CN1067659C - Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process - Google Patents
Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process Download PDFInfo
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Abstract
本发明涉及一种用控制结晶法制备高密度球形氢氧化镍的工艺。该工艺过程为：一定浓度的镍盐水溶液在络合剂存在下与碱水溶液反应生成球形氢氧化镍多晶体颗粒，然后经过固液分离、洗涤和干燥后得以氢氧化镍产品。本发明的特点在于使用的络合剂是两种或两种以上的对镍离子具有不同络合能力的混合络合剂。使用该混合络合剂与使用单一络合剂相比，能有效地控制氢氧化镍的结晶速度和结晶度，使最终产品具有更高的电化学活性。The invention relates to a process for preparing high-density spherical nickel hydroxide by a controlled crystallization method. The process is as follows: a certain concentration of nickel salt solution reacts with an alkali solution in the presence of a complexing agent to form spherical nickel hydroxide polycrystalline particles, and then the nickel hydroxide product is obtained after solid-liquid separation, washing and drying. The present invention is characterized in that the complexing agent used is two or more mixed complexing agents with different complexing abilities to nickel ions. Compared with using a single complexing agent, the use of the mixed complexing agent can effectively control the crystallization speed and crystallinity of nickel hydroxide, so that the final product has higher electrochemical activity.
Description
本发明涉及一种用控制结晶法制备高密度球形氢氧化镍的工艺，属于化学工程及新材料领域。The invention relates to a process for preparing high-density spherical nickel hydroxide by a controlled crystallization method, which belongs to the field of chemical engineering and new materials.
高密度球形氢氧化镍(Ni(OH)2)主要用作碱性充电电池的正极活性材料。目前充电电池正向高比容量的方向发展，这就要求正极活性材料要具有高密度和高活性的特点，而影响其活性的主要因素是氢氧化镍的结晶度。制备球形氢氧化镍的控制结晶工艺的基本点是通过加入某种络合剂来调节和控制镍盐和碱的反应速度及反应产物氢氧化镍的结晶速度，从而控制其结晶度。目前，国内外在该工艺中通常都是采用氨水或铵盐这种单一的络合剂。在采用氨或铵盐一种络合剂制备球形氢氧化镍的工艺中，为了保证产物具有较高的密度，氢氧化镍的结晶度必须较高才行，因此影响了其活性。High-density spherical nickel hydroxide (Ni(OH) 2 ) is mainly used as a positive electrode active material for alkaline rechargeable batteries. At present, rechargeable batteries are developing in the direction of high specific capacity, which requires the positive electrode active material to have the characteristics of high density and high activity, and the main factor affecting its activity is the crystallinity of nickel hydroxide. The basic point of the controlled crystallization process for preparing spherical nickel hydroxide is to adjust and control the reaction rate of nickel salt and alkali and the crystallization rate of the reaction product nickel hydroxide by adding a certain complexing agent, so as to control its crystallinity. At present, the single complexing agent such as ammonia water or ammonium salt is usually used in this process both at home and abroad. In the process of preparing spherical nickel hydroxide using a complexing agent such as ammonia or ammonium salt, in order to ensure that the product has a higher density, the crystallinity of nickel hydroxide must be higher, thus affecting its activity.
本发明的目的是提出一种用控制结晶法制备高密度球形氢氧化镍的工艺，选择至少两种对镍离子具有不同的络合能力的络合剂混合使用，在保证氢氧化镍具有较高密度的前提下，适当降低其结晶度，从而提高其活性。The purpose of this invention is to propose a kind of technology that prepares high-density spherical nickel hydroxide with controlled crystallization method, select at least two kinds of complexing agents that have different complexing abilities to nickel ions to mix and use, in order to ensure that nickel hydroxide has a higher Under the premise of increasing the density, its crystallinity can be appropriately reduced, so as to improve its activity.
