Gas-produced water is an accompanying wastewater in the natural gas extraction process,and it is a potential liquid lithium resource that contains a considerable amount of lithium.This study investigated the feasibili...Gas-produced water is an accompanying wastewater in the natural gas extraction process,and it is a potential liquid lithium resource that contains a considerable amount of lithium.This study investigated the feasibility of using manganese-based ion sieves to adsorb and extract lithium from gas-produced water.And we focused on the applicability of two different granulation methods,extrusion and droplet,in gas-produced water systems.Two types of H_(1.33)Mn_(1.67)O_(4) particles were prepared by the extrusion method(EHMO)and the droplet method(DHMO).The porosity of DHMO was much higher than that of EHMO,and the adsorption performance of DHMO increased with the decrease of binder concentration.DHMO prepared with a binder concentration of 0.14 g·ml^(-1)exhibited the best adsorption performance in gas-produced water,and the Li^(+)adsorption capacity could reach 25.14 mg·g^(-1).In gas-produced water,the adsorption equilibrium of DHMO only took 9 h,and the adsorption process conformed to the Langmuir model and pseudo-second-order kinetic model.The pore diffusion model(PDM)could well describe its adsorption process.Besides,DHMO showed a great selectivity to Li^(+),and the selectivity order of DHMO in gas-produced water was Li^(+)>Ba^(2+)>>Mg^(2+),Ca^(2+),Sr^(2+)>>Na^(+)>>K^(+).After 20 cycles,the Li^(+)adsorption capacity was still higher than 17.30 mg·g^(-1),and the rate of manganese dissolution was less than 1%.展开更多
Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibri...Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.展开更多
Constructing heterojunctions and hollow multi-shelled structures can render materials with fascinating physicochemical properties,and have been regarded as two promising strategies to overcome the severe shuttling and...Constructing heterojunctions and hollow multi-shelled structures can render materials with fascinating physicochemical properties,and have been regarded as two promising strategies to overcome the severe shuttling and sluggish kinetics of polysulfide in lithium-sulfur(Li-S)batteries.However,a single strategy can only take limited effect.Modulating catalytic hosts with synergistic effects are urgently desired.Herein,Mn_(3)O_(4)-MnS heterogeneous multi-shelled hollow spheres are meticulously designed by controlled sulfuration of Mn2O3 hollow spheres,and then applied as advanced encapsulation hosts for Li-S batteries.Benefiting from the separated spatial confinement by hollow multi-shelled structure,ample exposed active sites and built-in electric field by heterogeneous interface,and synergistic effects between Mn_(3)O_(4)(strong adsorption)and MnS(fast conversion)components,the assembled battery achieves prominent rate capability and decent cyclability(0.016%decay per cycle at 2 C,1000 cycles).More crucially,satisfactory areal capacity reaches up to 7.1 mAh cm^(-2)even with high sulfur loading(8.0 mg cm^(-2))and lean electrolyte(E/S=4.0 pL mg^(-1))conditions.This work will provide inspiration for the rational design of hollow multi-shelled heterostructure for various electrocatalysis applications.展开更多
The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its...The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its practical application is hindered by the lack of a compatible electrolyte.Herein,a spray pyrolysis-based energy-saving synthesis method as well as a diluted low concentration electrolyte(0.5 M LiPF_(6) in a mixture of fluoroethylene carbonate/dimethyl carbonate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(FEC:DMC:TTE,1:4:5 by volume))are proposed to address these challenges.Owing to the unique features of the precursor prepared by spray pyrolysis,well-crystallized LNMO single-crystal can be obtained within 1 h calcination at 900℃.Besides,the fluorinated interphases derived from the diluted low concentration electrolyte not only mitigate the Mn dissolution and Al corrosion at the cathode side,but also suppresses dendritic Li deposition at the anode side,thus enabling stable cycling of both LNMO and Li metal anode.Thus,30μm Li|LNMO(1.75 m A h cm^(-2))cells achieve a high capacity retention(90.9%)after 168 cycles in the diluted low concentration electrolyte.展开更多
Because of their large volume variation and inferior electrical conductivity,Mn_(3)O_(4)-based oxide anode materials have short cyclic lives and poor rate capability,which obstructs their development.In this study,we ...Because of their large volume variation and inferior electrical conductivity,Mn_(3)O_(4)-based oxide anode materials have short cyclic lives and poor rate capability,which obstructs their development.In this study,we successfully prepared a Mn_(3)O_(4)/N-doped honeycomb carbon composite using a smart and facile synthetic method.The Mn_(3)O_(4)nanopolyhedra are grown on N-doped honeycomb carbon,which evidently mitigates the volume change in the charging and discharging processes but also improves the electrochemical reaction kinetics.More importantly,the Mn-O-C bond in the Mn_(3)O_(4)/N-doped honeycomb carbon composite benefits electrochemical reversibility.These features of the Mn_(3)O_(4)/N-doped honeycomb carbon(NHC)composite are responsible for its superior electrochemical performance.When used for Li-ion batteries,the Mn_(3)O_(4)/N-doped honeycomb carbon anode exhibits a high reversible capacity of 598 mAh·g^(−1)after 350 cycles at 1 A·g^(−1).Even at 2 A·g^(−1),the Mn_(3)O_(4)/NHC anode still delivers a high capacity of 472 mAh·g^(−1).This work provides a new prospect for synthesizing and developing manganese-based oxide materials for energy storage.展开更多
基金supported by National Key R&D Program of China(2021YFC2902603)Shanghai Pujiang Program(2019PJD011)。
文摘Gas-produced water is an accompanying wastewater in the natural gas extraction process,and it is a potential liquid lithium resource that contains a considerable amount of lithium.This study investigated the feasibility of using manganese-based ion sieves to adsorb and extract lithium from gas-produced water.And we focused on the applicability of two different granulation methods,extrusion and droplet,in gas-produced water systems.Two types of H_(1.33)Mn_(1.67)O_(4) particles were prepared by the extrusion method(EHMO)and the droplet method(DHMO).The porosity of DHMO was much higher than that of EHMO,and the adsorption performance of DHMO increased with the decrease of binder concentration.DHMO prepared with a binder concentration of 0.14 g·ml^(-1)exhibited the best adsorption performance in gas-produced water,and the Li^(+)adsorption capacity could reach 25.14 mg·g^(-1).In gas-produced water,the adsorption equilibrium of DHMO only took 9 h,and the adsorption process conformed to the Langmuir model and pseudo-second-order kinetic model.The pore diffusion model(PDM)could well describe its adsorption process.Besides,DHMO showed a great selectivity to Li^(+),and the selectivity order of DHMO in gas-produced water was Li^(+)>Ba^(2+)>>Mg^(2+),Ca^(2+),Sr^(2+)>>Na^(+)>>K^(+).After 20 cycles,the Li^(+)adsorption capacity was still higher than 17.30 mg·g^(-1),and the rate of manganese dissolution was less than 1%.
