Conductive hydrogel membranes with nanofluids channels represent one of the most promising capacitive electrodes due to their rapid kinetics of ion transport.The construction of these unique structures always requires...Conductive hydrogel membranes with nanofluids channels represent one of the most promising capacitive electrodes due to their rapid kinetics of ion transport.The construction of these unique structures always requires new self-assembly behaviors with different building blocks,intriguing phenomena of colloidal chemistry.In this work,by delicately balancing the electrostatic repulsions between 2D inorganic nanosheets and the electrostatic adsorption with cations,we develop a general strategy to fabricate stable free-standing 1T molybdenum disulphide(MoS_(2))hydrogel membranes with abundant fluidic channels.Given the interpenetrating ionic transport network,the MoS_(2)hydrogel membranes exhibit a highlevel capacitive performance 1.34 F/cm^(2)at an ultrahigh mass loading of 11.2 mg/cm^(2).Furthermore,the interlayer spacing of MoS_(2)in the hydrogel membranes can be controlled with angstrom-scale precision using different cations,which can promote further fundamental studies and potential applications of the transition-metal dichalcogenides hydrogel membranes.展开更多
Despite great advancements in organic mixed ionic-electronic conductors(OMIECs),their applications remain predominantly restricted to three-electrode organic electro-chemical transistors(OECTs),which rely on an additi...Despite great advancements in organic mixed ionic-electronic conductors(OMIECs),their applications remain predominantly restricted to three-electrode organic electro-chemical transistors(OECTs),which rely on an additional electrolyte layer to balance ionic and electronic transport,resulting in indirect coupling of charge carriers.While direct coupling has the potential to greatly simplify device architectures,it remains underexplored in OMIECs due to the inherent imbalance between electronic and ionic conductivities.In this study,we introduce a straightforward approach to achieve balanced OMIECs and employ them as channel materials in two-electrode organic electrochemical memristors.These devices provide clear evidence of direct coupling between electronic and ionic carriers and exhibit exceptional performance in synaptic device applications.Our findings offer new insights into charge carrier transport mechanisms in OMIECs and establish organic electrochemical memristors as a promising new class of organic electronic devices for next-generation neuromorphic applications.展开更多
Lithium-rich antiperovskites are promising solid-state electrolytes for all-solid-state lithium-ion batteries because of their high structural tolerance and good formability.However,the experimentally reported proton-...Lithium-rich antiperovskites are promising solid-state electrolytes for all-solid-state lithium-ion batteries because of their high structural tolerance and good formability.However,the experimentally reported proton-free Li_(3)OCl is plagued by its inferior interfacial compatibility and harsh synthesis conditions.In contrast,Li_(2)OHCl is a thermodynamically favored phases and is easier to achieve than Li_(3)OCl.Due to the proton inside this material,it exhibits interesting lithium diffusion mechanisms.Herein,we present a systematic investigation of the ionic transport,phase stability,and electrochemicalchemical stability of Li_(2)OHCl using first-principles calculations.Our results indicate that Li_(2)OHCl is thermodynamically metastable and is an electronic insulator.The wide electrochemical stability window and high chemical stability of Li_(2)OHCl against various electrodes are confirmed.The charged defects are the dominant conduction mechanism for Li-transport,with a low energy barrier of~0.50 eV.The Li-ion conductivity estimated by ab initio molecular dynamics simulations is about 1.3×10^(-4) S cm^(-1) at room temperature.This work identifies the origin of the high interfacial stability and ionic conductivity of Li_(2)OHCl,which can further lead to the design of such as a cathode coating.Moreover,all computational methods for calculating the properties of Li_(2)OHCl are general and can guide the design of highperformance solid-state electrolytes.展开更多
The water dissociation mechanism on a bipolar membrane under the electrical field was investigated and characterized in terms of ionic transport and limiting current density. It is considered that the depletion layer ...The water dissociation mechanism on a bipolar membrane under the electrical field was investigated and characterized in terms of ionic transport and limiting current density. It is considered that the depletion layer exists at the junction of a bipolar membrane, which is coincided with the viewpoint of the most literatures, but we also consider that the thickness and conductivity of this layer is not only related with the increase of the applied voltage but also with the limiting current density. Below the limiting current density, the thickness of the depletion layer keeps a constant and the conductivity decreases with the increase of the applied voltage; while above the limiting current density, the depletion thickness will increase with the increase of the applied voltage and the conductivity keeps a very low constant. Based on the data reported in the literatures and independent determinations, the limiting current density was calculated and the experimental curves Ⅰ-Ⅴ in the two directions were com展开更多
