Silicon-air batteries(SABs)hold significant potential as efficient energy conversion devices due to their high theoretical energy density,theoretical discharge voltage,and favorable energy-to-cost ratios.However,their...Silicon-air batteries(SABs)hold significant potential as efficient energy conversion devices due to their high theoretical energy density,theoretical discharge voltage,and favorable energy-to-cost ratios.However,their applicability has been hindered by low output discharge potential,high discharge polarizations,and singular aqueous configuration.To address these,the catalyst with faster oxygen reduction reaction(ORR)kinetic rate,nitrogen-doped carbon materials functionalized with FeMo metal clusters(FeMo-NC),was designed in acid electrolyte and thus high output voltage and energy density SABs with asymmetric-electrolytes have been developed.This innovative design aligns the reaction rates of the cathode and anode in SABs,achieving stable discharge around 1.7 V for 188 h.Furthermore,an all-in-one quasisolid-state SAB(QSSSAB)was first developed using a suitable acid-base gel electrolyte.This all-in-one QSSSAB showcases good safety,low cost,and portability,with open-circuit voltage of 1.6 V and energy density of 300.2 Wh kg^(-1),surpassing the energy density of most previously reported aqueous SABs.In terms of application,these compact all-in-one QSSSABs can provide stable and reliable power support for portable small electronic devices(such as electronic players,diodes,and electronic watches).展开更多
Ionogels,generally formed by immobilizing ionic liquids(ILs)with polymer gelators,hold considerable promise as quasi-solid-state electrolytes(QSSEs)for lithium metal batteries(LMBs)due to their high safety and electro...Ionogels,generally formed by immobilizing ionic liquids(ILs)with polymer gelators,hold considerable promise as quasi-solid-state electrolytes(QSSEs)for lithium metal batteries(LMBs)due to their high safety and electrode compatibility.However,their practical use in high-temperature LMBs suffers from the softened polymer chains of gelator at high temperatures,leading to liquid leakage and severe growth of Li dendrite.Here,a novel inorganic ionogel(PCNIL)combining lithium salt-containing IL with porous graphitic carbon nitride nanosheets(PCN)is developed through direct physical mixing.PCNIL exhibits a superior ionic conductivity(0.75 mS cm^(-1))at room temperature similar to that of neat IL electrolyte(LiIL)and a Li^(+)transference number(0.56)greatly higher than that of Li-IL(0.20).Furthermore,PCNIL maintains a temperature-independent shear storage modulus of up to 5 MPa from room temperature to 150℃.Consequently,the Li|PCNIL|Li symmetrical cell demonstrates extended reversible lithium plating/stripping over 1200 h without dendritic growth.The robust mechanical strength,excellent thermal stability,and electrochemical stability of PCNIL allow Li|PCNIL|LiFePO_(4)cells to operate stably in a wide temperature range of 25–150℃.展开更多
Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode...Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode,low intrinsic conductivity of sulfur cathode,and severe shuttling effect of sodium polysulfides(NaPSs)pose significant challenges in the actual reversible capacity and cycle life of Na-S batteries.Herein,a self-supporting electrode made of nitrogen-doped carbon fiber embedded with cobalt nanoparticles(Co/NC-CF)is designed to load sulfur.Meanwhile,gel polymer electrolyte(GPE)with high ion transfer ability is obtained by in-situ polymerization inside the battery.During the polymerization process,an integrated electrode-electrolyte and a continuous ion-electron conduction network in a composite cathode are constructed inside the Na-S battery.It is noteworthy that the designed GPE demonstrates superior ionic conductivity and effective adsorption of NaPSs that can significantly suppress the shuttle effect.Leveraging the synergistic interplay between the designed GPE and self-supporting cathode,the assembled quasi-solid-state(QSS)Na-S battery exhibits great cycling stability.These experimental results are further corroborated by COMSOL Multiphysics simulations and density functional theory(DFT)calculations,which mechanistically validate the enhanced electrochemical performance.The findings of this study offer new and promising perspectives for advancing the development of nextgeneration solid-state batteries.展开更多
Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries(SSBs),due to their high safety and long operation life span.However,the two major factors that impede the expec...Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries(SSBs),due to their high safety and long operation life span.However,the two major factors that impede the expected performance of batteries are:the easy formation of lithium dendrites due to the concentration gradient of anions,and the low ionic conductivity at room temperature,which prevents reaching ideal electrochemical performance.Single-ion quasi-solid-state electrolytes(SIQSSEs)could provide higher safety and energy density,owing to absence of anion concentration gradient and solvent,as well as good lithium-ion transport ability.The porous covalent organic frameworks(COFs)are beneficial for con-structing appropriate lithium-ion transport pathway,due to the ordered 1D channel.In addition,the boroxine COFs(COF-5)offers strong ability of withdrawing anion part of lithium salt.Last but not the least,boron atom could play the role of coordinate site due to its electron deficiency.These advantages afford an opportunity to obtain a SIQSSE with high ionic conductivity and high lithium transference number(LTN)simultaneously.The COF-5 based SIQSSEs delivered a high ionic conductivity of 6.3×10^(-4)S·cm^(-1),with a high LTN of 0.92 and a wide electrochemical stable window(ESW)of 4.7 V at room temperature.The LiFePO4(LFP)/Li cells,which was assembled with COF-5 based SIQSSE,exhibited outstanding long cycle stability,high initial capacity and favorable rate performance.The results indicated COFs could be an ideal material for single-ion solid-state electrolytes in next-generation batteries.展开更多
One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible p...One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.展开更多
Solid-state sodium batteries offer new opportunities for emerging applications with sensitivity to safety and cost.However,the prevailing composite electrolyte structure,as a core component,is still poorly conductive ...Solid-state sodium batteries offer new opportunities for emerging applications with sensitivity to safety and cost.However,the prevailing composite electrolyte structure,as a core component,is still poorly conductive to Na ions.Herein,a 3D architecture design of Na^(+)conductive Na_(3)Zr_(2)Si_(2)PO_(12)framework is introduced to in situ compound with polymer electrolyte,subtly inducing an anion-enriched interface that acts as rapid ion immigration channel.Multiple continuous and fast Na^(+)transport pathways are built via the amorphization of polymer matrix,the consecutive skeleton,and the induced anion-adsorbed interface,resulting in a high ionic conductivity of4.43×10^(-4)S.cm^(-1).Notably,the design of 3D skeleton not only enables the content of inorganic part exceeds 60wt%without any sign of agglomeration,but also endows the composite electrolyte reach a high transference number of 0.61 by immobilizing the anions.The assembled quasisolid-state cells exhibit high practical safety and can stably work for over 1500 cycles with 83.1%capacity retention.This tactic affords new insights in designing Na^(+)conductive composite electrolytes suffering from slow ion immigration for quasi-solid-state sodium batteries.展开更多
