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CN108365181A - A kind of nickelic layered cathode material method of modifying - Google Patents

A kind of nickelic layered cathode material method of modifying Download PDF

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CN108365181A
CN108365181A CN201711178891.XA CN201711178891A CN108365181A CN 108365181 A CN108365181 A CN 108365181A CN 201711178891 A CN201711178891 A CN 201711178891A CN 108365181 A CN108365181 A CN 108365181A
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王波
蔡飞鹏
杨改
高剑
蒋波
秦显忠
陈花
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Shandong Aia Kesimao New Material Co Ltd
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Abstract

一种高镍层状正极材料改性方法，包括如下步骤：(1)将高镍层状过渡金属氧化物材料与含有M‑O和M‑P的前驱体均匀混合；(2)通过化学反应，将在LiNixX1‑xO2(x>0.5)表面形成的M‑O和M‑P前驱体包覆层转化，在活性材料表面形成一层纳米尺度、均匀分布的M‑O和M‑P包覆层；(3)对步骤(2)得到的包覆层进行热处理，得到电极材料表面含有M‑O和/或L‑M‑O、以及M‑P和/或L‑M‑P的锂电池阳极材料。所述方法制备的正极材料不仅可以大大降低表面锂残留的含量，还能在材料表现形成惰性保护层和锂导电层，从而改善材料的倍率性能和循环稳定性，提高安全性能。

A method for modifying a high-nickel layered positive electrode material, comprising the steps of: (1) uniformly mixing a high-nickel layered transition metal oxide material with a precursor containing M-O and M-P; (2) by chemical reaction , convert the M-O and M-P precursor coating layer formed on the surface of LiNixX1-xO2 (x>0.5), and form a layer of nano-scale, uniformly distributed M-O and M-P coating on the surface of the active material layer; (3) the coating layer obtained in step (2) is heat-treated to obtain a lithium battery containing M-O and/or L-M-O and M-P and/or L-M-P on the surface of the electrode material anode material. The positive electrode material prepared by the method can not only greatly reduce the residual lithium content on the surface, but also form an inert protective layer and a lithium conductive layer on the surface of the material, thereby improving the rate performance and cycle stability of the material, and improving the safety performance.

Description

一种高镍层状正极材料改性方法A kind of high-nickel layered positive electrode material modification method

技术领域technical field

本发明涉及一种锂离子电池电极材料，具体涉及一种高镍层状正极材料及其制备方法。The invention relates to a lithium-ion battery electrode material, in particular to a high-nickel layered positive electrode material and a preparation method thereof.

背景技术：Background technique:

随着工业的发展和汽车数量的快速增加，温室气体的排放日益严重，导致全球变暖，成为亟待解决的全球性问题。化石燃料的消耗是造成这一问题的重要原因之一，因此，开发和利用可再生能源日益迫切。然而，以太阳能、风能为代表的可再生能源是间歇性的。因此，需要选择一种高效的能量存储体系。基于重量、存储容量，大小和持久性等因素，锂离子电池成为最主要的能量存储设备之一。With the development of industry and the rapid increase in the number of automobiles, the emission of greenhouse gases is becoming more and more serious, leading to global warming and becoming a global problem that needs to be solved urgently. The consumption of fossil fuels is one of the important reasons causing this problem, therefore, it is increasingly urgent to develop and utilize renewable energy. However, renewable energy represented by solar energy and wind energy is intermittent. Therefore, it is necessary to choose an efficient energy storage system. Based on factors such as weight, storage capacity, size, and durability, lithium-ion batteries have emerged as one of the most dominant energy storage devices.

锂离子电池主要由正极、负极、电解液和隔膜等几部分组成。目前，主要的正极材料包括层状LiCoO2、层状LiNi1-x-yCoxMnyO2，层状LiNi0.8Co0.15Al0.05O2、尖晶石Li2MnO4和橄榄石LiFePO4等。其中，层状结构LiNi1-x-yCoxMnyO2(1-x-y>0.5)和LiNi0.8Co0.15Al0.05O2高镍三元材料具有大于180mA·hg-1的放电比容量和接近3.8V的操作电压，可能达到800Wh·kg-1的能量密度，因此，有望成为下一代锂离子电池正极材料之一。Lithium-ion batteries are mainly composed of positive electrode, negative electrode, electrolyte and separator. At present, the main cathode materials include layered LiCoO 2 , layered LiNi 1-xy Co x Mny O 2 , layered LiNi 0.8 Co 0.15 Al 0.05 O 2 , spinel Li 2 MnO 4 and olivine LiFePO 4 and so on. Among them, the layered structure LiNi 1-xy Co x Mn y O 2 (1-xy>0.5) and LiNi 0.8 Co 0.15 Al 0.05 O 2 high-nickel ternary materials have a discharge specific capacity greater than 180mA·hg -1 and close to 3.8 The operating voltage of V may reach an energy density of 800 Wh kg -1 , so it is expected to become one of the cathode materials for next-generation lithium-ion batteries.

