Electrochemical and Physical Properties of Imidazolium Chloride Ionic Liquids with Pyrrolidinium or Piperidinium Cation Addition and Their Application in Dual‐Ion Batteries

Lv, Zichuan; Sun, Junhui; Zhou, Shuai; Bian, Yinghui; Chen, Hui; Li, Yuxia; Lin, Meng

doi:10.1002/ente.202000432

Cited by 8 publications

(8 citation statements)

References 53 publications

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“…The calculated ECW of BMP-AlCl 4 (4.06 V) is little higher compared to that of BMP-OTf of (3.90 V). Our calculated ECW using AIMD-min of BMP-AlCl 4 is 4.06 V, which is comparable to that of the experimentally reported pyrrolidinium-based IL Pyr1,3-AlCl 4 (3.7 V) . The AIMD-min-calculated ECW value of DMPI-AlCl 4 is 3.48 V, which is higher compared to the calculated values of other imidazolium-based ILs, which is also in agreement with the previous report .…”

Section: Resultssupporting

confidence: 90%

Screening of Ionic Liquid-Based Electrolytes for Al Dual-Ion Batteries: Thermodynamic Cycle and Combined MD-DFT Approaches

Manna

Pathak

2023

J. Phys. Chem. C

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The electrochemical window (ECW) of the ionic liquid (IL) is the fundamental parameter to understand the stability of the electrolyte for a given electrode material. Here, we have considered room-temperature and molten salt-based 16 IL-based electrolytes, consisting of imidazolium-, pyrrolidinium-, urea-, and acetamide-based cations coupled with AlCl4 and OTf (trifluoromethanesulfonate) anions. Three different high-throughput computational screening techniques have been implemented to calculate the ECW of these electrolytes for dual-ion batteries (DIBs). The thermodynamic cycle method has been employed to calculate the oxidation and reduction potentials with respect to the Al3+/Al reference electrode for the individual ions of the IL. Classical molecular dynamics followed by DFT methods (MD + DFT) have been considered to calculate anodic and cathodic limiting potentials. From the MD + DFT, we have classified two methods, AIMD-min and AIMD-sp. The calculated ECWs for all considered ILs using the AIMD-min method are found to be close to experimental outcomes compared to other two methods. We show that the alkyl group of the imidazolium ring has a very limited effect on the ECW values. On the other hand, aromatic imidazolium rings are more prone to reduction compared to the nonaromatic pyrrolidinium ring. Moreover, we have investigated the contribution of cations and anions in cathodic and anodic potentials, from the study of density of states. Along with that, we have tested the robustness capability of the AIMD-min method and established a superior technique for other liquid systems to calculate the ECW. This work facilitates a step forward in selecting nonaqueous electrolytes for rechargeable DIBs.

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Section: Resultssupporting

confidence: 90%

Screening of Ionic Liquid-Based Electrolytes for Al Dual-Ion Batteries: Thermodynamic Cycle and Combined MD-DFT Approaches

Manna

Pathak

2023

J. Phys. Chem. C

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Section: Electrode Design For Dibsmentioning

confidence: 99%

“…Cations and anions of the ILs can also be intercalated into the host materials, though limited study has been observed on this concept both experimentally and computationally. [25,27,[70][71][72] In general, carbonaceous host materials such as graphite and polycyclic aromatic hydrocarbons (PAHs) are used as electrodes, which have enough space to accommodate the large size cations and anions of ILs. [50] We have conceptually demonstrated the dual graphite battery (DGB) with DMPI-AlCl 4 ionic liquid electrolyte, upon mixing of 1 : 1 ratio of 1,2-dimethyl-3propyl imidazolium chloride (DMPIÀ Cl) and AlCl 3 salt.…”

Section: Ionic Liquid Intercalating Electrodesmentioning

confidence: 99%

Recent Advancements in Devising Computational Strategies for Dual‐Ion Batteries

2022

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Dual-ion batteries (DIBs) have been considered a viable alternative to increasingly costly and hazard-prone lithium-ion batteries (LIBs), which have reached a level of saturation. DIBs differ from LIBs in the way that the cations and anions originate from the electrolyte, thus signifying the active role played by electrolyte. In this Review, the major developments in research in the field of DIBs are summarized with a major emphasis on computational approaches in this direction. The various computational methods for understanding and designing electrodes are discussed. The advancements in electrode and electrolyte design for efficient DIBs are highlighted. Further, the ways to investigate solid-electrolyte interphase formation through simulations to comprehend the role of various components are discussed. Finally, directions are given on which future computational research can be carried out to design futuristic DIBs to provide useful guidelines to the researchers to understand and design DIBs.

