Science China-Chemistry
·
2020
·Vol. 63
·期 9
·1306-1314
·
IF 6.356
Xie Huanyu,Hao Qing,Jin Hongchang,Xie Shuai,Sun Zhaowei,Ye Yadong,Zhang Chaohui,Wang Dong,Ji Hengxing,Wan Li-Jun
Because of its high theoretical specific capacity and low reduction potential, Li metal is considered to be key to reaching high energy density in rechargeable batteries. In this context, most of the research has focused on suppressing dendrite formation during Li deposition to improve the cycling reversibility and safety of the batteries. Here, covalent organic framework (COF) film coating on a commercial polypropylene separator is applied as an ion redistributor to eliminate Li dendrites. The COF crystallites consist of ordered nanochannels that hinder the movement of anions while allowing Li-ions to transport across, leading to a high Li-ion transference number of 0.77±0.01. The transport of Li-ions across the COF film can be considered to be analogous to beads passing through a Galton Board, a model that demonstrates a statistical concept of a normal distribution. Thus, an even distribution of Li-ions is obtained at the COF Li metal interface. The controlled Li-ion flux yields a smooth Li metal surface after 1,000 h (500 times) of cycling, leading to a significantly improved cycling stability and reversibility, as demonstrated by Cu||Li half cells, Li||Li symmetric cells, and LiFePO 4 ||Li full cells. These results suggest that, following the principle of a Galton Board, nanopore insulators such as COF-based materials are effective ion distributors for the different energy storage or conversion systems.
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DOI
高影响因子
IONICS
·
2021
·Vol. 27
·期 9
·3895-3902
·
IF 2.817
Long Canghai,Li Libo,Shan Yuhang,Zhai Mo,Chen Xiaochuan,Zhao Yangmingyue,Cui Wenjun,Zhou Da,Du Jintian
Lithium-sulfur (Li–S) battery has a very remarkably specific capacity of 1675 mAh g −1 . To avoid the shuttle effect and build the safety and stability of the Li–S battery system, we demonstrated a new conductive carbon as the host material with 0.35-nm micropores and mesopores prepared by a one-step process for a quasi-solid electrolyte. PVDF acted as a precursor and PMMA acted as an additive in this one-step preparation process. In addition, the mesopores enhanced the contact area and the content of sulfur, while the 0.35-nm micropores provided a trap site for the polysulfide by an effective physical absorption when the sulfur embedded in the host material. Finally, the PVDF-based quasi-solid polymer electrolyte avoided the inflammable and explosive risk and achieved an initial specific capacity of 1038 mAh g −1 at 0.1 C, and maintained at 441 mAh g −1 even after 500 cycles (a decay of 0.12% per cycle).
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Long Pan,Shuo Sun,Genxi Yu,Xiong Xiong Liu,Shengfa Feng,Wei Zhang,Muhammadali Turgunov,Yaping Wang,ZhengMing Sun
Solid electrolytes are fundamental for next-generation solid-state Li-metal batteries that promise high energy density and safety. However, various solid electrolytes suffer from chemical/electrochemical instability against Li metal and poor interfacial contact with electrodes. Herein, a polymer-in-salt (PiS) artificial protection layer composed of fluoropolymer in highly-concentrated lithium salt (labeled as PiSPL) is introduced to address these problems using NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) as a typical solid electrolyte . The resulted PiSPL layer exhibits small thickness (10 μm), good chemical/electrochemical stability, and excellent ionic conductivity (0.5 and 1.8 mS cm −1 at 25 and 60 °C, respectively). These properties endow the LATP/Li interface with improved contact, favorable Li + diffusion, and, most importantly, inhibited interfacial reactions, which is examined using ex-situ X-ray photoelectron spectroscopy and electrochemical analyses and morphological observations. Consequently, Li||LATP@PiSPL||Li symmetric cells can deliver small overpotentials at various current densities and long lifetime at 0.16 mA cm −2 over 400 h. On the contrary, the same configuration cells with LATP die after only 50 h. Moreover, the LiFePO 4 ||LATP@PiSPL||Li solid-state full cells exhibit excellent rate capability (124.0 mA h g −1 at 2.0C) and cyclability (148.9 and 140.6 mA h g −1 after 200 cycles at 0.2C and 300 cycles at 1.0C, respectively). The PiS strategy represents a general and effective approach to stabilize various solid electrolyte/Li interfaces to push solid-state Li-metal batteries forward.
