Key Takeaways & Executive Findings
- •• • Commercial LIBs retain only 80% capacity at −20 °C and 90% at 55 °C relative to room temperature, establishing the baseline performance gap that electrolyte additives must close for electric vehicles in cold climates and tropical high-power applications. • • LiPF6 hydrolysis at elevated temperatures generates corrosive HF, accelerating SEI/CEI instability and transition-metal dissolution; additives such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) inhibit cyclic ether polymerization, enabling wide-temperature-range high-rate cycling in LIBs (Adv. Sci. 2024, 12, 2409259). • • Low-temperature operation is limited by sluggish Li+ desolvation and increased electrolyte viscosity; nitrile-based electrolytes with engineered passivation layers (Energy Fuels 2025, 39, 7538–7549) and localized high-concentration 1,3-dioxolane systems with LiNO3 (Adv. Energy Mater. 2024, 14, 2401961) demonstrate improved Li+ migration and dendrite suppression at ultralow temperatures. • • Multifunctional additives such as those in Nat. Commun. 2025, 16, 3344 enable high-power lithium metal batteries at ultra-low temperatures, while non-flammable formulations (J. Mater. Chem. A 2021, 9, 15363–15372) extend cycle life over a wide temperature range, directly addressing safety and longevity bottlenecks for grid storage and defense applications.
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Abstract
Rechargeable lithium batteries (LBs) capable of withstanding extreme high and low temperatures (HT/LT) are indispensable for carbon neutrality, yet commercial cells deliver only 80% of room-temperature capacity at −20 °C and 90% at 55 °C. This review systematically examines the failure mechanisms of electrolytes under HT/LT conditions, including thermally driven side reactions, LiPF6 hydrolysis generating corrosive HF, transition-metal dissolution, sluggish Li+ desolvation, and unstable solid electrolyte interphase (SEI) formation. Electrolyte additives, characterized by small dosage, low cost, and minimal energy-density penalty, are classified by their working mechanisms, functions, advantages, and disadvantages. Design principles for advanced additives are proposed, emphasizing synergistic optimization of oxidative stability at HT and ion mobility at LT. Although tailored to lithium-based systems, the strategies offer transferable insights for sodium and potassium batteries facing temperature-dependent degradation. Key empirical benchmarks from the literature include nitrile-based passivation layers, localized high-concentration electrolytes with lithium nitrate, and polymer-like glass-forming electrolytes enabling fast ion transport at low temperatures. The review consolidates 130 references, providing a rigorous framework for additive selection and interface engineering to extend operational temperature ranges.
1. Introduction
Rechargeable lithium batteries (LBs) that operate reliably under extreme thermal conditions are a prerequisite for carbon neutrality, yet current commercial systems exhibit severe performance decay: only 80% of room-temperature capacity at −20 °C and 90% at 55 °C. The failure modes diverge by temperature. At high temperatures, accelerated electrolyte decomposition, LiPF6 hydrolysis to HF, and transition-metal dissolution destabilize the cathode-electrolyte interphase (CEI) and solid electrolyte interphase (SEI), triggering thermal runaway and capacity fade. At low temperatures, solvation and desolvation of Li+ become sluggish, electrolyte viscosity rises, interfacial transfer resistance increases exponentially, and lithium dendrite growth is exacerbated in both lithium-ion and lithium metal batteries. These mechanisms collectively degrade operational reliability in electric vehicles, space exploration (≤−90 °C), defense systems, and renewable energy storage.
Electrolyte additives offer a pragmatic intervention: small dosage, low cost, and minimal reduction in energy density. This review systematically classifies state-of-the-art additives by their working mechanisms, functions, advantages, and disadvantages, and proposes design principles that emphasize synergistic optimization of oxidative stability at high temperature and ion mobility at low temperature. By consolidating empirical benchmarks from 130 references—including nitrile-based passivation layers, localized high-concentration electrolytes with lithium nitrate, and polymer-like glass-forming electrolytes—the analysis provides a rigorous framework for extending the operational temperature range of lithium-based systems and offers transferable insights for sodium and potassium batteries facing analogous temperature-dependent degradation.
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ZHOU Bingxin, YANG Zhuo, ZHANG Quan, FANG Baizeng, WILKINSON David P., ZHANG Jiujun, RAO Zhonghao (2025). Electrolyte additives for extending the operational temperature range of rechargeable lithium batteries. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3514-3
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Frequently Asked Questions
What are the dominant failure mechanisms of LiPF6-based electrolytes at high temperatures, and how do additives mitigate them?
At high temperatures, LiPF6 hydrolyzes to HF, which corrodes the SEI/CEI and dissolves transition metals, leading to cathode structural collapse and capacity fade. Additives such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) inhibit cyclic ether polymerization and stabilize interfaces, as demonstrated in wide-temperature-range high-rate LIBs (Adv. Sci. 2024, 12, 2409259). Non-flammable formulations (J. Mater. Chem. A 2021, 9, 15363–15372) further suppress thermal runaway, extending cycle life at elevated temperatures.
Which additive strategies enable lithium metal batteries to operate at ultra-low temperatures, and what performance metrics are achieved?
Localized high-concentration electrolytes based on 1,3-dioxolane with lithium nitrate (Adv. Energy Mater. 2024, 14, 2401961) and multifunctional additives (Nat. Commun. 2025, 16, 3344) enhance Li+ desolvation kinetics and suppress dendrite growth. Nitrile-based electrolytes with engineered passivation layers (Energy Fuels 2025, 39, 7538–7549) reduce interfacial resistance, enabling high-power lithium metal batteries at ultra-low temperatures. These systems maintain stable cycling where conventional carbonate electrolytes fail below −20 °C.
What are the cost and scalability barriers to adopting advanced electrolyte additives in commercial lithium batteries?
Additives are typically used at <5 wt% dosage, minimizing cost and energy-density penalty. However, scalability depends on synthetic complexity and compatibility with existing electrolyte manufacturing. For example, localized high-concentration electrolytes require precise salt ratios and may increase viscosity, complicating filling and wetting. Machine learning-driven exploration (J. Energy Storage 2021, 42, 103012) can accelerate additive screening, but industrial adoption demands validated cycle life and safety data under realistic abuse conditions.
How do additive-derived interphases differ between high-temperature and low-temperature operation, and can a single additive address both extremes?
High-temperature interphases require oxidative stability and resistance to HF attack, often achieved with sulfur- or nitrogen-containing additives that form robust CEI/SEI layers. Low-temperature operation demands fast Li+ transport and low desolvation energy, favoring nitrile or ether-based additives that weaken Li+-solvent interactions. A single additive rarely optimizes both; synergistic blends, such as those combining film-forming and ion-conducting moieties, are needed. The review proposes design principles for such dual-function additives, but empirical validation across −40 to 60 °C remains limited.
What transferable insights do lithium electrolyte additives offer for sodium and potassium batteries facing similar temperature challenges?
The fundamental mechanisms—suppressing side reactions, stabilizing interphases, and enhancing ion mobility—are metal-agnostic. Additives that form flexible, ion-conducting SEI layers on lithium can be adapted for sodium and potassium systems, though ion size and solvation shell differences require re-optimization. For instance, nitrile-based passivation layers may need modified chain lengths to accommodate larger Na+ or K+ ions. The review emphasizes that while direct translation is not trivial, the design framework accelerates development for other metal-based batteries.
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