技术领域technical field
本发明涉及本发明涉及锂离子电池正极材料技术领域，特别是涉及一种锂离子电池富锂锰基正极材料及其喷雾干燥制备方法。The present invention relates to the technical field of positive electrode materials for lithium ion batteries, in particular to a lithium-rich manganese-based positive electrode material for lithium ion batteries and a preparation method thereof by spray drying.
背景技术Background technique
锂离子动力电池因其工作电压高、比能量大、循环性能好、工作温度范围宽、安全无记忆效应等优点在电动汽车上得到广泛使用，随着电动汽车的迅速发展，市场对于高比容量和高能密度的正极材料的需要在不断增长。Lithium-ion power batteries are widely used in electric vehicles due to their high operating voltage, large specific energy, good cycle performance, wide operating temperature range, safety and no memory effect. With the rapid development of electric vehicles, the market for high specific capacity The demand for cathode materials with high energy density is growing.
传统的镍酸锂(LiNiO2)作为动力电池正极材料,虽然具有较高的比容量，但是它的循环性能差，限制了其在市场的发展。可以通过掺杂Co和Mn来改善它的性能，融合LiCoO2、LiNiO2和LiMnO2的优点，掺杂Co可以改善LiNiO2的循环性能，掺入Mn可以改善其热稳定性。因三元镍钴锰酸锂材料继承了钴酸锂、镍酸锂、锰酸锂的优点具有比容量高，平台电压高，振实密度大，晶体结构稳定，制备工艺简单，运行成本低等特点，已成为锂离子电池正极材料的必备选择之一。Although the traditional lithium nickelate (LiNiO2 ) is used as the positive electrode material of the power battery, although it has a high specific capacity, its cycle performance is poor, which limits its development in the market. Its performance can be improved by doping Co and Mn, combining the advantages of LiCoO2 , LiNiO2 and LiMnO2 , doping Co can improve the cycle performance of LiNiO2 , and doping Mn can improve its thermal stability. Because the ternary nickel-cobalt lithium manganese oxide material inherits the advantages of lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide, it has high specific capacity, high platform voltage, high tap density, stable crystal structure, simple preparation process, and low operating cost. It has become one of the necessary choices for lithium-ion battery cathode materials.
合成三元镍钴锰酸锂的主要方法有固相法、溶胶一凝胶法、共沉淀法等，固相法工艺简单、成本低，但镍钴锰不能达到原子级别的均匀混合，导致产品电化学性能差；溶胶—凝胶法合成工艺复杂，成本高，不适合大规模工业化生产；共沉淀法所需的制备周期长，工序繁多，产品电化学性能均一性较差。因此，进一步开发正极材料的制备方法具有非常重要的意义。The main methods for synthesizing ternary nickel-cobalt-manganese oxide include solid-phase method, sol-gel method, co-precipitation method, etc. The solid-phase method has simple process and low cost, but nickel-cobalt-manganese cannot achieve uniform mixing at the atomic level, resulting in product The electrochemical performance is poor; the sol-gel synthesis process is complicated and the cost is high, and it is not suitable for large-scale industrial production; the preparation period required by the co-precipitation method is long, the process is numerous, and the uniformity of the electrochemical performance of the product is poor. Therefore, it is of great significance to further develop the preparation method of cathode materials.
公开号为CN107180950A的中国专利申请，公开了一种锂离子电池三元正极材料NCM、NCA的喷雾干燥法制备方法，采用共沉淀法，固体物料经过砂磨再喷雾干燥的方法制备前驱体，再高温焙烧得到三元正极材料，在制备过程中需要静置陈化并且会产生废水。The Chinese patent application with the publication number CN107180950A discloses a preparation method of a lithium-ion battery ternary positive electrode material NCM and NCA by spray drying method. Co-precipitation method is used to prepare the precursor by sand-milling and spray-drying the solid material, and then The ternary cathode material is obtained by high-temperature calcination, which needs to be aged and waste water will be generated during the preparation process.
