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
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
Zn-air batteries(ZABs)as a class of promising energy storage setups are generally powered by efficient and robust catalysts at the oxygen-involving cathode.Although the existing non-noble catalysts have outperformed n...Zn-air batteries(ZABs)as a class of promising energy storage setups are generally powered by efficient and robust catalysts at the oxygen-involving cathode.Although the existing non-noble catalysts have outperformed noble Pt benchmark in the alkaline liquid-state ZABs,to the best of our knowledge few have excelled Pt in quasi-solid-state(QSS)ZABs.Herein,we found that an integrated Mn-Co cathode derived from the bimetallic Mn/Co metal organic frameworks generates a 1.4-fold greater power density in the QSS ZABs than a Pt cathode while its power density in liquid-state ZABs is only 0.8-fold of the latter.Moreover,such Mn-Co catalyst delivers high-rate oxygen reduction reaction(ORR)capability with half-wave potential of 0.84 V.The in-depth characterizations and analyses have demonstrated that the Co and Mn species show the specific affinity towards H_(2)O and O_(2),respectively,synergizing the ORR process in the water-deficient environment of QSS ZABs.This work has enlightened the rational design of non-noble metal catalysts to improve the power density of QSS ZABs.展开更多
Due to the poor Fenton reactivity,single-atom Mn-based materials are generally identified as one of the most promising active catalysts for oxygen reduction reaction(ORR).Regulating the electronic density and coordina...Due to the poor Fenton reactivity,single-atom Mn-based materials are generally identified as one of the most promising active catalysts for oxygen reduction reaction(ORR).Regulating the electronic density and coordination environment of atomically dispersed Mn centers is an effective strategy to enhance ORR activity of Mn-based materials.By introducing Zn sites,atomically dispersed Mn centers with multitudes of coordination(including Zn/Mn–Nx and Mn–Nx moieties)can be constructed to form Mn-based ORR catalyst(Zn/Mn-NC)with dual-atom sites.Around Mn–Nx sites,the Zn atoms can effectively modulate the electronic structure and coordination state of Mn centers in Zn/Mn-NC through d–d orbital coupling.The electronic interaction between Zn and Mn sites improves ORR activity,thereby optimizing the oxygen adsorption energy of Mn sites in Zn/Mn-NC and reducing the overall energy barrier.Zn/Mn-NC displays higher ORR half-wave potential than Pt/C(0.89 V vs 0.86 V).The quasi-solid-state zinc-air battery(ZAB)with Zn/Mn-NC as the cathode displayed excellent rechargeability,recyclability,and mechanical robustness.The strategy presented regulates the electronic density and coordination environment of singleatom Mn-based ORR catalysts in quasi-solid-state ZABs.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 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
The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previo...The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previous studies using Zn I_(2)additive,this work designs an aqueous Bi I_(3)-Zn battery with selfsupplied I^(-).Ex situ tests reveal the conversion of Bi I_(3)into Bi(discharge)and Bi OI(charge)at the 1st cycle and the dissolved I^(-)in electrolyte.The active I^(-)species enhances the specific capacity and discharge medium voltage of electrode as well as improves the generation of Zn dendrite and by-product.Furthermore,the porous hard carbon is introduced to enhance the electronic/ionic conductivity and adsorb iodine species,proven by experimental and theoretical studies.Accordingly,the well-designed Bi I_(3)-Zn battery delivers a high reversible capacity of 182 m A h g^(-1)at 0.2 A g^(-1),an excellent rate capability with 88 m A h g^(-1)at 10 A g^(-1),and an impressive cyclability with 63%capacity retention over 20 K cycles at 10 A g^(-1).An excellent electrochemical performance is obtained even at a high mass loading of 6 mg cm^(-2).Moreover,a flexible quasi-solid-state Bi I_(3)-Zn battery exhibits satisfactory battery performances.This work provides a new idea for designing high-performance aqueous battery with dual mechanisms.展开更多
应用3D打印技术制备准固态微型超级电容器(MSCs)在可编程结构设计和高质量负载电极制造方面具有固有的优势.然而,缺乏高性能的可打印墨水和厚电极内缓慢的离子传输,对其实际电荷存储能力提出了重大挑战.本文成功开发了一种具有优异流变...应用3D打印技术制备准固态微型超级电容器(MSCs)在可编程结构设计和高质量负载电极制造方面具有固有的优势.然而,缺乏高性能的可打印墨水和厚电极内缓慢的离子传输,对其实际电荷存储能力提出了重大挑战.本文成功开发了一种具有优异流变性能的新型NiCo_(2)S_(4)基纳米复合墨水,并结合直墨书写的3D打印技术合理设计了准固态MSCs的三维结构.得益于牢固锚定在还原氧化石墨烯(rGO)表面的NiCo_(2)S_(4)纳米颗粒和有序的三维微孔,锯齿状厚电极提供了丰富的反应位点并增强了离子传输.因此,三层锯齿状MSCs的面电容高达416.7 mF cm^(-2).在1 mA cm^(-2)的电流密度下,单层、双层和三层电极的锯齿状MSCs的面电容与相对应的网格状MSCs相比,分别增加了127.1%、349.8%和585.9%.本工作为高面电容MSCs的材料和电极结构的跨尺度设计提供了新见解,推动了MSCs在柔性便携式电子设备中的集成应用研究.展开更多
