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Electrolyte design for rechargeable anion shuttle batteries

Yao Wang, Xu Yang, Zhijia Zhang, Xia Hu, Yuefeng Meng, Xia Wang, Dong Zhou, Hao Liu, Baohua Li, Guoxiu Wang

, doi: 10.1016/j.esci.2022.10.003

Abstract(46) PDF(4)

Abstract:
As an emerging new type of battery chemistry, the anion shuttle battery (ASB), based on the shuttling and storage of anions, is considered a sustainable alternative to gigawatt-scale energy storage due to the associated resource abundance, low cost, high safety, and high energy density. Although significant progress has been achieved, practical applications of ASBs are still hindered by tough challenges, such as short lifetime, limited reversible capacity, and low Coulombic efficiency. Therefore, it is very necessary to design and explore new electrolyte systems with high electrochemical/chemical stability, sufficient compatibility towards electrodes, and excellent kinetics/reversibility for anion electrochemical reactions. Here, we review the recent achievements and main challenges in developing electrolytes for ASBs, which include solid, non-aqueous, and aqueous electrolytes. We mainly focus on the unique properties and basic principles of designing these electrolytes, and their various performance parameters. Perspectives on design strategies for ASB electrolytes are also presented, which could facilitate the development of advanced ASBs for grid-scale energy storage.

Differentiating grain and grain boundary ionic conductivities of Li-ion antiperovskite electrolytes

Jingfeng Zheng, Jocelyn Elgin, Jieren Shao, Yiying Wu

, doi: 10.1016/j.esci.2022.10.002

Abstract(41)

Abstract:
Recently, antiperovskites such as Li₂OHX (X = Cl, Br) have gained attention as possible solidstate electrolytes for use in all-solid-state batteries. Their low melting point allows for scalable manufacturing, making them more attractive than other inorganic solid-state electrolytes, and their high ion selectivity and good mechanical rigidity are superior to those of polymer electrolytes. However, there is significant variation of up to three orders of magnitude between reported ionic conductivities in different studies. One of the likely reasons is that studies have not separated Liion conduction contributions from the grain and the grain boundaries. Therefore, in this study, we present an electrochemical impedance analysis of Li-ion antiperovskites (Li₂OHBr and Li₂OHCl) prepared by different methods: cold press, hot press, and melt casting. We thereby separate the contributions from grain ionic conduction and grain boundary ionic conduction. While each method gives the same grain conductivity, the grain boundary conductivity depends on the preparation method. The largest improvement in grain boundary conductivity was found using the melt-casting method. These results provide an explanation for the reported variations in ionic conductivity.

Deformation-tolerant metal anodes for flexible sodium-air fiber batteries

Lei Ye, Xiangran Cheng, Meng Liao, Tiancheng Zhao, Xinlin Huang, Xinyue Kang, Kun Zhang, Xuemei Sun, Bingjie Wang, Huisheng Peng

, doi: 10.1016/j.esci.2022.10.001

Abstract(49)

Abstract:
Although flexible sodium-air (Na-air) batteries with high theoretical energy density offer promising opportunities for next-generation smart electronics,enhancing the safety and efficiency of flexible sodium metal anodes under dynamic and continuous deformation remains a challenge.Here,a flexible sodiated carbon nanotube layer to suppress dendrite growth under various deformations is demonstrated through a Fermi level-driven spontaneous synthetic process.The resulting sodiated carbon nanotube layer,which has a spontaneously formed solid-electrolyte interface and a robust interlocked structure,creates a uniformly distributed electric field and stable interface even under deformation,affording dendrite-free flexible Na metal anodes.With this deformation-tolerant Na metal anode,we have constructed a new family of highly flexible Na-air fiber batteries with excellent cycling performance for 400 cycles at 1000 mA·g^-1 and 500 mAh·g^-1 under dynamic deformation.These Na-air fiber batteries can be further woven into self-powering systems to support flexible electronic devices.