The stable operation of solid-state lithium metal batteries at low temperatures is plagued by severe restrictions from inferior electrolyte-electrode interface compatibility and increased energy barrier for Li^(+)migr...The stable operation of solid-state lithium metal batteries at low temperatures is plagued by severe restrictions from inferior electrolyte-electrode interface compatibility and increased energy barrier for Li^(+)migration.Herein,we prepare a dual-salt poly(tetrahydrofuran)-based electrolyte consisting of lithium hexafluorophosphate and lithium difluoro(oxalato)borate(LiDFOB).The Li-salt anions(DFOB−)not only accelerate the ring-opening polymerization of tetrahydrofuran,but also promote the formation of highly ion-conductive and sustainable interphases on Li metal anodes without sacrificing the Li^(+)conductivity of electrolytes,which is favorable for Li^(+)transport kinetics at low temperatures.Applications of this polymer electrolyte in Li||LiFePO_(4)cells show 82.3%capacity retention over 1000 cycles at 30℃and endow stable discharge capacity at−30℃.Remarkably,the Li||LiFePO4 cells retain 52%of their room-temperature capacity at−20℃and 0.1 C.This rational design of dual-salt polymer-based electrolytes may provide a new perspective for the stable operation of quasi-solid-state batteries at low temperatures.展开更多
Quasi-solid-state lithium metal batteries(QSSLMBs)assembled with polyvinylidene fluoride(PVDF)are a promising class of next-generation rechargeable batteries due to their safety,high energy density,and superior interf...Quasi-solid-state lithium metal batteries(QSSLMBs)assembled with polyvinylidene fluoride(PVDF)are a promising class of next-generation rechargeable batteries due to their safety,high energy density,and superior interfacial properties.However,PVDF has a series of inherent drawbacks such as low ionic conductivity,ease of crystallization,and hydrophobic character that leading to poor cell properties.To tackle these issues,a lignin-reinforced PVDF electrolyte is proposed in this work to solve these drawbacks of PVDF and enhance the comprehensive performance of QSSBs.The lithophilic polar groups of lignin can promote uniform deposition of Li on the electrodes.Cooperating with the improved mechanical properties can efficiently prevent Li dendrites penetration through the separator.In addition,more active sites provided by lignin can also enhance Li^(+)transport and lead to a faster electrochemical reaction kinetic.Benefitting from the ingenious design,Li symmetric cells with 5%lignin-PVDF quasi-solid-state electrolyte can operate for 900 h at a high current density/capacity of 5 mA·cm^(-2)/5 mAh·cm^(-2),while shortcircuiting occurs after 56 h for the counterpart(pure PVDF).Moreover,a full cell of Li/5%lignin-PVDF/LFP cell demonstrates a high capacity of 96.2 mAh·g^(-1)after 2000 cycles at 10 C.This work is expected to open up promising opportunities to develop other high-energy/power-density QSSLMBs.展开更多
Silver-zinc(Ag-Zn)batteries are a promising battery system for flexible electronics owing to their high safety,high energy density,and stable output voltage.However,poor cycling performance,low areal capacity,and infe...Silver-zinc(Ag-Zn)batteries are a promising battery system for flexible electronics owing to their high safety,high energy density,and stable output voltage.However,poor cycling performance,low areal capacity,and inferior flexibility limit the practical application of Ag-Zn batteries.Herein,we develop a flexible quasi-solid-state Ag-Zn battery system with superior performance by using mild electrolyte and binder-free electrodes.Copper foam current collector is introduced to impede the growth of Zn dendrite,and the structure of Ag cathode is engineered by electrodeposition and chloridization process to improve the areal capacity.This novel battery demonstrates a remarkable cycle retention of 90%for 200 cycles at 3 mA cm^(-2).More importantly,this binder-free battery can afford a high capacity of 3.5 mAh cm^(-2)at 3 mA cm^(-2),an outstanding power density of 2.42 mW cm^(-2),and a maximum energy density of 3.4 mWh cm^(-2).An energy management circuit is adopted to boost the output voltage of a single battery,which can power electronic ink display and Bluetooth temperature and humidity sensor.The developed battery can even operate under the extreme conditions,such as being bent and sealed in solid ice.This work offers a path for designing electrodes and electrolyte toward high-performance flexible Ag-Zn batteries.展开更多
The practical application of aqueous zinc-ion batteries(AZIBs)is limited by zinc dendrites,parasitic reactions,and self-discharging.Quasi-solid-state electrolytes(QSSEs)are promising solutions but have high costs,low ...The practical application of aqueous zinc-ion batteries(AZIBs)is limited by zinc dendrites,parasitic reactions,and self-discharging.Quasi-solid-state electrolytes(QSSEs)are promising solutions but have high costs,low conductivity,and inadequate self-discharge-suppression capability.This study introduces a novel“water-in-montmorillonite(Mont)”(WiME)electrolyte to address these limitations.WiME leverages the layered struc-ture of the inexpensive Mont to confine water,achieving a high ionic conductivity of 64.82 mS/cm and remark-able self-discharge suppression capability and maintaining 92.7%capacity after 720 h.The WiME architec-ture facilitates uniform Zn deposition and promotes cycling stability at high current densities.WiME-based symmetric cells show excellent long-term cycling,surpassing 1900 h,and full Zn||MnOOH cells display stable cycling for 500 cycles without capacity decay,demonstrating synergy among mitigated parasitic reactions,homogenous zinc deposition,and enhanced interfacial stability enabled by WiMEs.This study presents a low-cost and high-performance strategy for advancing the practical application of AZIBs for various fields.展开更多
Lithium(Li) metal,possessing an extremely high theoretical specific capacity(3860 mAh/g) and the most negative electrode potential(-3.040 V vs.standard hydrogen electrode),is one the most favorable anode materials for...Lithium(Li) metal,possessing an extremely high theoretical specific capacity(3860 mAh/g) and the most negative electrode potential(-3.040 V vs.standard hydrogen electrode),is one the most favorable anode materials for future high-energy-density batteries.However,the poor cyclability and safety issues induced by extremely unstable interfaces of traditional liquid Li metal batteries have limited their practical applications.Herein,a quasi-solid battery is constructed to offer superior interfacial stability as well as excellent interfacial contact by the incorporation of Li@composite solid electrolyte integrated electrode and a limited amount of liquid electrolyte(7.5 μL/cm2).By combining the inorganic garnet Aldoped Li6.75La3Zr1.75Ta0.25O12(LLZO) with high mechanical strength and ionic conductivity and the o rganic ethylene-vinyl acetate copolymer(EVA) with good flexibility,the composite solid electrolyte film could provide sufficient ion channels,sustained interfacial contact and good mechanical stability at the anode side,which significantly alleviates the thermodynamic corrosion and safety problems induced by liquid electrolytes.This innovative and facile quasi-solid strategy is aimed to promote the intrinsic safety and stability of working Li metal anode,shedding light on the development of next-generation highperformance Li metal batteries.展开更多
