The shuttle effect is among the most characteristic and formidable challenges in the pursuit of high-performance lithium-sulfur(Li-S)batteries.Herein,phosphorylated cellulose nanofibers(pCNF)are intentionally engineer...The shuttle effect is among the most characteristic and formidable challenges in the pursuit of high-performance lithium-sulfur(Li-S)batteries.Herein,phosphorylated cellulose nanofibers(pCNF)are intentionally engineered to establish an ion-sieving barrier against polysulfide shuttling and thereby improve battery performance.The phosphorylation,involving the grafting of phosphate groups onto the cellulose backbone,imparts an exceptional electronegativity that repels the polysulfide anions from penetrating through the separator.Moreover,the electrolyte wettability and Li^(+)transfer can be significantly promoted by the polar nature of pCNF and the facile Li^(+)disassociation.As such,rational ion management is realized,contributing to enhanced reversibility in both sulfur and lithium electrochemistry.As a result,Li-S cells equipped with the self-standing pCNF separator demonstrate outstanding long-term cyclability with a minimum fading rate of 0.013%per cycle over 1000 cycles at 1 C,and a decent areal capacity of 5.37 mA h cm^(-2) even under elevated sulfur loading of 5.0 mg cm^(-2) and limited electrolyte of 6.0 mL g^(-1).This work provides a facile and effective pathway toward the well-tamed shuttle effect and highly durable Li-S batteries.展开更多
In light of the burgeoning energy technology sector and the ever-growing demand for lithium across diverse industrial domains,conventional lithium extraction methods have been proven inadequate due to their limited pr...In light of the burgeoning energy technology sector and the ever-growing demand for lithium across diverse industrial domains,conventional lithium extraction methods have been proven inadequate due to their limited production capacity and high operational costs.This work introduces a novel approach to the manganese-titanium based composite HMTO(Mn:Ti=1:4)lithium ion-sieve(LIS)nanospheres,employing lithium acetate dihydrate,manganese carbonate and titanium dioxide P25 as the primary materials.These nanospheres exhibit relatively uniform spherical morphology,narrow size distribution,small average particle size(ca.55 nm),large specific surface area(43.58 m^(2)g^(-1))and high surface O_(2)-content(59.01%).When utilized as the adsorbents for Li^(+)ions,the HMTO(Mn:Ti=1:4)LIS demonstrates a fast adsorption rate,approaching equilibrium within 6.0 h with an equilibrium adsorption capacity(qe)of 79.5 mg g^(-1)and a maximum adsorption capacity(qm)of 87.26 mg g^(-1)(initial concentration CO:1.8 g L^(-1)).In addition,the HMTO(Mn:Ti=1:4)also delivers a high lithium extraction from the simulated high magnesium-lithium molar ratio salt lake brine(Mg:Li=103),achieving a qeof 33.85 mg g^(-1)along with a remarkable selectivity(α_(Mg)^(Li)=2192.76).Particularly,the HMTO(Mn:Ti=1:4)LIS showcases a satisfactory recycling adsorption performance.The adsorption capacity remains at a high level,even that determined after the 5th cycle(55.45 mg g^(-1))surpasses that of the most recently reported adsorbents.Ultimately,the fantastic synergistic lithium adsorption mechanism is deliberately uncovered by leveraging the ion exchange principles and molecular dynamics(MD)simulations.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
Supercapacitor has been widely known as a representative electrochemical energy storage device with high power density and long lifespan.Recently,with the deeper understanding of its charge storage mechanism,unidirect...Supercapacitor has been widely known as a representative electrochemical energy storage device with high power density and long lifespan.Recently,with the deeper understanding of its charge storage mechanism,unidirectional-charging supercapacitor,also called supercapacitor diode(CAPode),is successfully developed based on the ion-sieving effect of its working electrode towards electrolyte ions.Because CAPode integrates mobile ion and mobile electron in one hybrid circuit,it has a great potential in the emerging fields of ion/electron coupling logic operations,human–machine interface,neural network interaction,and in vivo diagnosis and treatment.Accordingly,we herein elucidate the working mechanism and design philosophy of CAPode,and summarize the electrode materials that are suitable for constructing CAPode.Meanwhile,some other supercapacitor-based devices beyond CAPode are also introduced,and their potential applications are instructively presented.Finally,we outline the challenges and chances of CAPode-related techniques.展开更多