The commercial application of non-precious metal-based electrocatalysts is not only limited by the intrinsic activity of the catalysts,but also the stability of the catalysts is extremely important.Herein,we fabricate...The commercial application of non-precious metal-based electrocatalysts is not only limited by the intrinsic activity of the catalysts,but also the stability of the catalysts is extremely important.Herein,we fabricated an ultra-stable NiFe armored catalyst(Ar-NiFe/NC)by a simple secondary pyrolysis strategy.The as-obtained Ar-NiFe/NC electrocatalyst exhibits an excellent bifunctional oxygen electrocatalytic performance with an activity indicatorΔE of 0.74 V vs.reversible hydrogen electrode(RHE).More importantly,the Ar-NiFe/NC electrocatalyst also shows a remarkable operational and storage stability.After accelerated durability test(ADT)cycles,no obvious degradation of oxygen electrocatalytic performance could be observed.In addition,the Ar-NiFe/NC electrocatalyst still exhibits an unbated oxygen electrocatalytic performance comparable to fresh catalysts after three months of air-exposed storage.The assembled liquid and flexible quasi-solid-state rechargeable Zn-air batteries with the Ar-NiFe/NC electrocatalyst exhibit impressive performance.The liquid rechargeable Zn-air batteries possess a high open-circuit voltage(OCV)of 1.43 V and a salient peak power density of 146.40 mW·cm^(−2),while the flexible quasi-solid-state rechargeable Zn-air batteries also exhibit an excellent OCV of 1.60 V and an exciting peak power density of 41.99 mW·cm^(−2).展开更多
The key to construct high-energy supercapacitors is to maximize the capacitance of electrode and the voltage of the device. Realizing this purpose by utilizing sustainable and low-cost resources is still a big challen...The key to construct high-energy supercapacitors is to maximize the capacitance of electrode and the voltage of the device. Realizing this purpose by utilizing sustainable and low-cost resources is still a big challenge. Herein, N, B co-doped carbon nanosheets are obtained through the proposed dual-template assisted approach by using methyl cellulose as the precursor. Due to the synergistic effects form the high surface area with the hierarchical porous structure, N/B dual doping, and a high degree of graphitization, the resultant carbon electrode exhibits a high capacitance of 572 F g^(-1)at 0.5 A g^(-1)and retains 281 F g^(-1)at 50 A g^(-1)in an acidic electrolyte. Furthermore, the symmetric device assembled using bacterial cellulose-based gel polymer electrolyte can deliver high energy density of 43 W h kg^(-1)and excellent cyclability with 97.8% capacity retention after 20 000 cycles in “water in salt” electrolyte. This work successfully realizes the fabrication of high-performance allcellulose-based quasi-solid-state supercapacitors, which brings a cost-effective insight into jointly designing electrodes and electrolytes for supporting highly efficient energy storage.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
Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and...Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and low cycle life due to the shuttle effect.To mitigate the shuttle effect induced by soluble selenium chloroaluminate compound that tends to migrate towards the negative electrode,a quasi-solid-state Al-Se battery was fabricated through the synthesis of a multi-aperture structure quasisolid-state electrolyte(MOF@GPE)based on metal-organic framework(MOF)material and gel-polymer electrolyte(GPE).The high ionic conductivity(1.13×10^(-3)S cm^(-1))of MOF@GPE at room temperature,coupled with its wide electrochemical stability window(2.45 V),can facilitate ion transport kinetics and enhance the electrochemical performance of Al-Se batteries.The MOF@GPE-based quasi-solidstate Al-Se batteries exhibit outstanding long-life cycling stability,delivering a high specific discharge capacity of 548 mA h g^(-1)with a maintained discharge specific capacity of 345 mA h g^(-1)after 500 cycles at a current density of 200 mA g^(-1).The stable ion transmission and high ion transport kinetics in MOF@GPE can be attributed to the stable structure and permeable channel of MOF,which effectively captures the soluble selenium chloroaluminate compound and further restrains the shuttle effect,resulting in improved cycling performance.展开更多
