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.

A Review on Engineering Design for Enhancing Interfacial Contact in Solid-State Lithium–Sulfur Batteries

The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.

Effect of phosphorus content on interfacial heat transfer and film deposition behavior during the high-temperature simulation of strip casting

The interfacial wettability and heat transfer behavior are crucial in the strip casting of high phosphorus-containing steel.A hightemperature simulation of strip casting was conducted using the droplet solidification technique with the aims to reveal the effects of phosphorus content on interfacial wettability,deposited film,and interfacial heat transfer behavior.Results showed that when the phosphorus content increased from 0.014wt%to 0.406wt%,the mushy zone enlarged,the complete solidification temperature delayed from1518.3 to 1459.4℃,the final contact angle decreased from 118.4°to 102.8°,indicating improved interfacial contact,and the maximum heat flux increased from 6.9 to 9.2 MW/m2.Increasing the phosphorus content from 0.081wt%to 0.406wt%also accelerated the film deposition rate from 1.57 to 1.73μm per test,resulting in a thickened naturally deposited film with increased thermal resistance that advanced the transition point of heat transfer from the fifth experiment to the third experiment.

Multiphase Interfacial Regulation Based on Hierarchical Porous Molybdenum Selenide to Build Anticorrosive and Multiband Tailorable Absorbers

Electromagnetic wave(EMW)absorbing materials have an irreplaceable position in the field of military stealth as well as in the field of electromagnetic pollution control.And in order to cope with the complex electromagnetic environment,the design of multifunctional and multiband high efficiency EMW absorbers remains a tremendous challenge.In this work,we designed a three-dimensional porous structure via the salt melt synthesis strategy to optimize the impedance matching of the absorber.Also,through interfacial engineering,a molybdenum carbide transition layer was introduced between the molybdenum selenide nanoparticles and the three-dimensional porous carbon matrix to improve the absorption behavior of the absorber.The analysis indicates that the number and components of the heterogeneous interfaces have a significant impact on the EMW absorption performance of the absorber due to mechanisms such as interfacial polarization and conduction loss introduced by interfacial engineering.Wherein,the prepared MoSe_(2)/MoC/PNC composites showed excellent EMW absorption performance in C,X,and Ku bands,especially exhibiting a reflection loss of−59.09 dB and an effective absorption bandwidth of 6.96 GHz at 1.9 mm.The coordination between structure and components endows the absorber with strong absorption,broad bandwidth,thin thickness,and multi-frequency absorption characteristics.Remarkably,it can effectively reinforce the marine anticorrosion property of the epoxy resin coating on Q235 steel substrate.This study contributes to a deeper understanding of the relationship between interfacial engineering and the performance of EMW absorbers,and provides a reference for the design of multifunctional,multiband EMW absorption materials.

Interfacial Modification of NiO_(x)by Self-assembled Monolayer for Efficient and Stable Inverted Perovskite Solar Cells

NiO_(x)as a hole transport material for inverted perovskite solar cells has received great attention owing to its high transparency,low fabrication temperature,and superior stability.However,the mismatched energy levels and possible redox reactions at the NiO_(x)/perovskite interface severely limit the performance of NiO_(x) based inverted perovskite solar cells.Herein,we introduce a p-type self-assembled monolayer between NiO_(x)and perovskite layers to modify the interface and block the undesirable redox reaction between perovskite and NiO_(x)The selfassembled monolayer molecules all contain phosphoric acid function groups,which can be anchored onto the NiOr surface and passivate the surface defect.Moreover,the introduction of self-assembled monolayers can regulate the energy level structure of NiO_(x),reduce the interfacial band energy offset,and hence promote the hole transport from perovskite to NiO_(x)layer.Consequently,the device performance is significantly enhanced in terms of both power conversion efficiency and stability.

In-situ interfacial passivation and self-adaptability synergistically stabilizing all-solid-state lithium metal batteries

The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.

Interfacial modulation of bifunctional electrolyte additive engineering for dendrite-free and robust lithium metal anode

Anode materials for rechargeable electric car batteries are obtained from Li-metal owing to their extremely high specific capacity and low redox potential.Unfortunately,safety concerns related to dendrite formation on the anode surface caused by the uneven distribution of Li-ions during the discharge process interfere with the use of Li-metal in industrial batteries.In this study,methyl vinyl sulfone(MVS),a sulfone-based functional electrolyte additive,is used in an additive engineering strategy to control Lielectrolyte interactions and address the aforementioned problems.Li dendrite growth may be restricted,and transition metal degradation on the surface of the cathode can be reduced by the MVS-derived functional electrolyte additive interfacial layer.The electrochemical performance of an ethylene carbonate/dimethyl carbonate(EC/DMC)+1 wt% MVS Li-metal anode of a Li||Li symmetric cell exhibits remarkable cycle stability,maintaining a low overvoltage for over 750 h at 1 mA cm^(-2),and capacity of 1 mA h cm^(-2).Additionally,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) full cells with the MVS additive exhibit enhanced electrochemical stability for 250 cycles at a current density of 100 mA g^(-1).This study provides an innovative approach for stabilizing the metal-electrolyte interfacial layer that may be used for practical applications in metal-based rechargeable batteries.

