Optimizing Ion Transport in Polyether-Based Electrolytes for Lithium Batteries

Zheng, Qi; Pesko, Danielle M.; Savoie, Brett M.; Timachova, Ksenia; Hasan, Alexandra L.; Smith, Mackensie C.; Miller, Thomas F.; Coates, Geoffrey W.; Balsara, Nitash P.

doi:10.1021/acs.macromol.7b02706

Cited by 97 publications

(157 citation statements)

References 79 publications

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“…The product of the cation transference number, t+, and the total conductivity, σtotal, thus provides a measure of the cation conductivity. 27 A more precise definition of transference number depends on the method used for measurement.…”

Section: Figurementioning

confidence: 99%

“…It is possible that this is due to solvation site connectivity, which has been shown to play a dominant role in mobility for lithiumpolyether systems. 27 Thus, there remains significant opportunity to identify chemistries alternative to PEO that exhibit higher ionic conductivities for multivalent systems. Ion mobility depends strongly on the glass transition temperature of the polymer electrolyte, and thus it is important to understand how Tg changes with polymer identity and ion identity and concentration.…”

Section: Articlementioning

confidence: 99%

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Multivalent ion conduction in solid polymer systems

Schauser

Seshadri

Segalman

2019

Mol. Syst. Des. Eng.

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While polymer electrolytes hold the promise of improving safety and mechanical durability of electrochemical devices, most suffer from relatively low ionic conductivities especially at ambient temperature. Furthermore, much of the conductivity in polymer electrolytes stems from the mobile anions, rather than the metal cations necessary for energy storage. This combination of challenges becomes even more pronounced in the conduction of the multivalent metal ions likely to be necessary for next generation, high energy density energy storage devices where the ions are likely to have complex, multifunctional interactions with the polyelectrolyte matrix. Herein, we will review the current state of understanding of the mechanisms of multivalent ion transport through polymers and the specific challenges relative to lithium ion transport. This fundamental understanding will lead to the design of new polymer electrolytes for multivalent ion transport, including single-ion conductors and anion-trapping polymers for enhanced cation mobility.

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Section: Figurementioning

confidence: 99%

Section: Articlementioning

confidence: 99%

Multivalent ion conduction in solid polymer systems

Schauser

Seshadri

Segalman

2019

Mol. Syst. Des. Eng.

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“…[ 33,36,37 ] Many strategies, such as adding inorganic nanoparticles, [ 38–40 ] blending, [ 41 ] copolymerization, [ 42 ] and crosslinking [ 43–45 ] have been adopted to effectively suppress the crystallization of PEO and improve the ionic conductivity of PEO‐based SPEs. Coat et al [ 46 ] reported the synthesis of poly(diethylene oxide‐alt‐oxymethylene) (P(2EO‐MO)) as a polymer matrix for SPE, which has higher T g than that of PEO in the electrolyte. They found the P(2EO‐MO)/LiTFSI electrolyte exhibits a slightly lower ionic conductivity due to higher T g , but much higher Li ion transference number can be obtained in P(2EO‐MO)/LiTFSI electrolyte (0.36) than that in PEO/LiTFSI (0.19).…”

Section: Figurementioning

confidence: 99%

Investigation on the Copolymer Electrolyte of Poly(1,3‐dioxolane‐co‐formaldehyde)

Liu

Yang

et al. 2020

Macromol. Rapid Commun.