尽管存在明显的优势，高镍三元正极材料仍然存在很多的问题，阻碍了其实际应用。表面锂残留是几个严重问题之一。表面锂残留的主要组成是LiOH、Li2CO3等杂质。在操作过程中，锂杂质能够与电解液反应，生成CO2、N2等气体，造成电池涨气，引起电池性能的恶化。此外，在电池制备的混浆过程中，当pH较高时，能够引起浆料的凝胶。因此，在制备电池前，必须有效去除表面锂残留。目前，去除锂残留的方法是冲洗，然后再二次烧结。这种工艺可部分去除锂残留，但是在空气中二次烧结时，会引起容量保持率的下降。此外，这种处理方法并不能有效保护活性材料表面。Despite the obvious advantages, high-nickel ternary cathode materials still have many problems that hinder their practical application. Surface lithium residue is one of several serious problems. The main components of lithium residues on the surface are impurities such as LiOH and Li 2 CO 3 . During operation, lithium impurities can react with the electrolyte to generate gases such as CO 2 and N 2 , causing gas inflation in the battery and deterioration of battery performance. In addition, during the mixing process of battery preparation, when the pH is high, the gel of the slurry can be caused. Therefore, it is necessary to effectively remove the lithium residue on the surface before fabricating the battery. Currently, the method for removing lithium residues is flushing followed by secondary sintering. This process can partially remove lithium residues, but it will cause a decline in capacity retention when secondary sintering in air. In addition, this treatment method cannot effectively protect the surface of the active material.

高镍过渡金属氧化物正极材料的另外一个重要的问题是，在循环过程中的表面结构的恶化。这种结构恶化由阳离子混排引起，从材料表面开始，并逐步向内层蔓延。在高操作电压和高温下，更加明显。此外，伴随着结构恶化，O2从晶格中释放出来，在高温或者高电压操作时，释氧更加剧烈。当O2与有机电解液接触并遇到明火时，极易发生燃烧和爆炸。因此，抑制阳离子混排，减少释氧，对提高材料的循环性能和安全性能，十分重要。Another important issue for high-nickel transition metal oxide cathode materials is the deterioration of the surface structure during cycling. This structural deterioration is caused by cation mixing, starting from the surface of the material and gradually spreading to the inner layer. It is more pronounced at high operating voltage and high temperature. In addition, with the deterioration of the structure, O2 is released from the lattice, and the oxygen release is more intense when operating at high temperature or high voltage. When O2 comes into contact with organic electrolyte and encounters an open flame, it is very easy to burn and explode. Therefore, it is very important to suppress cation mixing and reduce oxygen release to improve the cycle performance and safety performance of materials.

表面包覆是改善材料性能的一种有效方法，目前的包覆材料主要是金属氧化物(如Al2O3、MgO、ZnO、SiO2等)，金属氟化物(AlF3、MgF2等)和金属磷酸盐(AlPO4、FePO4等)，这些包覆材料大部分属于惰性包覆，其本质是在活性材料表面形成一种惰性层，将材料表面与有机电解液隔绝，起到物理保护层和HF清除剂的作用。这种表面改性方法能够提高材料的结构稳定性，因而改善循环稳定性和安全性，但是可能会造成倍率性能的下降；另外一种包覆方法是锂导电包覆，是在活性材料表面形成一种锂导电层，主要有LiAlO2、Li2MnO3、Li2SiO3、Li3PO4等，不仅可以提高材料的结构稳定性，同时能够改善材料的倍率性能。但这种方法，在包覆过程中，往往需要另外的锂源与包覆前驱体再次发生反应，并不能有效降低表面锂杂质的含量。Surface coating is an effective method to improve material properties. The current coating materials are mainly metal oxides (such as Al 2 O 3 , MgO, ZnO, SiO 2, etc.), metal fluorides (AlF 3 , MgF 2 , etc.) and metal phosphates (AlPO 4 , FePO 4 , etc.), most of these coating materials are inert coatings, and their essence is to form an inert layer on the surface of the active material to isolate the surface of the material from the organic electrolyte for physical protection. layer and the role of HF scavengers. This surface modification method can improve the structural stability of the material, thereby improving cycle stability and safety, but may cause a decrease in the rate performance; another coating method is lithium conductive coating, which is formed on the surface of the active material. A lithium conductive layer mainly includes LiAlO 2 , Li 2 MnO 3 , Li 2 SiO 3 , Li 3 PO 4 , etc., which can not only improve the structural stability of the material, but also improve the rate performance of the material. However, this method often requires another lithium source to react with the coating precursor again during the coating process, which cannot effectively reduce the content of lithium impurities on the surface.

