Low-temperature Lithium-ion Batteries Research Articles

Concentration Controlling of Carboxylic Ester-Based Electrolyte for Low Temperature Lithium-Ion Batteries.

Low temperature has been a major challenge for lithium-ion batteries (LIBs) to maintain satisfied electrochemical performance, and the main reason is the deactivation of electrolyte with the decreasing temperature. To address this point, in present work, we develop a low-temperature resistant electrolyte which includes ethyl acetate (EA) and fluoroethylene carbonate (FEC) as solvent and lithium difluoro(oxalato)borate (LiDFOB) as the primary lithium salt. Due to the preferential decomposition of LiDFOB and FEC, a solid electrolyte interface rich in LiF is formed on the lithium metal anodes (LMAs) and lithium cobalt oxide (LCO) cathodes, contributing to higher stability and rapid desolvation of Li+ ions. The batteries with the optimized electrolyte can undergo cycling tests at -40 °C, with a capacity retention of 83.9 % after 200 cycles. Furthermore, the optimized electrolyte exhibits excellent compatibility with both LCO cathodes and graphite (Gr) anodes, enabling a Gr/LCO battery to maintain a capacity retention of 90.3 % after multiple cycles at -25 °C. This work proposes a cost-effective electrolyte that can activate potential LIBs in practical scenarios, especially in low-temperature environments.

Quantification of Charge Transport and Mass Deprivation in Solid Electrolyte Interphase for Kinetically-Stable Low-Temperature Lithium-Ion Batteries.

Graphite (Gr)-based lithium-ion batteries with admirable electrochemical performance below -20 °C are desired but are hindered by sluggish interfacial charge transport and desolvation process. Li salt dissociation via Li+-solvent interaction enables mobile Li+ liberation and contributes to bulk ion transport, while is contradictory to fast interfacial desolvation. Designing kinetically-stable solid electrolyte interphase (SEI) without compromising strong Li+-solvent interaction is expected to compatibly improve interfacial charge transport and desolvation kinetics. However, the relationship between physicochemical features and temperature-dependent kinetics properties of SEI remains vague. Herein, we propose four key thermodynamics parameters of SEI potentially influencing low-temperature electrochemistry, including electron work function, Li+ transfer barrier, surface energy, and desolvation energy. Based on the above parameters, we further define a novel descriptor, separation factor of SEI (SSEI), to quantitatively depict charge (Li+/e-) transport and solvent deprivation processes at Gr/electrolyte interface. A Li3PO4-based, inorganics-enriched SEI derived by Li difluorophosphate (LiDFP) additive exhibits the highest SSEI (4.89×103) to enable efficient Li+ conduction, e- blocking and rapid desolvation, and as a result, much suppressed Li-metal precipitation, electrolyte decomposition and Gr sheets exfoliation, thus improving low-temperature battery performances. Overall, our work originally provides visualized guides to improve low-temperature reaction kinetics/thermodynamics by constructing desirable SEI chemistry.

Anchored Weakly-Solvated Electrolytes for High-Voltage and Low-Temperature Lithium-ion Batteries.

Electrolytes endowed with high oxidation/reduction interfacial stability, fast Li-ion desolvation process and decent ionic conductivity over wide temperature region are known critical for low temperature and fast-charging performance of energy-dense batteries, yet these characteristics are rarely satisfied simultaneously. Here, we report anchored weakly-solvated electrolytes (AWSEs), that are designed by extending the chain length of polyoxymethylene ether electrolyte solvent, can achieve the above merits at moderate salt concentrations. The -O-CH2-O- segment in solvent enables the weak four-membered ring Li+ coordination structure and the increased number of segments can anchor the solvent by Li+ without largely sacrificing the ionic dissociation ability. Therefore, the single salt/single solvent AWSEs enable solvent co-intercalation-free behavior towards graphite (Gr) anode and high oxidation stability towards high-nickel cathode (LiNi0.8Co0.1Mn0.1O2-NCM811), as well as the formation of inorganic rich electrode/electrolyte interphase on both of them due to the anion-rich solvation shells. The capacity retention of Gr||NCM811 Ah-class pouch cell can reach 70.85 % for 1000 cycles at room-temperature and 75.86 % for 400 cycles at -20 °C. This work points out a promising path toward the molecular design of electrolyte solvents for high-energy/power battery systems that are adaptive for extreme conditions.

