尖晶石型锰系氧化物的合成及超级电容性能研究
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摘要
超级电容器是一种介于电池和传统电容器之间的新型储能器件,具有高功率、高能量密度、长循环寿命和对环境无污染等优点。本文研究了锰系尖晶石型电极材料(LiMn_2O_4和λ-MnO_2),其具有三维离子通道,锂离子可以可逆地从尖晶石晶格中脱嵌,具有能量密度高、循环性能稳定、可进行大电流放电、价格低廉等优点。因此对于尖晶石型锰系电极材料的超级电容性能研究,将使电化学超级电容器的发展前景更加广阔。
主要采用操作简单、易于工业化生产的高温固相法制备LiMn_2O_4电极材料。利用X射线衍射(X-ray Diffraction XRD),扫描电子显微镜(Scanningelectron micrograph SEM)以及各种电化学性能测试方法研究了合成原料、煅烧温度、煅烧时间、反应物配比等对LiMn_2O_4的结构和电容性能的影响,发现采用固相合成法制备尖晶石LiMn_2O_4时,Li_2CO_3和电解二氧化锰(EMD)是最优的锂源和锰源。在800℃下烧制4h,产物的晶型结构已较完整,进一步延长煅烧时间对性能影响不大。Li/Mn摩尔比为1.08/2时所制材料具有较高放电容量。偏离该数值后,所制材料放电容量均会下降。
将LiMn_2O_4与稀酸作用得到λ-MnO_2,其仍然保持了尖晶石的面心立方点阵,研究了LiMn_2O_4和λ-MnO_2在不同电解液中的电化学性能。在(NH_4)_2SO_4溶液中,LiMn_2O_4和λ-MnO_2电极在电位窗口0～1.OV(vs SCE)范围内时具有较好的电容行为。电解液的浓度对电容性能也有影响,浓度越高,比容量也越高,并对LiMn_2O_4在中性电解液中产生电容的机理进行了初步探讨。
制备了不同LiMn_2O_4含量的LiMn_2O_4/C和LiMn_2O_4/MnO_2复合材料,研究了其在LiMn_2O_4溶液中的电化学性能,复合活性碳后的电极材料的伏安行为既体现有双电层的电容行为,又有法拉第电容行为,含80%活性炭的LiMn_2O_4/C复合电极容量达到最大,复合了20%LiMn_2O_4的LiMn_2O_4/MnO_2电极材料的比容量为151F·g~(-1),比MnO_2电极增加了22%,更适合用作超级电容器电极材料。这些特性表明复合电极材料是比较理想的超级电容器材料。
分析了尖晶石型化合物LiMn_2O_4的晶格结构,比较了八面体场中可供掺杂的金属离子价电子组态的稳定性及掺杂金属离子对LiMn_2O_4晶体场稳定化能的影响,为掺杂金属离子的选择提供了理论指导。XRD和SEM研究结果表明,在研究范围内掺入Al,Co,Ni,Zn和Ti后,LiM_0.1Mn_1.9O_4仍为单一的正尖晶石相结构。电化学性能研究发现:掺杂适量的Al,Co,Ni,Zn,Ti后,能提高LiMn_2O_4电极的放电比容量,改善电极材料的循环性能,使其真正具有实用价值。
制备了不同电极材料的混合超级电容器。采用LiMn_2O_4和AC组成混合超级电容器时,在Li_2SO_4水溶液中比在(NH_4)_2SO_4水溶液具有更好的电容性能,其工作电压可达1.8V。当电流密度为2mA·cm~(-2)时,其比容量、能量密度分别为62.3F.g~(-1)和28.0Wh·kg~(-1)。采用LiA1_0.1Mn_1.9O_4代替LiMn_2O_4与AC组成混合超级电容器时,当电流密度大于10mA·cm~(-2)时,具有较LiMn_2O_4高的比容量和能量密度。所以Al掺杂后的电极材料更适合大电流充放电,更具有实用性。首次将λ-Mn0_2用作混合超级电容器电极材料,λ-MnO_2/Li_2SO_4/AC混合超级电容器的工作电位可高达2.2V,其具有较大的功率密度和能量密度,具有较好的电容性能。λ-Mn0_2用作混合超级电容器电极材料的研究,为拓展λ-MnO_2的用途提供了依据,并使电化学超级电容器的发展前景更加广阔。
Supercapacitors are new storage devices between batteries and traditional capacitors. They have a lot of advantages, such as high power density, high energy density, longer cycle life, low toxicity. In this dissertation, spinel electrode materials (LiMn_2O_4 andλ-MnO_2) were investigated and exploited. They have spinel structure with a space group Fd3m where the lithium ions can reversibly insert/extract into/out the spinel crystal lattice. In addition, they have high energy density, steady cycle performance, charge-discharge performance at great current and low price, etc. Therefore, the performance study of electrode materials of spinel manganese series will have a wider foreground in development of electrochemical supercapacitor.
