中，对于活性物质、粘结剂、导电剂、溶剂和增稠剂的种类选择和用量没有特别的限定，可以分别为本领域相应组分的常规的种类选择和用量，出于电池能量密度和电池综合性能的考虑，优选情况下，以所述锂离子电池复合活性物质的重量为基准，粘结剂以干基计的含量为0.5-5重量％，导电剂的含量为0.5-5重量％，溶剂的含量为50-210重量％，增稠剂的含量为0-3重量％。其中，增稠剂一般在锂离电池正极浆料中不使用，而在锂离子电池负极浆料中使用，以所述锂离子电池复合活性物质的重量为基准，含量为0.5-3重量％。It should be understood by those skilled in the art that the lithium ion battery electrode slurry of the present invention may be a lithium ion battery positive electrode slurry or a lithium ion battery negative electrode slurry. In the lithium ion battery positive electrode slurry or the lithium ion battery negative electrode slurry, the selection and amount of the active material, the binder, the conductive agent, the solvent and the thickener are not particularly limited, and may be respectively the corresponding components in the field. The conventional type selection and dosage, for the purpose of considering the energy density of the battery and the comprehensive performance of the battery, preferably, the content of the binder on a dry basis is 0.5 based on the weight of the composite active material of the lithium ion battery. 5 wt%, the content of the conductive agent is 0.5 to 5% by weight, the content of the solvent is 50 to 210% by weight, and the content of the thickener is 0 to 3% by weight. Wherein, the thickener is generally not used in the lithium-ion battery positive electrode slurry, but is used in the lithium ion battery negative electrode slurry, and the content is 0.5 to 3% by weight based on the weight of the lithium ion battery composite active material.

其中，锂离子电池正极浆料中，对于锂离子电池复合活性物质中的正极活性物质没有特别的限定，可以为如前文所述的各种正极活性物质，在此不再重复赘述。In the lithium ion battery positive electrode slurry, the positive electrode active material in the lithium ion battery composite active material is not particularly limited, and may be various positive electrode active materials as described above, and the description thereof will not be repeated here.

其中，锂离子电池负极浆料中，对于锂离子电池复合活性物质中的负极活性物质没有特别的限定，可以为如前文所述的各种负极活性物质，在此不再重复赘述。In the lithium ion battery negative electrode slurry, the negative electrode active material in the lithium ion battery composite active material is not particularly limited, and may be various negative electrode active materials as described above, and the description thereof will not be repeated here.

锂离子电池正极浆料和锂离子电池负极浆料中，对于粘结剂没有特别的限定，可以为本领域常规使用的各种粘结剂，优选情况下，粘结剂为聚丙烯酰胺、聚偏二氟乙烯、聚四氟乙烯、丁苯橡胶、纤维素基聚合物、聚乙烯醇、聚烯烃、氟化橡胶和聚胺酯中的至少一种，纤维素基聚合物可以选自甲基纤维素、乙基纤维素、羟丙基甲基纤维素和羟丙基乙基纤维素中的一种或几种。前述粘结剂为聚合物时，各聚合物的数均分子量一般为30-150万。In the lithium ion battery positive electrode slurry and the lithium ion battery negative electrode slurry, the binder is not particularly limited, and various binders conventionally used in the art may be used. Preferably, the binder is polyacrylamide or poly. At least one of vinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, fluorinated rubber, and polyurethane, the cellulose-based polymer may be selected from methyl cellulose One or more of ethyl cellulose, hydroxypropyl methyl cellulose, and hydroxypropyl ethyl cellulose. When the binder is a polymer, the number average molecular weight of each polymer is generally from 3 to 1.5 million.

锂离子电池正极浆料和锂离子电池负极浆料中，对于导电剂没有特别的限定，可以为本领域常规使用的各种导电剂，优选情况下，导电剂为科琴黑、乙炔黑、石墨烯、碳纳米管、碳纤维(VGCF)、微晶石墨和导电碳黑(Super-P)中的至少一种。In the lithium ion battery positive electrode slurry and the lithium ion battery negative electrode slurry, the conductive agent is not particularly limited, and various conductive agents conventionally used in the art may be used. Preferably, the conductive agent is Ketjen black, acetylene black, and graphite. At least one of an olefin, a carbon nanotube, a carbon fiber (VGCF), microcrystalline graphite, and conductive carbon black (Super-P).

其中，对于溶剂没有特别的限定，可以为本领域常规使用的各种溶剂，优选情况下，溶剂为N-甲基吡咯烷酮(NMP)、去离子水、四氢呋喃、二甲基亚砜、乙醇和异丙醇中的至少一种。其中，进一步优选地，在锂离子电池正极浆料中，溶剂为N-甲基吡咯烷酮；在锂离子电池负极浆料中，溶剂为去离子水和/或N-甲基吡咯烷酮。Here, the solvent is not particularly limited and may be various solvents conventionally used in the art. Preferably, the solvent is N-methylpyrrolidone (NMP), deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and the like. At least one of propanol. Further, it is further preferred that in the lithium ion battery positive electrode slurry, the solvent is N-methylpyrrolidone; and in the lithium ion battery negative electrode slurry, the solvent is deionized water and/or N-methylpyrrolidone.

其中，增稠剂多应用于锂离子电池负极浆料中，在锂离子电池正极浆料中是否添加增稠剂可以根据实际应用情况进行选择，具体选择为本领域技术人员所熟知，优选情况下，增稠剂为羧甲基纤维素钠(CMC)、聚乙烯吡咯烷酮、聚乙二醇和聚乙烯醇中的至少一种。Among them, the thickener is mostly used in the negative electrode slurry of the lithium ion battery, and whether or not the thickener is added to the positive electrode slurry of the lithium ion battery can be selected according to the actual application, and the specific selection is well known to those skilled in the art, and preferably, The thickener is at least one of sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.

其中，对于本发明的锂离子电池电极浆料的制备方法没有特别的限定，可以为本领域常用的各种方法，只要能够将含有前述组分的浆料混合均匀即可，例如，含有锂离子电池复合活性物质、粘结剂、导电剂、溶剂和任选的增稠剂的浆料可以通过先将粘结剂和溶剂混合，得到混合液，然后将锂离子电池复合活性物质、导电剂和任选的增稠剂与混合液进行混合，或者可以通过将增稠剂或粘结剂和溶剂混合，得到混合液，然后将锂离子电池复合活性物质、导电剂和粘结剂或增稠剂与混合液进行混合。The method for preparing the lithium ion battery electrode slurry of the present invention is not particularly limited, and various methods commonly used in the art may be used as long as the slurry containing the above components can be uniformly mixed, for example, containing lithium ions. A slurry of a battery composite active material, a binder, a conductive agent, a solvent, and an optional thickener may be obtained by first mixing a binder and a solvent to obtain a mixed liquid, and then combining the active material of the lithium ion battery with the conductive agent and The optional thickener is mixed with the mixed solution, or may be mixed by adding a thickener or a binder and a solvent to obtain a mixed liquid, and then the lithium ion battery composite active material, the conductive agent, and the binder or thickener Mix with the mixture.

本发明的锂离子电池正极或负极中，对于活性物质、粘结剂、导电剂、增稠剂的具体选择，可以参见前文相应描述，在此不再重复赘述。For the specific selection of the active material, the binder, the conductive agent and the thickener in the positive electrode or the negative electrode of the lithium ion battery of the present invention, reference may be made to the corresponding description above, and the detailed description is not repeated herein.

本发明的锂离子电池正极或负极中，为了进一步提高制备得到的锂离子电池的安全性同时兼顾电池能量密度和电池综合性能，以电极敷料的干重为基准，添加剂的含量为0.05-23重量％，进一步优选为3-16重量％，更优选为5.5-10重量％。本领域技术人员应该理解的是，电极敷料的干重是指涂覆在集流体上的所有浆料烘干后得到的物质的重量。 In the positive electrode or the negative electrode of the lithium ion battery of the present invention, in order to further improve the safety of the prepared lithium ion battery while taking into consideration the energy density of the battery and the comprehensive performance of the battery, the content of the additive is 0.05-23 by weight based on the dry weight of the electrode dressing. % is further preferably from 3 to 16% by weight, more preferably from 5.5 to 10% by weight. It will be understood by those skilled in the art that the dry weight of the electrode dressing refers to the weight of the material obtained after drying all of the slurry coated on the current collector.

其中，对于制备锂离子电池正极或负极的方法没有特别的限定，可以为本领域常用的各种方法，例如可以包括：将本发明所述的锂离子电池电极浆料涂覆在集流体上，烘干。The method for preparing the positive electrode or the negative electrode of the lithium ion battery is not particularly limited, and may be various methods commonly used in the art, for example, may include: coating the lithium ion battery electrode slurry of the present invention on a current collector, drying.

其中，锂离子电池正极中，对于集流体没有特别的限定，可以为本领域常用的各种正极集流体，例如正极集流体可以为铝箔。In the positive electrode of the lithium ion battery, the current collector is not particularly limited, and various positive electrode current collectors commonly used in the art may be used. For example, the positive electrode current collector may be aluminum foil.

其中，锂离子电池负极中，对于集流体没有特别的限定，可以为本领域常用的各种负极集流体，例如负极集流体可以为铜箔。In the negative electrode of the lithium ion battery, the current collector is not particularly limited, and various negative electrode current collectors commonly used in the art may be used. For example, the negative electrode current collector may be a copper foil.

其中，对于涂覆的方法没有特别的限定，可以为本领域常用的各种方法，此为本领域技术人所熟知，在此不再赘述。There is no particular limitation on the method of coating, and various methods commonly used in the art can be used, which are well known to those skilled in the art and will not be described herein.

其中，对于烘干的方法没有特别的限定，可以为本领域常用的各种方法，优选情况下，烘干的条件包括：温度为80-180℃。The method for drying is not particularly limited and may be various methods commonly used in the art. Preferably, the drying conditions include: a temperature of 80-180 ° C.

本发明的锂离子电池中，本领域技术人员应该理解的是，正极和负极中的至少一个电极为由本发明所述的锂离子电池复合活性物质制备得到的正极或负极，即，正极为本发明所述的锂离子电池正极，或者负极为本发明所述的锂离子电池负极，或者，正极和负极同时分别为本发明所述的锂离子电池正极和负极。In the lithium ion battery of the present invention, it should be understood by those skilled in the art that at least one of the positive electrode and the negative electrode is a positive electrode or a negative electrode prepared by the lithium ion battery composite active material of the present invention, that is, the positive electrode is the invention. The positive electrode of the lithium ion battery or the negative electrode is the negative electrode of the lithium ion battery according to the present invention, or the positive electrode and the negative electrode are respectively the positive electrode and the negative electrode of the lithium ion battery according to the present invention.

本发明的锂离子电池中，形成锂离子电池的隔膜和电解液可以为本领域常规使用的隔膜和非水电解液。In the lithium ion battery of the present invention, the separator and the electrolytic solution forming the lithium ion battery may be a separator and a nonaqueous electrolyte which are conventionally used in the art.

其中，隔膜设置于正极和负极之间，它具有电绝缘性能和液体保持性能，并使电芯组件和非水电解液一起容纳在电池壳中。隔膜可以为本领域常用的各种隔膜，如高分子聚合物微孔薄膜，包括聚丙稀微孔薄膜和聚丙稀与聚乙烯的多层复合微孔薄膜。隔膜的位置、性质和种类为本领域技术人员所熟知，在此不再赘述。Wherein the separator is disposed between the positive electrode and the negative electrode, and has electrical insulating properties and liquid retaining properties, and the cell assembly and the non-aqueous electrolyte are housed together in the battery can. The separator may be various separators commonly used in the art, such as a polymer microporous film, including a polypropylene microporous film and a multilayer composite microporous film of polypropylene and polyethylene. The position, nature and type of the separator are well known to those skilled in the art and will not be described herein.

其中，非水电解液为电解质锂盐和非水溶剂的混合溶液，对它没有特别限定，可以使用本领域常规的非水电解液。比如电解质锂盐选自六氟磷酸锂(LiPF₆)、高氯酸锂、四氟硼酸锂、六氟砷酸锂、卤化锂、氯铝酸锂及氟烃基磺酸锂中的一种或几种。非水溶剂选用链状酸酯和环状酸酯混合溶液，其中链状酸酯可以为碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)以及其它含氟、含硫或含不饱和键的链状有机酯类中的至少一种，环状酸酯可以为碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸亚乙烯酯(VC)、γ-丁内酯(γ-BL)、磺内酯以及其它含氟、含硫或含不饱和键的环状有机酯类中的至少一种。电解液的注入量一般为5-8克/安时，电解液的浓度一般为0.8-1.2摩尔/升。Among them, the nonaqueous electrolytic solution is a mixed solution of an electrolyte lithium salt and a nonaqueous solvent, and it is not particularly limited, and a conventional nonaqueous electrolytic solution in the art can be used. For example, the electrolyte lithium salt is selected from one or more of lithium hexafluorophosphate (LiPF ₆ ), lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium halide, lithium chloroaluminate, and lithium fluorocarbon sulfonate. The non-aqueous solvent is a mixed solution of a chain acid ester and a cyclic acid ester, wherein the chain acid ester may be dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and methyl propylene carbonate. At least one of ester (MPC), dipropyl carbonate (DPC) and other fluorine-containing, sulfur-containing or unsaturated chain-containing chain organic esters, and the cyclic acid ester may be ethylene carbonate (EC) or carbonic acid. At least one of propylene ester (PC), vinylene carbonate (VC), γ-butyrolactone (γ-BL), sultone and other fluorine-containing, sulfur-containing or unsaturated bond-containing cyclic organic esters Kind. The injection amount of the electrolyte is generally 5-8 g/amperes, and the concentration of the electrolyte is generally 0.8-1.2 mol/liter.