发明内容Contents of the invention
针对现有的技术问题，本发明的目的在于提供一种电化学性能好，工艺简单，制备周期短且无污染的喷雾干燥制备富锂锰基正极材料的方法。In view of the existing technical problems, the purpose of the present invention is to provide a method for preparing lithium-rich manganese-based positive electrode materials by spray drying with good electrochemical performance, simple process, short preparation cycle and no pollution.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
一种锂电池富锂锰基正极材料的喷雾干燥制备方法，该富锂锰基正极材料的化学式为Li1.2Ni0.13Co0.13Mn0.54O2，其制备方法包括以下步骤：A method for preparing a lithium-rich manganese-based cathode material by spray drying for a lithium battery. The chemical formula of the lithium-rich manganese-based cathode material is Li1.2 Ni0.13 Co0.13 Mn0.54 O2 , and the preparation method includes the following steps:
(1)将镍盐、钴盐和锰盐按照摩尔比Ni:Co:Mn＝1:1:4溶于200ml纯水制备成金属离子溶度为0.2mol/L的均匀溶液，再按照摩尔比Li:(Ni+Co+Mn)＝1.3～1.6:1加入锂源混合，得到混合溶液；(1) Dissolve nickel salt, cobalt salt and manganese salt in 200ml of pure water according to the molar ratio Ni:Co:Mn=1:1:4 to prepare a uniform solution with a metal ion solubility of 0.2mol/L, and then according to the molar ratio Li:(Ni+Co+Mn)=1.3～1.6:1 add lithium source and mix to obtain mixed solution;
(2)将柠檬酸溶于150ml纯水中搅拌得到1.5mol/L的均匀溶液B；(2) Dissolve citric acid in 150ml pure water and stir to obtain a homogeneous solution B of 1.5mol/L;
(3)将溶解的柠檬酸溶液逐滴加入到步骤(1)中的混合溶液中，该过程中混合溶液处于一直搅拌的状态；(3) The citric acid solution of dissolving is added dropwise in the mixed solution in step (1), and mixed solution is in the state of stirring all the time in this process;
(4)加完柠檬酸后，往一直搅拌的混合溶液中加入25％氨水调节PH值到7～11。(4) After adding citric acid, add 25% ammonia water to the mixed solution that has been stirred to adjust the pH value to 7-11.
(5)在喷雾干燥机上制得前驱体；(5) Precursor is prepared on a spray dryer;
(6)将前驱体在空气环境下在马弗炉中焙烧，制得富锂锰基正极材料。(6) The precursor was roasted in a muffle furnace in an air environment to prepare a lithium-rich manganese-based cathode material.
进一步地，所述镍盐为硝酸镍、硫酸镍、醋酸镍、草酸镍中一种。Further, the nickel salt is one of nickel nitrate, nickel sulfate, nickel acetate, and nickel oxalate.
进一步地，所述钴盐为硝酸钴、硫酸钴、醋酸钴、草酸钴中一种。Further, the cobalt salt is one of cobalt nitrate, cobalt sulfate, cobalt acetate and cobalt oxalate.
进一步地，所述锰盐为硝酸锰、硫酸锰、醋酸锰、草酸锰中一种。Further, the manganese salt is one of manganese nitrate, manganese sulfate, manganese acetate and manganese oxalate.
进一步地，所述锂源为碳酸锂、醋酸锂、氢氧化锂、草酸锂、氟化锂中一种。Further, the lithium source is one of lithium carbonate, lithium acetate, lithium hydroxide, lithium oxalate, and lithium fluoride.
进一步地，喷雾干燥的进料速度为300-1500ml/h，风机频率设定值在40-60Hz，进风温度控制在120-200℃，出风温度控制在20-120℃。Further, the feed rate of spray drying is 300-1500ml/h, the fan frequency is set at 40-60Hz, the inlet air temperature is controlled at 120-200°C, and the outlet air temperature is controlled at 20-120°C.
进一步地，喷雾干燥的进料速度为300-1500ml/h，风机频率设定值在40-60Hz，进风温度控制在120-200℃，出风温度控制在20-120℃。Further, the feed rate of spray drying is 300-1500ml/h, the fan frequency is set at 40-60Hz, the inlet air temperature is controlled at 120-200°C, and the outlet air temperature is controlled at 20-120°C.
