Mitigated reaction kinetics between lithium metal anodes and electrolytes by alloying lithium metal with low-content magnesium

Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.

Stable anode-free zinc-ion batteries enabled by alloy network-modulated zinc deposition interface

Newly-proposed anode-free zinc-ion batteries(ZIBs)are promising to remarkably enhance the energy density of ZIBs,but are restricted by the unfavorable zinc deposition interface that causes poor cycling stability.Herein,we report a Cu-Zn alloy network-modulated zinc deposition interface to achieve stable anode-free ZIBs.The alloy network can not only stabilize the zinc deposition interface by suppressing 2D diffusion and corrosion reactions but also enhance zinc plating/stripping kinetics by accelerating zinc desolvation and nucleation processes.Consequently,the alloy network-modulated zinc deposition interface realizes high coulombic efficiency of 99.2%and high stability.As proof,Zn//Zn symmetric cells with the alloy network-modulated zinc deposition interface present long operation lifetimes of 1900 h at 1 m A/cm^(2)and 1200 h at 5 m A/cm^(2),significantly superior to Zn//Zn symmetric cells with unmodified zinc deposition interface(whose operation lifetime is shorter than 50 h),and meanwhile,Zn3V3O8cathodebased ZIBs with the alloy network-modified zinc anodes show notably enhanced rate capability and cycling performance than ZIBs with bare zinc anodes.As expected,the alloy network-modulated zinc deposition interface enables anode-free ZIBs with Zn3V3O8cathodes to deliver superior cycling stability,better than most currently-reported anode-free ZIBs.This work provides new thinking in constructing high-performance anode-free ZIBs and promotes the development of ZIBs.

Designing Conformal Electrode-electrolyte Interface by Semi-solid NaK Anode for Sodium Metal Batteries

Solid-state Na metal batteries(SSNBs),known for its low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of NaK alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the intimate contact of electrode-electrolyte interface.Additionally,the filling of SiO_(2)nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 h.The full cell coupled with Na_(3)V_(3)(PO_(4))_(2)cathodes had an initial discharge capacity of 106.8 mAh·g^(-1)with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1)even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.

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.

High-Performance 3D Li-B-C-Al Alloy Anode and its Twofold Li Electrostripping and Plating Mechanism Revealed by Synchrotron X-Ray Tomography

The uncontrollable Li electrostripping and plating process that results in dendritic Li growth and huge volume change of Li anode limits the practicality of Li metal batteries(LMBs).To simultaneously address these issues,designing three-dimensional(3D),lithiophilic and mechanically robust electrodes seems to be one of the cost-effective strategies.Herein,a new 3D Li-B-C-Al alloy anode is designed and fabricated.The prepared 3D alloy anode exhibits not only superior lithiophilicity that facilitates uniform Li nucleation and growth but also sufficient mechanical stability that maintains its structural integrity.Superior performance of the prepared 3D alloy is demonstrated through comprehensive electrochemical tests.In addition,non-destructive and 3D synchrotron X-ray computed tomography(SX-CT)technique is employed to investigate the underlying working mechanisms of the prepared alloy anode.A unique twofold Li electrostripping and plating mechanism under different electrochemical cycling conditions is revealed.Lastly,improved performance of the full cells built with the 3D alloy anode and LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode corroborate its potential application capability.Overall,the current work not only showcases the superiority of the 3D alloy as potential anode material for LMBs but also provides fundamental insights into its underlying working mechanisms that may further propel its research and development.

Effectiveness Evaluation Study of Self-made Zinc Alloy Sacrificial Anode under Chloride Salt Erosion Environment

To investigate the effectiveness of self-made zinc alloy sacrificial anode material for the protection of reinforcement in concrete under chlorine salt erosion environment,salt solution immersion corrosion and electromigration accelerated corrosion tests were used to evaluate the effectiveness of self-made zinc alloy anode with the help of relevant cathodic protection guidelines and evaluation criteria for the corrosion of reinforcement in concrete.The results showed that the protection was effective because the potential of the zinc alloy anode protection steel bar in the salt solution satis?ed the“-780 mV(SCE)”validity criterion.The self-corrosion potential(E_(corr))of the sacri?cial anode protection steel in concrete was greater than-276 mV,and the protective current density of the zinc alloy anode was 1-3μA·cm^(-2),which met the standards of EN12696-2000,further indicating that the self-made zinc alloy sacri?cial anode had a good protection combining with the polarization resistance and the appearance of the corroded surface of the steel in concrete.The microscopic morphology of the corroded surface and the composition of the corrosion products indicates that the mortar of the self-made zinc alloy anode has a lower pH than the imported anodes,so the long-term protection of the selfmade zinc alloy sacri?cial anode needs to be further improved.