发明内容：Invention content:

本发明提供了一种针对高镍层状正极材料的表面改性方法，通过这种方法，不仅可以大大降低表面锂残留的含量，还能在材料表现形成惰性保护层和锂导电层，从而改善材料的倍率性能和循环稳定性，提高安全性能。The invention provides a surface modification method for high-nickel layered positive electrode materials. Through this method, not only can the content of residual lithium on the surface be greatly reduced, but also an inert protective layer and a lithium conductive layer can be formed on the material performance, thereby improving The rate performance and cycle stability of the material improve the safety performance.

本发明提供一种改性高镍层状正极材料，包括高镍层状过渡金属氧化物体相层以及由M-O和/或L-M-O、以及M-P和/或L-M-P组成的复合包覆层，所述高镍层状过渡金属氧化物可用LiNixX1-xO2表示，其中0.5<x<1，X是Co，Mn，Al等元素中的一种或几种；所述M-O化合物是指含M元素的氧化物；所述M-P是指含有M元素的磷酸盐；所述L-M-O化合物是指M元素的锂氧化物；所述L-M-P是指M元素的锂磷酸盐。The invention provides a modified high-nickel layered positive electrode material, comprising a high-nickel layered transition metal oxide bulk layer and a composite coating layer composed of MO and/or LMO, and MP and/or LMP, the high-nickel Layered transition metal oxides can be represented by LiNi x X 1-x O 2 , where 0.5<x<1, X is one or more of elements such as Co, Mn, Al; the MO compound refers to the element containing M The oxide; the MP refers to the phosphate containing the M element; the LMO compound refers to the lithium oxide of the M element; the LMP refers to the lithium phosphate of the M element.

所述M元素选自Mg、Ca、Y、Ti、Zr、V、Nb、Ta、Cr、Mo、W、Mn、Fe、Ru、Co、Rh、Ni、Cu、Zn、B、Al、Ga、Si、Ge、Sn元素中的一种或者几种，优选是V、Mn、Fe、Co、Zr、B中的一种或多种。The M element is selected from Mg, Ca, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ni, Cu, Zn, B, Al, Ga, One or more of Si, Ge, Sn elements, preferably one or more of V, Mn, Fe, Co, Zr, B.

所述高镍层状过渡金属氧化物正极材料优选是LiNi0.6Co0.2Mn0.2O2、LiNi0.7Co0.15Mn0.15O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2、LiNi0.9Co0.05Mn0.05O2。The high-nickel layered transition metal oxide cathode material is preferably LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.7 Co 0.15 Mn 0.15 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 0.9 Co 0.05 Mn 0.05 O 2 .

所述M-O化合物是Al2O3、Co3O4、TiO2、TiO、Ti2O3、ZrO2、SnO2、SnO、MnO2、B2O3、SiO2、V2O5、V2O3、VO2、VO、Nb2O5、NbO、NbO2、Ta2O5、MoO3、RuO2、Fe3O4、Cr2O3、Ga2O3、GeO2、Rh2O3、P2O5、WO3中的一种或多种，优选是V2O5、V2O3、VO2、Fe3O4、Co3O4、ZrO2、B2O3中的一种或多种。The MO compound is Al 2 O 3 , Co 3 O 4 , TiO 2 , TiO, Ti 2 O 3 , ZrO 2 , SnO 2 , SnO, MnO 2 , B 2 O 3 , SiO 2 , V 2 O 5 , V 2 O 3 , VO 2 , VO, Nb 2 O 5 , NbO, NbO 2 , Ta 2 O 5 , MoO 3 , RuO 2 , Fe 3 O 4 , Cr 2 O 3 , Ga 2 O 3 , GeO 2 , Rh 2 One or more of O 3 , P 2 O 5 , WO 3 , preferably V 2 O 5 , V 2 O 3 , VO 2 , Fe 3 O 4 , Co 3 O 4 , ZrO 2 , B 2 O 3 one or more of.