Abstract Lithium λ-MnO2 ion-sieves were prepared from spinel LiMn2O4 via treatment with nitric acid. The LiMn2O4 was synthesized by a solid state reaction between LiOH· H2O and MnO2. The effects of the calcinati...Abstract Lithium λ-MnO2 ion-sieves were prepared from spinel LiMn2O4 via treatment with nitric acid. The LiMn2O4 was synthesized by a solid state reaction between LiOH· H2O and MnO2. The effects of the calcination time and temperature on the preparation of the LiMn2O4 precursor and the lithium ion-sieve were investigated. In addition, the Li^＋ extraction ratio, the Mn^2＋ dissolving ratio and the adsorption properties of the lithium ion-sieve were all measured. The lithium ion-sieve had a high exchange capacity and was selective for Li^＋. Specifically, at pH = 13, the ion exchange capacity of Li^＋ was 30.9mg/g in 10 mmol/L LiCl solution and the lithium extraction ratio and manganese dissolving ratio were 95% and 25%, respec- tively.展开更多
Lithium is one of the most important light metals,which is widely used as raw materials for large-capacity rechargeable batteries,light aircraft alloys and nuclear fusion fuel.Seawater,which contains 250 billion tons ...Lithium is one of the most important light metals,which is widely used as raw materials for large-capacity rechargeable batteries,light aircraft alloys and nuclear fusion fuel.Seawater,which contains 250 billion tons of lithium in total,has thus recently been noticed as a possible resource of lithium.While,since the aver-age concentration of lithium in seawater is quite low(0.17 mg$L–1),enriching it to an adequate high density becomes the primary step for industrial applications.The adsorption method is the most prospective technology for increasing the concentration of lithium in liquid.Among the adsorbents for lithium,the ion-sieve is a kind of special absorbent which has high selectivity for Li+,especially the spinel manganese oxides(SMO),which among the series of ion-sieves,has become the most promising adsorption material for lithium.In this study,the SMO ion-sieve was prepared by a coprecipitation method.The preparation conditions were discussed and the sample characters were analyzed.Recovery of Li+from seawater were studied in batch experiments using prepared ion-sieve,and the effect of solution pH and the uptake rates were also investigated in different Li+solutions.展开更多
Driven by the increasing global demand for lithium,significant attention has been directed toward developing efficient technologies for lithium extraction from Salt Lake brines.Li_(1.6)Mn_(1.6)O_(4) spinel shows high ...Driven by the increasing global demand for lithium,significant attention has been directed toward developing efficient technologies for lithium extraction from Salt Lake brines.Li_(1.6)Mn_(1.6)O_(4) spinel shows high lithium selectivity and notable theoretical uptake capacity,indicating strong application potential in lithium extraction.However,the industrial application of this material is limited by its strong Jahn-Teller effect and manganese dissolution loss.In this study,LiOH and MnCO3 were selected as the raw materials and La_(2)O_(3) was used as the doping modifier.The La^(3+)-doped Li1.6Mn1.6O4 precursor(La-LMO)was fabricated through hydrothermal and high-temperature solid-phase synthesis techniques.Then La^(3+)doped H1.6Mn1.6O4 lithium ion-sieve(La-HMO)was prepared by pickling.The materials'structure and morphology were examined using XRD,SEM,TEM,and XPS techniques.La^(3+)doping does not alter the spinel structure of LMO but reduces Mn^(3+)content,mitigates the Jahn-Teller effect,lowers the manganese dissolution rate,and enhances structural stability.Adsorption of Li+onto La-HMO follows pseudo-second-order kinetics and fits the Langmuir model,suggesting homogeneous monolayer adsorption driven by chemisorption.In the lithium extraction experiment from the brine of West Tai Kinel Salt Lake,La-HMO demonstrated high adsorption capacity and superior selectivity for Li^(+).After five cycles,La-HMO maintained an adsorption capacity of 33.10 mg/g,higher than the 26.80 mg/g for undoped HMO.The manganese dissolution rate dropped from 4.65%to 4.04%.The study significantly improved the adsorption properties and structural stability of HMO by doping La^(3+),which has broad application prospects in the separation and extraction of lithium resources in Salt Lake.展开更多
