Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the sol...Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the solid-electrolyte interphase(SEI)during extended cycling use may result in dendrite growth,which can penetrate the separator and pose significant short-circuit risks.Forming a stable SEI is essential for the long-term operation of the batteries.Fluorine-rich SEI has garnered significant attention for its ability to effectively passivate electrodes,regulate lithium deposition,and inhibit electrolyte corrosion.Understanding the structural components and preparation methods of existing fluorinated SEI is crucial for optimizing lithium metal anode performance.This paper reviews the research on optimizing LiF passivation interfaces to protect lithium metal anodes.It focuses on four types of compositions in fluorinated SEI that work synergistically to enhance SEI performance.For instance,combining compounds with LiF can further enhance the mechanical strength and ionic conductivity of the SEI.Integrating metals with LiF significantly improves electrochemical performance at the SEI/anode interface,with a necessary focus on reducing electron tunneling risks.Additionally,incorporating polymers with LiF offers balanced improvements in interfacial toughness and ionic conductivity,though maintaining structural stability over long cycles remains a critical area for future research.Although alloys combined with LiF increase surface energy and lithium affinity,challenges such as dendrite growth and volume expansion persist.In summary,this paper emphasizes the crucial role of interfacial structures in LMBs and offers comprehensive guidance for future design and development efforts in battery technology.展开更多
High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based ...High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based electrolytes,particularly at extreme temperatures.In this study,we develop a stable electrolyte incorporating lithium difluorophosphate(LiDFP)as an additive to enhance the electrochemical performance of DIBs over a wide temperature range.LiDFP preferentially decomposes to form a rapid anion-transporting,mechanically robust CEI layer on graphite,which provides better protection by suppressing graphite's volume expansion,preventing electrolyte oxidative decomposition,and enhancing reaction kinetics.As a result,Li||graphite half cells using LiDFP electrolyte exhibit outstanding rate performance(90.8% capacity retention at 30 C)and excellent cycle stability(82.2% capacity retention after 5000 cycles)at room temperature.Moreover,graphite||graphite full cells with LiDFP electrolyte demonstrate stable discharge capacity across a temperature range of-20 to 40℃,expanding the potential applications of LiDFP.This work establishes a novel strategy for optimizing the interphase through electrolyte design,paving the way for all-climate DIBs with improved performance and stability.展开更多
The electrochemical instability of traditional ether-based electrolytes poses a challenge for their use in high-voltage lithium metal batteries.Herein,a synergetic optimization strategy was proposed by introducing an ...The electrochemical instability of traditional ether-based electrolytes poses a challenge for their use in high-voltage lithium metal batteries.Herein,a synergetic optimization strategy was proposed by introducing an additive with a strong electron-withdrawing group and significant steric hindrance-isosorbide dinitrate(ISDN),reconstructing the solvation structure and solid electrolyte interphase(SEI),enabling highly stable and efficient lithium metal batteries.We found that ISDN can strengthen the interaction between Li^(+)and the anions of lithium salts and weaken the interaction between Li^(+)and the solvent in the solvation structure.It promotes the formation of a LiF-rich and LiN_(x)O_(y)-rich SEI layer,enhancing the uniformity and compactness of Li deposition and inhibiting solvent decomposition,which effectively expands the electrochemical window to 4.8 V.The optimized Li‖Li cells offer stable cycling over 1000 h with an overpotential of only 57.7 mV at 1 mA cm^(-2).Significantly,Li‖3.7 mA h LiFePO_(4)cells retain 108.3%of initial capacity after 546 cycles at a rate of 3 C.Under high-loading conditions(Li‖4.9 mA h LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)full cells)and a cutoff voltage of 4.5 V,the ISDN-containing electrolyte enables stable cycling for 140 cycles.This study leverages steric hindrance and electron-withdrawing effect to synergistically reconstruct the Li^(+)solvation structure and promote stable SEI formation,establishing a novel electrolyte paradigm for high-energy lithium metal batteries.展开更多
Anode-free sodium metal batteries(AFSMBs)have gained attention as next-generation storage systems with high energy density and cost-effectiveness.However,non-uniform sodium(Na)deposition and an unsteady solid electrol...Anode-free sodium metal batteries(AFSMBs)have gained attention as next-generation storage systems with high energy density and cost-effectiveness.However,non-uniform sodium(Na)deposition and an unsteady solid electrolyte interphase(SEI)lead to dendrite-related issues and severe irreversible Na^(+)plating/stripping,greatly aggravating their cycle deterioration.In this study,we effectively modified the 3D current collector's electronic structure by introducing Zn-N_(x)active sites(Zn-CNF),which enhances lateral Na^(+)diffusion and the Na planar growth,enabling uniform deep Na deposition at an exceptionally high capacity of 10 mA h cm^(-2).Furthermore,the Zn-N_(x)bonds enhance the adsorption capacity of PF6and contribute to forming a stable inorganic-rich SEI layer.Consequently,Zn-CNF with the electronic structure regulation endows an ultra-low nucleation overpotential(8 mV)and ultra-high Coulombic efficiency of 99.94%over 1,600 cycles.Symmetric cells demonstrate stable Na^(+)plating/stripping behavior for more than 4,400 h at 1 mA cm^(-2).Moreover,under high cathode loading(7.97 mg cm^(-2)),the AFSMBs achieve a high energy density of 374 W h kg^(-1)and retain a high discharge capacity of 82.49 mA h g^(-1)with a capacity retention of 80.4%after 120 cycles.This work proposes a viable strategy to achieving high-energy-density AFSMBs.展开更多
FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium stor...FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.展开更多
The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated...The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.展开更多
Aqueous zinc batteries offer significant potential for large-scale energy storage,wearable devices,and medium-to low-speed transportation due to their safety,affordability,and environmental friendliness.However,the un...Aqueous zinc batteries offer significant potential for large-scale energy storage,wearable devices,and medium-to low-speed transportation due to their safety,affordability,and environmental friendliness.However,the uneven zinc deposition at the anode side caused by localized reaction activity from the passivation layer presents challenges that significantly impact the battery's stability and lifespan.In this study,we have proposed an expandable and maneuverable gel sustained-release(GSR)treatment to polish the Zn metal,which in situ converts its native passivation layer into a composite interphase layer with nanocrystal zinc phosphate and flexible polyvinyl alcohol.Such a thin and uniform interface contributes to fast and homogeneous Zn ion transport and improved anti-corrosion ability,enabling uniform zinc deposition without dendrite growth and thereby improving the battery performance with high-rate ability and long cycle life.This GSR treatment method,characterized by its simplicity,low cost,and universality,facilitates the widespread application of aqueous zinc batteries.展开更多
