Jimin Shim

High-Performance Reverse Osmosis CNT/Polyamide Nanocomposite Membrane by Controlled Interfacial Interactions

Polyamide reverse osmosis (RO) membranes with carbon nanotubes (CNTs) are prepared by interfacial polymerization using trimesoyl chloride (TMC) solutions in n-hexane and aqueous solutions of m-phenylenediamine (MPD) containing functionalized CNTs. The functionalized CNTs are prepared by the reactions of pristine CNTs with acid mixture (sulfuric acid and nitric acid of 3:1 volume ratio) by varying amounts of acid, reaction temperature, and reaction time. CNTs prepared by an optimized reaction condition are found to be well-dispersed in the polyamide layer, which is confirmed from atomic force microscopy, scanning electron microscopy, and Raman spectroscopy studies. The polyamide RO membranes containing well-dispersed CNTs exhibit larger water flux values than polyamide membrane prepared without any CNTs, although the salt rejection values of these membranes are close. Furthermore, the durability and chemical resistance against NaCl solutions of the membranes containing CNTs are found to be improved compared with those of the membrane without CNTs. The high membrane performance (high water flux and salt rejection) and the improved stability of the polyamide membranes containing CNTs are ascribed to the hydrophobic nanochannels of CNTs and well-dispersed states in the polyamide layers formed through the interactions between CNTs and polyamide in the active layers.

Novel composite polymer electrolytes containing poly(ethylene glycol)-grafted graphene oxide for all-solid-state lithium-ion battery applications

A series of composite polymer electrolytes were prepared using an organic/inorganic hybrid branched-graft copolymer (BCP) based on poly(ethylene glycol) methyl ether methacrylate (PEGMA) and 3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo-[9.5.1.13,9.15,15.17,13]octasiloxane-1-yl)propyl methacrylate (MA-POSS) as the polymer matrix and poly(ethylene glycol)-grafted graphene oxide (PGO) as the filler material, and they were applied as solid-state polymer electrolytes (SPEs) for lithium-ion battery applications. The ionic conductivity of the composite polymer electrolyte containing 0.2 wt% of PGO (2.1 × 10−4 S cm−1 at 30 °C) was found to be one order of magnitude higher than that of the BCP (1.1 × 10−5 S cm−1 at 30 °C); the pristine polymer matrix, because of the larger amount of lithium salt, can be dissociated in the composite polymer electrolyte by Lewis acid–base interactions between the PGO and lithium salt. The thermal and mechanical stabilities of the composite polymer electrolytes were also improved by introducing PGO fillers and reasonable storage modulus values were maintained even at elevated temperatures up to 150 °C. All-solid-state battery performance was evaluated with the composite polymer electrolyte containing 0.2 wt% of PGO, resulting in superior cycle performance compared to that of the BCP due to the enhanced ionic conductivity as well as additional ion-conducting paths provided by the PGO fillers.

Polymer Composite Electrolytes Having Core–Shell Silica Fillers with Anion-Trapping Boron Moiety in the Shell Layer for All-Solid-State Lithium-Ion Batteries

Core-shell silica particles with ion-conducting poly(ethylene glycol) and anion-trapping boron moiety in the shell layer were prepared to be used as fillers for polymer composite electrolytes based on organic/inorganic hybrid branched copolymer as polymer matrix for all-solid-state lithium-ion battery applications. The core-shell silica particles were found to improve mechanical strength and thermal stability of the polymer matrix and poly(ethylene glycol) and boron moiety in the shell layer increase compatibility between filler and polymer matrix. Furthermore, boron moiety in the shell layer increases both ionic conductivity and lithium transference number of the polymer matrix because lithium salt can be more easily dissociated by the anion-trapping boron. Interfacial compatibility with lithium metal anode is also improved because well-dispersed silica particles serve as protective layer against interfacial side reactions. As a result, all-solid-state battery performance was found to be enhanced when the copolymer having core-shell silica particles with the boron moiety was used as solid polymer electrolyte.

