Lithium-rich layered oxides (LLOs) are increasingly recognized as promising cathode materials for nextgeneration high-energy-density lithium-ion batteries (LIBs).However,they suffer from voltage decay and low initial ...Lithium-rich layered oxides (LLOs) are increasingly recognized as promising cathode materials for nextgeneration high-energy-density lithium-ion batteries (LIBs).However,they suffer from voltage decay and low initial Coulombic efficiency (ICE) due to severe structural degradation caused by irreversible O release.Herein,we introduce a three-in-one strategy of increasing Ni and Mn content,along with Li/Ni disordering and TM–O covalency regulation to boost cationic and anionic redox activity simultaneously and thus enhance the electrochemical activity of LLOs.The target material,Li_(1.2)Ni_(0.168)Mn_(0.558)Co_(0.074)O_(2)(L1),exhibits an improved ICE of 87.2%and specific capacity of 293.2 mA h g^(-1)and minimal voltage decay of less than 0.53 m V cycle-1over 300 cycles at 1C,compared to Li_(1.2)Ni_(0.13)Mn_(0.54)Co_(0.13)O_(2)(Ls)(274.4 mA h g^(-1)for initial capacity,73.8%for ICE and voltage decay of 0.84 mV/cycle over 300 cycles at 1C).Theoretical calculations reveal that the density of states (DOS) area near the Fermi energy level for L1 is larger than that of Ls,indicating higher anionic and cationic redox reactivity than Ls.Moreover,L1 exhibits increased O-vacancy formation energy due to higher Li/Ni disordering of 4.76%(quantified by X-ray diffraction Rietveld refinement) and enhanced TM–O covalency,making lattice O release more difficult and thus improving electrochemical stability.The increased Li/Ni disordering also leads to more Ni^(2+)presence in the Li layer,which acts as a pillar during Li+de-embedding,improving structural stability.This research not only presents a viable approach to designing low-Co LLOs with enhanced capacity and ICE but also contributes significantly to the fundamental understanding of structural regulation in high-performance LIB cathodes.展开更多
Oxygen evolution reaction(OER)is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion.To further accelerate the sluggish kinetics of OER,a cation and anion modulation strategy...Oxygen evolution reaction(OER)is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion.To further accelerate the sluggish kinetics of OER,a cation and anion modulation strategy is reported here,which has been proven to be effective in preparing highly active electrocatalyst.For example,the cobalt,sulfur,and phosphorus modulated nickel hydroxide(denoted as NiCoPSOH)only needs an overpotential of 232 mV to reach a current density of 20 mA cm^(–2),demonstrating excellent OER performances.The cation and anion modulation facilitates the generation of high-valent Ni species,which would activate the lattice oxygen and switch the OER reaction pathway from conventional adsorbate evolution mechanism to lattice oxygen mechanism(LOM),as evidenced by the results of electrochemical measurements,Raman spectroscopy and differential electrochemical mass spectrometry.The LOM pathway of NiCoPSOH is further verified by the theoretical calculations,including the upshift of O 2p band center,the weakened Ni–O bond and the lowest energy barrier of rate-limiting step.Thus,the anion and cation modulated catalyst NiCoPSOH could effectively accelerate the sluggish OER kinetics.Our work provides a new insight into the cation and anion modulation,and broadens the possibility for the rational design of highly active electrocatalysts.展开更多
The development of flexible zinc-ion batteries(ZIBs)faces a threeway trade-off among the ionic conductivity,Zn^(2+)mobility,and the electrochemical stability of hydrogel electrolytes.To address this challenge,we desig...The development of flexible zinc-ion batteries(ZIBs)faces a threeway trade-off among the ionic conductivity,Zn^(2+)mobility,and the electrochemical stability of hydrogel electrolytes.To address this challenge,we designed a cationic hydrogel named PAPTMA to holistically improve the reversibility of ZIBs.The long cationic branch chains in the polymeric matrix construct express pathways for rapid Zn^(2+)transport through an ionic repulsion mechanism,achieving simultaneously high Zn^(2+)transference number(0.79)and high ionic conductivity(28.7 mS cm−1).Additionally,the reactivity of water in the PAPTMA hydrogels is significantly inhibited,thus possessing a strong resistance to parasitic reactions.Mechanical characterization further reveals the superior tensile and adhesion strength of PAPTMA.Leveraging these properties,symmetric batteries employing PAPTMA hydrogel deliver exceeding 6000 h of reversible cycling at 1 mA cm^(−2) and maintain stable operation for 1000 h with a discharge of depth of 71%.When applied in 4×4 cm2 pouch cells with MnO_(2) as the cathode material,the device demonstrates remarkable operational stability and mechanical robustness through 150 cycles.This work presents an eclectic strategy for designing advanced hydrogels that combine high ionic conductivity,enhanced Zn^(2+)mobility,and strong resistance to parasitic reactions,paving the way for long-lasting flexible ZIBs.展开更多
Emulsification is one of the important mechanisms of surfactant flooding. To improve oil recovery for low permeability reservoirs, a highly efficient emulsification oil flooding system consisting of anionic surfactant...Emulsification is one of the important mechanisms of surfactant flooding. To improve oil recovery for low permeability reservoirs, a highly efficient emulsification oil flooding system consisting of anionic surfactant sodium alkyl glucosyl hydroxypropyl sulfonate(APGSHS) and zwitterionic surfactant octadecyl betaine(BS-18) is proposed. The performance of APGSHS/BS-18 mixed surfactant system was evaluated in terms of interfacial tension, emulsification capability, emulsion size and distribution, wettability alteration, temperature-resistance and salt-resistance. The emulsification speed was used to evaluate the emulsification ability of surfactant systems, and the results show that mixed surfactant systems can completely emulsify the crude oil into emulsions droplets even under low energy conditions. Meanwhile,the system exhibits good temperature and salt resistance. Finally, the best oil recovery of 25.45% is achieved for low permeability core by the mixed surfactant system with a total concentration of 0.3 wt%while the molar ratio of APGSHS:BS-18 is 4:6. The current study indicates that the anionic/zwitterionic mixed surfactant system can improve the oil flooding efficiency and is potential candidate for application in low permeability reservoirs.展开更多