Flexible power sources featuring high-performance,prominent flexibility and raised safety have received mounting attention in the area of wearable electronic devices.However,many great challenges remain to be overcome...Flexible power sources featuring high-performance,prominent flexibility and raised safety have received mounting attention in the area of wearable electronic devices.However,many great challenges remain to be overcome,notably the design and fabrication of flexible electrodes with excellent electrochemical performance and matching them with safe and reliable electrolytes.Herein,a facile approach for preparing flexible electrodes,which employs carbon cloth derived from commercial cotton cloth as the substrate of cathode and a flexible anode,is proposed and investigated.The promising cathode(NVPOF@FCC)with high conductivity and outstanding flexibility is prepared by efficiently coating Na_(3)V_(2)(PO_(4))_(2)O_(2)F(NVPOF)on flexible carbon cloth(FCC),which exhibits remarkable electrochemical performance and the significantly improved reaction kinetics.More importantly,a novel flexible quasi-solid-state sodium-ion full battery(QSFB)is feasibly assembled by sandwiching a P(VDF-HFP)-NaClO_(4) gel-polymer electrolyte film between the advanced NVPOF@FCC cathode and FCC anode.And the QSFBs are further evaluated in flexible pouch cells,which not only demonstrates excellent energy-storage performance in aspect of great cycling stability and high-rate capability,but also impressive flexibility and safety.This work offers a feasible and effective strategy for the design of flexible electrodes,paving the way for the progression of practical and sustainable flexible batteries.展开更多
Lithium–sulfur(Li–S)battery as a high-energy density electrochemical energy storage system has attracted many researchers’attention.However,the shuttle effect of Li–S batteries and the challenges associated with l...Lithium–sulfur(Li–S)battery as a high-energy density electrochemical energy storage system has attracted many researchers’attention.However,the shuttle effect of Li–S batteries and the challenges associated with lithium metal anode caused poor cycle performance.In this work,the organosulfide poly(sulfur-1,3-diisopropenylbenzene)(PSD)was prepared as cathode material and additive of P(VDFHFP)polymer electrolyte(P(VDF-HFP)).It was verified that P(VDF-HFP)polymer electrolyte with 10%PSD(P(VDF-HFP)-10%PSD)showed a higher ionic conductivities than that of liquid electrolyte up to2.27×10-3 S cm-1 at room temperature.The quasi-solid-state Li-S batteries fabricated with organosulfide cathode material PSD and P(VDF-HFP)based functional polymer electrolyte delivered good cycling stability(780 m Ah g-1 after 200 th cycle at 0.1 C)and rate performance(613 m Ah g-1 at 1 C).The good cycling performance could be attributed to the synergistic effect of components,including the interaction between polysulfides and polymer main chain in the organosulfide cathode,the sustained organic/inorganic hybrid stable SEI layer formed by polymer electrolyte additive PSD,the improved cathode/electrolyte interface and the good affinity between P(VDF-HFP)based functional polymer electrolyte and Li metal surface.This strategy herein may provide a new route to fabricate high-performance Li–S batteries through the organosulfide cathode and functional polymer electrolyte.展开更多
The practical applications of solid-state electrolytes in lithium-ion batteries(LIBs)are hindered by their low ionic conductivity and high interfacial resistance.Herein,an ethoxylated trimethylolpropane triacrylate ba...The practical applications of solid-state electrolytes in lithium-ion batteries(LIBs)are hindered by their low ionic conductivity and high interfacial resistance.Herein,an ethoxylated trimethylolpropane triacrylate based quasi-solid-state electrolyte(ETPTAQSSE)with a three-dimensional(3D)network is prepared by a one-step in-situ photopolymerization method.The 3D network is designed to overcome the contradiction between the plasticizer-related ionic conductivity and the thickness-dependent mechanical property of quasi-solid-state electrolytes.The ETPTA-QSSE achieves superb room-temperature ionic conductivity up to 4.55×10^(−3)S cm^(−1),a high lithium ion transference number of 0.57,along with a wide electrochemical window of 5.3 V(vs.Li+/Li),which outperforms most ever of the reported solid-state electrolytes.Owing to the robust network structure and the cathodeelectrolyte integrated electrode design,Li metal symmetrical cells show reduced interface resistance and reinforced electrode/electrolyte interface stability.When applying the ETPTA-QSSE in LiFePO_(4)||Li cells,the quasi-solid-state cell demonstrates an enhanced initial discharge capacity(155.5 mAh g^(−1)at 0.2 C)accompanied by a high average Coulombic efficiency of greater than 99.3%,offering capacity retention of 92%after 200 cycles.Accordingly,this work sheds light on the strategy of enhancing ionic conductivity and reducing interfacial resistance of quasi-solid-state electrolytes,which is promising for high-voltage LIBs.展开更多
