Stabilizing Metallic Na Anodes via Sodiophilicity Regulation: A Review

This review focuses on the Na wetting challenges and relevant strategies regarding stabilizing sodium-metal anodes in sodium-metal batteries (SMBs). The Na anode is the essential component of three key energy storage systems, including molten SMBs (i.e., intermediate-temperature Na-S and ZEBRA batteries), all-solid-state SMBs, and conventional SMBs using liquid electrolytes. We begin with a general description of issues encountered by different SMB systems and point out the common challenge in Na wetting. We detail the emerging strategies of improving Na wettability and stabilizing Na metal anodes for the three types of batteries, with the emphasis on discussing various types of tactics developed for SMBs using liquid electrolytes. We conclude with a discussion of the overlooked yet critical aspects (Na metal utilization, N/P ratio, critical current density, etc.) in the existing strategies for an individual battery system and propose promising areas (anolyte incorporation and catholyte modifications for lower-temperature molten SMBs, cell evaluation under practically relevant current density and areal capacity, etc.) that we believe to be the most urgent for further pursuit. Comprehensive investigations combining complementary post-mortem, in situ, and operando analyses to elucidate cell-level structure-performance relations are advocated

Recent Progress in Cathode Materials for Sodium-Metal Halide Batteries

Transitioning from fossil fuels to renewable energy sources is a critical goal to address greenhouse gas emissions and climate change. Major improvements have made wind and solar power increasingly cost-competitive with fossil fuels. However, the inherent intermittency of renewable power sources motivates pairing these resources with energy storage. Electrochemical energy storage in batteries is widely used in many fields and increasingly for grid-level storage, but current battery technologies still fall short of performance, safety, and cost. This review focuses on sodium metal halide (Na-MH) batteries, such as the well-known Na-NiCl2 battery, as a promising solution to safe and economical grid-level energy storage. Important features of conventional Na-MH batteries are discussed, and recent literature on the development of intermediate-temperature, low-cost cathodes for Na-MH batteries is highlighted. By employing lower cost metal halides (e.g., FeCl2, and ZnCl2, etc.) in the cathode and operating at lower temperatures (e.g., 190 °C vs. 280 °C), new Na-MH batteries have the potential to offer comparable performance at much lower overall costs, providing an exciting alternative technology to enable widespread adoption of renewables-plus-storage for the grid

Valve Regulated Lead Acid Battery Evaluation under Peak Shaving and Frequency Regulation Duty Cycles

This work highlights the performance metrics and the fundamental degradation mechanisms of lead-acid battery technology and maps these mechanisms to generic duty cycles for peak shaving and frequency regulation grid services. Four valve regulated lead acid batteries have been tested for two peak shaving cycles at different discharge rates and two frequency regulation duty cycles at different SOC ranges. Reference performance and pulse resistance tests are done periodically to evaluate battery degradation over time. The results of the studies are expected to provide a valuable understanding of lead acid battery technology suitability for grid energy storage applications

Valve Regulated Lead Acid Battery Evaluation under Peak Shaving and Frequency Regulation Duty Cycles

This work highlights the performance metrics and the fundamental degradation mechanisms of lead-acid battery technology and maps these mechanisms to generic duty cycles for peak shaving and frequency regulation grid services. Four valve regulated lead acid batteries have been tested for two peak shaving cycles at different discharge rates and two frequency regulation duty cycles at different SOC ranges. Reference performance and pulse resistance tests are done periodically to evaluate battery degradation over time. The results of the studies are expected to provide a valuable understanding of lead acid battery technology suitability for grid energy storage applications

An Ambient Temperature Molten Sodium–Vanadium Battery with Aqueous Flowing Catholyte

