WO2015131850A1 - 一种动力型镍钴锰酸锂材料及其制备方法和应用 - Google Patents

一种动力型镍钴锰酸锂材料及其制备方法和应用 Download PDF

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WO2015131850A1
WO2015131850A1 PCT/CN2015/073773 CN2015073773W WO2015131850A1 WO 2015131850 A1 WO2015131850 A1 WO 2015131850A1 CN 2015073773 W CN2015073773 W CN 2015073773W WO 2015131850 A1 WO2015131850 A1 WO 2015131850A1
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Prior art keywords
nickel
manganese
source
cobalt
lithium
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PCT/CN2015/073773
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English (en)
French (fr)
Inventor
欧彦楠
余海军
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普报废汽车循环有限公司
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Priority to US15/123,653 priority Critical patent/US20170084907A1/en
Publication of WO2015131850A1 publication Critical patent/WO2015131850A1/zh

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    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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Definitions

  • the invention belongs to the technical field of preparation of lithium cobalt cobalt manganate cathode material, in particular to a dynamic nickel-cobalt-manganese material material and preparation method and application thereof
  • a power battery is a battery used to power a tool such as a new energy vehicle.
  • the performance of the power battery determines the performance and endurance of the new energy vehicle.
  • the positive electrode material determines the specific capacity and cycle life of the power battery.
  • Commercially available cathode materials are mainly lithium cobaltate, lithium manganate, lithium nickel cobalt manganese oxide and lithium iron phosphate. In recent years, due to its large specific capacity and long cycle life, lithium nickel cobalt manganese oxide is gradually favored by the new energy automobile industry.
  • the method for synthesizing lithium nickel cobalt manganese oxide material mainly includes: solid phase method, coprecipitation method, low thermal solid phase method, complex method, sol-gel method and the like.
  • the above-mentioned conventional synthesis method can obtain a lithium nickel cobalt manganese oxide material, the size of the particles is large and difficult to control.
  • the primary object of the present invention is to provide a preparation of a dynamic nickel-cobalt-manganese material.
  • the method utilizes the technique of sol-gel-electrospinning method to control the size of lithium nickel cobalt manganate, which provides a new way for the preparation of dynamic nickel-cobalt-manganese material.
  • Another object of the present invention is to provide a power-type lithium nickel cobalt manganate material prepared by the above method, which has a higher capacitance than existing materials.
  • Still another object of the present invention is to provide an application of the above-described power type lithium nickel cobalt manganate material in the preparation of a battery.
  • a method for preparing a dynamic nickel-cobalt-manganese hydride material by adding an organic acid to a mixed aqueous solution of a lithium source, a nickel source, a cobalt source and a manganese source, and aging to obtain a sol precursor, and obtaining a gel by electrospinning After the fiber is calcined, a power type lithium nickel cobalt manganese oxide material is obtained.
  • the concentration of the nickel source is 1 to 3 mol/L
  • the concentration of the cobalt source is 1 to 3 mol/L
  • the concentration of the manganese source is 1 to 3.
  • the concentration of the lithium source is 1 to 2 times the total concentration of the nickel source, the cobalt source and the manganese source.
  • the amount of organic acid used is 3 ⁇ 5 mol/L of organic acid in the system after adding organic acid.
  • the lithium source is at least one of lithium acetate, lithium hydroxide and lithium carbonate.
  • the nickel source is preferably at least one of nickel acetate, nickel hydroxide and nickel carbonate.
  • the cobalt source is preferably at least one of cobalt acetate, cobalt hydroxide and cobalt carbonate.
  • the manganese source is preferably at least one of manganese acetate, manganese hydroxide, and manganese carbonate.
  • the aging refers to heating to 60-70 ° C for 8-10 h to transparent, and continuing to age at room temperature until the viscosity is 2 ⁇ 3 Pa•S.
  • the electrospinning process conditions are as follows: the nozzle has a pore size of 500 ⁇ m, the feeding speed is 5-10 mL/h, and the voltage is 20-40. kV, the curing distance between the nozzle and the collector is 10 ⁇ 30 cm, and the pressure is 0.3 ⁇ 0.5 MPa.
  • the calcination process conditions are: heating from room temperature to 0.5 to 1 ° C / min to 300 ⁇ 400 ° C, maintaining 1 ⁇ 3 h, then increase the temperature to 600 ⁇ 800 °C at 2 ⁇ 4 °C/min for 8 ⁇ 10 h.
  • the gel fiber is obtained by electrospinning and dried at 70 ° C for 1 h and then calcined.
