LiCoO_(2) is the preferred cathode material for consumer electronic products due to its high volumetric energy density. However, the unfavorable phase transition and surface oxygen release limits the practical applica...LiCoO_(2) is the preferred cathode material for consumer electronic products due to its high volumetric energy density. However, the unfavorable phase transition and surface oxygen release limits the practical application of LiCoO_(2)at a high-voltage of 4.6 V to achieve a higher energy density demanded by the market. Herein, both bulk and surface structures of LiCoO_(2)are stabilized at 4.6 V through oxygen charge regulation by Gd-gradient doping. The enrichment of highly electropositive Gd on LiCoO_(2) surface will increase the effective charge on oxygen and improve the oxygen framework stability against oxygen loss.On the other hand, Gd ions occupy the Co-sites and suppress the unfavorable phase transition and microcrack. The modified LiCoO_(2) exhibits superior cycling stability with capacity retention of 90.1% over 200 cycles at 4.6 V, and also obtains a high capacity of 145.7 m Ah/g at 5 C. This work shows great promise for developing high-voltage LiCoO_(2) at 4.6 V and the strategy could also contribute to optimizing other cathode materials with high voltage and large capacity, such as cobalt-free high-nickel and lithiumrich manganese-based cathode materials.展开更多
为进一步提高高镍三元放电比容量,将充电截止电压从4.3 V提高到4.5/4.7 V,放电比容量可从200 mAh g^(-1)提高到230 mAh g^(-1),这对提高能量密度是非常有利的,但同时会导致界面稳定性进一步降低.本文在商业电解液(1 mol L^(-1)LiPF_(6)/...为进一步提高高镍三元放电比容量,将充电截止电压从4.3 V提高到4.5/4.7 V,放电比容量可从200 mAh g^(-1)提高到230 mAh g^(-1),这对提高能量密度是非常有利的,但同时会导致界面稳定性进一步降低.本文在商业电解液(1 mol L^(-1)LiPF_(6)/EC:DEC=1:1,体积比)基础上,加入双添加剂二氟草酸硼酸锂(LiDFOB)和三甲基硅基磷酸酯(TMSP),一方面形成富含F,B,Si等元素的无机组分界面膜增加高电压下界面稳定性;另一方面,TMSP中的Si-O键具有清除电解液中高腐蚀性HF的作用,以此增加电解液的稳定性.在成膜和除HF的双重作用下,抑制了4.5/4.7 V高截止电压下的界面反应、过渡金属溶出、表面相变及产气.组装的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li电池在4.5 V下具有800圈的循环寿命,在4.7 V下具有500圈的循环寿命.展开更多
本文采用球磨和喷雾干燥法,制备了类西瓜型可控内膨胀核-缓冲-壳结构Si/电化学剥离石墨烯/C(Si/EG/C)复合材料.在纳米硅和碳壳之间填充了含大量褶皱和空隙的EG,不仅缓冲了Si/EG/C颗粒内部硅的体积变化,还提供了锂离子的快速传输通道.凭...本文采用球磨和喷雾干燥法,制备了类西瓜型可控内膨胀核-缓冲-壳结构Si/电化学剥离石墨烯/C(Si/EG/C)复合材料.在纳米硅和碳壳之间填充了含大量褶皱和空隙的EG,不仅缓冲了Si/EG/C颗粒内部硅的体积变化,还提供了锂离子的快速传输通道.凭借这些优势,核-缓冲-壳结构的Si/EG/C表现出优异的电化学性能.半电池中Si/EG/C负极在100次循环后相对于初始容量没有下降(834 mA h g^(-1)).此外,Si/EG/C//LiCoO_(2)全电池在500次循环后相对于初始放电容量的容量保持率接近100%.这些结果表明Si/EG/C在下一代锂离子电池中具有潜在应用前景.展开更多
基金supported by the National Natural Science Foundation of China (52102249, 52172201, 51732005, 51902118)the China Postdoctoral Science Foundation (2019M662609 and 2020T130217)+1 种基金the international postdoctoral exchange fellowship program (PC2021026)the Major Technological Innovation Project of Hubei Province (2019AAA019) for financial support。
文摘LiCoO_(2) is the preferred cathode material for consumer electronic products due to its high volumetric energy density. However, the unfavorable phase transition and surface oxygen release limits the practical application of LiCoO_(2)at a high-voltage of 4.6 V to achieve a higher energy density demanded by the market. Herein, both bulk and surface structures of LiCoO_(2)are stabilized at 4.6 V through oxygen charge regulation by Gd-gradient doping. The enrichment of highly electropositive Gd on LiCoO_(2) surface will increase the effective charge on oxygen and improve the oxygen framework stability against oxygen loss.On the other hand, Gd ions occupy the Co-sites and suppress the unfavorable phase transition and microcrack. The modified LiCoO_(2) exhibits superior cycling stability with capacity retention of 90.1% over 200 cycles at 4.6 V, and also obtains a high capacity of 145.7 m Ah/g at 5 C. This work shows great promise for developing high-voltage LiCoO_(2) at 4.6 V and the strategy could also contribute to optimizing other cathode materials with high voltage and large capacity, such as cobalt-free high-nickel and lithiumrich manganese-based cathode materials.
基金supported by the National Natural Science Foundation of China(52172201,51732005,51902118,and 52102249)China Postdoctoral Science Foundation(2019M662609 and 2020T130217)。
文摘为进一步提高高镍三元放电比容量,将充电截止电压从4.3 V提高到4.5/4.7 V,放电比容量可从200 mAh g^(-1)提高到230 mAh g^(-1),这对提高能量密度是非常有利的,但同时会导致界面稳定性进一步降低.本文在商业电解液(1 mol L^(-1)LiPF_(6)/EC:DEC=1:1,体积比)基础上,加入双添加剂二氟草酸硼酸锂(LiDFOB)和三甲基硅基磷酸酯(TMSP),一方面形成富含F,B,Si等元素的无机组分界面膜增加高电压下界面稳定性;另一方面,TMSP中的Si-O键具有清除电解液中高腐蚀性HF的作用,以此增加电解液的稳定性.在成膜和除HF的双重作用下,抑制了4.5/4.7 V高截止电压下的界面反应、过渡金属溶出、表面相变及产气.组装的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/Li电池在4.5 V下具有800圈的循环寿命,在4.7 V下具有500圈的循环寿命.
基金supported by the National Key R&D Program of China(2018YFB0905400)the Key Laboratory Open Project of Guangdong Province(2018B030322001)the National Natural Science Foundation of China(52172201,51732005 and 11905081)。
文摘本文采用球磨和喷雾干燥法,制备了类西瓜型可控内膨胀核-缓冲-壳结构Si/电化学剥离石墨烯/C(Si/EG/C)复合材料.在纳米硅和碳壳之间填充了含大量褶皱和空隙的EG,不仅缓冲了Si/EG/C颗粒内部硅的体积变化,还提供了锂离子的快速传输通道.凭借这些优势,核-缓冲-壳结构的Si/EG/C表现出优异的电化学性能.半电池中Si/EG/C负极在100次循环后相对于初始容量没有下降(834 mA h g^(-1)).此外,Si/EG/C//LiCoO_(2)全电池在500次循环后相对于初始放电容量的容量保持率接近100%.这些结果表明Si/EG/C在下一代锂离子电池中具有潜在应用前景.