Anion exchange membranes(AEMs)combining high hydroxide conductivity and alkali-resistant stability have become a major challenge for the long-term development of anion exchange membrane fuel cells(AEMFCs).Here,we desi...Anion exchange membranes(AEMs)combining high hydroxide conductivity and alkali-resistant stability have become a major challenge for the long-term development of anion exchange membrane fuel cells(AEMFCs).Here,we designed a series of poly(mequitazine-terphenyl piperidinium)(QPMTP-X)AEMs with dual-functionalized quaternary ammonium cations by introducing a certain proportion of large steric hindrance mequitazine(MEQ)molecular building unit into the poly(aryl piperidinium)backbone.QPMTP-X retains the excellent mechanical properties of the poly(aryl piperidinium),while also combining the alkaline stability and high ionic conductivity exhibited by MEQ with flexible quinuclidinium side chains,achieving an overall improvement of membrane performance.Notably,QPMTP-30 exhibits an ultra-high conductivity of up to 206.83 mS cm^(-1)and excellent alkaline stability(over 95%conductivity is maintained after 1000 h of conditioning in 2 M NaOH at 80℃).In fuel cell performance test,QPMTP-30 achieves a peak power density(PPD)of 974.5 mW cm^(-2)and operates stably at 80℃for more than 60 h(0.1 A cm^(-2)).Incorporating large steric hindrance building blocks and multi-cations into the poly(aryl piperidinium)backbone not only synergizes the development of highperformance AEMs but also opens up new ideas for the structural design of future AEMs.展开更多
Symmetric secondary batteries are expected to become promising storage devices on account of their low cost,environmentally friendly and high safety.Nevertheless,the further development of symmetric batteries needs to...Symmetric secondary batteries are expected to become promising storage devices on account of their low cost,environmentally friendly and high safety.Nevertheless,the further development of symmetric batteries needs to rely on bipolar electrodes with superior performance.Cation-disordered rocksalt(DRX)Li_(2)FeTiO_(4)shows promising properties as symmetric electrodes,based on the ability of iron to undergo multiple electrochemical reactions over a wide voltage window.Unfortunately,this cation-disordered structure would not provide a cross-path for the rapid migration of Li^(+),ultimately resulting in inferior electrochemical dynamics and cycle stability.Herein,Li_(2)FeTiO_(4)nanoparticles assembled by ultrafine nanocrystals are synthesized via a sol-gel method through an orderly reaction regulation strategy of precursor reactants.Such ultrafine nanocrystals increase the active sites to promote the reversibility of multi-cationic(e.g.,stable Fe^(2+)/Fe^(3+),Ti^(3+)/Ti^(4+)and moderated Fe^(3+)/Fe^(4+))and anionic redox,and maintain the DRX structure well during the cycling process.The half cells with nano-sized Li_(2)FeTiO_(4)as the cathode/anode exhibit a high reversible capacity of 127.8/500.8 mAh/g,respectively.Besides,the Li_(2)FeTiO_(4)//Li_(2)FeTiO_(4)symmetric full cell could provide a reversible capacity of 95.4 mAh/g at 0.1 A/g after 200 cycles.This hierarchical self-assembly by nanocrystal strategy could offer effective guidance for high-performance electrode design for rechargeable secondary batteries.展开更多
The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic...The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic frameworks formed by B–O and B–O–F units significantly determine the physical properties of fluorooxoborates.Therefore,the rational design of anionic frameworks could facilitate the materials discovery process.Herein,we propose that a candidate anionic framework can be efficiently derived from an existing one by slightly altering its oxygen content.Following this idea,we hypothesized the existence of a 1D[B_(3)O_(5)F]_(∞)chain from the wellknown 2D[B_(6)O_(9)F_(2_)]_(∞)layer.Accordingly,seven CaB_(3)O_(5)F structures with the expected anionic framework were successfully predicted.First-principles calculations show that all these structures have potential in the UV/DUV birefringent or nonlinear optical(NLO)material field,indicating that the 1D[B_(3)O_(5)F]_(∞)chain is indeed a promising anionic framework for achieving UV/DUV birefringent and NLO performance.展开更多
Electrides,characterized by spatially confined anionic electrons,have emerged as a promising class of materials for catalysis,magnetism,and superconductivity.However,transition-metal-based electrides with diverse elec...Electrides,characterized by spatially confined anionic electrons,have emerged as a promising class of materials for catalysis,magnetism,and superconductivity.However,transition-metal-based electrides with diverse electron dimensionalities remain largely unexplored.Here,we perform a comprehensive first-principles investigation of Y-Co electrides,focusing on Y_(3)Co,Y_(3)Co_(2),and YCo.Our calculations reveal a striking dimensional evolution of anionic electrons:from two-dimensional(2D)confinement in YCo to one-dimensional(1D)in Y_(3)Co_(2)and zero-dimensional(0D)in Y_(3)Co.Remarkably,the YCo monolayer exhibits intrinsic ferromagnetism,with a magnetic moment of 0.65μB per formula unit arising from spin-polarized anionic electrons mediating long-range coupling between Y and Co ions.The monolayer also shows a low exfoliation energy(1.66 J/m^(2)),indicating experimental feasibility.All three electrides exhibit low work functions(2.76 eV-3.11 eV)along with Co-centered anionic states.This work expands the family of transition-metal-based electrides and highlights dimensionality engineering as a powerful strategy for tuning electronic and magnetic properties.展开更多
Developing cost-effective single-crystalline Ni-rich Co-poor cathodes operating at high-voltage is one of the most important ways to achieve higher energy Li-ion batteries. However, the Li/O loss and Li/Ni mixing unde...Developing cost-effective single-crystalline Ni-rich Co-poor cathodes operating at high-voltage is one of the most important ways to achieve higher energy Li-ion batteries. However, the Li/O loss and Li/Ni mixing under high-temperature lithiation result in electrochemical kinetic hysteresis and structural instability. Herein, we report a highly-ordered single-crystalline LiNi0.85Co0.05Mn0.10O2(NCM85) cathode by doping K+and F-ions. To be specific, the K-ion as a fluxing agent can remarkably decrease the solid-state lithiation temperature by ~30°C, leading to less Li/Ni mixing and oxygen vacancy. Meanwhile, the strong transitional metal(TM)-F bonds are helpful for enhancing de-/lithiation kinetics and limiting the lattice oxygen escape even at 4.5 V high-voltage. Their advantages synergistically endow the single-crystalline NCM85 cathode with a very high reversible capacity of 222.3 mAh g-1. A superior capacity retention of 91.3% is obtained after 500 times at 1 C in pouch-type full cells, and a prediction value of 75.3% is given after cycling for 5000 h. These findings are reckoned to expedite the exploitation and application of high-voltage single-crystalline Ni-rich cathodes for next-generation Li-ion batteries.展开更多
In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-ba...In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.展开更多
Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surf...Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surface.Oxygen release has been widely accepted as the ringleader of surficial structure instability.However,the role of TM in surface stability has been much overlooked,not to mention its interplay with oxygen release.Herein,TM dissolution and oxygen release are comparatively investigated in Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2).Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn,facilitating subsequent oxygen release of the ARR process.Intriguingly,surface reorganization occurs following regulated Ni dissolution,enabling the stabilization of the surface and elimination of oxygen release in turn.Accordingly,a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure.Battery performance can be effectively improved,with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle,and cycle stability improved from 66.77%to 90.01%after 100 cycles.This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.展开更多
Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding pro...Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.展开更多
Na_(3)V_(2)(PO_(4))_(2)O_(2)F (VP) is recognized as a promising cathode material for sodium-ion batteries due to its stable structural framework and high specific capacity.Density functional theory (DFT) and finite el...Na_(3)V_(2)(PO_(4))_(2)O_(2)F (VP) is recognized as a promising cathode material for sodium-ion batteries due to its stable structural framework and high specific capacity.Density functional theory (DFT) and finite element simulations show that incorporating SO_(4)^(2-)into VP decreases its band gap,lowers the migration energy barrier,and ensures a uniform Na+concentration gradient and stress distribution during charge and discharge cycles.Consequently,the average Na+diffusion coefficient of Na_(3)V_(2)(PO_(4))_(1.95)(SO_(4))_(0.05)O_(2)F(VPS-1) is roughly double that of VP,leading to enhanced rate capability (80 C,75.5 mAh g^(-1)) and cycling stability (111.0 mAh g^(-1)capacity after 1000 cycles at 10 C current density) for VPS-1.VPS-1 exhibits outstanding fast-charging capabilities,achieving an 80%state of charge in just 8.1 min.The assembled VPS-1//SbSn/NPC full cell demonstrated stable cycling over 200 cycles at a high 5 C current,maintaining an average coulombic efficiency of 95.35%.展开更多
The rapidly growing electric cars and energy storage systems have extremely promoted the development of advanced lithium and sodium ion batteries and stimulated evolution of high-capacity cathodes.Li/Na-rich layered c...The rapidly growing electric cars and energy storage systems have extremely promoted the development of advanced lithium and sodium ion batteries and stimulated evolution of high-capacity cathodes.Li/Na-rich layered cathodes consisting cationic and anionic reactions as the most typical representative of high-capacity cathodes have shown its tremendous potential.However,there is a long way to go before commercialization because of unsatisfactory performances including large voltage hysteresis,voltage fade and poor cycle performance.Numerous investigations on redox mechanisms and engineering strategies have been performed from the point view of structure and made significant progress,which has been well reviewed.Meanwhile,the unacceptable issues are essentially correlated to the electronic configuration of anionic redox and its interaction with adjacent transition metal cations,which can be well depicted from electronic structure.However,the investigations on anionic reaction process in the viewpoint of electronic structure have been much less summarized.This review aims to compile the current knowledge of anionic redox from the point view of electronic structure,including configuration,origination,evolution,detection and coupling relationship with cationic redox.This work is attempted to inspire new perspectives and design approaches for the development of high-capacity cathodes.展开更多
P3-type manganese-iron-based cathodes with high specific capacity and abundant resource have attracted considerable attention for sodium-ion batteries.However,the long-term cycle stability of P3-type cathodes is still...P3-type manganese-iron-based cathodes with high specific capacity and abundant resource have attracted considerable attention for sodium-ion batteries.However,the long-term cycle stability of P3-type cathodes is still not satisfactory.In this work,we design a new quaternary manganese-iron-based cathode material(P3-Na_(0.54)Mn_(0.64)Fe_(_(0.1)6)Mg_(0.1)Cu_(0.1)O_(2))by Cu substitution.The strong covalent Cu-O bonds improve the structural stability and the reversibility of O redox during charge and discharge processes.Cu substitution also mitigates the structure change with less unit cell volume variation,and improves the Na-ion transport kinetics effectively.As a result,NMFMC delivers much improved cycling stability and rate capability compared with NMFM.It reveals that the charge compensation of NMFMC is mainly contributed by Mn^(3+/4+),Fe^(3+/3.5+)and O_(2-/-)during the charge and discharge processes,and Cu substitution can also enhance the activity and reversibility of Fe redox.This strategy provides a new pathway toward improving the stability and O redox reversibility of P3-type cathode materials for sodium-ion batteries.展开更多
Dendrite growth represents one of the most significant challenges that impede the development of aqueous zinc-ion batteries.Herein,Gd^(3+)ions are introduced into conventional electrolytes as a microlevelling agent to...Dendrite growth represents one of the most significant challenges that impede the development of aqueous zinc-ion batteries.Herein,Gd^(3+)ions are introduced into conventional electrolytes as a microlevelling agent to achieve dendrite-free zinc electrodeposition.Simulation and experimental results demonstrate that these Gd^(3+)ions are preferentially adsorbed onto the zinc surface,which enables dendritefree zinc anodes by activating the microlevelling effect during electrodeposition.In addition,the Gd^(3+)additives effectively inhibit side reactions and facilitate the desolvation of[Zn(H_(2)O)_(6)]^(2+),leading to highly reversible zinc plating/stripping.Due to these improvements,the zinc anode demonstrates a significantly prolonged cycle life of 2100 h and achieves an exceptional average Coulombic efficiency of 99.72%over 1400 cycles.More importantly,the Zn//NH_(4)V_(4)O_(10)full cell shows a high capacity retention rate of 85.6%after 1000 cycles.This work not only broadens the application of metallic cations in battery electrolytes but also provides fundamental insights into their working mechanisms.展开更多
Despite the growing interest in fast-cha rging solid-state lithium(Li)-metal batteries(SSLMBs),their practical implementation has yet to be achieved,primarily due to an incomplete understanding of the disparate and of...Despite the growing interest in fast-cha rging solid-state lithium(Li)-metal batteries(SSLMBs),their practical implementation has yet to be achieved,primarily due to an incomplete understanding of the disparate and often conflicting requirements of the bulk electrolyte and the electrode-electrolyte interphase.Here,we present a weakly coordinating cationic polymer electrolyte(WCPE)specifically designed to regulate the Li^(+)coordination structure,thereby enabling fast-charging SSLMBs.The WCPE comprises an imidazolium-based polycationic matrix combined with a succinonitrile(SN)-based highconcentration electrolyte.Unlike conventional neutral polymer matrices,the polycationic matrix in the WCPE competes with Li^(+)for interactions with SN,weakening the original coordination between SN and Li^(+).This modulation of SN-Li^(+)interaction improves both Li^(+)conductivity of the WCPE(σ_(Li^(+))=1.29mS cm^(-1))and redox kinetics at the electrode-electrolyte interphase.Consequently,SSLMB cells(comprising LiFePO_(4)cathodes and Li-metal anodes)with the WCPE achieve fast-charging capability(reaching over 80%state of charge within 10 min),outperforming those of previously reported polymer electrolytebased SSLMBs.展开更多
