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1.
Dual‐Confined Flexible Sulfur Cathodes Encapsulated in Nitrogen‐Doped Double‐Shelled Hollow Carbon Spheres and Wrapped with Graphene for Li–S Batteries
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Batteries with high energy and power densities along with long cycle life and acceptable safety at an affordable cost are critical for large‐scale applications such as electric vehicles and smart grids, but is challenging. Lithium–sulfur (Li‐S) batteries are attractive in this regard due to their high energy density and the abundance of sulfur, but several hurdles such as poor cycle life and inferior sulfur utilization need to be overcome for them to be commercially viable. Li–S cells with high capacity and long cycle life with a dual‐confined flexible cathode configuration by encapsulating sulfur in nitrogen‐doped double‐shelled hollow carbon spheres followed by graphene wrapping are presented here. Sulfur/polysulfides are effectively immobilized in the cathode through physical confinement by the hollow spheres with porous shells and graphene wrapping as well as chemical binding between heteronitrogen atoms and polysulfides. This rationally designed free‐standing nanostructured sulfur cathode provides a well‐built 3D carbon conductive network without requiring binders, enabling a high initial discharge capacity of 1360 mA h g?1 at a current rate of C/5, excellent rate capability of 600 mA h g?1 at 2 C rate, and sustainable cycling stability for 200 cycles with nearly 100% Coulombic efficiency, suggesting its great promise for advanced Li–S batteries. 相似文献
2.
Kuan‐Hung Chen Adrian J. Sanchez Eric Kazyak Andrew L. Davis Neil P. Dasgupta 《Liver Transplantation》2019,9(4)
Improving the performance of Li metal anodes is a critical bottleneck to enable next‐generation battery systems beyond Li‐ion. However, stability issues originating from undesirable electrode/electrolyte interactions and Li dendrite formation have impaired long‐term cycling of Li metal anodes. Herein, a bottom‐up fabrication process is demonstrated for a current collector for Li metal electrodeposition and dissolution composed of highly uniform vertically aligned Cu pillars. By rationally controlling geometric parameters of the 3D current collector architecture, including pillar diameter, spacing, and length, the morphology of Li plating/stripping upon cycling can be controlled and optimal cycling performance can be achieved. In addition, it is demonstrated that deposition of an ultrathin layer of ZnO by atomic layer deposition on the current collector surface can facilitate the initial Li nucleation, which dictates the morphology and reversibility of subsequent cycling. This core–shell pillar architecture allows for the effects of geometry and surface chemistry to be decoupled and individually controlled to optimize the electrode performance in a synergistic manner. Using this platform, Li metal anodes are demonstrated with Coulombic efficiency up to 99.5%, providing a pathway toward high‐efficiency and long‐cycle life Li metal batteries with reduced excess Li loading. 相似文献
3.
Yuwon Park Nam‐Soon Choi Sangjin Park Seung Hee Woo Soojin Sim Bo Yun Jang Seung M. Oh Soojin Park Jaephil Cho Kyu Tae Lee 《Liver Transplantation》2013,3(2):206-212
Remarkable improvements in the electrochemical performance of Si materials for Li‐ion batteries have been recently achieved, but the inherent volume change of Si still induces electrode expansion and external cell deformation. Here, the void structure in Si‐encapsulating hollow carbons is optimized in order to minimize the volume expansion of Si‐based anodes and improve electrochemical performance. When compared to chemical etching, the hollow structure is achieved via electroless etching is more advanced due to the improved electrical contact between carbon and Si. Despite the very thick electrodes (30 ~ 40 μm), this results in better cycle and rate performances including little capacity fading over 50 cycles and 1100 mA h g?1 at 2C rate. Also, an in situ dilatometer technique is used to perform a comprehensive study of electrode thickness change, and Si‐encapsulating hollow carbon mitigates the volume change of electrodes by adoption of void space, resulting in a small volume increase of 18% after full lithiation corresponding with a reversible capacity of about 2000 mA h g?1. 相似文献
4.