所述M-P是AlPO4、CoPO4、Co3(PO4)2、Mn3(PO4)2、FePO4、Fe3(PO4)2、Mg3(PO4)2、Zn3(PO4)2、VPO4、Ni3(PO4)2Cu3(PO4)2、Ca3(PO4)2、YPO4、BPO4、W(PO4)2、TiPO4中的一种或多种，优选是CoPO4、Co3(PO4)2、FePO4、Fe3(PO4)2、VPO4、W(PO4)2中的一种或多种。The MP is AlPO 4 , CoPO 4 , Co 3 (PO 4 ) 2 , Mn 3 (PO 4 ) 2 , FePO 4 , Fe 3 (PO 4 ) 2 , Mg 3 (PO 4 ) 2 , Zn 3 (PO 4 ) 2 , VPO 4 , Ni 3 (PO 4 ) 2 Cu 3 (PO 4 ) 2 , Ca 3 (PO 4 ) 2 , YPO 4 , BPO 4 , W(PO 4 ) 2 , TiPO 4 species, preferably one or more of CoPO 4 , Co 3 (PO 4 ) 2 , FePO 4 , Fe 3 (PO 4 ) 2 , VPO 4 , W(PO 4 ) 2 .

本发明还提供一种高镍层状正极材料改性方法，包括如下步骤：The present invention also provides a method for modifying a high-nickel layered positive electrode material, comprising the following steps:

(1)将高镍层状过渡金属氧化物材料与含有M-O和M-P的前驱体均匀混合；(1) uniformly mix the high-nickel layered transition metal oxide material with the precursor containing M-O and M-P;

(2)通过化学反应，将在LiNixX1-xO2(x>0.5)表面形成的M-O和M-P前驱体包覆层转化，在活性材料表面形成一层纳米尺度、均匀分布的M-O和M-P包覆层；(2) Transform the coating layer of MO and MP precursors formed on the surface of LiNi x X 1-x O 2 (x>0.5) through chemical reaction, and form a layer of nanoscale, uniformly distributed MO and MP on the surface of the active material. MP coating;

(3)对步骤(2)得到的包覆层进行热处理，得到电极材料表面含有M-O和/或L-M-O、以及M-P和/或L-M-P的锂电池阳极材料。(3) heat-treating the coating layer obtained in step (2) to obtain a lithium battery anode material containing M-O and/or L-M-O and M-P and/or L-M-P on the surface of the electrode material.

步骤(1)中所述前驱体包覆层是采用涂覆或者浸渍的方法获得。The precursor coating layer in step (1) is obtained by coating or impregnation.

步骤(2)中所述化学反应指将步骤(1)得到的负载M-O和M-P前驱体包覆层的高镍层状过渡金属氧化物材料，放入磷酸或可溶性磷酸盐的溶液中，使得M-P前驱物发生沉淀反应，得到M-P包覆层；然后在高温下分解，得到M-O包覆层，所述分解反应温度是400-600℃。The chemical reaction described in step (2) refers to putting the high-nickel layered transition metal oxide material loaded with M-O and M-P precursor coating layers obtained in step (1) into a solution of phosphoric acid or soluble phosphate, so that M-P The precursor undergoes a precipitation reaction to obtain an M-P coating layer; and then decomposes at a high temperature to obtain an M-O coating layer, and the decomposition reaction temperature is 400-600°C.

步骤(3)中所述热处理气氛是在氧气、空气或者惰性气体气氛下进行；所述热处理温度是指500-750℃，所述热处理时间是4-8h；所述惰性气体如氮气、氩气。The heat treatment atmosphere in step (3) is carried out under oxygen, air or inert gas atmosphere; the heat treatment temperature refers to 500-750°C, and the heat treatment time is 4-8h; the inert gas is such as nitrogen, argon .

所述M-O的前驱体是指可生成M-O化合物的，含有M元素的化合物，具体包括含有M的盐和含M的有机物中的一种或者多种，优选含M的硝酸盐、碳酸盐、有机酸盐。The precursor of M-O refers to a compound containing M elements that can generate M-O compounds, specifically including one or more of M-containing salts and M-containing organic substances, preferably M-containing nitrates, carbonates, Organic acid salts.

所述M-P的前驱体是指可生成M-P化合物的，含有M元素的前驱体，具体包括含有M的盐、含M的酸、和含M的有机物中的一种或者多种，优选含M的有机酸。The M-P precursor refers to a precursor containing M elements that can generate M-P compounds, specifically including one or more of M-containing salts, M-containing acids, and M-containing organic substances, preferably M-containing organic acids.