The ionic transport in sub-nanochannels plays a key role in energy storage,yet suffers from a high energy barrier.Wetting sub-nanochannels is crucial to accelerate ionic transport,but the introduction of water is chal...The ionic transport in sub-nanochannels plays a key role in energy storage,yet suffers from a high energy barrier.Wetting sub-nanochannels is crucial to accelerate ionic transport,but the introduction of water is challenging because of the hydrophobic extreme confinement.We propose wetting the channels by the exothermic hydration process of pre-intercalated ions,the effect of which varies distinctly with different ionic hydration structures and energies.Compared to the failed pre-intercalation of SO_(4)^(2-),HSO_(4)^(-) with weak hydration energy results in a marginal effect on the HOMO(Highest Occupied Molecular Orbital)level of water to avoid water splitting during the electrochemical intercalation.Meanwhile,the ability of water introduction is reserved by the initial incomplete dissociation state of HSO_(4)^(-),so the consequent exothermic reionization and hydration processes of the intercalated HSO_(4)^(-) promote the water introduction into sub-nanochannels,finally forming the stable confined water through hydrogen bonding with functional groups.The wetted channels exhibit a significantly enhanced ionic diffusion coef-ficient by~9.4 times.展开更多
The confined ionic liquid(IL) in solid polymer composite electrolytes(SCPEs) can improve the performance of lithium metal batteries. However, the impact/role and working mechanism of confined IL in SCPEs remain ambigu...The confined ionic liquid(IL) in solid polymer composite electrolytes(SCPEs) can improve the performance of lithium metal batteries. However, the impact/role and working mechanism of confined IL in SCPEs remain ambiguous. Herein, IL was immobilized on SiO_(2)(SiO_(2)@IL-C) and then used to prepare the confined SCPEs together with LiTFSI and PEO to study the impacts of confined-IL on the properties and performance of electrolytes and reveal the Li+transport mechanism. The results show that, compared to the IL-unconfined SCPE, the IL-confined ones exhibit better performance of electrolytes and cells, such as higher ionic conductivity, higher t+Li, and wider electrochemical windows, as well as more stable cycle performance, due to the increased dissociation degree of lithium salt and enlarged polymer amorphousness. The finite-element/molecular-dynamics simulations suggest that the IL confined on the SiO_(2) provided an additional Li+transport pathway(Li+→ SiO_(2)@IL-C) that can accelerate ion transfer and alleviate lithium dendrites, leading to ultrastable stripping/plating cycling over 1900 h for the Li/SCPEs/Li symmetric cells. This study demonstrates that IL-confinement is an effective strategy for the intelligent approach of high-performance lithium metal batteries.展开更多
All-solid-state lithium batteries(ASSLBs)are important for enhancing safety across various applications related to lithium-ion batteries(LIBs).Lithium iron phosphate(LiFePO4)is a widely utilized commercial cathode in ...All-solid-state lithium batteries(ASSLBs)are important for enhancing safety across various applications related to lithium-ion batteries(LIBs).Lithium iron phosphate(LiFePO4)is a widely utilized commercial cathode in LIBs,prized for its stable cycling performance,thermal stability,and low cost.However,low electronic conductivity and slow ion diffusion kinetics limit its application at high rates and low temper-atures.Herein,Ti3C2Tx MXene nanosheets(NSs)are introduced into the LiFePO4 cathode.The continu-ous electron-conducting networks are constructed due to the high electrical conductivity of Ti3C2Tx NSs.Meanwhile,the coordination environment of lithium ions in the cathode is weakened by the oxygenated end groups of Ti3C2Tx NSs,and thus efficient ion-percolating networks are constructed.Therefore,the ionic and electronic conductivities of the modified cathode are significantly improved.Assembled all-solid-state LiFePO4/Li full cells with poly(ethylene oxide)as electrolyte exhibits high initial discharged capacities of 91.5 mAh g^(-1) at 10 C,and capacities of 155.1 mAh g^(-1) after 1000 cycles at 1 C with a re-tention rate of 93.8%.Furthermore,the cells still deliver excellent performance at high loading,room temperature,and low temperature.This work offers a facile and scalable strategy for designing high-performance ASSLBs.展开更多
The high safety of aqueous magnesium ion batteries(AMIBs)contrasts with their limited electrochemical performance.To overcome electrolyte-induced parasitic reactions,it is essential to understand the dynamic evolution...The high safety of aqueous magnesium ion batteries(AMIBs)contrasts with their limited electrochemical performance.To overcome electrolyte-induced parasitic reactions,it is essential to understand the dynamic evolution of concentration-dependent metal ion solvation structures(MISSs).This study systematically reveals the solvation structure evolution of MgCl_(2) aqueous solutions across a full concentration range(0-30 M)and its impact on electrochemical properties using molecular dynamics simulations and density functional theory calculations.Results indicate that six characteristic solvation configurations exist,exhibiting a dynamic,concentration-dependent inter-evolution defined as the solvation structure evolutionary processes(SSEP).The four-phase glass transition mechanism in solvation structure evolution is revealed by analyzing the percentage of each type of solvation structure in different concentrations.The study shows that conductivity is directly related to the dynamic transitions of dominant solvation structures,with a shift in the Mg^(2+) coordination mode—from octahedral through pentahedral intermediates to tetrahedral—revealing a concentration-dependent ion transport mechanism.At low concentrations,free-state stochastic diffusion predominates,reaching a maximum conductivity before transitioning to relay transport within a restricted network at high concentrations.Key contributions include:a general strategy for electrolyte design based on the solvation structure evolution process,which quantitatively correlates structural occupancy with migration properties,and the“Concentration Window”regulation model that balances high conductivity with reduced side reactions.These findings clarify the structural origins of anomalous conductivity in highly concentrated electrolytes and establish a mapping between microstructural evolution and macroscopic performance,providing a theoretical basis for engineering high-security electrolytes of AMIBs.展开更多