本发明设计的用控制结晶法制备高密度球形氢氧化镍的工艺，包括以下各步骤：The technique that the present invention designs prepares high-density spherical nickel hydroxide with controlled crystallization method, comprises the following steps:
(1)在镍浓度为1～2.2摩尔/升的硫酸镍水溶液中加入添加剂和络合剂备用，其中的添加剂为钴、锌或镉的硫酸盐，加入量的摩尔比为Co∶Ni=0.005～0.1∶1,Zn∶Ni=0.02～0.06∶1,Cd∶Ni=0.02～0.06∶1，其中的络合剂为柠檬酸钠、谷氨酸钠、酒石酸钾钠、乙二胺四乙酸二钠中的任何一种或二种，加入量的摩尔比为：络合剂∶镍=0.001～0.5∶1；(1) add additive and complexing agent in the nickel sulfate aqueous solution that nickel concentration is 1～2.2 mol/liter for subsequent use, wherein additive is the sulfate of cobalt, zinc or cadmium, and the molar ratio of addition is Co:Ni=0.005 ～0.1:1, Zn:Ni=0.02～0.06:1, Cd:Ni=0.02～0.06:1, the complexing agent is sodium citrate, sodium glutamate, potassium sodium tartrate, ethylenediaminetetraacetic acid di Any one or two of sodium, the molar ratio of the added amount is: complexing agent: nickel = 0.001 ~ 0.5: 1;
(2)用氢氧化钠和络合剂氨配制碱水溶液备用，其中氢氧化钠的浓度为4～6摩尔/升，氨和氢氧化钠的摩尔比为：氨∶氢氧化钠=0.1～0.5∶1；(2) Prepare alkaline aqueous solution with sodium hydroxide and complexing agent ammonia for subsequent use, wherein the concentration of sodium hydroxide is 4～6 mol/liter, and the mol ratio of ammonia and sodium hydroxide is: ammonia: sodium hydroxide=0.1～0.5 : 1;
(3)用计量泵将上述二种溶液连续泵入结晶反应器中，通过调节碱水溶液的流量控制反应的pH值为10～13，反应温度为40～60℃，反应时间为：4～10小时；(3) The above two solutions are continuously pumped into the crystallization reactor with a metering pump, and the pH value of the reaction is controlled by adjusting the flow rate of the aqueous alkali solution to be 10 to 13, the reaction temperature is 40 to 60°C, and the reaction time is: 4 to 10 Hour;
(4)上述第三步反应产物经固液分离器进行固液分离，分离得到的氢氧化镍经洗涤器洗涤后，在60～100℃下干燥2～4小时，即为高密度球形氢氧化镍产品。(4) The reaction product of the third step above is subjected to solid-liquid separation by a solid-liquid separator, and the separated nickel hydroxide is washed by a scrubber and dried at 60-100°C for 2-4 hours to form a high-density spherical hydroxide. Nickel products.
本发明提出的使用混合络合剂的控制结晶工艺与使用单一氨水或铵盐为络合剂的工艺相比，所得的球形氢氧化镍具有同样高的密度，但其比表面积更大，晶粒更细，电化学活性更高。The controlled crystallization technique using mixed complexing agent proposed by the present invention is compared with the technique using single ammonia or ammonium salt as complexing agent, and the resulting spherical nickel hydroxide has the same high density, but its specific surface area is larger, and the crystal grain Finer and more electrochemically active.
下面介绍本发明的实施例：Introduce the embodiment of the present invention below:
实施例一、镍盐水溶液的成分为硫酸镍，添加剂和络合剂，其中添加剂为硫酸钴和硫酸锌，硫酸镍的浓度是1.9摩尔/升，Co∶Zn∶Ni=2.5∶5.0∶100(摩尔比)，络合剂为柠檬酸三钠，浓度为0.07摩尔/升。碱水溶液的成分为氢氧化钠和络合剂氨，氢氧化钠的浓度是5.0摩尔/升，氨的浓度是1.0摩尔/升。结晶反应器的有效体积5升，用计量泵将上述镍盐水溶液和碱水溶液分别连续定量输入到结晶反应器中，搅拌速度为700转/分。通过调节碱水溶液的流量来控制反应的pH值，pH值为11.00±0.05。反应温度50±0.5℃，反应时间为7小时。生成的氢氧化镍经固液分离，水洗，80℃干燥两小时得到样品。测得该样品为β-Ni(OH)2，球形，振实密度2.10g/cm3，平均粒径10-15μm，BET比表面积23m2/g，(101)晶面X光衍射峰半高宽为1.01°，0.2C充放电时的放电比容量为284mAh/g。Embodiment one, the composition of nickel salt aqueous solution is nickel sulfate, additive and complexing agent, and wherein additive is cobalt sulfate and zinc sulfate, and the concentration of nickel sulfate is 1.9 mol/liter, Co: Zn: Ni=2.5: 5.0: 100 ( mol ratio), the complexing agent is trisodium citrate, and the concentration is 0.07 mol/liter. The composition of the alkali aqueous solution is sodium hydroxide and complexing agent ammonia, the concentration of sodium hydroxide is 5.0 mol/liter, and the concentration of ammonia is 1.0 