锂离子电池正极材料锂钒氧系列化合物的制备、结构及性能研究
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摘要
自从发现钒氧化物在锂离子电池中作为正极材料具有充放电行为以来，由于其具有深度放电和较大放电容量的特性，已引起科学界的极大关注。本论文重点探讨了新的锂钒氧系列化合物的制备、结构、性能及其相互间的关系。
本工作用水热合成法成功制备了[Li_6(H_2O)_(16)V_(10)O_(28)]_n、{[LiNa_2(H_2O)_9]_2V_(10)O_(28)}_n、Li_2(H_2O)_(10)(NH_4)_4V_(10)O_(28)和(NH_4)_2[Ni(H_2O)_6]_2V_(10)O_(28)·4H_2O四种晶体，在此基础上采用低温脱水或脱氨的方法制备了新的Li_6V_(10)O_(28)、Li_2Na_4V_(10)O_(28)、H_4Li_2V_(10)O_(28)和H_2Ni_2V_(10)O_(28)系列锂离子活性材料。文中对前四种化合物进行了单晶x射线衍射结构分析，首次发现了[Li_6(H_2O)_(16)V_(10)O_(28)]_n、{[LiNa_2(H_2O)_9]_2V_(10)O_(28)}_n和(NH_4)_2[Ni(H_2O)_6]_2V_(10)O_(28)·4H_2O三种晶体结构；对后四种粉晶化合物进行了粉末x射线衍射及其它结构分析和形貌表征，并对其电化学性能进行了初步测试，首次描述了Li_6V_(10)O_(28)、Li_2Na_4V_(10)O_(28)、H_2Ni_2V_(10)O_(28)、H_4Li_2V_(10)O_(28)结构和性能。在这系列研究中取得了一些有价值的结果。
单晶X射线衍射结构分析表明，在合成单晶化合物中，由不同的阳离子形成的十钒酸盐化合物，其空间构型是不同的，但它们均能借助分子间氢键作用聚集形成三维有序的超分子结构；单晶中的阳离子均以水合离子或铵离子的结构形式分布在其结构框架之中，占有比未配位的阳离子本身体积大几倍的空间。
采用晶体低温脱水、脱氨均能得到纳米尺寸的粉晶，同时在晶体内部产生大量缺陷。粉晶团聚颗粒大小约为50nm～10μm，团聚颗粒均由更细小的晶粒和空隙构成，晶粒大小约为10～50nm，空隙大多为小于5nm的缝隙。晶粒的纳米尺寸的高比表面和隧道效应及缺陷的存在有利于离子的电迁移和充放电时锂离子的嵌入与脱嵌。
脱水、脱氨后的化合物粉晶结构均保持其前驱物的结构框架，即框架中存在较大的离子通道。离子通道有隧道型的，也有层状型的，这为充放电锂离子的嵌入与脱嵌提供了较大的空间。
用Gaussian03量化计算程序对[Li_6(H_2O)_(16)V_(10)O_(28)]_n化合物中的钒氧簇阴离子V_(10)O_(28)~(6-)结构单元的电荷分布进行了理论计算，首次得到V_(10)O_(28)~(6-)结构单元表面上氧原子电荷分布的理论数据，其理论电荷分布密度在0.450864～0.350250范围内，这数据说明了充放电的锂离子在活性材料中的定向迁移主要来自正负离子的相互作用，同时阻力较小，这将有利于锂离子的嵌入与脱嵌。钒簇阴离子的最高占有轨道和最低空轨道的能级差为3.55ev，该能级差决定钒簇阴离子接受电子的能力。
采用变温电阻测试和交流阻抗法研究了该系列纯活性材料的导电能力和作为正极材料锂离子在电池正极界面的阻抗及扩散系数。纯活性材料均为典型的n-p离子型半导体，常温下其电导率为10~(-1)～10Sm~(-1)(除H_2Ni_2V_(10)O_(28)的电导率为0.00143Sm~(-1)以外)；稳态时正电极界面阻抗为26～125ohm，其对应的扩散系数为10~(-7)～10~(-9)cm~2／s。
对照充放电曲线和循环伏安曲线讨论了活性材料的电化学氧化还原行为和放电能力，并计算了放电过程的嵌锂量。活性材料均有较大的嵌锂量，其中每摩尔H_2Ni_2V_(10)O_(28)活性材料的最大嵌锂量可达22.340摩尔；在恒电流为0.2mA／cm~2的条件下，H_2Ni_2V_(10)O_(28)活性材料在充放电电压区间为4.5～1.0V时的最大可逆放电容量为333mAh／g，当充放电衰减幅度较小时其可逆放电容量稳定在200mAh／g左右，充放电效率均可达98％以上；当电压区间4.5～0.2V时，H_2Ni_2V_(10)O_(28)活性材料可逆放电容量可达556mAh／g。活性材料的放电能力与材料的空间框架结构有关。所有结果表明，本工作制备的锂钒氧系列活性物质是一类很有希望的锂离子电池正极材料。
Polyoxovanadate cluster compounds have attracted much attention because of low cost and large charge/discharge capability used as cathode material in li-ion batteries. In this work, different decavanadate lithium salt compounds have been prepared, and their structure, propertie and the interactions between them have been discussed detailed.[Li_6(H_2O)_(16)V_(10)O_(28)]_n, {[LiNa_2(H_2O)_9]_2V_(10)O_(28)}_n, Li_2(H_2O)_(10)(NH_4)_4V_(10)O_(28), and (NH_4)_2[Ni(H_2O)_6]_2V_(10)O_(28)·4H_2O single crystals have been successfully synthesized by hydrothermal method. X-ray diffraction method has been used to determine the structure and find that [Li_6(H_2O)_(16)V_(10)O_(28)]_n, {[LiNa_2(H_2O)_9]_2V_(10)O_(28)}_n and (NH_4)_2[Ni(H_2O)_6]_2 V_(10)O_(28)·4H_2O single crystals are firstly discovered in the world. By low temperature pyrogenation method, Li_6V_(10)O_(28), Li_2Na_4V_(10)O_(28), H_4Li_2V_(10)O_(28) and H_2Ni_2V_(10)O_(28) compounds have been obtained, and their three-dimensional structures were determined by x-ray diffraction method. Various measurements have