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1.
Lithium Difluorophosphate‐Based Dual‐Salt Low Concentration Electrolytes for Lithium Metal Batteries
Hao Zheng Hongfa Xiang Fuyang Jiang Yongchao Liu Yi Sun Xin Liang Yuezhan Feng Yan Yu 《Liver Transplantation》2020,10(30)
The safety hazards and low Coulombic efficiency originating from the growth of lithium dendrites and decomposition of the electrolyte restrict the practical application of Li metal batteries (LMBs). Inspired by the low cost of low concentration electrolytes (LCEs) in industrial applications, dual‐salt LCEs employing 0.1 m Li difluorophosphate (LiDFP) and 0.4 m LiBOB/LiFSI/LiTFSI are proposed to construct a robust and conductive interphase on a Li metal anode. Compared with the conventional electrolyte using 1 m LiPF6, the ionic conductivity of LCEs is reduced but the conductivity decrement of the separator immersed in LCEs is moderate, especially for the LiDFP–LiFSI and LiDFP–LiTFSI electrolytes. The accurate Coulombic efficiency (CE) of the Li||Cu cells increases from 83.3% (electrolyte using 1 m LiPF6) to 97.6%, 94.5%, and 93.6% for LiDFP–LiBOB, LiDFP–LiFSI, and LiDFP–LiTFSI electrolytes, respectively. The capacity retention of Li||LiFePO4 cells using the LiDFP–LiBOB electrolyte reaches 95.4% along with a CE over 99.8% after 300 cycles at a current density of 2.0 mA cm?2 and the capacity reaches 103.7 mAh g?1 at a current density of up to 16.0 mA cm?2. This work provides a dual‐salt LCE for practical LMBs and presents a new perspective for the design of electrolytes for LMBs. 相似文献
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Jean‐Marie Doux Han Nguyen Darren H. S. Tan Abhik Banerjee Xuefeng Wang Erik A. Wu Chiho Jo Hedi Yang Ying Shirley Meng 《Liver Transplantation》2020,10(1)
All‐solid‐state batteries are expected to enable batteries with high energy density with the use of lithium metal anodes. Although solid electrolytes are believed to be mechanically strong enough to prevent lithium dendrites from propagating, various reports today still show cell failure due to lithium dendrit growth at room temperature. While cell parameters such as current density, electrolyte porosity, and interfacial properties have been investigated, mechanical properties of lithium metal and the role of applied stack pressure on the shorting behavior are still poorly understood. Here, failure mechanisms of lithium metal are investigated in all‐solid‐state batteries as a function of stack pressure, and in situ characterization of the interfacial and morphological properties of the buried lithium is conducted in solid electrolytes. It is found that a low stack pressure of 5 MPa allows reliable plating and stripping in a lithium symmetric cell for more than 1000 h, and a Li | Li6PS5Cl | LiNi0.80Co0.15Al0.05O2 full cell, plating more than 4 µm of lithium per charge, is able to cycle over 200 cycles at room temperature. These results suggest the possibility of enabling the lithium metal anode in all‐solid‐state batteries at reasonable stack pressures. 相似文献
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Xiao‐Ru Chen Bo‐Quan Li Cheng Zhu Rui Zhang Xin‐Bing Cheng Jia‐Qi Huang Qiang Zhang 《Liver Transplantation》2019,9(39)
Lithium (Li) metal is one of the most promising anode materials to construct next‐generation rechargeable batteries owing to its ultrahigh theoretical capacity and the lowest electrochemical potential. Unfortunately, practical application of Li metal batteries is severely hindered by short lifespan and safety concerns caused by Li dendrite growth during cycling. Herein, a coaxial‐interweaved hybrid Li metal anode is proposed for dendrite inhibition that significantly improves the cycling stability of Li metal batteries. The hybrid Li metal anode is fabricated by Li composition into a 3D interweaved scaffold, where each fiber of the interwoven scaffold is composed of a conductive skeleton and a coaxial lithiophilic layer modified on the surface. The coaxial‐interweaved structure endows the hybrid anode with favored Li affinity to guide uniform Li deposition, sufficient channels for ion transportation and electron conduction, and enhanced stability during Li plating and stripping. Consequently, the hybrid Li metal anode affords high Coulombic efficiency over 98.5% for 750 cycles with dendrite‐free morphologies in half cells and improved capacity retention of 80.1% after 100 cycles in LiFePO4 full cells. The innovative coaxial‐interweaved hybrid Li metal anode demonstrates multiscale design strategy from lithiophilic modification to scaffold construction and promises the prospect of Li metal batteries for future applications. 相似文献
