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In Situ Growth of 2D Metal-Organic Framework ion sieve Interphase for Reversible Zinc Anodes

ENERGY & ENVIRONMENTAL MATERIALS 2024年第6期7卷 158-166页

作者： Sun, Jing Jian, Qinping Liu, Bin Lin, Pengzhu Zhao, Tianshou Hong Kong Univ Sci & Technol Dept Mech & Aerosp Engn Kowloon Clear Water Bay Hong Kong Peoples R China Southern Univ Sci & Technol Dept Mech & Energy Engn Shenzhen 518055 Peoples R China

Zinc metal anodes are gaining popularity in aqueous electrochemical energy storage systems for their high safety, cost-effectiveness, and high capacity. However, the service life of zinc metal anodes is severely constrained by critical challenges, including dendrites, water-induced hydrogen evolution, and passivation. In this study, a protective two-dimensional metal-organic framework interphase is in situ constructed on the zinc anode surface with a novel gel vapor deposition method. The ultrathin interphase layer (similar to 1 mu m) is made of layer-stacking 2D nanosheets with angstrom-level pores of around 2.1 angstrom, which serves as an ion sieve to reject large solvent-ion pairs while homogenizes the transport of partially desolvated zinc ions, contributing to a uniform and highly reversible zinc deposition. With the shielding of the interphase layer, an ultra-stable zinc plating/stripping is achieved in symmetric cells with cycling over 1000 h at 0.5 mA cm(-2) and similar to 700 h at 1 mA cm(-2), far exceeding that of the bare zinc anodes (250 and 70 h). Furthermore, as a proof-of-concept demonstration, the full cell paired with MnO2 cathode demonstrates improved rate performances and stable cycling (1200 cycles at 1 A g(-1)). This work provides fresh insights into interphase design to promote the performance of zinc metal anodes.

关键词： 2D MOF desolvation interphase ion sieve zinc anode DEPOSITion KINETICS CRYSTAL

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Preparation and evaluation of α-Al2O3 supported lithium ion sieve membranes for Li^+ extraction

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Chinese Journal of Chemical Engineering 2020年第9期28卷 2312-2318页

作者： Feng Xue Xiaoxian Zhang Yue Niu Chenhao Yi Shengui Ju Weihong Xing College of Chemical Engineering Nanjing Tech UniversityNanjing 211816China

Spinel lithium manganese oxide ion-sieves have been considered the most promising adsorbents to extract Li^+ from brines and sea ***,we report a lithium ion-sieve which was successfully loaded onto tubular α-Al2 O3 ceramic substrates by dipping crystallization and post-calcination *** lithium manganese oxide Li4 Mn5 O(12)was first synthesized onto tubular α-Al2 O3 ceramic substrates as the ion-sieve precursor(i.e.L-AA),and the corresponding lithium ion-sieve(i.e.H-AA) was obtained after acid *** chemical and morphological properties of the ion-sieve were confirmed by X-ray diffraction(XRD) and scanning electron microscopy(SEM).Both L-AA and H-AA showed characteristic peaks of α-Al2 O3 and cubic phase Li4 Mn5 O(12) and the peaks representing cubic phase could still exist after *** lithium manganese oxide Li4 Mn5 O(12) could be uniformly loaded not only on the surface of α-Al2 O3 ubstrates but also inside the ***,we found that the equilibrium adsorption capacity of H-AA was 22.9 mg·g^-*** 12 h adsorption,the adsorption balance was *** 5 cycles of adsorption,the adsorption capacity of H-AA was 60.88% of the initial adsorption *** process of H-AA adsorption for Li^+correlated with pseudo-second order kinetic model and Langmuir *** thermodynamic parameters regarding enthalpy(△N), Gibbs free energy(△G) and entropy(AS) were *** the dynamic adsorptiondesorption process of H-AA,the H-AA exhibited excellent adsorption performance to Li^+ with the Li^+ dynamic adsorption capacity of 9.74 mg·g^-1 and the Mn^2+dissolution loss rate of 0.99%.After 3 dynamic adsorption-desorption cycles,80% of the initial dynamic adsorption capacity was still kept.