LiF modified hard carbon from date seeds as an anode material for enhanced low-temperature lithium-ion batteries

The performance of traditional Li-ion batteries deteriorates when operating at sub-zero temperatures mainly due to the slow diffusion of Li-ions in commercial negative electrode materials. Various alternative anodes have been explored, but complex fabrication methods hinder practical implementation. This work proposes a cost-effective anode material, a porous structured nitrogen-doped hard carbon synthesized from date seeds with further LiF modification to achieve an artificial LiF-rich solid electrolyte interphase (SEI) layer. The resulting anode material showcases promising characteristics, achieving a specific capacity of 525 mAh g−1 after 50 cycles at room temperature. Furthermore, it maintains a substantial capacity of 280 mAh g−1 after 100 cycles at −20 °C. Notably, even when subjected to a high current of 2C at −20 °C, the electrode still provides a remarkable capacity of 72 mAh g−1 after 500 cycles. The outstanding charge storage performance at low temperatures is attributed to the predominance of capacitance-controlled charge storage mechanisms in the prepared anode. Post-mortem analysis confirms structural stability and formation of a uniform LiF-rich SEI layer. This novel approach presents a practical solution to the difficulties encountered by LIBs in cold environments, paving the way for improved battery performance and longevity.

Enhanced Low-Temperature Resistance of Lithium-Metal Rechargeable Batteries Based on Electrolyte Including Ethyl Acetate and LiDFOB Additives.

To meet the demand for higher energy density in lithium-ion batteries and expand their application range, coupling lithium metal anodes with high-voltage cathodes is an ideal solution. However, the compatibility between lithium metal batteries and electrolytes affects their applicability. In this study, proposes a locally concentrated electrolyte based on ethyl acetate (EA) as the solvent, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as the lithium salt, and lithium difluorooxoborate (LiDFOB) as a sacrificial agent to enhance the low-temperature and high-voltage endurance of Li//Lithium cobalt oxide (LCO) batteries. The Li//LCO battery can operate within the voltage range of 3 to 4.5 V, with an initial discharge specific capacity of 174.5 mAh g-1 at 20 °C. At -40 °C, after 200 cycles, the capacity retention rate is 87.7 %. It can operate under extreme conditions of -70 °C, with a discharge specific capacity of 112.6 mAh g-1. Additionally, LCO//HC batteries using this electrolyte demonstrate excellent performance. Present work provides a new perspective for the optimization of electrolytes for low-temperature lithium-ion batteries.

Enhanced diffusion kinetics in Y-doped SnO2 anodes for low-temperature lithium-ion batteries: A combined theoretical and experimental study

In recent years, there has been an increasing demand for lithium-ion batteries suitable for low temperatures in various fields. SnO2, with its high theoretical specific capacity, has emerged as an ideal candidate for low-temperature lithium-ion batteries. However, tin oxide exhibits inherent issues such as poor conductivity and limited cycle reversibility. Enhancing the diffusion rate of lithium ions in tin oxide is crucial for improving its low-temperature performance. We use first-principles calculations based on Density Functional Theory (DFT) to investigate the doping models of various transition metal elements (Sc, Y, Ti, Zr, V, Nb, Gr, Mo, Mn, Fe, Co, Ni) with a rational ratio of 4 % in SnO2. The results indicate that Y doping decreases the band gap of SnO2 by 0.253 eV, leading to a significant reduction in the Li-ion diffusion barrier of α-Sn. Furthermore, the synthesized SnO2 doped with Y (Y-SnO2) electrode exhibited excellent cyclic stability as an anode and achieved a high reversible capacity of 672 mAh g−1 at −10°C, surpassing that of the pure SnO2 (450 mAh g−1). Moreover, it demonstrated a higher diffusion coefficient of lithium ions and lower charge transfer impedance at both low and room temperatures.

