Next-generation Battery Technologies Research Articles

Functional Polymer Materials for Advanced Lithium Metal Batteries: A Review and Perspective.

Lithium metal batteries (LMBs) are promising next-generation battery technologies with high energy densities. However, lithium dendrite growth during charge/discharge results in severe safety issues and poor cycling performance, which hinders their wide applications. The rational design and application of functional polymer materials in LMBs are of crucial importance to boost their electrochemical performances, especially the cycling stability. In this review, recent advances of advanced polymer materials are examined for boosting the stability and cycle life of LMBs as different components including artificial solid electrolyte interface (SEI) and functional interlayers between the separator and lithium metal anode. Thereafter, the research progress in the design of advanced polymer electrolytes will be analyzed for LMBs. At last, the major challenges and key perspectives will be discussed for the future development of functional polymers in LMBs.

Unexpected pressure effects on sulfide-based polymer-in-ceramic solid electrolytes for all-solid-state batteries

Among the next-generation battery technologies, all-solid-state lithium batteries (ASLBs) are the most attractive because of the high safety and high energy density. The critical difference between ASLBs and conventional lithium-ion batteries (LIBs) is the replacement of the liquid electrolyte with a solid electrolyte (SE). Thus, for battery development, the investigation of ionic conductivities of SEs is essential. Sulfide-type ion conductors are representative SEs having high ionic conductivities and are ductile. However, sulfide-type SEs suffers from H2S gas release and degradation when exposed to the moisture in the air, and, as a result, the study and optimization of the fabrication parameters is challenging. In this study, we fabricated a polymer-in-ceramic SE as a thin, large-area, free-standing SE. Crucially, to optimize the fabrication conditions, we used a model inorganic particles that do not suffer from the moisture sensitivity typical of sulfide-based SEs. Interestingly, the ionic conductivity of the polymer-in-ceramic SE changed with applied pressure, behavior unlike that of a conventional pellet-type SEs prepared from sulfide powders. To understand this phenomenon, we carried out digital twinned 3D structure simulation analysis, which revealed changes in the specific contact area and distribution of ionic density in the polymer-in-ceramic SE. As a result, we propose a model composition that will facilitate the exploration of polymer-in-ceramic SEs and their characteristics and, thus, enhance the practical use of ASLBs.

A high power density solid electrolyte based on polycaprolactone for high-performance all-solid-state flexible lithium batteries

All-solid-state lithium batteries (ASSLBs) have been regarded as the next-generation battery technology owing to the superiority of safety, potentially high enetgy density and long cycling life. However, the slow charging limitations of ASSLBs hinder their practical applications. To tackle this issue, composite polymer electrolytes (CPEs) based on polycaprolactone (PCL) are developed to achieve satisfactroy enhancements for charging/discharging performances of ASSLBs. The addition of ceramic powder in PCL-based CPEs suppresses the crystallization of PCL and at the same time enhances the Li-ion transport behaivor. The present ASSLBs within PCL-based CPEs display excellent cycling performance with the initial discharge specific capacity of 108.2 mAh g-1, as well as good capacity retention of 75% after 500 cycles at a current density of 2 C at 55 °C. The high performance of ASSLBs is attributed to the high Li-ion transference number of 0.8 and excellent interfacial stability and wettability originated from the addition of ceramic components. It is demonstated that the PCL-based CPEs exhibit high Young's Modulus (2.8 GPa) and to the long-term cycling stability of ASSLBs. This study opens up new possibilities for the development of fast-charging batteries with an emphasis on the design of new polymer electrolytes.

Superionic Conduction in One-Dimensional Nanostructures.

