Comparison of Chloroaluminate Melts for Aluminum Graphite Dual‐Ion Battery Application

Elia, Giuseppe Antonio; Hoeppner, Katrin; Hahn, Robert W.

doi:10.1002/batt.202000244

Cited by 14 publications

(8 citation statements)

References 29 publications

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“…The detailed information of these electrolytes is provided in Table S1 (Supporting Information). [14,16,17,[26][27][28] It can be seen that although the displacement of organic salts in chloroaluminate ILs can improve the high-voltage stability, all electrolytes with no additive show oxidation onset potential below 2.6 V versus Al 3+ /Al. With the additive of LiBOB, an IL electrolyte of AlCl 3 /[EMIm]Cl can deliver a good high-voltage stability at 100 °C.…”

Section: Resultsmentioning

confidence: 99%

High‐Voltage Deep Eutectic Solvent Electrolyte with Fluorine‐Substituted Acetamide Additive for Aluminum‐ion Battery

Chu,

Zhang,

Zhao

et al. 2023

Adv Funct Materials

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The high‐voltage stability of electrolytes profoundly determines electrochemical reactions, which is still one of the major obstacles for developing advanced Al‐ion batteries (AIBs). Herein, a fluorine‐adjustment strategy is proposed to improve the high‐voltage stability of a low‐cost AlCl3/acetamide (AcA) deep eutectic solvent electrolyte. By using a fluorine‐substituted AcA additive, the AlCl3/AcA electrolyte exhibits a lifted oxidation onset potential from 2.21 to 2.78 V versus Al3+/Al. Based on a series of structural investigations, it is found that the additive can adjust the coordination configurations and improve the anti‐oxidation capability of electrolytes. Moreover, the additive induces an F‐rich interphase layer, which can stabilize the plating/stripping reactions of Al electrode with accelerated kinetics. Based on the optimized electrolyte, a high‐voltage Al–S battery relying on the S cationic redox shows good performance with little voltage fading for 300 cycles. This study provides important insights into the exploration of high‐performance and low‐cost electrolytes for AIBs.

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Section: Resultsmentioning

confidence: 99%

High‐Voltage Deep Eutectic Solvent Electrolyte with Fluorine‐Substituted Acetamide Additive for Aluminum‐ion Battery

Chu,

Zhang,

Zhao

et al. 2023

Adv Funct Materials

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“…Conversely, Azimi et al reported conductivities decreasing from 22.6 to 14.7 mS cm –1 for LA:LB compositions between 1:1 and 2:1 with AlCl 3 :EMIM-Cl liquids . Other reports have found conductivities of 16.1, 15.5, and 9.2 mS cm –1 for AlCl 3 :EMIM-Cl liquids with a 1.5:1 mole ratio. On the other hand, for urea-based liquids, the conductivities are an order of magnitude lower than that of EMIM-Cl based liquids.…”

Section: Introductionmentioning

confidence: 93%

Measuring and Enhancing the Ionic Conductivity of Chloroaluminate Electrolytes for Al-Ion Batteries

et al. 2023

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At the core of the aluminum (Al) ion battery is the liquid electrolyte, which governs the underlying chemistry. Optimizing the rheological properties of the electrolyte is critical to advance the state of the art. In the present work, the chloroaluminate electrolyte is made by reacting AlCl3 with a recently reported acetamidinium chloride (Acet-Cl) salt in an effort to make a more performant liquid electrolyte. Using AlCl3:Acet-Cl as a model electrolyte, we build on our previous work, which established a new method for extracting the ionic conductivity from fitting voltammetric data, and in this contribution, we validate the method across a range of measurement parameters in addition to highlighting the model electrolytes’ conductivity relative to current chloroaluminate liquids. Specifically, our method allows the extraction of both the ionic conductivity and voltammetric data from a single, simple, and routine measurement. To bring these results in the context of current methods, we compare our results to two independent standard conductivity measurement techniques. Several different measurement parameters (potential scan rate, potential excursion, temperature, and composition) are examined. We find that our novel method can resolve similar trends in conductivity to conventional methods, but typically, the values are a factor of two higher. The values from our method, on the other hand, agree closely with literature values reported elsewhere. Importantly, having now established the approach for our new method, we discuss the conductivity of AlCl3:Acet-Cl-based formulations. These electrolytes provide a significant improvement (5–10× higher) over electrolytes made from similar Lewis base salts (e.g., urea or acetamide). The Lewis base salt precursors have a low economic cost compared to state-of-the-art imidazolium-based salts and are non-toxic, which is advantageous for scale-up. Overall, this is a noteworthy step at designing cost-effective and performant liquid electrolytes for Al-ion battery applications.

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“…The state-of-the-art electrolytes for room-temperature rechargeable nonaqueous aluminum metal batteries are ionic liquid electrolytes (ILEs) consisting of 1ethyl-3-methylimidazolium chloride (EmimCl) and aluminum chloride (AlCl 3 ). [22] The viscosity of [EmimCl] 1 [AlCl 3 ] 1.5 is reported to be 19.4 mPa s at 20 °C, [23] while the electrolyte viscosity for commercial LIBs is usually lower than 10 mPa s. [24] The high viscosity hinders the penetration of electrolytes into thick electrodes, leading to a low utilization of sulfur encapsulated in porous host materials. [25] It is expected that this negative effect would become more pronounced at sub-zero temperatures due to the further decreased electrolyte fluidity.…”

Section: Introductionmentioning

confidence: 99%

Locally Concentrated Ionic Liquid Electrolytes for Wide‐Temperature‐Range Aluminum‐Sulfur Batteries

Xu,

Diemant,

Mariani

et al. 2024

Angew Chem Int Ed

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Aluminum sulfur (Al‐S) batteries are promising energy storage devices due to their high theoretical capacity, low cost, and high safety. However, the high viscosity and inferior ion transport of conventionally used ionic liquid electrolytes (ILEs) limit the kinetics of Al‐S batteries, especially at sub‐zero temperatures. Herein, locally concentrated ionic liquid electrolytes (LCILE) formed via diluting the ILEs with non‐solvating 1,2‐difluorobenzene (dFBn) co‐solvent are proposed for wide‐temperature‐range Al‐S batteries. The addition of dFBn effectively promotes the fluidity and ionic conductivity without affecting the AlCl4‐/Al2Cl7‐ equilibrium, which preserves the reversible stripping/plating of aluminum and further promotes the overall kinetics of Al‐S batteries. As a result, Al‐S cells employing the LCILE exhibit higher specific capacity, better cyclability, and lower polarization with respect to the neat ILE in a wide temperature range from ‐20 to 40 °C. For instance, Al‐S batteries employing the LCILE sustain a remarkable capacity of 507 mAh g‐1 after 300 cycles at 20 °C, while only 229 mAh g‐1 is delivered with the dFBn‐free electrolyte under the same condition. This work demonstrates the favorable use of LCILEs for wide‐temperature Al‐S batteries.

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Comparison of Chloroaluminate Melts for Aluminum Graphite Dual‐Ion Battery Application

Cited by 14 publications

References 29 publications

High‐Voltage Deep Eutectic Solvent Electrolyte with Fluorine‐Substituted Acetamide Additive for Aluminum‐ion Battery

High‐Voltage Deep Eutectic Solvent Electrolyte with Fluorine‐Substituted Acetamide Additive for Aluminum‐ion Battery

Measuring and Enhancing the Ionic Conductivity of Chloroaluminate Electrolytes for Al-Ion Batteries

Locally Concentrated Ionic Liquid Electrolytes for Wide‐Temperature‐Range Aluminum‐Sulfur Batteries

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