本发明的锂离子电池中，对于电池壳体没有特别的限定，可以为本领域常用的各种电池壳体，此为本领域技术人员所熟知，在此不再赘述。In the lithium ion battery of the present invention, the battery case is not particularly limited, and various battery cases commonly used in the art can be used, which are well known to those skilled in the art and will not be described herein.

本发明的锂离子电池中，制备电池的方法为本领域的常用方法，一般来说，将正极和负极与隔膜构成一个电芯组件，将得到的电芯组件和非水电解液密封在电池壳中，即可得到锂离子电池。具体方法为本领域技术人员所熟知，在此不再赘述。In the lithium ion battery of the present invention, the method for preparing the battery is a common method in the art. Generally, the positive electrode and the negative electrode and the separator form a cell assembly, and the obtained cell assembly and non-aqueous electrolyte are sealed in the battery case. In the middle, you can get a lithium-ion battery. The specific methods are well known to those skilled in the art and will not be described herein.

实施例Example

以下将通过实施例对本发明进行详细描述，但并不因此限制本发明，如无特别说明，所用的材料均可通过商购获得，所用的方法均为本领域的常规方法，且室温均为25℃。The invention is described in detail below by way of examples, without restricting the invention, unless otherwise specified, the materials used are commercially available, the methods used are all conventional methods in the art, and the room temperature is 25 °C.

锂镍钴锰氧LiNi_0.5Co_0.2Mn_0.3O₂购自上海杉杉科技有限公司。Lithium nickel cobalt manganese oxide LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} purchased from Shanghai Shanshan Technology Co., Ltd.

钴酸锂LiCoO₂购自天津巴莫科技股份有限公司。Lithium cobaltate LiCoO _{2 was} purchased from Tianjin Bamo Technology Co., Ltd.

锂镍钴铝氧LiNi_0.8Co_0.15Al_0.05O₂购自日本户田工业株式会社。Lithium nickel cobalt aluminum oxide LiNi _0.8 Co _0.15 Al _0.05 O _{2 was} purchased from Toda Industry Co., Ltd., Japan.

Pvdf粘结剂HSV900购自法国阿科玛公司。The Pvdf binder HSV900 was purchased from Arkema, France.

PTFE乳液粘结剂D210固含量为60％，购自日本大金工业株式会社。The PTFE emulsion binder D210 had a solid content of 60% and was purchased from Daikin Industries Co., Ltd., Japan.

导电剂Super-P购自瑞士特密高公司。The conductive agent Super-P was purchased from the Swiss company Temco.

天然石墨购自深圳贝特瑞新能源材料股份有限公司。Natural graphite was purchased from Shenzhen Beitray New Energy Materials Co., Ltd.

增稠剂CMC购自日本第一工业制药株式会社。The thickener CMC was purchased from Japan Daiichi Pharmaceutical Co., Ltd.

丁苯橡胶乳胶粘结剂固含量为50％，购自日本瑞翁株式会社。The styrene-butadiene rubber latex binder has a solid content of 50% and was purchased from Japan Rayon Co., Ltd.

实施例1 Example 1

a.表面包覆碱式碳酸镁添加剂的复合活性物质的制备a. Preparation of composite active material coated with basic magnesium carbonate additive

将2560g六水硝酸镁用10000g去离子水溶解，制得硝酸镁溶液，将160g氢氧化钠、848g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，280rpm强力搅拌的条件下，将硝酸镁溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L1，取100g L1，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.35g，由此推算滤饼L1固含量为31.35％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入285g滤饼L1中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。2560 g of magnesium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a magnesium nitrate solution, and 160 g of sodium hydroxide and 848 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The magnesium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 280 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L1, 100 g of L1 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 31.35 g, whereby the solid content of the filter cake L1 was estimated to be 31.35%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 285 g of filter cake L1, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (by the weight of the composite active material) The standard, the content of the additive was 8.2% by weight).

b.单体电池的制作b. Production of single cells

(1)电池正极极片制备(1) Preparation of battery positive electrode sheets

将23375g上述制备得到的正极复合活性物质、775g粘结剂HSV900、850g导电剂Super-P混合，具体方法为：先以25000g NMP为溶剂，将粘结剂HSV900溶解，并在搅拌下分别将正极复合活性物质、导电剂Super-P与上述粘结剂的溶液混合，之后搅拌形成均匀的正极浆料；23375 g of the positive electrode composite active material prepared above, 775 g of the binder HSV900, and 850 g of the conductive agent Super-P were mixed by the method of dissolving the binder HSV900 with 25000 g of NMP as a solvent, and respectively, stirring the cathode. The composite active material and the conductive agent Super-P are mixed with the solution of the above binder, and then stirred to form a uniform positive electrode slurry;

将该正极浆料均匀涂覆在厚度为25μm的铝箔上，涂覆宽度为160mm，敷料双面面密度为340.0g/m²(敷料双面面密度以烘干后的重量计，下同，且以电极敷料的干重为基准，添加剂的含量为7.7重量％)，然后在110℃下烘干，得到正极极片。The positive electrode slurry was uniformly coated on an aluminum foil having a thickness of 25 μm, the coating width was 160 mm, and the double-sided surface density of the dressing was 340.0 g/m ² (the double-sided surface density of the dressing was measured by the weight after drying, the same below, The content of the additive was 7.7% by weight based on the dry weight of the electrode dressing, and then dried at 110 ° C to obtain a positive electrode tab.

(2)电池负极极片制备(2) Preparation of battery negative pole piece

将12480g天然石墨负极材料、125g增稠剂CMC、135g导电剂Super-P和520g丁苯橡胶乳胶粘结剂混合，具体方法为：先以12500g去离子水为溶剂，将增稠剂CMC溶解，并在搅拌下分别将丁苯橡胶乳胶粘结剂、导电剂Super-P、天然石墨负极材料与上述增稠剂的溶液混合，之后搅拌形成均匀的负极浆料；12480g natural graphite anode material, 125g thickener CMC, 135g conductive agent Super-P and 520g styrene-butadiene rubber latex binder are mixed, the specific method is: first dissolve the thickener CMC with 12500g deionized water as solvent And stirring, respectively, the styrene-butadiene rubber latex binder, the conductive agent Super-P, the natural graphite anode material and the above thickener solution are mixed, and then stirred to form a uniform anode slurry;

将该负极浆料均匀涂覆在厚度为18μm的铜箔上，涂覆宽度为164mm，敷料双面面密度为161.6g/m²(以烘干后的重量计，下同)，然后在100℃下烘干，得到负极极片。The negative electrode slurry was uniformly coated on a copper foil having a thickness of 18 μm, the coating width was 164 mm, and the double-sided surface density of the dressing was 161.6 g/m ² (based on the weight after drying, the same below), and then at 100 Drying at ° C to obtain a negative electrode tab.

(3)单体电池的装配(3) Assembly of single cells

将正极极片裁剪成120mm×160mm的尺寸作为正极，将负极极片裁剪成125mm×164mm的尺寸作为负极，以聚丙烯膜为隔膜，组装成电芯组件，放入软包铝塑膜电池壳体中，并将正负极极耳分别与铝塑膜焊接在一起，过程中保证极耳与电池壳体的绝缘，经过核算，锂镍钴锰氧活性成分的重量约为191g，负极活性物质天然石墨的重量约为104g，电池的标称容量为30Ah。随后将LiPF₆按1摩尔/升的浓度溶解在EC/DMC＝1:1(体积比)的混合溶剂中形成非水电解液，在氮气气氛保护下将160g此电解液注入上述电池半成品中，并将电池封口。将该电池在45℃的条件下陈化48小时，之后以0.6A的电流充电至4.00V，再在45℃的条件下二次陈化48小时，最后在氮气气氛保护下将电池中产生的气体抽出并将电池二次封口，得到锂离子电池A1。The positive electrode piece is cut into a size of 120 mm×160 mm as a positive electrode, the negative electrode piece is cut into a size of 125 mm×164 mm as a negative electrode, and a polypropylene film is used as a separator, assembled into a battery core assembly, and placed in a soft aluminum-plastic film battery case. In the body, the positive and negative poles are respectively welded with the aluminum plastic film, and the insulation between the polar ear and the battery case is ensured in the process. After calculation, the weight of the lithium nickel cobalt manganese active ingredient is about 191 g, and the negative electrode active material Natural graphite weighs approximately 104g and the battery has a nominal capacity of 30Ah. Subsequently, LiPF _{6 was} dissolved in a mixed solvent of EC/DMC=1:1 (volume ratio) at a concentration of 1 mol/liter to form a non-aqueous electrolyte, and 160 g of this electrolyte was injected into the above-mentioned battery semi-finished product under the protection of a nitrogen atmosphere. And seal the battery. The battery was aged at 45 ° C for 48 hours, then charged to 4.00 V with a current of 0.6 A, and then aged for another 48 hours at 45 ° C. Finally, the battery was produced under the protection of a nitrogen atmosphere. The gas was taken out and the battery was sealed twice to obtain a lithium ion battery A1.

实施例2Example 2

按照实施例1的方法制备锂离子电池A2，不同的是，用碱式醋酸铜(归一化通式为Cu(OH)_1.50(OCOCH₃)_0.50·0.50H₂O)添加剂包覆LiNi_0.8Co_0.15Al_0.05O₂的正极复合活性物质代替用碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式醋酸铜(归一化通式为Cu(OH)_1.50(OCOCH₃)_0.50·0.50H₂O)添加剂包覆LiNi_0.8Co_0.15Al_0.05O₂的正极复合活性物质按如下方法制备：A lithium ion battery A2 was prepared according to the method of Example 1, except that the LiNi _0.8 Co was coated with a basic copper acetate (normalized to Cu(OH) _1.50 (OCOCH ₃ ) _0.50 · 0.50H ₂ O) additive. A positive electrode composite active material of _0.15 Al _0.05 O ₂ was used instead of the positive electrode of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ with basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O). a composite active material, wherein a basic composite active material of a basic copper acetate (normalized to Cu(OH) _1.50 (OCOCH ₃ ) _0.50 ·0.50H ₂ O) coated with LiNi _0.8 Co _0.15 Al _0.05 O ₂ is used Prepared as follows:

将2000g一水醋酸铜用20000g去离子水溶解，制得醋酸铜溶液，将600g氢氧化钠用20000g去离子水溶解，得到氢氧化钠溶液。在室温下，230rpm强力搅拌的条件下，将醋酸铜溶液与氢氧化钠溶液混合，控制混合时间为2小时，得到悬浮液，将该悬浮液加热至沸腾，并保持2小时，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L2，取100g L2，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为33.41g，由此推算滤饼L2固含量为33.41％。将作为活性成分的1000g化学式为LiNi_0.8Co_0.15Al_0.05O₂的锂镍钴铝氧正极材料加入267g滤饼L2中，加入1500g去离子水，370rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式醋酸铜(归一化通式为Cu(OH)_1.50(OCOCH₃)_0.50·0.50H₂O)包覆LiNi_0.8Co_0.15Al_0.05O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。2000 g of copper acetate monohydrate was dissolved in 20,000 g of deionized water to prepare a copper acetate solution, and 600 g of sodium hydroxide was dissolved in 20,000 g of deionized water to obtain a sodium hydroxide solution. The copper acetate solution was mixed with the sodium hydroxide solution at room temperature under vigorous stirring at 230 rpm, and the mixing time was controlled for 2 hours to obtain a suspension. The suspension was heated to boiling and kept for 2 hours, and filtered to obtain precipitation. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L2, 100 g of L2 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 33.41 g, whereby the solid content of the filter cake L2 was estimated to be 33.41%. 1000 g of a lithium nickel cobalt aluminum oxide positive electrode material having a chemical formula of LiNi _0.8 Co _0.15 Al _0.05 O ₂ as an active ingredient was added to 267 g of filter cake L2, 1500 g of deionized water was added, vigorously stirred at 370 rpm for 5 hours, and spray dried at 110 ° C. A basic composite active material coated with a basic copper acetate (normalized to Cu(OH) _1.50 (OCOCH ₃ ) _0.50 ·0.50H ₂ O) coated with LiNi _0.8 Co _0.15 Al _0.05 O ₂ (by weight of the composite active material) The content of the additive was 8.2% by weight based on the basis.