It is indicated from a study of transport of rare earth ions through the emulsion liquid mem- brane of bis(2,4,4-trimethylpentyl)phosphinic acid-Span 80-toluene that transporting rare earth ions com- pletely and rapid...It is indicated from a study of transport of rare earth ions through the emulsion liquid mem- brane of bis(2,4,4-trimethylpentyl)phosphinic acid-Span 80-toluene that transporting rare earth ions com- pletely and rapidly was realized under the optimum experimental conditions:1.0×10^(-3)～3.0×10^(-3)mol/L bis(2,4,4-trimethylpentyl)phosphinic acid and 2%～4%(W/V)Span 80 in toluene solution as membrane phase,0.50～2.0 mol/L HCl as inner phase,rare earth ion solutions with pH 3.5～5.0 as outer phase.Ac- cording to the differences of transport behavior for rare earth ions,it is possible to separate rare earth ions from mixed solutions of rare earth ions by this liquid membrane system.展开更多
Soils in part of rice production areas have been seriously contaminated by cadmium （Cd）. Rice with high Cd content over allowable limit produced in these areas is widely concerned. Low accumulation varieties can rem...Soils in part of rice production areas have been seriously contaminated by cadmium （Cd）. Rice with high Cd content over allowable limit produced in these areas is widely concerned. Low accumulation varieties can remarkably decrease the Cd content in rice as well as the risk of food safety. The translocation of Cd either from soil to root system or from roots to aboveground parts is identified by a lot of ion transport proteins. Transport efficiency of Cd in some rice varieties is regulated by special metal ionic transporters. However, most varieties transport Cd by cation transporters or universal ionic transporters. Both the expression levels and time of gens controlling ionic transporters directly influence the Cd transport rates inside rice plant and the accumulation amount in different organs. Screening and utilizing specific Cd transport genes are the genetic basis of breeding low accumulation varieties.展开更多
An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and de signing better electrolyte materials. Ionic conductivity is one of the most important indices of t...An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and de signing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell （to convey ions while isolate electrons）, and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state elec- trolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes.展开更多
In co-ionic conducting solid oxide fuel cell （SOFC）, both oxygen ion （O2） and proton （H＋） can transport through the electrolyte, generating steam in both the an-ode and cathode. Thus the mass transport phenomen...In co-ionic conducting solid oxide fuel cell （SOFC）, both oxygen ion （O2） and proton （H＋） can transport through the electrolyte, generating steam in both the an-ode and cathode. Thus the mass transport phenomenon in the electrodes is quite different from that in conventional SOFC with oxygen ion conducting electrolyte （O-SOFC） or with proton conducting electrolyte （H-SOFC）. The generation of steam in both electrodes also affects the concentration over-potential loss and further the SOFC performance. However, no detailed modeling study on SOFCs with co-ionic electrolyte has been reported yet. In this paper, a new mathematical model for SOFC based on co-ionic electrolyte was developed to predict its actual performance considering three major kinds of overpotentials. Ohm＇s law and the Butler-Volmer formula were used to model the ion conduction and electrochemical reactions, respectively. The dusty gas model （DGM） was employed to simulate the mass transport processes in the porous electrodes. Parametric simulations were performed to investigate the effects of proton transfer number （tH） and current density （jtotal） on the cell performance. It is interesting to find that the co-ionic conducting SOFC could perform better than O-SOFC and H-SOFC by choosing an appropriate proton transfer number. In addition, the co-ionic SOFC shows smaller difference between the anode and cathode concentration overpotentials than O-SOFC and H-SOFC at certain t H values. The results could help material selection for enhancing SOFC performance.展开更多
