WO2024103706A1 - Method for removing residual lithium in high-nickel ternary positive electrode material - Google Patents

Method for removing residual lithium in high-nickel ternary positive electrode material Download PDF

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WO2024103706A1
WO2024103706A1 PCT/CN2023/100358 CN2023100358W WO2024103706A1 WO 2024103706 A1 WO2024103706 A1 WO 2024103706A1 CN 2023100358 W CN2023100358 W CN 2023100358W WO 2024103706 A1 WO2024103706 A1 WO 2024103706A1
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positive electrode
nickel ternary
electrode material
ternary positive
residual lithium
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PCT/CN2023/100358
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French (fr)
Chinese (zh)
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黄宏威
张军
李洪伟
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乳源东阳光新能源材料有限公司
韶关东阳光科技研发有限公司
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Publication of WO2024103706A1 publication Critical patent/WO2024103706A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Lithium-ion ternary cathode materials are one of the most highly regarded cathode materials by current battery manufacturers due to their advantages of high energy density and low manufacturing cost, especially high-nickel ternary cathode materials, which are considered to be one of the best cathode materials for developing low-cost and high-specific energy density lithium-ion batteries.
  • the residual lithium in high-nickel ternary cathode materials is relatively high, which will affect a series of properties of the material.
  • the more common method to reduce the residual lithium in high-nickel ternary positive electrode materials is to wash, dehydrate and then dry the high-nickel ternary positive electrode materials.
  • the washing process will consume a lot of water resources, and the generated waste liquid contains a large amount of impurity ions, mainly Li + , OH - , CO 3 2- , SO 4 2- and some small particles of metal ions, which must be treated to meet the standards before being discharged, resulting in a significant increase in processing costs and waste of materials; in addition, the crystal surface structure of the high-nickel ternary positive electrode material after washing will be damaged to a certain extent, and the moisture inside the crystal is difficult to remove, which will cause the performance of the high-nickel ternary positive electrode material to decline.
  • a washing method for removing residual alkali on the surface of a positive electrode material is prepared by mixing and dispersing a non-protonic non-polar solution with water to obtain a mixed solution, and then adding a ternary material to the mixed solution for washing. Subsequently, the ternary material with the residual alkali on the surface removed is obtained through standing and stratifying, dehydrating, filtering, and drying.
  • the standing and stratifying takes a relatively long time, and a large amount of water resources are consumed and the wastewater generated cannot be treated, resulting in an increase in processing costs.
  • defects will appear on the particle surface of the ternary material and the specific surface area will increase, which will have a negative impact on the ternary material.
  • the invention relates to a method for washing and reducing alkali of ternary materials for lithium-ion batteries that can be recycled.
  • the method comprises the following steps: putting ternary cathode materials and deionized water into a stirring barrel in a certain proportion, stirring and washing, and after preliminary solid-liquid separation, washing the filter cake with a small amount of deionized water, and performing solid-liquid separation again to obtain a powder material; the filtrate after separation enters a circulating storage tank, and an acidic solution is added to adjust the pH value.
  • the obtained filtrate can be used to treat the next batch of ternary cathode materials, and the filtrate can be recycled to treat a certain After the number of times, the filtrate is introduced into the wastewater treatment system, and the lithium in the wastewater is recovered by filtering and evaporating devices.
  • This method adjusts the pH value by adding an acidic solution (including sulfuric acid, phosphoric acid, hydrochloric acid, boric acid, acetic acid, oxalic acid, etc.), which will introduce more heteroanions into the filtrate, such as SO 4 2- , P4O 3 3- , etc., resulting in a high impurity content.
  • the presence of more heteroanions will also affect the dissolution of residual lithium in the ternary material in the recycling process, resulting in poor effect of reducing residual lithium.
  • the primary purpose of the present invention is to overcome the problems of the above-mentioned existing methods of reducing the residual lithium of high-nickel ternary positive electrode materials, such as poor effect, large water consumption and negative impact on the electrical properties of the materials, and provide a method for removing residual lithium from high-nickel ternary positive electrode materials.
  • the removal method does not require the consumption of water resources, reduces the cost of production and manufacturing, and can not only effectively reduce the residual lithium content of high-nickel ternary positive electrode materials, but also improve the electrical properties of high-nickel ternary positive electrode materials.
  • a method for removing residual lithium from a high-nickel ternary positive electrode material comprises the following steps:
  • the high-nickel ternary cathode material is mixed with (NH 4 ) n MF 6 , and reacted for 4 to 8 hours at a temperature of 300 to 500° C. and a pressure of -0.07 to -0.09 MPa, thereby removing the residual lithium in the high-nickel ternary cathode material;
  • the mass ratio of the high nickel ternary positive electrode material to (NH 4 ) n MF 6 is 100:(0.1-0.5);
  • M is Ti, Mg, Sb, Nb, V or Y, and n is 3 or 4.
  • the inventors of the present invention have discovered through multiple studies that mixing a high-nickel ternary positive electrode material with (NH 4 ) n MF 6 and reacting the mixture under specific reaction conditions can effectively remove residual lithium from the high-nickel ternary positive electrode material, and the processing performance of the material is also improved. Moreover, the electrical properties (discharge first efficiency and discharge specific capacity) of the obtained high-nickel ternary positive electrode material are not only not reduced but are improved to a certain extent compared with the high-nickel ternary positive electrode material before removing the residual lithium.
  • (NH 4 ) n MF 6 can react with residual lithium (including lithium carbonate and lithium hydroxide) on the surface of high-nickel ternary positive electrode material particles, and NH 4 + can combine with OH- and CO 3 2- to generate NH 3 ⁇ H 2 O and (NH 4 ) 2 CO 3 , and NH 3 H 2 O and (NH 4 ) 2 CO 3 are further decomposed into NH 3 , CO 2 and H 2 O, thereby achieving effective removal of residual lithium; and MF 6 n- in (NH 4 ) n MF 6 can react with Li + of residual lithium to generate compound Lin MF 6.
  • Lin MF 6 has good conductivity. On the one hand, it can improve the conductivity of the material.
  • the removal method of the present invention does not consume water resources and does not generate wastewater, which not only effectively reduces the production cost of the enterprise, but also complies with the development concept of green environmental protection.
  • the removal method of the present invention does not need to consume water resources, thus reducing the cost of production. It can not only effectively reduce the residual lithium content of the high-nickel ternary positive electrode material, but also improve the electrical properties of the high-nickel ternary positive electrode material.
  • the removal method of the present invention is applicable to high-nickel ternary positive electrode materials commonly used in the art.
  • the high-nickel ternary positive electrode material is LiNi x Co y Mn 1-x-y O 2 or LiNi x Co y Al 1-x-y O 2 , wherein 0.80 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.20.