所述L-M-O是指含有M元素的锂氧化物中的一种或多种，优选LiAlO2、Li2TiO3、Li2ZrO3、Li2SiO3、Li2MnO3、Li2MnP2O7、Li3BO3、Li3B7O12、Li2B4O7、LiNbO2、LiNbO3、Li3NbO4、LiTaO3、Li2MoO4、Li2WO4、LiVO3、Li2SnO3、LiFeO2、Li5FeO4、Li2WO4等。The LMO refers to one or more of lithium oxides containing M elements, preferably LiAlO 2 , Li 2 TiO 3 , Li 2 ZrO 3 , Li 2 SiO 3 , Li 2 MnO 3 , Li 2 MnP 2 O 7 , Li 3 BO 3 , Li 3 B 7 O 12 , Li 2 B 4 O 7 , LiNbO 2 , LiNbO 3 , Li 3 NbO 4 , LiTaO 3 , Li 2 MoO 4 , Li 2 WO 4 , LiVO 3 , Li 2 SnO 3. LiFeO 2 , Li 5 FeO 4 , Li 2 WO 4 , etc.

所述Li-M-P是指含有M元素的锂磷酸盐中的一种或者多种，优选LiCoPO4、Li2MnP2O7、Li2Fe3(P2O7)2、LiZnPO4、Li3V2(PO4)3、Li2Ti2(PO4)3等。The Li-MP refers to one or more of lithium phosphates containing M elements, preferably LiCoPO 4 , Li 2 MnP 2 O 7 , Li 2 Fe 3 (P 2 O 7 ) 2 , LiZnPO 4 , Li 3 V 2 (PO 4 ) 3 , Li 2 Ti 2 (PO 4 ) 3 , etc.

步骤(2)所述的混合方式是指研磨、球磨、搅拌加热、旋转蒸发方式中的一种或者多种。The mixing method described in step (2) refers to one or more of grinding, ball milling, stirring and heating, and rotary evaporation.

本发明的优点：Advantages of the present invention:

本发明通过电极材料表面改性，大大降低了电极材料表面锂杂质残留，提高材料的结构稳定性，因而改善循环稳定性和安全性，同时避免了电极倍率性能的下降。The present invention greatly reduces the residue of lithium impurities on the surface of the electrode material by modifying the surface of the electrode material, improves the structural stability of the material, thereby improving cycle stability and safety, while avoiding the decline in the rate performance of the electrode.

附图说明Description of drawings

图1：本发明所述技术方案的技术路线图；Fig. 1: the technical roadmap of the technical solution of the present invention;

图2：Zr表面改性的LiNi0.8Co0.1Mn0.1O2电极材料扫描电镜图像；Figure 2: SEM images of Zr surface-modified LiNi 0.8 Co 0.1 Mn 0.1 O 2 electrode materials;

图3：Zr表面改性的LiNi0.8Co0.1Mn0.1O2电极材料扫描电镜图像；Figure 3: SEM images of Zr surface-modified LiNi 0.8 Co 0.1 Mn 0.1 O 2 electrode materials;

图4：表面改性LiNi0.6Co0.2Mn0.2O2的电学性能；Figure 4: Electrical properties of surface-modified LiNi 0.6 Co 0.2 Mn 0.2 O 2 ;

图5：表面改性LiNi0.6Co0.2Mn0.2O2的倍率性能；Figure 5: Rate performance of surface-modified LiNi 0.6 Co 0.2 Mn 0.2 O 2 ;

具体实施例specific embodiment

实施例1：Example 1:

取20g高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2，将1g硝酸钒溶解于100ml水中，加热至95℃并不断搅拌，超声波分散30min；加入磷酸溶液，继续用超声波搅拌至水分完全挥发；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2转移到马弗炉中，在空气气氛，450℃下热处理2h，升温到600℃处理5h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2。Take 20g of high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 , dissolve 1g of vanadium nitrate in 100ml of water, heat to 95°C and keep stirring, ultrasonically disperse for 30min; add phosphoric acid solution, continue ultrasonically stirring until The moisture is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 is transferred to a muffle furnace, heat-treated at 450 ° C for 2 h in an air atmosphere, and then heated to 600 ° C for 5 h , to obtain a surface-modified high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 .

实施例2：Example 2:

取15g高镍层状过渡金属氧化物材料LiNi0.8Co0.15Al0.05O2，将0.5g硝酸锆和0.2g硝酸锰溶解于100ml水中，加热至90℃并不断搅拌，超声波分散20min；加入磷酸溶液，继续用超声波搅拌至水分完全挥发；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Al0.05O2转移到马弗炉中，在空气气氛，400℃下热处理1h，升温到650℃处理3h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Al0.05O2。Take 15g of high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Al 0.05 O 2 , dissolve 0.5g of zirconium nitrate and 0.2g of manganese nitrate in 100ml of water, heat to 90°C and keep stirring, ultrasonically disperse for 20min; add phosphoric acid solution , continue to use ultrasonic stirring until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Al 0.05 O 2 is transferred to a muffle furnace and heat-treated at 400 ° C for 1 h in an air atmosphere. The temperature was raised to 650° C. for 3 hours to obtain a surface-modified high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Al 0.05 O 2 .

