Synthesis and Fundamental Properties of Carbon Dioxide/Alkylene Oxide Copolymers as Ion-Conductive Polymers

Nanthana, Vannasa; Tominaga, Yoichi

doi:10.1295/koron.70.23

Cited by 9 publications

(11 citation statements)

References 7 publications

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“…To obtain lower T g for polycarbonates, we have previously synthesized polycarbonates possessing short side chains, such as alkyl and ether groups. [13][14][15][16] The introduction of ether side chains into polycarbonates decreased T g and increased the conductivity of the electrolytes at low salt concentrations. The value of t + decreased with increasing number of ethereal oxygen atoms in the side chain, however, because the ethereal oxygens trap the dissociated Li + via coordination and inhibit migration.…”

Section: Ion Migration In Peo Arises From the Segmental Motionmentioning

confidence: 99%

“…The higher T g of the polymer is usually unfavorable to ionic conduction, because it is correlated with the lower segmental motion of the polymer chains. To obtain lower T g for polycarbonates, we have previously synthesized polycarbonates possessing short side chains, such as alkyl and ether groups . The introduction of ether side chains into polycarbonates decreased T g and increased the conductivity of the electrolytes at low salt concentrations.…”

Section: Introductionmentioning

confidence: 99%

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Ion-Conductive Properties of a Polymer Electrolyte Based on Ethylene Carbonate/Ethylene Oxide Random Copolymer

Morioka

Nakano

Tominaga

2017

Macromol. Rapid Commun.

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A random copolymer of ethylene oxide with CO , namely, poly(ethylene carbonate/ethylene oxide) (P(EC/EO)), has been synthesized as a novel candidate for polymer electrolytes. Electrolyte composed of P(EC/EO) and lithium bis(fluorosulfonyl)imide has an ionic conductivity of 0.48 mS cm and a Li transference number (t ) of 0.66 at 60 °C. To study ion-conductive behavior of P(EC/EO)-based electrolytes, the Fourier transform infrared (FT-IR) technique is used to analyze the interactions between Li and functional groups of the copolymer. The carbonate groups may interact preferentially with Li rather than the ether groups in P(EC/EO). This study suggests that copolymerization of carbonate and flexible ether units can realize both high conductivity and t for polymer electrolytes. High-performance P(EC/EO) electrolyte is expected to be a candidate material for use in all-solid-state batteries.

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Section: Ion Migration In Peo Arises From the Segmental Motionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ion-Conductive Properties of a Polymer Electrolyte Based on Ethylene Carbonate/Ethylene Oxide Random Copolymer

Morioka

Nakano

Tominaga

2017

Macromol. Rapid Commun.

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“…[6][7][8] We focused on the chemical structure of the copolymer, which has a single carbonate group (-O-(C=O)-O-) in each repeating unit of the main chain. Carbonate-based organic solvents are usually used as the electrolyte solution in Li-ion batteries, because of their high dielectric constant.…”

mentioning

confidence: 99%

Effect of Anions on Lithium Ion Conduction in Poly(ethylene carbonate)-based Polymer Electrolytes

