Electrolyte Modification Research Articles

Bismuth and Fluorine Dual‐Doping of Lithium Argyrodite toward High‐Performance All‐Solid‐State Lithium Metal Batteries

The chlorine‐rich lithium argyrodite is considered a promising superionic conductor electrolyte, but its practical application is limited due to poor air stability and instability toward lithium metal. In this work, BiF3 is proposed as a multi‐functional dopant for electrolyte modification, and the effects on the ionic conductivity, air stability, critical current density, and electrolyte/Li metal interfacial stability are studied. The results show that the doped electrolyte Li5.54P0.98Bi0.02S4.5Cl1.44F0.06 (LPBiSClF0.06) still maintains a relatively high ionic conductivity of 5.37 mS cm−1. Additionally, the formation of BiS45− unit and LiBiS2 phase provides high air/moisture resistibility. Meanwhile, the critical current density of the Li/LPBiSClF0.06/Li cell is increased two‐fold (2.1 mA cm−2). The in‐situ formation of LiF and Li‐Bi alloy at the lithium metal/electrolyte interface plays a key role in achieving high performance. As a result, the assembled LCO@LNO/LPBiSClF0.06/Li battery retains 78.4% of its capacity after 100 cycles at 0.2C.

Imidazolium-based ionic liquids as proton reservoir for stable polyaniline cathode in zinc-iodine batteries

Aqueous zinc (Zn)-iodine (I2) batteries (ZIBs) are promising large-scale energy storage systems with high safety and low cost. However, the practical application of ZIBs is hindered by the dissolution of I3- ions, which leads to the shuttle effect and the loss of active iodine. Herein, we adopt an electrolyte modification strategy using two imidazolium-based ionic liquids (1-butyl-3-methylimidazolium iodide ([BMIM]I) and 1-ethyl-3-methylimidazolium iodide ([EMIM]I)) as electrolyte additives to restrain the dissolution of I3- ions and enhance the performance of ZIBs. To be specific, the imidazole rings in [BMIM]+ and [EMIM]+ can be used as the proton sources, promoting the conversion of imine to protonated amines –NH+= in the polyaniline and subsequent adsorption of I3- ions. Therefore, the dissolution of I3- ions and shuttle effect are prevented, facilitating the reaction kinetics of cathode. As a proof of concept, the ZIB using [BMIM]I and [EMIM]I as electrolyte additives demonstrates remarkable cycling performance (72.2 % capacity retention after 1000 cycles) at a high current density of 20 mA cm−2

Harnessing biological insights: Integrating proton regulation, pH buffer and zincophility for highly stable Zn anode

Zinc anodes are severely threatened by hydrogen evolution, dendrite growth and by-products. Inspired by the mechanisms of L-carnosine (L-car) in maintaining intracellular pH stability and fostering mucosal repair in biological systems, this study innovatively proposed a comprehensive strategy integrating proton regulation, pH buffer and zincophility by introducing L-car as an electrolyte additive to achieve remarkable stability of zinc anode. Experimental validations and theoretical calculations demonstrate that the abundant N and O sites in L-car can form robust hydrogen bonds with protons, effectively impeding interfacial proton transport and substantially mitigating HER. Moreover, dual pH buffering sites of L-car facilitate dynamic modulation of proton concentration, stabilizing the pH of electrolyte, and suppressing Zn corrosion/passivation/by-product. Concurrently, the robust chelation between L-car and Zn2+ orchestrates uniform zinc ion deposition. This synergistic trifecta of L-car endows Zn ion batteries with an extraordinary cycling stability, extending to an ultralong duration of 5500 h. Furthermore, the Zn//MnO2 full battery, demonstrates remarkable stability, retaining a specific capacity of 106.1 mAh/g with 79.2 % retention after 1000 cycles at 3 A/g. This study pioneers the interdisciplinary application of L-car in electrolyte modification, presenting a novel paradigm for stabilizing zinc anodes.

Synchronous Modulation of H-bond Interaction and Steric Hindrance via Bio-molecular Additive Screening in Zn Batteries.