Together with the development of high-performance advanced electronics,flexible supercapacitors(SCs)with tailored nanostructures have great attraction.Electrochemically deposited nanosheet arrays of nickel magnesium s...Together with the development of high-performance advanced electronics,flexible supercapacitors(SCs)with tailored nanostructures have great attraction.Electrochemically deposited nanosheet arrays of nickel magnesium selenide(NixMg3-xSe4,NMgS)with high capacitance provide high potentials as a positive electrode in flexible SCs.To further enhance their electrochemical properties and long-term cycling stability,a promising strategy of surface engineering with conducting polymer poly(3,4-ethylenedioxythiophene)(PEDOT)is proposed.The present work proposes the construction of PEDOT shielded NMgS(P@NMgS-2)on a flexible carbon cloth substrate via a hierarchical electrodeposition technique.Benefitting from the synergistic effect,the P@NMgS-2 exhibits an excellent areal capacitance value of 1440 mF cm^(-2)at 4 mA cm^(-2).A novel shape-adaptable polymer gel electrolyte-assisted flexible quasi-solid-state hybrid SC(FQHSC)device constructed with P@NMgS-2 as a positive electrode and activated carbon as a negative electrode demonstrates the maximum power and energy density values of 14.13 mW cm^(-2)and 0.18 mWh cm^(-2),respectively,followed by outstanding cycling stability(∼100%capacitance retention over 50,000 cycles).Furthermore,the FQHSC device successfully powered electronic devices with no serious degradation upon bending and twisting for wearable electronic applications.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
Aqueous rechargeable batteries with high safety have been considered as the main energy source to power portable and wearable electronics.Herein,we report the first construction of quasi-solid-state aqueous tin-iodine...Aqueous rechargeable batteries with high safety have been considered as the main energy source to power portable and wearable electronics.Herein,we report the first construction of quasi-solid-state aqueous tin-iodine batteries by exploiting Sn foil as anode,carbon cloth as cathode,and gel electrolytes.The anode reversibly converts from K_(2)Sn(OH)_(6) to metal Sn,thus eliminating the formation of metal dendrites.Meanwhile,gel electrolytes alleviate anode corrosion and enhance the utilization of the anode.Therefore,the asfabricated quasi-solid-state batteries manifest an areal capacity of 700μAh cm^(-2)(211 mAh g^(-1) equal to theoretical capacity)and excellent cycling stability without obvious capacity degradation after 120 cycles at 1mA cm^(-2).Remarkably,the designed batteries sealed by different package materials including plastic,glass,wood,and cardboard operated steadily,thereby enlarging the application scenario for these batteries.This work enriches the family of aqueous rechargeable batteries and sheds light on the construction of high-performance quasi-solid-state aqueous batteries.展开更多
The ever-growing demand for next-generation high-energy-density devices drives the development of lithium metal batteries with enough safety and high performance,in which quasi-solid-state composite electrolytes(QSCEs...The ever-growing demand for next-generation high-energy-density devices drives the development of lithium metal batteries with enough safety and high performance,in which quasi-solid-state composite electrolytes(QSCEs)with high ionic conductivity and lithium ion transference number(urn:x-wiley:1001604X:media:cjoc202300232:cjoc202300232-math-0001)are highly desirable.Herein,we successfully synthesize a kind of two-dimensional(2D)molecular brush(GO-g-PFIL)via grafting poly(ionic liquid)side-chain(poly(3-(3,3,4,4,4-pentafluorobutyl)-1-vinyl-1H-imidazol-3-ium bis(trifluoromethanesulfonyl)imide),denoted as PFIL)on the surface of 2D graphene oxide(GO)sheet.GO-g-PFIL is used as multifunctional filler to prepare novel composite membranes and corresponding QSCEs(e.g.,QSCE-PH/GPFIL3/P).The as-obtained QSCE-PH/GPFIL3/P integrates features of PFIL side-chain-enhanced lithium ion conduction,poly(vinylidene fluoride-co-hexafluoropropene)backbone-induced flexibility,and GO-strengthened mechanical property.As a result,our ultrathin(21μm)self-supporting QSCE-PH/GPFIL3/P exhibits high ionic conductivity(3.24×10^(−4)S·cm^(−1))and excellent urn:x-wiley:1001604X:media:cjoc202300232:cjoc202300232-math-0002(0.82)at room temperature,and Li/LFP full cell with QSCE-PH/GPFIL3/P shows superior rate performance(high specific capacities of 79 mAh·g^(−1)at 30°C and 5 C)and excellent cycling performance(high capacity retention of 91%after 500 cycles at 80°C and 1 C).展开更多
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support of the Fundamental Research Funds for the Central Universities(No.40120631)National Natural Science Foundation of China(No.52202291)for the support.
