共查询到20条相似文献,搜索用时 32 毫秒
1.
Kai Chen Gang Huang Jin‐Ling Ma Jin Wang Dong‐Yue Yang Xiao‐Yang Yang Yue Yu Xin‐Bo Zhang 《Angewandte Chemie (International ed. in English)》2020,59(38):16661-16667
The lithium (Li)–air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O2), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O2?, and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li‐air battery. Even worse, the water and/or CO2 in air bring parasitic reactions and safety issues. Therefore, applying such systems in open‐air environment is challenging. Herein, contrary to previous assertions, we have found that CO2 can improve the stability of both anode and electrolyte, and a high‐performance rechargeable Li–O2/CO2 battery is developed. The CO2 not only facilitates the in situ formation of a passivated protective Li2CO3 film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O2?. Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li2CO3. The Li–O2/CO2 battery achieves a full discharge capacity of 6628 mAh g?1 and a long life of 715 cycles, which is even better than those of pure Li–O2 batteries. 相似文献
2.
Moran Balaish Prof. Emanuel Peled Prof. Diana Golodnitsky Prof. Yair Ein‐Eli 《Angewandte Chemie (International ed. in English)》2015,54(2):436-440
Non‐aqueous lithium–oxygen batteries are considered as most advanced power sources, albeit they are facing numerous challenges concerning almost each cell component. Herein, we diverge from the conventional and traditional liquid‐based non‐aqueous Li–O2 batteries to a Li–O2 system based on a solid polymer electrolyte (SPE‐) and operated at a temperature higher than the melting point of the polymer electrolyte, where useful and most applicable conductivity values are easily achieved. The proposed SPE‐based Li‐O2 cell is compared to Li–O2 cells based on ethylene glycol dimethyl ether (glyme) through potentiodynamic and galvanostatic studies, showing a higher cell discharge voltage by 80 mV and most significantly, a charge voltage lower by 400 mV. The solid‐state battery demonstrated a comparable discharge‐specific capacity to glyme‐based Li–O2 cells when discharged at the same current density. The results shown here demonstrate that the safer PEO‐based Li–O2 battery is highly advantageous and can potentially replace the contingent of liquid‐based cells upon further investigation. 相似文献
3.
Active Salt/Silica‐Templated 2D Mesoporous FeCo‐Nx‐Carbon as Bifunctional Oxygen Electrodes for Zinc–Air Batteries 下载免费PDF全文
Shuang Li Dr. Chong Cheng Xiaojia Zhao Dr. Johannes Schmidt Prof. Dr. Arne Thomas 《Angewandte Chemie (International ed. in English)》2018,57(7):1856-1862
Two types of templates, an active metal salt and silica nanoparticles, are used concurrently to achieve the facile synthesis of hierarchical meso/microporous FeCo‐Nx‐carbon nanosheets (meso/micro‐FeCo‐Nx‐CN) with highly dispersed metal sites. The resulting meso/micro‐FeCo‐Nx‐CN shows high and reversible oxygen electrocatalytic performances for both ORR and OER, thus having potential for applications in rechargeable Zn–air battery. Our approach creates a new pathway to fabricate 2D meso/microporous structured carbon architectures for bifunctional oxygen electrodes in rechargeable Zn–air battery as well as opens avenues to the scale‐up production of rationally designed heteroatom‐doped catalytic materials for a broad range of applications. 相似文献
4.