Nickel(Ni)-rich layered oxides have drawn great attention as cathode for lithium batteries due to their high capacity,high working voltage and competitive cost.Unfortunately,the operation of Ni-rich cathodes suffers f...Nickel(Ni)-rich layered oxides have drawn great attention as cathode for lithium batteries due to their high capacity,high working voltage and competitive cost.Unfortunately,the operation of Ni-rich cathodes suffers from the notorious structural degradation and interfacial side reactions with electrolytes and thus incurs premature failure,especially at high charge cut-off voltages(≥4.4 V).For this,various structural and interphase regulation strategies(such as coating modification,element doping,and electrolyte engineering)are developed to enhance the cycling survivability of Ni-rich cathodes.Among them,electrolyte engineering by changing solvation structure and introducing additives has been considered an efficient method for constructing robust cathode-electrolyte interphases(CEI),inhibiting the formation of harmful species(such as HF and H_(2)O)or restraining the dissolution of transition metal ions.However,there is still an absence of systematic guidelines for selecting and designing competitive electrolyte systems for Ni-rich layered cathodes.In this review,we comprehensively summarize the recent research progress on electrolyte engineering for Ni-rich layered cathodes according to their working mechanisms.Moreover,we propose future perspectives of improving the electrolyte performance,which will provide new insights for designing novel electrolytes toward high-performance Ni-rich layered cathodes.展开更多
Compared to aqueous-phase electrocatalytic nitrogen reduction reaction(NRR),lithium-mediated NRR(Li-NRR)theoretically enhances the intrinsic activity of NH3 production through spontaneous exothermic reactions between ...Compared to aqueous-phase electrocatalytic nitrogen reduction reaction(NRR),lithium-mediated NRR(Li-NRR)theoretically enhances the intrinsic activity of NH3 production through spontaneous exothermic reactions between Li and N_(2).However,the in-situ generated solid electrolyte interphase(SEI)during the reaction slows down the Li^(+)transport and nucleation kinetics,which further hinders the subsequent activation and protonation processes.Herein,a sophisticated amorphous-crystalline heterostructured SEI of Zn-LiF is formed by additive engineering.The concerted electron interplay between amorphous and crystalline domains is prone to generate lithiophobic Zn and lithiophilic LiF sites,where lithiophobic Zn accelerates Li^(+)diffusion within the SEI and avoids high concentration polarization,and lithiophilic LiF ensures homogeneous nucleation of diffused Li^(+)and its participation in subsequent reactions.Therefore,compared to conventional SEI,a more than 8-fold performance improvement is achieved in the additive-engineered heterogeneous lithiophobic-lithiophilic SEI,which exhibits a high NH_(3)yield rate of 11.58 nmol s^(−1)cm^(−2)and a Faradaic efficiency of 32.97%.Thus,exploiting the synergistic effects in heterogeneous lithiophobic-lithiophilic structures to achieve functional complementarity between different components opens a new avenue toward high-performance Li-NRR.展开更多
The substantial influences of Mo contents varying from 0 to 0.26 and 0.50 wt.%on the microstructural evolution and MX(M=Nb,V and Mo;X=C and N)precipitation characteristics of Nb–V–N microalloyed steels processed by ...The substantial influences of Mo contents varying from 0 to 0.26 and 0.50 wt.%on the microstructural evolution and MX(M=Nb,V and Mo;X=C and N)precipitation characteristics of Nb–V–N microalloyed steels processed by hot deformation and continuous cooling were studied using a Gleeble 3800 thermomechanical simulator.Metallographic analysis showed that the ferrite microstructure transformed from polygonal ferrite(PF)in 0Mo steel to both acicular ferrite(AF)and PF in 0.26Mo and 0.50Mo steels,and AF content first increased and then decreased.The thermodynamic calculations and the experimental results proved that the quantity of solid solution of Mo in austenite obviously increased,which reduced the austenite(γ)to ferrite(α)transformation temperature,consequently promoting AF formation in 0.26Mo steel and bainite transformation in 0.50Mo steel.Moreover,the submicron Nb-rich MX particles that precipitated at the temperature of the austenite region further induced AF heterogeneous nucleation with an orientation relationship of(100)_(MX)//(100)_(Ferrite)and[■][001]Ferrite.The interphase precipitation of the nanosized V-rich MX particles with Mo partitioning that precipitated duringγ→αtransformation exhibited a Baker–Nutting orientation relationship of(100)_(MX)//(100)Ferrite and[001]_(MX)//[■]_(Ferrite)with respect to the ferrite matrix.With increasing Mo content from 0 to 0.26 and 0.50 wt.%,the sheet spacing decreased from 46.9–49.0 to 34.6–38.6 and 25.7–28.0 nm,respectively,which evidently hindered dislocation movement and greatly enhanced precipitation strengthening.Furthermore,facilitating AF formation and interphase precipitation was beneficial to improving steel properties,and the optimal Mo content was 0.26 wt.%.展开更多
Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic react...Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic reactions in zinc perchlorate electrolytes,which is caused by the fast corrosive kinetics at room temperature.Herein,a concentrated perchlorate-based electrolyte consisting of 4.0 M Zn(ClO_(4))_(2)and saturated NaClO_(4)solution is developed to achieve dendrite-free and stable AZIBs at room temperature.The ClO_(4)−participates in the primary solvation sheath of Zn^(2+),facilitating the in situ formation of Zn_(5)(OH)_(8)Cl_(2)·H_(2)O-rich solid electrolyte interphase(SEI)to suppress the corrosion effect of ClO_(4)^(−).The Zn anode protected by the SEI achieves stable Zn plating/stripping over 3000 h.Furthermore,the MnO_(2)||Zn full cells manifest a stable specific capacity of 200 mAh·g^(−1)at 28℃and 101 mAh·g^(−1)at−20℃.This work introduces a promising approach for boosting the room-temperature performance of perchlorate-based electrolytes for AZIBs.展开更多
Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have garnered significant attention due to their potential for high energy density and enhanced safety.However,their practical application is hindered by c...Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have garnered significant attention due to their potential for high energy density and enhanced safety.However,their practical application is hindered by challenges such as uneven lithium(Li)deposition and the growth of Li dendrites.In this contribution,we propose an amorphous fluorinated interphase(AFI),composed of amorphous LiF and lithiated graphite,to regulate the interfacial Li-ion transport kinetics through in-situ interface chemistry.Amorphous LiF,which exhibits a significantly enhanced Li-ion diffusion compared to its crystalline counterpart,works synergistically with lithiated graphite to promote both short-range and long-range Li-ion transport kinetics at the Li/electrolyte interface.As a result,the Li anode with AFI demonstrates a remarkably enhanced critical current density of 1.6 mA cm^(−2)and an extended cycle life exceeding 1100 h.The Li||LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell also achieves a high discharge capacity of 125.7 mA h g^(−1)and retains 71.2%of its initial capacity after 200 cycles.This work provides valuable insights into the rational design of artificial anodic interphase to regulate interfacial Li-ion transport kinetics in ASSLMBs.展开更多