进一步地，所述的焙烧是采用两段法焙烧，第一段焙烧温度为400-500℃，焙烧时间为4-12h，将焙烧所得物研磨后进行第二段焙烧，焙烧温度为650-850℃烧结8-24h，线性升温速度1-5℃/min。Further, the calcination is performed in two stages, the first stage calcination temperature is 400-500°C, the calcination time is 4-12h, the roasted product is ground and the second stage calcination is carried out, the calcination temperature is 650-850°C ℃ sintering 8-24h, linear heating rate 1-5 ℃/min.
所述的喷雾干燥制备方法制备的锂离子电池富锂锰基正极材料，其特征在于：该富锂锰基正极材料的化学通式为Li1.2Ni0.13Co0.13Mn0.54O2，所述正极材料的微观组织成枝状颗粒，所述枝状颗粒由椭圆形纳米颗粒攒聚而成。The lithium-rich manganese-based cathode material for lithium ion batteries prepared by the spray-drying preparation method is characterized in that: the general chemical formula of the lithium-rich manganese-based cathode material is Li1.2 Ni0.13 Co0.13 Mn0.54 O2 , and the cathode material The microstructure of the dendritic particles is composed of oval nanoparticles.
与现有技术流行的“先共沉淀法合成镍钴锰氢氧化物前驱体，再与Li化合物混合烧结得到镍钴锰酸锂正极材料”的两步合成法相比，本发明采用喷雾干燥合成法，其进步体现在：Compared with the popular two-step synthesis method of "synthesizing nickel-cobalt-manganese hydroxide precursor by co-precipitation method, and then mixing and sintering with Li compound to obtain nickel-cobalt lithium manganate cathode material", the present invention adopts spray-drying synthesis method , its progress is reflected in:
(1)工艺简单，制备周期短。(1) The process is simple and the preparation period is short.
(2)本产品是在无色无味的柠檬酸体系中合成，是清洁生产工艺。(2) This product is synthesized in a colorless and odorless citric acid system, which is a clean production process.
(3)共沉淀法制备前驱体时会产生氨氮废水，不仅污染环境而且废水处理也增加了生产成本，本发明采用液相法，混合溶液直接喷雾干燥制备前驱体，再经过两段焙烧制备正极材料，无需等待静置而且不会产生废水废料，具有制备时间短，操作简单，清洁环保的优点。(3) Ammonia-nitrogen waste water will be produced when the precursor is prepared by the co-precipitation method, which not only pollutes the environment but also increases the production cost. The present invention adopts the liquid phase method, and the mixed solution is directly sprayed and dried to prepare the precursor, and then the positive electrode is prepared through two stages of roasting The material does not need to wait for standing still and does not generate waste water and waste, and has the advantages of short preparation time, simple operation, cleanliness and environmental protection.
(4)本发明采用喷雾干燥的工艺使得水分迅速蒸发，物料得到充分干燥，得到均一致密的前驱体，制备得到的锂电池富锂锰基正极材料具有优秀的充放电性能和循环性能。(4) The present invention adopts a spray-drying process to rapidly evaporate water, fully dry the material, and obtain a uniform and dense precursor. The prepared lithium-rich manganese-based positive electrode material for lithium batteries has excellent charge-discharge performance and cycle performance.
附图说明Description of drawings
图1为本发明所述锂电池富锂锰基正极材料的喷雾干燥制备方法的流程图。Fig. 1 is a flow chart of the spray-drying preparation method of lithium-rich manganese-based positive electrode materials for lithium batteries according to the present invention.
图2为实施例1喷雾干燥工艺制备的正极材料在1C倍率下放电循环性能和前三周充放电曲线。Figure 2 shows the discharge cycle performance and the charge-discharge curves of the first three weeks of the positive electrode material prepared by the spray drying process in Example 1 at a rate of 1C.
图3中(a)、(b)、(c)为实例1喷雾干燥工艺制备的富锂锰基正极材料的SEM图。(a), (b), and (c) in FIG. 3 are SEM images of the lithium-rich manganese-based cathode material prepared by the spray drying process in Example 1.