mol/liter. The crystallization reactor has an effective volume of 5 liters, and the above-mentioned nickel salt solution and alkaline aqueous solution are continuously quantitatively input into the crystallization reactor respectively by a metering pump, and the stirring speed is 700 rpm. The pH value of the reaction is controlled by adjusting the flow rate of the alkaline aqueous solution, and the pH value is 11.00±0.05. The reaction temperature is 50±0.5°C, and the reaction time is 7 hours. The generated nickel hydroxide was subjected to solid-liquid separation, washed with water, and dried at 80°C for two hours to obtain a sample. The sample was measured to be β-Ni(OH) 2 , spherical, with a tap density of 2.10g/cm 3 , an average particle size of 10-15μm, a BET specific surface area of 23m 2 /g, and a half-height of the (101) crystal plane X-ray diffraction peak. The width is 1.01°, and the discharge specific capacity at 0.2C charge and discharge is 284mAh/g.
实施例二、镍盐水溶液中所加络合剂是谷氨酸钠，浓度是0.038摩尔/升，碱水溶液中的氨浓度为0.5摩尔/升，其他条件同实施例一。本实施例的氢氧化镍样品经测试为β-Ni(OH)2，球形，振实密度2.12g/cm3，平均粒径10-15μm，BET比表面积25m2/g，(101)晶面X光衍射峰半高宽为1.05°，0.2C充放电时的放电比容量为287mAh/g。Embodiment two, the complexing agent added in the nickel salt solution is sodium glutamate, and the concentration is 0.038 mol/liter, and the ammonia concentration in the aqueous alkali solution is 0.5 mol/liter, and other conditions are with embodiment one. The nickel hydroxide sample in this example is tested to be β-Ni(OH) 2 , spherical, with a tap density of 2.12g/cm 3 , an average particle size of 10-15μm, a BET specific surface area of 25m 2 /g, and a (101) crystal plane. The half-maximum width of the X-ray diffraction peak is 1.05°, and the discharge specific capacity at 0.2C charge and discharge is 287mAh/g.
实施例三、镍盐水溶液中络合剂是酒石酸钾钠，浓度是0.10摩尔/升，反应的pH值为10.90±0.05，其他条件同实施例一。本实施例的氢氧化镍样品经测试为β-Ni(OH)2，球形，振实密度2.10g/cm3，平均粒径10-15μm，BET比表面积22m2/g，(101)晶面X光衍射峰半高宽为0.96°，0.2C充放电时的放电比容量为281mAh/g。Embodiment three, the complexing agent in the nickel salt solution is potassium sodium tartrate, the concentration is 0.10 mol/liter, the pH value of the reaction is 10.90 ± 0.05, other conditions are the same as embodiment one. The nickel hydroxide sample in this example is tested to be β-Ni(OH) 2 , spherical, with a tap density of 2.10 g/cm 3 , an average particle size of 10-15 μm, a BET specific surface area of 22 m 2 /g, and a (101) crystal plane. The half-maximum width of the X-ray diffraction peak is 0.96°, and the discharge specific capacity at 0.2C charge and discharge is 281mAh/g.
实施例四、镍盐水溶液中络合剂是乙二胺四乙酸二钠，浓度是0.02摩尔/升，碱水溶液中所加络合剂氨的浓度为1.2摩尔/升，反应的pH值为11.10±0.05，其他条件同实施例一。本实施例的氢氧化镍样品经测试为β-Ni(OH)2，球形，振实密度2.15g/cm3，平均粒径10-15μm，BET比表面积21m2/g，(101)晶面X光衍射峰半高宽为0.99°，0.2C充放电时的放电比容量为286mAh/g。Embodiment four, complexing agent is edetate disodium in the nickel salt aqueous solution, and concentration is 0.02 mol/liter, and the concentration of complexing agent ammonia added in the alkali aqueous solution is 1.2 mol/liter, and the pH value of reaction is 11.10 ±0.05, other conditions are the same as in Example 1. The nickel hydroxide sample in this example is tested to be β-Ni(OH) 2 , spherical, with a tap density of 2.15 g/cm 3 , an average particle size of 10-15 μm, a BET specific surface area of 21 m 2 /g, and a (101) crystal plane. The half-maximum width of the X-ray diffraction peak is 0.99°, and the discharge specific capacity at 0.2C charge and discharge is 286mAh/g.