Progress in the fast charging of high-capacity silicon monoxide(SiO)-based anode is currently hindered by insufficient conductivity and notable volume expansion.The construction of an interface conductive network effe...Progress in the fast charging of high-capacity silicon monoxide(SiO)-based anode is currently hindered by insufficient conductivity and notable volume expansion.The construction of an interface conductive network effectively addresses the aforementioned problems;however,the impact of its quality on lithium-ion transfer and structure durability is yet to be explored.Herein,the influence of an interface conductive network on ionic transport and mechanical stability under fast charging is explored for the first time.2D modeling simulation and Cryo-transmission electron microscopy precisely reveal the mitigation of interface polarization owing to a higher fraction of conductive inorganic species formation in bilayer solid electrolyte interphase is mainly responsible for a linear decrease in ionic diffusion energy barrier.Furthermore,atomic force microscopy and Raman shift exhibit substantial stress dissipation generated by a complete conductive network,which is critical to the linear reduction of electrode residual stress.This study provides insights into the rational design of optimized interface SiO-based anodes with reinforced fast-charging performance.展开更多
Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utiliz...Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode.Herein,a functionalized high-toughness polyimide(PDMI) is synthesized by copolymerizing the 4,4'-Oxydiphthalic anhydride(ODPA) with 4,4'-oxydianiline(ODA),2,3-diaminobenzoic acid(DABA),and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane(DMS).The combination of rigid benzene rings and flexible oxygen groups(-O-) in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness.The plentiful polar carboxyl(-COOH) groups establish robust bonding strength.Rapid ionic transport is achieved by incorporating the flexible siloxane segment(Si-O-Si),which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport(9.8 × 10^(-10) cm^(2) s^(-1) vs.16 × 10^(-10) cm^(2) s~(-1)).As expected,the SiO_x@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85% over 500 cycles at 1.3 A g^(-1).The well-designed functionalized polyimide also significantly enhances the electrochemical properties of Si nanoparticles electrode.Meanwhile,the assembled SiO_x@PDMI-1.5/NCM811 full cell delivers a high retention of 80% after 100 cycles.The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity electrodes for high-energy-density batteries.展开更多
comb-shaped polynier (BM350) with oligo-oxyetliylene side chains of thetype-O (CH_2CH_2O )_7CH_3 was prepared from methyl vinyl ether /maleic anhydridecopolymer- Honiogeneous aniorplious polymer electrolyte cornplexes...comb-shaped polynier (BM350) with oligo-oxyetliylene side chains of thetype-O (CH_2CH_2O )_7CH_3 was prepared from methyl vinyl ether /maleic anhydridecopolymer- Honiogeneous aniorplious polymer electrolyte cornplexes were madefrom the conib polymer and LiCF_3SO_3 by solvent casting from acetone, and theirconductivities were nieasured as a function of temperature and salt concentration.Maxiniuni conductivity close to 5. 08 ×10￣(-5) Scm￣(-1) was obtained at room tempera-tureancl at a [Li]/[EO] ratio of about 0. 12. The conductivity which displayednon-Arrheni us behaviour was analyzed using the Vogel-Tammann-Fulcher equationand interpreted on the basis of the configurational entropy model. The results ofmid-IR sliowed that the coortlination of Li￣+ to side chains made the C-O-C bandbecome broader and shift sliglitly- X-ray photoelectron spectroscopy analysis indi-cated that the oxygen atonis in the two situations could coordinate to Li￣+ and thiscoortlination resulted in the reduction of the electron orbit binding energy of F andS.展开更多
The practical application of the Li metal anode has long been hindered by the uncontrolled growth of Li dendrites,heterogeneous and fragile solid electrolyte interface(SEI)layer,and large volume swelling.Herein,a robu...The practical application of the Li metal anode has long been hindered by the uncontrolled growth of Li dendrites,heterogeneous and fragile solid electrolyte interface(SEI)layer,and large volume swelling.Herein,a robust artificial SEI layer,polyaryoxadiazole lithium sulfonate(PODLi),was successfully fabricated to stabilize the interface between the Li metal and electrolyte.The lithiophilic PODLi film afforded fast ionic transport channels to form a dendrite-free,lithium fluoride-rich anode.The Li@Cu-PODLi symmetric cell achieved excellent cycling performance at a high current density of 10 mA cm^(−2) with an areal capacity of 10 mAh cm^(−2) for more than 770 h.A full cell with the LiFPO_(4) cathode exhibited ultralong-term stable operation over 500 cycles at a high current density of 3.45 mA cm^(−2) with a low-capacity decay rate of 0.038%per cycle.This work demonstrates a cost-effective and scalable strategy for high-energy-density Li metal batteries.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22078214,21905206,and 22065013)Special Fund for Science and Technology Innovation Team of Shanxi Province(No.202204051001009)。
文摘Conductive hydrogel membranes with nanofluids channels represent one of the most promising capacitive electrodes due to their rapid kinetics of ion transport.The construction of these unique structures always requires new self-assembly behaviors with different building blocks,intriguing phenomena of colloidal chemistry.In this work,by delicately balancing the electrostatic repulsions between 2D inorganic nanosheets and the electrostatic adsorption with cations,we develop a general strategy to fabricate stable free-standing 1T molybdenum disulphide(MoS_(2))hydrogel membranes with abundant fluidic channels.Given the interpenetrating ionic transport network,the MoS_(2)hydrogel membranes exhibit a highlevel capacitive performance 1.34 F/cm^(2)at an ultrahigh mass loading of 11.2 mg/cm^(2).Furthermore,the interlayer spacing of MoS_(2)in the hydrogel membranes can be controlled with angstrom-scale precision using different cations,which can promote further fundamental studies and potential applications of the transition-metal dichalcogenides hydrogel membranes.
