以金属锂作为负极的固态锂‐氧气电池由于超高的比能量和宽操作温度而成为当前国际研究的热点,但是金属锂的高反应活性使基于金属锂负极的固态锂金属电池难以在高温下稳定地工作.用高离子导体的三元碱金属锂盐作为金属锂(Li)负极与固态...以金属锂作为负极的固态锂‐氧气电池由于超高的比能量和宽操作温度而成为当前国际研究的热点,但是金属锂的高反应活性使基于金属锂负极的固态锂金属电池难以在高温下稳定地工作.用高离子导体的三元碱金属锂盐作为金属锂(Li)负极与固态电解质(Li_(1.5)Al_(0.5)Ge_(1.5)P_(3)O_(12),LAGP)之间的人工界面层,改善Li/LAGP之间的界面接触,降低其界面阻抗,提高界面稳定性.基于此制备的固态锂‐氧气电池在150℃可以释放出1.58 m Ah·cm^(12)的容量,对应库伦效率接近100%,在定容0.1 m Ah·cm^(12)时,可稳定循环40周期.为高温电池的研究和开发提供了有效的途径.展开更多
Density functional theory calculations together with ab initio molecular dynamics(AIMD)simulations have been used to study the solvation,diffusion and transformation of Li^(+)and LiO_(2)upon O_(2)reduction in three or...Density functional theory calculations together with ab initio molecular dynamics(AIMD)simulations have been used to study the solvation,diffusion and transformation of Li^(+)and LiO_(2)upon O_(2)reduction in three organic electrolytes.These processes are critical for the performance of Li-air batteries.Apart from studying the structure of the solvation shells in detail,AIMD simulations have been used to derive the diffusivity and together with the Blue Moon ensemble approach to explore LiO_(2)formation from Li^(+)and O_(2)−and the subsequent disproportionation of 2LiO_(2)into Li_(2)O_(2)+O_(2).By comparing the results of the simulations to gas phase calculations,the impact of electrolytes on these reactions is assessed which turns out to be more pronounced for the ionic species involved in these reactions.展开更多
Electrolytes are widely considered as a key component in Li–O;batteries (LOBs) because they greatly affect the discharge-charge reaction kinetics and reversibility.Herein,we report that 1,3-dimethyl-2-imidazolidinone...Electrolytes are widely considered as a key component in Li–O;batteries (LOBs) because they greatly affect the discharge-charge reaction kinetics and reversibility.Herein,we report that 1,3-dimethyl-2-imidazolidinone (DMI) is an excellent electrolyte solvent for LOBs.Comparing with conventional ether and sulfone based electrolytes,it has higher Li_(2)O_(2)and Li_(2)CO_(3)solubility,which on the one hand depresses cathode passivation during discharge,and on the other hand promotes the liquid-phase redox shuttling during charge,and consequently lowers the overpotential and improves the cyclability of the battery.However,despite the many advantages at the cathode side,DMI is not stable with bare Li anode.Thus,we have developed a pretreatment method to grow a protective artificial solid-state electrolyte interface(SEI) to prevent the unfavorable side-reactions on Li.The SEI film was formed via the reaction between fluorine-rich organic reagents and Li metal.It is composed of highly Li^(+)-conducting Li_(x)BO_(y),LiF,Li_(x)NO_(y),Li_(3)N particles and some organic compounds,in which Li_(x)BO_(y)serves as a binder to enhance its mechanical strength.With the protective SEI,the coulombic efficiency of Li plating/stripping in DMI electrolyte increased from 20%to 98.5%and the fixed capacity cycle life of the assembled LOB was elongated to205 rounds,which was almost fivefold of the cycle life in dimethyl sulfoxide (DMSO) or tetraglyme(TEGDME) based electrolytes.Our work demonstrates that molecular polarity and ionic solvation structure are the primary issues to be considered when designing high performance Li–O;battery electrolytes,and cross-linked artificial SEI is effective in improving the anodic stability.展开更多