Highly aligned lithiophilic electrospun nanofiber membrane for the multiscale suppression of Li dendrite growth

Jianan Wang, Qianyue Ma, Shiyi Sun, Kai Yang, Qiong Cai, Emilia Olsson, Xin Chen, Ze Wang, Amr. M. Abdelkader, Yinshi Li, Wei Yan, Shujiang Ding, Kai Xi

, doi: 10.1016/j.esci.2022.09.001

Abstract(40) PDF(11)

Abstract:
Using inorganic fibrous membranes as protective layers has yielded success in suppressing dendrite growth. However, conventional fibrous membranes usually have large voids and low affinity for Li, promoting inhomogeneous charge distribution and allowing some dendrites to grow. Herein, we introduce a highly aligned TiO₂/SiO₂ (ATS) electrospun nanofiber membrane as a protective layer for the Li metal anode. The A-TS membrane is fabricated by a custom-made electrospinning system with an automatic fiber alignment collector that allows control of the fibers' orientation. At the scale of the individual fibers, their high binding energies with Li can attract more "dead" Li by reacting with the SiO₂ component of the composite, avoiding uncontrollable deposition on the metal anode. At the membrane scale, these highly ordered structures achieve homogeneous contact and charge distribution on the Li metal surface, leaving no vulnerable areas to nucleate dendrite formation. Additionally, the excellent mechanical and thermal stability properties of the A-TS membrane prevent any potential puncturing by dendrites or thermal runaway in a battery. Hence, an A-TS@Li anode exhibits stable cycling performance when used in both Li-S and Li-NCM811 batteries, highlighting significant reference values for the future design and development of high-energy-density metal-based battery systems.

ITO/Cu multilayer electrodes for high-brightness electrochromic displays

Xueqing Tang, Zishou Hu, Zhen Wang, Jian Chen, Xinyang Mu, Ge Song, Peiyan Sun, Zhengji Wen, Jiaming Hao, Shan Cong, Zhigang Zhao

, doi: 10.1016/j.esci.2022.08.005

Abstract(42)

Abstract:
Fabry-Perot (F-P) nanocavity-type electrochromic devices with multicolor tunability have attracted significant interest in the past two years for their potential uses in a wide variety of applications, such as electronic display, military camouflage, and dynamic decoration. However, challenges such as insufficient brightness, lengthy switching times, and poor cycling stability have yet to be overcome. Herein, we demonstrate electrochromic electrodes based on ITO/Cu as both the current collector and the reflective layer, with WO₃ as the electrochromic material, forming a unique three-layered structure. The constituted WO₃/ITO/Cu films present a high brightness value of about 84% before coloration, and a decent brightness value of 48% after coloration at -0.8 V. Moreover, a fast switching time between different coloration states (t_c=2.2 s; t_b=1 s) is recorded, attributed to the extremely low sheet resistivity of the ITO/Cu current collector. The films also reveal excellent electrochemical cycling stability across 2,000 cycles.

Amorphous germanium-crystalline bismuth films as a promising anode for magnesium-ion batteries

Zhonghua Zhang, Meijia Song, Conghui Si, Wenrun Cui, Yan Wang

, doi: 10.1016/j.esci.2022.07.004

Abstract(54) PDF(3)

Abstract:
Magnesium-ion batteries (MIBs) are promising alternatives to lithium-ion batteries due to their safety and high theoretical specific capacity, and the abundance of magnesium reserves. However, their anodes and electrolytes severely restrict the development of MIBs, so alloy-type anodes provide an effective strategy to circumvent the surface passivation issue encountered with Mg metal in conventional electrolytes. Theoretically, a germanium anode can deliver a high specific capacity of 1476 mAh g^-1, but hitherto, no experimental reports have described Ge in MIBs. Herein, we experimentally verified that Ge could reversibly react with Mg²⁺ ions through the design of dual-phase Ge-Bi film electrodes fabricated by magnetron co-sputtering. Notably, a Ge₅₇Bi₄₃ electrode delivered a high specific capacity of 847.5 mAh g^-1, owing to the joint alloying reactions of Ge and Bi with Mg, which was much higher than the specific capacity of Bi (around 385 mAh g^-1). Moreover, the Ge-Bi anode showed excellent rate performance, good cycling stability, and superior compatibility with conventional electrolytes such as Mg(TFSI)₂. More importantly, the Mg storage mechanism of the Ge-Bi anode was unveiled by operando X-ray diffraction, and density functional theory calculations rationalized that the introduction of Bi to form Ge-Bi evidently decreased the defect formation energy and effectively boosted the electrochemical reactivity of Ge with Mg.

