Engineering hydrophobic protective layers on zinc anodes for enhanced performance in aqueous zinc-ion batteries

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.

Experimental research on methane control of mining upper protective layers

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.

Determination of protection range of mining upper protective layers and its numerical simulation

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.

An analysis on the effect of mining height and floor lithology on pressure relief of upper protective layers

In order to understand the effect of mining height and floor lithology at the upper protective layer face on the pressure relief of protected coal seams, this paper uses a numerical simulation method to model the pressure changes at protected coal seam during mining upper protective layer. The results show that the taller the mining height at the upper protective layer face, the greater the protection on protected coal seam due to the higher level of pressure release; the upper protective layer face with hard rock floor impedes the pressure release at the protected coal seam, which affects the overall effect of the pressure release at protected coal seam using the protective layer mining method.

Study on the countermeasures against methane outburst of mining multiple upper protective layers in coal seams cluster

In order to prevent coal and methane outbursts, mining protective layers is an effective means, yet no precedents of mining multiple protective layers is discoveried in seams which includes several seams are prone to outburst like Xinzhuangzi Mine. This paper perfected the related theories through analyzing mining multiple upper protective layers. By means of examining several parameters, it synthetically analyzed and ascer- tains the protected effectiveness and scope and reasonable parameters, finally obtained the specific indexes and effectiveness of mining multiple protective layers in coal seams cluster.

Anode surface engineering of zinc-ion batteries using tellurium nanobelt as a protective layer for enhancing energy storage performance

Over the years,zinc-ion batteries(ZIBs)have attracted attention as a promising next-generation energy storage technology because of their excellent safety,long cycling performance,eco-friendliness,and high-power density.However,issues,such as the corrosion and dissolution of the Zn anode,limited wet-tability,and lack of sufficient nucleation sites for Zn plating,have limited their practical application.The introduction of a protective layer comprising of tellurium(Te)nanobelts onto the surface of Zn anode has emerged as a promising approach to overcome these limitations and improve the electrochemical behav-ior by enhancing the safety and wettability of ZIBs,as well as providing numerous nucleation sites for Zn plating.In the presence of a Te-based protective layer,the energy power density of the surface-engineered Zn anode improved significantly(ranging from 310 to 144 W h kg^(-1),over a power density range of 270 to 1,800 W kg^(-1)),and the lifespan capability was extended.These results demonstrate that the proposed strategy of employing Te nanobelts as a protective layer holds great promise for enhancing the energy storage performance of zIBs,making them even more attractive as a viable energy storage solution forthefuture.

Dual-function protective layer for highly reversible Zn anode

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.

Engineering of carbon and other protective coating layers for stabilizing silicon anode materials

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.

Lithium-Ion Charged Polymer Channels Flattening Lithium Metal Anode

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.

Formation mechanism of the protective layer in a blast furnace hearth

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.

Formation mechanism of the graphite-rich protective layer in blast furnace hearths

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.

Revisiting aluminum current collector in lithium-ion batteries:Corrosion and countermeasures

With the large-scale service of lithium-ion batteries(LIBs),their failures have attracted significant attentions.While the decay of active materials is the primary cause for LIB failures,the degradation of auxiliary materials,such as current collector corrosion,should not be disregarded.Therefore,it is necessary to conduct a comprehensive review in this field.In this review,from the perspectives of electrochemistry and materials,we systematically summarize the corrosion behavior of aluminum cathode current collector and propose corresponding countermeasures.Firstly,the corrosion type is clarified based on the properties of passivation layers in different organic electrolyte components.Furthermore,a thoroughgoing analysis is presented to examine the impact of various factors on aluminum corrosion,including lithium salts,organic solvents,water impurities,and operating conditions.Subsequently,strategies for electrolyte and protection layer employed to suppress corrosion are discussed in detail.Lastly and most importantly,we provide insights and recommendations to prevent corrosion of current collectors,facilitate the development of advanced current collectors and the implementation of next-generation high-voltage stable LIBs.

Simulation of Corrosion-Induced Cracking of Reinforced Concrete Based on Fracture Phase Field Method

Accurate simulation of the cracking process caused by rust expansion of reinforced concrete(RC)structures plays an intuitive role in revealing the corrosion-induced failure mechanism.Considering the quasi-brittle fracture of concrete,the fracture phase field driven by the compressive-shear term is constructed and added to the traditional brittle fracture phase field model.The rationality of the proposed model is verified by a mixed fracture example under a shear displacement load.Then,the extended fracture phase model is applied to simulate the corrosion-induced cracking process of RC.The cracking patterns caused by non-uniform corrosion expansion are discussed for RC specimens with homogeneous macroscopically or heterogeneous with different polygonal aggregate distributions at the mesoscopic scale.Then,the effects of the protective layer on the crack propagation trajectory and cracking resistance are investigated,illustrating that the cracking angle and cracking resistance increase with the increase of the protective layer thickness,consistent with the experimental observation.Finally,the corrosion-induced cracking process of concrete specimens with large and small spacing rebars is simulated,and the interaction of multiple corrosion cracking is easily influenced by the reinforcement spacing,which increases with the decrease of the steel bar interval.These conclusions play an important role in the design of engineering anti-corrosion measures.The fracture phase field model can provide strong support for the life assessment of RC structures.

A two-dimension laminar composite protective layer for dendrite-free lithium metal anode

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].

