Thickness deposition is a crucial issue on the application of electroformed micro mold inserts. Edge concentration effect is the main source of the non-uniformity. The techniques of adopting a non-conducting shield, a...Thickness deposition is a crucial issue on the application of electroformed micro mold inserts. Edge concentration effect is the main source of the non-uniformity. The techniques of adopting a non-conducting shield, a secondary electrode and a movable cathode were explored to improve the thickness deposition uniformity during the nickel electroforming process. Regarding these techniques, a micro electroforming system with a movable cathode was particularly developed. The thickness variation of a 16 mm×16 mm electroformed sample decreased respectively from 150% to 35%, 12% and 18% by these three techniques. Combining these validated methods, anickelmold insert for microlens array was electroformed with satisfactory mechanical properties and high replication precision. It could be applied to the following injection molding process.展开更多
It is well accepted that a lithiophilic interface can effectively regulate Li deposition behaviors,but the influence of the lithiophilic interface is gradually diminished upon continuous Li deposition that completely ...It is well accepted that a lithiophilic interface can effectively regulate Li deposition behaviors,but the influence of the lithiophilic interface is gradually diminished upon continuous Li deposition that completely isolates Li from the lithiophilic metals.Herein,we perform in-depth studies on the creation of dynamic alloy interfaces upon Li deposition,arising from the exceptionally high diffusion coefficient of Hg in the amalgam solid solution.As a comparison,other metals such as Au,Ag,and Zn have typical diffusion coefficients of 10-20 orders of magnitude lower than that of Hg in the similar solid solution phases.This difference induces compact Li deposition pattern with an amalgam substrate even with a high areal capacity of 55 mAh cm^(-2).This finding provides new insight into the rational design of Li anode substrate for the stable cycling of Li metal batteries.展开更多
The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein...The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.展开更多
Piezoelectric ceramic and polymeric separators have been proposed to effectively regulate Li deposition and suppress dendrite growth,but such separators still fail to satisfactorily support durable operation of lithiu...Piezoelectric ceramic and polymeric separators have been proposed to effectively regulate Li deposition and suppress dendrite growth,but such separators still fail to satisfactorily support durable operation of lithium metal batteries owing to the fragile ceramic layer or low-piezoelectricity polymer as employed.Herein,by combining PVDF-HFP and ferroelectric BaTiO_(3),we develop a homogeneous,single-layer composite separator with strong piezoelectric effects to inhibit dendrite growth while maintaining high mechanical strength.As squeezed by local protrusion,the polarized PVDF-HFP/BaTiO_(3)composite separator generates a local voltage to suppress the local-intensified electric field and further deconcentrate regional lithium-ion flux to retard lithium deposition on the protrusion,hence enabling a smoother and more compact lithium deposition morphology than the unpoled composite separator and the pure PVDF-HFP separator,especially at high rates.Remarkably,the homogeneous incorporation of BaTiO_(3)highly improves the piezoelectric performances of the separator with residual polarization of 0.086 pC cm^(-2)after polarization treatment,four times that of the pure PVDF-HFP separator,and simultaneously increases the transference number of lithium-ion from 0.45 to 0.57.Beneficial from the prominent piezoelectric mechanism,the polarized PVDF-HFP/BaTiO_(3)composite separator enables stable cyclic performances of Li||LiFePO_(4)cells for 400 cycles at 2 C(1 C=170 mA g^(-1))with a capacity retention above 99%,and for 600 cycles at 5 C with a capacity retention over 85%.展开更多
Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition be...Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition behavior still occurs at the top of 3D frameworks owing to the local accumulation of Li ions.To promote uniform Li deposition without top dendrite growth,herein,a layered multifunctional framework based on oxidation-treated polyacrylonitrile(OPAN) and metal-organic framework(MOF) derivatives was proposed for rationally regulating the distribution of Li ions flux,nucleation sites,and electrical conductivity.Profiting from these merits,the OPAN/carbon nano fiber-MOF(CMOF) composite framework demonstrated a reversible Li plating/stripping behavior for 500 cycles with a stable Coulombic efficiency of around 99.0% at the current density of 2 mA/cm~2.Besides,such a Li composite anode exhibited a superior cycle lifespan of over 1300 h under a low polarized voltage of 18 mV in symmetrical cells.When the Li composite anode was paired with LiFePO_(4)(LFP) cathode,the obtained full cell exhibited a stable cycling over 500 cycles.Moreover,the COMSOL Multiphysics simulation was conducted to reveal the effects on homogeneous Li ions distribution derived from the above-mentioned OPAN/CMOF framework and electrical insulation/conduction design.These electrochemical and simulated results shed light on the difficulties of designing stable and safe Li metal anode via optimizing the 3D frameworks.展开更多
The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previo...The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previous studies using Zn I_(2)additive,this work designs an aqueous Bi I_(3)-Zn battery with selfsupplied I^(-).Ex situ tests reveal the conversion of Bi I_(3)into Bi(discharge)and Bi OI(charge)at the 1st cycle and the dissolved I^(-)in electrolyte.The active I^(-)species enhances the specific capacity and discharge medium voltage of electrode as well as improves the generation of Zn dendrite and by-product.Furthermore,the porous hard carbon is introduced to enhance the electronic/ionic conductivity and adsorb iodine species,proven by experimental and theoretical studies.Accordingly,the well-designed Bi I_(3)-Zn battery delivers a high reversible capacity of 182 m A h g^(-1)at 0.2 A g^(-1),an excellent rate capability with 88 m A h g^(-1)at 10 A g^(-1),and an impressive cyclability with 63%capacity retention over 20 K cycles at 10 A g^(-1).An excellent electrochemical performance is obtained even at a high mass loading of 6 mg cm^(-2).Moreover,a flexible quasi-solid-state Bi I_(3)-Zn battery exhibits satisfactory battery performances.This work provides a new idea for designing high-performance aqueous battery with dual mechanisms.展开更多