Generating highly active oxide-phosphide heterostructure through interfacial engineering to break the energy scaling relation toward urea-assisted natural seawater electrolysis

Urea-assisted natural seawater electrolysis is an emerging technology that is effective for grid-scale carbon-neutral hydrogen mass production yet challenging.Circumventing scaling relations is an effective strategy to break through the bottleneck of natural seawater splitting.Herein,by DFT calculation,we demonstrated that the interface boundaries between Ni_(2)P and MoO_(2) play an essential role in the selfrelaxation of the Ni-O interfacial bond,effectively modulating a coordination number of intermediates to control independently their adsorption-free energy,thus circumventing the adsorption-energy scaling relation.Following this conceptual model,a well-defined 3D F-doped Ni_(2)P-MoO_(2) heterostructure microrod array was rationally designed via an interfacial engineering strategy toward urea-assisted natural seawater electrolysis.As a result,the F-Ni_(2)P-MoO_(2) exhibits eminently active and durable bifunctional catalysts for both HER and OER in acid,alkaline,and alkaline sea water-based electrolytes.By in-situ analysis,we found that a thin amorphous layer of NiOOH,which is evolved from the Ni_(2)P during anodic reaction,is real catalytic active sites for the OER and UOR processes.Remarkable,such electrode-assembled urea-assisted natural seawater electrolyzer requires low voltages of 1.29 and 1.75 V to drive 10 and600 mA cm^(-2)and demonstrates superior durability by operating continuously for 100 h at 100 mA cm^(-2),beyond commercial Pt/C||RuO_(2) and most previous reports.

An ultrathin and robust single-ion conducting interfacial layer for dendrite-free lithium metal batteries

The practical application of rechargeable lithium metal batteries(LMBs) encounters significant challenges due to the notorious dendrite growth triggered by uneven Li deposition behaviors. In this work,a mechanically robust and single-ion-conducting interfacial layer, fulfilled by the strategic integration of flexible cellulose acetate(CA) matrix with rigid graphene oxide(GO) and Li F fillers(termed the CGL layer), is rationally devised to serve as a stabilizer for dendrite-free lithium(Li) metal batteries. The GCL film exhibits favorable mechanical properties with high modulus and flexibility that help to relieve interface fluctuations. More crucially, the electron-donating carbonyl groups(C=O) enriched in GCL foster a strengthened correlation with Li^(+), which availably aids the Li^(+)desolvation process and expedites facile Li^(+)mobility, yielding exceptional Li^(+) transference number of 0.87. Such single-ion conductive properties regulate rapid and uniform interfacial transport kinetics, mitigating the growth of Li dendrites and the decomposition of electrolytes. Consequently, stable Li anode with prolonged cycle stabilities and flat deposition morphologies are realized. The Li||LiFePO_(4) full cells with CGL protective layer render an outstanding cycling capability of 500 cycles at 3 C, and an ultrahigh capacity retention of 99.99% for over 220 cycles even under harsh conditions. This work affords valuable insights into the interfacial regulation for achieving high-performance LMBs.

Regulating interfacial behavior of zinc metal anode via metal-organic framework functionalized separator

Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framework(MOF)functionalized glass fiber separator(GF-PFC-31)was used to regulate interfacial behavior of zinc metal anode,enabling the development of high-performance AZIBs.In PFC-31,there areπ-πinteractions between two adjacent benzene rings with a spacing of 3.199 A.This spacing can block the passage of[Zn(H_(2)O)_6]^(2+)(8.6 A in diameter)through the GF-PFC-31 separator to a certain extent,which promotes the deposition process of Zn ions.In addition,the sulfonic acid group(-S03H)contained in GF-PFC-31 can form a hydrogen bonding network with H_(2)O,which can provide a desolvation effect and reduce the side reaction.Consequently,GF-PFC-31 separator achieves uniform deposition of Zn ions.The Zn‖GF-PFC-31‖Zn symmetric cell exhibits stable cycle life(3000 h at 1.2 mA cm^(-2),2000 h at 0.3 mA cm^(-2),and 2000 h at 5.0 mA cm^(-2)),and Zn‖GF-PFC-31‖MnO_(2) full cell with GF-PFC-31 separator can cycle for 1000 cycles at 1.2 A g^(-1)with capacity retention rate of 82.5%.This work provides a promising method to achieve high-performance AZIBs.

