锂离子电池正极材料尖晶石锰酸锂的制备与改性研究
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摘要
尖晶石型LiMn_2O_4具有工作电压高、安全性能好、生产成本低、对环境友好等特点，是21世纪最具有发展前景的锂离子电池正极材料之一。但尖晶石型LiMn_2O_4的理论比容量较低，电化学循环性能较差阻碍着其规模化应用。为寻找提高尖晶石型LiMn_2O_4的体积比能量和抑制容量衰减的有效方法，本文进行了高密度锰氧化物的制备、尖晶石型LiMn_2O_4的制备、掺杂对尖晶石型LiMn_2O_4的影响和Li~+离子脱／嵌过程探索等研究工作。
以电解锰粉为原料，采取低温焙烧-机械活化-高温焙烧的工艺制备高密度锰氧化物。考查了焙烧温度、焙烧时间和升温速率对物化性能和微观形貌的影响。结果表明：低温过程是锰的氧化过程，高温过程是锰氧化物的晶化过程。优化的热处理制度为：低温焙烧温度为700℃，保温7h，高温焙烧温度为1050℃，保温时间为7h。高密度锰氧化物为Mn_3O_4和Mn_2O_3的混合物，D_(50)≈4.0μm时粉体的振实密度为2.70g·cm~(-3)。
以高密度锰氧化物为前驱体，以Li_2CO_3为锂源，采用机械活化和固相烧结相结合的二段烧结法制备了尖晶石LiMn_2O_4。研究了烧结温度、烧结时间和配锂量对尖晶石结构、微观形貌和电化学性能的影响，结果表明：烧结温度对尖晶石结构、微观形貌和电化学性能有显著影响。烧结时间对尖晶石结构、微观形貌和电化学性能影响较小。配锂量对微观形貌影响小，对电化学性能影响大。缺锂型锂锰氧化物电化学循环性能差，富锂型锂锰氧化物电化学循环性能好，尖晶石锰酸锂的首次放电比容量的最大值出现在配锂量x(Li_xMn_2O_4)＝1.0附近，其中Li_(1.015)Mn_2O_4的首次放电比容量最高，为111.25mAh·g~(-1)(0.1C，4.2V，vs．C、)，循环30周期容量保持率为95.03％。
分别以CO_3O_4、NiO、TiO_2和ZrO_2为掺杂体，制备了掺杂锂锰氧化物Li_(1.015)Mn_(2-x)M_xO_4(M＝Co、Ni、Ti、Zr)。考查了掺杂离子、掺杂量对锂锰氧化物结构、微观形貌和电化学性能的影响，结果表明：掺杂改善了锂锰氧化物体系中阳离子混排程度，而未明显改变尖晶石结构。Ni掺杂改善了颗粒微观形貌，Co、Zr掺杂细化了微观颗粒。Ti掺杂提高了首次放电比容量。随着掺杂量的增大，首次放电比容量降低，电化学循环稳定性增强，掺杂有效抑制了电化学容量衰减。
采用交流阻抗技术对尖晶石型LiMn_2O_4脱／嵌锂过程进行了探索，结果表明：掺杂提高了交换电流密度，稳定了尖晶石结构，也对锂离子扩散系数有影响。
Spinel LiMn_2O_4 is one of the most promising cathode materials of 21st century because of high working voltage, excellent security, low manufacture cost, and environment friendly. But large-scale application is restricted because of low theoretical specific capacity and poor electrochemical performance. This dissertation emphasized on searching for resultful methods to improve bulk specific energy density and to restrain capacity fading. And the article mainly included preparation of high density manganese oxide, preparation of spinel LiMn_2O_4, doping effects on spinel LiMn_2O_4 and discussion about Li deintercalation/intercalation process.