Nanostructuring has become a powerful tool for tuning the electronic properties of materials and enhancing transport. As an example of relevance to next-generation battery technologies, nanocrystals have shown promise for realizing fast-ion conduction in solids; however, dissipationless ion transport over extended length scales is hindered by lossy interfaces formed between nanocrystals in a solid. Here we address this challenge by exploiting one-dimensional nanostructures for ion transport. Superionic conduction, with a record-high ionic conductivity of ∼4 S/cm at 150 °C, is demonstrated in solid electrolytes fabricated from nanowires of the earth-abundant solid copper selenide. This quasi-one-dimensional ionic conductivity is ∼5× higher than that in bulk cuprous selenide. Nanoscale dimensions in the radial direction lower ion-hopping barriers, while mesoscopically long, interface-free transport paths are available for ion transport in the axial direction. One-dimensional nanostructures can exceptionally boost solid-state devices that rely on ion transport.

Electrolyte Role on the Thermal Runaway Characteristics of LFP Chemistry

Lithium-ion batteries have become the power source of choice in grid storage applications and electric powertrains, given its high energy density and extended cycle life. However, lithium-ion batteries carry significant safety risks and are a growing hazard due to thermal runaway that can be caused by overheating, cell deformation, overcharging and short-circuits. It is well understood that thermal runaway occurs when the self-heating rate in the cell exceeds the heat dissipation out of the cell. This self-heating is the product of undesired side-reactions in the cell, such as SEI decomposition or oxygen evolution from the cathode, triggered by abuse conditions that then result in thermal runaway. The key to inhibiting thermal runaway is to modify the cell such that the self-heating rate under abuse conditions is significantly reduced.These risks are believed to be mitigated by compromising energy density with safety through the choice of lithium iron phosphate (LFP) as the cathode. LFP is known to demonstrate lower rates of self-heating and achieve lower maximum temperatures during thermal runaway relative to mixed metal oxide cathodes (NMCs). LFP has other reported advantages over NMCs, such as superior cycle life, rate capability, no questionably sourced metals, and significantly lower cost. However, the safety aspect of LFP is only relative to their less stable metal oxide competitors, as LFP cells are still known to evolve oxygen and enter thermal runaway, particularly in larger cells and packs. This concern will increase in the near future as the next obvious battery design choice will be to pair LFP with silicon dominant anodes or lithium metal to create cells with energy densities on par with conventional metal oxide chemistries. There is a need to reduce cell self-heating without further compromising energy density. Therefore our approach is to modify the electrolyte system to reduce the overall cell self-heating rate. This is a tunable, drop-in solution to addressing the need for improving battery safety.We report an alternative electrolyte design to improve the robustness of the SEI and overall stability of the electrolyte system, which carries significance in improving cycle life and abuse tolerance in LFP chemistries in both conventional graphite and silicon-dominant anodes. These electrode pairings are investigated in coin cells, 2 Ah and 30 Ah pouch cells. The choice of electrolyte formulation is shown to impact the abuse tolerance of cells on both the material level, i.e. the electrolyte-electrode interaction and on the cell level.We evaluate the thermal profiles of delithiated LFP paired with lithiated graphite and silicon combined with electrolyte via differential scanning calorimetry (DSC). Our findings suggest that the primary driver of thermal instability in LFP systems arises from the anode in both graphite as well as silicon. The presented electrolyte systems demonstrate reduced overall energy and peak heat flow in the thermal profiles. These findings correlate electrolyte choice with lower self-heating rates in an accelerating rate calorimeter (ARC) heat-wait-seek test on LFP pouch cells. This approach carries significance in not just safer cells but also in enabling next-generation lithium-ion battery technology premised on low-cost cobalt-free cathodes.

A high-voltage and stable zinc-air battery enabled by dual-hydrophobic-induced proton shuttle shielding

<h2>Summary</h2> Rechargeable zinc-air batteries (ZABs) stand out among next-generation battery technologies due to their high energy density and high safety but suffer from electrochemical irreversibility. Herein, we report a hybrid ZAB with a long lifespan and high working voltage; it uses a neutral anolyte, an acidic catholyte, and a proton-shuttle-shielding dual-hydrophobic membrane to isolate the two electrolytes. The hybrid ZAB operates through the stable electrochemical plating and stripping of zinc (Zn) in a neutral anolyte and a high-voltage O₂ redox reaction in acidic catholyte. The designed proton-shuttle-shielding dual-hydrophobic membrane selectively transports hydrophobic bis(trifluoromethylsulfonyl)imide anions (TFSI⁻) and effectively avoids the crossover of protons. As a result, the hybrid ZAB exhibits a high working voltage (1.50 V) and stable operation (up to 2,000.0 h) in ambient air. This strategy not only overcomes the severe irreversibility of conventional ZABs but also promotes development of electrolyte-decoupled systems.

