Microwave irradiation was employed to assist the synthesis of poly(amino-quinone) (PAQ) from p-benzoquinone and diamines in solid state. The effects of power, time, and pattern (continuously or intermittently) o...Microwave irradiation was employed to assist the synthesis of poly(amino-quinone) (PAQ) from p-benzoquinone and diamines in solid state. The effects of power, time, and pattern (continuously or intermittently) of microwave irradiation on yield and intrinsic viscosity of PAQs were studied. It is shown that the continuous microwave irradiation at a high power leads to rapid increase of yield and a sudden halt in polymerization afterwards, due to the subsequent loss of volatile reactants at a high reaction temperature. Alternatively, the high-power microwave irradiation is applicable to raising the yield if used intermittently. In contras4 the low-power microwave irradiation favours the way of continuous exposure to ensure sufficient heat for polymerization. In both cases of high and low power, the yield and intrinsic viscosity can be further promoted by prolonging the exposure time. It is found that under a preliminarily optimized condition of intermittent irradiation at 490 W with six sequences of 5 min irradiation followed by 5 rain interval, the yield and intrinsic viscosity of PAQ from p-benzoquinone and p-phenylene diamine can reach as high as 83% and 41.9 mL/g, respectively.展开更多
This work demonstrates a novel polymerization-derived polymer electrolyte consisting of methyl methacrylate,lithium bis(trifluoromethanesulfonyl)imide and fluoroethylene carbonate.The polymerization of MMA was initiat...This work demonstrates a novel polymerization-derived polymer electrolyte consisting of methyl methacrylate,lithium bis(trifluoromethanesulfonyl)imide and fluoroethylene carbonate.The polymerization of MMA was initiated by the amino compounds following an anionic catalytic mechanism.LiTFSI plays both roles including the initiator and Li ion source in the polymer electrolyte.Normally,lithium bis(trifluoromethanesulfonyl)imide has difficulty in initiating the polymerization reaction of methyl methacrylate monomer,a very high concentration of lithium bis(trifluoromethanesulfonyl)imide is needed for initiating the polymerization.However,the fluoroethylene carbonate additive can work as a supporter to facilitate the degree of dissociation of lithium bis(trifluoromethanesulfonyl)imide and increase its initiator capacity due to the high dielectric constant.The as-prepared poly-methyl methacrylate-based polymer electrolyte has a high ionic conductivity(1.19×10^(−3)S cm^(−1)),a wide electrochemical stability window(5 V vs Li^(+)/Li),and a high Li ion transference number(t_(Li^(+)))of 0.74 at room temperature(RT).Moreover,this polymerization-derived polymer electrolyte can effectively work as an artificial protective layer on Li metal anode,which enabled the Li symmetric cell to achieve a long-term cycling performance at 0.2 mAh cm^(−2)for 2800 h.The LiFePO_(4)battery with polymerization-derived polymer electrolyte-modified Li metal anode shows a capacity retention of 91.17%after 800 cycles at 0.5 C.This work provides a facile and accessible approach to manufacturing poly-methyl methacrylate-based polymerization-derived polymer electrolyte and shows great potential as an interphase in Li metal batteries.展开更多
Poly(bisphenol A carbonate) (BPA-PC) was post-polymerized by solid-state polymerization (SSP) after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesteri...Poly(bisphenol A carbonate) (BPA-PC) was post-polymerized by solid-state polymerization (SSP) after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesterification reaction. The effects of the crystallization conditions on melting behavior and SSP of BPA-PC were investigated with differential scanning calorimetry (DSC), Ubbelohde viscosity method and gel permeation chromatography (GPC). The reaction kinetics of the SSP of crystallized prepolymers was studied as a function of reaction temperatures for various reaction periods. As a result, the viscosity average molecular weight of BPA-PC particles (2 mm) increased from 1.9 × 10^4 g/mol to 2.8 × 10^4 g/mol after SSP. More importantly, the significantly enhanced thermal stability and mechanical properties of solid-state polymerized BPA-PC, compared with those of melt transesterification polymerized BPA-PC with the same molecular weight, can be ascribed to the substantial avoidance of undergoing high temperature during polymerization. Our work provides a useful method to obtain practical product of BPA-PC with high quality and high molecular weight.展开更多
Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves t...Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves the rational design of solid-state-C≡N functionalized P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs and its synthesis by in-situ free radical polymerization of vinyl ethylene carbonate(VEC) and 2-cyanoethyl acrylate(CEA).In situ polymerization yields electrode/electrolyte interfaces with low interfacial resistance,forming a stable SEI layer enriched with LiF,Li_(3)N,and RCOOLi,ensuring stable Li plating/stripping for over 1400 h.The-C≡N moiety renders the αH on the adjacent αC positively charged,thereby endowing it with the capability to anchor TFSI^(-).Simultaneously,the incorporation of-C≡N moiety diminishes the electron-donating ability of the C=O,C-O-C,and-C≡N functional groups,facilitating not only the ion conductivity enhancement but also a more rapid Li^(+)migration proved by DFT theoretical calculations and Raman spectroscopy.At room temperature,t_(Li+) of 0.60 for P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs is achieved when the ionic conductivity σ_(Li+)is 2.63×10^(-4) S cm^(-1) and the electrochemical window is expanded to5.0 V.Both coin cells with high-areal-loading cathodes and the 6.5-mAh pouch cell,exhibit stable charge/discharge cycling.At 25℃,the 4.45-V Li|P(VEC_1-CEA_(0.3))/LiTFSI@CE|LiCoO_(2) battery performs stable cycling over 200 cycles at 0.2 C,with a capacity retention of 82.1%.展开更多
Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and ...Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and application. Herein, a laminar MXene functional layer-thin SPE layer-cathode integration(MXene-PEO-LFP) is designed and fabricated. The MXene functional layer formed by stacking rigid MXene nanosheets imparts higher compressive strength relative to PEO electrolyte layer. And the abundant negatively-charged groups on MXene functional layer effectively repel anions and attract cations to adjust the charge distribution behavior at electrolyte–anode interface. Furthermore,the functional layer with rich lithiophilic groups and outstanding electronic conductivity results in low Li nucleation overpotential and nucleation energy barrier. In consequence, the cell assembled with MXene-PEO-LFP, where the PEO electrolyte layer is only 12 μm, much thinner than most solid electrolytes, exhibits uniform, dendrite-free Li+deposition and excellent cycling stability. High capacity(142.8 mAh g-1), stable operation of 140 cycles(capacity decay per cycle, 0.065%), and low polarization potential(0.5 C) are obtained in this Li|MXene-PEO-LFP cell,which is superior to most PEO-based electrolytes under identical condition. This integrated design may provide a strategy for the large-scale application of thin polymer electrolytes in all-solid-state battery.展开更多
Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorgani...Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorganic solid electrolytes are desirable properties for realizing high-performance safe solid-state batteries by replacing conventional liquid electrolytes.However,the low chemical and electrochemical stability of sulfide-based inorganic solid electrolytes hinder the commercialization of sulfide-based safe solid-state batteries.Particularly,the instability of sulfide-based inorganic solid electrolytes is intensified in the cathode,comprising various materials.In this study,carbonate-based ionic conductive polymers are introduced to the cathode to protect cathode materials and suppress the reactivity of sulfide electrolytes.Several instruments,including electrochemical spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy,confirm the chemical and electrochemical stability of the polymer electrolytes in contact with sulfide-based inorganic solid electrolytes.Sulfide-based solid-state cells show stable electrochemical performance over 100 cycles when the ionic conductive polymers were applied to the cathode.展开更多
Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility wit...Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.展开更多
Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)co...Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)containing NH_(2)-MIL-53(Al),[PP_(13)][TFSI],LiTFSI,and PVDF-HFP was prepared using a simple method of solution casting.The effects of encapsulating different ratios of ionic liquid([PP_(13)][TFSI])into the micropores of functionalized metal-organic frameworks(NH_(2)-MIL-53(Al))on the electrochemical properties were compared.XRD,SEM,nitrogen adsorption-desorption isotherms,and electrochemical measurements were conducted.This GPE demonstrates a superior ionic conductivity of 8.08×10^(-4)S·cm^(-1)at 60℃and can sustain a discharge specific capacity of 156.6 mA·h·g^(-1)at 0.2 C for over 100 cycles.This work might offer a potential approach to alleviate the solid-solid contact with the solid-state electrolyte and electrodes and broaden a new window for the creation of all-solid-state batteries.展开更多
Eukaryotic deoxyribonucleic acid(DNA)is wrapped around histone octamers(HOs)to form nucleosome core particles(NCPs),which in turn interact with linker DNA and linker histones to assemble chromatin fibers with more com...Eukaryotic deoxyribonucleic acid(DNA)is wrapped around histone octamers(HOs)to form nucleosome core particles(NCPs),which in turn interact with linker DNA and linker histones to assemble chromatin fibers with more complex,high-order structures.The molecular properties of chromatin are dynamically regulated by several factors,such as post-translational modifications and effector proteins,to maintain genome stability.In the past two decades,high-resolution techniques have led to many breakthroughs in understanding the molecular mechanisms that govern chromatin regulation.Nuclear magnetic resonance(NMR)has emerged as one of the major techniques in this field,providing new insights into the nucleosomes and nucleosome-protein complexes in different states ranging from soluble form to condensed states.Solution-state NMR has proven valuable in elucidating the conformational dynamics and molecular interactions for histone N-terminal tails,histone core regions and DNA with the combination of specific isotopic labeling.Solid-state NMR,which is not constrained by the high molecular weights of complexes like nucleosomes,has been applied to capture the structural and dynamical characteristics of both flexible tails and rigid histone core regions in nucleosomes and their complexes with effector proteins.Furthermore,the combination of the two techniques allows tracking molecular properties of nucleosomes during phase separation processes,which potentially play essential roles in chromatin regulation.This review summarizes recent advances in NMR studies of chromatin structure and dynamics.It highlighted that NMR revealed unique molecular characteristics for nucleosomes that are often invisible experimentally by other techniques like cryogenic electron microscopy(cryo-EM)and X-ray diffraction(XRD).I envision that,with future ef-forts such as the development of NMR methods and optimization of sample production protocols,solution-state NMR and solid-state NMR will provide invaluable information to expand our understanding of chromatin activity and its regulatory processes.展开更多
