钴基化合物及其复合材料的制备与电化学性能研究
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摘要
高比能电池体系对发展新能源与清洁能源技术,特别是电动汽车电源和大规模风能与太阳能的电力储存十分重要。采用具有多电子反应特征的电池体系原理上可以获得比常规单电子反应电池体系更高的能量密度。探索多电子反应电极材料、构建新型高能电池体系是电池技术发展的关键科学问题。基于金属Co和Co(Ⅱ)在电化学反应过程中进行2电子转移反应,可实现多电子反应功能,本论文以钻基化合物及其复合材料作为碱性二次电池的负极材料,对其电化学性能进行了研究,探索了其多电子反应机制,并在此基础上设计了一种新型二次电池体系。论文主要研究内容和结果如下：
在本论文中,通过机械合金化法制备了Co-Si3N4复合材料,通过XRD、TEM、XPS对复合材料的结构、形貌和表面及体相的化学状态进行了表征,通过恒流充放电和循环伏安测试研究了复合材料用作碱性二次电池负极的电化学行为。研究结果表明,金属Co和Si3N4经高能球磨处理后,形成了纳米尺度的金属Co,并分散镶嵌在非晶态Si3N4化合物的表面。钴元素在复合材料中主要以金属态的形式存在,仅在样品表面存在一层CoO氧化层。基于金属Co和Co(Ⅱ)之间的可逆电化学氧化还原反应,Co-Si3N4复合材料(Co/Si物质的量比为2/1)在碱液中表现出403 mAh/g的高放电容量,且电极具有良好的循环稳定性。另外,将该材料添加到稀土镁基合金中可显著提高合金的首次放电容量。
论文研究了采用热分解Co(OH)2前驱体制备了CoO和Co304材料,并将其用于碱性二次电池负极材料,研究了其电化学性能。采用XRD、SEM表征了样品的微观结构和形貌。通过恒流充放电和循环伏安测试研究了电极的放电容量及电化学反应机制。研究显示,制备的CoO在60 mA/g放电电流密度下,放电比容量较高,能够实现507 mAh/g的可逆电化学容量,其放电平台位于-0.8V附近,电化学反应归属为Co的氧化还原。研究同时表明,C0304的电化学容量也来自于Co的可逆氧化,由于在充电过程中C0304难以完全被还原生成金属Co,活性物质的利用不充分,电极的最高放电容量为391 mAh/g。以上研究结果表明,CoO和C0304在低电流密度放电情况下具有较高的放电容量,在大电流放电条件下具有稳定的循环性能。
论文采用均相沉淀法合成了α-Co(OH)2和β-Co(OH)2,通过XRD和SEM对其结构和形貌进行了表征,重点研究了Co(OH)2电极材料的高倍率性能。其中,β-Co(OH)2较α-Co(OH)2具有更加优异的电化学性能,在1C和10C充放电倍率下放电容量分别达到455和338 mAh/g,且循环性能稳定。其中,β-Co(OH)2在电化学氧化还原过程中可实现平均转移数为1.58个电子,该研究成果为探索多电子反应材料提供了新思路。在此基础上,探索构筑了一种新的Ni/Co电池体系。该Ni/Co电池体系以α-Ni(OH)2为正极活性物质,α-Co(OH)2或β-Co(OH)2为负极活性物质。该Ni/Co模拟电池在1C充放电倍率下放电比能量能够达到165Wh/kg(以α-Ni(OH)2和β-Co(OH)2为活性物质),循环50周以后能量保持在158.8Wh/kg,其能量保持率为96.2%。该研究结果有助于探索和发展新型二次电池体系。
The need for high energy density batteries becomes increasingly important for the development of new and clean energy technologies, such as electric vehicles and electrical storage from wind and solar power. In principle, the rechargeable battery system based on electrode-active materials with multi-electron reaction can achieve higher energy density as compared to a battery system built on conventional electrode materials with a single-electron redox. Therefore, it is critical to explore electrode-active materials with multi-electron reaction and construct novel battery-systems with dramatically increased energy density for the development of battery technology. As a two-electron reaction process between metallic Co and Co2+ ions is involved in the electrochemcial reaction, multi-electron transfer can been realized in Co-based compounds or composites. In this thesis, the electrochemical properties of Co-based compounds and composites as negative-active materials for alkaline rechargeable battery were investigated in detail. Furthermore, a new rechargeable battery system was constructed based on the explorement of the new Co-based negative materials. The main contents and results presented in this thesis are shown as following:
In this work, Co-Si3N4 composites were synthesized by direct ball-milling metallic Co and Si3N4 powders. The microstructure, morphology and chemical state of the ball-milled Co-Si3N4 composites were characterized by X-ray diffraction(XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of Co-Si3N4 composites used as negative materials in alkaline solution was investigated by galvanostatic charge-discharge process and cyclic voltammetry. It is demonstrated that Co exists as metallic state in the bulk phase of the composites except a trace of CoO on the surface. The metallic Co nanoparticles are highly dispersed on the amorphous inactive Si3N4 matrix. The maximum discharge capacity (403 mAh/g) of the Co-Si3N4 composites is obtained at the molar ratio of Co/Si=2/1 based on the reversible faradic reaction between Co and Co(Ⅱ). The Co-Si3N4 composite with the molar ratio of Co/Si=2/1 presents good cycle stability. Moreover, it is shown that the addition of Co-Si3N4 composites to the hydrogen storage PrMg12-Ni composite can notably enhance the initial discharge capacity of the hydrogen storage composite based on both the hydrogen electrochemical oxidation and Co electrochemical redox reaction.
