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Green Energy & Environment · 2024 · IF 10.7

Constructing lithiophilic sites–rich artificial solid electrolyte interphase to enable dendrite−free and corrosion−free lithium–sulfur batteries

Wei Lu,Anshun Zhao,Qiuxu Chen,Sihan Liu,Mingxi Yu,Zihao Wang,Ze Gao,Xue Zhao,Guiru Sun,Ming Feng

An artificial solid electrolyte interphase (SEI) with lithiophilic sites and chemical bonds anchoring lithium polysulfides (LiPSs) has been developed as a potential solution to protect the lithium (Li) metal anode of Lithium−sulfur (Li–S) batteries. This strategy aims to guide consistent Li deposition and relieve lithium corrosion. Herein, the evolution process of lithiophilic sites based on aluminum fluoride (AlF 3 ) in an artificial SEI is disclosed in Li–S batteries with metal−based lithiophilic sites. The polyester polymer (PMMA and PPC)/AlF 3 artificial SEI (MPAF−SEI) was homogeneously anchored on Li anode by in−situ polymerization. The conversion of AlF 3 into Li–Al and LiF lithiophilic sites effectively reduce the Li nucleation overpotential and prevents the formation of Li dendrites. At the same time, the polymer can anchor LiPSs by chemical bonds and prevents Li corrosion. The optimized MPAF−SEI protected Li demonstrates excellent stability for over 3000 h at a capacity of 1 mAh cm −2 in Li || Li symmetric cells. The Li–S battery with low N/P (4) exhibits a capacity of 532.6 mAh g −1 over 300 cycles lifespan at 0.5 C.

研究领域: 材料科学 · 电化学
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MOLECULES · 2022 ·Vol. 27 ·期 22 ·7827 · IF 4.927

Building Polymeric Framework Layer for Stable Solid Electrolyte Interphase on Natural Graphite Anode

Yunhao Zhao,Yueyue Wang,Rui Liang,Guobin Zhu,Weixing Xiong,Honghe Zheng

The overall electrochemical performance of natural graphite is intimately associated with the solid electrolyte interphase (SEI) layer developed on its surface. To suppress the interfacial electrolyte decomposition reactions and the high irreversible capacity loss relating to the SEI formation on a natural graphite (NG) surface, we propose a new design of the artificial SEI by the functional molecular cross-linking framework layer, which was synthesized by grafting acrylic acid (AA) and N,N′−methylenebisacrylamide (MBAA) via an in situ polymerization reaction. The functional polymeric framework constructs a robust covalent bonding onto the NG surface with —COOH and facilitates Li+conduction owing to the effect of the —CONH group, contributing to forming an SEI layer of excellent stability, flexibility, and compactness. From all the benefits, the initial coulombic efficiency, rate performance, and cycling performance of the graphite anode are remarkably improved. In addition, the full cell using the LiNi0.5Co0.2Mn0.3O2cathode against the modified NG anode exhibits much-prolonged cycle life with a capacity retention of 82.75% after 500 cycles, significantly higher than the cell using the pristine NG anode. The mechanisms relating to the artificial SEI growth on the graphite surface were analyzed. This strategy provides an efficient and feasible approach to the surface optimization for the NG anode in LIBs.Keywords:natural graphite;artificial SEI;in situ polymerization;lithium-ion batteries

CAS / MDL: 79-10-7
研究领域: 材料科学 · 电化学
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Energy & Environmental Science · 2020 ·Vol. 14 ·期 1 ·382-395 · IF 30.289

Lithium-activated SnS–graphene alternating nanolayers enable dendrite-free cycling of thin sodium metal anodes in carbonate electrolyte

Wei Liu,Zidong Chen,Zheng Zhang,Pingxian Jiang,Yungui Chen,Eunsu Paek,Yixian Wang,David Mitlin