Composite solid-state electrolytes represent a critical pathway that balances the interface compatibility and lithium-ion conductivity in all-solid-state batteries.The quest for stable and highly ion-conductive combin...Composite solid-state electrolytes represent a critical pathway that balances the interface compatibility and lithium-ion conductivity in all-solid-state batteries.The quest for stable and highly ion-conductive combinations between polymers and fillers is vital,but blind attempts are often made due to a lack of understanding of the mechanisms involved in the interaction between polymers and fillers.Herein,we employ in-situ polymerization to prepare a polymer based on an ether-nitrile copolymer with high cathode stability as the foundation and discuss the performance enhancement mechanisms of argyrodite and nano-alumina.With 1%content of sulfide interacting with the polymer at the two-phase interface,the local enhancement of lithium-ion migration capability can be achieved,avoiding the reduction in capacity due to the low ion conductivity of the passivation layer during cycling.The capacity retention after 50cycles at 0.5 C increases from 83.5%to 94.4%.Nano-alumina,through anchoring the anions and interface inhibition functions,eventually poses an initial discharge capacity of 136.8 m A h g^(-1)at 0.5 C and extends the cycling time to 1000 h without short-circuiting in lithium metal batteries.Through the combined action of dual fillers on the composite solid-state electrolyte,promising insights are provided for future material design.展开更多
Elastomer blends,among which natural rubber(NR)and butadiene rubber(BR),are involved in many components of the automotive/tire industry.A comprehensive understanding of their mechanical behavior requires,among other f...Elastomer blends,among which natural rubber(NR)and butadiene rubber(BR),are involved in many components of the automotive/tire industry.A comprehensive understanding of their mechanical behavior requires,among other features,a detailed description of the crosslink density in these mixtures.In the case of vulcanized immiscible blends,the distribution of the cross-link density within each of the NR-and BR-rich domains is key information,but difficult to determine using the conventional approaches used for one-component crosslinked elastomers.In this study,the vulcanization within NR/BR blends is investigated using a robust^(1)H double-quantum(DQ)MAS recoupling experiment,BaBa-xy16.Two kinds of cross-linked NR/BR blends were considered with two different microstructures for the BR component.The bulk organization of the resulting blends was first probed by analyzing the^(1)H spin-lattice relaxation behavior.In a second step,BaBa-xy16 was used to investigate,in a selective way,the cross-link heterogeneities within NR/BR blends.In particular,for immiscible NR/BR mixtures,the distribution of the cross-link density between both phases was compared and the observed differences were discussed.展开更多
Solid-state electrolytes(SSEs)play a pivotal role in advancing next-generation lithium metal battery technology.However,they commonly encounter substantial interfacial resistance and poor stability when interfacing wi...Solid-state electrolytes(SSEs)play a pivotal role in advancing next-generation lithium metal battery technology.However,they commonly encounter substantial interfacial resistance and poor stability when interfacing with lithium metal,hindering practical applications.Herein,we introduce a flexible metal-organic framework(MOF:NUS-6)-incorporated polymeric layer,denoted as NP,designed to protect the sodium superionic conductor(NASICON)-type Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)electrolyte from Li metal anodes.The NP matrix establishes a soft interface with the LATP surface,effectively reducing voids and gaps that may arise between the LATP electrolyte and Li metal.Moreover,the MOF component in NP enhances ionic conductivity,offers abundant Li^(+)transport sites,and provides hierarchical ion channels,ensuring a homogeneous Li^(+)flow and thus effectively inhibiting Li dendrite formation.Utilizing NP,we fabricate Li symmetrical cells cycled for over 1600 h at 0.2 mA cm^(-2)and all-solid-state LiINP-LATPI LiFePO_(4)batteries,achieving a remarkable 99.3%capacity retention after 200 cycles at 0.2 C.This work outlines a general strategy for designing long-lasting and stable solid-state Li metal batteries.展开更多
High Li^(+)transference number electrolytes have long been understood to provide attractive candidates for realizing uniform deposition of Li^(+).However,such electrolytes with immobilized anions would result in incom...High Li^(+)transference number electrolytes have long been understood to provide attractive candidates for realizing uniform deposition of Li^(+).However,such electrolytes with immobilized anions would result in incomplete solid electrolyte interphase(SEI)formation on the Li anode because it suffers from the absence of appropriate inorganic components entirely derived from anions decomposition.Herein,a boron-rich hexagonal polymer structured all-solid-state polymer electrolyte(BSPE+10%LiBOB)with regulated intermolecular interaction is proposed to trade off a high Li^(+)transference number against stable SEI properties.The Li^(+)transference number of the as-prepared electrolyte is increased from 0.23 to 0.83 owing to the boron-rich cross-linker(BC)addition.More intriguingly,for the first time,the experiments combined with theoretical calculation results reveal that BOB^(-)anions have stronger interaction with B atoms in polymer chain than TFSI^(-),which significantly induce the TFSI^(-)decomposition and consequently increase the amount of LiF and Li3N in the SEI layer.Eventually,a LiFePO_(4)|BSPE+10%LiBOBlLi cell retains 96.7%after 400 cycles while the cell without BC-resisted electrolyte only retains 40.8%.BSPE+10%LiBOB also facilitates stable electrochemical cycling of solid-state Li-S cells.This study blazes a new trail in controlling the Li^(+)transport ability and SEI properties,synergistically.展开更多
Dihexylfluorene and N-butylcarbazole were copolymerized by solid-state oxidative coupling polymerization in the presence of anhydrous FeCl3 at room temperature. The solid-state films of the copolymers emitted blue lig...Dihexylfluorene and N-butylcarbazole were copolymerized by solid-state oxidative coupling polymerization in the presence of anhydrous FeCl3 at room temperature. The solid-state films of the copolymers emitted blue light after beating at 150 ℃ in air for 24 h, no red-shifted emission was observed by fluorescence spectroscopy.展开更多
Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage ...Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.展开更多
The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined ...The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.展开更多
Solid-state batteries are commonly acknowledged as the forthcoming evolution in energy storage technologies.Recent development progress for these rechargeable batteries has notably accelerated their trajectory toward ...Solid-state batteries are commonly acknowledged as the forthcoming evolution in energy storage technologies.Recent development progress for these rechargeable batteries has notably accelerated their trajectory toward achieving commercial feasibility.In particular,all-solid-state lithium-sulfur batteries(ASSLSBs)that rely on lithium-sulfur reversible redox processes exhibit immense potential as an energy storage system,surpassing conventional lithium-ion batteries.This can be attributed predominantly to their exceptional energy density,extended operational lifespan,and heightened safety attributes.Despite these advantages,the adoption of ASSLSBs in the commercial sector has been sluggish.To expedite research and development in this particular area,this article provides a thorough review of the current state of ASSLSBs.We delve into an in-depth analysis of the rationale behind transitioning to ASSLSBs,explore the fundamental scientific principles involved,and provide a comprehensive evaluation of the main challenges faced by ASSLSBs.We suggest that future research in this field should prioritize plummeting the presence of inactive substances,adopting electrodes with optimum performance,minimizing interfacial resistance,and designing a scalable fabrication approach to facilitate the commercialization of ASSLSBs.展开更多
The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high in...The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.展开更多
Gel-based polymer electrolytes are limited by the polarity of the residual solvent,which restricts the coupling-breaking behaviour during Li^(+)conduction,resulting in the Li^(+)transport kinetics being greatly affect...Gel-based polymer electrolytes are limited by the polarity of the residual solvent,which restricts the coupling-breaking behaviour during Li^(+)conduction,resulting in the Li^(+)transport kinetics being greatly affected.Here,we designed anion competitive gel polymer electrolyte(ACPE)by introducing lithium difluoro(oxalato)borate(LiDFOB)anion into the 1,3-dioxolane(DOL)in situ polymerisation system.ACPE enhances the ionic dipole interaction between Li^(+)and the solvent molecules and synergizes with Li^(+)across the solvation site of the polymer ethylene oxide(EO)unit,combination that greatly improves the Li^(+)transport efficiency.As a result,ACPE exhibits 1.12 mS cm^(−1)ionic conductivity and 0.75 Li^(+)transfer number at room temperature.Additionally,this intra-polymer solvation sheath allows preferential desolvation of DFOB−,which contributes to the formation of kinetically stable anion-derived interphase and effectively mitigates side reactions.Our results demonstrate that the assembled Li||NCM622 solid-state battery exhibits lifespan of over 300 cycles with average Coulombic efficiency of 98.8%and capacity retention of 80.3%.This study introduces a novel approach for ion migration and interface design,paving the way for high-safety and high-energy-density batteries.展开更多
All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,si...All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,since ASSLMBs lack the wetting properties of liquid electrolytes,they require stacking pressure to prevent contact loss between electrodes and SEs.Though previous studies showed that stacking pressure could impact certain performance aspects,a comprehensive investigation into the effects of stacking pressure has not been conducted.To address this gap,we utilized the Li_(6)PS_(5)Cl solid electrolyte as a reference and investigated the effects of stacking pressures on the performance of SEs and ASSLMBs.We also developed models to explain the underlying origin of these effects and predict battery performance,such as ionic conductivity and critical current density.Our results demonstrated that an appropriate stacking pressure is necessary to achieve optimal performance,and each step of applying pressure requires a specific pressure value.These findings can help explain discrepancies in the literature and provide guidance to establish standardized testing conditions and reporting benchmarks for ASSLMBs.Overall,this study contributes to the understanding of the impact of stacking pressure on the performance of ASSLMBs and highlights the importance of careful pressure optimization for optimal battery performance.展开更多
基金Project(50804055) supported by the National Natural Science Foundation of China
文摘Microwave irradiation was employed to assist the synthesis of poly(amino-quinone) (PAQ) from p-benzoquinone and diamines in solid state. The effects of power, time, and pattern (continuously or intermittently) of microwave irradiation on yield and intrinsic viscosity of PAQs were studied. It is shown that the continuous microwave irradiation at a high power leads to rapid increase of yield and a sudden halt in polymerization afterwards, due to the subsequent loss of volatile reactants at a high reaction temperature. Alternatively, the high-power microwave irradiation is applicable to raising the yield if used intermittently. In contras4 the low-power microwave irradiation favours the way of continuous exposure to ensure sufficient heat for polymerization. In both cases of high and low power, the yield and intrinsic viscosity can be further promoted by prolonging the exposure time. It is found that under a preliminarily optimized condition of intermittent irradiation at 490 W with six sequences of 5 min irradiation followed by 5 rain interval, the yield and intrinsic viscosity of PAQ from p-benzoquinone and p-phenylene diamine can reach as high as 83% and 41.9 mL/g, respectively.