High-performance lithium ion capacitors(LICs) have been seriously hindered by the very low capacity and unclear capacitive mechanism of carbon cathode.Herein,after the combination of experimental results and theoretic...High-performance lithium ion capacitors(LICs) have been seriously hindered by the very low capacity and unclear capacitive mechanism of carbon cathode.Herein,after the combination of experimental results and theoretical calculations,it is found that the critical pore size of 0.8 nm for PF_6~-ion adsorption decreases strong interactive repulsion of electrons and largely reduces adsorption energy barrier,which greatly improves the charge accommodation capacity in electrical double-layer behavior.Most importantly,the chemical-bond evolution process of C=O group has been firstly revealed by X-ray photoelectron spectroscopy(XPS),indicating that the introduction of C=O group can provide abundant redox active sites for PF_6~-ion adsorption accompanied with enhanced pseudocapacitive capacity.Attributed to the synergistic effect of dual capacitive mechanism,porous carbon sheet(PCS) cathode shows a reversible specific capacity of 53.6 mAh g^(-1) even at a high current density of 50 A g^(-1).Significantly,the quasisolid-state LIC manifests state-of-the-art electrochemical performances with an integrated maximum energy density of 163 Wh kg^(-1) and an outstanding power density of 15,000 W kg^(-1).This elaborate work promotes better fundamental understanding about capacitive mechanism of PF_6~-ion and offers a rational dual-capacitive strategy for the design of advanced carbon cathodes.展开更多
Vanadium-based cathodes have attracted great interest in aqueous zinc ion batteries(AZIBs)due to their large capacities,good rate performance and facile synthesis in large scale.However,their practical application is ...Vanadium-based cathodes have attracted great interest in aqueous zinc ion batteries(AZIBs)due to their large capacities,good rate performance and facile synthesis in large scale.However,their practical application is greatly hampered by vanadium dissolution issue in conventional dilute electrolytes.Herein,taking a new potassium vanadate K0.486V2O5(KVO)cathode with large interlayer spacing(~0.95 nm)and high capacity as an example,we propose that the cycle life of vanadates can be greatly upgraded in AZIBs by regulating the concentration of ZnCl2 electrolyte,but with no need to approach“water-in-salt”threshold.With the optimized moderate concentration of 15 m ZnCl2 electrolyte,the KVO exhibits the best cycling stability with ~95.02% capacity retention after 1400 cycles.We further design a novel sodium carboxymethyl cellulose(CMC)-moderate concentration ZnCl2 gel electrolyte with high ionic conductivity of 10.08 mS cm^-1 for the first time and assemble a quasi-solid-state AZIB.This device is bendable with remarkable energy density(268.2 Wh kg^−1),excellent stability(97.35% after 2800 cycles),low self-discharge rate,and good environmental(temperature,pressure)suitability,and is capable of powering small electronics.The device also exhibits good electrochemical performance with high KVO mass loading(5 and 10 mg cm^-2).Our work sheds light on the feasibility of using moderately concentrated electrolyte to address the stability issue of aqueous soluble electrode materials.展开更多
Solid-state and quasi-solid-state electrolytes have been attracting the scientific community’s attention in the last decade. These electrolytes provide significant advantages, such as the absence of leakage and separ...Solid-state and quasi-solid-state electrolytes have been attracting the scientific community’s attention in the last decade. These electrolytes provide significant advantages, such as the absence of leakage and separators for devices and safety for users. They also allow the assembly of stretchable and bendable supercapacitors. Comparing solid-state to quasi-solid-states, the last provides the most significant energy and power densities due to the better ionic conductivity. Our goal here is to present recent advances on quasisolid-state electrolytes, including gel-polymer electrolytes. We reviewed the most recent literature on quasi-solid-state electrolytes with different solvents for supercapacitors. Organic quasi-solid-state electrolytes need greater attention once they reach an excellent working voltage window greater than 2.5 V.Meanwhile, aqueous-based solid-state electrolytes have a restricted voltage window to less than 2 V. On the other hand, they are easier to handle, provide greater ionic conductivity and capacitance. Recent water-in-salt polymer-electrolytes have shown stability as great as 2 V encouraging further development in aqueous-based quasi-solid-state electrolytes. Moreover, hydrophilic conductive polymers have great commercial appeal for bendable devices. Thus, these electrolytes can be employed in flexible and bendable devices, favoring the improvement of portable electronics and wearable devices(376 references were evaluated and summarized here).展开更多
A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Amo...A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Among the various SSEs,the single Li-ion conductor has advantages in terms of enhancing the ion conductivity,eliminating interfacial side reactions,and broadening the electrochemical window.Covalent organic frameworks(COFs)are optimal platforms for achieving single Li-ion conduction behavior because of wellordered one-dimensional channels and precise chemical modification features.Herein,we study in depth three types of Li-carboxylate COFs(denoted LiOOC-COFn,n=1,2,and 3)as single Li-ion conducting SSEs.Benefiting from well-ordered directional ion channels,the single Li-ion conductor LiOOC-COF3 shows an exceptional ion conductivity of 1.36×10^(-5) S cm^(-1) at room temperature and a high transference number of 0.91.Moreover,it shows excellent electrochemical performance with long-term cycling,high-capacity output,and no dendrites in the quasi-solid-state organic battery,with the organic small molecule cyclohexanehexone(C_(6)O_(6))as the cathode and the Li metal as the anode,and enables effectively avoiding dissolution of the organic electrode by the liquid electrolyte.展开更多
The development of an air electrode that is flexible in physical property and highly active and durable at different geometric status for both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of cruc...The development of an air electrode that is flexible in physical property and highly active and durable at different geometric status for both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of crucial importance for the rational design of flexible rechargeable Zn-air batteries(ZABs).Considering their good elasticity,high conductivity,and superior thermal and chemical stability,carbon nanotubes have been widely used as a catalyst support in various electrocatalysts,while oxide or metal nanoparticles have been frequently deposited on the carbon nanotube substrate to perform as the active materials.Considering the poor contact between active materials and carbon nanotubes may introduce a challenge for long-term operating stability,in particular in flexible devices,pure carbon electrocatalyst is highly appreciated.Herein,a free-standing air electrode with cobalt nanoparticles encapsulated N-codoped carbon nanotube arrays uniformly grown on the surface of carbon fiber cloth is developed by a two-step in situ growth method.Such a carbon-based electrode shows outstanding activity for both ORR and OER.The flexible ZAB with such air electrode shows superior flexibility and stability working under extreme bending conditions.Moreover,the polarization and round-trip efficiency for the flexible battery is 0.67 V and 64.4%at 2 mA/cm2,respectively,even after being operated for 30 hours.This study provides a feasible way to design all carbon-based free-standing and flexible electrode and enlightens the electrode design for flexible energy conversion/storage devices.展开更多
