Perspective on Thermal Stability and Safety of Sodium-Ion Batteries
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Perspective on Thermal Stability and Safety of Sodium-Ion Batteries
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ACS Energy Letters

Cite this: ACS Energy Lett. 2025, 10, 11, 5383–5397
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https://doi.org/10.1021/acsenergylett.5c02345
Published October 21, 2025

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Abstract

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Sodium-ion batteries (SIBs) are gaining traction as an emerging contender for sustainable and cost-effective energy storage, due to the abundance and low cost of sodium resources. Although notable advancements have been made in improving electrochemical performance, the thermal stability of SIBs and the role of intrinsic degradation pathways are yet to be fully understood. This Perspective examines the mechanistic interactions that drive thermal instability in SIBs across material, electrode, and cell levels under operational extremes and abuse conditions. We analyze the thermo-electrochemical characteristics of key electrode and electrolyte components, including their interphases, to identify the underlying factors responsible for the distinct thermal response of SIBs compared to lithium-ion batteries (LIBs). By benchmarking current SIB prototypes against commercial LIB technologies in terms of cost–performance trade-offs, we outline critical challenges that must be addressed to enable safe and scalable deployment of SIB systems.

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The energy storage paradigm has been fundamentally reshaped by lithium-ion batteries (LIBs), which have enabled transformative advances in portable electronics, electric vehicles, and the integration of renewable energy into the grid. However, the accelerating demand for critical elements such as lithium, cobalt, and nickel has raised concerns regarding long-term resource sustainability, price volatility, and environmental impact. (1−3) In this context, sodium-ion batteries (SIBs) have emerged as a promising contender due to the natural abundance of sodium and the compatibility of SIBs with existing LIB manufacturing infrastructure. Beyond cost-effectiveness and sustainability, SIBs offer compelling advantages in stationary energy storage, grid stabilization, and cost-effective commuter vehicles. This drives a shift toward more diversified energy storage chemistries. (4) However, their commercial viability remains constrained by complex interactions at various electrode/electrolyte interfaces, underscoring the need to understand the degradation mechanisms and safety responses under thermo-electrochemical extremes and abuse conditions. (5−8)
Research on SIBs began in the 1970s alongside the early development of LIBs, both motivated by the pursuit of rechargeable energy storage technologies. Although LIBs quickly outpaced SIBs due to their higher energy density and electrochemical stability, interest in sodium-based systems was rekindled in the 1980s with the discovery of stable sodium transition metal oxides, which expanded the landscape of positive electrode (cathode) chemistries. (2,9) Momentum for SIBs increased after the mid-2000s, driven by the discovery of hard carbon (HC) as a viable negative electrode (anode) material, laying the foundation for the development of practical full cell configurations. By 2010, industrial interest in SIBs intensified, leading to commercial development and pilot-scale initiatives (Figure 1(a)). (10,11) Recent progress in SIB development has accelerated, fueled by disruptions in the LIB supply chain. The similar redox chemistry between sodium-ion and lithium-ion systems facilitates the seamless integration of SIB into existing LIB manufacturing infrastructure. This positions SIBs as a compelling alternative for applications where cost, scalability, and resource security take precedence over maximizing gravimetric energy density. The demand for SIBs is thus, driven by a combination of factors, including supply chain security, system-level cost advantages such as abundant cathode materials, use of aluminum current collectors, and application-specific advantages in areas like stationary grid storage and low-cost commuter vehicles. These factors provide the rationale for continued research and development of SIB technology, establishing them as a complementary solution to LIBs.

Figure 1

Figure 1. (a) Historical timeline of sodium-ion battery (SIB) development, highlighting key discoveries in cathode and anode chemistries, along with the emergence of recent commercial and mass-manufacturing efforts. (b) Comparison of energy storage capacities of various cathode and anode materials. (6,23−25) (Electrochemical properties are provided in Table S1 in the Supporting Information.) (c) Comparison of key characteristics of sodium ions and lithium ions. (26−28) (d) Schematic overview of key considerations for developing practical SIBs.

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Early materials research has converged on three primary classes of cathode materials: layered oxides, polyanionic compounds, and Prussian blue analogues (PBAs). Each class presents distinct trade-offs in terms of capacity, operating voltage, and structural stability. For instance, PBAs exhibit excellent rate capability and fast sodium-ion diffusion, while polyanionic compounds offer enhanced thermal stability and operating voltages (Figure 1(b)). (12−16) On the anode side, HC remains the most commercially viable and electrochemically stable material. Although alloying- and conversion-type anodes such as lead, antimony, and tin offer higher theoretical capacities, their practical application is hindered by severe volumetric changes during cycling, leading to rapid capacity fade and poor cycle life. As a result of their lower average cell voltages and the higher atomic mass of sodium-based materials, SIBs currently exhibit lower energy densities than state-of-the-art LIBs. (17−19) These differences originate from fundamental physicochemical distinctions between sodium ions (Na+) and lithium ions (Li+). Na+ is approximately 34% larger in ionic radius, on average has 28% lower desolvation energy, and exhibits a lower standard redox potential. Collectively, these factors contribute to slower solid-state diffusion kinetics, challenges in forming stable solid–electrolyte interphases (SEIs), and a reduction in achievable cell voltage compared to LIBs (Figure 1(c)). (20,21) Despite substantial progress in SIB development, a comprehensive understanding of the underpinning degradation-safety interactions remains limited, particularly the coupling between electrochemical aging and thermal instability. Addressing this knowledge gap requires synergistic studies that leverage advanced thermo-electrochemical diagnostics and operando techniques under off-nominal operating conditions and abuse scenarios. Rather than serving as a direct replacement for LIBs, SIBs should be regarded as a strategic and application-specific complement, particularly in cases where cost-effectiveness, supply chain resilience, and operational safety outweigh the need for enhanced energy densities. (22)

Rather than serving as a direct replacement for lithium-ion batteries, sodium-ion batteries should be regarded as a strategic and application-specific complement, particularly in cases where cost-effectiveness, supply chain resilience, and operational safety outweigh the need for enhanced energy densities.

As illustrated in Figure 1(d), advances in electrode design, electrolyte formulation, and cell architecture, coupled with cost considerations, are essential for enabling the broader commercial adoption of SIBs. Within this context, this Perspective examines how thermal behavior in SIBs arises from fundamental material-scale degradation and interfacial instability, propagating into cell-level thermal runaway scenarios under fast charging, elevated temperatures, and long-term cycling. We highlight the critical role of SEI and cathode–electrolyte interphase (CEI) evolution, electrolyte decomposition pathways, and electrode–electrolyte interactions in governing the thermal stability and safety of SIBs. Based on these factors, we present a comparative analysis of the intrinsic thermal safety differences between sodium-ion and lithium-ion systems. These insights aim to bridge the gap between the underlying degradation mechanisms, thermal stability, and resulting performance metrics, guiding the development of thermally resilient and high-performance SIB technologies.