  • the dynamic lithium nickel cobalt manganate material prepared by the above method has a nano fiber structure, uniform size and increased specific capacity, and is suitable for use as an electrode material in a battery.
  • the mechanism of the invention is:
  • the structure is uniform in size, which effectively reduces the surface energy, thereby reducing the Coulomb repulsion between lithium ions and enhancing the capacity of lithium ions.
  • the nanofiber structure can reduce the impedance of lithium ions diffusing during the insertion and removal process, so that lithium ions diffuse rapidly.
  • the nano-scale material has a larger surface area and a larger number of reactive sites than the micro-scale material made by the conventional deposition method, and can provide a higher specific capacity.
  • the present invention has the following advantages and beneficial effects:
  • the lithium nickel cobalt manganate material of the present invention has a nanofiber structure of uniform size, which can effectively enhance the capacity of lithium ions.
  • the lithium nickel cobalt manganate material of the present invention has a large surface area, a large number of reactive sites, and a higher specific capacity.
  • the sol-gel-electrospinning method of the present invention is simple in process, and electrospinning can be realized without adding a polymer reagent, which not only reduces the use cost of the polymer, but also reduces the influence of the polymer on the nanostructure. This is because, on the one hand, conventional electrospinning requires the addition of a soluble polymer to improve the spinnability of the raw material, but the present invention can obtain a spinnable precursor by adding an organic acid to form a sol. On the other hand, the conventional method first introduces a polymer and then calcines to remove the polymer. Since the spun "polymer-lithium nickel cobalt manganate" has been tightly fused, the removal of the polymer will result in the structure of the lithium nickel cobalt manganate material. Defects that affect application performance.
  • Example 1 is an SEM image of a lithium nickel cobalt manganese oxide material prepared in Example 1.
  • Example 2 is a graph showing charge and discharge capacities of nickel-cobalt-manganese hydride materials of Example 1 and Comparative Example.
  • Example 1 Preparation of a Powered Nickel-Cobalt Manganate Material
  • the dry gel fiber obtained in the step (2) is placed in a calciner, and heated to a temperature of 300 ° C from room temperature at 0.5 ° C / min in air, maintaining 1 h, then raise the temperature to 600 ° C at 2 ° C / min, keep 8 h, a power type lithium nickel cobalt manganese oxide material is obtained.
  • the SEM scan was performed, and the results are shown in Fig. 1.
  • the dynamic lithium nickel cobalt manganate material of the present invention has a uniform nanofiber structure.
  • Example 2 Preparation of a power type lithium nickel cobalt manganate material
  • the sol is loaded into a syringe with a nozzle aperture of 500 ⁇ m at a feed rate of 7.5 mL/h, a voltage of 30 kV, a curing distance between the nozzle and the collector of 20 cm, and a filling of N 2 to a pressure of 0.4 MPa, spinning under the above conditions, to obtain a gel fiber, which was dried at 70 ° C for 1 h.
  • step (3) placing the xerogel fiber obtained in the step (2) in a calciner, and raising the temperature from room temperature to 350 ° C at room temperature from 1 ° C / min, keeping 2 h, and then heated to 700 ° C at 3 ° C / min, held for 9 h, to obtain a power type lithium nickel cobalt manganese oxide material.
  • the sol is loaded into a syringe with a nozzle aperture of 500 ⁇ m at a feed rate of 10 mL/h, a voltage of 30 kV, a curing distance between the nozzle and the collector of 30 cm, and a filling of N 2 to a pressure of 0.5 MPa, spinning under the above conditions, to obtain a gel fiber, which was dried at 70 ° C for 1 h.
  • the dry gel fiber obtained in the step (2) is placed in a calciner, and is heated from room temperature to 1 ° C / min to 400 ° C in air, maintaining 3 h, and then heated to 800 ° C at 4 ° C / min, held for 10 h, to obtain a power type lithium nickel cobalt manganese oxide material.
  • lithium nickel cobalt manganese oxide materials of Example 1 and Comparative Example were used as positive electrodes, respectively, and assembled into a battery, and a discharge test was performed at a rate of 1 C.
  • the results are shown in FIG. 2 .
  • the results show that the specific capacity of the lithium nickel cobalt manganate cathode material of the present invention is higher than that of the conventional sol-gel method at a ratio of 1 C, which is about 170. mAh/g.