Yingying Mi Dr. Wen Liu Dr. Ke R. Yang Dr. Jianbing Jiang Dr. Qi Fan Dr. Zhe Weng Yiren Zhong Zishan Wu Prof. Gary W. Brudvig Prof. Victor S. Batista Prof. Henghui Zhou Prof. Hailiang Wang 《Angewandte Chemie (International ed. in English)》2016,55(47):14818-14822
Confining lithium polysulfide intermediates is one of the most effective ways to alleviate the capacity fade of sulfur‐cathode materials in lithium–sulfur (Li–S) batteries. To develop long‐cycle Li–S batteries, there is an urgent need for material structures with effective polysulfide binding capability and well‐defined surface sites; thereby improving cycling stability and allowing study of molecular‐level interactions. This challenge was addressed by introducing an organometallic molecular compound, ferrocene, as a new polysulfide‐confining agent. With ferrocene molecules covalently anchored on graphene oxide, sulfur electrode materials with capacity decay as low as 0.014 % per cycle were realized, among the best of cycling stabilities reported to date. With combined spectroscopic studies and theoretical calculations, it was determined that effective polysulfide binding originates from favorable cation–π interactions between Li+ of lithium polysulfides and the negatively charged cyclopentadienyl ligands of ferrocene. 相似文献
5.
Yutao Li Henghui Xu Po‐Hsiu Chien Nan Wu Sen Xin Leigang Xue Kyusung Park Yan‐Yan Hu John B. Goodenough 《Angewandte Chemie (International ed. in English)》2018,57(28):8587-8591
Solid‐oxide Li+ electrolytes of a rechargeable cell are generally sensitive to moisture in the air as H+ exchanges for the mobile Li+ of the electrolyte and forms insulating surface phases at the electrolyte interfaces and in the grain boundaries of a polycrystalline membrane. These surface phases dominate the total interfacial resistance of a conventional rechargeable cell with a solid–electrolyte separator. We report a new perovskite Li+ solid electrolyte, Li0.38Sr0.44Ta0.7Hf0.3O2.95F0.05, with a lithium‐ion conductivity of σLi=4.8×10?4 S cm?1 at 25 °C that does not react with water having 3≤pH≤14. The solid electrolyte with a thin Li+‐conducting polymer on its surface to prevent reduction of Ta5+ is wet by metallic lithium and provides low‐impedance dendrite‐free plating/stripping of a lithium anode. It is also stable upon contact with a composite polymer cathode. With this solid electrolyte, we demonstrate excellent cycling performance of an all‐solid‐state Li/LiFePO4 cell, a Li‐S cell with a polymer‐gel cathode, and a supercapacitor. 相似文献
6.
Johannes Wandt Peter Jakes Josef Granwehr Hubert A. Gasteiger Rüdiger‐A. Eichel 《Angewandte Chemie (International ed. in English)》2016,55(24):6892-6895
Aprotic lithium–oxygen (Li–O2) batteries have attracted considerable attention in recent years owing to their outstanding theoretical energy density. A major challenge is their poor reversibility caused by degradation reactions, which mainly occur during battery charge and are still poorly understood. Herein, we show that singlet oxygen (1Δg) is formed upon Li2O2 oxidation at potentials above 3.5 V. Singlet oxygen was detected through a reaction with a spin trap to form a stable radical that was observed by time‐ and voltage‐resolved in operando EPR spectroscopy in a purpose‐built spectroelectrochemical cell. According to our estimate, a lower limit of approximately 0.5 % of the evolved oxygen is singlet oxygen. The occurrence of highly reactive singlet oxygen might be the long‐overlooked missing link in the understanding of the electrolyte degradation and carbon corrosion reactions that occur during the charging of Li–O2 cells. 相似文献
7.
Superior Rechargeability and Efficiency of Lithium–Oxygen Batteries: Hierarchical Air Electrode Architecture Combined with a Soluble Catalyst 下载免费PDF全文
Hee‐Dae Lim Hyelynn Song Jinsoo Kim Hyeokjo Gwon Youngjoon Bae Kyu‐Young Park Jihyun Hong Haegyeom Kim Taewoo Kim Prof. Yong Hyup Kim Xavier Lepró Raquel Ovalle‐Robles Prof. Ray H. Baughman Prof. Kisuk Kang 《Angewandte Chemie (International ed. in English)》2014,53(15):3926-3931
The lithium–oxygen battery has the potential to deliver extremely high energy densities; however, the practical use of Li‐O2 batteries has been restricted because of their poor cyclability and low energy efficiency. In this work, we report a novel Li‐O2 battery with high reversibility and good energy efficiency using a soluble catalyst combined with a hierarchical nanoporous air electrode. Through the porous three‐dimensional network of the air electrode, not only lithium ions and oxygen but also soluble catalysts can be rapidly transported, enabling ultra‐efficient electrode reactions and significantly enhanced catalytic activity. The novel Li‐O2 battery, combining an ideal air electrode and a soluble catalyst, can deliver a high reversible capacity (1000 mAh g?1) up to 900 cycles with reduced polarization (about 0.25 V). 相似文献
8.
