JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2023
·
IF 2.6
Qing Hao,Huan Zhou,Jing Yu Chang,Jie Li,Yun Zhao
Brine deposited in Chaerhan salt lake belongs to the chloride type and can be simplified into the hexnary system Li+, Na+, K+, Mg2+, Ca2+, Cl––H2O. The known solubility data indicate that significant salting-in effects exist in its subsystems of KCl–LiCl–H2O and KCl–CaCl2–H2O, which inevitably affect the properties and solubility behavior of actual brine. In this work, the solubility behavior study and phase diagram determination are extended to the quaternary system of Li+, K+, and Ca2+∥Cl––H2O. The phase equilibrium data at 298.15 and 273.15 K are reported, and five solid species, including two double salts KCl·CaCl2 and LiCl·CaCl2·5H2O, are found. The salting-in effect is still exhibited in the Li+, K+, and Ca2+∥Cl––H2O system and results in a very high total salt content at invariant points; e.g., they are 59.08 and 46.93% at 298.15 and 273.15 K, respectively.
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高影响因子
ELECTROCHIMICA ACTA
·
2023
·
IF 6.6
Yue Meng,Jiali Li,Shaonan Gu,Yulong Fu,Zhi Wang,Junhao Liu,Xuzhong Gong
To increase cycle life and reduce costs for natural graphite anode, graphite tailings grafted with polyether amine (PEA) is prepared for artificial solid electrolyte interphase (SEI). The complex of PEA and Li + has a well-tuned lowest unoccupied molecular orbital (LUMO) energy (0.216 eV∼-0.239 eV) to improve the chemical stability of SEI components, effectively hinders electron transfer from anode to electrolyte, and inhibits electrolyte decomposition. Meanwhile, the strong adsorption between Li + and PEA enhances the de-solvation ability of SEI, thus improving the rate performance of the anode. After 1000 cycles, the capacity retention of the anode material with grafted PEA molecular weight of 2000 is increased from 22% to 98%. The method can also improve rate performance for graphite anode, with the capacity retention rate at a current density of 1 A g −1 (vs. 0.1 A g −1 ) increasing from 42% to 72%. As expected, the full cell life with LiFePO 4 as the cathode material is significantly extended, the capacity retention improved from 44% to 77% after 200 cycles.
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高影响因子
Small
·
2023
·Vol. 19
·期 33
·2301391
·
IF 13.3
Wenjing Zhang,Jian Zheng,Ruoyu Wang,Li Huang,Junkai Wang,Tianran Zhang,Xiangfeng Liu
Lithium–oxygen (Li–O 2 ) batteries have received extensive attention owing to ultrahigh theoretical energy density. Compared to typical discharge product Li 2 O 2 , LiOH has attracted much attention for its better chemical and electrochemical stability. Large-scale applications of Li–O 2 batteries with LiOH chemistry are hampered by the serious internal shuttling of the water additives with the desired 4e − electrochemical reactions. Here, a metal organic framework-derived “water-trapping” single-atom-Co-N 4 /graphene catalyst (Co-SA-rGO) is provided that successfully mitigates the water shuttling and enables the direct 4e − catalytic reaction of LiOH in the aprotic Li–O 2 battery. The Co-N 4 center is more active toward proton-coupled electron transfer, benefiting - direction 4e − formation of LiOH. 3D interlinked networks also provide large surface area and mesoporous structures to trap ≈12 wt% H 2 O molecules and offer rapid tunnels for O 2 diffusion and Li + transportation. With these unique features, the Co-SA-rGO based Li–O 2 battery delivers a high discharge platform of 2.83 V and a large discharge capacity of 12 760.8 mAh g −1 . Also, the battery can withstand corrosion in the air and maintain a stable discharge platform for 220 cycles. This work points out the direction of enhanced electron/proton transfer for the single-atom catalyst design in Li–O 2 batteries.
