Model block–graft copolymer via anionic living polymerization: Preparation and characterization of polystyrene‐block‐[poly(p‐hydroxystyrene)‐graft‐poly(ethylene oxide)]‐block‐polystyrene

Se, Kazunori; Miyawaki, Kazushige; Hirahara, Kazuro; Takano, Atsushi; Fujimoto, Teruo

doi:10.1002/(sici)1099-0518(199812)36:17<3021::aid-pola3>3.3.co;2-j

Cited by 28 publications

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“…The detailed discussion about the structure and properties for the MS polymer could be find in the previous work of one of the authors. 10 The dynamics modulus data are given in Fig. 3.…”

Section: Resultsmentioning

confidence: 99%

“…[13][14][15] Interfacial stability with metallic lithium and cathode.-The electrochemical stability of the block-graft copolymer on a smooth blocking electrode ͑a platinum working electrode͒ was reported to be stable up to 4.5 V vs. Li/Li ϩ at 80°C in Ref. 10. However, as demonstrated in our previous work, 16 in a real battery system, a polymer electrolyte works with a composite electrode rather than a smooth inert electrode.…”

Section: Resultsmentioning

confidence: 99%

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All Solid-State Lithium-Polymer Battery Using a Self-Cross-Linking Polymer Electrolyte

Wang¹,

Sakai²,

Watanabe³

et al. 2003

J. Electrochem. Soc.

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A self-cross-linking polymer electrolyte based on polystyrene-incorporated poly͑ethylene oxide͒ ͑PEO͒ containing LiTFSI has been tested in an all solid-state lithium-polymer battery (Li/SP-E/Li x MnO 2 with a solid polymer electrolyte. The polymer electrolyte showed high stability toward metallic lithium. Mechanical properties of the electrolyte film were much improved by incorporating the polystyrene, but ion conductivity was decreased to half of the value obtained in pure PEO electrolyte film. The cell was charged and discharged at a high temperature ͑80°C͒, providing about 80% utilization of the positive electrode. The cell showed good cycle life at 80°C, keeping 90% of the initial capacity after 50 cycles.Lithium-ion technology is rapidly contributing to the state-of-art of secondary systems and has been commercially used in popular portable devices such as cellular phones and note-size computers. However, such batteries are not being rapidly developed for electric vehicles ͑EVs͒ in view of the safety of the devices because the use of a liquid electrolyte may result in problems, i.e., leakage of a flammable electrolyte, production of gases upon overcharge or overdischarge, and a thermal runaway reaction when the battery is heated to high temperatures. On the other hand, an all solid-state lithium/polymer battery ͑LPB͒ using a metallic lithium anode and solvent-free polymer electrolyte has been demonstrated to be the most promising secondary battery for EV applications because of its absence of risk for leakage of liquid electrolyte, its higher energy density, and its shape flexibility. One of the paramount approaches is to use a thin film of polymer electrolyte with high ionic conductivity and strong mechanical integrity. 1-9 High ionic conductivity is expected to improve rate capability. Good mechanical properties are required to protect against shortages, to assure safety reliability, and to make a feasible thin film, thus improving battery-specific energy and rate capability. However, it is difficult to optimize both the energy and rate capability. In the present work, we used a polystyrene-poly͑ethylene oxide͒ ͑PEO͒ block-graft copolymer, which has a microphase-separated structure, a lamellar shape, good ionic conductivity, and excellent mechanical properties, as the polymer electrolyte for a Li/Li x MnO 2 cell. The electrochemical performance, especially the effect of the film thickness on rate capability, was evaluated. ExperimentalThe detailed synthesis condition of the polystyrene-poly͑ethylene oxide͒ block-graft copolymer ͑SE-P͒ is reported elsewhere. 10 The structure of the polymer is shown in Fig. 1. The average molecular weight is 3.4 ϫ 10 5 with an ethylene oxide ͑EO͒ content of 60 wt %. Battery-grade lithium bis͑trifluoromethanesulfonyl͒imide ͑LiTFSI Kishida Chemical Co., Ltd͒ was used as the electrolyte salt and was vacuum dried for 24 h before use. The polymer electrolyte film was prepared by a well-known solvent-casting technique: a known amount of SE-P and LiTFSI, normally an EO/Li ratio of ...