文摘Zn-air batteries(ZABs)as a class of promising energy storage setups are generally powered by efficient and robust catalysts at the oxygen-involving cathode.Although the existing non-noble catalysts have outperformed noble Pt benchmark in the alkaline liquid-state ZABs,to the best of our knowledge few have excelled Pt in quasi-solid-state(QSS)ZABs.Herein,we found that an integrated Mn-Co cathode derived from the bimetallic Mn/Co metal organic frameworks generates a 1.4-fold greater power density in the QSS ZABs than a Pt cathode while its power density in liquid-state ZABs is only 0.8-fold of the latter.Moreover,such Mn-Co catalyst delivers high-rate oxygen reduction reaction(ORR)capability with half-wave potential of 0.84 V.The in-depth characterizations and analyses have demonstrated that the Co and Mn species show the specific affinity towards H_(2)O and O_(2),respectively,synergizing the ORR process in the water-deficient environment of QSS ZABs.This work has enlightened the rational design of non-noble metal catalysts to improve the power density of QSS ZABs.
基金support of the National Natural Science Foundation of China(grant nos.22278193 and 22178148)Jiangsu Province and Education Ministry Cosponsored Synergistic Innovation Center of Modern Agricultural Equipment(grant no.XTCX2029)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Due to the poor Fenton reactivity,single-atom Mn-based materials are generally identified as one of the most promising active catalysts for oxygen reduction reaction(ORR).Regulating the electronic density and coordination environment of atomically dispersed Mn centers is an effective strategy to enhance ORR activity of Mn-based materials.By introducing Zn sites,atomically dispersed Mn centers with multitudes of coordination(including Zn/Mn–Nx and Mn–Nx moieties)can be constructed to form Mn-based ORR catalyst(Zn/Mn-NC)with dual-atom sites.Around Mn–Nx sites,the Zn atoms can effectively modulate the electronic structure and coordination state of Mn centers in Zn/Mn-NC through d–d orbital coupling.The electronic interaction between Zn and Mn sites improves ORR activity,thereby optimizing the oxygen adsorption energy of Mn sites in Zn/Mn-NC and reducing the overall energy barrier.Zn/Mn-NC displays higher ORR half-wave potential than Pt/C(0.89 V vs 0.86 V).The quasi-solid-state zinc-air battery(ZAB)with Zn/Mn-NC as the cathode displayed excellent rechargeability,recyclability,and mechanical robustness.The strategy presented regulates the electronic density and coordination environment of singleatom Mn-based ORR catalysts in quasi-solid-state ZABs.
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funding from National Natural Science Foundation of China(52103053,52102312)Huxiang Young Talents of Hunan Province(2022RC1004)+1 种基金Macao Young Scholars Program(AM2021011)Foundation of State Key Laboratory of Utilization of Woody Oil Resource(GZKF202126)。
文摘The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previous studies using Zn I_(2)additive,this work designs an aqueous Bi I_(3)-Zn battery with selfsupplied I^(-).Ex situ tests reveal the conversion of Bi I_(3)into Bi(discharge)and Bi OI(charge)at the 1st cycle and the dissolved I^(-)in electrolyte.The active I^(-)species enhances the specific capacity and discharge medium voltage of electrode as well as improves the generation of Zn dendrite and by-product.Furthermore,the porous hard carbon is introduced to enhance the electronic/ionic conductivity and adsorb iodine species,proven by experimental and theoretical studies.Accordingly,the well-designed Bi I_(3)-Zn battery delivers a high reversible capacity of 182 m A h g^(-1)at 0.2 A g^(-1),an excellent rate capability with 88 m A h g^(-1)at 10 A g^(-1),and an impressive cyclability with 63%capacity retention over 20 K cycles at 10 A g^(-1).An excellent electrochemical performance is obtained even at a high mass loading of 6 mg cm^(-2).Moreover,a flexible quasi-solid-state Bi I_(3)-Zn battery exhibits satisfactory battery performances.This work provides a new idea for designing high-performance aqueous battery with dual mechanisms.
基金financially supported by the National Natural Science Foundation of China (No.U22A20118)Natural Science Foundation of Fujian Province (No.2023J01400)+1 种基金Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China (No.2021ZZ122)Award Program for Fujian Minjiang Scholar Professorship。
文摘应用3D打印技术制备准固态微型超级电容器(MSCs)在可编程结构设计和高质量负载电极制造方面具有固有的优势.然而,缺乏高性能的可打印墨水和厚电极内缓慢的离子传输,对其实际电荷存储能力提出了重大挑战.本文成功开发了一种具有优异流变性能的新型NiCo_(2)S_(4)基纳米复合墨水,并结合直墨书写的3D打印技术合理设计了准固态MSCs的三维结构.得益于牢固锚定在还原氧化石墨烯(rGO)表面的NiCo_(2)S_(4)纳米颗粒和有序的三维微孔,锯齿状厚电极提供了丰富的反应位点并增强了离子传输.因此,三层锯齿状MSCs的面电容高达416.7 mF cm^(-2).在1 mA cm^(-2)的电流密度下,单层、双层和三层电极的锯齿状MSCs的面电容与相对应的网格状MSCs相比,分别增加了127.1%、349.8%和585.9%.本工作为高面电容MSCs的材料和电极结构的跨尺度设计提供了新见解,推动了MSCs在柔性便携式电子设备中的集成应用研究.