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高影响因子
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2021
·Vol. 168
·期 10
·102505
·
IF 4.316
Chenteng Sun,Qian Xu,Yongxiang Yang,Xingli Zou,Hongwei Cheng,Xionggang Lu
The electrochemical behaviors of Li+ and Nd3+ were investigated on W, liquid Sn pool and Sn film electrodes in LiCl-KCl-NdCl3 melt at 673 K. Various electrochemical techniques, such as cyclic voltammogram, square wave voltammogram, and open circuit chronopotentiometry, were conducted to evaluate the electrochemical behaviors of Li+ and Nd3+. The reduction of Nd3+ was found to be a two-step process in the W electrode and a one-step process in the liquid Sn electrode. During the formation of the Nd-Sn intermetallic compounds, only the NdSn3 would be formed without the reduction of the Li+ in the liquid Sn electrode. When the reduction potential moves over −2.77 V vs Cl2/Cl−, the Li+ in the electrolyte would inevitable be reduced into the liquid Sn electrode. The Nd-Sn intermetallic compounds were deposited on the liquid Sn pool electrode at −2.74 V vs Cl2/Cl− in the LiCl-KCl-NdCl3 melts for 5 h. The products were characterized by SEM-EDS and XRD. The loose product on the surface of the deposition displayed the existence of NdSn3 in Nd-Sn intermetallic compounds. The high content of Nd inclusion formed by segregation was detected in the solidified Sn electrode.
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高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Zhikai Huang,Zhihao Yan,Dingding Zhu,Xuedong Zhang,Shuaiyu He,Jianyu Huang,Guobao Xu
Despite lithium-argyrodite electrolytes have attracted great attention due to the high ionic conductivity and relatively lower cost, their applications are hindered by the inferior air stability and poor Li compatibility. Herein, we report a Sn/I co-doping the Li 6 PS 5 Cl strategy to overcome above obstacles. The optimized LPSC-0.05SnI 4 exhibits high ionic conductivity of 3.9 × 10 −3 S cm −1 at room temperature, and improved air stability. More importantly, an in situ formed LiI-rich interface on the lithium anode is introduced through the LPSC-0.05SnI 4 . As a result, the Li/LPSC-0.05SnI 4 /Li symmetric batteries deliver high critical current density of 1.45 mA cm −2 and a remarkable steady Li plating/stripping performance over 6000 h at 0.1 mA cm −2 . The assembled LNO@NMC811/LPSC-0.05SnI 4 /Li all-solid-state batteries display prominent capacity and cycling stability. This work provides a practical and effective method for designing versatile and high-performance sulfide-based solid electrolytes .
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高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Yuan Gao,Jing Gao,Zhibin Zhang,Yue Wu,Xiaolin Sun,Fuhua Zhao,Yuan Zhang,Depeng Song,Wenyan Si,Qing Zhao,Xun Yuan,Jianfei Wu
Sulfide solid-state electrolytes have garnered considerable attention owing to their notable ionic conductivity and mechanical properties. However, achieving an electrolyte characterized by both high ionic conductivity and a stable interface between the electrode and electrolyte remains challenging, impeding its widespread application. In this work, we present a novel sulfide solid-state electrolyte, Li3.04P0.96Zn0.04S3.92F0.08, prepared through a solid-phase reaction, and explore its usage in all-solid-state lithium sulfur batteries (ASSLSBs). The findings reveal that the Zn, F co-doped solid-state electrolyte exhibits an ionic conductivity of 1.23 × 10–3 S cm–1 and a low activation energy (Ea) of 9.8 kJ mol–1 at room temperature, illustrating the aliovalent co-doping’s facilitation of Li-ion migration. Furthermore, benefiting from the formation of a LiF-rich interfacial layer between the electrolyte and the Li metal anode, the Li/Li3.04P0.96Zn0.04S3.92F0.08/Li symmetrical cell exhibits critical current densities (CCDs) of up to 1 mA cm–2 and maintains excellent cycling stability. Finally, the assembled ASSLSBs exhibit an initial discharge capacity of 1295.7 mAh g–1 at a rate of 0.05 C and at room temperature. The cell maintains a capacity retention of 70.5% for more than 600 cycles at a high rate of 2 C, representing a substantial improvement compared to the cell with Li3PS4. This work provides a new idea for the design of solid-state electrolytes and ASSLSBs.