Discontinuous streaming potential via liquid gate

Jian Zhang, Kan Zhan, Shusong Zhang, Yigang Shen, Yaqi Hou, Jing Liu, Yi Fan, Yunmao Zhang, Shuli Wang, Yanbo Xie, Xinyu Chen, Xu Hou

, doi: 10.1016/j.esci.2022.08.001

Abstract(71)

Abstract:
Streaming potential is mainly related to electrokinetic energy conversion, which has been considered to show promising potential for frontier technologies, especially sensing. The inherent property of streaming potential is that the energy conversion process is always a continuous state. However, practical applications include many cases of discontinuous states, such as nonlinear sensing. Here, we report a discontinuous streaming potential electrokinetic energy conversion fluid system. Experiments and theoretical calculations reveal that this system exhibits a discontinuous electrokinetic effect and provides a gating liquid slip in micropores, offering the advantages of gating liquid charge coupling and interfacial drag reduction. Moreover, the system is demonstrated in a wearable fall-down alert application. We expect this liquid gating energy conversion system to open up a platform for the design and application of autonomous health monitoring devices, seismic sea wave warning systems, and beyond.

Bioinspired iron porphyrins with appended polypyridine/amine units for boosted electrocatalytic CO₂ reduction reaction

Jinxiu Han, Ni Wang, Xialiang Li, Haitao Lei, Yabo Wang, Hongbo Guo, Xiaotong Jin, Qingxin Zhang, Xinyang Peng, Xue-Peng Zhang, Wei Zhang, Ulf-Peter Apfel, Rui Cao

, doi: 10.1016/j.esci.2022.06.003

Abstract(86)

Abstract:

Developing highly efficient electrocatalysts for the CO₂ reduction reaction (CO₂RR) has attracted increasing interest in the past decade. Herein, we report on the design and synthesis of Fe porphyrin 1 with an appended N,N-di(2- picolyl)ethylenediamine (DPEN) unit that boosts electrocatalytic activity for CO₂-toCO conversion in acetonitrile with water as the proton source. By mimicking carbon monoxide dehydrogenase (CODH), 1 has poly-pyridine/amine units located at the active site to form hydrogen-bonded water-containing networks that enable fast proton transfer. The protonated and positively charged DPEN unit can also stabilize CO₂ reduction intermediates through electrostatic and hydrogen-bonding interactions. These factors make 1 a highly active electrocatalyst for the CO₂RR by achieving a TOF_max of 5.0 × 10⁴ s⁻¹ with water providing the protons. These critical roles of the DPEN unit in the CO₂RR are further supported by theoretical studies. This work is significant to highlight the benefits of using molecular catalysts to elucidate structural effects.

Perspectives

Quasi-compensatory effect in emerging anode-free lithium batteries

Li Peng, Kim Hun, Ming Jun, Jung Hung-Gi, Belharouak Ilias, Sun Yang-Kook

, doi: 10.1016/j.esci.2021.10.002

Abstract(162) HTML (112)

Abstract:
As electric vehicle (EV) sales grew approximately 50% year-over-year, surpassing 3.2 million units in 2020, the "roaring era" of EV is around the corner. To meet the increasing demand for low cost and high energy density batteries, anode-free configuration, with no heavy and voluminous host material on the current collector, has been proposed and further investigated. Nevertheless, it always suffers from several nonnegligible "bottlenecks", such as fragile solid electrolyte interface, deteriorated cycling reversibility, and uncontrolled dendrite formation. Inspired by the "compensatory effect" of some disabled people with other specific functions strengthened to make up for their inconvenience, corresponding quasi-compensatory measures after anode removal, involving dimensional compensation, SEI robustness compensation, lithiophilicity compensation, and lithium source compensation, have been carried out and achieved significant battery performance enhancement. In this review, the chemistry, challenges, and rationally designed "quasi-compensatory effect" associated with anode-free lithium-ion battery are systematically discussed with several possible R&D directions that may aid, direct, or facilitate future research on lithium storage in anode-free configuration essentially emphasized.