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PubMed
高影响因子
Nanoscale
·
2022
·Vol. 15
·期 2
·588-598
·
IF 8.307
Zhenbo Wang,Yanfeng Yin,Guanjie He,Huiling Zhao,Ying Bai
With large specific capacity, wide voltage window, and high energy density, Li-rich layered oxides have been considered as a promising cathode candidate for advanced lithium-ion batteries (LIBs). However, their commercial application is challenging due to severe capacity degradation and voltage fading caused by irreversible oxygen evolution and phase transition upon repeated cycling. This work proposes an effective strategy to improve the long-term electrochemical performances of Li1.2Mn0.56Ni0.17Co0.07O2 (LMNCO) by constructing multifunctional nanolayers composed of element-doping, layered-spinel heterostructural connection, and fast ion conductor shell via a facile method. The Li0.09B0.97PO4 (LBPO) coating shell acts as a fast ion carrier and physical screen to promote Li+ diffusion and isolate side reactions at the cathode-electrolyte interface; moreover, two-phase transitional region provides three-dimensional channel to facilitate Li+ transport and inhibit phase transition. Besides, B3+ and PO43−-doping collaborates with oxygen vacancies to stabilize lattice oxygen and restrain oxygen evolution from the bulk active cathode. The optimized LMNCO@LBPO material exhibits a superior capacity retention of 78.6%, higher than that of the pristine sample (49.3%), with the mitigated voltage fading of 0.73 mV per cycle after 500 cycles at 1 C. This study opens up an avenue for the surface modification to the electrochemical properties and perspective application of Li-rich cathodes in high-performance LIBs.
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高影响因子
ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Yi Rong,Zhengyi Lu,Chao Jin,Yadong Xu,Lin Peng,Ruhua Shi,Tianyi Gu,Chengyi Lu,Ruizhi Yang
Surface functionalization is an effective strategy to reduce the chemical reactivity between a Li1.3Al0.3Ti1.7(PO4)3 (LATP) electrolyte and Li metal anode and optimize the interfacial contact of different components. Herein, sodium itaconate (SI) is introduced to modify the surfaces of LATP particles (LATP@SI) via a self-polymerizing process, and a composite solid electrolyte (CSE) composed of poly(ethylene oxide) (PEO) and LATP@SI is fabricated. Benefiting from the protection of the SI nanolayer, LATP demonstrates chemical compatibility with the Li metal anode, while the reduced surface energy renders a good dispersion of LATP in PEO. Furthermore, abundant carboxyl groups in SI can offer a bridge between LATP and PEO to accelerate Li+ transmission. As a result, the as-prepared PEO-LATP@SI-6 CSE exhibits a high ionic conductivity of 1.15 × 10–4 S cm–1 at 30 °C and 1.20 × 10–3 S cm–1 at 60 °C, a wide electrochemical stable window beyond 5.0 V, an improved Li+ transference number of 0.41, and an optimized lithium compatibility over 1200 h with Li dendrite free. The as-assembled Li||PEO-LATP@SI-6 CSE||LiFePO4 full battery delivers a high reversible capacity of 155 mAh g–1 and an outstanding capacity retention of 89% after 200 cycles. The Li||LiFePO4 pouch cell also successfully runs 50 cycles with a terminal discharge capacity of 116.6 mA h g–1. This study opens a new avenue to protect LATP. The developed surface functionalization technique promises a facile and efficient method for interfacial engineering to accelerate the practical application of LATP in solid-state lithium batteries.
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高影响因子
Sustainable Materials and Technologies
·
2023
·
IF 9.6
Yunchun Zha,Zitong Fei,Zelong Yang,Qi Meng,Peng Dong,Yingjie Zhang,Yong Li
Recycling of spent lithium-ion batteries is an urgent task in view of the resource shortage and environmental concerns. Pretreatment as the first step in recycling of spent lithium-ion batteries has become urgent issue for efficient separation of spent cathode materials from aluminum foil . Herein, a facile ternary molten salts approach is presented for efficient separation of cathode material and aluminum foil synchronous implementation of regeneration of spent cathode material. The separation efficiency reaches 99.98% at molar ratio of LiNO 3 : LiOH·H 2 O: Li 2 CO 3 (LNOC) of 3:2:0.5 with mass ratio of spent cathode pieces to the ternary molten salts of 1:2 holding at 300 °C for 15 min. The regenerated materials show discharging capacity of 122.2 mAhg −1 at 1C with retention rate of 99.97% after 100 cycles. The ternary molten salts are also made available for separation of other spent cathode materials with achieving high separation efficiency.