图4为实施例2喷雾干燥工艺制备的正极材料在1C倍率下放电循环性能和前三周充放电曲线。Fig. 4 shows the discharge cycle performance and the charge-discharge curves of the first three weeks of the positive electrode material prepared by the spray drying process in Example 2 at a rate of 1C.
图5为实施例3喷雾干燥工艺制备的正极材料在1C倍率下放电循环性能和前三周充放电曲线。Fig. 5 shows the discharge cycle performance and the charge and discharge curves of the first three weeks of the positive electrode material prepared by the spray drying process in Example 3 at a rate of 1C.
图6为实施例4喷雾干燥工艺制备的正极材料在1C倍率下放电循环性能和前三周充放电曲线。Fig. 6 shows the discharge cycle performance and the charge and discharge curves of the first three weeks of the positive electrode material prepared by the spray drying process in Example 4 at a rate of 1C.
具体实施方式Detailed ways
下面结合附图以及具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited thereto.
如图1所示，本发明所述的锂电池富锂锰基正极材料的喷雾干燥制备方法，该富锂锰基正极材料的化学式为Li1.2Ni0.13Co0.13Mn0.54O2，其制备方法包括以下步骤：As shown in Figure 1, the spray-drying preparation method of the lithium-rich manganese-based positive electrode material for lithium batteries according to the present invention, the chemical formula of the lithium-rich manganese-based positive electrode material is Li1.2 Ni0.13 Co0.13 Mn0.54 O2 , and the preparation method includes The following steps:
(1)将镍盐、钴盐和锰盐按照摩尔比Ni:Co:Mn＝1:1:4溶于200ml纯水制备成金属离子溶度为0.2mol/L的均匀溶液，再按照摩尔比Li:(Ni+Co+Mn)＝1.3～1.6:1加入锂源混合，得到混合溶液；(1) Dissolve nickel salt, cobalt salt and manganese salt in 200ml of pure water according to the molar ratio Ni:Co:Mn=1:1:4 to prepare a uniform solution with a metal ion solubility of 0.2mol/L, and then according to the molar ratio Li:(Ni+Co+Mn)=1.3～1.6:1 add lithium source and mix to obtain mixed solution;
(2)将柠檬酸溶于150ml纯水中搅拌得到1.5mol/L的均匀溶液B；(2) Dissolve citric acid in 150ml pure water and stir to obtain a homogeneous solution B of 1.5mol/L;
(3)将溶解的柠檬酸溶液逐滴加入到步骤(1)中的混合溶液中，该过程中混合溶液处于一直搅拌的状态；(3) The citric acid solution of dissolving is added dropwise in the mixed solution in step (1), and mixed solution is in the state of stirring all the time in this process;
(4)加完柠檬酸后，往一直搅拌的混合溶液中加入25％氨水调节PH值到7～11。(4) After adding citric acid, add 25% ammonia water to the mixed solution that has been stirred to adjust the pH value to 7-11.
(5)在喷雾干燥机上制得前驱体；(5) Precursor is prepared on a spray dryer;
(6)将前驱体在空气环境下在马弗炉中焙烧，制得富锂锰基正极材料。(6) The precursor was roasted in a muffle furnace in an air environment to prepare a lithium-rich manganese-based cathode material.
实施例1Example 1
(1)将四水合乙酸镍、四水合乙酸钴和四水合乙酸锰按照摩尔比Ni:Co:Mn＝1:1:4溶于200ml纯水中混合搅拌配制成金属离子溶度为0.2mol/L均匀溶液，再按照摩尔比Li:(Ni+Co+Mn)＝1.5:1加入醋酸锂混合得到混合溶液；同时将柠檬酸溶于150ml纯水中搅拌配制成1.5mol/L均匀溶液；(1) Dissolve nickel acetate tetrahydrate, cobalt acetate tetrahydrate and manganese acetate tetrahydrate in 200ml pure water according to the molar ratio Ni:Co:Mn=1:1:4 and mix and stir to make the metal ion solubility be 0.2mol/ L homogeneous solution, then according to molar ratio Li:(Ni+Co+Mn)=1.5:1, add lithium acetate and mix to obtain mixed solution; Simultaneously citric acid is dissolved in 150ml pure water and stirred to be mixed with 1.5mol/L homogeneous solution;
(2)将溶解的柠檬酸逐滴加入到步骤(1)中的混合溶液中。该过程中步骤(1)中的混合溶液处于一直搅拌的状态；加完柠檬酸后，往一直搅拌的混合溶液中加入25％氨水调节PH值到9。(2) Add the dissolved citric acid dropwise to the mixed solution in step (1). During this process, the mixed solution in step (1) is in the state of constant stirring; after adding citric acid, add 25% ammonia water to the mixed solution that has been stirred to adjust the pH value to 9.