In addressing challenges such as side reaction and dendrite formation, electrolyte modification with bio-molecule sugar species has emerged as a promising avenue for Zn anode stabilization. Nevertheless, considering the structural variability of sugar, a comprehensive screening strategy is meaningful yet remains elusive. Herein, we report the usage of sugar additives as a representative of bio-molecules to develop a screening descriptor based on the modulation of the hydrogen bond component and electron transfer kinetics. It is found that xylo-oligosaccharide (Xos) with the highest H-bond acceptor ratio enables efficient water binding, affording stable Zn/electrolyte interphase to alleviate hydrogen evolution. Meanwhile, sluggish reduction originated from the steric hindrance of Xos contributes to optimized Zn deposition. With such a selected additive in hand, the Zn||ZnVO full cells demonstrate durable operation. This study is anticipated to provide a rational guidance in sugar additive selection for aqueous Zn batteries.

Eliminating Charge Transfer at Cathode-Electrolyte Interface for Ultrafast Kinetics in Na-Ion Batteries.

Sodium-ion batteries suffer from kinetic problems stemming from sluggish ion transport across the electrode-electrolyte interface, causing rapid energy decay during fast-charging or low-temperature operation. One exciting prospect to enhance kinetics is constructing neuron-like electrodes that emulate fast signal transmission in a nervous system. It has been considered that these bioinspired designs enhance electron/ion transport of the electrodes through carbon networks. However, whether they can avoid sluggish charge transfer at the electrode-electrolyte interface remains unknown. By connecting the openings of carbon nanotubes with the surface of carbon-coated Na3V2O2(PO4)2F cathode nanoparticles, here we use carbon nanotubes to trap Na+ ions released from the nanoparticles during charge. Therefore, Na+ movement is confined only inside the neuron-like cathode, eliminating ion transport between the electrolyte and cathode, which has been scarcely achieved in conventional batteries. As a result, a 14-fold reduction in interfacial charge transfer resistance is achieved when compared to unmodified cathodes, leading to superior fast-charging performance and excellent cyclability up to 200C, and surprisingly, reversible operation at low temperatures down to -60 °C without electrolyte modification, surpassing other Na3V2O2(PO4)2F-based batteries reported to date. As battery operation has relied on charge transfer at the electrode-electrolyte interface for over 200 years, our approach departs from this traditional ion transport paradigm, paving the way for building better batteries that work under harsh conditions.

Advancements in Graphite Anodes for Lithium‐Ion and Sodium‐Ion Batteries: A Review

Amidst the escalating global energy demand and the rapid advancement of renewable energy technologies, battery technology plays an indispensable role in energy storage. As a crucial anode material, Graphite enhances performance with significant economic and environmental benefits. This review provides an overview of recent advancements in the modification techniques for graphite materials utilized in lithium‐ion and sodium‐ion batteries. This review initially presents various modification approaches for graphite materials in lithium‐ion batteries, such as electrolyte modification, interfacial engineering, purification and morphological modification, composite modification, surface modification, and structural modification, while also addressing the applications and challenges of graphite anode materials

Descriptors for Electrochemical CO2 Reduction in Imidazolium-Based Electrolytes.

Electrochemical CO2 reduction (CO2R) allows us to close the carbon cycle and store intermittent renewable energy into chemical products. Among these, syngas, a mixture of hydrogen and carbon monoxide, is particularly valuable due to its high market share and the low energy required for its electrocatalytic production. In addition to catalyst optimization, lately, electrolyte modifications to achieve a suitable CO/H2 ratio have also been considered. Ionic liquid (IL)-based electrolytes have enabled high faradaic efficiency toward CO, depending on the chemical properties of the IL. In this work, we rationalized through density functional theory (DFT) descriptors the competition between hydrogen evolution (HER) and CO2R on silver in imidazolium-based electrolytes, developing a DFT-based analytical model. The electrolyte anion regulates the concentration ratio between cationic and carbene species of ILs cation, respectively, between the 1-ethyl-3-methylimidazolium cation (EMIM+) and carbene (EMIM:) species and between the 1-butyl-3-methylimidazolium cation (BMIM+) and carbene (BMIM:). The latter species, if formed, hinders the CO2R by blocking the active sites or trapping CO2 in solution. In the case of weak Lewis base anions as fluorinated ones, EMIM+ (BMIM+) cations, which serve as cocatalysts in CO2R, are more abundant, allowing high CO partial current densities and high electrochemically active surface area. Applying the here-defined descriptors to ILs not yet tested makes it possible to predict the HER and CO2R selectivity on silver, thus enabling guidelines for designing better ILs for CO2R.