Aqueous zinc ion batteries(ZIBs)feature high theoretical capacity,low cost,and high safety,but they suffer from moderate reversibility arising from electrolyte decomposition,Zn corrosion/passivation,and dendrite growt...Aqueous zinc ion batteries(ZIBs)feature high theoretical capacity,low cost,and high safety,but they suffer from moderate reversibility arising from electrolyte decomposition,Zn corrosion/passivation,and dendrite growth.To address this issue,an effective strategy is to construct a functional solid electrolyte interface(SEI)in situ.However,this is substantially challenging owing to the severe hydrogen evolution reaction(HER)and a lack of substances that can be decomposed to form SEI in the aqueous electrolytes.Herein,we propose the fabrication of a stable SEI in situ via a synergistic electrochemical reductionchemical precipitation approach.By chemically capturing the hydroxide ions(OH-)from HER,fatty acid methyl ester ethoxylate(FMEE),as an aqueous electrolyte additive,undergoes ester group hydrolysis following by a combination with Zn^(2+)to form insoluble fatty acid-zinc,enabling intelligent growth of a SEI on the Zn anode surface.As a result,the enhanced Zn anode exhibits a prolonged cycling life of up to 2700 h at 1 m A/cm^(2)and 1 m Ah/cm^(2).The Zn-V_(2)O_(5)full cell with the designed electrolyte demonstrates excellent rate capability and significantly improved cycling stability.This study presents a simple and practical strategy for in-situ formation of SEI in aqueous electrolytes,advancing the development of high-performance aqueous batteries.展开更多
Lithium(Li)deposition and nucleation at solid electrolyte interphase(SEI)is the main origin for the capacity decay in Li metal batteries(LMBs).SEI conversion with enhanced electrochemical and mechanical properties is ...Lithium(Li)deposition and nucleation at solid electrolyte interphase(SEI)is the main origin for the capacity decay in Li metal batteries(LMBs).SEI conversion with enhanced electrochemical and mechanical properties is an effective approach to achieve uniform nucleation of Li^(+)and stabilize the lithium metal anode.However,complex interfacial reaction mechanisms and interface compatibility issues hinder the development of SEI conversion strategies for stabilizing lithium metal anodes.Herein,we presented the release of I_(3)^(-)in–NH_(2)-modified metal–organic frameworks for a Li metal surface SEI phase conversion strategy.The–NH_(2)group in MOF pores induced the formation of I_(3)^(-)from I_(2),which was further spontaneously reacted with inactive Li_(2)O transforming into high-performance LiI and LiIO_(3)interphase.Furthermore,theoretical calculation provided deeply insight into the unique reconstructed interfacial formation and electrochemical mechanism of rich LiI and LiIO_(3)SEI.As a result,the Li^(+)deposition and nucleation were improved,facilitating the transport kinetics of Li^(+)and inhibiting the growth of lithium dendrites.The assembled solid-state Li||LiFePO_(4)full cells exhibited superior long-term stability of 800 cycles and high Coulombic efficiency(>99%),Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)pouch cell also displayed superior practical performance over 200 cycles at 2 C,high loading of 5 mg cm^(-2)and safety performance.This innovative SEI design strategy promotes the development of high-performance solid-state Li metal batteries.展开更多
Lithium-rich manganese-based oxides(LRMOs;xLi_(2)MnO_(3)(1−x)LiMO_(2);M=transition metal,0<x<1)with excellent specific capacity(>300 mAh/g)and high operating voltage(≥4.8V)are the preferred cathode materials...Lithium-rich manganese-based oxides(LRMOs;xLi_(2)MnO_(3)(1−x)LiMO_(2);M=transition metal,0<x<1)with excellent specific capacity(>300 mAh/g)and high operating voltage(≥4.8V)are the preferred cathode materials for high-specific-energy lithium metal batteries(LMBs)[1].However,LRMOs face a series of serious problems such as irreversible lattice oxygen loss,transition metal(TM)migration,phase transfer,and interfacial side reactions at high voltages,resulting in rapid decay of capacity and voltage[2,3].In situ generating well-functional CEI through electrolyte engineering can effectively address these challenges[4].展开更多
The NASICON-structured Na_(3)MnTi(PO_(4))_(3)(NMTP)cathode has attracted widespread attention due to its prominent thermal stability,stable 3D structure and rapid sodium ion transport channel.However,the poor cycling ...The NASICON-structured Na_(3)MnTi(PO_(4))_(3)(NMTP)cathode has attracted widespread attention due to its prominent thermal stability,stable 3D structure and rapid sodium ion transport channel.However,the poor cycling stability,limited electronic conductivity and phase transition represent significant obstacles to for its commercialization.Herein,an innovative mixed-conducting interphase,comprising amorphous carbon and Ti_(3)C_(2)-MXene,was developed for NMTP.NMTP particles are evenly dispersed on the MXene sheets through electrostatic adsorption,and MXenes can also regulate the growth of NMTP crystals and provide a large number of active sites in contact with the electrolyte.Furthermore,DFT calculations demonstrate that MXene enhances both electron and ion transport processes.Therefore,the mixedconducting interphase,forming an interconnected network on the NMTP surface,serves as an artificial cathode electrolyte interface,significantly enhancing the dynamic processes and cycle stability of the NMTP cathode.The NMTP/C@Ti_(3)C_(2)exhibits a fully reversible three-electron redox reaction and inhibited voltage hysteresis.An excellent reversible capacity of 158.2 mAh/g is achieved at 0.2 C,corresponding to an extremely high energy density of 466.6 Wh/kg.This study presents an effective approach for developing high-energy SIB cathodes.展开更多
The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research.However,the practical implementation of lithium metal anodes is impeded b...The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research.However,the practical implementation of lithium metal anodes is impeded by challenges such as dendrite formation and the inherent instability of the native oxide layer.This study introduces a novel liquid-source plasma technique to create a high-quality solid electrolyte interphase(SEI)composed of LiBr and LiBO_(2).According to first-principal calculation,LiBO_(2)optimizes the electrochemical dynamics and LiBr improves Li diffusion at the interfaces,thus protecting the Li metal from severe Li dendrite growth.This well-designed artificial SEI endows the Li metal with remarkable cycling stability over 550 cycles at a current density of 1 m A/cm^(2),significantly superior to the bare Li anode.Meanwhile,the full cell paired with a high-voltage LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)cathode delivers long-term stability with capacity retention(78%after 200 cycles)at 1 C and excellent rate performance.The findings highlight the importance of interface engineering in optimizing battery performance and longevity.展开更多
