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ChemElectroChem · 2019 ·Vol. 6 ·期 10 ·2707-2714 · IF 3.975

Synthesis and Application of a Conjugated Polydianion-Based Single-Ion Conducting Polymer for High-Performance Solid Lithium-Ion Batteries

Dan Li,Zhixiang Zeng,Di Lu,Feng Nie,Lele Wen,Lijing Zhu

Graphical Ask the conductor :A polyanionic perfluoroimide-based conducting Li salt (LiPFSDI) is synthesized and blended with polyethylene oxide (PEO) to fabricate the polymer electrolyte membrane. The PEO-LiPFSDI composite electrolyte exhibits high ionic conductivity, a wide electrochemical window (up to 6 V versus Li + /Li), high t Li + (0.89), and excellent cycling performance. Fluorosulfonimide lithium salts have been widely used as conductors in solid polymer electrolytes for solid Li-ion batteries (LIBs). However, low conductivity and poor compatibility with the polymer host (usually polyethylene oxide, PEO) remain challenges in the design of these salts. In this paper, we synthesized a highly Li + -conductive salt containing the poly(perfluoroalkylsulfonyl)diimide (PFSDI − ) dianion for the first time. LiPFSDI represents the first example of a single Li-ion-conducting polymer (SLICP) with a conjugated sulfonimide moiety (−SO 2 −N (−) −SO 2 −N (−) −SO 2 −). The PEO−LiPFSDI blend electrolyte exhibits significant enhancements in ionic conductivity (2.24×10 −4 S cm −1 at 80 °C)and electrochemical stability (up to 6 V vs. Li + /Li). A prototype LiFePO 4 /Li battery with the PEO−LiPFSDI composite electrolyte shows excellent cycling performance with a high reversible capacity of 148 mAh g −1 at a rate of 0.1 C and 135 mAh g −1 at 0.2 C (70 °C), and maintains 100 stable cycles for over 1500 hours.

研究领域: 材料科学 · 能源化学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Mxene-based lithium-ion sieve polymer membrane for sustainable lithium adsorption

Zhennan Chen,Jingjing Du,Jianbo Shi

Lithium, an emerging mineral of critical global significance, is recognized as a strategic resource by major economies worldwide, leading to an increased demand for this essential element. The extraction of lithium from rich sources, such as seawater and brine, has become commonplace. Among various liquid lithium extraction techniques, the lithium-ion sieve (LIS) adsorption method has attracted substantial attention owing to its simplicity, high recovery rate, and relatively low energy consumption. Despite significant advancements in LIS technology, the powdery nature of these materials poses challenges to handling and recycling, leading to inevitable adsorbent loss and limited practical applications. LISs are typically recycled through powder shaping, but the commonly employed shaping methods may result in a reduction in the adsorbent’s adsorption capacity. Therefore, it is urgent to develop a technology that can not only realize the recycling of LISs but also avoid the loss of the adsorbent’s adsorption capacity. We synthesized a titanium-based LIS (HTO) hybrid membrane by incorporating 2D MXene, known for its excellent properties across various applications. The incorporation of MXene into the membrane significantly increased the pore structure, enhancing adsorption site exposure and facilitating Li + migration. The HTO/MXene@PVC hybrid film demonstrated favorable adsorption properties, with an Li + adsorption capacity of 25.4 mg·g −1 within 24 h. Additionally, the film exhibited notable selectivity capacity and maintained its adsorption capacity above 90 % even after eight adsorption–desorption cycles, indicating excellent cycling performance. This study introduces a novel design concept for adsorbents, specifically for extracting Li + from liquid lithium sources, offering new insights for the development of Li + adsorbents aimed at enhancing lithium recovery.