Revealing the Dynamic Evolution of Electrolyte Configuration on the Cathode‐Electrolyte Interface by Visualizing (De) Solvation Processes

AbstractElectrolyte engineering is crucial for improving cathode electrolyte interphase (CEI) to enhance the performance of lithium‐ion batteries, especially at high charging cut‐off voltages. However, typical electrolyte modification strategies always focus on the solvation structure in the bulk region, but consistently neglect the dynamic evolution of electrolyte solvation configuration at the cathode‐electrolyte interface, which directly influences the CEI construction. Herein, we reveal an anti‐synergy effect between Li+‐solvation and interfacial electric field by visualizing the dynamic evolution of electrolyte solvation configuration at the cathode‐electrolyte interface, which determines the concentration of interfacial solvated‐Li+. The Li+ solvation in the charging process facilitates the construction of a concentrated (Li+‐solvent/anion‐rich) interface and anion‐derived CEI, while the repulsive force derived from interfacial electric field induces the formation of a diluted (solvent‐rich) interface and solvent‐derived CEI. Modifying the electrochemical protocols and electrolyte formulation, we regulate the “inflection voltage” arising from the anti‐synergy effect and prolong the lifetime of the concentrated interface, which further improves the functionality of CEI architecture.

Effect of Inorganic Additive Strategy on the Stability of in Vanadium Redox Flow Battery Electrolyte by Molecular Dynamics.

Inorganic ions are considered to be effective additives to improve the temperature stability of all-vanadium redox flow batteries. In this study, molecular dynamics simulation has been performed to study the solvation structure and dynamic properties of VO2+ in the positive electrolyte by doping Na+, K+, and NH4+ in the presence of V2O5 precipitation. The results show that VO2+ ions aggregate into chainlike clusters in the electrolyte due to the induction of SO42-. The additives, which are stable in the solvation layers of VO2+, can work as protective shells to inhibit cluster growth. NH4+ is a superior dispersant compared with Na+ and K+ as it can stably exist in both the first solvation layer and the second solvation layer of VO2+. This work performed the molecular dynamics simulation of the electrolyte of vanadium redox flow batteries, and it gives some insights into the theoretical study of the modification of the cathode electrolyte.

Composite electrochemical coatings of Ni-CrB2 from sulfuric acid and sulfamate electrolytes: formation, structure and properties

Electrodeposited coatings are in demand in many industries: due to the high adhesive strength to the base metal, they can be applied to complex-shaped products, and the thickness of the deposited coating can be controlled. However, standard electrolytic coatings do not always meet the necessary operating requirements. In this case, the formation of composite electrolytic coatings, which consist in the modification of electrolytes by various dispersed particles, becomes an urgent task. These particles are introduced into the electrolyte and deposited together with the precipitate metals, which leads to changes in the coating properties. In this article, the structure, adhesive and corrosion properties of nickel-chromium diboride composite coatings obtained in the electrodeposition process are studied. Precipitation was carried out in sulfuric acid and sulfamate electrolytes with a concentration of dispersed chromium diboride particles of 10-40 g/l. The coatings consist of nickel and CrB2 phases. The adhesive strength of the coating with a steel base is satisfactory; chipping and peeling were not observed. The corrosion resistance of sulfamate electrolyte coatings is higher than that of the coatings obtained from sulfuric acid electrolyte due to the compactness of nickel precipitates. Chromium diboride in the coating provides 1.5-2 times greater corrosion resistance.

In-depth exploration of the interface mechanism of aqueous ammonium-ion batteries with ionic liquids

Aqueous ammonium-ion batteries have emerged as a research focus in recent years because of their distinctive advantages. Nevertheless, issues such as the side reaction of water, electrode element dissolution and others have an impact on their stability. The experimental findings demonstrate that the system incorporating ionic liquids (ILs) exhibits gratifying electrochemical performance. The Molecular Dynamics (MD) simulation approach was employed to investigate the alterations of NH4Cl aqueous batteries prior to and subsequent to the addition of imidazolium ionic liquids (ILs), with a focus on the impact on the anode's interface. It is found that the addition of ILs can reduce the interfacial water’s content at low charge. Interestingly, in the case of high charge, the water content at the interface didn’t decrease; instead, it increased. This phenomenon is associated with the initial increase followed by a decrease in the number of ionic liquid (IL) cations. Three conformations for IL cations were found near the interface, which are “parallel”, “slant” and “vertical”, and the proportion of the three had a certain influence on the content of interfacial water. The "parallel" configuration is more effective in reducing the interfacial water content, establishing it as the dominant conformation. The findings reported above will offer new theoretical support for the design and modification of aqueous ammonium ion electrolytes.