实施例3Example 3

按照实施例1的方法制备锂离子电池A3，不同的是，用碱式碳酸镍(归一化通式为Ni(OH)_4/3(CO₃)_1/3·4/3H₂O)包覆LiCoO₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸镍(归一化通式为Ni(OH)_4/3(CO₃)_1/3·4/3H₂O)包覆LiCoO₂的正极复合活性物质按如下方法制备：A lithium ion battery A3 was prepared in the same manner as in Example 1, except that basic nickel carbonate (normalized to Ni(OH) _4/3 (CO ₃ ) _1/3 · 4/3H ₂ O) was used. A positive electrode composite active material coated with LiCoO _{2 as} a positive electrode composite active material coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) Wherein, the basic composite active material of the basic nickel carbonate (normalized to Ni(OH) _4/3 (CO ₃ ) _1/3 ·4/3H ₂ O) coated with LiCoO ₂ is prepared as follows:

将2910g六水硝酸亚镍用20000g去离子水溶解，制得硝酸亚镍溶液。将534g氢氧化钠、354g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在氮气保护下，在室温下，310rpm强力搅拌的条件下，将硝酸亚镍溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。在氮气保护下，将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L3，取100g L3，用无水乙醇置换其中的水，然后在氮气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为32.77g，由此推算滤饼L3固含量为32.77％。在氮气保护下，将作为活性成分的1000g化学式为LiCoO₂的钴酸锂正极材料加入273g滤饼L3中，加入1500g去离子水，350rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸镍(归一化通式为Ni(OH)_4/3(CO₃)_1/3·4/3H₂O)包覆LiCoO₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。2910 g of nickel nitrate hexahydrate was dissolved in 20,000 g of deionized water to prepare a nickel nitrate solution. 534 g of sodium hydroxide and 354 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. Under a nitrogen atmosphere, the nickel nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at room temperature at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. Under a nitrogen atmosphere, the precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L3, 100 g of L3 was taken, water was replaced with absolute ethanol, and then under a nitrogen atmosphere, 100 After heat treatment at ° C for 5 hours, a dry solid was obtained, and the weight was found to be 32.77 g, whereby the solid content of the filter cake L3 was estimated to be 32.77%. Under nitrogen protection, 1000 g of lithium cobaltate cathode material of the formula LiCoO ₂ as an active ingredient was added to 273 g of filter cake L3, 1500 g of deionized water was added, vigorously stirred at 350 rpm for 5 hours, and spray dried at 110 ° C to obtain a basic form. Nickel carbonate (normalized to Ni(OH) _4/3 (CO ₃ ) _1/3 ·4/3H ₂ O) coated with LiCoO _{2 as} a positive electrode composite active material (based on the weight of the composite active material, additive) The content is 8.2% by weight).

实施例4Example 4

按照实施例1的方法制备锂离子电池A4，不同的是：A lithium ion battery A4 was prepared in accordance with the method of Example 1, except that:

(1)LiNi_0.5Co_0.2Mn_0.3O₂锂镍钴锰氧正极材料未用添加剂进行表面包覆，电池正极极片制备采用未进行表面包覆的LiNi_0.5Co_0.2Mn_0.3O₂锂镍钴锰氧正极材料，且在电池正极极片制备时，敷料双面面密度为312.1g/m²；(1) LiNi _0.5 Co _0.2 Mn _0.3 O ₂ lithium nickel cobalt manganese oxide cathode material was not surface coated with additives, and the battery positive electrode sheet was prepared by surface coating without LiNi _0.5 Co _0.2 Mn _0.3 O ₂ lithium nickel cobalt manganese. Oxygen cathode material, and when the battery positive electrode sheet is prepared, the double-sided surface density of the dressing is 312.1 g/m ² ;

(2)电池负极极片制备时，采用表面包覆碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)添加剂的天然石墨替代未进行表面包覆的天然石墨，制备表面包覆碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)添加剂的天然石墨的具体方法为：(2) When preparing the negative electrode of the battery, the surface is coated with natural graphite with a basic magnesium carbonate (normalized by Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O) instead of surface coating. The natural graphite, the specific method for preparing natural graphite coated with basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O) additive is:

将2560g六水硝酸镁用10000g去离子水溶解，制得硝酸镁溶液，将160g氢氧化钠、848g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，280rpm强力搅拌的条件下，将硝酸镁溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L4，取100g L4，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.52g，由此推算滤饼L4固含量为31.52％。将作为活性成分的1000g天然石墨负极材料加入283g滤饼L4中，加入1500g去离子水，290rpm下强力搅拌5小时，115℃下喷雾干燥，得到碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆天然石墨的负极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。2560 g of magnesium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a magnesium nitrate solution, and 160 g of sodium hydroxide and 848 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The magnesium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 280 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L4, 100 g of L4 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 31.52 g, whereby the solid content of the filter cake L4 was estimated to be 31.52%. 1000 g of natural graphite negative electrode material as an active ingredient was added to 283 g of filter cake L4, 1500 g of deionized water was added, vigorously stirred at 290 rpm for 5 hours, and spray dried at 115 ° C to obtain basic magnesium carbonate (normalized formula was Mg ( OH) _0.40 (CO ₃ ) _0.80 · H ₂ O) A negative electrode composite active material coated with natural graphite (the content of the additive is 8.2% by weight based on the weight of the composite active material).

(3)负极敷料双面面密度调整为176.0g/m²。(3) The density of the double-sided surface of the negative electrode dressing was adjusted to 176.0 g/m ² .

实施例5Example 5

按照实施例1的方法制备锂离子电池A5，不同的是，(1)表面包覆碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)添加剂的正极复合活性物质按如下方法制备：A lithium ion battery A5 was prepared according to the method of Example 1, except that (1) the surface was coated with a basic magnesium carbonate (normalized by the formula Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O). The positive electrode composite active material was prepared as follows:

将2560g六水硝酸镁用10000g去离子水溶解，制得硝酸镁溶液，将160g氢氧化钠、848g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，280rpm强力搅拌的条件下，将硝酸镁溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L5，取100g L5，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.64g，由此推算滤饼L5固含量为31.64％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入209g滤饼L5中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为6.2重量％)。2560 g of magnesium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a magnesium nitrate solution, and 160 g of sodium hydroxide and 848 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The magnesium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 280 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L5, 100 g of L5 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 31.64 g, whereby the solid content of the filter cake L5 was estimated to be 31.64%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 209 g of filter cake L5, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (by the weight of the composite active material) The standard, the content of the additive was 6.2% by weight).

(2)电池正极极片制备时，正极敷料双面面密度调整为332.7g/m²(电池中正极锂镍钴锰氧活性成分的重量与实施例1相同)。(2) When the positive electrode tab of the battery was prepared, the density of the double-sided surface of the positive electrode dressing was adjusted to 332.7 g/m ² (the weight of the positive electrode lithium nickel cobalt manganese oxide active component in the battery was the same as in Example 1).

实施例6Example 6

按照实施例1的方法制备锂离子电池A6，不同的是，(1)表面包覆碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)添加剂的正极复合活性物质按如下方法制备：A lithium ion battery A6 was prepared according to the method of Example 1, except that (1) the surface was coated with a basic magnesium carbonate (normalized by the formula Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O). The positive electrode composite active material was prepared as follows:

将2560g六水硝酸镁用10000g去离子水溶解，制得硝酸镁溶液，将160g氢氧化钠、848g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，280rpm强力搅拌的条件下，将硝酸镁溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L6，取100g L6，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.23g，由此推算滤饼L6固含量为31.23％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入352g滤饼L6中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为9.9重量％)。2560 g of magnesium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a magnesium nitrate solution, and 160 g of sodium hydroxide and 848 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The magnesium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 280 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L6, 100 g of L6 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 31.23 g, whereby the solid content of the filter cake L6 was estimated to be 31.23%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 352 g of filter cake L6, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (by the weight of the composite active material) The standard, the content of the additive was 9.9% by weight).

(2)电池正极极片制备时，正极敷料双面面密度调整为346.4g/m²(电池中正极锂镍钴锰氧活性成分的重量与实施例1相同)。(2) When the positive electrode tab of the battery was prepared, the density of the double-sided surface of the positive electrode dressing was adjusted to 346.4 g/m ² (the weight of the positive electrode lithium nickel cobalt manganese oxide active component in the battery was the same as in Example 1).

实施例7Example 7

按照实施例1的方法制备锂离子电池A7，不同的是，(1)表面包覆碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)添加剂的正极复合活性物质按如下方法制备：A lithium ion battery A7 was prepared according to the method of Example 1, except that (1) the surface was coated with a basic magnesium carbonate (normalized by the formula Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O). The positive electrode composite active material was prepared as follows:

将2560g六水硝酸镁用10000g去离子水溶解，制得硝酸镁溶液，将160g氢氧化钠、848g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，280rpm强力搅拌的条件下，将硝酸镁溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L7，取100g L7，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.11g，由此推算滤饼L7固含量为31.11％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入110g滤饼L7中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为3.3重量％)。2560 g of magnesium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a magnesium nitrate solution, and 160 g of sodium hydroxide and 848 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The magnesium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 280 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L7, 100 g of L7 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 31.11 g, whereby the solid content of the filter cake L7 was estimated to be 31.11%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 110 g of filter cake L7, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (by the weight of the composite active material) The standard, the content of the additive was 3.3% by weight).

(2)电池正极极片制备时，正极敷料双面面密度调整为322.7g/m²(电池中正极锂镍钴锰氧活性成分的重量与实施例1相同)。(2) Preparation of battery positive electrode sheet, positive electrode-sided surface density of the dressing is adjusted to 322.7g / m ² (in the same weight of the positive battery lithium nickel cobalt manganese oxide of the active ingredient in Example 1).

实施例8Example 8

按照实施例1的方法制备锂离子电池A8，不同的是，(1)表面包覆碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)添加剂的正极复合活性物质按如下方法制备：A lithium ion battery A8 was prepared according to the method of Example 1, except that (1) the surface was coated with a basic magnesium carbonate (normalized by the formula Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O). The positive electrode composite active material was prepared as follows:

将2560g六水硝酸镁用10000g去离子水溶解，制得硝酸镁溶液，将160g氢氧化钠、848g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，280rpm强力搅拌的条件下，将硝酸镁溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L8，取100g L8，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.42g，由此推算滤饼L8固含量为31.42％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入29g滤饼L8中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为0.9重量％)。2560 g of magnesium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a magnesium nitrate solution, and 160 g of sodium hydroxide and 848 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The magnesium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 280 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L8, 100 g of L8 was taken, and the water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 31.42 g, whereby the solid content of the filter cake L8 was estimated to be 31.42%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 29 g of filter cake L8, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (by the weight of the composite active material) The standard, the content of the additive was 0.9% by weight).

(2)电池正极极片制备时，正极敷料双面面密度调整为314.9g/m²(电池中正极锂镍钴锰氧活性成分的重量与实施例1相同)。(2) When the positive electrode tab of the battery was prepared, the density of the double-sided surface of the positive electrode dressing was adjusted to 314.9 g/m ² (the weight of the positive electrode lithium nickel cobalt manganese active component in the battery was the same as in Example 1).

实施例9 Example 9

按照实施例1的方法制备锂离子电池A9，不同的是，(1)表面包覆碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)添加剂的正极复合活性物质按如下方法制备：A lithium ion battery A9 was prepared according to the method of Example 1, except that (1) the surface was coated with a basic magnesium carbonate (normalized by the formula Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O). The positive electrode composite active material was prepared as follows:

将2560g六水硝酸镁用10000g去离子水溶解，制得硝酸镁溶液，将160g氢氧化钠、848g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，280rpm强力搅拌的条件下，将硝酸镁溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L9，取100g L9，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为32.08g，由此推算滤饼L9固含量为32.08％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入529g滤饼L9中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为14.5重量％)。2560 g of magnesium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a magnesium nitrate solution, and 160 g of sodium hydroxide and 848 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The magnesium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 280 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L9, 100 g of L9 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 32.08 g, whereby the solid content of the filter cake L9 was estimated to be 32.08%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 529 g of filter cake L9, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (by the weight of the composite active material) The standard, the content of the additive was 14.5% by weight).

(2)电池正极极片制备时，正极敷料双面面密度调整为365.0g/m²(电池中正极锂镍钴锰氧活性成分的重量与实施例1相同)。(2) When the positive electrode tab of the battery was prepared, the density of the double-sided surface of the positive electrode dressing was adjusted to 365.0 g/m ² (the weight of the positive electrode lithium nickel cobalt manganese oxide active component in the battery was the same as in Example 1).