been carried out to determine the structure, appearance and propertie of the samples, especially used as cathode materials for lithium ion batteries. Some valuable results obtained are as follows.The structure analysis results indicate that, in these four single crystal compounds, different space frameworks of decavanadate salts are formed by the assemble of different cations, which forms a three-dimensional supermolecular structure by interactions of intermolecular hydrogen bond. All cations are the form of hydration ion and ammonium ion distributed in the framework structure of single crystals, and have much larger space volume than that of themselves.After dehydration or deammonium at low temperature, the obtained powder crystals was nano-sized particles with a large number of defects. The presence of large specific surface, tunnel effect and defects make the transfer of ion, insertion and extraction of Li ion readily during the charge/discharge processes used as cathode materials in Li ion betteries.The powder crystals still remain the primary framework structure after dehydration or deammonium, which provides a large number of ion passage as the model of tunnel or samdwich. It supplys preferable interspace for Li ion inseriton and extraction during charge/discharge processes.
The negative charge distribution on oxygen is in the range of 0.450864 to 0.350250 obtained by the theoretical calculation with Gaussian03w quantification computational procedure based on the surface atoms of the decavanadate anion in [Li_6(H_2O)_(16)V_(10)O_(28)]_n compound. The results show that the transfer of Li ion has lesser resistance due to the interactions of the cation and anion, it is helpful to the insertion and extraction of Li ion during charge-discharge processes.
The conductance of the pure material was studied using a resistance versus temperature, and internal resistances of the electrode and diffused coefficient of Li in the bulk of material were determined using exchange impedance spectroscopy techniques in a Li-ion battery model. The conductance of materials at room tempearture are in the range of 10~(-1)～10Sm~(-1), and the diffusing coefficient is in the range of 10~(-7)～10~(-9) cm~2/s.
The electrochemical behaviors and charge/discharge properties of materials are discussed by cyclic voltammetry and charge-discharge measurements. These materials show high Li-ion insertion capability. The largest Li-ion insertion capacity in H_2Ni_2V_(10)O_(28) reaches 22.34 mole Li. The discharge capacity of H_2Ni_2V_(10)O_(28) material can reaches 333mAh/g at the potential of 4.5～1.0V at 0.2mA/cm~2 discharge current. The large discharge capacity at 4.5～0.2V is 556mAh/g. At the same time, these materials show good reversibility during charge-discharge processes. The excellent electrochemical properities of the materials could be attributed to the framework structure. All the results suggest that the polyoxovanadate cluster compounds would be a promising cathode materials for Li-ion batteries.