关键词： Lithium α-Al2O3 tube ion sieve Adsorption Li4Mn5O(12)

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Spray-drying assisted layer-structured H_(2)TiO_(3) ion sieve synthesis and lithium adsorption performance

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Chinese Journal of Chemical Engineering 2022年第5期35卷 258-267页

作者： Minxia Liu Dang Wu Dongling Qin Gang Yang College of Chemical Engineering Nanjing Tech UniversityNanjing 211816China

A spray-drying assisted solid-state method to prepare spherical layer-structured H_(2)TiO_(3) ion sieve(LSTIS)particles is reported *** effects of synthesis parameters(calcination temperature,calcination time,and the lithium-titanium molar ratio)on adsorption-desorption performance(the delithiation ratio,titanium dissolution loss,and the adsorption capacity)were *** as-prepared LSTIS exhibited an equilibrium adsorption capacity of 30.08 mg·g^(-1)(average of 25.85 mg·g^(-1) over 5 cycles)and ultra-low titanium dissolution loss of less than 0.12%(average of 0.086%over 5 cycles).The LSTIS showed excellent selectivity toward Li^(+) in Na^(+),K^(+),Mg^(2+),and Ca^(2+) coexisting saline solutions where its adsorption capacity reached 27.45 mg·g^(-1) and the separation factors of Li^(+) over the coexisting cations exceeded *** data suggests that the LSTIS is promising to competitively enrich Li^(+) from saline solutions.

关键词： Spray-drying ion sieve Adsorption Lithium Dissolution loss

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Synthesis of porous lithium ion sieve and its application for lithium recovery from geothermal water

Synthesis of porous lithium ion sieve and its application fo...

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中国化学会第七届全国热分析动力学与热动力学学术会议

作者： Hongyu Lin Xiaoping Yu Mingli Li Ji Duo Yafei Guo Tianlong Deng Tianjin Key Laboratory of Marine Resources and Chemistry College of Chemical Engineering and Materials ScienceTianjin University of Science and Technology Central Laboratory of Geological Mineral Exploration and Development Bureau of Tibet Autonomous Region

Lithium,as the lightest alkali metal,is widely used in ceramics,glasses,lubricating greases,especially in lithium-ion batteries .The market demands for lithium are expected to increase up to 160%until 2020 with the increasing usage of portable electronics,as well as electric and hybrid ***,the development and utilization of lithium attract extensive attention *** present,lithium mainly results from lithium ores such as spodumene and ***,with the gradual depletion of solid mineral resources,scientists have transferred their attention to the brine resources including salt lake brine,underground brine,geothermal water,***,the concentration of Liin geothermal water is usually low at the range of 20～50 mg/*** to realize swift and eco-friendly recovery of Lifrom such low concentration of geothermal water is thus a great *** recovery of low concentration of lithium from geothermal water was carried out in this work by adsorption using lithium ion sieve(HTO).The precursor of HTO was first synthesized by the solid-phase calcination method and the hydrothermal method,*** powdery HTO synthesized by the former exhibited excellent adsorption performances and was subsequently granulated using polyvinyl chloride (PVC)as a binder to decrease dissolution loss and facilitate adsorption *** the adsorption capacity and rate of the spherical PVC-HTO were lower than the powdery HTO,they were successfully improved by regulation using polyethylene glycol (PEG) as a *** the polyporous PVC-HTO was applied for the recovery of lithium from geothermal water,the adsorption capacity reached to 12.23 mg/g at 328.15 K with equilibrium time about 12 *** results of adsorption kinetics,thermodynamics,and cycle tests all demonstrate the reliability of this developed material,and it thus can be used as a candidate for the recovery of low concentration of lithium from geothermal water or other kinds of solution

关键词： Lithium ion sieve PVC-HTO Geothermal water

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