Material-Level Thermal Stability

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The structural and electrochemical instabilities of SIB cathode materials at elevated temperatures are governed by their crystallographic frameworks and redox characteristics (Figure 2(a)). Layered transition metal oxides, such as Na0.5Ni0.3Mn0.3Co0.3O2, are particularly prone to oxygen release from the transition metal–oxygen (TM−O) lattice. In comparison to their lithium-based counterparts, sodium systems exhibit intrinsically weaker Na–O bonds, which promote oxygen evolution at elevated temperatures (∼180 °C). This oxygen release affects the lattice integrity and initiates irreversible phase transitions. For instance, temperature-dependent X-ray diffraction (XRD) analysis of Na0.8Ni0.33Mn0.67O2 reveals thermally induced phase changes, such as P2-to-Z and P2′-to-P2 transitions, in the 200–400 °C range (Figure 2(c)). These high-temperature phase transitions correspond to lattice collapse and the release of oxygen and volatile species. Thus, released volatile species exhibit severe exothermic reactions in the presence of electrolyte or other constituent material, posing potential safety challenges at the cell-level. (29−34) In contrast, lithium-based layered cathodes generally exhibit delayed decomposition, often initiating above 230 °C due to their more densely packed oxygen sublattices and higher cationic field strengths. (35) These structural features impart greater material-level thermal and mechanical stability. The smaller ionic radius of Li+ (0.76 Å) compared to Na+ (1.02 Å) enables tighter atomic packing within the unit cell, further reinforces the TM−O framework, and enhances lattice rigidity. Comparative analyses of these phase transitions during electrochemical cycling further corroborate this distinction, as shown in Figure 2(b). (36−40)

Figure 2

Figure 2. (a) Schematic illustration of typical thermal degradation pathways in sodium-ion cathodes upon heating, including layered, PBA, and polyanionic compounds. (b) Comparison of phase transitions during charging for layered sodium-ion cathodes: NaNi0.33Mn0.33Co0.33O2 (NNMCO), NaNi0.5Mn0.5O2 (NNMO), and NaCoO2 (NCO) with their lithium-ion counterparts, LiCoO2 (LCO) and LiNi0.33Mn0.33Co0.33O2 (NMC). Here, each number corresponds to different phases exhibited by the cathode, as provided in Table S2 of the Supporting Information. (37,38,56) (c) In situ XRD profile of Na0.8Ni0.33Mn0.67O2 (NNMO) during heating using X-ray beam of wavelength 0.154 nm (Reproduced with permission from ref (32). Copyright 2025 Wiley-VCH GmbH, Weinheim.) (d) Thermodynamic phase diagram of the Na-Pb binary alloy system. (Adapted from ref (57). Copyright 2024 Electrochemical Society (ECS) & IOP Science.) (e) Schematic showing the influence of hard carbon (HC) fabrication temperature on anode microstructure and sodium metal agglomeration. (f) Influence of fabrication temperature on the ion storage mechanism in HC. (Adapted from ref (52). Copyright 2020 Royal Society of Chemistry (RSC).)

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Additionally, exposure to air and moisture significantly affects the thermal stability of SIB cathodes. In layered oxides, atmospheric humidity induces Na+/H+ exchange, leading to the formation of surface hydroxides and carbonates. These parasitic surface layers increase charge-transfer resistance and exacerbate heat generation during cycling, further affecting the structural integrity. (41,42) PBAs, despite their open three-dimensional frameworks, are particularly susceptible to lattice-trapped water (Figure 2(a)). Incomplete removal of interstitial water can cause structural collapse at moderate temperatures (<200 °C), triggering the release of trapped H2O and cyanide (CN2) gas. (43,44) This mechanism contributes to capacity fade, increases interfacial impedance, and elevates the risk of hazardous reactions at the full-cell level. In comparison, lithium-based PBAs are generally less prone to moisture-induced degradation due to differences in synthesis and drying protocols. These findings underscore the importance of thermal preconditioning, such as drying at temperatures above 150 °C for extended durations (>12 h), to stabilize PBAs prior to cycling. (14) Furthermore, the application of protective surface coatings, such as Al2O3 and ZrO2, as well as controlled synthesis environments, are key considerations to enhance material stability under ambient exposure and high-temperature operation. (45) Among sodium-ion cathode families, polyanionic cathodes such as Na3V2(PO4)3 (NVP) exhibit the highest intrinsic thermal stability. This is evidenced by minimal gas evolution and the absence of structural degradation during thermal exposure. Their robust PO43– framework effectively suppresses oxygen release and inhibits thermally induced structural rearrangements, resulting in high decomposition thresholds exceeding 300 °C. This improved stability could be attributed to the strong inductive effect of the phosphate group, which reduces electron delocalization and mitigates reactivity under overcharge or abuse conditions. (46−48)
On the other hand, the thermal stability of sodium alloy anodes is strongly influenced by complex phase transformations that occur during cycling. The formation and evolution of metastable phases govern electrochemical performance, volume expansion behavior, and internal heat generation. As illustrated in Figure 2(d), the sodium–lead (Na-Pb) phase diagram contains multiple intermediate phases (α-, β-, and γ-NaPbx) across a broad temperature and compositional range. These phases are voltage-dependent and highly temperature-sensitive, suggesting that dynamic thermal environments can shift phase equilibria during operation. Such phase transitions arising from differences in lattice structure and mechanical properties can intensify particle cracking and pulverization, while simultaneously compromising the stability of the SEI. This exposes fresh electrode surfaces to the electrolyte, thereby amplifying exothermic reactions under elevated temperature conditions. Compared to lithium-based analogues, sodium alloys undergo a dynamic phase evolution and exhibit a stronger propensity for amorphization. While this may accommodate volumetric strain, it also increases the likelihood of electrochemical hysteresis, interfacial cracking, and thermal runaway under off-nominal conditions. (49,50)
HC is widely regarded as the most stable intercalation anode for SIBs, yet its thermal stability remains highly dependent on the synthesis conditions. As shown in Figure 2(e), carbonization temperature critically influences the resulting microstructure, transitioning from porous, defect-rich matrices at lower temperatures (∼1000 °C) to denser, more graphitized frameworks at higher temperatures (∼1900 °C). Although high temperature treatment enhances interfacial stability and improves capacity retention, it introduces a key thermal trade-off. Specifically, HC synthesized at intermediate temperatures (1300–1500 °C) may exhibit higher reversible capacity but has also been associated with increased formation of metallic sodium during cycling (Figure 2(f)), raising safety concerns particularly under high-rate conditions. (48) This behavior could be attributed to microstructural evolution at elevated synthesis temperatures, where larger pore volumes promote sodium-ion storage in metallic clusters rather than via conventional intercalation mechanisms (Figure 2(e)). The accumulation of metallic sodium can be exacerbated under off-nominal conditions, such as high-rate cycling and thermal extremes. Since sodium is more reactive than lithium, the associated safety implications should be carefully considered. For instance, moisture leakage under abuse can initiate an explosive runaway reaction, owing to the coulomb expansion-driven fragmentation of metallic sodium, sustaining its highly exothermic reaction with water. (51) Such reaction is not observed in case of metallic lithium due to its higher melting point, ionization energy, and stronger metallic bond. These insights highlight that optimizing HC for SIBs requires a careful balance between capacity, structural ordering, the dominant sodium storage mechanism (intercalation vs plating), and the material’s thermal stability under extreme operating conditions. (52,53)

The accumulation of metallic sodium can be exacerbated under off-nominal conditions, such as high-rate cycling and thermal extremes. Since sodium is more reactive than lithium, the associated safety implications should be carefully considered.

