The inherent safety,high theoretical specific capacity and low raw material cost of aqueous batteries make them potential candidates in large-scale energy storage.However,uncontrolled dendrite growth,parasitic reactio...The inherent safety,high theoretical specific capacity and low raw material cost of aqueous batteries make them potential candidates in large-scale energy storage.However,uncontrolled dendrite growth,parasitic reactions and sluggish mass transfer on the anode-electrolyte interface are the main challenges restricting the application prospect of aqueous zinc-ion batteries.In general,eukaryotic cells utilize specific ion channels to achieve ion migration with the merits of low energy consumption and rapid speed.Herein,migrating the concept of ion channels to aqueous batteries,a crown species encapsulated zeolitic imidazolate framework(ZIF)interfacial layer(denoted as ZIF@Crown)was ex situ decorated onto the Zn anode.Similar to biological ion channels,the ZIF@Crown layer can homogenize the distribution of Zn^(2+)on the anode,accelerate the desolvation of hydrated Zn^(2+)and reduce the energy barrier for Zn^(2+)deposition,which were verified by theoretical calculations and experimental characterizations.Benefiting from these efficacious modulation mechanisms,the Zn@ZIF@Crown symmetrical cell could achieve a long calendar life of over 1900 h and the Zn@ZIF@Crown||Cu also sustained 600 cycles with a high Coulombic efficiency(97%).Furthermore,the full cells containing ZIF@Crown layer exhibit desirable electrochemical performance.This work provides an innovative avenue toward the optimization of aqueous batteries via bionic interfacial engineering.展开更多
Cake layer formation is inevitable over time for ultrafiltration(UF)membrane-based drinking water treatment.Although the cake layer is always considered to cause membrane fouling,it can also act as a"dynamic prot...Cake layer formation is inevitable over time for ultrafiltration(UF)membrane-based drinking water treatment.Although the cake layer is always considered to cause membrane fouling,it can also act as a"dynamic protection layer",as it further adsorbs pollutants and dramatically reduces their chance of getting to the membrane surface.Here,the UF membrane fouling performance was investigated with pre-deposited loose flocs in the presence of humic acid(HA).The results showed that the floc dynamic protection layer played an important role in removing HA.The higher the solution pH,the more negative the floc charge,resulting in lower HA removal efficiency due to the electrostatic repulsion and large pore size of the floc layer.With decreasing solution pH,a positively charged floc dynamic protection layer was formed,and more HA molecules were adsorbed.The potential reasons were ascribed to the smaller floc size,greater positive charge,and higher roughness of the floc layer.However,similar membrane fouling performance was also observed for the negative and positive floc dynamic protection layers due to their strong looseness characteristics.In addition,the molecular weight(MW)distribution of HA also played an important role in UF membrane fouling behavior.For the small MW HA molecules,the chance of forming a loose cake layer was high with a negatively charged floc dynamic protection layer,while for the large MW HA molecules it was high with a positively charged floc dynamic protection layer.As a result,slight UF membrane fouling was induced.展开更多
ZrCoCe getter films with thickness of ~2.3 lm were deposited on Si(100) wafers by direct current(DC)magnetron sputtering process. A 400-nm-thick Pd protection layer was then deposited on the as-deposited ZrCoCe film w...ZrCoCe getter films with thickness of ~2.3 lm were deposited on Si(100) wafers by direct current(DC)magnetron sputtering process. A 400-nm-thick Pd protection layer was then deposited on the as-deposited ZrCoCe film without exposure to atmosphere. Microstructure, surface morphology and surface chemical state of the films were analyzed. Moreover, hydrogen sorption properties were determined. The results show that the ZrCoCe film displays a cauliflower-like morphology and a porous columnar-like structure which is composed of nanocrystal grains. The Pd protection layer tightly adheres to the surface of the ZrCoCe film and efficiently prevents the oxidation of Zr under exposure to atmosphere. We find that the hydrogen sorption properties of the Pd-ZrCoCe film are significantly improved,in comparison with those of the as-deposited ZrCoCe film.展开更多
Lithium sulfur batteries have attracted much attention due to their high theoretical specific energy and environmental friendliness.However,the practical application is severely plagued by the cycling life issues resu...Lithium sulfur batteries have attracted much attention due to their high theoretical specific energy and environmental friendliness.However,the practical application is severely plagued by the cycling life issues resulting from the uncontrollable generation and growth of Li dendrites.Herein,an innovative 3D flexible self-supporting Li anode protection layer of P-Mn_(3)O_(4-x)is constructed via a facile solvothermal method followed by an annealing process.Benefiting from the rich oxygen vacancies coupled with the 3D flexible self-supporting skeleton,abundant lithiophilic sites and high ionic conductivity are obtained,which succeed in guiding Li+homogeneous adsorption and redistribution,accelerating Li+diffusion rate,inducing Li+uniform deposition and nucleation.DFT calculations and experimental results conclusively demonstrate such a protection mechanism.Meanwhile,the effective anchoring and catalytic nature of polar P-Mn_(3)O_(4-x)can also be applied as an immobilization-diffusion-conversion host to improve polysulfides redox.Taking advantage of these merits,super-stable functions for Li symmetric cell matched with P-Mn_(3)O_(4-x)layer are achieved,which exhibits an ultralong lifespan of>5000 h with an ultralow overpotential of 20 m V,far lower than that of bare Li symmetric cell(overpotential of 800 m V only after 250 h)at high current densities of 5 m A cm^(-2)and high plating/stripping capacity of 10 m A h cm^(-2).Even in Li|P-Mn_(3)O_(4-x)||S full cell at 1 C,a high initial discharge specific capacity of 843.1 m A h g^(-1)is still delivered with ultralow capacity fading rate of 0.07%per cycle after 250 cycles,further confirming the synergistic regulation of P-Mn_(3)O_(4-x)for Li nucleation behavior.This work illustrates a sufficient guarantee of 3D protection layer coupled with oxygen vacancies in guiding Li diffusion and nucleation behavior and provides new guidance for promoting the development of advanced Li-S batteries.展开更多