Qiang Song Huibo Yan Kedi Liu Keyu Xie Wei Li Wenhan Gai Guohui Chen Hejun Li Chao Shen Qiangang Fu Shouyang Zhang Leilei Zhang Bingqing Wei 《Liver Transplantation》2018,8(22)
Inhomogeneous mass and charge transfers induce severe Li dendrite formation, impeding the service of Li metal anodes in rechargeable batteries. Various 3D hosts are proposed to address the related issues. To enable better progress, hybrid micro/nanostructures with the ability to realize spatial control of Li deposition over nucleation should be developed. Here, it is demonstrated that edge‐rich graphene (ERG), which is vertically grown on a 3D carbon nanofiber (CNF) substrate via a simple chemical vapor deposition method, can serve as nanoseeds to reduce the nucleation overpotential of Li effectively and guide the Li deposition on the 3D CNF substrate uniformly, free from dendrites. Different from the case in other sp2 carbon featuring interconnected graphitic structures such as planar graphene, the zero nucleation overpotential presented by ERG is attributed to its unique electron properties (i.e., the enhanced surface electronegativity) and its open architecture. Compared to the pristine CNF host, the ERG‐hybridized one resolves the problems of the Li metal anode better, endowing a practical Li battery with a long lifespan of 1000 cycles with a Coulombic efficiency of 99.7%. The results present novel sights for developing next‐generation Li‐carbon anodes with high cycling stability. 相似文献
5.
Pengbo Zhai Tianshuai Wang Weiwei Yang Shiqiang Cui Peng Zhang Anmin Nie Qianfan Zhang Yongji Gong 《Liver Transplantation》2019,9(18)
For a long time lithium (Li) metal has been considered one of the most promising anodes for next‐generation rechargeable batteries. Despite decades of concentrated research, its practical application is still hindered by dendritic Li deposition and infinite volume change of Li metal anodes. Here, atomically dispersed metals doped graphene is synthesized to regulate Li metal nucleation and guide Li metal deposition. The single‐atom (SA) metals, supported on the nitrogen‐doped graphene can not only increase the Li adsorption energy of the localized area around the metal atomic sites with a moderate adsorption energy gradient but also improve the atomic structural stability of the overall materials by constructing a coordination mode of M‐Nx‐C (M, N, and C denoted as metal, nitrogen, and carbon atoms, respectively). As a result, the as‐obtained electrode exhibits an ultralow voltage hysteresis of 19 mV, a high average Coulombic efficiency of 98.45% over 250 cycles, and a stable Li plating/stripping performance even at a high current density of 4.0 mA cm?2. This work demonstrates the application of SA metal doping in the rational design of Li metal anodes and provides a new concept for further development of Li metal batteries. 相似文献
6.
A three‐dimensional porous core‐shell Sn@carbon anode on nickel foam substrate was fabricated by electrostatic spray deposition (ESD) technique followed by high temperature treatment. The carbon shell with a thickness of about 3.2 nm was formed on porous Sn structure at high temperature. 3D porous structure and carbon shell were designed to buffer volume expansion/shrinkage of Sn lattice upon cycling and increase the electrical conductivity. After 315 charge/discharge cycles Sn@carbon anode exhibited high specific capacity of 638 mAh g?1 with the low capacity fade of average 0.11 mAh g?1 per cycle. Sn@carbon based anodes was demonstrated to have promising potential for high performance lithium ion batteries application. 相似文献
7.