Synthesis and properties of organic/inorganic hybrid branched-graft copolymers and their application to solid-state electrolytes for high-temperature lithium-ion batteries

A series of organic/inorganic hybrid branched (BCPs) and linear (LCPs)-graft copolymers comprising poly(ethylene glycol) methyl ether methacrylate (PEGMA), 3-(3,5,7,9,11,13,15-heptaisobutyl-pentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane-1-yl)propyl methacrylate (MA-POSS), and ethylene glycol dimethacrylate (EGDMA) were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization for application to solid polymer electrolyte (SPE) materials in high-temperature lithium-ion batteries. Dimensionally stable free-standing films were obtained when the MA-POSS contents in BCPs and LCPs are larger than 21 mol% and maintained their original shape and storage modulus even if the temperature increases up to 90 °C. The maximum ionic conductivity value of the BCP electrolyte containing 21 mol% of MA-POSS was 1.6 × 10−4 S cm−1 at 60 °C and that of the LCP electrolyte containing 21 mol% of MA-POSS was 5.6 × 10−5 S cm−1 at 60 °C, indicating that the branched-graft copolymer electrolyte has higher ionic conductivity than the linear-graft counterpart, due to the increased chain mobility, as estimated by a smaller Tg value. All-solid-state batteries prepared using the BCP electrolyte showed a reasonable cell performance at 60 °C without causing safety problems, demonstrating great potential of BCPs as SPE materials for high-temperature battery systems.

2D boron nitride nanoflakes as a multifunctional additive in gel polymer electrolytes for safe, long cycle life and high rate lithium metal batteries

The multifunctional properties of 2D boron nitride nanoflakes (BNNFs) in gel polymer electrolytes (GPEs) are presented. A small addition (0.5 wt%) of BNNFs into the GPE substantially improves all the advantageous properties of the GPE including ionic conductivity, Li+ transference number, mechanical modulus, and dendrite-suppressing capability, thereby enabling high performance lithium metal batteries.

Gel Polymer Electrolytes Containing Anion-Trapping Boron Moieties for Lithium-Ion Battery Applications

Gel polymer electrolytes (GPEs) based on semi-interpenetrating polymer network (IPN) structure for lithium-ion batteries were prepared by mixing boron-containing cross-linker (BC) composed of ethylene oxide (EO) chains, cross-linkable methacrylate group, and anion-trapping boron moiety with poly(vinylidene fluoride) (PVDF) followed by ultraviolet light-induced curing process. Various physical and electrochemical properties of the GPEs were systematically investigated by varying the EO chain length and boron content. Dimensional stability at high temperature without thermal shrinkage, if any, was observed due to the presence of thermally stable PVDF in the GPEs. GPE having 80 wt % of BC and 20 wt % of PVDF exhibited an ionic conductivity of 4.2 mS cm-1 at 30 °C which is 1 order of magnitude larger than that of the liquid electrolyte system containing the commercial Celgard separator (0.4 mS cm-1) owing to the facile electrolyte uptake ability of EO chain and anion-trapping ability of the boron moiety. As a result, the lithium-ion battery cell prepared using the GPE with BC showed an excellent cycle performance at 1.0 C maintaining 87% of capacity during 100 cycles.

Solid Polymer Electrolytes Based on Functionalized Tannic Acids from Natural Resources for All-Solid-State Lithium-Ion Batteries.

Solid polymer electrolytes (SPEs) for all-solid-state lithium-ion batteries are prepared by simple one-pot polymerization induced by ultraviolet (UV) light using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as an ion-conducting monomeric unit and tannic acid (TA)-based crosslinking agent and plasticizer. The crosslinking agent and plasticizer based on natural resources are obtained from the reaction of TA with glycidyl methacrylate and glycidyl poly(ethylene glycol), respectively. Dimensionally stable free-standing SPE having a large ionic conductivity of 5.6×10(-4)  Scm(-1) at room temperature can be obtained by the polymerization of PEGMA into P(PEGMA) with a very small amount (0.1 wt %) of the crosslinking agent and 2.0 wt % of the plasticizer. The ionic conductivity value of SPE with a crosslinked structure is one order of magnitude larger than that of linear P(PEGMA) in the waxy state.