High tap density manganese oxide was prepared through low temperature sintering-mechanical activation-high temperature sintering route with electrolytic manganese powder as raw material. The effects of sintering temperature, dwelling time and calefactive velocity on physical-chemistry property of manganese oxide were studied, and showed that the low temperature sintering process is the oxidation of Mn, and the high temperature sintering process actually the crystallization process of manganese oxide prepared in low temperature sintering. And heat treatment system is as follows: low sintering temperature is 700℃and dwelling time is 7h, high temperature sintering 1050℃, respectively, and dwelling time is 7h. X-ray-diffraction spectra indicated that the manganese oxides were the mixture of Mn_3O_4 and Mn_2O_3, and its tap density is 2.70g·cm~(-3)(D_(50)≈4.0μm).
LiMn_2O_4 was prepared with high tap density manganese oxides we as precursor and Li_2CO_3 as Li sources through the mechanical activation-high temperature solid state route. Effect of sintering temperature, sintering time and x(Li_xMn_2O_4) on spinel structure, morphology and electrochemical property, and the result showed that Sintering temperature affected Spinel structure, morphology and electrochemical property evidently. Sintering time affected spinel structure, morphology and electrochemical property slightly. Electrochemical property was affected by X(Li_xMn_2O_4) remarkably, Li-rich spinel LiMn_2O_4 exhibited good capacity retention, and Li-poor spinel LiMn_2O_4 showed poor capacity retention. And the initial discharge specific capacity of Li_(1.015)Mn_2O_4 is 111.25mAh·g~(-1)(0.1C, 4.2V, vs.C) and is the maximum among the different Li/Mn molar ratio, and has a high capacity retention of 95.03% after 30 cycles.
Lithium manganese oxides of Li_(1.015)Mn_(2-x)M_xO_4(M=Co、Ni、Ti、Zr) were prepared with Co_3O_4、NiO、TiO_2、ZrO_2 as dopant. Effects on structure, morphology and electrochemical property were investigated, and the results indicated that Li_(1.015)Mn_(2-x)M_xO_4(M=Co、Ni、Ti、Zr; x≤0.1) exhibited a cubic pure spinel structure, except Li_(1.015)Mn_(1.9)Zr_(0.1)O_4. Cations order was optimized. With the increasing of dopant content, initial specific capacity deceased and electrochemical performance was enhanced. Initial specific capacity deceased unnotably when x≤0.01 but notably when x＞0.1. Particle sizes became smaller and tap density decreased in a way with the import of substituted ionic.
Li deintercalation/intercalation process from spinel LiMn_2O_4 was studied by AC impedance measurement. It was found that the exchange current density and structure stability were enhanced through doping, and diffusion coefficient of Li~+ was also affected by doping.
以电解锰粉为原料，采取低温焙烧-机械活化-高温焙烧的工艺制备高密度锰氧化物。考查了焙烧温度、焙烧时间和升温速率对物化性能和微观形貌的影响。结果表明：低温过程是锰的氧化过程，高温过程是锰氧化物的晶化过程。优化的热处理制度为：低温焙烧温度为700℃，保温7h，高温焙烧温度为1050℃，保温时间为7h。高密度锰氧化物为Mn_3O_4和Mn_2O_3的混合物，D_(50)≈4.0μm时粉体的振实密度为2.70g·cm~(-3)。
以高密度锰氧化物为前驱体，以Li_2CO_3为锂源，采用机械活化和固相烧结相结合的二段烧结法制备了尖晶石LiMn_2O_4。研究了烧结温度、烧结时间和配锂量对尖晶石结构、微观形貌和电化学性能的影响，结果表明：烧结温度对尖晶石结构、微观形貌和电化学性能有显著影响。烧结时间对尖晶石结构、微观形貌和电化学性能影响较小。配锂量对微观形貌影响小，对电化学性能影响大。缺锂型锂锰氧化物电化学循环性能差，富锂型锂锰氧化物电化学循环性能好，尖晶石锰酸锂的首次放电比容量的最大值出现在配锂量x(Li_xMn_2O_4)＝1.0附近，其中Li_(1.015)Mn_2O_4的首次放电比容量最高，为111.25mAh·g~(-1)(0.1C，4.2V，vs．C、)，循环30周期容量保持率为95.03％。
分别以CO_3O_4、NiO、TiO_2和ZrO_2为掺杂体，制备了掺杂锂锰氧化物Li_(1.015)Mn_(2-x)M_xO_4(M＝Co、Ni、Ti、Zr)。考查了掺杂离子、掺杂量对锂锰氧化物结构、微观形貌和电化学性能的影响，结果表明：掺杂改善了锂锰氧化物体系中阳离子混排程度，而未明显改变尖晶石结构。Ni掺杂改善了颗粒微观形貌，Co、Zr掺杂细化了微观颗粒。Ti掺杂提高了首次放电比容量。随着掺杂量的增大，首次放电比容量降低，电化学循环稳定性增强，掺杂有效抑制了电化学容量衰减。