实施例10Example 10

按照实施例1的方法制备锂离子电池A10，不同的是，用碱式磷酸钙(归一化通式为Ca(PO₄)_0.60(OH)_0.20)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸钙(归一化通式为Ca(PO₄)_0.60(OH)_0.20)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A10 was prepared according to the method of Example 1, except that the basic calcium phosphate (normalized to Ca(PO ₄ ) _0.60 (OH) _0.20 ) was coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ . the positive electrode active material in place of the composite basic magnesium carbonate (normalized formula _{_{Mg (OH) 0.40 (CO 3}} ) 0.80 · H 2 O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive active material composite, wherein the alkali Calcium phosphate (normalized to Ca(PO ₄ ) _0.60 (OH) _0.20 ) The positive electrode composite active material coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将1640g无水硝酸钙用20000g去离子水溶解，制得硝酸钙溶液，将984g磷酸三钠用20000g去离子水溶解，得到磷酸三钠溶液。在室温下，340rpm强力搅拌的条件下，将硝酸钙溶液与磷酸三钠溶液混合，并用2摩尔每升浓度的氢氧化钠溶液控制混合体系的pH值为10.0，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L10，取100g L10，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为34.12g，由此推算滤饼L10固含量为34.12％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入262g滤饼L10中，加入1500g去离子水，270rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸钙(归一化通式为Ca(PO₄)_0.60(OH)_0.20)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。1640 g of anhydrous calcium nitrate was dissolved in 20,000 g of deionized water to prepare a calcium nitrate solution, and 984 g of trisodium phosphate was dissolved in 20,000 g of deionized water to obtain a trisodium phosphate solution. The calcium nitrate solution was mixed with the trisodium phosphate solution at room temperature under vigorous stirring at 340 rpm, and the pH of the mixed system was controlled to be 10.0 with 2 moles of sodium hydroxide solution per liter, and the mixing time was controlled to be 2 hours. The suspension was filtered to give a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L10, 100 g of L10, and water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 34.12 g, whereby the solid content of the filter cake L10 was estimated to be 34.12%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 262 g of filter cake L10, 1500 g of deionized water was added, vigorously stirred at 270 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic calcium phosphate (normalized to Ca(PO ₄ ) _0.60 (OH) _0.20 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the additive The content was 8.2% by weight).

实施例11Example 11

按照实施例1的方法制备锂离子电池A11，不同的是，用碱式磷酸锶(归一化通式为Sr(PO₄)_0.60(OH)_0.20)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸锶(归一化通式为Sr(PO₄)_0.60(OH)_0.20)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A11 was prepared according to the method of Example 1, except that the basic yttrium phosphate (normalized formula: Sr(PO ₄ ) _0.60 (OH) _0.20 ) was coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ . A positive electrode composite active material in which a positive electrode composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the base The ruthenium phosphate (normalized formula: Sr(PO ₄ ) _0.60 (OH) _0.20 ) is coated with LiNi _0.5 Co _0.2 Mn _0.3 O _{2 as} a positive electrode composite active material as follows:

将2117g无水硝酸锶用20000g去离子水溶解，制得硝酸锶溶液，将984g磷酸三钠用20000g去离子水溶解，得到磷酸三钠溶液。在室温下，280rpm强力搅拌的条件下，将硝酸锶溶液与磷酸三钠溶液混合，并用2摩尔每升浓度的氢氧化钠溶液控制混合体系的pH值为10.0，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L11，取100g L11，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为28.26g，由此推算滤饼L11固含量为28.26％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入316g滤饼L11中，加入1500g去离子水，250rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸锶(归一化通式为Sr(PO₄)_0.60(OH)_0.20)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。2117 g of anhydrous cerium nitrate was dissolved in 20,000 g of deionized water to prepare a cerium nitrate solution, and 984 g of trisodium phosphate was dissolved in 20,000 g of deionized water to obtain a trisodium phosphate solution. The mixture of lanthanum nitrate solution and trisodium phosphate solution was mixed at room temperature under vigorous stirring at 280 rpm, and the pH of the mixed system was controlled to be 10.0 with 2 moles of sodium hydroxide solution per liter, and the mixing time was controlled to be 2 hours. The suspension was filtered to give a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L11, 100 g of L11 was taken, and the water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 28.26 g, whereby the solid content of the filter cake L11 was estimated to be 28.26%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 316 g of filter cake L11, 1500 g of deionized water was added, vigorously stirred at 250 rpm for 5 hours, and spray dried at 110 ° C. A basic composite active material of a basic yttrium phosphate (normalized formula of Sr(PO ₄ ) _0.60 (OH) _0.20 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the additive The content was 8.2% by weight).

实施例12Example 12

按照实施例1的方法制备锂离子电池A11，不同的是，用碱式碳酸锌(归一化通式为Zn(OH)_4/3(CO₃)_1/3·1/3H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸锌(归一化通式为Zn(OH)_4/3(CO₃)_1/3·1/3H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A11 was prepared in accordance with the method of Example 1, except that basic zinc carbonate (normalized to the formula Zn(OH) _4/3 (CO ₃ ) _1/3 · 1/3H ₂ O) was used. The positive electrode composite active material coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is substituted for basic magnesium carbonate (normalized formula is Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O A positive electrode composite active material of ₂ , wherein basic zinc carbonate (normalized to Zn(OH) _4/3 (CO ₃ ) _1/3 · 1/3H ₂ O) is coated with LiNi _0.5 Co _0.2 Mn _0.3 O The positive electrode composite active material of ₂ was prepared as follows:

将2970g六水硝酸锌用10000g去离子水溶解，制得硝酸锌溶液，将636g碳酸钠用20000g去离子水溶解，得到碳酸钠溶液。在45℃下，260rpm强力搅拌的条件下，将硝酸锌溶液与碳酸钠溶液并流，控制硝酸锌溶液的滴加时间为2小时，并通过控制碳酸钠溶液的滴加速度来控制反应过程中pH值为7.0，在硝酸锌溶液滴加完后，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L12，取100g L12，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为32.17g，由此推算滤饼L12固含量为32.17％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入278g滤饼L12中，加入1500g去离子水，290rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸锌(归一化通式为Zn(OH)_4/3(CO₃)_1/3·1/3H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。2970 g of zinc nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a zinc nitrate solution, and 636 g of sodium carbonate was dissolved in 20,000 g of deionized water to obtain a sodium carbonate solution. The mixture of zinc nitrate solution and sodium carbonate solution was co-flowed at 45 ° C under vigorous stirring at 260 rpm to control the dropping time of the zinc nitrate solution for 2 hours, and the pH during the reaction was controlled by controlling the dropping rate of the sodium carbonate solution. The value was 7.0, and after the dropwise addition of the zinc nitrate solution, a suspension was obtained, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L12, 100 g of L12 was taken, and the water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 32.17 g, whereby the solid content of the filter cake L12 was estimated to be 32.17%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 278 g of filter cake L12, 1500 g of deionized water was added, vigorously stirred at 290 rpm for 5 hours, and spray dried at 110 ° C. A basic composite active material of basic zinc carbonate (normalized to Zn(OH) _4/3 (CO ₃ ) _1/3 · 1/3H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained ( The content of the additive was 8.2% by weight based on the weight of the composite active material.

实施例13Example 13

按照实施例1的方法制备锂离子电池A13，不同的是，用碱式碳酸钇(归一化通式为Y(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸钇(归一化通式为Y(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A13 was prepared according to the method of Example 1, except that the positive electrode composite of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with basic cesium carbonate (normalized formula Y(OH)(CO ₃ )). An active material instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) is coated with a positive electrode composite active material of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein basic carbonic acid The positive electrode composite active material of ruthenium (normalized to Y(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将3830g六水硝酸钇用10000g去离子水溶解，制得硝酸钇溶液，将400g氢氧化钠、1060g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，300rpm强力搅拌的条件下，将硝酸钇溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L13，取100g L13，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为34.83g，由此推算滤饼L13固含量为34.83％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入256g滤饼L13中，加入1500g去离子水，310rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸钇(归一化通式为Y(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。3830 g of cerium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a cerium nitrate solution, and 400 g of sodium hydroxide and 1060 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The cerium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 300 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L13, 100 g of L13 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 34.83 g, whereby the solid content of the filter cake L13 was estimated to be 34.83%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 256 g of filter cake L13, 1500 g of deionized water was added, vigorously stirred at 310 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic yttrium carbonate (normalized formula Y(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive is 8.2% by weight).

实施例14Example 14

按照实施例1的方法制备锂离子电池A14，不同的是，用碱式碳酸钪(归一化通式为Sc(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸钪(归一化通式为Sc(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A method for preparing a lithium ion battery A14 in Example 1, except that, with the scandium hydroxide carbonate (normalized formula _{Sc (OH) (CO 3)} ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive electrode composite An active material instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) is coated with a positive electrode composite active material of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein basic carbonic acid The positive electrode composite active material of ruthenium (normalized to Sc(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将3390g六水硝酸钪用10000g去离子水溶解，制得硝酸钪溶液，将400g氢氧化钠、1060g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，270rpm强力搅拌的条件下，将硝酸钪溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L14，取100g L14，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为30.79g，由此推算滤饼L14固含量为30.79％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入290g滤饼L14中，加入1500g去离子水，380rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸钪(归一化通式为Sc(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。3390 g of cerium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a cerium nitrate solution, and 400 g of sodium hydroxide and 1060 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The cerium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 270 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L14, 100 g of L14 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 30.79 g, whereby the solid content of the filter cake L14 was estimated to be 30.79%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 290 g of filter cake L14, 1500 g of deionized water was added, vigorously stirred at 380 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic bismuth carbonate (normalized to Sc(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive is 8.2% by weight).

实施例15Example 15

按照实施例1的方法制备锂离子电池A15，不同的是，用碱式碳酸镧(归一化通式为La(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸镧(归一化通式为La(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A15 was prepared according to the method of Example 1, except that the positive electrode composite of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with bismuth subcarbonate (normalized to La(OH)(CO ₃ )). An active material instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) is coated with a positive electrode composite active material of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein basic carbonic acid The positive electrode composite active material of ruthenium (normalized to La(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将4330g六水硝酸镧用10000g去离子水溶解，制得硝酸镧溶液，将400g氢氧化钠、1060g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，250rpm强力搅拌的条件下，将硝酸镧溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L15，取100g L15，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为33.46g，由此推算滤饼L15固含量为33.46％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入267g滤饼L15中，加入1500g去离子水，340rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸镧(归一化通式为La(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。4330 g of cerium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a cerium nitrate solution, and 400 g of sodium hydroxide and 1060 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The cerium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under a condition of vigorous stirring at 250 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L15, 100 g of L15 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 33.46 g, whereby the solid content of the filter cake L15 was estimated to be 33.46%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 267 g of filter cake L15, 1500 g of deionized water was added, vigorously stirred at 340 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic cerium carbonate (normalized formula of La(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive is 8.2% by weight).

实施例16Example 16

按照实施例1的方法制备锂离子电池A16，不同的是，用碱式碳酸铈(归一化通式为Ce(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸铈(归一化通式为Ce(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A16 was prepared according to the method of Example 1, except that the positive electrode composite of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with basic lanthanum carbonate (normalized to Ce(OH)(CO ₃ )). An active material instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) is coated with a positive electrode composite active material of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein basic carbonic acid The positive electrode composite active material of ruthenium (normalized to Ce(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将4340g六水硝酸铈用10000g去离子水溶解，制得硝酸铈溶液，将400g氢氧化钠、1060g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，220rpm强力搅拌的条件下，将硝酸铈溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L16，取100g L16，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为29.39g，由此推算滤饼L16固含量为29.39％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入304g滤饼L16中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸铈(归一化通式为Ce(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。4340 g of cerium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a cerium nitrate solution, and 400 g of sodium hydroxide and 1060 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The cerium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 220 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L16, 100 g of L16 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 29.39 g, whereby the solid content of the filter cake L16 was 29.39%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 304 g of filter cake L16, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic cerium carbonate (normalized to Ce(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive is 8.2% by weight).

实施例17Example 17

按照实施例1的方法制备锂离子电池A17，不同的是，用碱式碳酸钕(归一化通式为Nd(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸钕(归一化通式为Nd(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A17 was prepared according to the method of Example 1, except that the positive electrode composite of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with basic cesium carbonate (normalized by Nd(OH)(CO ₃ )). An active material instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) is coated with a positive electrode composite active material of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein basic carbonic acid The positive electrode composite active material of ruthenium (normalized to Nd(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将4380g六水硝酸钕用10000g去离子水溶解，制得硝酸钕溶液，将400g氢氧化钠、1060g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，240rpm强力搅拌的条件下，将硝酸钕溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L17，取100g L17，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为32.57g，由此推算滤饼L17固含量为32.57％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入274g滤饼L17中，加入1500g去离子水，250rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸钕(归一化通式为Nd(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。4380 g of cerium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a cerium nitrate solution, and 400 g of sodium hydroxide and 1060 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The cerium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 240 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L17, 100 g of L17 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 32.57 g, whereby the solid content of the filter cake L17 was estimated to be 32.57%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 274 g of filter cake L17, 1500 g of deionized water was added thereto, vigorously stirred at 250 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic bismuth carbonate (normalized formula of Nd(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive is 8.2% by weight).

