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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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
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
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2021
·
IF 8.128
Zhiheng Ren,Jixiao Li,Yangyang Gong,Xianliang Li,Jianneng Liang,Yongliang Li,Chuanxin He,Qianling Zhang,Xiangzhong Ren
The practical application of Lithium-sulfur (Li-S) batteries is significantly inhibited by (i) the notable ‘shuttle effect’ of lithium polysulfides (LiPS), (ii) the corrosion of the lithium interface, and (iii) the sluggish redox reaction kinetics. The functional separator in the Li-S battery has the potential to provide the perfect solution to these problems. Herein a triple-layer multifunctional PVDF-based nanofiber separator, which contains GoTiN/PVDF layer on the top and bottom and ZnTPP/PVDF layer on the middle, is designed. The polarity and porous structure of this multifunctional separator can greatly improve the wettability of electrolytes and enhance the transportation of Li + . With the zinc-based porphyrin framework (ZnTPP) structure, this separator has a strong chemisorption and LiPS conversion ability, which greatly prevent the ‘shuttle effect’. Consequently, the designed multilayer separator showed excellent electrochemical performance. As a result, the cell with GoTiN@ZnTPP@GoTiN nanofiber membrane displayed an initial discharge capacity of 1180 mAh/g with a benign capacity retention of 65.9% at 0.5C and high coulombic efficiency of more than 98.5% after 100 cycles. Even at 2C, it can still release a capacity of 798 mAh/g. Moreover, the remarkable capacity of 591 mAh/g could be achieved with a high sulfur load of 5.76 mg/cm 2 under a current density of 0.1C. Based on these merits, this novel and scalable multifunctional separator is a promising candidate to replace the conventional PP separator for advanced Li-S batteries to deal with various challenges.
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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
ELECTROCHIMICA ACTA
·
2018
·
IF 5.116
Chunhai Jiang,Zhimin Zou
Sheet-like lithium-rich cathode materials Li 1.2 Mn 0.54 Ni 0.16 Co 0.10 O 2 (LMNCO) assembled by primary grains of 100–500 nm in sizes were facilely prepared by a glucose-urea bubbling and post-annealing process. The post-annealing temperature was found to play an important role on the grain size , crystallinity , cation ordering and electrochemical performance of the cathode materials. The sample post-annealed at 900 °C showed larger grains, higher crystallinity, better layered structure, higher lithium storage capacity and better rate performance than the one annealed at 800 °C. An initial discharge capacity of above 300 mA h g −1 was obtained at 0.1 C (20 mA g −1 ) for the sample annealed at 900 °C, and at 1, 2, 5 and 10 C, discharge papacies of 223, 192, 157 and 128 mA h g −1 were achieved respectively. The material synthesizing process proposed in this study may be extended to prepare a wide range of sheet-like functional oxides that may be potentially applied in energy storage or other fields.
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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
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
ELECTROCHIMICA ACTA
·
2019
·
IF 5.383
Xinrui Huang,Jingsong Liu,Mengshi Zeng,Xiaowei Yang,Xiaojiang Liu
In this article, the MgO imporous fibers, MgO porous fibers and hydrofluoric acid (HF) modified MgO porous fibers were researched as the electrolyte binders in Li–Si/LiCl–KCl/FeS 2 thermal batteries respectively. The results show that the wettability between the LiCl–KCl molten salt and the MgO fiber binders increases significantly in order of MgO porous fibers and HF modified MgO porous fibers. The separator pellet using the MgO porous fiber modified by 40 mol% (of the MgO fiber) HF solution as the electrolyte binder exhibits an extremely small amount of electrolyte leakages (19.6 mg cm −2 ) and the highest ionic conductivity (0.66 S cm −1 at 450 °C). Meanwhile, the corresponding thermal battery shows the largest discharge capacity (425 mA h g −1 at 1.0 V voltage plateau). Moreover, the effect of HF modification on the ion migration was analyzed based on the analysis of element diffusion and the formed MgF 2 phase. In summary, modification of MgO porous fiber binder by HF solution is a potential way to improve the performance of thermal batteries.
