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1.
Fengling Zhang Dr. Jingning Lai Zhengqiang Hu Anbin Zhou Huirong Wang Xin Hu Lijuan Hou Bohua Li Wen Sun Dr. Nan Chen Prof. Li Li Prof. Feng Wu Prof. Renjie Chen 《Angewandte Chemie (International ed. in English)》2023,62(16):e202301772
Lithium-oxygen batteries (LOBs) are well known for their high energy density. However, their reversibility and rate performance are challenged due to the sluggish oxygen reduction/evolution reactions (ORR/OER) kinetics, serious side reactions and uncontrollable Li dendrite growth. The electrolyte plays a key role in transport of Li+ and reactive oxygen species in LOBs. Here, we tailored a dilute electrolyte by screening suitable crown ether additives to promote lithium salt dissociation and Li+ solvation through electrostatic interaction. The electrolyte containing 100 mM 18-crown-6 ether (100-18C6) exhibits enhanced electrochemical stability and triggers a solution-mediated Li2O2 growth pathway in LOBs, showing high discharge capacity of 10 828.8 mAh gcarbon−1. Moreover, optimized electrode/electrolyte interfaces promote ORR/OER kinetics on cathode and achieve dendrite-free Li anode, which enhances the cycle life. This work casts new lights on the design of low-cost dilute electrolytes for high performance LOBs. 相似文献
2.
Yulu Yang Huaping Wang Chunlei Zhu Prof. Jianmin Ma 《Angewandte Chemie (International ed. in English)》2023,62(22):e202300057
Lithium metal batteries (LMBs) comprising Li metal anode and high-voltage nickel-rich cathode could potentially realize high capacity and power density. However, suitable electrolytes to tolerate the oxidation on the cathode at high cut-off voltage are urgently needed. Herein, we present an armor-like inorganic-rich cathode electrolyte interphase (CEI) strategy for exploring oxidation-resistant electrolytes for sustaining 4.8 V Li||LiNi0.6Co0.2Mn0.2O2 (NCM622) batteries with pentafluorophenylboronic acid (PFPBA) as the additive. In such CEI, the armored lithium borate surrounded by CEI up-layer represses the dissolution of inner CEI moieties and also improves the Li+ conductivity of CEI while abundant LiF is distributed over whole CEI to enhance the mechanical stability and Li+ conductivity compared with polymer moieties. With such robust Li+ conductive CEI, the Li||NCM622 battery delivered excellent stability at 4.6 V cut-off voltage with 91.2 % capacity retention after 400 cycles. The excellent cycling performance was also obtained even at 4.8 V cut-off voltage. 相似文献
3.
Boor Singh Lalia Yarjan Abdul Samad Raed Hashaikeh 《Journal of Solid State Electrochemistry》2013,17(3):575-581
Nanocrystalline cellulose (NCC)-reinforced poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP) composite mats have been prepared by electrospinning method. Polymer electrolytes formed by activating the composite mats with 1 M lithium bis(trifluoromethanesulfonyl)imide/1-butyl-3-methypyrrolidinium bis(trifluoromethanesulfonyl)imide electrolyte solution. The addition of 2 wt% NCC in PVdF-HFP improved the electrolyte retention and storage modulus of the separator by 63 and 15 %, respectively. The developed electrolyte demonstrated high value of ionic conductivity viz. 4?×?10?4?S?cm?1 at 30 °C. Linear scan voltammetry revealed a wide electrochemical stability of the composite mat separator up to 5 V (vs. Li+/Li). Cyclic voltammetry of the polymer electrolyte with a graphite electrode in 2.5 to 0 V (vs. Li+/Li) potential range showed a reversible intercalation/de-intercalation of Li+ ions in the graphite. No peaks were observed related to the reduction of the electrolyte on the anode. 相似文献
4.