  • the (NH 4 ) n MF 6 is (NH 4 ) 3 VF 6 , (NH 4 ) 4 MgF 6 , (NH 4 ) 3 SbF 6 , (NH 4 ) 3 NbF 6 , (NH 4 ) 4 TiF 6 , or (NH 4 ) 3 YF 6 .
  • the (NH 4 ) n MF 6 is one or both of (NH 4 ) 3 VF 6 and (NH 4 ) 3 YF 6 .
  • the mixing is carried out in a mixer.
  • the rotation speed of the mixer is 300-500 rpm.
  • the mixing time is 10 to 30 minutes.
  • the reaction is carried out in a coulter dryer.
  • the coulter dryer is connected to a waste treatment device, and the waste treatment device is used to collect the gas generated during the reaction process.
  • the waste treatment device By connecting with the waste treatment device, the NH 3 and CO 2 gases generated during the reaction can be collected and treated to avoid pollution to the environment.
  • the residual lithium is at least one of lithium carbonate or lithium hydroxide.
  • the present invention has the following beneficial effects:
  • the removal method of the present invention does not consume water resources, reduces the cost of production and manufacturing, and can not only effectively reduce the residual lithium content of the high-nickel ternary positive electrode material, but also improve the electrical properties of the high-nickel ternary positive electrode material.
  • FIG1 is a SEM image of the high nickel ternary positive electrode material of Example 1 before removing residual lithium;
  • FIG. 2 is a SEM image of the high-nickel ternary positive electrode material after removing residual lithium in Example 1.
  • This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
  • This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
  • This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
  • This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
  • This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
  • This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material.
  • the removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 4 MgF 6 .
  • This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material.
  • the removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 3 SbF 6 .
  • This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material.
  • the removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 3 NbF 6 .
  • This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material.
  • the removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 4 TiF 6 .
  • This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material.
  • the removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 3 YF 6 .
  • This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material.
  • the removal method is basically the same as that of Embodiment 1, except that LiNi 0.8 Co 0.1 Mn 0.1 O 2 is replaced with an equal amount of LiNi 0.8 Co 0.1 Al 0.1 O 2 .
  • This comparative example provides a method for removing residual lithium from a high-nickel ternary positive electrode material.
  • the removal method is substantially the same as that of Example 1, except that: the amount of (NH 4 ) 3 VF 6 used is 0.05 kg.
  • This comparative example provides a method for removing residual lithium from a high-nickel ternary positive electrode material.
  • the removal method is substantially the same as that of Example 1, except that: the amount of (NH 4 ) 3 VF 6 used is 0.6 kg.
  • This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material.
  • the removal method is basically the same as that of Example 1, except that the temperature is raised to 200° C. and the reaction is carried out at 200° C.
  • This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material.
  • the removal method is basically the same as that of Example 1, except that the temperature is raised to 600° C. and the reaction is carried out at 600° C.
  • This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material.
  • the removal method is basically the same as Example 1, except that the pressure in the plow dryer is -0.06 MPa, and the reaction is carried out under the condition of -0.06 MPa.
  • This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material.
  • the removal method is basically the same as Example 1, except that the pressure in the plow dryer is -0.10 MPa, and the reaction is carried out under the condition of -0.10 MPa.
  • This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material.
  • the removal method is basically the same as that in Example 1, except that the reaction time is 3 hours.
  • This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material.
  • the removal method is basically the same as that in Example 1, except that the reaction time is 9 hours.
  • FIG. 1 is a SEM image of the high-nickel ternary positive electrode material before the residual lithium is removed
  • Figure 2 is a SEM image of the high-nickel ternary positive electrode material after the residual lithium is removed.
  • the surface of the high-nickel ternary positive electrode material particles and the grain boundaries after the residual lithium is removed are filled with Li n MF 6 (Li 3 VF 6 ), which effectively modifies the surface defects of the material particles, thereby effectively improving the electrical properties of the high-nickel ternary positive electrode material.
  • the SEM images of the high-nickel ternary positive electrode materials after the residual lithium is removed from Examples 2 to 11 are similar to those of the high-nickel ternary positive electrode materials after the residual lithium is removed from Example 1.
  • the high nickel ternary cathode material was mixed with the conductive agent carbon black and the binder PVDF in a mass ratio of 90:5:5 to make a slurry, which was then evenly mixed and coated on aluminum foil to make a cathode sheet.
  • a lithium metal sheet was used as the anode
  • Celgard2300 was used as the separator
  • 1 mol/L LiPF 6 /EC:DMC volume ratio 1:1
  • the charge and discharge test selected a voltage of 3.0-4.3V and a current density of 0.2C/0.2C to test the electrical properties of the high nickel ternary cathode material.
  • the high-nickel ternary positive electrode materials before removing residual lithium in Examples 1 to 10 and Comparative Examples 1 to 8 are from the same batch of LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
  • the high-nickel ternary positive electrode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 has a Li 2 CO 3 content of 5061 ppm, a LiOH content of 5516 ppm, a first discharge efficiency of 82.6%, and a discharge specific capacity of 188.7 mAh/g.
  • Li 2 CO 3 content of the high nickel ternary positive electrode material LiNi 0.8 Co 0.1 Al 0.1 O 2 before removing residual lithium in Example 11 The content of lithium ion battery is 5213ppm, the content of LiOH is 5862ppm, the first discharge efficiency is 82.4%, and the discharge specific capacity is 187.6mAh/g.
  • the method for removing residual lithium from high-nickel ternary positive electrode materials of the present invention can effectively remove the residual lithium content in high-nickel ternary positive electrode materials, and can improve the electrical properties of high-nickel ternary positive electrode materials.
  • the Li 2 CO 3 content of the high-nickel ternary positive electrode material treated by the removal method of the present invention can be reduced to below 1851ppm, and the LiOH content can be reduced to below 3231ppm, while the first discharge efficiency can be increased to above 86.3%, and the discharge specific capacity can be increased to above 196.5mAh/g.
  • the reason may be that (NH 4 ) 3 VF 6 will react with the matrix lithium Li+ of the high-nickel ternary positive electrode material, which has a negative impact on the high-nickel ternary positive electrode material; the negative pressure of Example 5 is too small, the generated gases such as carbon dioxide cannot be effectively discharged, and the reaction is not sufficient; the effect on removing residual lithium from the material and improving the electrical performance is limited; the negative pressure of Example 6 is too large, some small particles of ( NH4 ) 3VF6 and small particles of high-nickel ternary positive electrode material will be extracted, the reaction is not sufficient, and the particle size distribution of the high-nickel ternary positive electrode material will be changed to a certain extent, thereby having a poor effect on improving the electrical performance; the reaction time of Example 7 is too short, and the effect on removing residual lithium and improving the electrical performance is relatively poor; the reaction time of Example 8 is too long, and the improvement of the electrical performance is limited.