Sodium metal battery (SMB, NMB) anodes can become dendritic due to an electrochemically unstable native Na-based solid electrolyte interphase (SEI). Herein Li-ion activated tin sulfide graphene nanocomposite membrane (A-SnS–G) is employed as an artificial SEI layer, allowing cyclability of record-thin 100 μm Na metal foils. The thin Na metal is prepared by a self-designed metallurgical rolling protocol. A-SnS–G is initially placed onto the polypropylene (PP) separator but becomes in situ transferred onto the Na metal surface. Symmetric metal cells protected by A-SnS–G achieve low-overpotential extended high-rate cycling in a standard carbonate electrolyte (EC : DEC = 1 : 1, 5% FEC). Accumulated capacity of 1000 mA h cm−2 is obtained after 500 cycles at 4 mA cm−2, with accumulated capacity-to-foil capacity (A/F) ratio of 90.9. This is among the most favorable cycle life, accumulated capacity, and anode utilization combinations reported. Protection by non-activated SnS–G membrane yields significantly worse cycling, albeit still superior to the baseline unprotected sodium. Post-mortem and dedicated light optical analysis indicate that metal swelling, dendrite growth and dead metal formation is extensive for the unprotected sample, but is suppressed with A-SnS–G. Per XPS, post-100 cycles near-surface structure of A-SnS–G is rich in metallic Sn alloys and inorganic carbonate salts. Even after 300 cycles, Li-based SEI components ROCO2-Li, Li2CO3 and LiF are detected with A-SnS–G. As a proof of principle, an SMB with a high mass loading (6 mg cm−2) NVP cathode and a A-SnS–G protected anode delivered extended cyclability, achieving 74 mA h g−1 after 400 cycles at 0.4C.

CAS / MDL: 7782-42-5
研究领域: 材料科学 · 电化学
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Small · 2023 ·Vol. 20 ·期 2 ·2305639 · IF 13.3

Interphase Engineering Enhanced Electro-chemical Stability of Prelithiated Anode

Shiwei Xu,Qiu Fang,Jipeng Wu,Suting Weng,Xiaoyun Li,Qiuyan Liu,Qiyu Wang,Xiqian Yu,Liquan Chen,Yejing Li,Zhaoxiang Wang,Xuefeng Wang

Prelithiation is an essential technology to compensate for the initial lithium loss of lithium-ion batteries due to the formation of solid electrolyte interphase (SEI) and irreversible structure change. However, the prelithiated materials/electrodes become more reactive with air and electrolyte resulting in unwanted side reactions and contaminations, which makes it difficult for the practical application of prelithiation technology. To address this problem, herein, interphase engineering through a simple solution treatment after chemical prelithiation is proposed to protect the prelithiated electrode. The used solutions are carefully selected, and the composition and nanostructure of the as-formed artificial SEIs are revealed by cryogenic electron microscopy and X-ray photoelectron spectroscopy. The electrochemical evaluation demonstrates the unique merits of this artificial SEI, especially for the fluorinated interphase, which not only enhances the interfacial ion transport but also increases the tolerance of the prelithiated electrode to the air. The treated graphite electrode shows an initial Coulombic efficiency of 129.4%, a high capacity of 170 mAh g −1 at 3 C, and negligible capacity decay after 200 cycles at 1 C. These findings not only provide a facile, universal, and controllable method to construct an artificial SEI but also enlighten the upgrade of battery fabrication and the alternative use of advanced electrolytes.

研究领域: 材料科学 · 电化学 · 电池技术
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

MOF-derived defect-rich CeO2 as ion-selective smart artificial SEI for dendrite-free Zn-ion battery