Jiale Fu Dr. Xiao Ji Dr. Ji Chen Dr. Long Chen Prof. Xiulin Fan Prof. Daobin Mu Prof. Chunsheng Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22378-22385
The electrolytes in lithium metal batteries have to be compatible with both lithium metal anodes and high voltage cathodes, and can be regulated by manipulating the solvation structure. Herein, to enhance the electrolyte stability, lithium nitrate (LiNO3) and 1,1,2,2-tetrafuoroethyl-2′,2′,2′-trifuoroethyl(HFE) are introduced into the high-concentration sulfolane electrolyte to suppress Li dendrite growth and achieve a high Coulombic efficiency of >99 % for both the Li anode and LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Molecular dynamics simulations show that NO3− participates in the solvation sheath of lithium ions enabling more bis(trifluoromethanesulfonyl)imide anion (TFSI−) to coordinate with Li+ ions. Therefore, a robust LiNxOy−LiF-rich solid electrolyte interface (SEI) is formed on the Li surface, suppressing Li dendrite growth. The LiNO3-containing sulfolane electrolyte can also support the highly aggressive LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode, delivering a discharge capacity of 190.4 mAh g−1 at 0.5 C for 200 cycles with a capacity retention rate of 99.5 %. 相似文献
5.
Ester Modified Pyrrolidinium Based Ionic Liquids as Electrolyte Component Candidates in Rechargeable Lithium Batteries
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Xia Cao Stephan Röser Babak Rezaeirad Xin He Benjamin Streipert Martin Winter Isidora Cekic‐Laskovic 《无机化学与普通化学杂志》2015,641(14):2536-2542
Room temperature ionic liquids (RTILs), especially pyrrolidinium based RTILs with bis(trifluoromethane‐sulfonyl)imide (TFSI) as counterion, are frequently proposed as promising electrolyte component candidates thanks to their high thermal as well as high oxidation stability. In order to avoid a resource intensive experimental approach, mainly based on trial and error experiments, a computational screening method for pre‐selecting suitable candidate molecules was adopted and three homologous series compounds were synthesized by modifying the cation structure of pyrrolidinium RTILs. The obtained high purity RTILs: methyl‐methylcarboxymethyl pyrrolidinium TFSI (MMMPyrTFSI), methyl‐ethylcarboxymethyl pyrrolidinium TFSI (MEMPyrTFSI) and methylpropylcarboxymethyl pyrrolidinium TFSI (MPMPyrTFSI) revealed excellent thermal stabilities higher than 300 °C. Furthermore, MMMPyrTFSI and MPMPyrTFSI exhibit high oxidation stability up to 5.4 V vs. Li/Li+. No aluminum corrosion of current collector was observed at 5 V vs. Li/Li+. In addition to that, these RTILs display a superior salt (LiTFSI) solubility (3.0–3.5 M), compared to the unmodified RTIL 1‐butyl‐1‐methylpyrrolidinium TFSI (Pyr14TFSI) (1.5–2.0 M) at room temperature. All these properties make novel ester modified RTILs promising and interesting candidates for application in rechargeable lithium batteries. 相似文献
6.
Dr. Yichao Cai Yunpeng Hou Dr. Yong Lu Dr. Qiu Zhang Dr. Zhenhua Yan Prof. Jun Chen 《Angewandte Chemie (International ed. in English)》2023,62(17):e202218014
Li−O2 batteries with bis(trifluoromethanesulfonyl)imide-based ionic liquid (TFSI-IL) electrolyte are promising because TFSI-IL can stabilize O2− to lower charge overpotential. However, slow Li+ transport in TFSI-IL electrolyte causes inferior Li deposition. Here we optimize weak solvating molecule (anisole) to generate anisole-doped ionic aggregate in TFSI-IL electrolyte. Such unique solvation environment can realize not only high Li+ transport parameters but also anion-derived solid electrolyte interface (SEI). Thus, fast Li+ transport is achieved in electrolyte bulk and SEI simultaneously, leading to robust Li deposition with high rate capability (3 mA cm−2) and long cycle life (2000 h at 0.2 mA cm−2). Moreover, Li−O2 batteries show good cycling stability (a small overpotential increase of 0.16 V after 120 cycles) and high rate capability (1 A g−1). This work provides an effective electrolyte design principle to realize stable Li deposition and high-performance Li−O2 batteries. 相似文献
7.