研究领域: 材料科学 · 环境科学
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ACS Applied Engineering Materials · 2022 · IF 0

Electrochemical Solvometallurgy Pathway for the Sustainable Recovery of Bulk Metallic Lithium

Baoguo Zhang,Haoyu Zhang,Bing Ai,Kefeng Pan,Weimin Zhang,Degang Li,Lipeng Zhang,Zhongning Shi

Due to the wide range of potential applications of metallic Li and other active metals, the development of simple and cost-effective electrochemical methods for extracting these metals from their salts is greatly important. Accordingly, herein, an electrochemical solvometallurgy technology pathway is proposed to realize the recovery of metallic Li at room temperature. A low-cost aprotic polar molecular liquid, dimethylformamide (DMF), was selected for electrowinning of Li with abundant LiCl as the raw material. Subsequently, the electrolyte structure of the optimized binary DMF/LiCl system (0.7 M LiCl) was analyzed using 7Li nuclear magnetic resonance spectroscopy, Fourier-transform infrared spectroscopy, and theoretical calculations. Electrochemical reaction mechanisms were elucidated through cyclic voltammetry and ultraviolet–visible absorption spectrometry. Finally, the Li coating was successfully obtained using potentiostatic deposition on a high-purity In substrate in the form of nanoalloy sheets. To realize the transformation of electrodeposited materials from the “thin film” to the “bulk”, a continuous, direct smelting electrodeposited film short-process technique was proposed to achieve recovery of stable metallic Li in the form of a bulk Li–In intermediate alloy. This low-energy, low-carbon, and sustainable strategy can be applied for the low-temperature electrochemical recovery of reactive (Li, Mg, Al, and Ti) and rare-earth metals.

研究领域: 材料科学 · 冶金工程 · 电化学
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Battery Energy · 2025 · IF 9.9

In Situ Coating Li3PO4 on Li6.5La3Zr1.5Ta0.5O12 Achieving Lithium Dendrites Inhibition and High Chemical Stability

Jun Ma,Ruilin He,Yidong Jiang,Ludan Zhang,Hongli Xu,Hongbo Zeng,Chaoyang Wang,Xiaoxiong Xu,Yonghong Deng,Jun Wang,Shang-Sen Chi

Solid-state electrolyte (SSE) is a potential way to solve the safety problems of lithium metal batteries (LMBs), and Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZTO) is one of the most extensive research SSEs due to its good air stability and wide electrochemical window. However, the residual alkali on LLZTO surface limits its application with polyvinylidene difluoride (PVDF)-contained binders, and the uncontrollable lithium dendrites growing between the grain boundaries of LLZTO particles would lead to rapid capacity fading and potential short circuit risk. Herein, by in situ coating Li 3 PO 4 (LPO) on LLZTO particles (LLZTO@LPO) evenly, the residual alkali on the LLZTO surface is neutralized and the pH value is reduced to 8.84. The modified LLZTO can be mixed with PVDF solution and shows good fluidity without a cross-linking reaction, making the subsequent ceramic coating on the separator feasible. The LLZTO@LPO coating polyethylene (PE) separator can achieve 1400 h (115% increase) stable cycling under 1 mA cm −2 current density in the Li∥Li symmetrical cell and 80% capacity retention after 260 cycles (NCM622-Li coin cell with 3 mAh cm −2 loading). Furthermore, the LLZTO SSE pellets were prepared with the LLZTO@LPO and assembled in coin cell. The critical current density (CCD) result increases from 0.7 to 1.6 mA cm −2 owing to that the LPO coating effectively inhibits the lithium dendrites formation through LLZTO grain boundaries. This work provides a strategy for fabricating the coating layer on LLZTO to improve the stability of LMBs.