We have realized robust quantum anomalous Hall samples by protecting Cr-doped（Bi,Sb）2Te3 topological insulator films with a combination of LiF and A1Ox capping layers.The AlOx/LiF composite capping layer well keeps ...We have realized robust quantum anomalous Hall samples by protecting Cr-doped（Bi,Sb）2Te3 topological insulator films with a combination of LiF and A1Ox capping layers.The AlOx/LiF composite capping layer well keeps the quantum anomalous Hall states of Cr-doped（Bi,Sb）2Te3 films and effectively prevent them from degradation induced by ambient conditions.The progress is a key step towards the realization of the quantum phenomena in heterostructures and devices based on quantum anomalous Hall system.展开更多
The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction(HER)at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries...The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction(HER)at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries.In this work,we propose sorbitan oleate(Span 80)as a novel amphiphilic electrolyte additive for 2 mol/L ZnSO_(4),demonstrating multifunctional performance.The unique ultra-long hydrophobic carbon chains of Span 80 effectively reduce free water molecules at the Zn anode-electrolyte interface,forming a robust hydrophobic interfacial layer that significantly suppresses HER and corrosion reactions.Simultaneously,carbon chains can enhance the desolvation effect of[Zn(H_(2)O)_(6)]^(2+),leading to improve rate performance.Additionally,the hydrophilic sorbitan groups in Span 80 selectively adsorb onto active sites of the Zn anode,promoting uniform Zn^(2+)deposition and suppressing dendrite growth.The optimized Zn||Zn symmetric cell exhibits outstanding cycling stability,sustaining reversible plating/stripping for 570 h at 50 mA/cm^(2) and the Zn||V_(2)O_(5) full cell retains exceptional stability over 2000 cycles at 1 A/g.Our work presents a promising strategy for suppressing interfacial side reactions by constructing a hydrophobic protective layer through the use of ultra-long carbon chain surfactants.This approach offers new insights into enhancing the performance of aqueous Zn-ion batteries.展开更多
Aiming at the limitation of the traditional method for determination of protection region, combined with the actual situation of a mine, a new method for determination of protection region was put forward （including ...Aiming at the limitation of the traditional method for determination of protection region, combined with the actual situation of a mine, a new method for determination of protection region was put forward （including the protection of working face layout and development direction）, that is, gas flow observation analysis on the spot and gas content contrast method. The protection region was determined by gas flow observation analysis, gas content contrast, and computer numerical simulation combined with engineering practice. In the process of gas content test, the fixed sampling method ＂big hole drill reaming, small orifice drill rod connected with core tube＂ was employed. The results show that the determined protection region is in accordance with the actual site situation. The fixed sampling method ensures the accuracy of gas measurement of gas content.展开更多
Aqueous zinc-ion batteries(AZIBs)are promising for future large-scale energy storage systems,however,suffer from inferior cycling life due to the dendrites growth and side reaction on Zn metal anode.Herein,a fast ion ...Aqueous zinc-ion batteries(AZIBs)are promising for future large-scale energy storage systems,however,suffer from inferior cycling life due to the dendrites growth and side reaction on Zn metal anode.Herein,a fast ion conductor Na_(5)YSi_(4)O_(12)(NYSO)was synthesized and fabricated as a protection layer of the Zn metal anode.By adjusting the thickness,an optimized NYSO coating of 20.3μm was obtained and the corresponding symmetry cell demonstrates an extended life span of 1896 h at the current density of 0.5 mA cm^(−2).In addition,a favorable rate performance of the NYSO@Zn anode at a high current density of 10 mA cm^(−2)was achieved.Benefiting from the NYSO coating,uniform diffusion and deposition of Zn^(2+)on the Zn anode could be realized,leading to the elimination of Zn dendrites and side reactions.Therefore,the aqueous NYSO@Zn|CNT@MnO_(2)full cell shows superior capacity and cycling stability to that of the bare Zn full cell.展开更多
Rechargeable aqueous zinc(Zn)-metal batteries hold great promise for next-generation energy storage systems.However,their practical application is hindered by several challenges,including dendrite formation,corrosion,...Rechargeable aqueous zinc(Zn)-metal batteries hold great promise for next-generation energy storage systems.However,their practical application is hindered by several challenges,including dendrite formation,corrosion,and the competing hydrogen evolution reaction.To address these issues,we designed and fabricated a composite protective layer for Zn anodes by integrating carbon nanotubes(CNTs)with chitosan through a simple and scalable scraping process.The CNTs ensure uniform electric field distribution due to their high electrical conductivity,while protonated chitosan regulates ion transport and suppresses dendrite formation at the anode interface.The chitosan/CNTs composite layer also facilitates smooth Zn^(2+)deposition,enhancing the stability and reversibility of the Zn anode.As a result,the chitosan/CNTs@Zn anode demonstrates exceptional cycling stability,achieving over 3000 h of plating/stripping with minimal degradation.When paired with a V_(2)O_(5)cathode,the composite-protected anode significantly improves the cycle stability and energy density of the full cell.Techno-economic analysis confirms that batteries incorporating the chitosan/CNTs protective layer outperform those with bare Zn anodes in terms of energy density and overall performance under optimized conditions.This work provides a scalable and sustainable strategy to overcome the critical challenges of aqueous Zn-metal batteries,paving the way for their practical application in next-generation energy storage systems.展开更多
