All-Solid-State Thin-Film Lithium-Sulfur Batteries

Lithium-sulfur(Li-S)system coupled with thin-film solid electrolyte as a novel high-energy micro-battery has enormous potential for complementing embedded energy harvesters to enable the autonomy of the Internet of Things microdevice.However,the volatility in high vacuum and intrinsic sluggish kinetics of S hinder researchers from empirically integrating it into allsolid-state thin-film batteries,leading to inexperience in fabricating all-solid-state thin-film Li-S batteries(TFLSBs).Herein,for the first time,TFLSBs have been successfully constructed by stacking vertical graphene nanosheets-Li2S(VGsLi2S)composite thin-film cathode,lithium-phosphorous-oxynitride(LiPON)thin-film solid electrolyte,and Li metal anode.Fundamentally eliminating Lipolysulfide shuttle effect and maintaining a stable VGs-Li2S/LiPON interface upon prolonged cycles have been well identified by employing the solid-state Li-S system with an“unlimited Li”reservoir,which exhibits excellent longterm cycling stability with a capacity retention of 81%for 3,000 cycles,and an exceptional high temperature tolerance up to 60℃.More impressively,VGs-Li2S-based TFLSBs with evaporated-Li thin-film anode also demonstrate outstanding cycling performance over 500 cycles with a high Coulombic efficiency of 99.71%.Collectively,this study presents a new development strategy for secure and high-performance rechargeable all-solid-state thin-film batteries.

3D打印可穿戴微型超级电容器的锯齿状NiCo_(2)S_(4)基电极

应用3D打印技术制备准固态微型超级电容器(MSCs)在可编程结构设计和高质量负载电极制造方面具有固有的优势.然而,缺乏高性能的可打印墨水和厚电极内缓慢的离子传输,对其实际电荷存储能力提出了重大挑战.本文成功开发了一种具有优异流变性能的新型NiCo_(2)S_(4)基纳米复合墨水,并结合直墨书写的3D打印技术合理设计了准固态MSCs的三维结构.得益于牢固锚定在还原氧化石墨烯(rGO)表面的NiCo_(2)S_(4)纳米颗粒和有序的三维微孔,锯齿状厚电极提供了丰富的反应位点并增强了离子传输.因此,三层锯齿状MSCs的面电容高达416.7 mF cm^(-2).在1 mA cm^(-2)的电流密度下,单层、双层和三层电极的锯齿状MSCs的面电容与相对应的网格状MSCs相比,分别增加了127.1%、349.8%和585.9%.本工作为高面电容MSCs的材料和电极结构的跨尺度设计提供了新见解,推动了MSCs在柔性便携式电子设备中的集成应用研究.

Tape-casting electrode architecture permits low-temperature manufacturing of all-solid-state thin-film microbatteries

Along with the constantly evolving functional microsystems toward more diversification,the more rigorous design deliberation of pursuing higher mass-loading of electrode materials and low-temperature fabrication compatibility have imposed unprecedented demand on integrable all-solid-state thin-film microbatteries.While the classic thin-film intercalation cathode prepared by vacuum-based techniques inevitably encountered a post-annealing process,tape-casting technologies hold great merits both in terms of high-mass loading and low-temperature processing.In this work,a novel microbattery configura-tion is developed by the combination of traditional tape-casting thick electrodes and sputtered inorganic thin-film solid electrolytes(~3μm lithium phosphorus oxynitride).Enabled by physically pressed or vapor-deposited Li as an anode,solid-state batteries with tape-casted LiFePO_(4) electrodes exhibit outstanding cyclability and stability.To meet integration requirements,LiFePO4/LiPON/Si microbatteries were successfully fabricated at low temperatures and found to achieve a wide operating temperature range.This novel configuration has good prospects in promoting the thin-film microbattery enabling a paradigm shift and satisfying diversified requirements.

用于微电池的超高功率密度铁氧硫化物薄膜

作为微电池的核心指标之一,面积功率密度决定了微电池与应用于物联网的微电子器件集成时所需的面积.目前,由于微电子器件尺寸有限,微电池的实际应用受到低面积功率密度的限制.本文研究发现,经过原位等离子体预处理衬底后,溅射的铁氧硫化物薄膜(FeOxSy)具备超高功率特性.这种原位等离子体预处理可作为一种通用的界面优化策略来抑制长循环过程中的机械衰变.该正极薄膜展现出极高的功率密度和稳定的循环性能,这是由其高度的结构完整性(强大的界面粘附性和应力释放的岛)、完美的电化学可逆性以及近表面电荷交换(赝电容锂存储机制)的协同作用导致的.预处理的FeOxSy薄膜可以输出高达14.6 mW cm-2的功率密度和291μW h cm^(-2)μm^(-1)的体积能量密度.制备得到的正极薄膜的功率密度优于已报道的具有相当面积容量的溅射薄膜.本工作提出了一种简单且高效的预处理方法来制备具有超高功率密度且稳定的微电池薄膜电极.