  • the reason may be that ( NH4 ) 3VF6 will react with

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Abstract

A method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps: mixing a high-nickel ternary positive electrode material with (NH4)nMF6, and reacting for 4-8 hours at a temperature of 300-500°C and a pressure of -0.07 to -0.09 MPa, thereby completing the removal of residual lithium in the high-nickel ternary positive electrode material, wherein the mass ratio of the high-nickel ternary positive electrode material to (NH4)nMF6 is 100: (0.1-0.5), M is Ti, Mg, Sb, Nb, V or Y, and n is 3 or 4. The method does not need to consume water resources, reduces the production cost, can effectively reduce the content of residual lithium in a high-nickel ternary positive electrode material, and can improve the electrical properties of the high-nickel ternary positive electrode material.

Description

一种高镍三元正极材料中残锂的去除方法A method for removing residual lithium from high-nickel ternary positive electrode material 技术领域Technical Field
本发明涉及锂离子电池技术领域，更具体地，涉及一种高镍三元正极材料中残锂的去除方法。The present invention relates to the technical field of lithium-ion batteries, and more specifically, to a method for removing residual lithium in a high-nickel ternary positive electrode material.
背景技术Background technique
锂离子三元正极材料由于其具有能量密度高，制造成本低的优势，是当下电池厂家最为推崇的正极材料之一，尤其是高镍三元正极材料，被认为是开发低成本高比能量密度锂离子电池的最佳正极材料之一。但高镍三元正极材料中残锂较高，会影响到材料的一系列性能，尤其是在制浆涂布过程中过多的残锂会加速吸水并与粘结剂及溶剂发生反应形成果冻状的凝胶，影响材料的加工性能；另外，残锂加速电解液分解，降低界面稳定性，导致材料的电性能变差；在高温高压条件下，残锂分解产出二氧化碳会使得电池容易出现胀气、***等不安全问题。这些问题极大限制了高镍三元正极材料的实际应用。Lithium-ion ternary cathode materials are one of the most highly regarded cathode materials by current battery manufacturers due to their advantages of high energy density and low manufacturing cost, especially high-nickel ternary cathode materials, which are considered to be one of the best cathode materials for developing low-cost and high-specific energy density lithium-ion batteries. However, the residual lithium in high-nickel ternary cathode materials is relatively high, which will affect a series of properties of the material. In particular, excessive residual lithium in the pulping and coating process will accelerate water absorption and react with the binder and solvent to form a jelly-like gel, affecting the processing performance of the material; in addition, residual lithium accelerates the decomposition of the electrolyte, reduces the interface stability, and causes the electrical properties of the material to deteriorate; under high temperature and high pressure conditions, the decomposition of residual lithium produces carbon dioxide, which makes the battery prone to unsafe problems such as flatulence and explosion. These problems have greatly limited the practical application of high-nickel ternary cathode materials.
目前，比较普遍的降低高镍三元正极材料残锂的方法是对高镍三元正极材料进行水洗、脱水再干燥，水洗工艺将消耗大量水资源，而且产生的废液中含大量杂质离子，主要为Li+、OH-、CO3 2-、SO4 2-以及一些小颗粒金属离子等，必须经过处理达标后才能排放，造成加工成本的明显上升以及材料的浪费；此外，经过水洗后的高镍三元正极材料，其晶体表面结构会受到一定破坏，且晶体内部的水分比较难清除，这都会造成高镍三元正极材料性能的下降。比如名称为一种去除正极材料表面残碱的洗涤方法通过将非质子非极性溶液与水混合分散均匀得到混合液，再将三元材料加入到混合液中进行洗涤，随后经静置分层、除水、过滤、干燥得到去除表面残碱的三元材料，其中静置分层需要比较长的时间，且需要消耗的大量水资源以及产生的废水未能需要处理，造成加工成本上升；此外，除去残锂后，三元材料的颗粒表面会出现缺陷，比表也会增大，从而给三元材料的负面影响。At present, the more common method to reduce the residual lithium in high-nickel ternary positive electrode materials is to wash, dehydrate and then dry the high-nickel ternary positive electrode materials. The washing process will consume a lot of water resources, and the generated waste liquid contains a large amount of impurity ions, mainly Li + , OH - , CO 3 2- , SO 4 2- and some small particles of metal ions, which must be treated to meet the standards before being discharged, resulting in a significant increase in processing costs and waste of materials; in addition, the crystal surface structure of the high-nickel ternary positive electrode material after washing will be damaged to a certain extent, and the moisture inside the crystal is difficult to remove, which will cause the performance of the high-nickel ternary positive electrode material to decline. For example, a washing method for removing residual alkali on the surface of a positive electrode material is prepared by mixing and dispersing a non-protonic non-polar solution with water to obtain a mixed solution, and then adding a ternary material to the mixed solution for washing. Subsequently, the ternary material with the residual alkali on the surface removed is obtained through standing and stratifying, dehydrating, filtering, and drying. The standing and stratifying takes a relatively long time, and a large amount of water resources are consumed and the wastewater generated cannot be treated, resulting in an increase in processing costs. In addition, after removing the residual lithium, defects will appear on the particle surface of the ternary material and the specific surface area will increase, which will have a negative impact on the ternary material.
名称为一种锂离子电池三元材料可循环的水洗降碱方法通过将三元正极材料与去离子水按一定比例投入搅拌桶，进行搅拌洗涤，初步固液分离后，用少量去离子水冲洗滤饼，再次固液分离得到粉体材料；分离后的滤液进入循环储罐，加入酸性溶液调节pH值，所得滤液可处理下一批三元正极材料，循环处理一定 次数后，将滤液导入废水处理***，通过过滤、蒸发装置回收废水中的锂。该方法通过加入酸性溶液(包括硫酸、磷酸、盐酸、硼酸、乙酸、草酸等)来调节pH值，会使滤液中引入了比较多的杂阴离子，如SO4 2-、P4O3 3-等，从而导致杂质含量偏高，同时比较多的杂阴离子存在也会影响循环使用中三元材料中的残锂溶于水中，导致降低残锂的效果不佳。The invention relates to a method for washing and reducing alkali of ternary materials for lithium-ion batteries that can be recycled. The method comprises the following steps: putting ternary cathode materials and deionized water into a stirring barrel in a certain proportion, stirring and washing, and after preliminary solid-liquid separation, washing the filter cake with a small amount of deionized water, and performing solid-liquid separation again to obtain a powder material; the filtrate after separation enters a circulating storage tank, and an acidic solution is added to adjust the pH value. The obtained filtrate can be used to treat the next batch of ternary cathode materials, and the filtrate can be recycled to treat a certain After the number of times, the filtrate is introduced into the wastewater treatment system, and the lithium in the wastewater is recovered by filtering and evaporating devices. This method adjusts the pH value by adding an acidic solution (including sulfuric acid, phosphoric acid, hydrochloric acid, boric acid, acetic acid, oxalic acid, etc.), which will introduce more heteroanions into the filtrate, such as SO 4 2- , P4O 3 3- , etc., resulting in a high impurity content. At the same time, the presence of more heteroanions will also affect the dissolution of residual lithium in the ternary material in the recycling process, resulting in poor effect of reducing residual lithium.