Hee‐Dae Lim Hyeokjun Park Hyungsub Kim Jinsoo Kim Byungju Lee Youngjoon Bae Hyeokjo Gwon Prof. Kisuk Kang 《Angewandte Chemie (International ed. in English)》2015,54(33):9663-9667
Primary Li–SO2 batteries offer a high energy density in a wide operating temperature range with exceptionally long shelf life and have thus been frequently used in military and aerospace applications. Although these batteries have never been demonstrated as a rechargeable system, herein, we show that the reversible formation of Li2S2O4, the major discharge product of Li–SO2 battery, is possible with a remarkably smaller charging polarization than that of a Li–O2 battery without the use of catalysts. The rechargeable Li–SO2 battery can deliver approximately 5400 mAh g?1 at 3.1 V, which is slightly higher than the performance of a Li–O2 battery. In addition, the Li–SO2 battery can be operated with the aid of a redox mediator, exhibiting an overall polarization of less than 0.3 V, which results in one of the highest energy efficiencies achieved for Li–gas battery systems. 相似文献
9.
Structural and Electrochemical Study of Vanadium‐Doped TiO2 Ramsdellite with Superior Lithium Storage Properties for Lithium‐Ion Batteries 下载免费PDF全文
Dr. Juan Carlos Pérez‐Flores Dr. Markus Hoelzel Dr. Flaviano García‐Alvarado Dr. Alois Kuhn 《Chemphyschem》2016,17(7):1062-1069
Titanium‐oxide‐based materials are considered attractive and safe alternatives to carbonaceous anodes in Li‐ion batteries. In particular, the ramsdellite form TiO2(R) is known for its superior lithium‐storage ability as the bulk material when compared with other titanates. In this work, we prepared V‐doped lithium titanate ramsdellites with the formula Li0.5Ti1?xVxO2 (0≤x≤0.5) by a conventional solid‐state reaction. The lithium‐free Ti1?xVxO2 compounds, in which the ramsdellite framework remains virtually unaltered, are easily obtained by a simple aqueous oxidation/ion‐extraction process. Neutron powder diffraction is used to locate the Li channel site in Li0.5Ti1?xVxO2 compounds and to follow the lithium extraction by difference‐Fourier maps. Previously delithiated Ti1?xVxO2 ramsdellites are able to insert up to 0.8 Li+ per transition‐metal atom. The initial gravimetric capacities of 270 mAh g?1 with good cycle stability under constant current discharge conditions are among the highest reported for bulk TiO2‐related intercalation compounds for the threshold of one e? per formula unit. 相似文献
10.
Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc–Air Batteries 下载免费PDF全文
Dr. Xien Liu Minjoon Park Dr. Min Gyu Kim Shiva Gupta Prof. Gang Wu Prof. Jaephil Cho 《Angewandte Chemie (International ed. in English)》2015,54(33):9654-9658
The lack of high‐efficient, low‐cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc–air batteries. A nanocomposite CoO‐NiO‐NiCo bifunctional electrocatalyst supported by nitrogen‐doped multiwall carbon nanotubes (NCNT/CoO‐NiO‐NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO‐NiO‐NiCo catalysts further demonstrated superior performance to state‐of‐the‐art Pt/C or Pt/C+IrO2 catalysts in primary and rechargeable zinc–air batteries. 相似文献
11.