The isolated inorganic particles within composite polymer electrolytes(CPEs) are not correlated to the Li^(+)transfer network,resulting in the polymer dominating the low ionic conductivity of CPEs.Therefore,we develop...The isolated inorganic particles within composite polymer electrolytes(CPEs) are not correlated to the Li^(+)transfer network,resulting in the polymer dominating the low ionic conductivity of CPEs.Therefore,we developed novel quasi-solid-state CPEs of a Ce-doped Na super ion conductors(NASICON)Na_(1.3+x)Al_(0.3)Ce_(x)Ti_(1.7-x)(PO_(4))_(3)(NCATP) chemically coupled poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)/Li-bis(trifluoromethanes-ulfonyl)imide(LiTFSI) matrix.A strong interaction between Ce^(3+)from NCATP and TFSI-anion from the polymer matrix contributes to the fast Li+transportation at the interface.The PVDF-HFP/NCATP CPEs exhibit an ionic conductivity of 2.16 × 0^(-3) S cm^(-1) and a Li^(+) transference number of 0.88.A symmetric Li/Li cell with NCATP-integrated CPEs at 0.1 mA cm^(-2) presents outstanding cycling stability over 2000 h at 25℃.The quasi-solid-state Li metal batteries of Li/CPEs/LiFePO_(4) at 2 C after 400 cycles and Li/CPEs/LiCoO_(2) at 0.2 C after 120 cycles deliver capacities of 100 and 152 mAh g^(-1) at 25℃,respectively.展开更多
Gel polymer electrolytes(GPEs)are one of the promising candidates for high-energy-density quasi-solid-state lithium metal batteries(QSSLMBs),for their high ionic conductivity and excellent interfacial compatibility.Th...Gel polymer electrolytes(GPEs)are one of the promising candidates for high-energy-density quasi-solid-state lithium metal batteries(QSSLMBs),for their high ionic conductivity and excellent interfacial compatibility.The comprehension of dynamic evolution and structure-reactivity correlation at the GPE/Li interface becomes significant.Here,in situ electrochemical atomic force microscopy(EC-AFM)provides insights into the LiNO_(3)-regulated micromechanism of the Li plating/stripping processes upon cycles in GPE-based LMBs at nanoscale.The additive LiNO_(3)induces the formation of amorphous nitride SEI film and facilitates Li^(+) ion diffusion.It stabilizes a compatible interface and regulates the Li nucleation/growth at steady kinetics.The deposited Li is in the shape of chunks and tightly compact.The Li dissolution shows favorable reversibility,which guarantees the cycling performance of LMBs.In situ AFM monitoring provides a deep understanding into the dynamic evolution of Li deposition/dissolution and the interphasial properties of tunable SEI film,regulating the rational design of electrolyte and optimizing interfacial establishment for GPE-based QSSLMBs.展开更多
The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Po...The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Polymer-based gel electrolytes with high ionic conductivity,great flexibility,easy processing,and high safety have been studied by many scholars in recent years.In this work,a novel porous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membrane is prepared by a phase inversion method.By immersing porous PVDF-HFP membranes in MgCl2-AlCl3/TEGDME(Tetraethylene glycol dimethyl ether)electrolytes,porous PVDF-HFP based electrolytes(PPEs)are formed.The PPE exhibits a high ionic conductivity(4.72×10^(-4) S cm-1,25℃),a high liquid electrolyte uptake of 162%,as well as a wide voltage window(3.1 V).The galvanostatic cycling test of Mg//Mg symmetric cell with PPE reveals that the reversible magnesium ion(Mg^(2+))plating/stripping occurs at low overpotentials(~0.13 V).Excellent long cycle stability(65.5 mAh g^(-1) over 1700 cycles)is achieved for the quasisolid-state RMB assembled with MoS2/C cathode and Mg anode.Compared with the liquid electrolyte,the PPE could effectively reduce the side reactions and make Mg^(2+)plating/stripping more uniformly on the Mg electrode side.This strategy herein provides a new route to fabricate high-performance RMB through suitable cathode material and polymer electrolyte with excellent performance.展开更多
Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply.Despite intensive efforts on electrolytes,uncontrolled interfacial reactions on lit...Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply.Despite intensive efforts on electrolytes,uncontrolled interfacial reactions on lithium with electrolyte and patchy interfacial contacts still hinder its practical process.Herein,we bring in rationally designed F contained groups into polymer skeleton via in-situ gelation for the first time to establish quasi-solid-state battery.This method achieves a capacity retention of 90%after 1000 cycles at 0.5C with LiFePO_(4)cathodes.The interface constructed by polymer skeleton and reaction with–CF_(3)lead to the predicted solid electrolyte interface species with high stability.Furthermore,we optimize molecular reactivity and interface stability with regulating F contained end groups in the polymer.Comparisons on different structures reveal that high performance solid stable lithium metal batteries rely on chemical modification as well as stable polymer skeleton,which is more critical to construct robust and steady SEI with uniform lithium deposition.New approach with functional groups regulation proposes a more stable cycling process with a capacity retention of 94.2%at 0.5C and 87.6%at 1C after 1000 cycles with LiFePO_(4) cathodes,providing new insights for the practical development of quasi-solid-state lithium metal battery.展开更多
基金National Natural Science Foundation of China,Grant/Award Number:62264006。
文摘Silicon-air batteries(SABs)hold significant potential as efficient energy conversion devices due to their high theoretical energy density,theoretical discharge voltage,and favorable energy-to-cost ratios.However,their applicability has been hindered by low output discharge potential,high discharge polarizations,and singular aqueous configuration.To address these,the catalyst with faster oxygen reduction reaction(ORR)kinetic rate,nitrogen-doped carbon materials functionalized with FeMo metal clusters(FeMo-NC),was designed in acid electrolyte and thus high output voltage and energy density SABs with asymmetric-electrolytes have been developed.This innovative design aligns the reaction rates of the cathode and anode in SABs,achieving stable discharge around 1.7 V for 188 h.Furthermore,an all-in-one quasisolid-state SAB(QSSSAB)was first developed using a suitable acid-base gel electrolyte.This all-in-one QSSSAB showcases good safety,low cost,and portability,with open-circuit voltage of 1.6 V and energy density of 300.2 Wh kg^(-1),surpassing the energy density of most previously reported aqueous SABs.In terms of application,these compact all-in-one QSSSABs can provide stable and reliable power support for portable small electronic devices(such as electronic players,diodes,and electronic watches).