因此，需解决现有方法降低高镍三元正极材料的残锂的效果不佳、耗水量大以及对材料的电性能有负面影响的问题。Therefore, it is necessary to solve the problems that the existing methods are not effective in reducing the residual lithium of high-nickel ternary positive electrode materials, consume a lot of water, and have a negative impact on the electrical properties of the materials.
发明内容Summary of the invention
本发明的首要目的是克服上述现有现有方法降低高镍三元正极材料的残锂的效果不佳、耗水量大以及对材料的电性能有负面影响的问题，提供一种高镍三元正极材料中残锂的去除方法。该去除方法不需消耗水资源，降低了生产制造的成本，其不仅可以有效降低高镍三元正极材料的残锂含量，而且还能提升高镍三元正极材料的电性能。The primary purpose of the present invention is to overcome the problems of the above-mentioned existing methods of reducing the residual lithium of high-nickel ternary positive electrode materials, such as poor effect, large water consumption and negative impact on the electrical properties of the materials, and provide a method for removing residual lithium from high-nickel ternary positive electrode materials. The removal method does not require the consumption of water resources, reduces the cost of production and manufacturing, and can not only effectively reduce the residual lithium content of high-nickel ternary positive electrode materials, but also improve the electrical properties of high-nickel ternary positive electrode materials.
本发明的上述目的通过以下技术方案实现：The above-mentioned object of the present invention is achieved by the following technical solutions:
一种高镍三元正极材料中残锂的去除方法，包括如下步骤：A method for removing residual lithium from a high-nickel ternary positive electrode material comprises the following steps:
将高镍三元正极材料与(NH4)nMF6混合，在温度为300～500℃以及压强为-0.07～-0.09MPa的条件下反应4～8小时，即完成高镍三元正极材料中残锂的去除；The high-nickel ternary cathode material is mixed with (NH 4 ) n MF 6 , and reacted for 4 to 8 hours at a temperature of 300 to 500° C. and a pressure of -0.07 to -0.09 MPa, thereby removing the residual lithium in the high-nickel ternary cathode material;
所述高镍三元正极材料与(NH4)nMF6的质量比为100：(0.1～0.5)；The mass ratio of the high nickel ternary positive electrode material to (NH 4 ) n MF 6 is 100:(0.1-0.5);
其中，M为Ti、Mg、Sb、Nb、V或Y，n为3或4。Wherein, M is Ti, Mg, Sb, Nb, V or Y, and n is 3 or 4.
本发明的发明人通过多次研究发现，将高镍三元正极材料与(NH4)nMF6混合并在特定的反应条件下进行反应，可以有效去除高镍三元正极材料中的残锂，材料的加工性能也得到提高，且得到高镍三元正极材料的电性能(放电首效和放电比容量)相对去除残锂前的高镍三元正极材料不仅没有降低，而且有一定程度的提升。其原因是：在特定的温度和压强下，(NH4)nMF6可与高镍三元正极材料颗粒表面的残锂(包括碳酸锂和氢氧化锂)发生反应，NH4 +可与OH-和CO3 2-结合生成NH3·H2O和(NH4)2CO3，而NH3H2O和(NH4)2CO3再进一步分解为NH3、CO2和H2O，从而实现残锂的有效去除；而(NH4)nMF6中的MF6 n-能与残锂的Li+反应生成化合物LinMF6,LinMF6具有良好的导电性，一方面可以提高材料的导电性，另一方面其生成之后可填充在高镍三元正极材料的晶界间以及颗粒的表面， 对高镍三元正极材料的颗粒表面缺陷进行有效修饰，从而提升高镍三元正极材料的电性能。The inventors of the present invention have discovered through multiple studies that mixing a high-nickel ternary positive electrode material with (NH 4 ) n MF 6 and reacting the mixture under specific reaction conditions can effectively remove residual lithium from the high-nickel ternary positive electrode material, and the processing performance of the material is also improved. Moreover, the electrical properties (discharge first efficiency and discharge specific capacity) of the obtained high-nickel ternary positive electrode material are not only not reduced but are improved to a certain extent compared with the high-nickel ternary positive electrode material before removing the residual lithium. The reason is: under specific temperature and pressure, (NH 4 ) n MF 6 can react with residual lithium (including lithium carbonate and lithium hydroxide) on the surface of high-nickel ternary positive electrode material particles, and NH 4 + can combine with OH- and CO 3 2- to generate NH 3 ·H 2 O and (NH 4 ) 2 CO 3 , and NH 3 H 2 O and (NH 4 ) 2 CO 3 are further decomposed into NH 3 , CO 2 and H 2 O, thereby achieving effective removal of residual lithium; and MF 6 n- in (NH 4 ) n MF 6 can react with Li + of residual lithium to generate compound Lin MF 6. Lin MF 6 has good conductivity. On the one hand, it can improve the conductivity of the material. On the other hand, after it is generated, it can be filled in the grain boundaries of high-nickel ternary positive electrode materials and the surface of particles. The particle surface defects of high-nickel ternary positive electrode materials are effectively modified, thereby improving the electrical properties of high-nickel ternary positive electrode materials.
此外，本发明的去除方法不需消耗水资源，不会产生废水，不仅有效降低了企业的生产成本，而且符合绿色环保的发展理念。In addition, the removal method of the present invention does not consume water resources and does not generate wastewater, which not only effectively reduces the production cost of the enterprise, but also complies with the development concept of green environmental protection.
即本发明的去除方法不需消耗水资源，降低了生产制造的成本，其不仅可以有效降低高镍三元正极材料的残锂含量，而且还能提升高镍三元正极材料的电性能。That is, the removal method of the present invention does not need to consume water resources, thus reducing the cost of production. It can not only effectively reduce the residual lithium content of the high-nickel ternary positive electrode material, but also improve the electrical properties of the high-nickel ternary positive electrode material.
本发明的去除方法适用于本领域常用的高镍三元正极材料。The removal method of the present invention is applicable to high-nickel ternary positive electrode materials commonly used in the art.
优选地，所述高镍三元正极材料为LiNixCoyMn1-x-yO2或LiNixCoyAl1-x-yO2，其中0.80≤x＜1，0＜y≤0.20。Preferably, the high-nickel ternary positive electrode material is LiNi x Co y Mn 1-x-y O 2 or LiNi x Co y Al 1-x-y O 2 , wherein 0.80≤x＜1, 0＜y≤0.20.