实施例五、镍盐水溶液中所加络合剂是谷氨酸钠和乙二胺四乙酸二钠。谷氨酸钠的浓度0.017摩尔/升，乙二胺四乙酸二钠的浓度为0.01摩尔/升，其他条件同实施例一。本实施例的氢氧化镍样品经测试为β-Ni(OH)2，球形，振实密度2.15g/cm3，平均粒径10-15μm，BET比表面积21m2/g，(101)晶面X光衍射峰半高宽为1.03°，0.2C充放电时的放电比容量为285mAh/g。Embodiment five, the complexing agent added in the nickel salt solution is sodium glutamate and disodium edetate. The concentration of sodium glutamate is 0.017 mol/liter, the concentration of disodium edetate is 0.01 mol/liter, and other conditions are the same as in Example 1. The nickel hydroxide sample in this example is tested to be β-Ni(OH) 2 , spherical, with a tap density of 2.15 g/cm 3 , an average particle size of 10-15 μm, a BET specific surface area of 21 m 2 /g, and a (101) crystal plane. The half-maximum width of the X-ray diffraction peak is 1.03°, and the discharge specific capacity at 0.2C charge and discharge is 285mAh/g.
实施例六、镍盐水溶液中所用添加剂为硫酸钴和硫酸镉，Co∶Cd∶Ni=2.5∶5.0∶100(摩尔比)，其他条件同实施例五。本实施例的氢氧化镍样品经测试为β-Ni(OH)2，球形，振实密度2.17g/cm3，平均粒径10-15μm，BET比表面积24m2/g，(101)晶面X光衍射峰半高宽为1.05°，0.2C充放电时的放电比容量为288mAh/g。Embodiment six, the additive used in the nickel salt solution is cobalt sulfate and cadmium sulfate, Co: Cd: Ni=2.5: 5.0: 100 (molar ratio), other conditions are the same as embodiment five. The nickel hydroxide sample in this example is tested to be β-Ni(OH) 2 , spherical, with a tap density of 2.17g/cm 3 , an average particle size of 10-15μm, a BET specific surface area of 24m 2 /g, and a (101) crystal plane. The half-maximum width of the X-ray diffraction peak is 1.05°, and the discharge specific capacity at 0.2C charge and discharge is 288mAh/g.
实施例七、结晶反应器的有效体积为5立方米，镍盐水溶液流量400升/小时，碱水溶液流量为300升/小时，搅拌速度200转/分，其他条件同实施例五。本实施例的氢氧化镍样品，经测试为β-Ni(OH)2，球形，振实密度2.19g/cm3，平均粒径10-15μm，BET比表面积22m2/g，(101)晶面X光衍射峰半高宽为1.03°，0.2C充放电时的放电比容量为287mAh/g。Embodiment 7, the effective volume of the crystallization reactor is 5 cubic meters, the nickel salt aqueous solution flow rate is 400 liters/hour, the alkali aqueous solution flow rate is 300 liters/hour, the stirring speed is 200 rpm, and other conditions are the same as embodiment five. The nickel hydroxide sample in this example is tested to be β-Ni(OH) 2 , spherical, with a tap density of 2.19g/cm 3 , an average particle size of 10-15μm, a BET specific surface area of 22m2/g, and a (101) crystal plane. The half-maximum width of the X-ray diffraction peak is 1.03°, and the discharge specific capacity at 0.2C charge and discharge is 287mAh/g.