The structural and electronic properties of Li4+xTi5O12 compounds (with 0≤x≤6)—to be used as anode materials for lithium‐ion batteries—are studied by means of first principles calculations. The results suggest that Li4Ti5O12 can be lithiated to the state Li8.5Ti5O12, which provides a theoretical capacity that is about 1.5 times higher than that of the compound lithiated to Li7Ti5O12. Further insertion of lithium species into the Li8.5Ti5O12 lattice results in a clear structural distortion. The small lattice expansion observed upon lithium insertion (about 0.4 % for the lithiated material Li8.5Ti5O12) and the retained [Li1Ti5]16dO12 framework indicate that the insertion/extraction process is reversible. Furthermore, the predicted intercalation potentials are 1.48 and 0.05 V (vs Li/Li+) for the Li4Ti5O12/Li7Ti5O12 and Li7Ti5O12/Li8.5Ti5O12 composition ranges, respectively. Electronic‐structure analysis shows that the lithiated states Li4+xTi5O12 are metallic, which is indicative of good electronic‐conduction properties. 相似文献
12.
Dr. Tingting Yang Peng Jia Qiunan Liu Dr. Liqiang Zhang Congcong Du Jingzhao Chen Hongjun Ye Xiaomei Li Yanshuai Li Prof. Tongde Shen Dr. Yongfu Tang Dr. Jianyu Huang 《Angewandte Chemie (International ed. in English)》2018,57(39):12750-12753
Lithium metal is an ideal anode for next‐generation lithium batteries owing to its very high theoretical specific capacity of 3860 mAh g?1 but very reactive upon exposure to ambient air, rendering it difficult to handle and transport. Air‐stable lithium spheres (ASLSs) were produced by electrochemical plating under CO2 atmosphere inside an advanced aberration‐corrected environmental transmission electron microscope. The ASLSs exhibit a core–shell structure with a Li core and a Li2CO3 shell. In ambient air, the ASLSs do not react with moisture and maintain their core–shell structures. Furthermore, the ASLSs can be used as anodes in lithium‐ion batteries, and they exhibit similar electrochemical behavior to metallic Li, indicating that the surface Li2CO3 layer is a good Li+ ion conductor. The air stability of the ASLSs is attributed to the surface Li2CO3 layer, which is barely soluble in water and does not react with oxygen and nitrogen in air at room temperature, thus passivating the Li core. 相似文献
13.
Core–Shell‐Structured CNT@RuO2 Composite as a High‐Performance Cathode Catalyst for Rechargeable Li–O2 Batteries 下载免费PDF全文
Dr. Zelang Jian Dr. Pan Liu Dr. Fujun Li Dr. Ping He Dr. Xianwei Guo Prof. Mingwei Chen Prof. Haoshen Zhou 《Angewandte Chemie (International ed. in English)》2014,53(2):442-446
A RuO2 shell was uniformly coated on the surface of core CNTs by a simple sol–gel method, and the resulting composite was used as a catalyst in a rechargeable Li–O2 battery. This core–shell structure can effectively prevent direct contact between the CNT and the discharge product Li2O2, thus avoiding or reducing the formation of Li2CO3, which can induce large polarization and lead to charge failure. The battery showed a high round‐trip efficiency (ca. 79 %), with discharge and charge overpotentials of 0.21 and 0.51 V, respectively, at a current of 100 mA gtotal?1. The battery also exhibited excellent rate and cycling performance. 相似文献
14.