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高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Chengzhou Tao,Tianle Zheng,Pengfei Jia,Wuze Gong,Guma Yila,Lina Wang,Tianxi Liu
Hindered by the high diffusion energy barrier of Li+ in graphite anode layers, the low-temperature application of traditional Li-ion batteries is limited. Lithium metal without intercalation and with excellent specific capacity is expected to support battery operation at low temperatures. However, due to the low conductivity, high freezing point, and strong solvation energy of traditional carbonate electrolytes, the application of lithium–metal batteries at low temperatures remains challenged. In this paper, an all-ester-based ternary solvent electrolyte based on fluorinated carbonate and methyl acetate is developed to improve the cyclic efficiency of the Li-metal anode at subzero temperatures. Methyl acetate, with low viscosity and low freezing point, endows Li+ with efficient transfer in the bulk phase at low temperatures. Fluorinated cosolvent regulates the solvation structure, thereby facilitating Li+ desolvation while forming a LiF-rich solid electrolyte interphase. The electrolyte exhibits good compatibility with the Li-metal anode, as confirmed by the significantly reduced kinetic barrier of Li+ diffusion at the interface. The theoretical calculations suggest that anions occupy the dominant positions within the inner solvation sheath. The in situ/ex situ characterizations provide straightforward evidence of a dendrite-free Li-metal electrode during cycling. As a result, the symmetric Li||Li cell is able to cycle stably for thousands of hours at current densities of 0.5 mA cm–2 and 1 mAh cm–2. When paired with a LiFePO4 cathode, the battery at 0.2 C (1 C = 170 mA g–1) has a capacity retention of 95.4% after 200 cycles at −15 °C and 92.6% after 100 cycles at −20 °C, respectively.
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高影响因子
DALTON TRANSACTIONS
·
2012
·Vol. 41
·期 29
·8822-8828
·
IF 3.838
Dezhi Chen,Wei Wei,Ruining Wang,Xiu-feng Lang,Yu Tian,Lin Guo
Olivine-structured LiMnPO4 with 3D foldaway-lantern-like hierarchical structures have been prepared via a one-step, template-free, solvothermal approach in ethylene glycol. The foldaway-lantern-like LiMnPO4 microstructures are composed of numerous nanoplates with thickness of about 20 nm. A series of electron microscopy characterization results indicate that the obtained primary LiMnPO4 nanoplates are single crystalline in nature, growing along the [010] direction in the (100) plane. Time-dependent morphology evolution suggests that ethylene glycol plays dual roles in oriented growth and self-assembly of such unique structures. After carbon coating, the as-prepared LiMnPO4 cathode demonstrated a flat potential at 4.1 V versus Li/Li+ with a specific capacity close to 130 mA h g−1 at 0.1 C, along with excellent cycling stability.
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高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Chia-Tse Lee,Haoyuan Zheng,Chen Jin,Hang Che,Li Wang,Yuyuan Zhao,Shixuan He,Xinhua Wang,Yifeng Yu,Mi Yan
Metal nitrogen hydride (Li-Mg-N-H) is regarded as an ideal hydrogen storage material for automotive applications due to its advantages of high hydrogen storage capacity (5.6 wt%), low operating temperature, and good cycling performance, but the comprehensive hydrogen storage performance of this material still could be improved. For this reason, this paper constructed a Li-Na-Mg-N-H composite system by synthesizing NaMgH 3 to replace MgH 2 in the Li-Mg-N-H system. The improvement of the hydrogen absorption and desorption properties of the composite system after the replacement of MgH 2 by NaMgH 3 was investigated. Various properties and test results showed that the composite system after the replacement of MgH 2 by NaMgH 3 showed better hydrogen absorption and desorption properties. The initial/peak hydrogen release temperatures of Li-Na-Mg-N-H decreased from 135 ˚C/245 ˚C to 105 ˚C/145 ˚C, and the apparent activation energy of hydrogen release was reduced from 114.90 to 104.05 kJ/mol which means the kinetics of hydrogen absorption and desorption was greatly improved. The mechanism study shows that NaMgH 3 will react with LiNH 2 and forms the intermediate product Li 3 Na(NH 2 ) 4 during the hydrogen release process, which changes the hydrogen desorption pathway of the composite system and thus the hydrogen absorption and desorption kinetics were improved.