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高影响因子
Separations
·
2022
·Vol. 10
·期 1
·24
·
IF 3.344
Huifang Li,Lijuan Li,Wu Li
Lithium extraction from salt lake brine with a high mass ratio of Mg/Li by counter-current method using TBP-DIBK extraction system was investigated in this study. In the extraction process, TBP and DIBK acted as extractant, kerosene was used as diluent, and FeCl3was used as co-extractant. The operation conditions of extraction, scrubbing, stripping, and regeneration were investigated. In this study, 5.5 mol/L LiCl + 0.5 mol/L HCl was used as a scrubbing solution for purifying products, and 6 mol/L HCl solution was used as a stripping agent to transfer Li+from organic phase to aqueous phase. Furthermore, 2 mol/L NaOH and saturated MgCl2were used as the regeneration agent to remove H+from organic phase. The counter-current extraction experiments of 3-1-1-3 stages were carried out. After 10 cycles, the lithium extraction efficiency reached 99.90%; the separation factor of Li/Mg, Li/K, Li/Na, and Li/Ca was 5.215 × 104, 2.159 × 103, 3.659 × 102, and 3.104 × 102, respectively. The results indicated that the TBP-DIBK extraction system was effective at extracting lithium from salt lake brine with a high mass ratio of Mg/Li. Furthermore, the study of extraction thermodynamics suggested that lithium extraction was an exothermic process and that lower temperature promoted lithium extraction.Keywords:lithium extraction;salt lake brine;TBP-DIBK;extraction thermodynamics
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Huanhuan Wu,Haoyue Zhao,Yakai Lin,Xin Liu,Lin Wang,Hong Yao,Yuanhui Tang,Lixin Yu,Haihui Wang,Xiaolin Wang
Positively charged nanofiltration membrane has gained significant interest in magnesium and lithium separation due to its separation mechanism, especially in salt lake-based lithium industry. To obtain a high-density positive charged surface and high Li + /Mg 2+ selectivity, a novel thin-film nanocomposite (TFN) nanofiltration (NF) membrane for recovery of Li + from Mg/Li mixtures with Mg 2+ /Li + ratios of 20 was successfully prepared by using polymeric amine polyethyleneimine (PEI) and monomeric amine silane coupling agent (3-diamino-methyl-cyclohexyl triethoxysilane, DTES). Then the effect of DTES on the surface properties and performance of the prepared DTES/PEI/TMC TFN membranes were investigated. Chemical composition analysis revealed that DTES not only hydrolyzed to Si–OH and then self-polymerized to Si–O–Si, but also reacted with the self-carrying acyl chloride of 1,3,5-benzene trichloromethane (TMC). Moreover, SiO 2 nanoparticles were in-situ generated from DTES inside the PA layer with high compatibility. Due to the compatible properties with the positively charged PEI polymer, the reacted DTES was distributed uniformly in the formed TFN selective layer with no noticeable aggregation. The doping of SiO 2 into the polyamide network gave rise to the enlargement of the membrane pore size, enhanced the surface hydrophilicity, and reinforced the surface positive charges. The water flux of the DTES/PEI/TMC membrane improved from 36.9 L m −2 h −1 to 49.58 L m −2 h −1 compared to the PEI/TMC membrane. Additionally, the Mg 2+ and Li + rejection of the optimized membranes was 91.46% and −10.5%, respectively, with permeability and selectivity (S Li, Mg = 12.95) superior to that of the commercial NF membranes. Considering the commercial availability of DTES, this study not only offers a high-performance nanofiltration membrane for recovering lithium from brines but also provides a feasible strategy for industrial separation of other monovalent and divalent ions.
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高影响因子
ADVANCED MATERIALS
·
2023
·Vol. 35
·期 12
·2208951
·
IF 29.4
Jie Biao,Bing Han,Yidan Cao,Qidong Li,Guiming Zhong,Jiabin Ma,Likun Chen,Ke Yang,Jinshuo Mi,Yonghong Deng,Ming Liu,Wei Lv,Feiyu Kang,Yan-Bing He
Poor ion and high electron transport at the grain boundaries (GBs) of ceramic electrolytes are the primary reasons for lithium filament infiltration and short-circuiting of all-solid-state lithium metal batteries (ASLMBs). Herein, it is discovered that Li 2 CO 3 at the GBs of Li 7 La 3 Zr 2 O 12 (LLZO) sheets is reduced to highly electron-conductive LiC x during cycling, resulting in lithium penetration of LLZO. The ionic and electronic conductivity of the GBs within LLZO can be simultaneously tuned using sintered Li 3 AlF 6 . The generated LiAlO 2 (LAO) infusion and F-doping at the GBs of LLZO (LAO-LLZOF) significantly reduce the Li 2 CO 3 content and broaden the energy bandgap of LLZO, which decreases the electronic conductivity of LAO-LLZOF. LAO forms a 3D continuous ion transport network at the GB that significantly improves the total ionic conductivity. Lithium penetration within LLZO is suppressed and an all-solid-state LiFePO 4 /LAO-LLZOF/Li battery stably cycled for 5500 cycles at 3 C. This work reveals the chemistry of Li 2 CO 3 at the LLZO GBs during cycling, presents a novel lithium penetration mechanism within garnet electrolytes, and provides an innovative method to simultaneously regulate the ion and electron transport at the GBs in garnet electrodes for advanced ASLMBs.