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Ali Eftekhari 《Liver Transplantation》2018,8(24)
Owing to the high voltage of lithium‐ion batteries (LIBs), the dominating electrolyte is non‐aqueous. The idea of an aqueous rechargeable lithium battery (ARLB) dates back to 1994, but it had attracted little attention due to the narrow stable potential window of aqueous electrolytes, which results in low energy density. However, aqueous electrolytes were employed during the 2000s for the fundamental studies of electrode materials in the absence of side reactions such as the decomposition of organic species. The high solubility of lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in water has introduced new opportunities for high‐voltage ARLBs. Nonetheless, these ideas are somehow overshadowed by the common perception about the essential limitation of the aqueous electrolyte. The electrochemical behaviour of conventional electrode materials can be substantially tuned in the water‐in‐salt electrolytes. The latest idea of utilising a graphite anode in the aqueous water‐in‐salt electrolytes has paved the way towards not only 4‐V ARLB but also a new generation of Li?S batteries with a higher operating voltage and energy efficiency. Furthermore, aqueous electrolytes can provide a cathodically stable environment for Li?O2 batteries. The present paper aims to highlight these emerging opportunities possibly leading to a new generation of LIBs, which can be substantially cheaper and safer. 相似文献
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Rachid Amine Jianzhao Liu Ilona Acznik Tian Sheng Katarzyna Lota Hui Sun Cheng‐Jun Sun Krzysztof Fic Xiaobing Zuo Yang Ren Deia Abd EI‐Hady Wael Alshitari Abdullah S. Al‐Bogami Zonghai Chen Khalil Amine Gui‐Liang Xu 《Liver Transplantation》2020,10(25)
Lithium–sulfur batteries are attractive for automobile and grid applications due to their high theoretical energy density and the abundance of sulfur. Despite the significant progress in cathode development, lithium metal degradation and the polysulfide shuttle remain two critical challenges in the practical application of Li–S batteries. Development of advanced electrolytes has become a promising strategy to simultaneously suppress lithium dendrite formation and prevent polysulfide dissolution. Here, a new class of concentrated siloxane‐based electrolytes, demonstrating significantly improved performance over the widely investigated ether‐based electrolytes are reported in terms of stabilizing the sulfur cathode and Li metal anode as well as minimizing flammability. Through a combination of experimental and computational investigation, it is found that siloxane solvents can effectively regulate a hidden solvation‐ion‐exchange process in the concentrated electrolytes that results from the interactions between cations/anions (e.g., Li+, TFSI?, and S2?) and solvents. As a result, it could invoke a quasi‐solid‐solid lithiation and enable reversible Li plating/stripping and robust solid‐electrolyte interphase chemistries. The solvation‐ion‐exchange process in the concentrated electrolytes is a key factor in understanding and designing electrolytes for other high‐energy lithium metal batteries. 相似文献
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Jingyi Wu Zhixiang Rao Zexiao Cheng Lixia Yuan Zhen Li Yunhui Huang 《Liver Transplantation》2019,9(46)