Pengxian Li,Junfeng Ren,Caixia Li,Jiaxu Li,Kai Zhang,Tingting Wu,Bin Li,Lei Wang

Interface engineering is considered as an effective way to inhibit dendrite growth and side reactions in rechargeable zinc ion batteries (ZIBs). Herein, to explore the best treatment routes on how to construct multi-functional protective layers with MOF-based nanomaterials, defect-rich CeO 2 polycrystals are designed with Ce-MOF-808 precursor as ion-selective smart artificial SEI for ZIBs. Interestingly, crystal defects which can provide active sites for Zn 2+ transfer, are introduced to MOF-CeO 2 via pyrolysis. Furthermore, the negative Zeta potential gives high selectivity to cations and shielding effect to anions, inhibiting the side reactions. Besides, MOF-CeO 2 can promote the desolvation process of Zn[(H 2 O) 6 ] 2+ and balance Zn-ion flux by pores. Impressively, synergistic effects on dendrite inhibition by chemical stability, crystal defects, surface charge properties, and hierarchically porous structure are investigated comprehensively. Therefore, MOF-CeO 2 @Zn anode exhibited ultra-stable plating/stripping behavior (more than 3200 h) and high Coulomb efficiency (99.5 % at 2 mA cm −2 ). This multi-functional protective layer also significantly improves the overall performance of Zn||MnVO full battery, with high-capacity retention at 5 A/g after 10,000 cycles.

CAS / MDL: 1306-38-3
研究领域: 材料科学 · 电化学 · 纳米技术
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Journal of Energy Storage · 2024 · IF 8.9

Cs-based artificial SEI enable high voltage Li metal battery with soft-matter electrolyte

Qingyang Mei,Yutong Zhai,Feilong Dong,Yanju Gou,Haiming Xie,Yulong Liu

Soft-matter electrolytes have garnered significant attention due to their improved safety features, rendering them viable options for the creation of Li metal batteries with high energy densities. However, establishing effective interfacial contact between the electrodes and soft-matter electrolyte remains a significant challenge, necessitating modifications at the interface. In this study, we design an artificial composite electrolyte interphase (PEG-Cs SEI) on the surface of the Li metal anode to improve ion transport between the soft-matter electrolyte and Li metal. The PEG-Cs SEI layer exhibits high flexibility and mechanical strength, effectively mitigating the lithium dendrite growth and volume expansion. As a result, Li||Li cells assembled with PEG-Cs SEI-modified lithium metal anodes exhibit stable performance for more than 1700 h, maintaining small overpotential even at high current densities and capacities (2.45 mAh cm −2 ). With a LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode, the battery shows a capacity up to 182 mAh g −1 at first discharge with cut-off voltage of 4.5 V. Furthermore, in a pouch cell configuration, the battery achieves 100 % capacity retention over 90 cycles and successfully passes safety tests, without fire or smoke. Combining the modified lithium metal anode with soft-matter electrolytes paves a promising way for the effective implementation of high-energy-density Li metal cells.

研究领域: 材料科学 · 电化学
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Journal of Materials Chemistry A · 2022 ·Vol. 11 ·期 6 ·2754-2768 · IF 14.511

Modified lithium metal anode via anion-planting protection mechanisms for dendrite-free long-life lithium metal batteries

Fulu Chu,Jie Lei,Rongyu Deng,You Zhou,Feixiang Wu

Lithium metal anodes (LMAs) are being researched to enhance their potential as ideal candidates for high-energy-density rechargeable batteries. However, an unstable solid–electrolyte interphase (SEI) layer and dendrite formation severely hinder their practical operations due to poor coulombic efficiency (CE) and potential security risks. Herein, an artificial SEI layer with various inorganic species was constructed via a strategy involving pre-planting various salt anions on the LMA. The as-prepared layer with multifunctional properties could stabilize liquid–electrode interfaces and proactively regulate even distribution and facilitate the homogeneous diffusion of the ion flux. Moreover, the anion-release behavior of this layer would be an additional attribute that could compensate for the anion consumption during cycling. As a result, the performance of modified LMAs could be significantly improved via this artificial SEI. Li–Cu cells provided CEs of above 98% among a range of current densities with long lifespans, and the symmetric cells showed stable cycling for over 1800 h at 1 mA cm−2. In practice, an assembled LiFePO4/Li cell displayed excellent cyclability of over 1000 cycles with high CEs at 2C. This strategy via., anions-planting protection mechanisms sheds light on tuning robust artificial SEI layers and can offer a fresh perspective to guide the design of high-performance LMAs.