In this study, we have investigated the key factors dictating the cyclic performance of a new type of hybrid sodium-based flow batteries (HNFBs) that can operate at room temperature with high cell voltages (>3 V), multiple electron transfer redox reactions per active ion, and decoupled design of power and energy. HNFBs are composed of a molten Na–Cs alloy anode, flowing aqueous catholyte, and a Na-β″-Al₂O₃ solid electrolyte as the separator. The surface functionalization of graphite felt electrodes for the flowing aqueous catholyte has been studied for its effectiveness in enhancing V²⁺/V³⁺, V³⁺/V⁴⁺, and V⁴⁺/V⁵⁺ redox couples. The V⁴⁺/V⁵⁺ redox reaction has been further investigated at different cell operation temperatures for its cyclic stability and how the properties of the solid electrolyte membrane play a role in cycling. These fundamental understandings provide guidelines for improving the cyclic performance and stability of HNFBs with aqueous catholytes. We show that the HNFB with aqueous V-ion catholyte can reach high storage capacity (∼70% of the theoretical capacity) with good Coulombic efficiency (90% ± 1% in 2–30 cycles) and cyclic performance (>99% capacity retention for 30 cycles). It demonstrates, for the first time, the potential of high capacity HNFBs with aqueous catholytes, good capacity retention and long cycling life. This is also the first demonstration that Na-β″-Al₂O₃ solid electrolyte can be used with aqueous electrolyte at near room temperature for more than 30 cycles

LiCoPO4 cathode from a CoHPO4·xH2O nanoplate precursor for high voltage Li-ion batteries

A highly crystalline LiCoPO4/C cathode material has been synthesized without noticeable impurities via a single step solid-state reaction using CoHPO4·xH2O nanoplate as a precursor obtained by a simple precipitation route. The LiCoPO4/C cathode delivered a specific capacity of 125 mAhg−1 at a charge/discharge rate of C/10. The nanoplate precursor and final LiCoPO4/C cathode have been characterized using X-ray diffraction, thermogravimetric analysis − differential scanning calorimetry (TGA-DSC), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) and the electrochemical cycling stability has been investigated using different electrolytes, additives and separators

Advanced Na-NiCl₂ Battery Using Nickel-Coated Graphite with Core–Shell Microarchitecture

Stationary electric energy storage devices (rechargeable batteries) have gained increasing prominence due to great market needs, such as smoothing the fluctuation of renewable energy resources and supporting the reliability of the electric grid. With regard to raw materials availability, sodium-based batteries are better positioned than lithium batteries due to the abundant resource of sodium in Earth’s crust. However, the sodium–nickel chloride (Na-NiCl₂) battery, one of the most attractive stationary battery technologies, is hindered from further market penetration by its high material cost (Ni cost) and fast material degradation at its high operating temperature. Here, we demonstrate the design of a core–shell microarchitecture, nickel-coated graphite, with a graphite core to maintain electrochemically active surface area and structural integrity of the electron percolation pathway while using 40% less Ni than conventional Na-NiCl₂ batteries. An initial energy density of 133 Wh/kg (at ∼C/4) and energy efficiency of 94% are achieved at an intermediate temperature of 190 °C

Nanorod Niobium Oxide as Powerful Catalysts for an All Vanadium Redox Flow Battery

A powerful low-cost electrocatalyst, nanorod Nb₂O₅, is synthesized using the hydrothermal method with monoclinic phases and simultaneously deposited on the surface of a graphite felt (GF) electrode in an all vanadium flow battery (VRB). Cyclic voltammetry (CV) study confirmed that Nb₂O₅ has catalytic effects toward redox couples of V­(II)/V­(III) at the negative side and V­(IV)/V­(V) at the positive side to facilitate the electrochemical kinetics of the vanadium redox reactions. Because of poor conductivity of Nb₂O₅, the performance of the Nb₂O₅ loaded electrodes is strongly dependent on the nanosize and uniform distribution of catalysts on GF surfaces. Accordingly, an optimal amount of W-doped Nb₂O₅ nanorods with minimum agglomeration and improved distribution on GF surfaces are established by adding water-soluble compounds containing tungsten (W) into the precursor solutions. The corresponding energy efficiency is enhanced by ∼10.7% at high current density (150 mA·cm^–2) as compared with one without catalysts. Flow battery cyclic performance also demonstrates the excellent stability of the as prepared Nb₂O₅ catalyst enhanced electrode. These results suggest that Nb₂O₅-based nanorods, replacing expensive noble metals, uniformly decorating GFs holds great promise as high-performance electrodes for VRB applications