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ACS Applied Energy Materials · 2022 · IF 6.959

Regulating the Solvation Structure of Potassium Ions Using a Multidentate Ether in Potassium Metal Batteries

Chao Chen,Ji Zhou,Wenbin Gong,Xueying Fan,Xiaodong Meng,Shang Chen,Longhua Sun,Yongqiang Meng,Kangjia Tao,Burak Ülgüt,Pingchuan Sun,Christopher W. Bielawski,Jianxin Geng

Potassium (K) is regarded as an alternative to lithium (Li) for use in contemporary energy storage devices owing to its high abundance and low electrochemical potential. However, because K ions are larger than Li ions, they exhibit different solvation properties that can ultimately affect device performance. Herein, a multidentate ether-based electrolyte is demonstrated to effectively solvate K ions and the solvation structures can be further modulated with cosolvents. The use of the multidentate ether-based electrolyte also suppresses the formation of K dendrites and significantly enhances the cycling stability of K//K symmetric cells (e.g., over 2000 h at 0.25 mA cm–2).

CAS / MDL: 7440-09-7 16627-68-2
研究领域: 材料科学 · 电化学
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Energy Storage Materials · 2022 · IF 20.831

Intercalation-deposition mechanism induced by aligned carbon fiber toward dendrite-free metallic potassium batteries

Kuikui Xiao,Jian-Fang Wu,Hanghang Yan,Ying Mo,Wang Zhou,Yufan Peng,Shi Chen,Xiangyang Cui,Lei Chen,Chaohe Xu,Jilei Liu

Metallic potassium (K) anodes are highly desirable for high energy density batteries . However, challenges lie in uncontrollable dendrite growth and/or inevitable generation of dead K. Here, composite anodes are constructed by covering a layer of aligned carbon fiber on the surface of each metallic K anode (K-ACF). Symmetrical K-ACF//K-ACF cells can work stably without short circuit for over 600 h, which is quite longer than cells using composite anodes with unaligned carbon fiber (K-UCF) and bare metallic K anodes. Comprehensive characterizations reveal a stepwise intercalation-deposition process on the K-ACF anode during the K plating, and the intercalation is proved to be necessary for the uniform K + flux due to the improved potassiophility of potassiated ACF. Besides, the aligned structure of ACF offers a uniform current density and K + ion flux on the surface of composite anodes, promoting the stable K stripping/plating. The K-ACF//Prussian blue (PB) cell exhibits a high discharge capacity of 83.6 mAh g −1 (267.4 Wh kg −1 based on the mass of PB) under a charge/discharge rate of 200 mA g −1 with a capacity loss rate of 0.044% per cycle. This work opens up a new avenue toward high energy and dendrite-free potassium batteries.

CAS / MDL: 7440-09-7
研究领域: 材料科学 · 电化学
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Journal of Materials Chemistry A · 2024 ·Vol. 12 ·期 12 ·6968-6982 · IF 10.7

Synergy of Cu-foam/Sb2O3/rGO for stable potassium anodes of high-rate and low-temperature potassium metal batteries

Jing Qi,Chengkai Lin,Shuqi Deng,Yinze Zuo,Hui Zheng,Xuechao Jiao,Wei Yan,Jiujun Zhang

Potassium (K) with higher abundance than lithium has been explored as an anode material for K metal batteries (KMBs) for possible application in large-scale energy storage. However, the unstable solid electrolyte interface (SEI) at the K anode due to uncontrolled growth of K dendrites is a challenge in KMB development. In this paper, a multifunctional interface containing Sb2O3 and reduced graphene oxide (rGO) on Cu foam to form a current collector (Cu@Sb2O3@rGO) is developed for a KMB anode through structural regulation, where the Cu form with a large surface area can reduce the volume change during charge and discharge processes, Sb2O3 can provide potassiophilicity toward uniform K plating and stripping to give a dendrite-free K anode, and rGO can provide abundant defects for increasing the ion transport and reaction kinetics. Such a Cu@Sb2O3@rGO current collector exhibits a remarkable reversibility of K plating/stripping for up to 600 cycles at 0.5 mA cm−2/2 mA h cm−2, and the formed Cu@Sb2O3@rGO@K anode demonstrates an extended cycle lifespan of 1300 hours under 0.2 mA cm−2/0.2 mA h cm−2 in symmetric cells. This anode-constructed PTCDA‖ Cu@Sb2O3@rGO@K full battery exhibits both exceptional cycling stability (over 2000 cycles) and outstanding rate capability (112.8 mA h g−1 at 10 C). Furthermore, even under extremely low temperature (−20 °C), this battery can still maintain an impressive 55% of its room temperature capacity. In situ Raman spectroscopic techniques and electrochemical methods including in situ EIS, half cell, symmetric cell, and full cell tests and theoretical DFT calculations are carried out to probe the structure–performance relationship and the reaction mechanisms for fundamental understanding toward further optimizing the performance of such the K anode and the corresponding KMBs. The strategy for stabilizing the K metal anode in this work may provide a guidance for further development of advanced low-temperature potassium metal batteries.