CAS / MDL: 90076-65-6 7790-69-4
研究领域: 材料科学 · 电化学
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ACS Nano · 2025 · IF 16

Regulating the Interfacial Solvation Environment by a Pyran-Based Polymer for High-Areal-Capacity and Low-Temperature-Endurable Magnesium Metal Batteries

Tengfei Wang,Keyi Chen,Guyue Li,Zhang Chen,Yanfeng Gao,Chilin Li

Regulating the artificial solid electrolyte interphase (SEI) and interfacial solvation structure of the electrolyte is crucial for developing rechargeable magnesium batteries (RMBs) with long cycling life, high current density tolerance, and fast ion transport capability operated under extreme environments, such as low temperatures. Herein, an effective strategy using oligomeric poly(3,4-dihydro-2H-pyran) (polyDHP) is proposed to modulate the interfacial solvation structure of RMBs, with the construction of an artificial SEI with rapid Mg-ion conductivity. The steric hindrance of polyDHP and its electrostatic interaction with Mg2+ reduce the solvent molecules in the first solvation shell, allowing polyDHP molecules to participate in coordination, thus lowering the desolvation energy barrier of Mg2+ and facilitating their deposition and stripping. Furthermore, due to the glass transition behavior, oligomeric polyDHP exhibits a more ordered structure with more continuous internal ion transport channels at −20 °C, therefore enabling stable RMB operation at lower temperatures for the first time. The corresponding Mg symmetric cells display a much lower overpotential (400 mV) and excellent cycling stability at both room temperature (over 5000 h at 5 mA cm–2 and 10 mA h cm–2) and a low temperature of −20 °C (over 1300 h at 3 mA cm–2 and 3 mA h cm–2). This strategy supports the stable cycling of CuS∥Mg full cells for over 200 cycles at −20 °C. This work reveals the importance of regulating the interfacial solvation structure, promoting the realistic applications of RMBs under extreme conditions.

CAS / MDL: 110-87-2
研究领域: 材料科学 · 电化学
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JOURNAL OF POWER SOURCES · 2024 · IF 8.1

Imidazole-2-carboxaldehyde additive participation in construction of artificial SEI enabling ultra-stable Zn anode

Zhongxu Chen,Guancheng Xu,Jiahui Jiang,Qihao Wu,Shuai Liu,Yuying Feng,Yixuan Li,Li Zhang,Xian Sun

Poor stability caused by side reactions such as corrosion, Zn dendrite and hydrogen evolution are crucial factors hindering commercial application in queous zinc ion energy storage systems. This article offers a strategy, zinc-rich artificial solid electrolyte interphase (ASEI) layer with polar groups by imidazole-2-carboxaldehyde (2-ICA) electrolyte additive, which helps form stable electrode/electrolyte interface and rapid Zn 2+ transfer interface with low resistance. Firstly, the chelation with Zn 2+ of 2-ICA and its zincophilic capability enable the rapid formation of the ASEI layer and result in more sites for initial nucleation, which then guides the uniform Zn 2+ deposition. Additionally, the introduced ASEI with polar groups accelerates the de-solvation kinetics of Zn 2+ and the Zn 2+ transfer ability in electrode/electrolyte interface, which enable high-rate charge and discharge. Therefore, the symmetric battery based on 2-ICA electrolyte exhibits excellent cycling stability at 20 mA cm −2 (cycling up to 800 h). At the same time, assembled Zn//Cu also has a high average Coulombic efficiency (99.2 %). The zinc-ion hybrid capacitors (ZICs) assembled based on this electrolyte also exhibit outstanding electrochemical properties. This work offers a simple and novel way to realize high performance and great safety zinc-based energy storage devices.

CAS / MDL: 7446-20-0
研究领域: 材料科学 · 电化学 · 能源存储
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ADVANCED FUNCTIONAL MATERIALS · 2023 ·Vol. 33 ·期 36 ·2303020 · IF 19

In Situ Artificial Hybrid SEI Layer Enabled High-Performance Prelithiated SiOx Anode for Lithium-Ion Batteries

Yi Sun,Kuanxin Zhang,Run Chai,Yueda Wang,Xianhong Rui,Kang Wang,Huaxia Deng,Hongfa Xiang