研究领域: 材料科学 · 电化学
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Advanced Energy Materials · 2018 ·Vol. 8 ·期 16 ·1702374 · IF 21.875

Germanium Thin Film Protected Lithium Aluminum Germanium Phosphate for Solid-State Li Batteries

Yijie Liu,Chao Li,Bojie Li,Hucheng Song,Zhu Cheng,Minrui Chen,Ping He,Haoshen Zhou

Solid-state Li batteries using Na + superionic conductor type solid electrolyte attracts wide interest because of its safety and high theoretical energy density. The NASCION type solid electrolyte LAGP (Li 1. 5 Al 0.5 Ge 0.5 P 3 O 12 ) shows favorable conductivity as well as good mechanical strength to prevent Li dendrite penetration. However, the instability of LAGP with Li metal remains a great challenge. In this work, an amorphous Ge thin film is sputtered on an LAGP surface, which can not only suppress the reduction reaction of Ge 4+ and Li, but also produces intimate contact between the Li metal and the LAGP solid electrolyte. The symmetric cell with the Ge-coated LAGP solid electrolyte shows superior stability and cycle performance for 100 cycles at 0.1 mA cm −2 . A quasi-solid-state Li–air battery has also been assembled to further demonstrate this advantage. A stable cycling performance of 30 cycles in ambient air can be obtained. This work helps to achieve a stable and ionic conducting interface in solid-state Li batteries.

研究领域: 材料科学 · 电化学
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DESALINATION · 2024 · IF 8.3

Porous polyvinyl alcohol/polyacrylamide hydrogels loaded with HTO lithium-ion sieves for highly rapid and efficient Li+ extraction

Xunshuang Zhang,Junxiang Wu,Yu He,Chenhao Zhao,Minfang An,Liangbin Li

Lithium (Li) reserves in liquid resources are significantly higher than solid lithium ores and can fully meet the growing demand for Li. Lithium-ion sieves (LIS) adsorption of Li from liquid resources is one of the most promising methods. However, conventional polymeric adsorption materials encapsulate most LIS in dense structures, leading to low adsorption capacity and slow adsorption rate. Therefore, HTO-PVA/PAAm hydrogel was synthesized from titanium-type lithium-ion sieves (HTO), acrylamide, and polyvinyl alcohol by free radical polymerization. The HTO-PVA/PAAm hydrogel is characterized by a soft three-dimensional (3D) network, continuously adjustable pore structure, high specific surface area, and excellent hydrophilicity. Accordingly, the HTO-PVA/PAAm owns an excellent Li + adsorption capacity (22.16 and 31.31 mg·g −1 in pH 7.2 and 12 of LiCl solutions, respectively) among reported advanced adsorbents. 90 % of Li + is desorbed within 60 min, indicating the efficient and rapid Li + desorption response of the hydrogel. Meanwhile, this hydrogel still maintains a Li + adsorption capacity of 90 % after eight adsorption-desorption cycles, during which Ti loss is <0.42 % in each cycle. In this work, HTO-PVA/PAAm hydrogel synthesized by an environmentally friendly and low-cost approach shows great application potential as a new strategy for Li + adsorption from liquid resources.

研究领域: 材料科学 · 环境工程
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Poly(vinylidene fluoride)-based Janus separators with an ultrathin conductive layer for suppressing lithium dendrite growth

Ruiqi Che,Sha Cheng,Cheng Huang,Ming Liu,Zhongao Chen,Jin Han,Wen Chen,Pengchao Zhang

Lithium dendrites, growing during the charging and discharging processes, can pierce the separators and lead to internal short circuits, which is one of the main factors resulting in thermal runaway of lithium metal batteries (LMBs). In this work, we developed a poly(vinylidene fluoride) (PVDF)-based Janus separator with an ultrathin polypyrrole (PPy) layer towards efficiently suppressing lithium dendrite growth. The PPy layer with thickness of approximately 200 nm has Pyrrole-N with lone pairs of electrons, which can act as nucleation sites for lithium ions. As a result, lateral lithium deposition can be achieved on the anode, thus preventing the lithium dendrites from piercing the separators. Stable stripping/plating performance over extended cycling and a capacity retention rate of 76.8% after 1000 cycles have been achieved in the Janus PVDF/PPy separator-based Li//Li symmetric cells and Li//LiFePO 4 half cells, respectively. The development of Janus separators with conductive polymer layers presents a promising solution for improving the safety and electrochemical performance of LMBs.