(3)将得到的混合溶液进行喷雾干燥，通过调节进料速度400ml/h、进风温度180℃、风机频率55Hz，制得前驱体；(3) Spray-dry the obtained mixed solution, and prepare the precursor by adjusting the feed rate to 400ml/h, the inlet air temperature to 180°C, and the fan frequency to 55Hz;
(4)将上述前驱体在空气环境下在马弗炉中采用两段法焙烧，制得富锂锰基正极材料。第一段焙烧温度为480℃，焙烧时间为5h，将焙烧所得物研磨后进行第二段焙烧，焙烧温度为850℃，烧结时间为10h，线性升温速度5℃/min。(4) The above precursor was roasted in a muffle furnace in an air environment by a two-stage method to prepare a lithium-rich manganese-based cathode material. The first-stage calcination temperature is 480°C, and the calcination time is 5h. The roasted product is ground and then subjected to the second-stage calcination. The calcination temperature is 850°C, the sintering time is 10h, and the linear heating rate is 5°C/min.
图2是喷雾干燥制备的富锂锰基正极材料在1C倍率下放电循环比容量曲线和前三周充放电曲线，经过120周循环后，放电比容量保持在260mAh/g左右，充放电效率保持在100左右，说明该材料具有较好的循环稳定性和充放电性能。图3是制备出的正极材料的SEM图，可以看出该材料是颗粒粒径大小为1μm的枝状颗粒，该枝状颗粒由100nm大小且均匀分布的椭圆纳米颗粒攒聚而成。Figure 2 is the discharge cycle specific capacity curve and the first three-week charge-discharge curve of the lithium-rich manganese-based cathode material prepared by spray drying at a rate of 1C. After 120 cycles, the discharge specific capacity remains at about 260mAh/g, and the charge-discharge efficiency maintains It is around 100, indicating that the material has good cycle stability and charge-discharge performance. Fig. 3 is an SEM image of the prepared positive electrode material. It can be seen that the material is a dendritic particle with a particle size of 1 μm, and the dendritic particle is composed of elliptical nanoparticles with a size of 100 nm and uniform distribution.
实施例2Example 2
(1)将硝酸镍、硝酸钴和硝酸锰按照摩尔比Ni:Co:Mn＝1:1:4溶于200ml纯水中混合搅拌配制成金属离子溶度为0.2mol/L均匀溶液，再按照摩尔比Li:(Ni+Co+Mn)＝1.3:1加入碳酸锂混合；同时将柠檬酸溶于150ml纯水中搅拌配制成1.5mol/L均匀溶液；(1) Dissolve nickel nitrate, cobalt nitrate and manganese nitrate in 200ml pure water according to the molar ratio Ni:Co:Mn=1:1:4 and mix and stir to make metal ion solubility be 0.2mol/L homogeneous solution, then according to Molar ratio Li:(Ni+Co+Mn)=1.3:1 Add lithium carbonate and mix; simultaneously dissolve citric acid in 150ml pure water and stir to prepare a 1.5mol/L homogeneous solution;
(2)将溶解的柠檬酸逐滴加入到步骤(1)中的混合溶液中。该过程中步骤(1)中的混合溶液处于一直搅拌的状态；加完柠檬酸后，往一直搅拌的混合溶液中加入25％氨水调节PH值到8。(2) Add the dissolved citric acid dropwise to the mixed solution in step (1). During this process, the mixed solution in step (1) is in the state of constant stirring; after adding citric acid, add 25% ammonia water to the mixed solution that has been stirred to adjust the pH value to 8.