Cardanol-Derived Epoxy Resins as Biobased Gel Polymer Electrolytes for Potassium-Ion Conduction.

In this study, biobased gel polymer electrolyte (GPE) membranes were developed via the esterification reaction of a cardanol-based epoxy resin with glutaric anhydride, succinic anhydride, and hexahydro-4-methylphthalic anhydride. Nonisothermal differential scanning calorimetry was used to assess the optimal curing time and temperature of the formulations, evidencing a process activation energy of ∼65–70 kJ mol–1. A rubbery plateau modulus of 0.65–0.78 MPa and a crosslinking density of 2 × 10–4 mol cm–3 were found through dynamic mechanical analysis. Based on these characteristics, such biobased membranes were tested for applicability as GPEs for potassium-ion batteries (KIBs), showing an excellent electrochemical stability toward potassium metal in the −0.2–5 V voltage range and suitable ionic conductivity (10–3 S cm–1) at room temperature. This study demonstrates the practical viability of these biobased materials as efficient GPEs for the fabrication of KIBs, paving the path to increased sustainability in the field of next-generation battery technologies.

Recent progress in the development of glass and glass-ceramic cathode/solid electrolyte materials for next-generation high capacity all-solid-state sodium-ion batteries: A review

The lithium-ion battery (LIB) has been the dominant technology in the rechargeable energy storage market for more than twenty years. However, to meet the increasing need for electric vehicles, stationary electricity storage, and portable electronics, there is an emerging demand for alternative battery technologies. One promising candidate is an all-solid-state sodium-ion battery (ASSSIB) that can provide high power density with good safety and cycle durability, making it a potential next-generation battery technology. Recently the development of glass and glass-ceramic cathode/solid electrolytes showed specific interest in developing all-solid-state sodium-ion batteries (ASSIBs) due to optimization of their crystalline structure for fast Na+ ion diffusion, high cycle performance, excellent thermal stability, high electronic and ionic conductivity. Until now, there are no reports on the research progress in the development of ASSIBs based on glass or glass-ceramic cathode/solid electrolyte. The challenges and opportunities associated with these glass and glass-ceramic systems are reviewed in this paper. In addition, this review will focus on a better understanding of glass and glass-ceramic electrode and electrolyte materials for used to development of ASSIBs.

Carmakers invest in next-generation battery technology

Carmakers invest in next-generation battery technology

Mitigating Interfacial Mismatch between Lithium Metal and Garnet-Type Solid Electrolyte by Depositing Metal Nitride Lithiophilic Interlayer.

Solid-state lithium batteries are generally considered as the next-generation battery technology that benefits from inherent nonflammable solid electrolytes and safe harnessing of high-capacity lithium metal. Among various solid-electrolyte candidates, cubic garnet-type Li7La3Zr2O12 ceramics hold superiority due to their high ionic conductivity (10–3 to 10–4 S cm−1) and good chemical stability against lithium metal. However, practical deployment of solid-state batteries based on such garnet-type materials has been constrained by poor interfacing between lithium and garnet that displays high impedance and uneven current distribution. Herein, we propose a facile and effective strategy to significantly reduce this interfacial mismatch by modifying the surface of such garnet-type solid electrolyte with a thin layer of silicon nitride (Si3N4). This interfacial layer ensures an intimate contact with lithium due to its lithiophilic nature and formation of an intermediate lithium–metal alloy. The interfacial resistance experiences an exponential drop from 1197 to 84.5 Ω cm2. Lithium symmetrical cells with Si3N4-modified garnet exhibited low overpotential and long-term stable plating/stripping cycles at room temperature compared to bare garnet. Furthermore, a hybrid solid-state battery with Si3N4-modified garnet sandwiched between lithium metal anode and LiFePO4 cathode was demonstrated to operate with high cycling efficiency, excellent rate capability, and good electrochemical stability. This work represents a significant advancement toward use of garnet solid electrolytes in lithium metal batteries for the next-generation energy storage devices.