研究领域: 材料科学 · 电化学 · 能源存储
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Nature Communications · 2023 ·Vol. 14 ·期 1 ·1-11 · IF 16.6

Low-temperature anode-free potassium metal batteries

Tang Mengyao,Dong Shuai,Wang Jiawei,Cheng Liwei,Zhu Qiaonan,Li Yanmei,Yang Xiuyi,Guo Lin,Wang Hua

In contrast to conventional batteries, anode-free configurations can extend cell-level energy densities closer to the theoretical limit. However, realizing alkali metal plating/stripping on a bare current collector with high reversibility is challenging, especially at low temperature, as an unstable solid-electrolyte interphase and uncontrolled dendrite growth occur more easily. Here, a low-temperature anode-free potassium (K) metal non-aqueous battery is reported. By introducing Si-O-based additives, namely polydimethylsiloxane, in a weak-solvation low-concentration electrolyte of 0.4 M potassium hexafluorophosphate in 1,2-dimethoxyethane, the in situ formed potassiophilic interface enables uniform K deposition, and offers K||Cu cells with an average K plating/stripping Coulombic efficiency of 99.80% at −40 °C. Consequently, anode-free Cu||prepotassiated 3,4,9,10-perylene-tetracarboxylicacid-dianhydride full batteries achieve stable cycling with a high specific energy of 152 Wh kg −1 based on the total mass of the negative and positive electrodes at 0.2 C (26 mA g −1 ) charge/discharge and −40 °C.

研究领域: 材料科学 · 电化学
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Energy & Environmental Science · 2023 ·Vol. 16 ·期 3 ·1166-1175 · IF 32.5

In situ formed uniform and elastic SEI for high-performance batteries

Mingyuan Gu,Apparao M. Rao,Jiang Zhou,Bingan Lu

The solid electrolyte interphase (SEI) is one of the most important components of a battery, and plays a crucial role in the battery performance. Here, a uniform and elastic SEI was constructed by in situ electro-polymerization (ISEP-SEI) of ionic liquid electrolytes. The excellent uniformity of ISEP-SEI and its excellent contact with the substrate could passivate the electrode surface effectively. At the same time, the superior elasticity of ISEP-SEI could enable the electrode to sustain a large number of volume changes during cycling and maintain its structural integrity. Both these features are essential for building high-performance batteries. With ISEP-SEI, the potassium metal symmetric batteries stably cycled for 5000 h with only a piece of separator and no special treatment of the potassium metal surface. Moreover, a Prussian Blue (PB) cathode matched with potassium metal operated for more than 3000 cycles at 1000 mA g−1. The graphite anode, which does not cycle stably in traditional electrolytes, can be operated for more than 1000 cycles after an ISEP-SEI formed on its surface. Importantly, the flame-retardant ionic liquid guaranteed the batteries' safety. The electrochemical performance of full batteries, PB||K batteries at high temperatures, and lithium batteries with ISEP-SEI have also been explored.

研究领域: 材料科学 · 电化学 · 能源存储
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ACS Applied Materials & Interfaces · 2021 · IF 9.229

Highly Potassiophilic Carbon Nanofiber Paper Derived from Bacterial Cellulose Enables Ultra-Stable Dendrite-Free Potassium Metal Anodes

Mengfan Zhou,Weiyan Qi,Zongmin Hu,Mingren Cheng,Xinxin Zhao,Peixun Xiong,Hai Su,Mengjie Li,Jimin Hu,Yunhua Xu

Potassium–metal batteries are attractive candidates for low-cost and large-scale energy storage systems due to the abundance of potassium. However, K metal dendrite growth as well as volume expansion of K metal anodes on cycling have significantly hindered its practical applications. Although enhanced performance has been reported using carbon hosts with complicated structure engineering, they are not suitable for mass production. Herein, a highly potassiophilic carbon nanofiber paper with abundant oxygen-containing functional groups on the surface and a 3D interconnected network architecture is fabricated through a facile, scalable, and environmental-friendly biosynthesis method. As a host for K metal anode, uniform K nucleation and stable plating/stripping performance are demonstrated, with a stable cycling of 1400 h and a low overpotential of 45 mV, which are much better than all carbon hosts without complicated structure engineering. Moreover, full cells pairing the carbon nanofiber paper/K composite anodes with K4Fe(CN)6 cathodes exhibit excellent cycle stability and rate capability. The results provide a promising way for realizing dendrite-free K metal anodes and high-performance potassium–ion batteries.