基金funded by the National Key Research and Development Program of China(no.2020YFC1909604)Shenzhen Key Projects of Technological Research(JSGG20200925145800001)Shenzhen Basic Research Project(no.JCYJ20190808145203535).
文摘This work demonstrates a novel polymerization-derived polymer electrolyte consisting of methyl methacrylate,lithium bis(trifluoromethanesulfonyl)imide and fluoroethylene carbonate.The polymerization of MMA was initiated by the amino compounds following an anionic catalytic mechanism.LiTFSI plays both roles including the initiator and Li ion source in the polymer electrolyte.Normally,lithium bis(trifluoromethanesulfonyl)imide has difficulty in initiating the polymerization reaction of methyl methacrylate monomer,a very high concentration of lithium bis(trifluoromethanesulfonyl)imide is needed for initiating the polymerization.However,the fluoroethylene carbonate additive can work as a supporter to facilitate the degree of dissociation of lithium bis(trifluoromethanesulfonyl)imide and increase its initiator capacity due to the high dielectric constant.The as-prepared poly-methyl methacrylate-based polymer electrolyte has a high ionic conductivity(1.19×10^(−3)S cm^(−1)),a wide electrochemical stability window(5 V vs Li^(+)/Li),and a high Li ion transference number(t_(Li^(+)))of 0.74 at room temperature(RT).Moreover,this polymerization-derived polymer electrolyte can effectively work as an artificial protective layer on Li metal anode,which enabled the Li symmetric cell to achieve a long-term cycling performance at 0.2 mAh cm^(−2)for 2800 h.The LiFePO_(4)battery with polymerization-derived polymer electrolyte-modified Li metal anode shows a capacity retention of 91.17%after 800 cycles at 0.5 C.This work provides a facile and accessible approach to manufacturing poly-methyl methacrylate-based polymerization-derived polymer electrolyte and shows great potential as an interphase in Li metal batteries.
基金financially supported by the National Natural Science Foundation of China(No.51173112)
文摘Poly(bisphenol A carbonate) (BPA-PC) was post-polymerized by solid-state polymerization (SSP) after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesterification reaction. The effects of the crystallization conditions on melting behavior and SSP of BPA-PC were investigated with differential scanning calorimetry (DSC), Ubbelohde viscosity method and gel permeation chromatography (GPC). The reaction kinetics of the SSP of crystallized prepolymers was studied as a function of reaction temperatures for various reaction periods. As a result, the viscosity average molecular weight of BPA-PC particles (2 mm) increased from 1.9 × 10^4 g/mol to 2.8 × 10^4 g/mol after SSP. More importantly, the significantly enhanced thermal stability and mechanical properties of solid-state polymerized BPA-PC, compared with those of melt transesterification polymerized BPA-PC with the same molecular weight, can be ascribed to the substantial avoidance of undergoing high temperature during polymerization. Our work provides a useful method to obtain practical product of BPA-PC with high quality and high molecular weight.
基金National Natural Science Foundation of China (22078228)。
文摘Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves the rational design of solid-state-C≡N functionalized P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs and its synthesis by in-situ free radical polymerization of vinyl ethylene carbonate(VEC) and 2-cyanoethyl acrylate(CEA).In situ polymerization yields electrode/electrolyte interfaces with low interfacial resistance,forming a stable SEI layer enriched with LiF,Li_(3)N,and RCOOLi,ensuring stable Li plating/stripping for over 1400 h.The-C≡N moiety renders the αH on the adjacent αC positively charged,thereby endowing it with the capability to anchor TFSI^(-).Simultaneously,the incorporation of-C≡N moiety diminishes the electron-donating ability of the C=O,C-O-C,and-C≡N functional groups,facilitating not only the ion conductivity enhancement but also a more rapid Li^(+)migration proved by DFT theoretical calculations and Raman spectroscopy.At room temperature,t_(Li+) of 0.60 for P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs is achieved when the ionic conductivity σ_(Li+)is 2.63×10^(-4) S cm^(-1) and the electrochemical window is expanded to5.0 V.Both coin cells with high-areal-loading cathodes and the 6.5-mAh pouch cell,exhibit stable charge/discharge cycling.At 25℃,the 4.45-V Li|P(VEC_1-CEA_(0.3))/LiTFSI@CE|LiCoO_(2) battery performs stable cycling over 200 cycles at 0.2 C,with a capacity retention of 82.1%.
基金This work is supported by National Natural Science Founda-tion of China(U2004199)National Key Research and Devel-opment Program of China(2018YFD0200606)+1 种基金China Postdoctoral Science Foundation(2021T140615),Natural Sci-enceFoundationofHenanProvince(212300410285)Young Talent Support Project of Henan Province(2021HYTP028).