Li^(+)Solvation Mediated Interfacial Kinetic of Alloying Matrix for Stable Li Anodes

Severe lithium(Li)dendrite growth caused by the uneven overpotential deposition is a formidable challenge for high energy density Li metal batteries(LMBs).Herein,we investigate a synergetic interfacial kinetic to regulate Li deposition behavior and stabilize Li metal anode.Through constructing Li alloying matrix with a bi-functional silver(Ag)-Li_(3)N blended interface,fast Li^(+)conductivity and high Li affinity can be achieved simultaneously,resulting in both decreased Li nucleation and mass transfercontrolled overpotentials.Beyond these properties,a more important feature is demonstrated herein;that is,the inward diffusion depth of the Li adatoms inside of the Ag site can be restricted by the Li^(+)solvation structure in a highly coordinating environment.The latter feature can ensure the durability of the operational Ag sites,thereby elongating the Li protection ability of the Ag-Li_(3)N interface greatly.This work provides a deep insight into the synergetic effect of functional alloying structure and Li^(+)solvation mediated interfacial kinetic on Li metal protection.

Electrochemical properties of magnesium alloy anodes discharged in seawater

Magnesium alloys can be developed as anode materials for seawater activated batteries. The electrochemical properties of AZ31, AP65 and Mg-3%Ga-2%Hg alloy anodes discharged in seawater were studied. The potentiodynamic polarization shows that the Mg-3%Ga-2%Hg alloy provides more negative corrosion potentials than AZ31 or AP65 alloy. The galvanostatic discharge results show that the Mg-3%Ga-2%Hg alloy exhibits good electrochemical properties as anodes in seawater. And the EIS studies reveal that the magnesium alloy anode/seawater interfacial process is determined by an activation controlled reaction. The Mg3Hg and Mg21Ga5Hg3 phases in Mg-3%Ga-2%Hg alloy improve its electrochemical properties better than the Mg17（Al,Zn）12 phase in AZ31 and Mg（Pb） solid solution phase in AP65 alloys.

Effects of Hg and Ga on microstructures and electrochemical corrosion behaviors of Mg anode alloys

The effects of Hg and Ga on the electrochemical corrosion behaviors of the Mg-2%Hg, Mg-2%Ga and Mg-2%Hg-2%Ga (mass fraction) alloys were investigated by measurements of polarization curves, galvanostatic tests and measurements of electrochemical impedance spectroscopy. Scanning electron microscopy, X-ray diffractometry and energy dispersive spectrometry were employed to characterize the microstructures and the corroded surface of the above alloys. The results demonstrate that the microstructure of the Mg-2%Ga alloy is solid solution and the Mg-2%Hg and Mg-2%Hg-2%Ga alloys have white second-phases at the grain boundaries. The Mg-2%Ga alloy has the worst electrochemical activity and the best corrosion resistance, showing a mean potential of -1.48 V and a corrosion current density of 0.15 mA/cm2. The Mg-2%Hg-2%Ga alloy has the best electrochemical activity and the worst corrosion resistance, showing a mean potential of -1.848 V and a corrosion current density of 2.136 mA/cm2. The activation mechanism of the Mg-Hg-Ga alloy is dissolution-deposition of the Hg and Ga atoms.