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“…Ionic liquids (ILs) have played an important role in designing a new class of electrolytes due to them possessing certain interesting properties, such as a higher ionic conductivity, a low vapor pressure, and a broad electrochemical window, which are important in the development of the battery technology. − The electrochemical reaction has mainly been focused on due to it possessing a high oxidative and reductive stability of the IL electrolyte, which results in a higher electrochemical stability window, thus accepting the high cut-off charging voltage (4.0–5.0 V). ,, Carlin et al have studied different metal-free IL-based cations, such as 2,3-dimethyl-1-propyl imidazolium (DMPI + ),1-ethyl-3-methyl imidazolium (EMI + ), and N -butyl- N -methyl pyrrolidinium (BMP + ) coupled with anions such as AlCl 4 – , CF 3 SO 3 – , PF 6 – , and BF 4 – as electrolytes in DIBs. ,− Our previous computational study has demonstrated DGB with a DMPI-AlCl 4 IL-based electrolyte, where the natural graphite-based battery shows a higher discharge voltage of 3.74 V, which is in good accordance with the experimental voltages . Owing to the large size of the organic DMPI cation, the interlayer distance of the graphite anode is expanded from 3.4 to 7.8 Å in the charging process.…”

Section: Introductionmentioning

confidence: 99%

Pyrrolidinium-Based Organic Cation (BMP)-Intercalated Organic (Coronene) Anode for High-Voltage Dual-Ion Batteries: A Comparative Study with Graphite

Manna

Pathak

2022

J. Phys. Chem. C

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Among the post-lithium-ion batteries, rechargeable dual-ion batteries (DIBs) have bright opportunities for the development of cheap and safe batteries possessing a good electrochemical performance. The DIBs with pure ionic liquid (IL) electrolytes featuring a high voltage, sustainability, and environmental friendliness have received attention from researchers. Owing to intercalation/deintercalation of large size IL cations, the conventional dual-graphite batteries (DGBs) have suffered from severe volume expansion, thus limiting the overall reversibility of the DGBs. Herein, we have modeled two DIBs, introducing an organic cation-intercalated polycyclic aromatic hydrocarbon anode (coronene) coupled with a graphite cathode and a DGB in the other case. Pyrrolidinium-based IL, N-butyl-N-methyl pyrrolidinium chloride (BMP-Cl) with the AlCl3 salt has been employed as an electrolyte. Applying the first-principles calculation, we have investigated the systematic intercalation of the BMP cation into the coronene and graphite anodes. The BMP-intercalated graphite anode shows a higher binding energy (2.36 eV) compared to that of the coronene anode (1.71 eV). In the fully charged state, a calculated discharge voltage of 3.1 and 3.05 V and a maximum capacity of 116 and 130 mA h g–1 have been observed for the graphite coronene dual-ion battery (GCDIB) and DGB, respectively. However, the percentage of volume expansion of the graphite anode is higher (148%) compared to that of the coronene anode (53%) upon a full intercalation of BMP cations, indicating more exfoliation-prone nature of graphite compared to coronene. The density of states and Bader charge analysis reveal that the BMP cation is intercalated successfully, indicating a reduction of electrode materials during the charging process. Furthermore, we have explained the merits of choosing the AlCl4 anion compared to other commonly used anions such as TFSI in DIBs. These results support a clear understanding of BMP cation intercalation into both coronene and graphite anodes and motivate the fabrication of a new class of low-cost organic anode DIBs with an optimum electrochemical performance.

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Electrochemical and Physical Properties of Imidazolium Chloride Ionic Liquids with Pyrrolidinium or Piperidinium Cation Addition and Their Application in Dual‐Ion Batteries

Cited by 8 publications

References 53 publications

Screening of Ionic Liquid-Based Electrolytes for Al Dual-Ion Batteries: Thermodynamic Cycle and Combined MD-DFT Approaches

Screening of Ionic Liquid-Based Electrolytes for Al Dual-Ion Batteries: Thermodynamic Cycle and Combined MD-DFT Approaches

Recent Advancements in Devising Computational Strategies for Dual‐Ion Batteries

Pyrrolidinium-Based Organic Cation (BMP)-Intercalated Organic (Coronene) Anode for High-Voltage Dual-Ion Batteries: A Comparative Study with Graphite

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