优选地，所述(NH4)nMF6为(NH4)3VF6、(NH4)4MgF6、(NH4)3SbF6、(NH4)3NbF6、(NH4)4TiF6、或(NH4)3YF6。Preferably, the (NH 4 ) n MF 6 is (NH 4 ) 3 VF 6 , (NH 4 ) 4 MgF 6 , (NH 4 ) 3 SbF 6 , (NH 4 ) 3 NbF 6 , (NH 4 ) 4 TiF 6 , or (NH 4 ) 3 YF 6 .
更为优选地，所述(NH4)nMF6为(NH4)3VF6或(NH4)3YF6中的一种或两种。More preferably, the (NH 4 ) n MF 6 is one or both of (NH 4 ) 3 VF 6 and (NH 4 ) 3 YF 6 .
优选地，所述混合在混料机中进行。Preferably, the mixing is carried out in a mixer.
更为优选地，所述混料机的转速为300～500转/分钟。More preferably, the rotation speed of the mixer is 300-500 rpm.
优选地，所述混合的时间为10～30min。Preferably, the mixing time is 10 to 30 minutes.
优选地，所述反应在犁刀干燥机中进行。Preferably, the reaction is carried out in a coulter dryer.
更为优选地，所述犁刀干燥机与废弃处理装置连通，所述废弃处理装置用于收集反应过程中产生的气体。More preferably, the coulter dryer is connected to a waste treatment device, and the waste treatment device is used to collect the gas generated during the reaction process.
通过与废弃处理装置连通，可以将反应过程中产生的NH3、CO2气体进行收集处理，避免对环境产生污染。By connecting with the waste treatment device, the NH 3 and CO 2 gases generated during the reaction can be collected and treated to avoid pollution to the environment.
优选地，所述残锂为碳酸锂或氢氧化锂中的至少一种。Preferably, the residual lithium is at least one of lithium carbonate or lithium hydroxide.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the present invention has the following beneficial effects:
本发明的去除方法不需消耗水资源，降低了生产制造的成本，其不仅可以有效降低高镍三元正极材料的残锂含量，而且还能提升高镍三元正极材料的电性能。The removal method of the present invention does not consume water resources, reduces the cost of production and manufacturing, and can not only effectively reduce the residual lithium content of the high-nickel ternary positive electrode material, but also improve the electrical properties of the high-nickel ternary positive electrode material.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1的去除残锂前的高镍三元正极材料的SEM图；FIG1 is a SEM image of the high nickel ternary positive electrode material of Example 1 before removing residual lithium;
图2为实施例1的去除残锂后的高镍三元正极材料的SEM图。 FIG. 2 is a SEM image of the high-nickel ternary positive electrode material after removing residual lithium in Example 1.
具体实施方式Detailed ways
为了更清楚、完整的描述本发明的技术方案，以下通过具体实施例进一步详细说明本发明，应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明，可以在本发明权利限定的范围内进行各种改变。In order to more clearly and completely describe the technical solution of the present invention, the present invention is further described in detail through specific embodiments below. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention. Various changes can be made within the scope of the rights of the present invention.
实施例1Example 1
本实施例提供一种高镍三元正极材料中残锂的去除方法，包括如下步骤：This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
将100kg高镍三元正极材料LiNi0.8Co0.1Mn0.1O2和0.3kg(NH4)3VF6加入到混料机内，在400转/分的转速下混合20分钟，得混合料。然后将混合料投入犁刀干燥机内，再升温至400℃，并对犁刀干燥机抽负压使得犁刀干燥机内的压强为-0.08MPa，在400℃和-0.08MPa的条件下反应6小时，即完成高镍三元正极材料中残锂的去除。犁刀干燥机与废气处理装置以实现对反应过程中产生的气体的收集处理。100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 and 0.3kg (NH 4 ) 3 VF 6 were added to the mixer and mixed at a speed of 400 rpm for 20 minutes to obtain a mixture. The mixture was then put into a coulter dryer, heated to 400°C, and negative pressure was drawn to the coulter dryer so that the pressure inside the coulter dryer was -0.08MPa. The reaction was carried out at 400°C and -0.08MPa for 6 hours to complete the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the exhaust gas treatment device are used to collect and treat the gas generated during the reaction.
实施例2Example 2
本实施例提供一种高镍三元正极材料中残锂的去除方法，包括如下步骤：This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
将100kg高镍三元正极材料LiNi0.8Co0.1Mn0.1O2和0.1kg(NH4)3VF6加入到混料机内，在400转/分的转速下混合20分钟，得混合料。然后将混合料投入犁刀干燥机内，再升温至400℃，并对犁刀干燥机抽负压使得犁刀干燥机内的压强为-0.08MPa，在400℃和-0.08MPa的条件下反应6小时，即完成高镍三元正极材料中残锂的去除。犁刀干燥机与废气处理装置以实现对反应过程中产生的气体的收集处理。100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 and 0.1kg (NH 4 ) 3 VF 6 were added to the mixer and mixed at 400 rpm for 20 minutes to obtain a mixture. The mixture was then put into a coulter dryer, heated to 400°C, and negative pressure was drawn to the coulter dryer so that the pressure inside the coulter dryer was -0.08MPa. The reaction was carried out at 400°C and -0.08MPa for 6 hours to complete the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the exhaust gas treatment device are used to collect and treat the gas generated during the reaction.
实施例3Example 3
本实施例提供一种高镍三元正极材料中残锂的去除方法，包括如下步骤：This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
将100kg高镍三元正极材料LiNi0.8Co0.1Mn0.1O2和0.5kg(NH4)3VF6加入到混料机内，在400转/分的转速下混合20分钟，得混合料。然后将混合料投入犁刀干燥机内，再升温至400℃，并对犁刀干燥机抽负压使得犁刀干燥机内的压强为-0.08MPa，在400℃和-0.08MPa的条件下反应6小时，即完成高镍三元正极材料中残锂的去除。犁刀干燥机与废气处理装置以实现对反应过程中产生的气体的收集处理。 100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 and 0.5kg (NH 4 ) 3 VF 6 were added to the mixer and mixed at a speed of 400 rpm for 20 minutes to obtain a mixture. The mixture was then put into a coulter dryer, heated to 400°C, and negative pressure was drawn to the coulter dryer so that the pressure inside the coulter dryer was -0.08MPa. The reaction was carried out at 400°C and -0.08MPa for 6 hours to complete the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the exhaust gas treatment device are used to collect and treat the gas generated during the reaction.
实施例4Example 4
本实施例提供一种高镍三元正极材料中残锂的去除方法，包括如下步骤：This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
将100kg高镍三元正极材料LiNi0.8Co0.1Mn0.1O2和0.1kg(NH4)3VF6加入到混料机内，在400转/分的转速下混合20分钟，得混合料。然后将混合料投入犁刀干燥机内，再升温至300℃，并对犁刀干燥机抽负压使得犁刀干燥机内的压强为-0.07MPa，在300℃和-0.07MPa的条件下反应4小时，即完成高镍三元正极材料中残锂的去除。犁刀干燥机与废气处理装置以实现对反应过程中产生的气体的收集处理。100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 and 0.1kg (NH 4 ) 3 VF 6 were added to the mixer and mixed at a speed of 400 rpm for 20 minutes to obtain a mixture. The mixture was then put into a coulter dryer, heated to 300°C, and negative pressure was drawn to the coulter dryer so that the pressure inside the coulter dryer was -0.07MPa. The reaction was carried out at 300°C and -0.07MPa for 4 hours to complete the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the exhaust gas treatment device are used to collect and treat the gas generated during the reaction.