Zinc metal batteries have been considered as a promising candidate for next-generation batteries due to their high safety and low cost.However,their practical applications are severely hampered by the poor cyclability...Zinc metal batteries have been considered as a promising candidate for next-generation batteries due to their high safety and low cost.However,their practical applications are severely hampered by the poor cyclability that caused by the undesired dendrite growth of metallic Zn.Herein,Ti_(3)C_(2)T_(x) MXene was first used as electrolyte additive to facilitate the uniform Zn deposition by controlling the nucleation and growth process of Zn.Such MXene additives can not only be absorbed on Zn foil to induce uniform initial Zn deposition via providing abundant zincophilic-O groups and subsequently participate in the formation of robust solid-electrolyte interface film,but also accelerate ion transportation by reducing the Zn^(2+) concentration gradient at the electrode/electrolyte interface.Consequently,MXene-containing electrolyte realizes dendrite-free Zn plating/striping with high Coulombic efficiency(99.7%)and superior reversibility(stably up to 1180 cycles).When applied in full cell,the Zn-V_(2)O_(5)cell also delivers significantly improved cycling performances.This work provides a facile yet effective method for developing reversible zinc metal batteries.展开更多
Lithium metal is the ultimate anode material for next-generation high-energy batteries.Yet,the practical application of lithium metal anodes is limited by the formation of Li dendrites and large volume changes.Herein,...Lithium metal is the ultimate anode material for next-generation high-energy batteries.Yet,the practical application of lithium metal anodes is limited by the formation of Li dendrites and large volume changes.Herein,an effective multi-dimensional hybrid flexible film(MD-HFF)composed of iodine ion(0 dimension),CNTs(1 dimension)and graphene(2 dimensions)is designed for regulating Li deposition and mitigating volume changes.The multi-dimensional components serve separate roles:(1)iodine ion enhances the conductivity of the electrode and provides lithiophilic sites,(2)CNTs strengthen interlaminar conductance and mechanical strength,acting as a spring in the layered structure to alleviate volume changes during Li plating and stripping and(3)graphene provides mechanical flexibility and electrical conductivity.The resulting MD-HFF material supports stable Li plating/stripping and high Coulombic efficiency(99%)over 230 cycles at 1 mA cm^(-2) with a deposition capacity of 1 mAh cm^(-2).Theoretical calculations indicate that LiI contributes to the lateral growth of Li on the MD-HFF surface,thereby inhibiting the formation of Li dendrites.When paired with a typical NCM811 cathode,the assembled MD-HFF‖NCM811 cell exhibit improved capability and stable cycling performance.This research serves to guide material design in achieving Li anode materials that do not suffer from dendrite formation and volume changes.展开更多
One of the key challenges for achieving stable lithium(Li) metal anode is the construction of the rational solid electrolyte interphase(SEI),but its realization still faces enormous challenges.In this work,a robust ar...One of the key challenges for achieving stable lithium(Li) metal anode is the construction of the rational solid electrolyte interphase(SEI),but its realization still faces enormous challenges.In this work,a robust artificial fluorinated hybrid interphase consisting of lithium-bismuth(Li3Bi) alloy and lithium-fluoride(LiF) was designed to regulate Li deposition without Li dendrite growth.The obtained hybrid interphase showed the high Li+diffusion rate(3.5 × 10^(-4)S cm^(-1)),high electron resistivity(9.04 × 10^(4)Ω cm),and high mechanical strength(1348 MPa),thus enabling the uniform Li deposition at the Li/SEI interface.Specifically,Li3Bi alloy,as a superionic conductor,accelerated the Li+transport and stabilized the hybrid interphase.Meanwhile,LiF was identified as a superior electron-blocker to inhibit the electron tunneling from the Li anode into the SEI.As a result,the modified Li anode showed the stable Li plating/stripping behaviors over 1000 cycles even at 20 mA cm^(-2).Moreover,it also enabled the Li(50 μm)‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(4.4 mA h cm^(-2)) full cell to achieve an average Coulombic efficiency(CE) of 99.6%and a high-capacity retention of 79.2% after 100 cycles,whereas the bare Li anode only exhibited a low-capacity retention of 8.0%.This work sheds light on the internal mechanism of Li+transport within the hybrid interface and provides an effective approach to stabilize the interface of Li metal anode.展开更多
Lithium metal has aroused extensive research interests as the anode for next-generation rechargeable batteries.However,the well-known dendritic Li growth and consequent safety issues still impair the long-term cycling...Lithium metal has aroused extensive research interests as the anode for next-generation rechargeable batteries.However,the well-known dendritic Li growth and consequent safety issues still impair the long-term cycling performance.Herein,a hybrid structure composed of 3 D carbon cloth and vesicleshaped hollow ZIF-8 modification shell(HZS@CC)was prepared as a smart host for guiding uniform Li deposition.The long-range interconnected 3 D carbon fiber network enables the reduced local current density with homogeneous electrons distribution.Synergistically,abundant surface polar groups and the ultrastructure on ZIF-8 particles effectively guide a well-distributed Li-ions flow to promote the uniform Li nucleation and growth.As a result,stable Li plating/stripping for 2000 h with a low overpotential(≈15 mV)at 1 mA cm^(-2) were achieved in symmetric cells.Coupling with LiFePO_(4) cathode,the full cell delivered long life over 1200 cycles at 6 C.This research demonstrated that a homogenization guiding of Li-ions is of great importance to better make use of the structural advantage of 3 D hosts and achieve improved electrochemical performance.展开更多
Li metal,possessing advantages of high theoretical specific capacity and low electrochemical potential,is regarded as the most promising anode material for next-generation batteries.However,despite decades of intensiv...Li metal,possessing advantages of high theoretical specific capacity and low electrochemical potential,is regarded as the most promising anode material for next-generation batteries.However,despite decades of intensive research,its practical application is still hindered by safety hazard and low Coulombic efficiency,which is primarily caused by dendritic Li deposition.To address this issue,restraining dendrite growth at the nucleation stage is deemed as the most effective method.By utilizing the difference of electronegativity between boron atoms and carbon atoms,carbon atoms around boron atoms in boron-doped graphene(BG)turn into lithiophilic sites,which can enhance the adsorption capacity to Li^(+)at the nucleation stage.Consequently,an ultralow overpotential of 10 mV at a current density of 0.5 mA/cm^(2) and a high average Coulombic efficiency of 98.54%over more than 140 cycles with an areal capacity of 2 mAh/cm^(2) at a current density of 1 m A/cm^(2) were achieved.BG-Li|LiFePO_(4) full cells delivered a long lifespan of480 cycles at 0.5 C and excellent rate capability.This work provides a novel method for rational design of dendrite-free Li metal batteries by regulating nucleation process.展开更多