High‐Energy,High‐Rate,Lithium–Sulfur Batteries: Synergetic Effect of Hollow TiO2‐Webbed Carbon Nanotubes and a Dual Functional Carbon‐Paper Interlayer
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Jang‐Yeon Hwang Hee Min Kim Sang‐Kyu Lee Joo‐Hyeong Lee Ali Abouimrane Mohammad Ahmed Khaleel Ilias Belharouak Arumugam Manthiram Yang‐Kook Sun 《Liver Transplantation》2016,6(1)
A novel nanocomposite cathode consisting of sulfur and hollow‐mesoporous titania (HMT) embedded within carbon nanotubes (CNT), which is designated as S‐HMT@CNT, has been obtained by encapsulating elemental sulfur into the pores of hollow‐mesoporous, spherical TiO2 particles that are connected via CNT. A carbon‐paper interlayer, referred to as dual functional porous carbon wall (DF‐PCW), has been obtained by filling the voids in TiO2 spheres with carbon and then etching the TiO2 template with a chemical process. The DF‐PCW interlayer provides a medium for scavenging the lithium polysulfides and suppressing them from diffusing to the anode side when it is inserted between the sulfur cathode and the separator. Lithium–sulfur cells fabricated with the thus prepared S‐HMT@CNT cathode and the DF‐PCW interlayer exhibit superior performance due to the containment of sulfur in TiO2 and improved lithium–ion and electron transports. The Li–S cells display high capacity with excellent capacity retention at rates as high as 1C, 2C, and 5C rates. 相似文献
8.
Muqin Wang Zhe Peng Wenwei Luo Feihong Ren Zhendong Li Qiang Zhang Haiyong He Chuying Ouyang Deyu Wang 《Liver Transplantation》2019,9(12)
Lithium (Li) metal is a key anode material for constructing next generation high energy density batteries. However, dendritic Li deposition and unstable solid electrolyte interphase (SEI) layers still prevent practical application of Li metal anodes. In this work, it is demonstrated that an uniform Li coating can be achieved in a lithium fluoride (LiF) decorated layered structure of stacked graphene (SG), leading to the formation of an SEI‐functionalized membrane that retards electron transfer by three orders of magnitude to avoid undesirable Li deposition on the top surface, and ameliorates Li+ ion migration to enable uniform and dendrite‐free Li deposition beneath such an interlayer. Surface chemistry analysis and density functional theory calculations demonstrate that these beneficial features arise from the formation of C–Fx surface components on the SG sheets during the Li coating process. Based on such an SEI‐functionalized membrane, stable cycling at high current densities up to 3 mA cm?2 and Li plating capacities up to 4 mAh cm?2 can be realized in LiPF6/carbonate electrolytes. This work elucidates the promising strategy of modifying Li plating behavior through the SEI‐functionalized carbon structure, with significantly improved cycling stability of rechargeable Li metal anodes. 相似文献
9.
Mesoporous TiO2‐Sn/C Core‐Shell Nanowire Arrays as High‐Performance 3D Anodes for Li‐Ion Batteries
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Three‐dimensional mesoporous TiO2‐Sn/C core‐shell nanowire arrays are prepared on Ti foil as anodes for lithium‐ion batteries. Sn formed by a reduction of SnO2 is encapsulated into TiO2 nanowires and the carbon layer is coated onto it. For additive‐free, self‐supported anodes in Li‐ion batteries, this unique core‐shell composite structure can effectively buffer the volume change, suppress cracking, and improve the conductivity of the electrode during the discharge‐charge process, thus resulting in superior rate capability and excellent long‐term cycling stability. Specifically, the TiO2‐Sn/C nanowire arrays display rechargeable discharge capacities of 769, 663, 365, 193, and 90 mA h g?1 at 0.1C, 0.5C, 2C 10C, and 30C, respectively (1C = 335 mA g?1). Furthermore, the TiO2‐Sn/C nanowire arrays exhibit a capacity retention rate of 84.8% with a discharge capacity of over 160 mA h g?1, even after 100 cycles at a high current rate of 10C. 相似文献
10.
Wenqing Guo Shan Liu Xuze Guan Xinyue Zhang Xinjiang Liu Jiayan Luo 《Liver Transplantation》2019,9(20)
Li metal batteries are considered a promising candidate for next‐generation rechargeable batteries. However, the practical application of Li metal batteries has been hindered by many challenges, especially the cycling stability of Li anodes due to their uncontrollable dendrite growth, volume fluctuation, and side reactions. These problems are more severe under high‐rate charge/discharge process. Therefore, the realization of stable cycling of Li anodes under high current density is crucial for the practical application of Li metal batteries. In this Progress Report, the authors focus on the stability of metallic Li through interphase design or microstructure construction. The advantages and drawbacks of the first‐generation 3D scaffolds are summarized, and a review of recent research progress in this area is generated. As high‐rate cycling of metallic Li is a complex dynamic problem, a scaffold with high mixed ionic and electronic conductivity may be a promising approach. The different design strategies of mixed ion and electron‐conductive scaffolds working with liquid and solid electrolytes are discussed, along with their technical challenges. Further directions of mixed ion and electron‐conductive scaffolds are also proposed. 相似文献
11.