The high-temperature conditions of deep oil and gas reservoirs notably affect the porosity and permeability of rocks.In situ temperature-preserved coring(ITP-Coring)technology is crucial for accurately assessing rock ...The high-temperature conditions of deep oil and gas reservoirs notably affect the porosity and permeability of rocks.In situ temperature-preserved coring(ITP-Coring)technology is crucial for accurately assessing rock properties in deep reservoirs.High-performance thermal insulation materials are crucial for supporting ITP-Coring during deep oil and gas exploration.This study explores the impact of high-temperature and high-pressure(HTHP)conditions on hollow glass microsphere/epoxy(HGM/EP)thermal insulation materials,focusing on the interphase.Investigations of HGM/EP materials with varying hollow glass microsphere(HGM)strengths and volume fractions reveal that elevated temperatures cause the molecular chains of the epoxy resin matrix to relax,leading to matrix softening and a decline in mechanical properties.Additionally,high-pressure water infiltrates the material,damaging the interphase and HGMs,further compromising material performance.The combined HTHP environment accelerates this degradation.Dynamic mechanical analysis(DMA)shows that S60HS HGMs,which possess higher strength,interact more strongly with the matrix and exhibit higher entanglement density,resulting in superior interphase adhesion.This enhances stress transfer efficiency and reduces the loss of storage modulus at the interphase.Theoretical analysis indicates that the interphase thickness and modulus of S-f40 remain mostly unaffected after HTHP treatment,with values higher than the epoxy matrix.This correlates with DMA results,demonstrating that S-f40 has the smallest adhesion factor(A),indicating the highest interfacial stress transfer efficiency.S-f40 also exhibits optimal thermal conductivity and mechanical properties,making it ideal for ITP-Coring in deep reservoirs.These findings provide insights for optimizing materials in HTHP environments for deep reservoir exploration.展开更多
Exploiting high-performance electrolyte holds the key for realization practical application of rechargeable magnesium batteries(RMBs).Herein,a new non-nucleophilic mononuclear electrolyte was developed and its electro...Exploiting high-performance electrolyte holds the key for realization practical application of rechargeable magnesium batteries(RMBs).Herein,a new non-nucleophilic mononuclear electrolyte was developed and its electrochemical active species was identified as[Mg(DME)_(3)][GaCl_(4)]_(2) through single-crystal X-ray diffraction analysis.The as-synthesized Mg(GaCl_(4))_(2)-IL-DME electrolyte could achieve a high ionic conductivity(9.85 m S cm^(-1)),good anodic stability(2.9 V vs.Mg/Mg^(2+)),and highly reversible Mg plating/stripping.The remarkable electrochemical performance should be attributed to the in-situ formation of Mg^(2+)-conducting Ga_(5)Mg_(2)alloy layer at the Mg/electrolyte interface during electrochemical cycling,which not only efficiently protects the Mg anode from passivation,but also allows for rapid Mg-ion transport.Significantly,the Mg(GaCl_(4))_(2)-IL-DME electrolyte showed excellent compatibility with both conversion and intercalation cathodes.The Mg/S batteries with Mg(Ga Cl_(4))_(2)-IL-DME electrolyte and KB/S cathode showed a high specific capacity of 839 m Ah g^(-1)after 50 cycles at 0.1 C with the Coulombic efficiency of~100%.Moreover,the assembled Mg|Mo_6 S_8 batteries delivered a reversible discharge capacity of 85 m Ah g^(-1)after 120 cycles at 0.2 C.This work provides a universal electrolyte for the realization of high-performance and practical RMBs,especially Mg/S batteries.展开更多
As a potential candidate for high-energy lithium-ion batteries (LIBs),nickel-rich cathodes encounter significant challenges due to structural instability arising from interphases.In this work,tris(ethenyl)-tris(etheny...As a potential candidate for high-energy lithium-ion batteries (LIBs),nickel-rich cathodes encounter significant challenges due to structural instability arising from interphases.In this work,tris(ethenyl)-tris(ethenyl)silyloxysilane (HVDS) with Si–O bonds and unsaturated bonds is introduced as additive designing functional electrolyte to enhance the long-cycle stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)/graphite LIBs at elevated temperature.The preferential oxidization and component of HVDS facilitate the generation of an extremely robust and ultra-thin cathode electrolyte interphase (CEI) comprising a chemically bonded silane polymer.This interphase effectively suppresses side-reactions of electrolyte,mitigates HF erosion,and reduces irreversible phase transitions.Benefiting from the above merits,the batteries’capacity retention shows a remarkable increase from 20% to 92% after nearly 1550 cycles conducted at room temperature.And under elevated temperature conditions (45℃),the capacity retention remains 80%after 670 cycles,in comparison to a drop to 80%after only 250 cycles with the blank electrolyte.These findings highlight HVDS’s potential to functionalize the electrolyte,marking a breakthrough in improving the longevity and reliability of NCM811/graphite LIBs under challenging conditions.展开更多
基金support from the National Natural Science Foundation of China(No.U2333210)the Sichuan Science and Technology Program,China(No.21SYSX0011)。
文摘Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the solid-electrolyte interphase(SEI)during extended cycling use may result in dendrite growth,which can penetrate the separator and pose significant short-circuit risks.Forming a stable SEI is essential for the long-term operation of the batteries.Fluorine-rich SEI has garnered significant attention for its ability to effectively passivate electrodes,regulate lithium deposition,and inhibit electrolyte corrosion.Understanding the structural components and preparation methods of existing fluorinated SEI is crucial for optimizing lithium metal anode performance.This paper reviews the research on optimizing LiF passivation interfaces to protect lithium metal anodes.It focuses on four types of compositions in fluorinated SEI that work synergistically to enhance SEI performance.For instance,combining compounds with LiF can further enhance the mechanical strength and ionic conductivity of the SEI.Integrating metals with LiF significantly improves electrochemical performance at the SEI/anode interface,with a necessary focus on reducing electron tunneling risks.Additionally,incorporating polymers with LiF offers balanced improvements in interfacial toughness and ionic conductivity,though maintaining structural stability over long cycles remains a critical area for future research.Although alloys combined with LiF increase surface energy and lithium affinity,challenges such as dendrite growth and volume expansion persist.In summary,this paper emphasizes the crucial role of interfacial structures in LMBs and offers comprehensive guidance for future design and development efforts in battery technology.