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Abstract

本发明属于镍钴锰酸锂正极材料制备技术领域，公开了一种动力型镍钴锰酸锂材料及其制备方法和应用。该制备方法通过把有机酸加入锂源、镍源、钴源、锰源的混合水溶液中，陈化，得到溶胶前驱体，经静电纺丝得到凝胶纤维，煅烧后，得到动力型镍钴锰酸锂材料。本发明通过溶胶凝胶-静电纺丝法制备得到纳米纤维结构的镍钴锰酸锂材料，其结构尺寸均一，有效降低表面能，增强锂离子的容量；且纳米纤维结构能减少锂离子在嵌脱过程中扩散的阻抗，使锂离子快速扩散。同时，材料表面积更大，反应活性位点多，能提供更高的比容量。本发明方法工艺简单，无需添加聚合物试剂，即可实现静电纺丝，不仅减少聚合物的使用成本，而且减少聚合物对纳米结构的影响。

Description

一种动力型镍钴锰酸锂材料及其制备方法和应用
技术领域
本发明属于镍钴锰酸锂正极材料制备技术领域，特别涉及一种动力型镍钴锰酸锂材料及其制备方法和应用
背景技术
全球能源、环境状况的日趋紧张和恶化，强化了人们发展节能及新能源动力汽车的共识。我国逐步推出相应政策措施，推动关键技术进步，促进消费市场成型，我国动力汽车的产量正在上涨。动力电池是用于为新能源汽车等工具提供动力来源的电池。动力电池的性能决定了新能源汽车的性能及续航能力，其中正极材料决定了动力电池的比容量及循环寿命。现在商业化的正极材料主要有钴酸锂、锰酸锂、镍钴锰酸锂和磷酸铁锂。近年来，由于镍钴锰酸锂比容量大，循环寿命长，逐渐受到新能源汽车行业的青睐。
然而，由于制备方法的限制，镍钴锰酸锂的实际容量离理论容量仍有一段距离，制约了新能源汽车的发展。合成镍钴锰酸锂材料的方法主要包括：固相法、共沉淀法、低热固相法、络合法、溶胶-凝胶法等。但上述现有的合成方法虽然可以获得镍钴锰酸锂材料，但颗粒的尺寸较大，且难以控制。
发明内容
为了克服上述现有技术中镍钴锰酸锂材料的实际容量小的缺点与颗粒尺寸较大，且难以控制的不足，本发明的首要目的在于提供一种动力型镍钴锰酸锂材料的制备方法。该方法利用溶胶凝胶-静电纺丝法的技术，控制镍钴锰酸锂的尺寸，为动力型镍钴锰酸锂材料的制备提供了新的途径。
本发明另一目的在于提供上述方法制备的动力型镍钴锰酸锂材料，该镍钴锰酸锂材料相对于现有材料具有更高的电容。
本发明再一目的在于提供上述动力型镍钴锰酸锂材料在制备电池中的应用。
本发明的目的通过下述方案实现：
一种动力型镍钴锰酸锂材料的制备方法，通过把有机酸加入锂源、镍源、钴源、锰源的混合水溶液中，陈化，得到溶胶前驱体，经静电纺丝得到凝胶纤维，煅烧后，得到动力型镍钴锰酸锂材料。
所述混合水溶液中，镍源的浓度为1~3 mol/L，钴源的浓度为1~3 mol/L，锰源的浓度为1~3 mol/L，锂源的浓度为镍源、钴源、锰源总浓度的1~2倍。
所用有机酸的量为添加有机酸后体系中有机酸浓度为3~5 mol/L。
所述的有机酸为柠檬酸、酒石酸和草酸中的至少一种。本发明加入有机酸，通过控制一系列实验条件，与镍、钴、锰等金属离子形成可溶性络合物，减少溶液中的自由离子，从而形成均匀、透明的溶胶。通过添加有机酸，才能获得具有足够粘度的可纺性前驱体。
优选地，所述的锂源为醋酸锂、氢氧化锂和碳酸锂中的至少一种。
所述的镍源优选为醋酸镍、氢氧化镍和碳酸镍中的至少一种。
所述的钴源优选为醋酸钴、氢氧化钴和碳酸钴中的至少一种。
所述的锰源优选为醋酸锰、氢氧化锰和碳酸锰中的至少一种。
所述的陈化指先加热到60~70℃陈化8~10 h至透明，在室温下继续陈化至粘度为2~3 Pa•S。
所述静电纺丝的工艺条件为：喷头孔径为500 μm，供料速度为5~10 mL/h，电压为20~40 kV，喷头与收集器之间的固化距离为10~30 cm，压强为0.3~0.5 MPa。