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
12.
The high‐polarity β‐phase poly(vinylidene difluoride) (β‐PVDF), which has all trans conformation with F and H atoms located on the opposite sides of the polymer backbone, is demonstrated to be a promising artificial solid‐electrolyte interphase coating on both Cu and Li metal anodes for dendrite‐free Li deposition/stripping and enhanced cycling performance. A thin (≈4 µm) β‐PVDF coating on Cu enables uniform Li deposition/stripping at high current densities up to 5 mA cm?2, Li‐plating capacity loadings of up to 4 mAh cm?2, and excellent cycling stability over hundreds of cycles under practical conditions (1 mA cm?2 with 2 mAh cm?2). Full cells containing an LiFePO4 cathode and an anode of either β‐PVDF coated Cu or Li also exhibit excellent cycling stability. The profound effects of the high‐polarity PVDF coating on dendrite suppression are attributed to the electronegative F‐rich interface that favors layer‐by‐layer Li deposition. This study offers a new strategy for the development of dendrite‐free metal anode technology. 相似文献
13.
N‐Doped Graphene Modified 3D Porous Cu Current Collector toward Microscale Homogeneous Li Deposition for Li Metal Anodes
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Rui Zhang Shuaiwei Wen Ning Wang Kaiqiang Qin Enzuo Liu Chunsheng Shi Naiqin Zhao 《Liver Transplantation》2018,8(23)
Lithium metal is the most promising anode material for high‐energy‐density batteries due to its high specific capacity of 3860 mAh g?1 and low reduction potential of ?3.04 V versus standard hydrogen electrode. However, huge volume change, safety concerns, and low efficiency impede the practical applications of Li metal anodes. Herein, it is shown that the nitrogen‐doped graphene modified 3D porous Cu (3DCu@NG) current collector can mitigate the above problems. The N‐doped graphene, coating on the surface of 3D current collector, not only contributes to a uniform Li+ flux, but also leads to a scattered distribution of electrons throughout the surface, finally contributing to a uniform Li deposition and the improved electrochemical performance. In addition, the continuously porous structure of 3DCu@NG provides a space for the metallic Li deposition and could effectually accommodate the volume expansion during cycling. As a result, the Li‐3DCu@NG anode exhibits a high areal capacity of 4 mAh cm?2, a high Li utilization of ≈98%, and an ultralow voltage hysteresis of ≈19 mV. The multifunctional N‐doped graphene modified 3D porous current collector promisingly provides a strategy for safe and high‐energy lithium metal anodes. 相似文献
14.
The electrochemical performance of mesoporous carbon (C)/tin (Sn) anodes in Na‐ion and Li‐ion batteries is systematically investigated. The mesoporous C/Sn anodes in a Na‐ion battery shows similar cycling stability but lower capacity and poorer rate capability than that in a Li‐ion battery. The desodiation potentials of Sn anodes are approximately 0.21 V lower than delithiation potentials. The low capacity and poor rate capability of C/Sn anode in Na‐ion batteries is mainly due to the large Na‐ion size, resulting in slow Na‐ion diffusion and large volume change of porous C/Sn composite anode during alloy/dealloy reactions. Understanding of the reaction mechanism between Sn and Na ions will provide insight towards exploring and designing new alloy‐based anode materials for Na‐ion batteries. 相似文献
15.