基金the financial support received from the National Natural Science Foundation of China(22378426,22138013)the Natural Science Foundation of Shandong Province(ZR2022MB088)the Taishan Scholar Project(ts201712020)。
文摘High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based electrolytes,particularly at extreme temperatures.In this study,we develop a stable electrolyte incorporating lithium difluorophosphate(LiDFP)as an additive to enhance the electrochemical performance of DIBs over a wide temperature range.LiDFP preferentially decomposes to form a rapid anion-transporting,mechanically robust CEI layer on graphite,which provides better protection by suppressing graphite's volume expansion,preventing electrolyte oxidative decomposition,and enhancing reaction kinetics.As a result,Li||graphite half cells using LiDFP electrolyte exhibit outstanding rate performance(90.8% capacity retention at 30 C)and excellent cycle stability(82.2% capacity retention after 5000 cycles)at room temperature.Moreover,graphite||graphite full cells with LiDFP electrolyte demonstrate stable discharge capacity across a temperature range of-20 to 40℃,expanding the potential applications of LiDFP.This work establishes a novel strategy for optimizing the interphase through electrolyte design,paving the way for all-climate DIBs with improved performance and stability.
基金Recruitment Program of Global Experts(China)the Hundred-Talent Project of Fujian+1 种基金Fuzhou UniversityFuda Zijin Hydrogen Energy Technology Co.,Ltd for the financial support。
文摘The electrochemical instability of traditional ether-based electrolytes poses a challenge for their use in high-voltage lithium metal batteries.Herein,a synergetic optimization strategy was proposed by introducing an additive with a strong electron-withdrawing group and significant steric hindrance-isosorbide dinitrate(ISDN),reconstructing the solvation structure and solid electrolyte interphase(SEI),enabling highly stable and efficient lithium metal batteries.We found that ISDN can strengthen the interaction between Li^(+)and the anions of lithium salts and weaken the interaction between Li^(+)and the solvent in the solvation structure.It promotes the formation of a LiF-rich and LiN_(x)O_(y)-rich SEI layer,enhancing the uniformity and compactness of Li deposition and inhibiting solvent decomposition,which effectively expands the electrochemical window to 4.8 V.The optimized Li‖Li cells offer stable cycling over 1000 h with an overpotential of only 57.7 mV at 1 mA cm^(-2).Significantly,Li‖3.7 mA h LiFePO_(4)cells retain 108.3%of initial capacity after 546 cycles at a rate of 3 C.Under high-loading conditions(Li‖4.9 mA h LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)full cells)and a cutoff voltage of 4.5 V,the ISDN-containing electrolyte enables stable cycling for 140 cycles.This study leverages steric hindrance and electron-withdrawing effect to synergistically reconstruct the Li^(+)solvation structure and promote stable SEI formation,establishing a novel electrolyte paradigm for high-energy lithium metal batteries.
基金supports by Central South University Innovation-Driven Research Programme(2023CXQD038)the Fundamental Research Funds for the Central Universities of Central South University(2025ZZTS0089)supported by the High Performance Computing Center of Central South University.
文摘Anode-free sodium metal batteries(AFSMBs)have gained attention as next-generation storage systems with high energy density and cost-effectiveness.However,non-uniform sodium(Na)deposition and an unsteady solid electrolyte interphase(SEI)lead to dendrite-related issues and severe irreversible Na^(+)plating/stripping,greatly aggravating their cycle deterioration.In this study,we effectively modified the 3D current collector's electronic structure by introducing Zn-N_(x)active sites(Zn-CNF),which enhances lateral Na^(+)diffusion and the Na planar growth,enabling uniform deep Na deposition at an exceptionally high capacity of 10 mA h cm^(-2).Furthermore,the Zn-N_(x)bonds enhance the adsorption capacity of PF6and contribute to forming a stable inorganic-rich SEI layer.Consequently,Zn-CNF with the electronic structure regulation endows an ultra-low nucleation overpotential(8 mV)and ultra-high Coulombic efficiency of 99.94%over 1,600 cycles.Symmetric cells demonstrate stable Na^(+)plating/stripping behavior for more than 4,400 h at 1 mA cm^(-2).Moreover,under high cathode loading(7.97 mg cm^(-2)),the AFSMBs achieve a high energy density of 374 W h kg^(-1)and retain a high discharge capacity of 82.49 mA h g^(-1)with a capacity retention of 80.4%after 120 cycles.This work proposes a viable strategy to achieving high-energy-density AFSMBs.
基金supported by the National Natural Science Foundation of China(22179063,22479078,and 22409093)the Natural Science Foundation of Jiangsu Province of China(BK20240579)。
文摘FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.
基金financially supported by Jilin Province Science and Technology Department Program(Nos.YDZJ202201ZYTS304,20220201130GX and 20240101004JJ)the National Natural Science Foundation of China(Nos.52171210 and 52471229)the Science and Technology Project of Jilin Provincial Education Department(No.JJKH20220428KJ)
文摘The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.
基金supported by the National Key R&D Program of China(Grant 2022YFB2402200)National Natural Science Foundation of China(Grant 92372206,52271140,52171194)+2 种基金Jilin Province Science and Technology Development Plan Funding Project(Grant YDZJ202301-ZYTS545)National Natural Science Foundation of China Excellent Young Scientists(Overseas)Youth Innovation Promotion Association CAS(Grant 2020230)。
文摘Aqueous zinc batteries offer significant potential for large-scale energy storage,wearable devices,and medium-to low-speed transportation due to their safety,affordability,and environmental friendliness.However,the uneven zinc deposition at the anode side caused by localized reaction activity from the passivation layer presents challenges that significantly impact the battery's stability and lifespan.In this study,we have proposed an expandable and maneuverable gel sustained-release(GSR)treatment to polish the Zn metal,which in situ converts its native passivation layer into a composite interphase layer with nanocrystal zinc phosphate and flexible polyvinyl alcohol.Such a thin and uniform interface contributes to fast and homogeneous Zn ion transport and improved anti-corrosion ability,enabling uniform zinc deposition without dendrite growth and thereby improving the battery performance with high-rate ability and long cycle life.This GSR treatment method,characterized by its simplicity,low cost,and universality,facilitates the widespread application of aqueous zinc batteries.
基金supported by the National Key Research and Development Program of China(2021YFF0500600)National Natural Science Foundation of China(Nos.U2001220,52203298 and 523B2022)+2 种基金National Science Fund for Distinguished Young Scholars(No.52325206)Shenzhen Technical Plan Project(Nos.RCJC20200714114436091,JCYJ20220530143012027,JCYJ20220818101003008 and JCYJ20220818101003007)Tsinghua Shenzhen International Graduate School-Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(No.SZPR2023006).