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高影响因子
ELECTROCHIMICA ACTA
·
2017
·
IF 4.798
Chunhai Jiang,Jingxia Wang,Zhonghui Chen,Zhiyang Yu,Zhenyu Lin,Zhimin Zou
Hierarchical nitrogen-doped carbon spheres (NCSs) prepared by annealing the MnO 2 -templated spherical polypyrrole (PPy) at 450 or 600 °C were tested as anode materials of Li-ion batteries. The NCSs annealed at 450 °C exhibited higher nitrogen content, more amorphous carbon structure, and lower surface area as compared to the sample annealed at 600 °C. The specific capacities and rate performances of both NCSs samples were much higher than that of commercial mesocarbon microbeads (MCMBs). The NCSs annealed at 600 °C exhibited higher capacity at low current density (<0.5 A g −1 ) but more rapid capacity decay at elevated current rates referring to the sample annealed at 450 °C. The NCSs annealed at higher temperature also possessed inferior cycling stability, possibly due to its lower electronic conductivity and higher degree of graphitization. A high specific capacity of 250.8 mAh g −1 was achieved on the NCSs annealed at 450 °C at 3 A g −1 , demonstrating their high potentiality as anode of high power Li-ion batteries.
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高影响因子
APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Pengzu Kou,Zhigui Zhang,Zhaoyang Dong,Runguo Zheng,Zhishuang Song,Zhiyuan Wang,Hongyu Sun,Yanguo Liu
Lithium-rich manganese-based cathode (LRM) is considered to be the most promising cathode materials for next-generation lithium-ion batteries due to its high energy density. However, the low initial coulombic efficiency and poor rate performance are severe problems in the commercialization of LRM. Herein, we use an ascorbic acid (VC) modulation strategy to create spinel-carbon composite coatings and dual defects (oxygen vacancies, stack faults) on the surface of LRM. The composite surface coating and defects play a synergistic role in inhibiting interfacial side reactions, enhancing structural stability, and improving electrical conductivity as well as lithium-ion diffusion kinetics. As a result, the modified LRMs exhibit a specific capacity of 251.7mAh/g with an improved initial coulombic efficiency (ICE) of 82.3 % (pristine 72.9 %), enhanced rate capability (135 mAh/g at 5C), and long-term cyclability of 90 % retention after 200 cycles compared with the pristine (78 % retention after 200 cycles). The performance improvement of the modified LRMs is attributable to the composite coating and the dual defects, which ensure the LRM with a more stable structure (smaller volume change of 2.4 % compared with the original sample of 3.65 %). This strategy provides an efficient and environmentally friendly idea of surface modification for boosting the electrochemical performance.
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高影响因子
Materials Today Communications
·
2025
·
IF 4.5
Wujie Ge,Yuanxiang Fu,Chaonan Wang,Lirong Yan,Qi Feng,Bing Yan,Xiang Li
The high-nickel cathode material LiNi 0.865 Co 0.095 Al 0.04 O 2 (NCA) has garnered significant attention due to its high energy density and cost-effectiveness in production. However, this material is also prone to rapid capacity degradation, primarily due to phase transitions occurring during the redox process. In this paper, the co-modification with Na and B cations is employed to stabilize the lattice structure and enhance the electrochemical performance of the NCA material. It can be found that the incorporation of Na and B cations in the lattice can reduce cation mixing, expand the Li-layer spacing and improve crystal stability, thereby increasing the specific capacity and cyclic stability of the NCA material. Specifically, the co-doped NCA-2 sample exhibits a specific capacity of 202.1 mAh/g at 0.1 C and maintains a capacity retention of 78.75 % at 1 C after 300 cycles, representing a substantial improvement over the pristine material (187.2 mAh/g and 61.68 % capacity retention). Moreover, at a current density of 10 C, the co-doped NCA-2 sample demonstrates a high specific capacity of 133.9 mAh/g, compared to 110.1 mAh/g for the pristine material. The Na/B co-doping strategy presented in this study offers a straightforward method to improve the cyclability and rate behavior of cathode materials, highlighting its potential for commercial applications.
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