实施例3：Example 3:

取25g高镍层状过渡金属氧化物材料LiNi0.6Co0.2Mn0.2O2，将1g硼酸和0.2g硝酸钒溶解于100ml水中，加热至80℃并不断搅拌，超声波分散40min；加入磷酸氢铵溶液，继续用超声波搅拌至水分完全挥发；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.6Co0.2Mn0.2O2转移到马弗炉中，在氧气气氛，450℃下热处理2h，升温到700℃处理3h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.6Co0.2Mn0.2O2。Take 25g of high-nickel layered transition metal oxide material LiNi 0.6 Co 0.2 Mn 0.2 O 2 , dissolve 1g of boric acid and 0.2g of vanadium nitrate in 100ml of water, heat to 80°C and keep stirring, ultrasonically disperse for 40min; add ammonium hydrogen phosphate solution , and continue to use ultrasonic stirring until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi 0.6 Co 0.2 Mn 0.2 O 2 is transferred to a muffle furnace and heat-treated at 450 ° C for 2 h in an oxygen atmosphere. The temperature was raised to 700° C. for 3 hours to obtain a surface-modified high-nickel layered transition metal oxide material LiNi 0.6 Co 0.2 Mn 0.2 O 2 .

实施例4：Example 4:

取15g高镍层状过渡金属氧化物材料LiNi0.8Co0.15Mn0.05O2，将0.5g硝酸锆溶解于100ml水中，加热至90℃并不断搅拌，超声波分散30min；加入磷酸溶液，继续用超声波搅拌至水分完全挥发；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Mn0.05O2转移到马弗炉中，在空气气氛，400℃下热处理2h，升温到700℃处理5h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Mn0.05O2。Take 15g of high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Mn 0.05 O 2 , dissolve 0.5g of zirconium nitrate in 100ml of water, heat to 90°C and keep stirring, ultrasonically disperse for 30min; add phosphoric acid solution, continue ultrasonically stirring until the moisture is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Mn 0.05 O 2 is transferred to a muffle furnace, heat-treated at 400 ° C for 2 h in an air atmosphere, and then heated to 700 ° C After 5 hours, a surface-modified high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Mn 0.05 O 2 was obtained.

实施例5：Example 5:

取30g高镍层状过渡金属氧化物材料LiNi0.8Co0.15Mn0.05O2，将1g硝酸锆和0.5g硼酸溶解于100ml水中，加热至95℃并不断搅拌，超声波分散30min；加入磷酸溶液，继续用超声波搅拌至水分完全挥发；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Mn0.05O2转移到马弗炉中，在空气气氛，400℃下热处理2h，升温到650℃处理4h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Mn0.05O2。Take 30g of high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Mn 0.05 O 2 , dissolve 1g of zirconium nitrate and 0.5g of boric acid in 100ml of water, heat to 95°C and keep stirring, ultrasonically disperse for 30min; add phosphoric acid solution, continue Stir with ultrasonic waves until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Mn 0.05 O 2 is transferred to a muffle furnace, heat-treated at 400 °C for 2 h in an air atmosphere, and heated to After treatment at 650°C for 4 hours, a surface-modified high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Mn 0.05 O 2 was obtained.

实施例6：Embodiment 6:

取30g高镍层状过渡金属氧化物材料LiNi0.8Co0.15Mn0.05O2，将0.8g硝酸铁溶解于100ml水中，加热至95℃并不断搅拌，超声波分散30min；加入磷酸溶液，继续用超声波搅拌至水分完全挥发；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Mn0.05O2转移到马弗炉中，在空气气氛，440℃下热处理2h，升温到600℃处理4h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Mn0.05O2。Take 30g high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Mn 0.05 O 2 , dissolve 0.8g ferric nitrate in 100ml water, heat to 95°C and keep stirring, ultrasonically disperse for 30min; add phosphoric acid solution, continue ultrasonically stirring until the moisture is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Mn 0.05 O 2 is transferred to a muffle furnace, heat-treated at 440°C for 2 hours in an air atmosphere, and then heated to 600°C for treatment After 4 hours, a surface-modified high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Mn 0.05 O 2 was obtained.