基金the financial support from the National Natural Science Foundation of China(22109072)the Natural Science Foundation of Jiangsu Province(BK20210349)+1 种基金the Fundamental Research Funds for the Central Universities(30922010304)the Open Fund of National Forestry and Grassland Administration Key Laboratory of Plant Fiber Functional Materials(2022KFJJ06)。
文摘The shuttle effect is among the most characteristic and formidable challenges in the pursuit of high-performance lithium-sulfur(Li-S)batteries.Herein,phosphorylated cellulose nanofibers(pCNF)are intentionally engineered to establish an ion-sieving barrier against polysulfide shuttling and thereby improve battery performance.The phosphorylation,involving the grafting of phosphate groups onto the cellulose backbone,imparts an exceptional electronegativity that repels the polysulfide anions from penetrating through the separator.Moreover,the electrolyte wettability and Li^(+)transfer can be significantly promoted by the polar nature of pCNF and the facile Li^(+)disassociation.As such,rational ion management is realized,contributing to enhanced reversibility in both sulfur and lithium electrochemistry.As a result,Li-S cells equipped with the self-standing pCNF separator demonstrate outstanding long-term cyclability with a minimum fading rate of 0.013%per cycle over 1000 cycles at 1 C,and a decent areal capacity of 5.37 mA h cm^(-2) even under elevated sulfur loading of 5.0 mg cm^(-2) and limited electrolyte of 6.0 mL g^(-1).This work provides a facile and effective pathway toward the well-tamed shuttle effect and highly durable Li-S batteries.
基金supported by the National Natural Science Foundation of China(22075304,22378390)Natural Science Foundation of Shandong Province,China(ZR2022MB075)+2 种基金State Key Laboratory of Organic-Inorganic Composites(oic-202401016)State Key Laboratory of Chemical Engineering(SKL-ChE-24A02)Beijing Natural Science Foundation,China(3222050).
文摘In light of the burgeoning energy technology sector and the ever-growing demand for lithium across diverse industrial domains,conventional lithium extraction methods have been proven inadequate due to their limited production capacity and high operational costs.This work introduces a novel approach to the manganese-titanium based composite HMTO(Mn:Ti=1:4)lithium ion-sieve(LIS)nanospheres,employing lithium acetate dihydrate,manganese carbonate and titanium dioxide P25 as the primary materials.These nanospheres exhibit relatively uniform spherical morphology,narrow size distribution,small average particle size(ca.55 nm),large specific surface area(43.58 m^(2)g^(-1))and high surface O_(2)-content(59.01%).When utilized as the adsorbents for Li^(+)ions,the HMTO(Mn:Ti=1:4)LIS demonstrates a fast adsorption rate,approaching equilibrium within 6.0 h with an equilibrium adsorption capacity(qe)of 79.5 mg g^(-1)and a maximum adsorption capacity(qm)of 87.26 mg g^(-1)(initial concentration CO:1.8 g L^(-1)).In addition,the HMTO(Mn:Ti=1:4)also delivers a high lithium extraction from the simulated high magnesium-lithium molar ratio salt lake brine(Mg:Li=103),achieving a qeof 33.85 mg g^(-1)along with a remarkable selectivity(α_(Mg)^(Li)=2192.76).Particularly,the HMTO(Mn:Ti=1:4)LIS showcases a satisfactory recycling adsorption performance.The adsorption capacity remains at a high level,even that determined after the 5th cycle(55.45 mg g^(-1))surpasses that of the most recently reported adsorbents.Ultimately,the fantastic synergistic lithium adsorption mechanism is deliberately uncovered by leveraging the ion exchange principles and molecular dynamics(MD)simulations.
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.
基金We acknowledge the financial support from the China Postdoctoral Science Foundation(Grant Nos.BX20220139 and 2021M701530)the National Natural Science Foundation of China(Grant No.61874166)+1 种基金the Fundamental Research Funds for the Central Universities(Grant No.lzujbky-2021-sp50)the Science and Technology Program of Qinghai Province(Grant No.2022-ZJ-703).