The thermal stability of liquid electrolytes (LEs) in SIBs is strongly influenced by both the salt and solvent properties. For sodium salts, thermal behavior is governed by factors such as ionic bond strength, lattice energy, and solvation dynamics. Salts with weaker ionic bonds and lower lattice energies, such as sodium hexafluorophosphates (NaPF6), tend to decompose at lower temperatures, whereas salts like sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) exhibit greater thermal stability, attributed to their chemically stable anionic frameworks and higher oxidative stability. (54) However, amount of heat released on thermal degradation does not follow the onset temperature and is dependent on the interplay between ionic bond strength and size of the solvation shell formed by respective salts in the solvent. For solvents, thermal stability is directly correlated to physio-thermal properties such as density, volatility, reactive species generation, and flash and boiling points (Table S6). (55) A comprehensive, material-level approach is therefore essential to design SIBs capable of safe electrochemical operation across a broad temperature range.

Interface and Interphase-Level Mechanistic Interactions

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The composition and stability of electrode interphases influence electrochemical performance, capacity retention, and thermal behavior in SIBs. Compared to lithium-ion systems, interphases in SIBs exhibit distinct structural and chemical characteristics, owing to the unique reactivity of sodium salts and their interactions with electrode interfaces.
The thermal stability of the SEI formed at the HC surface is observed to be strongly influenced by both the salt and solvent properties, as illustrated in Figure 3(a). The interfacial stability is dictated by sodium salt’s ionic bond strength, propensity of ion-pair formation, and solvation dynamics in the respective solvent. Salts with higher ion-pair formation such as NaClO4 tend to form an interphase that is organically rich, thus triggering its decomposition at lower temperatures, whereas salts like NaTFSI that exhibit lower ion-pair formation result in the formation of an inorganic-rich SEI that has higher thermal resilience. Although salts such as NaFTFSI have low ion-pair formation, the large anion cluster results in a solvation shell rich in organic species from electrolyte, which consequently forms an organic-rich interphase with poor thermal stability. The reduced stability can cause early SEI cracking and expose fresh active material to LE, increasing parasitic reaction and internal cell temperature. Consequently, the intrinsic stability of the salt, coupled with its decomposition mechanism, and the solvation energy strongly influence the thermal response of both the electrolyte and electrode–electrolyte interface at higher temperatures. (58−61)

Figure 3

Figure 3. (a) Comparison of thermal stability of the anode interphase for various salt–solvent combinations used in SIBs (additional details are provided in Table S3 of the Supporting Information). (59,73) (b) Schematic illustration showing the relationship between solvation energy and thermal stability of the anode interphase. (c) Spider chart depicting thermal stability characteristics of different Sn alloy anodes with and without FEC additives after cycling. (Adapted from ref (55). Copyright 2025 American Chemical Society (ACS).) Here μ-Sn and n-Sn refer to micro-Sn and nano-Sn, respectively. (d) SEM images of pristine and cycled n-Sn particles showing nonuniform interphase formation after cycling without additives. (Reproduced with permission from ref (66). Copyright 2022 American Chemical Society (ACS).) (e) Comparison of the effect of FEC on the CE of HC and Sn anodes. (66,72)

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The composition and stability of electrode interphases influence electrochemical performance, capacity retention, and thermal behavior in SIBs. Compared to lithium-ion systems, interphases in SIBs exhibit distinct structural and chemical characteristics, owing to the unique reactivity of sodium salts and their interactions with electrode interfaces.

The dielectric constant, donor number, and molecular structure of the solvent play critical roles in determining the thermal stability of interphase. High donor number solvents, such as ethylene carbonate (EC), promote strong sodium-ion solvation but often result in SEI layers that are rich in organic components and structurally fragile under thermal stress. In contrast, solvents such as acetonitrile reduce solvation strength but tend to form thinner, more inorganic-rich interphases that exhibit improved thermal stability. (62,63) This trade-off is particularly evident when comparing the two primary solvent classes employed in SIBs, carbonate-based and ether-based electrolytes. Carbonate solvents, such as EC and propylene carbonate (PC), offer high polarity and strong donor characteristics that facilitate sodium-ion transport improving ionic conductivity. However, they result in the formation of a SEI that is prone to thermal decomposition at relatively low temperatures (∼100–150 °C) and generates volatile and flammable byproducts on decomposition.
On the other hand, ether-based solvents such as diethylene glycol dimethyl ether (DEGDME) and dimethoxyethane (DME) possess lower donor numbers and solvation energies, which tend to favor the formation of inorganic-rich SEI layers (e.g., NaF) that offer improved thermal stability. However, this advantage comes at the expense of reduced oxidative stability, which limits the long-term electrochemical performance of ether-based systems, especially at higher voltages. (64,65) Additionally, the solvation energy of the LE affects the chemical composition of the interphase, particularly on the anode side (Figure 3(b)). Electrolytes with high solvation energies facilitate efficient sodium-ion transport but typically promote SEI layers rich in organic species, which are susceptible to decomposition under moderate heating. In contrast, low-solvation energy systems favor the formation of more inorganic-dominated interphase, such as NaF-rich SEI layers, that exhibit superior thermal stability. (20) Thus, the salt decomposition characteristics and solvent coordination strength influence the composition and thermo-electrochemical stability of electrode interphases.
Electrolyte additives exhibit distinct electrochemical and thermal behaviors depending on the anode chemistry. In alloy-based anodes such as Sn, the incorporation of fluoroethylene carbonate (FEC), in both carbonate- and ether-based electrolytes, has been shown to stabilize the SEI by promoting the formation of uniform, inorganic-rich interphases. This stabilization leads to higher initial Coulombic efficiency (CE) and improved cycling performance. (66) However, enhanced electrochemical performance does not necessarily correlate with improved thermal stability (Figure 3(c)). For instance, FEC can delay the onset of thermal runaway in nanostructured Sn (n-Sn) anodes, but it also significantly increases the total heat released during decomposition. This behavior is likely attributed to extensive interphase buildup during prolonged cycling, which increases interfacial thickness and contributes to a larger exothermic response during thermal breakdown. Thus, while a uniform and passivating SEI is crucial for mitigating parasitic electrolyte reactions, excessive interphase growth may increase heat release under abuse conditions and must be controlled. (67) This phenomenon is corroborated by scanning electron microscopy (SEM) images of pristine and cycled n-Sn particles, which reveal nonuniform interphase formation in the absence of additives (Figure 3(d)). In contrast, the addition of FEC improves CE (68) and promotes more homogeneous SEI growth, which mitigates volume-change-induced cracking and reduces irreversible capacity loss (Figure 3(e)). (69)
HC anodes typically exhibit lower CE compared to Sn anodes when using FEC additives. Although FEC is beneficial in alloy systems, its use in HC tends to promote excessive NaF formation, resulting in a brittle and resistive SEI that impedes ionic transport and degrades long-term cycling stability. (70,71) These contrasting behaviors stem from fundamentally different interactions between electrolyte decomposition products and the anode surface. Differences in surface chemistry, mechanical compliance, and redox activity govern how additives influence interphase formation and evolution. (60,72) To further advance our understanding, additive behavior should be evaluated with careful attention to anode-specific surface chemistry and interfacial dynamics. Similarly, while most studies have focused on initial CE and cycling performance, integrating complementary assessments of thermal stability and interfacial morphology would provide a more comprehensive perspective on the factors governing thermal safety under practical operating conditions.
The thermal stability of CEIs in SIBs reveals key distinctions influenced by differences in redox chemistry, lattice robustness, and interfacial reactivity. In layered sodium transition metal oxides, CEI degradation typically initiates with electrolyte reduction at the charged cathode surface, resulting in a reduction of transition metal (TM) valency. This process is often accompanied by TM migration and lattice oxygen release, which destabilize the cathode structure (Figure 4(a)). Although the overall degradation mechanism is similar to that observed in lithium-ion layered cathodes, sodium-based materials tend to undergo these transitions at lower onset temperatures, leading to earlier thermal instabilities. (74,75) For instance, in situ XRD analysis of charged Na0.5Ni0.3Fe0.3Mn0.3O2 (NFM) cathodes shows peak broadening and the emergence of Mn3O4 diffraction signals upon heating, indicating phase decomposition and oxygen release (Figure 4(b)). (76,70) The disappearance of (003) and (101) reflections near 180 °C signifies collapse of the layered structure, confirming that lattice oxygen release is closely coupled with interfacial degradation and the onset of exothermic thermal events. (77) The oxygen released from the cathode undergoes highly exothermic reactions with the organic solvents present in the electrolyte. These reactions generate substantial heat and produce highly reactive radical species, which further intensify parasitic degradation pathways. The confluence of gas evolution and exothermic reactions can significantly raise internal cell pressure. This sequence of events leads to the structural breakdown of the cathode active material and increases the likelihood of catastrophic cell failure, particularly under thermal or electrochemical abuse conditions. (78,79) These real-time observations highlight the intrinsic link between lattice integrity and CEI stability in governing the thermal stability of layered cathodes. In contrast, PBAs follow a fundamentally different degradation mechanism. Upon heating, the release of interstitial water from their lattice reacts exothermically with anionic radicals formed during electrolyte decomposition. This reaction generates additional heat and yields acidic byproducts that chemically degrade the CEI, promoting further structural and interfacial breakdown (Figure 4(a)).

