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高电压氟磷酸钠钒纳米棒阵列实现高性能柔性钠离子电池

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Science China materials 2023年第10期66卷 3837-3845页

作者：许东明陈瑞强陈本强周双张杨璞常智潘安强 School of materials Science and Engineering Central South UniversityChangsha 410083China Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province Central South UniversityChangsha 410083China

柔性钠离子电池(SIBs)在便携式和可穿戴设备中具有巨大的应用潜力,因为它们在特定情况下具有适用性和价格优势.在正极材料中,磷酸盐电极材料具有结构稳定性好、工作电位高和寿命长的优点.然而,由于对制造要求苛刻,反应复杂,以及柔性基... 详细信息

柔性钠离子电池(SIBs)在便携式和可穿戴设备中具有巨大的应用潜力,因为它们在特定情况下具有适用性和价格优势.在正极材料中,磷酸盐电极材料具有结构稳定性好、工作电位高和寿命长的优点.然而,由于对制造要求苛刻,反应复杂,以及柔性基材的缺失等问题,柔性磷酸盐电极材料的设计仍然是一个巨大的挑战.在此,我们报道了在柔性多孔碳纳米纤维上垂直生长的VO_(2)纳米片原位转化为三维氟磷酸钒钠纳米棒阵列(PCNF@NVOPF NR).PCNF@NVOPF NR实现了兼具柔性与高压正极电极的特点,并具有长期循环稳定性(4500次循环后容量保持率为87.6%).阵列结构可以确保快速的钠反应动力学和低界面电阻.此外,PCNF@NVOPF NR//PCNF@VO_(2)NS@C钠离子全电池表现出高能量和功率密度(220.5 W h kg^(-1)和9400 W kg^(-1)).这种用于柔性正极的材料设计策略可促进实用钠离子电池的商业化.

关键词： Na_(3)(VO)_(2)(PO_(4))_(2)F high voltage cathode flexible electrode sodium-ion battery nanoarrays

Reconstructing interfacial manganese deposition for durable aqueous zinc-manganese batteries

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National Science Review 2023年第10期10卷 139-150页

作者： Yida Hu Zhexuan Liu Lanyan Li Shan Guo Xuefang Xie Zhigao Luo Guozhao Fang Shuquan Liang School of materials Science and Engineering Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan ProvinceCentral South University School of Science Hunan University of Technology and Business College of Physical Science and Technology Xinjiang University College of Chemistry Xiangtan University

Low-cost,high-satety,and broad-prospect aqueous zinc-manganese batteries(ZMBs) are limited by complex interracial reactions.The solid-liquid interfacial state of the cathode dominates the Mn dissolution/deposition process of aqueous ZMBs,especially the important influence on the mass and charge transfer behavior of Zn2+and Mn2+.We proposed a quasi-eutectic electrolyte(QEE) that would stabilize the reversible behavior of interracial deposition and favorable interracial reaction kinetic of manganese-based cathodes in a long cycle process by optimizing mass and charge transfer.We emphasize that the initial interfacial reaction energy barrier is not the main factor affecting cycling performance,and the good reaction kinetics induced by interfacial deposition during the cycling process is more conducive to the stable cycling of the battery,which has been confirmed by theoretical analysis,quartz crystal microbalance with dissipation monitoring,depth etching X-ray photon-electron spectroscopy,etc.As a result,the QEE electrolyte maintained a stable specific capacity of 250 mAh g-1at 0.5 A g-1after 350 cycles in zinc-manganese batteries.The energy density retention rate of the ZMB with QEE increased by 174%compared to that of conventional aqueous electrolyte.Furthermore,the multi-stacked soft-pack battery with a cathodic mass load of 54.4 mg maintained a stable specific capacity of 200 mAh g-1for 100 cycles,demonstrating its commercial potential.This work proves the feasibility of adapting lean-water QEE to the stable aqueous ZMBs.

关键词： quasi-eutectic electrolyte aqueous zinc −manganese batteries solid −liquid interfacial state mass transfer charge transfer

Fundamental Understanding and Effect of Anionic Chemistry in Zinc Batteries

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Energy & Environmental materials 2022年第1期5卷 186-200页

作者： Yuxin Gao Zhexuan Liu Shan Guo Xinxin Cao Guozhao Fang Jiang Zhou Shuquan Liang School of materials Science and Engineering Central South UniversityChangsha 410083China Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province Central South UniversityChangsha 410083China

With the merit of high capacity,high safety,and low cost,zinc-ion batteries(ZIBs)possess huge application potential in the domain of large-scale energy storage.However,due to the relatively narrow voltage window and large lattice distortion of cationic redox reaction,ZIBs tend to present low energy density,poor kinetics,and unstable cyclic performance.Anion chemistry seems to provide a novel strategy to solve these issues from different aspects,such as enhanced operating voltage,extra capacity contribution,and boosted reaction kinetics.Considering the significance of this theory and the lack of relevant literatures,herein,in-depth comprehension of anionic chemistry and its positive effects on zinc storage performance have been emphasized and summarized.This review aims to present a full scope of anionic chemistry and furnish systematic cognition for rational design of advanced ZIBs with high energy density.Furthermore,insightful analysis and perspectives based on the current research status also have been proposed,which may point out some scientific suggestions and directions for the future research.