本工作用水热合成法成功制备了[Li_6(H_2O)_(16)V_(10)O_(28)]_n、{[LiNa_2(H_2O)_9]_2V_(10)O_(28)}_n、Li_2(H_2O)_(10)(NH_4)_4V_(10)O_(28)和(NH_4)_2[Ni(H_2O)_6]_2V_(10)O_(28)·4H_2O四种晶体，在此基础上采用低温脱水或脱氨的方法制备了新的Li_6V_(10)O_(28)、Li_2Na_4V_(10)O_(28)、H_4Li_2V_(10)O_(28)和H_2Ni_2V_(10)O_(28)系列锂离子活性材料。文中对前四种化合物进行了单晶x射线衍射结构分析，首次发现了[Li_6(H_2O)_(16)V_(10)O_(28)]_n、{[LiNa_2(H_2O)_9]_2V_(10)O_(28)}_n和(NH_4)_2[Ni(H_2O)_6]_2V_(10)O_(28)·4H_2O三种晶体结构；对后四种粉晶化合物进行了粉末x射线衍射及其它结构分析和形貌表征，并对其电化学性能进行了初步测试，首次描述了Li_6V_(10)O_(28)、Li_2Na_4V_(10)O_(28)、H_2Ni_2V_(10)O_(28)、H_4Li_2V_(10)O_(28)结构和性能。在这系列研究中取得了一些有价值的结果。
单晶X射线衍射结构分析表明，在合成单晶化合物中，由不同的阳离子形成的十钒酸盐化合物，其空间构型是不同的，但它们均能借助分子间氢键作用聚集形成三维有序的超分子结构；单晶中的阳离子均以水合离子或铵离子的结构形式分布在其结构框架之中，占有比未配位的阳离子本身体积大几倍的空间。
采用晶体低温脱水、脱氨均能得到纳米尺寸的粉晶，同时在晶体内部产生大量缺陷。粉晶团聚颗粒大小约为50nm～10μm，团聚颗粒均由更细小的晶粒和空隙构成，晶粒大小约为10～50nm，空隙大多为小于5nm的缝隙。晶粒的纳米尺寸的高比表面和隧道效应及缺陷的存在有利于离子的电迁移和充放电时锂离子的嵌入与脱嵌。
脱水、脱氨后的化合物粉晶结构均保持其前驱物的结构框架，即框架中存在较大的离子通道。离子通道有隧道型的，也有层状型的，这为充放电锂离子的嵌入与脱嵌提供了较大的空间。
用Gaussian03量化计算程序对[Li_6(H_2O)_(16)V_(10)O_(28)]_n化合物中的钒氧簇阴离子V_(10)O_(28)~(6-)结构单元的电荷分布进行了理论计算，首次得到V_(10)O_(28)~(6-)结构单元表面上氧原子电荷分布的理论数据，其理论电荷分布密度在0.450864～0.350250范围内，这数据说明了充放电的锂离子在活性材料中的定向迁移主要来自正负离子的相互作用，同时阻力较小，这将有利于锂离子的嵌入与脱嵌。钒簇阴离子的最高占有轨道和最低空轨道的能级差为3.55ev，该能级差决定钒簇阴离子接受电子的能力。
采用变温电阻测试和交流阻抗法研究了该系列纯活性材料的导电能力和作为正极材料锂离子在电池正极界面的阻抗及扩散系数。纯活性材料均为典型的n-p离子型半导体，常温下其电导率为10~(-1)～10Sm~(-1)(除H_2Ni_2V_(10)O_(28)的电导率为0.00143Sm~(-1)以外)；稳态时正电极界面阻抗为26～125ohm，其对应的扩散系数为10~(-7)～10~(-9)cm~2／s。
对照充放电曲线和循环伏安曲线讨论了活性材料的电化学氧化还原行为和放电能力，并计算了放电过程的嵌锂量。活性材料均有较大的嵌锂量，其中每摩尔H_2Ni_2V_(10)O_(28)活性材料的最大嵌锂量可达22.340摩尔；在恒电流为0.2mA／cm~2的条件下，H_2Ni_2V_(10)O_(28)活性材料在充放电电压区间为4.5～1.0V时的最大可逆放电容量为333mAh／g，当充放电衰减幅度较小时其可逆放电容量稳定在200mAh／g左右，充放电效率均可达98％以上；当电压区间4.5～0.2V时，H_2Ni_2V_(10)O_(28)活性材料可逆放电容量可达556mAh／g。活性材料的放电能力与材料的空间框架结构有关。所有结果表明，本工作制备的锂钒氧系列活性物质是一类很有希望的锂离子电池正极材料。
Polyoxovanadate cluster compounds have attracted much attention because of low cost and large charge/discharge capability used as cathode material in li-ion batteries. In this work, different decavanadate lithium salt compounds have been prepared, and their structure, propertie and the interactions between them have been discussed detailed.[Li_6(H_2O)_(16)V_(10)O_(28)]_n, {[LiNa_2(H_2O)_9]_2V_(10)O_(28)}_n, Li_2(H_2O)_(10)(NH_4)_4V_(10)O_(28), and (NH_4)_2[Ni(H_2O)_6]_2V_(10)O_(28)·4H_2O single crystals have been successfully synthesized by hydrothermal method. X-ray diffraction method has been used to determine the structure and find that [Li_6(H_2O)_(16)V_(10)O_(28)]_n, {[LiNa_2(H_2O)_9]_2V_(10)O_(28)}_n and (NH_4)_2[Ni(H_2O)_6]_2 V_(10)O_(28)·4H_2O single crystals are firstly discovered in the world. By low temperature pyrogenation method, Li_6V_(10)O_(28), Li_2Na_4V_(10)O_(28), H_4Li_2V_(10)O_(28) and H_2Ni_2V_(10)O_(28) compounds have been obtained, and their three-dimensional structures were determined by x-ray diffraction method. Various measurements have been carried out to determine the structure, appearance and propertie of the samples, especially used as cathode materials