CAS / MDL: 7727-54-0 109-97-7
研究领域: 材料科学 · 能源存储
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Advanced Energy Materials · 2025 · IF 26

Insertion Type Li3VO4 Lithiophilic Sites Boosting Dendrite-Free Lithium Deposition in Trapping-and-leveling Model

Bing Sun,Lingling Kuang,Meichun He,Qin Zhang,Yunfeng Guan,Chengzhi Zhang,Dongmei Zhang,Cunyuan Pei,Pengju Li,Shibing Ni

Lithium (Li) metal batteries offer high energy densities but suffer from uncontrolled lithium deposition, causing serious dendrite growth and volume fluctuation. Tailorable Li nucleation and uniform early-stage plating are essential for homogenous Li deposition. Herein, insertion type Li 3 VO 4 is first demonstrated as efficient lithiophilic sites trapping Li + ions for homogenous nucleation. By homogenizing the distribution of electric field and ions flux via an ingenious architecture design with Li 3 VO 4 nanodots grown on the carbon fibers (LVO@CNFs), leveling Li metal deposition after nucleation is also realized. These, together, result in smooth and dendrite-free Li deposition on the LVO@CNFs via a trapping-and-leveling model, giving rise to unprecedented performance (highly stable Li plating/stripping exceeding 2500 h at 2 mA cm −2 under 3 mA h cm −2 capacity, high-capacity retention of 82.5% over 500 cycles in a Li@LVO@CNFs//LiFePO 4 battery). The successful design of Li metal deposition host via insertion-type Li 3 VO 4 may pave a new way for long lifespan Li metal batteries.

CAS / MDL: 7790-69-4
研究领域: 材料科学 · 能源存储
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ACS Applied Nano Materials · 2024 · IF 5.3

Lithium-Ion Battery Separator with Dual Safety of Regulated Lithium Dendrite Growth and Thermal Closure by Assisted Assembly Technology

Zhen Zhang,Xiao-Feng Xu,Yu-Ze Sun,Zhao-Jian Li,Hong Gao,Yun-Ze Long,Hong-Di Zhang

Lithium metal batteries offer a huge opportunity to develop energy storage systems with high energy density and high discharge platforms. However, the battery is prone to thermal runaway and the problem of lithium dendrites accompanied by high energy density and excessive charge and discharge. This study presents an assisted assembly technique (AAT) based on flexible barium titanate (BTO) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers for preparation of a battery separator. AAT was used to combine the BTO diaphragms with high thermal stability and the PVDF-HFP diaphragms with good Elasticity and piezoelectricity, and the thermal stability was improved by 200 and 125% increase in battery cycle life compared to PVDF-HFP diaphragms alone. And demonstrated excellent thermal closure performance between 160 and 200 °C. Furthermore, the piezoelectric effect of the composite film prevents the growth of lithium dendrites in the vertical direction, avoiding the trouble of lithium dendrites penetrating the battery separator. Therefore, the two safety guarantee properties of the composite separator greatly enhance the safety and service life of the battery, which allows the application of lithium batteries to be further improved in the application scenario and application scale.

CAS / MDL: 12190-79-3 9003-39-8
研究领域: 材料科学 · 能源存储
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DESALINATION · 2024 · IF 8.3

Lithium aluminium titanium phosphate based ceramic composite membrane for selective lithium-ion separation via a scalable membrane-based electrodialysis process

Jilong Han,Kuihu Wang,Siyu Chen,Huanzhang Lu,Zhikun Zhang,Zhengjie Li,Lilong Zhou,Yongsheng Du,Qingfen Meng,Allana Lewis,Yi Huang