An industrial pathway to emerging presodiation strategies for increasing the reversible ions in sodium-ion batteries and capacitors

Sodium-ion batteries (SIBs) and capacitors (SICs) have been drawing considerable interest in recent years and are considered two of the most promising candidates for next-generation battery technologies in the energy storage industry. Therefore, it is essential to explore feasible strategies to increase the energy density and cycling lifespan of these technologies for their future commercialization. However, relatively low Coulombic efficiency severely limits the energy density of sodium-ion full cells, particularly in the initial cycle, which gradually decreases the number of recyclable ions. Presodiation techniques are regarded as effective approaches to counteract the irreversible capacity in the initial cycle and boost the energy density of SIBs and SICs. Their cyclic stability can also be enhanced by the slow release of supplemental sodium and high-content recyclable ions during cycling. In this review, a general understanding of the sodium-ion loss pathways and presodiation process towards full cells with high Coulombic efficiency is summarized. From the perspectives of safety, operability and efficiency, the merits and drawbacks of various presodiation techniques are evaluated. This review attempts to provide a fundamental understanding of presodiation principles and strategies to promote the industrial development of SIBs and SICs.

Battery partnerships surge

Several partnerships to develop next-generation battery technology have been announced as the race intensifies to increase electric vehicle battery performance and reduce production costs. Woburn, Massachusetts–based Factorial Energy, one of C&EN’s 10 Start-Ups to Watch in 2021 , has formed partnerships with the automakers Mercedes-Benz and Stellantis, both of which are investing in Factorial. The start-up develops solid-electrolyte lithium-ion batteries that are highly energy dense. “With Factorial as our new partner, we are taking research and development in the field of promising solid-state batteries to the next level,” Markus Schäfer, board member of Daimler and Mercedes-Benz, says in a press release announcing the deal . “We are investing a high double-digit million dollar amount in Factorial.” Factorial claims its battery offers 20–50% greater range per charge while remaining cost competitive with conventional lithium-ion batteries. The engine manufacturer Cummins has formed a partnership with Sion Power, a Tucson, Arizona–based developer of

Development and Progression of Polymer Electrolytes for Batteries: Influence of Structure and Chemistry.

Polymer electrolytes continue to offer the opportunity for safer, high-performing next-generation battery technology. The benefits of a polymeric electrolyte system lie in its ease of processing and flexibility, while ion transport and mechanical strength have been highlighted for improvement. This report discusses how factors, specifically the chemistry and structure of the polymers, have driven the progression of these materials from the early days of PEO. The introduction of ionic polymers has led to advances in ionic conductivity while the use of block copolymers has also increased the mechanical properties and provided more flexibility in solid polymer electrolyte development. The combination of these two, ionic block copolymer materials, are still in their early stages but offer exciting possibilities for the future of this field.

Achieving a Stable Solid Electrolyte Interphase and Enhanced Thermal Stability by a Dual-Functional Electrolyte Additive toward a High-Loading LiNi0.8Mn0.1Co0.1O2 /Lithium Pouch Battery.