A review on anode materials for lithium/sodium-ion batteries

Since lithium-ion batteries(LIBs) have been substantially researched in recent years, they now possess exceptional energy and power densities, making them the most suited energy storage technology for use in developed and developing industries like stationary storage and electric cars, etc. Concerns about the cost and availability of lithium have prompted research into alternatives, such as sodium-ion batteries(SIBs), which use sodium instead of lithium as the charge carrier. This is especially relevant for stationary applications, where the size and weight of battery are less important. The working efficiency and capacity of these batteries are mainly dependent on the anode, cathode, and electrolyte. The anode,which is one of these components, is by far the most important part of the rechargeable battery.Because of its characteristics and its structure, the anode has a tremendous impact on the overall performance of the battery as a whole. Keeping the above in view, in this review we critically reviewed the different types of anodes and their performances studied to date in LIBs and SIBs. The review article is divided into three main sections, namely:(i) intercalation reaction-based anode materials;(ii) alloying reaction-based anode materials;and(iii) conversion reaction-based anode materials, which are further classified into a number of subsections based on the type of material used. In each main section, we have discussed the merits and challenges faced by their particular system. Afterward, a brief summary of the review has been discussed. Finally, the road ahead for better application of Li/Na-ion batteries is discussed, which seems to mainly depend on exploring the innovative materials as anode and on the inoperando characterization of the existing materials for making them more capable in terms of application in rechargeable batteries.

Influence of Mg and Ti on the microstructure and electrochemical performance of aluminum alloy sacrificial anodes

The experiments focused on the influence of magnesium and titanium as additional alloying elements on the microstructure and electro-chemical behavior of Al-Zn-In sacrificial anodes. The electrochemical behavior of the aluminum sacrificial anode with 3 wt.% sodium chloride solution was studied by electrochemical impedance spectroscopy (EIS) tests. It was found that a microstructure with few precipitates and refined grains could be achieved by adding 1 wt.% Mg and 0.05 wt.% Ti to the Al-Zn-In alloy,resulting...

In Situ Reaction Fabrication of a Mixed-Ion/Electron-Conducting Skeleton Toward Stable Lithium Metal Anodes

Lithium metal batteries are emerging as a strong candidate in the future energy storage market due to its extremely high energy density.However,the uncontrollable lithium dendrites and volume change of lithium metal anodes severely hinder its application.In this work,the porous Cu skeleton modified with Cu_(6)Sn_(5)layer is prepared via dealloying brass foil following a facile electroless process.The porous Cu skeleton with large specific surface area and high electronic conductivity effectively reduces the local current density.The Cu_(6)Sn_(5)can react with lithium during the discharge process to form lithiophilic Li_(7)Sn_(2)in situ to promote Li-ions transport and reduce the nucleation energy barrier of lithium to guide the uniform lithium deposition.Therefore,more than 300 cycles at 1 mA cm^(−2)are achieved in the half-cell with an average Coulombic efficiency of 97.5%.The symmetric cell shows a superior cycle life of more than 1000 h at 1 mA cm^(−2)with a small average hysteresis voltage of 16 mV.When coupled with LiFePO_(4)cathode,the full cell also maintains excellent cycling and rate performance.

Review of silicon-based alloys for lithium-ion battery anodes

Silicon(Si)is widely considered to be the most attractive candidate anode material for use in next-generation high-energy-density lithium(Li)-ion batteries(LIBs)because it has a high theoretical gravimetric Li storage capacity,relatively low lithiation voltage,and abundant resources.Consequently,massive efforts have been exerted to improve its electrochemical performance.While some progress in this field has been achieved,a number of severe challenges,such as the element’s large volume change during cycling,low intrinsic electronic conductivity,and poor rate capacity,have yet to be solved.Methods to solve these problems have been attempted via the development of nanosized Si materials.Unfortunately,reviews summarizing the work on Si-based alloys are scarce.Herein,the recent progress related to Si-based alloy anode materials is reviewed.The problems associated with Si anodes and the corresponding strategies used to address these problems are first described.Then,the available Si-based alloys are divided into Si/Li-active and inactive systems,and the characteristics of these systems are discussed.Other special systems are also introduced.Finally,perspectives and future outlooks are provided to enable the wider application of Si-alloy anodes to commercial LIBs.