文摘Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and application. Herein, a laminar MXene functional layer-thin SPE layer-cathode integration(MXene-PEO-LFP) is designed and fabricated. The MXene functional layer formed by stacking rigid MXene nanosheets imparts higher compressive strength relative to PEO electrolyte layer. And the abundant negatively-charged groups on MXene functional layer effectively repel anions and attract cations to adjust the charge distribution behavior at electrolyte–anode interface. Furthermore,the functional layer with rich lithiophilic groups and outstanding electronic conductivity results in low Li nucleation overpotential and nucleation energy barrier. In consequence, the cell assembled with MXene-PEO-LFP, where the PEO electrolyte layer is only 12 μm, much thinner than most solid electrolytes, exhibits uniform, dendrite-free Li+deposition and excellent cycling stability. High capacity(142.8 mAh g-1), stable operation of 140 cycles(capacity decay per cycle, 0.065%), and low polarization potential(0.5 C) are obtained in this Li|MXene-PEO-LFP cell,which is superior to most PEO-based electrolytes under identical condition. This integrated design may provide a strategy for the large-scale application of thin polymer electrolytes in all-solid-state battery.
基金supported by the Enhancement of Performance and Production Technology of Lithium-based Next-generation Rechargeable Battery(project number 20012371)from the Ministry of Trade,Industry and Energy(MOTIE)of Koreasupported by project number KS2322-20(A Study on the Convergence Materials for Off-Grid Energy Conversion/Storage Integrated Devices)of the Korea Research Institute of Chemical Technology(KRICT).
文摘Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorganic solid electrolytes are desirable properties for realizing high-performance safe solid-state batteries by replacing conventional liquid electrolytes.However,the low chemical and electrochemical stability of sulfide-based inorganic solid electrolytes hinder the commercialization of sulfide-based safe solid-state batteries.Particularly,the instability of sulfide-based inorganic solid electrolytes is intensified in the cathode,comprising various materials.In this study,carbonate-based ionic conductive polymers are introduced to the cathode to protect cathode materials and suppress the reactivity of sulfide electrolytes.Several instruments,including electrochemical spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy,confirm the chemical and electrochemical stability of the polymer electrolytes in contact with sulfide-based inorganic solid electrolytes.Sulfide-based solid-state cells show stable electrochemical performance over 100 cycles when the ionic conductive polymers were applied to the cathode.
基金supported by the National Natural Science Foundation of China(52003293,51927806,52272258)the Fundamental Research Funds for the Central Universities(2023ZKPYJD07)the Beijing Nova Program(20220484214).
文摘Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.
基金financially supported by National Natural Science Foundation of China(21701083)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_3137)。
文摘Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)containing NH_(2)-MIL-53(Al),[PP_(13)][TFSI],LiTFSI,and PVDF-HFP was prepared using a simple method of solution casting.The effects of encapsulating different ratios of ionic liquid([PP_(13)][TFSI])into the micropores of functionalized metal-organic frameworks(NH_(2)-MIL-53(Al))on the electrochemical properties were compared.XRD,SEM,nitrogen adsorption-desorption isotherms,and electrochemical measurements were conducted.This GPE demonstrates a superior ionic conductivity of 8.08×10^(-4)S·cm^(-1)at 60℃and can sustain a discharge specific capacity of 156.6 mA·h·g^(-1)at 0.2 C for over 100 cycles.This work might offer a potential approach to alleviate the solid-solid contact with the solid-state electrolyte and electrodes and broaden a new window for the creation of all-solid-state batteries.
基金supported by funds from the National Natural Science Foundation of China(grant number:32201006)Guangdong Province(grant number:2021QN02Y103,2022ZDZX2061,2022KCXTD034)2023 Stable Support Plan Program of Shenzhen Colleges and Universities Fund.
文摘Eukaryotic deoxyribonucleic acid(DNA)is wrapped around histone octamers(HOs)to form nucleosome core particles(NCPs),which in turn interact with linker DNA and linker histones to assemble chromatin fibers with more complex,high-order structures.The molecular properties of chromatin are dynamically regulated by several factors,such as post-translational modifications and effector proteins,to maintain genome stability.In the past two decades,high-resolution techniques have led to many breakthroughs in understanding the molecular mechanisms that govern chromatin regulation.Nuclear magnetic resonance(NMR)has emerged as one of the major techniques in this field,providing new insights into the nucleosomes and nucleosome-protein complexes in different states ranging from soluble form to condensed states.Solution-state NMR has proven valuable in elucidating the conformational dynamics and molecular interactions for histone N-terminal tails,histone core regions and DNA with the combination of specific isotopic labeling.Solid-state NMR,which is not constrained by the high molecular weights of complexes like nucleosomes,has been applied to capture the structural and dynamical characteristics of both flexible tails and rigid histone core regions in nucleosomes and their complexes with effector proteins.Furthermore,the combination of the two techniques allows tracking molecular properties of nucleosomes during phase separation processes,which potentially play essential roles in chromatin regulation.This review summarizes recent advances in NMR studies of chromatin structure and dynamics.It highlighted that NMR revealed unique molecular characteristics for nucleosomes that are often invisible experimentally by other techniques like cryogenic electron microscopy(cryo-EM)and X-ray diffraction(XRD).I envision that,with future ef-forts such as the development of NMR methods and optimization of sample production protocols,solution-state NMR and solid-state NMR will provide invaluable information to expand our understanding of chromatin activity and its regulatory processes.