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Junyuan Hua,Jintao He,Hongchang Pei,Xiaohua Ma,S. Ranil Wickramasinghe,Jianxin Li
Worldwide demand for lithium is increasing rapidly. Implementing an efficient extraction for lithium from salt-lake brines with low concentration and high Mg/Li (m/m) ratio remains challenging. A supported ionic liquid membrane (PI@14C4-SILM) contactor was developed in this work using a crown ether functionalized polyimide membrane material (Poly(DAB14C4-6FDA)) as the support and tributyl phosphate (TBP) and (1-butyl-3-methylimidazolium bis-trifluoromethylsulfonimide salt) ([C 4 mim][NTf 2 ]) mixture as the liquid phase for high-efficiency Li recovery. The results show that when the feed phase Mg/Li ratio is 35 and the stripping phase is 0.5 mol/L HCl , the Li + penetration rate, initial flux and Li/Mg selectivity of PI@14C4-SILM contactor are 0.354 μm/s, 0.128 mol/m 2 ·h and 19.1, respectively. Molecular dynamics (MD) simulation results show that Poly(DAB14C4-6FDA) and TBP have greater interaction with Li + than other ions (Na, Mg, K). Meanwhile, the binding energies of Poly(DAB14C4-6FDA)-Li-NTf 2 and TBP-Li-NTf 2 were calculated by density functional theory (DFT), which were −163.26 and −182.1 kcal/mol, respectively. The higher binding energies of the complexes indicated that their structures were more stable. The mechanism of the PI@14C4-SILM contactor's excellent Li + mass transfer performance may be the formation of a fast Li + transfer channel between the solid phase containing the crown ether structure and the liquid mobile phase in the pore structure . Besides, the TBP·Li·NTf 2 and TBP·H·NTf 2 structures in the liquid membrane phase effectively maintained the cyclic operation of the SILM system. This study provides an effective solution for selective separation of Mg/Li and utilization of Li resources in salt lake water.
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高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Jian Li,Kai Yang,Yun Zheng,Shuyu Gao,Jingchao Chai,Xiaohua Lei,Zhuo Zhan,Yuanjian Xu,Maige Chen,Zhihong Liu,Qingzhong Guo
Silicon suboxide (SiOx) anodes have attracted considerable attention owing to their excellent cycling performance and rate capability compared to silicon (Si) anodes. However, SiOx anodes suffer from high volume expansion similar to Si anodes, which has been a challenge in developing suitable commercial binders. In this study, a water-soluble polyamide acid (WS-PAA) binder with ionic bonds was synthesized. The amide bonds inherent in the WS-PAA binder form a stable hydrogen bond with the SiOx anode and provide sufficient mechanical strength for the prepared electrodes. In addition, the ionic bonds introduced by triethylamine (TEA) induce water solubility and new Li+ transport channels to the binder, achieving enhanced electrochemical properties for the resulting SiOx electrodes, such as cycling and rate capability. The SiOx anode with the WS-PAA binder exhibited a high initial capacity of 1004.7 mAh·g–1 at a current density of 0.8 A·g–1 and a capacity retention of 84.9% after 200 cycles. Therefore, WS-PAA is a promising binder for SiOx anodes compared with CMC and SA.
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高影响因子
ELECTROCHIMICA ACTA
·
2023
·
IF 6.6
Bohan Li,Xiaolong Ren,Zhouyang Qin,Chong Wang,Liangliang Li,Chenhui Luan,Wanci Shen,Feiyu Kang,Ruitao Lv,Ding Nan,Zheng-Hong Huang
Flexible lithium ion capacitors (FLICs) integrating the advantages of high energy batteries and high power capacitors are promising for wearable electronic devices. However, the imbalance of the two electrodes in kinetics and capacity impedes their practicable application. To address this challenge, in this article, metal-organic frameworks (MOFs) were introduced to the fiber precursors of both anode and cathode materials to improve the electrochemical performance. Free-standing Cu-BTC derived CuS x /CF-1.5 anode material and ZIF-8 derived Zn-PCF-900 °C cathode material were separately prepared through the facile blow-spinning technique. Benefitting from the uniformly carbon-encapsulated CuS x nanoparticles , multilevel mesoporous structure of the CuS x /CF-1.5 anode and the hierarchical pore structure , large BET surface area of the Zn-PCF-900 °C cathode, Li-ion capacitor (LIC) based on these electrodes can effectively alleviate both the kinetic and capacity imbalance and deliver remarkable energy and power densities (106 Wh kg −1 at 243 W kg −1 , 10 Wh kg −1 at 90 kW kg −1 ). In addition, the FLIC pouch cell also demonstrates its chargeable ability under different bending conditions, revealing good application prospects in high-performance flexible electronic devices.
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高影响因子
危险品化学品经营许可证（带存储）