Defect Engineering:Can it Mitigate Strong Coulomb Effect of Mg^(2+)in Cathode Materials for Rechargeable Magnesium Batteries?

Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.

Dual-Defect Engineering Strategy Enables High-Durability Rechargeable Magnesium-Metal Batteries

Rechargeable magnesium-metal batteries(RMMBs)are promising next-generation secondary batteries;however,their development is inhibited by the low capacity and short cycle lifespan of cathodes.Although various strategies have been devised to enhance the Mg^(2+)migration kinetics and structural stability of cathodes,they fail to improve electronic conductivity,rendering the cathodes incompatible with magnesium-metal anodes.Herein,we propose a dual-defect engineering strategy,namely,the incorporation of Mg^(2+)pre-intercalation defect(P-Mgd)and oxygen defect(Od),to simultaneously improve the Mg^(2+)migration kinetics,structural stability,and electronic conductivity of the cathodes of RMMBs.Using lamellar V_(2)O_(5)·nH_(2)O as a demo cathode material,we prepare a cathode comprising Mg_(0.07)V_(2)O_(5)·1.4H_(2)O nanobelts composited with reduced graphene oxide(MVOH/rGO)with P-Mgd and Od.The Od enlarges interlayer spacing,accelerates Mg^(2+)migration kinetics,and prevents structural collapse,while the P-Mgd stabilizes the lamellar structure and increases electronic conductivity.Consequently,the MVOH/rGO cathode exhibits a high capacity of 197 mAh g^(−1),and the developed Mg foil//MVOH/rGO full cell demonstrates an incredible lifespan of 850 cycles at 0.1 A g^(−1),capable of powering a light-emitting diode.The proposed dual-defect engineering strategy provides new insights into developing high-durability,high-capacity cathodes,advancing the practical application of RMMBs,and other new secondary batteries.

Groundwater recharge via precipitation in the Badain Jaran Desert,China

Precipitation infiltration serves as a significant source of groundwater in the Badain Jaran Desert.To investigate variations in precipitation infiltration within the desert,this study collected data on moisture content and temperature from the vadose zone through in-situ field monitoring.Utilizing these data,a numerical model is employed to explore the mechanism of groundwater recharge via precipitation.The results are as follows:(1)Moisture content and temperature in the shallow vadose zone exhibit significant seasonal variations,with moisture content diminishing with increasing depth;(2)Groundwater recharge via precipitation infiltration initially increases and then decreases with groundwater level depth(GWD).Peak groundwater recharge via precipitation occurs at a GWD of 0.75 m,decreasing to merely 0.012 cm at GWDs exceeding 2 m;(3)Groundwater is no longer susceptible to phreatic water evaporation when the GWD reaches approximately 3.7 m.Therefore,GWD plays a crucial role in governing groundwater recharge via precipitation in the Badain Jaran Desert.

Co/CoO heterojunction rich in oxygen vacancies introduced by O_(2) plasma embedded in mesoporous walls of carbon nanoboxes covered with carbon nanotubes for rechargeable zinc-air battery

Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well designed through zeolite-imidazole framework(ZIF-67)carbonization,chemical vapor deposition,and O_(2) plasma treatment.As a result,the threedimensional NHCNBs coupled with NCNTs and unique heterojunction with rich oxygen vacancies reduce the charge transport resistance and accelerate the catalytic reaction rate of the P-Co/CoOV@NHCNB@NCNT,and they display exceedingly good electrocatalytic performance for oxygen reduction reaction(ORR,halfwave potential[EORR,1/2=0.855 V vs.reversible hydrogen electrode])and oxygen evolution reaction(OER,overpotential(η_(OER,10)=377mV@10mA cm^(−2)),which exceeds that of the commercial Pt/C+RuO_(2) and most of the formerly reported electrocatalysts.Impressively,both the aqueous and flexible foldable all-solid-state rechargeable zinc-air batteries(ZABs)assembled with the P-Co/CoOV@NHCNB@NCNT catalyst reveal a large maximum power density and outstanding long-term cycling stability.First-principles density functional theory calculations show that the formation of heterojunctions and oxygen vacancies enhances conductivity,reduces reaction energy barriers,and accelerates reaction kinetics rates.This work opens up a new avenue for the facile construction of highly active,structurally stable,and cost-effective bifunctional catalysts for ZABs.