Figure 4

Figure 4. (a) Schematic illustration of typical thermal instability pathways of the CEI in layered oxide and PBA cathodes. (b) In situ XRD pattern of charged NFM in 1 M NaPF6 in propylene carbonate:ethyl methyl carbonate (PC:EMC) with 2 wt% FEC using an X-ray beam of wavelength 0.012 nm. (Reproduced with permission from ref (77). Copyright 2018 American Chemical Society (ACS).) (c) Comparative analysis of gas evolution normalized to volumetric energy density for NVPF and LFP cathodes. (Adapted from ref (82). Copyright 2022 American Chemical Society (ACS).) (d) Comparison of the thermal stability of different cathodes based on the relationship between the onset temperature for thermal degradation and cutoff voltage (figure numbers for the representative data sets are summarized in Table S4 of the Supporting Information). (e) Thermal stability profile of carbon-coated NVP as a function of SOC. (Adapted from ref (83). Copyright 2024 Elsevier.) (f) Schematic depiction of how increasing SOC in layered oxide cathodes influences degradation mechanisms and the severity of thermal runaway.

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Additionally, the thermal decomposition of cyano-ligated materials such as PBAs leads to the release of CN2-containing gases. Although these gases may not directly react with the electrolyte, their high toxicity and ability to elevate internal cell pressure pose safety concerns, particularly in the event of mechanical damage or venting. It is noted that CN2 gas emissions have also been observed in LIBs during thermal runaway and combustion scenarios. However, in PBA-based sodium systems, this behavior is closely linked to the thermal instability of the CEI and the presence of residual lattice water, which accelerate interfacial degradation and gas evolution at elevated temperatures. The severity of this mechanism can be evaluated by normalizing gas evolution to the cell’s volumetric energy density, enabling a chemistry-agnostic comparison of safety risks across different cell chemistries. As shown in Figure 4(c), Na3V2(PO4)2F3 (NVPF) cathodes generate a greater quantity of gas per unit of energy density compared to LiFePO4 (LFP), despite being considered among the most thermally stable sodium-based cathodes at the material level. The evolved gases from NVPF are predominantly carbonate species, (80) with small amounts of H2 and CO2, whereas LFP tends to produce a lower overall gas volume comprising a broader spectrum of volatile byproducts. Interestingly, when LFP is compared to lithium nickel manganese oxide (NMC) cathodes, LFP can emit larger quantities of hydrogen under certain conditions. (81) These findings indicate that while the polyanionic framework in NVPF effectively suppresses bulk oxygen release and mitigates structural collapse, it does not necessarily ensure thermal stability of the electrode–electrolyte interface. One possible explanation is that although the phosphate lattice delays thermal instability, localized interfacial reactions may still proceed, particularly under high-voltage or high state-of-charge (SOC) conditions. In such cases, residual electrolyte species, surface coatings, or conductive additives can undergo oxidative decomposition, contributing to interfacial degradation despite the intrinsic thermal stability of the active cathode material. (32,82)
Moreover, the relationship between cutoff voltage and the onset temperature for thermal decomposition reveals distinct trends across different cathode chemistries (Figure 4(d)). In layered transition metal oxides, increasing the upper cutoff voltage from 3.8 V to 4.3 V vs Na+/Na reduces the decomposition temperature. This behavior could be attributed to transition metal oxidation, which destabilizes the TM−O framework and facilitates oxygen evolution. A similar trend is observed for polyanionic cathodes such as NVPF, where raising the cutoff voltage from 3.8 V to 4.5 V also lowers the onset temperature for thermal decomposition. However, the absolute onset temperatures for NVPF remain significantly higher than those of layered oxides. Although polyanionic materials possess strong resistance to structural degradation at the bulk level, their interfacial stability remains susceptible to voltage-induced decomposition reactions, especially at elevated SOCs. (83) These observations emphasize the importance of developing interface-specific stabilization strategies in SIBs, even for cathode chemistries with inherently stable crystalline frameworks. Under practical conditions, interfacial degradation processes such as electrolyte oxidation, surface reconstruction, and localized heat generation can dominate the cell level thermal response, despite the intrinsic stability of the bulk material.
Increasing SOC has a pronounced destabilizing effect on cathode thermal behavior across various material classes. For carbon-coated NVPF, the onset temperature for thermal decomposition decreases consistently with an increase in SOC, reflecting enhanced lattice stress and surface reactivity due to higher TM oxidation states (Figure 4(e)). However, unlike layered oxides, the total heat release in NVPF does not scale proportionally with SOC. This indicates that mechanical strain may initiate earlier degradation, but the robust polyanionic framework limits TM dissolution and suppresses the evolution of reactive gases. In contrast, layered oxide cathodes at high SOC experience deeper TM oxidation, which weakens the metal–oxygen bonding network and increases lattice strain. This degradation triggers volumetric expansion, surface cracking, and localized oxygen release (Figure 4(f)). In situ XRD patterns further confirm SOC-induced lattice distortion and oxygen evolution, aligning with the onset of structural breakdown. (77) The difference in thermal behavior between polyanionic and layered cathodes at high SOC primarily arises from the absence of bulk oxygen release in polyanionic systems, which limits heat generation. Gas evolution studies support this behavior, showing that polyanionic cathodes such as NVPF emit significantly fewer reactive gases than layered oxides, even at comparable volumetric energy densities. (84,85) This reflects a partial decoupling between degradation onset and total heat release, due to the structural rigidity of the polyanionic framework.
Degradation response in SIBs is influenced by various factors such as interstitial species, cutoff voltage, and the covalency of the host lattice. Importantly, the onset temperature for thermal decomposition does not provide a comprehensive understanding of safety, and mechanistic descriptors capturing reaction kinetics and total heat release should also be considered. Advancing thermally stable SIBs will require a synergistic approach that ensures both bulk and interfacial stability at high SOCs. This can be achieved through tailored electrolyte formulations, surface-engineered electrode materials, and optimized charge protocols. Further, the deployment of operando diagnostic techniques capable of tracking phase transitions, gas evolution and interfacial transformations will be essential for guiding the design of thermally stable electrode–electrolyte interfaces.