All‐solid‐state batteries are promising candidates for the next‐generation safer batteries. However, a number of obstacles have limited the practical application of all‐solid‐state Li batteries (ASSLBs), such as moderate ionic conductivity at room temperature. Here, unlike most of the previous approaches, superior performances of ASSLBs are achieved by greatly reducing the thickness of the solid‐state electrolyte (SSE), where ionic conductivity is no longer a limiting factor. The ultrathin SSE (7.5 µm) is developed by integrating the low‐cost polyethylene separator with polyethylene oxide (PEO)/Li‐salt (PPL). The ultrathin PPL shortens Li+ diffusion time and distance within the electrolyte, and provides sufficient Li+ conductance for batteries to operate at room temperature. The robust yet flexible polyethylene offers mechanical support for the soft PEO/Li‐salt, effectively preventing short‐circuits even under mechanical deformation. Various ASSLBs with PPL electrolyte show superior electrochemical performance. An initial capacity of 135 mAh g?1 at room temperature and the high‐rate capacity up to 10 C at 60 °C can be achieved in LiFePO4/PPL/Li batteries. The high‐energy‐density sulfur cathode and MoS2 anode employing PPL electrolyte also realize remarkable performance. Moreover, the ASSLB can be assembled by a facile process, which can be easily scaled up to mass production. 相似文献
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Seung Ho Choi Seung Jong Lee Dong‐Joo Yoo Jun Ho Park Jae‐Hyuk Park You Na Ko Jungjin Park Yung‐Eun Sung Sung‐Yoon Chung Heejin Kim Jang Wook Choi 《Liver Transplantation》2019,9(41)
Due to unparalleled theoretical capacity and operation voltage, metallic Li is considered as the most attractive candidate for lithium‐ion battery anodes. However, Li metal electrodes suffer from uncontrolled dendrite growth and consequent interfacial instability, which result in an unacceptable level of performance in cycling stability and safety. Herein, it is reported that a marginal amount (1.5 at%) of magnesium (Mg) doping alters the surface properties of Li metal foil drastically in such a way that upon Li plating, a highly dense Li whisker layer is induced, instead of sharp dendrites, with enhanced interfacial stability and cycling performance. The effect of Mg doping is explained in terms of increased surface energy, which facilitates plating of Li onto the main surface over the existing whiskers. The present study offers a useful guideline for Li metal batteries, as it largely resolves the longstanding shortcoming of Li metal electrodes without significantly sacrificing their main advantages. 相似文献
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Yawei Chen Jianming Li Zhanwu Lei Yakun Huo Lanlan Yang Suyuan Zeng Honghe Ding Yi Qin Yulin Jie Fanyang Huang Qi Li Junfa Zhu Ruiguo Cao Genqiang Zhang Shuhong Jiao Dongsheng Xu 《Liver Transplantation》2020,10(7)
Transition metal sulfides hold promising potentials as Li‐free conversion‐type cathode materials for high energy density lithium metal batteries. However, the practical deployment of these materials is hampered by their poor rate capability and short cycling life. In this work, the authors take the advantage of hollow structure of CuS nanoboxes to accommodate the volume expansion and facilitate the ion diffusion during discharge–charge processes. As a result, the hollow CuS nanoboxes achieve excellent rate performance (≈371 mAh g?1 at 20 C) and ultra‐long cycle life (>1000 cycles). The structure and valence evolution of the CuS nanobox cathode are identified by scanning electron microscopy, transmission electron microscopy, and X‐ray photoelectron spectroscopy. Furthermore, the lithium storage mechanism is revealed by galvanostatic intermittent titration technique and operando Raman spectroscopy for the initial charge–discharge process and the following reversible processes. These results suggest that the hollow CuS nanobox material is a promising candidate as a low‐cost Li‐free cathode material for high‐rate and long‐life lithium metal batteries. 相似文献
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Recent Developments and Understanding of Novel Mixed Transition‐Metal Oxides as Anodes in Lithium Ion Batteries
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Yang Zhao Xifei Li Bo Yan Dongbin Xiong Dejun Li Stephen Lawes Xueliang Sun 《Liver Transplantation》2016,6(8)
Mixed transition‐metal oxides (MTMOs), including stannates, ferrites, cobaltates, and nickelates, have attracted increased attention in the application of high performance lithium‐ion batteries. Compared with traditional metal oxides, MTMOs exhibit enormous potential as electrode materials in lithium‐ion batteries originating from higher reversible capacity, better structural stability, and high electronic conductivity. Recent advancements in the rational design of novel MTMO micro/nanostructures for lithium‐ion battery anodes are summarized and their energy storage mechanism is compared to transition‐metal oxide anodes. In particular, the significant effects of the MTMO morphology, micro/nanostructure, and crystallinity on battery performance are highlighted. Furthermore, the future trends and prospects, as well as potential problems, are presented to further develop advanced MTMO anodes for more promising and large‐scale commercial applications of lithium‐ion batteries. 相似文献