The escalating global demand for lithium necessitates efficient extraction methods, particularly from natural sources such as brine. Herein, we report a novel, thin, and dense functionalised composite ceramic membrane that is employed in conjunction with electrodialysis technology for selective lithium extraction from salt lakes. This membrane exhibits high mechanical strength, low ionic impedance, and high lithium conductivity. The thin functional layer, ~20 μm-thick NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) superionic conductor material, is deposited on high-strength and porous alumina membrane via a facile dip-coating method, providing structural stability for the composite membrane. The preparation and sintering processes of LATP-Al 2 O 3 ceramic composite membrane were systematically studied and precisely controlled to improve its morphology and performance. A membrane-based electrodialysis set-up was designed specifically for lithium extraction demonstrated the remarkable performance of the composite-LATP membrane in separating lithium from magnesium-lithium solutions with a high Mg/Li ratio. The LATP composite membrane effectively reduced the Mg/Li ratio from 40 to 2.1 after three-stage electrodialysis. Moreover, the Li + recovery reached 77.15% from the feed solution with an estimated power consumption of ~47.6 kWh per 1 kg of lithium carbonate. These findings have significant implications for the development of low-cost and environmentally friendly inorganic membrane separation technologies, which are important for promoting technological innovation in the lithium industry chain.

研究领域: 材料科学 · 环境工程
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Metal-organic frameworks-derived CoP anchored on MXene toward an efficient bifunctional electrode with enhanced lithium storage

Hui Zong,Le Hu,Zhenguo Wang,Ruijuan Qi,Ke Yu,Ziqiang Zhu

It is significant to exploit novel electrode materials because at present the severe capacity decline and slow ion kinetics limit the broad application of lithium-based batteries. Herein, we have prepared the metal–organic frameworks-derived CoP anchored on Ti 3 C 2 MXene (MOFs-CoP@MXene) and fully explored its synergy as an efficient bifunctional electrode for enhanced lithium storage for the first time. It is gratifying that the prepared MOFs-CoP@MXene provides a high capacity of 706.5 mAh g −1 after 200 cycles at 0.2 A g −1 , as the anode for lithium-ion batteries (LIBs). It can provide 585.8 mAh g −1 after 1000 cycles with 0.5 A g −1 . The MOFs-CoP@MXene anode has robust lithium-ion storage capacity, indicating that it can increase the charge transfer rate and improve Li + diffusion kinetics with enhanced electrochemical activity. As lithium-sulfur batteries (LSBs) cathode, MOFs-CoP@MXene/S shows 796.9 mAh g −1 after 300 cycles at 0.2C. MOFs-derived CoP coupling with MXene exhibits enhanced capture capacity of sulfur, facilitating the conversion of polysulfides. The results show that the MOFs-CoP@MXene composite prepared for the first time are feasible as both the anode of LIBs and the cathode of LSBs.

研究领域: 材料科学 · 电化学 · 能源存储
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JOURNAL OF ALLOYS AND COMPOUNDS · 2020 · IF 4.65

Direct regeneration of spent LiFePO4 cathode materials with pre-oxidation and V-doping

Peiwen Liu,Yannan Zhang,Peng Dong,Yingjie Zhang,Qi Meng,Siyuan Zhou,Xuan Yang,Mingyu Zhang,Xi Yang

Direct regeneration has been widely applied in recovery of LiFePO 4 batteries. However, excess residual carbon and inherent low electronic and ionic conductivity of spent LiFePO 4 /C cathode materials lead to the reduction of electrochemical performance. Herein, a facile and simple regeneration process of pre-oxidation and vanadium doping is developed to regenerate LiFePO 4 /C cathode materials . Pre-oxidation was applied to remove excess carbon at 500 °C for 3 h in air. Vanadium doping was applied to improve electronic and ionic conductivity of regenerated cathode materials. Among the regenerated cathode materials, the 3 mol% V doped sample possesses discharge capacity of 134.3 mAh/g after 200 cycle at 1C with the discharge capacity retention of 99.1%. At 2, 5, 10C, the discharge capacities are 134, 124.1, 111.5 mAh/g, respectively. The vanadium doping regeneration process with oxidation pre-oxidation is simple, and feasible to be applied in the recovery of spent LiFePO 4 cathode materials.

研究领域: 材料科学 · 能源存储与转换
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