基金supported by the National Natural Science Foundation of China(4020969,62405044,and 52173156)Fund by Science Research Project of Hebei Education Department(HY2024050011)+1 种基金Natural Science Foundation of Sichuan Province(25NSFSC1287)Foundation of Yanshan University(1050030 and 8190299).
文摘Despite great advancements in organic mixed ionic-electronic conductors(OMIECs),their applications remain predominantly restricted to three-electrode organic electro-chemical transistors(OECTs),which rely on an additional electrolyte layer to balance ionic and electronic transport,resulting in indirect coupling of charge carriers.While direct coupling has the potential to greatly simplify device architectures,it remains underexplored in OMIECs due to the inherent imbalance between electronic and ionic conductivities.In this study,we introduce a straightforward approach to achieve balanced OMIECs and employ them as channel materials in two-electrode organic electrochemical memristors.These devices provide clear evidence of direct coupling between electronic and ionic carriers and exhibit exceptional performance in synaptic device applications.Our findings offer new insights into charge carrier transport mechanisms in OMIECs and establish organic electrochemical memristors as a promising new class of organic electronic devices for next-generation neuromorphic applications.
基金supported by the National Key Research and Development Program of China(Grant No.2018YFB0905400)the National Natural Science Foundation of China(Grant No.12004145)+2 种基金the Science and Technology Research Project of Jiangxi Provincial Department of Education(Grant No.GJJ201030)the PhD Start-up Fund of Natural Science Foundation of Jinggangshan University(Grant No.JZB2013)supported by the Faraday Institution(grant No.FIRG017).
文摘Lithium-rich antiperovskites are promising solid-state electrolytes for all-solid-state lithium-ion batteries because of their high structural tolerance and good formability.However,the experimentally reported proton-free Li_(3)OCl is plagued by its inferior interfacial compatibility and harsh synthesis conditions.In contrast,Li_(2)OHCl is a thermodynamically favored phases and is easier to achieve than Li_(3)OCl.Due to the proton inside this material,it exhibits interesting lithium diffusion mechanisms.Herein,we present a systematic investigation of the ionic transport,phase stability,and electrochemicalchemical stability of Li_(2)OHCl using first-principles calculations.Our results indicate that Li_(2)OHCl is thermodynamically metastable and is an electronic insulator.The wide electrochemical stability window and high chemical stability of Li_(2)OHCl against various electrodes are confirmed.The charged defects are the dominant conduction mechanism for Li-transport,with a low energy barrier of~0.50 eV.The Li-ion conductivity estimated by ab initio molecular dynamics simulations is about 1.3×10^(-4) S cm^(-1) at room temperature.This work identifies the origin of the high interfacial stability and ionic conductivity of Li_(2)OHCl,which can further lead to the design of such as a cathode coating.Moreover,all computational methods for calculating the properties of Li_(2)OHCl are general and can guide the design of highperformance solid-state electrolytes.
基金National Natural Science Foundation of China(29976040),Natural Science Foundation of AnhuiProvince(99045431),Foundation of Environments and Resources of USTC and Youth Foundation of USTC.
文摘The water dissociation mechanism on a bipolar membrane under the electrical field was investigated and characterized in terms of ionic transport and limiting current density. It is considered that the depletion layer exists at the junction of a bipolar membrane, which is coincided with the viewpoint of the most literatures, but we also consider that the thickness and conductivity of this layer is not only related with the increase of the applied voltage but also with the limiting current density. Below the limiting current density, the thickness of the depletion layer keeps a constant and the conductivity decreases with the increase of the applied voltage; while above the limiting current density, the depletion thickness will increase with the increase of the applied voltage and the conductivity keeps a very low constant. Based on the data reported in the literatures and independent determinations, the limiting current density was calculated and the experimental curves Ⅰ-Ⅴ in the two directions were com
基金supported by the National Key Research and Development Program of China(2021YFA1101300)the National Natural Science Foundation of China(Grant No.22225801,21776197,22078214,and 21905206)Special Fund for Science and Technology Innovation Team of Shanxi Province(No.202204051001009).