实施例18Example 18

按照实施例1的方法制备锂离子电池A18，不同的是，用碱式碳酸钐(归一化通式为Sm(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸钐(归一化通式为Sm(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A18 was prepared according to the method of Example 1, except that the positive electrode composite of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with basic lanthanum carbonate (normalized to Sm(OH)(CO ₃ )). An active material instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) is coated with a positive electrode composite active material of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein basic carbonic acid The positive electrode composite active material of ruthenium (normalized to Sm(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将4440g六水硝酸钐用10000g去离子水溶解，制得硝酸钐溶液，将400g氢氧化钠、1060g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，370rpm强力搅拌的条件下，将硝酸钐溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L18，取100g L18，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为30.95g，由此推算滤饼L18固含量为30.95％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入289g滤饼L18中，加入1500g去离子水，220rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸钐(归一化通式为Sm(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。4440 g of cerium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a cerium nitrate solution, and 400 g of sodium hydroxide and 1060 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The cerium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 370 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L18, 100 g of L18 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 30.95 g, whereby the solid content of the filter cake L18 was estimated to be 30.95%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 289 g of filter cake L18, 1500 g of deionized water was added, vigorously stirred at 220 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic bismuth carbonate (normalized to Sm(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive is 8.2% by weight).

实施例19Example 19

按照实施例1的方法制备锂离子电池A19，不同的是，用碱式碳酸钆(归一化通式为Gd(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸钆(归一化通式为Gd(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A19 was prepared according to the method of Example 1, except that the positive electrode composite of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with basic lanthanum carbonate (normalized to Gd(OH)(CO ₃ )). An active material instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) is coated with a positive electrode composite active material of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein basic carbonic acid The positive electrode composite active material of ruthenium (normalized to Gd(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将4510g六水硝酸钆用10000g去离子水溶解，制得硝酸钆溶液，将400g氢氧化钠、1060g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，390rpm强力搅拌的条件下，将硝酸钆溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L19，取100g L19，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为28.84g，由此推算滤饼L19固含量为28.84％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入310g滤饼L19中，加入1500g去离子水，270rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸钆(归一化通式为Gd(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。4510 g of cerium nitrate hexahydrate was dissolved in 10,000 g of deionized water to prepare a cerium nitrate solution, and 400 g of sodium hydroxide and 1060 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The cerium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 390 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L19, 100 g of L19 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and its weight was 28.84 g, thereby estimating the solid content of the filter cake L19 to be 28.84%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 310 g of filter cake L19, 1500 g of deionized water was added thereto, vigorously stirred at 270 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic bismuth carbonate (normalized formula of Gd(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive is 8.2% by weight).

实施例20Example 20

按照实施例1的方法制备锂离子电池A20，不同的是，用碱式碳酸铒(归一化通式为Er(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸铒(归一化通式为Er(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A20 was prepared according to the method of Example 1, except that the positive electrode composite of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with basic lanthanum carbonate (normalized formula Er(OH)(CO ₃ )). An active material instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) is coated with a positive electrode composite active material of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein basic carbonic acid The positive electrode composite active material of ruthenium (normalized to Er(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将4430g五水硝酸铒用10000g去离子水溶解，制得硝酸铒溶液，将400g氢氧化钠、1060g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在室温下，300rpm强力搅拌的条件下，将硝酸铒溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L20，取100g L20，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.08g，由此推算滤饼L20固含量为31.08％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入287g滤饼L20中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸铒(归一化通式为Er(OH)(CO₃))包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。4430 g of cerium nitrate pentahydrate was dissolved in 10,000 g of deionized water to prepare a cerium nitrate solution, and 400 g of sodium hydroxide and 1060 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. The cerium nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under vigorous stirring at 300 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L20, 100 g of L20 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 31.08 g, whereby the solid content of the filter cake L20 was estimated to be 31.08%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 287 g of filter cake L20, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic cerium carbonate (normalized formula of Er(OH)(CO ₃ )) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive is 8.2% by weight).

实施例21Example 21

按照实施例1的方法制备锂离子电池A21，不同的是，用碱式磷酸钛(归一化通式为Ti(OH)_1.66(PO₄)_0.78)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸钛(归一化通式为Ti(OH)_1.66(PO₄)_0.78)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A21 was prepared according to the method of Example 1, except that the basic titanium phosphate (normalized to Ti(OH) _1.66 (PO ₄ ) _0.78 ) was coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ . A positive electrode composite active material in which a positive electrode composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the base Titanium phosphate (normalized to Ti(OH) _1.66 (PO ₄ ) _0.78 ) The positive electrode composite active material coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将880g氢氧化钠、1640g磷酸三钠用20000g去离子水溶解，得到氢氧化钠、磷酸三钠混合溶液。在室温下，280rpm强力搅拌的条件下，将1897g四氯化钛液体缓慢加入氢氧化钠、磷酸三钠混合溶液，控制加料时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L21，取100g L21，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为33.29g，由此推算滤饼L21固含量为33.29％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入268g滤饼L21中，加入1500g去离子水，290rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸钛(归一化通式为Ti(OH)_1.66(PO₄)_0.78)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。880 g of sodium hydroxide and 1640 g of trisodium phosphate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and trisodium phosphate. 1897 g of titanium tetrachloride liquid was slowly added to a mixed solution of sodium hydroxide and trisodium phosphate at room temperature under vigorous stirring at 280 rpm, and the addition time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L21, 100 g of L21 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 33.29 g, whereby the solid content of the filter cake L21 was estimated to be 33.29%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 268 g of filter cake L21, 1500 g of deionized water was added, vigorously stirred at 290 rpm for 5 hours, and spray dried at 110 ° C. A basic composite active material of a basic titanium phosphate (normalized to Ti(OH) _1.66 (PO ₄ ) _0.78 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the additive The content was 8.2% by weight).

实施例22Example 22

按照实施例1的方法制备锂离子电池A22，不同的是，用碱式磷酸碳酸锆(归一化通式为Zr(OH)_1.45(PO₄)_0.60(CO₃)_0.375)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸碳酸锆(归一化通式为Zr(OH)_1.45(PO₄)_0.60(CO₃)_0.375)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A method for preparing a lithium ion battery A22 in Example 1, except that the (normalized formula _{_{Zr (OH) 1.45 (PO 4}} ) 0.60 (CO 3) 0.375) coated with LiNi _0.5 Co basic zirconium carbonate phosphate A positive electrode composite of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ coated with a positive electrode composite active material of _0.2 Mn _0.3 O ₂ instead of basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) The active material, wherein the basic zirconium phosphate phosphate (normalized formula: Zr(OH) _1.45 (PO ₄ ) _0.60 (CO ₃ ) _0.375 ) is coated with LiNi _0.5 Co _0.2 Mn _0.3 O _{2 as} a positive electrode composite active material as follows Method preparation:

将800g氢氧化钠、1312g磷酸三钠、636g碳酸钠用20000g去离子水溶解，得到氢氧化钠、磷酸三钠、碳酸钠的混合溶液。在室温下，330rpm强力搅拌的条件下，将2330g四氯化锆粉末缓慢加入至上述混合溶液中，控制加料时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L22，取100g L22，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为30.79g，由此推算滤饼L22固含量为30.79％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入290g滤饼L22中，加入1500g去离子水，320rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸碳酸锆(归一化通式为Zr(OH)_1.45(PO₄)_0.60(CO₃)_0.375)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。800 g of sodium hydroxide, 1312 g of trisodium phosphate, and 636 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide, trisodium phosphate, and sodium carbonate. 2330 g of zirconium tetrachloride powder was slowly added to the above mixed solution under vigorous stirring at 330 rpm at room temperature, and the addition time was controlled to 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L22, 100 g of L22 was taken, and the water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 30.79 g, whereby the solid content of the filter cake L22 was estimated to be 30.79%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 290 g of filter cake L22, 1500 g of deionized water was added thereto, vigorously stirred at 320 rpm for 5 hours, and spray dried at 110 ° C. A basic composite active material of a basic type of zirconium phosphate zirconium phosphate (normalized formula: Zr(OH) _1.45 (PO ₄ ) _0.60 (CO ₃ ) _0.375 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ (as a composite active material) The content of the additive was 8.2% by weight based on the weight.

实施例23Example 23

按照实施例1的方法制备锂离子电池A23，不同的是，用碱式磷酸钒(归一化通式为V(OH)_1.62(PO₄)_0.46)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸钒(归一化通式为V(OH)_1.62(PO₄)_0.46)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A23 was prepared according to the method of Example 1, except that the basic vanadium phosphate (normalized to V(OH) _1.62 (PO ₄ ) _0.46 ) was coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ . A positive electrode composite active material in which a positive electrode composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the base A vanadium phosphate (normalized formula of V(OH) _1.62 (PO ₄ ) _0.46 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is prepared as follows:

将1640g磷酸三钠、1440g氢氧化钠用20000g去离子水溶解，得到磷酸三钠、氢氧化钠混合溶液。在氮气保护下，在室温下，360rpm强力搅拌的条件下，将1570g三氯化钒粉末缓慢加入15升2摩尔每升浓度的盐酸水溶液中溶解，得到三氯化钒溶液。将三氯化钒溶液缓慢加入至上述磷酸三钠、氢氧化钠混合溶液中，控制加料时间为2小时，得到悬浮液，经过过滤，得到沉淀。在氮气保护下，将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L23，取100g L23，用无水乙醇置换其中的水，然后在氮气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为33.79g，由此推算滤饼L23固含量为33.79％。在氮气保护下，将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入264g滤饼L23中，加入1500g去离子水，230rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸钒(归一化通式为V(OH)_1.62(PO₄)_0.46)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。1640 g of trisodium phosphate and 1440 g of sodium hydroxide were dissolved in 20,000 g of deionized water to obtain a mixed solution of trisodium phosphate and sodium hydroxide. Under nitrogen atmosphere, 1570 g of vanadium trichloride powder was slowly added to 15 liters of a 2 molar solution of hydrochloric acid per liter of hydrochloric acid at room temperature under vigorous stirring at 360 rpm to obtain a vanadium trichloride solution. The vanadium trichloride solution was slowly added to the above mixed solution of trisodium phosphate and sodium hydroxide, and the addition time was controlled to 2 hours to obtain a suspension, which was filtered to obtain a precipitate. Under a nitrogen atmosphere, the precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L23, 100 g of L23 was taken, water was replaced with absolute ethanol, and then under a nitrogen atmosphere, 100 After heat treatment at ° C for 5 hours, a dry solid was obtained, and the weight was found to be 33.79 g, whereby the solid content of the filter cake L23 was estimated to be 33.79%. Under nitrogen protection, 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 264 g of filter cake L23, and 1500 g of deionized water was added thereto, and vigorously stirred at 230 rpm for 5 hours, 110 Spray-drying at ° C to obtain a basic composite active material of a basic vanadium phosphate (normalized to V(OH) _1.62 (PO ₄ ) _0.46 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ (by the weight of the composite active material) The content of the additive was 8.2% by weight based on the basis.

实施例24Example 24

按照实施例1的方法制备锂离子电池A24，不同的是，用碱式磷酸铌(归一化通式为Nb(OH)_1.22(PO₄)_1.26)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸铌(归一化通式为Nb(OH)_1.22(PO₄)_1.26)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A24 was prepared according to the method of Example 1, except that the basic yttrium phosphate (normalized by the formula Nb(OH) _1.22 (PO ₄ ) _1.26 ) was coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ . A positive electrode composite active material in which a positive electrode composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the base The ruthenium phosphate (normalized to Nb(OH) _1.22 (PO ₄ ) _1.26 ) is coated with LiNi _0.5 Co _0.2 Mn _0.3 O _{2 as} a positive electrode composite active material as follows:

将18040g磷酸三钠、6720g氢氧化钠用300000g去离子水溶解，得到磷酸三钠、氢氧化钠混合溶液。将929g金属铌溶解于由3200g质量分数为65％的浓硝酸和5000g质量分数为40％的氢氟酸组成的混合溶液中，制得铌液。在室温下，390rpm强力搅拌的条件下，将铌液缓慢加入至上述磷酸三钠、氢氧化钠混合溶液中，控制加料时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L24，取100g L24，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.45g，由此推算滤饼L24固含量为31.45％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入284g滤饼L24中，加入1500g去离子水，260rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸铌(归一化通式为Nb(OH)_1.22(PO₄)_1.26)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。 18040 g of trisodium phosphate and 6720 g of sodium hydroxide were dissolved in 300,000 g of deionized water to obtain a mixed solution of trisodium phosphate and sodium hydroxide. The mash was prepared by dissolving 929 g of metal ruthenium in a mixed solution consisting of 3200 g of concentrated nitric acid having a mass fraction of 65% and 5000 g of hydrofluoric acid having a mass fraction of 40%. The mash was slowly added to the above-mentioned mixed solution of trisodium phosphate and sodium hydroxide at room temperature under vigorous stirring at 390 rpm, and the addition time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L24, 100 g of L24 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 31.45 g, whereby the solid content of the filter cake L24 was estimated to be 31.45%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 284 g of filter cake L24, 1500 g of deionized water was added, vigorously stirred at 260 rpm for 5 hours, and spray dried at 110 ° C. A basic composite active material of a basic yttrium phosphate (normalized to Nb(OH) _1.22 (PO ₄ ) _1.26 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the additive The content was 8.2% by weight).