In this work,we design and fabricate AlGaN/GaN-based Schottky barrier diodes(SBDs)on a silicon substrate with a trenched n^(+)-GaN cap layer.With the developed physical models,we find that the n^(+)-GaN cap layer prov...In this work,we design and fabricate AlGaN/GaN-based Schottky barrier diodes(SBDs)on a silicon substrate with a trenched n^(+)-GaN cap layer.With the developed physical models,we find that the n^(+)-GaN cap layer provides more electrons into the AlGaN/GaN channel,which is further confirmed experimentally.When compared with the reference device,this increases the two-dimensional electron gas(2DEG)density by two times and leads to a reduced specific ON-resistance(Ron,sp)of~2.4 mΩ·cm^(2).We also adopt the trenched n^(+)-GaN structure such that partial of the n^(+)-GaN is removed by using dry etching process to eliminate the surface electrical conduction when the device is set in the off-state.To suppress the surface defects that are caused by the dry etching process,we also deposit Si_(3)N_(4)layer prior to the deposition of field plate(FP),and we obtain a reduced leakage current of~8×10^(−5)A·cm^(−2)and breakdown voltage(BV)of 876 V.The Baliga’s figure of merit(BFOM)for the proposed structure is increased to~319 MW·cm^(−2).Our investigations also find that the pre-deposited Si_(3)N_(4)layer helps suppress the electron capture and transport processes,which enables the reduced dynamic R_(on,sp).展开更多
The differential cubature solution to the problem of a Mindlin plate lying on the Winkler foundation with two simply supported edges and two clamped edges was derived.Discrete numerical technology and shape functions ...The differential cubature solution to the problem of a Mindlin plate lying on the Winkler foundation with two simply supported edges and two clamped edges was derived.Discrete numerical technology and shape functions were used to ensure that the solution is suitable to irregular shaped plates.Then,the mechanical model and the solution were employed to model the protection layer that isolates the mining stopes from sea water in Sanshandao gold mine,which is the first subsea mine of China.Furthermore,thickness optimizations for the protection layers above each stope were conducted based on the maximum principle stress criterion,and the linear relations between the best protection layer thickness and the stope area under different safety factors were regressed to guide the isolation design.The method presented in this work provides a practical way to quickly design the isolation layer thickness in subsea mining.展开更多
The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based...The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.展开更多
A variety of techniques, such as chemical analysis, scanning electron microscopy-energy dispersive spectroscopy, and X-ray diffraction, were applied to characterize the adhesion protective layer formed below the blast...A variety of techniques, such as chemical analysis, scanning electron microscopy-energy dispersive spectroscopy, and X-ray diffraction, were applied to characterize the adhesion protective layer formed below the blast furnace taphole level when a certain amount of titanium-bearing burden was used. Samples of the protective layer were extracted to identify the chemical composition, phase assemblage, andistribution. Furthermore, the formation mechanism of the protective layer was determined after clarifying the source of each componenFinally, a technical strategy was proposed for achieving a stable protective layer in the hearth. The results show that the protective layemainly exists in a bilayer form in the sidewall, namely, a titanium-bearing layer and a graphite layer. Both the layers contain the slag phaswhose major crystalline phase is magnesium melilite（Ca2Mg Si2O7） and the main source of the slag phase is coke ash. It is clearly determinethat solid particles such as graphite, Ti（C,N） and Mg Al2O4play an important role in the formation of the protective layer, and the key factofor promoting the formation of a stable protective layer is reasonable control of the evolution behavior of coke.展开更多
A long campaign life of blast furnaces is heavily linked to the existence of a protective layer in their hearths. In this work, we conducted dissection studies and investigated damage in blast furnace hearths to estim...A long campaign life of blast furnaces is heavily linked to the existence of a protective layer in their hearths. In this work, we conducted dissection studies and investigated damage in blast furnace hearths to estimate the formation mechanism of the protective layer. The results illustrate that a significant amount of graphite phase was trapped within the hearth protective layer. Furthermore, on the basis of the thermodynamic and kinetic calculations of the graphite precipitation process, a precipitation potential index related to the formation of the graphite-rich protective layer was proposed to characterize the formation ability of this layer. We determined that, under normal operating conditions, the precipitation of graphite phase ~om hot metal was thermodynamically possible. Among elements that exist in hot metal, C, Si, and P favor graphite precipitation, whereas Mn and Cr inhibit this process. Moreover, at the same hot-face temperature, an increase of carbon concentration in hot metal can shorten the precipitation time. Finally, the results suggest that measures such as reducing the hot-face tem- perature and increasing the degree of carbon saturation in hot metal are critically important to improve the precipitation potential index.展开更多
Lithium(Li)metal anodes with the high theoretical specific capacity(3860 mAh g^(-1))and most negative reduction potential(-3.04 V vs.standard hydrogen electrode)have been considered as an ultimate choice for energy st...Lithium(Li)metal anodes with the high theoretical specific capacity(3860 mAh g^(-1))and most negative reduction potential(-3.04 V vs.standard hydrogen electrode)have been considered as an ultimate choice for energy storage devices with high energy density[1-4].However,the practical applications of Li metalbased batteries(LMBs)are confronted with two tough issues:Li dendrite growth induced by uneven Li depositions and unstable solid electrolyte interphase(SEI)(Fig.1a)[5,6].展开更多
