Fast Li-ion conduction in poly(ethylene carbonate)-based electrolytes and composites filled with TiO<sub>2</sub> nanoparticles

Tominaga, Yoichi; Yamazaki, Kenta

doi:10.1039/c3cc49588d

Cited by 289 publications

(285 citation statements)

References 27 publications

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“…2(b) presented the temperature dependence of ionic conductivity for PDEC-LiTFSI and PTEC-LiTFSI electrolytes. It could be observed that the temperature dependence agreed well with the Arrhenius equation over the range of C. These electrolytes behaved like the poly(ethylene carbonate) based electrolytes due to similar chemical structures, which was in good accordance with the previous reports by Tominaga [46,47]. The ionic conductivity of PDEC-LiTFSI was 3.81 Â10 À6 S cm À1 at 25 C and 8.11 Â10 À5 S cm À1 at 80 C, respectively.…”

Section: Resultssupporting

confidence: 78%

“…These results were much superior to the PEO based lithium batteries [60] and comparable to the PEC and P (CL-co-TMC) based lithium batteries [46,47,49]. The rate capability of the Li/LiFePO 4 cell from 0.1C to 0.5C at 55 C is presented in Fig.…”

Section: à2mentioning

confidence: 61%

“…It was noted that PTEC possessing one more EO repeating unit in the main chains presented higher ionic conductivity and lower activation energy than those of PDEC. The high ionic conductivity up to 10 À5 S cm À1 was comparable to the PEC and P(CL-co-TMC) based polymer electrolytes reported by others [46,47,49]. The lithium ion transference number of PTECLiTFSI electrolyte estimated to be 0.39 by a steady-state current method (Fig.…”

Section: à4mentioning

confidence: 90%

“…Inspired by the advantages of the conventional liquid carbonate electrolytes readily decomposed into polycarbonate species and resulting in stable SEI on both electrodes [2], polycarbonate-based electrolytes have recently attracted great interests in lithium battery field. Since poly(vinylene carbonate) and poly(trimethylene carbonate) based solid electrolyte were firstly reported by Shriver and Smith, respectively, fifteen years ago [44,45], Some more polycarbonate-based solid polymer electrolytes, such as poly (ethylene carbonate) [46,47], p(CL-co-TMC) [48][49][50] and poly (propylene carbonate) [51] have achieved great success in high performance of solid polymer lithium batteries. Moreover, poly (ethylene carbonate) and poly(vinylene carbonate) electrolytes possessing short ethylene oxide (EO) side chains were also reported and both revealed that longer side chains favored better ionic conductivity [52,53].…”

Section: Introductionmentioning

confidence: 99%

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Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

Cui

Liu

et al. 2017

Electrochimica Acta

137

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A B S T R A C TThe classic poly(ethylene oxide) (PEO) based solid polymer electrolyte suffers from poor ionic conductivity of ambient temperature, low lithium ion transference number and relatively narrow electrochemical window (<4.0 V vs. Li + /Li). Herein, the carbonate-linked PEO solid polymer such as poly (diethylene glycol carbonate) (PDEC) and poly(triethylene glycol carbonate) (PTEC) were explored to find out the feasibility of resolving above issues. It was proven that the optimized ionic conductivity of PTEC based electrolyte reached up to 1.12 Â 10 À5 S cm À1 at 25 C with a decent lithium ion transference number of 0.39 and a wide electrochemical window about 4.5 V vs. Li + /Li. In addition, the PTEC based Li/LiFePO 4 cell could be reversibly charged and discharged at 0.05 C-rates at ambient temperature. Moreover, the higher voltage Li/LiFe 0.2 Mn 0.8 PO 4 cell (cutoff voltage 4.35 V) possessed considerable rate capability and excellent cycling performance even at ambient temperature. Therefore, these carbonate-linked PEO electrolytes were demonstrated to be fascinating candidates for the next generation solid state lithium batteries simultaneously with high energy and high safety.

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Section: Resultssupporting

confidence: 78%

Section: à2mentioning

confidence: 61%

Section: à4mentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

Cui

Liu

et al. 2017

Electrochimica Acta

137

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“…It is now fairly routine to report both σ and t +,SS of newly-developed polymer electrolytes. 41,44,45,47,48,[58][59][60] The question of limits on i ss /i 0 , or equivalently, t +,SS is an interesting open question. While most papers have reported i ss /i 0 values between 0 and 1, there is at least one report wherein i ss /i 0 obtained from an electrolyte was greater than 1.…”