LiMn_2O_4 electrode materials were mainly synthesized by high temperature solid-state reaction with simple operation and easy industrialization. X-ray Diffraction(XRD), Scanning electron micrograph(SEM) and various electrochemical testing methods were employed to investigate the effect of synthesized materials, calcining temperature, calcining time, and ratio of reactant on the structure and capacitance performance of LiMn_2O_4 The results suggest that Li_2CO_3 and EMD are optimum lithium and manganese origin when LiMn_2O_4 was prepared by solid-state synthesis reaction. The crystal structure of the product has already been integrity by calcining at 800℃for 4h, and the calcining time further prolonged is insignificant. When the mol ratio of Li/Mn is 1.08/2, the synthesized material has high discharge capacitance. Once the mol ratio deviates from the value, discharge capacitance of the synthesized material will decrease.
λ-MnO_2 was obtained by reaction of LiMn_2O_4 and dilutes acid, and the pure cubic spinel structure still is preserved. The electrochemical performances of LiMn_2O_4 andλ-MnO_2 were studied in different electrolytes. In the (NH_4)_2SO_4 solution, the electrodes of LiMn_2O_4 andλ-MnO_2 exhibit good capacitance behavior in the potential window of 0-1V(vs.SCE). The capacitance performances are also affected by the concentration of electrolytes. Higher the concentration is, higher the specific capacitance is. Besides, the mechanism of LiMn_2O_4 occurring capacitance has been discussed.
The composite materials of LiMn_2O_4/C and LiMn_2O_2/MnO_2 with different LiMn_2O_4 contents were prepared, and its electrochemical performances were investigated in Li_2SO_4 solution. It is summarized that the behavior of cyclic voltammogram of electrode materials with composite carbon not only exhibits the capacitance behavior of double-layer capacitance, but also has capacitance behavior of Faraday. The composite electrode of LiMn_2O_4/C with 80% active carbon can reach to the highest capacitance. The specific capacitance of electrode material of LiMn_2O_4/MnO_2 with 20% LiMn_2O_4 is 151 F·g~(-1),increasing 22% than that of electrode of MnO_2.It is suitable to be used as electrode material of supercapacitor. These performances determine that composite electrode materials are relatively perfect materials of supercapacitor.
Crystal lattice structure of spinel LiMn_2O_4 was analyzed, and the stability of electronic configuration of doping metallic ions in octahedrons-field and effect of doping metallic ions on crystal-field stabilization energy of LiMn_2O_4 also were analyzed and compared. All of these supply theory guide for doped metallic ions. The research results of XRD and SEM indicate LiM_(0.1)Mn_(1.9)O_4 still is pure spinel phase structure with different contents of doped Al,Co,Ni,Zn,and Ti.The researches of electrochemical performances show that the discharge specific capacitances of LiMn_2O_4 electrodes by doping appropriate amount of Al,Co,Ni, Zn, and Ti can be improved, and cyclic performance of electrode material also can be improved. The results display that LiMn_2O_4 possesses practical value.
Different kinds of hybrid supercapacitors were prepared. When hybrid supercapacitor was composed of LiMn_2O_4 and AC, a better capacitance capability was attained in Li_2SO_4 solution than in (NH_4)_2SO_4. Monocase working voltage can reach to 1.8V.Its specific capacitance and energy density is 62.3F·g~(-1) and 28.0Wh·kg~(-1) at the current density of 2mA·cm~2,respectively.When hybrid supercapacitor was composed of LiAl_(0.1)Mn_(1.9)O_4 and AC and the current density was bigger than 10mA·cm~2,the specific capacitance and energy density of LiAl_(0.1)Mn_(1.9)O_4 is higher than that of LiMn_2O_4.Therefore, the electrode material with doped Al is suitable to be charged/discharged at great current, having better capacitance performance.λ-MnO_2 used as electrode material of supercapacitor has good capacitance performance. The working potential of hybrid supercapacitor ofλ-MnO_2/Li_2SO_4/AC can reach 2.2V. It possesses high power density, energy density, and excellent capacitance performance, which supply basis for the research and application ofλ-MnO_2 used electrode materials of hybrid supercapacitor. Consequently, the studies ofλ-MnO_2 used electrode materials of hybrid supercapacitor make development of electrochemical supercapacitor have a wider prospect.
