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ENVIRONMENTAL TECHNOLOGY · 2023 · IF 2.8

A feasible process for recycling valuable metals from LiNi0.5Co0.2Mn0.3O2 cathode materials of spent Li-ion batteries

Dong-yan Liu,Shi-neng Sun,Duan-yang Li

The recycling of cathode materials for spent NCM has always been a major concern for the energy industry. However, among the current processing methods, the general leaching efficiency of Li is between 85% and 93%, with much room for improvement. The recovery of Ni, Co and Mn requires a high cost of secondary purification. In this study, to recycle the NCM cathode material, a route of sulphated reduction roasting – selective Li water leaching – efficiency acid leaching of Ni, Co, Mn – extraction separation – crystallisation was adopted. The results showed that after roasting (a temperature of 800 °C, a reaction time of 90 min, a carbon content of 26%, and a sulphuric acid addition of nH2SO4:nLi = 0.85), Li water leaching efficiency was 98.6%, followed by acid leaching of Ni, Co and Mn at around 99%. Mn, Co were extracted with Di-(2-ethylhexyl) phosphoric acid and 2-Ethylhexyl phosphonic acid mono-2-ethylhexyl ester respectively to obtain Ni, Co, Mn solutions, which eventually were crystallized for manganese sulphate, cobalt sulphate, lithium carbonate and nickel sulphate products, with high purity of 99.40%, 98.95%, 99.10%, and 99.95%. The results of this study improved the leaching efficiency of Li and were closely linked to the actual industrial preparation of Ni, Co and Mn sulphates, providing a feasible and promising basis for spent NCM cathode materials industrial recovery.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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Materials Today Chemistry · 2023 · IF 7.3

High-temperature-operating (over 140 °C) Li-ion supercapacitor via water-locking bimodal cross-linked hydrogel

S.Y. Fan,X.L. Xu,W.J. Wu

The utilization of quasi-solid conducting medium possessing superior interfacial properties represents a significant approach in tackling the issue of leakage and stability in supercapacitors . However, preserving the conductivity of ions like Li + and enabling their adaptability to high-temperature environments pose significant challenges to the improvement of water-locking capacity. Herein, a bimodal cross-linked hydrogel with a mesoporous structure has been developed based on the polyacrylamide-lithium chloride (PAM-LiCl) hydrogel system using polyethylene glycol (PEG). This hydrogel not only exhibits a high water-binding capacity but also facilitates the migration of Li-ions. Using activated carbon as the electrode material, the assembled quasi-solid state supercapacitor devices achieve a single electrode specific capacitance of 32.6 F/g at 0.1 A/g and an energy density of 1.77 W h/kg by varying the ratio of acrylamide and polyethylene glycol (AM/PEG). The findings of this study demonstrate that utilizing a bimodal cross-linked hydrogel can enable the operation of a supercapacitor at high temperatures above 140 °C.

CAS / MDL: 110-26-9
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APPLIED SURFACE SCIENCE · 2021 · IF 6.707

High flux Mg2+/Li+ nanofiltration membranes prepared by surface modification of polyethylenimine thin film composite membranes

Hao Luo,Huawen Peng,Qiang Zhao

Nanofiltration plays emerging roles in lithium extraction from salt-lake brines with high magnesium-to-lithium (Mg 2+ /Li + ) ratio, yet current lithium extraction nanofiltration membranes show relatively low water permeability. A new monomer (1-(2-hydroxyethyl)-1,3,5,7-tetraazaadamantane-1-ium bromide, HMTAB) was designed to improve membrane separation performances by means of surface modification. Infrared characterizations show that the HMTAB monomer was anchored the pristine polyethylenimine (PEI) thin film composite membrane through esterification condensation. Average roughness of the HMTAB membrane is relatively small (5.7 nm), while the thickness of the top-layer was increased by ∼ 20%, i.e., from 90 to 110 nm. Water flux of the HMTAB membrane in filtrating Mg 2+ /Li + mixture (2000 ppm, Mg 2+ /Li + : 100) at 6 bar pressure is 97.9 L m -2 h −1 , which is 3.6 times as high as the pristine PEI membrane. Meanwhile, the Mg 2+ /Li + ion selectivity of the HMTAB membrane is maintained, and the membrane reduced the high Mg 2+ /Li + ratio (50) in the feed to a relatively low value (4.9) in the permeate. Last, the modified membrane exhibits stable performance in 40 h’ continuous nanofiltration.

