Gel electrolytes with a wide potential window for high-rate Al-ion batteries

Yu, Zhijing; Jiao, Shuqiang; Tu, Jiguo; Song, Wei‐Li; Lei, Haiping; Jiao, Handong; Chen, Haosen; Fang, Daining

doi:10.1039/c9ta06815e

Cited by 61 publications

(68 citation statements)

References 45 publications

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“…Even if a decrease in electroactivity occurs when using PEO as a gelling polymer, Figure 5 demonstrates that these gel electrolytes can be at the same time as a solid and yet retain substantially the electroactivity of the liquid electrolyte, in this case uralumina. This has been postulated as not possible [ 11 , 12 , 13 , 14 ] based on the interaction between electroactive Al 2 Cl 7 − species and the ether in the oxyethylenic units. Although the interaction of the oxyethylenic units in PEO reduces electroactivity of uralumina, the low amount of UHMW polymer required compensates with its effect on the speciation of the liquid electrolyte.…”

Section: Resultsmentioning

confidence: 99%

“…These authors studied electrolytes with different polymer ratios, and concluded that those with the higher fraction of liquid electrolyte (80 wt%) were promising Al electrolytes, which enabled the stripping and plating of Al. Other authors [ 13 , 14 ] have repeated the exact procedure [ 12 ], in one case, to prepare electrolytes containing 80 wt% of the same EMICl:AlCl 3 , and in another, the room temperature ionic liquid formed with triethylamonium chloride (Et 3 NHCl) and AlCl 3 (Et 3 NHCl: AlCl 3 1:1.6 molar ratio). All these electrolytes were said to be solid, however no rheological measurements or qualitative characterizations of the solid state, for instance using the well-known inverted tube test, were done.…”

Section: Introductionmentioning

confidence: 99%

“…The deleterious interaction of molecules bearing lone pairs of electrons with aluminum electrolytes has led the scientific community to rule out the use of many well-known polymers in the field of solid electrolytes for the preparation of gel Al electrolytes. This includes, for instance, polyethylene oxide (PEO), polymethylmethacrylate (PMMA) or polyacrylonitrile (PAN) [ 11 , 12 , 13 , 14 ]. This view is supported by experiments showing that PEO based electrolytes [ 9 ] are not able to sustain electroplating of aluminum [ 16 ].…”

Section: Introductionmentioning

confidence: 99%

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Tough Polymer Gel Electrolytes for Aluminum Secondary Batteries Based on Urea: AlCl3, Prepared by a New Solvent-Free and Scalable Procedure

et al. 2020

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Polymer gel electrolytes have been prepared with polyethylene oxide (PEO) and the deep eutectic mixture of AlCl3: urea (uralumina), a liquid electrolyte which has proved to be an excellent medium for the electrodeposition of aluminum. The polymer gel electrolytes are prepared by mixing PEO in the liquid electrolyte at T > 65 °C, which is the melting point of PEO. This procedure takes a few minutes and requires no subsequent evaporation steps, being a solvent-free, and hence more sustainable procedure as compared to solvent-mediated ones. The absence of auxiliary solvents and evaporation steps makes their preparation highly reproducible and easy to scale up. PEO of increasing molecular weight (Mw = 1 × 105, 9 × 105, 50 × 105 and 80 × 105 g mol−1), including an ultra-high molecular weight (UHMW) polymer, has been used. Because of the strong interactions between the UHMW PEO and uralumina, self-standing gels can be produced with as little as 2.5 wt% PEO. These self-standing polymer gels maintain the ability to electrodeposit and strip aluminum, and are seen to retain a significant fraction of the current provided by the liquid electrolyte. Their gels’ rheology and electrochemistry are stable for months, if kept under inert atmosphere, and their sensitivity to humidity is significantly lower than that of liquid uralumina, improving their stability in the event of accidental exposure to air, and hence, their safety. These polymer gels are tough and thermoplastic, which enable their processing and molding into different shapes, and their recyclability and reprocessability. Their thermoplasticity also allows the preparation of concentrated batches (masterbatch) for a posteriori dilution or additive addition. They are elastomeric (rubbery) and very sticky, which make them very robust, easy to manipulate and self-healing.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Tough Polymer Gel Electrolytes for Aluminum Secondary Batteries Based on Urea: AlCl3, Prepared by a New Solvent-Free and Scalable Procedure

et al. 2020

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“…Current densities gradually improved with increasing scan cycles, indicating that reduction of oxide film remaining on the Al plate. The ionic conductivities [148]; (d) conductivity-temperature curve for the solid polymer electrolyte, and (e) the relationship between room-temperature conductivity and the time evolution of solid polymer electrolyte [151]. Reproduced from Refs.…”