基金supported by the National Natural Science Foundation of China(No.22102132)the Funds for Basic Scientific Research in Central Universities and the Youth Project of the Natural Science Foundation of Shaanxi Province,China(No.2021JQ-087)+1 种基金Ningbo Natural Science Foundation(No.2021J053)the open research fund of Key Laboratory for Organic Electronics and Information Displays.
文摘The commercial application of non-precious metal-based electrocatalysts is not only limited by the intrinsic activity of the catalysts,but also the stability of the catalysts is extremely important.Herein,we fabricated an ultra-stable NiFe armored catalyst(Ar-NiFe/NC)by a simple secondary pyrolysis strategy.The as-obtained Ar-NiFe/NC electrocatalyst exhibits an excellent bifunctional oxygen electrocatalytic performance with an activity indicatorΔE of 0.74 V vs.reversible hydrogen electrode(RHE).More importantly,the Ar-NiFe/NC electrocatalyst also shows a remarkable operational and storage stability.After accelerated durability test(ADT)cycles,no obvious degradation of oxygen electrocatalytic performance could be observed.In addition,the Ar-NiFe/NC electrocatalyst still exhibits an unbated oxygen electrocatalytic performance comparable to fresh catalysts after three months of air-exposed storage.The assembled liquid and flexible quasi-solid-state rechargeable Zn-air batteries with the Ar-NiFe/NC electrocatalyst exhibit impressive performance.The liquid rechargeable Zn-air batteries possess a high open-circuit voltage(OCV)of 1.43 V and a salient peak power density of 146.40 mW·cm^(−2),while the flexible quasi-solid-state rechargeable Zn-air batteries also exhibit an excellent OCV of 1.60 V and an exciting peak power density of 41.99 mW·cm^(−2).
基金supported by the National Natural Science Foundation of China (No.22179123 and 21471139)the Shandong Provincial Natural Science Foundation,China (ZR2020ME038)+2 种基金the Fundamental Research Funds for the Central Universities (No.201941010)the Shandong Provincial Key R&D Plan and the Public Welfare Special Program,China (2019GGX102038)the Qingdao City Programs for Science and Technology Plan Projects (19-6-2-77-cg)。
文摘The key to construct high-energy supercapacitors is to maximize the capacitance of electrode and the voltage of the device. Realizing this purpose by utilizing sustainable and low-cost resources is still a big challenge. Herein, N, B co-doped carbon nanosheets are obtained through the proposed dual-template assisted approach by using methyl cellulose as the precursor. Due to the synergistic effects form the high surface area with the hierarchical porous structure, N/B dual doping, and a high degree of graphitization, the resultant carbon electrode exhibits a high capacitance of 572 F g^(-1)at 0.5 A g^(-1)and retains 281 F g^(-1)at 50 A g^(-1)in an acidic electrolyte. Furthermore, the symmetric device assembled using bacterial cellulose-based gel polymer electrolyte can deliver high energy density of 43 W h kg^(-1)and excellent cyclability with 97.8% capacity retention after 20 000 cycles in “water in salt” electrolyte. This work successfully realizes the fabrication of high-performance allcellulose-based quasi-solid-state supercapacitors, which brings a cost-effective insight into jointly designing electrodes and electrolytes for supporting highly efficient energy storage.
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.
基金supported by the National Natural Science Foundation of China(51874019 and 51725401)the China Postdoctoral Science Foundation(2020M680347 and 2021T140051)the Fundamental Research Funds for the Central Universities(FRFTP-20-045A1)。
文摘Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and low cycle life due to the shuttle effect.To mitigate the shuttle effect induced by soluble selenium chloroaluminate compound that tends to migrate towards the negative electrode,a quasi-solid-state Al-Se battery was fabricated through the synthesis of a multi-aperture structure quasisolid-state electrolyte(MOF@GPE)based on metal-organic framework(MOF)material and gel-polymer electrolyte(GPE).The high ionic conductivity(1.13×10^(-3)S cm^(-1))of MOF@GPE at room temperature,coupled with its wide electrochemical stability window(2.45 V),can facilitate ion transport kinetics and enhance the electrochemical performance of Al-Se batteries.The MOF@GPE-based quasi-solidstate Al-Se batteries exhibit outstanding long-life cycling stability,delivering a high specific discharge capacity of 548 mA h g^(-1)with a maintained discharge specific capacity of 345 mA h g^(-1)after 500 cycles at a current density of 200 mA g^(-1).The stable ion transmission and high ion transport kinetics in MOF@GPE can be attributed to the stable structure and permeable channel of MOF,which effectively captures the soluble selenium chloroaluminate compound and further restrains the shuttle effect,resulting in improved cycling performance.