基金support from National Natural Science Foundation of China(52072118 and 52373206)the Open Foundation of State Key Laboratory of Advanced Design and Manufacturing Technology for Vehicle(72275002)+2 种基金Research fund of Yue Lu Mountain Industrial Innovation Center(2023YCII0137)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(2024Z04)Natural Science Foundation of Hunan Province(2024JJ5076)。
文摘Ionogels,generally formed by immobilizing ionic liquids(ILs)with polymer gelators,hold considerable promise as quasi-solid-state electrolytes(QSSEs)for lithium metal batteries(LMBs)due to their high safety and electrode compatibility.However,their practical use in high-temperature LMBs suffers from the softened polymer chains of gelator at high temperatures,leading to liquid leakage and severe growth of Li dendrite.Here,a novel inorganic ionogel(PCNIL)combining lithium salt-containing IL with porous graphitic carbon nitride nanosheets(PCN)is developed through direct physical mixing.PCNIL exhibits a superior ionic conductivity(0.75 mS cm^(-1))at room temperature similar to that of neat IL electrolyte(LiIL)and a Li^(+)transference number(0.56)greatly higher than that of Li-IL(0.20).Furthermore,PCNIL maintains a temperature-independent shear storage modulus of up to 5 MPa from room temperature to 150℃.Consequently,the Li|PCNIL|Li symmetrical cell demonstrates extended reversible lithium plating/stripping over 1200 h without dendritic growth.The robust mechanical strength,excellent thermal stability,and electrochemical stability of PCNIL allow Li|PCNIL|LiFePO_(4)cells to operate stably in a wide temperature range of 25–150℃.
基金supported by the National Natural Science Foundation of China(No.52130101)the Project of Science and Technology Development Plan of Jilin Province in China(Nos.20210402058GH and 20220201114GX)。
文摘Sodium-sulfur(Na-S)batteries are believed as the hopeful energy storage and conversion techniques owing to the high specific capacity and low cost.Nevertheless,unstable sodium(Na)deposition/stripping of Na metal anode,low intrinsic conductivity of sulfur cathode,and severe shuttling effect of sodium polysulfides(NaPSs)pose significant challenges in the actual reversible capacity and cycle life of Na-S batteries.Herein,a self-supporting electrode made of nitrogen-doped carbon fiber embedded with cobalt nanoparticles(Co/NC-CF)is designed to load sulfur.Meanwhile,gel polymer electrolyte(GPE)with high ion transfer ability is obtained by in-situ polymerization inside the battery.During the polymerization process,an integrated electrode-electrolyte and a continuous ion-electron conduction network in a composite cathode are constructed inside the Na-S battery.It is noteworthy that the designed GPE demonstrates superior ionic conductivity and effective adsorption of NaPSs that can significantly suppress the shuttle effect.Leveraging the synergistic interplay between the designed GPE and self-supporting cathode,the assembled quasi-solid-state(QSS)Na-S battery exhibits great cycling stability.These experimental results are further corroborated by COMSOL Multiphysics simulations and density functional theory(DFT)calculations,which mechanistically validate the enhanced electrochemical performance.The findings of this study offer new and promising perspectives for advancing the development of nextgeneration solid-state batteries.
基金financially supported by the National Natural Science Foundation of China (Nos. 22075130 and 21875102)the Fundamental Research Funds for the Central Universities
文摘Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries(SSBs),due to their high safety and long operation life span.However,the two major factors that impede the expected performance of batteries are:the easy formation of lithium dendrites due to the concentration gradient of anions,and the low ionic conductivity at room temperature,which prevents reaching ideal electrochemical performance.Single-ion quasi-solid-state electrolytes(SIQSSEs)could provide higher safety and energy density,owing to absence of anion concentration gradient and solvent,as well as good lithium-ion transport ability.The porous covalent organic frameworks(COFs)are beneficial for con-structing appropriate lithium-ion transport pathway,due to the ordered 1D channel.In addition,the boroxine COFs(COF-5)offers strong ability of withdrawing anion part of lithium salt.Last but not the least,boron atom could play the role of coordinate site due to its electron deficiency.These advantages afford an opportunity to obtain a SIQSSE with high ionic conductivity and high lithium transference number(LTN)simultaneously.The COF-5 based SIQSSEs delivered a high ionic conductivity of 6.3×10^(-4)S·cm^(-1),with a high LTN of 0.92 and a wide electrochemical stable window(ESW)of 4.7 V at room temperature.The LiFePO4(LFP)/Li cells,which was assembled with COF-5 based SIQSSE,exhibited outstanding long cycle stability,high initial capacity and favorable rate performance.The results indicated COFs could be an ideal material for single-ion solid-state electrolytes in next-generation batteries.
基金supported by the National Key Research and Development Program(2019YFA0705701)National Natural Science Foundation of China(22075329,22008267,21978332 and 22179149)+1 种基金Research and Development Project of Henan Academy Sciences China(232018002)Guangdong Basic and Applied Basic Research Foundation(2021A1515010731)。
文摘One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.
基金financially supported by Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515011055 and 2022A1515011438)the Key Project of Shenzhen Basic Research(No.JCYJ2022081800003006)the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen(No.JCYJ20220531101013028)。
文摘Solid-state sodium batteries offer new opportunities for emerging applications with sensitivity to safety and cost.However,the prevailing composite electrolyte structure,as a core component,is still poorly conductive to Na ions.Herein,a 3D architecture design of Na^(+)conductive Na_(3)Zr_(2)Si_(2)PO_(12)framework is introduced to in situ compound with polymer electrolyte,subtly inducing an anion-enriched interface that acts as rapid ion immigration channel.Multiple continuous and fast Na^(+)transport pathways are built via the amorphization of polymer matrix,the consecutive skeleton,and the induced anion-adsorbed interface,resulting in a high ionic conductivity of4.43×10^(-4)S.cm^(-1).Notably,the design of 3D skeleton not only enables the content of inorganic part exceeds 60wt%without any sign of agglomeration,but also endows the composite electrolyte reach a high transference number of 0.61 by immobilizing the anions.The assembled quasisolid-state cells exhibit high practical safety and can stably work for over 1500 cycles with 83.1%capacity retention.This tactic affords new insights in designing Na^(+)conductive composite electrolytes suffering from slow ion immigration for quasi-solid-state sodium batteries.
基金funding from the Natural Science Foundation of Hubei Province,China(Grant No.2022CFA031)supported by the Natural Science Foundation of China(Grant No.22309056).