实施例5Example 5
本实施例提供一种高镍三元正极材料中残锂的去除方法，包括如下步骤：This embodiment provides a method for removing residual lithium in a high-nickel ternary positive electrode material, comprising the following steps:
将100kg高镍三元正极材料LiNi0.8Co0.1Mn0.1O2和0.1kg(NH4)3VF6加入到混料机内，在400转/分的转速下混合20分钟，得混合料。然后将混合料投入犁刀干燥机内，再升温至500℃，并对犁刀干燥机抽负压使得犁刀干燥机内的压强为-0.09MPa，在500℃和-0.09MPa的条件下反应8小时，即完成高镍三元正极材料中残锂的去除。犁刀干燥机与废气处理装置以实现对反应过程中产生的气体的收集处理理。100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 and 0.1kg (NH 4 ) 3 VF 6 were added to the mixer and mixed at a speed of 400 rpm for 20 minutes to obtain a mixture. The mixture was then put into a coulter dryer, heated to 500°C, and negative pressure was drawn to the coulter dryer so that the pressure inside the coulter dryer was -0.09MPa. The reaction was carried out at 500°C and -0.09MPa for 8 hours to complete the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the exhaust gas treatment device are used to collect and treat the gas generated during the reaction.
实施例6Example 6
本实施例提供一种高镍三元正极材料中残锂的去除方法，该去除方法与实施例1基本相同，不同之处在于：将(NH4)3VF6替换成同等用量的(NH4)4MgF6。This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material. The removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 4 MgF 6 .
实施例7Example 7
本实施例提供一种高镍三元正极材料中残锂的去除方法，该去除方法与实施例1基本相同，不同之处在于：将(NH4)3VF6替换成同等用量的(NH4)3SbF6、。This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material. The removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 3 SbF 6 .
实施例8Example 8
本实施例提供一种高镍三元正极材料中残锂的去除方法，该去除方法与实施例1基本相同，不同之处在于：将(NH4)3VF6替换成同等用量的(NH4)3NbF6、。This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material. The removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 3 NbF 6 .
实施例9Example 9
本实施例提供一种高镍三元正极材料中残锂的去除方法，该去除方法与实施例1基本相同，不同之处在于：将(NH4)3VF6替换成同等用量的(NH4)4TiF6。 This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material. The removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 4 TiF 6 .
实施例10Example 10
本实施例提供一种高镍三元正极材料中残锂的去除方法，该去除方法与实施例1基本相同，不同之处在于：将(NH4)3VF6替换成同等用量的(NH4)3YF6。This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material. The removal method is substantially the same as that of Embodiment 1, except that (NH 4 ) 3 VF 6 is replaced with an equal amount of (NH 4 ) 3 YF 6 .
实施例11Embodiment 11
本实施例提供一种高镍三元正极材料中残锂的去除方法，该去除方法与实施例1基本相同，不同之处在于：将LiNi0.8Co0.1Mn0.1O2替换成同等用量的LiNi0.8Co0.1Al0.1O2。This embodiment provides a method for removing residual lithium from a high-nickel ternary positive electrode material. The removal method is basically the same as that of Embodiment 1, except that LiNi 0.8 Co 0.1 Mn 0.1 O 2 is replaced with an equal amount of LiNi 0.8 Co 0.1 Al 0.1 O 2 .
对比例1Comparative Example 1
本对比例提供一种高镍三元正极材料中残锂的去除方法，该去除方法与实施例1基本相同，不同之处在于：(NH4)3VF6的用量为0.05kg。This comparative example provides a method for removing residual lithium from a high-nickel ternary positive electrode material. The removal method is substantially the same as that of Example 1, except that: the amount of (NH 4 ) 3 VF 6 used is 0.05 kg.
对比例2Comparative Example 2
本对比例提供一种高镍三元正极材料中残锂的去除方法，该去除方法与实施例1基本相同，不同之处在于：(NH4)3VF6的用量为0.6kg。This comparative example provides a method for removing residual lithium from a high-nickel ternary positive electrode material. The removal method is substantially the same as that of Example 1, except that: the amount of (NH 4 ) 3 VF 6 used is 0.6 kg.
对比例3Comparative Example 3
本对比例提供一种高镍三元正极材料中残锂的去除方法，该去除方法的与实施例1基本相同，不同之处在于：升温至200℃，在200℃的条件下反应。This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material. The removal method is basically the same as that of Example 1, except that the temperature is raised to 200° C. and the reaction is carried out at 200° C.
对比例4Comparative Example 4
本对比例提供一种高镍三元正极材料中残锂的去除方法，该去除方法的与实施例1基本相同，不同之处在于：升温至600℃，在600℃的条件下反应。This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material. The removal method is basically the same as that of Example 1, except that the temperature is raised to 600° C. and the reaction is carried out at 600° C.
对比例5Comparative Example 5
本对比例提供一种高镍三元正极材料中残锂的去除方法，该去除方法的与实施例1基本相同，不同之处在于：犁刀干燥机内的压强为-0.06MPa，在-0.06MPa的条件下反应。This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material. The removal method is basically the same as Example 1, except that the pressure in the plow dryer is -0.06 MPa, and the reaction is carried out under the condition of -0.06 MPa.
对比例6Comparative Example 6
本对比例提供一种高镍三元正极材料中残锂的去除方法，该去除方法的与实施例1基本相同，不同之处在于：犁刀干燥机内的压强为-0.10MPa，在-0.10MPa的条件下反应。 This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material. The removal method is basically the same as Example 1, except that the pressure in the plow dryer is -0.10 MPa, and the reaction is carried out under the condition of -0.10 MPa.
对比例7Comparative Example 7
本对比例提供一种高镍三元正极材料中残锂的去除方法，该去除方法的与实施例1基本相同，不同之处在于：反应的时间为3小时。This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material. The removal method is basically the same as that in Example 1, except that the reaction time is 3 hours.
对比例8Comparative Example 8
本对比例提供一种高镍三元正极材料中残锂的去除方法，该去除方法的与实施例1基本相同，不同之处在于：反应的时间为9小时。This comparative example provides a method for removing residual lithium in a high-nickel ternary positive electrode material. The removal method is basically the same as that in Example 1, except that the reaction time is 9 hours.