Effect of Mo and ZrO_(2)nanoparticles addition on interfacial properties and shear strength of Sn58Bi/Cu solder joint

The influence of Mo and ZrO_(2)nanoparticles addition on the interfacial properties and shear strength of Sn58Bi solder joint was investigated.The interfacial microstructures of Sn58Bi/Cu,Sn58Bi+Mo/Cu and Sn58Bi+ZrO_(2)/Cu solder joints were analysed using a scanning electron microscope(SEM)coupled with energy dispersive X-ray(EDX)and the X-ray diffraction(XRD).Intermetallic compounds(IMCs)of MoSn_(2)are detected in the Sn58Bi+Mo/Cu solder joint,while SnZr,Zr_(5)Sn_(3),ZrCu and ZrSn_(2)are detected in Sn58Bi+ZrO_(2)/Cu solder joint.IMC layers for both composite solders comprise of Cu_(6)Sn_(5) and Cu_(3)Sn.The SEM images of these layers were used to measure the IMC layer’s thickness.The average IMC layer’s thickness is 1.4431μm for Sn58Bi+Mo/Cu and 0.9112μm for Sn58Bi+ZrO_(2)/Cu solder joints.Shear strength of the solder joints was investigated via the single shear lap test method.The average maximum load and shear stress of the Sn58Bi+Mo/Cu and Sn58Bi+ZrO_(2)/Cu solder joints are increased by 33%and 69%,respectively,as compared to those of the Sn58Bi/Cu solder joint.By comparing both composite solder joints,the latter prevails better as adding smaller sized ZrO_(2)nanoparticles improves the interfacial properties granting a stronger solder joint.

Mechanical properties and interfacial characteristics of 6061 Al alloy plates fabricated by hot-roll bonding

This work aims to investigate the mechanical properties and interfacial characteristics of 6061 Al alloy plates fabricated by hotroll bonding(HRB)based on friction stir welding.The results showed that ultimate tensile strength and total elongation of the hot-rolled and aged joints increased with the packaging vacuum,and the tensile specimens fractured at the matrix after exceeding 1 Pa.Non-equilibrium grain boundaries were formed at the hot-rolled interface,and a large amount of Mg_(2)Si particles were linearly precipitated along the interfacial grain boundaries(IGBs).During subsequent heat treatment,Mg_(2)Si particles dissolved back into the matrix,and Al_(2)O_(3) film remaining at the interface eventually evolved into MgO.In addition,the local IGBs underwent staged elimination during HRB,which facilitated the interface healing due to the fusion of grains at the interface.This process was achieved by the dissociation,emission,and annihilation of dislocations on the IGBs.

Combined effects of ultrasonic vibration and FeCoNiCrCu coating on interfacial microstructure and mechanical properties of Al/Mg bimetal by compound casting

In this work,a new treatment method combining ultrasonic vibration with FeCoNiCrCu high entropy alloy(HEA)coating was used to prepared Al/Mg bimetal through the lost foam compound casting.The effects of composite treatment involving ultrasonic vibration and HEA coating on interfacial microstructure and mechanical properties of Al/Mg bimetal were studied.Results demonstrate that the interface thickness of the Al/Mg bimetal with composite treatment significantly decreases to only 26.99%of the thickness observed in the untreated Al/Mg bimetal.The HEA coating hinders the diffusion between Al and Mg,resulting the significant reduction in Al/Mg intermetallic compounds in the interface.The Al/Mg bimetal interface with composite treatment is composed of Al_(3)Mg_(2)and Mg_(2)Si/AlxFeCoNiCrCu+FeCoNiCrCu/δ-Mg+Al_(12)Mg_(17)eutectic structures.The interface resulting from the composite treatment has a lower hardness than that without treatment.The acoustic cavitation and acoustic streaming effects generated by ultrasonic vibration promote the diffusion of Al elements within the HEA coating,resulting in a significant improvement in the metallurgical bonding quality on the Mg side.The fracture position shifts from the Mg side of the Al/Mg bimetal only with HEA coating to the Al side with composite treatment.The shear strength of the Al/Mg bimetal increases from 32.16 MPa without treatment to 63.44 MPa with ultrasonic vibration and HEA coating,increasing by 97.26%.