Li metal batteries with high-capacity cathodes emerge as promising candidates for next-generation battery technologies. However, the poor reversibility of the Li deposition/stripping process severely reduces its lifespan, and safety also remains a major issue for the Li metal anodes. Herein, we propose (ethoxy)-penta-fluoro-cyclo-triphosphazene (DFA) as a dual-functional electrolyte additive to solve the engineering problem of balancing the cycle life and thermal stability of Li metal batteries. The NCM811/lithium metal pouch batteries (2900 mA h) are assembled using the commercial high areal capacity cathode (3.5 mA h cm-2). Compared with the NCM811/Li batteries without DFA, the heat generation and heat generation power of lithium metal batteries with DFA are significantly reduced by half during charging. Moreover, the NCM811/Li pouch batteries with DFA show excellent stability in both hot-oven and adiabatic rate calorimeter experiments. Furthermore, a nonlinear phase field simulation is carried out for mechanism investigation, which confirms that the stable solid electrolyte interphase formed by DFA will improve the cycle life of the NCM811/Li pouch. The DFA is verified to be an effective additive to improve the cycle stability and safety simultaneously, providing new opportunities for developing high energy density Li metal batteries.

Asymmetric Impact of External Pressure on Li/Solid-Electrolyte Interfacial Stability

All solid-state batteries (SSB) have attracted a lot of attention as next-generation battery technology with exceptional potential to achieve high energy density, high safety and low cost. Despite development of a wide range of new solid electrolytes, poor interfacial stability within SSB is limiting its success as it leads to poor power density, low coulombic efficiency and short cycle life. Although there is adequate progress in Li/solid electrolyte interface, it still requires better understanding and improvements. The present work uses a Li/Li symmetric cell with a solid composite electrolyte (SCE) to showcase the non-trivial impact of pressure on the lithium stripping/plating at Li/solid electrolyte interface. Evolution of interphase between Li and solid electrolyte is influenced by applied pressure and whether lithium metal went through initial plating or stripping. SSB performance and stability exhibits a significant sensitivity to the applied uniaxial pressure. There is a non-monotonic correlation among the applied pressure, cell polarization, and coulombic efficiency. The performance enhancement reaches an optimum level after which there is a degradation of electrochemical performance with increased external pressure. The intermittent electrochemical characterization of the Li/SCE/Li cells during long-term cycling together with the postmortem analyses of the components are used to shed light on the impact of pressure on the interfacial stability of SSB.

Unravel SEI Formation on Li Metal Interfaces By Mechanistic Multi-Scale Modelling

Nowadays, lithium metal anodes are often referred to as the ‘holy grail’ of next-generation battery technology. Compared to graphite anodes used in state-of-the-art lithium-ion batteries they promise several times higher energy densities [1]. However, Li metal shows a high reactivity with liquid electrolytes and uncontrolled dendrite growth which hinders a safe and efficient cyclability and therefore the commercial application in rechargeable batteries. Thus, stabilization of the solid-electrolyte interphase (SEI) between liquid electrolyte and the lithium surface is the key challenge to be solved before bringing this promising battery technology to market. In order to suppress unwanted effects such as dendrite formation, persistent loss of active material and high kinetic losses, this layer of electrolyte decomposition products needs to be electrically insulating and should prevent direct contact of metal with electrolyte while ensuring a good ionic conductivity and mechanical stability.Such a beneficial SEI design requires detailed understanding of the fundamental formation mechanism and the resulting chemical SEI composition and structure depending on electrolyte composition. In literature, a large range of experimental methods are applied to characterize the SEI under various conditions [2]. These approaches are mainly descriptive and struggle to identify and understand the underlying mechanisms. Theoretical approaches like density functional theory (DFT), ab-initio molecular dynamics (MD) or classical MD are well suited to determine reaction mechanisms and to model the very beginning of SEI formation in the ns-range. However, they are too computationally expensive to model technical relevant length- and time scales [3].Therefore, this work focuses on overcoming these restrictions by developing an efficient multiscale-model with input from ab-initio calculations. The acceleration originates from focusing on rare events such as reaction or diffusion processes in a 3-dimensional kinetic Monte Carlo instead of considering the vibrational motions of single atoms like in molecular dynamics. Thereby, every process is represented by a probability derived from ab-initio calculations to ensure physical correctness. An additional coupling with efficient ordinary differential equations as shown in [4] ensures electroneutrality in the simulation box.Implementation of the degradation reactions for a 1.2M LiPF6/EC electrolyte obtained from molecular simulations (see Figure 1, appendix), allows to unravel the initial SEI formation, the emerging structure and its composition within the first µs. The simulation suggests an almost instantaneous formation of SEI species on the pristine Li metal within the first nanoseconds after immersion. Due to this early passivation layer the formation process slows down continuously until electron tunneling is blocked by SEI species and a first passivation of the lithium surface is reached. Interestingly, the formed passivation layer mainly consists of inorganic species such as LiF close to the lithium metal surface and Li2CO3 throughout the whole layer but only of minor organic (CH2OCO2Li)2-molecules, suggesting that organic species are mainly formed at larger time scales which is the reason for the typical layering structure of the SEI.In summary this novel approach allows unprecedented insight of initial SEI-formation and thereby extends the accessible insight, time- and length-scales compared to molecular simulations.