性能测试Performance Testing
取实施例1去除残锂前后的高镍三元正极材料，分别进行SEM电镜扫描，结果如图1和图2所示，图1为去除残锂前的高镍三元正极材料的SEM图，图2为去除残锂后的高镍三元正极材料的SEM图。从图2可知，去除残锂后的高镍三元正极材料颗粒表面及晶界间填充着LinMF6(Li3VF6)，有效的对材料的颗粒的表面缺陷进行修饰，从而有效的高镍三元正极材料的电性能。实施例2～11去除残锂后的高镍三元正极材料的SEM图与实施例1去除残锂后的高镍三元正极材料的相似。The high-nickel ternary positive electrode material before and after the residual lithium is removed from Example 1 was taken, and SEM electron microscope scanning was performed respectively. The results are shown in Figures 1 and 2. Figure 1 is a SEM image of the high-nickel ternary positive electrode material before the residual lithium is removed, and Figure 2 is a SEM image of the high-nickel ternary positive electrode material after the residual lithium is removed. As can be seen from Figure 2, the surface of the high-nickel ternary positive electrode material particles and the grain boundaries after the residual lithium is removed are filled with Li n MF 6 (Li 3 VF 6 ), which effectively modifies the surface defects of the material particles, thereby effectively improving the electrical properties of the high-nickel ternary positive electrode material. The SEM images of the high-nickel ternary positive electrode materials after the residual lithium is removed from Examples 2 to 11 are similar to those of the high-nickel ternary positive electrode materials after the residual lithium is removed from Example 1.
对去除残锂前的高镍三元正极材料和各实施例和对比例的去除残锂后的高镍三元正极材料的残锂(Li2CO3和LiOH)含量、以及材料制备成的扣式电池的放电首效和放电比容量进行测定。其中：The residual lithium (Li 2 CO 3 and LiOH) content of the high nickel ternary positive electrode material before removing the residual lithium and the high nickel ternary positive electrode material after removing the residual lithium in each embodiment and comparative example, as well as the discharge first efficiency and discharge specific capacity of the button battery prepared from the material were measured.
1、使用盐酸标液，利用电位滴定法测试高镍三元正极材料的残锂。1. Use hydrochloric acid standard solution to test the residual lithium of high-nickel ternary positive electrode material by potentiometric titration.
2、高镍三元正极材料制备成的扣式电池的方法如下：2. The method for preparing button batteries from high-nickel ternary positive electrode materials is as follows:
将高镍三元正极材料与导电剂炭黑、粘结剂PVDF质量比为90:5:5，制成浆混合均匀后涂于铝箔上制成正极片，在手套箱中以金属锂片为负极，以Celgard2300为隔膜，1mol/L LiPF6/EC:DMC(体积比1:1)为电解液组装成2016型扣式电池。充放电测试选取电压为3.0-4.3V，电流密度为0.2C/0.2C测试高镍三元正极材料的电性能。The high nickel ternary cathode material was mixed with the conductive agent carbon black and the binder PVDF in a mass ratio of 90:5:5 to make a slurry, which was then evenly mixed and coated on aluminum foil to make a cathode sheet. In a glove box, a lithium metal sheet was used as the anode, Celgard2300 was used as the separator, and 1 mol/L LiPF 6 /EC:DMC (volume ratio 1:1) was used as the electrolyte to assemble a 2016-type button cell. The charge and discharge test selected a voltage of 3.0-4.3V and a current density of 0.2C/0.2C to test the electrical properties of the high nickel ternary cathode material.
其中，实施例1～10、对比例1～8的去除残锂前的高镍三元正极材料为同一批LiNi0.8Co0.1Mn0.1O2，在去除残锂前，该高镍三元正极材料LiNi0.8Co0.1Mn0.1O2的Li2CO3含量为5061ppm、LiOH含量为5516ppm、放电首效为82.6％、放电比容量为188.7mAh/g。Among them, the high-nickel ternary positive electrode materials before removing residual lithium in Examples 1 to 10 and Comparative Examples 1 to 8 are from the same batch of LiNi 0.8 Co 0.1 Mn 0.1 O 2 . Before removing residual lithium, the high-nickel ternary positive electrode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 has a Li 2 CO 3 content of 5061 ppm, a LiOH content of 5516 ppm, a first discharge efficiency of 82.6%, and a discharge specific capacity of 188.7 mAh/g.
实施例11的去除残锂前的高镍三元正极材料LiNi0.8Co0.1Al0.1O2的Li2CO3含 量为5213ppm、LiOH含量为5862ppm、放电首效为82.4％、放电比容量为187.6mAh/g。Li 2 CO 3 content of the high nickel ternary positive electrode material LiNi 0.8 Co 0.1 Al 0.1 O 2 before removing residual lithium in Example 11 The content of lithium ion battery is 5213ppm, the content of LiOH is 5862ppm, the first discharge efficiency is 82.4%, and the discharge specific capacity is 187.6mAh/g.
各实施例和对比例去除残锂后的高镍三元正极材料的残锂含量、以及材料制备成的扣式电池的放电首效和放电比容量的测试结果如表1所示。The residual lithium content of the high-nickel ternary positive electrode materials after removing the residual lithium in each embodiment and comparative example, as well as the test results of the discharge first efficiency and discharge specific capacity of the button batteries prepared from the materials are shown in Table 1.
表1各实施例和对比例去除残锂后的高镍三元正极材料的性能测试结果
Table 1 Performance test results of high nickel ternary positive electrode materials after removing residual lithium in various embodiments and comparative examples
从表1的实施例1～11可知，本发明的高镍三元正极材料中残锂的去除方法可有效去除高镍三元正极材料中残锂含量，且可使高镍三元正极材料的电性能有 所提升。具体地，本发明去除方法处理后的高镍三元正极材料，其Li2CO3含量可降到1851ppm以下，LiOH含量降到3231ppm以下，同时其放电首效可提高到86.3％以上，放电比容量提高到196.5mAh/g以上。It can be seen from Examples 1 to 11 in Table 1 that the method for removing residual lithium from high-nickel ternary positive electrode materials of the present invention can effectively remove the residual lithium content in high-nickel ternary positive electrode materials, and can improve the electrical properties of high-nickel ternary positive electrode materials. Specifically, the Li 2 CO 3 content of the high-nickel ternary positive electrode material treated by the removal method of the present invention can be reduced to below 1851ppm, and the LiOH content can be reduced to below 3231ppm, while the first discharge efficiency can be increased to above 86.3%, and the discharge specific capacity can be increased to above 196.5mAh/g.