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Frontiers in Chemistry · 2021 · IF 5.221

Li-Rich Antiperovskite/Nitrile Butadiene Rubber Composite Electrolyte for Sheet-Type Solid-State Lithium Metal Battery

Bian Juncao,Yuan Huimin,Li Muqing,Ling Sifan,Deng Bei,Luo Wen,Chen Xuedan,Yin Lihong,Li Shuai,Kong Long,Zhao Ruo,Lin Haibin,Xia Wei,Zhao Yusheng,Lu Zhouguang

Lithium-rich antiperovskites (LiRAPs) hold great promise to be the choice of solid-state electrolytes (SSEs) owing to their high ionic conductivity, low activation energy, and low cost. However, processing sheet-type solid-state Li metal batteries (SSLiB) with LiRAPs remains challenging due to the lack of robust techniques for battery processing. Herein, we propose a scalable slurry-based procedure to prepare a flexible composite electrolyte (CPE), in which LiRAP (e.g., Li2OHCl0.5Br0.5, LOCB) and nitrile butadiene rubber (NBR) serve as an active filler and as a polymer scaffold, respectively. The low-polar solvent helps to stabilize the LiRAP phase during slurry processing. It is found that the addition of LOCB into the NBR polymer enhances the Li ion conductivity for 2.3 times at 60°C and reduces the activation energy (max. 0.07 eV). The as-prepared LOCB/NBR CPE film exhibits an improved critical current of 0.4 mA cm−2 and can stably cycle for over 1000 h at 0.04 mA cm−2 under 60°C. In the SSLiB with the sheet-type configuration of LiFePO4(LFP)||LOCB/NBR CPE||Li, LFP exhibits a capacity of 137 mAh/g under 60 at 0.1°C. This work delivers an effective strategy for fabrication of LiRAP-based CPE film, advancing the LiRAP-family SSEs toward practical applications.

✓ 已验证 DOI PubMed 高影响因子
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JOURNAL OF SOLID STATE CHEMISTRY · 2021 · IF 3.498

High capacity of microspheric manganese and cobalt trimesic dual-metal organic framework for Li-ion battery

Wen Zheng,Tao Hu,Yaobing Fang,Li Li,Wenhui Yuan

Metal organic frameworks (MOFs) have received great interest for Li-ion batteries (LIBs) owing to their variable structure and morphology. Herein, a microspheric manganese and cobalt trimesic dual-metal organic framework (MnCo-T) with diameters between 1 and 2 ​μm has been synthesized. The microspheric MnCo-T retains a high capacity of 819 mAh g −1 at 200 ​mA ​g −1 after 200cycles and exhibits good rate performance (148 mAh g −1 at 4000 ​mA ​g −1 ). Notably, it can maintain a considerable lithium storage capacity (337 mAh g −1 after 600 galvanostatic charging/discharging cycles at 1000 ​mA ​g −1 ), indicating that the design of dual-metal organic frameworks is an effective strategy for enhancing Li storage performance.

CAS / MDL: 10026-22-9
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HYDROMETALLURGY · 2021 · IF 4.156

Preparation of Mg-doped Li1.6Mn1.6O4 with enhanced Li+ adsorption performance and anti-dissolution properties of Mn

Luri Bao,Jingze Zhang,Jie Wu,Guotai Zhang,Yang Yang,Weiping Tang,Mei Xue

Owing to the increasing global demand for lithium, extraction of lithium from salt lake brine water has received considerable attention. In this study, the magnesium doping to produce Li 1.6 Mg x Mn 1.6-x O 4 (LMMO) was designed to overcome the limitation caused by the loss of Mn due to dissolution. The chemical and morphological properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The XRD results confirmed that the crystal structure of Li 1.6 Mn 1.6 O 4 was retained after Mg-doping. Scanning electron microscopy and energy-dispersive X-ray spectroscopy showed that LMMO has a flake-shaped structure and the Mg 2+ ions were uniformly distributed in the precursor. The doping of Mg 2+ led to the decrease of Mn 3+ content in the precursor, improving its structural stability. The adsorption capacity of LMMO-6% was 35.6 mg g −1 , which was greater than that of the undoped sample (33.2 mg g −1 ). After the tenth cycle, the dissolution loss of Mn in LMMO-6% was 0.55%, and it is smaller than that for lithium manganese oxide (0.94%). Results confirm that the structural stability was improved compared to undoped adsorbents. Moreover, batch adsorption experiments demonstrated the potential of the HMMO-6% adsorbent to be used for lithium adsorption from real salt lake brine.