基金financially supported by the National Natural Science Foundation of China(No.51904250)the China Postdoctoral Science Foundation(No.2021M692254)+2 种基金the Sichuan Science and Technology Program(No.2022YFG0098)the Fundamental Research Funds for the Central Universities(Nos.2021CDSN-02,2022SCU12002,2022CDZG-17,2022CDSN-08,2022CDZG-9)the Hohhot Science and Technology Program(No.2023-Jie Bang Gua Shuai-Gao-3)。
文摘Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.
基金The support from the National Natural Science Foundation of China(No.51971083)the Natural Science Foundation of Heilongjiang Province,China(YQ 2020E007)is gratefully acknowledgedfinancially sponsored by Heilongjiang Touyan Team Program.
文摘Constructing heterojunctions and hollow multi-shelled structures can render materials with fascinating physicochemical properties,and have been regarded as two promising strategies to overcome the severe shuttling and sluggish kinetics of polysulfide in lithium-sulfur(Li-S)batteries.However,a single strategy can only take limited effect.Modulating catalytic hosts with synergistic effects are urgently desired.Herein,Mn_(3)O_(4)-MnS heterogeneous multi-shelled hollow spheres are meticulously designed by controlled sulfuration of Mn2O3 hollow spheres,and then applied as advanced encapsulation hosts for Li-S batteries.Benefiting from the separated spatial confinement by hollow multi-shelled structure,ample exposed active sites and built-in electric field by heterogeneous interface,and synergistic effects between Mn_(3)O_(4)(strong adsorption)and MnS(fast conversion)components,the assembled battery achieves prominent rate capability and decent cyclability(0.016%decay per cycle at 2 C,1000 cycles).More crucially,satisfactory areal capacity reaches up to 7.1 mAh cm^(-2)even with high sulfur loading(8.0 mg cm^(-2))and lean electrolyte(E/S=4.0 pL mg^(-1))conditions.This work will provide inspiration for the rational design of hollow multi-shelled heterostructure for various electrocatalysis applications.
基金supported by the Fund of University of South China (No.201RGC013 and N0.200XQD052)。
文摘The Co-free Li Ni_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising cathode for lithium-ion batteries owing to its high operating voltage and low costs.However,the synthesis of LNMO is generally time and energy consuming,and its practical application is hindered by the lack of a compatible electrolyte.Herein,a spray pyrolysis-based energy-saving synthesis method as well as a diluted low concentration electrolyte(0.5 M LiPF_(6) in a mixture of fluoroethylene carbonate/dimethyl carbonate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(FEC:DMC:TTE,1:4:5 by volume))are proposed to address these challenges.Owing to the unique features of the precursor prepared by spray pyrolysis,well-crystallized LNMO single-crystal can be obtained within 1 h calcination at 900℃.Besides,the fluorinated interphases derived from the diluted low concentration electrolyte not only mitigate the Mn dissolution and Al corrosion at the cathode side,but also suppresses dendritic Li deposition at the anode side,thus enabling stable cycling of both LNMO and Li metal anode.Thus,30μm Li|LNMO(1.75 m A h cm^(-2))cells achieve a high capacity retention(90.9%)after 168 cycles in the diluted low concentration electrolyte.
基金financially supported by the Natural Science Foundation of Henan Province of China(No.222300420252)Nanyang Normal University(Nos.2020ZX013 and 2020ZX014).
文摘Because of their large volume variation and inferior electrical conductivity,Mn_(3)O_(4)-based oxide anode materials have short cyclic lives and poor rate capability,which obstructs their development.In this study,we successfully prepared a Mn_(3)O_(4)/N-doped honeycomb carbon composite using a smart and facile synthetic method.The Mn_(3)O_(4)nanopolyhedra are grown on N-doped honeycomb carbon,which evidently mitigates the volume change in the charging and discharging processes but also improves the electrochemical reaction kinetics.More importantly,the Mn-O-C bond in the Mn_(3)O_(4)/N-doped honeycomb carbon composite benefits electrochemical reversibility.These features of the Mn_(3)O_(4)/N-doped honeycomb carbon(NHC)composite are responsible for its superior electrochemical performance.When used for Li-ion batteries,the Mn_(3)O_(4)/N-doped honeycomb carbon anode exhibits a high reversible capacity of 598 mAh·g^(−1)after 350 cycles at 1 A·g^(−1).Even at 2 A·g^(−1),the Mn_(3)O_(4)/NHC anode still delivers a high capacity of 472 mAh·g^(−1).This work provides a new prospect for synthesizing and developing manganese-based oxide materials for energy storage.