Cell-Level Thermal Stability and Safety

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Thermal instability at the cell level arises from a complex interplay of factors, including electrode decomposition (both primary and secondary materials), interfacial degradation, electrolyte breakdown, and structural changes. The onset of thermal instability is often triggered by parasitic reactions at the anode, while cathode instability (e.g., at high SOCs) drives the system toward thermal runaway. In sodium-based layered cathodes, high-valent TM states and weaker metal–oxygen bonds facilitate structural phase transitions and lattice oxygen release. The released oxygen reacts exothermically with the organic electrolyte, generating free radicals and accelerating solvent decomposition. This cascade of reactions leads to rapid temperature rise, triggering additional material breakdown and interfacial degradation, ultimately resulting in catastrophic failure (Figure 5(a)).

Figure 5

Figure 5. (a) Schematic illustration of the typical thermal runaway pathways in SIB cells. (b) Thermal safety characteristics in NaxTMO2 (NTM) and LFP cathodes. (Adapted from ref (87). Copyright 2024 Elsevier.) (c) Heat release comparison between LIB and SIB cells with cathode and anode contributions. (Adapted from ref (86). Copyright 2021 American Chemical Society (ACS).) (d) SEM micrographs of SIB cathode and anode after thermal abuse testing. (Reproduced with permission from ref (88). Copyright 2018 Elsevier.) (e) Microcalorimetry profile showing heat generation during a single charge/discharge cycle in a pristine NVP/HC full cell. (92) (f) Comparison of heat release during thermal abuse tests of different cathodes and anodes (more details regarding the electrode–electrolyte combination for this data set are provided in Table S5 in the Supporting Information). (g) Maximum temperatures observed during nail penetration and overcharge tests for SIBs using NVPF, NFM, and NCFMO cathodes, compared to LFP-based cells (8,89,93)

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Oxygen released from the cathode can also diffuse through the separator and react exothermically with the anode, enhancing heat generation through electrode crosstalk. This creates a positive feedback loop in which rising temperatures accelerate further reactions, amplifying the thermal response. Compared to LIBs, SIBs exhibit distinct thermo-electrochemical signatures, driven by inherent differences in material properties and interfacial chemistry. For example, sodium layered oxides typically display lower onset temperatures for thermal instability, faster heat release rates, and shorter time intervals to thermal runaway than LFP (Figure 5(b)). These behaviors are largely attributed to weaker Na–O bonding and greater structural distortion in sodium-based cathodes. (86,87) In Figure 5(b), T1 marks the onset temperature for self-heating, T2 corresponds to the onset temperature for thermal runaway, T3 denotes the maximum cell temperature, dT/dt denotes the maximum rate of temperature increase, and t2 – t1 refers to the time duration between T1 and T2.
Quantitative comparisons of heat generation in SIB and LIB full cells further highlight their divergent thermal behaviors (Figure 5(c)). Although both lithium and sodium systems follow similar degradation pathways, beginning with parasitic anode reactions that raise internal temperatures and trigger oxygen release from the cathode, SIBs tend to exhibit earlier oxygen evolution owing to the weaker Na–O bonds. Such oxygen release is expected to trigger thermal runaway through its exothermic reaction with intermediate species in the electrolyte, leading to a rapid and significant increase in cell temperature. This interpretation is supported by post-abuse SEM analysis, which reveals pronounced delamination of the cathode structure, while the anode remains comparatively intact (Figure 5(d)). (88) While cathode governs the onset of runaway, on degradation, anode is observed to release higher peak energy owing to their higher mass loading and lower C–C bond strength (Figure 5(c)). The cathode’s influence on cell-level thermal stability extends beyond abuse scenarios. During cycling, SIBs often generate more heat during discharge due to higher polarization at the cathode (i.e., during sodium-ion deintercalation), particularly under high-rate conditions (Figure 5(e)).
Comparative thermal analysis of sodium-based cathodes reveals that layered oxides such as NFM and NaCuxFeyMnzO (NCFMO) exhibit the lowest onset temperatures for thermal instability, followed by PBAs, while polyanionic cathodes demonstrate the highest thermal stability (Figure 5(f)). (89) However, the heat released by layered oxide is noticed to be significantly influenced by the chemical composition of the CEI and the stability of the TM–O bond, whereas for PBA it is dependent on the amount of interstitial water in the cathode lattice. Polyanionic cathodes exhibit the least variation to the salt-solvent type and release the lowest heat, reflecting their strong resistance to oxygen evolution. This is in contrast to layered oxides and PBAs, which can potentially release reactive gases, oxygen, and water, followed by exothermic reactions with other cell components. However, this does not necessarily translate that polyanionic cathodes are thermally resilient, as recent investigations on LIBs with LFP cathodes have reported highly exothermic reactions with Li metal, driven by direct redox reaction that elevate temperatures above 2500 °C. (90) Such thermite reactions pose serious safety risks, as they can occur independently of lattice oxygen release, with their severity and onset governed by the surface area and quantity of Li metal present. While analogous reactions have not yet been systematically examined in SIBs, their possibility cannot be excluded given the high reactivity of metallic Na, especially under off-nominal conditions, where excessive Na plating is expected.
Anode chemistry also significantly affects cell-level thermal response. Alloy and conversion-type anodes, despite their higher capacities, pose greater thermal risks due to elevated side reactions and nonuniform interphase growth, leading to increased heat release relative to intercalation-based anodes with conversion electrodes exhibiting the lowest magnitude. Meanwhile intercalation anodes exhibit the lowest onset temperature owing to the poor interphase stability followed by alloy-based and conversion counterparts. Intercalation-based anodes also show maximum variation of heat release and onset temperature, primarily being dictated by the solvent properties (boiling and flash points) and the thermal stability of the SEI. (55) Though fluorine-based LEs enable inorganic-rich interphase with higher thermal stability, they can generate species such as hydrofluoric acid (HF) or bis(trifluoromethanesulfonyl)imide (TFSI) that could corrode the current collector, leading to mechanical failure of the electrode and an earlier onset of thermal runaway. At higher temperatures, reaction of binder decomposition products with LE can generate HF, which can potentially react with the anode and plated Na, resulting in thermal instability.
Further, as shown in Figure 5(g), SIBs exhibit significantly different thermal responses compared to LIBs under abuse scenarios such as overcharge and nail penetration. (46,91) SIBs can exhibit lower tolerance to overcharging, which is potentially associated with the reduced mechanical robustness of the cathode lattice and the higher tendency for metallic plating at the anode relative to lithium-ion systems. (78) Due to the larger ionic radius of Na+ compared to Li+, the insertion and extraction processes tend to induce greater lattice strain, potentially leading to structural degradation under aggressive electrochemical conditions such as overcharging. Additionally, SIBs are more susceptible to sodium plating at the anode during overcharge scenarios. Unlike lithium, sodium exhibits a higher propensity to deposit on the anode surface once intercalation capacity is exceeded, especially in hard carbon systems, which may not accommodate sodium as uniformly under extreme potentials. This increases the risk of dendrite formation and short circuits. Together, these cathode- and anode-related limitations constrain the thermal and electrochemical stability window of SIBs, making overcharge protection a more critical challenge in their practical deployment. Thus, thermal runaway in SIBs is typically triggered by parasitic reactions at the anode, with cathode instability acting as the driver of the thermal runaway cascade. Enhancing thermal safety in SIBs requires moving beyond material-level considerations like flammability and decomposition temperature and focus on designing electrochemically stable interphases and electrodes that resist generating reactive byproducts under abuse conditions. Real-time monitoring of SEI chemistry and gas evolution using advanced diagnostics is crucial for guiding the development of safer, high-performance SIBs.