实施例25Example 25

按照实施例1的方法制备锂离子电池A25，不同的是，用碱式磷酸铬(归一化通式为Cr(OH)_0.90(PO₄)_0.70)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸铬(归一化通式为Cr(OH)_0.90(PO₄)_0.70)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A25 was prepared according to the method of Example 1, except that the basic chromium phosphate (normalized to Cr(OH) _0.90 (PO ₄ ) _0.70 ) was coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ . A positive electrode composite active material in which a positive electrode composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the base The chromium composite chromium phosphate (normalized to Cr(OH) _0.90 (PO ₄ ) _0.70 ) is coated with LiNi _0.5 Co _0.2 Mn _0.3 O _{2 as} a positive electrode composite active material as follows:

将1148g磷酸三钠用20000g去离子水溶解，得到磷酸三钠溶液。将4000g九水硝酸铬溶解在15000g去离子水中，制得硝酸铬溶液。在室温下，350rpm强力搅拌的条件下，将硝酸铬溶液与磷酸三钠溶液混合，并用质量分数为25％的氨水溶液控制混合体系的pH值为10.0，控制加料时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L25，取100g L25，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为33.80g，由此推算滤饼L25固含量为33.80％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入264g滤饼L25中，加入1500g去离子水，290rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸铬(归一化通式为Cr(OH)_0.90(PO₄)_0.70)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。1148 g of trisodium phosphate was dissolved in 20,000 g of deionized water to obtain a trisodium phosphate solution. 4000 g of chromium nitrate nonahydrate was dissolved in 15,000 g of deionized water to prepare a chromium nitrate solution. The chromium nitrate solution was mixed with the trisodium phosphate solution at room temperature under vigorous stirring at 350 rpm, and the pH of the mixed system was controlled to be 10.0 with a 25% by mass aqueous ammonia solution, and the feeding time was controlled for 2 hours to obtain a suspension. After filtration, a precipitate was obtained. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L25, 100 g of L25 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 33.80 g, whereby the solid content of the filter cake L25 was estimated to be 33.80%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 264 g of filter cake L25, 1500 g of deionized water was added, vigorously stirred at 290 rpm for 5 hours, and spray dried at 110 ° C. A basic composite active material of a basic chromium phosphate (normalized to Cr(OH) _0.90 (PO ₄ ) _0.70 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the additive The content was 8.2% by weight).

实施例26Example 26

按照实施例1的方法制备锂离子电池A26，不同的是，用碱式磷酸钼(归一化通式为Mo(OH)_0.75(PO₄)_0.75)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸钼(归一化通式为Mo(OH)_0.75(PO₄)_0.75)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A26 was prepared according to the method of Example 1, except that the basic lithium molybdate (normalized to Mo(OH) _0.75 (PO ₄ ) _0.75 ) was coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ . A positive electrode composite active material in which a positive electrode composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the base The positive electrode composite active material of the molybdenum phosphate (normalized to Mo(OH) _0.75 (PO ₄ ) _0.75 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将1230g磷酸三钠用20000g去离子水溶解，得到磷酸三钠溶液。将2560g三水三氯化钼溶解在15000g去离子水中，制得三氯化钼溶液。在室温下，270rpm强力搅拌的条件下，将三氯化钼溶液与磷酸三钠溶液混合，并用质量分数为25％的氨水溶液控制混合体系的pH值为10.0，控制加料时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L26，取100g L26，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为34.40g，由此推算滤饼L26固含量为34.40％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入260g滤饼L26中，加入1500g去离子水，360rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸钼(归一化通式为Mo(OH)_0.75(PO₄)_0.75)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。1230 g of trisodium phosphate was dissolved in 20,000 g of deionized water to obtain a trisodium phosphate solution. 2560 g of molybdenum trichloride trihydrate was dissolved in 15000 g of deionized water to prepare a molybdenum trichloride solution. Under the condition of strong stirring at 270 rpm, the molybdenum trichloride solution was mixed with the trisodium phosphate solution, and the pH of the mixed system was controlled to be 10.0 with a 25% ammonia aqueous solution, and the feeding time was controlled to be 2 hours. The suspension was filtered to give a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L26, 100 g of L26 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 34.40 g, whereby the solid content of the filter cake L26 was estimated to be 34.40%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 260 g of filter cake L26, 1500 g of deionized water was added, vigorously stirred at 360 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic type of molybdenum phosphate (normalized to Mo(OH) _0.75 (PO ₄ ) _0.75 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the additive The content was 8.2% by weight).

实施例27Example 27

按照实施例1的方法制备锂离子电池A27，不同的是，用碱式碳酸锰(归一化通式为Mn(OH)(CO₃)_0.50)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸锰(归一化通式为Mn(OH)(CO₃)_0.50)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A27 was prepared according to the method of Example 1, except that the positive electrode of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with basic manganese carbonate (normalized by Mn(OH)(CO ₃ ) _0.50 ). A composite active material in which a composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the basic formula Manganese carbonate (normalized to Mn(OH)(CO ₃ ) _0.50 ) The positive electrode composite active material coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将3580g的50重量％硝酸亚锰水溶液用20000g去离子水稀释，制得硝酸亚锰溶液。将400g氢氧化钠、530g碳酸钠用20000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在氮气保护下，在室温下，220rpm强力搅拌的条件下，将硝酸亚锰溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。在氮气保护下，将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L27，取100g L27，用无水乙醇置换其中的水，然后在氮气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.65g，由此推算滤饼L27固含量为31.65％。在氮气保护下，将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入282g滤饼L27中，加入1500g去离子水，390rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸锰(归一化通式为Mn(OH)(CO₃)_0.50)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。3580 g of a 50% by weight aqueous solution of manganese nitrate was diluted with 20,000 g of deionized water to prepare a manganese nitrate solution. 400 g of sodium hydroxide and 530 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. Under a nitrogen atmosphere, the manganese nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under a condition of vigorous stirring at 220 rpm, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. Under a nitrogen atmosphere, the precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L27, 100 g of L27, and water was replaced with absolute ethanol, and then under a nitrogen atmosphere, 100 After heat treatment at ° C for 5 hours, a dry solid was obtained, and the weight was found to be 31.65 g, whereby the solid content of the filter cake L27 was estimated to be 31.65%. Under the protection of nitrogen, 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 282 g of filter cake L27, and 1500 g of deionized water was added thereto, and vigorously stirred at 390 rpm for 5 hours, 110 Spray drying at °C to obtain a basic composite active material of basic manganese carbonate (normalized to Mn(OH)(CO ₃ ) _0.50 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ (by the weight of the composite active material) The standard, the content of the additive was 8.2% by weight).

实施例28Example 28

按照实施例1的方法制备锂离子电池A28，不同的是，用碱式磷酸铁(归一化通式为 Fe(OH)_0.60(PO₄)_0.80·0.40H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸铁(归一化通式为Fe(OH)_0.60(PO₄)_0.80·0.40H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A28 was prepared in the same manner as in Example 1, except that the basic iron phosphate (normalized to Fe(OH) _0.60 (PO ₄ ) _0.80 · 0.40H ₂ O) was coated with LiNi _0.5 Co _0.2 The positive electrode composite activity of Mn _0.3 O ₂ cathode composite active material instead of basic magnesium carbonate (normalized formula Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ a substance in which a basic composite active material coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is prepared by the following method: basic calcium phosphate (normalized to Fe(OH) _0.60 (PO ₄ ) _0.80 ·0.40H ₂ O) :

将984g磷酸三钠用20000g去离子水溶解，得到磷酸三钠溶液。将4040g九水硝酸铁用15000g去离子水溶解，制得硝酸铁溶液。在室温下，270rpm强力搅拌的条件下，将硝酸铁溶液与磷酸三钠溶液混合，并用2摩尔每升浓度的氢氧化钠溶液控制混合体系的pH值为10.0，控制混合时间为2小时，得到悬浮液，将悬浮液转移至水热反应釜，200℃保持8小时，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L28，取100g L28，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为30.96g，由此推算滤饼L28固含量为30.96％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入289g滤饼L28中，加入1500g去离子水，300rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸铁(归一化通式为Fe(OH)_0.60(PO₄)_0.80·0.40H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。984 g of trisodium phosphate was dissolved in 20,000 g of deionized water to obtain a trisodium phosphate solution. 4040 g of iron nitrate nonahydrate was dissolved in 15000 g of deionized water to prepare a ferric nitrate solution. The iron nitrate solution was mixed with the trisodium phosphate solution at room temperature under vigorous stirring at 270 rpm, and the pH of the mixed system was controlled to be 10.0 with 2 moles of sodium hydroxide solution per liter, and the mixing time was controlled to be 2 hours. The suspension was transferred to a hydrothermal reaction kettle, maintained at 200 ° C for 8 hours, and filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L28, 100 g of L28 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 30.96 g, whereby the solid content of the filter cake L28 was estimated to be 30.96%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 289 g of filter cake L28, 1500 g of deionized water was added, vigorously stirred at 300 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic iron phosphate (normalized formula of Fe(OH) _0.60 (PO ₄ ) _0.80 ·0.40H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (by the weight of the composite active material) The content of the additive was 8.2% by weight based on the basis.

实施例29Example 29

按照实施例1的方法制备锂离子电池A29，不同的是，用碱式碳酸钴(归一化通式为Co(OH)_1.20(CO₃)_0.40·0.20H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸钴(归一化通式为Co(OH)_1.20(CO₃)_0.40·0.20H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A29 was prepared according to the method of Example 1, except that the basic cobalt carbonate (normalized to Co(OH) _1.20 (CO ₃ ) _0.40 · 0.20H ₂ O) was coated with LiNi _0.5 Co _0.2 The positive electrode composite activity of Mn _0.3 O ₂ cathode composite active material instead of basic magnesium carbonate (normalized formula Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ a substance in which a basic cobalt carbonate (normalized to Co(OH) _1.20 (CO ₃ ) _0.40 · 0.20H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is prepared as follows. :

将2910g六水硝酸亚钴用15000g去离子水溶解，制得硝酸亚钴溶液。将480g氢氧化钠、424g碳酸钠用10000g去离子水溶解，得到氢氧化钠、碳酸钠混合溶液。在氮气保护下，在室温下，290rpm强力搅拌的条件下，将硝酸亚钴溶液与氢氧化钠、碳酸钠混合溶液混合，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。在氮气保护下，将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L29，取100g L29，用无水乙醇置换其中的水，然后在氮气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为29.43g，由此推算滤饼L29固含量为29.43％。在氮气保护下，将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入304g滤饼L29中，加入1500g去离子水，320rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸钴(归一化通式为Co(OH)_1.20(CO₃)_0.40·0.20H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。2910 g of cobalt hexahydrate was dissolved in 15000 g of deionized water to prepare a cobaltous nitrate solution. 480 g of sodium hydroxide and 424 g of sodium carbonate were dissolved in 10,000 g of deionized water to obtain a mixed solution of sodium hydroxide and sodium carbonate. Under a nitrogen atmosphere, the cobalt nitrate solution was mixed with a sodium hydroxide and sodium carbonate mixed solution under a condition of vigorous stirring at 290 rpm, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. Under a nitrogen atmosphere, the precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L29, 100 g of L29 was taken, water was replaced with absolute ethanol, and then under a nitrogen atmosphere, 100 After heat treatment at ° C for 5 hours, a dry solid was obtained, and the weight was found to be 29.43 g, whereby the solid content of the filter cake L29 was estimated to be 29.43%. Under the protection of nitrogen, 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 304 g of filter cake L29, and 1500 g of deionized water was added thereto, and vigorously stirred at 320 rpm for 5 hours, 110 Spray drying at ° C to obtain a basic composite active material of basic cobalt carbonate (normalized to Co(OH) _1.20 (CO ₃ ) _0.40 ·0.20H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ The content of the additive was 8.2% by weight based on the weight of the composite active material.

实施例30Example 30

按照实施例1的方法制备锂离子电池A30，不同的是，用碱式醋酸铝(归一化通式为Al(OH)(OCOCH₃)₂)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式醋酸铝(归一化通式为Al(OH)(OCOCH₃)₂)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A30 was prepared according to the method of Example 1, except that the positive electrode of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with basic aluminum acetate (normalized by Al(OH)(OCOCH ₃ ) ₂ ). A composite active material in which a composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the basic formula The positive electrode composite active material of aluminum acetate (normalized to Al(OH)(OCOCH ₃ ) ₂ ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将820g偏铝酸钠用20000g去离子水溶解，制得偏铝酸钠溶液。将1320g冰醋酸用10000g去离子水溶解，得到醋酸溶液。在室温下，340rpm强力搅拌的条件下，将醋酸溶液与偏铝酸钠溶液混合，控制混合时间为2小时，得到悬浮液，将该悬浮液加热至沸腾，并保持2小时，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L30，取100g L30，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为34.98g，由此推算滤饼L30固含量为34.98％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入255g滤饼L30中，加入1500g去离子水，220rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式醋酸铝(归一化通式为Al(OH)(OCOCH₃)₂)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。820 g of sodium metaaluminate was dissolved in 20,000 g of deionized water to prepare a sodium metaaluminate solution. 1320 g of glacial acetic acid was dissolved in 10,000 g of deionized water to obtain an acetic acid solution. The acetic acid solution was mixed with the sodium metaaluminate solution under vigorous stirring at 340 rpm at room temperature, and the mixing time was controlled for 2 hours to obtain a suspension. The suspension was heated to boiling and kept for 2 hours, and filtered to obtain precipitation. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L30, 100 g of L30 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 34.98 g, whereby the solid content of the filter cake L30 was estimated to be 34.98%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 255 g of filter cake L30, 1500 g of deionized water was added, vigorously stirred at 220 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic aluminum acetate (normalized formula of Al(OH)(OCOCH ₃ ) ₂ ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive) It is 8.2% by weight).

