Effect of zwitterions on electrochemical properties of oligoether-based electrolytes

Solid polymer electrolytes show great potential in electrochemical devices. Poly(ethylene oxide) (PEO) has been studied as a matrix for solid polymer electrolytes because it has relatively high ionic conductivity. In order to investigate the effect of zwitterions on the electrochemical properties of poly(ethylene glycol) dimethyl ether (G5)/lithium bis(fluorosulfonyl) amide (LiFSA) electrolytes, a liquid zwitterion (ImZ2) was added to the G5-based electrolytes. In this study, G5, which is a small oligomer, was used as a model compound for PEO matrices. The thermal properties, ionic conductivity, and electrochemical stability of the electrolytes with ImZ2 were evaluated. The thermal stabilities of all the G5-based electrolytes with ImZ2 were above 150 °C, and the ionic conductivity values were in the range of 0.8–3.0 mS cm−1 at room temperature. When the electrolytes contained less than 5.5 wt% ImZ2, the ionic conductivity values were almost the same as that of the electrolyte without ImZ2. The electrochemical properties were improved with the incorporation of ImZ2. The anodic limit of the electrolyte with 5.5 wt% ImZ2 was 5.3 V vs. Li/Li+, which was over 1 V higher than that of G5/LiFSA

Effect of β-Cyclodextrin on Physicochemical Properties of an Ionic Liquid Electrolyte Composed of N-Methyl-N-Propylpyrrolidinium bis(trifluoromethylsulfonyl)amide

Ionic liquids (ILs) are promising electrolyte materials for developing next-generation rechargeable batteries. In order to improve their properties, several kinds of additives have been investigated. In this study, β-cyclodextrin (β-CD) was chosen as a new additive in IL electrolytes because it can form an inclusion complex with bis(trifluoromethylsulfonyl)amide (TFSA) anions. We prepared the composites by mixing N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl)amide/LiTFSA and a given amount of triacetyl-β-cyclodextrin (Acβ-CD). The thermal behaviors and electrochemical properties of the composites were analyzed by several techniques. In addition, pulse field gradient NMR measurements were conducted to determine the self-diffusion coefficients of the component ions. The addition of Acβ-CD to the IL electrolytes results in the decrease in the conductivity value and the increase in the viscosity value. In contrast, the addition of Acβ-CD to the IL electrolytes induced an improvement in the anodic stability because of the formation of an inclusion complex between the Acβ-CD and TFSA anions. CDs are potential candidates as additives in IL electrolytes for electrochemical applications

Oligoether/Zwitterion Diblock Copolymers: Synthesis and Application as Cathode-Coating Material for Li Batteries

Poly (ethylene oxide) (PEO) has been investigated as an ion-conductive matrix for several decades due to its excellent properties. However, further improvements are needed to enable a PEO-based ion-conductive matrix for practical applications. In order to develop novel solid polymer electrolytes based on zwitterions, we synthesized diblock copolymers (PPEGMA-b-SPBs) with oligoether and zwitterionic side-chains and evaluated their physico-chemical properties. PPEGMA-b-SPBs with various unit ratios were synthesized by RAFT polymerization. PPEGMA-b-SPBs with/without LiTFSA exhibited two distinct glass transition temperatures regardless of the unit ratio of PEGMA and SPB. AFM observations clearly revealed phase-separated structures. The ionic conductivity of PPEGMA-b-SPBs increased even at a high salt concentrations such as [EO]:[Li] = 6:1 and was over 10−5 S cm−1 at 25 °C. This tendency is unusual in a PEO matrix. The oxidation stability of PPEGMA-b-SPBs was about 5.0 V vs. Li/Li+, which is a higher value than that of PEO. The improvement of the electrochemical properties is attributed to the introduction of the SPB block into the block copolymers. PPEGMA-b-SPBs were evaluated as cathode-coating materials for Li batteries. The discharge capacity and coulombic efficiency of the cells employing the cathode (LiNi1/3Mn1/3Co1/3O2 (NMC)) coated with the block copolymers were much higher than those of the cell employing the pristine cathode at the 50th cycle in the cut-off voltage range of 3.0–4.6 V

A new class of proton-conducting ionic plastic crystals based on organic cations and dihydrogen phosphate

Choline dihydrogen phosphate ([N1.1.1.2OH]DHP) and 1-butyl-3-methylimidazolium dihydrogen phosphate ([C4mim]DHP) were synthesized as a new class of proton-conducting ionic plastic crystals. Both [N1.1.1.2OH]DHP and [C4mim]DHP showed solid&ndash;solid phase transition(s) and showed a final entropy of fusion lower than 20 J K&minus;1 mol&minus;1 which is consistent with Timmerman&rsquo;s criterion for molecular plastic crystals. The ionic conductivity of [N1.1.1.2OH]DHP was in the range of 10&minus;6 S cm&minus;1&ndash;10&minus;3 S cm&minus;1 in the plastic crystalline phase. On the other hand, the ionic conductivity of [C4mim]DHP showed about 10&minus;5 S cm&minus;1 in the plastic crystalline phase. [N1.1.1.2OH]DHP showed one order of magnitude higher ionic conductivity than [C4mim]DHP in the temperature range where the plastic phase is stable.<br /

Improvement of charge/discharge properties of oligoether electrolytes by zwitterions with an attached cyano group for use in lithium-ion secondary batteries

Zwitterions with a cyano group on the side chain (CZ) were synthesized. Although the addition of CZ caused a slightly negative effect on viscosity, ionic conductivity, limiting current density, and lithium transference number, the oxidation limit of PEGDME/lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) composites was improved to over 5 V. For charge/discharge testing using Li|electrolyte|LiCoO2 cells, the cycle stability of PEGDME/LiTFSA with CZ in the voltage range of 3.0-4.6 V was much higher than that of PEGDME/LiTFSA. Incorporating a small mole fraction of CZ into PEGDME-based electrolytes prevented an increase in the interface resistance between the electrolyte and cathode with increasing numbers of the cycle