文摘Supercapacitor has been widely known as a representative electrochemical energy storage device with high power density and long lifespan.Recently,with the deeper understanding of its charge storage mechanism,unidirectional-charging supercapacitor,also called supercapacitor diode(CAPode),is successfully developed based on the ion-sieving effect of its working electrode towards electrolyte ions.Because CAPode integrates mobile ion and mobile electron in one hybrid circuit,it has a great potential in the emerging fields of ion/electron coupling logic operations,human–machine interface,neural network interaction,and in vivo diagnosis and treatment.Accordingly,we herein elucidate the working mechanism and design philosophy of CAPode,and summarize the electrode materials that are suitable for constructing CAPode.Meanwhile,some other supercapacitor-based devices beyond CAPode are also introduced,and their potential applications are instructively presented.Finally,we outline the challenges and chances of CAPode-related techniques.
文摘Abstract Lithium λ-MnO2 ion-sieves were prepared from spinel LiMn2O4 via treatment with nitric acid. The LiMn2O4 was synthesized by a solid state reaction between LiOH· H2O and MnO2. The effects of the calcination time and temperature on the preparation of the LiMn2O4 precursor and the lithium ion-sieve were investigated. In addition, the Li^＋ extraction ratio, the Mn^2＋ dissolving ratio and the adsorption properties of the lithium ion-sieve were all measured. The lithium ion-sieve had a high exchange capacity and was selective for Li^＋. Specifically, at pH = 13, the ion exchange capacity of Li^＋ was 30.9mg/g in 10 mmol/L LiCl solution and the lithium extraction ratio and manganese dissolving ratio were 95% and 25%, respec- tively.
文摘Lithium is one of the most important light metals,which is widely used as raw materials for large-capacity rechargeable batteries,light aircraft alloys and nuclear fusion fuel.Seawater,which contains 250 billion tons of lithium in total,has thus recently been noticed as a possible resource of lithium.While,since the aver-age concentration of lithium in seawater is quite low(0.17 mg$L–1),enriching it to an adequate high density becomes the primary step for industrial applications.The adsorption method is the most prospective technology for increasing the concentration of lithium in liquid.Among the adsorbents for lithium,the ion-sieve is a kind of special absorbent which has high selectivity for Li+,especially the spinel manganese oxides(SMO),which among the series of ion-sieves,has become the most promising adsorption material for lithium.In this study,the SMO ion-sieve was prepared by a coprecipitation method.The preparation conditions were discussed and the sample characters were analyzed.Recovery of Li+from seawater were studied in batch experiments using prepared ion-sieve,and the effect of solution pH and the uptake rates were also investigated in different Li+solutions.
基金We thank National Natural Science Foundation of China(grant No.22465030)the Programs of Science and Technology of Qinghai Province(grant No.2023-HZ-811)Kunlun Talents Leading Technological Talent in Qinghai Province.
文摘Driven by the increasing global demand for lithium,significant attention has been directed toward developing efficient technologies for lithium extraction from Salt Lake brines.Li_(1.6)Mn_(1.6)O_(4) spinel shows high lithium selectivity and notable theoretical uptake capacity,indicating strong application potential in lithium extraction.However,the industrial application of this material is limited by its strong Jahn-Teller effect and manganese dissolution loss.In this study,LiOH and MnCO3 were selected as the raw materials and La_(2)O_(3) was used as the doping modifier.The La^(3+)-doped Li1.6Mn1.6O4 precursor(La-LMO)was fabricated through hydrothermal and high-temperature solid-phase synthesis techniques.Then La^(3+)doped H1.6Mn1.6O4 lithium ion-sieve(La-HMO)was prepared by pickling.The materials'structure and morphology were examined using XRD,SEM,TEM,and XPS techniques.La^(3+)doping does not alter the spinel structure of LMO but reduces Mn^(3+)content,mitigates the Jahn-Teller effect,lowers the manganese dissolution rate,and enhances structural stability.Adsorption of Li+onto La-HMO follows pseudo-second-order kinetics and fits the Langmuir model,suggesting homogeneous monolayer adsorption driven by chemisorption.In the lithium extraction experiment from the brine of West Tai Kinel Salt Lake,La-HMO demonstrated high adsorption capacity and superior selectivity for Li^(+).After five cycles,La-HMO maintained an adsorption capacity of 33.10 mg/g,higher than the 26.80 mg/g for undoped HMO.The manganese dissolution rate dropped from 4.65%to 4.04%.The study significantly improved the adsorption properties and structural stability of HMO by doping La^(3+),which has broad application prospects in the separation and extraction of lithium resources in Salt Lake.