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高影响因子
JOURNAL OF POROUS MATERIALS
·
2022
·Vol. 29
·期 3
·629-640
·
IF 2.523
Li Dongdong,Hu Xuli,Zhao Hongyuan,Ding Kunjie,Li Fang,Han Shixing,Wang Hongliang,Bai Lianyang,Liu Runqiang
Carbonaceous nanomaterials have exhibited huge practical prospects as conductive sensitizers for the modification of electrodes. In this work, the nanocomposite of graphitized multi-walled carbon nanotubes@Super P Li carbon nanoparticles (GCNTs@SP-Li) was designed via a simple ultrasonication-assisted strategy, and then the GCNTs@SP-Li/GCE sensor based on the synthesized GCNTs@SP-Li nanocomposite decorating glassy carbon electrode (GCE) was successfully applied in the sensitive detection of isoproturon (ISO). For the GCNTs@SP-Li nanocomposite, GCNTs with porous structure presented excellent adsorption property, which contributed to the preconcentration of ISO and facilitated the electrolyte penetration. Additionally, GCNTs possessed good electrical conductivity owing its higher graphitization degree. More importantly, the interconnected dot-line-like structure of GCNTs@SP-Li nanocomposite acted as conductive “highways” to remarkably reduce the electron transport distance, which could significantly accelerate the process of redox reaction. Benefiting from the synergistic effect of GCNTs and SP-Li, the optimized GCNTs@SP-Li/GCE sensor showed a low detection limit of 0.1653 μM in the linear concentration of 0.7–30 μM. Additionally, the proposed sensor exhibited satisfactory recoveries from 97.2 to 101.6% towards the determination of ISO in river water and tap water. This work offers a feasible and cost-effective idea in developing the high-performance ISO electrochemical sensor.
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高影响因子
Nano Research
·
2024
·
IF 9.5
Chen Jieshuangyang,Lei Jie,Zhou Jinwei,Chen Xuanfeng,Deng Rongyu,Qian Mingzhi,Chen Ya,Wu Feixiang
The development of electrocatalysts with high catalytic activity is conducive to enhancing polysulfides adsorption and reducing activation energy of polysulfides conversion, which can effectively reduce polysulfide shuttling in Li-S batteries. Herein, a novel catalyst NiCo-MoO x /rGO (rGO = reduced graphene oxides) with ultra-nanometer scale and high dispersity is derived from the Anderson-type polyoxometalate precursors, which are electrostatically assembled on the multilayer rGO. The catalyst material possesses dual active sites, in which Ni-doped MoO x exhibits strong polysulfide anchoring ability, while Co-doped MoO x facilitates the polysulfides conversion reaction kinetics, thus breaking the Sabatier effect in the conventional electrocatalytic process. In addition, the prepared NiCo-MoO x /rGO modified PP separator (NiCo-MoO x /rGO@PP) can serve as a physical barrier to further inhibit the polysulfide shuttling effect and realize the rapid Li + migration. The results demonstrate that Li-S coin cell with NiCo-MoO x /rGO@PP separator shows excellent cycling performance with the discharge capacity of 680 mAh·g −1 after 600 cycles at 1 C and the capacity fading of 0.064% per cycle. The rate performance is also impressive with the remained capacity of 640 mAh·g −1 after 200 cycles even at 4 C. When the sulfur loading is 4.0 mg·cm −2 and electrolyte volume/sulfur mass ratio (E/S) ratio is 6.0 μL·mg −1 , a specific capacity of 830 mAh·g −1 is achieved after 200 cycles with a capacity decay of 0.049% per cycle. More importantly, the cell with NiCo-MoO x /rGO@PP separator exhibits cycling performance under wide operating temperature with the reversible capacities of 518, 715, and 915 mAh·g −1 after 100 cycles at −20, 0, and 60 °C, respectively. This study provides a new design approach of highly efficient catalysts for sulfur conversion reaction in Li-S batteries.
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高影响因子
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