Next, the electrochemical performance of CoO and Co3O4 used as negative-active materials for rechargeable alkaline battery was also investigated. CoO and Co3O4 were obtained by decomposition of the a-Co(OH)2 precursor at 450℃in Ar and air atmosphere, respectively. XRD and SEM were used to characterize their microstructure and morphology. The discharge capacity and reversible faradic reaction involved in the material were elucidated through galvanostatic charge-discharge process and cycle voltammetry (CV) technique. It is shown that CoO has the highest capacity of up to 507 mAh/g at the discharge current density of 60 mA/g. The discharge potential plateau is around-0.8 V, consistent with Co redox potential in alkaline solution. The electrochemical reaction process of Co3O4 is similar to that of CoO. The maximum discharge capacity of Co3O4 is 391 mAh/g, indicating a low utilization of active materials due to the partially irreversible conversion between Co and Co3O4. It is concluded that CoO and Co3O4 electrodes exhibit a good capacity retention at the large discharge current density (400 mA/g), and enhanced capacity at the low discharge current density (60 mA/g).
Finally, a-Co(OH)2 andβ-Co(OH)2 were synthesized controllably via homogeneous precipitation, their microstructure as well as morphology were examined in detail by XRD and SEM. The high-rate discharge ability of cobalt hydroxides using as negative-active material in alkaline solution was investigated. It is shown thatβ-Co(OH)2 exhibits improved discharge capacity and excellent electrochemical durability as compared toα-Co(OH)2. The maximum discharge capacities of 455 and 338mAh/g are achieved for theβ-Co(OH)2 electrode at 1 and 10 C rate, respectively. In particular, on average,1.58 electrons are involved in the practical electrochemical process of theβ-Co(OH)2 electrode. Meanwhile, a new rechargeable battery system, consisting of a-Ni(OH)2 as the positive-active material andβ-Co(OH)2 as the negative-active material, is proposed on the basis of multi-electron reactions. The output energy density of Ni/Co prototype cell reaches 165 Wh/kg (based on the weights of both a-Ni(OH)2 and (3-Co(OH)2 active materials) and stabilizes at 158.8 Wh/kg after 50 cycles, revealing an energy retention of 96.2%. The strategy adapted in the present study could be helpful to explore and develop new power sources with a high energy density.
在本论文中,通过机械合金化法制备了Co-Si3N4复合材料,通过XRD、TEM、XPS对复合材料的结构、形貌和表面及体相的化学状态进行了表征,通过恒流充放电和循环伏安测试研究了复合材料用作碱性二次电池负极的电化学行为。研究结果表明,金属Co和Si3N4经高能球磨处理后,形成了纳米尺度的金属Co,并分散镶嵌在非晶态Si3N4化合物的表面。钴元素在复合材料中主要以金属态的形式存在,仅在样品表面存在一层CoO氧化层。基于金属Co和Co(Ⅱ)之间的可逆电化学氧化还原反应,Co-Si3N4复合材料(Co/Si物质的量比为2/1)在碱液中表现出403 mAh/g的高放电容量,且电极具有良好的循环稳定性。另外,将该材料添加到稀土镁基合金中可显著提高合金的首次放电容量。
论文研究了采用热分解Co(OH)2前驱体制备了CoO和Co304材料,并将其用于碱性二次电池负极材料,研究了其电化学性能。采用XRD、SEM表征了样品的微观结构和形貌。通过恒流充放电和循环伏安测试研究了电极的放电容量及电化学反应机制。研究显示,制备的CoO在60 mA/g放电电流密度下,放电比容量较高,能够实现507 mAh/g的可逆电化学容量,其放电平台位于-0.8V附近,电化学反应归属为Co的氧化还原。研究同时表明,C0304的电化学容量也来自于Co的可逆氧化,由于在充电过程中C0304难以完全被还原生成金属Co,活性物质的利用不充分,电极的最高放电容量为391 mAh/g。以上研究结果表明,CoO和C0304在低电流密度放电情况下具有较高的放电容量,在大电流放电条件下具有稳定的循环性能。
论文采用均相沉淀法合成了α-Co(OH)2和β-Co(OH)2,通过XRD和SEM对其结构和形貌进行了表征,重点研究了Co(OH)2电极材料的高倍率性能。其中,β-Co(OH)2较α-Co(OH)2具有更加优异的电化学性能,在1C和10C充放电倍率下放电容量分别达到455和338 mAh/g,且循环性能稳定。其中,β-Co(OH)2在电化学氧化还原过程中可实现平均转移数为1.58个电子,该研究成果为探索多电子反应材料提供了新思路。在此基础上,探索构筑了一种新的Ni/Co电池体系。该Ni/Co电池体系以α-Ni(OH)2为正极活性物质,α-Co(OH)2或β-Co(OH)2为负极活性物质。该Ni/Co模拟电池在1C充放电倍率下放电比能量能够达到165Wh/kg(以α-Ni(OH)2和β-Co(OH)2为活性物质),循环50周以后能量保持在158.8Wh/kg,其能量保持率为96.2%。该研究结果有助于探索和发展新型二次电池体系。
The need for high energy density batteries becomes increasingly important for the development of new and clean energy technologies, such as electric vehicles and electrical storage from wind and solar power. In principle, the rechargeable battery system based on electrode-active materials with multi-electron reaction can achieve higher energy density as compared to a battery system built on conventional electrode materials with a single-electron redox. Therefore, it is critical to explore electrode-active materials with multi-electron reaction and construct novel battery-systems with dramatically increased energy density for the development of battery technology. As a two-electron reaction process between metallic Co and Co2+ ions is involved in the electrochemcial reaction, multi-electron transfer can been realized in Co-based compounds or composites. In this thesis, the electrochemical properties of Co-based compounds and composites as negative-active materials for alkaline rechargeable battery were investigated in detail. Furthermore, a new rechargeable battery system was constructed based on the explorement of the new Co-based negative materials. The main contents and results presented in this thesis are shown as following:
