Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes

Singh, Mohit; Odusanya, Omolola; Wilmes, Gregg M.; Eitouni, Hany Basam; Gomez, Enrique D.; Patel, Amish J.; Chen, Vincent; Park, Moon Jeong; Fragouli, Panagiota G.; Iatrou, Hermis; Hadjichristidis, Nikos; Cookson, David J.; Balsara, Nitash P.

doi:10.1021/ma0629541

Cited by 474 publications

(770 citation statements)

References 52 publications

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“…Therefore, amphiphilic copolymers are widely used in many industrial applications, e.g. templates for the preparation of inorganic nano-particles (Gorna et al 2007;Sun and Gutmann 2004), crystal growth modifiers (Rudloff et al 2002), electrolyte components for rechargeable batteries (Singh et al 2007), "vehicles" of active substances release (Khanal and Nakashima 2005;Kojima et al 2008), etc.…”

Section: Introductionmentioning

confidence: 99%

Early Age Hydration, Microstructure and Micromechanical Properties of Cement Paste Modified with Polymeric Vesicles

Koleva

et al. 2013

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The influence of limited concentration, of 0.025 wt.% per cement weight, poly (ethylene oxide) -block -polystyrene vesicles on the hydration process, microstructure and micromechanical properties of cement paste at early hydration age of maximum 7 days are discussed. Isothermal calorimetry and non-evaporable water content tests indicate that the admixed vesicles have no apparent influence on the process of cement hydration, but affect microstructural properties. Whereas nitrogen adsorption tests reveal that the gel pore structure of the vesicles-modified matrix is almost identical to the vesicles-free one, mercury intrusion porosimetry proves refined capillary porosity and reduced total porosity in the presence of admixed vesicles. Nano-indentation supports the above observations and indicates that the admixed vesicles act as nucleation sites, leading to a more uniform distribution of low density hydration products.

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Section: Introductionmentioning

confidence: 99%

Early Age Hydration, Microstructure and Micromechanical Properties of Cement Paste Modified with Polymeric Vesicles

Koleva

et al. 2013

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“…The separator comprised a poly(styrene)-b-poly(ethylene oxide) (PS-PEO) copolymer and LiTFSI. 5,6 Simulations show that the decreasing electronic conductivity during discharge is an essential feature that governs the shape of the potential vs. capacity curve. The model is used to provide insight into the nature of the discharge process: state-of-charge (SOC) of the electrode and electronic conductivity of the P3HT-PEO binder as a function of distance from the current collector.…”

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confidence: 99%

Discharge Characteristics of Lithium Battery Electrodes with a Semiconducting Polymer Studied by Continuum Modeling and Experiment

Javier

Devaux

et al. 2014

J. Electrochem. Soc.

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Conducting polymers such as poly(3-hexylthiophene) (P3HT) can be used to convey electronic charge in battery electrodes. The electronic conductivity of P3HT (and other electronically conducting polymers) is potential-dependent. The main advance in this work is to quantify the effect of this potential dependency on battery performance. The discharge characteristics of a battery consisting of a cathode with LiFePO 4 particles in a poly(3-hexylthiophene)-b-poly(ethylene oxide) (P3HT-PEO) copolymer matrix that conveys electrons and ions to the active particles, a polystyrene-b-poly(ethylene oxide) (PS-PEO) copolymer electrolyte layer, and a lithium metal anode were examined by experiments and macro-homogeneous modeling; lithium bis (trifluoromethanesulfonyl) imide was the salt in the cathode and the electrolyte. By comparing the model predictions with experiments, we conclude that the electronic conductivity of the polymer in the cathode is significantly lower than that obtained from measurements in the absence of active particles. The potential-dependent conductivity is manifested in the shape of the discharge curve wherein the slope increases continuously with capacity. The model provides insight into the underpinnings of the observed rate-dependency of electrode capacity, thereby guiding the design of the next generation of electrodes. In conventional rechargeable lithium-ion batteries, a slurry of active particles such as LiFePO 4 , graphite, or LiCoO 2 are mixed with electronically conducting carbon particles and an inert polymer binder such as poly(vinylidene fluoride) (PVDF) and cast onto a current collector to yield porous electrodes. In the last step of battery assembly, the pores in the electrode are filled with a liquid electrolyte. During discharge of the cathode, electrons flow to the active particles through the conducting carbon network while the electrolyte in the pores conveys the lithium ions necessary to complete the redox reaction. An example of such a reaction isThe reverse reaction above occurs during charge. The resistance to electron transport is independent of time and electrode potential in conventional batteries as the carbon particles form a simple ohmic conducting network.There have been many previous studies wherein electronic charge in a battery electrode is conveyed by a conducting polymer such as poly(3-hexylthiophene) (P3HT). 1 The main difference between such electrodes and conventional battery electrodes is that the polymer is a semiconductor wherein electronic conductivity is a function of electrode potential. In addition to oxidation and reduction of the active particles (Reaction 1), the conducting polymer gets oxidized and reduced. An example of such a reaction is P 3 HT ↔ P 3 HT + + 1ewhere P3HT + represents a P3HT chain with one oxidized monomer. We note in passing that P3HT is a hole conductor and the formal reaction should have h + on the left hand side of Reaction 2 instead of 1e − on the right hand side. In electrodes with a conducting polymer Reactions 1 and 2 occur sim...