The occurrence,development,and metastasis of tumors often entail abnormal expression of genetic substances.Monitoring and regulating changes in intracellular nucleic acid substances hold promise for achieving accurate...The occurrence,development,and metastasis of tumors often entail abnormal expression of genetic substances.Monitoring and regulating changes in intracellular nucleic acid substances hold promise for achieving accurate tumor diagnosis and effective treatment.However,the effectiveness of integrated tumor diagnosis and treatment based on functional nucleic acids still needs to be improved.In this study,we engineered a multifunctional nucleic acid delivery system grounded in a cationic covalent organic framework carrier.This system not only showcases effective gene silencing but also boasts high sensitivity in detecting miR21 levels within tumor cells,enabling real-time monitoring of tumor gene therapy efficacy.The construction of this integrated functional nucleic acid delivery platform provides new ideas for precise tumor detection and effective tumor treatment.展开更多
Aqueous zinc ion batteries(AZIBs)have excellent development prospects due to their high theoretical capacity and low cost.Nevertheless,the commercial separator represented by glass fiber(GF)in AZIBs usually exhibits u...Aqueous zinc ion batteries(AZIBs)have excellent development prospects due to their high theoretical capacity and low cost.Nevertheless,the commercial separator represented by glass fiber(GF)in AZIBs usually exhibits uneven porosity,poor zincophilicity,and insufficient functional groups,resulting in the emergence of the zinc anode dendrites and side reactions.Designing a separator with specific interfacial ion transport behavior is essential to achieve a highly stable reversible zinc anode.Herein,an anionic metal-organic framework(MOF)functionalized separator(GF-Bio-MOF-100)was presented to accelerate the desolvation process and modulate Zn^(2+)flux,thereby delivering the decreased nucleation overpotential and uniform Zn^(2+)deposition.The in-depth kinetics investigations combined with the in-situ Raman spectroscopy demonstrate that the carbonyl group within the Bio-MOF-100 is capable of capturing the H_(2)O molecules of[Zn(H_(2)O)_(6)]^(2+)via the H-bond interaction,which further accelerates the desolvation process and transport kinetics of Zn^(2+).Meanwhile,the anionic framework of the GFBio-MOF-100 separator acts as an interfacial ion channel to regulate the Zn^(2+)flux and enables dendrite-free Zn^(2+)deposition and growth.Consequently,the Zn|GF-Bio-MOF-100|Zn symmetric cell exhibited a stable Zn^(2+)plating/stripping behavior and it could cycle for 2000 h at 0.3 mA cm^(-2).Additionally,the assembled Zn|GF-Bio-MOF-100|MnO_(2)full cell delivers a capacity retention of 83.9% after 1000 cycles at 0.5 A g^(-1).This work provides new insights into the design of functionalized separators for long-life AZIBs.展开更多
Crystallographic engineering of Zn anodes to favor the exposure of(002)planes is an effective approach for improving stability in aqueous electrolytes.However,achieving non-epitaxial electrodeposition with a pronounce...Crystallographic engineering of Zn anodes to favor the exposure of(002)planes is an effective approach for improving stability in aqueous electrolytes.However,achieving non-epitaxial electrodeposition with a pronounced(002)texture and maintaining this orientation during extended cycling remains challenging.This study questions the prevailing notion that a single(002)-textured Zn anode inherently ensures superior stability,showing that such anodes cannot sustain their texture in ZnSO_(4)electrolytes.We then introduced a novel electrolyte additive,benzyltriethylammonium chloride(TEBAC),which preserves the(002)texture over prolonged cycling.Furthermore,we successfully converted commercial Zn foils into highly crystalline(002)-textured Zn without any pretreatment.Experiments and theoretical calculations revealed that the cationic TEBA^(+)selectively adsorbs onto the anode surface,promoting the exposure of the Zn(002)plane and suppressing dendrite formation.A critical discovery was the pitting corrosion caused by chloride ions from TEBAC,which we mitigated by anion substitution.This modification leads to a remarkable lifespan of 375 days for the Zn||Zn symmetric cells at 1 m A cm^(-2)and 1 m Ah cm^(-2).Furthermore,a TEBA^(+)-modified Zn||VO_(2)full cell demonstrates high specific capacity and robust cycle stability at 10.0 Ag^(-1).These results provide valuable insights and strategies for developing long-life Zn ion batteries.展开更多
基金National Natural Science Foundation of China (No.52202046)Natural Science Foundation of Shaanxi Province (No.2021JQ-034)。
文摘Lithium-rich layered oxides (LLOs) are increasingly recognized as promising cathode materials for nextgeneration high-energy-density lithium-ion batteries (LIBs).However,they suffer from voltage decay and low initial Coulombic efficiency (ICE) due to severe structural degradation caused by irreversible O release.Herein,we introduce a three-in-one strategy of increasing Ni and Mn content,along with Li/Ni disordering and TM–O covalency regulation to boost cationic and anionic redox activity simultaneously and thus enhance the electrochemical activity of LLOs.The target material,Li_(1.2)Ni_(0.168)Mn_(0.558)Co_(0.074)O_(2)(L1),exhibits an improved ICE of 87.2%and specific capacity of 293.2 mA h g^(-1)and minimal voltage decay of less than 0.53 m V cycle-1over 300 cycles at 1C,compared to Li_(1.2)Ni_(0.13)Mn_(0.54)Co_(0.13)O_(2)(Ls)(274.4 mA h g^(-1)for initial capacity,73.8%for ICE and voltage decay of 0.84 mV/cycle over 300 cycles at 1C).Theoretical calculations reveal that the density of states (DOS) area near the Fermi energy level for L1 is larger than that of Ls,indicating higher anionic and cationic redox reactivity than Ls.Moreover,L1 exhibits increased O-vacancy formation energy due to higher Li/Ni disordering of 4.76%(quantified by X-ray diffraction Rietveld refinement) and enhanced TM–O covalency,making lattice O release more difficult and thus improving electrochemical stability.The increased Li/Ni disordering also leads to more Ni^(2+)presence in the Li layer,which acts as a pillar during Li+de-embedding,improving structural stability.This research not only presents a viable approach to designing low-Co LLOs with enhanced capacity and ICE but also contributes significantly to the fundamental understanding of structural regulation in high-performance LIB cathodes.