实施例31Example 31

按照实施例1的方法制备锂离子电池A31，不同的是，用碱式碳酸锡(归一化通式为Sn(OH)(CO₃)_0.50)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为 Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸锡(归一化通式为Sn(OH)(CO₃)_0.50)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A31 was prepared in the same manner as in Example 1, except that the positive electrode of LiNi _0.5 Co _0.2 Mn _0.3 O _{2 was} coated with basic tin carbonate (normalized by Sn(OH)(CO ₃ ) _0.50 ). A composite active material in which a composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the basic formula The positive electrode composite active material of tin carbonate (normalized to Sn(OH)(CO ₃ ) _0.50 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

将2257g二水二氯化锡溶解在20000g无水乙醇中，得到澄清二氯化锡溶液。将520g氢氧化钠、689g碳酸钠用20000g去离子水溶解，得到氢氧化钠、磷酸三钠混合溶液。在室温下，310rpm强力搅拌的条件下，将二氯化锡溶液加入氢氧化钠、磷酸三钠混合溶液，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L31，取100g L31，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为31.32g，由此推算滤饼L31固含量为31.32％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入285g滤饼L31中，加入1500g去离子水，330rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸锡(归一化通式为Sn(OH)(CO₃)_0.50)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。2257 g of tin dichloride dihydrate was dissolved in 20,000 g of absolute ethanol to obtain a clear tin dichloride solution. 520 g of sodium hydroxide and 689 g of sodium carbonate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and trisodium phosphate. The tin dichloride solution was added to a mixed solution of sodium hydroxide and trisodium phosphate at room temperature under vigorous stirring at 310 rpm, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform cake L31, 100 g of L31 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and the weight was found to be 31.32 g, whereby the solid content of the filter cake L31 was estimated to be 31.32%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 285 g of filter cake L31, 1500 g of deionized water was added, vigorously stirred at 330 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of basic nickel carbonate (normalized to Sn(OH)(CO ₃ ) _0.50 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the content of the additive) It is 8.2% by weight).

实施例32Example 32

按照实施例1的方法制备锂离子电池A32，不同的是，用碱式磷酸铋(归一化通式为Bi(PO₄)_0.84(OH)_0.48)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式磷酸铋(归一化通式为Bi(PO₄)_0.84(OH)_0.48)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：A lithium ion battery A32 was prepared according to the method of Example 1, except that the basic yttrium phosphate (normalized to Bi(PO ₄ ) _0.84 (OH) _0.48 ) was coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ . the positive electrode active material in place of the composite basic magnesium carbonate (normalized formula _{_{Mg (OH) 0.40 (CO 3}} ) 0.80 · H 2 O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive active material composite, wherein the alkali The ruthenium phosphate (normalized to Bi(PO ₄ ) _0.84 (OH) _0.48 ) is coated with LiNi _0.5 Co _0.2 Mn _0.3 O _{2 as} a positive electrode composite active material as follows:

将4850g五水硝酸铋加入质量分数为2％的20000g稀硝酸水溶液中溶解，制得硝酸铋溶液。将520g氢氧化钠、1722g磷酸三钠用20000g去离子水溶解，得到氢氧化钠、磷酸三钠混合溶液。在室温下，310rpm强力搅拌的条件下，将硝酸铋溶液加入氢氧化钠、磷酸三钠混合溶液，控制混合时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L32，取100g L32，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为32.89g，由此推算滤饼L32固含量为32.89％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入272g滤饼L32中，加入1500g去离子水，350rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式磷酸铋(归一化通式为Bi(PO₄)_0.84(OH)_0.48)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。4850 g of lanthanum nitrate pentahydrate was added to 20,000 g of dilute aqueous nitric acid solution having a mass fraction of 2% to prepare a cerium nitrate solution. 520 g of sodium hydroxide and 1722 g of trisodium phosphate were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium hydroxide and trisodium phosphate. The cerium nitrate solution was added to a mixed solution of sodium hydroxide and trisodium phosphate at room temperature under vigorous stirring at 310 rpm, and the mixing time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L32, 100 g of L32 was taken, and the water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dried solid was obtained, and the weight was found to be 32.89 g, whereby the solid content of the filter cake L32 was estimated to be 32.89%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 272 g of filter cake L32, 1500 g of deionized water was added, vigorously stirred at 350 rpm for 5 hours, and spray dried at 110 ° C. A positive electrode composite active material of a basic yttrium phosphate (normalized to Bi(PO ₄ ) _0.84 (OH) _0.48 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the additive The content was 8.2% by weight).

实施例33Example 33

按照实施例1的方法制备锂离子电池A33，不同的是，用碱式碳酸锑(归一化通式为Sb(OH)_1.40(CO₃)_0.80)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质代替碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质，其中，碱式碳酸锑(归一化通式为Sb(OH)_1.40(CO₃)_0.80)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质按如下方法制备：Preparation of the lithium ion battery A33 according to the method of Example 1, except that, with antimony hydroxide carbonate (normalized formula _{_{Sb (OH) 1.40 (CO 3}} ) 0.80) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ of A positive electrode composite active material in which a positive electrode composite active material is substituted for basic magnesium carbonate (normalized to Mg(OH) _0.40 (CO ₃ ) _0.80 ·H ₂ O) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , wherein the base Barium carbonate (normalized to Sb(OH) _1.40 (CO ₃ ) _0.80 ) The positive electrode composite active material coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ was prepared as follows:

在搅拌条件下，将2280g三氯化锑溶解在25000g无水乙醇中，得到三氯化锑溶液。将1060g碳酸钠、680g质量分数为25％的氨水用20000g去离子水溶解，得到碳酸钠、氨水混合溶液。在室温下，390rpm强力搅拌的条件下，将三氯化锑溶液加入碳酸钠、氨水混合溶液，控制加料时间为2小时，得到悬浮液，经过过滤，得到沉淀。将该沉淀用去离子水洗涤以去除其中的杂质，真空抽滤后得到均匀的滤饼L33，取100g L33，用无水乙醇置换其中的水，然后在空气气氛下，100℃热处理5小时，得到干燥的固体，测得其重量为28.10g，由此推算滤饼L33固含量为28.10％。将作为活性成分的1000g化学式为LiNi_0.5Co_0.2Mn_0.3O₂的锂镍钴锰氧正极材料加入318g滤饼L33中，加入1500g去离子水，270rpm下强力搅拌5小时，110℃下喷雾干燥，得到碱式碳酸锑(归一化通式为Sb(OH)_1.40(CO₃)_0.80)包覆LiNi_0.5Co_0.2Mn_0.3O₂的正极复合活性物质(以复合活性物质的重量为基准，添加剂的含量为8.2重量％)。2280 g of antimony trichloride was dissolved in 25000 g of absolute ethanol under stirring to obtain a cerium trichloride solution. 1060 g of sodium carbonate and 680 g of 25% by mass aqueous ammonia were dissolved in 20,000 g of deionized water to obtain a mixed solution of sodium carbonate and ammonia. The cerium trichloride solution was added to a mixed solution of sodium carbonate and ammonia at room temperature under vigorous stirring at 390 rpm, and the feeding time was controlled for 2 hours to obtain a suspension, which was filtered to obtain a precipitate. The precipitate was washed with deionized water to remove impurities therein, and vacuum filtered to obtain a uniform filter cake L33, 100 g of L33 was taken, water was replaced with absolute ethanol, and then heat-treated at 100 ° C for 5 hours in an air atmosphere. A dry solid was obtained, and its weight was determined to be 28.10 g, whereby the solid content of the filter cake L33 was estimated to be 28.10%. 1000 g of a lithium nickel cobalt manganese oxide positive electrode material having a chemical formula of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as an active ingredient was added to 318 g of filter cake L33, 1500 g of deionized water was added, and the mixture was vigorously stirred at 270 rpm for 5 hours, and spray dried at 110 ° C. A basic composite active material of a basic bismuth carbonate (normalized to Sb(OH) _1.40 (CO ₃ ) _0.80 ) coated with LiNi _0.5 Co _0.2 Mn _0.3 O ₂ is obtained (based on the weight of the composite active material, the additive The content was 8.2% by weight).

对比例1Comparative example 1

按照实施例1的方法制备锂离子电池D1，不同的是，(1)LiNi_0.5Co_0.2Mn_0.3O₂锂镍钴锰氧正极材料未用添加剂进行表面包覆，电池正极极片制备时采用未进行表面包覆的LiNi_0.5Co_0.2Mn_0.3O₂锂镍钴锰氧正极材料；A lithium ion battery D1 was prepared according to the method of Example 1, except that (1) LiNi _0.5 Co _0.2 Mn _0.3 O ₂ lithium nickel cobalt manganese oxide cathode material was not surface-coated with an additive, and the battery positive electrode sheet was prepared without Surface-coated LiNi _0.5 Co _0.2 Mn _0.3 O ₂ lithium nickel cobalt manganese oxide cathode material;

(2)电池正极极片制备时，正极敷料双面面密度调整为312.1g/m²(电池中正极锂镍钴锰氧活性成分的重量与实施例1相同)。 (2) When the positive electrode tab of the battery was prepared, the density of the double-sided surface of the positive electrode dressing was adjusted to 312.1 g/m ² (the weight of the positive electrode lithium nickel cobalt manganese active component in the battery was the same as in Example 1).

对比例2Comparative example 2

按照实施例2的方法制备锂离子电池D2，不同的是，(1)LiNi_0.8Co_0.15Al_0.05O₂锂镍钴铝氧正极材料未用添加剂进行表面包覆，电池正极极片制备时采用未进行表面包覆的LiNi_0.8Co_0.15Al_0.05O₂锂镍钴铝氧正极材料；A lithium ion battery D2 was prepared according to the method of Example 2, except that (1) LiNi _0.8 Co _0.15 Al _0.05 O ₂ lithium nickel cobalt aluminum oxide cathode material was not surface-coated with an additive, and the battery positive electrode sheet was prepared without Surface coated LiNi _0.8 Co _0.15 Al _0.05 O ₂ lithium nickel cobalt aluminum oxide cathode material;

(2)电池正极极片制备时，正极敷料双面面密度调整为312.1g/m²(电池中正极锂镍钴铝氧活性成分的重量与实施例2相同)。(2) When the positive electrode tab of the battery was prepared, the density of the double-sided surface of the positive electrode dressing was adjusted to 312.1 g/m ² (the weight of the positive electrode lithium nickel cobalt aluminum oxide active component in the battery was the same as in Example 2).

对比例3Comparative example 3

按照实施例3的方法制备锂离子电池D3，不同的是，(1)钴酸锂LiCoO₂正极材料未用添加剂进行表面包覆，电池正极极片制备采用未进行表面包覆的钴酸锂LiCoO₂正极材料；Lithium ion battery D3 was prepared according to the method of Example 3, except that (1) lithium cobaltate LiCoO ₂ cathode material was not surface-coated with an additive, and the battery positive electrode sheet was prepared by using lithium cobalt oxide LiCoO which was not surface-coated. ₂ cathode material;

(2)电池正极极片制备时，正极敷料双面面密度调整为312.1g/m²(电池中正极钴酸锂活性成分的重量与实施例3相同)。(2) When the positive electrode tab of the battery was prepared, the density of the double-sided surface of the positive electrode dressing was adjusted to 312.1 g/m ² (the weight of the active component of the positive electrode lithium cobaltate in the battery was the same as in Example 3).

试验例Test case

单体电池的滥用测试Single cell abuse test

1、过充测试1, overcharge test

将单体电池(包括实施例1-33制得的锂离子电池A1-A33以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至8.5V，并在8.5V的电压下恒压保持1小时，观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表1。The single cells (including the lithium ion batteries A1-A33 prepared in Examples 1-33 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 8.5 V, and at 8.5 V. The constant pressure was maintained for 1 hour under voltage, and the phenomenon during the process was observed and recorded. Each of the 30 single cells was tested in parallel. The results are shown in Table 1.

2、30％挤压测试2, 30% extrusion test

将单体电池(包括实施例1-33制得的锂离子电池A1-A33以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至4.25V，并在4.25V的电压下恒压充电直至电流小于1.5A。用两块半径为75mm的半圆柱体的端面从垂直于电池极片方向挤压电池，挤压速度为5mm/s，直至电池变形量达到30％，挤压完成后停留一小时，观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表2。The single cells (including the lithium ion batteries A1-A33 prepared in Examples 1-33 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. Extend the battery from the end face of the semi-cylindrical body with a radius of 75 mm from the direction perpendicular to the pole piece of the battery. The extrusion speed is 5 mm/s until the deformation of the battery reaches 30%. After the extrusion is completed, stay for one hour, observe and record. The phenomenon in the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 2.