CAS / MDL: 598-62-9 7647-01-0
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Journal of the Taiwan Institute of Chemical Engineers · 2023 · IF 5.7

Photocatalytic degradation of antibiotics using a Li-C3N4/ZnO/BiOI: Insights on the electron transport pathways

Jiawei Jiang,Yaru Wei,Junren Chen,Jianan Dai,Jing Ma,Liangsheng Qiang,Juanqin Xue,Weiwei Liu

Background Environmental pollution demands the fabrication of suitable nano-photocatalyst that works under visible-light irradiation. The effective interfacial engineering is required for better separation of charges. Semiconductor heterostructure promotes the practical separation of electron-hole pairs and enhances the carrier separation efficiency, which has broad application prospects in photocatalytic degradation of Antibiotics. However, it remains a significant challenge to construct high-quality directly heterostructure effectively. Methods In this work, a hierarchical ternary heterojunction (Li-C 3 N 4 /ZnO/BiOI) was facilely synthesized by employing an in-situ hydrothermal strategy with different ratios using Li-C 3 N 4 as an anchor, in which the interaction at heterointerfaces was enhanced to improve the photocatalytic performance. Significant findings The photocatalytic degradation experiment was carried out with Tetracycline (TC), and the effect of the molar ratio of Li-C 3 N 4 /ZnO to BiOI on the photocatalytic degradation performance was quantitatively investigated. Benefiting from the unique electronic structure of heterostructure, the results show that a degradation rate of 92.62% was achieved for 10 mg/L TC solution within 20 min. Moreover, Li-C 3 N 4 /ZnO/BiOI-5 offered high photocatalytic activity due to the type II and Z transport, resulting in a small forbidden band gap. The charge transport pathway improves the separation of photogenerated electron-hole pairs in Li-C 3 N 4 /ZnO/BiOI. This study provides a promising avenue for rational design and application of ternary composites.

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ADVANCED MATERIALS · 2023 · IF 29.4

Bifunctional Interphase Promotes Li+ De-Solvation and Transportation Enabling Fast-Charging Graphite Anode at Low Temperature

Yingshan Huang,Chaonan Wang,Haifeng Lv,Yuansen Xie,Shaoyun Zhou,Yadong Ye,En Zhou,Tianyuan Zhu,Huanyu Xie,Wei Jiang,Xiaojun Wu,Xianghua Kong,Hongchang Jin,Hengxing Ji

The most successful lithium-ion batteries (LIBs) based on ethylene carbonate electrolytes and graphite anodes still suffer from severe energy and power loss at temperatures below −20 °C, which is because of high viscosity or even solidification of electrolytes, sluggish de-solvation of Li + at the electrode surface, and slow Li + transportation in solid electrolyte interphase (SEI). Here, a coherent lithium phosphide (Li 3 P) coating firmly bonding to the graphite surface to effectively address these challenges is engineered. The dense, continuous, and robust Li 3 P interphase with high ionic conductivity enhances Li + transportation across the SEI. Plus, it promotes Li + de-solvation through an electron transfer mechanism, which simultaneously accelerates the charge transport kinetics and stands against the co-intercalation of low-melting-point solvent molecules, such as propylene carbonate (PC), 1,3-dioxolane, and 1,2-dimethoxyethane. Consequently, an unprecedented combination of high-capacity retention and fast-charging ability for LIBs at low temperatures is achieved. In full-cells encompassing the Li 3 P-coated graphite anode and PC electrolytes, an impressive 70% of their room-temperature capacity is attained at −20 °C with a 4 C charging rate and a 65% capacity retention is achieved at −40 °C with a 0.05 C charging rate. This research pioneers a transformative trajectory in fortifying LIB performance in cryogenic environments.

CAS / MDL: 872-50-4
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Advanced Energy Materials · 2023 ·Vol. 13 ·期 45 ·2302443 · IF 27.8

Boosting Fast-Charging Capability of High-Voltage Li Metal Batteries with Ionic Liquid Modified Ethereal Electrolyte

Kai Ding,Elijah J. Begin,Shouyi Yuan,Mingyang Zhong,Yang Wang,Yingjie Zhang,Xiaoyuan Zeng,Junwei Lucas Bao,Yonggang Wang

Given the high compatibility with Li metal anodes, ethereal electrolytes have found widespread use in Li metal batteries. Unfortunately, their applications in high-voltage Li metal batteries are hampered by a limited electrochemical window. In this study, a diluted ethereal electrolyte (with Li salt concentration < 1.5 m ) is developed containing 1 m lithium bis(fluorosulfonyl) imide (FSI) and 0.3 m LiNO 3 in a N -methyl- N -propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13TFSI):dimethyl ether (DME) (v:v = 1:4) mixture for Li metal batteries with an aggressive high-voltage cathode via the formation of an anion-enriched solvation sheath. In contrast to high-concentration electrolytes, the formation of the anion-enriched solvation sheath in this design is facilitated by the addition of ionic liquids. Further theoretical calculations indicate that the presence of FSI − and NO 3 − anions in the first solvation sheath weakens the desolvation energy of the DME solvent, suggesting a faster desolvation process at the electrode interphase. Consequently, the designed electrolyte enables long-term cycling of Li || LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) full cells over 1000 cycles at a high rate of 10 C. More notably, it also allows for a long cycle life of 100 cycles under a high rate of 5 C, even with limited negative capacity to positive capacity (N/P) ratio of 1.