文摘The ionic transport in sub-nanochannels plays a key role in energy storage,yet suffers from a high energy barrier.Wetting sub-nanochannels is crucial to accelerate ionic transport,but the introduction of water is challenging because of the hydrophobic extreme confinement.We propose wetting the channels by the exothermic hydration process of pre-intercalated ions,the effect of which varies distinctly with different ionic hydration structures and energies.Compared to the failed pre-intercalation of SO_(4)^(2-),HSO_(4)^(-) with weak hydration energy results in a marginal effect on the HOMO(Highest Occupied Molecular Orbital)level of water to avoid water splitting during the electrochemical intercalation.Meanwhile,the ability of water introduction is reserved by the initial incomplete dissociation state of HSO_(4)^(-),so the consequent exothermic reionization and hydration processes of the intercalated HSO_(4)^(-) promote the water introduction into sub-nanochannels,finally forming the stable confined water through hydrogen bonding with functional groups.The wetted channels exhibit a significantly enhanced ionic diffusion coef-ficient by~9.4 times.
基金support from European Union’s Horizon 2020 research,innovation programme under grant agreement No. 958174, Vinnova (Swedish Governmental Agency for Innovation Systems)the financial support from the LTU CREATERNITY program+2 种基金the J. Gust Richert Foundationthe Swedish Energy Agency,STINT (CH2019-8287),and Bio4energythe National Natural Science Foundation of China (No.U23A20122)。
文摘The confined ionic liquid(IL) in solid polymer composite electrolytes(SCPEs) can improve the performance of lithium metal batteries. However, the impact/role and working mechanism of confined IL in SCPEs remain ambiguous. Herein, IL was immobilized on SiO_(2)(SiO_(2)@IL-C) and then used to prepare the confined SCPEs together with LiTFSI and PEO to study the impacts of confined-IL on the properties and performance of electrolytes and reveal the Li+transport mechanism. The results show that, compared to the IL-unconfined SCPE, the IL-confined ones exhibit better performance of electrolytes and cells, such as higher ionic conductivity, higher t+Li, and wider electrochemical windows, as well as more stable cycle performance, due to the increased dissociation degree of lithium salt and enlarged polymer amorphousness. The finite-element/molecular-dynamics simulations suggest that the IL confined on the SiO_(2) provided an additional Li+transport pathway(Li+→ SiO_(2)@IL-C) that can accelerate ion transfer and alleviate lithium dendrites, leading to ultrastable stripping/plating cycling over 1900 h for the Li/SCPEs/Li symmetric cells. This study demonstrates that IL-confinement is an effective strategy for the intelligent approach of high-performance lithium metal batteries.
基金supported by the Natural Science Foundation of Shandong Province(Nos.ZR2022QE014 and ZR2021QH237)the National Natural Science Foundation of China(Grant Nos.52401221,51971120,and U1902221)the Medical StaffScience and Technology Plan of Shandong Province(No.SDYWZGKCJH2022073).
文摘All-solid-state lithium batteries(ASSLBs)are important for enhancing safety across various applications related to lithium-ion batteries(LIBs).Lithium iron phosphate(LiFePO4)is a widely utilized commercial cathode in LIBs,prized for its stable cycling performance,thermal stability,and low cost.However,low electronic conductivity and slow ion diffusion kinetics limit its application at high rates and low temper-atures.Herein,Ti3C2Tx MXene nanosheets(NSs)are introduced into the LiFePO4 cathode.The continu-ous electron-conducting networks are constructed due to the high electrical conductivity of Ti3C2Tx NSs.Meanwhile,the coordination environment of lithium ions in the cathode is weakened by the oxygenated end groups of Ti3C2Tx NSs,and thus efficient ion-percolating networks are constructed.Therefore,the ionic and electronic conductivities of the modified cathode are significantly improved.Assembled all-solid-state LiFePO4/Li full cells with poly(ethylene oxide)as electrolyte exhibits high initial discharged capacities of 91.5 mAh g^(-1) at 10 C,and capacities of 155.1 mAh g^(-1) after 1000 cycles at 1 C with a re-tention rate of 93.8%.Furthermore,the cells still deliver excellent performance at high loading,room temperature,and low temperature.This work offers a facile and scalable strategy for designing high-performance ASSLBs.