文摘Oxygen evolution reaction(OER)is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion.To further accelerate the sluggish kinetics of OER,a cation and anion modulation strategy is reported here,which has been proven to be effective in preparing highly active electrocatalyst.For example,the cobalt,sulfur,and phosphorus modulated nickel hydroxide(denoted as NiCoPSOH)only needs an overpotential of 232 mV to reach a current density of 20 mA cm^(–2),demonstrating excellent OER performances.The cation and anion modulation facilitates the generation of high-valent Ni species,which would activate the lattice oxygen and switch the OER reaction pathway from conventional adsorbate evolution mechanism to lattice oxygen mechanism(LOM),as evidenced by the results of electrochemical measurements,Raman spectroscopy and differential electrochemical mass spectrometry.The LOM pathway of NiCoPSOH is further verified by the theoretical calculations,including the upshift of O 2p band center,the weakened Ni–O bond and the lowest energy barrier of rate-limiting step.Thus,the anion and cation modulated catalyst NiCoPSOH could effectively accelerate the sluggish OER kinetics.Our work provides a new insight into the cation and anion modulation,and broadens the possibility for the rational design of highly active electrocatalysts.
基金financially supported by the General Research Fund(CityU 11315622 and CityU 11310123)National Natural Science Foundation(NSFC 52372229 and NSFC 52172241)+3 种基金Green Tech Fund(GTF202220105)Guangdong Basic and Applied Basic Research Foundation(2024A1515011008)City University of Hong Kong(No.9020002)the Shenzhen Research Institute of City University of Hong Kong.
文摘The development of flexible zinc-ion batteries(ZIBs)faces a threeway trade-off among the ionic conductivity,Zn^(2+)mobility,and the electrochemical stability of hydrogel electrolytes.To address this challenge,we designed a cationic hydrogel named PAPTMA to holistically improve the reversibility of ZIBs.The long cationic branch chains in the polymeric matrix construct express pathways for rapid Zn^(2+)transport through an ionic repulsion mechanism,achieving simultaneously high Zn^(2+)transference number(0.79)and high ionic conductivity(28.7 mS cm−1).Additionally,the reactivity of water in the PAPTMA hydrogels is significantly inhibited,thus possessing a strong resistance to parasitic reactions.Mechanical characterization further reveals the superior tensile and adhesion strength of PAPTMA.Leveraging these properties,symmetric batteries employing PAPTMA hydrogel deliver exceeding 6000 h of reversible cycling at 1 mA cm^(−2) and maintain stable operation for 1000 h with a discharge of depth of 71%.When applied in 4×4 cm2 pouch cells with MnO_(2) as the cathode material,the device demonstrates remarkable operational stability and mechanical robustness through 150 cycles.This work presents an eclectic strategy for designing advanced hydrogels that combine high ionic conductivity,enhanced Zn^(2+)mobility,and strong resistance to parasitic reactions,paving the way for long-lasting flexible ZIBs.
基金financially supported by National Natural Science Foundation of China(No.22302229)Beijing Municipal Excellent Talent Training Funds Youth Advanced Individual Project(No.2018000020124G163)。
文摘Emulsification is one of the important mechanisms of surfactant flooding. To improve oil recovery for low permeability reservoirs, a highly efficient emulsification oil flooding system consisting of anionic surfactant sodium alkyl glucosyl hydroxypropyl sulfonate(APGSHS) and zwitterionic surfactant octadecyl betaine(BS-18) is proposed. The performance of APGSHS/BS-18 mixed surfactant system was evaluated in terms of interfacial tension, emulsification capability, emulsion size and distribution, wettability alteration, temperature-resistance and salt-resistance. The emulsification speed was used to evaluate the emulsification ability of surfactant systems, and the results show that mixed surfactant systems can completely emulsify the crude oil into emulsions droplets even under low energy conditions. Meanwhile,the system exhibits good temperature and salt resistance. Finally, the best oil recovery of 25.45% is achieved for low permeability core by the mixed surfactant system with a total concentration of 0.3 wt%while the molar ratio of APGSHS:BS-18 is 4:6. The current study indicates that the anionic/zwitterionic mixed surfactant system can improve the oil flooding efficiency and is potential candidate for application in low permeability reservoirs.
基金financial support of this work by the Natural Science Foundation of China(Grant Nos.U24A20505,52473205)Chang Bai Mountain Scholars Program of Jilin Province and Jilin Provincial Science&Technology Department(Grant No.YDZJ202401357).