基金supported by the National Natural Science Foundation of China(No.91963118)Science Technology Program of Jilin Province(No.20200201066JC)+2 种基金Fundamental Research Funds for the Central Universities(No.2412020QD013)China Postdoctoral Science Foundation(No.2019M661187)the National Postdoctoral Program for Innovative Talents(BX20190064).
文摘Flexible power sources featuring high-performance,prominent flexibility and raised safety have received mounting attention in the area of wearable electronic devices.However,many great challenges remain to be overcome,notably the design and fabrication of flexible electrodes with excellent electrochemical performance and matching them with safe and reliable electrolytes.Herein,a facile approach for preparing flexible electrodes,which employs carbon cloth derived from commercial cotton cloth as the substrate of cathode and a flexible anode,is proposed and investigated.The promising cathode(NVPOF@FCC)with high conductivity and outstanding flexibility is prepared by efficiently coating Na_(3)V_(2)(PO_(4))_(2)O_(2)F(NVPOF)on flexible carbon cloth(FCC),which exhibits remarkable electrochemical performance and the significantly improved reaction kinetics.More importantly,a novel flexible quasi-solid-state sodium-ion full battery(QSFB)is feasibly assembled by sandwiching a P(VDF-HFP)-NaClO_(4) gel-polymer electrolyte film between the advanced NVPOF@FCC cathode and FCC anode.And the QSFBs are further evaluated in flexible pouch cells,which not only demonstrates excellent energy-storage performance in aspect of great cycling stability and high-rate capability,but also impressive flexibility and safety.This work offers a feasible and effective strategy for the design of flexible electrodes,paving the way for the progression of practical and sustainable flexible batteries.
基金Financial supports from the National Natural Science Foundation of China(51532002 and 51872027)Beijing Natural Science Foundation(L172023)National Basic Research Program of China(2016YFA0202500,2017YFE0113500,and 2018YFB0104300)。
文摘Lithium–sulfur(Li–S)battery as a high-energy density electrochemical energy storage system has attracted many researchers’attention.However,the shuttle effect of Li–S batteries and the challenges associated with lithium metal anode caused poor cycle performance.In this work,the organosulfide poly(sulfur-1,3-diisopropenylbenzene)(PSD)was prepared as cathode material and additive of P(VDFHFP)polymer electrolyte(P(VDF-HFP)).It was verified that P(VDF-HFP)polymer electrolyte with 10%PSD(P(VDF-HFP)-10%PSD)showed a higher ionic conductivities than that of liquid electrolyte up to2.27×10-3 S cm-1 at room temperature.The quasi-solid-state Li-S batteries fabricated with organosulfide cathode material PSD and P(VDF-HFP)based functional polymer electrolyte delivered good cycling stability(780 m Ah g-1 after 200 th cycle at 0.1 C)and rate performance(613 m Ah g-1 at 1 C).The good cycling performance could be attributed to the synergistic effect of components,including the interaction between polysulfides and polymer main chain in the organosulfide cathode,the sustained organic/inorganic hybrid stable SEI layer formed by polymer electrolyte additive PSD,the improved cathode/electrolyte interface and the good affinity between P(VDF-HFP)based functional polymer electrolyte and Li metal surface.This strategy herein may provide a new route to fabricate high-performance Li–S batteries through the organosulfide cathode and functional polymer electrolyte.
基金supported by the Recruitment Program of Global Expertsthe Hundred-Talent Project of FujianFuzhou University
文摘The practical applications of solid-state electrolytes in lithium-ion batteries(LIBs)are hindered by their low ionic conductivity and high interfacial resistance.Herein,an ethoxylated trimethylolpropane triacrylate based quasi-solid-state electrolyte(ETPTAQSSE)with a three-dimensional(3D)network is prepared by a one-step in-situ photopolymerization method.The 3D network is designed to overcome the contradiction between the plasticizer-related ionic conductivity and the thickness-dependent mechanical property of quasi-solid-state electrolytes.The ETPTA-QSSE achieves superb room-temperature ionic conductivity up to 4.55×10^(−3)S cm^(−1),a high lithium ion transference number of 0.57,along with a wide electrochemical window of 5.3 V(vs.Li+/Li),which outperforms most ever of the reported solid-state electrolytes.Owing to the robust network structure and the cathodeelectrolyte integrated electrode design,Li metal symmetrical cells show reduced interface resistance and reinforced electrode/electrolyte interface stability.When applying the ETPTA-QSSE in LiFePO_(4)||Li cells,the quasi-solid-state cell demonstrates an enhanced initial discharge capacity(155.5 mAh g^(−1)at 0.2 C)accompanied by a high average Coulombic efficiency of greater than 99.3%,offering capacity retention of 92%after 200 cycles.Accordingly,this work sheds light on the strategy of enhancing ionic conductivity and reducing interfacial resistance of quasi-solid-state electrolytes,which is promising for high-voltage LIBs.