for lithium ion batteries. Some valuable results obtained are as follows.The structure analysis results indicate that, in these four single crystal compounds, different space frameworks of decavanadate salts are formed by the assemble of different cations, which forms a three-dimensional supermolecular structure by interactions of intermolecular hydrogen bond. All cations are the form of hydration ion and ammonium ion distributed in the framework structure of single crystals, and have much larger space volume than that of themselves.After dehydration or deammonium at low temperature, the obtained powder crystals was nano-sized particles with a large number of defects. The presence of large specific surface, tunnel effect and defects make the transfer of ion, insertion and extraction of Li ion readily during the charge/discharge processes used as cathode materials in Li ion betteries.The powder crystals still remain the primary framework structure after dehydration or deammonium, which provides a large number of ion passage as the model of tunnel or samdwich. It supplys preferable interspace for Li ion inseriton and extraction during charge/discharge processes.
The negative charge distribution on oxygen is in the range of 0.450864 to 0.350250 obtained by the theoretical calculation with Gaussian03w quantification computational procedure based on the surface atoms of the decavanadate anion in [Li_6(H_2O)_(16)V_(10)O_(28)]_n compound. The results show that the transfer of Li ion has lesser resistance due to the interactions of the cation and anion, it is helpful to the insertion and extraction of Li ion during charge-discharge processes.
The conductance of the pure material was studied using a resistance versus temperature, and internal resistances of the electrode and diffused coefficient of Li in the bulk of material were determined using exchange impedance spectroscopy techniques in a Li-ion battery model. The conductance of materials at room tempearture are in the range of 10~(-1)～10Sm~(-1), and the diffusing coefficient is in the range of 10~(-7)～10~(-9) cm~2/s.
The electrochemical behaviors and charge/discharge properties of materials are discussed by cyclic voltammetry and charge-discharge measurements. These materials show high Li-ion insertion capability. The largest Li-ion insertion capacity in H_2Ni_2V_(10)O_(28) reaches 22.34 mole Li. The discharge capacity of H_2Ni_2V_(10)O_(28) material can reaches 333mAh/g at the potential of 4.5～1.0V at 0.2mA/cm~2 discharge current. The large discharge capacity at 4.5～0.2V is 556mAh/g. At the same time, these materials show good reversibility during charge-discharge processes. The excellent electrochemical properities of the materials could be attributed to the framework structure. All the results suggest that the polyoxovanadate cluster compounds would be a promising cathode materials for Li-ion batteries.
引文
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