Yongjian Huai Jiamin Deng Rengui Li Zhenghua Deng Jishuan Suo 《Journal of Solid State Electrochemistry》2013,17(1):209-215
In this work, a polymer/ceramic phase-separation porous membrane is first prepared from polyvinyl alcohol–polyacrylonitrile water emulsion mixed with fumed nano-SiO2 particles by the phase inversion method. This porous membrane is then wetted by a non-aqueous Li–salt liquid electrolyte to form the polymer/colloid dual-phase electrolyte membrane. Compared to the liquid electrolyte in conventional polyolefin separator, the obtained electrolyte membrane has superior properties in high ionic conductivity (1.9 mS?cm?1 at 30 °C), high Li+ transference number (0.41), high electrochemical stability (extended up to 5.0 V versus Li+/Li on stainless steel electrode), and good interfacial stability with lithium metal. The test cell of Li/LiCoO2 with the electrolyte membrane as separator also shows high-rate capability and excellent cycle performance. The polymer/colloid dual-phase electrolyte membrane shows promise for application in rechargeable lithium batteries. 相似文献
8.
P. Cignini M. Icovi S. Panero G. Pistoia C. Temperoni 《Journal of Electroanalytical Chemistry》1979,102(3):333-341
Some non-stoichiometric Mo oxides have been tested as cathodes for primary Li cells. Their performance has been evaluated as a function of current density, electrolyte, temperature, cathode porosity and formulation. Specific capacities exceeding 0.4·Ah g?1 could be reached at low rates. As found with MoO3, these oxides give rise to the formation of ternary phases of the type LimyMomO3m?1. Li+ insertion in the lattices allows structure retention for Li/Mo ratios lower than 0.7–0.8, whereas higher Li+ contents result in the appearance of new phases. 相似文献
9.
《中国化学快报》2023,34(6):107711
Increasing the charging cut-off potential of lithium cobalt oxide (LiCoO2, LCO) can effectively improve the energy density of the lithium-ion batteries, which are the mainstream energy storage devices used in 3C electronic products. However, the continuous decomposition of the electrolyte and dissolution of Co from the electrode will occur at high-potential operation, which deteriorate the performances of LCO. Here, a cathode-electrolyte interface (CEI) layer containing MgF2 is constructed to enhance the electrochemical stability of LCO at 4.6 V (vs. Li+/Li). The Mg2+ added to the cathode gradually releases into the electrolyte during cycling, which forms a stable MgF2-rich protective layer. In addition, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TTE) is added to the electrolyte acting as a F source to increase the content of MgF2 in the CEI layer. The MgF2-rich CEI layer effectively suppresses the decomposition of electrolyte components and the dissolution of Co of LCO, which makes the Li||LiCoO2 (Li||LCO) cell cycled stably at 3∼4.6 V (vs. Li+/Li) in 200 cycles with a retention of 83.9%. 相似文献
10.
Dr. Sen Xin Dr. Shuai Li Dr. Jinlong Zhu Dr. Xujie Lü Dr. Zhiming Cui Prof. Quanxi Jia Prof. Jianshi Zhou Prof. Yusheng Zhao Prof. John B. Goodenough 《Angewandte Chemie (International ed. in English)》2016,55(34):9965-9968
A fluorine‐doped antiperovskite Li‐ion conductor Li2(OH)X (X=Cl, Br) is shown to be a promising candidate for a solid electrolyte in an all‐solid‐state Li‐ion rechargeable battery. Substitution of F? for OH? transforms orthorhombic Li2OHCl to a room‐temperature cubic phase, which shows electrochemical stability to 9 V versus Li+/Li and two orders of magnitude higher Li‐ion conductivity than that of orthorhombic Li2OHCl. An all‐solid‐state Li/LiFePO4 with F‐doped Li2OHCl as the solid electrolyte showed good cyclability and a high coulombic efficiency over 40 charge/discharge cycles. 相似文献
11.