Lithium metal anode is the most potential anode material for the next generation high-energy rechargeable batteries owing to its highest specific capacity and lowest redox potential.Unfortunately,the uneven deposition...Lithium metal anode is the most potential anode material for the next generation high-energy rechargeable batteries owing to its highest specific capacity and lowest redox potential.Unfortunately,the uneven deposition of Li during plating/stripping and the formation of uncontrolled Li dendrites,which might cause poor battery performance and serious safety problems,are demonstrating to be a huge challenge for its practical application.Here,we show that a flexible and free-standing film hybriding with polypyrrole(PPy) nanotubes and reduced graphene oxide(rGO) can significantly regulate the Li nucleation and deposition,and further prohibit the formation of Li dendrites,owing to the large specific surface area,rich of nitrogen functional groups and porous structures.Finally,the high Coulombic efficiency and stable Li plating/stripping cycling performance with 98% for 230 cycles at 0.5 mA cm^(-2) and more than 900 hours stable lifespan are achieved.No Li dendrites form even at a Li deposition capacity as high as4.0 mA h cm^(-2).Besides,the designed PPy/rGO hybrid anode scaffold can also drive a superior battery performance in the lithium-metal full cell applications.展开更多
Lithium(Li)metal is the most potential anode material for the next-generation high-energy rechargeable batteries.However,intrinsic surface unevenness and‘hostless’nature of Li metal induces infinite volume effect an...Lithium(Li)metal is the most potential anode material for the next-generation high-energy rechargeable batteries.However,intrinsic surface unevenness and‘hostless’nature of Li metal induces infinite volume effect and uncontrollable dendrite growth.Herein,we design the in-situ grown lithiophilic Ni_(2)P nanoarrays inside nickel foam(PNF).Uniform Ni_(2)P nanoarrays coating presents a very low nucleation overpotential,which induces the homogeneous Li deposition in the entire spaces of three-dimensional(3D)metal framework.Specifically,the lithiophilic Ni_(2)P nanoarrays possess characteristics of electrical conductivity and structural stability,which have almost no expansion and damage during repeating Li plating/stripping.Therefore,they chronically inhibit the growth of Li dendrites.This results in an outstanding Coulombic efficiency(CE)of 98% at 3 mA cm^(-2) and an ultra long cycling life over 2000 cycles with a low overpotential.Consequently,the PNF-Li||LiFePO_(4) battery maintains a capacity retention of 95.3% with a stable CE of 99.9% over 500 cycles at 2 C.展开更多
Effects of operating parameters in the thermal gradient chemical vapor infiltration of propane such as thermal gradient, diffusion, infiltrations time, and concentration of propane were studied by focusing on the visu...Effects of operating parameters in the thermal gradient chemical vapor infiltration of propane such as thermal gradient, diffusion, infiltrations time, and concentration of propane were studied by focusing on the visualizations of the intrinsic effects of these parameters. A uniform deposition in the preform was obtained with a gradually increasing temperature along the gas flow. The uniformity of deposition through the preform got improved with increasing deposition time. Results of numerical modeling estimated the experimental data very well when the pre-exponential factor of the overall rate of carbon deposition from propane reported by Vaidyaraman[1] was multiplied by 4. The average density of a preform increased by about 3 times from 0.38 to 1.15 g/cm3 after 60 hr deposition with a thermal gradient under the conditions of 3% propane in nitrogen and 840 to 900 ℃.展开更多
Lithium metal batteries are considered as high energy density battery systems with very promising prospects and have bee n widely studied.However,The uncon trollable plating/strippi ng behavior,infinite volume change ...Lithium metal batteries are considered as high energy density battery systems with very promising prospects and have bee n widely studied.However,The uncon trollable plating/strippi ng behavior,infinite volume change and den drites formation of lithium metal anode restrict the applicati on.The unc on trolled n ucleati on of lithium caused by the non uniform multi-physical field distributions,can lead to the undesirable lithium deposition.Herein,a graphene composite uniformly loaded with Ag nano-particles(Ag NPs)is prepared through a facile Gamma ray irradiation method and assembled into self-supported film with layered structure(Ag-rGO film).Whe n such film is used as a lithium metal an ode host,the uncontrolled deposition is converted into a highly nucleation-induced process.On one hand,the Ag NPs distributed between the in terlayers of graphe ne can preferentially induce lithium nu cleati on and en able uniform deposition morphology of lithium between interlayers.On the other hand,the stable layered graphene structure can accommodate volume change,stabilize the interface between anode and electrolyte and inhibit dendrites formation.Therefore,the layered Ag-rGO film as anode host can reach a high Coulombic efficiency over 93.3% for 200 cycle(786 h)at a current density of 1 mA cm^(-2) for 2 mAh cm^(-2) in carbonate-based electrolyte.This work proposes a facile Gamma ray irradiation method to prepare metal/3D-skeleton structure as lithium anode host and demonstrates the potential to regulate the lithium metal deposition behaviors via manipulating the distribution of lithiophilic metal(e.g.Ag)in 3D frameworks.This may offer a practicable thinking for the subsequent design of the lithium metal anode.展开更多
Sodium(Na)metal anode exhibits a potential candidate in next-generation rechargeable batteries owing to its advantages of high earth abundance and low cost.Unfortunately,the practical development of sodium metal batte...Sodium(Na)metal anode exhibits a potential candidate in next-generation rechargeable batteries owing to its advantages of high earth abundance and low cost.Unfortunately,the practical development of sodium metal batteries is inherently plagued by challenges such as the side reactions and the growth of Na dendrites.Herein we report a highly stable Bi-based“sodiophilic”substrate to stabilize Na anode,which is created by in-situ electrochemical reactions of 3D hierarchical porous Bi_(2)MoO_(6)(BMO)microspheres.BMO is initially transformed into the Bi“nanoseeds”embedded in the Na-Mo-O matrix.Subsequently,the Bi nanoseeds working as preferential nucleation sites through the formation of BiNa alloy enable the non-dendritic Na deposition.The asymmetric cells based on such BMO-based substrate can deliver a long-term cycling for 600 cycles at a large capacity of 4 m Ah cm^(-2) and for 800 cycles at a high current density of 10 m A cm^(-2).Even at a high depth of discharge(66.67%),the Na-predeposited BMO(Na@BMO)electrodes can cycle for more than 1600 h.The limited Na@BMO anodes coupled with the Na_(3)V_(2)(PO_(4))_(3) cathodes(N/P ratio of 3)in full cells also show excellent electrochemical performance with a capacity retention of about 97.4%after 1100 cycles at 2 C.展开更多