Articles

Integration of homogeneous and heterogeneous nucleation growth via 3D alloy framework for stable Na/K metal anode

Ye Shufen, Wang Lifeng, Liu Fanfan, Shi Pengcheng, Yu Yan

, doi: 10.1016/j.esci.2021.09.003

Abstract(162) HTML (103) PDF(34)

Abstract:
Sodium/Potassium (Na/K) metal anodes have been considered as the promising anodes for next-generation Na/K secondary batteries owing to their ultrahigh specific capacity, low redox potential and low cost. However, their practical application is still hampered due to unstable solid electrolyte interphase, infinite volume change, and dendrite growth. Herein, we design a 3D-Na₃Bi/3D-K₃Bi alloy host which enables the homogeneous and heterogeneous nucleation growth of Na/K metal. The unique structure with periodic alternating of electron and ion conductivity improves the mass transfer kinetics and prevents the volume expansion during cycling. Meanwhile, the sodiophilicity of Na₃Bi/potassiophilicity of K₃Bi framework can avoid dendritic growth. Cycling lifespans over 700 h with 1 mAh cm⁻² for 3D-Na₃Bi@Na electrode and about 450 h with 1 mAh cm⁻² for 3D-K₃Bi@K electrode are achieved, respectively. 3D-Na₃Bi@Na||Na₃V₂(PO₄)₃ full battery shows sustainable cycle performance over 400 cycles. This design provides a simple but effective approach for achieving safety of sodium/potassium metal anodes.

A branched dihydrophenazine-based polymer as a cathode material to achieve dual-ion batteries with high energy and power density

Xu Shuaifei, Dai Huichao, Zhu Shaolong, Wu Yanchao, Sun Mingxuan, Chen Yuan, Fan Kun, Zhang Chenyang, Wang Chengliang, Hu Wenping

, doi: 10.1016/j.esci.2021.08.002

Abstract(216) HTML (112) PDF(39)

Abstract:

Organic electrode materials have exhibited good electrochemical performance in batteries, but their voltages and rate capabilities still require improvement to meet the increasing demand for batteries with high energy and power density. Herein, we design and synthesize a branched dihydrophenazine-based polymer (p-TPPZ) as a cathode material for dual-ion batteries (DIBs) through delicate molecular design. Compared with the linear dihydrophenazine-based polymer (p-DPPZ, with a theoretical capacity of 209 mAh g^–1), p-TPPZ possessed a higher theoretical capacity of 233 mAh g^–1 and lower highest occupied molecular orbital energy levels, which resulted in a high actual capacity (169.3 mAh g^–1 at 0.5 C), an average discharge voltage of 3.65 V (vs. Li⁺/Li) and a high energy density (618.2 Wh kg^–1, based on the cathode materials). The branched structure of p-TPPZ led to a larger specific surface area than that of p-DPPZ, which was beneficial for the electrolyte infiltration and fast ionic transport, contributing to the high power density. Due to the fast reaction kinetics, even at a power density of 23, 725 W kg^–1 (40 C), the energy density still reached 474.5 Wh kg^–1. We also made a detailed investigation of the p-TPPZ cathode's charge storage mechanism. This work will stimulate the further molecular design to develop organic batteries with both high energy and power density.