Silicon(Si)has been attracting extensive attention for rechargeable lithium(Li)‐ion batteries due to its high theoretical capacity and low potential vs Li/Li+.However,it remains challenging and problematic to stabili...Silicon(Si)has been attracting extensive attention for rechargeable lithium(Li)‐ion batteries due to its high theoretical capacity and low potential vs Li/Li+.However,it remains challenging and problematic to stabilize the Si materials during electrochemical cycling because of the huge volume expansion,which results in losing electric contact and pulverization of Si particles.Consequently,the Si anode materials generally suffer from poor cycling,poor rate performance,and low coulomb efficiency,preventing them from practical applications.Up‐to‐date,there are numerous reports on the engineering of Si anode materials at microscale and nanoscale with significantly improved electrochemical performances.In this review,we will concentrate on various precisely designed protective layers for silicon‐based materials,including carbon layers,inorganic layers,and conductive polymer protective layer.First,we briefly introduced the alloying and failure mechanism of Si as anode materials upon electrochemical reactions.Following that,representative cases have been introduced and summarized to illustrate the purpose and advancement of protective coating layers,for instance,to alleviate pulverization and improve conductivity caused by volume expansion of Si particles during charge/discharge process,and maintain the surface stability of Si particles to form a stable solid‐electrolyte interphase layer.At last,possible strategies on the protective coating layer for stabilizing silicon anode materials that can be applied in the future have been indicated.展开更多
The intrinsically safe Zn||I_(2) battery,one of the leading candidates aiming to replace traditional Pb-acid batteries,is still seriously suffering from short shelf and cycling lifespan,due to the uncontrolled I_(3)^(...The intrinsically safe Zn||I_(2) battery,one of the leading candidates aiming to replace traditional Pb-acid batteries,is still seriously suffering from short shelf and cycling lifespan,due to the uncontrolled I_(3)^(−)-shuttling and dynamic parasitic reactions on Zn anodes.Considering the fact that almost all these detrimental processes terminate on the surfaces of Zn anodes,modifying Zn anodes’surface with protecting layers should be one of the most straightforward and thorough approaches to restrain these processes.Herein,a facile zeolite-based cation-exchange protecting layer is designed to comprehensively suppress the unfavored parasitic reactions on the Zn anodes.The negatively-charged cavities in the zeolite lattice provide highly accessible migration channels for Zn^(2+),while blocking anions and electrolyte from passing through.This low-cost cation-exchange protecting layer can simultaneously suppress self-discharge,anode corrosion/passivation,and Zn dendrite growth,awarding the Zn||I_(2) batteries with ultra-long cycle life(91.92%capacity retention after 5600 cycles at 2 A g^(−1)),high coulombic efficiencies(99.76%in average)and large capacity(203–196 mAh g^(−1) at 0.2 A g^(−1)).This work provides a highly affordable approach for the construction of high-performance Zn-I_(2) aqueous batteries.展开更多
Aqueous zinc anodes have attracted the attention of many researchers owing to their high safety,low cost,and high theoretical specific capacity.However,its practical application is severely limited by the dendrite gro...Aqueous zinc anodes have attracted the attention of many researchers owing to their high safety,low cost,and high theoretical specific capacity.However,its practical application is severely limited by the dendrite growth on zinc anode.Herein,we develop an intrinsically zincophobic barium-titanate protective layer with a porous structure to suppress the zinc dendrite formation by homogenizing the ion distribution on the anode surface,increasing the nucleation sites,and limiting the irregular zinc growth.Based on these synergistic effects,the coated zinc anode can exhibit long cycle life(840 h at 0.5 mA/cm^(2) for 0.5 mAh/cm^(2))and low voltage hysteresis(36 mV).This work can provide a feasible direction for the design of intrinsically zincophobic coating materials to uniformize the zinc stripping and plating.展开更多
Aqueous zinc-ion batteries possess substantial potential for energy storage applications;however,they are hampered by challenges such as dendrite formation and uncontrolled side reactions occurring at the zinc anode.I...Aqueous zinc-ion batteries possess substantial potential for energy storage applications;however,they are hampered by challenges such as dendrite formation and uncontrolled side reactions occurring at the zinc anode.In our investigation,we sought to mitigate these issues through the utilization of in situ zinc complex formation reactions to engineer hydrophobic protective layers on the zinc anode surface.These robust interfacial layers serve as effective barriers,isolating the zinc anode from the electrolyte and active water molecules and thereby preventing hydrogen evolution and the generation of undesirable byproducts.Additionally,the presence of numerous zincophilic sites within these protective layers facilitates uniform zinc deposition while concurrently inhibiting dendrite growth.Through comprehensive evaluation of functional anodes featuring diverse functional groups and alkyl chain lengths,we meticulously scrutinized the underlying mechanisms influencing performance variations.This analysis involved precise modulation of interfacial hydrophobicity,rapid Zn^(2+)ion transport,and ordered deposition of Zn^(2+)ions.Notably,the optimized anode,fabricated with octadecylphosphate(OPA),demonstrated exceptional performance characteristics.The Zn//Zn symmetric cell exhibited remarkable longevity,exceeding 4000 h under a current density of 2 mA cm^(-2)and a capacity density of 2 mA h cm^(-2),Furthermore,when integrated with a VOH cathode,the complete cell exhibited superior capacity retention compared to anodes modified with alternative organic molecules.展开更多
In order to solve coal and gas outbursts during mining coal seam,studying on related problems were carried out. According to the theories of mining upper protective layer,proper mining plan were designed and performed...In order to solve coal and gas outbursts during mining coal seam,studying on related problems were carried out. According to the theories of mining upper protective layer,proper mining plan were designed and performed through field experiment. By means of examining several parameters obtained from the field experiment,the protective effects were evaluated and the protective scope and related parameters were determined. The results of field experiment show that the danger of outbursts was evidently eliminated and the method of mining protective layers is effective and the safety and economic benefits are remarkable. The research has really applied worth and will give beneficial references to mining area with analogous conditions.展开更多
基金supported by research grants from the National Key Research and Development Program of China(No.2022YFB3803300)the Natural Science Foundation of China(Nos.52173235 and 62074022)+2 种基金the Venture&Innovation Support Program for Chongqing Overseas Returnees(No.CX2021018)the Youth Talent Support Program of Chongqing(No.CQYC2021059206)the Program of Graduate Education and Teaching in Chongqing(No.yjg223016).
