公开(公告)号：EP2679543A2

公开(公告)日：2014-01-01

申请号：EP13165123.4

申请日：2013-04-24

申请人： Guizhou Redstar Developing Co., Ltd. ,  Shenzhen Haoyitong Investment And Development Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong ,  LIU, Zhengtao ,  ZENG, Kaiwen

IPC分类号： C01G45/00 ,  C01G45/02

CPC分类号： C01G45/02 ,  C01G45/00 ,  C01P2002/72 ,  C01P2004/03 ,  C01P2004/51 ,  C01P2004/61 ,  C01P2004/62 ,  C01P2006/12 ,  C01P2006/80 ,  C30B7/14 ,  C30B29/16 ,  Y02E60/122 ,  Y10T428/2982

摘要： The present invention provides methods for preparing trimanganese tetroxide with low BET specific surface area and methods for controlling particle size of trimanganese tetroxide and trimanganese tetroxide product. The preparation methods and the methods for controlling particle size comprise following processes: (1) Purifying air by spraying dilute aqueous ammonia; (2) Pretreating of removing impurities from MnSO 4 solution with concentration in a range of 150~200g/L; (3) Process for preparing seed crystal: Cooling MnSO 4 solution to a temperature of less than 40°C, and introducing liquid NH 3 into the cooled MnSO 4 solution until pH value reaches 10.5-11.0, and then separating the mixture by solid-liquid separation to obtain filtrate and solid; adding NH 4 HCO 3 to the filtrate to recovery Mn element, and then forming slurry, introducing the purified air, and oxidizing the slurry into Mn 3 O 4 ; (4) Process for obtaining the final product by controlling oxidization: adding Mn 3 O 4 seed crystal to the MnSO 4 solution, Al containing salt is optionally added, turning on the recycle pump, controlling the temperature of the system in the range of 25 ± 5°C, and controlling pH value of the reaction system in a range of 6.5-7.5, which makes the MnSO 4 solution circulate more than 6 times per hour, not stopping the reaction until MnSO 4 content of the reaction solution is ≤1.5g/L, so as to obtain Mn 3 O 4 product.The trimanganese tetroxide product has properties that the particle is spherical, impurities content is low, the crystalline phase is pure, particle size distribution is narrow, which meets the international requirements for trimanganese tetroxide used for preparation manganese cathode materials for lithium ion secondary battery. The trimanganese tetroxide product has properties that BET specific surface area is less than 1m 2 /g, D 50 is 10-12µm or 14-16µm, weight content of Fe is less than 10ppm, and weight content of Cu, Zn, Pb and Cd are less than 0.1ppm.

摘要翻译： 本发明提供了用于制备具有低的BET比表面积和用于控制四氧化三锰和四氧化三锰产品的颗粒尺寸的方法四氧化三锰的方法。 的制备方法和用于控制粒径的方法包括以下过程：（1）通过喷雾稀氨水wässrige净化空气; （2）从硫酸锰溶液同浓度的范围为150〜200克/ L中除去杂质的前处理; 冷却硫酸锰溶液到低于40℃的温度，并引入液体NH 3到冷却的硫酸锰溶液直至pH值达到10.5-11.0，然后由固分离混合物：（3）用于制备晶种的方法 液分离，得到滤液和固体; 加入NH 4 HCO 3向滤液中回收的Mn元素，然后形成用浆料，将精制的空气，并将该浆料氧化成的Mn 3 O 4; （4），用于通过控制氧化获得最终产物的方法：添加Mn 3 O 4晶种到硫酸锰溶液，含Al盐可任选地加入，接通循环泵，控制系统的温度在25的范围内 ±5℃，并且控制在范围6.5-7.5，这使得该溶液硫酸锰循环6次以上每小时，不停止，直到反应溶液的反应硫酸锰含量为‰¤反应体系的pH值 1.5克/ L，从而获得的Mn 3 O 4产物。四氧化三锰产品具有属性做的颗粒是球形的，杂质含量低，结晶相是纯的，粒径分布窄，符合国际要求 用于制备锰正极材料的锂离子二次电池四氧化三锰。 的四氧化三锰产品具有属性确实BET比表面积小于1米2 /克，D 50是10-12μm或14-16μm，铁的重量含量低于10ppm的，和重量含量铜，锌，铅和镉的 小于的0.1ppm。

公开(公告)号：EP2679543A3

公开(公告)日：2016-03-23

申请号：EP13165123.4

申请日：2013-04-24

申请人： Guizhou Redstar Developing Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong ,  LIU, Zhengtao ,  ZENG, Kaiwen

IPC分类号： C01G45/00 ,  C01G45/02

CPC分类号： C01G45/02 ,  C01G45/00 ,  C01P2002/72 ,  C01P2004/03 ,  C01P2004/51 ,  C01P2004/61 ,  C01P2004/62 ,  C01P2006/12 ,  C01P2006/80 ,  C30B7/14 ,  C30B29/16 ,  Y02E60/122 ,  Y10T428/2982

摘要： The present invention provides methods for preparing trimanganese tetroxide with low BET specific surface area and methods for controlling particle size of trimanganese tetroxide and trimanganese tetroxide product. The preparation methods and the methods for controlling particle size comprise following processes: (1) Purifying air by spraying dilute aqueous ammonia; (2) Pretreating of removing impurities from MnSO 4 solution with concentration in a range of 150~200g/L; (3) Process for preparing seed crystal: Cooling MnSO 4 solution to a temperature of less than 40°C, and introducing liquid NH 3 into the cooled MnSO 4 solution until pH value reaches 10.5-11.0, and then separating the mixture by solid-liquid separation to obtain filtrate and solid; adding NH 4 HCO 3 to the filtrate to recovery Mn element, and then forming slurry, introducing the purified air, and oxidizing the slurry into Mn 3 O 4 ; (4) Process for obtaining the final product by controlling oxidization: adding Mn 3 O 4 seed crystal to the MnSO 4 solution, Al containing salt is optionally added, turning on the recycle pump, controlling the temperature of the system in the range of 25 ± 5°C, and controlling pH value of the reaction system in a range of 6.5-7.5, which makes the MnSO 4 solution circulate more than 6 times per hour, not stopping the reaction until MnSO 4 content of the reaction solution is ≤1.5g/L, so as to obtain Mn 3 O 4 product.The trimanganese tetroxide product has properties that the particle is spherical, impurities content is low, the crystalline phase is pure, particle size distribution is narrow, which meets the international requirements for trimanganese tetroxide used for preparation manganese cathode materials for lithium ion secondary battery. The trimanganese tetroxide product has properties that BET specific surface area is less than 1m 2 /g, D 50 is 10-12µm or 14-16µm, weight content of Fe is less than 10ppm, and weight content of Cu, Zn, Pb and Cd are less than 0.1ppm.