Towards advanced zinc anodes by interfacial modification strategies for efficient aqueous zinc metal batteries

Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.

Recent advances in interfacial modification of zinc anode for aqueous rechargeable zinc ion batteries

To tackle energy crisis and achieve sustainable development, aqueous rechargeable zinc ion batteries have gained widespread attention in large-scale energy storage for their low cost, high safety, high theoretical capacity, and environmental compatibility in recent years. However, zinc anode in aqueous zinc ion batteries is still facing several challenges such as dendrite growth and side reactions(e.g., hydrogen evolution), which cause poor reversibility and the failure of batteries. To address these issues, interfacial modification of Zn anodes has received great attention by tuning the interaction between the anode and the electrolyte. Herein, we present recent advances in the interfacial modification of zinc anode in this review. Besides, the challenges of reported approaches of interfacial modification are also discussed.Finally, we provide an outlook for the exploration of novel zinc anode for aqueous zinc ion batteries.We hope that this review will be helpful in designing and fabricating dendrite-free and hydrogenevolution-free Zn anodes and promoting the practical application of aqueous rechargeable zinc ion batteries.

Room temperature operation of all-solid-state battery using a closo-type complex hydride solid electrolyte and a LiCoO_(2) cathode by interfacial modification

We report on an all-solid-state battery that employs a closo-type complex hydride solid electrolyte and a LiCoO2 cathode.Interfacial modification between the solid electrolyte and cathode with a LiNbO3 buffer layer enables reversible charge-discharge cycling with a cell voltage of 3.9V (vs.Li^+/Li) at room temperature.Electrochemical analyses clarify that the given modification effectively suppresses side reactions at the cathode/solid electrolyte interface.The interfacial resistance is lowered by ca.10 times with a 5 nm thick LiNbO3 buffer layer compared to that without a buffer layer,so that a discharge capacity of 109 mAh g^-1 is achieved.These results suggest that interfacial modification can be a viable approach to the development of high-voltage all-solid-state batteries using closo-type complex hydride solid electrolytes and oxide cathodes.

Preparation of hysteresis-free flexible perovskite solar cells via interfacial modification

In recent years, flexible perovskite solar cells have received extensive attention and rapid development due to their advantages of lightweight, portability, wearability and applications in near-space. However,due to the limitations of their preparation process and other factors, high-efficiency and large-area flexible perovskite solar cells still have a lot of room for development. In our work, a flexible perovskite solar cell(PEN/ITO/Sn O2/KCl/Cs0.05(MA0.17 FA0.83)0.95 Pb(I0.83 Br0.17)3/spiro/Au) was prepared using a low temperature(no higher than 100°C) solution process, and the device with the highest efficiency of 16.16%was obtained by adjusting the concentration of the KCl modified layer. Meanwhile, the efficiency of the large area(1 cm2) flexible solar cell was higher than 13%. At the same time, the passivation of the KCl interface modification layer inhibits the formation of the defect states, which reduced the surface recombination of the perovskite and improved the carrier transport performance, and the hysteresis effect of the device was also reduced accordingly.

Interfacial Modification,Electrode/Solid‑Electrolyte Engineering,and Monolithic Construction of Solid‑State Batteries

Solid-state lithium-metal batteries(SLMBs)have been regarded as one of the most promising next-generation devices because of their potential high safety,high energy density,and simple packing procedure.However,the practical applications of SLMBs are restricted by a series of static and dynamic interfacial issues,including poor interfacial contact,(electro-)chemical incompatibility,dynamic Li dendrite penetration,etc.In recent years,considerable attempts have been made to obtain mechanistic insight into interfacial failures and to develop possible strategies towards excellent interfacial properties for SLMBs.The static and dynamic failure mechanisms at interfaces between solid electrolytes(SEs)and electrodes are comprehensively summarized,and design strategies involving interfacial modification,electrode/SE engineering,and the monolithic construction of SLMBs are discussed in detail.Finally,possible research methodologies such as theoretical calcu-lations,advanced characterization techniques,and versatile design strategies are provided to tackle these interfacial problems.

Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability

Achieving a highly robust zinc(Zn)metal anode is extremely important for improving the performance of aqueous Zn-ion batteries(AZIBs)for advancing“carbon neutrality”society,which is hampered by the uncontrollable growth of Zn dendrite and severe side reactions including hydrogen evolution reaction,corrosion,and passivation,etc.Herein,an interlayer containing fluorinated zincophilic covalent organic framework with sulfonic acid groups(COF-S-F)is developed on Zn metal(Zn@COF-S-F)as the artificial solid electrolyte interface(SEI).Sulfonic acid group(-SO_(3)H)in COF-S-F can effectively ameliorate the desolvation process of hydrated Zn ions,and the three-dimensional channel with fluoride group(-F)can provide interconnected channels for the favorable transport of Zn ions with ion-confinement effects,endowing Zn@COF-S-F with dendrite-free morphology and suppressed side reactions.Consequently,Zn@COF-S-F symmetric cell can stably cycle for 1,000 h with low average hysteresis voltage(50.5 m V)at the current density of 1.5 m A cm^(-2).Zn@COF-S-F|Mn O_(2)cell delivers the discharge specific capacity of 206.8 m Ah g^(-1)at the current density of 1.2 A g^(-1)after 800 cycles with high-capacity retention(87.9%).Enlightening,building artificial SEI on metallic Zn surface with targeted design has been proved as the effective strategy to foster the practical application of high-performance AZIBs.

Reinforced SnO_(2) tensile-strength and“buffer-spring”interfaces for efficient inorganic perovskite solar cells

Suppressing nonradiative recombination and releasing residual strain areprerequisites to improving the efficiency and stability of perovskite solar cells(PSCs).Here,long-chain polyacrylic acid(PAA)is used to reinforce SnO_(2)film and passivate SnO_(2)defects,forming a structure similar to“reinforcedconcrete”with high tensile strength and fewer microcracks.Simultaneously,PAA is also introduced to the SnO_(2)/perovskite interface as a“buffer spring”torelease residual strain,which also acts as a“dual-side passivation interlayer”to passivate the oxygen vacancies of SnO_(2)and Pb dangling bonds in halideperovskites.As a result,the best inorganic CsPbBr_(3)PSC achieves a championpower conversion efficiency of 10.83%with an ultrahigh open-circuit voltageof 1.674 V.The unencapsulated PSC shows excellent stability under 80%relative humidity and 80℃over 120 days.

The interface structure and property of magnesium matrix composites:A review

Magnesium matrix composites have garnered significant attention in recent years owing to their exceptional lightweight properties and notable potential in various engineering applications.The interface generally acts as a“bridge”between the matrix and reinforcement,playing crucial roles in critical processes such as load transfer,failure behavior,and carrier transport.A deep understanding of the interfacial structures,properties,and effects holds paramount significance in the study of composites.This paper presents a comprehensive review of prior researches related to the interface of Mg matrix composites.Firstly,the different interfacial structures and interaction mechanisms encompassing mechanical,physical,and chemical bonding are introduced.Subsequently,the interfacial mechanical properties and their influence on the overall properties are discussed.Finally,the paper addresses diverse interface modification methods including matrix alloying and reinforcement surface treatment.

Interfacial/bulk synergetic effects accelerating charge transferring for advanced lithium-ion capacitors

The exploration of advanced materials through rational structure/phase design is the key to develop highperformance lithium-ion capacitors(LICs).However,high complexity of material preparation and difficulty in quantity production largely hinder the further development.Herein,Cu_(5)FeS_(4-x)/C(CFS@C)heterojunction with rich sulfur vacancies has successfully achieved from natural bornite,presenting low costeffective and bulk-production prospect.Density functional theory(DFT)calculations indicate that rich vacancies in bulk phase can decrease band gap of bornite and thus improve its intrinsic electron conductivity,as well as the heterojunction spontaneously evokes a built-in electric field between its interfacial region,largely reducing the migration barrier from 1.27 e V to 0.75 e V.Benefited from these merits,the CFS@C electrodes deliver outperformed lithium storage performance,e.g.,high reversible capacity(822.4m Ah/g at 0.1 A/g),excellent cycling stability(up to 820 cycles at 2 A/g and 540 cycles at 5 A/g with respective capacity retention of over or nearly 100%).With CFS@C as anode and porous carbon nanosheets(PCS)as cathode,the assembled CFS@C//PCS LIC full cells exhibit high energy/power density characteristics of 139.2 Wh/kg at 2500 W/kg.This work is expected to offer significant insights into structure modifications/devising toward natural minerals for advanced energy-storage systems.