In this work, Co-Si3N4 composites were synthesized by direct ball-milling metallic Co and Si3N4 powders. The microstructure, morphology and chemical state of the ball-milled Co-Si3N4 composites were characterized by X-ray diffraction(XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of Co-Si3N4 composites used as negative materials in alkaline solution was investigated by galvanostatic charge-discharge process and cyclic voltammetry. It is demonstrated that Co exists as metallic state in the bulk phase of the composites except a trace of CoO on the surface. The metallic Co nanoparticles are highly dispersed on the amorphous inactive Si3N4 matrix. The maximum discharge capacity (403 mAh/g) of the Co-Si3N4 composites is obtained at the molar ratio of Co/Si=2/1 based on the reversible faradic reaction between Co and Co(Ⅱ). The Co-Si3N4 composite with the molar ratio of Co/Si=2/1 presents good cycle stability. Moreover, it is shown that the addition of Co-Si3N4 composites to the hydrogen storage PrMg12-Ni composite can notably enhance the initial discharge capacity of the hydrogen storage composite based on both the hydrogen electrochemical oxidation and Co electrochemical redox reaction.
Next, the electrochemical performance of CoO and Co3O4 used as negative-active materials for rechargeable alkaline battery was also investigated. CoO and Co3O4 were obtained by decomposition of the a-Co(OH)2 precursor at 450℃in Ar and air atmosphere, respectively. XRD and SEM were used to characterize their microstructure and morphology. The discharge capacity and reversible faradic reaction involved in the material were elucidated through galvanostatic charge-discharge process and cycle voltammetry (CV) technique. It is shown that CoO has the highest capacity of up to 507 mAh/g at the discharge current density of 60 mA/g. The discharge potential plateau is around-0.8 V, consistent with Co redox potential in alkaline solution. The electrochemical reaction process of Co3O4 is similar to that of CoO. The maximum discharge capacity of Co3O4 is 391 mAh/g, indicating a low utilization of active materials due to the partially irreversible conversion between Co and Co3O4. It is concluded that CoO and Co3O4 electrodes exhibit a good capacity retention at the large discharge current density (400 mA/g), and enhanced capacity at the low discharge current density (60 mA/g).
Finally, a-Co(OH)2 andβ-Co(OH)2 were synthesized controllably via homogeneous precipitation, their microstructure as well as morphology were examined in detail by XRD and SEM. The high-rate discharge ability of cobalt hydroxides using as negative-active material in alkaline solution was investigated. It is shown thatβ-Co(OH)2 exhibits improved discharge capacity and excellent electrochemical durability as compared toα-Co(OH)2. The maximum discharge capacities of 455 and 338mAh/g are achieved for theβ-Co(OH)2 electrode at 1 and 10 C rate, respectively. In particular, on average,1.58 electrons are involved in the practical electrochemical process of theβ-Co(OH)2 electrode. Meanwhile, a new rechargeable battery system, consisting of a-Ni(OH)2 as the positive-active material andβ-Co(OH)2 as the negative-active material, is proposed on the basis of multi-electron reactions. The output energy density of Ni/Co prototype cell reaches 165 Wh/kg (based on the weights of both a-Ni(OH)2 and (3-Co(OH)2 active materials) and stabilizes at 158.8 Wh/kg after 50 cycles, revealing an energy retention of 96.2%. The strategy adapted in the present study could be helpful to explore and develop new power sources with a high energy density.
引文
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