掺杂锰酸锂的合成及其锂离子的反应—扩散过程研究
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摘要
尖晶石LiMn_2O_4具有电压高、安全性好、价格便宜、污染小等优点,被认为最有希望的正极材料之一。但尖晶石LiMn_2O_4在高温下容量衰减严重,限制了它的实际应用。
为了提高LiMn_2O_4的高温性能,本文主要用单因素实验和正交实验法优化了固相反应法制备尖晶石LiMn_2O_4的工艺,用均匀设计法优化了LiMn_2O_4的掺杂工艺,并结合X射线衍射(XRD)、扫描电镜(SEM)、恒电流充放电技术研究了合成工艺对材料结构、形态、比容量和循环性能的影响。用电化学阻抗研究了0.7 mol·L~(-1)LiBOB/PC-DEC(V_(PC):V_(DEC)=3:7)电解液中LiMn_2O_4和掺杂LiMn_2O_4的脱锂过程。
固相反应法制备LiMn_2O_4的工艺条件为:600℃预烧6h,750℃反应30h,600℃退火6h。所得LiMn_2O_4在25℃、55℃下初始放电容量分别为138mAh·g~(-1)和136mAh·g~(-1),50次循环后容量保持率为86.3%和66.2%。
单一Al~(3+)、Li~+或F~-掺杂能有效地提高LiMn_2O_4的高温循环性能,却降低了材料的放电比容量;Al~(3+)、Li~+、F~-复合掺杂的材料具有较高的比容量和较好的高温循环性能,其中Li_(1.03)Al_(0.03)Mn_(1.94)O_(3.94)F_(0.06)在55℃的放电比容量为127mAh·g~(-1),经过50次循环的容量保持率为91.3%。
电化学阻抗研究表明,锰酸锂的脱锂过程是一个包括表面膜扩散、界面电荷传递和体相扩散的Li~+反应—扩散过程,Al~(3+)、Li~+和F~-复合掺杂可提高正极材料表面膜的稳定性、降低膜厚度和电荷传递阻抗,但对Li~+的体相扩散系数影响不大。LiMn_2O_4和Li_(1.03)Al_(0.03)Mn_(1.94)O_(3.94)F_(0.06)表面膜扩散过程的平均活化能分别为30.04 kJ·mol~(-1)和17.51 kJ·mol~(-1),界面电荷传递平均活化能为4.71 kJ·mol~(-1)和7.21 kJ·mol~(-1),体相扩散过程的平均活化能分别为52.74kJ·mol~(-1)和52.46 kJ·mol~(-1)。三个过程的活化能表明Li~+体相扩散过程是整个脱嵌过程的控制步骤。
Lithium manganese oxide(LiMn_2O_4)has been considered as a promising cathode material for lithium ion batteries,since it is high cell voltage,high safety,low cost and low toxicity.Despite such merits,LiMn_2O_4 still has difficulty in practical applications,owing to its severe capacity depletion.To overcome this problem,many approaches have been carried out.
In this work,pure and doped LiMn_2O_4 were synthesized by a solid-state reaction.The effects of the synthesis conditions on their microstructure and electrochemical performance of spinel lithium manganese oxide were investigated by X-ray diffraction(XRD),scanning electron microscopy(SEM)and charge-discharge experiments.Electrochemical impedance spectroscopy(EIS)was used to investigate the effects of the substitution on the lithium extraction in the LiBOB based electrolyte.
The optimal synthesis conditions of pure LiMn_2O_4 were found to be a preheating temperature 600℃,preheating time 6h,calcination temperature 750℃,calcination time 30h, annealing temperature 600℃and annealing time 6h.The material synthesized using the optimal conditions provided an initial discharge capacity of 138mAh·g~(-1)、136mAh·g~(-1)and capacity retention of 86.3%during 50 cycles at 25℃.But its capacity retention was 66.2%at elevated temperature(55℃).
The results revealed that the samples substituted by Al~(3+),Li~+and F~-had a lower fade rate and a lower capacity than pure LiMn_2O_4.But the Al~(3+),Li~+ and F~-co-substituted sample had better cycle performance and higher initial capacity.Among these doped materials, Li_(1.03)Al_(0.03)Mn_(1.94)O_(3.94)F_(0.06)had the best cycle performance.Its initial capacity was 127 mAh·g~(-1)and its capacity retention was 91.3%after 50 cycles at 55℃.
The EIS tests showed that the Al~(3+),Li~+ and F~-co-substitution improved the stability of the surface film,reduced its thickness and the resistance of charge transfer,but it had little effect on the solid diffusion coefficient of Li~+.From the analysis of EIS,the lithium extraction processes of pure and doped LiMn_2O_4 was a the reaction-diffusion process of Li~+,which includes the Li~+ surface film diffusion processes,the charge transfer processes and Li~+ solid diffusion in the materials host.The average activation energy of the film diffusion,the charge transfer and the solid diffusion in LiMn_2O_4 was 30.04 kJ·mol~(-1),4.71 kJ·mol~(-1)and 52.74 kJ·mol~(-1),respectively,and that in Li_(1.03)Al_(0.03)Mn_(1.94)O_(3.94)F_(0.06)was calculated to be 17.51 kJ·mol~(-1),7.21 kJ·mol~(-1)and 52.46 kJ·mol~(-1).Compared to the values of the average activation energy of three processes,Li~+ solid diffusion in the host was supposed to be the rate-determining-step of the electrode process.