文摘利用工艺简单,成本低廉的共沉淀法制得Co OOH,并用作非水性锂-氧气电池阴极催化剂。通过恒流充放电、线性伏安扫描(LSV)和电化学阻抗(EIS)测试研究了电极的电化学性能。结果表明:由于Co OOH能够明显提高氧气还原反应(ORR)的催化活性,与未使用Co OOH的电极相比较,使用Co OOH为催化剂的电极首次放电容量高达5 093 m Ah·g^(-1),提高了1.7倍。电池的充电过电压降低了约460 m V,充电可逆性得到增强,充放电可逆性提高,使得循环性能得到显著改善。
文摘以金属锂作为负极的固态锂‐氧气电池由于超高的比能量和宽操作温度而成为当前国际研究的热点,但是金属锂的高反应活性使基于金属锂负极的固态锂金属电池难以在高温下稳定地工作.用高离子导体的三元碱金属锂盐作为金属锂(Li)负极与固态电解质(Li_(1.5)Al_(0.5)Ge_(1.5)P_(3)O_(12),LAGP)之间的人工界面层,改善Li/LAGP之间的界面接触,降低其界面阻抗,提高界面稳定性.基于此制备的固态锂‐氧气电池在150℃可以释放出1.58 m Ah·cm^(12)的容量,对应库伦效率接近100%,在定容0.1 m Ah·cm^(12)时,可稳定循环40周期.为高温电池的研究和开发提供了有效的途径.
基金supported by the German Research Foundation (DFG) through contract GR 1503/38-1。
文摘Density functional theory calculations together with ab initio molecular dynamics(AIMD)simulations have been used to study the solvation,diffusion and transformation of Li^(+)and LiO_(2)upon O_(2)reduction in three organic electrolytes.These processes are critical for the performance of Li-air batteries.Apart from studying the structure of the solvation shells in detail,AIMD simulations have been used to derive the diffusivity and together with the Blue Moon ensemble approach to explore LiO_(2)formation from Li^(+)and O_(2)−and the subsequent disproportionation of 2LiO_(2)into Li_(2)O_(2)+O_(2).By comparing the results of the simulations to gas phase calculations,the impact of electrolytes on these reactions is assessed which turns out to be more pronounced for the ionic species involved in these reactions.
文摘Electrolytes are widely considered as a key component in Li–O;batteries (LOBs) because they greatly affect the discharge-charge reaction kinetics and reversibility.Herein,we report that 1,3-dimethyl-2-imidazolidinone (DMI) is an excellent electrolyte solvent for LOBs.Comparing with conventional ether and sulfone based electrolytes,it has higher Li_(2)O_(2)and Li_(2)CO_(3)solubility,which on the one hand depresses cathode passivation during discharge,and on the other hand promotes the liquid-phase redox shuttling during charge,and consequently lowers the overpotential and improves the cyclability of the battery.However,despite the many advantages at the cathode side,DMI is not stable with bare Li anode.Thus,we have developed a pretreatment method to grow a protective artificial solid-state electrolyte interface(SEI) to prevent the unfavorable side-reactions on Li.The SEI film was formed via the reaction between fluorine-rich organic reagents and Li metal.It is composed of highly Li^(+)-conducting Li_(x)BO_(y),LiF,Li_(x)NO_(y),Li_(3)N particles and some organic compounds,in which Li_(x)BO_(y)serves as a binder to enhance its mechanical strength.With the protective SEI,the coulombic efficiency of Li plating/stripping in DMI electrolyte increased from 20%to 98.5%and the fixed capacity cycle life of the assembled LOB was elongated to205 rounds,which was almost fivefold of the cycle life in dimethyl sulfoxide (DMSO) or tetraglyme(TEGDME) based electrolytes.Our work demonstrates that molecular polarity and ionic solvation structure are the primary issues to be considered when designing high performance Li–O;battery electrolytes,and cross-linked artificial SEI is effective in improving the anodic stability.