Zixu Sun Sudarshan Vijay Hendrik H. Heenen Alex Yong Sheng Eng Wenguang Tu Yunxing Zhao See Wee Koh Pingqi Gao Zhi Wei Seh Karen Chan Hong Li 《Liver Transplantation》2020,10(22)
The lithium–sulfur (Li–S) battery is widely regarded as a promising energy storage device due to its low price and the high earth‐abundance of the materials employed. However, the shuttle effect of lithium polysulfides (LiPSs) and sluggish redox conversion result in inefficient sulfur utilization, low power density, and rapid electrode deterioration. Herein, these challenges are addressed with two strategies 1) increasing LiPS conversion kinetics through catalysis, and 2) alleviating the shuttle effect by enhanced trapping and adsorption of LiPSs. These improvements are achieved by constructing double‐shelled hollow nanocages decorated with a cobalt nitride catalyst. The N‐doped hollow inner carbon shell not only serves as a physiochemical absorber for LiPSs, but also improves the electrical conductivity of the electrode; significantly suppressing shuttle effect. Cobalt nitride (Co4N) nanoparticles, embedded in nitrogen‐doped carbon in the outer shell, catalyze the conversion of LiPSs, leading to decreased polarization and fast kinetics during cycling. Theoretical study of the Li intercalation energetics confirms the improved catalytic activity of the Co4N compared to metallic Co catalyst. Altogether, the electrode shows large reversible capacity (1242 mAh g?1 at 0.1 C), robust stability (capacity retention of 658 mAh g?1 at 5 C after 400 cycles), and superior cycling stability at high sulfur loading (4.5 mg cm?2). 相似文献
16.
Ran Yi Fang Dai Mikhail L. Gordin Hiesang Sohn Donghai Wang 《Liver Transplantation》2013,3(11):1507-1515
Silicon has been intensively pursued as the most promising anode material for Li‐ion batteries due to its high theoretical capacity of 3579 mAh/g. Micro‐sized Si–C composites composed of nanoscale primary building blocks are attractive Si‐based anodes for practical application because they not only achieve excellent cycling stability, but also offer both gravimetric and volumetric capacity. However, the effects of key parameters in designing such materials on their electrochemical performance are unknown and how to optimize them thus remains to be explored. Herein, the influence of Si nanoscale building block size and carbon coating on the electrochemical performance of the micro‐sized Si–C composites is investigated. It is found that the critical Si building block size is 15 nm, which enables a high capacity without compromising the cycling stability, and that carbon coating at higher temperature improves the first cycle coulombic efficiency (CE) and the rate capability. Corresponding reasons underlying electrochemical performance are revealed by various characterizations. Combining both optimized Si building block size and carbon coating temperature, the resultant composite can sustain 600 cycles at 1.2 A/g with a fixed lithiation capacity of 1200 mAh/g, the best cycling performance with such a high capacity for micro‐sized Si‐based anodes. 相似文献
17.
Tianhui Xu Peng Gao Peirong Li Kai Xia Na Han Jun Deng Yanguang Li Jun Lu 《Liver Transplantation》2020,10(8)
Li metal anodes are going through a great revival but they still encounter grand challenges. One often neglected issue is that most reported Li metal anodes are only cyclable under relatively low current density (<5 mA cm?2) and small areal capacity (<5 mAh cm?2), which essentially limits their high‐power applications and results in ineffective Li utilization (<1%). Herein, it is reported that surface alloyed Li metal anodes can enable reversible cycling with ultrafast rate and ultralarge areal capacity. Low‐cost Si wafers are used and are chemically etched down to 20–30 µm membranes. Simply laminating a Si membrane onto Li foil results in the formation of LixSi alloy film fused onto Li metal with mechanical robustness and high Li‐ion conductivity. Symmetric cell measurements show that the surface alloyed Li anode has excellent cycling stability, even under high current density up to 25 mA cm?2 and unprecedented areal capacity up to 100 mAh cm?2. Furthermore, the surface alloyed Li anode is paired with amorphous MoS3 cathode and achieves remarkable full‐cell performance. 相似文献
18.