In situ growth of ultra-thin perovskitoid layer to stabilize and passivate MAPbI₃ for efficient and stable photovoltaics

Miao Yanfeng, Wang Xingtao, Zhang Haijuan, Zhang Taiyang, Wei Ning, Liu Xiaomin, Chen Yuetian, Chen Jie, Zhao Yixin

, doi: 10.1016/j.esci.2021.09.005

Abstract(96) HTML (47) PDF(14)

Abstract:

The efficiency and stability of typical three-dimensional (3D) MAPbI₃ perovskite-based solar cells are highly restricted, due to the weak interaction between methylammonium (MA⁺) and [PbI₆]^4-octahedra in the 3D structure, which can cause the ion migration and the related defects. Here, we found that the in situ-grown perovskitoid TEAPbI₃ layer on 3D MAPbI₃ can inhibit the MA⁺ migration in a polar solvent, thus enhancing the thermal and moisture stability of perovskite films. The crystal structure and orientation of TEAPbI₃ are reported for the first time by single crystal and synchrotron radiation analysis. The ultra-thin perovskitoid layer can reduce the trap states and accelerate photo-carrier diffusion in perovskite solar cells, as confirmed by ultra-fast spectroscopy. The power conversion efficiency of TEAPbI₃-MAPbI₃ based solar cells increases from 18.87% to 21.79% with enhanced stability. This work suggests that passivation and stabilization by in situ-grown perovskitoid can be a promising strategy for efficient and stable perovskite solar cells.

Promoting the sulfur redox kinetics by mixed organodiselenides in high-energy-density lithium–sulfur batteries

Zhao Meng, Li Xi-Yao, Chen Xiang, Li Bo-Quan, Kaskel Stefan, Zhang Qiang, Huang Jia-Qi

, doi: 10.1016/j.esci.2021.08.001

Abstract(592) HTML (331) PDF(108)

Abstract:
Lithium–sulfur (Li–S) batteries are considered as a highly promising energy storage system due to their ultrahigh theoretical energy density. However, the sluggish kinetics of the complex multi-electron sulfur redox reactions seriously hinders the actual battery performance especially under practical working conditions. Homogeneous redox mediation, through elaborately designing the additive molecules, is an effective approach to promote the sulfur redox kinetics. Herein a promoter of mixed organodiselenides (mixed-Se) is proposed to comprehensively improve the sulfur redox kinetics following the redox comediation principles. Concretely, diphenyl diselenide promotes the liquid–liquid conversion between polysulfides and the solid–liquid conversion regarding lithium sulfide oxidation to polysulfides, while dimethyl diselenide enhances the liquid–solid conversion regarding lithium sulfide deposition. Consequently, the mixed-Se promoter endows a high discharge capacity of 1002 mAh g⁻¹ with high sulfur loading of 4.0 mg cm⁻², a high capacity retention of 81.6% after 200 cycles at 0.5 C, and a high actual energy density of 384 Wh kg⁻¹ at 0.025 C in 1.5 Ah-level Li–S pouch cells. This work affords an effective kinetic promoter to construct high-energy-density Li–S batteries and inspires molecular design of kinetic promoters toward targeted energy-related redox reactions.

Reviews

Pillararene/calixarene-Based systems for battery and supercapacitor applications

Cao Shuai, Zhang Huacheng, Zhao Yuxin, Zhao Yanli

, doi: 10.1016/j.esci.2021.10.001

Abstract(352) HTML (198) PDF(54)

Abstract:

Pillararene/calixarene-based functional materials have garnered significant attention for their unique topological/chemical structures and physicochemical properties, and their extended applications in electrochemistry have given rise to a promising area of research. This review details current advance in developing electrochemical energy materials based on pillararene/calixarene systems from the viewpoint of both fundamental theoretical simulations and research on practical applications. First, we discuss the underlying mechanisms of applying pillararene/calixarene-based systems for electrochemical energy applications. Second, we summarize simulation studies on pillarquinone and calixquinone with intrinsic structures for applications in batteries. In addition, state-of-the-art applications of pillararene/calixarene-based systems in electrochemical energy storage devices such as lithium/sodium-ion batteries and supercapacitors are highlighted. The diverse roles they play and the various design strategies that have been investigated for high-performance pillararene/calixarene-based batteries are analyzed. Finally, we discuss the prospects for further developments in this emerging field. This review not only describes recent advances in pillararene/calixarene-based batteries and supercapacitors but also lays a firm groundwork for their further application in electrochemical energy engineering.

Contents View all issues

ISSN:2667-1417

Editor-in-Chief:Jun Chen

Sponsored by:NanKai University

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