文摘The stable operation of solid-state lithium metal batteries at low temperatures is plagued by severe restrictions from inferior electrolyte-electrode interface compatibility and increased energy barrier for Li^(+)migration.Herein,we prepare a dual-salt poly(tetrahydrofuran)-based electrolyte consisting of lithium hexafluorophosphate and lithium difluoro(oxalato)borate(LiDFOB).The Li-salt anions(DFOB−)not only accelerate the ring-opening polymerization of tetrahydrofuran,but also promote the formation of highly ion-conductive and sustainable interphases on Li metal anodes without sacrificing the Li^(+)conductivity of electrolytes,which is favorable for Li^(+)transport kinetics at low temperatures.Applications of this polymer electrolyte in Li||LiFePO_(4)cells show 82.3%capacity retention over 1000 cycles at 30℃and endow stable discharge capacity at−30℃.Remarkably,the Li||LiFePO4 cells retain 52%of their room-temperature capacity at−20℃and 0.1 C.This rational design of dual-salt polymer-based electrolytes may provide a new perspective for the stable operation of quasi-solid-state batteries at low temperatures.
基金financially supported by the National Natural Science Foundation of China(No.22208039)the Basic Scientific Research Project of the Educational Department of Liaoning Province(No.LJKMZ20220878)+1 种基金the Dalian Science and Technology Talent Innovation Support Plan(No.2022RQ036)Dalian Polytechnic University(No.222002023044,No.6102072202)。
文摘Quasi-solid-state lithium metal batteries(QSSLMBs)assembled with polyvinylidene fluoride(PVDF)are a promising class of next-generation rechargeable batteries due to their safety,high energy density,and superior interfacial properties.However,PVDF has a series of inherent drawbacks such as low ionic conductivity,ease of crystallization,and hydrophobic character that leading to poor cell properties.To tackle these issues,a lignin-reinforced PVDF electrolyte is proposed in this work to solve these drawbacks of PVDF and enhance the comprehensive performance of QSSBs.The lithophilic polar groups of lignin can promote uniform deposition of Li on the electrodes.Cooperating with the improved mechanical properties can efficiently prevent Li dendrites penetration through the separator.In addition,more active sites provided by lignin can also enhance Li^(+)transport and lead to a faster electrochemical reaction kinetic.Benefitting from the ingenious design,Li symmetric cells with 5%lignin-PVDF quasi-solid-state electrolyte can operate for 900 h at a high current density/capacity of 5 mA·cm^(-2)/5 mAh·cm^(-2),while shortcircuiting occurs after 56 h for the counterpart(pure PVDF).Moreover,a full cell of Li/5%lignin-PVDF/LFP cell demonstrates a high capacity of 96.2 mAh·g^(-1)after 2000 cycles at 10 C.This work is expected to open up promising opportunities to develop other high-energy/power-density QSSLMBs.
基金financial support from the Australian Research Council(LP1900113)
文摘Silver-zinc(Ag-Zn)batteries are a promising battery system for flexible electronics owing to their high safety,high energy density,and stable output voltage.However,poor cycling performance,low areal capacity,and inferior flexibility limit the practical application of Ag-Zn batteries.Herein,we develop a flexible quasi-solid-state Ag-Zn battery system with superior performance by using mild electrolyte and binder-free electrodes.Copper foam current collector is introduced to impede the growth of Zn dendrite,and the structure of Ag cathode is engineered by electrodeposition and chloridization process to improve the areal capacity.This novel battery demonstrates a remarkable cycle retention of 90%for 200 cycles at 3 mA cm^(-2).More importantly,this binder-free battery can afford a high capacity of 3.5 mAh cm^(-2)at 3 mA cm^(-2),an outstanding power density of 2.42 mW cm^(-2),and a maximum energy density of 3.4 mWh cm^(-2).An energy management circuit is adopted to boost the output voltage of a single battery,which can power electronic ink display and Bluetooth temperature and humidity sensor.The developed battery can even operate under the extreme conditions,such as being bent and sealed in solid ice.This work offers a path for designing electrodes and electrolyte toward high-performance flexible Ag-Zn batteries.
基金supported by National Key Research and Development Program of China(Grant No.2022YFB2404500)Shenzhen Outstanding Talents Training Fund(Grant No.01090100002)+1 种基金National Natural Science Foundation of China(Grant No.52201280)Natural Science Foundation of Shandong Province(Grant No.ZR2021QB200).
文摘The practical application of aqueous zinc-ion batteries(AZIBs)is limited by zinc dendrites,parasitic reactions,and self-discharging.Quasi-solid-state electrolytes(QSSEs)are promising solutions but have high costs,low conductivity,and inadequate self-discharge-suppression capability.This study introduces a novel“water-in-montmorillonite(Mont)”(WiME)electrolyte to address these limitations.WiME leverages the layered struc-ture of the inexpensive Mont to confine water,achieving a high ionic conductivity of 64.82 mS/cm and remark-able self-discharge suppression capability and maintaining 92.7%capacity after 720 h.The WiME architec-ture facilitates uniform Zn deposition and promotes cycling stability at high current densities.WiME-based symmetric cells show excellent long-term cycling,surpassing 1900 h,and full Zn||MnOOH cells display stable cycling for 500 cycles without capacity decay,demonstrating synergy among mitigated parasitic reactions,homogenous zinc deposition,and enhanced interfacial stability enabled by WiMEs.This study presents a low-cost and high-performance strategy for advancing the practical application of AZIBs for various fields.
基金supported by National Key Research and Development Program(No.2016YFA0202500)National Natural Science Foundation of China(Nos.21776019,21808124)Beijing Natural Science Foundation(No.L182021)。
文摘Lithium(Li) metal,possessing an extremely high theoretical specific capacity(3860 mAh/g) and the most negative electrode potential(-3.040 V vs.standard hydrogen electrode),is one the most favorable anode materials for future high-energy-density batteries.However,the poor cyclability and safety issues induced by extremely unstable interfaces of traditional liquid Li metal batteries have limited their practical applications.Herein,a quasi-solid battery is constructed to offer superior interfacial stability as well as excellent interfacial contact by the incorporation of Li@composite solid electrolyte integrated electrode and a limited amount of liquid electrolyte(7.5 μL/cm2).By combining the inorganic garnet Aldoped Li6.75La3Zr1.75Ta0.25O12(LLZO) with high mechanical strength and ionic conductivity and the o rganic ethylene-vinyl acetate copolymer(EVA) with good flexibility,the composite solid electrolyte film could provide sufficient ion channels,sustained interfacial contact and good mechanical stability at the anode side,which significantly alleviates the thermodynamic corrosion and safety problems induced by liquid electrolytes.This innovative and facile quasi-solid strategy is aimed to promote the intrinsic safety and stability of working Li metal anode,shedding light on the development of next-generation highperformance Li metal batteries.