Aqueous Zn-iodine(Zn-I_(2))batteries have attracted extensive research interest as an emerging redox conversion energy storage system due to the low cost and high safety.However,the shuttling effects of polyiodides ar...Aqueous Zn-iodine(Zn-I_(2))batteries have attracted extensive research interest as an emerging redox conversion energy storage system due to the low cost and high safety.However,the shuttling effects of polyiodides arising from incomplete redox conversion and inhomogeneous Zn plating on the Zn anode surface always hinder the commercial application of Zn-I_(2)batteries.In this work,a two-birds-with-one-stone strategy is reported for long-life Zn-I_(2)batteries.Based on the strategy,the sulfonate-functionalized carbon fiber not only acts as the excellent iodine limiter to inhibit iodine species shuttling,but also as the uniform Zn plating guidance layer on the Zn anode surface to prevent the inhomogeneous deposition of Zn^(2+).Consequently,a superior cycling stability(a capacity of 124 mAh g^(-1)after 10,000 cycles at 5 A g^(-1))is achieved.Theoretical calculations illustrate that sulfonate groups successfully induce charge redistribution on the carbon substrate,thereby strengthening the electronic interactions of the iodine species with the carbon substrate.The charge-enriched sulfonate groups can guide the uniform deposition of Zn^(2+)through a strong Coulombic effect with Zn^(2+).This work gives a new perspective on the integrated design of cathodes and anodes for rechargeable batteries.展开更多
Ineffective control of dendrite growth and side reactions on Zn anodes significantly retards commercialization of aqueous Zn-ion batteries.Unlike conventional interfacial modification strategies that are primarily foc...Ineffective control of dendrite growth and side reactions on Zn anodes significantly retards commercialization of aqueous Zn-ion batteries.Unlike conventional interfacial modification strategies that are primarily focused on component optimization or microstructural tuning,herein,we propose a crystallinity engineering strategy by developing highly crystalline carbon nitride protective layers for Zn anodes through molten salt treatment.Interestingly,the highly ordered structure along with sufficient functional polar groups and pre-intercalated Kþendows the coating with high ionic conductivity,strong hydrophilicity,and accelerated ion diffusion kinetics.Theoretical calculations also confirm its enhanced Zn adsorption capability compared to commonly reported carbon nitride with amorphous or semi-crystalline structure and bare Zn.Benefiting from the aforementioned features,the as-synthesized protective layer enables a calendar lifespan of symmetric cells for 1100 h and outstanding stability of full cells with capacity retention of 91.5%after 1500 cycles.This work proposes a new conceptual strategy for Zn anode protection.展开更多
The practical application of Na metal anode is plagued by the dendrite growth,unstable solid electrolyte interphase(SEI)formation and volume change during the cycling process.Herein,poly(tetrafluoroethylene)(noted as ...The practical application of Na metal anode is plagued by the dendrite growth,unstable solid electrolyte interphase(SEI)formation and volume change during the cycling process.Herein,poly(tetrafluoroethylene)(noted as PTFE)coating microcrystalline graphite is designed as the sodium metal anode host by a facile and cost-effective strategy.The isotropous microcrystalline graphite(MG)is conducive to guiding Na+to form a co-intercalation structure into MG.And the PTFE coating layer can form NaF as artificial SEI film for uniform ion transport and deposition.As a result,the gained PTFE coating MG electrode can deliver a long-life span over 1,200 cycles with an average Coulombic efficiency(CE)of 99.88%.To note,almost the CE in each cycle is around 99.8%–100%.When assembled with Na_(3)V_(2)(PO_(4))_(2)F_(3)cathode as full cells,the full cell paired with PTFE coating MG electrode can operate much stable than that of MG electrode for the existence of PTFE coating layer.Even utilized as sodium-free Na metal anode paired with Na_(3)V_(2)(PO_(4))_(2)F_(3)cathode,it can also deliver a high initial CE of 76.27%at 0.5 C.After 100 cycles,it still has a high discharge capacity of 83.5 mAh·g^(−1).展开更多
Although lithium metal and sodium metal are promised as ideal anodes for lithium ion batteries(LIBs)and sodium ion batteries(SIBs),they still suffer from inevitable dendrite growth.In light of this,silver nanoparticle...Although lithium metal and sodium metal are promised as ideal anodes for lithium ion batteries(LIBs)and sodium ion batteries(SIBs),they still suffer from inevitable dendrite growth.In light of this,silver nanoparticles(Ag NPs)are sputtered onto three-dimensional carbon nanotube decorated graphene foam(3D CNT-GF)to construct superior 3D Ag/CNT-GF composite matrix for lithium metal anodes(LMAs)and sodium metal anodes(SMAs).With this design,lithiophilic/sodiophilic Ag NPs could provide favorable sites to guide Li/Na metal nucleation and growth,thus leading to low nucleation overpotentials,high Coulombic efficiency and long cycle performance.Accordingly,3D Ag/CNT-GF electrodes can stably cy-cle for 1000 and 750 cycles at 3 mA cm^(−2)with 1 mAh cm^(−2)for SMAs and LMAs,respectively.More attractively,it can also stably sustain 300 cycles(SMAs)and 500 cycles(LMAs)at a large current den-sity of 5 mA cm^(−2)with 1 mAh cm^(−2).The excellent electrochemical performance can be attributed to the lithiophilic/sodiophilic electrode surface,3D porous electrode structure and the dendrite-free mor-phology as demonstrated by ex-situ scanning electron microscopy(SEM)and in-situ optical microscopy analyses.Furthermore,full cells based on Na@3D Ag/CNT-GF||Na 3 V 2(PO 4)3@carbon(NVP@C)and Li@3D Ag/CNT-GF||LiFePO 4(LFP)could deliver highly reversible capacities of 90.1 and 106.4 mAh g^(−1),respec-tively,at 100 mA g^(−1)after 200 cycles for SIBs and LIBs,respectively.This work demonstrates a novel 3D Ag/CNT-GF matrix for boosting Li/Na deposition stability for their future applications.展开更多
基金Projects(51305465,91123012)supported by the National Natural Science Foundation of China
文摘Thickness deposition is a crucial issue on the application of electroformed micro mold inserts. Edge concentration effect is the main source of the non-uniformity. The techniques of adopting a non-conducting shield, a secondary electrode and a movable cathode were explored to improve the thickness deposition uniformity during the nickel electroforming process. Regarding these techniques, a micro electroforming system with a movable cathode was particularly developed. The thickness variation of a 16 mm×16 mm electroformed sample decreased respectively from 150% to 35%, 12% and 18% by these three techniques. Combining these validated methods, anickelmold insert for microlens array was electroformed with satisfactory mechanical properties and high replication precision. It could be applied to the following injection molding process.