Heteroatom anchors Fe-Mn dual-atom catalysts with bi-functional oxygen catalytic activity for low-temperature rechargeable flexible Zn-air batteries

M-N-C(M=Fe,Co,Ni,etc.) catalyst owns high catalytic activity in the oxygen catalytic reaction which is the most likely to replace the Pt-based catalysts.But it is still a challenge to further increase the active site density.This article constructs the high-efficiency FeMn-N/S-C-1000 catalyst to realize ORR/OER bifunctional catalysis by hetero-atom,bimetal(Fe,Mn) doped simultaneously strategy.When evaluated it as bi-functional electro-catalysts,FeMn-N/S-C-1000 exhibits excellent catalytic activity(E_(1/2)=0.924 V,E_(j=10)=1.617 V) in alkaline media,outperforms conventional Pt/C,RuO_(2) and most non-precious-metal catalysts reported recently,Such outstanding performance is owing to N,S co-coordinated with metal to form multi-types of single atom,dual atom active sites to carry out bi-catalysis.Importantly,nitrite poison test provides the proof that the active sites of FeMn-N/S-C are more than that of single-atom catalysts to promote catalytic reactions directly.To better understand the local structure of Fe and Mn active sites,XAS and DFT were employed to reveal that FeMn-N_5/S-C site plays the key role during catalysis.Notably,the FeMn-N/S-C-1000 based low-temperature rechargeable flexible Zn-air also exhibits superior discharge performance and extraordinary durability at-40℃.This work will provide a new idea to design diatomic catalysts applied in low-temperature rechargeable batteries.

Clogging caused by coupled grain migration and compaction effect during groundwater recharge for unconsolidated sandstone reservoir in groundwater-source heat pump

In unconsolidated sandstone reservoirs,presence of numerous movable grains and a complex grain size composition necessitates a clear understanding of the physical clogging process for effective groundwater recharge in groundwater-source heat pump systems.To investigate this,a series of seepage experiments was conducted under in situ stress conditions using unconsolidated sandstone samples with varying grain compositions.The clogging phenomenon arises from the combined effects of grain migration and compaction,wherein the migration of both original and secondary crushed fine-grain particles blocks the seepage channels.Notably,grain composition influences the migration and transport properties of the grains.For samples composed of smaller grains,the apparent permeability demonstrates a transition from stability to decrease.In contrast,samples with larger grains experience a skip at the stability stage and directly enter the decrease stage,with a minor exception of a slight increase observed.Furthermore,a unique failure mode characterized by diameter shrinkage in the upper part of the sample is observed due to the combined effects of grain migration and in situ stress-induced compaction.These testing results contribute to a better understanding of the clogging mechanism caused by the coupled effects of grain migration and compaction during groundwater recharge in unconsolidated sandstone reservoirs used in groundwater-source heat pump systems.

A non-nucleophilic electrolyte based on all-inorganic salts with conditioning-free characteristic for rechargeable magnesium batteries

Conditioning-free electrolytes with high reversibility of Mg plating/stripping are of vital importance for the commercialization of the superior rechargeable magnesium batteries(RMBs).In the present work,a non-nucleophilic electrolyte(denoted as MLCH)based on all-inorganic salts of MgCl_(2),LiCl and CrCl_(3) for RMBs is prepared by a straightforward one-step reaction.As a result,the MLCH electrolyte shows the noticeable performance of high ionic conductivity(3.40 mS cm^(−1)),low overpotential(∼46 mV vs Mg/Mg^(2+)),high Coulombic efficiency(∼93%),high anodic stability(SS,∼2.56 V vs Mg/Mg^(2+))and long-term(more than 500 h)cycling stability,especially the conditioning-free characteristic.The main equilibrium species in the MLCH electrolyte are confirmed to be the tetracoordinated anions of[LiCl2(THF)2]−and solvated dimers of[Mg_(2)(μ-Cl)3(THF)6]+.The addition of LiCl can assist the dissolution of MgCl_(2) and activation of the electrode/electrolyte interface,resulting in a superior Mg plating/stripping efficiency.The synergistic effect of LiCl,CrCl_(3),a small amount of HpMS and the absence of polymerization THF enable the conditioning-free characteristic of the MLCH electrolyte.Moreover,the MLCH electrolyte exhibits decent compatibility with the cathodic materials of CuS.The Mg/CuS full cell using the MLCH electrolyte presents a discharge specific capacity of 215 mAh g^(−1)at 0.1 C and the capacity can retain∼72%after 40 cycles.Notably,the MLCH electrolyte has other superiorities such as the broad sources of materials,low-cost and easy-preparation,leading to the potential prospect of commercial application.