文摘Anion exchange membranes(AEMs)combining high hydroxide conductivity and alkali-resistant stability have become a major challenge for the long-term development of anion exchange membrane fuel cells(AEMFCs).Here,we designed a series of poly(mequitazine-terphenyl piperidinium)(QPMTP-X)AEMs with dual-functionalized quaternary ammonium cations by introducing a certain proportion of large steric hindrance mequitazine(MEQ)molecular building unit into the poly(aryl piperidinium)backbone.QPMTP-X retains the excellent mechanical properties of the poly(aryl piperidinium),while also combining the alkaline stability and high ionic conductivity exhibited by MEQ with flexible quinuclidinium side chains,achieving an overall improvement of membrane performance.Notably,QPMTP-30 exhibits an ultra-high conductivity of up to 206.83 mS cm^(-1)and excellent alkaline stability(over 95%conductivity is maintained after 1000 h of conditioning in 2 M NaOH at 80℃).In fuel cell performance test,QPMTP-30 achieves a peak power density(PPD)of 974.5 mW cm^(-2)and operates stably at 80℃for more than 60 h(0.1 A cm^(-2)).Incorporating large steric hindrance building blocks and multi-cations into the poly(aryl piperidinium)backbone not only synergizes the development of highperformance AEMs but also opens up new ideas for the structural design of future AEMs.
基金supported by the National Natural Science Foundation of China(No.22278347)the Excellent Doctoral Student Research Innovation Project of Xinjiang University of China(No.XJU2022BS048)the Postgraduate Innovation Project of Xinjiang Uygur Autonomous Region of China(No.XJ2023G027)。
文摘Symmetric secondary batteries are expected to become promising storage devices on account of their low cost,environmentally friendly and high safety.Nevertheless,the further development of symmetric batteries needs to rely on bipolar electrodes with superior performance.Cation-disordered rocksalt(DRX)Li_(2)FeTiO_(4)shows promising properties as symmetric electrodes,based on the ability of iron to undergo multiple electrochemical reactions over a wide voltage window.Unfortunately,this cation-disordered structure would not provide a cross-path for the rapid migration of Li^(+),ultimately resulting in inferior electrochemical dynamics and cycle stability.Herein,Li_(2)FeTiO_(4)nanoparticles assembled by ultrafine nanocrystals are synthesized via a sol-gel method through an orderly reaction regulation strategy of precursor reactants.Such ultrafine nanocrystals increase the active sites to promote the reversibility of multi-cationic(e.g.,stable Fe^(2+)/Fe^(3+),Ti^(3+)/Ti^(4+)and moderated Fe^(3+)/Fe^(4+))and anionic redox,and maintain the DRX structure well during the cycling process.The half cells with nano-sized Li_(2)FeTiO_(4)as the cathode/anode exhibit a high reversible capacity of 127.8/500.8 mAh/g,respectively.Besides,the Li_(2)FeTiO_(4)//Li_(2)FeTiO_(4)symmetric full cell could provide a reversible capacity of 95.4 mAh/g at 0.1 A/g after 200 cycles.This hierarchical self-assembly by nanocrystal strategy could offer effective guidance for high-performance electrode design for rechargeable secondary batteries.
基金supported by the National Natural Science Foundation of China(Grant No.52403305)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0880000)+1 种基金Tianchi Talent Program of Xinjiang Uygur Autonomous Region(Grant No.2024000068)Postdoctoral Fellow-ship Program(Grade C)(Grant No.GZC20232959)。
文摘The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic frameworks formed by B–O and B–O–F units significantly determine the physical properties of fluorooxoborates.Therefore,the rational design of anionic frameworks could facilitate the materials discovery process.Herein,we propose that a candidate anionic framework can be efficiently derived from an existing one by slightly altering its oxygen content.Following this idea,we hypothesized the existence of a 1D[B_(3)O_(5)F]_(∞)chain from the wellknown 2D[B_(6)O_(9)F_(2_)]_(∞)layer.Accordingly,seven CaB_(3)O_(5)F structures with the expected anionic framework were successfully predicted.First-principles calculations show that all these structures have potential in the UV/DUV birefringent or nonlinear optical(NLO)material field,indicating that the 1D[B_(3)O_(5)F]_(∞)chain is indeed a promising anionic framework for achieving UV/DUV birefringent and NLO performance.
基金funding support from the National Science Fund for Distinguished Young Scholars(Grant No.T2225027)the National Natural Science Foundation of China(Grant Nos.12074013 and 12204419)the China Postdoctoral Science Foundation(Grant No.2021M702956)。
文摘Electrides,characterized by spatially confined anionic electrons,have emerged as a promising class of materials for catalysis,magnetism,and superconductivity.However,transition-metal-based electrides with diverse electron dimensionalities remain largely unexplored.Here,we perform a comprehensive first-principles investigation of Y-Co electrides,focusing on Y_(3)Co,Y_(3)Co_(2),and YCo.Our calculations reveal a striking dimensional evolution of anionic electrons:from two-dimensional(2D)confinement in YCo to one-dimensional(1D)in Y_(3)Co_(2)and zero-dimensional(0D)in Y_(3)Co.Remarkably,the YCo monolayer exhibits intrinsic ferromagnetism,with a magnetic moment of 0.65μB per formula unit arising from spin-polarized anionic electrons mediating long-range coupling between Y and Co ions.The monolayer also shows a low exfoliation energy(1.66 J/m^(2)),indicating experimental feasibility.All three electrides exhibit low work functions(2.76 eV-3.11 eV)along with Co-centered anionic states.This work expands the family of transition-metal-based electrides and highlights dimensionality engineering as a powerful strategy for tuning electronic and magnetic properties.
基金supported by the National Natural Science Foundation of China(U22A20429 and 22308103)Shanghai Pilot Program for Basic Research(22TQ1400100-13)+2 种基金Postdoctoral Fellowship Program of CPSF(GZB20230214)China Postdoctoral Science Foundation(2023M731083)the Fundamental Research Funds for the Central Universities.
文摘Developing cost-effective single-crystalline Ni-rich Co-poor cathodes operating at high-voltage is one of the most important ways to achieve higher energy Li-ion batteries. However, the Li/O loss and Li/Ni mixing under high-temperature lithiation result in electrochemical kinetic hysteresis and structural instability. Herein, we report a highly-ordered single-crystalline LiNi0.85Co0.05Mn0.10O2(NCM85) cathode by doping K+and F-ions. To be specific, the K-ion as a fluxing agent can remarkably decrease the solid-state lithiation temperature by ~30°C, leading to less Li/Ni mixing and oxygen vacancy. Meanwhile, the strong transitional metal(TM)-F bonds are helpful for enhancing de-/lithiation kinetics and limiting the lattice oxygen escape even at 4.5 V high-voltage. Their advantages synergistically endow the single-crystalline NCM85 cathode with a very high reversible capacity of 222.3 mAh g-1. A superior capacity retention of 91.3% is obtained after 500 times at 1 C in pouch-type full cells, and a prediction value of 75.3% is given after cycling for 5000 h. These findings are reckoned to expedite the exploitation and application of high-voltage single-crystalline Ni-rich cathodes for next-generation Li-ion batteries.
