Preparation and characterization of a lithium ion conducting electrolyte based on poly(trimethylene carbonate)

Smith, Michael J.; Silva, Maria Manuela; Cerqueira, Sandra; MacCallum, J.R.

doi:10.1016/s0167-2738(01)00815-3

Cited by 73 publications

(49 citation statements)

References 14 publications

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“…For each diffusion measurement, 32 experiments of varying gradient strength were performed, and the change in amplitude of the attenuated signal was fit to obtain the parameter D i . All measured signal attenuations were single exponential decays, and R 2 values for all fits were greater than 0.99 for both 19 F and 7 Li. Only one data point was collected for each r value, because of the complexity and length of the PFG-NMR measurements at slow diffusion times.…”

Section: Methodsmentioning

confidence: 89%

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

Pesko

Timachova

Bhattacharya

et al. 2017

J. Electrochem. Soc.

185

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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Section: Methodsmentioning

confidence: 89%

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

Pesko

Timachova

Bhattacharya

et al. 2017

J. Electrochem. Soc.

185

367

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“…Furthermore, the optimized cell comprising PTMC 8 LiTFSI and PTMC oligomer shows good long-term stability with a coulombic efficiency of close to 100% after N 140 cycles. This can likely be attributed to the formation of a more stable solid electrode/electrolyte interphase (SEI) layer at the electrode/SPE interface and a wider electrochemical stability window for PTMC-based electrolytes [16,17]. Moreover, the effect of two different oligomers of comparable molecular weight, PTMC and PEGDME, as interfacial mediators was compared (see Fig.…”

Section: Resultsmentioning

confidence: 99%

“…In the pursuit of high cell performance, including good rate capability, long-term cyclability and stability, alternative SPEs should possess more favorable properties not least in terms of ionic conductivity, but also enabling sufficient cationic diffusion and stable electrode/electrolyte interfaces to achieve fast charge/discharge and long lifespan. Within this context, polycarbonates -a high-molecular weight analogue to linear and cyclic carbonate solvents -have been considered promising polymer host candidates [13][14][15][16][17]. In our previous work on poly(trimethylene carbonate) (PTMC) [17], we demonstrated, for the first time, battery cycling performance of such polycarbonate-based polymer electrolytes in LiFePO 4 half-cells at elevated temperature.…”

Section: Introductionmentioning

confidence: 99%

Realization of high performance polycarbonate-based Li polymer batteries

Sun

Mindemark

Edström

et al. 2015

Electrochemistry Communications

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“…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%

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

Cui

Liu

et al. 2017

Electrochimica Acta

133

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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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Preparation and characterization of a lithium ion conducting electrolyte based on poly(trimethylene carbonate)

Cited by 73 publications

References 14 publications

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

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

Realization of high performance polycarbonate-based Li polymer batteries

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

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