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JOURNAL OF SOLID STATE CHEMISTRY · 2023 · IF 3.3

Metal-organic framework-derived Nickel Diselenide grown in situ on carbon for high-performance Li storage

Wen Zheng,Li Li,Yaobing Fang,Wenhui Yuan

The creation of innovative anodes to replace graphite in lithium-ion batteries (LIBs) is necessary to meet the rising demand for energy storage devices. Based on the large Li storage capacity, transition metal selenides (TMSs) draw considerable interest for LIBs. However, volume expansion of TMSs during the cycling process hinders their large-scale commercial application for LIBs. Herein, the NiSe 2 particle grown in situ on the porous carbon framework (NiSe 2 @C) is prepared by selenization of metal-organic frameworks (MOFs) in an argon atmosphere. NiSe 2 @C exhibits a high reversible Li storage capacity (770 mAh g −1 at 200 mA g −1 after 100 cycles), long cycling life (308 mAh g −1 at 1 A g −1 after 1000 cycles), and good rate capability (214 mAh g −1 at 5.0 A g −1 ). The long cycling performance can be attributed to the fact that NiSe 2 @C can withstand volume expansion during the Li + insertion and desertion process. Furthermore, cyclic voltammetry (CV) tests at various scan rates are conducted to investigate the kinetics of NiSe 2 @C for LIBs, indicating that the Li storage behaviour of NiSe 2 @C is primarily controlled by the capacitive process. The fabrication of the TMS@C composites by selenization of MOFs is a potential way to obtain anodes for high-performance Li storage.

CAS / MDL: 7782-49-2
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Nanomaterials · 2023 ·Vol. 13 ·期 20 ·2777 · IF 5.3

Construction of a Two-Dimensional GO/Ti3C2TX Composite Membrane and Investigation of Mg2+/Li+ Separation Performance

Zhenhua Feng,Chengwen Liu,Binbin Tang,Xiaojun Yang,Wenjie Jiang,Peng Wang,Xianjun Tang,Hongshan Wang,Xiangdong Zeng,Guangyong Zeng

Graphene oxide (GO) two-dimensional (2D) membranes with unique layer structures and tunable layer spacing have special advantages and great potential in the field of water treatment. However, GO membranes face the issues of weak anti-swelling ability as well as poor permeability. We prepared GO/Ti3C2TX2D composite membranes with 2D/2D structures by intercalating Ti3C2TXnanosheets with slightly smaller sizes into GO membranes. Ti3C2TXintercalation can effectively expand the layer spacing of GO, thereby substantially enhancing the flux of the composite membrane (2.82 to 6.35 L·m−2·h−1). Moreover, the GO/Ti3C2TXcomposite membrane exhibited a good Mg2+/Li+separation capability. For the simulated brine, the separation factor of M2 was 3.81, and the salt solution flux was as high as 5.26 L·m−2·h−1. Meanwhile, the incorporation of Ti3C2TXnanosheets significantly improved the stability of GO/Ti3C2TXmembranes in different pH environments. This study provides a unique insight into the preparation of highly permeable and ion-selective GO membranes.Keywords:graphene oxide;Ti3C2TXnanosheets;two-dimensional materials membrane;Mg2+/Li+separation

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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

In-situ assembly of Al-Li-Si alloy powders with enhanced thermal stability and tailored combustion

Wei Le,Wanjun Zhao,Yanli Zhu,Xin Zeng,Dazhi Liu,Qingjie Jiao

Aluminum (Al)-lithium (Li) alloys are ambitious candidates for application in energetic materials, however, the high reactivity of Al-Li compound and Li in alloys affects their thermal stability, which results in gradually lower active content and diminished performance, impeding their further application in energetics. In this study, the specific content of silicon (Si) was introduced into Al-Li alloy via the centrifugal atomization that allows in-situ assembly of Al , Li, and Si at the single particle level, thus resulting in more stable Al-Li-Si compounds instead of active Al-Li compounds and Li and enhancing their thermal stability. The results show that Al-Li-Si alloy powders are in a high degree of sphericity, which are composed of αAl and AlLiSi. Compared to Al-Li alloys, Al-Li-Si alloys initiate the oxidization at a higher temperature (∼600 ℃) since the existence of more stable Al-Li-Si compounds than Li in Al-Li alloys, which indicates a higher thermal stability. Al-Li-Si alloys also show high heat release and combustion efficiency similar to Al-Li alloys. In the meanwhile, Al-Li-Si alloy-based composites maintain almost the same combustion properties compared to Al-Li/PTFE energetics, along with prolonged combustion duration. Therefore, Al-Li-Si alloy powders are promising candidates for application in energetic materials considering their higher thermal stability and tunable combustion properties.

CAS / MDL: 9002-84-0
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