Lithium (Li) metal anodes are promising candidates for high‐energy‐density batteries. However, uncontrollable dendritic plating behavior and infinite volume expansion are hindering their practical applications. Herein, a novel CuO@Ti‐mesh (CTM) is prepared by microwave‐assisted reactions, followed by pressing on Li wafers, leading to Li/CuO@Ti‐mesh (LCTM) composite anodes. The lithiophilic CuO nanoflowers on Ti‐mesh provides evenly distributed nucleation sites, inducing uniform Li‐ion lateral plating, which can effectively inhibit the growth of Li dendrites and volume expansion during cycling. The as‐prepared LCTM composite anode exhibits high Coulombic efficiency (CE) of 94.2% at 10 mA cm‐2 over 90 cycles. Meanwhile, the LCTM anode shows a low overpotential of 50 mV at 10 mA cm‐2 over 16 000 cycles and a low overpotential of 90 and 250 mV even at ultrahigh current densities of 20 and 40 mA cm‐2. When paired with Li4Ti5O12 (LTO), it enhances the capacity retention of LTO/Li wafer full cells by about two times from 36.6% to 73.0% and 42.0% to 80.0% at 5C and 10C with long‐term cycling. It is hoped that this LCTM anode with ultrahigh rates and ultralong cycle life may put Li‐metal anode forward to practical applications, such as in Li–S, Li‐air batteries, etc. 相似文献
19.
Pengbo Zhai Yi Wei Jing Xiao Wei Liu Jinghan Zuo Xiaokang Gu Weiwei Yang Shiqiang Cui Bin Li Shubin Yang Yongji Gong 《Liver Transplantation》2020,10(8)
Rational structure design of the current collector along with further engineering of the solid‐electrolyte interphases (SEI) layer is one of the most promising strategies to achieve uniform Li deposition and inhibit uncontrolled growth of Li dendrites. Here, a Li2S layer as an artificial SEI with high compositional uniformity and high lithium ion conductivity is in situ generated on the surface of the 3D porous Cu current collector to regulate homogeneous Li plating/stripping. Both simulations and experiments demonstrate that the Li2S protective layer can passivate the porous Cu skeleton and balance the transport rate of lithium ions and electrons, thereby alleviating the agglomerated Li deposition at the top of the electrode or at the defect area of the SEI layer. As a result, the modified current collector exhibits long‐term cycling of 500 cycles at 1 mA cm?2 and stable electrodeposition capabilities of 4 mAh cm?2 at an ultrahigh current density of 4 mA cm?2. Furthermore, full batteries (LiFePO4 as cathode) paired with this designed 3D anode with only ≈200% extra lithium show superior stability and rate performance than the batteries paired with lithium foil (≈3000% extra lithium). These explorations provide new strategies for developing high‐performance Li metal anodes. 相似文献
20.
Takatoshi Munaoka Xuzhou Yan Jeffrey Lopez John W. F. To Jihye Park Jeffrey B.‐H. Tok Yi Cui Zhenan Bao 《Liver Transplantation》2018,8(14)
A self‐healing polymer (SHP) with abundant hydrogen bonds, appropriate viscoelasticity, and stretchability is a promising binder to improve cycle performance of Si microparticle anodes in lithium (Li) ion batteries. Besides high capacity and long cycle life, efficient rate performance is strongly desirable for practical Si anode implementation. Here, polyethylene glycol (PEG) groups are incorporated into the SHP, facilitating Li ionic conduction within the binder. The concept of the SHP‐PEG binder involves improving the interface between Si microparticles and electrolytes after cycling based on the combination of self‐healing ability and fast Li ionic conduction. Through the systematic study of mixing PEG Mw and ratio, the polymeric binder combining SHP and PEG with Mw 750 in an optimal ratio of 60:40 (mol%) achieves a high discharging capacity of ≈2600 mA h g?1, reasonable rate performance especially when >1C and maintains 80% of their initial capacity even after ≈150 cycles at 0.5C. The described concept for the polymeric binder, embedding both self‐healing ability and high Li ionic conductivity, should be equally useful for next generation batteries utilizing high capacity materials which suffer from huge volume change during cycling. 相似文献