关键词： anionic chemistry electrode modification electrolyte regulation high energy density zinc-ion batteries

超薄蛭石纳米片基人工界面层调控Zn^(2+)离子通量助力高性能锌金属负极

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Science Bulletin 2023年第12期68卷 1283-1294,M0004页

作者：李建文周双孟欣雨陈逸宁傅纯雁 Alireza Azizi 赵晓光解维闵常智潘安强 School of materials Science and Engineering Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan ProvinceCentral South UniversityChangsha 410083China School of Minerals Processing and Bioengineering Central South UniversityChangsha 410083China

水系锌离子电池因其成本低、安全性高成为了近年来的研究热点,然而循环过程中的枝晶生长和界面腐蚀等问题严重限制了此类电池的实际应用。本文利用超薄蛭石纳米片(Vermiculite sheets,VS)在锌金属负极表面制备了具有核壳结构的多功能离... 详细信息

水系锌离子电池因其成本低、安全性高成为了近年来的研究热点,然而循环过程中的枝晶生长和界面腐蚀等问题严重限制了此类电池的实际应用。本文利用超薄蛭石纳米片(Vermiculite sheets,VS)在锌金属负极表面制备了具有核壳结构的多功能离子整流器(Ionrectifier,IRT)人工界面层.其中,疏水性聚偏二氟乙烯(PVDF)外壳能够将H_(2)O从锌负极表面驱离,赋予其优异的抗腐蚀效率(94.8%);VS内核的天然负电层间能够促进Zn^(2+)的迁移动力学(t_(+)=0.79)和密实沉积.结果表明,锌负极的电化学稳定性和沉积一致性大大提高,即使在高电流密度(3mA cm^(-2))下,IRT保护下的锌负极仍能稳定工作1600小时以上,并获得2400mAh cm^(-2)的累积放电容量.同时,利用该人工界面层组装的Zn//NH_(4)V_(4)O_(10)软包电池在1Ag^(-1)下循环150圈后的容量保持率高达94.3%.这种低成本、高效率的负极界面改性策略为水系电池的商业化提供了可能。

关键词：锌负极锌离子电池电化学稳定性放电容量整流器软包电池循环过程锌金属

Synthesis and characterization of soluble intrinsic black polyimide with excellent comprehensive properties

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Science China(Technological Sciences) 2023年第12期66卷 3604-3614页

作者： TAN JingHua SHEN JunYi HUANG Jie ZHAO ChunBo LI HuiPeng LIU XueYuan XIE FengYun LIU YiWu National and Local Joint Engineering Research Center for advanced packaging materials and Technology Key Laboratory of Advanced Packaging Materials and Technology of Hunan ProvinceSchool of Packaging and Materials EngineeringHunan University of TechnologyZhuzhou 412007China

Black polyimides(BPIs)have attracted increasing attention owing to their growing demand in optoelectronics.However,commonly used black polyimides doped with black fillers suffer from poor mechanical and electrical properties.To address these issues,a new diamine(2,5-bis(4′-amino-[1,1′-biphenyl]-4-yl)-3,4-bis(4-fluorophenyl)cyclopenta-2,4-dien-1-one,TPCPFPDA)bearing a tetraphenylcyclopentadienone(TPCP)moiety bonded with benzene and fluorine units was synthesized.The diamine was reacted with 4,4′-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)to yield a soluble intrinsic black polyimide(TPCPFPPI).Bonding fluorine(auxochrome group)and benzene units to TPCP can increase the conjugation ofπ-electrons systems and facilitate the movement of electron throughout the bigπbond,respectively.Owing to the structural features,the synthesized TPCPFPPI exhibited complete visible-light absorption with high blackness and opacity.Its cutoff wavelength(λ_(cut))and CIE(Commission Internationale de I′Eclairage)parameter L^(*)were 684 nm and 1.33,respectively.Moreover,TPCPFPPI displayed exceptional electrical,mechanical,and thermal properties as well as excellent solubility.A detailed theoretical calculation was conducted to gain better insight into the electronic properties of the TPCPFPPI.Results showed that the blackness of TPCPFPPI was chiefly attributed to the electron transition from highest occupied molecular orbital(HOMO)to lowest unoccupied molecular orbital(LUMO)in the diamines,where the charges primarily migrated from the aryl groups in the 2-and 5-positions to the cyclopentadienone center.The as-obtained intrinsic BPI(TPCPFPPI),exhibiting both high solubility and outstanding overall properties,has important applications in photo-electronics.

