电池正极材料尖晶石LiMn_2O_4的合成及其性能的优化
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摘要
尖晶石LiMn_2O_4因其放电电压高,成本低,制备工艺简单,结构稳定,绿色环保,是很有应用前景的锂离子电池正极材料。本文针对尖晶石LiMn_2O_4材料目前存在的问题进行了探究,得到了对其实际应用有着重要意义的发现成果。主要内容包括:
1、高密度前驱体的制备:通过共沉淀和二次干燥法制备了高密度的尖晶石LiMn_2O_4正极材料的前驱体。并分别从滤饼含水量,烘干方式,聚沉剂的添加方式的角度对前驱体振实密度的影响进行制备工艺的改进优化。探究出了最佳制备高密度、高纯度前驱体的条件,为合成高性能尖晶石LiMn_2O_4正极材料提供了重要的参考。
2、前驱体的不同处理方式对材料电性能的影响:通过采用共沉淀法经压滤、二次干燥制备出的锰氧化合物用作合成尖晶石LiMn_2O_4正极材料的前驱体,在共沉淀过程中,通过添加还原剂水合肼、通入保护气体氮气、添加氧化剂双氧水与空白试验作对比,研究了前驱体的不同处理方式对烧结合成的LiMn_2O_4结构与常温、高温下电化学性能的影响。实验结果表明:加入水合肼和通入氮气都能保证烧结产物LiMn_2O_4的纯度,并且二者结合可以有效地调产物LiMn_2O_4的纯度与颗粒粒径大小,并有较高的振实密度,高温高倍率下有较好的放电性能。
3、电极制作细节对电池电性能的影响:在无水乙醇为分散剂进行充分研磨,并选择900oC的条件下烧结15h合成正极材料的基础上,通过改进电极的制作细节如超声波分散时间的延长,静置分层,改进碾压方式及烘干方法。实验结果证明这些细节的改进都有助于提高电池的循环性能。
4、不同锰源对电池正极材料性能的影响:通过使用草酸钠法准确地测定了购买的EMD中MnO_2的含量,并使用EDTA直接滴定法测定了Mn2+的含量。用金属锰片和硫酸反应制备硫酸锰溶液,不仅节约了成本而且为前驱体的合成及以后的工作提供了准确的数据,有利于以后实验步骤的科学准确地开展。我们探究了电解二氧化锰用硝酸处理与非处理,自制的硫酸锰和草酸锰对电池材料性能的影响,发现不同锰源对电池性能有着一定的影响。
5、LiMn_2O_4的掺杂改性的研究:通过共沉淀和二次干燥法,在氮气和水合肼的保护下,通过掺杂铝离子制备前驱体,进而烧结制备尖晶石LiAl_xMn_(2-x)O_4,结果表明随着掺杂铝含量的增加晶胞参数a逐渐变小,晶格的稳定性增强,虽然放电比容量和放电平台有所降低,但高温高倍率的循环性能得到提高,这有望解决锂离子电池在高温条件下容易出现的安全性问题。通过研究对比我们发现用Li_2CO_3制备的正极材料的振实密度相对较高,并且掺杂Al_2O_3的振实密度相对较高。这些性能的改进将对工业生产有着重要的指导意义。
Spinel LiMn_2O_4 as one of the most promising alternative cathode materiales because it has the advantages of high vlatage, naturally abundant, low cost, simple in preparation, structure stability, no toxicity, good safety and environmentally benign nature. we carried out a series of studies in order to resolve the present remaining problems of spinel LiMn_2O_4. And we obtained some meaningful results. Main points of these are listed as below:
1. Synthesis of spinel LiMn_2O_4 precursor with high density: The precursor of spinel LiMn_2O_4 cathode material with high density was synthesized by co-precipitation and two-dryness method. we studied the relationship between the density of precursor and remaining water in filter cake, manner of dryness, manner of adding agglomerating agent. Our results provide an important reference on synthesis of high density spinel LiMn_2O_4 cathode material.