(3)将得到的混合溶液进行喷雾干燥，通过调节进料速度450ml/h、进风温度150℃、风机频率45Hz，制得前驱体；(3) Spray-dry the obtained mixed solution, and prepare the precursor by adjusting the feed rate to 450ml/h, the inlet air temperature to 150°C, and the fan frequency to 45Hz;
(4)将上述前驱体在空气环境下在马弗炉中采用两段法焙烧，制得富锂锰基正极材料。第一段焙烧温度为400℃，焙烧时间为6h，将焙烧所得物研磨后进行第二段焙烧，焙烧温度为700，烧结时间为12h，线性升温速度2℃/min。(4) The above precursor was roasted in a muffle furnace in an air environment by a two-stage method to prepare a lithium-rich manganese-based cathode material. The first-stage calcination temperature is 400°C, and the calcination time is 6h. The roasted product is ground and then subjected to the second-stage calcination. The calcination temperature is 700°C, the sintering time is 12h, and the linear heating rate is 2°C/min.
图4是喷雾干燥制备的富锂锰基正极材料在1C倍率下放电循环比容量曲线和前三周充放电曲线，经过80周循环后，放电比容量保持在150mAh/g左右，说明该材料具有较好的循环稳定性，但是与实施例1相比容量性能不好。Figure 4 is the discharge cycle specific capacity curve and the charge-discharge curve of the first three weeks of the lithium-rich manganese-based positive electrode material prepared by spray drying at a rate of 1C. After 80 cycles, the discharge specific capacity remains at about 150mAh/g, indicating that the material has Better cycle stability, but poor capacity performance compared with Example 1.
实施例3Example 3
(1)将硫酸镍、硫酸钴和硫酸锰按照摩尔比Ni:Co:Mn＝1:1:4溶于200ml纯水中混合搅拌配制成金属离子溶度为0.2mol/L均匀溶液，再按照摩尔比Li:(Ni+Co+Mn)＝1.4:1加入氢氧化锂混合；同时将柠檬酸溶于150ml纯水中搅拌配制成1.5mol/L均匀溶液；(1) Nickel sulfate, cobalt sulfate and manganese sulfate are dissolved in 200ml pure water according to the molar ratio Ni:Co:Mn=1:1:4 and mixed and stirred to prepare a metal ion solubility of 0.2mol/L uniform solution, and then according to Molar ratio Li:(Ni+Co+Mn)=1.4:1 Add lithium hydroxide and mix; at the same time, dissolve citric acid in 150ml pure water and stir to prepare a 1.5mol/L uniform solution;
(2)将溶解的柠檬酸逐滴加入到步骤(1)中的混合溶液中。该过程中步骤(1)中的混合溶液处于一直搅拌的状态；加完柠檬酸后，往一直搅拌的混合溶液中加入25％氨水调节PH值到9.5。(2) Add the dissolved citric acid dropwise to the mixed solution in step (1). During this process, the mixed solution in step (1) is in the state of constant stirring; after adding citric acid, add 25% ammonia water to the mixed solution that has been stirred to adjust the pH value to 9.5.
(3)将得到的混合溶液进行喷雾干燥，通过调节进料速度500ml/h、进风温度170℃、风机频率50Hz，制得前驱体；(3) Spray-dry the obtained mixed solution, and prepare the precursor by adjusting the feed rate to 500ml/h, the inlet air temperature to 170°C, and the fan frequency to 50Hz;
(4)将上述前驱体在空气环境下在马弗炉中采用两段法焙烧，制得富锂锰基正极材料。第一段焙烧温度为450℃，焙烧时间为8h，将焙烧所得物研磨后进行第二段焙烧，焙烧温度为750℃，烧结时间为14h，线性升温速度3℃/min。(4) The above precursor was roasted in a muffle furnace in an air environment by a two-stage method to prepare a lithium-rich manganese-based cathode material. The first-stage calcination temperature is 450°C, and the calcination time is 8h. The roasted product is ground and then subjected to the second-stage calcination. The calcination temperature is 750°C, the sintering time is 14h, and the linear heating rate is 3°C/min.