Cost Considerations and Thermal Stability Metrics for Commercialization of SIBs

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While SIB prototypes have demonstrated significant technological progress, they still trail commercial LIBs in key cost–performance metrics. Benchmarking energy density and cycle life at 80% capacity retention across leading SIB developers such as Faradion, HiNa, Tiamat, CATL, and Atris against established LIB platforms like BYD’s lithium-ion blade battery reveals that SIBs demonstrate approximately 30% lower energy density and 20% shorter cycle life on average (Figure 6(a)). From a materials cost perspective, SIBs benefit from the widespread availability and lower cost of sodium-based salts and precursors, resulting in reduced active material cost per kilowatt-hour, as shown in Figure 6(b). However, this advantage is partially offset by higher manufacturing and processing costs, which remain high due to early-stage supply chains and limited economies of scale. Additionally, because of their lower gravimetric and volumetric energy densities, SIBs often require larger or heavier battery packs to deliver equivalent usable capacity, reducing volumetric efficiency and increasing system-level costs. (94)

Figure 6

Figure 6. (a) Comparison of energy density and cycle life (at 80% capacity retention) of various SIB prototypes from different manufacturers relative to BYD’s lithium-ion blade battery. (Adapted from refs (96and97). Copyright 2023 Springer Nature and 2023 MDPI.) (b) Breakdown of material and processing costs for commercially available LIB and SIB systems. (Adapted from refs (98and99). Copyright 2019 MDPI and 2025 Cell Press.) (c) Specific energy comparison of different cathode materials as a function of areal loading. (Adapted from ref (94). Copyright 2021 Elsevier.) (d) Effect of heating power during thermal abuse tests on the maximum temperature (T3) and time interval between onset of self-heating and thermal runaway (t2 – t1) for layered oxide-based SIBs. (Adapted from ref (95). Copyright 2025 Elsevier.) (e) Representative illustration of heat generation as a function of charging rate. (f) Schematic showing the hierarchical set of factors (i.e., at the particle, interphase, and electrode levels) affecting SIB safety.

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Cathode chemistry plays a central role in determining practical energy density. While sodium-based cathodes such as NVPF, PBAs, and layered sodium transition metal oxides can achieve competitive specific energies at low to moderate areal loadings, their energy density declines at higher loadings. In contrast, LIB cathodes like LiNi0.33Mn0.33Co0.33O2 (NMC111) sustain superior energy density even at elevated areal loadings (Figure 6(c)), which makes them suitable for high-energy applications such as long-range electric vehicles. Thus, although SIBs hold promise as cost-effective alternatives for stationary energy storage and grid support, broader commercial adoption will depend on concurrent advancements in energy density, cycle life, and scalable manufacturing.
Thermal stability is critical for successful realization of SIBs, especially under practical conditions such as fast charging and ambient temperature fluctuations, which can affect cell safety. SIBs exhibit a shorter time window between the onset of self-heating and thermal runaway (i.e., t2 – t1), reducing the available response time during thermal abuse events (Figure 5(b)). As shown in Figure 6(d), variations in external heating power can significantly affect this margin: faster heating rates compress the t2 – t1 interval and intensify exothermic reactions, leading to higher peak temperatures during abuse testing. These trends emphasize the need for standardized thermal testing protocols to ensure reliable assessment of safety margins. Under accelerated heating, the reduced intervention window requires passive (e.g., thermal buffers) and active (e.g., real-time thermal sensors) safety mechanisms in cell design. Additionally, operational extremes such as fast charging can accelerate internal heat generation, primarily through ohmic losses and reaction heat (Figure 6(e)).