基金supported by the National Key Research and Development Program of China(2019YFA0205700)Scientific Research Projects of Colleges and Universities in Hebei Province(JZX2023004)+2 种基金Research Program of Local Science and Technology Development under the Guidance of Central(216Z4402G)support from Ministry of Science and Higher Education of Russian Federation(project FFSG-2022-0001(122111700046-3),"Laboratory of perspective electrode materials for chemical power sources")support from"Yuanguang"Scholar Program of Hebei University of Technology
文摘It is well accepted that a lithiophilic interface can effectively regulate Li deposition behaviors,but the influence of the lithiophilic interface is gradually diminished upon continuous Li deposition that completely isolates Li from the lithiophilic metals.Herein,we perform in-depth studies on the creation of dynamic alloy interfaces upon Li deposition,arising from the exceptionally high diffusion coefficient of Hg in the amalgam solid solution.As a comparison,other metals such as Au,Ag,and Zn have typical diffusion coefficients of 10-20 orders of magnitude lower than that of Hg in the similar solid solution phases.This difference induces compact Li deposition pattern with an amalgam substrate even with a high areal capacity of 55 mAh cm^(-2).This finding provides new insight into the rational design of Li anode substrate for the stable cycling of Li metal batteries.
基金the financial support from the National Natural Science Foundation of China(Nos.22205191 and 52002346)the Science and Technology Innovation Program of Hunan Province(No.2021RC3109)+1 种基金the Natural Science Foundation of Hunan Province,China(No.2022JJ40446)Guangxi Key Laboratory of Low Carbon Energy Material(No.2020GXKLLCEM01)。
文摘The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.
基金supported by the Science Foundation of National Key Laboratory of Science and Technology on Advanced Composites in Special Environmentsthe National Natural Science Foundation of China(12002109)
文摘Piezoelectric ceramic and polymeric separators have been proposed to effectively regulate Li deposition and suppress dendrite growth,but such separators still fail to satisfactorily support durable operation of lithium metal batteries owing to the fragile ceramic layer or low-piezoelectricity polymer as employed.Herein,by combining PVDF-HFP and ferroelectric BaTiO_(3),we develop a homogeneous,single-layer composite separator with strong piezoelectric effects to inhibit dendrite growth while maintaining high mechanical strength.As squeezed by local protrusion,the polarized PVDF-HFP/BaTiO_(3)composite separator generates a local voltage to suppress the local-intensified electric field and further deconcentrate regional lithium-ion flux to retard lithium deposition on the protrusion,hence enabling a smoother and more compact lithium deposition morphology than the unpoled composite separator and the pure PVDF-HFP separator,especially at high rates.Remarkably,the homogeneous incorporation of BaTiO_(3)highly improves the piezoelectric performances of the separator with residual polarization of 0.086 pC cm^(-2)after polarization treatment,four times that of the pure PVDF-HFP separator,and simultaneously increases the transference number of lithium-ion from 0.45 to 0.57.Beneficial from the prominent piezoelectric mechanism,the polarized PVDF-HFP/BaTiO_(3)composite separator enables stable cyclic performances of Li||LiFePO_(4)cells for 400 cycles at 2 C(1 C=170 mA g^(-1))with a capacity retention above 99%,and for 600 cycles at 5 C with a capacity retention over 85%.
基金supported by the National Natural Science Foundation of China (52302292, 52302058, 52302085)the China Postdoctoral Science Foundation (2021M702225)+1 种基金the Anhui Province University Natural Science Research Project (2023AH030093, 2023AH040301)the Startup Research Fund of Chaohu University (KYQD-2023005, KYQD-2023051)。
文摘Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition behavior still occurs at the top of 3D frameworks owing to the local accumulation of Li ions.To promote uniform Li deposition without top dendrite growth,herein,a layered multifunctional framework based on oxidation-treated polyacrylonitrile(OPAN) and metal-organic framework(MOF) derivatives was proposed for rationally regulating the distribution of Li ions flux,nucleation sites,and electrical conductivity.Profiting from these merits,the OPAN/carbon nano fiber-MOF(CMOF) composite framework demonstrated a reversible Li plating/stripping behavior for 500 cycles with a stable Coulombic efficiency of around 99.0% at the current density of 2 mA/cm~2.Besides,such a Li composite anode exhibited a superior cycle lifespan of over 1300 h under a low polarized voltage of 18 mV in symmetrical cells.When the Li composite anode was paired with LiFePO_(4)(LFP) cathode,the obtained full cell exhibited a stable cycling over 500 cycles.Moreover,the COMSOL Multiphysics simulation was conducted to reveal the effects on homogeneous Li ions distribution derived from the above-mentioned OPAN/CMOF framework and electrical insulation/conduction design.These electrochemical and simulated results shed light on the difficulties of designing stable and safe Li metal anode via optimizing the 3D frameworks.
基金funding from National Natural Science Foundation of China(52103053,52102312)Huxiang Young Talents of Hunan Province(2022RC1004)+1 种基金Macao Young Scholars Program(AM2021011)Foundation of State Key Laboratory of Utilization of Woody Oil Resource(GZKF202126)。
文摘The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previous studies using Zn I_(2)additive,this work designs an aqueous Bi I_(3)-Zn battery with selfsupplied I^(-).Ex situ tests reveal the conversion of Bi I_(3)into Bi(discharge)and Bi OI(charge)at the 1st cycle and the dissolved I^(-)in electrolyte.The active I^(-)species enhances the specific capacity and discharge medium voltage of electrode as well as improves the generation of Zn dendrite and by-product.Furthermore,the porous hard carbon is introduced to enhance the electronic/ionic conductivity and adsorb iodine species,proven by experimental and theoretical studies.Accordingly,the well-designed Bi I_(3)-Zn battery delivers a high reversible capacity of 182 m A h g^(-1)at 0.2 A g^(-1),an excellent rate capability with 88 m A h g^(-1)at 10 A g^(-1),and an impressive cyclability with 63%capacity retention over 20 K cycles at 10 A g^(-1).An excellent electrochemical performance is obtained even at a high mass loading of 6 mg cm^(-2).Moreover,a flexible quasi-solid-state Bi I_(3)-Zn battery exhibits satisfactory battery performances.This work provides a new idea for designing high-performance aqueous battery with dual mechanisms.
基金the National Natural Science Foundation of China(No.51902036,51702138,22075115)Natural Science Foundation of Chongqing Science&Technology Commission(No.cstc2019jcyj-msxm1407)+4 种基金Natural Science Foundation of Chongqing Technology and Business University(No.1952009)the Venture&Innovation Support Program for Chongqing Overseas Returnees(Grant No.CX2018129)the Science and Technology Research Program of Chongqing Municipal Education Commission(Grant No.KJQN201900826 and KJQN201800808)the Innovation Group of New Technologies for Industrial Pollution Control of Chongqing Education Commission(Grant No.CXQT19023)Key Disciplines of Chemical Engineering and Technology in Chongqing Colleges and Universities during the 13th Five Year Plan provided the financial support.