Surface‑Alloyed Nanoporous Zinc as Reversible and Stable Anodes for High‑Performance Aqueous Zinc‑Ion Battery

Metallic zinc(Zn)is one of the most attractive multivalent-metal anode materials in post-lithium batteries because of its high abundance,low cost and high theoretical capacity.However,it usually suffers from large voltage polarization,low Coulombic efficiency and high propensity for dendritic failure during Zn stripping/plating,hindering the practical application in aqueous rechargeable zinc-metal batteries(AR-ZMBs).Here we demonstrate that anionic surfactant-assisted in situ surface alloying of Cu and Zn remarkably improves Zn reversibility of 3D nanoporous Zn electrodes for potential use as high-performance AR-ZMB anode materials.As a result of the zincophilic ZnxCuy alloy shell guiding uniform Zn deposition with a zero nucleation overpotential and facilitating Zn stripping via the ZnxCuy/Zn galvanic couples,the self-supported nanoporous ZnxCuy/Zn electrodes exhibit superior dendrite-free Zn stripping/plating behaviors in ambient aqueous electrolyte,with ultralow polarizations under current densities up to 50 mA cm^(‒2),exceptional stability for 1900 h and high Zn utilization.This enables AR-ZMB full cells constructed with nanoporous ZnxCuy/Zn anode and K_(z)MnO_(2)cathode to achieve specific energy of as high as~430 Wh kg^(‒1)with~99.8%Coulombic efficiency,and retain~86%after long-term cycles for>700 h.

Microstructure and battery performance of Mg-Zn-Sn alloys as anodes for magnesium-air battery

Four Mg-x Zn-y Sn(x=2,4 and y=1,3 wt.%)alloys are investigated as anode materials for magnesium-air(Mg-air)battery.The self-corrosion and battery discharge behavior of these four Mg-Zn-Sn alloys are analyzed by electrochemical measurements and Mg-air battery tests.The results show that addition of Sn stimulates the electrochemical activity and significantly improves the anodic efficiency and specific capacity of Mg-Zn alloy anodes.Among the four alloy anodes,Mg-2Zn-3Sn(ZT23)shows the best battery discharge performance at low current densities(≤5 m A cm^(-2)),achieving high energy density of 1367 m Wh g^(-1)at 2 mA cm^(-2).After battery discharging,the surface morphology and electrochemical measurement results illustrate that a ZnO and SnO/SnO_(2)mixed film on alloy anode surface decreases self-corrosion and improves anodic efficiency during discharging.The excessive intermetallic phases lead to the failure of passivation films,acting as micro-cathodes to accelerate self-corrosion.

Effect of rolling processing on microstructure and electrochemical properties of high active aluminum alloy anode

The effect of rolling processing on the microstructure,electrochemical property and anti-corrosion property of Al-Mg-Sn-Bi-Ga-In alloy anode in alkaline solution(80℃,Na2SnO3+5 mol/L NaOH)was analyzed by the chronopotentiometry (E-T curves),hydrogen collection tests and modern microstructure analysis.The results show that when the rolling temperature is 370℃,the electrochemical activity of Al anode decreases gradually with the increase of pass deformation in rolling,while the anti-corrosion property is improved in the beginning and then declined rapidly.When the pass deformation of rolling is 40%,the Al anode has good electrochemical activity as good as the anti-corrosion property and with the increase of rolling temperature,both electrochemical activity and anti-corrosion property of Al anode increase first and then decrease.When the rolling temperature is 420 ℃,the aluminum alloy anode has the most negative electrode potential of about-1.521 V(vs Hg/HgO)and the lowest hydrogen evolution rate of 0.171 6 mL/(min·cm2).The optimum comprehensive performance of Al alloy anode is obtained.

Ultrafine nano-scale Cu_(2)Sb alloy confined in three-dimensional porous carbon as an anode for sodium-ion and potassium-ion batteries

Ultrafine nano-scale Cu2Sb alloy confined in a three-dimensional porous carbon was synthesized using NaCl template-assisted vacuum freeze-drying followed by high-temperature sintering and was evaluated as an anode for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs).The alloy exerts excellent cycling durability(the capacity can be maintained at 328.3 mA·h·g^(-1) after 100 cycles for SIBs and 260 mA·h·g^(-1) for PIBs)and rate capability(199 mA·h·g^(-1) at 5 A·g^(-1) for SIBs and 148 mA·h·g^(-1) at 5 A·g^(-1) for PIBs)because of the smooth electron transport path,fast Na/K ion diffusion rate,and restricted volume changes from the synergistic effect of three-dimensional porous carbon networks and the ultrafine bimetallic nanoalloy.This study provides an ingenious design route and a simple preparation method toward exploring a high-property electrode for K-ion and Na-ion batteries,and it also introduces broad application prospects for other electrochemical applications.