Hierarchical Factors Affecting SIB Safety

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At the particle level, rapid sodium-ion insertion and extraction generate significant mechanical stress, which can lead to particle cracking (Figure 6(f)) and exacerbate thermal runaway risk. (39) While similar degradation mechanisms are observed in LIBs under high-rate conditions, they are often more pronounced in SIBs due to the larger ionic radius and higher desolvation energy of sodium ions (Figure 1(c)). Microstructural fractures from rapid cycling can reduce electrochemical contact and expose fresh electrode surfaces, causing unwanted side reactions. Concentration gradients at the particle scale introduce localized overpotentials, increasing internal heat generation and promoting uneven sodium-ion flux, potentially leading to inhomogeneous degradation.
At the interphase level, intensified electrolyte decomposition can affect SEI stability, resulting in nonuniform regrowth, fluctuating impedance, and the formation of resistive domains that further elevate internal temperatures (Figure 6(f)). These changes trigger additional solvent breakdown, establishing a feedback loop between increasing heat generation and gas evolution. At the electrode scale, heterogeneous current distribution aggravates the likelihood of sodium plating, particularly at structural defects, creating localized hotspots and mechanical stress accumulation (Figure 6(f)). This behavior increases internal resistance, limits ionic transport, and impacts both thermal stability and cycling response. Moreover, SIBs tend to exhibit a higher proportion of reaction heat compared to LIBs under high-rate conditions, further emphasizing the need for precise thermal control to ensure safe operation. (95)
The commercial success of SIBs depends on addressing their intrinsic electrochemical limitations and thermal stability challenges. The abundance and low cost of sodium make SIBs promising for grid-scale and non-power-centric applications. However, key hurdles remain, including achieving competitive energy density, enhancing interfacial stability, scaling up manufacturing, and ensuring thermal safety. Sodium-ion electrodes differ fundamentally from lithium-based systems, exhibiting greater volume changes, earlier oxygen release, and more dynamic SEI evolution, particularly under high charging rates and elevated SOCs. Thermal runaway in SIBs often involves the coupled effects of interfacial breakdown, gas evolution, and temperature rise, and capturing these mechanisms in real time is essential for accurately assessing safety risks. While HC anodes are typically stable, synthesis-dependent variability can lead to sodium plating. Alloy and conversion-type anodes introduce additional thermal safety challenges due to structural collapse. Cathodes such as layered oxides and PBAs release reactive gases under high voltage, increasing the susceptibility to thermal instability.

Enabling safe, fast-charging SIBs requires material-level thermal stability considerations, along with the development of standardized testing protocols and safety metrics to evaluate the cell’s behavior under abuse conditions.

While many strategies for improving SIBs can be adapted from LIB development, the unique physicochemical properties of sodium demand tailored, comprehensive solutions. A multiscale approach is therefore essential for advancing SIBs, focusing on both performance and safety. At the material level, future research must center on designing electrode materials with high capacity and minimal volumetric strain, a critical step toward closing the energy density gap with LIBs. This includes innovating Na-ion cathodes with high structural stability to mitigate mechanical stress and degradation, while for anodes the focus should be on lowering the Na+ intercalation potential without compromising interfacial stability. For electrolytes, formulations should aim to widen the stable electrochemical window, suppress parasitic reactions, and promote the formation of a thermally resilient SEI that can reduce heat generation during thermal runaway. Beyond intrinsic material properties, advancements in electrode architecture are crucial to improve Na+ diffusion kinetics and prevent plating under operational extremes. At the system level, thermal management strategies, such as using phase-change materials and embedded sensors, must be specifically adapted to the distinct thermal behavior of SIBs. Enabling safe, fast-charging SIBs requires material-level thermal stability considerations, along with the development of standardized testing protocols and safety metrics to evaluate the cell’s behavior under abuse conditions. An integrated strategy is key to achieving widespread and safe deployment of SIB technology. SIBs should be viewed not as a direct replacement for LIBs but as complementary technology uniquely suited for applications where cost-effectiveness, resource abundance, and enhanced safety are the primary considerations.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.5c02345.

  • Summary of electrochemical properties of sodium-ion cathodes and anodes (Table S1), Comparison of phase behavior of different sodium-ion and lithium-ion layered oxides (Table S2), Exothermic parameters of different sodium salt-solvent combinations with the salt concentration of 1 M (Table S3), Thermal stability of different sodium-ion cathodes as a function of cutoff voltages (Table S4), Typical electrode–electrolyte configurations used in thermal stability investigations of sodium-ion batteries (Table S5), Properties of commonly used solvents in sodium-ion batteries (Table S6) (PDF)

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Author Information

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  • Corresponding Authors
  • Authors
    • Kausthubharam - School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States;  Orcidhttps://orcid.org/0000-0002-6427-9210
    • Bairav S. Vishnugopi - School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States;  Orcidhttps://orcid.org/0009-0002-6357-9358
    • Abhinanda Sengupta - School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
    • Dhevathi Rajan Rajagopalan Kannan - Electrochemical Safety Research Institute, UL Research Institutes, Houston, Texas 77204, United States
    • Vinay Premnath - Electrochemical Safety Research Institute, UL Research Institutes, Houston, Texas 77204, United States
    • Wan Si Tang - Electrochemical Safety Research Institute, UL Research Institutes, Houston, Texas 77204, United States;  Orcidhttps://orcid.org/0000-0002-7893-3025
  • Author Contributions

    K., B.S.V., and A.S. contributed equally to this work.

  • Notes
    The authors declare no competing financial interest.

Biographies

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Kausthubharam is a doctoral candidate in the School of Mechanical Engineering at Purdue University. He received his M.S. in Mechanical Engineering from Seoul National University, Korea, in 2023. His research focuses on interrogating the thermo-electrochemical interactions and degradation pathways in beyond Li-ion chemistries.

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Bairav S. Vishnugopi is a Research Assistant Professor in the School of Mechanical Engineering at Purdue University. His research focuses on understanding the electro-chemo-mechanical, transport, and thermal interactions in electrode architectures and interfaces for energy storage. He has co-authored more than 60 journal publications spanning different battery chemistries and applications.

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Abhinanda Sengupta is a postdoctoral associate in the School of Mechanical Engineering at Purdue University. She received her doctorate degree from the Indian Institute of Technology Bombay, India. Her research focuses on fundamental interrogation of electrochemical and thermal instability for sodium-ion batteries using operando experiments and thermo-electrochemical analytics.

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Dhevathi Rajan Rajagopalan Kannan is a Research Scientist at UL Research Institutes (ULRI). He has over seven years of experience in battery research. Before joining ULRI, he worked in automotive and solid-state battery companies. His current research focuses on the safety and performance of various lithium-ion and sodium-ion battery chemistries.

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Vinay Premnath is the Director of Research with focus on energy storage safety at the Electrochemical Safety Research Institute (UL Research Institutes). Prior to joining UL Research Institutes, Vinay was a Principal Engineer at Southwest Research Institute. Vinay received his MS degree from the University of Minnesota, Twin Cities.

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Wan Si Tang is the Director of Research at the Electrochemical Safety Research Institute (UL Research Institutes). She has 15+ years of experience in novel functional materials for energy storage and conversion and advanced battery manufacturing. Wan Si is the recipient of the 2025 ECD Jubilee Global Diversity Award. (https://wansitang.wordpress.com/)

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Judith A. Jeevarajan is the Vice President and Executive Director for the Electrochemical Safety Research Institute at UL Research Institutes (ULRI). With more than 29 years of experience, she specializes in battery safety for lithium-ion and sodium-ion cells and modules, recycling, thermal runaway, fire, smoke, particulate emissions, and fire suppressants.