比较实施例一、镍盐水溶液的成份为硫酸镍及添加剂硫酸钴和硫酸锌，硫酸镍的浓度为1.9摩尔/升，Co∶Zn∶Ni=2.5∶5.0∶100(摩尔比)，碱水溶液的成份为氢氧化钠和络合剂氨，氢氧化钠的浓度为5.0摩尔/升，氨的浓度为1.2摩尔/升，其他条件同实施例一。比较实施例的氢氧化镍样品经测试为β-Ni(OH)2，球形，振实密度2.12g/cm3，平均粒径10-15μm，BET比表面积15m2/g，(101)晶面X光衍射峰半高宽为0.87°，0.2C充放电时的放电比容量为273mAh/g。Comparative example one, the composition of nickel salt aqueous solution is nickel sulfate and additive cobalt sulfate and zinc sulfate, and the concentration of nickel sulfate is 1.9 mol/liter, Co: Zn: Ni=2.5: 5.0: 100 (molar ratio), the alkali aqueous solution Composition is sodium hydroxide and complexing agent ammonia, and the concentration of sodium hydroxide is 5.0 mol/liter, and the concentration of ammonia is 1.2 mol/liter, and other conditions are with embodiment one. The nickel hydroxide sample of Comparative Example was tested to be β-Ni(OH) 2 , spherical, with a tap density of 2.12 g/cm 3 , an average particle size of 10-15 μm, a BET specific surface area of 15 m 2 /g, and a (101) crystal plane The half-maximum width of the X-ray diffraction peak is 0.87°, and the discharge specific capacity at 0.2C charge and discharge is 273mAh/g.
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| TW520575B (en) * | 2000-04-21 | 2003-02-11 | Sony Corp | Positive electrode material and nickel-zinc battery |
| CN100406392C (en) * | 2006-12-29 | 2008-07-30 | 北京工业大学 | A kind of preparation method of the nickel hydroxide thin film of nano structure |
| CN101577333B (en) * | 2009-06-10 | 2011-09-28 | 江门市长优实业有限公司 | High specific capacity discharge platform spherical nickel hydroxide |
| CN101635356B (en) * | 2009-06-10 | 2011-06-22 | 江门市长优实业有限公司 | Spherical nickel hydroxide for high-temperature nickel batteries and preparation method thereof |
| CN102267729B (en) * | 2011-06-30 | 2013-06-12 | 合肥工业大学 | Preparation method of spherical nickel hydroxide used as battery cathode material |
| CN103259010B (en) * | 2013-04-23 | 2015-06-17 | 宁夏东方钽业股份有限公司 | Preparation method of amphoteric metal element doped lithium-ion cathode material precursor |
| CN106186088A (en) * | 2016-07-11 | 2016-12-07 | 潮州三环（集团）股份有限公司 | A kind of nickel oxide powder body and preparation method thereof |
| CN106025265B (en) * | 2016-07-12 | 2019-07-02 | 广东工业大学 | A kind of method for preparing alpha nickel hydroxide |
| CN111675247A (en) * | 2020-06-12 | 2020-09-18 | 福建常青新能源科技有限公司 | A method for preparing NCM high nickel ternary cathode material precursor |
| CN115924986B (en) * | 2021-10-19 | 2024-09-03 | 浙江海创锂电科技有限公司 | Preparation method of high-nickel ternary precursor material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684323A (en) * | 1979-12-06 | 1981-07-09 | Sumitomo Metal Mining Co Ltd | Removing method for cobalt from aqueous nickel sulfate solution |
| CN1075697A (en) * | 1993-04-09 | 1993-09-01 | 河南师范大学 | Preparation method of corpuscle ball type nickel hydroxide |
| JPH0848506A (en) * | 1994-08-05 | 1996-02-20 | Nikko Metal Pureeteingu Kk | Production of metal hydroxide powder |
| US5498403A (en) * | 1994-05-20 | 1996-03-12 | Hyundai Motor Company | Method for preparing high density nickel hydroxide used for alkali rechargeable batteries |
-
1998
- 1998-12-11 CN CN98123187A patent/CN1067659C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684323A (en) * | 1979-12-06 | 1981-07-09 | Sumitomo Metal Mining Co Ltd | Removing method for cobalt from aqueous nickel sulfate solution |
| CN1075697A (en) * | 1993-04-09 | 1993-09-01 | 河南师范大学 | Preparation method of corpuscle ball type nickel hydroxide |
| US5498403A (en) * | 1994-05-20 | 1996-03-12 | Hyundai Motor Company | Method for preparing high density nickel hydroxide used for alkali rechargeable batteries |
| JPH0848506A (en) * | 1994-08-05 | 1996-02-20 | Nikko Metal Pureeteingu Kk | Production of metal hydroxide powder |
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