主要采用操作简单、易于工业化生产的高温固相法制备LiMn_2O_4电极材料。利用X射线衍射(X-ray Diffraction XRD),扫描电子显微镜(Scanningelectron micrograph SEM)以及各种电化学性能测试方法研究了合成原料、煅烧温度、煅烧时间、反应物配比等对LiMn_2O_4的结构和电容性能的影响,发现采用固相合成法制备尖晶石LiMn_2O_4时,Li_2CO_3和电解二氧化锰(EMD)是最优的锂源和锰源。在800℃下烧制4h,产物的晶型结构已较完整,进一步延长煅烧时间对性能影响不大。Li/Mn摩尔比为1.08/2时所制材料具有较高放电容量。偏离该数值后,所制材料放电容量均会下降。
将LiMn_2O_4与稀酸作用得到λ-MnO_2,其仍然保持了尖晶石的面心立方点阵,研究了LiMn_2O_4和λ-MnO_2在不同电解液中的电化学性能。在(NH_4)_2SO_4溶液中,LiMn_2O_4和λ-MnO_2电极在电位窗口0～1.OV(vs SCE)范围内时具有较好的电容行为。电解液的浓度对电容性能也有影响,浓度越高,比容量也越高,并对LiMn_2O_4在中性电解液中产生电容的机理进行了初步探讨。
制备了不同LiMn_2O_4含量的LiMn_2O_4/C和LiMn_2O_4/MnO_2复合材料,研究了其在LiMn_2O_4溶液中的电化学性能,复合活性碳后的电极材料的伏安行为既体现有双电层的电容行为,又有法拉第电容行为,含80%活性炭的LiMn_2O_4/C复合电极容量达到最大,复合了20%LiMn_2O_4的LiMn_2O_4/MnO_2电极材料的比容量为151F·g~(-1),比MnO_2电极增加了22%,更适合用作超级电容器电极材料。这些特性表明复合电极材料是比较理想的超级电容器材料。
分析了尖晶石型化合物LiMn_2O_4的晶格结构,比较了八面体场中可供掺杂的金属离子价电子组态的稳定性及掺杂金属离子对LiMn_2O_4晶体场稳定化能的影响,为掺杂金属离子的选择提供了理论指导。XRD和SEM研究结果表明,在研究范围内掺入Al,Co,Ni,Zn和Ti后,LiM_0.1Mn_1.9O_4仍为单一的正尖晶石相结构。电化学性能研究发现:掺杂适量的Al,Co,Ni,Zn,Ti后,能提高LiMn_2O_4电极的放电比容量,改善电极材料的循环性能,使其真正具有实用价值。
制备了不同电极材料的混合超级电容器。采用LiMn_2O_4和AC组成混合超级电容器时,在Li_2SO_4水溶液中比在(NH_4)_2SO_4水溶液具有更好的电容性能,其工作电压可达1.8V。当电流密度为2mA·cm~(-2)时,其比容量、能量密度分别为62.3F.g~(-1)和28.0Wh·kg~(-1)。采用LiA1_0.1Mn_1.9O_4代替LiMn_2O_4与AC组成混合超级电容器时,当电流密度大于10mA·cm~(-2)时,具有较LiMn_2O_4高的比容量和能量密度。所以Al掺杂后的电极材料更适合大电流充放电,更具有实用性。首次将λ-Mn0_2用作混合超级电容器电极材料,λ-MnO_2/Li_2SO_4/AC混合超级电容器的工作电位可高达2.2V,其具有较大的功率密度和能量密度,具有较好的电容性能。λ-Mn0_2用作混合超级电容器电极材料的研究,为拓展λ-MnO_2的用途提供了依据,并使电化学超级电容器的发展前景更加广阔。
Supercapacitors are new storage devices between batteries and traditional capacitors. They have a lot of advantages, such as high power density, high energy density, longer cycle life, low toxicity. In this dissertation, spinel electrode materials (LiMn_2O_4 andλ-MnO_2) were investigated and exploited. They have spinel structure with a space group Fd3m where the lithium ions can reversibly insert/extract into/out the spinel crystal lattice. In addition, they have high energy density, steady cycle performance, charge-discharge performance at great current and low price, etc. Therefore, the performance study of electrode materials of spinel manganese series will have a wider foreground in development of electrochemical supercapacitor.