2. Effects of the precursor treated on the structure and electrochemical properties of spinel LiMn_2O_4 cathode: The precursor of spinel LiMn_2O_4 cathode material was synthesized by co-precipitation and two-dryness method. In this paper, based on our previous studies, we via a two-step drying method to pretreat the precursor of LiMn_2O_4 in different methods. Effects of N2, hydrazine, H2O2 on the structure of LiMn_2O_4 and discharge capacity at room temperature and elevated temperature are researched in detail. Experiments show that with the precursor treated by adding hydrazine and puring N2 to synthesize LiMn_2O_4 with complete lattice, uniform paricle size, a very pure spinel phase with an ordered octahedron crystal morphology and a large tap density.The electrochemical results show that it has higher specific capacity and higher cyclic lif than other samples, especially at elevated temperature and high discharge current.
3. Effects of the preparation process on the electrochemical properties of spinel LiMn_2O_4 cathode : The precursor and lithium salt were fully grinded with anhydrous alcohol as dispersant. The mixture was heated to 900oC for 15h, we improved the details in assembling batteries such as: prolong the time of spreating the mixture in an ultrasound, leave the pulp standing for a long time to layer, roller way and manner of dryness, et al. These measures can improve the cycle performance of cathode material.
4. Effects of the raw materials on the electrochemical properties of spinel LiMn_2O_4 cathode : we accurately tested the MnO_2 content in EMD bought by using Na2C_2O_4, and using EDTA direct titrimetric method to measure the content of Mn2+. We use Mn and sulphuric acid to synthesis the solution of MnSO4 and measure it’s concentration of the solution.This not only cut the cost but also provide correct data to the experiment hereafter. We studied the effect on the electrochemical properties of spinel LiMn_2O_4 cathode of refluxed EMD, EMD, self-made MnSO4 and Na2C_2O_4. Accordingly we choosed the self-made MnSO_4 as the most suitable manganese source.
5. The doping modification of LiMn_2O_4: Nitrogen, a certain amount of hydrazine and aluminum ions were added in while synthesizing LiAl_xMn_(2-x)O_4 precursor by co-precipitation and two-dryness method.The sintered product spinel LiAl_xMn_(2-x)O_4 with the increase of content of aluminum ions the lattice parameters get smaller enhance the crystal lattices. Although the discharge capacity decrease and plateau fall and become narrow with the increasing content of Al, these improve the cycle performance of cathode.
1、高密度前驱体的制备:通过共沉淀和二次干燥法制备了高密度的尖晶石LiMn_2O_4正极材料的前驱体。并分别从滤饼含水量,烘干方式,聚沉剂的添加方式的角度对前驱体振实密度的影响进行制备工艺的改进优化。探究出了最佳制备高密度、高纯度前驱体的条件,为合成高性能尖晶石LiMn_2O_4正极材料提供了重要的参考。
2、前驱体的不同处理方式对材料电性能的影响:通过采用共沉淀法经压滤、二次干燥制备出的锰氧化合物用作合成尖晶石LiMn_2O_4正极材料的前驱体,在共沉淀过程中,通过添加还原剂水合肼、通入保护气体氮气、添加氧化剂双氧水与空白试验作对比,研究了前驱体的不同处理方式对烧结合成的LiMn_2O_4结构与常温、高温下电化学性能的影响。实验结果表明:加入水合肼和通入氮气都能保证烧结产物LiMn_2O_4的纯度,并且二者结合可以有效地调产物LiMn_2O_4的纯度与颗粒粒径大小,并有较高的振实密度,高温高倍率下有较好的放电性能。
3、电极制作细节对电池电性能的影响:在无水乙醇为分散剂进行充分研磨,并选择900oC的条件下烧结15h合成正极材料的基础上,通过改进电极的制作细节如超声波分散时间的延长,静置分层,改进碾压方式及烘干方法。实验结果证明这些细节的改进都有助于提高电池的循环性能。
4、不同锰源对电池正极材料性能的影响:通过使用草酸钠法准确地测定了购买的EMD中MnO_2的含量,并使用EDTA直接滴定法测定了Mn2+的含量。用金属锰片和硫酸反应制备硫酸锰溶液,不仅节约了成本而且为前驱体的合成及以后的工作提供了准确的数据,有利于以后实验步骤的科学准确地开展。我们探究了电解二氧化锰用硝酸处理与非处理,自制的硫酸锰和草酸锰对电池材料性能的影响,发现不同锰源对电池性能有着一定的影响。
5、LiMn_2O_4的掺杂改性的研究:通过共沉淀和二次干燥法,在氮气和水合肼的保护下,通过掺杂铝离子制备前驱体,进而烧结制备尖晶石LiAl_xMn_(2-x)O_4,结果表明随着掺杂铝含量的增加晶胞参数a逐渐变小,晶格的稳定性增强,虽然放电比容量和放电平台有所降低,但高温高倍率的循环性能得到提高,这有望解决锂离子电池在高温条件下容易出现的安全性问题。通过研究对比我们发现用Li_2CO_3制备的正极材料的振实密度相对较高,并且掺杂Al_2O_3的振实密度相对较高。这些性能的改进将对工业生产有着重要的指导意义。