实施例7：Embodiment 7:

取30g高镍层状过渡金属氧化物材料LiNi0.8Co0.15Al0.05O2，将1.2g硝酸钴溶解于100ml水中，加热至95℃并不断搅拌，超声波分散30min；加入磷酸溶液，继续用超声波搅拌至水分完全挥发；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Al0.05O2转移到马弗炉中，在空气气氛，450℃下热处理2h，升温到700℃处理5h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.8Co0.15Al0.05O2。Take 30g of high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Al 0.05 O 2 , dissolve 1.2g of cobalt nitrate in 100ml of water, heat to 95°C and keep stirring, ultrasonically disperse for 30min; add phosphoric acid solution, continue to stir with ultrasonic until the moisture is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Al 0.05 O 2 is transferred to a muffle furnace, heat-treated at 450°C for 2 hours in an air atmosphere, and then heated to 700°C for treatment After 5 hours, a surface-modified high-nickel layered transition metal oxide material LiNi 0.8 Co 0.15 Al 0.05 O 2 was obtained.

实施例8：Embodiment 8:

取40g高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2，将1.2g硝酸钴和0.5g硼酸溶解于100ml水中，加热至95℃并不断搅拌，超声波分散30min；加入磷酸溶液，继续用超声波搅拌至水分完全挥发；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2转移到马弗炉中，在空气气氛，450℃下热处理2h，升温到700℃处理5h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2。Take 40g of high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 , dissolve 1.2g of cobalt nitrate and 0.5g of boric acid in 100ml of water, heat to 95°C and keep stirring, ultrasonically disperse for 30min; add phosphoric acid solution, Continue to use ultrasonic stirring until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 is transferred to a muffle furnace, heat-treated at 450 ° C for 2 h in an air atmosphere, and the temperature is raised to Treat at 700° C. for 5 hours to obtain a surface-modified high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 .

对比例1Comparative example 1

其他过程都与实施例1相同，但只在高镍层状过渡金属氧化物材料负载M金属氧化物。具体制备过程如下：Other processes are the same as in Example 1, but only the M metal oxide is loaded on the high-nickel layered transition metal oxide material. Concrete preparation process is as follows:

取20g高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2，将1g硝酸钒溶解于100ml水中，加热至95℃并不断搅拌，超声波分散30min；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2转移到马弗炉中，在空气气氛，450℃下热处理2h，升温到600℃处理5h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2。Take 20g of high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 , dissolve 1g of vanadium nitrate in 100ml of water, heat to 95°C with constant stirring, and ultrasonically disperse for 30min; the obtained high-nickel layer loaded with transition metal The transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 was transferred to a muffle furnace, heat-treated at 450 ° C for 2 h in an air atmosphere, and then heated to 600 ° C for 5 h to obtain a surface-modified high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 .

对比例2Comparative example 2

其他过程都与实施例1相同，但只在高镍层状过渡金属氧化物材料负载M金属磷酸盐。具体制备过程如下：Other processes are the same as in Example 1, but only M metal phosphate is loaded on the high-nickel layered transition metal oxide material. Concrete preparation process is as follows:

取20g高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2，将1g硝酸钒和5g磷酸溶解于100ml水中，加热至95℃并不断搅拌，超声波分散30min；得到的负载过渡金属的高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2转移到马弗炉中，在空气气氛，450℃下热处理2h，升温到600℃处理5h，得到表面改性的高镍层状过渡金属氧化物材料LiNi0.8Co0.1Mn0.1O2。Take 20g of high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 , dissolve 1g of vanadium nitrate and 5g of phosphoric acid in 100ml of water, heat to 95°C with constant stirring, and ultrasonically disperse for 30min; The high-nickel layered transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 was transferred to a muffle furnace, heat-treated at 450 °C for 2 h in an air atmosphere, and then heated to 600 °C for 5 h to obtain a surface-modified high-nickel layered Transition metal oxide material LiNi 0.8 Co 0.1 Mn 0.1 O 2 .

对本发明所述技术方案得到的实施例1-8和按照现有技术制备的对比例1-2进行放电容量和放电循环保持率的性能测试，结果如下表所示：The embodiment 1-8 obtained by the technical solution of the present invention and the comparative example 1-2 prepared according to the prior art carry out the performance test of discharge capacity and discharge cycle retention rate, and the results are shown in the following table:

从上表的实验数据可以看到，采用本发明的方法制备的电极材料具有比较好的放电性能，同时耐老化放电性能也明显获得了改进，取得了显著的进步。It can be seen from the experimental data in the above table that the electrode material prepared by the method of the present invention has relatively good discharge performance, and at the same time, the aging resistance discharge performance has also been significantly improved, and significant progress has been made.

