In Situ Growth of 2D Metal–Organic Framework Ion Sieve Interphase for Reversible Zinc Anodes

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(~1μm)is made of layer-stacking 2D nanosheets with angstrom-level pores of around 2.1Å,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~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 MnO_(2) 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.

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

Spinel lithium manganese oxide ion-sieves have been considered the most promising adsorbents to extract Li^+ from brines and sea water.Here,we report a lithium ion-sieve which was successfully loaded onto tubular α-Al2 O3 ceramic substrates by dipping crystallization and post-calcination method.The 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 pickling.The 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 pickling.The 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 pores.Moreover,we found that the equilibrium adsorption capacity of H-AA was 22.9 mg·g^-1.After 12 h adsorption,the adsorption balance was reached.After 5 cycles of adsorption,the adsorption capacity of H-AA was 60.88% of the initial adsorption capacity.The process of H-AA adsorption for Li^+correlated with pseudo-second order kinetic model and Langmuir model.Adsorption thermodynamic parameters regarding enthalpy(△N), Gibbs free energy(△G) and entropy(AS) were calculated.For 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.

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

A spray-drying assisted solid-state method to prepare spherical layer-structured H_(2)TiO_(3) ion sieve(LSTIS)particles is reported herein.The 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 investigated.The 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 100.The data suggests that the LSTIS is promising to competitively enrich Li^(+) from saline solutions.

Structure and stability of Li-Mn-Ni composite oxides as lithium ion sieve precursors in acidic medium

A series of spinel Li-Mn-Ni composite oxides with theoretical chemical formula of LiNixMn2-xO4 （0〈_x〈_1.0） were synthesized by liquid phase method. Their structure and morphology were characterized by X-ray diffractometry （XRD） and scanning electron microscopy （SEM）, respectively. The stability of these Ni-substituted spinel oxides prepared at different temperatures was investigated in acidic medium as well. The results show that Ni can be brought into the spinel framework completely to form well-crystallized product when x〈_0.5 and the optimized synthesis temperature is 800℃. LiNi0.4Mn1.6O4 prepared at 800℃ can maintain the spinel structure and morphology with Li extraction ratio of 30.37%, Mn extraction ratio of 8.78% and Ni extraction ratio of 1,82% during acid treatment. The incorporated Ni not only inhibits the dissolution of Mn, but also reduces the extraction of Li due to the lattice contraction

Zr-doped titanium lithium ion sieve and EP-granulated composite:Superb adsorption and recycling performance

Lithium ion sieve(LIS)has attracted great attention due to its high adsorption selectivity towards Li+.Herein,a new type of Zr-doped Ti-LIS(HZrTO)was synthesized by a simple calcination method.The adsorption capacity increased from 56.3 mgg-1(before doping)to 93.2 mgg-1 after doping in LiOH solution(lithium 1.8gL-1).The adsorption isotherm and adsorption kinetics of HZrTO accord with the Langmuir isotherm and the pseudo-second-order kinetic equation,respectively.Batch experiments showed that HZrTO has good stability and selectivity.In addition,HZrTO was granulated via epoxy resin(E-12),and the obtained granular adsorbent showed good adsorption capacity,excellent stability and high selectivity towards Li+.

An ultrathin and crack-free metal-organic framework film for effective polysulfide inhibition in lithium-sulfur batteries

Due to their extensive microporous structure,metal-organic frameworks(MOFs)find widespread application in constructing modification layers,functioning as ion sieves.However,the modification layers prepared by existing methods feature gaps between MOFs that are noticeably larger than the inherent MOF pore dimensions.Polysulfides and lithium ions unavoidably permeate through these gaps,hindering the full exploitation of the structural advantages.Herein,an ultrathin(20 nm)and crack-free MOF film is formed on the separator by atomic layer deposition for the first time.Based on the separator,the mechanism of different MOF layers has been verified by phase field simulation and in situ Raman spectroscopy.The results accurately prove that the MOF particle layer can relieve the shuttle of polysulfides,but it does not have the effect of homogenizing lithium ions.Only the ultrathin and crack-free MOF film with proper pore size can act as the ion sieve for both polysulfides and lithium ions.As a result,under the test condition of 2mA cm^(-2)-2 mAh cm^(-2),the overpotential of the Li/Li symmetric battery is only 18 mV after 2500 h.The capacity retention rate of the lithium-sulfur battery is 95.6% after 500 cycles and 80% after 1000 cycles at 2 C.

Recovery of lithium using H_(4)Mn_(3.5)Ti_(1.5)O_(12)/reduced graphene oxide/polyacrylamide composite hydrogel from brine by Ads-ESIX process

Powdery Li^(+)-imprinted manganese oxides adsorbent was widely used to the recovery of Li^(+),but there are some difficulties,such as poor stability in acid solution,inconvenience of operation and separation.In this work,a useful hydrogel composite based H_(4)Mn_(3.5)Ti_(1.5)O_(12)/reduced graphene oxide/polyacrylamide(HMTO-rGO/PAM)was fabricated by thermal initiation method with promising stable,conductive and selective properties.The resulting materials were characterized by field emission scanning electron microscope,infrared absorption spectrum,X-ray diffraction,X-ray photoelectron spectroscopy and electrochemical techniques.The recovery of Li^(+)was investigated using HMTO-rGO/PAM from brine by a separated two-stage sorption statically and electrically switched ion exchange desorption process.The adsorption capacity of 51.5 mg·g^(-1)could be achieved with an initial Li^(+)concentration of 200 mg·L^(-1)in pH 10,at 45℃ for 12 h.Li^(+)ions could be quickly desorbed by cyclic voltammetry(CV)in pH 3,0.1 mol·L^(-1)HCl/NH;Cl accompanying the exchange of Li^(+)and H+(NH;)and the transfer of LMTO-rGO/PAM to HMTO-rGO/PAM.

Ion sieving in graphene oxide membranes via cationic control of interlayer spacing

With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Fang Haiping(方海平)from Shanghai Institute of Applied Physics,Chinese Academy of Sciences,Prof.Wu Minghong(吴明红)from Shanghai Applied Radiation Institute。