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Nagaphani B. Aetukuri Shintaro Kitajima Edward Jung Leslie E. Thompson Kumar Virwani Maria‐Louisa Reich Miriam Kunze Meike Schneider Wolfgang Schmidbauer Winfried W. Wilcke Donald S. Bethune J. Campbell Scott Robert D. Miller Ho‐Cheol Kim 《Liver Transplantation》2015,5(14)
The use of metallic lithium anodes enables higher energy density and higher specific capacity Li‐based batteries. However, it is essential to suppress lithium dendrite growth during electrodeposition. Li‐ion‐conducting ceramics (LICC) can mechanically suppress dendritic growth but are too fragile and also have low Li‐ion conductivity. Here, a simple, versatile, and scalable procedure for fabricating flexible Li‐ion‐conducting composite membranes composed of a single layer of LICC particles firmly embedded in a polymer matrix with their top and bottom surfaces exposed to allow for ionic transport is described. The membranes are thin (<100 μm) and possess high Li‐ion conductance at thicknesses where LICC disks are mechanically unstable. It is demonstrated that these membranes suppress Li dendrite growth even when the shear modulus of the matrix is lower than that of lithium. It is anticipated that these membranes enable the use of metallic lithium anodes in conventional and solid‐state Li‐ion batteries as well as in future Li? S and Li? O2 batteries. 相似文献
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Xing Li Jianming Zheng Xiaodi Ren Mark H. Engelhard Wengao Zhao Qiuyan Li Ji‐Guang Zhang Wu Xu 《Liver Transplantation》2018,8(15)
The instability of lithium (Li) metal anodes due to dendritic growth and low Coulombic efficiency (CE) hinders the practical application of high‐energy‐density Li metal batteries. Here, the systematic studies of improving the stability of Li metal anodes and the electrochemical performance of Li metal batteries through the addition of combinational additives and the optimization of solvent compositions in dual‐salt/carbonate electrolytes are reported. A dendrite‐free and high CE of 98.1% for Li metal anode is achieved. The well‐protected Li metal anode and the excellent cyclability and rate capability of the 4‐V Li metal batteries are obtained. This is attributed to the formation of a robust, denser, more polymeric, and higher ionic conductive surface film on the Li metal anode via the electrochemical reductive decompositions of the electrolyte components and the ring‐opening polymerization of additives and cyclic carbonate solvents. The key findings of this work indicate that the optimization of solvent compositions and the manipulation of additives are facile and effective ways to enhance the performances of Li metal batteries. 相似文献
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Qiang Ma Xian‐Xiang Zeng Junpei Yue Ya‐Xia Yin Tong‐Tong Zuo Jia‐Yan Liang Qi Deng Xiong‐Wei Wu Yu‐Guo Guo 《Liver Transplantation》2019,9(13)
Herein, a composite polymer electrolyte with a viscoelastic and nonflammable interface is designed to handle the contact issue and preclude Li dendrite formation. The composite polymer electrolyte (cellulose acetate/polyethylene glycol/Li1.4Al0.4Ti1.6P3O12) exhibits a wide electrochemical window of 5 V (vs Li+/Li), a high Li+ transference number of 0.61, and an excellent ionic conductivity of above 10?4 S cm?1 at 60 °C. In particular, the intimate contact, low interfacial impedance, and fast ion‐transport process between the electrodes and solid electrolytes can be simultaneously achieved by the viscoelastic and nonflammable layer. Benefiting from this novel design, solid lithium metal batteries with either LiFePO4 or LiCoO2 as cathode exhibit superior cyclability and rate capability, such as a discharge capacity of 157 mA h g?1 after 100 cycles at C/2 and 97 mA h g?1 at 5C for LiFePO4 cathode. Moreover, the smooth and uniform Li surface after long‐term cycling confirms the successful suppression of dendrite formation. The viscoelastic and nonflammable interface modification of solid electrolytes provides a promising and general strategy to handle the interfacial issues and improves the operative safety of solid lithium metal batteries. 相似文献