Covalent Organic Frameworks Interfacial Modification of Ceramic Electrolytes for Enhanced Electrochemical Performance

AbstractThe interface instability between inorganic ceramic electrolytes and lithium metal anodes seriously affects the cycling behavior of high‐performance lithium‐metal batteries. Herein, an in situ interfacial modification strategy is proposed to build the precise hybrid organic/inorganic lithium‐ion conducting layer where the Li1.3Al0.3Ti1.7(PO4)3 (LATP) particle surface is anchored by ion‐conducting covalent organic frameworks (COF) with affluent poly(ethylene glycol) (PEG) moieties. This interlayer features ion transport regulation to avoid high interfacial resistance and enhances interfacial stability by building a functional COF‐based shield against electrons. These as‐prepared particles are employed to fabricate flexible quasi‐solid electrolyte membranes interconnected by polytetrafluoroethylene binder based on the dry process. The obtained membranes perform two‐fold increase in ion conductivity at 30 °C of 2.55 × 10−3 S cm−1 and the prolonged lithium deposition up to 1000 h compared to the pristine, which are attributed to synergistic effects in the inorganic/organic phase. Moreover, an integrated cathode/electrolytes design is proposed and exhibits excellent cycling performance with capacity retention of 98.8% after 200 cycles at 1 C. The corresponding pouch cells can light up LED after bending and recovery. This research provides new insights into the great potential of fabricating soft ceramic‐based membranes in a low‐cost and green way for highly‐stable lithium‐metal batteries.

Interfacial challenges and recent advances of solid‐state lithium metal batteries

AbstractGrowing market demands on portable electronics, electric vehicles, and energy storage system calls for the development of high‐energy density lithium (Li) batteries. Li metal is considered as a promising anode material owing to their high capacity and low electrochemical potential. However, high reactivity of Li metal with conventional flammable liquid electrolytes easily forms Li dendrites, which may cause short‐circuit and even catching fire, obstructing the wide application of Li metal batteries. Although non−/less‐flammable solid electrolytes have replaced the conventional liquid electrolytes, solid‐state Li metal batteries (SSLMBs) suffer from lower Li+ conductivities, chemical/electrochemical incompatibilities toward Li metal, and inhomogeneous Li+ flux at the interfaces. Therefore, many researchers have devoted themselves to solve these problems. For a better understanding on the current issues and recent advances, this article provides (1) a review on various solid electrolytes with high Li+ conductivity and their interfacial issues in SSLMBs, and (2) recent progress in stabilization of the interface between the Li node and solid electrolytes, including an electrolyte modification (e.g., composition, additives) and introduction of an interlayer.

Enhancing the performance of LiNi0.8Mn0.1Co0.1O2-based pouch cells through advanced electrolyte additive systems for high-temperature lithium-ion batteries

Next-generation lithium-ion batteries, which achieve high energy densities and prolonged cycle performance, require cathode materials with high operating voltages and specific capacities. Because of their high capacity and operating voltage, nickel-rich layered oxides like LiNi0.8Mn0.1Co0.1O2 (NMC811) are attractive cathodes; nevertheless, they have drawbacks such capacity loss, poor cycle performance, structural instability, and thermal instability. Enhancing the stability of the NMC811 cathode-electrolyte interphase demands improvements in both cathode materials and electrolytes. This study explores the enhancement of NMC811-based battery systems through electrolyte modification, focusing on mixed additive combinations to evaluate their synergistic effects at elevated temperatures, relevant for tropical climates. A ternary additive system comprising vinylene carbonate (VC), lithium difluorophosphate (LiPO2F2), and p-toluenesulfonyl isocyanate (PTSI) in a LiPF6-based electrolyte showed significant improvements. This system mitigated capacity fading for cells cycled over 3 V–4.2 V at both 25 °C and 45 °C, outperforming the baseline electrolyte. The designed electrolyte stabilized the electrode-electrolyte interface, enhancing cell performance and the cathode's structural integrity. Notably, the graphite/NMC811 pouch cell's cycling performance showed an increase in capacity retention from 82.4% to 90.2% after 150 cycles at C/2 at 45 °C. Moreover, the deactivation of PF5 by PTSI can help to suppress the side reaction from the instability of LiPF6-based electrolytes, especially at elevated temperatures. These findings carried out from this strategic electrolyte additive system can substantially improve nickel-rich LIBs, especially in challenging thermal environments.

