Aqueous sodium-ion batteries are known for poor rechargeability because of the competitive water decomposition reactions and the high electrode solubility.Improvements have been reported by saltconcentrated and organi...Aqueous sodium-ion batteries are known for poor rechargeability because of the competitive water decomposition reactions and the high electrode solubility.Improvements have been reported by saltconcentrated and organic-hybridized electrolyte designs,however,at the expense of cost and safety.Here,we report the prolonged cycling of ASIBs in routine dilute electrolytes by employing artificial electrode coatings consisting of NaX zeolite and NaOH-neutralized perfluorinated sulfonic polymer.The as-formed composite interphase exhibits a molecularsieving effect jointly played by zeolite channels and size-shrunken ionic domains in the polymer matrix,which enables high rejection of hydrated Na^(+)ions while allowing fast dehydrated Na^(+)permeance.Applying this coating to electrode surfaces expands the electrochemical window of a practically feasible 2 mol kg^(-1) sodium trifluoromethanesulfonate aqueous electrolyte to 2.70 V and affords Na_(2)MnFe(CN)_(6)//NaTi_(2)(PO_(4))_(3) full cells with an unprecedented cycling stability of 94.9%capacity retention after 200 cycles at 1 C.Combined with emerging electrolyte modifications,this molecular-sieving interphase brings amplified benefits in long-term operation of ASIBs.展开更多
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,a...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.展开更多
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-A...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.展开更多
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 diffractom...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 °C. LiNi0.4Mn1.6O4 prepared at 800 °C 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.展开更多
MnO 2 was prepared by column method from normal spinel LiMn 2O 4 with purity of 99.38%.The influence of LiMn 2O 4 grain size and acidity of leaching solution on the lithium leaching process was studied.The result...MnO 2 was prepared by column method from normal spinel LiMn 2O 4 with purity of 99.38%.The influence of LiMn 2O 4 grain size and acidity of leaching solution on the lithium leaching process was studied.The results show that the appropriate range of LiMn 2O 4 grain size was 60-160 meshes and the concentration of leaching solution HCl was 0.1 mol·L -1.The adsorption capacity Q of λ-MnO 2 for lithium increased with the increase of pH and changed markedly at pH 6.0-10.0.It was 3.80mmol/g at pH 12.0.The distribution coefficients K d of Li + and Na + were 3.406×10 4 and 2.300 respectively,and the separation coefficient α Li Na was 1.481×10 4 at pH 6.5.As a result,λ-MnO 2 is a high performance ion-sieve material for lithium ion.展开更多
The exchange performances and the distribution coefficient of Cesium Ion-Sieve (Cs-IS) for cesium and for some rare earth elements were compared. In particula r, the effects of neodymium on the cesium ion exchange an...The exchange performances and the distribution coefficient of Cesium Ion-Sieve (Cs-IS) for cesium and for some rare earth elements were compared. In particula r, the effects of neodymium on the cesium ion exchange and the Cs+ selectivity v ariation on Cs-IS owing to introduction of rare earth elements into HLLW were s tudied. Though rare earth elements exhibit a small influence on the distributio n coefficient for Cs+, they impair Cs-exchange capacity of Cs-IS to some ext ent. This interruption on the selectivity to Cs+ can be significantly eliminat ed provided an appropriate ratio of liquid to solid V:m is used.展开更多
Ion conductive membranes(ICMs)with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices.However,it is extremely challenging to construct fast proton-selecti...Ion conductive membranes(ICMs)with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices.However,it is extremely challenging to construct fast proton-selective transport channels in ICMs.Herein,a membrane with highly conductive proton selectivity was fabricated by incorporating porous carbon sieving nanospheres with a hollow structure(HCSNs)in a polymer matrix.Due to the precise ion sieving ability of the microporous carbon shells and the fast proton transport through their accessible internal cavities,this advanced membrane presented a proton conductivity(0.084 S·cm^(-1))superior to those of a commercial Nation 212(N212)membrane(0.033S·cm^(-1))and a pure polymer membrane(0.049 S·cm^(-1)).The corresponding proton selectivity of the membrane(6.68×10^(5) S·min·cm^(-3))was found to be enhanced by about 5.9-fold and 4.3-fold,respectively,compared with those of the N212 membrane(1.13×10^(5) S·min·cm^(-3))and the pure membrane(1.56×10^(5) S·min·cm^(-3)).Low-field nuclear magnetic resonance(LF-NMR)clearly revealed the fast protonselective transport channels enabled by the HCSNs in the polymeric membrane.The proposed membrane exhibited an outstanding energy efficiency(EE)of 84%and long-term stability over 1400 cycles with a0.065%capacity decay per cycle at 120 mA·cm^(-2) in a typical vanadium flow battery(VFB)system.展开更多
基金supported by the National Key R&D Program of China(Grant No.2022YFB2402604)the National Natural Science Foundation of China(21975271,22209194)+3 种基金Shandong Natural Science Foundation(ZR2020ZD07,ZR2023YQ010 and ZR2021QB106)the Taishan Scholars of Shandong Province(No.ts201511063,tsqn202211277)the Shandong Energy Institute(SEI I202127)Qingdao New Energy Shandong Laboratory(QIBEBT/SEI/QNESLS202304).