基金National Key Research and Development Program of China,Grant/Award Number:2022YFB2502000National Natural Science Foundation of China,Grant/Award Number:52207244。
文摘In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.
基金supported by the National Key Research and Development Program (2019YFA0405601)National Science Foundation of China(No. 22309097, 22179066, 21902179)+1 种基金Shandong Provincial Natural Science Foundation (2023KJ228, ZR2021QE061, ZR202103010205)the Startup Foundation for Advanced Talents in Qingdao University (DC2000005106)
文摘Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surface.Oxygen release has been widely accepted as the ringleader of surficial structure instability.However,the role of TM in surface stability has been much overlooked,not to mention its interplay with oxygen release.Herein,TM dissolution and oxygen release are comparatively investigated in Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2).Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn,facilitating subsequent oxygen release of the ARR process.Intriguingly,surface reorganization occurs following regulated Ni dissolution,enabling the stabilization of the surface and elimination of oxygen release in turn.Accordingly,a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure.Battery performance can be effectively improved,with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle,and cycle stability improved from 66.77%to 90.01%after 100 cycles.This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.
基金financially supported by the National Natural Science Foundation of China(No.52373011)。
文摘Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.
基金National Natural Science Foundation of China (52372224 and 52072299)Major Project of Shaanxi Coal Joint Fund of Shaanxi Provincial Science and Technology Department (2019JLZ-07)。
文摘Na_(3)V_(2)(PO_(4))_(2)O_(2)F (VP) is recognized as a promising cathode material for sodium-ion batteries due to its stable structural framework and high specific capacity.Density functional theory (DFT) and finite element simulations show that incorporating SO_(4)^(2-)into VP decreases its band gap,lowers the migration energy barrier,and ensures a uniform Na+concentration gradient and stress distribution during charge and discharge cycles.Consequently,the average Na+diffusion coefficient of Na_(3)V_(2)(PO_(4))_(1.95)(SO_(4))_(0.05)O_(2)F(VPS-1) is roughly double that of VP,leading to enhanced rate capability (80 C,75.5 mAh g^(-1)) and cycling stability (111.0 mAh g^(-1)capacity after 1000 cycles at 10 C current density) for VPS-1.VPS-1 exhibits outstanding fast-charging capabilities,achieving an 80%state of charge in just 8.1 min.The assembled VPS-1//SbSn/NPC full cell demonstrated stable cycling over 200 cycles at a high 5 C current,maintaining an average coulombic efficiency of 95.35%.
基金financially supported by the National Key Research and Development Program of China(No.2019YFA0405601)the National Natural Science Foundation of China(No.52130202)the Scientific Research Foundation for High-level Talents of Anhui University of Science and Technology(No.2022yjrc105)。
文摘The rapidly growing electric cars and energy storage systems have extremely promoted the development of advanced lithium and sodium ion batteries and stimulated evolution of high-capacity cathodes.Li/Na-rich layered cathodes consisting cationic and anionic reactions as the most typical representative of high-capacity cathodes have shown its tremendous potential.However,there is a long way to go before commercialization because of unsatisfactory performances including large voltage hysteresis,voltage fade and poor cycle performance.Numerous investigations on redox mechanisms and engineering strategies have been performed from the point view of structure and made significant progress,which has been well reviewed.Meanwhile,the unacceptable issues are essentially correlated to the electronic configuration of anionic redox and its interaction with adjacent transition metal cations,which can be well depicted from electronic structure.However,the investigations on anionic reaction process in the viewpoint of electronic structure have been much less summarized.This review aims to compile the current knowledge of anionic redox from the point view of electronic structure,including configuration,origination,evolution,detection and coupling relationship with cationic redox.This work is attempted to inspire new perspectives and design approaches for the development of high-capacity cathodes.
基金supported by the National Key Scientific Research Project(No.2022YFB2502300)the National Natural Science Foundation of China(No.52071085).
文摘P3-type manganese-iron-based cathodes with high specific capacity and abundant resource have attracted considerable attention for sodium-ion batteries.However,the long-term cycle stability of P3-type cathodes is still not satisfactory.In this work,we design a new quaternary manganese-iron-based cathode material(P3-Na_(0.54)Mn_(0.64)Fe_(_(0.1)6)Mg_(0.1)Cu_(0.1)O_(2))by Cu substitution.The strong covalent Cu-O bonds improve the structural stability and the reversibility of O redox during charge and discharge processes.Cu substitution also mitigates the structure change with less unit cell volume variation,and improves the Na-ion transport kinetics effectively.As a result,NMFMC delivers much improved cycling stability and rate capability compared with NMFM.It reveals that the charge compensation of NMFMC is mainly contributed by Mn^(3+/4+),Fe^(3+/3.5+)and O_(2-/-)during the charge and discharge processes,and Cu substitution can also enhance the activity and reversibility of Fe redox.This strategy provides a new pathway toward improving the stability and O redox reversibility of P3-type cathode materials for sodium-ion batteries.
基金supported by the Scientific Research and Technology Development Project of China National Petroleum Corporation(Grant Nos.2024ZG50,2022DQ03-03)the National Natural Science Foundation of China(Grant Nos.52372252)the Science and Technology Innovation Program of Hunan Province(Grant Nos.2024RC1022).