Toward Practical Li–S Batteries: On the Road to a New Electrolyte

AbstractThe lithium–sulfur (Li–S) battery system has attracted considerable attention due to its ultrahigh theoretical energy density and promising applications. However, with the increasing demands on S loading and electrolyte content, practical Li–S batteries still face several serious challenges, such as slow reaction kinetics at the cathode interface, unstable anode interface reactions, and undesirable crosstalk effects between the cathode and anode. Traditional electrolyte systems often struggle to address these challenges under practical conditions, thereby rendering it imperative to establish a new electrolyte system for practical Li–S batteries. This review first discusses the necessity of establishing a new electrolyte and propose specific parameter requirements, such as the electrolyte‐to‐sulfur mass ratio (Em/S). Subsequently, some electrolyte modification strategies proposed by researchers are summarized to address the different challenges associated with practical Li–S batteries. Finally, the combination of different strategies is reviewed, aiming to reveal more effective design approaches that simultaneously address multiple challenges, while providing guidance for establishing a new balanced electrolyte for practical Li–S batteries. This article promotes the development of new electrolytes for practical Li–S batteries and can act as a reference for the development of electrolytes for other secondary batteries.

Achievement of advanced alkaline Ni-Zn batteries with good durability at a high areal capacity of 10 mAh cm−2 via the synergistic regulation of dual electrolyte additives

Though obvious advantages in terms of safety, cost, environmental compatibility and electrochemical performance (e.g, power and energy density), the commercial application of alkaline Ni-Zn batteries, a number of traditional aqueous batteries, is still under great restrictions owing to the poor durability (commonly less than 100 cycles). In this work, an effective electrolyte modification process using dual additives of hydroxy-rich carboxymethyl cellulose (CMC) that can inhibit hydrogen evolution reaction (HER) and suppress Zn dendrites, and benzyltrimethylammonium bromide (BTMAB) that can mitigate passivation and oxygen evolution reaction (OER) is developed. Meanwhile, our home made C coated ZnO (ZnO@C) microspheres were used as initial anode materials without the using of any other expensive composites. With a fixed areal charge capacity of 10 mAh cm−2, the flat type full cell matched with commercial Ni(OH)2 cathode can deliver a high average discharge capacity of ∼9.6 mAh cm−2 (corresponding to an average CE of 96 %) for a long lifespan of over 390 cycles, which drops to 8.2 mAh cm−2 at 400th cycle accompanied by the appearance of a peak in the charge curve. The cumulative discharge capacity of a full cell can reach ∼4,000 mAh cm−2 in 420 cycles’ cycling, much larger than that using commercial Zn/ZnO anode and the ZnO@C anode in unmodified or single additive modified electrolyte (less than 1,500 mAh cm−2).

"Water-in-Salt" Electrolyte Suppressed MnVOPO4·2H2O Cathode Dissolution for Stable High-Voltage Platform and Cycling Performance for Aqueous Zinc Metal Battery.

Vanadium-based materials have the advantages of abundant valence states and stable structures, having great application potential as cathode materials in metal-ion batteries. However, their low voltage and vanadium dissolution in traditional water-based electrolytes greatly limit their application and development in aqueous zinc metal batteries (AZMBs). Herein, phosphate- and vanadium-based cathode materials (MnVOPO4·2H2O) with stacked layers and few defects were prepared via a condensation reflux method and then combined with a high-concentration electrolyte (21 m LiTFSI + 1 M Zn(CF3SO3)2) to address these limitations. The specific capacity and cycle stability accompanying the stable high voltage of 1.39 V were significantly enhanced compared with those for the traditional electrolyte of 3 M Zn(CF3SO3)2, benefiting from the suppressed vanadium dissolution. The cathode materials of MnVOPO4·2H2O achieved a high specific capacity of 152 mAh g-1 at 0.2 A g-1, with a retention rate of 86% after 100 cycles for AZMBs. A high energy density of 211.78 Wh kg-1 was also achieved. This strategy could illuminate the significance of electrolyte modification and provide potential high-voltage cathode materials for AZMBs and other rechargeable batteries.