基金This work was supported by the National Research Foundation of Korea Grant funded by the Korea government(MSIP)(No.2018R1A6A1A03025708 and No.2020R1A2B5B01002318).
文摘Together with the development of high-performance advanced electronics,flexible supercapacitors(SCs)with tailored nanostructures have great attraction.Electrochemically deposited nanosheet arrays of nickel magnesium selenide(NixMg3-xSe4,NMgS)with high capacitance provide high potentials as a positive electrode in flexible SCs.To further enhance their electrochemical properties and long-term cycling stability,a promising strategy of surface engineering with conducting polymer poly(3,4-ethylenedioxythiophene)(PEDOT)is proposed.The present work proposes the construction of PEDOT shielded NMgS(P@NMgS-2)on a flexible carbon cloth substrate via a hierarchical electrodeposition technique.Benefitting from the synergistic effect,the P@NMgS-2 exhibits an excellent areal capacitance value of 1440 mF cm^(-2)at 4 mA cm^(-2).A novel shape-adaptable polymer gel electrolyte-assisted flexible quasi-solid-state hybrid SC(FQHSC)device constructed with P@NMgS-2 as a positive electrode and activated carbon as a negative electrode demonstrates the maximum power and energy density values of 14.13 mW cm^(-2)and 0.18 mWh cm^(-2),respectively,followed by outstanding cycling stability(∼100%capacitance retention over 50,000 cycles).Furthermore,the FQHSC device successfully powered electronic devices with no serious degradation upon bending and twisting for wearable electronic applications.
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sponsored by the NSFC(grant nos.21671020,51673026,22035005,and 52073159)the Natural Science Foundation of Beijing Municipality(grant no.2222075)+1 种基金the National Key R&D Program of China(grant no.2017YFB1104300)the Analysis&Testing Center,Beijing Institute of Technology.
文摘Aqueous rechargeable batteries with high safety have been considered as the main energy source to power portable and wearable electronics.Herein,we report the first construction of quasi-solid-state aqueous tin-iodine batteries by exploiting Sn foil as anode,carbon cloth as cathode,and gel electrolytes.The anode reversibly converts from K_(2)Sn(OH)_(6) to metal Sn,thus eliminating the formation of metal dendrites.Meanwhile,gel electrolytes alleviate anode corrosion and enhance the utilization of the anode.Therefore,the asfabricated quasi-solid-state batteries manifest an areal capacity of 700μAh cm^(-2)(211 mAh g^(-1) equal to theoretical capacity)and excellent cycling stability without obvious capacity degradation after 120 cycles at 1mA cm^(-2).Remarkably,the designed batteries sealed by different package materials including plastic,glass,wood,and cardboard operated steadily,thereby enlarging the application scenario for these batteries.This work enriches the family of aqueous rechargeable batteries and sheds light on the construction of high-performance quasi-solid-state aqueous batteries.
基金This work was supported by the projects of National Key Research and Development Program of China(2021YFF0500600)National Natural Science Foundation of China(51925308)+1 种基金Fundamental Research Funds for the Central Universities,Sun Yat-sen University(23yxqntdo02)Natural Science Foundation of Guangdong Province(2023A1515030160,2022A1515011778).
文摘The ever-growing demand for next-generation high-energy-density devices drives the development of lithium metal batteries with enough safety and high performance,in which quasi-solid-state composite electrolytes(QSCEs)with high ionic conductivity and lithium ion transference number(urn:x-wiley:1001604X:media:cjoc202300232:cjoc202300232-math-0001)are highly desirable.Herein,we successfully synthesize a kind of two-dimensional(2D)molecular brush(GO-g-PFIL)via grafting poly(ionic liquid)side-chain(poly(3-(3,3,4,4,4-pentafluorobutyl)-1-vinyl-1H-imidazol-3-ium bis(trifluoromethanesulfonyl)imide),denoted as PFIL)on the surface of 2D graphene oxide(GO)sheet.GO-g-PFIL is used as multifunctional filler to prepare novel composite membranes and corresponding QSCEs(e.g.,QSCE-PH/GPFIL3/P).The as-obtained QSCE-PH/GPFIL3/P integrates features of PFIL side-chain-enhanced lithium ion conduction,poly(vinylidene fluoride-co-hexafluoropropene)backbone-induced flexibility,and GO-strengthened mechanical property.As a result,our ultrathin(21μm)self-supporting QSCE-PH/GPFIL3/P exhibits high ionic conductivity(3.24×10^(−4)S·cm^(−1))and excellent urn:x-wiley:1001604X:media:cjoc202300232:cjoc202300232-math-0002(0.82)at room temperature,and Li/LFP full cell with QSCE-PH/GPFIL3/P shows superior rate performance(high specific capacities of 79 mAh·g^(−1)at 30°C and 5 C)and excellent cycling performance(high capacity retention of 91%after 500 cycles at 80°C and 1 C).