Pomegranate‐Inspired Design of Highly Active and Durable Bifunctional Electrocatalysts for Rechargeable Metal–Air Batteries 下载免费PDF全文
Dr. Ge Li Dr. Xiaolei Wang Jing Fu Dr. Jingde Li Moon Gyu Park Dr. Yining Zhang Gregory Lui Prof. Zhongwei Chen 《Angewandte Chemie (International ed. in English)》2016,55(16):4977-4982
Rational design of highly active and durable electrocatalysts for oxygen reactions is critical for rechargeable metal–air batteries. Herein, we report the design and development of composite electrocatalysts based on transition metal oxide nanocrystals embedded in a nitrogen‐doped, partially graphitized carbon framework. Benefiting from the unique pomegranate‐like architecture, the composite catalysts possess abundant active sites, strong synergetic coupling, enhanced electron transfer, and high efficiencies in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The Co3O4‐based composite electrocatalyst exhibited a high half‐wave potential of 0.842 V for ORR, and a low overpotential of only 450 mV at the current density of 10 mA cm?2 for OER. A single‐cell zinc–air battery was also fabricated with superior durability, holding great promise in the practical implementation of rechargeable metal–air batteries. 相似文献
15.
Meng Zhao Hong‐Jie Peng Bo‐Quan Li Xiao Chen Jin Xie Xinyan Liu Qiang Zhang Jia‐Qi Huang 《Angewandte Chemie (International ed. in English)》2020,59(23):9011-9017
In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium–sulfur (Li‐S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal‐based pre‐catalysts (Co4N) in working Li‐S batteries that renders highly active electrocatalysts (CoSx). Electrochemical cycling induces the transformation from single‐crystalline Co4N to polycrystalline CoSx that are rich in active sites. This transformation propels all‐phase polysulfide‐involving reactions. Consequently, Co4N enables stable operation of high‐rate (10 C, 16.7 mA cm?2) and electrolyte‐starved (4.7 μL mgS?1) Li‐S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low‐valence metal compounds. 相似文献
16.
Shuang Jiang Dr. Yong Lu Dr. Yanying Lu Dr. Mo Han Haixia Li Prof. Zhanliang Tao Prof. Zhiqiang Niu Prof. Jun Chen 《化学:亚洲杂志》2018,13(10):1379-1385
Lithium–sulfur (Li–S) batteries have shown great potential as high energy‐storage devices. However, the stability of the Li metal anode is still a major concern. This is due to the formation of lithium dendrites and severe side reactions with polysulfide intermediates. We herein develop an anode protection method by coating a Nafion/TiO2 composite layer on the Li anode to solve these problems. In this architecture, Nafion suppresses the growth of Li dendrites, protects the Li anode, and prevents side reactions between polysulfides and the Li anode. Moreover, doped TiO2 further improves the ionic conductivity and mechanical properties of the Nafion membrane. Li–S batteries with a Nafion/TiO2‐coated Li anode exhibit better cycling stability (776 mA h g?1 after 100 cycles at 0.2 C, 1 C=1672 mA g?1) and higher rate performance (787 mA h g?1 at 2 C) than those with a pristine Li anode. This work provides an alternative way to construct stable Li anodes for high‐performance Li–S batteries. 相似文献
17.
Insight into the Interfacial Process and Mechanism in Lithium–Sulfur Batteries: An In Situ AFM Study 下载免费PDF全文
Shuang‐Yan Lang Yang Shi Prof. Dr. Yu‐Guo Guo Prof. Dr. Dong Wang Prof. Dr. Rui Wen Prof. Dr. Li‐Jun Wan 《Angewandte Chemie (International ed. in English)》2016,55(51):15835-15839
Lithium–sulfur (Li–S) batteries are highly appealing for large‐scale energy storage. However, performance deterioration issues remain, which are highly related to interfacial properties. Herein, we present a direct visualization of the interfacial structure and dynamics of the Li–S discharge/charge processes at the nanoscale. In situ atomic force microscopy and ex situ spectroscopic methods directly distinguish the morphology and growth processes of insoluble products Li2S2 and Li2S. The monitored interfacial dynamics show that Li2S2 nanoparticle nuclei begin to grow at 2 V followed by a fast deposition of lamellar Li2S at 1.83 V on discharge. Upon charging, only Li2S depletes from the interface, leaving some Li2S2 undissolved, which accumulates during cycling. The galvanostatic precipitation of Li2S2 and/or Li2S is correlated to current rates and affects the specific capacity. These findings reveal a straightforward structure–reactivity correlation and performance fading mechanism in Li–S batteries. 相似文献
18.