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“…The detailed discussion about the structure and properties for the MS polymer could be find in the previous work of one of the authors. 10 The dynamics modulus data are given in Fig. 3.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

All Solid-State Lithium-Polymer Battery Using a Self-Cross-Linking Polymer Electrolyte

Wang¹,

Sakai²,

Watanabe³

et al. 2003

J. Electrochem. Soc.

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“…The precursor polymers are subjected to acidic hydrolysis in order to remove the protective t-butyl group. [8] The reaction is performed in acetone, a good solvent for both PBOS and PHOS. The success of hydrolysis is identified by the disappearance of the characteristic peaks at 1 365 and 1 390 cm À1 assigned to the t-butyl group (Figure 1a).…”

Section: Synthesis Of Polyelectrolytesmentioning

confidence: 99%

Well‐Defined Flexible Polyelectrolytes with Two Cationic Sites per Monomeric Unit

Mountrichas

Mantzaridis

Pispas

2006

Macromol. Rapid Commun.

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Summary: Well‐defined flexible, annealed, and quenched polyelectrolytes with two cationic sites per monomeric unit are synthesized. The synthetic scheme involves the synthesis of narrowly distributed poly(p‐tert‐butoxystyrene) precursors by anionic polymerization high vacuum techniques, hydrolysis to poly(p‐hydroxystyrene), and subsequent quantitative functionalization by a Mannich‐type reaction, to yield annealed polyelectrolytes with two dimethylamino groups per monomer. In a last step, the dimethylamino groups are converted into quaternary ammonium salts by reaction with methyl iodide to give high‐charge‐density quenched cationic polyelectrolytes. The polymers are molecularly characterized by NMR and FT‐IR spectroscopy, while their solution behavior is studied by potentiometric titrations, turbidimetry, and fluorescence spectroscopy as a function of pH, in the case of the annealed polyelectrolytes, as well as by viscometry in the case of the quenched polyelectrolytes.Schematic diagram of the synthesis of the polyelectrolytes.magnified imageSchematic diagram of the synthesis of the polyelectrolytes.

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“…Because of their asymmetric shapes, non-linear block copolymers, such as mikto-arm star block copolymers [1], block-graft copolymers [2,3], and rod-coil block copolymers [4], have shown some unique physical properties [5], such as liquid crystallinity [6], anisotropic solution, and dielectric [7] and rheological behaviors [8]. To prepare these non-linear block copolymers, synthetic routes might be sophisticated and the final products would be small in quantity.…”

Section: Introductionmentioning

confidence: 99%

Anionic living polymerization of macromonomers: Preparation of a particle-like purging reagent and characterization of poly(macromonomer)s

Inoue

Yamashita

2005

Polymer

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A cross-linked polystyrene particle (Merrifield resin, R-C 6 H 5 ) was reacted with benzoyl chloride in nitrobenzene to produce R-C 6 H 4 -COC 6 H 5 having a benzophenone group, and the R-C 6 H 5 -COC 6 H 5 was reacted with a sodium mirror in THF under 10 K5 mmHg to produce R-C 6 H 5 -CO K C 6 H 5 Na C containing a benzophenone sodium as a particle-like purging reagent (PPBNa). (4-vinylbenzyl)Polystyrene macromonomers (PSM4: M n Z4.6 2 !10 3 , M w /M n Z1.0 3 and PSM7: M n Z7.1 0 !10 3 , M w /M n Z1.0 2 ) were dried under 10 K6 mmHg for more than 72 h, purified by a special procedure using the PPBNa, and then were living anionically polymerized by sec-BuLi in benzene or n-BuLi in tetrahydrofuran to produce the corresponding poly(PSM) n star polymers. The resultant star polymers were characterized by gel permeation chromatography equipped with low-angle laser light-scattering (GPC-LALLS), membrane osmometry (OSM), and light-scattering (LS). Anionic living polymerization of the PSM macromonomers was confirmed by the fact that the molecular weight of the poly(PSM) n increased and by the fact that the initiation efficiency was constant despite an increase in the polymer yields. Some solution properties and specific dimensions characteristic to the poly(PSM) n star polymers are discussed by comparing the GPC-LALLS, OSM, and LS results for those polymers with the results for linear polystyrenes. q

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Model block–graft copolymer via anionic living polymerization: Preparation and characterization of polystyrene‐block‐[poly(p‐hydroxystyrene)‐graft‐poly(ethylene oxide)]‐block‐polystyrene

Cited by 28 publications

References 0 publications

All Solid-State Lithium-Polymer Battery Using a Self-Cross-Linking Polymer Electrolyte

All Solid-State Lithium-Polymer Battery Using a Self-Cross-Linking Polymer Electrolyte

Well‐Defined Flexible Polyelectrolytes with Two Cationic Sites per Monomeric Unit

Anionic living polymerization of macromonomers: Preparation of a particle-like purging reagent and characterization of poly(macromonomer)s

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