Tominaga

Yamazaki

Nanthana

2015

J. Electrochem. Soc.

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123

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Poly(ethylene carbonate)-based polymer electrolytes with lithium salts (LiX; X = TFSI, ClO 4 , BF 4 and PF 6 ) were prepared, and their lithium transference numbers (t + ) were measured to make comparison between different anion radius and salt concentrations. The LiTFSI electrolytes had the highest t + and Li-ion conductivities of all samples at 80 • C; these values increased with increasing salt concentration. According to the results of FT-IR measurements for all concentrated samples, the changes of band fraction, which divide at around 1720 cm −1 for carbonyl groups interact, with Li + (C=O -Li + ), are strongly related to the mobility of Li + ions. For four decades polymer electrolytes have gained attention as soft ionic materials suitable for novel battery systems such as Li-ion secondary batteries, 1,2 because of their greater safety than liquid electrolytes, their flexibility and their light weight. Unfortunately, the conductivity of typical polyether-based electrolytes such as poly(ethylene oxide) (PEO)-metal salt mixtures is not greater than about 10 −4 S cmat room temperature. 3-5 Moreover, it is extremely difficult to increase the lithium transference number above 0.5.We have recently considered polycarbonates, obtained by the alternating copolymerization of carbon dioxide with epoxides, and potential novel polymers for use as electrolytes.6-8 We focused on the chemical structure of the copolymer, which has a single carbonate group (-O-(C=O)-O-) in each repeating unit of the main chain. Carbonate-based organic solvents are usually used as the electrolyte solution in Li-ion batteries, because of their high dielectric constant. The carbonate group therefore provides a suitable structure for the polymer framework. We reported in our previous studies that a commercial polycarbonate, poly(ethylene carbonate) (PEC) can be used as a novel polymer matrix for the electrolyte, and has extraordinary ion-conductive properties. 9 The ionic conductivity of PEC-Li salt electrolytes increases with increasing salt concentration, whereas the conductivities of typical PEO-based electrolytes are maximum at around 5 mol% and decrease with increasing concentration.9 Moreover, we recently found that the lithium transference numbers (t + ) of PECbased electrolytes are greater than 0.5, and that for their composites filled with small amount of TiO 2 the values are extremely high, more than 0.8. 10 In the present study, we focused on the effect of anions on Li-ion conduction in PEC, and studied t + as a function of anion radius and salt concentration. Interactions between PEC and ions were also studied using FT-IR measurement for the first time. ExperimentalPreparation of PEC-Li salt electrolytes.-Poly(ethylene carbonate) (PEC, M n = 3.7×10 4 ) was donated by a Japanese company. PEC was dissolved as received in chloroform, and the solution was added to excess methanol. The PEC precipitated was dried in a vacuum oven at 60• C for 24 h. The 1 H and 13 C NMR spectra of the purified PEC were observed, and the ratio of the carbona...

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“…Recently, polymers with the same structures as liquid electrolytes (carbonate compounds), such as polycarbonates, have attracted much attention because of their promising potential as SPEs. Several linear -4 -polycarbonates have been synthesized for the development of high-ionic-conductivity SPEs using polycarbonates [12][13][14][15][16][17][18][19][20][21][22][23][24]. For example, Shriver and Wei used poly (vinylene carbonate) as an SPE [12].…”

Section: Introductionmentioning

confidence: 99%

“…Smith and Brandell and their respective co-workers reported poly(trimethylene carbonate) [13][14][15][16]. Tominaga and co-workers reported poly(ethylene carbonate) derivatives for use in SPEs [17][18][19][20][21][22]. The poly(ethylene carbonate)s have carbonate groups in their polymer backbones and show relatively high ionic conductivities in the presence of lithium salts.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of an aliphatic hyper-branched polycarbonate and determination of its physical properties for solid polymer electrolyte use

Motokucho

Yamada

Suga

et al. 2018

Polymer

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• Aliphatic hyper-branched polycarbonate (HBPC) was synthesized by polycondensation. • HBPC films containing LiClO4 were evaluated as solid polymer electrolytes (SPEs). • The Li ion conductivities were compared with that of linear polycarbonate-based SPE. • The SPEs showed relatively high ionic conductivity and low activation energy. • Introduction of branched structure is effective for the lithium ion transport.

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Synthesis and Fundamental Properties of Carbon Dioxide/Alkylene Oxide Copolymers as Ion-Conductive Polymers

Cited by 9 publications

References 7 publications

Ion-Conductive Properties of a Polymer Electrolyte Based on Ethylene Carbonate/Ethylene Oxide Random Copolymer

Ion-Conductive Properties of a Polymer Electrolyte Based on Ethylene Carbonate/Ethylene Oxide Random Copolymer

Effect of Anions on Lithium Ion Conduction in Poly(ethylene carbonate)-based Polymer Electrolytes

Synthesis of an aliphatic hyper-branched polycarbonate and determination of its physical properties for solid polymer electrolyte use

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