Zhiwei Zhao Prof. Dr. Jun Huang Prof. Dr. Zhangquan Peng 《Angewandte Chemie (International ed. in English)》2018,57(15):3874-3886
The lithium–air battery (LAB) is envisaged as an ultimate energy storage device because of its highest theoretical specific energy among all known batteries. However, parasitic reactions bring about vexing issues on the efficiency and longevity of the LAB, among which the formation and decomposition of lithium carbonate Li2CO3 is of paramount importance. The discovery of Li2CO3 as the main discharge product in carbonate‐based electrolytes once brought researchers to “the end of the idyll“ in the early 2010s. In the past few years, tremendous efforts have been made to understand the formation and decomposition mechanisms of Li2CO3, as well as to conceive novel chemical/material strategies to suppress the Li2CO3 formation and to facilitate the Li2CO3 decomposition. Moreover, the study on Li2CO3 in LABs is opening up a new research field in energy technology. Considering the rapid development and innumerous emerging issues, it is timely to recapitulate the current understandings, define the ambiguities and the scientific gaps, and discuss topics of high priority for future research, which is the aim of this Minireview. 相似文献
19.
Dr. Jun Ma Dr. Yong‐Ning Zhou Dr. Yurui Gao Prof. Qingyu Kong Prof. Zhaoxiang Wang Prof. Xiao‐Qing Yang Prof. Liquan Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(28):8723-8730
Lithium‐rich layer‐structured oxides xLi2MnO3? (1?x)LiMO2 (0<x<1, M=Mn, Ni, Co, etc.) are interesting and potential cathode materials for high energy‐density lithium ion batteries. However, the characteristic charge compensation contributed by O2? in Li2MnO3 leads to the evolution of oxygen during the initial Li+ ion extraction at high voltage and voltage fading in subsequent cycling, resulting in a safety hazard and poor cycling performance of the battery. Molybdenum substitution was performed in this work to provide another electron donor and to enhance the electrochemical activity of Li2MnO3‐based cathode materials. X‐ray diffraction and adsorption studies indicated that Mo5+ substitution expands the unit cell in the crystal lattice and weakens the Li?O and Mn?O bonds, as well as enhancing the activity of Li2MnO3 by lowering its delithiation potential and suppressing the release of oxygen. In addition, the chemical environment of O2? ions in molybdenum‐substituted Li2MnO3 is more reversible than in the unsubstituted sample during cycling. Therefore molybdenum substitution is expected to improve the performances of the Li2MnO3‐based lithium‐rich cathode materials. 相似文献
20.
Lei Qin Neng Xiao Songwei Zhang Xiaojuan Chen Yiying Wu 《Angewandte Chemie (International ed. in English)》2020,59(26):10498-10501
Although using an air cathode is the goal for superoxide‐based potassium‐oxygen (K‐O2) batteries, prior studies were limited to pure oxygen. Now, the first K‐air (dry) battery based on reversible superoxide electrochemistry is presented. Spectroscopic and gas chromatography analyses are applied to evaluate the reactivity of KO2 in ambient air. Although KO2 reacts with water vapor and CO2 to form KHCO3, it is highly stable in dry air. With this knowledge, rechargeable K‐air (dry) batteries were successfully demonstrated by employing dry air cathode. The reduced partial pressure of oxygen plays a critical role in boosting battery lifespan. With a more stable environment for the K anode, a K‐air (dry) battery delivers over 100 cycles (>500 h) with low round‐trip overpotentials and high coulombic efficiencies as opposed to traditional K‐O2 battery that fails early. This work sheds light on the benefits and restrictions of employing the air cathode in superoxide‐based batteries. 相似文献