Section: Electrolytementioning

confidence: 99%

“…Reproduced from Refs. [146,148] with permission from The Royal Society of Chemistry. Reproduced from Refs.…”

Section: Electrolytementioning

confidence: 99%

Advancement of technology towards high-performance non-aqueous aluminum-ion batteries

Wei

Peng

et al. 2021

Journal of Energy Chemistry

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Stable Quasi‐Solid‐State Aluminum Batteries

et al. 2022

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nonflammable ionic liquid (IL) electrolytes. Thus, they have been considered as one of the candidates for next-generation batteries in large-scale energy storage. [2] Particularly, Al-graphite batteries with a chloroaluminate-based IL electrolyte are the most promising RAB systems due to their high stability, reliability, and low-cost advantages. [3] Nevertheless, the IL electrolytes with their high moisture sensitivity can cause several critical problems in Algraphite batteries, including undesirable volume expansion in the cell, decreased Coulombic efficiency, and irreversible capacity decay, which have limited their practical applications. [2b,c] In the ambient environment, chloroaluminate-based IL electrolytes are prone to absorb H 2 O, and would subsequently react with chloroaluminate-based anions to produce H 2 , Cl 2 , and HCl, which greatly impacts the battery stability (Figure 1a). [4] Meanwhile, the gas will change the geometry of electrode/ electrolyte interface and affect the mass transfer process, resulting in unbalanced energy storage and output. [5] More importantly, the degradation of the chloroaluminate-based IL will substantially undermine the active ions in the electrolytes, which leads to severe performance decay. [6] In the early attempts, the chloroaluminate-based IL was encapsulated in the polymeric frameworks, including polyacrylamide, poly-(3,4-ethylenedioxythiophene), and polyamide, for achieving gel electrolytes, where the IL provides active ions and polymers act as a protective framework from moisture. [4b,5-7] Although the air stability of IL-based gel electrolytes has been improved due to the shielding effect of polymer frameworks, they still have strong hygroscopic properties. The critical issues of gas production and activity loss have not been effectively addressed in the battery operation, because of very high content of IL (over 90%) and limited protection from the polymer frameworks. [4b] In comparison with liquid electrolytes, employment of a (quasi-) solid-state electrolyte could effectively enhance the stability of the IL-based electrolyte in air, thus substantially promoting the stability in practical RABs (Figure 1b). [8] Therefore, it is urgent to develop an appropriate framework that enables the chloroaluminate-based IL to be carried, for achieving quasi-solid-state electrolytes. As a typical high porosity framework material, metal-organic frameworks (MOFs) can store large amounts of large molecules and clusters via strong absorptive capability. [9] The stable frameworks in MOFs give rise to a confinement effect on the large molecules and clusters, and thus behave Nonaqueous rechargeable aluminum batteries (RABs) of low cost and high safety are promising for next-generation energy storage. With the presence of ionic liquid (IL) electrolytes, their high moisture sensitivity and poor stability would lead to critical issues in liquid RABs, including undesirable gas production, irreversible activity loss, and an unstable electrode interface, undermining the operation ...

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Gel electrolytes with a wide potential window for high-rate Al-ion batteries

Abstract: A novel gel electrolyte with wide electrochemical potential window for high-rate Al ion batteries is achieved.

Cited by 61 publications

References 45 publications

Tough Polymer Gel Electrolytes for Aluminum Secondary Batteries Based on Urea: AlCl3, Prepared by a New Solvent-Free and Scalable Procedure

Tough Polymer Gel Electrolytes for Aluminum Secondary Batteries Based on Urea: AlCl3, Prepared by a New Solvent-Free and Scalable Procedure

Advancement of technology towards high-performance non-aqueous aluminum-ion batteries

Stable Quasi‐Solid‐State Aluminum Batteries

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