Simultaneous bottom-up double-layer synergistic engineering by multifunctional natural molecules for efficient and stable SnO2-based planar perovskite solar cells

The performance and stability of perovskite solar cells(PSCs)is limited by detrimental defects,mostly distributed at the grain boundary(GB)of bulk perovskite film and interface,which induce serious carrier non-radiative recombination.Therefore,there is particularly urgent to realize simultaneous passivation of bulk defects and interfacial defects.In this work,a simple,low-cost and effective multifunctional modification strategy is developed by introducing theλ-Carrageenan(λ-C)as the interfacial layer of SnO_(2)/perovskite.The sulfate groups ofλ-C not only play a positive role in passivating the Sn4+from SnO_(2)film,resulting in high conductivity,but also effectively passivate the defects at the SnO_(2)/perovskite interface.Meanwhile,λ-C can effectively passivate the defects in the perovskite film due to the strong binding force between the high content of sulfate groups and PbI2.The synergistic effect ofλ-C simultaneously achieves interfacial defects and bulk defects passivation,better crystalline quality,suppressed charge recombination,released interfacial stress and more favorable interfacial energy level alignment.Based on the above efficient synergy,theλ-C-modified device achieves a high efficiency of 23.81%,which is~24.53%higher than the control device(19.12%).To our best knowledge,23.81%of power conversion efficiency(PCE)is the highest reported PCE value of PSCs employing green natural additives.Moreover,long-term and thermal stabilities are significantly improved after interface modification.Thus,this work provides an idea for developing multifunctional natural materials towards the attainment of the efficient and stable PSCs.

Can the efficiencies of simplified perovskite solar cells go higher?

In recent years, metal halide perovskites have emerged as star semiconducting materials in the field of optoelectronic devices owing to their fascinating optoelectronic properties. Of particular interest are perovskite solar cells (PSCs), which have witnessed skyrocketing power conversion efficiencies (PCEs) within a short period of time, and were recently certified to reach 25.5%, which is already higher than other thin film photovoltaic technologies[1]. Nevertheless, multiple layers are still needed for state-of-theart PSCs to achieve high PCEs over 21%.

Eco-friendly glucose assisted structurally simplified high-efficiency tin-lead mixed perovskite solar cells

Achieving highly-efficient and stable perovskite solar cells(PSCs) with a simplified structure remains challenging, despite the tremendous potential for reducing preparation cost and facile processability by removing hole transport layer(HTL). In this work, eco-friendly glucose(Gl) as an interface modifier for HTL-free narrow bandgap tin-lead(Sn-Pb) PSCs is proposed. Gl not only enhances the wettability of the indium tin oxide to promote perovskite heterogeneous nucleation on substrate, but also realizes defect passivation by interacting with uncoordinated Pb^(2+) and Sn^(2+) in perovskite films. As a result, the quality of the perovskite films has been significantly improved, accompanied by reduced defects of bottom interface and optimized energy level structure of device, leading to an efficiency increase and a less nonradiative voltage loss of 0.102 V(for a bandgap of ~1.26 eV). Consequently, the optimized PSC delivers an unprecedented efficiency over 21% with high open-circuit voltage and enhanced stability, outperforming the control device. This work demonstrates a cost-effective approach to develop simplified structure high efficiency HTL-free Sn-Pb PSC.

Interfacial engineering for high-performance garnet-based solid-state lithium batteries

Solid-state batteries represent the future of energy storage technology,offering improved safety and energy density.Garnet-type Li_(7)La_(3)Zr_(2)O_(12)(LLZO)solidstate electrolytes-based solid-state lithium batteries(SSLBs)stand out for their appealingmaterial properties and chemical stability.Yet,their successful deployment depends on conquering interfacial challenges.This review article primarily focuses on the advancement of interfacial engineering for LLZO-based SSLBs.We commence with a concise introduction to solid-state electrolytes and a discussion of the challenges tied to interfacial properties in LLZO-based SSLBs.We deeply explore the correlations between structure and properties and the design principles vital for achieving an ideal electrode/electrolyte interface.Subsequently,we delve into the latest advancements and strategies dedicated to overcoming these challenges,with designated sections on cathode and anode interface design.In the end,we share our insights into the advancements and opportunities for interface design in realizing the full potential of LLZO-based SSLBs,ultimately contributing to the development of safe and high-performance energy storage solutions.