Promoting Preferential Zn (002) Deposition with a Low-Concentration Electrolyte Additive for Highly Reversible Zn-Ion Batteries.

Aqueous zinc-ion batteries have promising potential as energy storage devices due to their low cost and environmental friendliness. However, their development has been hindered by zinc dendrite formation and parasitic side reactions. Herein, we introduce a low-concentration sodium benzoate (NaBZ) electrolyte additive to stabilize the electrode-electrolyte interface and promote deposition on the Zn (002) crystal plane. From experimental characterization and computational analyses, NaBZ was found to adsorb on the Zn surface and inhibit side reactions while guiding homogeneous Zn deposition on the (002) plane. Consequently, Zn|Zn symmetric cells with the NaBZ additive cycled stably for over 1000 h at a current density of 0.5 mA cm-2 and an areal capacity of 0.5 mAh cm-2, while Zn|Cu cells showed excellent reversibility with a Coulombic efficiency of 99.05%. Moreover, Zn|Na0.33V2O5 full cells achieve a high specific capacity of 124 mAh g-1 while cycling for 600 h at 2 A g-1. These findings present a low-cost electrolyte modification strategy for reversible zinc-ion batteries.

Cation Adsorption Engineering Enables Dual Stabilizations for Fast‐Charging Zn─I2 Batteries

AbstractAqueous zinc‐iodine (Zn─I2) battery is a promising energy storage system due to its inherent safety, high theoretical capacity, sustainability, and cost‐effectiveness. However, the shuttle effect of polyiodide severely affects the stable loading of active iodine and even accelerates the corrosion of the Zn anode, thus impeding its further advancement. Herein, a unique trimethylsulfonium cation (TMS+) with strong adsorption is proposed to stabilize both the iodine cathode and Zn anode. Benefiting from the robust interaction between TMS+ and polyiodide, the electrolyte can effectively immobilize large‐capacity iodine in the form of oily precipitate, thus avoiding the shuttle effect of polyiodide and the Zn corrosion. Additionally, TMS+ can be preferentially adsorbed on various Zn facets, inducing an electrostatic shielding effect to inhibit Zn dendrite growth. Consequently, Zn anode can be stably cycled over 3400 h at 5 mA cm−2/5 mAh cm−2, and a large areal capacity of 2.71 mAh cm−2 as well as long‐life stability over 6400 cycles is achieved for Zn─I2 battery. Furthermore, cation adsorption engineering is practically utilized in pouch cells, realizing superior fast‐charging stability over 790 cycles. This electrolyte modification with dual stabilizations is anticipated to be applied to other metal‐iodine batteries as a cost‐effective, facile, and safe strategy.

Panthenol Additives with Multiple Coordination Sites Induce Uniform Zinc Deposition and Inhibited Side Reactions for High Performance Aqueous Zinc Metal Battery.

Application of aqueous zinc metal batteries (AZMBs) in large-scale new energy systems (NESs) is challenging owing to the growth of dendrites and frequent side reactions. Here, this study proposes the use of Panthenol (PB) as an electrolyte additive in AZMBs to achieve highly reversible zinc plating/stripping processes and suppressed side reactions. The PB structure is rich in polar groups, which led to the formation of a strong hydrogen bonding network of PB-H2O, while the PB molecule also builds a multi-coordination solvated structure, which inhibits water activity and reduces side reactions. Simultaneously, PB and OTF- decomposition, in situ formation of SEI layer with stable organic-inorganic hybrid ZnF2-ZnS interphase on Zn anode electrode, can inhibit water penetration into Zn and homogenize the Zn2+ plating. The effect of the thickness of the SEI layer on the deposition of Zn ions in the battery is also investigated. Hence, this comprehensive regulation strategy contributes to a long cycle life of 2300h for Zn//Zn cells assembled with electrolytes containing PB additives. And the assembled Zn//NH4V4O10 pouch cells with homemade modules exhibit stable cycling performance and high capacity retention. Therefore, the proposed electrolyte modification strategy provides new ideas for AZMBs and other metal batteries.