所述煅烧的工艺条件为：从室温以0.5~1℃/min升温至300~400℃，保持1~3 h，再以2~4℃/min升温至600~800℃，保持8~10 h。
优选地，静电纺丝得到凝胶纤维后在70℃下干燥1 h再进行煅烧。
上述方法制备得到的动力型镍钴锰酸锂材料具有纳米纤维结构，且尺寸均一，比容量增大，适用于电池中作为电极材料。
本发明的机理为：
本发明通过溶胶凝胶-静电纺丝法制备得到纳米纤维结构的镍钴锰酸锂材料。首先加入有机酸，通过控制一系列实验条件，与镍、钴、锰等金属离子形成可溶性络合物，减少溶液中的自由离子，从而形成均匀、透明的溶胶。将具有足够粘度的溶胶前驱体，应用静电纺丝仪器，控制适当的纺丝条件，可控地喷射出凝胶纤维。最后，经过程序升温煅烧，提高镍钴锰酸锂材料的结晶度。其结构尺寸均一，有效减少表面能，从而使锂离子之间的库伦斥力降低，增强锂离子的容量。且纳米纤维结构能减少锂离子在嵌脱过程中扩散的阻抗，使锂离子快速扩散。同时，纳米级的材料与传统沉积方法做成的微米级材料相比，表面积更大，反应活性位点多，能提供更高的比容量。
本发明相对于现有技术，具有如下的优点及有益效果：
（1）本发明的镍钴锰酸锂材料具有尺寸均一的纳米纤维结构，可有效增强锂离子的容量。
（2）本发明的镍钴锰酸锂材料表面积大，反应活性位点多，具有更高的比容量。
（3）本发明的溶胶凝胶-静电纺丝法工艺简单，无需添加聚合物试剂，即可实现静电纺丝，不仅减少聚合物的使用成本，而且减少聚合物对纳米结构的影响。这是因为，一方面，传统的静电纺丝需要加入可溶性聚合物提高原料的可纺性，但本发明通过加入有机酸形成溶胶即可得到可纺性前驱体。另一方面，传统方法先引入聚合物，然后煅烧去除聚合物，由于已纺的“聚合物-镍钴锰酸锂”已经紧密融合，因此去除聚合物会在镍钴锰酸锂材料结构上产生缺陷，影响应用性能。
附图说明
图1为实施例1制备得到的镍钴锰酸锂材料的SEM图。
图2为实施例1和对比例的镍钴锰酸锂材料充放电容量曲线图。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1：动力型镍钴锰酸锂材料的制备
（1）按浓度为醋酸锂3 mol/L、醋酸镍1 mol/L、醋酸钴1 mol/L、醋酸锰1 mol/L配置100 mL混合水溶液，加入柠檬酸，使体系中柠檬酸钠浓度为3 mol/L，在60℃下陈化10 h至粘稠透明，在室温下继续陈化至粘度为2 Pa•S，得到溶胶前驱体。
（2）将溶胶装入喷头孔径为500 μm的注射器中，供料速度为5 mL/h，电压为20 kV，喷头与收集器之间的固化距离为10 cm，充入N2至压强为0.3 MPa，在以上条件下进行纺丝，得到凝胶纤维，在70℃下干燥1 h。
（3）将步骤（2）得到的干凝胶纤维置于煅烧炉中，在空气中，从室温以0.5℃/min升温至300℃，保持1 h，再以2℃/min升温至600℃，保持8 h，得到动力型镍钴锰酸锂材料。对其进行SEM扫描，结果见图1。由图1可见，本发明的动力型镍钴锰酸锂材料具有均一的纳米纤维结构。
实施例2：动力型镍钴锰酸锂材料的制备
（1）按浓度为氢氧化锂9 mol/L、氢氧化镍2 mol/L、氢氧化钴2 mol/L、氢氧化锰2 mol/L配置100 mL混合水溶液，加入酒石酸，使体系中酒石酸浓度为4 mol/L，在65℃下陈化9 h至粘稠透明，在室温下继续陈化至粘度为2.5 Pa•S，得到溶胶前驱体。
（2）将溶胶装入喷头孔径为500 μm的注射器中，供料速度为7.5 mL/h，电压为30 kV，喷头与收集器之间的固化距离为20 cm，充入N2至压强为0.4 MPa，在以上条件下进行纺丝，得到凝胶纤维，在70℃下干燥1 h。
（3）将步骤（2）得到的干凝胶纤维置于煅烧炉中，在空气中，从室温以1℃/min升温至350℃，保持2 h，再以3℃/min升温至700℃，保持9 h，得到动力型镍钴锰酸锂材料。
实施例3：动力型镍钴锰酸锂材料的制备