关键词： intrinsic black polyimide complete visible light absorption excellent solubility tetraphenylcyclopentadienone chromophore theoretical calculation

Recent advances in multifunctional metal-organic frameworks for lithium metal batteries

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Science China Chemistry 2024年第3期67卷 759-773页

作者： Jiaqi Li Zheng Weng Zuosu Qin Ying Zhang Ning Zhang Xiaohe Liu Chuankun Jia Gen Chen Jiang Zhou School of materials Science and Engineering Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan ProvinceCentral South University Zhongyuan Critical Metals laboratory Zhengzhou University College of materials Science and Engineering Changsha University of Science&Technology

In view of novel materials in the field of lithium metal batteries(LMBs), metal-organic frameworks(MOFs) have attracted extensive research interest owing to their controllable pore size, unsaturated metal sites and multifunctional organic groups. A variety of MOFs have been elaborately calculated and synthesized to be applied as separator coating, electrolyte modulators and solid-state electrolyte fillers in LMBs. In this mini-review, we summarize the mechanism of MOFs to limit the migration of anions, improve the Li-ion transference number and prolong the lifespan of LMBs. Suitable pore structure of MOFs can physically restrict the movement of Li^(+). Unsaturated metal sites can adsorb anions by electrostatic interaction. In addition,multifunctional organic functional groups that limit the migration of anions are discussed. Finally, the key challenges and perspectives in the development direction of MOFs-based separators and electrolytes are further elaborated.

关键词： metal-organic frameworks lithium metal battery separator electrolyte

Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc-ion Batteries

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Energy & Environmental materials 2020年第2期3卷 146-159页

作者： Canpeng Li Xuesong Xie Shuquan Liang Jiang Zhou School of materials Science and Engineering Central South UniversityChangsha Hunan 410083China Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province Changsha Hunan 410083China

Rechargeable aqueous zinc-ion batteries(ZIBs) featuring the merits of low cost,eco-friendliness,and enhanced safety have attracted extensive interests and considered as the most promising energy storage system.However,much efforts are devoted to the exploration of cathode materials and their storage mechanisms in this system,and inadequate attentions are received in regard to anode side especially in neutral or mild acidic electrolyte.Therefore,in this review,the fundamental understanding of existing issues including dendrite formation,corrosion,and hydrogen evolution are mainly revealed,as well as their interaction in neutral or mild acidic medium.In addition,the currently existing solution strategies on the anode are summarized and the mechanisms that contained are simultaneously investigated.Finally,perspectives on future anode modification and innovation direction are provided for the further development and research of Zn-based ZIBs.

关键词： dendrite formation hydrogen evolution zinc corrosion zinc metal anode zinc-ion batteries

Suppressing by-product via stratified adsorption effect to assist highly reversible zinc anode in aqueous electrolyte

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Journal of Energy Chemistry 2021年第4期30卷 549-556页

作者： Miao Zhou Shan Guo Guozhao Fang Hemeng Sun Xinxin Cao Jiang Zhou Anqiang Pan Shuquan Liang School of materials Science and Engineering Central South UniversityChangsha 410083HunanChina Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province Central South UniversityChangsha 410083HunanChina

The development of promising zinc anodes mainly suffers from their low plating/stripping coulombic efficiencies when using aqueous electrolyte,which are mainly associated with the interfacial formation of irreversible by-products.It is urgent to develop technologies that can solve this issue fundamentally.Herein,we report an artificial Sc_(2)O_(3) protective film to construct a new class of interface for Zn anode.The density functional theory simulation and experimental results have proven that the interfacial side reaction was inhibited via a stratified adsorption effect between this artificial layer and Zn anode.Benefiting from this novel structure,the Sc_(2)O_(3)-coated Zn anode can run for more than 100 cycles without short circuit and exhibit low voltage hysteresis,and the coulombic efficiency increases by 1.2%.Importantly,it shows a good application prospect when matched with two of popular manganese-based and vanadium-based cathodes.The excellent electrochemical performance of the Sc_(2)O_(3)-coated Zn anode highlights the importance of rational design of anode materials and demonstrates a good way for developing high-performance Zn anodes with long lifespan and high efficiency.

关键词： Zn anode Artificial protective film Stratified adsorption Interfacial reaction Zn4SO4(OH)6·H2O by-products

Layered hydrated vanadium oxide as highly reversible intercalation cathode for aqueous Zn-ion batteries

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Carbon Energy 2020年第2期2卷 294-301页

作者： Pinji Wang Xiaodong Shi Zhuoxi Wu Shan Guo Jiang Zhou Shuquan Liang School of materials Science and Engineering Central South UniversityChangshaHunanChina Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province Central South UniversityChangshaHunanChina

Aqueous Zn-ion batteries(ZIBs)hold great potential in large-scale energy storage systems due to the merits of low-cost and high safety.However,the unstable structure of cathode materials and sluggish(de)intercalation kinetics of Zn2+pose challenges for further development.Herein,highly reversible aqueous ZIBs are constructed with layered hydrated vanadium oxide as a cathode material.The electrochemical performances are further tested with the optimized electrolyte of 3M Zn(CF3SO3)2 and a cut-off voltage of 0.4 to 1.3 V,exhibiting a remarkable capacity of 290mAh g−1 at 0.5Ag−1,and long-term cycling stability at high current density.Furthermore,the Zn2+storage mechanism of V3O7⋅H2O is recognized as a highly reversible(de)intercalation process with good structural stability,implying the potential application in the field of large-scale energy storage.

关键词： cut-off voltage hydrated vanadium oxide layered structure zinc storage mechanism Zn-ion battery