Considered the promising anode material for next-generation high-energy lithium-ion batteries, SiO x has been slow to commercialize due to its low initial Coulombic efficiency (ICE) and unstable solid electrolyte interface (SEI) layer, which leads to reduced full-cell energy density, short cycling lives, and poor rate performance. Herein, a novel strategy is proposed to in situ construct an artificial hybrid SEI layer consisting of LiF and Li 3 Sb on a prelithiated SiO x anode via spontaneous chemical reaction with SbF 3 . In addition to the increasing ICE (94.5%), the preformed artificial SEI layer with long-term cycle stability and enhanced Li + transport capability enables a remarkable improvement in capacity retention and rate capability for modified SiO x . Furthermore, the full cell using Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 and a pre-treated anode exhibits high ICE (86.0%) and capacity retention (86.6%) after 100 cycles at 0.5 C. This study provides a fresh insight into how to obtain stable interface on a prelithiated SiO x anode for high energy and long lifespan lithium-ion batteries.

研究领域: 电化学 · 材料科学 · 能源存储 · 锂离子电池 · 界面化学 · 纳米材料
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LANGMUIR · 2017 · IF 3.833

LiF as an Artificial SEI Layer to Enhance the High-Temperature Cycle Performance of Li4Ti5O12

Lan Zhang,Kaihang Zhang,Zhaohui Shi,Suojiang Zhang

Li4Ti5O12 (LTO) is a promising anode material for electric vehicles (EVs) and electrochemical energy storage applications because of its safety, good rate capability, and long cycle life. At elevated temperature, such as 60 °C, it always shows poor cycle performance because of the instability between the electrode material and electrolyte, which may also lead to a serious gassing issue. In this article, a facile hydrothermal method is adopted to coat the LTO powder with a thin LiF layer, in which the LiF acts as an artificial solid electrolyte interface (SEI) layer to prevent the direct contact of LTO and electrolyte, thus improving the high-temperature cycle performance. Electrochemical tests prove that the LiF coating layer has no influence on the kinetics at ambient temperature and greatly enhances the high-temperature cycle stability, and the LTO@LiF composite material keeps 87% of its initial discharge capacity in 300 1C cycles at 60 °C. Moreover, the LiF coating layer exhibits a special self-driven reforming process during the initial cycles, which makes it uniform and more effective at enhancing the stability between electrode/electrolyte interfaces.

CAS / MDL: 7789-24-4
研究领域: 材料科学 · 电化学
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Energy Storage Materials · 2022 · IF 20.831

Self-exfoliated covalent organic framework nano-mesh enabled regular charge distribution for highly stable lithium metal battery

Yunrui Zhang,Wenbo Wang,Meiling Hou,Yantao Zhang,Yaying Dou,Zehua Yang,Xiaoyang Xu,Haining Liu,Shanlin Qiao

Li metal batteries have won the fame for the enlarged cell potential and higher theoretical specific capacity. Nevertheless, the commercial implementation is still confronted with inevitable Li dendritic growth and depressed Coulombic efficiency. The Li + transfer behavior is the vital factor to ameliorate the durability of solid electrolyte interphase (SEI). Herein, a self-exfoliated TpTG covalent organic framework (COF) was developed to construct an artificial SEI film. The versatile cationic-skeleton of TpTG could spontaneously drive the formation of nano-mesh with thickness of 3∼6 nm, and facilitate uniform dispersibility on the Li metal surface. Moreover, the 7 Li solid-state nuclear magnetic resonance spectra, Fourier-transform infrared spectra, and density functional theory calculations have identified the energetic lithiophilicity and TFSI – repulsion features. The Cl – coordinated TpTG endowed with abundant lithiophilic sites can reconfigure the charge distribution and expedite the uniform Li + migration adjacent to the electrode|electrolyte interface. The uniform Li + flux distribution redounds to reversible lithium stripping/plating and tames the dendrite formation especially at high-rate protocols. The overwhelming evidences of lower polarization, prolonged lifespan, and compact Li deposition, corroborate the practicability of self-exfoliated TpTG to achieve the goal of high-energy-density Li metal batteries.

研究领域: 材料科学 · 电化学
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