文摘The inherent safety,high theoretical specific capacity and low raw material cost of aqueous batteries make them potential candidates in large-scale energy storage.However,uncontrolled dendrite growth,parasitic reactions and sluggish mass transfer on the anode-electrolyte interface are the main challenges restricting the application prospect of aqueous zinc-ion batteries.In general,eukaryotic cells utilize specific ion channels to achieve ion migration with the merits of low energy consumption and rapid speed.Herein,migrating the concept of ion channels to aqueous batteries,a crown species encapsulated zeolitic imidazolate framework(ZIF)interfacial layer(denoted as ZIF@Crown)was ex situ decorated onto the Zn anode.Similar to biological ion channels,the ZIF@Crown layer can homogenize the distribution of Zn^(2+)on the anode,accelerate the desolvation of hydrated Zn^(2+)and reduce the energy barrier for Zn^(2+)deposition,which were verified by theoretical calculations and experimental characterizations.Benefiting from these efficacious modulation mechanisms,the Zn@ZIF@Crown symmetrical cell could achieve a long calendar life of over 1900 h and the Zn@ZIF@Crown||Cu also sustained 600 cycles with a high Coulombic efficiency(97%).Furthermore,the full cells containing ZIF@Crown layer exhibit desirable electrochemical performance.This work provides an innovative avenue toward the optimization of aqueous batteries via bionic interfacial engineering.
基金supported by the National Natural Science Foundation for Young Scientists of China(No.51608514)the Funds for International Cooperation and Exchange of the National Natural Science Foundation of China(No.51820105011)+1 种基金the National Key R&D Program of China(No.2016YFC0400802)the Program of the Youth Innovation Promotion Association of Chinese Academy of Sciences
文摘Cake layer formation is inevitable over time for ultrafiltration(UF)membrane-based drinking water treatment.Although the cake layer is always considered to cause membrane fouling,it can also act as a"dynamic protection layer",as it further adsorbs pollutants and dramatically reduces their chance of getting to the membrane surface.Here,the UF membrane fouling performance was investigated with pre-deposited loose flocs in the presence of humic acid(HA).The results showed that the floc dynamic protection layer played an important role in removing HA.The higher the solution pH,the more negative the floc charge,resulting in lower HA removal efficiency due to the electrostatic repulsion and large pore size of the floc layer.With decreasing solution pH,a positively charged floc dynamic protection layer was formed,and more HA molecules were adsorbed.The potential reasons were ascribed to the smaller floc size,greater positive charge,and higher roughness of the floc layer.However,similar membrane fouling performance was also observed for the negative and positive floc dynamic protection layers due to their strong looseness characteristics.In addition,the molecular weight(MW)distribution of HA also played an important role in UF membrane fouling behavior.For the small MW HA molecules,the chance of forming a loose cake layer was high with a negatively charged floc dynamic protection layer,while for the large MW HA molecules it was high with a positively charged floc dynamic protection layer.As a result,slight UF membrane fouling was induced.
基金financially supported by the National Natural Science Foundation of China(No.61874137)。
文摘ZrCoCe getter films with thickness of ~2.3 lm were deposited on Si(100) wafers by direct current(DC)magnetron sputtering process. A 400-nm-thick Pd protection layer was then deposited on the as-deposited ZrCoCe film without exposure to atmosphere. Microstructure, surface morphology and surface chemical state of the films were analyzed. Moreover, hydrogen sorption properties were determined. The results show that the ZrCoCe film displays a cauliflower-like morphology and a porous columnar-like structure which is composed of nanocrystal grains. The Pd protection layer tightly adheres to the surface of the ZrCoCe film and efficiently prevents the oxidation of Zr under exposure to atmosphere. We find that the hydrogen sorption properties of the Pd-ZrCoCe film are significantly improved,in comparison with those of the as-deposited ZrCoCe film.
基金supported by the Natural Science Foundation of Shandong Province(ZR2021MB101,ZR2021ME113,ZR2021ME177,and ZR2021QE096)。
文摘Lithium sulfur batteries have attracted much attention due to their high theoretical specific energy and environmental friendliness.However,the practical application is severely plagued by the cycling life issues resulting from the uncontrollable generation and growth of Li dendrites.Herein,an innovative 3D flexible self-supporting Li anode protection layer of P-Mn_(3)O_(4-x)is constructed via a facile solvothermal method followed by an annealing process.Benefiting from the rich oxygen vacancies coupled with the 3D flexible self-supporting skeleton,abundant lithiophilic sites and high ionic conductivity are obtained,which succeed in guiding Li+homogeneous adsorption and redistribution,accelerating Li+diffusion rate,inducing Li+uniform deposition and nucleation.DFT calculations and experimental results conclusively demonstrate such a protection mechanism.Meanwhile,the effective anchoring and catalytic nature of polar P-Mn_(3)O_(4-x)can also be applied as an immobilization-diffusion-conversion host to improve polysulfides redox.Taking advantage of these merits,super-stable functions for Li symmetric cell matched with P-Mn_(3)O_(4-x)layer are achieved,which exhibits an ultralong lifespan of>5000 h with an ultralow overpotential of 20 m V,far lower than that of bare Li symmetric cell(overpotential of 800 m V only after 250 h)at high current densities of 5 m A cm^(-2)and high plating/stripping capacity of 10 m A h cm^(-2).Even in Li|P-Mn_(3)O_(4-x)||S full cell at 1 C,a high initial discharge specific capacity of 843.1 m A h g^(-1)is still delivered with ultralow capacity fading rate of 0.07%per cycle after 250 cycles,further confirming the synergistic regulation of P-Mn_(3)O_(4-x)for Li nucleation behavior.This work illustrates a sufficient guarantee of 3D protection layer coupled with oxygen vacancies in guiding Li diffusion and nucleation behavior and provides new guidance for promoting the development of advanced Li-S batteries.