Charged Block Copolymers: From Fundamentals to Electromechanical Applications.

Charged block copolymers are promising materials for next-generation battery technologies and soft electronics. Although once it was only possible to prepare randomly organized structures, nowadays, well-ordered charged block copolymers can be prepared. In addition, theoretical and experimental analyses of the thermodynamic properties of charged polymers have provided insights into how to control nanostructures via electrostatic interactions and improve the ionic conductivity without compromising mechanical strength, which is crucial for practical applications. In this Account, we discuss methods to control the self-assembly and ion diffusion behavior of charged block copolymers by varying the type of tethered ionic moieties, local concentration of embedded ions with controlled electrostatic interactions, and nanoscale morphology. We discuss with particular emphasis on the structure-transport relationship of charged block copolymers using various ionic additives to control the phase behavior electrostatically as well as the ion transport properties. Through this, we establish the role of interconnected ionic channels in promoting ion-conduction and the importance of developing three-dimensional interconnected morphologies such as gyroid, orthorhombic Fddd (O70) networks, body-centered cubic (bcc), face-centered cubic (fcc), and A15 structures with well-defined interfaces in creating less tortuous ion-conduction pathways. Our prolonged surge and synthetic advances are pushing the frontiers of charged block copolymers to have virtually homogeneous ionic domains with suppressed ion agglomeration via the nanoconfinement of closely bound ionic moieties, resulting in efficient ion conduction and high mechanical strength.Subsequently, we discuss how, by using zwitterions, we have radically improved the ionic conductivity of single-ion conducting polymers, which have potential for use in next-generation electrochemical devices owing to the constrained anion depletion. Key to the improvement stems from hierarchically ordered ionic crystals in nanodomains of the single-ion block copolymers through the self-organization of the dipolar/ionic moieties under confinement. By precisely tuning the distances between ionic sites and the dipolar orientation in the ionic domains with varied zwitterion contents, unprecedented dielectric constants close to those of aqueous electrolytes have been achieved, leading to the development of high-conductivity solid-state single-ion conducting polymers with leak-free characteristics. Further, using these materials, low-voltage-driven artificial muscles have been prepared that show a large bending strain and millisecond-scale mechanical deformations at 1 V in air without fatigue, exceeding the performance of previously reported polymer actuators. Finally, smart multiresponsive actuators based on tailor-made charged polymers capable of programmable deformation with high force and self-locking without power consumption are suggested as candidates for use in soft robotics.

On the Parameters Affecting Calcium Plating and Stripping from Organic Electrolytes – Cases of Electrolyte Optimization