Boosting fast interfacial Li^(+)transport in solid-state Li metal batteries via ultrathin Al buffer layer

Na superionic conductor(NASICON)-type Li_(1.5)Al_(0.5)Ge_(0.5)P_(3)O_(12)(LAGP)solid state electrolytes(SSEs)have attracted significant interests thanks to the prominent ionic conductivity(>10^(–4)S·cm^(–1))at room temperature and superb stability in air.Unfortunately,its application has been hindered by the lithium dendrites and the intrinsic interfacial instability of LAGP towards metallic Li,etc.Herein,by magnetron sputtering(MS),an ultrathin Al film is deposited on the surface of the LAGP pellet(Al-LAGP).By in-situ alloying reaction,the spontaneously formed LiAl buffer layer inhibits the side reaction between LAGP SSEs and Li metal,induces the uniform distribution of interfacial electric field as well.Density functional theory(DFT)calculations demonstrate that the LiAl alloy surface promotes the diffusion of lithium atoms due to the lower energy barrier,thereby inhibiting the formation of lithium dendrites.Consequently,the Li/Al-LAGP-Al/Li symmetric cells show a low resistance of 210Ωand a durable lifespan over 1,200 h at a high current density of 0.1 mA·cm^(-2).Assembled all solid state lithium metal batteries(ASSLMBs)with LiFePO_(4)(LFP)cathode significantly improve cycle stability and rate performance,proving a promising stabilization strategy towards the NASIOCN type electrolyte/anode interface in solid state Li metal batteries.

Facile Modification on Buried Interface for Highly Efficient and Stable FASn_(0.5)Pb_(0.5)I_(3) Perovskite Solar Cells with NiOx Hole-Transport layers

Formamidinium(FA)-based Sn-Pb perovskite solar cells(FAPb_(0.5)Sn_(0.5)I_(3) PSCs)with ideal bandgap and impressive thermal stability have caught enormous attention recently.However,it still suffers from the challenge of realizing high efficiency due to the surface imperfections of the transport materials and the energy-level mismatch between functional contacts.Herein,it is demonstrated that the modification on buried interface with alkali metal salts is a viable strategy to alleviate these issues.We systematically investigate the role of three alkali metal bromide salts(NaBr,KBr,CsBr)by burying them between the NiOx hole transport layer(HTL)and the perovskite light-absorbing layer,which can effectively passivate interface defects,improve energy-level matching and release the internal residual strain in perovskite layers.The device with CsBr buffer layer exhibits the best power conversion efficiency(PCE)approaching 20%,which is one of the highest efficiencies for FA-based Sn-Pb PSCs employing NiO_(x) HTLs.Impressively,the long-term storage stability of the unencapsulated device is also greatly boosted.Our work provides an efficient strategy to prepare desired FA-based ideal-bandgap Sn-Pb PSCs which could be applied in tandem solar cells.

Managing interfacial properties of planar perovskite solar cells using Y_(3)N@C_(80)endohedral metallofullerene

Fullerene derivatives have a wide range of applications in perovskite solar cells(PSCs),such as electron transport layers(ETLs),interfacial modifiers,and additives.However,there have been few studies of the use of endohedral metallofullerenes(EMFs)to improve the performance of PSCs.Here,a novel EMF(Y_(3)N@C_(80))was synthesized and used as an interfacial modifier in PSC devices based on a SnO_(2)ETL.Energy level mismatches and detrimental carrier recombination have been observed in devices with a pristine SnO_(2)ETL,but these issues are alleviated with the assistance of Y_(3)N@C_(80).A significant increase in open-circuit voltage from 1.106 V(SnO_(2))to 1.14 V(SnO_(2)-Y_(3)N@C_(80)),an increase in power conversion efficiency from 20.59%to 21.66%,and a marked reduction in hysteresis were observed,which were attributed to the more suitable conduction band energy levels and more effective electron extraction at the SnO_(2)-Y_(3)N@C_(80)/perovskite interface.In addition,the stability of the target devices was improved,which may be due to the hydrophobicity of Y_(3)N@C_(80)and a reduction in trap states.

Double-side modification strategy for efficient carbon-based,allinorganic CsPbIBr2 perovskite solar cells with high photovoltage

CsPbIBr_(2)has attracted great attention due to its balanced bandgap and stability features.However,onestep prepared CsPbIBr_(2)films are generally of poor quality,hindering the performance improvement of the resulting perovskite solar cells(PSCs).Herein,we report the fabrication of high-performance carbonbased,all-inorganic CsPbIBr_(2)PSCs with a double-side modification strategy using PEAI/PEABr.We tune the crystallization behavior and passivate the defects of CsPbIBr_(2)films with modifications of their bottom and top surfaces with PEAI and PEABr,respectively.This causes the PEA cation to form a double layer of armor on both sides of the CsPbIBr_(2)precursor film and can provide the anions of the required I and Br.The collaborative strategy of crystallization and defect passivation for CsPbIBr_(2)films is exceptionally effective.It produces a fully covered CsPbIBr_(2)film with an average grain size increase of more than 50%,few grain boundaries,and high crystallinity.Moreover,this strategy also suppresses pinhole formation,reduces the charge trap density,and prolongs the carrier recombination lifetime.Hence,carbon-based all-inorganic PSCs with the desired CsPbIBr_(2)films yield an optimized efficiency of 9.96%with a particularly high photovoltage of 1.32 V.Our work provides guidance for simultaneous crystallization control and defect passivation to further improve the performance of PSCs.