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have been found in preventing the pen etration of Li dendrites. [15][16][17] However, the excessive interfacial resistance and the complex processing art of inorganic SSEs limit their practical application. [18][19][20] Solid polymer electrolytes (SPEs), on the other hand, can offer good flexibility and stable contact between the electrodes and electrolytes. [20][21][22][23] Several types of polymer matrices have been developed, such as poly(ethyleneoxide) (PEO), [24][25][26] poly carbonate, [27][28][29] and polysiloxane. [30][31][32] SPEs are prepared by mixing polymer matrices with Li salts. PEO is the most popular and deeply studied polymer matrix, [33] and the ethylene oxide chain segments in PEO can dissolve Li salts as well as form complexes with Li + and dis sociated Li salts. [34] Li + is conducted by repeatedly carrying out a "decomplexa tion-recomplexation" process through the movement of chain segments in an amorphous polymer region. [35] The movement of chain segments in an amorphous polymer region is affected by the glass transition temperature (T g ) and crystallinity. Low T g and crystallinity are beneficial for the move ment of chain segments as well as the ionic conductivity. Due to the high crystallinity of PEO, PEObased SPEs have a low ionic conductivity (10 −8 -10 −7 S cm −1 ) at room temperature, which does not meet the requirement for ionic conductivity (>10 −4 S cm −1 at room temperature) of electrolytes with prom ising applications. [33,36,37] Many strategies, such as adding inorganic nanoparticles, [38][39][40] blending, [41] copolymerization, [42] and crosslinking [43][44][45] have been adopted to effectively sup press the crystallization of PEO and improve the ionic conduc tivity of PEObased SPEs. Coat et al. [46] reported the synthesis of poly(diethylene oxidealtoxymethylene) (P(2EOMO)) as a polymer matrix for SPE, which has higher T g than that of PEO in the electrolyte. They found the P(2EOMO)/LiTFSI electro lyte exhibits a slightly lower ionic conductivity due to higher T g , but much higher Li ion transference number can be obtained in P(2EOMO)/LiTFSI electrolyte (0.36) than that in PEO/ LiTFSI (0.19). So tailoring the main chain structure is the most feasible way to optimize the performance of SPEs.Recently, the strategy of in situ polymerizing SPEs in the batteries has attracted extensive attention due to the ability to construct stable ionic conduction networks inside the electrodes to reduce the interfacial resistance, the biggest challenge faced by most SSEs. Cui et al. [13] in situ prepared A series of copolymers are prepared via cationic ring-opening polymerization with 1,3-dioxolane (DOL) and trioxymethylene (TOM) as monomers. The crystallization behaviors of the copolymers can be suppressed by adjusting the ratio of DOL/TOM. With LiBF 4 as a source for a BF 3 initiator, copolymer electrolytes (CPEs) can be prepared in situ inside cells without needing nonelectrolyte catalysts or initiators. The ionic conductivities and Li + diffusion coefficients (D Li + ) of the CPEs inc...

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“…Moreover, polyether‐based electrolytes show high ionic conductivities . The introduction of highly polar chains in conjugated polythiophene derivatives can effectively enhance the ionic sensitivity .…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, polyether-based electrolytes show high ionic conductivities. [23][24][25][26][27] The introduction of highly polar chains in conjugated polythiophene derivatives can effectively enhance the ionic sensitivity. [28][29][30][31][32][33][34][35][36] Many attempts have been paid on polythiophene, [31][32][33][34][35] and 3,4-alkylenedioxythiophene (XDOT)based ECPs.…”

Section: Introductionmentioning

confidence: 99%

The Effect of Oligo(Ethylene Oxide) Side Chains: A Strategy to Improve Contrast and Switching Speed in Electrochromic Polymers

et al. 2020

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Solution‐processable electrochromic polymers (ECPs) with high performance are urgently needed for extensive applications. Nevertheless, they suffer from slow switching speed because of low ionic conductivities. Herein, we present an effective strategy to improve the contrast and switching speed in ECPs via facile side‐chain engineering. A novel electrochromic thieno[3,2‐b]thiophene‐based polymer (PmOTTBTD) is designed and successfully synthesized by introducing oligo(ethylene oxide) side chains with high ionic conductivity. Compared to the counterpart POTTBTD without modification by oligo(ethylene oxide) chains, PmOTTBTD demonstrates nearly double contrast (42 % vs. 24 %) with a fast oxidation switching process that just takes half of the time when detected under 400 nm, as well as much higher coloration efficiencies (e. g. 239.04 cm2 C−1 vs. 226.26 cm2 C−1 @ 400 nm and 314.04 cm2 C−1 vs. 174.00 cm2 C−1 @ 650∼700 nm). Besides, PmOTTBTD exhibits excellent stability with negligible decay after 3000 cycles. Our work suggests a facile strategy that could be adopted to realize high‐performance ECPs via molecular design tuning.

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Optimizing Ion Transport in Polyether-Based Electrolytes for Lithium Batteries

Cited by 97 publications

References 79 publications

Multivalent ion conduction in solid polymer systems

Multivalent ion conduction in solid polymer systems

Investigation on the Copolymer Electrolyte of Poly(1,3‐dioxolane‐co‐formaldehyde)

The Effect of Oligo(Ethylene Oxide) Side Chains: A Strategy to Improve Contrast and Switching Speed in Electrochromic Polymers

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