基金supported by the National Natural Science Foundation of China(Grant No.11325421)
文摘We have realized robust quantum anomalous Hall samples by protecting Cr-doped（Bi,Sb）2Te3 topological insulator films with a combination of LiF and A1Ox capping layers.The AlOx/LiF composite capping layer well keeps the quantum anomalous Hall states of Cr-doped（Bi,Sb）2Te3 films and effectively prevent them from degradation induced by ambient conditions.The progress is a key step towards the realization of the quantum phenomena in heterostructures and devices based on quantum anomalous Hall system.
基金supported by the financial support from the Guangdong Basic and Applied Basic Research Foundation(No.2023B1515120095)the National Natural Science Foundation of China(Nos.52471229 and 52171210)the Jilin Province Science and Technology Department Program(No.20240101004JJ).
文摘The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction(HER)at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries.In this work,we propose sorbitan oleate(Span 80)as a novel amphiphilic electrolyte additive for 2 mol/L ZnSO_(4),demonstrating multifunctional performance.The unique ultra-long hydrophobic carbon chains of Span 80 effectively reduce free water molecules at the Zn anode-electrolyte interface,forming a robust hydrophobic interfacial layer that significantly suppresses HER and corrosion reactions.Simultaneously,carbon chains can enhance the desolvation effect of[Zn(H_(2)O)_(6)]^(2+),leading to improve rate performance.Additionally,the hydrophilic sorbitan groups in Span 80 selectively adsorb onto active sites of the Zn anode,promoting uniform Zn^(2+)deposition and suppressing dendrite growth.The optimized Zn||Zn symmetric cell exhibits outstanding cycling stability,sustaining reversible plating/stripping for 570 h at 50 mA/cm^(2) and the Zn||V_(2)O_(5) full cell retains exceptional stability over 2000 cycles at 1 A/g.Our work presents a promising strategy for suppressing interfacial side reactions by constructing a hydrophobic protective layer through the use of ultra-long carbon chain surfactants.This approach offers new insights into enhancing the performance of aqueous Zn-ion batteries.
文摘Aiming at the limitation of the traditional method for determination of protection region, combined with the actual situation of a mine, a new method for determination of protection region was put forward （including the protection of working face layout and development direction）, that is, gas flow observation analysis on the spot and gas content contrast method. The protection region was determined by gas flow observation analysis, gas content contrast, and computer numerical simulation combined with engineering practice. In the process of gas content test, the fixed sampling method ＂big hole drill reaming, small orifice drill rod connected with core tube＂ was employed. The results show that the determined protection region is in accordance with the actual site situation. The fixed sampling method ensures the accuracy of gas measurement of gas content.
基金supported by National Natural Science Foundation of China with Grant No.12274176 and 51972142support from the Fundamental Research Funds for the Center Universities,and Department of Science and Technology of Jilin Province with Grant No.20220201118GX.
文摘Aqueous zinc-ion batteries(AZIBs)are promising for future large-scale energy storage systems,however,suffer from inferior cycling life due to the dendrites growth and side reaction on Zn metal anode.Herein,a fast ion conductor Na_(5)YSi_(4)O_(12)(NYSO)was synthesized and fabricated as a protection layer of the Zn metal anode.By adjusting the thickness,an optimized NYSO coating of 20.3μm was obtained and the corresponding symmetry cell demonstrates an extended life span of 1896 h at the current density of 0.5 mA cm^(−2).In addition,a favorable rate performance of the NYSO@Zn anode at a high current density of 10 mA cm^(−2)was achieved.Benefiting from the NYSO coating,uniform diffusion and deposition of Zn^(2+)on the Zn anode could be realized,leading to the elimination of Zn dendrites and side reactions.Therefore,the aqueous NYSO@Zn|CNT@MnO_(2)full cell shows superior capacity and cycling stability to that of the bare Zn full cell.
基金supported by the National Natural Science Foundation of China(22279139,62227815,22465026,22469015)the National Key R&D Program of China(2022YFA1504500)+1 种基金the Natural Science Foundation of Inner Mongolia Autonomous Region of China(2024JQ06,2022MS2010,2024MS05005)Inner Mongolia University Postgraduate Scientific Research Innovation Project(11200-5223737)。
文摘Rechargeable aqueous zinc(Zn)-metal batteries hold great promise for next-generation energy storage systems.However,their practical application is hindered by several challenges,including dendrite formation,corrosion,and the competing hydrogen evolution reaction.To address these issues,we designed and fabricated a composite protective layer for Zn anodes by integrating carbon nanotubes(CNTs)with chitosan through a simple and scalable scraping process.The CNTs ensure uniform electric field distribution due to their high electrical conductivity,while protonated chitosan regulates ion transport and suppresses dendrite formation at the anode interface.The chitosan/CNTs composite layer also facilitates smooth Zn^(2+)deposition,enhancing the stability and reversibility of the Zn anode.As a result,the chitosan/CNTs@Zn anode demonstrates exceptional cycling stability,achieving over 3000 h of plating/stripping with minimal degradation.When paired with a V_(2)O_(5)cathode,the composite-protected anode significantly improves the cycle stability and energy density of the full cell.Techno-economic analysis confirms that batteries incorporating the chitosan/CNTs protective layer outperform those with bare Zn anodes in terms of energy density and overall performance under optimized conditions.This work provides a scalable and sustainable strategy to overcome the critical challenges of aqueous Zn-metal batteries,paving the way for their practical application in next-generation energy storage systems.
基金supported by National Natural Science Foundation of China under grant U23A20361Key Area R&D Program of Guangdong Province under grant 2022B0701180001.