文摘Zinc metal batteries have been considered as a promising candidate for next-generation batteries due to their high safety and low cost.However,their practical applications are severely hampered by the poor cyclability that caused by the undesired dendrite growth of metallic Zn.Herein,Ti_(3)C_(2)T_(x) MXene was first used as electrolyte additive to facilitate the uniform Zn deposition by controlling the nucleation and growth process of Zn.Such MXene additives can not only be absorbed on Zn foil to induce uniform initial Zn deposition via providing abundant zincophilic-O groups and subsequently participate in the formation of robust solid-electrolyte interface film,but also accelerate ion transportation by reducing the Zn^(2+) concentration gradient at the electrode/electrolyte interface.Consequently,MXene-containing electrolyte realizes dendrite-free Zn plating/striping with high Coulombic efficiency(99.7%)and superior reversibility(stably up to 1180 cycles).When applied in full cell,the Zn-V_(2)O_(5)cell also delivers significantly improved cycling performances.This work provides a facile yet effective method for developing reversible zinc metal batteries.
基金supported by the Sichuan Province Science and Technology Support Program of 2020YFG0339, 2020YFH0097 and 2018GZ0007。
文摘Lithium metal is the ultimate anode material for next-generation high-energy batteries.Yet,the practical application of lithium metal anodes is limited by the formation of Li dendrites and large volume changes.Herein,an effective multi-dimensional hybrid flexible film(MD-HFF)composed of iodine ion(0 dimension),CNTs(1 dimension)and graphene(2 dimensions)is designed for regulating Li deposition and mitigating volume changes.The multi-dimensional components serve separate roles:(1)iodine ion enhances the conductivity of the electrode and provides lithiophilic sites,(2)CNTs strengthen interlaminar conductance and mechanical strength,acting as a spring in the layered structure to alleviate volume changes during Li plating and stripping and(3)graphene provides mechanical flexibility and electrical conductivity.The resulting MD-HFF material supports stable Li plating/stripping and high Coulombic efficiency(99%)over 230 cycles at 1 mA cm^(-2) with a deposition capacity of 1 mAh cm^(-2).Theoretical calculations indicate that LiI contributes to the lateral growth of Li on the MD-HFF surface,thereby inhibiting the formation of Li dendrites.When paired with a typical NCM811 cathode,the assembled MD-HFF‖NCM811 cell exhibit improved capability and stable cycling performance.This research serves to guide material design in achieving Li anode materials that do not suffer from dendrite formation and volume changes.
基金supported by the Natural Science Foundation of Henan Province (202300410163)the Innovative Research Team(in Science and Technology) in University of Henan Province(20IRTSTHN016)+1 种基金the Outstanding Talent Introduction Project of University of Electronic Science and Technology of China(08JC00303)the Innovative Research Team of Sichuan Fuhua New Energy High-Tech Co.,Ltd (621006)。
文摘One of the key challenges for achieving stable lithium(Li) metal anode is the construction of the rational solid electrolyte interphase(SEI),but its realization still faces enormous challenges.In this work,a robust artificial fluorinated hybrid interphase consisting of lithium-bismuth(Li3Bi) alloy and lithium-fluoride(LiF) was designed to regulate Li deposition without Li dendrite growth.The obtained hybrid interphase showed the high Li+diffusion rate(3.5 × 10^(-4)S cm^(-1)),high electron resistivity(9.04 × 10^(4)Ω cm),and high mechanical strength(1348 MPa),thus enabling the uniform Li deposition at the Li/SEI interface.Specifically,Li3Bi alloy,as a superionic conductor,accelerated the Li+transport and stabilized the hybrid interphase.Meanwhile,LiF was identified as a superior electron-blocker to inhibit the electron tunneling from the Li anode into the SEI.As a result,the modified Li anode showed the stable Li plating/stripping behaviors over 1000 cycles even at 20 mA cm^(-2).Moreover,it also enabled the Li(50 μm)‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(4.4 mA h cm^(-2)) full cell to achieve an average Coulombic efficiency(CE) of 99.6%and a high-capacity retention of 79.2% after 100 cycles,whereas the bare Li anode only exhibited a low-capacity retention of 8.0%.This work sheds light on the internal mechanism of Li+transport within the hybrid interface and provides an effective approach to stabilize the interface of Li metal anode.
基金financially supported by the National Key Research and Development Program of China(2017YFA0206703)the National Natural Science Foundation of China(21671183)。
文摘Lithium metal has aroused extensive research interests as the anode for next-generation rechargeable batteries.However,the well-known dendritic Li growth and consequent safety issues still impair the long-term cycling performance.Herein,a hybrid structure composed of 3 D carbon cloth and vesicleshaped hollow ZIF-8 modification shell(HZS@CC)was prepared as a smart host for guiding uniform Li deposition.The long-range interconnected 3 D carbon fiber network enables the reduced local current density with homogeneous electrons distribution.Synergistically,abundant surface polar groups and the ultrastructure on ZIF-8 particles effectively guide a well-distributed Li-ions flow to promote the uniform Li nucleation and growth.As a result,stable Li plating/stripping for 2000 h with a low overpotential(≈15 mV)at 1 mA cm^(-2) were achieved in symmetric cells.Coupling with LiFePO_(4) cathode,the full cell delivered long life over 1200 cycles at 6 C.This research demonstrated that a homogenization guiding of Li-ions is of great importance to better make use of the structural advantage of 3 D hosts and achieve improved electrochemical performance.
基金supported by the National Key R&D Program of China(Grant No.2018YFA0306900)the National Natural Science Foundation of China(Nos.51872012)the Fundamental Research Funds for the Central Universities and the 111 Project(B17002)。
文摘Li metal,possessing advantages of high theoretical specific capacity and low electrochemical potential,is regarded as the most promising anode material for next-generation batteries.However,despite decades of intensive research,its practical application is still hindered by safety hazard and low Coulombic efficiency,which is primarily caused by dendritic Li deposition.To address this issue,restraining dendrite growth at the nucleation stage is deemed as the most effective method.By utilizing the difference of electronegativity between boron atoms and carbon atoms,carbon atoms around boron atoms in boron-doped graphene(BG)turn into lithiophilic sites,which can enhance the adsorption capacity to Li^(+)at the nucleation stage.Consequently,an ultralow overpotential of 10 mV at a current density of 0.5 mA/cm^(2) and a high average Coulombic efficiency of 98.54%over more than 140 cycles with an areal capacity of 2 mAh/cm^(2) at a current density of 1 m A/cm^(2) were achieved.BG-Li|LiFePO_(4) full cells delivered a long lifespan of480 cycles at 0.5 C and excellent rate capability.This work provides a novel method for rational design of dendrite-free Li metal batteries by regulating nucleation process.