LiMn_2O_4 electrode materials were mainly synthesized by high temperature solid-state reaction with simple operation and easy industrialization. X-ray Diffraction(XRD), Scanning electron micrograph(SEM) and various electrochemical testing methods were employed to investigate the effect of synthesized materials, calcining temperature, calcining time, and ratio of reactant on the structure and capacitance performance of LiMn_2O_4 The results suggest that Li_2CO_3 and EMD are optimum lithium and manganese origin when LiMn_2O_4 was prepared by solid-state synthesis reaction. The crystal structure of the product has already been integrity by calcining at 800℃for 4h, and the calcining time further prolonged is insignificant. When the mol ratio of Li/Mn is 1.08/2, the synthesized material has high discharge capacitance. Once the mol ratio deviates from the value, discharge capacitance of the synthesized material will decrease.
λ-MnO_2 was obtained by reaction of LiMn_2O_4 and dilutes acid, and the pure cubic spinel structure still is preserved. The electrochemical performances of LiMn_2O_4 andλ-MnO_2 were studied in different electrolytes. In the (NH_4)_2SO_4 solution, the electrodes of LiMn_2O_4 andλ-MnO_2 exhibit good capacitance behavior in the potential window of 0-1V(vs.SCE). The capacitance performances are also affected by the concentration of electrolytes. Higher the concentration is, higher the specific capacitance is. Besides, the mechanism of LiMn_2O_4 occurring capacitance has been discussed.
The composite materials of LiMn_2O_4/C and LiMn_2O_2/MnO_2 with different LiMn_2O_4 contents were prepared, and its electrochemical performances were investigated in Li_2SO_4 solution. It is summarized that the behavior of cyclic voltammogram of electrode materials with composite carbon not only exhibits the capacitance behavior of double-layer capacitance, but also has capacitance behavior of Faraday. The composite electrode of LiMn_2O_4/C with 80% active carbon can reach to the highest capacitance. The specific capacitance of electrode material of LiMn_2O_4/MnO_2 with 20% LiMn_2O_4 is 151 F·g~(-1),increasing 22% than that of electrode of MnO_2.It is suitable to be used as electrode material of supercapacitor. These performances determine that composite electrode materials are relatively perfect materials of supercapacitor.
Crystal lattice structure of spinel LiMn_2O_4 was analyzed, and the stability of electronic configuration of doping metallic ions in octahedrons-field and effect of doping metallic ions on crystal-field stabilization energy of LiMn_2O_4 also were analyzed and compared. All of these supply theory guide for doped metallic ions. The research results of XRD and SEM indicate LiM_(0.1)Mn_(1.9)O_4 still is pure spinel phase structure with different contents of doped Al,Co,Ni,Zn,and Ti.The researches of electrochemical performances show that the discharge specific capacitances of LiMn_2O_4 electrodes by doping appropriate amount of Al,Co,Ni, Zn, and Ti can be improved, and cyclic performance of electrode material also can be improved. The results display that LiMn_2O_4 possesses practical value.
Different kinds of hybrid supercapacitors were prepared. When hybrid supercapacitor was composed of LiMn_2O_4 and AC, a better capacitance capability was attained in Li_2SO_4 solution than in (NH_4)_2SO_4. Monocase working voltage can reach to 1.8V.Its specific capacitance and energy density is 62.3F·g~(-1) and 28.0Wh·kg~(-1) at the current density of 2mA·cm~2,respectively.When hybrid supercapacitor was composed of LiAl_(0.1)Mn_(1.9)O_4 and AC and the current density was bigger than 10mA·cm~2,the specific capacitance and energy density of LiAl_(0.1)Mn_(1.9)O_4 is higher than that of LiMn_2O_4.Therefore, the electrode material with doped Al is suitable to be charged/discharged at great current, having better capacitance performance.λ-MnO_2 used as electrode material of supercapacitor has good capacitance performance. The working potential of hybrid supercapacitor ofλ-MnO_2/Li_2SO_4/AC can reach 2.2V. It possesses high power density, energy density, and excellent capacitance performance, which supply basis for the research and application ofλ-MnO_2 used electrode materials of hybrid supercapacitor. Consequently, the studies ofλ-MnO_2 used electrode materials of hybrid supercapacitor make development of electrochemical supercapacitor have a wider prospect.
引文
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