Li3PO4-Enriched SEI on Graphite Anode Boosts Li+ De-Solvation Enabling Fast-Charging and Low-Temperature Lithium-Ion Batteries.

Li+ de-solvation at solid-electrolyte interphase (SEI)-electrolyte interface stands as a pivotal step that imposes limitations on the fast-charging capability and low-temperature performance of lithium-ion batteries (LIBs). Unraveling the contributions of key constituents in the SEI that facilitate Li+ de-solvation and deciphering their mechanisms, as a design principle for the interfacial structure of anode materials, is still a challenge. Herein, we conducted a systematic exploration of the influence exerted by various inorganic components (Li2CO3, LiF, Li3PO4) found in the SEI on their role in promoting the Li+ de-solvation. The findings highlight that Li3PO4-enriched SEI effectively reduces the de-solvation energy due to its ability to attenuate the Li+-solvent interaction, thereby expediting the de-solvation process. Building on this, we engineer Li3PO4 interphase on graphite (LPO-Gr) anode via a simple solid-phase coating, facilitating the Li+ de-solvation and building an inorganic-rich SEI, resulting in accelerated Li+ transport crossing the electrode interfaces and interphases. Full cells using the LPO-Gr anode can replenish its 80 % capacity in 6.5 minutes, while still retaining 70 % of the room temperature capacity even at -20 °C. Our strategy establishes connection between the de-solvation characteristics of the SEI components and the interfacial structure design of anode materials for high performance LIBs.

Revealing the key role of non-solvating diluents for fast-charging and low temperature Li-ion batteries

Fast-charging and low temperature operation are of vital importance for the further development of lithium-ion batteries (LIBs), which is hindered by the utilization of conventional carbonate-based electrolytes due to their slow kinetics, narrow operating temperature and voltage range. Herein, an acetonitrile (AN)-based localized high-concentration electrolyte (LHCE) is proposed to retain liquid state and high ionic conductivity at ultra-low temperatures while possessing high oxidation stability. We originally reveal the excellent thermal shielding effect of non-solvating diluent to prevent the aggregation of Li+ solvates as temperature drops, maintaining the merits of fast Li+ transport and facile desolvation as at room temperature, which bestows the graphite electrode with remarkable low temperature performance (264 mA h g−1 at −20 °C). Remarkably, an extremely high capacity retention of 97% is achieved for high-voltage high-energy graphite||NCM batteries after 250 cycles at −20 °C, and a high capacity of 110 mA h g−1 (71% of its room-temperature capacity) is retained at −30 °C. The study unveils the key role of the non-solvating diluents and provides instructive guidance in designing electrolytes towards fast-charging and low temperature LIBs.

Dominant Solvent-Separated Ion Pairs in Electrolytes Enable Superhigh Conductivity for Fast-Charging and Low-Temperature Lithium Ion Batteries.

The low ionic conductivities of aprotic electrolytes hinder the development of extreme fast charging technologies and applications at low temperatures for lithium-ion batteries (LIBs). Herein, we present an electrolyte with LiFSI in acetone (DMK). In DMK electrolytes, the solvation number is three, and solvent-separated ion pairs (SSIPs) are the dominant structure, which is largely different from other linear aprotic electrolytes where salts primarily exist as contact ion pairs (CIPs). With incompact solvation structures due to the weak solvation ability of DMK with Li+, the ionic conductivity reaches 45 mS/cm at room temperature. The percentage of SSIPs increases as temperatures decrease in DMK electrolytes, which is totally different from the carbonate-based electrolytes but greatly beneficial to low-temperature ionic conductivity. With the appropriate addition of VC and FEC, DMK-based electrolytes still exhibit a superhigh ionic conductivity. Even at -40 °C, the ionic conductivity is greater than 10 mS/cm. With DMK-based electrolytes, LIBs with thick LiFePO4 electrodes can be cycled at high rates and at low temperatures.

Co-Intercalation-Free Graphite Anode Enabled by an Additive Regulated Interphase in an Ether-Based Electrolyte for Low-Temperature Lithium-Ion Batteries.