文摘Nickel(Ni)-rich layered oxides have drawn great attention as cathode for lithium batteries due to their high capacity,high working voltage and competitive cost.Unfortunately,the operation of Ni-rich cathodes suffers from the notorious structural degradation and interfacial side reactions with electrolytes and thus incurs premature failure,especially at high charge cut-off voltages(≥4.4 V).For this,various structural and interphase regulation strategies(such as coating modification,element doping,and electrolyte engineering)are developed to enhance the cycling survivability of Ni-rich cathodes.Among them,electrolyte engineering by changing solvation structure and introducing additives has been considered an efficient method for constructing robust cathode-electrolyte interphases(CEI),inhibiting the formation of harmful species(such as HF and H_(2)O)or restraining the dissolution of transition metal ions.However,there is still an absence of systematic guidelines for selecting and designing competitive electrolyte systems for Ni-rich layered cathodes.In this review,we comprehensively summarize the recent research progress on electrolyte engineering for Ni-rich layered cathodes according to their working mechanisms.Moreover,we propose future perspectives of improving the electrolyte performance,which will provide new insights for designing novel electrolytes toward high-performance Ni-rich layered cathodes.
基金supported by the National Natural Science Foundation of China(22178361,22378402,52302310)the International Partnership Project of CAS(039GJHZ2022029GC)+3 种基金the National Key R&D Program of China(2020YFA0710200)the Foundation of the Innovation Academy for Green Manufacture Institute,Chinese Academy of Sciences(IAGM2022D07)QinChuangYuan Cites High-level Innovation and Entrepreneurship Talent Programs(QCYRCXM-2022-335)the Open Project Program of Anhui Province International Research Center on Advanced Building Materials(JZCL2303KF).
文摘Compared to aqueous-phase electrocatalytic nitrogen reduction reaction(NRR),lithium-mediated NRR(Li-NRR)theoretically enhances the intrinsic activity of NH3 production through spontaneous exothermic reactions between Li and N_(2).However,the in-situ generated solid electrolyte interphase(SEI)during the reaction slows down the Li^(+)transport and nucleation kinetics,which further hinders the subsequent activation and protonation processes.Herein,a sophisticated amorphous-crystalline heterostructured SEI of Zn-LiF is formed by additive engineering.The concerted electron interplay between amorphous and crystalline domains is prone to generate lithiophobic Zn and lithiophilic LiF sites,where lithiophobic Zn accelerates Li^(+)diffusion within the SEI and avoids high concentration polarization,and lithiophilic LiF ensures homogeneous nucleation of diffused Li^(+)and its participation in subsequent reactions.Therefore,compared to conventional SEI,a more than 8-fold performance improvement is achieved in the additive-engineered heterogeneous lithiophobic-lithiophilic SEI,which exhibits a high NH_(3)yield rate of 11.58 nmol s^(−1)cm^(−2)and a Faradaic efficiency of 32.97%.Thus,exploiting the synergistic effects in heterogeneous lithiophobic-lithiophilic structures to achieve functional complementarity between different components opens a new avenue toward high-performance Li-NRR.
基金supported by the National Natural Science Foundation of China(Grant No.52104333)the Program for Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(Grant No.NJYT24070)+1 种基金the Natural Science Foundation of Inner Mongolia(Grant No.2024MS05029)the Research Project of Carbon Peak and Carbon Neutrality in Universities of Inner Mongolia Autonomous Region(Grant No.STZX202316).
文摘The substantial influences of Mo contents varying from 0 to 0.26 and 0.50 wt.%on the microstructural evolution and MX(M=Nb,V and Mo;X=C and N)precipitation characteristics of Nb–V–N microalloyed steels processed by hot deformation and continuous cooling were studied using a Gleeble 3800 thermomechanical simulator.Metallographic analysis showed that the ferrite microstructure transformed from polygonal ferrite(PF)in 0Mo steel to both acicular ferrite(AF)and PF in 0.26Mo and 0.50Mo steels,and AF content first increased and then decreased.The thermodynamic calculations and the experimental results proved that the quantity of solid solution of Mo in austenite obviously increased,which reduced the austenite(γ)to ferrite(α)transformation temperature,consequently promoting AF formation in 0.26Mo steel and bainite transformation in 0.50Mo steel.Moreover,the submicron Nb-rich MX particles that precipitated at the temperature of the austenite region further induced AF heterogeneous nucleation with an orientation relationship of(100)_(MX)//(100)_(Ferrite)and[■][001]Ferrite.The interphase precipitation of the nanosized V-rich MX particles with Mo partitioning that precipitated duringγ→αtransformation exhibited a Baker–Nutting orientation relationship of(100)_(MX)//(100)Ferrite and[001]_(MX)//[■]_(Ferrite)with respect to the ferrite matrix.With increasing Mo content from 0 to 0.26 and 0.50 wt.%,the sheet spacing decreased from 46.9–49.0 to 34.6–38.6 and 25.7–28.0 nm,respectively,which evidently hindered dislocation movement and greatly enhanced precipitation strengthening.Furthermore,facilitating AF formation and interphase precipitation was beneficial to improving steel properties,and the optimal Mo content was 0.26 wt.%.
基金supported by Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City(No.2021JJLH0069)the Project of Sanya Yazhou Bay Science and Technology City(No.SCKJ-JYRC-2023-55)Hainan Provincial Natural Science Foundation of China(No.522CXTD516).
文摘Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic reactions in zinc perchlorate electrolytes,which is caused by the fast corrosive kinetics at room temperature.Herein,a concentrated perchlorate-based electrolyte consisting of 4.0 M Zn(ClO_(4))_(2)and saturated NaClO_(4)solution is developed to achieve dendrite-free and stable AZIBs at room temperature.The ClO_(4)−participates in the primary solvation sheath of Zn^(2+),facilitating the in situ formation of Zn_(5)(OH)_(8)Cl_(2)·H_(2)O-rich solid electrolyte interphase(SEI)to suppress the corrosion effect of ClO_(4)^(−).The Zn anode protected by the SEI achieves stable Zn plating/stripping over 3000 h.Furthermore,the MnO_(2)||Zn full cells manifest a stable specific capacity of 200 mAh·g^(−1)at 28℃and 101 mAh·g^(−1)at−20℃.This work introduces a promising approach for boosting the room-temperature performance of perchlorate-based electrolytes for AZIBs.