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Haiping Wu Yaobin Xu Xiaodi Ren Bin Liu Mark H. Engelhard Michael S. Ding Patrick Z. El‐Khoury Linchao Zhang Qiuyan Li Kang Xu Chongmin Wang Ji‐Guang Zhang Wu Xu 《Liver Transplantation》2019,9(41)
Due to the limited oxidation stability (<4 V) of ether oxygen in its polymer structure, polyethylene oxide (PEO)‐based polymer electrolytes are not compatible with high‐voltage (>4 V) cathodes, thus hinder further increases in the energy density of lithium (Li) metal batteries (LMBs). Here, a new type of polymer‐in‐“quasi‐ionic liquid” electrolyte is designed, which reduces the electron density on ethereal oxygens in PEO and ether solvent molecules, induces the formation of stable interfacial layers on both surfaces of the LiNi1/3Mn1/3Co1/3O2 (NMC) cathode and the Li metal anode in Li||NMC batteries, and results in a capacity retention of 88.4%, 86.7%, and 79.2% after 300 cycles with a charge cutoff voltage of 4.2, 4.3, and 4.4 V for the LMBs, respectively. Therefore, the use of “quasi‐ionic liquids” is a promising approach to design new polymer electrolytes for high‐voltage and high‐specific‐energy LMBs. 相似文献
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Nan Piao Xiao Ji Hong Xu Xiulin Fan Long Chen Sufu Liu Mounesha N. Garaga Steven G. Greenbaum Li Wang Chunsheng Wang Xiangming He 《Liver Transplantation》2020,10(10)
Development of electrolytes that simultaneously have high ionic conductivity, wide electrochemical window, and lithium dendrite suppression ability is urgently required for high‐energy lithium‐metal batteries (LMBs). Herein, an electrolyte is designed by adding a countersolvent into LiFSI/DMC (lithium bis(fluorosulfonyl)amide/dimethyl carbonate) electrolytes, forming countersolvent electrolytes, in which the countersolvent is immiscible with the salt but miscible with the carbonate solvents. The solvation structure and unique properties of the countersolvent electrolyte are investigated by combining electroanalytical technology with a Molecular Dynamics simulation. Introducing the countersolvent alters the coordination shell of Li+ cations and enhances the interaction between Li+ cations and FSI? anions, which leads to the formation of a LiF‐rich solid electrolyte interphase, arising from the preferential reduction of FSI? anions. Notably, the countersolvent electrolyte suppresses Li dendrites and enables stable cycling performance of a Li||NCM622 battery at a high cut‐off voltage of 4.6 V at both 25 and 60 °C. This study provides an avenue to understand and design electrolytes for high‐energy LMBs in the future. 相似文献
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Correlating Electrode–Electrolyte Interface and Battery Performance in Hybrid Solid Polymer Electrolyte‐Based Lithium Metal Batteries
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Qiwei Pan Dmitri Barbash Derrick M. Smith Hao Qi Sarah E. Gleeson Christopher Y. Li 《Liver Transplantation》2017,7(22)
Solid polymer electrolytes (SPEs) are desirable in lithium metal batteries (LMBs) since they are nonflammable and show excellent lithium dendrite growth resistance. However, fabricating high performance polymer LMBs is still a grand challenge because of the complex battery system. In this work, a series of tailor‐designed hybrid SPEs are used to prepare LMBs with a LiFePO4‐based cathode. High performance LMBs with both excellent rate capability and long cycle life are obtained at 60 and 90 °C. The well‐controlled network structure in this series of hybrid SPEs offers a model system to study the relationship between the SPE properties and the LMB performance. It is shown that the cycle life of the polymer LMBs is closely correlated with the SPE–Li interface ionic conductivity, underscoring the importance of the solid electrolyte interface in LMB operation. LMB performance is further correlated with the molecular network structure. It is anticipated that results from this study will shed light on designing SPEs for high performance LMB applications. 相似文献