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Partha P. Mukherjee is a University Faculty Scholar and Professor of Mechanical Engineering at Purdue University, specializing in mesoscale modeling and experimental analytics of transport, chemistry, microstructure, and interface interactions in energy storage and conversion. He has published >250 journal articles on different battery chemistries and energy conversion systems. (https://engineering.purdue.edu/ETSL/)

Acknowledgments

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The funding for this research was provided by UL Research Institutes through the Center for Advances in Resilient Energy Storage (CARES).

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  • Abstract

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    Figure 1

    Figure 1. (a) Historical timeline of sodium-ion battery (SIB) development, highlighting key discoveries in cathode and anode chemistries, along with the emergence of recent commercial and mass-manufacturing efforts. (b) Comparison of energy storage capacities of various cathode and anode materials. (6,23−25) (Electrochemical properties are provided in Table S1 in the Supporting Information.) (c) Comparison of key characteristics of sodium ions and lithium ions. (26−28) (d) Schematic overview of key considerations for developing practical SIBs.

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    Figure 2

    Figure 2. (a) Schematic illustration of typical thermal degradation pathways in sodium-ion cathodes upon heating, including layered, PBA, and polyanionic compounds. (b) Comparison of phase transitions during charging for layered sodium-ion cathodes: NaNi0.33Mn0.33Co0.33O2 (NNMCO), NaNi0.5Mn0.5O2 (NNMO), and NaCoO2 (NCO) with their lithium-ion counterparts, LiCoO2 (LCO) and LiNi0.33Mn0.33Co0.33O2 (NMC). Here, each number corresponds to different phases exhibited by the cathode, as provided in Table S2 of the Supporting Information. (37,38,56) (c) In situ XRD profile of Na0.8Ni0.33Mn0.67O2 (NNMO) during heating using X-ray beam of wavelength 0.154 nm (Reproduced with permission from ref (32). Copyright 2025 Wiley-VCH GmbH, Weinheim.) (d) Thermodynamic phase diagram of the Na-Pb binary alloy system. (Adapted from ref (57). Copyright 2024 Electrochemical Society (ECS) & IOP Science.) (e) Schematic showing the influence of hard carbon (HC) fabrication temperature on anode microstructure and sodium metal agglomeration. (f) Influence of fabrication temperature on the ion storage mechanism in HC. (Adapted from ref (52). Copyright 2020 Royal Society of Chemistry (RSC).)

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    Figure 3

    Figure 3. (a) Comparison of thermal stability of the anode interphase for various salt–solvent combinations used in SIBs (additional details are provided in Table S3 of the Supporting Information). (59,73) (b) Schematic illustration showing the relationship between solvation energy and thermal stability of the anode interphase. (c) Spider chart depicting thermal stability characteristics of different Sn alloy anodes with and without FEC additives after cycling. (Adapted from ref (55). Copyright 2025 American Chemical Society (ACS).) Here μ-Sn and n-Sn refer to micro-Sn and nano-Sn, respectively. (d) SEM images of pristine and cycled n-Sn particles showing nonuniform interphase formation after cycling without additives. (Reproduced with permission from ref (66). Copyright 2022 American Chemical Society (ACS).) (e) Comparison of the effect of FEC on the CE of HC and Sn anodes. (66,72)

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    Figure 4

    Figure 4. (a) Schematic illustration of typical thermal instability pathways of the CEI in layered oxide and PBA cathodes. (b) In situ XRD pattern of charged NFM in 1 M NaPF6 in propylene carbonate:ethyl methyl carbonate (PC:EMC) with 2 wt% FEC using an X-ray beam of wavelength 0.012 nm. (Reproduced with permission from ref (77). Copyright 2018 American Chemical Society (ACS).) (c) Comparative analysis of gas evolution normalized to volumetric energy density for NVPF and LFP cathodes. (Adapted from ref (82). Copyright 2022 American Chemical Society (ACS).) (d) Comparison of the thermal stability of different cathodes based on the relationship between the onset temperature for thermal degradation and cutoff voltage (figure numbers for the representative data sets are summarized in Table S4 of the Supporting Information). (e) Thermal stability profile of carbon-coated NVP as a function of SOC. (Adapted from ref (83). Copyright 2024 Elsevier.) (f) Schematic depiction of how increasing SOC in layered oxide cathodes influences degradation mechanisms and the severity of thermal runaway.

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    Figure 5

    Figure 5. (a) Schematic illustration of the typical thermal runaway pathways in SIB cells. (b) Thermal safety characteristics in NaxTMO2 (NTM) and LFP cathodes. (Adapted from ref (87). Copyright 2024 Elsevier.) (c) Heat release comparison between LIB and SIB cells with cathode and anode contributions. (Adapted from ref (86). Copyright 2021 American Chemical Society (ACS).) (d) SEM micrographs of SIB cathode and anode after thermal abuse testing. (Reproduced with permission from ref (88). Copyright 2018 Elsevier.) (e) Microcalorimetry profile showing heat generation during a single charge/discharge cycle in a pristine NVP/HC full cell. (92) (f) Comparison of heat release during thermal abuse tests of different cathodes and anodes (more details regarding the electrode–electrolyte combination for this data set are provided in Table S5 in the Supporting Information). (g) Maximum temperatures observed during nail penetration and overcharge tests for SIBs using NVPF, NFM, and NCFMO cathodes, compared to LFP-based cells (8,89,93)

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    Figure 6

    Figure 6. (a) Comparison of energy density and cycle life (at 80% capacity retention) of various SIB prototypes from different manufacturers relative to BYD’s lithium-ion blade battery. (Adapted from refs (96and97). Copyright 2023 Springer Nature and 2023 MDPI.) (b) Breakdown of material and processing costs for commercially available LIB and SIB systems. (Adapted from refs (98and99). Copyright 2019 MDPI and 2025 Cell Press.) (c) Specific energy comparison of different cathode materials as a function of areal loading. (Adapted from ref (94). Copyright 2021 Elsevier.) (d) Effect of heating power during thermal abuse tests on the maximum temperature (T3) and time interval between onset of self-heating and thermal runaway (t2 – t1) for layered oxide-based SIBs. (Adapted from ref (95). Copyright 2025 Elsevier.) (e) Representative illustration of heat generation as a function of charging rate. (f) Schematic showing the hierarchical set of factors (i.e., at the particle, interphase, and electrode levels) affecting SIB safety.

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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.5c02345.

    • Summary of electrochemical properties of sodium-ion cathodes and anodes (Table S1), Comparison of phase behavior of different sodium-ion and lithium-ion layered oxides (Table S2), Exothermic parameters of different sodium salt-solvent combinations with the salt concentration of 1 M (Table S3), Thermal stability of different sodium-ion cathodes as a function of cutoff voltages (Table S4), Typical electrode–electrolyte configurations used in thermal stability investigations of sodium-ion batteries (Table S5), Properties of commonly used solvents in sodium-ion batteries (Table S6) (PDF)


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