基金supported by the Science and Technology Commission of Shanghai Municipality(No.19DZ2270100),China。
文摘Composite solid-state electrolytes represent a critical pathway that balances the interface compatibility and lithium-ion conductivity in all-solid-state batteries.The quest for stable and highly ion-conductive combinations between polymers and fillers is vital,but blind attempts are often made due to a lack of understanding of the mechanisms involved in the interaction between polymers and fillers.Herein,we employ in-situ polymerization to prepare a polymer based on an ether-nitrile copolymer with high cathode stability as the foundation and discuss the performance enhancement mechanisms of argyrodite and nano-alumina.With 1%content of sulfide interacting with the polymer at the two-phase interface,the local enhancement of lithium-ion migration capability can be achieved,avoiding the reduction in capacity due to the low ion conductivity of the passivation layer during cycling.The capacity retention after 50cycles at 0.5 C increases from 83.5%to 94.4%.Nano-alumina,through anchoring the anions and interface inhibition functions,eventually poses an initial discharge capacity of 136.8 m A h g^(-1)at 0.5 C and extends the cycling time to 1000 h without short-circuiting in lithium metal batteries.Through the combined action of dual fillers on the composite solid-state electrolyte,promising insights are provided for future material design.
基金financial support from the French National Research Agency(ANR)[grant number ANR-22-CE06-0031]。
文摘Elastomer blends,among which natural rubber(NR)and butadiene rubber(BR),are involved in many components of the automotive/tire industry.A comprehensive understanding of their mechanical behavior requires,among other features,a detailed description of the crosslink density in these mixtures.In the case of vulcanized immiscible blends,the distribution of the cross-link density within each of the NR-and BR-rich domains is key information,but difficult to determine using the conventional approaches used for one-component crosslinked elastomers.In this study,the vulcanization within NR/BR blends is investigated using a robust^(1)H double-quantum(DQ)MAS recoupling experiment,BaBa-xy16.Two kinds of cross-linked NR/BR blends were considered with two different microstructures for the BR component.The bulk organization of the resulting blends was first probed by analyzing the^(1)H spin-lattice relaxation behavior.In a second step,BaBa-xy16 was used to investigate,in a selective way,the cross-link heterogeneities within NR/BR blends.In particular,for immiscible NR/BR mixtures,the distribution of the cross-link density between both phases was compared and the observed differences were discussed.
基金supported by the National Key R&D Program of China(2022YFB2404700)the Natural Science Foundation of China(22109186)+1 种基金the Guangdong Innovative and Entrepreneurial Research Team Program(2021ZT09L227)supported by the Fundamental Research Funds for the Central Universities,Sun Yat-sen University(22hytd01)。
文摘Solid-state electrolytes(SSEs)play a pivotal role in advancing next-generation lithium metal battery technology.However,they commonly encounter substantial interfacial resistance and poor stability when interfacing with lithium metal,hindering practical applications.Herein,we introduce a flexible metal-organic framework(MOF:NUS-6)-incorporated polymeric layer,denoted as NP,designed to protect the sodium superionic conductor(NASICON)-type Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)electrolyte from Li metal anodes.The NP matrix establishes a soft interface with the LATP surface,effectively reducing voids and gaps that may arise between the LATP electrolyte and Li metal.Moreover,the MOF component in NP enhances ionic conductivity,offers abundant Li^(+)transport sites,and provides hierarchical ion channels,ensuring a homogeneous Li^(+)flow and thus effectively inhibiting Li dendrite formation.Utilizing NP,we fabricate Li symmetrical cells cycled for over 1600 h at 0.2 mA cm^(-2)and all-solid-state LiINP-LATPI LiFePO_(4)batteries,achieving a remarkable 99.3%capacity retention after 200 cycles at 0.2 C.This work outlines a general strategy for designing long-lasting and stable solid-state Li metal batteries.
基金supported by the National Natural Science Foundation of China(Nos.21905041,22279014)Jilin Province Major Science and Technology special project(Nos.20220301004GX+4 种基金20220301005GX)R&D Program of Power Batteries with Low Temperature and High Energy,Science and Technology Bureau of Changchun(No.19SS013)Key Subject Construction of Physical Chemistry of Northeast Normal UniversitySpecial foundation of Jilin Province Industrial Technology Research and Development(No.2019C042)the Fundamental Research Funds for the Central Universities(No.2412020FZ008)
文摘High Li^(+)transference number electrolytes have long been understood to provide attractive candidates for realizing uniform deposition of Li^(+).However,such electrolytes with immobilized anions would result in incomplete solid electrolyte interphase(SEI)formation on the Li anode because it suffers from the absence of appropriate inorganic components entirely derived from anions decomposition.Herein,a boron-rich hexagonal polymer structured all-solid-state polymer electrolyte(BSPE+10%LiBOB)with regulated intermolecular interaction is proposed to trade off a high Li^(+)transference number against stable SEI properties.The Li^(+)transference number of the as-prepared electrolyte is increased from 0.23 to 0.83 owing to the boron-rich cross-linker(BC)addition.More intriguingly,for the first time,the experiments combined with theoretical calculation results reveal that BOB^(-)anions have stronger interaction with B atoms in polymer chain than TFSI^(-),which significantly induce the TFSI^(-)decomposition and consequently increase the amount of LiF and Li3N in the SEI layer.Eventually,a LiFePO_(4)|BSPE+10%LiBOBlLi cell retains 96.7%after 400 cycles while the cell without BC-resisted electrolyte only retains 40.8%.BSPE+10%LiBOB also facilitates stable electrochemical cycling of solid-state Li-S cells.This study blazes a new trail in controlling the Li^(+)transport ability and SEI properties,synergistically.