基金financially supported by the National Key Research and Development Program of China (2018YFC1901605)the National Natural Science Foundation of China (52004338)+2 种基金the Hunan Provincial Natural Science Foundation of China (2020JJ5696)the Guangdong Provincial Department of Natural Resources (2020-011)the Fundamental Research Funds for the Central Universities of Central South University (2020zzts058)。
文摘High-performance lithium ion capacitors(LICs) have been seriously hindered by the very low capacity and unclear capacitive mechanism of carbon cathode.Herein,after the combination of experimental results and theoretical calculations,it is found that the critical pore size of 0.8 nm for PF_6~-ion adsorption decreases strong interactive repulsion of electrons and largely reduces adsorption energy barrier,which greatly improves the charge accommodation capacity in electrical double-layer behavior.Most importantly,the chemical-bond evolution process of C=O group has been firstly revealed by X-ray photoelectron spectroscopy(XPS),indicating that the introduction of C=O group can provide abundant redox active sites for PF_6~-ion adsorption accompanied with enhanced pseudocapacitive capacity.Attributed to the synergistic effect of dual capacitive mechanism,porous carbon sheet(PCS) cathode shows a reversible specific capacity of 53.6 mAh g^(-1) even at a high current density of 50 A g^(-1).Significantly,the quasisolid-state LIC manifests state-of-the-art electrochemical performances with an integrated maximum energy density of 163 Wh kg^(-1) and an outstanding power density of 15,000 W kg^(-1).This elaborate work promotes better fundamental understanding about capacitive mechanism of PF_6~-ion and offers a rational dual-capacitive strategy for the design of advanced carbon cathodes.
基金supported by grants from the National Natural Science Foundation of China(Grant Nos.51872104,51972257 and 51672205)the National Key R&D Program of China(Grant No.2016YFA0202602)the Natural Science Foundation of Hubei Province(2018CFB581).
文摘Vanadium-based cathodes have attracted great interest in aqueous zinc ion batteries(AZIBs)due to their large capacities,good rate performance and facile synthesis in large scale.However,their practical application is greatly hampered by vanadium dissolution issue in conventional dilute electrolytes.Herein,taking a new potassium vanadate K0.486V2O5(KVO)cathode with large interlayer spacing(~0.95 nm)and high capacity as an example,we propose that the cycle life of vanadates can be greatly upgraded in AZIBs by regulating the concentration of ZnCl2 electrolyte,but with no need to approach“water-in-salt”threshold.With the optimized moderate concentration of 15 m ZnCl2 electrolyte,the KVO exhibits the best cycling stability with ~95.02% capacity retention after 1400 cycles.We further design a novel sodium carboxymethyl cellulose(CMC)-moderate concentration ZnCl2 gel electrolyte with high ionic conductivity of 10.08 mS cm^-1 for the first time and assemble a quasi-solid-state AZIB.This device is bendable with remarkable energy density(268.2 Wh kg^−1),excellent stability(97.35% after 2800 cycles),low self-discharge rate,and good environmental(temperature,pressure)suitability,and is capable of powering small electronics.The device also exhibits good electrochemical performance with high KVO mass loading(5 and 10 mg cm^-2).Our work sheds light on the feasibility of using moderately concentrated electrolyte to address the stability issue of aqueous soluble electrode materials.
基金the funding agencies FAPESP(2014/02163-7,2017/11958-1,2020/14968-0)and CNPq(PQ-2 grant:Process 131234/2020-0&310544/2019-0)the funding from Shell and the importance of the support provided by the ANP(Brazil’s National Oil,Natural Gas,and Biofuels Agency)by the R&D levy regulation。
文摘Solid-state and quasi-solid-state electrolytes have been attracting the scientific community’s attention in the last decade. These electrolytes provide significant advantages, such as the absence of leakage and separators for devices and safety for users. They also allow the assembly of stretchable and bendable supercapacitors. Comparing solid-state to quasi-solid-states, the last provides the most significant energy and power densities due to the better ionic conductivity. Our goal here is to present recent advances on quasisolid-state electrolytes, including gel-polymer electrolytes. We reviewed the most recent literature on quasi-solid-state electrolytes with different solvents for supercapacitors. Organic quasi-solid-state electrolytes need greater attention once they reach an excellent working voltage window greater than 2.5 V.Meanwhile, aqueous-based solid-state electrolytes have a restricted voltage window to less than 2 V. On the other hand, they are easier to handle, provide greater ionic conductivity and capacitance. Recent water-in-salt polymer-electrolytes have shown stability as great as 2 V encouraging further development in aqueous-based quasi-solid-state electrolytes. Moreover, hydrophilic conductive polymers have great commercial appeal for bendable devices. Thus, these electrolytes can be employed in flexible and bendable devices, favoring the improvement of portable electronics and wearable devices(376 references were evaluated and summarized here).
基金National Natural Science Foundation of China,Grant/Award Number:52064049Key National Natural Science Foundation of Yunnan Province,Grant/Award Numbers:2018FA028,2019FY003023+1 种基金International Joint Research Center for Advanced Energy Materials of Yunnan Province,Grant/Award Number:202003AE140001Key Laboratory of Solid State Ions for Green Energy of Yunnan University,Grant/Award Number:2019。
文摘A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Among the various SSEs,the single Li-ion conductor has advantages in terms of enhancing the ion conductivity,eliminating interfacial side reactions,and broadening the electrochemical window.Covalent organic frameworks(COFs)are optimal platforms for achieving single Li-ion conduction behavior because of wellordered one-dimensional channels and precise chemical modification features.Herein,we study in depth three types of Li-carboxylate COFs(denoted LiOOC-COFn,n=1,2,and 3)as single Li-ion conducting SSEs.Benefiting from well-ordered directional ion channels,the single Li-ion conductor LiOOC-COF3 shows an exceptional ion conductivity of 1.36×10^(-5) S cm^(-1) at room temperature and a high transference number of 0.91.Moreover,it shows excellent electrochemical performance with long-term cycling,high-capacity output,and no dendrites in the quasi-solid-state organic battery,with the organic small molecule cyclohexanehexone(C_(6)O_(6))as the cathode and the Li metal as the anode,and enables effectively avoiding dissolution of the organic electrode by the liquid electrolyte.