基金supported by the National Natural Science Foundation of China(Nos.21603019,201503025)Key Program for International Science and Technology Cooperation Projects of Ministry of Science and Technology of China(No.2016YFE0125900)program for the Hundred Talents Program of Chongqing University。
文摘Lithium metal anode is the most potential anode material for the next generation high-energy rechargeable batteries owing to its highest specific capacity and lowest redox potential.Unfortunately,the uneven deposition of Li during plating/stripping and the formation of uncontrolled Li dendrites,which might cause poor battery performance and serious safety problems,are demonstrating to be a huge challenge for its practical application.Here,we show that a flexible and free-standing film hybriding with polypyrrole(PPy) nanotubes and reduced graphene oxide(rGO) can significantly regulate the Li nucleation and deposition,and further prohibit the formation of Li dendrites,owing to the large specific surface area,rich of nitrogen functional groups and porous structures.Finally,the high Coulombic efficiency and stable Li plating/stripping cycling performance with 98% for 230 cycles at 0.5 mA cm^(-2) and more than 900 hours stable lifespan are achieved.No Li dendrites form even at a Li deposition capacity as high as4.0 mA h cm^(-2).Besides,the designed PPy/rGO hybrid anode scaffold can also drive a superior battery performance in the lithium-metal full cell applications.
基金financial supported by the National Natural Science Foundation of China(Grant Nos.51874361 and 51904343)the Science and technology program of Hunan Province(2019RS3002)。
文摘Lithium(Li)metal is the most potential anode material for the next-generation high-energy rechargeable batteries.However,intrinsic surface unevenness and‘hostless’nature of Li metal induces infinite volume effect and uncontrollable dendrite growth.Herein,we design the in-situ grown lithiophilic Ni_(2)P nanoarrays inside nickel foam(PNF).Uniform Ni_(2)P nanoarrays coating presents a very low nucleation overpotential,which induces the homogeneous Li deposition in the entire spaces of three-dimensional(3D)metal framework.Specifically,the lithiophilic Ni_(2)P nanoarrays possess characteristics of electrical conductivity and structural stability,which have almost no expansion and damage during repeating Li plating/stripping.Therefore,they chronically inhibit the growth of Li dendrites.This results in an outstanding Coulombic efficiency(CE)of 98% at 3 mA cm^(-2) and an ultra long cycling life over 2000 cycles with a low overpotential.Consequently,the PNF-Li||LiFePO_(4) battery maintains a capacity retention of 95.3% with a stable CE of 99.9% over 500 cycles at 2 C.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT and Future Planning(NRF-2013R1A1A2007280)partially supported by the 2014 Hongik University Research Fund
文摘Effects of operating parameters in the thermal gradient chemical vapor infiltration of propane such as thermal gradient, diffusion, infiltrations time, and concentration of propane were studied by focusing on the visualizations of the intrinsic effects of these parameters. A uniform deposition in the preform was obtained with a gradually increasing temperature along the gas flow. The uniformity of deposition through the preform got improved with increasing deposition time. Results of numerical modeling estimated the experimental data very well when the pre-exponential factor of the overall rate of carbon deposition from propane reported by Vaidyaraman[1] was multiplied by 4. The average density of a preform increased by about 3 times from 0.38 to 1.15 g/cm3 after 60 hr deposition with a thermal gradient under the conditions of 3% propane in nitrogen and 840 to 900 ℃.
基金support from the National Natural Science Foundation of China(Grant No.21875195,21875198 and 22005257)the Fundamental Research Funds for the Central Universities(20720190040).
文摘Lithium metal batteries are considered as high energy density battery systems with very promising prospects and have bee n widely studied.However,The uncon trollable plating/strippi ng behavior,infinite volume change and den drites formation of lithium metal anode restrict the applicati on.The unc on trolled n ucleati on of lithium caused by the non uniform multi-physical field distributions,can lead to the undesirable lithium deposition.Herein,a graphene composite uniformly loaded with Ag nano-particles(Ag NPs)is prepared through a facile Gamma ray irradiation method and assembled into self-supported film with layered structure(Ag-rGO film).Whe n such film is used as a lithium metal an ode host,the uncontrolled deposition is converted into a highly nucleation-induced process.On one hand,the Ag NPs distributed between the in terlayers of graphe ne can preferentially induce lithium nu cleati on and en able uniform deposition morphology of lithium between interlayers.On the other hand,the stable layered graphene structure can accommodate volume change,stabilize the interface between anode and electrolyte and inhibit dendrites formation.Therefore,the layered Ag-rGO film as anode host can reach a high Coulombic efficiency over 93.3% for 200 cycle(786 h)at a current density of 1 mA cm^(-2) for 2 mAh cm^(-2) in carbonate-based electrolyte.This work proposes a facile Gamma ray irradiation method to prepare metal/3D-skeleton structure as lithium anode host and demonstrates the potential to regulate the lithium metal deposition behaviors via manipulating the distribution of lithiophilic metal(e.g.Ag)in 3D frameworks.This may offer a practicable thinking for the subsequent design of the lithium metal anode.
基金the support from the National Natural Science Foundation of China(22179079 and 52101264)the Science and Technology Commission of Shanghai Municipality(20010500400)the Westlake Education Foundation。
文摘Sodium(Na)metal anode exhibits a potential candidate in next-generation rechargeable batteries owing to its advantages of high earth abundance and low cost.Unfortunately,the practical development of sodium metal batteries is inherently plagued by challenges such as the side reactions and the growth of Na dendrites.Herein we report a highly stable Bi-based“sodiophilic”substrate to stabilize Na anode,which is created by in-situ electrochemical reactions of 3D hierarchical porous Bi_(2)MoO_(6)(BMO)microspheres.BMO is initially transformed into the Bi“nanoseeds”embedded in the Na-Mo-O matrix.Subsequently,the Bi nanoseeds working as preferential nucleation sites through the formation of BiNa alloy enable the non-dendritic Na deposition.The asymmetric cells based on such BMO-based substrate can deliver a long-term cycling for 600 cycles at a large capacity of 4 m Ah cm^(-2) and for 800 cycles at a high current density of 10 m A cm^(-2).Even at a high depth of discharge(66.67%),the Na-predeposited BMO(Na@BMO)electrodes can cycle for more than 1600 h.The limited Na@BMO anodes coupled with the Na_(3)V_(2)(PO_(4))_(3) cathodes(N/P ratio of 3)in full cells also show excellent electrochemical performance with a capacity retention of about 97.4%after 1100 cycles at 2 C.