mentioning

confidence: 99%

Negative Transference Numbers in Poly(ethylene oxide)-Based Electrolytes

Pesko

Timachova

Bhattacharya

et al. 2017

J. Electrochem. Soc.

192

367

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The performance of battery electrolytes depends on three independent transport properties: ionic conductivity, diffusion coefficient, and transference number. While rigorous experimental techniques for measuring conductivity and diffusion coefficients are well-established, popular techniques for measuring the transference number rely on the assumption of ideal solutions. We employ three independent techniques for measuring transference number, t + , in mixtures of polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt. Transference numbers obtained using the steady-state current method pioneered by Bruce and Vincent, t +,SS , and those obtained by pulsed-field gradient NMR, t +,NMR , are compared against a new approach detailed by Newman and coworkers, t +,Ne , for a range of salt concentrations. The latter approach is rigorous and based on concentrated solution theory, while the other two approaches only yield the true transference number in ideal solutions. Not surprisingly, we find that t +,SS and t +,NMR are positive throughout the entire salt concentration range, and decrease monotonically with increasing salt concentration. In contrast, t +,Ne has a non-monotonic dependence on salt concentration and is negative in the highly-concentrated regime. Our work implies that ion transport in PEO/LiTFSI electrolytes at high salt concentrations is dominated by the transport of ionic clusters. Energy density and safety of conventional lithium-ion batteries is limited by the use of liquid electrolytes comprising mixtures of flammable organic solvents and lithium salts. Polymer electrolytes have the potential to address both limitations. However, the power and lifetime of batteries containing solvent-free polymer electrolytes remain inadequate for most applications. The performance of electrolytes in batteries depends on three independent transport properties: ionic conductivity, σ, salt diffusion coefficient, D, and cation transference number, t + .1 The poor performance of batteries with polymer electrolytes is generally attributed to low conductivity, which is on the order of 10 −3 S/cm at 90• C for mixtures of polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, 2,3 compared to that of liquid electrolytes which is 10 −2 S/cm at ambient temperatures. 4 Much of the literature in this field has been devoted to increasing the ionic conductivity of these materials.5-32 The purpose of our work is to shed light on another transport property of polymer electrolytes, the transference number.In a pioneering study, Ma and coworkers showed that the transference number of a mixture of PEO and a sodium salt is negative. 33Following this approach, others have obtained t + <0 in polymers containing lithium or sodium salts. [34][35][36] Nevertheless, the majority of reports for t + in polymer electrolytes fall between zero and one. [37][38][39][40][41][42][43][44][45][46][47][48][49][50][51] In contrast, all reports of t + in non-aqueous liquid electrolytes containi...

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Solid‐State Batteries with Polymer Electrolytes

Iojoiu

Paillard

2020

Encyclopedia of Electrochemistry

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Expectations on solid‐state lithium batteries are at their highest as they are seen as a “next‐generation” technology, although solid polymer electrolytes have already enabled the commercialization of electrical vehicles for almost 10 years. These are powered by lithium metal batteries and use a polyethylene oxide (PEO)‐based electrolyte. Thus, after a quick review of the current state of the art on lithium batteries including various polymers electrolytes, we present some fundamentals about the lithium metal anode. We then give an overview of the different approaches that have been proposed in the past 40 years for improving the performance of these types of electrolytes. The trends that have led to the current generation of solid polymer electrolytes are reported first: They consisted in decreasing the crystallinity of PEO and increasing its chain segmental mobility while preventing electrolyte creeping at high temperature, and the use of plasticizers, fillers, statistical copolymers, and branched polymers such as cross‐linked and comb‐shaped polymers was developed. However, PEO and “dry” solid polymer electrolytes incorporating dissolved lithium salts, in general, suffer from intrinsic limitations. Thus, we then present as perspectives, the most promising polymer electrolyte concepts for improving lithium metal polymer batteries. In particular, the use of polycarbonates as alternative polymer matrixes, the use of polymers in hybrid organic/inorganic electrolytes, the use of block copolymers and liquid crystals for decorrelating conductivity from mechanical properties, and finally, the development of single‐ion conductors.

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Fast Li-ion conduction in poly(ethylene carbonate)-based electrolytes and composites filled with TiO₂ nanoparticles

Cited by 289 publications

References 27 publications

Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

Negative Transference Numbers in Poly(ethylene oxide)-Based Electrolytes

Solid‐State Batteries with Polymer Electrolytes

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Fast Li-ion conduction in poly(ethylene carbonate)-based electrolytes and composites filled with TiO2 nanoparticles

Cited by 289 publications

References 27 publications

Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

Negative Transference Numbers in Poly(ethylene oxide)-Based Electrolytes

Solid‐State Batteries with Polymer Electrolytes

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Fast Li-ion conduction in poly(ethylene carbonate)-based electrolytes and composites filled with TiO₂ nanoparticles