Graphite (Gr) anode, which is endowed with high electronic conductivity and low volume expansion after Li-ion intercalation, establishes the basis for the success of rocking-chair Li-ion batteries (LIBs). However, due to the high barrier of the Li-ion desolvation process, sluggish transport of Li ions through the solid electrolyte interphase (SEI) and the high freezing points of electrolytes, the Gr anode still suffers from great loss of capacity and severe polarization at low temperature. Here, 1,2-diethoxyethane (DEE) with an intrinsically wide liquid region and weak solvation ability is applied as an electrolyte solvent for LIBs. By rationally designing the additives of electrolytes, an intact SEI with fast Li-ion conductivity is constructed, enabling the co-intercalation-free Gr anode with long-term stability (91.8% after 500 cycles) and impressive low-temperature characteristics (82.6% capacity retention at -20 °C). Coupled with LiFePO4 and LiNi0.8Mn0.1Co0.1O2 cathodes, the optimized electrolyte also demonstrates low polarization under -20 °C. Our work offers a feasible approach to enable ether-based electrolytes for low-temperature LIBs.

Deshielding Anions Enable Solvation Chemistry Control of LiPF6-Based Electrolyte toward Low-Temperature Lithium-Ion Batteries.

Severe capacity decay under subzero temperatures remains a significant challenge for lithium-ion batteries (LIBs) due to the sluggish interfacial kinetics. Current efforts to mitigate this deteriorating interfacial behavior rely on high-solubility lithium salts (e.g., Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), Lithium bis(fluorosulfonyl)imide (LiFSI))-based electrolytes to construct anion participated solvation structures. However, such electrolytes bring issues of corrosion on the current collector and increased costs. Herein, the most commonly used Lithium hexafluorophosphate (LiPF6) instead, to establish a peculiar solvation structure with a high ratio of ion pairs and aggregates by introducing a deshielding NO3 - additive for low-temperature LIBs is utilized. The deshielding anion significantly reduces the energy barrier for interfacial behavior at low temperatures. Benefiting from this, the graphite (Gr) anode retains a high capacity of ≈72.3% at -20°C, which is far superior to the 32.3% and 19.4% capacity retention of counterpart electrolytes. Moreover, the LiCoO2/Gr full cell exhibits a stable cycling performance of 100 cycles at -20°C due to the inhibited lithium plating. This work heralds a new paradigm in LiPF6-based electrolyte design for LIBs operating at subzero temperatures.

A Self-heating and Charging Coordinated Strategy for Low-temperature Lithium-ion Batteries based on a Novel DAB-LC Converter

A Self-heating and Charging Coordinated Strategy for Low-temperature Lithium-ion Batteries based on a Novel DAB-LC Converter

Review of Low-Temperature Performance, Modeling and Heating for Lithium-Ion Batteries

Lithium-ion batteries (LIBs) have the advantages of high energy/power densities, low self-discharge rate, and long cycle life, and thus are widely used in electric vehicles (EVs). However, at low temperatures, the peak power and available energy of LIBs drop sharply, with a high risk of lithium plating during charging. This poor performance significantly impacts the application of EVs in cold weather and dramatically limits the promotion of EVs in high-latitude regions. This challenge recently attracted much attention, especially investigating the performance decrease for LIBs at low temperatures, and exploring the solutions; however, limited reviews exist on this topic. Here, we thoroughly review the state-of-the-arts about battery performance decrease, modeling, and preheating, aiming to drive effective solutions for addressing the low-temperature challenge of LIBs. We outline the performance limitations of LIBs at low temperatures and quantify the significant changes in (dis)charging performance and resistance of LIBs at low temperatures. The various models considering low-temperature influencing factors are also tabulated and summarized, with the modeling improvement for describing low-temperature performance highlighted. Furthermore, we categorize the existing heating methods, and the metrics such as heating rate, energy consumption, and lifetime impact are highlighted to provide fundamental insights into the heating methods. Finally, the limits of current research on low-temperature LIBs are outlined, and an outlook on future research direction is provided.

Co-Intercalation-Free Ether-Based Weakly Solvating Electrolytes Enable Fast-Charging and Wide-Temperature Lithium-Ion Batteries.