A perspective on the key factors of safety for rechargeable magnesium batteries

Rechargeable Mg batteries(RMBs)have become one of the best subsitutes for lithium-ion batteries due to the high volumetric capacity,abundant resources,and uniform plating behavior of Mg metal anode.However,the safety hazard induced by the formation of high-modulue Mg dendrites under a high current density(10 mA cm^(-1))was still revealed in recent years.It has forced researchers to re-examine the safety of RMBs.In this review,the intrinsic safety factors of key components in RMBs,such as uneven plating,pitting and flammability of Mg anode,heat release and crystalline water decomposition of cathode,strong corrosion,low oxidition stability and flammability of electrolytes,and soforth,are systematacially summarized.Their origins,formation mechanisms,and possible safety hazards are deeply discussed.To develop high-performance Mg anode,current strategies including designing artificial SEI,three-dimensional substrates,and Mg alloys are summarized.For practical electrolytes,the configurations of boron-centered anions and simple Mg salts and the functionalized solvent with high boiling point and low flammability are suggested to comprehensively design.In addition,the future study should more focus on the investigation on the thermal runaway and decomposition of cathode materials and separa-tors.This review aims to provide fundamental insights into the relationship between electrochemistry and safety,further promoting the sustainable development of RMBs.

Engineering single-atom Mn on nitrogen-doped carbon to regulate lithium-peroxide reaction kinetics for rechargeable lithium-oxygen batteries

Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-ity,and improving recycling stability of Li-O_(2) batteries.In this work,we employ metal-organic frameworks(MOFs)derivation and ion substitution strategies to construct atomically dispersed Mn-N_(4) moieties on hierarchical porous nitrogen-doped carbon(Mn SAs-NC)with the aim of reducing the over-potential and improving the cycling stability of Li-O_(2) batteries.The porous structure provides more chan-nels for mass transfer and exposes more highly active sites for electrocatalytic reactions,thus promoting the formation and decomposition of Li_(2)O_(2).The Li-O_(2) batteries with Mn SAs-NC cathode achieve lower overpotential,higher specific capacity(14290 mA h g^(-1) at 100 mAg^(-1)),and superior cycle stability(>100 cycles at 200 mA g^(-1))compared with the Mn NPs-NC and NC.Density functional theory(DFT)cal-culations reveal that the construction of Mn-N_(4) moiety tunes the charge distribution of the pyridinic N-rich vacancy and balances the affinity of the intermediates(LiO_(2) and Li_(2)O_(2)).The initial nucleation of Li_(2)O_(2) on Mn SAs-NC favors the O_(2)-→LiO_(2)→Li_(2)O_(2) surface-adsorption pathway,which mitigates the overpoten-tials of the oxygen reduction(ORR)and oxygen evolution reaction(OER).As a result,Mn SAs-NC with Mn-N_(4) moiety effectively facilitates the Li_(2)O_(2) nucleation and enables its reversible decomposition.This work establishes a methodology for constructing carbon-based electrocatalysts with high activity and selectivity for Li-O_(2)batteries.

Interfacial chemistry of anode/electrolyte interface for rechargeable magnesium batteries

Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte interfacial issues,including surface passivation,uneven Mg plating/stripping,and pulverization after cycling still result in a large overpotential,short cycling life,poor power density,and possible safety hazards of cells,severely impeding the commercial development of RMBs.In this review,a concise overview of recently advanced strategies to address these anode/electroyte interfacial issues is systematically classified and summarized.The design of magnesiophilic substrates,construction of artificial SEI layers,and modification of electrolyte are important and effective strategies to improve the uniformity/kinetics of Mg plating/stripping and achieve the stable anode/electrolyte interface.The key opportunities and challenges in this field are advisedly put forward,and the insights into future directions for stabilizing Mg metal anodes and the anode/electrolyte interface are highlighted.This review provides important references fordeveloping the high-performance and high-safety RMBs.