采用交流阻抗技术对尖晶石型LiMn_2O_4脱／嵌锂过程进行了探索，结果表明：掺杂提高了交换电流密度，稳定了尖晶石结构，也对锂离子扩散系数有影响。
Spinel LiMn_2O_4 is one of the most promising cathode materials of 21st century because of high working voltage, excellent security, low manufacture cost, and environment friendly. But large-scale application is restricted because of low theoretical specific capacity and poor electrochemical performance. This dissertation emphasized on searching for resultful methods to improve bulk specific energy density and to restrain capacity fading. And the article mainly included preparation of high density manganese oxide, preparation of spinel LiMn_2O_4, doping effects on spinel LiMn_2O_4 and discussion about Li deintercalation/intercalation process.
High tap density manganese oxide was prepared through low temperature sintering-mechanical activation-high temperature sintering route with electrolytic manganese powder as raw material. The effects of sintering temperature, dwelling time and calefactive velocity on physical-chemistry property of manganese oxide were studied, and showed that the low temperature sintering process is the oxidation of Mn, and the high temperature sintering process actually the crystallization process of manganese oxide prepared in low temperature sintering. And heat treatment system is as follows: low sintering temperature is 700℃and dwelling time is 7h, high temperature sintering 1050℃, respectively, and dwelling time is 7h. X-ray-diffraction spectra indicated that the manganese oxides were the mixture of Mn_3O_4 and Mn_2O_3, and its tap density is 2.70g·cm~(-3)(D_(50)≈4.0μm).
LiMn_2O_4 was prepared with high tap density manganese oxides we as precursor and Li_2CO_3 as Li sources through the mechanical activation-high temperature solid state route. Effect of sintering temperature, sintering time and x(Li_xMn_2O_4) on spinel structure, morphology and electrochemical property, and the result showed that Sintering temperature affected Spinel structure, morphology and electrochemical property evidently. Sintering time affected spinel structure, morphology and electrochemical property slightly. Electrochemical property was affected by X(Li_xMn_2O_4) remarkably, Li-rich spinel LiMn_2O_4 exhibited good capacity retention, and Li-poor spinel LiMn_2O_4 showed poor capacity retention. And the initial discharge specific capacity of Li_(1.015)Mn_2O_4 is 111.25mAh·g~(-1)(0.1C, 4.2V, vs.C) and is the maximum among the different Li/Mn molar ratio, and has a high capacity retention of 95.03% after 30 cycles.
Lithium manganese oxides of Li_(1.015)Mn_(2-x)M_xO_4(M=Co、Ni、Ti、Zr) were prepared with Co_3O_4、NiO、TiO_2、ZrO_2 as dopant. Effects on structure, morphology and electrochemical property were investigated, and the results indicated that Li_(1.015)Mn_(2-x)M_xO_4(M=Co、Ni、Ti、Zr; x≤0.1) exhibited a cubic pure spinel structure, except Li_(1.015)Mn_(1.9)Zr_(0.1)O_4. Cations order was optimized. With the increasing of dopant content, initial specific capacity deceased and electrochemical performance was enhanced. Initial specific capacity deceased unnotably when x≤0.01 but notably when x＞0.1. Particle sizes became smaller and tap density decreased in a way with the import of substituted ionic.
Li deintercalation/intercalation process from spinel LiMn_2O_4 was studied by AC impedance measurement. It was found that the exchange current density and structure stability were enhanced through doping, and diffusion coefficient of Li~+ was also affected by doping.
引文
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