对比例1的(NH4)3VF6用量太低，残锂去除效果不好，且因高镍三元正极材料表面还有一定的残锂的存在以及生成的Li3VF6相对较少，材料的电性能提升有限；对比例2的(NH4)3VF6用量太多，虽然对残锂的去除效果较好，但因过多的(NH4)3VF6未参与反应，而(NH4)3VF6的存在对高镍三元正极材料有负面影响，从而使得高镍三元正极材料的电性能提升有限；对比例3的温度太低，反应不够充分，对残锂的去除以及电性能的提升也相对较差；对比例4的温度太高，电性能的提升有限，其原因可能是(NH4)3VF6会与高镍三元正极材料的基体锂Li+发生反应，对高镍三元正极材料产生负面影响；对比例5的负压过小，产生的二氧化碳等气体为能有效排出，反应也不充分；对材料的残锂去除以及电性能提升的效果有限，对比例6的负压过大，部分小颗粒的(NH4)3VF6以及小颗粒的高镍三元正极材料的会被抽走，反应不充分，同时也会在一定程度上改变高镍三元正极材料的粒度分布，从而对电性能改善效果不好；对比例7的反应时间太短，对残锂的去除以及电性能的提升效果也相对较差；对比例8的反应时间太长，电性能的提升有限，其原因可能是(NH4)3VF6会与高镍三元正极材料的基体锂Li+发生反应，对高镍三元正极材料产生负面影响。In comparative example 1, the amount of (NH 4 ) 3 VF 6 is too low, the residual lithium removal effect is not good, and because there is still a certain amount of residual lithium on the surface of the high-nickel ternary positive electrode material and the generated Li 3 VF 6 is relatively small, the electrical performance of the material is limited; in comparative example 2, the amount of (NH 4 ) 3 VF 6 is too much. Although the residual lithium removal effect is good, too much (NH 4 ) 3 VF 6 does not participate in the reaction, and the presence of (NH 4 ) 3 VF 6 has a negative impact on the high-nickel ternary positive electrode material, so that the electrical performance of the high-nickel ternary positive electrode material is limited; the temperature of comparative example 3 is too low, the reaction is not sufficient, and the removal of residual lithium and the improvement of electrical performance are relatively poor; the temperature of comparative example 4 is too high, and the improvement of electrical performance is limited. The reason may be that (NH 4 ) 3 VF 6 will react with the matrix lithium Li+ of the high-nickel ternary positive electrode material, which has a negative impact on the high-nickel ternary positive electrode material; the negative pressure of Example 5 is too small, the generated gases such as carbon dioxide cannot be effectively discharged, and the reaction is not sufficient; the effect on removing residual lithium from the material and improving the electrical performance is limited; the negative pressure of Example 6 is too large, some small particles of ( NH4 ) 3VF6 and small particles of high-nickel ternary positive electrode material will be extracted, the reaction is not sufficient, and the particle size distribution of the high-nickel ternary positive electrode material will be changed to a certain extent, thereby having a poor effect on improving the electrical performance; the reaction time of Example 7 is too short, and the effect on removing residual lithium and improving the electrical performance is relatively poor; the reaction time of Example 8 is too long, and the improvement of the electrical performance is limited. The reason may be that ( NH4 ) 3VF6 will react with the matrix lithium Li + of the high-nickel ternary positive electrode material, which has a negative impact on the high-nickel ternary positive electrode material.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。 Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

  1. 一种高镍三元正极材料中残锂的去除方法，其特征在于，包括如下步骤：A method for removing residual lithium from a high-nickel ternary positive electrode material, characterized in that it comprises the following steps:
    将高镍三元正极材料与(NH4)nMF6混合，在温度为300～500℃以及压强为-0.07～-0.09MPa的条件下反应4～8小时，即完成高镍三元正极材料中残锂的去除；The high-nickel ternary cathode material is mixed with (NH 4 ) n MF 6 , and reacted for 4 to 8 hours at a temperature of 300 to 500° C. and a pressure of -0.07 to -0.09 MPa, thereby removing the residual lithium in the high-nickel ternary cathode material;
    所述高镍三元正极材料与(NH4)nMF6的质量比为100：(0.1～0.5)；The mass ratio of the high nickel ternary positive electrode material to (NH 4 ) n MF 6 is 100:(0.1-0.5);
    其中，M为Ti、Mg、Sb、Nb、V或Y，n为3或4。Wherein, M is Ti, Mg, Sb, Nb, V or Y, and n is 3 or 4.
  2. 根据权利要求1所述去除方法，其特征在于，所述高镍三元正极材料为LiNixCoyMn1-x-yO2或LiNixCoyAl1-x-yO2，其中0.80≤x＜1，0＜y≤0.20。The removal method according to claim 1 is characterized in that the high-nickel ternary positive electrode material is LiNi x Co y Mn 1-xy O 2 or LiNi x Co y Al 1-xy O 2 , wherein 0.80≤x＜1, 0＜y≤0.20.
  3. 根据权利要求1所述去除方法，其特征在于，所述(NH4)nMF6为(NH4)3VF6、(NH4)4MgF6、(NH4)3SbF6、(NH4)3NbF6、(NH4)4TiF6或(NH4)3YF6中的一种或多种。The removal method according to claim 1 is characterized in that the (NH 4 ) n MF 6 is one or more of (NH 4 ) 3 VF 6 , (NH 4 ) 4 MgF 6 , (NH 4 ) 3 SbF 6 , (NH 4 ) 3 NbF 6 , (NH 4 ) 4 TiF 6 or (NH 4 ) 3 YF 6 .
  4. 根据权利要求3所述去除方法，其特征在于，所述(NH4)nMF6为(NH4)3VF6或(NH4)3YF6中的一种或两种。The removal method according to claim 3 is characterized in that the (NH 4 ) n MF 6 is one or both of (NH 4 ) 3 VF 6 and (NH 4 ) 3 YF 6 .
  5. 根据权利要求1所述去除方法，其特征在于，所述混合在混料机中进行。The removal method according to claim 1 is characterized in that the mixing is carried out in a mixer.
  6. 根据权利要求5所述去除方法，其特征在于，所述混料机的转速为300～500转/分钟。The removal method according to claim 5 is characterized in that the rotation speed of the mixer is 300 to 500 rpm.
  7. 根据权利要求1所述去除方法，其特征在于，所述混合的时间为10～30min。The removal method according to claim 1 is characterized in that the mixing time is 10 to 30 minutes.
  8. 根据权利要求1所述去除方法，其特征在于，所述反应在犁刀干燥机中进行。The removal method according to claim 1, characterized in that the reaction is carried out in a coulter dryer.
  9. 根据权利要求8所述去除方法，其特征在于，所述犁刀干燥机与废弃处理装置连通，所述废弃处理装置用于收集反应过程中产生的气体。The removal method according to claim 8 is characterized in that the coulter dryer is connected to a waste treatment device, and the waste treatment device is used to collect the gas generated during the reaction process.
  10. 根据权利要求1所述去除方法，其特征在于，所述残锂为碳酸锂或氢氧化锂中的至少一种。 The removal method according to claim 1 is characterized in that the residual lithium is at least one of lithium carbonate or lithium hydroxide.
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