An artificial interphase enables stable PVDF-based solid-state Li metal batteries

Composite polymer electrolytes(CPEs)have attracted much attention for high energy density solid-state lithium-metal batteries owing to their flexibility,low cost,and easy scale-up.However,the unstable Li/CPE interface is always challengeable for the practical utilization of CPEs.Herein,a polymer interlayer containing K+prepared by ultraviolet(UV)-curing precursor solution is coated on Li surface to stabilize the interface between poly(vinylidene difluoride)(PVDF)composite electrolytes and Li anode.Benefiting from the physical barrier of the interlayer,the continuous decomposition of PVDF is restrained and the intimate contact between electrode and electrolyte is also achieved to reduce the interface impedance.Moreover,the added K+is utilized to further regulate smooth Li deposition.As a consequence,the symmetric Li|Li cell with coated Li demonstrates steady cycling at 0.4 mAh·cm^(-2) and a high critical current density of 1 mA·cm^(-2).The assembled Li|LiFePO_(4) cell presents outstanding cycling stability(capacity retention of 90%after 400 cycles at 1 C)and good rate performance.The associated pouch cell performs impressive flexibility and safety.This work provides a convenient strategy to achieve stable Li/PVDF interface for high-performance PVDF-based solid state Li metal batteries.

Vanadyl Sulfate Based Hole-Transporting Layer Enables Efficient Organic Solar Cells

It remains an urgent task to develop alternative hole-transporting layer(HTL)materials beyond commonly used PEDOT:PSS to increase the shelf-life of organic solar cells(OSCs).Inorganic metal oxide type materials,such as NiO_(x),CoO_(x)and VO_(x),with suitable work functions have attracted numerous research attention recently.In this work,more abundant and easily accessible oxygenated salt,vanadyl sulfate(VOSO_(4))has been demonstrated to be excellent choice as HTL for OSCs.The VOSO_(4)-based HTL can be readily processed by spin-coating from the precursor solution with subsequent thermal annealing and UVO treatment.As a consequence,a high power conversion efficiency(PCE)of 18.72%can be achieved for PM8:L8-BO based OSCs with the VOSO_(4)-based HTL.High transmittance,smooth film surface,suitable energy level and high conductivity were revealed to contribute to the high OSC performance.More importantly,compared to device with PEDOT:PSS,VOSO_(4)-based OSCs exhibit improved stability when stored in the N_(2)filled glove box.After being stored for 600 h,VOSO_(4)-based device can retain 89%of its initial efficiency.Notably,VOSO_(4)can be used as general HTL in PM6:BTP-BO-4Cl and PM6:IT-4F based OSCs,yielding high PCEs of 17.87%and 13.85%,respectively.

LPEO enhanced LAGP composite solid electrolytes for lithium metal batteries

The application of solid electrolyte is expected to realize the commercialization of high energy density lithium metal batteries(LMBs).While the interfacial contact between solid inorganic electrolyte and electrodes has become a stumbling block for achieving stable cycling in LMBs.In this work,a Li-containing polyethylene oxide(LPEO)was introduced between LAGP and electrodes as a buffer layer to regulate the interfacial compatibility and reduce interfacial impedance,inhibiting the side reactions.Moreover,ether-oxygen bond on LPEO chain can coordinate with Li+and guide the transportation of Li+,achieving fast Li+diffusion between Li1+xAlxGe2-x(PO4)3(LAGP)and electrodes.Specifically,the growth of lithium dendrites is effectively suppressed in LAGP with LPEO modification,which would lead to remarkable cycling stability and rate capability.Therefore,the Li|LPEO-LAGP|Li battery can cycle stably for more than 600 h at 0.1 mA cm−2.In addition,long-term performance of Li|LPEO-LAGP|LiFePO4(LFP)battery was achieved at a rate of 0.4 C,and capacity retention is more than 74%after 200 cycles.The Li|LPEO-LAGP|LiNi0.8Co0.1Mn0.1O2 also realized the steady operation in the voltage range of 2.8-4.3 V.