Numerical simulation on pressure-relief deformation characteristics of underlying coal-rock mass after upper protective layer excavation

Based on the occurrence features of Group B coal-seams at a coal mine in the Huainan coal mining area, the elasto-plastic mechanical damage constitutive functions and numerical model for the protective layer excavation were established. With the UDEC2D computer program, after the upper protective layer was mined, the stress field change trends, crack development, and expansion deformation trends of underlying coal rock seams in the floor of the working face were simulated and analyzed. The simulation results show the stress changes in coal rock seams, the evolution process of pre-cracks during the process of upper protective layer mining, the caved zone and fractured zone of the underlying coal rock seams. At the same time, the results from the actual investigation and analysis of protected layer deformation match the simulation values, which verifies the validity and accuracy of numerical simulation results. The study results have an important guiding significance for gas management in low permeability and high gas coal seams with similar mining conditions.

Practice and adaptable conditions classification of aquifer-protective mining in longwall coalface for shallow seam with thin bedrock

A set of adaptable conditions classification of aquifer-protective mining in the Iongwall coalface for shallow coal seams with thin bedrock was put forward to deal with the conflict between water protection and high efficiency for the mining field in west China. This classification was suitable for shallow coal seams with different thickness and was beneficial to the local environmental protection. Using the 3-Universal Distinct Element Code （3DEC） numerical software, the height of the fractured zones for shallow coal seams with thin bedrock was calculated and analyzed, and its predicting formula was achieved. Meanwhile, according to the lithology and the weathering degree of the shallow coal seam the thickness of the protective layer was determined as 10 m and the overlying water body of loose water-bearing sand for shallow coal seams with thin bedrock was divided into three types, namely, weak, medium and strong. Based on these, the necessary bedrock thickness of the Iongwall coalface for shallow coal seams with thin bedrock was confined according to the different mining height and water yield nature of the overlying loose water-bearing sand. Combined with the present mining status, a set of new methods of adaptable conditions classification of aquifer-protective mining technology in the Iongwall coalface for shallow coal seams with thin bedrock was put forward.

Reimagining the Visceral Protective Layer with Tailored Manipulation: A Case Report

The visceral protective layer is a standard component of the ABTHERATM systems for temporary abdominal closures. Nonetheless, there are circumstances where the standard, fenestrated visceral protective layer is too large to be successfully applied into every patient’s open abdomen, such as within the abdomen of a child, smaller adult or a patient with previously placed ostomies or drains. The fenestrated, visceral protective layer may require alterations or tailoring for adequate deployment instead of placing the bulk of the visceral protective layer entirely into the open abdomen for temporary abdominal closure. This case report illustrates how the visceral protective layer can be adapted or “reimagined” to conform to a patient with unique or complex abdominal domain features when utilizing the ABTHERATM device prior to facial closure or abdominal wall reconstruction. Photographs are utilized in a step-by-step fashion to aid the clinician in these detailed maneuvers.

Upcycling of phosphogypsum waste for efficient zinc-ion batteries

Zinc metal is a promising anode material for next-generation aqueous batteries,but its practical application is limited by the formation of zinc dendrite.To prevent zinc dendrite growth,various Zn^(2+)-conducting but water-isolating solid-electrolyte interphase(SEI)films have been developed,however,the required high-purity chemical materials are extremely expensive.In this work,phosphogypsum(PG),an industrial byproduct produced from the phosphoric acid industry,is employed as a multifunctional protective layer to navigate uniform zinc deposition.Theoretical and experimental results demonstrate that PG-derived CaSO_(4)2H_(2)O can act as an artificial SEI layer to provide fast channels for Zn^(2+)transport.Moreover,CaSO_(4)2H_(2)O could release calcium ions(Ca^(2+))due to its relatively high Kspvalue,which have a higher binding energy than that of Zn^(2+)on the Zn surface,thus preferentially adsorbing to the tips of the protuberances to force zinc ions to nucleate at inert region.As a result,the Zn@PG anode achieves a high Coulombic efficiency of 99.5%during 500 cycles and long-time stability over 1000 hours at 1 m A cm^(-2).Our findings will not only construct a low-cost artificial SEI film for practical metal batteries,but also achieve a high-value utilization of phosphogypsum waste.

Anti-Corrosion and Reconstruction of Surface Crystal Plane for Zn Anodes by an Advanced Metal Passivation Technique

For the aqueous Zn-ion battery,dendrite formation,corrosion,and interfacial parasitic reactions are major issues,which greatly inhibits their practical application.How to develop a method of Zn construction or treatment to solve these issues for Zn anodes are still great challenges.Herein,a simple and cheap metal passivation technique is proposed for Zn anodes from a corrosion science perspective.Similar to the metal anticorrosion engineering,the formed interfacial protective layer in a chemical way can sufficiently solve the corrosion issues.Furthermore,the proposed passivity approach can reconstruct Zn surface-preferred crystal planes,exposing more(002)planes and improving surface hydrophilicity,which inhibits the formation of Zn dendrites and hydrogen evolution effectively.As expected,the passivated Zn achieves outstanding cycling life(1914 h)with low voltage polarization(<40 mV).Even at 6 mA cm^(−2) and 3 mA h cm^(−2),it can achieve stable Zn deposition over 460 h.The treated Zn anode coupled with MnO_(2) cathode shows prominently reinforced full batteries service life,making it a potential Zn anode candidate for excellent performance aqueous Zn-ion batteries.The proposed passivation approach provides a guideline for other metal electrodes preparation in various batteries and establishes the connections between corrosion science and batteries.

Tuning Li nucleation and growth via oxygen vacancy-enriched 3D flexible self-supporting protection layer of P-Mn_(3)O_(4-x)for advanced lithium-sulfur batteries

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.