Ether-based electrolytes are competitive choices to meet the growing requirements for fast-charging and low-temperature lithium-ion batteries (LIBs) due to the low viscosity and low melting point of ether solvents. Unfortunately, the graphite (Gr) electrode is incompatible with commonly used ether solvents due to their irreversible co-intercalation into Gr interlayers. Here, we propose cyclopentyl methyl ether (CPME) as a co-intercalation-free ether solvent, which contains a cyclopentane group with large steric hindrance to obtain weakly solvating power with Li+ and a wide liquid-phase temperature range (-140 to +106 °C). A weakly solvating electrolyte (WSE) based on CPME and fluoroethylene carbonate (FEC) cosolvents can simultaneously achieve fast desolvation ability and high ionic conductivity, which also induces a LiF-rich solid electrolyte interphase (SEI) on the Gr anode. Therefore, the Gr/Li half-cell with this WSE can deliver outstanding rate capability, stable cycling performance, and high specific capacity (319 mAh g-1) at an ultralow temperature of -60 °C. Furthermore, a practical LiFePO4 (loading ≈25 mg cm-2)/Gr (loading ≈12 mg cm-2) pouch cell with this WSE also reveals outstanding rate capability and stable long-term cycling performance above 1000 cycles with a high Coulombic efficiency (≈99.9%) and achieves an impressive low-temperature application potential at -60 °C.

Synergetic modulation on solvation structure and electrode interface to achieve lithium-ion batteries cycled at ultra-low temperature

The performance of rechargeable lithium-ion batteries (LIBs) in cold environments remains a challenge due to the insufficient ionic conductivity of electrolyte and lithium plating at graphite anodes. Herein, we demonstrate that the synergistic effect of ether-based electrolyte and niobium oxide with high intercalation potential can significantly improve the low-temperature charging/discharging performance of LIBs. Theoretical calculations and in-situ characterizations prove that the weak desolvation energy of electrolyte and the strong binding energy Li+-O bridging coordination synergistically accelerate the interfacial reaction kinetics. The full cells by coupling the niobium oxide anode with LiFePO4 cathode show 95.6% of the initial capacity after 500 cycles at −30 °C, and exhibit excellent rechargeability at −50 °C. This work verifies that the synergism of solvating power of solvent and Li+ intercalation behavior is crucial in low-temperature LIBs.

Electrolyte design for ultra-stable, low-temperature lithium-ion batteries

Electrolyte design for ultra-stable, low-temperature lithium-ion batteries

Inhibiting gas generation to achieve ultralong-lifespan lithium-ion batteries at low temperatures

•Revealing the gas generation mechanism in low-temperature lithium-ion batteries •Proposing a high-concentration electrolyte strategy to inhibit gas generation •The Ah-level pouch cell exhibits a record-breaking lifespan of over 1 year at −20°C The notorious low-temperature sensitivity of contemporary lithium-ion batteries (LIBs) has long restricted their low-temperature applications. Introduction of high-content low-freezing-point solvents significantly expands the low-temperature operation border of LIBs. However, they react violently with metallic lithium (Li) plated at low temperatures (−20°C or lower), resulting in severe gas generation and a limited lifespan. We reveal the mechanism of gas generation and develop a high-concentration ethyl acetate (EA)-based electrolyte. The dense and uniform solid electrolyte interphase formed by the joint decomposition of rich anions and additive effectively passivate the plated Li at low temperatures. The proposed electrolyte enables the LiNi0.8Co0.1Mn0.1O2 (NCM811)/graphite pouch cell to be stably cycled at −20°C and 0.2 C for a record-breaking lifetime of more than 1 year (1,400 cycles). The NCM811/graphite pouch cell exhibits good fast-charging capability (0.5 C) at −20°C with a capacity decay rate as low as 0.0097% per cycle during 4,000 cycles. The notorious low-temperature sensitivity of contemporary lithium-ion batteries (LIBs) has long restricted their low-temperature applications. Introduction of high-content low-freezing-point solvents significantly expands the low-temperature operation border of LIBs. However, they react violently with metallic lithium (Li) plated at low temperatures (−20°C or lower), resulting in severe gas generation and a limited lifespan. We reveal the mechanism of gas generation and develop a high-concentration ethyl acetate (EA)-based electrolyte. The dense and uniform solid electrolyte interphase formed by the joint decomposition of rich anions and additive effectively passivate the plated Li at low temperatures. The proposed electrolyte enables the LiNi0.8Co0.1Mn0.1O2 (NCM811)/graphite pouch cell to be stably cycled at −20°C and 0.2 C for a record-breaking lifetime of more than 1 year (1,400 cycles). The NCM811/graphite pouch cell exhibits good fast-charging capability (0.5 C) at −20°C with a capacity decay rate as low as 0.0097% per cycle during 4,000 cycles.