基金supported by the Beijing Municipal Natural Science Foundation(L223009)the National Natural Science Foundation of China(22209014,22479012)+1 种基金the Hebei Natural Science Foundation(E2024208084)the Fundamental Research Funds for the Central Universities(2023CX01031)。
文摘Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have garnered significant attention due to their potential for high energy density and enhanced safety.However,their practical application is hindered by challenges such as uneven lithium(Li)deposition and the growth of Li dendrites.In this contribution,we propose an amorphous fluorinated interphase(AFI),composed of amorphous LiF and lithiated graphite,to regulate the interfacial Li-ion transport kinetics through in-situ interface chemistry.Amorphous LiF,which exhibits a significantly enhanced Li-ion diffusion compared to its crystalline counterpart,works synergistically with lithiated graphite to promote both short-range and long-range Li-ion transport kinetics at the Li/electrolyte interface.As a result,the Li anode with AFI demonstrates a remarkably enhanced critical current density of 1.6 mA cm^(−2)and an extended cycle life exceeding 1100 h.The Li||LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell also achieves a high discharge capacity of 125.7 mA h g^(−1)and retains 71.2%of its initial capacity after 200 cycles.This work provides valuable insights into the rational design of artificial anodic interphase to regulate interfacial Li-ion transport kinetics in ASSLMBs.
基金supported by the National Natural Science Foundation of China(No.22309211)the Guangdong Basic and Applied Basic Research Foundation(No.2024A1515010158)+1 种基金the Guangzhou Science and Technology Programme(No.SL2023A04J01514)the Lanzhou Chengguan District Science and Technology Plan Project(No.2022-rc-4)。
文摘Aqueous zinc ion batteries(ZIBs)feature high theoretical capacity,low cost,and high safety,but they suffer from moderate reversibility arising from electrolyte decomposition,Zn corrosion/passivation,and dendrite growth.To address this issue,an effective strategy is to construct a functional solid electrolyte interface(SEI)in situ.However,this is substantially challenging owing to the severe hydrogen evolution reaction(HER)and a lack of substances that can be decomposed to form SEI in the aqueous electrolytes.Herein,we propose the fabrication of a stable SEI in situ via a synergistic electrochemical reductionchemical precipitation approach.By chemically capturing the hydroxide ions(OH-)from HER,fatty acid methyl ester ethoxylate(FMEE),as an aqueous electrolyte additive,undergoes ester group hydrolysis following by a combination with Zn^(2+)to form insoluble fatty acid-zinc,enabling intelligent growth of a SEI on the Zn anode surface.As a result,the enhanced Zn anode exhibits a prolonged cycling life of up to 2700 h at 1 m A/cm^(2)and 1 m Ah/cm^(2).The Zn-V_(2)O_(5)full cell with the designed electrolyte demonstrates excellent rate capability and significantly improved cycling stability.This study presents a simple and practical strategy for in-situ formation of SEI in aqueous electrolytes,advancing the development of high-performance aqueous batteries.
基金financial support from National Natural Science Foundation of China(22271178,U2032131,21972103)International Cooperation Key Project of Science and Technology Department of Shaanxi,China(2022KWZ-06)+3 种基金the Youth Talent Promotion Project of Science and Technology Association of Universities of Shaanxi Province(20210602)Research Project of Xi’an Science and Technology Bureau(2022GXFW0011)Science and Technology New Star in Shaanxi Province(2023KJXX-045)Shaanxi Provincial Department of Education Service Local Special Project,Industrialization Cultivation Project(23JC007)。
文摘Lithium(Li)deposition and nucleation at solid electrolyte interphase(SEI)is the main origin for the capacity decay in Li metal batteries(LMBs).SEI conversion with enhanced electrochemical and mechanical properties is an effective approach to achieve uniform nucleation of Li^(+)and stabilize the lithium metal anode.However,complex interfacial reaction mechanisms and interface compatibility issues hinder the development of SEI conversion strategies for stabilizing lithium metal anodes.Herein,we presented the release of I_(3)^(-)in–NH_(2)-modified metal–organic frameworks for a Li metal surface SEI phase conversion strategy.The–NH_(2)group in MOF pores induced the formation of I_(3)^(-)from I_(2),which was further spontaneously reacted with inactive Li_(2)O transforming into high-performance LiI and LiIO_(3)interphase.Furthermore,theoretical calculation provided deeply insight into the unique reconstructed interfacial formation and electrochemical mechanism of rich LiI and LiIO_(3)SEI.As a result,the Li^(+)deposition and nucleation were improved,facilitating the transport kinetics of Li^(+)and inhibiting the growth of lithium dendrites.The assembled solid-state Li||LiFePO_(4)full cells exhibited superior long-term stability of 800 cycles and high Coulombic efficiency(>99%),Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)pouch cell also displayed superior practical performance over 200 cycles at 2 C,high loading of 5 mg cm^(-2)and safety performance.This innovative SEI design strategy promotes the development of high-performance solid-state Li metal batteries.
文摘Lithium-rich manganese-based oxides(LRMOs;xLi_(2)MnO_(3)(1−x)LiMO_(2);M=transition metal,0<x<1)with excellent specific capacity(>300 mAh/g)and high operating voltage(≥4.8V)are the preferred cathode materials for high-specific-energy lithium metal batteries(LMBs)[1].However,LRMOs face a series of serious problems such as irreversible lattice oxygen loss,transition metal(TM)migration,phase transfer,and interfacial side reactions at high voltages,resulting in rapid decay of capacity and voltage[2,3].In situ generating well-functional CEI through electrolyte engineering can effectively address these challenges[4].
基金supported by the National Natural Science Foundation of China(Nos.51604089,51874110 and 22479035)Natural Science Foundation of Heilongjiang Province(No.YQ2021B004)。
文摘The NASICON-structured Na_(3)MnTi(PO_(4))_(3)(NMTP)cathode has attracted widespread attention due to its prominent thermal stability,stable 3D structure and rapid sodium ion transport channel.However,the poor cycling stability,limited electronic conductivity and phase transition represent significant obstacles to for its commercialization.Herein,an innovative mixed-conducting interphase,comprising amorphous carbon and Ti_(3)C_(2)-MXene,was developed for NMTP.NMTP particles are evenly dispersed on the MXene sheets through electrostatic adsorption,and MXenes can also regulate the growth of NMTP crystals and provide a large number of active sites in contact with the electrolyte.Furthermore,DFT calculations demonstrate that MXene enhances both electron and ion transport processes.Therefore,the mixedconducting interphase,forming an interconnected network on the NMTP surface,serves as an artificial cathode electrolyte interface,significantly enhancing the dynamic processes and cycle stability of the NMTP cathode.The NMTP/C@Ti_(3)C_(2)exhibits a fully reversible three-electron redox reaction and inhibited voltage hysteresis.An excellent reversible capacity of 158.2 mAh/g is achieved at 0.2 C,corresponding to an extremely high energy density of 466.6 Wh/kg.This study presents an effective approach for developing high-energy SIB cathodes.