文摘In this work,we design and fabricate AlGaN/GaN-based Schottky barrier diodes(SBDs)on a silicon substrate with a trenched n^(+)-GaN cap layer.With the developed physical models,we find that the n^(+)-GaN cap layer provides more electrons into the AlGaN/GaN channel,which is further confirmed experimentally.When compared with the reference device,this increases the two-dimensional electron gas(2DEG)density by two times and leads to a reduced specific ON-resistance(Ron,sp)of~2.4 mΩ·cm^(2).We also adopt the trenched n^(+)-GaN structure such that partial of the n^(+)-GaN is removed by using dry etching process to eliminate the surface electrical conduction when the device is set in the off-state.To suppress the surface defects that are caused by the dry etching process,we also deposit Si_(3)N_(4)layer prior to the deposition of field plate(FP),and we obtain a reduced leakage current of~8×10^(−5)A·cm^(−2)and breakdown voltage(BV)of 876 V.The Baliga’s figure of merit(BFOM)for the proposed structure is increased to~319 MW·cm^(−2).Our investigations also find that the pre-deposited Si_(3)N_(4)layer helps suppress the electron capture and transport processes,which enables the reduced dynamic R_(on,sp).
基金Projects(51504044,51204100)supported by National Natural Science Foundation of ChinaProject(14KF05)supported by the Research Fund of The State Key Laboratory of Coal Resources and Mine Safety,CUMT,China+3 种基金Project(cstc2016jcyj A1861)supported by the Research Fund of Chongqing Basic Science and Cutting-Edge Technology Special Projects,ChinaProject(2015CDJXY)supported by the Fundamental Research Funds for the Central UniversitiesProject supported by the China Postdoctoral Science FoundationProject(2011DA105287-MS201503)supported by the Independent Subject of State Key Laboratory of Coal Mine Disaster Dynamics and Control,China
文摘The differential cubature solution to the problem of a Mindlin plate lying on the Winkler foundation with two simply supported edges and two clamped edges was derived.Discrete numerical technology and shape functions were used to ensure that the solution is suitable to irregular shaped plates.Then,the mechanical model and the solution were employed to model the protection layer that isolates the mining stopes from sea water in Sanshandao gold mine,which is the first subsea mine of China.Furthermore,thickness optimizations for the protection layers above each stope were conducted based on the maximum principle stress criterion,and the linear relations between the best protection layer thickness and the stope area under different safety factors were regressed to guide the isolation design.The method presented in this work provides a practical way to quickly design the isolation layer thickness in subsea mining.
基金Natural Science Foundation of Hunan Province (No.2020JJ4734)High Performance Computing Center of Central South University。
文摘The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.
基金financially supported by the Natural Science Foundation of China(No.51304014)the Natural Science Foundation of China and Baosteel(No.51134008)the National Basic Research Program of China(No.2012CB720401)
文摘A variety of techniques, such as chemical analysis, scanning electron microscopy-energy dispersive spectroscopy, and X-ray diffraction, were applied to characterize the adhesion protective layer formed below the blast furnace taphole level when a certain amount of titanium-bearing burden was used. Samples of the protective layer were extracted to identify the chemical composition, phase assemblage, andistribution. Furthermore, the formation mechanism of the protective layer was determined after clarifying the source of each componenFinally, a technical strategy was proposed for achieving a stable protective layer in the hearth. The results show that the protective layemainly exists in a bilayer form in the sidewall, namely, a titanium-bearing layer and a graphite layer. Both the layers contain the slag phaswhose major crystalline phase is magnesium melilite（Ca2Mg Si2O7） and the main source of the slag phase is coke ash. It is clearly determinethat solid particles such as graphite, Ti（C,N） and Mg Al2O4play an important role in the formation of the protective layer, and the key factofor promoting the formation of a stable protective layer is reasonable control of the evolution behavior of coke.
基金supported the National Science Foundation for Young Scientists of China (No. 51304014)the Open Foundation of the State Key Laboratory of Advanced Metallurgy (No. 41603007)
文摘A long campaign life of blast furnaces is heavily linked to the existence of a protective layer in their hearths. In this work, we conducted dissection studies and investigated damage in blast furnace hearths to estimate the formation mechanism of the protective layer. The results illustrate that a significant amount of graphite phase was trapped within the hearth protective layer. Furthermore, on the basis of the thermodynamic and kinetic calculations of the graphite precipitation process, a precipitation potential index related to the formation of the graphite-rich protective layer was proposed to characterize the formation ability of this layer. We determined that, under normal operating conditions, the precipitation of graphite phase ~om hot metal was thermodynamically possible. Among elements that exist in hot metal, C, Si, and P favor graphite precipitation, whereas Mn and Cr inhibit this process. Moreover, at the same hot-face temperature, an increase of carbon concentration in hot metal can shorten the precipitation time. Finally, the results suggest that measures such as reducing the hot-face tem- perature and increasing the degree of carbon saturation in hot metal are critically important to improve the precipitation potential index.
基金supported by National Key Research and Development Program,China(2016YFA0202500 and 2016YFA0200102)National Natural Science Foundation of China,China(21805161,21808124,U1932220)Fundamental Research Funds for the Central Universites of Central South University,China(2020zzts471)。
文摘Lithium(Li)metal anodes with the high theoretical specific capacity(3860 mAh g^(-1))and most negative reduction potential(-3.04 V vs.standard hydrogen electrode)have been considered as an ultimate choice for energy storage devices with high energy density[1-4].However,the practical applications of Li metalbased batteries(LMBs)are confronted with two tough issues:Li dendrite growth induced by uneven Li depositions and unstable solid electrolyte interphase(SEI)(Fig.1a)[5,6].
基金Japan Society for the Promotion of Science,Grant/Award Number:18H03869National Natural Science Foundation of China,Grant/Award Numbers:51872333,51874357。
文摘Silicon(Si)has been attracting extensive attention for rechargeable lithium(Li)‐ion batteries due to its high theoretical capacity and low potential vs Li/Li+.However,it remains challenging and problematic to stabilize the Si materials during electrochemical cycling because of the huge volume expansion,which results in losing electric contact and pulverization of Si particles.Consequently,the Si anode materials generally suffer from poor cycling,poor rate performance,and low coulomb efficiency,preventing them from practical applications.Up‐to‐date,there are numerous reports on the engineering of Si anode materials at microscale and nanoscale with significantly improved electrochemical performances.In this review,we will concentrate on various precisely designed protective layers for silicon‐based materials,including carbon layers,inorganic layers,and conductive polymer protective layer.First,we briefly introduced the alloying and failure mechanism of Si as anode materials upon electrochemical reactions.Following that,representative cases have been introduced and summarized to illustrate the purpose and advancement of protective coating layers,for instance,to alleviate pulverization and improve conductivity caused by volume expansion of Si particles during charge/discharge process,and maintain the surface stability of Si particles to form a stable solid‐electrolyte interphase layer.At last,possible strategies on the protective coating layer for stabilizing silicon anode materials that can be applied in the future have been indicated.
