The capacity fade of spinel lithium manganese oxide in lithium-ion batteries is a bottleneck challenge for the large-scale application.The traditional opinion is that Mn（Ⅱ） ions in the anode are reduced to the meta...The capacity fade of spinel lithium manganese oxide in lithium-ion batteries is a bottleneck challenge for the large-scale application.The traditional opinion is that Mn（Ⅱ） ions in the anode are reduced to the metallic manganese that helps for catalyzing electrolyte decomposition.This could poison and damage the solid electrolyte interface（SEI） film,leading to the the capacity fade in Li-ion batteries.We propose a new mechanism that Mn（Ⅱ） deposites at the anode hinders and/or blocks the intercalation/de-intercalation of lithium ions,which leads to the capacity fade in Li-ion batteries.Based on the new mechanism assumption,a kind of new structure with core-shell characteristic is designed to inhabit manganese ion dissolution,thus improving electrochemical cycle performance of the cell.By the way,this mechanism hypothesis is also supported by the results of these experiments.The LiMn2-xTixO4 shell layer enhances cathode resistance to corrosion attack and effectively suppresses dissolution of Mn,then improves battery cycle performance with LiMn_2O_4 cathode,even at high rate and elevated temperature.展开更多
Lithium sulfur battery （LSB） offers several advantages such as very high energy density, low-cost, and environmental-friendliness. However, it suffers from serious degradation of its reversible capacity because of t...Lithium sulfur battery （LSB） offers several advantages such as very high energy density, low-cost, and environmental-friendliness. However, it suffers from serious degradation of its reversible capacity because of the dissolution of reaction intermediates, lithium polysulfides, into the electrolyte. To solve this limitation, there are many studies using graphene-based materials due to their excellent mechanical strength and high conductivity. Compared with graphene, graphene oxide （GO） contains various oxygen functional groups, which enhance the reaction with lithium polysulfides. Here, we investigated the positive effect of using GO mixed with carbon black on the performance of cathode in LSB. We have observed a smaller drop of capacity in GO mixed sulfur cathode. We further demonstrate that the mechanistic origin of reversibility improvement, as confirmed through CV and Raman spectra, can be explained by the stabilization of sulfur in lithium polysulfide intermediates by oxygen functional groups of GO to prevent dissolution. Our findings suggest that the use of graphene oxide-based cathode is a promising route to significantly improve the reversibility of current LSB.展开更多
A normal spinel LiMn_2O_4 as cathode material for lithium-ion cells wascycled galvanostatically (0.2 C) at 55 deg C. To determine the contribution of each voltage plateauto the total capacity fading of the cathode upo...A normal spinel LiMn_2O_4 as cathode material for lithium-ion cells wascycled galvanostatically (0.2 C) at 55 deg C. To determine the contribution of each voltage plateauto the total capacity fading of the cathode upon repeated cycling, the capacities in each plateauwere separated by differentiation of voltage vs. capacity. The results how that the capacity fadingin the upper voltage plateau is more rapidly than that in the lower during discharging, while incharging process, it fades slower than that in the lower voltage range. The increased capacity shiftand aggravated self-discharge/electrolyte oxidation during discharging contribute to a high fadingrate in the upper step. Capacity shift also takes place during charging process, which againenhancing the fading rate of the lower voltage plateau. An increase in capacity shift, as a resultof an increase in polarization of the cell, plays a major role in determining the fading rate ineach voltage plateau, further reflecting the thickening of the passivation layer on the activeparticles, and the accumulation of electrolyte decomposition. The relative capacity loss formodified spinels is well correlated with the relative increase in the polarization of thehalf-cells, confirming the above causes for capacity fade of this kind of cathode material.展开更多
基金Funded by the National Natural Science Foundation of China(Nos.21561016,21661015)Jiangxi Provincial Science&Technology Program(Nos.20133BBE50010,20142BDH80020,and 20161BBE50052)Science&Technology Program of Jiangxi Provincial Education Bureau(No.GJJ150775)
文摘The capacity fade of spinel lithium manganese oxide in lithium-ion batteries is a bottleneck challenge for the large-scale application.The traditional opinion is that Mn（Ⅱ） ions in the anode are reduced to the metallic manganese that helps for catalyzing electrolyte decomposition.This could poison and damage the solid electrolyte interface（SEI） film,leading to the the capacity fade in Li-ion batteries.We propose a new mechanism that Mn（Ⅱ） deposites at the anode hinders and/or blocks the intercalation/de-intercalation of lithium ions,which leads to the capacity fade in Li-ion batteries.Based on the new mechanism assumption,a kind of new structure with core-shell characteristic is designed to inhabit manganese ion dissolution,thus improving electrochemical cycle performance of the cell.By the way,this mechanism hypothesis is also supported by the results of these experiments.The LiMn2-xTixO4 shell layer enhances cathode resistance to corrosion attack and effectively suppresses dissolution of Mn,then improves battery cycle performance with LiMn_2O_4 cathode,even at high rate and elevated temperature.
基金supported by the Core Technology Development Program for Next-Generation Energy Storage of the Research Institute for Solar and Sustainable Energies (RISE) at GISTthe DOST UPD ERDT Faculty Development Program
文摘Lithium sulfur battery （LSB） offers several advantages such as very high energy density, low-cost, and environmental-friendliness. However, it suffers from serious degradation of its reversible capacity because of the dissolution of reaction intermediates, lithium polysulfides, into the electrolyte. To solve this limitation, there are many studies using graphene-based materials due to their excellent mechanical strength and high conductivity. Compared with graphene, graphene oxide （GO） contains various oxygen functional groups, which enhance the reaction with lithium polysulfides. Here, we investigated the positive effect of using GO mixed with carbon black on the performance of cathode in LSB. We have observed a smaller drop of capacity in GO mixed sulfur cathode. We further demonstrate that the mechanistic origin of reversibility improvement, as confirmed through CV and Raman spectra, can be explained by the stabilization of sulfur in lithium polysulfide intermediates by oxygen functional groups of GO to prevent dissolution. Our findings suggest that the use of graphene oxide-based cathode is a promising route to significantly improve the reversibility of current LSB.
文摘A normal spinel LiMn_2O_4 as cathode material for lithium-ion cells wascycled galvanostatically (0.2 C) at 55 deg C. To determine the contribution of each voltage plateauto the total capacity fading of the cathode upon repeated cycling, the capacities in each plateauwere separated by differentiation of voltage vs. capacity. The results how that the capacity fadingin the upper voltage plateau is more rapidly than that in the lower during discharging, while incharging process, it fades slower than that in the lower voltage range. The increased capacity shiftand aggravated self-discharge/electrolyte oxidation during discharging contribute to a high fadingrate in the upper step. Capacity shift also takes place during charging process, which againenhancing the fading rate of the lower voltage plateau. An increase in capacity shift, as a resultof an increase in polarization of the cell, plays a major role in determining the fading rate ineach voltage plateau, further reflecting the thickening of the passivation layer on the activeparticles, and the accumulation of electrolyte decomposition. The relative capacity loss formodified spinels is well correlated with the relative increase in the polarization of thehalf-cells, confirming the above causes for capacity fade of this kind of cathode material.