基金supported by the National Natural Science Foundation of China(No.11047164)the National Key Laboratory of Infrared Detection Technologies(No.IRDT-23-S01)the Shanghai Explorer Program(No.24TS1403400)。
文摘The high safety of aqueous magnesium ion batteries(AMIBs)contrasts with their limited electrochemical performance.To overcome electrolyte-induced parasitic reactions,it is essential to understand the dynamic evolution of concentration-dependent metal ion solvation structures(MISSs).This study systematically reveals the solvation structure evolution of MgCl_(2) aqueous solutions across a full concentration range(0-30 M)and its impact on electrochemical properties using molecular dynamics simulations and density functional theory calculations.Results indicate that six characteristic solvation configurations exist,exhibiting a dynamic,concentration-dependent inter-evolution defined as the solvation structure evolutionary processes(SSEP).The four-phase glass transition mechanism in solvation structure evolution is revealed by analyzing the percentage of each type of solvation structure in different concentrations.The study shows that conductivity is directly related to the dynamic transitions of dominant solvation structures,with a shift in the Mg^(2+) coordination mode—from octahedral through pentahedral intermediates to tetrahedral—revealing a concentration-dependent ion transport mechanism.At low concentrations,free-state stochastic diffusion predominates,reaching a maximum conductivity before transitioning to relay transport within a restricted network at high concentrations.Key contributions include:a general strategy for electrolyte design based on the solvation structure evolution process,which quantitatively correlates structural occupancy with migration properties,and the“Concentration Window”regulation model that balances high conductivity with reduced side reactions.These findings clarify the structural origins of anomalous conductivity in highly concentrated electrolytes and establish a mapping between microstructural evolution and macroscopic performance,providing a theoretical basis for engineering high-security electrolytes of AMIBs.
基金Supported by the National Natural Science Foundation of China
文摘It is indicated from a study of transport of rare earth ions through the emulsion liquid mem- brane of bis(2,4,4-trimethylpentyl)phosphinic acid-Span 80-toluene that transporting rare earth ions com- pletely and rapidly was realized under the optimum experimental conditions:1.0×10^(-3)～3.0×10^(-3)mol/L bis(2,4,4-trimethylpentyl)phosphinic acid and 2%～4%(W/V)Span 80 in toluene solution as membrane phase,0.50～2.0 mol/L HCl as inner phase,rare earth ion solutions with pH 3.5～5.0 as outer phase.Ac- cording to the differences of transport behavior for rare earth ions,it is possible to separate rare earth ions from mixed solutions of rare earth ions by this liquid membrane system.
基金Supported by the Fundamental Research Funds of Central Welfare Scientific Research Institutes(2013-szjj-lzq-04)the Agroecological Environment Protection Program(2013-072)
文摘Soils in part of rice production areas have been seriously contaminated by cadmium （Cd）. Rice with high Cd content over allowable limit produced in these areas is widely concerned. Low accumulation varieties can remarkably decrease the Cd content in rice as well as the risk of food safety. The translocation of Cd either from soil to root system or from roots to aboveground parts is identified by a lot of ion transport proteins. Transport efficiency of Cd in some rice varieties is regulated by special metal ionic transporters. However, most varieties transport Cd by cation transporters or universal ionic transporters. Both the expression levels and time of gens controlling ionic transporters directly influence the Cd transport rates inside rice plant and the accumulation amount in different organs. Screening and utilizing specific Cd transport genes are the genetic basis of breeding low accumulation varieties.
基金supported by the National Natural Science Foundation of China(Grant No.51372228)the Shanghai Pujiang Program,China(Grant No.14PJ1403900)the Shanghai Institute of Materials Genome from the Shanghai Municipal Science and Technology Commission,China(Grant No.14DZ2261200)
文摘An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and de signing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell （to convey ions while isolate electrons）, and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state elec- trolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes.
基金supported by Research Grant Council (RGC) of Hong Kong (PolyU 5238/11E)
文摘In co-ionic conducting solid oxide fuel cell （SOFC）, both oxygen ion （O2） and proton （H＋） can transport through the electrolyte, generating steam in both the an-ode and cathode. Thus the mass transport phenomenon in the electrodes is quite different from that in conventional SOFC with oxygen ion conducting electrolyte （O-SOFC） or with proton conducting electrolyte （H-SOFC）. The generation of steam in both electrodes also affects the concentration over-potential loss and further the SOFC performance. However, no detailed modeling study on SOFCs with co-ionic electrolyte has been reported yet. In this paper, a new mathematical model for SOFC based on co-ionic electrolyte was developed to predict its actual performance considering three major kinds of overpotentials. Ohm＇s law and the Butler-Volmer formula were used to model the ion conduction and electrochemical reactions, respectively. The dusty gas model （DGM） was employed to simulate the mass transport processes in the porous electrodes. Parametric simulations were performed to investigate the effects of proton transfer number （tH） and current density （jtotal） on the cell performance. It is interesting to find that the co-ionic conducting SOFC could perform better than O-SOFC and H-SOFC by choosing an appropriate proton transfer number. In addition, the co-ionic SOFC shows smaller difference between the anode and cathode concentration overpotentials than O-SOFC and H-SOFC at certain t H values. The results could help material selection for enhancing SOFC performance.