文摘Aqueous sodium-ion batteries are known for poor rechargeability because of the competitive water decomposition reactions and the high electrode solubility.Improvements have been reported by saltconcentrated and organic-hybridized electrolyte designs,however,at the expense of cost and safety.Here,we report the prolonged cycling of ASIBs in routine dilute electrolytes by employing artificial electrode coatings consisting of NaX zeolite and NaOH-neutralized perfluorinated sulfonic polymer.The as-formed composite interphase exhibits a molecularsieving effect jointly played by zeolite channels and size-shrunken ionic domains in the polymer matrix,which enables high rejection of hydrated Na^(+)ions while allowing fast dehydrated Na^(+)permeance.Applying this coating to electrode surfaces expands the electrochemical window of a practically feasible 2 mol kg^(-1) sodium trifluoromethanesulfonate aqueous electrolyte to 2.70 V and affords Na_(2)MnFe(CN)_(6)//NaTi_(2)(PO_(4))_(3) full cells with an unprecedented cycling stability of 94.9%capacity retention after 200 cycles at 1 C.Combined with emerging electrolyte modifications,this molecular-sieving interphase brings amplified benefits in long-term operation of ASIBs.
基金financially supported by the Prospective Joint Research Project of Industry,University and Research in Jiangsu Province(BY2016005-11)National Science and Technology Support Plan(No.2013BAE111B03)。
文摘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.
基金This work was financially supported by National Key Research and Development Program(2018YFE0203502),ChinaPrimary Research and Development Plan ofJiangsu Province(BE2019117),China and National Students'Platform for Innovation and Entrepreneurship Training(201910291051Z),China.
文摘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.
基金Project(2008BAB35B04) supported by the National Key Technology R&D Program of ChinaProject(CX2010B111) supported by the Innovation Program of Doctoral Research of Hunan Province, ChinaProject(2010QZZD003) supported by Advanced Research Program of Central South University, China
文摘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 °C. LiNi0.4Mn1.6O4 prepared at 800 °C 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.
基金theNationalNaturalScienceFoundationofChi na (No .5 9972 0 2 7)theNaturalScienceFoundationofHubeiProvince (No .2 0 0 2AB0 74) )
文摘MnO 2 was prepared by column method from normal spinel LiMn 2O 4 with purity of 99.38%.The influence of LiMn 2O 4 grain size and acidity of leaching solution on the lithium leaching process was studied.The results show that the appropriate range of LiMn 2O 4 grain size was 60-160 meshes and the concentration of leaching solution HCl was 0.1 mol·L -1.The adsorption capacity Q of λ-MnO 2 for lithium increased with the increase of pH and changed markedly at pH 6.0-10.0.It was 3.80mmol/g at pH 12.0.The distribution coefficients K d of Li + and Na + were 3.406×10 4 and 2.300 respectively,and the separation coefficient α Li Na was 1.481×10 4 at pH 6.5.As a result,λ-MnO 2 is a high performance ion-sieve material for lithium ion.
文摘The exchange performances and the distribution coefficient of Cesium Ion-Sieve (Cs-IS) for cesium and for some rare earth elements were compared. In particula r, the effects of neodymium on the cesium ion exchange and the Cs+ selectivity v ariation on Cs-IS owing to introduction of rare earth elements into HLLW were s tudied. Though rare earth elements exhibit a small influence on the distributio n coefficient for Cs+, they impair Cs-exchange capacity of Cs-IS to some ext ent. This interruption on the selectivity to Cs+ can be significantly eliminat ed provided an appropriate ratio of liquid to solid V:m is used.
基金the support from the National Key Research and Development Program of China(2021YFB3801301)the National Natural Science Foundation of China(22075076,21908098,and 21908054)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Ion conductive membranes(ICMs)with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices.However,it is extremely challenging to construct fast proton-selective transport channels in ICMs.Herein,a membrane with highly conductive proton selectivity was fabricated by incorporating porous carbon sieving nanospheres with a hollow structure(HCSNs)in a polymer matrix.Due to the precise ion sieving ability of the microporous carbon shells and the fast proton transport through their accessible internal cavities,this advanced membrane presented a proton conductivity(0.084 S·cm^(-1))superior to those of a commercial Nation 212(N212)membrane(0.033S·cm^(-1))and a pure polymer membrane(0.049 S·cm^(-1)).The corresponding proton selectivity of the membrane(6.68×10^(5) S·min·cm^(-3))was found to be enhanced by about 5.9-fold and 4.3-fold,respectively,compared with those of the N212 membrane(1.13×10^(5) S·min·cm^(-3))and the pure membrane(1.56×10^(5) S·min·cm^(-3)).Low-field nuclear magnetic resonance(LF-NMR)clearly revealed the fast protonselective transport channels enabled by the HCSNs in the polymeric membrane.The proposed membrane exhibited an outstanding energy efficiency(EE)of 84%and long-term stability over 1400 cycles with a0.065%capacity decay per cycle at 120 mA·cm^(-2) in a typical vanadium flow battery(VFB)system.