图5是喷雾干燥制备的富锂锰基正极材料在1C倍率下放电循环比容量曲线和前三周充放电曲线，经过120周循环后，放电比容量保持在180mAh/g以上，说明该材料具有较好的充放电比容量，但是曲线呈下降趋势，与实施例1相比循环稳定性不好。Figure 5 is the discharge cycle specific capacity curve and the first three-week charge-discharge curve of the lithium-rich manganese-based cathode material prepared by spray drying at a rate of 1C. After 120 cycles, the discharge specific capacity remains above 180mAh/g, indicating that the material has Better charge-discharge specific capacity, but the curve shows a downward trend, and compared with Example 1, the cycle stability is not good.
实施例4Example 4
(1)将草酸镍、草酸钴和草酸锰按照摩尔比Ni:Co:Mn＝1:1:4溶于200ml纯水中混合搅拌配制成金属离子溶度为0.2mol/L均匀溶液，再按照摩尔比Li:(Ni+Co+Mn)＝1.6:1加入草酸锂混合；同时将柠檬酸溶于150ml纯水中搅拌配制成1.5mol/L均匀溶液；(1) Dissolve nickel oxalate, cobalt oxalate and manganese oxalate in 200ml of pure water according to the molar ratio Ni:Co:Mn=1:1:4 and mix and stir to form a uniform solution with a metal ion solubility of 0.2mol/L. Molar ratio Li:(Ni+Co+Mn)=1.6:1 Add lithium oxalate and mix; at the same time, dissolve citric acid in 150ml pure water and stir to prepare a 1.5mol/L uniform solution;
(2)将溶解的柠檬酸逐滴加入到步骤(1)中的混合溶液中。该过程中步骤(1)中的混合溶液处于一直搅拌的状态；加完柠檬酸后，往一直搅拌的混合溶液中加入25％氨水调节PH值到10。(2) Add the dissolved citric acid dropwise to the mixed solution in step (1). During this process, the mixed solution in step (1) is in the state of constant stirring; after adding citric acid, add 25% ammonia water to the mixed solution that has been stirred to adjust the pH value to 10.
(3)将得到的混合溶液进行喷雾干燥，通过调节进料速度350ml/h、进风温度160℃、风机频率60Hz，制得前驱体；(3) Spray-dry the obtained mixed solution, and prepare the precursor by adjusting the feed rate to 350ml/h, the inlet air temperature to 160°C, and the fan frequency to 60Hz;
(4)将上述前驱体在空气环境下在马弗炉中采用两段法焙烧，制得富锂锰基正极材料。第一段焙烧温度为500℃，焙烧时间为7h，将焙烧所得物研磨后进行第二段焙烧，焙烧温度为800℃，烧结时间为16h，线性升温速度4℃/min。(4) The above precursor was roasted in a muffle furnace in an air environment by a two-stage method to prepare a lithium-rich manganese-based cathode material. The first-stage calcination temperature is 500°C, and the calcination time is 7h. The roasted product is ground and then subjected to the second-stage calcination. The calcination temperature is 800°C, the sintering time is 16h, and the linear heating rate is 4°C/min.
图6是喷雾干燥制备的富锂锰基正极材料在1C倍率下放电循环比容量曲线和前三周充放电曲线，经过90周循环后，放电比容量保持在160mAh/g以上，与实施例1相比，该材料循环性能较差，而且充放电比容量较低。Figure 6 is the discharge cycle specific capacity curve and the charge-discharge curve of the first three weeks of the lithium-rich manganese-based positive electrode material prepared by spray drying at a rate of 1C. After 90 cycles, the discharge specific capacity remains above 160mAh/g, which is consistent with that of Example 1. In comparison, this material has poor cycle performance and low charge-discharge specific capacity.
所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。The described embodiment is a preferred implementation of the present invention, but the present invention is not limited to the above-mentioned implementation, without departing from the essence of the present invention, any obvious improvement, replacement or modification that those skilled in the art can make Modifications all belong to the protection scope of the present invention.
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| CN201810507776.0ACN108878862A (en) | 2018-05-24 | 2018-05-24 | A kind of lithium ion battery lithium-rich manganese base and its spray drying preparation |
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