基金supported by National Natural Science Foundation of China(Nos.52372235,52073252,52002052,U20A20253,21972127,22279116)Key Scientific Research Project of Hangzhou(No.2024SZD1B12)+5 种基金Science and Technology Department of Zhejiang Province(Nos.2023C01231,Q23E020046,LD22E020006LY21E020005)Key Research and Development Project of Science and Technology Department of Sichuan Province(No.2022YFSY0004)Natural Science Foundation of Zhejiang Province(No.LQ23E020009)Sichuan Natural Science(No.2024NSFSC0951)Key Laboratory of Engineering Dielectrics and Its Application(Harbin University of Science and Technology),Ministry of Education(No.KFM 202303)。
文摘The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research.However,the practical implementation of lithium metal anodes is impeded by challenges such as dendrite formation and the inherent instability of the native oxide layer.This study introduces a novel liquid-source plasma technique to create a high-quality solid electrolyte interphase(SEI)composed of LiBr and LiBO_(2).According to first-principal calculation,LiBO_(2)optimizes the electrochemical dynamics and LiBr improves Li diffusion at the interfaces,thus protecting the Li metal from severe Li dendrite growth.This well-designed artificial SEI endows the Li metal with remarkable cycling stability over 550 cycles at a current density of 1 m A/cm^(2),significantly superior to the bare Li anode.Meanwhile,the full cell paired with a high-voltage LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)cathode delivers long-term stability with capacity retention(78%after 200 cycles)at 1 C and excellent rate performance.The findings highlight the importance of interface engineering in optimizing battery performance and longevity.
基金work was funded by the National Natural Science Foun-dation of China(No.52304033)the National Key Research and Development Program of China(No.2023YFB2390200)Guangdong Provincial Key Laboratory of Deep Earth Sciences and Geothermal Energy Exploitation and Utilization(No.DESGEEU-2023-10).
文摘The high-temperature conditions of deep oil and gas reservoirs notably affect the porosity and permeability of rocks.In situ temperature-preserved coring(ITP-Coring)technology is crucial for accurately assessing rock properties in deep reservoirs.High-performance thermal insulation materials are crucial for supporting ITP-Coring during deep oil and gas exploration.This study explores the impact of high-temperature and high-pressure(HTHP)conditions on hollow glass microsphere/epoxy(HGM/EP)thermal insulation materials,focusing on the interphase.Investigations of HGM/EP materials with varying hollow glass microsphere(HGM)strengths and volume fractions reveal that elevated temperatures cause the molecular chains of the epoxy resin matrix to relax,leading to matrix softening and a decline in mechanical properties.Additionally,high-pressure water infiltrates the material,damaging the interphase and HGMs,further compromising material performance.The combined HTHP environment accelerates this degradation.Dynamic mechanical analysis(DMA)shows that S60HS HGMs,which possess higher strength,interact more strongly with the matrix and exhibit higher entanglement density,resulting in superior interphase adhesion.This enhances stress transfer efficiency and reduces the loss of storage modulus at the interphase.Theoretical analysis indicates that the interphase thickness and modulus of S-f40 remain mostly unaffected after HTHP treatment,with values higher than the epoxy matrix.This correlates with DMA results,demonstrating that S-f40 has the smallest adhesion factor(A),indicating the highest interfacial stress transfer efficiency.S-f40 also exhibits optimal thermal conductivity and mechanical properties,making it ideal for ITP-Coring in deep reservoirs.These findings provide insights for optimizing materials in HTHP environments for deep reservoir exploration.
基金financially supported by National Natural Science Foundation of China(21773291,52303130,62205231,61904118,22002102)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(19KJA210005)+1 种基金Postgraduate Research&Practice Innovation Program of Jiangsu Province(SJCX23_1710)Postgraduate Research&Practice Innovation Program of Suzhou University of Science and Technology(CLKYCX23_06)。
文摘Exploiting high-performance electrolyte holds the key for realization practical application of rechargeable magnesium batteries(RMBs).Herein,a new non-nucleophilic mononuclear electrolyte was developed and its electrochemical active species was identified as[Mg(DME)_(3)][GaCl_(4)]_(2) through single-crystal X-ray diffraction analysis.The as-synthesized Mg(GaCl_(4))_(2)-IL-DME electrolyte could achieve a high ionic conductivity(9.85 m S cm^(-1)),good anodic stability(2.9 V vs.Mg/Mg^(2+)),and highly reversible Mg plating/stripping.The remarkable electrochemical performance should be attributed to the in-situ formation of Mg^(2+)-conducting Ga_(5)Mg_(2)alloy layer at the Mg/electrolyte interface during electrochemical cycling,which not only efficiently protects the Mg anode from passivation,but also allows for rapid Mg-ion transport.Significantly,the Mg(GaCl_(4))_(2)-IL-DME electrolyte showed excellent compatibility with both conversion and intercalation cathodes.The Mg/S batteries with Mg(Ga Cl_(4))_(2)-IL-DME electrolyte and KB/S cathode showed a high specific capacity of 839 m Ah g^(-1)after 50 cycles at 0.1 C with the Coulombic efficiency of~100%.Moreover,the assembled Mg|Mo_6 S_8 batteries delivered a reversible discharge capacity of 85 m Ah g^(-1)after 120 cycles at 0.2 C.This work provides a universal electrolyte for the realization of high-performance and practical RMBs,especially Mg/S batteries.
基金financially supported by the Scientific Research Innovation Project of Graduate School of South China Normal University (No. 2024KYLX081)。
文摘As a potential candidate for high-energy lithium-ion batteries (LIBs),nickel-rich cathodes encounter significant challenges due to structural instability arising from interphases.In this work,tris(ethenyl)-tris(ethenyl)silyloxysilane (HVDS) with Si–O bonds and unsaturated bonds is introduced as additive designing functional electrolyte to enhance the long-cycle stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)/graphite LIBs at elevated temperature.The preferential oxidization and component of HVDS facilitate the generation of an extremely robust and ultra-thin cathode electrolyte interphase (CEI) comprising a chemically bonded silane polymer.This interphase effectively suppresses side-reactions of electrolyte,mitigates HF erosion,and reduces irreversible phase transitions.Benefiting from the above merits,the batteries’capacity retention shows a remarkable increase from 20% to 92% after nearly 1550 cycles conducted at room temperature.And under elevated temperature conditions (45℃),the capacity retention remains 80%after 670 cycles,in comparison to a drop to 80%after only 250 cycles with the blank electrolyte.These findings highlight HVDS’s potential to functionalize the electrolyte,marking a breakthrough in improving the longevity and reliability of NCM811/graphite LIBs under challenging conditions.