文摘Dendrite growth represents one of the most significant challenges that impede the development of aqueous zinc-ion batteries.Herein,Gd^(3+)ions are introduced into conventional electrolytes as a microlevelling agent to achieve dendrite-free zinc electrodeposition.Simulation and experimental results demonstrate that these Gd^(3+)ions are preferentially adsorbed onto the zinc surface,which enables dendritefree zinc anodes by activating the microlevelling effect during electrodeposition.In addition,the Gd^(3+)additives effectively inhibit side reactions and facilitate the desolvation of[Zn(H_(2)O)_(6)]^(2+),leading to highly reversible zinc plating/stripping.Due to these improvements,the zinc anode demonstrates a significantly prolonged cycle life of 2100 h and achieves an exceptional average Coulombic efficiency of 99.72%over 1400 cycles.More importantly,the Zn//NH_(4)V_(4)O_(10)full cell shows a high capacity retention rate of 85.6%after 1000 cycles.This work not only broadens the application of metallic cations in battery electrolytes but also provides fundamental insights into their working mechanisms.
基金supported by the Basic Science Research Program(RS-2024-00344021,RS-2023-00261543,and RS-202300257666)through the National Research Foundation of Korea(NRF),the National Research Council of Science(000)Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(RS-2024-00420590,HRD Program for Industrial Innovation)The computational resources were provided by KITSI(KSC-2024-CRE-0143)。
文摘Despite the growing interest in fast-cha rging solid-state lithium(Li)-metal batteries(SSLMBs),their practical implementation has yet to be achieved,primarily due to an incomplete understanding of the disparate and often conflicting requirements of the bulk electrolyte and the electrode-electrolyte interphase.Here,we present a weakly coordinating cationic polymer electrolyte(WCPE)specifically designed to regulate the Li^(+)coordination structure,thereby enabling fast-charging SSLMBs.The WCPE comprises an imidazolium-based polycationic matrix combined with a succinonitrile(SN)-based highconcentration electrolyte.Unlike conventional neutral polymer matrices,the polycationic matrix in the WCPE competes with Li^(+)for interactions with SN,weakening the original coordination between SN and Li^(+).This modulation of SN-Li^(+)interaction improves both Li^(+)conductivity of the WCPE(σ_(Li^(+))=1.29mS cm^(-1))and redox kinetics at the electrode-electrolyte interphase.Consequently,SSLMB cells(comprising LiFePO_(4)cathodes and Li-metal anodes)with the WCPE achieve fast-charging capability(reaching over 80%state of charge within 10 min),outperforming those of previously reported polymer electrolytebased SSLMBs.
基金the National Key Research and Development Program of China(No.2021YFB3800900)National Natural Science Foundation of China(No.51925305)the talent cultivation project Funds for the Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(No.HRTP[2022]52)。
文摘The occurrence,development,and metastasis of tumors often entail abnormal expression of genetic substances.Monitoring and regulating changes in intracellular nucleic acid substances hold promise for achieving accurate tumor diagnosis and effective treatment.However,the effectiveness of integrated tumor diagnosis and treatment based on functional nucleic acids still needs to be improved.In this study,we engineered a multifunctional nucleic acid delivery system grounded in a cationic covalent organic framework carrier.This system not only showcases effective gene silencing but also boasts high sensitivity in detecting miR21 levels within tumor cells,enabling real-time monitoring of tumor gene therapy efficacy.The construction of this integrated functional nucleic acid delivery platform provides new ideas for precise tumor detection and effective tumor treatment.
基金supported by the National Natural Science Foundation of China(No.22278328)the Key Research and Development Program of Shaanxi Province(No.2023-YBGY-292)。
文摘Aqueous zinc ion batteries(AZIBs)have excellent development prospects due to their high theoretical capacity and low cost.Nevertheless,the commercial separator represented by glass fiber(GF)in AZIBs usually exhibits uneven porosity,poor zincophilicity,and insufficient functional groups,resulting in the emergence of the zinc anode dendrites and side reactions.Designing a separator with specific interfacial ion transport behavior is essential to achieve a highly stable reversible zinc anode.Herein,an anionic metal-organic framework(MOF)functionalized separator(GF-Bio-MOF-100)was presented to accelerate the desolvation process and modulate Zn^(2+)flux,thereby delivering the decreased nucleation overpotential and uniform Zn^(2+)deposition.The in-depth kinetics investigations combined with the in-situ Raman spectroscopy demonstrate that the carbonyl group within the Bio-MOF-100 is capable of capturing the H_(2)O molecules of[Zn(H_(2)O)_(6)]^(2+)via the H-bond interaction,which further accelerates the desolvation process and transport kinetics of Zn^(2+).Meanwhile,the anionic framework of the GFBio-MOF-100 separator acts as an interfacial ion channel to regulate the Zn^(2+)flux and enables dendrite-free Zn^(2+)deposition and growth.Consequently,the Zn|GF-Bio-MOF-100|Zn symmetric cell exhibited a stable Zn^(2+)plating/stripping behavior and it could cycle for 2000 h at 0.3 mA cm^(-2).Additionally,the assembled Zn|GF-Bio-MOF-100|MnO_(2)full cell delivers a capacity retention of 83.9% after 1000 cycles at 0.5 A g^(-1).This work provides new insights into the design of functionalized separators for long-life AZIBs.
基金supported by the National Natural Science Foundation of China(Grant No.52432007 and 52422212)。
文摘Crystallographic engineering of Zn anodes to favor the exposure of(002)planes is an effective approach for improving stability in aqueous electrolytes.However,achieving non-epitaxial electrodeposition with a pronounced(002)texture and maintaining this orientation during extended cycling remains challenging.This study questions the prevailing notion that a single(002)-textured Zn anode inherently ensures superior stability,showing that such anodes cannot sustain their texture in ZnSO_(4)electrolytes.We then introduced a novel electrolyte additive,benzyltriethylammonium chloride(TEBAC),which preserves the(002)texture over prolonged cycling.Furthermore,we successfully converted commercial Zn foils into highly crystalline(002)-textured Zn without any pretreatment.Experiments and theoretical calculations revealed that the cationic TEBA^(+)selectively adsorbs onto the anode surface,promoting the exposure of the Zn(002)plane and suppressing dendrite formation.A critical discovery was the pitting corrosion caused by chloride ions from TEBAC,which we mitigated by anion substitution.This modification leads to a remarkable lifespan of 375 days for the Zn||Zn symmetric cells at 1 m A cm^(-2)and 1 m Ah cm^(-2).Furthermore,a TEBA^(+)-modified Zn||VO_(2)full cell demonstrates high specific capacity and robust cycle stability at 10.0 Ag^(-1).These results provide valuable insights and strategies for developing long-life Zn ion batteries.