基金The authors thank the National Natural Science Foundation of China(51502194,22133005,21973107,and 22103093)the Natural Science Foundation of Shandong(ZR2020ME024)+2 种基金the Science and Technology Commission of Shanghai Municipality(21ZR1472900)the Key Laboratory for Palygorskite Science and Applied Technology of Jiangsu Province(HPK202103)for financial supportOpen access funding provided by Shanghai Jiao Tong University
文摘The intrinsically safe Zn||I_(2) battery,one of the leading candidates aiming to replace traditional Pb-acid batteries,is still seriously suffering from short shelf and cycling lifespan,due to the uncontrolled I_(3)^(−)-shuttling and dynamic parasitic reactions on Zn anodes.Considering the fact that almost all these detrimental processes terminate on the surfaces of Zn anodes,modifying Zn anodes’surface with protecting layers should be one of the most straightforward and thorough approaches to restrain these processes.Herein,a facile zeolite-based cation-exchange protecting layer is designed to comprehensively suppress the unfavored parasitic reactions on the Zn anodes.The negatively-charged cavities in the zeolite lattice provide highly accessible migration channels for Zn^(2+),while blocking anions and electrolyte from passing through.This low-cost cation-exchange protecting layer can simultaneously suppress self-discharge,anode corrosion/passivation,and Zn dendrite growth,awarding the Zn||I_(2) batteries with ultra-long cycle life(91.92%capacity retention after 5600 cycles at 2 A g^(−1)),high coulombic efficiencies(99.76%in average)and large capacity(203–196 mAh g^(−1) at 0.2 A g^(−1)).This work provides a highly affordable approach for the construction of high-performance Zn-I_(2) aqueous batteries.
基金supported by National Nature Science Foundation of China(Nos.U19A2019,U22109181)Hunan Provincial Science and Technology Plan Project of China(Nos.2017TP1001 and 2020JJ2042)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University。
文摘Aqueous zinc anodes have attracted the attention of many researchers owing to their high safety,low cost,and high theoretical specific capacity.However,its practical application is severely limited by the dendrite growth on zinc anode.Herein,we develop an intrinsically zincophobic barium-titanate protective layer with a porous structure to suppress the zinc dendrite formation by homogenizing the ion distribution on the anode surface,increasing the nucleation sites,and limiting the irregular zinc growth.Based on these synergistic effects,the coated zinc anode can exhibit long cycle life(840 h at 0.5 mA/cm^(2) for 0.5 mAh/cm^(2))and low voltage hysteresis(36 mV).This work can provide a feasible direction for the design of intrinsically zincophobic coating materials to uniformize the zinc stripping and plating.
基金financially supported by the Jiangsu Distinguished Professors Project (No.1711510024)the Funding for Scientific Research Startup of Jiangsu University (No.4111510015,19JDG044)+5 种基金the Jiangsu Provincial Program for High-Level Innovative and Entrepreneurial Talents Introductionthe National Natural Science Foundation of China (No.22008091)the Jiangsu Agriculture Science and Technology Innovation Fund (No.CX (21)1007)the Natural Science Foundation of Guangdong Province (2023A1515010894)the Open Project of Luzhou Key Laboratory of Fine Chemical Application Technology (HYJH-2302-A)the National Institute of Education,Singapore,under its Academic Research Fund (RI 1/21 EAH)。
文摘Aqueous zinc-ion batteries possess substantial potential for energy storage applications;however,they are hampered by challenges such as dendrite formation and uncontrolled side reactions occurring at the zinc anode.In our investigation,we sought to mitigate these issues through the utilization of in situ zinc complex formation reactions to engineer hydrophobic protective layers on the zinc anode surface.These robust interfacial layers serve as effective barriers,isolating the zinc anode from the electrolyte and active water molecules and thereby preventing hydrogen evolution and the generation of undesirable byproducts.Additionally,the presence of numerous zincophilic sites within these protective layers facilitates uniform zinc deposition while concurrently inhibiting dendrite growth.Through comprehensive evaluation of functional anodes featuring diverse functional groups and alkyl chain lengths,we meticulously scrutinized the underlying mechanisms influencing performance variations.This analysis involved precise modulation of interfacial hydrophobicity,rapid Zn^(2+)ion transport,and ordered deposition of Zn^(2+)ions.Notably,the optimized anode,fabricated with octadecylphosphate(OPA),demonstrated exceptional performance characteristics.The Zn//Zn symmetric cell exhibited remarkable longevity,exceeding 4000 h under a current density of 2 mA cm^(-2)and a capacity density of 2 mA h cm^(-2),Furthermore,when integrated with a VOH cathode,the complete cell exhibited superior capacity retention compared to anodes modified with alternative organic molecules.
文摘In order to solve coal and gas outbursts during mining coal seam,studying on related problems were carried out. According to the theories of mining upper protective layer,proper mining plan were designed and performed through field experiment. By means of examining several parameters obtained from the field experiment,the protective effects were evaluated and the protective scope and related parameters were determined. The results of field experiment show that the danger of outbursts was evidently eliminated and the method of mining protective layers is effective and the safety and economic benefits are remarkable. The research has really applied worth and will give beneficial references to mining area with analogous conditions.