3、50％挤压测试3, 50% extrusion test

将单体电池(包括实施例1-33制得的锂离子电池A1-A33以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至4.25V，并在4.25V的电压下恒压充电直至电流小于1.5A。用两块半径为75mm的半圆柱体的端面从垂直于电池极片方向挤压电池，挤压速度为5mm/s，直至电池变形量达到50％，挤压完成后停留一小时，观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表3。The single cells (including the lithium ion batteries A1-A33 prepared in Examples 1-33 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. Extend the battery from the end face of the semi-cylindrical body with a radius of 75 mm from the direction perpendicular to the pole piece of the battery. The extrusion speed is 5 mm/s until the deformation of the battery reaches 50%. After the extrusion is completed, it is allowed to stand for one hour, observe and record. The phenomenon in the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 3.

4、针刺测试4, acupuncture test

将单体电池(包括实施例1-33制得的锂离子电池A1-A33以及对比例1-3制得的锂离子电池D1-D3)以30A的电流充电至4.25V，并在4.25V的电压下恒压充电直至电流小于1.5A。用直径为6毫米的钉子沿垂直于电池长宽面的方向，以25mm/s的速度匀速穿过电池，并停留一小时，观察并记录过程中的现象。各取30只单体电池做平行测试。结果见表4。The single cells (including the lithium ion batteries A1-A33 prepared in Examples 1-33 and the lithium ion batteries D1-D3 prepared in Comparative Examples 1-3) were charged at a current of 30 A to 4.25 V, and at 4.25 V. Constant voltage charging under voltage until the current is less than 1.5A. A 6 mm diameter nail was passed through the battery at a rate of 25 mm/s in a direction perpendicular to the long and wide faces of the battery, and allowed to stand for one hour to observe and record the phenomenon during the process. Each of the 30 single cells was tested in parallel. The results are shown in Table 4.

表1Table 1

表2Table 2

表3table 3

表4Table 4

将表1-4中各实施例和对比例的数据比较可知，在制备正极或负极时引入本发明所述的由碱式盐添加剂包覆活性物质得到的锂离子电池复合活性物质，能够明显提高由此制备得到的锂离子电池的安全性。Comparing the data of the respective examples and comparative examples in Tables 1-4, it can be seen that the lithium ion battery composite active material obtained by coating the active material with the basic salt additive according to the present invention when preparing the positive electrode or the negative electrode can be significantly improved. The safety of the thus prepared lithium ion battery.

将表1-4中实施例1与实施例7-9的结果比较可知，在制备正极或负极时引入以锂离子电池复合活性物质的重量为基准，添加剂含量为5.6-10.1重量％的锂离子电池复合活性物质，能够进一步提高由此制备得到的锂离子电池的安全性，而当添加剂用量进一步增加时还能够进一步提高制备得到的锂离子电池在极苛刻条件下的安全性。Comparing the results of Example 1 and Examples 7-9 in Tables 1-4, it is understood that lithium ions having an additive content of 5.6-10.1% by weight based on the weight of the lithium ion battery composite active material are introduced in the preparation of the positive electrode or the negative electrode. The battery composite active material can further improve the safety of the lithium ion battery thus prepared, and can further improve the safety of the prepared lithium ion battery under extremely severe conditions when the amount of the additive is further increased.

将表1-4中实施例1-4与实施例10-33的结果比较可知，所述添加剂为碱式碳酸镁(归一化通式为Mg(OH)_0.40(CO₃)_0.80·H₂O)、碱式醋酸铜(归一化通式为Cu(OH)_1.50(OCOCH₃)_0.50·0.50H₂O)和碱式碳酸镍(归一化通式为Ni(OH)_4/3(CO₃)_1/3·4/3H₂O)中的至少一种时，能够进一步提高制备得到的锂离子电池的安全性。Comparing the results of Examples 1-4 in Tables 1-4 with Examples 10-33, the additive is basic magnesium carbonate (normalized formula is Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O), basic copper acetate (normalized formula Cu(OH) _1.50 (OCOCH ₃ ) _0.50 ·0.50H ₂ O) and basic nickel carbonate (normalized formula is Ni(OH) _4/3 ( When at least one of CO ₃ ) _1/3 · 4/3H ₂ O) can further improve the safety of the prepared lithium ion battery.

以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.

另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention has various possibilities. The combination method will not be described separately.

此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。 In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims

一种锂离子电池复合活性物质，其特征在于，所述锂离子电池复合活性物质为添加剂包覆的活性物质，所述添加剂为M(OH)_a(PO₄)_b(CO₃)_c(OCOCH₃)_d·eH₂O，其中，M为IIA族金属元素、IB族金属元素、IIB族金属元素、IIIB族金属元素、IVB族金属元素、VB族金属元素、VIB族金属元素、VIIB族金属元素、VIII族金属元素、IIIA族金属元素、IVA族金属元素和VA族金属元素中的至少一种元素，a>0，b≥0，c≥0，d≥0，且b，c，d不同时为0，e≥0。A lithium ion battery composite active material, characterized in that the lithium ion battery composite active material is an additive-coated active material, and the additive is M(OH) _a (PO ₄ ) _b (CO ₃ ) _c (OCOCH) ₃ ) _d · eH ₂ O, wherein M is a Group IIA metal element, a Group IB metal element, a Group IIB metal element, a Group IIIB metal element, a Group IVB metal element, a VB group metal element, a VIB group metal element, a VIIB group metal At least one of an element, a Group VIII metal element, a Group IIIA metal element, a Group IVA metal element, and a Group VA metal element, a>0, b≥0, c≥0, d≥0, and b, c, d It is not 0 at the same time, and e≥0.
根据权利要求1所述的锂离子电池复合活性物质，其中，所述添加剂中，所述IIA族金属元素为Mg、Ca和Sr中的至少一种，所述IB族金属元素为Cu，所述IIB族金属元素为Zn，所述IIIB族金属元素为Y、Sc、La、Ce、Nd、Sm、Gd和Er中的至少一种，所述IVB族金属元素为Ti和/或Zr，所述VB族金属元素为V和/或Nb，所述VIB族金属元素为Cr和/或Mo，所述VIIB族金属元素为Mn，所述VIII族金属元素为Fe、Co和Ni中的至少一种，所述IIIA族金属元素为Al，所述IVA族金属元素为Sn，所述VA族金属元素为Bi和/或Sb；The lithium ion battery composite active material according to claim 1, wherein, in the additive, the Group IIA metal element is at least one of Mg, Ca, and Sr, and the Group IB metal element is Cu, The Group IIB metal element is Zn, and the Group IIIB metal element is at least one of Y, Sc, La, Ce, Nd, Sm, Gd, and Er, and the Group IVB metal element is Ti and/or Zr. The Group VB metal element is V and/or Nb, the Group VIB metal element is Cr and/or Mo, the Group VIIB metal element is Mn, and the Group VIII metal element is at least one of Fe, Co and Ni. The Group IIIA metal element is Al, the Group IVA metal element is Sn, and the Group VA metal element is Bi and/or Sb;

优选地，所述添加剂为碱式碳酸镁、碱式醋酸铜和碱式碳酸镍中的至少一种；Preferably, the additive is at least one of basic magnesium carbonate, basic copper acetate and basic nickel carbonate;

进一步优选地，所述添加剂为Mg(OH)_0.40(CO₃)_0.80·H₂O、Cu(OH)_1.50(OCOCH₃)_0.50·0.50H₂O和Ni(OH)_4/3(CO₃)_1/3·4/3H₂O中的至少一种。Further preferably, the additive is Mg(OH) _0.40 (CO ₃ ) _0.80 · H ₂ O, Cu(OH) _1.50 (OCOCH ₃ ) _0.50 · 0.50H ₂ O and Ni(OH) _4/3 (CO ₃ ) At least one of _1/3 · 4/3H ₂ O.
根据权利要求1或2所述的锂离子电池复合活性物质，其中，以所述锂离子电池复合活性物质的重量为基准，所述添加剂的含量为0.05-33重量％，优选为3-16重量％，进一步优选为5.6-10.1重量％。The lithium ion battery composite active material according to claim 1 or 2, wherein the content of the additive is 0.05 to 33% by weight, preferably 3 to 16% by weight based on the weight of the lithium ion battery composite active material. % is further preferably 5.6 to 10.1% by weight.
根据权利要求1-3中任意一项所述的锂离子电池复合活性物质，其中，所述活性物质为正极活性物质或负极活性物质，所述正极活性物质为钴酸锂、锂镍氧、锂镍钴氧、锂镍钴铝氧、锂镍钴锰氧、锂镍锰氧、锰酸锂、钒酸锂、磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸锰铁镍锂、磷酸锰铁钴锂、磷酸锰铁镍钴锂、磷酸钒锂和硅酸铁锂中的至少一种，所述负极活性物质为石墨、钛酸锂、硅、硬碳、锡和氧化锡中的至少一种。The lithium ion battery composite active material according to any one of claims 1 to 3, wherein the active material is a positive electrode active material or a negative electrode active material, and the positive electrode active material is lithium cobaltate, lithium nickel oxide, lithium Nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium manganate, lithium vanadate, lithium iron phosphate, lithium manganese phosphate, lithium manganese iron phosphate, lithium manganese iron phosphate, manganese phosphate At least one of iron cobalt lithium, lithium manganese iron nickel cobalt oxide, lithium vanadium phosphate, and lithium iron silicate, the negative electrode active material being at least one of graphite, lithium titanate, silicon, hard carbon, tin, and tin oxide. Kind.
权利要求1-4中任意一项所述的锂离子电池复合活性物质的制备方法，其特征在于，该方法包括：制备元素M的碱式盐，在分散剂存在下，将所述元素M的碱式盐与活性物质混合，然后将所得混合物进行热处理。The method for producing a lithium ion battery composite active material according to any one of claims 1 to 4, characterized in that the method comprises: preparing a basic salt of the element M, and in the presence of the dispersing agent, the element M The basic salt is mixed with the active material, and then the resulting mixture is subjected to heat treatment.
根据权利要求5所述的方法，其中，所述分散剂为异丙醇、去离子水、乙醇、丁醇和丙酮中的至少一种。The method according to claim 5, wherein the dispersing agent is at least one of isopropyl alcohol, deionized water, ethanol, butanol, and acetone.
根据权利要求5所述的方法，其中，所述热处理的方式为喷雾干燥、微波干燥、流化床干燥或烘箱干燥，优选为喷雾干燥。The method according to claim 5, wherein the heat treatment is by spray drying, microwave drying, fluidized bed drying or oven drying, preferably spray drying.
一种锂离子电池电极浆料，其特征在于，所述电极浆料包括锂离子电池活性物质、粘结剂、导电剂、溶剂和任选的增稠剂，其中，所述锂离子电池活性物质为权利要求1-4中任意一项所述的锂离子电池复合活性物质；A lithium ion battery electrode slurry, characterized in that the electrode paste comprises a lithium ion battery active material, a binder, a conductive agent, a solvent and an optional thickener, wherein the lithium ion battery active material A lithium ion battery composite active material according to any one of claims 1 to 4;

优选地，以所述锂离子电池复合活性物质的重量为基准，所述粘结剂以干基计的含量为0.5-5重量％，所述导电剂的含量为0.5-5重量％，所述溶剂的含量为50-210重量％，所述增稠剂的含量为0-3重量％。Preferably, the binder is contained in an amount of 0.5 to 5% by weight on a dry basis, and the content of the conductive agent is 0.5 to 5% by weight, based on the weight of the lithium ion battery composite active material, The content of the solvent is from 50 to 210% by weight, and the content of the thickener is from 0 to 3% by weight.
一种锂离子电池正极或负极，其特征在于，所述锂离子电池正极或负极包括集流体及位于集流体上的电极敷料，所述电极敷料含有锂离子电池活性物质、粘结剂、导电剂和任选的增稠剂，其中，所述锂离子电池活性物质为权利要求1-4中任意一项所述的锂离子电池复合活性物质。A positive electrode or a negative electrode of a lithium ion battery, characterized in that the positive electrode or the negative electrode of the lithium ion battery comprises a current collector and an electrode dressing on the current collector, the electrode dressing containing a lithium ion battery active material, a binder and a conductive agent And an optional thickener, wherein the lithium ion battery active material is the lithium ion battery composite active material according to any one of claims 1 to 4.
一种锂离子电池，其特征在于，所述锂离子电池包括电池壳体以及位于电池壳体内部的电芯组件和电解液，所述电芯组件包括正极、负极和隔膜，且所述正极为权利要求9所述的锂离子电池正极，和/或所述负极为权利要求9所述的锂离子电池负极。 A lithium ion battery, comprising: a battery case; and a cell assembly and an electrolyte located inside the battery case, the cell assembly including a positive electrode, a negative electrode and a diaphragm, and the positive electrode is The lithium ion battery positive electrode according to claim 9, and/or the negative electrode is the lithium ion battery negative electrode according to claim 9.