（1）按浓度为碳酸锂18 mol/L、碳酸镍3 mol/L、碳酸钴3 mol/L、碳酸锰3 mol/L配置100 mL混合水溶液，加入草酸，使体系中有机酸浓度为5 mol/L，在70℃下陈化8 h至粘稠透明，在室温下继续陈化至粘度为3 Pa•S，得到溶胶前驱体。
（2）将溶胶装入喷头孔径为500 μm的注射器中，供料速度为10 mL/h，电压为30 kV，喷头与收集器之间的固化距离为30 cm，充入N2至压强为0.5 MPa，在以上条件下进行纺丝，得到凝胶纤维，在70℃下干燥1 h。
（3）将步骤（2）得到的干凝胶纤维置于煅烧炉中，在空气中，从室温以1℃/min升温至400℃，保持3 h，再以4℃/min升温至800℃，保持10 h，得到动力型镍钴锰酸锂材料。
对比例
（1）按浓度为醋酸锂3 mol/L、醋酸镍1 mol/L、醋酸钴1 mol/L、醋酸锰1 mol/L配置100 mL混合水溶液，加入柠檬酸，使体系中有机酸浓度为3 mol/L，在70℃下陈化至粘稠透明，在室温下继续陈化至粘度为2 Pa•S，得到溶胶前驱体。
（2）将步骤（1）得到的溶胶前驱体置于煅烧炉中，在空气中，从室温以0.5℃/min升温至300℃，保持1 h，再以2℃/min升温至600℃，保持8 h，得到镍钴锰酸锂对比材料。
检测例
以金属锂为负极，分别以实施例1和对比例的镍钴锰酸锂材料为正极，组装成电池，以1C倍率进行放电测试，结果如图2所示。结果显示，在1C倍率下，本发明的镍钴锰酸锂正极材料的比容量比普通溶胶-凝胶法的高，约为170 mAh/g。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种动力型镍钴锰酸锂材料的制备方法，其特征在于通过把有机酸加入锂源、镍源、钴源、锰源的混合水溶液中，陈化，得到溶胶前驱体，经静电纺丝得到凝胶纤维，煅烧后，得到动力型镍钴锰酸锂材料。
  2. 根据权利要求1所述的动力型镍钴锰酸锂材料的制备方法，其特征在于：所述混合水溶液中，镍源的浓度为1~3 mol/L，钴源的浓度为1~3 mol/L，锰源的浓度为1~3 mol/L，锂源的浓度为镍源、钴源、锰源总浓度的1~2倍。
  3. 根据权利要求1所述的动力型镍钴锰酸锂材料的制备方法，其特征在于：所用有机酸的量为添加有机酸后体系中有机酸浓度为3~5 mol/L。
  4. 根据权利要求1所述的动力型镍钴锰酸锂材料的制备方法，其特征在于：所述的有机酸为柠檬酸、酒石酸和草酸中的至少一种。
  5. 根据权利要求1所述的动力型镍钴锰酸锂材料的制备方法，其特征在于：所述的锂源为醋酸锂、氢氧化锂和碳酸锂中的至少一种；所述的镍源为醋酸镍、氢氧化镍和碳酸镍中的至少一种；所述的钴源为醋酸钴、氢氧化钴和碳酸钴中的至少一种；所述的锰源为醋酸锰、氢氧化锰和碳酸锰中的至少一种。
  6. 根据权利要求1所述的动力型镍钴锰酸锂材料的制备方法，其特征在于：所述陈化指先加热到60~70℃陈化8~10 h至透明，在室温下继续陈化至粘度为2~3 Pa•S。
  7. 根据权利要求1所述的动力型镍钴锰酸锂材料的制备方法，其特征在于：所述静电纺丝的工艺条件为：喷头孔径为500 μm，供料速度为5~10 mL/h，电压为20~40 kV，喷头与收集器之间的固化距离为10~30 cm，压强为0.3~0.5 MPa。
  8. 根据权利要求1所述的动力型镍钴锰酸锂材料的制备方法，其特征在于：所述煅烧的工艺条件为：从室温以0.5~1℃/min升温至300~400℃，保持1~3 h，再以2~4℃/min升温至600~800℃，保持8~10 h。
  9. 一种动力型镍钴锰酸锂材料，其特征在于根据权利要求1~8任一项所述的动力型镍钴锰酸锂材料的制备方法得到。
  10. 根据权利要求9所述的动力型镍钴锰酸锂材料在电池中的应用。
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