基金the National Natural Science Foundation of China(Nos.22209095 and 22238004).
文摘Progress in the fast charging of high-capacity silicon monoxide(SiO)-based anode is currently hindered by insufficient conductivity and notable volume expansion.The construction of an interface conductive network effectively addresses the aforementioned problems;however,the impact of its quality on lithium-ion transfer and structure durability is yet to be explored.Herein,the influence of an interface conductive network on ionic transport and mechanical stability under fast charging is explored for the first time.2D modeling simulation and Cryo-transmission electron microscopy precisely reveal the mitigation of interface polarization owing to a higher fraction of conductive inorganic species formation in bilayer solid electrolyte interphase is mainly responsible for a linear decrease in ionic diffusion energy barrier.Furthermore,atomic force microscopy and Raman shift exhibit substantial stress dissipation generated by a complete conductive network,which is critical to the linear reduction of electrode residual stress.This study provides insights into the rational design of optimized interface SiO-based anodes with reinforced fast-charging performance.
基金supported by the National Natural Science Foundation of China (51673017)the National Natural Science Foundation of China (21404005)+1 种基金the Fundamental Research Funds for the Central Universities (XK1802-2)the Natural Science Foundation of Jiangsu Province (BK20150273)。
文摘Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode.Herein,a functionalized high-toughness polyimide(PDMI) is synthesized by copolymerizing the 4,4'-Oxydiphthalic anhydride(ODPA) with 4,4'-oxydianiline(ODA),2,3-diaminobenzoic acid(DABA),and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane(DMS).The combination of rigid benzene rings and flexible oxygen groups(-O-) in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness.The plentiful polar carboxyl(-COOH) groups establish robust bonding strength.Rapid ionic transport is achieved by incorporating the flexible siloxane segment(Si-O-Si),which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport(9.8 × 10^(-10) cm^(2) s^(-1) vs.16 × 10^(-10) cm^(2) s~(-1)).As expected,the SiO_x@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85% over 500 cycles at 1.3 A g^(-1).The well-designed functionalized polyimide also significantly enhances the electrochemical properties of Si nanoparticles electrode.Meanwhile,the assembled SiO_x@PDMI-1.5/NCM811 full cell delivers a high retention of 80% after 100 cycles.The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity electrodes for high-energy-density batteries.
文摘comb-shaped polynier (BM350) with oligo-oxyetliylene side chains of thetype-O (CH_2CH_2O )_7CH_3 was prepared from methyl vinyl ether /maleic anhydridecopolymer- Honiogeneous aniorplious polymer electrolyte cornplexes were madefrom the conib polymer and LiCF_3SO_3 by solvent casting from acetone, and theirconductivities were nieasured as a function of temperature and salt concentration.Maxiniuni conductivity close to 5. 08 ×10￣(-5) Scm￣(-1) was obtained at room tempera-tureancl at a [Li]/[EO] ratio of about 0. 12. The conductivity which displayednon-Arrheni us behaviour was analyzed using the Vogel-Tammann-Fulcher equationand interpreted on the basis of the configurational entropy model. The results ofmid-IR sliowed that the coortlination of Li￣+ to side chains made the C-O-C bandbecome broader and shift sliglitly- X-ray photoelectron spectroscopy analysis indi-cated that the oxygen atonis in the two situations could coordinate to Li￣+ and thiscoortlination resulted in the reduction of the electron orbit binding energy of F andS.
基金supported by the National Key Research and Development Program of China(project no.2022YFA1205201)the State Key Laboratory of Polymer Materials Engineering,China(grant no.sklpme2022-2-04).
文摘The practical application of the Li metal anode has long been hindered by the uncontrolled growth of Li dendrites,heterogeneous and fragile solid electrolyte interface(SEI)layer,and large volume swelling.Herein,a robust artificial SEI layer,polyaryoxadiazole lithium sulfonate(PODLi),was successfully fabricated to stabilize the interface between the Li metal and electrolyte.The lithiophilic PODLi film afforded fast ionic transport channels to form a dendrite-free,lithium fluoride-rich anode.The Li@Cu-PODLi symmetric cell achieved excellent cycling performance at a high current density of 10 mA cm^(−2) with an areal capacity of 10 mAh cm^(−2) for more than 770 h.A full cell with the LiFPO_(4) cathode exhibited ultralong-term stable operation over 500 cycles at a high current density of 3.45 mA cm^(−2) with a low-capacity decay rate of 0.038%per cycle.This work demonstrates a cost-effective and scalable strategy for high-energy-density Li metal batteries.