Harnessing overlapped temperature-salinity gradient in solar-driven interfacial seawater evaporation for efficient steam and electricity generation

Solar-driven interfacial water evaporation(SIWE)offers a superb way to leverage concentrated solar heat to minimize energy dissipation during seawater desalination.It also engenders overlapped temperaturesalinity gradient(TSG)between water-air interface and adjacent seawater,affording opportunities of harnessing electricity.However,the efficiency of conventional SIWE technologies is limited by significant challenges,including salt passivation to hinder evaporation and difficulties in exploiting overlapped TSG simultaneously.Herein,we report self-sustaining hybrid SIWE for not only sustainable seawater desalination but also efficient electricity generation from TSG.It enables spontaneous circulation of salt flux upon seawater evaporation,inducing a self-cleaning evaporative interface without salt passivation for stable steam generation.Meanwhile,this design enables spatial separation and simultaneous utilization of overlapped TSG to enhance electricity generation.These benefits render a remarkable efficiency of90.8%in solar energy utilization,manifesting in co-generation of solar steam at a fast rate of 2.01 kg m^(-2)-h^(-1)and electricity power of 1.91 W m^(-2)with high voltage.Directly interfacing the hybrid SIWE with seawater electrolyzer constructs a system for water-electricity-hydrogen co-generation without external electricity supply.It produces hydrogen at a rapid rate of 1.29 L h^(-1)m^(-2)and freshwater with 22 times lower Na+concentration than the World Health Organization(WHO)threshold.

Unraveling the Stray Current-Induced Interfacial Transition Zone(ITZ)Effect on Sulfate Corrosion in Concrete

The rail transit in sulfate-rich areas faces the combined effects of stray current and salt corrosion;however,the sulfate ion transport and concrete degradation mechanisms under such conditions are still unclear.To address this issue,novel sulfate transport and mesoscale splitting tests were designed,with a focus on considering the differences between the interfacial transition zone(ITZ)and cement matrix.Under the influence of stray current,the ITZ played a pivotal role in regulating the transport and mechanical failure processes of sulfate attack,while the tortuous and blocking effects of aggregates almost disappeared.This phenomenon was termed the“stray current-induced ITZ effect.”The experimental data revealed that the difference in sulfate ion transport attributed to the ITZ ranged from 1.90 to 2.31 times,while the difference in splitting strength ranged from 1.56 to 1.64 times.Through the real-time synchronization of splitting experiments and microsecond-responsive particle image velocimetry(PIV)technology,the mechanical properties were exposed to the consequences of the stray currentinduced ITZ effect.The number of splitting cracks in the concrete increased,rather than along the central axis,which was significantly different from the conditions without stray current and the ideal Brazilian disk test.Furthermore,a sulfate ion mass transfer model that incorporates reactivity and electrodiffusion was meticulously constructed.The embedded finite element calculation exhibited excellent agreement with the experimental results,indicating its reliability and accuracy.Additionally,the stress field was determined utilizing analytical methods,and the mechanism underlying crack propagation was successfully obtained.Compared to the cement matrix,a stray current led to more sulfates,more microstructure degradation,and greater increases in thickness and porosity in the ITZ,which was considered to be the essence of the stray current-induced ITZ effect.

Metal-free two-dimensional phosphorene-based electrocatalyst with covalent P-N heterointerfacial reconstruction for electrolyte-lean lithium-sulfur batteries

The use of lithium-sulfur batteries under high sulfur loading and low electrolyte concentrations is severely restricted by the detrimental shuttling behavior of polysulfides and the sluggish kinetics in redox processes.Two-dimensional(2D)few layered black phosphorus with fully exposed atoms and high sulfur affinity can be potential lithium-sulfur battery electrocatalysts,which,however,have limitations of restricted catalytic activity and poor electrochemical/chemical stability.To resolve these issues,we developed a multifunctional metal-free catalyst by covalently bonding few layered black phosphorus nanosheets with nitrogen-doped carbon-coated multiwalled carbon nanotubes(denoted c-FBP-NC).The experimental characterizations and theoretical calculations show that the formed polarized P-N covalent bonds in c-FBP-NC can efficiently regulate electron transfer from NC to FBP and significantly promote the capture and catalysis of lithium polysulfides,thus alleviating the shuttle effect.Meanwhile,the robust 1D-2D interwoven structure with large surface area and high porosity allows strong physical confinement and fast mass transfer.Impressively,with c-FBP-NC as the sulfur host,the battery shows a high areal capacity of 7.69 mAh cm^(−2) under high sulfur loading of 8.74 mg cm^(−2) and a low electrolyte/sulfur ratio of 5.7μL mg^(−1).Moreover,the assembled pouch cell with sulfur loading of 4 mg cm^(−2) and an electrolyte/sulfur ratio of 3.5μL mg^(−1) shows good rate capability and outstanding cyclability.This work proposes an interfacial and electronic structure engineering strategy for fast and durable sulfur electrochemistry,demonstrating great potential in lithium-sulfur batteries.