Conventional and futuristic approaches for the computation of groundwater recharge:A comprehensive review

Groundwater recharge is a critical hydrologic component that determines groundwater availability and sustainability.Groundwater recharge estimation can be performed in a variety of ways,ranging from direct procedures to simulation models.The optimal strategy for recharge estimation depends on several factors,such as study objectives,climatic zones,hydrogeological conditions,data availability,methodology,and temporal and spatial constraints.Groundwater recharge is influenced by uncertainties in weather and hydrology.This study discusses conventional recharge estimation techniques and their application for optimal recharge calculation,and it also offers an overview of recent advances in recharge estimation methods.Most methods provide direct or indirect estimation of recharge across a small region on a point scale for a shorter time.With recent technological advancements and increased data availability,several advanced computational tools,including numerical,empirical,and artificial intelligence models,have been developed for efficient and reliable computation of groundwater recharge.This review article provides a thorough discussion of the techniques,assumptions,advantages,limitations,and selection procedures for estimating groundwater recharge.

Estimation of Groundwater Recharge Using Water Table Fluctuation Method in Bamako and Surrounding Areas, Mali

Bamako’s geographic and demographic expansion is sure to increase the need for water, and the slow development of the water supply network seems unable to meet this need. The knowledge of the approximate quantity of water reaching the groundwater is crucial, given the high dependence of this city and its surrounding area on groundwater. The aim of this study is to estimate the average groundwater recharge on a monthly scale, based on measurements taken over a 24-month period by using Water Table Fluctuation (WTF). The monthly recharge values obtained from the 15 piezometers in the study area by using WTF method vary from 1.04 to 38.81 mm with an average value of 9.74 mm. As part of the precipitations, these values represent respectively 1.29%, 48.52% and 12.17% of monthly average precipitation. It appears in this study that despite the piezometers belonging to the same climatic zone, the recharge rate can be different because of many factors such as the thickness of the aquifers, the soil and geology type, the local land cover and land use activities.

Study on the Change of Water Quality and Feasibility of Recharge in Xidagou of Lingwu in Ningxia

According to the annual variation of water discharge and water quality of Xidagou in Lingwu in Ningxia,combining local cropping system,the influence degree of ditch water recharge on soil and crop was studied,and the feasibility of ditch water recharge was analyzed in our paper,which could provide scientific basis for the utilization of ditch water recharge in local area.

Template synthesis of MnO_2/CNT nanocomposite and its application in rechargeable lithium batteries

Nanostructured MnO2/CNT composite was synthesized by a soft template approach in the presence of Pluronic P123 surfactant. The product was characterized by X-ray diffraction, thermogravimetric and differential thermal analyses, Fourier transformed infrared spectroscopy and high-resolution transmission electron microscopy. The results show that the sample consists of poor crystalline α-MnO2 nanorods with a diameter of about 10 nm and a length of 30-50 nm, which absorb on the carbon nanotubes. The electrochemical properties of the product as cathode material for Li-MnO2 cell are evaluated by galvanostatic charge-discharge and electrochemical impedance spectroscopy （EIS）. Compared with pure MnO2 electrode, the MnO2/CNT composite delivers a much larger initial capacity of 275.3 mA-h/g and better rate and cycling performance.

In Situ Coupling Strategy for Anchoring Monodisperse Co_9S_8 Nanoparticles on S and N Dual?Doped Graphene as a Bifunctional Electrocatalyst for Rechargeable Zn–Air Battery

An in situ coupling strategy to prepare Co_9S_8/S and N dual?doped graphene composite(Co_9S_8/NSG) has been proposed. The key point of this strategy is the function?oriented design of organic compounds. Herein, cobalt porphyrin derivatives with sulfo groups are employed as not only the coupling agents to form and anchor Co_9S_8 on the graphene in situ, but also the heteroatom?doped agent to generate S and N dual?doped graphene. The tight coupling of multiple active sites endows the composite materials with fast electrochemical kinetics and excellent stability for both oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The obtained electrocatalyst exhibits better activity parameter(ΔE = 0.82 V) and smaller Tafel slope(47.7 mV dec^(-1) for ORR and 69.2 mV dec^(-1) for OER) than commercially available Pt/C and RuO_2. Most importantly, as electrocatalyst for rechargeable Zn–air battery, Co_9S_8/NSG displays low charge–discharge voltage gap and outstanding long?term cycle stability over 138 h compared to Pt/C–RuO_2. To further broaden its application scope, a homemade all?solid?state Zn–air battery is also prepared, which displays good charge–discharge performance and cycle performance. The function?oriented design of N_4?metallomacrocycle derivatives might open new avenues to strategic construction of high?performance and long?life multifunctional electrocatalysts for wider electro?chemical energy applications.