STUDY ON KINETICS OF OXYGEN EVOLUTION ON LEAD ALLOY ANODES

A study was carried out on kinetics of oxygen evolution on lead alloy anodes in sulphuric acidicelectrolyte. The influence of alloy elements Ca, Ag and Sn on the overpotential of oxygen evolution was investigated. All anodes had been subjected to a pre-polarization before the measurement of potential-currentcurves for oxygen evolution. The overpotential of oxygen evolution was found to be decreased when the alloyanode contained Ca and Ag, whereas it remained unchanged when the alloy anode contained Sn. For oxygenevolution on lead alloy anodes the TAFEL equation was valid. The b vulue for Ph and Ph-Ca anodes was approx. 100, for Ph-Ag, Ph-Ag-Ca anodes it was approx. 140. The a value for Ph Ca, Ph-Ag, Ph-Ag-Ca anodes decreased with the increase of Ca or/and Ag content. The a and b value was not influenced by Sn in theanodes.

Magnesium alloys as anodes for neutral aqueous magnesium-air batteries

Magnesium(Mg)is abundant,green and low-cost element.Magnesium-air(Mg-air)battery has been used as disposable lighting power supply,emergency and reserve batteries.It is also one of the potential electrical energy storage devices for future electric vehicles(EVs)and portable electronic devices,because of its high theoretical energy density(6.8 k Wh·kg^(-1))and environmental-friendliness.However,the practical application of Mg-air batteries is limited due to the low anodic efficiency of Mg metal anode and sluggish oxygen reduction reaction of air cathode.Mg metal as an anode material is facing two main challenges:high self-corrosion rate and formation of a passivation layer Mg(OH)_(2)which reduces the active surface area.In last decades,a number of Mg alloys,including Mg-Ca,Mg-Zn,commercial Mg-Al-Zn,Mg-Al-Mn,and Mg-Al-Pb alloys,have been studied as anode materials for Mg-air batteries.This article reviews the effect of alloying elements on the battery discharge properties of Mg alloy anodes.The challenges of Mg-air batteries are also discussed,aiming to provide a depth understanding for the theoretical and practical development of high-performance Mg-air batteries.

Stable lithium metal anode enabled by a robust artificial fluorinated hybrid interphase

One of the key challenges for achieving stable lithium(Li) metal anode is the construction of the rational solid electrolyte interphase(SEI),but its realization still faces enormous challenges.In this work,a robust artificial fluorinated hybrid interphase consisting of lithium-bismuth(Li3Bi) alloy and lithium-fluoride(LiF) was designed to regulate Li deposition without Li dendrite growth.The obtained hybrid interphase showed the high Li+diffusion rate(3.5 × 10^(-4)S cm^(-1)),high electron resistivity(9.04 × 10^(4)Ω cm),and high mechanical strength(1348 MPa),thus enabling the uniform Li deposition at the Li/SEI interface.Specifically,Li3Bi alloy,as a superionic conductor,accelerated the Li+transport and stabilized the hybrid interphase.Meanwhile,LiF was identified as a superior electron-blocker to inhibit the electron tunneling from the Li anode into the SEI.As a result,the modified Li anode showed the stable Li plating/stripping behaviors over 1000 cycles even at 20 mA cm^(-2).Moreover,it also enabled the Li(50 μm)‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(4.4 mA h cm^(-2)) full cell to achieve an average Coulombic efficiency(CE) of 99.6%and a high-capacity retention of 79.2% after 100 cycles,whereas the bare Li anode only exhibited a low-capacity retention of 8.0%.This work sheds light on the internal mechanism of Li+transport within the hybrid interface and provides an effective approach to stabilize the interface of Li metal anode.