CAS / MDL: 13943-58-3
研究领域: 材料科学 · 能源存储 · 环境友好型制造
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Inorganic Chemistry Frontiers · 2024 · IF 6.1

Stable solid-state potassium metal batteries enabled by a KB11H14·2Me3NBH3 complex electrolyte

Guo-Guo Zhang,Pengtao Qiu,Jia-Xin Kang,Zhiwei Lu,An-Qi Zhu,Xiaohu Yu,Xuenian Chen

Solid-state potassium metal batteries have increasingly gained attention as promising alternatives in large-scale energy storage due to their safety and low cost. However, these batteries usually suffer from a lack of suitable K+ conducting solid electrolytes. Herein, a new KB11H14·2Me3NBH3 complex electrolyte with high ionic conductivity and relative stability against K metal is reported. The crystal structure was solved as a monoclinic P21/c lattice. Density functional theory (DFT) calculations confirm significantly enhanced K-ion diffusion in the structure. High K-ion conductivities of 2.63 × 10−6 S cm−1 at 25 °C and 3.25 × 10−4 S cm−1 at 75 °C are achieved, putting it among the leading K+ solid conductors. Moreover, it shows favorable interfacial stability against the K metal anode precoated with NH3B3H7. Batteries coupling the TiS2 cathode deliver long-term cycling stability. This work provides a new group of K-ion solid-state electrolytes for safe potassium metal batteries.

CAS / MDL: 14984-76-0
研究领域: 材料科学 · 电化学 · 能源存储
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Nature Communications · 2023 ·Vol. 14 ·期 1 ·1-11 · IF 16.6

Building electrode skins for ultra-stable potassium metal batteries

Ding Hongbo,Wang Jue,Zhou Jiang,Wang Chengxin,Lu Bingan

In nature, the human body is a perfect self-organizing and self-repairing system, with the skin protecting the internal organs and tissues from external damages. In this work, inspired by the human skin, we design a metal electrode skin (MES) to protect the metal interface. MES can increase the flatness of electrode and uniform the electric field distribution, inhibiting the growth of dendrites. In detail, an artificial film made of fluorinated graphene oxide serves as the first protection layer. At molecular level, fluorine is released and in-situ formed a robust SEI as the second protection “skin” for metal anode. As a result, Cu@MES | | K asymmetric cell is able to achieve an unprecedented cycle life (over 1600 cycles). More impressively, the full cell of K@MES | | Prussian blue exhibits a long cycle lifespan over 5000 cycles. This work illustrates a mechanism for metal electrode protection and provides a strategy for the applying bionics in batteries.

CAS / MDL: 872-50-4
研究领域: 材料科学 · 电化学 · 电池技术 · 纳米技术
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Potassium Decahydrido-closo-Decaborane Urea Complex as a Potential Solid-State Electrolyte for Potassium Metal Batteries

Zhiwei Lu,Pengtao Qiu,Jia-Xin Kang,Xinwei Chen,Guoguo Zhang,Yichun Zhang,Xuenian Chen

All-solid-state potassium metal batteries have been considered promising candidates for large-scale energy storage because of abundance and wide availability of K resources, elimination of flammable liquid organic electrolytes, and incorporation of high-capacity K metal anode. However, unideal K-ion conductivities of most reported K-ion solid electrolytes have restricted the development of these batteries. Herein, a novel K2B10H10·CO(NH2)2 complex is reported, forming by incorporating urea into K2B10H10, to achieve an enhanced K-ion conductivity. The crystal structure of K2B10H10·CO(NH2)2 was determined as a monoclinic lattice with the space group of C2/c (No. 15). K2B10H10·CO(NH2)2 delivers an ionic conductivity of 2.7 × 10–8 S cm–1 at 25 °C, and reaching 1.3 × 10–4 S cm–1 at 80 °C, which is about 4 orders of magnitude higher than that of K2B10H10. One possible reason is the anion expansion in size due to the presence of dihydrogen bonds in K2B10H10·CO(NH2)2, resulting in an increase in the K–H bond distance and the electrostatic potential, thereby enhancing the mobility of K+. The K-ion conductivity is also higher than those of most hydridoborate-based K-ion conductors reported. Besides, K2B10H10·CO(NH2)2 reveals a wide electrochemical stability window and remarkable interface compatibility with K metal electrodes, suggesting a promising electrolyte for all-solid-state K metal batteries.

CAS / MDL: 57-13-6 1112-67-0
研究领域: 材料科学 · 电化学 · 能源存储
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