基金supported by the National Natural Science Foundation of China(51772082 and 51804106)the Natural Science Foundation of Hunan Province(2023JJ10005)the Science and Technology Projects of the State Grid Corporation of China(5500-202323102A-11-ZN)。
文摘Aqueous Zn-iodine(Zn-I_(2))batteries have attracted extensive research interest as an emerging redox conversion energy storage system due to the low cost and high safety.However,the shuttling effects of polyiodides arising from incomplete redox conversion and inhomogeneous Zn plating on the Zn anode surface always hinder the commercial application of Zn-I_(2)batteries.In this work,a two-birds-with-one-stone strategy is reported for long-life Zn-I_(2)batteries.Based on the strategy,the sulfonate-functionalized carbon fiber not only acts as the excellent iodine limiter to inhibit iodine species shuttling,but also as the uniform Zn plating guidance layer on the Zn anode surface to prevent the inhomogeneous deposition of Zn^(2+).Consequently,a superior cycling stability(a capacity of 124 mAh g^(-1)after 10,000 cycles at 5 A g^(-1))is achieved.Theoretical calculations illustrate that sulfonate groups successfully induce charge redistribution on the carbon substrate,thereby strengthening the electronic interactions of the iodine species with the carbon substrate.The charge-enriched sulfonate groups can guide the uniform deposition of Zn^(2+)through a strong Coulombic effect with Zn^(2+).This work gives a new perspective on the integrated design of cathodes and anodes for rechargeable batteries.
基金National Natural Science Foundation of China,Grant/Award Number:22378055Applied Basic Research Program of Liaoning,Grant/Award Number:2022JH2/101300200+1 种基金Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2022A1515140188Fundamental Research Funds for the Central Universities,Grant/Award Numbers:N2002005,N2125004,N2225044,N232410019。
文摘Ineffective control of dendrite growth and side reactions on Zn anodes significantly retards commercialization of aqueous Zn-ion batteries.Unlike conventional interfacial modification strategies that are primarily focused on component optimization or microstructural tuning,herein,we propose a crystallinity engineering strategy by developing highly crystalline carbon nitride protective layers for Zn anodes through molten salt treatment.Interestingly,the highly ordered structure along with sufficient functional polar groups and pre-intercalated Kþendows the coating with high ionic conductivity,strong hydrophilicity,and accelerated ion diffusion kinetics.Theoretical calculations also confirm its enhanced Zn adsorption capability compared to commonly reported carbon nitride with amorphous or semi-crystalline structure and bare Zn.Benefiting from the aforementioned features,the as-synthesized protective layer enables a calendar lifespan of symmetric cells for 1100 h and outstanding stability of full cells with capacity retention of 91.5%after 1500 cycles.This work proposes a new conceptual strategy for Zn anode protection.
基金supported by the Natural Science Foundation of Hunan Province,China(No.2020JJ1007)the Key Deployed Projects of the Chinese Academy of Sciences(No.ZDRW-CN-2021-3).
文摘The practical application of Na metal anode is plagued by the dendrite growth,unstable solid electrolyte interphase(SEI)formation and volume change during the cycling process.Herein,poly(tetrafluoroethylene)(noted as PTFE)coating microcrystalline graphite is designed as the sodium metal anode host by a facile and cost-effective strategy.The isotropous microcrystalline graphite(MG)is conducive to guiding Na+to form a co-intercalation structure into MG.And the PTFE coating layer can form NaF as artificial SEI film for uniform ion transport and deposition.As a result,the gained PTFE coating MG electrode can deliver a long-life span over 1,200 cycles with an average Coulombic efficiency(CE)of 99.88%.To note,almost the CE in each cycle is around 99.8%–100%.When assembled with Na_(3)V_(2)(PO_(4))_(2)F_(3)cathode as full cells,the full cell paired with PTFE coating MG electrode can operate much stable than that of MG electrode for the existence of PTFE coating layer.Even utilized as sodium-free Na metal anode paired with Na_(3)V_(2)(PO_(4))_(2)F_(3)cathode,it can also deliver a high initial CE of 76.27%at 0.5 C.After 100 cycles,it still has a high discharge capacity of 83.5 mAh·g^(−1).
基金supported by the National Natural Science Foun-dation of China(Grant No.U1804132)Zhongyuan Youth Talent Support Program of Henan Province(Grant No.ZYQR201912152)Academic Improvement Program of Physics of Zhengzhou Univer-sity(GrantNo.2018WLTJ02),Zhengzhou University Youth Talent Start-up Grant.
文摘Although lithium metal and sodium metal are promised as ideal anodes for lithium ion batteries(LIBs)and sodium ion batteries(SIBs),they still suffer from inevitable dendrite growth.In light of this,silver nanoparticles(Ag NPs)are sputtered onto three-dimensional carbon nanotube decorated graphene foam(3D CNT-GF)to construct superior 3D Ag/CNT-GF composite matrix for lithium metal anodes(LMAs)and sodium metal anodes(SMAs).With this design,lithiophilic/sodiophilic Ag NPs could provide favorable sites to guide Li/Na metal nucleation and growth,thus leading to low nucleation overpotentials,high Coulombic efficiency and long cycle performance.Accordingly,3D Ag/CNT-GF electrodes can stably cy-cle for 1000 and 750 cycles at 3 mA cm^(−2)with 1 mAh cm^(−2)for SMAs and LMAs,respectively.More attractively,it can also stably sustain 300 cycles(SMAs)and 500 cycles(LMAs)at a large current den-sity of 5 mA cm^(−2)with 1 mAh cm^(−2).The excellent electrochemical performance can be attributed to the lithiophilic/sodiophilic electrode surface,3D porous electrode structure and the dendrite-free mor-phology as demonstrated by ex-situ scanning electron microscopy(SEM)and in-situ optical microscopy analyses.Furthermore,full cells based on Na@3D Ag/CNT-GF||Na 3 V 2(PO 4)3@carbon(NVP@C)and Li@3D Ag/CNT-GF||LiFePO 4(LFP)could deliver highly reversible capacities of 90.1 and 106.4 mAh g^(−1),respec-tively,at 100 mA g^(−1)after 200 cycles for SIBs and LIBs,respectively.This work demonstrates a novel 3D Ag/CNT-GF matrix for boosting Li/Na deposition stability for their future applications.