文摘Dihexylfluorene and N-butylcarbazole were copolymerized by solid-state oxidative coupling polymerization in the presence of anhydrous FeCl3 at room temperature. The solid-state films of the copolymers emitted blue light after beating at 150 ℃ in air for 24 h, no red-shifted emission was observed by fluorescence spectroscopy.
基金the National Natural Science Foundation of China(22178120)the China Postdoctoral Science Foundation(2022TQ0173,2023M731922,2022M720076,BX20220182,2023M731921,2023M731919,2023M741919).
文摘Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.
基金financially supported by the National Natural Science Foundation of China (51971080)the Shenzhen Bureau of Science,Technology and Innovation Commission (GXWD20201230155427003-20200730151200003 and JSGG20200914113601003)。
文摘The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.
基金funded by the Ministry of Science and ICT through the National Research Foundation of Korea(202300262366)the Basic Research Lab(RS-2023-00219710)the Ministry of Commerce,Industry,and Energy(20025720)of Korea.
文摘Solid-state batteries are commonly acknowledged as the forthcoming evolution in energy storage technologies.Recent development progress for these rechargeable batteries has notably accelerated their trajectory toward achieving commercial feasibility.In particular,all-solid-state lithium-sulfur batteries(ASSLSBs)that rely on lithium-sulfur reversible redox processes exhibit immense potential as an energy storage system,surpassing conventional lithium-ion batteries.This can be attributed predominantly to their exceptional energy density,extended operational lifespan,and heightened safety attributes.Despite these advantages,the adoption of ASSLSBs in the commercial sector has been sluggish.To expedite research and development in this particular area,this article provides a thorough review of the current state of ASSLSBs.We delve into an in-depth analysis of the rationale behind transitioning to ASSLSBs,explore the fundamental scientific principles involved,and provide a comprehensive evaluation of the main challenges faced by ASSLSBs.We suggest that future research in this field should prioritize plummeting the presence of inactive substances,adopting electrodes with optimum performance,minimizing interfacial resistance,and designing a scalable fabrication approach to facilitate the commercialization of ASSLSBs.
基金the funding support from the National Natural Science Foundation of China(22222902,22209062)the Natural Science Foundation of Jiangsu Province(BK20200047)+2 种基金the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB150004)the Youth Talent Promotion Project of Jiangsu Association for Science and Technology of China(JSTJ-2022-023)Undergraduate Innovation and Entrepreneurship Training Program(202310320066Z)。
文摘The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.
基金supported by the National Natural Science Foundation of China(22008053,52002111)the Natural Science Foundation of Hebei Province(B2021208061,B2022208006,B2023208014)the Beijing Natural Science Foundation(Z200011).
文摘Gel-based polymer electrolytes are limited by the polarity of the residual solvent,which restricts the coupling-breaking behaviour during Li^(+)conduction,resulting in the Li^(+)transport kinetics being greatly affected.Here,we designed anion competitive gel polymer electrolyte(ACPE)by introducing lithium difluoro(oxalato)borate(LiDFOB)anion into the 1,3-dioxolane(DOL)in situ polymerisation system.ACPE enhances the ionic dipole interaction between Li^(+)and the solvent molecules and synergizes with Li^(+)across the solvation site of the polymer ethylene oxide(EO)unit,combination that greatly improves the Li^(+)transport efficiency.As a result,ACPE exhibits 1.12 mS cm^(−1)ionic conductivity and 0.75 Li^(+)transfer number at room temperature.Additionally,this intra-polymer solvation sheath allows preferential desolvation of DFOB−,which contributes to the formation of kinetically stable anion-derived interphase and effectively mitigates side reactions.Our results demonstrate that the assembled Li||NCM622 solid-state battery exhibits lifespan of over 300 cycles with average Coulombic efficiency of 98.8%and capacity retention of 80.3%.This study introduces a novel approach for ion migration and interface design,paving the way for high-safety and high-energy-density batteries.
基金supported by National Key Research and Development Program of China(No.2021YFF0500600)Key R&D Projects in Henan Province(221111240100)China Postdoctoral Science Foundation(2022TQ0291 and 2022M712869)
文摘All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,since ASSLMBs lack the wetting properties of liquid electrolytes,they require stacking pressure to prevent contact loss between electrodes and SEs.Though previous studies showed that stacking pressure could impact certain performance aspects,a comprehensive investigation into the effects of stacking pressure has not been conducted.To address this gap,we utilized the Li_(6)PS_(5)Cl solid electrolyte as a reference and investigated the effects of stacking pressures on the performance of SEs and ASSLMBs.We also developed models to explain the underlying origin of these effects and predict battery performance,such as ionic conductivity and critical current density.Our results demonstrated that an appropriate stacking pressure is necessary to achieve optimal performance,and each step of applying pressure requires a specific pressure value.These findings can help explain discrepancies in the literature and provide guidance to establish standardized testing conditions and reporting benchmarks for ASSLMBs.Overall,this study contributes to the understanding of the impact of stacking pressure on the performance of ASSLMBs and highlights the importance of careful pressure optimization for optimal battery performance.