Spinel LiMn_2O_4 as one of the most promising alternative cathode materiales because it has the advantages of high vlatage, naturally abundant, low cost, simple in preparation, structure stability, no toxicity, good safety and environmentally benign nature. we carried out a series of studies in order to resolve the present remaining problems of spinel LiMn_2O_4. And we obtained some meaningful results. Main points of these are listed as below:
1. Synthesis of spinel LiMn_2O_4 precursor with high density: The precursor of spinel LiMn_2O_4 cathode material with high density was synthesized by co-precipitation and two-dryness method. we studied the relationship between the density of precursor and remaining water in filter cake, manner of dryness, manner of adding agglomerating agent. Our results provide an important reference on synthesis of high density spinel LiMn_2O_4 cathode material.
2. Effects of the precursor treated on the structure and electrochemical properties of spinel LiMn_2O_4 cathode: The precursor of spinel LiMn_2O_4 cathode material was synthesized by co-precipitation and two-dryness method. In this paper, based on our previous studies, we via a two-step drying method to pretreat the precursor of LiMn_2O_4 in different methods. Effects of N2, hydrazine, H2O2 on the structure of LiMn_2O_4 and discharge capacity at room temperature and elevated temperature are researched in detail. Experiments show that with the precursor treated by adding hydrazine and puring N2 to synthesize LiMn_2O_4 with complete lattice, uniform paricle size, a very pure spinel phase with an ordered octahedron crystal morphology and a large tap density.The electrochemical results show that it has higher specific capacity and higher cyclic lif than other samples, especially at elevated temperature and high discharge current.
3. Effects of the preparation process on the electrochemical properties of spinel LiMn_2O_4 cathode : The precursor and lithium salt were fully grinded with anhydrous alcohol as dispersant. The mixture was heated to 900oC for 15h, we improved the details in assembling batteries such as: prolong the time of spreating the mixture in an ultrasound, leave the pulp standing for a long time to layer, roller way and manner of dryness, et al. These measures can improve the cycle performance of cathode material.
4. Effects of the raw materials on the electrochemical properties of spinel LiMn_2O_4 cathode : we accurately tested the MnO_2 content in EMD bought by using Na2C_2O_4, and using EDTA direct titrimetric method to measure the content of Mn2+. We use Mn and sulphuric acid to synthesis the solution of MnSO4 and measure it’s concentration of the solution.This not only cut the cost but also provide correct data to the experiment hereafter. We studied the effect on the electrochemical properties of spinel LiMn_2O_4 cathode of refluxed EMD, EMD, self-made MnSO4 and Na2C_2O_4. Accordingly we choosed the self-made MnSO_4 as the most suitable manganese source.
5. The doping modification of LiMn_2O_4: Nitrogen, a certain amount of hydrazine and aluminum ions were added in while synthesizing LiAl_xMn_(2-x)O_4 precursor by co-precipitation and two-dryness method.The sintered product spinel LiAl_xMn_(2-x)O_4 with the increase of content of aluminum ions the lattice parameters get smaller enhance the crystal lattices. Although the discharge capacity decrease and plateau fall and become narrow with the increasing content of Al, these improve the cycle performance of cathode.
引文
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