Among the different next-generation battery technologies, the ones based on divalent cations have recently gained particular attention due to their higher raw material availability and potentially higher energy density when compared with Li-ion. Such is the case of calcium, being the 5th most abundant element in the earth crust and having a standard redox potential only 170 mV above metallic lithium. However, the development of a secondary calcium-metal battery had been hampered by the lack of organic electrolytes allowing for reversible plating and stripping, which was only recently reported by our group and others employing different electrolyte formulations.The different electrolyte components – salt(s), solvent(s) and additive(s) – are expected to play a significant role in the operation of a calcium-metal battery. Here we will show how the solvation structure of the cation evolves in relation to the solvent employed and the concentration of the salt. Combining conductivity measurements with Raman spectroscopy data, a high tendency to form contact ion pairs is evidenced, which significantly affects the mobility of the ions in the liquid media. The use of different anions and their bonding strength with Ca2+ in solution will be discussed. Combined, the anion and solvent characteristics dictate the solvation of the cation, which in turn can affect the Ca plating and stripping kinetics.Additionally, the presence of electrolyte contaminants will be explored. The crucial yet very challenging drying of electrolyte containing Ca(BF4)2 in carbonate solvents will be presented. The difficulties to obtain anhydrous and contaminant free solutions from commercially available salts will be discussed and two alternative routes for anhydrous synthesis of the target salt will be presented.

Li7La3Zr2O12 solid-State Electrolyte Modified LiNi0.8Mn0.1Co0.1O2 Cathode Materials for 18650 Lithium-Ion Batteries

Ni-rich layered oxide materials as LiNi0.8Mn0.1Co0.1O2 (NMC811) are considering to be the candidate for a next-generation battery technology due to its high energy density. Nonetheless, this material has been suffered from poor rate capability and fast capacity decay, leading to the hindrance of commercialization. In this work, Li7La3Zr2O12 (LLZO) solid-state electrolyte was employed as an additive of NMC811 cathode through the mechano-fusion technique. For the sake of high ionic conductivity and remarkable electrochemical and environmental stability of LLZO, the surface side reactions of NMC811 could be mitigated. As a result, NMC-LLZO in a cylindrical cell type (18650) lithium-ion battery provided the initial discharge capacity of 2300 mAh with a notable capacity retention of 91% after 150 cycles at 1C. Figure 1

Comparative Study to Investigate the Role of SEI Layer on the Formation of Dendrites on Lithium, Sodium and Zinc Metals

The huge theoretical capacities of metal anodes provide the potential for high energy density batteries that could have widespread applications in consumer devices. However, metallic anodes are plagued by challenges caused by the formation of unstable solid electrolyte interphase (SEI) layers, surface pitting, and dendritic plating morphologies leading to reductions in cycle life, low Coulombic efficiencies, and potential safety hazards. There currently exists a gap in understanding within the literature concerning the nucleation and morphology growth of dendrites upon metallic anodes during cycling. These dendritic morphologies lead to increased SEI layer formation, generation of “dead” metal which is no longer is physical or electrical contact with the electrode, and the potential for internal short circuits. So far, these drawbacks have prevented the widespread implementation of metallic anodes in secondary batteries. A better understanding of when dendrites nucleate and how plating morphologies evolve over cycling is needed for increasing reversibility of metallic anodes and facilitating next-generation battery technologies such as metal-air and metal-sulfur batteries.In this study, we employed various electrochemical methods including galvanostatic cycling and impedance spectroscopy as well as imaging tools such as scanning electron microscopy to investigate the dendrite formations on Li, Na and Zn metals. Herein, we compare the performances of symmetric cells comprised of three metals M (Li, Na, and Zn) in analogous perchlorate (M(ClO4)x) electrolytes and draw connections between voltage profile variations and metal morphology evolution using SEM. These 3 metal anodes where chosen owing to their range of reactivities, electrons involved in their charge transfer reactions, SEI layer composition, and electrolyte compatibilities. Additionally, recent research based on modeling the onset of lithium dendrite growth as a diffusion-limited process using Sand’s equation has correlated the appearance of lithium dendrites to the reduction in Li + ion concentration at the lithium-SEI interface to zero. This hypothesis has been further evaluated by comparison of lithium electrodeposition in an organic electrolyte (wherein an SEI layer is formed) to zinc electrodeposition in an aqueous electrolytes (which involves the formation of a minimal SEI layer) using a custom 3-electrode cell. The results of this study provide insights into the analysis of symmetric cell voltage profiles and the nucleation mechanism of dendrites during charging.