Xiang Zhao Xuan Qiu Haodong Xue Si Liu Dingli Liang Chuan Yan Weinan Chen Prof. Yonggang Wang Prof. Gang Zhou 《Angewandte Chemie (International ed. in English)》2023,62(9):e202216713
Organic p-type cathode materials have recently attracted increasing attention due to their higher redox potentials and rate capabilities in comparison to n-type cathodes. However, most of the p-type cathodes based on one-electron redox still suffer from limited stability and low specific capacity (<150 mAh g−1). Herein, two polymers, conjugated poly(diethyldihydrophenazine vinylene) ( CPP ) and non-conjugated poly(diethyldihydrophenazine ethylidene) ( NCPP ) containing two-electron redox dihydrophenazine, have been developed as p-type cathode materials. It is experimentally and theoretically found that the conjugated linkage among the redox centers in polymer CPP is more favorable for the effective charge delocalization on the conjugated polymer backbone and the sufficient oxidation in the higher potential region (3.3–4.2 V vs. Li/Li+). Consequently, the CPP cathode displays a higher reversible specific capacity of 184 mAh g−1 with excellent cycling stability. 相似文献
12.
《中国化学快报》2023,34(4):107494
Lithium rich layered oxide (LRLO) has been considered as one of the promising cathodes for lithium-ion batteries (LIBs). The high voltage and large capacity of LRLO depend on Li2MnO3 phase. To ameliorate the electrochemical performance of Li2MnO3, also written as Li(Li1/3Mn2/3)O2, we propose a strategy to substitute Mn4+ and Li+ in Mn/Li transition metal layer with Ti4+, which can stabilize the structure of Li2MnO3 by inhibiting the excessive oxidation of O2? above 4.5 V. More significantly, the unequal-valent substitution brings about the emergence of interlayer Li vacancies, which can promote the Li-ion diffusion based on the enlarged interlayer and increase the capacity by activating the Mn3+/4+ redox. We designed Li0.7[Li1/3Mn2/3]0.7Ti0.3O2 with high interlayer Li vacancies, which presents a high capacity (290 mAh/g at 10 mA/g) and stable cycling performance (84% over 60 cycles at 50 mA/g). We predict that this strategy will be helpful to further improve the electrochemical performance of LRLOs. 相似文献
13.
Dr. Tao Ma Dr. Youxuan Ni Diantao Li Dr. Zhengtai Zha Dr. Song Jin Weijia Zhang Liqun Jia Qiong Sun Dr. Weiwei Xie Prof. Zhanliang Tao Prof. Jun Chen 《Angewandte Chemie (International ed. in English)》2023,62(43):e202310761
Despite carbonate electrolytes exhibiting good stability to sulfurized polyacrylonitrile (SPAN), their chemical incompatibility with lithium (Li) metal anode leads to poor electrochemical performance of Li||SPAN full cells. While the SPAN employs conventional ether electrolytes that suffer from the shuttle effect, leading to rapid capacity fading. Here, we tailor a dilute electrolyte based on a low solvating power ether solvent that is both compatible with SPAN and Li metal. Unlike conventional ether electrolytes, the weakly solvating ether electrolyte enables SPAN to undergo reversibly “solid–solid” conversion. It features an anion–rich solvation structure that allows for the formation of a robust cathode electrolyte interphase on the SPAN, effectively blocking the dissolution of polysulfides into the bulk electrolyte and avoiding the shuttle effect. What's more, the unique electrolyte chemistry endowed Li ions with fast electroplating kinetics and induced high reversibility Li deposition/stripping process from 25 °C to −40 °C. Based on tailored electrolyte, Li||SPAN full cells matched with high loading SPAN cathodes (≈3.6 mAh cm−2) and 50 μm Li foil can operate stably over a wide range of temperatures. Additionally, Li||SPAN pouch cell under lean electrolyte and 5 % excess Li conditions can continuously operate stably for over a month. 相似文献
14.