Progress in aqueous rechargeable batteries

Over the past decades, a series of aqueous rechargeable batteries(ARBs) were explored, investigated and demonstrated. Among them,aqueous rechargeable alkali-metal ion(Li^+Na^+, K^+) batteries, aqueous rechargeable-metal ion(Zn^(2+),Mg^(2+), Ca^(2+), Al^(3+)) batteries and aqueous rechargeable hybrid batteries are standing out due to peculiar properties. In this review, we focus on the fundamental basics of these batteries, and discuss the scientific and/or technological achievements and challenges. By critically reviewing state-of-the-art technologies and the most promising results so far, we aim to analyze the benefits of ARBs and the critical issues to be addressed, and to promote better development of ARBs.

Isotope Method for Confined Groundwater Recharge of the Lower Reaches of the Heihe River,Inner Mongolia,China

Environmental isotopes have been appfied to analyze confined groundwater recharge in the lower reaches of the Heihe River, Inner Mongolia. CFC is regarded as a tracer that determines the date of groundwater, the date being less than 45 a. The confined groundwater within the Gurinai area and Ejin Basin other than the surface water of Heihe River might have originated from precipitation from Qilian Mountain or/and the Tibetan Plateau. The deep confined groundwater overflows into an upper aquifer and emerges into the ground, forming springs and lakes within the low-lying area. The recharge volume is estimated to be around 400 million-cubic meters.

An approach to delineate groundwater recharge potential sites in Ambalantota,Sri Lanka using GIS techniques

The demand for fresh water in Hambantota District, Sri Lanka is rapidly increasing with the enormous amount of ongoing development projects in the region. Nevertheless, the district experiences periodic water stress conditions due to seasonal precipitation patterns and scarcity of surface water resources.Therefore, management of available groundwater resources is critical, to fulfil potable water requirements in the area. However, exploitation of groundwater should be carried out together with artificial recharging in order to maintain the long term sustainability of water resources. In this study, a GIS approach was used to delineate potential artificial recharge sites in Ambalantota area within Hambantota. Influential thematic layers such as rainfall, lineament, slope, drainage, land use/land cover, lithology, geomorphology and soil characteristics were integrated by using a weighted linear combination method. Results of the study reveal high to moderate groundwater recharge potential in approximately 49% of Ambalantota area.

A field study of advanced municipal wastewater treatment technology for artificial groundwater recharge

Field studies were conducted to investigate the advanced treatment of the municipal secondary effluent and a subsequent artificial groundwater recharge at Gaobeidian Wastewater Treatment Plant, Beijing. To improve the secondary effluent quality, the combined process of powdered activated carbon adsorption, flocculation and rapid sand filtration was applied, which could remove about 400 dissolved organic carbon （DOC） and 70% adsorbable organic halogens. The results of liquid size exclusion chromatography indicate that in the adsorption unit the removed organic fraction was mainly low molecular weight compounds. The fractions removed by the flocculation unit were polysaccharides and high molecular weight compounds. The retention of water in summer in the open recharge basins resulted in a growth of algae. Consequently, DOC increased in the polysaccharide and high molecular weight humic substances fraction. The majority of the DOC removal during soil passage took place in the unsaturated area. A limited reduction of DOC was observed in the aquifer zone.

Potential groundwater recharge zones within New Zealand

Water resources in New Zealand are not evenly distributed across the country which makes it difficult to adequately allocate the use of water resources in every basin. Groundwater is a fundamental water resource in New Zealand for agricultural, industrial and domestic use. Detailed knowledge regarding groundwater recharge potential is a pre-requisite for sustainable groundwater management, including the assessment of its vulnerability to contamination by pollutants. In this study, a comprehensive GIS approach was used to map the potential groundwater recharge zones across New Zealand. National data sets of lithology, slope, aspect, land use, soil drainage and drainage density were converted to raster data sets with a spatial resolution of 500 m x 500 m and superimposed to derive groundwater potential zones. The resultant maps demonstrate that the potential is low in urban and mountainous areas, such as the Southern Alps, whereas the highest potential can be found in regions with large lakes and in the lower elevation plains areas, where Quaternary sediments prevail. The resulting maps can be used to identify areas of high nutrient leaching in zones where high groundwater recharge potential exists.