为了提高LiMn_2O_4的高温性能,本文主要用单因素实验和正交实验法优化了固相反应法制备尖晶石LiMn_2O_4的工艺,用均匀设计法优化了LiMn_2O_4的掺杂工艺,并结合X射线衍射(XRD)、扫描电镜(SEM)、恒电流充放电技术研究了合成工艺对材料结构、形态、比容量和循环性能的影响。用电化学阻抗研究了0.7 mol·L~(-1)LiBOB/PC-DEC(V_(PC):V_(DEC)=3:7)电解液中LiMn_2O_4和掺杂LiMn_2O_4的脱锂过程。
固相反应法制备LiMn_2O_4的工艺条件为:600℃预烧6h,750℃反应30h,600℃退火6h。所得LiMn_2O_4在25℃、55℃下初始放电容量分别为138mAh·g~(-1)和136mAh·g~(-1),50次循环后容量保持率为86.3%和66.2%。
单一Al~(3+)、Li~+或F~-掺杂能有效地提高LiMn_2O_4的高温循环性能,却降低了材料的放电比容量;Al~(3+)、Li~+、F~-复合掺杂的材料具有较高的比容量和较好的高温循环性能,其中Li_(1.03)Al_(0.03)Mn_(1.94)O_(3.94)F_(0.06)在55℃的放电比容量为127mAh·g~(-1),经过50次循环的容量保持率为91.3%。
电化学阻抗研究表明,锰酸锂的脱锂过程是一个包括表面膜扩散、界面电荷传递和体相扩散的Li~+反应—扩散过程,Al~(3+)、Li~+和F~-复合掺杂可提高正极材料表面膜的稳定性、降低膜厚度和电荷传递阻抗,但对Li~+的体相扩散系数影响不大。LiMn_2O_4和Li_(1.03)Al_(0.03)Mn_(1.94)O_(3.94)F_(0.06)表面膜扩散过程的平均活化能分别为30.04 kJ·mol~(-1)和17.51 kJ·mol~(-1),界面电荷传递平均活化能为4.71 kJ·mol~(-1)和7.21 kJ·mol~(-1),体相扩散过程的平均活化能分别为52.74kJ·mol~(-1)和52.46 kJ·mol~(-1)。三个过程的活化能表明Li~+体相扩散过程是整个脱嵌过程的控制步骤。
Lithium manganese oxide(LiMn_2O_4)has been considered as a promising cathode material for lithium ion batteries,since it is high cell voltage,high safety,low cost and low toxicity.Despite such merits,LiMn_2O_4 still has difficulty in practical applications,owing to its severe capacity depletion.To overcome this problem,many approaches have been carried out.
In this work,pure and doped LiMn_2O_4 were synthesized by a solid-state reaction.The effects of the synthesis conditions on their microstructure and electrochemical performance of spinel lithium manganese oxide were investigated by X-ray diffraction(XRD),scanning electron microscopy(SEM)and charge-discharge experiments.Electrochemical impedance spectroscopy(EIS)was used to investigate the effects of the substitution on the lithium extraction in the LiBOB based electrolyte.
The optimal synthesis conditions of pure LiMn_2O_4 were found to be a preheating temperature 600℃,preheating time 6h,calcination temperature 750℃,calcination time 30h, annealing temperature 600℃and annealing time 6h.The material synthesized using the optimal conditions provided an initial discharge capacity of 138mAh·g~(-1)、136mAh·g~(-1)and capacity retention of 86.3%during 50 cycles at 25℃.But its capacity retention was 66.2%at elevated temperature(55℃).
The results revealed that the samples substituted by Al~(3+),Li~+and F~-had a lower fade rate and a lower capacity than pure LiMn_2O_4.But the Al~(3+),Li~+ and F~-co-substituted sample had better cycle performance and higher initial capacity.Among these doped materials, Li_(1.03)Al_(0.03)Mn_(1.94)O_(3.94)F_(0.06)had the best cycle performance.Its initial capacity was 127 mAh·g~(-1)and its capacity retention was 91.3%after 50 cycles at 55℃.
The EIS tests showed that the Al~(3+),Li~+ and F~-co-substitution improved the stability of the surface film,reduced its thickness and the resistance of charge transfer,but it had little effect on the solid diffusion coefficient of Li~+.From the analysis of EIS,the lithium extraction processes of pure and doped LiMn_2O_4 was a the reaction-diffusion process of Li~+,which includes the Li~+ surface film diffusion processes,the charge transfer processes and Li~+ solid diffusion in the materials host.The average activation energy of the film diffusion,the charge transfer and the solid diffusion in LiMn_2O_4 was 30.04 kJ·mol~(-1),4.71 kJ·mol~(-1)and 52.74 kJ·mol~(-1),respectively,and that in Li_(1.03)Al_(0.03)Mn_(1.94)O_(3.94)F_(0.06)was calculated to be 17.51 kJ·mol~(-1),7.21 kJ·mol~(-1)and 52.46 kJ·mol~(-1).Compared to the values of the average activation energy of three processes,Li~+ solid diffusion in the host was supposed to be the rate-determining-step of the electrode process.
引文
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