Dr. Hang-Yu Zhou Yu Ou Shuai-Shuai Yan Dr. Jin Xie Pan Zhou Lei Wan Zi-Ang Xu Dr. Feng-Xiang Liu Dr. Wei-Li Zhang Dr. Yin-Chun Xia Prof. Kai Liu 《Angewandte Chemie (International ed. in English)》2023,62(35):e202306948
Improved durability, enhanced interfacial stability, and room temperature applicability are desirable properties for all-solid-state lithium metal batteries (ASSLMBs), yet these desired properties are rarely achieved simultaneously. Here, in this work, it is noticed that the huge resistance at Li metal/electrolyte interface dominantly impeded the normal cycling of ASSLMBs especially at around room temperature (<30 °C). Accordingly, a supramolecular polymer ion conductor (SPC) with “weak solvation” of Li+ was prepared. Benefiting from the halogen-bonding interaction between the electron-deficient iodine atom (on 1,4-diiodotetrafluorobenzene) and electron-rich oxygen atoms (on ethylene oxide), the O-Li+ coordination was significantly weakened. Therefore, the SPC achieves rapid Li+ transport with high Li+ transference number, and importantly, derives a unique Li2O-rich SEI with low interfacial resistance on lithium metal surface, therefore enabling stable cycling of ASSLMBs even down to 10 °C. This work is a new exploration of halogen-bonding chemistry in solid polymer electrolyte and highlights the importance of “weak solvation” of Li+ in the solid-state electrolyte for room temperature ASSLMBs. 相似文献
15.
A tetraethylene glycol dimethylether-lithium bis(oxalate)borate (TEGDME-LiBOB) electrolyte for advanced lithium ion batteries 总被引:1,自引:0,他引:1
Dong-Ju LeeJusef Hassoun Stefania PaneroYang-Kook Sun Bruno Scrosati 《Electrochemistry communications》2012,14(1):43-46
Tetraethylene glycol dimethylether-lithium bis(oxalate)borate (TEGDME-LiBOB) electrolyte is here studied. Electrochemical impedance spectroscopy (EIS) measurements demonstrate that the electrolyte has conductivity higher than 10− 3 S cm− 1 at room temperature and about 10− 2 S cm− 1 at 60 °C, while thermogravimetry indicates a stability extending up to 180 °C. Sweep voltammetry of the electrolyte shows anodic stability extending over 4.6 V vs. Li and cathodic peak at about 1.5 V vs. Li/Li+, caused by a decomposition of LiBOB salt, and following prevented by using a pre-treated Sn-C anode. Furthermore, LiFePO4 electrode is successfully used as cathode in a lithium cell using the TEGDME-LiBOB electrolyte. The promising electrochemical results, the low cost and the very high safety level candidate the electrolyte here reported as a valid alternative to the conventional electrolyte based on fluorinated salts presently used in the lithium ion battery field. 相似文献
16.
Qi Zhang Zewen Liu Xiaosheng Song Tengfei Bian Dr. Zhijie Guo Donghai Wu Jun Wei Sixin Wu Prof. Dr. Yong Zhao 《Angewandte Chemie (International ed. in English)》2023,62(30):e202302559
Polymer based quasi-solid-state electrolyte (QSE) has attracted great attention due to its assurance for high safety of rechargeable batteries including lithium metal batteries (LMB). However, it faces the issue of low ionic conductivity of electrolyte and solid-electrolyte-interface (SEI) layer between QSE and lithium anode. Herein, we firstly demonstrate that the ordered and fast transport of lithium ion (Li+) can be realized in QSE. Due to the higher coordination strength of Li+ on tertiary amine (−NR3) group of polymer network than that on carbonyl (−C=O) group of ester solvent, Li+ can diffuse orderly and quickly on −NR3 of polymer, significantly increasing the ionic conductivity of QSE to 3.69 mS cm−1. Moreover, −NR3 of polymer can induce in situ and uniform generation of Li3N and LiNxOy in SEI. As a result, the Li||NCM811 batteries (50 μm Li foil) with this QSE show an excellent stability of 220 cycles at ≈1.5 mA cm−2, 5 times to those with conventional QSE. LMBs with LiFePO4 can stably run for ≈8300 h. This work demonstrates an attractive concept for improving ionic conductivity of QSE, and also provides an important step for developing advanced LMB with high cycle stability and safety. 相似文献
17.