Microstructure,interfacial reaction behavior,and mechanical properties of Ti_3AlC_(2)reinforced Al6061 composites

The interfacial reaction behavior of Al and Ti_3AlC_(2)at different pouring temperatures and its effect on the microstructure and mechanical properties of the composites were investigated.The results show that the addition of3.0 wt.%Ti_3AlC_(2)refines the average grain size ofα(Al)in the composite by 50.1%compared to Al6061 alloy.Morphological analyses indicate that an in-situ Al_(3Ti)transition layer of-180 nm in thickness is generated around the edge of Ti_3AlC_(2)at 720℃,forming a well-bonded Al-Al_(3Ti)interface.At this processing temperature,the ultimate tensile strength of A16061-3.0 wt.%Ti_3AlC_(2)composite is 199.2 MPa,an improvement of 41.5%over the Al6061 matrix.Mechanism analyses further elucidate that 720℃is favourable for forming the nano-sized transition layer at the Ti_3AlC_(2)edges.And,the thermal mismatch strengthening plays a dominant role in this state,with a strengthening contribution of about 74.8%.

Interfacial engineering through lead binding using crown ethers in perovskite solar cells

In the domain of perovskite solar cells(PSCs),the imperative to reconcile impressive photovoltaic performance with lead-related issue and environmental stability has driven innovative solutions.This study pioneers an approach that not only rectifies lead leakage but also places paramount importance on the attainment of rigorous interfacial passivation.Crown ethers,notably benzo-18-crown-6-ether(B18C6),were strategically integrated at the perovskite-hole transport material interface.Crown ethers exhibit a dual role:efficiently sequestering and immobilizing Pb^(2+)ions through host-guest complexation and simultaneously establishing a robust interfacial passivation layer.Selected crown ether candidates,guided by density functional theory(DFT)calculations,demonstrated proficiency in binding Pb2+ions and optimizing interfacial energetics.Photovoltaic devices incorporating these materials achieved exceptional power conversion efficiency(PCE),notably 21.7%for B18C6,underscoring their efficacy in lead binding and interfacial passivation.Analytical techniques,including time-of-flight secondary ion mass spectrometry(ToF-SIMS),ultraviolet photoelectron spectroscopy(UPS),time-resolved photoluminescence(TRPL),and transient absorption spectroscopy(TAS),unequivocally affirmed Pb^(2+)ion capture and suppression of non-radiative recombination.Notably,these PSCs maintained efficiency even after enduring 300 h of exposure to 85%relative humidity.This research underscores the transformative potential of crown ethers,simultaneously addressing lead binding and stringent interfacial passivation for sustainable PSCs poised to commercialize and advance renewable energy applications.

Interfacial stress engineering toward enhancement of ferroelectricity in Al doped HfO_(2) thin films

Ferroelectric HfO_(2)has attracted much attention owing to its superior ferroelectricity at an ultra-thin thickness and good compatibility with Si-based complementary metal-oxide-semiconductor(CMOS)technology.However,the crystallization of polar orthorhombic phase(o-phase)HfO_(2)is less competitive,which greatly limits the ferroelectricity of the as-obtained ferroelectric HfO_(2)thin films.Fortunately,the crystallization of o-phase HfO_(2)can be thermodynamically modulated via interfacial stress engineering.In this paper,the growth of improved ferroelectric Al doped HfO_(2)(HfO_(2):Al)thin films on(111)-oriented Si substrate has been reported.Structural analysis has suggested that nonpolar monoclinic HfO_(2):Al grown on(111)-oriented Si substrate suffered from a strong compressive strain,which promoted the crystallization of(111)-oriented o-phase HfO_(2)in the as-grown HfO_(2):Al thin films.In addition,the in-plane lattice of(111)-oriented Si substrate matches well with that of(111)-oriented o-phase HfO_(2),which further thermally stabilizes the o-phase HfO_(2).Accordingly,an improved ferroelectricity with a remnant polarization(2P_(r))of 26.7C/cm^(2) has been obtained.The results shown in this work provide a simple way toward the preparation of improved ferroelectric HfO_(2)thin films.

Exploring the Cation Regulation Mechanism for Interfacial Water Involved in the Hydrogen Evolution Reaction by In Situ Raman Spectroscopy

Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.