基金Zongping Shao and Kaiming Liao thank the funding support provide by the National Key R&D Program of China(Grant no.2018YFB0905400)Kaiming Liao thanks the funding support provided by the National Natural Science Foundation of China(Grant no.51802152)the Natural Science Foundation of Jiangsu Province of China(Grant no.BK20170974).A Project Funded by Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘The development of an air electrode that is flexible in physical property and highly active and durable at different geometric status for both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of crucial importance for the rational design of flexible rechargeable Zn-air batteries(ZABs).Considering their good elasticity,high conductivity,and superior thermal and chemical stability,carbon nanotubes have been widely used as a catalyst support in various electrocatalysts,while oxide or metal nanoparticles have been frequently deposited on the carbon nanotube substrate to perform as the active materials.Considering the poor contact between active materials and carbon nanotubes may introduce a challenge for long-term operating stability,in particular in flexible devices,pure carbon electrocatalyst is highly appreciated.Herein,a free-standing air electrode with cobalt nanoparticles encapsulated N-codoped carbon nanotube arrays uniformly grown on the surface of carbon fiber cloth is developed by a two-step in situ growth method.Such a carbon-based electrode shows outstanding activity for both ORR and OER.The flexible ZAB with such air electrode shows superior flexibility and stability working under extreme bending conditions.Moreover,the polarization and round-trip efficiency for the flexible battery is 0.67 V and 64.4%at 2 mA/cm2,respectively,even after being operated for 30 hours.This study provides a feasible way to design all carbon-based free-standing and flexible electrode and enlightens the electrode design for flexible energy conversion/storage devices.
基金the National Key Research and Development Program of China (No. 2020YFC1909604)the Shenzhen Key Projects of Technological Research (JSGG2020092514 5800001)。
文摘The isolated inorganic particles within composite polymer electrolytes(CPEs) are not correlated to the Li^(+)transfer network,resulting in the polymer dominating the low ionic conductivity of CPEs.Therefore,we developed novel quasi-solid-state CPEs of a Ce-doped Na super ion conductors(NASICON)Na_(1.3+x)Al_(0.3)Ce_(x)Ti_(1.7-x)(PO_(4))_(3)(NCATP) chemically coupled poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)/Li-bis(trifluoromethanes-ulfonyl)imide(LiTFSI) matrix.A strong interaction between Ce^(3+)from NCATP and TFSI-anion from the polymer matrix contributes to the fast Li+transportation at the interface.The PVDF-HFP/NCATP CPEs exhibit an ionic conductivity of 2.16 × 0^(-3) S cm^(-1) and a Li^(+) transference number of 0.88.A symmetric Li/Li cell with NCATP-integrated CPEs at 0.1 mA cm^(-2) presents outstanding cycling stability over 2000 h at 25℃.The quasi-solid-state Li metal batteries of Li/CPEs/LiFePO_(4) at 2 C after 400 cycles and Li/CPEs/LiCoO_(2) at 0.2 C after 120 cycles deliver capacities of 100 and 152 mAh g^(-1) at 25℃,respectively.
基金financially supported by the National Key R&D Program of China(Grant No.2016YFA0202500)the National Natural Science Fund for Excellent Young Scholars(Grant No.21722508)。
文摘Gel polymer electrolytes(GPEs)are one of the promising candidates for high-energy-density quasi-solid-state lithium metal batteries(QSSLMBs),for their high ionic conductivity and excellent interfacial compatibility.The comprehension of dynamic evolution and structure-reactivity correlation at the GPE/Li interface becomes significant.Here,in situ electrochemical atomic force microscopy(EC-AFM)provides insights into the LiNO_(3)-regulated micromechanism of the Li plating/stripping processes upon cycles in GPE-based LMBs at nanoscale.The additive LiNO_(3)induces the formation of amorphous nitride SEI film and facilitates Li^(+) ion diffusion.It stabilizes a compatible interface and regulates the Li nucleation/growth at steady kinetics.The deposited Li is in the shape of chunks and tightly compact.The Li dissolution shows favorable reversibility,which guarantees the cycling performance of LMBs.In situ AFM monitoring provides a deep understanding into the dynamic evolution of Li deposition/dissolution and the interphasial properties of tunable SEI film,regulating the rational design of electrolyte and optimizing interfacial establishment for GPE-based QSSLMBs.
基金supported by the National Key Research and Development Program of China(2017YFE0113500)the National Natural Science Foundation of China(51872027)。
文摘The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Polymer-based gel electrolytes with high ionic conductivity,great flexibility,easy processing,and high safety have been studied by many scholars in recent years.In this work,a novel porous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membrane is prepared by a phase inversion method.By immersing porous PVDF-HFP membranes in MgCl2-AlCl3/TEGDME(Tetraethylene glycol dimethyl ether)electrolytes,porous PVDF-HFP based electrolytes(PPEs)are formed.The PPE exhibits a high ionic conductivity(4.72×10^(-4) S cm-1,25℃),a high liquid electrolyte uptake of 162%,as well as a wide voltage window(3.1 V).The galvanostatic cycling test of Mg//Mg symmetric cell with PPE reveals that the reversible magnesium ion(Mg^(2+))plating/stripping occurs at low overpotentials(~0.13 V).Excellent long cycle stability(65.5 mAh g^(-1) over 1700 cycles)is achieved for the quasisolid-state RMB assembled with MoS2/C cathode and Mg anode.Compared with the liquid electrolyte,the PPE could effectively reduce the side reactions and make Mg^(2+)plating/stripping more uniformly on the Mg electrode side.This strategy herein provides a new route to fabricate high-performance RMB through suitable cathode material and polymer electrolyte with excellent performance.
基金support from the National Natural Science Foundation of China(52034011)the Fundamental Research Funds for the Science and Technology Program of Hunan Province(2019RS3002)+1 种基金the Central Universities of Central South University(Grant No.2018zzts133)Science and Technology Innovation Program of Hunan Province(2020RC2006).
文摘Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply.Despite intensive efforts on electrolytes,uncontrolled interfacial reactions on lithium with electrolyte and patchy interfacial contacts still hinder its practical process.Herein,we bring in rationally designed F contained groups into polymer skeleton via in-situ gelation for the first time to establish quasi-solid-state battery.This method achieves a capacity retention of 90%after 1000 cycles at 0.5C with LiFePO_(4)cathodes.The interface constructed by polymer skeleton and reaction with–CF_(3)lead to the predicted solid electrolyte interface species with high stability.Furthermore,we optimize molecular reactivity and interface stability with regulating F contained end groups in the polymer.Comparisons on different structures reveal that high performance solid stable lithium metal batteries rely on chemical modification as well as stable polymer skeleton,which is more critical to construct robust and steady SEI with uniform lithium deposition.New approach with functional groups regulation proposes a more stable cycling process with a capacity retention of 94.2%at 0.5C and 87.6%at 1C after 1000 cycles with LiFePO_(4) cathodes,providing new insights for the practical development of quasi-solid-state lithium metal battery.