Junkai Shi Chao Xu Jiawei Lai Zhongliang Li Yuping Zhang Yan Liu Kui Ding Yue-Peng Cai Rui Shang Qifeng Zheng 《Angewandte Chemie (International ed. in English)》2023,62(13):e202218151
Lithium metal batteries hold great promise for promoting energy density and operating at low temperatures, yet they still suffer from insufficient Li compatibility and slow kinetic, especially at ultra-low temperatures. Herein, we rationally design and synthesize a new amphiphilic solvent, 1,1,2,2-tetrafluoro-3-methoxypropane, for use in battery electrolytes. The lithiophilic segment is readily to solvate Li+ to induce self-assembly of the electrolyte solution to form a peculiar core-shell-solvation structure. Such unique solvation structure not only largely improves the ionic conductivity to allow fast Li+ transport and lower the desolvation energy to enable facile desolvation, but also leads to the formation of a highly robust and conductive inorganic SEI. The resulting electrolyte demonstrates high Li efficiency and superior cycling stability from room temperature to −40 °C at high current densities. Meanwhile, anode-free high-voltage cell retains 87 % capacity after 100 cycles. 相似文献
18.
Yeguo Zou Dr. Zheng Ma Gang Liu Dr. Qian Li Dongming Yin Xuejian Shi Dr. Zhen Cao Zhengnan Tian Hun Kim Dr. Yingjun Guo Dr. Chunsheng Sun Prof. Luigi Cavallo Prof. Limin Wang Prof. Husam N. Alshareef Prof. Yang-Kook Sun Prof. Jun Ming 《Angewandte Chemie (International ed. in English)》2023,62(8):e202216189
Electrolyte design has become ever more important to enhance the performance of lithium-ion batteries (LIBs). However, the flammability issue and high reactivity of the conventional electrolytes remain a major problem, especially when the LIBs are operated at high voltage and extreme temperatures. Herein, we design a novel non-flammable fluorinated ester electrolyte that enables high cycling stability in wide-temperature variations (e.g., −50 °C–60 °C) and superior power capability (fast charge rates up to 5.0 C) for the graphite||LiNi0.8Co0.1Mn0.1O2 (NCM811) battery at high voltage (i.e., >4.3 V vs. Li/Li+). Moreover, this work sheds new light on the dynamic evolution and interaction among the Li+, solvent, and anion at the molecular level. By elucidating the fundamental relationship between the Li+ solvation structure and electrochemical performance, we can facilitate the development of high-safety and high-energy-density batteries operating in harsh conditions. 相似文献
19.
Nika Mahne Sara E. Renfrew Prof. Bryan D. McCloskey Dr. Stefan A. Freunberger 《Angewandte Chemie (International ed. in English)》2018,57(19):5529-5533
Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O2 batteries, and are believed to form and decompose reversibly in metal‐O2/CO2 cells. In these cathodes, Li2CO3 decomposes to CO2 when exposed to potentials above 3.8 V vs. Li/Li+. However, O2 evolution, as would be expected according to the decomposition reaction 2 Li2CO3→4 Li++4 e?+2 CO2+O2, is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen (1O2) forms upon oxidizing Li2CO3 in an aprotic electrolyte and therefore does not evolve as O2. These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding 1O2 in metal‐O2 batteries, question the possibility of a reversible metal‐O2/CO2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li2CO3. 相似文献
20.
Electrochemical SPM investigation of the solid electrolyte interphase film formed on HOPG electrodes
《Electrochemistry communications》2000,2(6):436-440
Solid electrolyte interphase (SEI) film formation on graphite electrodes was studied on highly oriented pyrolytic graphite (HOPG) in nonaqueous electrolyte by in situ electrochemical atomic force microscopy (AFM). For potentials negative to 0.7 V versus Li|Li+ a SEI film is formed on the HOPG electrode surface. After the first cycle the film is rough and covers the surface of the HOPG electrode only partially. After the second cycle the HOPG surface is fully covered by a compact film. The thickness of the SEI film was measured by increasing the pressure of the AFM tip and thus scraping a part of the electrode surface. In this way a thickness of about 25 nm was found for the SEI film formed after two scan cycles between 3 and 0.01 V versus Li|Li+. 相似文献