以上通过具体实施例说明了根据本发明的锂电池电极。本领域普通技术人员容易理解，实施本发明的一些细节描述并不局限于上述说明。文中虽然仅提供了针对锂电池电极的实施例，但是，本领域技术人员，在得到本发明的教导后，会很容易想到本发明的精神同样可以应用于其他二次电池，因此，本发明的保护范围并不局限于锂电池电极，而应以权利要求书的限定为准。The lithium battery electrode according to the present invention has been described above through specific examples. Those of ordinary skill in the art can easily understand that some detailed descriptions for implementing the present invention are not limited to the above descriptions. Although the text only provides the embodiment aimed at lithium battery electrodes, those skilled in the art, after obtaining the teaching of the present invention, can easily imagine that the spirit of the present invention can be applied to other secondary batteries as well. Therefore, the present invention The scope of protection is not limited to lithium battery electrodes, but should be defined by the claims.

Claims (10)

1. a kind of nickelic layered cathode material method of modifying, includes the following steps：
(1) nickelic stratiform transition metal oxide material is uniformly mixed with the presoma containing M-O and M-P；
It (2), will be in LiNi by chemical reactionxX1-xO2(x>0.5) M-O the and M-P presoma clads conversion that surface is formed, Surface of active material forms one layer of nanoscale, equally distributed M-O and M-P clads；
(3) clad obtained to step (2) is heat-treated, obtain electrode material surface contain M-O and/or L-M-O and The Anode of lithium cell material of M-P and/or L-M-P.
2. the method as described in claim 1, it is characterised in that presoma clad described in step (1) be using coating or The method of dipping obtains.
3. the method as described in claim 1, it is characterised in that chemical reaction, which refers to, described in step (2) obtains step (1) The nickelic stratiform transition metal oxide material for loading M-O and M-P presoma clads is put into phosphoric acid or soluble phosphate In solution so that precipitation reaction occurs for M-P predecessors, obtains M-P clads；Then it decomposes at high temperature, obtains M-O claddings Layer, the decomposition reaction temperature is 400-600 DEG C.
4. the method as described in claim 1, it is characterised in that heat-treating atmosphere described in step (3) be oxygen, air or It is carried out under person's inert gas atmosphere；The heat treatment temperature refers to 500-750 DEG C, and the heat treatment time is 4-8h；It is described lazy Property gas such as nitrogen, argon gas.
5. the method as described in claim 1, it is characterised in that the presoma of the M-O refers to producing M-O compounds, is contained The presoma for having M element includes the salt containing M and one or more of the organic matter containing M, nitrate, carbon preferably containing M Hydrochlorate, organic acid；The presoma of the M-P refers to producing M-P compounds, and the presoma containing M element specifically includes and contains There are the salt, the acid containing M and one or more of the organic matter containing M of M, the preferably acylate containing M.
6. the method as described in claim 1, it is characterised in that the hybrid mode refers to grinding, ball milling, agitating and heating, rotation Turn one or more of evaporation mode.
7. such as the nickelic layered cathode material of modification prepared by any one of claim 1-6 the methods, including nickelic stratiform transition Metal oxide body phase layer and the compound coating layer being made of M-O and/or L-M-O and M-P and/or L-M-P, the height Nickel layer shape transition metal oxide can use LiNixX1-xO2It indicates, wherein 0.5<x<1, X is Co, one kind in the elements such as Mn, Al or It is several；The M-O compounds refer to the oxide containing M element；The M-P refers to the phosphate containing M element；The L-M-O Compound refers to the oxidate for lithium of M element；The L-M-P refers to the lithium phosphate of M element.
8. positive electrode as claimed in claim 7, it is characterised in that the M element be selected from Mg, Ca, Y, Ti, Zr, V, Nb, Ta, One or several kinds in Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ni, Cu, Zn, B, Al, Ga, Si, Ge, Sn element, preferably V, It is one or more in Mn, Fe, Co, Zr, B.
9. positive electrode as claimed in claim 7, it is characterised in that the nickelic stratiform transition metal oxide positive electrode Preferably LiNi0.6Co0.2Mn0.2O2、LiNi0.7Co0.15Mn0.15O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2、 LiNi0.9Co0.05Mn0.05O2。
10. positive electrode as claimed in claim 7, it is characterised in that the L-M-O refers in the oxidate for lithium containing M element One or more, preferably LiAlO2、Li2TiO3、Li2ZrO3、Li2SiO3、Li2MnO3、Li2MnP2O7、Li3BO3、Li3B7O12、 Li2B4O7、LiNbO2、LiNbO3、Li3NbO4、LiTaO3、Li2MoO4、Li2WO4、LiVO3、Li2SnO3、LiFeO2、Li5FeO4、 Li2WO4；The Li-M-P refers to one or more of the lithium phosphate containing M element, preferably LiCoPO4、Li2MnP2O7、 Li2Fe3(P2O7)2、LiZnPO4、Li3V2(PO4)3、Li2Ti2(PO4)3。
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