Dendrite Suppression by Synergistic Combination of Solid Polymer Electrolyte Crosslinked with Natural Terpenes and Lithium-Powder Anode for Lithium-Metal Batteries

Lithium-metal anode has fundamental problems concerning formation and growth of lithium dendrites, which prevents practical applications of next generation of high-capacity lithium-metal batteries. The synergistic combination of solid polymer electrolyte (SPE) crosslinked with naturally occurring terpenes and lithium-powder anode is promising solution to resolve the dendrite issues by substituting conventional liquid electrolyte/separator and lithium-foil anode system. A series of SPEs based on polysiloxane crosslinked with natural terpenes are prepared by facile thiol-ene click reaction under mild condition and the structural effect of terpene crosslinkers on electrochemical properties is studied. Lithium powder with large surface area is prepared by droplet emulsion technique (DET) and used as anode material. The effect of the physical state of electrolyte (solid/liquid) and morphology of lithium-metal anode (powder/foil) on dendrite growth behavior is systematically studied. The synergistic combination of SPE and lithium-powder anode suggests an effective solution to suppress the dendrite growth owing to the formation of a stable solid-electrolyte interface (SEI) layer and delocalized current density.

Liquid crystal alignment behaviours on poly(methyl methacrylate) having polyhedral oligomeric silsesquioxane groups

A series of poly(methyl methacrylate) derivatives containing polyhedral oligomeric silsesquioxane (POSS) groups (MCP#) were synthesised via free radical polymerisation (FRP) using methacryl isobutyl POSS (MA-POSS) and methyl methacrylate as monomers to investigate liquid crystal (LC) alignment property of these polymer films. The LC cells made from the films of the polymers having 100 mol% of MA-POSS units (MCP100) showed vertical LC alignment having a pretilt angle of about 90°. The vertical LC alignment behaviour on the MCP100 film was ascribed to the very hydrophobic MCP100 surface having the surface energy value smaller than about 23 mJ/m2 generated by the nonpolar bulky POSS group. Good electro-optical characteristics, such as voltage holding ratio (VHR) and residual DC voltage (R-DC), were observed for the LC cells fabricated using MCP100 as a LC alignment layer.

Environmentally Sustainable Aluminum-Coordinated Poly(tetrahydroxybenzoquinone) as a Promising Cathode for Sodium Ion Batteries

Na-ion batteries are attractive as an alternative to Li-ion batteries because of their lower cost. Organic compounds have been considered as promising electrode materials due to their environmental friendliness and molecular diversity. Herein, aluminum-coordinated poly(tetrahydroxybenzoquinone) (P(THBQ-Al)), one of the coordination polymers, is introduced for the first time as a promising cathode for Na-ion batteries. P(THBQ-Al) is synthesized through a facile coordination reaction between benzoquinonedihydroxydiolate (C6O6H22-) and Al3+ as ligands and complex metal ions, respectively. Tetrahydroxybenzoquinone is environmentally sustainable, because it can be obtained from natural resources such as orange peels. Benzoquinonedihydroxydiolate also contributes to delivering high reversible capacity, because each benzoquinonedihydroxydiolate unit is capable of two electron reactions through the sodiation of its conjugated carbonyl groups. Electrochemically inactive Al3+ improves the structural stability of P(THBQ-Al) during cycling because of a lack of a change in its oxidation state. Moreover, P(THBQ-Al) is thermally stable and insoluble in nonaqueous electrolytes. These result in excellent electrochemical performance including a high reversible capacity of 113 mA h g-1 and stable cycle performance with negligible capacity fading over 100 cycles. Moreover, the reaction mechanism of P(THBQ-Al) is clarified through ex situ XPS and IR analyses, in which the reversible sodiation of C═O into C-O-Na is observed.