Electronic Modulation and Structural Engineering of Carbon-Based Anodes for Low-Temperature Lithium-Ion Batteries: A Review.

Lithium-ion batteries (LIBs) have become the preferred battery system for portable electronic devices and transportation equipment due to their high specific energy, good cycling performance, low self-discharge, and absence of memory effect. However, excessively low ambient temperatures will seriously affect the performance of LIBs, which are almost incapable of discharging at -40~-60 °C. There are many factors affecting the low-temperature performance of LIBs, and one of the most important is the electrode material. Therefore, there is an urgent need to develop electrode materials or modify existing materials in order to obtain excellent low-temperature LIB performance. A carbon-based anode is one candidate for use in LIBs. In recent years, it has been found that the diffusion coefficient of lithium ion in graphite anodes decreases more obviously at low temperatures, which is an important factor limiting its low-temperature performance. However, the structure of amorphous carbon materials is complex; they have good ionic diffusion properties, and their grain size, specific surface area, layer spacing, structural defects, surface functional groups, and doping elements may have a greater impact on their low-temperature performance. In this work, the low-temperature performance of LIBs was achieved by modifying the carbon-based material from the perspectives of electronic modulation and structural engineering.

Reversible lithium plating on working anodes enhances fast charging capability in low-temperature lithium-ion batteries

The low-temperature lithium plating on working anodes severely limits the fast-charging capability of lithium-ion batteries and brings serious lifespan degradations and potential safety hazards. However, strict control of lithium plating, which currently is the primary task of battery management, is very challenging to achieve and greatly limits the charging speed of rechargeable batteries. While by releasing the elastic and reversible lithium plating interval, superior charging performance can be obtained. In this contribution, we quantitively analyze the reversibility of lithium plating under various working conditions. The reversibility is not simply a matter of multiplying the quantity of lithium plating by a constant coefficient. Further, we propose a plating-weak fast charging (PWFC) strategy that keeps the charging rate relatively large throughout the charging process, therefore effectively reducing the charging duration at low temperatures. When lithium plating is necessary during fast charging, PWFC regulates high reversibility to avoid rapid degradation by fine-tuning the charging current that triggers the lithium plating, thereby breaking through the stereotypical limit of the plating-free boundary while achieving a 19.92% reduction in capacity loss after 70 cycles at 0 °C compared with the constant-current charging, or a 21.0% reduction in charging time compared with the plating-free charging. Strikingly, PWFC can guarantee the life of electric vehicles beyond the warranty period and further shorten the charging time in winter.

Low-temperature lithium-ion batteries: challenges and progress of surface/interface modifications for advanced performance.

Lithium-ion batteries are in increasing demand for operation under extreme temperature conditions due to the continuous expansion of their applications. A significant loss in energy and power densities at low temperatures is still one of the main obstacles limiting the operation of lithium-ion batteries at sub-zero temperatures. In addition to electrodes and electrolytes, more attention should be paid to the electrode-electrolyte interface, considering that the total internal resistance of batteries at low temperatures is dominated by interfacial charge transfer resistance. Here, we first review the main interfacial processes in lithium-ion batteries at low temperatures, including Li+ solvation or desolvation, Li+ diffusion through the solid electrolyte interphase and electron transport. Then, recent progress on the electrode surface/interface modifications in lithium-ion batteries for enhanced low-temperature performance is presented in detail. The lasting challenges and perspectives regarding electrode/electrolyte interface control in low-temperature lithium-ion batteries are finally discussed.