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“…For all samples, the amount of LiTFSI added was predetermined to obtain a molar ratio r of lithium ions (Li + ) to ethylene oxide (EO) moieties equal to 0.063 ± 0.06. This salt concentration is in the vicinity of the optimum salt concentration for SEO-based electrolytes [30]. The solution was stirred for several hours at 90°C until complete dissolution was visually observed, and then the THF was allowed to evaporate to obtain a solid polymer-salt mixture.…”

Section: Electrolyte Preparationmentioning

confidence: 99%

“…In studies utilizing block copolymers as SPE, the archetypal mechanical phase is made of a polymer with a high glass transition temperature (T g ) such as polystyrene (PS) [23,[28][29][30][31][32][33]. For symmetric PS-PEO diblock copolymers [30][31][32][33] (SEO), the ionic conductivity σ has been shown to increase with PEO chain length and a plateau value is reached as the molecular weight of the PEO block exceeds 100 kg/mol.…”

Section: Introductionmentioning

confidence: 99%

“…For symmetric PS-PEO diblock copolymers [30][31][32][33] (SEO), the ionic conductivity σ has been shown to increase with PEO chain length and a plateau value is reached as the molecular weight of the PEO block exceeds 100 kg/mol. In contrast, σ of PEO homopolymers decreases with increasing molecular weight, reaching a plateau as the molecular weight of the PEO block exceeds 4 kg/mol [9].…”

Section: Introductionmentioning

confidence: 99%

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Investigating polypropylene-poly(ethylene oxide)-polypropylene triblock copolymers as solid polymer electrolytes for lithium batteries

et al. 2014

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Syndiotactic polypropylene-b-poly(ethylene oxide)-b-syndiotactic polypropylene (PEOP) triblock copolymers were synthesized and solid polymer electrolytes were prepared by mixing with lithium bis(trifluoromethane) sulfonimide (LiTFSI) salt. PEOP formed strongly-segregated morphologies in the absence and presence of LiTFSI. LiTFSI inhibited poly(ethylene oxide) crystallization without affecting polypropylene crystallinity. The conductivity exhibited a non-monotonic dependence on molecular weight (M n ) with a maximum near 20 kg/mol. In contrast, polystyrene-b-poly(ethylene oxide) electrolytes exhibit conductivity increasing monotonically with M n , up to a plateau in the high-M n limit. This suggests that non-conducting semi-crystalline microphases interfere with conducting pathways, while non-conducting amorphous microphases formed well-connected conducting pathways.Published by Elsevier B.V.

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Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes

Cited by 474 publications

References 52 publications

Early Age Hydration, Microstructure and Micromechanical Properties of Cement Paste Modified with Polymeric Vesicles

Early Age Hydration, Microstructure and Micromechanical Properties of Cement Paste Modified with Polymeric Vesicles

Discharge Characteristics of Lithium Battery Electrodes with a Semiconducting Polymer Studied by Continuum Modeling and Experiment

Investigating polypropylene-poly(ethylene oxide)-polypropylene triblock copolymers as solid polymer electrolytes for lithium batteries

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