Design of ionic liquid like monomers towards easy-accessible single-ion conducting polymer electrolytes

Porcarelli, Luca; Vlasov, Petr S.; Ponkratov, Denis O.; Lozinskaya, Elena I.; Antonov, Dmitrii Yu.; Nair, Jijeesh Ravi; Mecerreyes, David; Shaplov, Alexander S.

doi:10.1016/j.eurpolymj.2018.08.014

Cited by 39 publications

(43 citation statements)

References 38 publications

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“…It was previously demonstrated by our group that the highest ionic conductivity for methacrylate SICs can be achieved by copolymerization of Li‐ion‐containing monomers with PEGM for [ILM]:[PEGM] molar ratio equal to 1:7.2 . PEGM was chosen due to the presence of oxyethylene fragments in its side chain that, by analogy with poly(ethylene oxide), should improve the solubility of ionic species, facilitate their dissociation and promote an increase in the conductivity of the resultant copolymers.…”

Section: Resultsmentioning

confidence: 99%

“…PEGM was chosen due to the presence of oxyethylene fragments in its side chain that, by analogy with poly(ethylene oxide), should improve the solubility of ionic species, facilitate their dissociation and promote an increase in the conductivity of the resultant copolymers. Moreover, copolymerization with PEGM often allows for a decrease in T g of resultant polyelectrolytes, which in its turn affects their ionic conductivity increasing it to a high level . In view of this and with the aim of appropriate comparison with previously published metharylate SICs, monomers 22 and 24 were copolymerized with PEGM using the optimal ratio of 1:7.2 (Table , entries 1 and 4).…”

Section: Resultsmentioning

confidence: 99%

“…Among the variety of those PIL polyelectrolytes, the so‐called ‘single‐ion conductors’ (SICs), carrying anionic functional groups chemically bonded to the polymer backbone and bearing lithium ions as the mobile counterpart, are of particular interest for battery applications . Such single lithium‐ion conducting anionic PILs (Scheme ) offer several advantages: (i) the increase of Li transference number to unity; (ii) the minimization of dendrite growth; (iii) the increase of oxidative stability; and (iv) the support of high charge/discharge rates . The described excellence is mainly governed by the fixation (chemical bonding) of the anion to the polymer backbone and subsequently the limitation of its migration to the anode surface where it can electrochemically degrade …”

Section: Introductionmentioning

confidence: 99%

“…Subsequent studies were further focused on charge delocalization by bonding of electron‐withdrawing groups to sulfonate fragment (Scheme , 4 , 5 , 6 ). Afterwards came the era of SICs incorporating anions structurally similar to the well‐known bis(trifluoromethylsulfonyl)imide (TFSI) ion (Scheme , 7 , 8 , 9 , 10 , 12 ). This was later extended by the development of PILs bearing the so‐called ‘super‐TFSI’ anion (Scheme , 11 ).…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, it was revealed that to increase the ion conductivity it is preferable to place the anion in the side chain rather than in polymer backbone (Scheme , 7 , 9 , 11 , 12 ). The longer the spacer between the attached anion and main polymer chain the higher is the conductivity (Scheme , 7 , 8 ). The transfer from random copolymers to complex macromolecular architectures (block or triblock copolymers) using reversible addition–fragmentation chain transfer or nitroxide‐mediated polymerization allowed an increase ion mobility and the realization of ionic conductivity in the solid state as high as 3 × 10 −6 S cm −1 .…”

Section: Introductionmentioning

confidence: 99%

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Expanding the chemistry of single‐ion conducting poly(ionic liquid)s with polyhedral boron anions

Lozinskaya

Cotessat

Shmal’ko

et al. 2019

Polymer International

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The synthesis of a new family of single‐ion conducting random copolymers bearing polyhedral boron anions is reported. For this purpose two novel ionic monomers, namely [B12H11(OCH2CH2)2OC(O)C(CH3)CH2]2−[(C4H9)4N+]2 and [8‐(OCH2CH2)2OC(O)C(CH3)CH2‐3,3′‐Co(1,2‐C2B9H10)(1′,2′‐C2B9H11)]−K+, having methacrylate function, diethylene glycol bridge and closo‐dodecaborate or cobalt bis(1,2‐dicarbollide) anions were designed. Such monomers differ from previously reported ones by (i) chemically attached highly delocalized boron anions, by (ii) valency of the anion (divalent anion and monovalent one) and by (iii) the presence of oxyethylene flexible spacer between the methacrylate group and bonded anion. Their free radical copolymerization with poly(ethylene glycol) methyl ether methacrylate and subsequent ion exchange provided lithium‐ion conducting polyelectrolytes showing low glass transition temperature (−53 to −49 °C), ionic conductivity up to 9.1 × 10−7 S cm−1, lithium transference number up to 0.61 (70 °C) and electrochemical stability up to 4.1 V versus Li+/Li (70 °C). The incorporation of propylene carbonate (20–40 wt%) into the copolymers resulted in the enhancement of their ionic conductivity by one order of magnitude and significantly increased their electrochemical stability up to 4.7 V versus Li+/Li (70 °C). © 2019 Society of Chemical Industry

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Expanding the chemistry of single‐ion conducting poly(ionic liquid)s with polyhedral boron anions

Lozinskaya

Cotessat

Shmal’ko

et al. 2019

Polymer International

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Ultra‐Stretchable, Ionic Conducting, Pressure‐Sensitive Adhesive with Dual Role for Stable Li‐Metal Batteries

Gao

Pan

et al. 2022

Adv Funct Materials

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The practical application of lithium (Li) metal battery is impeded by the Li dendrite growth and unstable solid electrolyte interphase (SEI) layer. Herein, an ultra‐stretchable and ionic conducting chemically crosslinked pressure‐sensitive adhesive (cPSA) synthesized via the copolymerization of 2‐ethylhexyl acrylate and acrylic acid with poly(ethyleneglycol)dimethacrylate as crosslinker (short for 70cPSA), is developed as both artificial SEI layer and solid polymer electrolyte (SPE) for stable Li‐metal electrode, enabling all‐solid‐state Li metal batteries with excellent cycling performance. As an artificial SEI layer, the 70cPSA‐modified electrodes exhibit excellent electrochemical performance in Li|70cPSA@Cu half cells and 70cPSA@Li|70cPSA@Li symmetric cells. In full cells with LiFePO4 (LFP) as cathode, the 70cPSA@Li|LFP cell exhibits stable cycling performance over 250 cycles. Utilized as SPE, the all‐solid‐state Li|SPE|LFP cell delivers excellent cycling stability with a capacity retention of 86% over 500 cycles. With high‐voltage LiNi0.8Mn0.1Co0.1O2 (NMC811) as cathode, the Li|SPE|NMC811 cell exhibits a discharge capacity of 124.3 mAh g−1 with a capacity retention of 71% after 200 cycles. The rational design of PSAs and investigation of their dual role for stable and safe Li‐metal batteries may shed a light on adhesive polymers for battery applications.

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Ion–Dipole Interaction Regulation Enables High‐Performance Single‐Ion Polymer Conductors for Solid‐State Batteries

et al. 2022

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Solid polymer electrolytes with large ionic conductivity, high ionic transference number, and good interfacial compatibility with electrodes are highly desired for solid‐state batteries. However, unwanted polarizations and side reactions occurring in traditional dual‐ion polymer conductors hinder their practical applications. Here, single‐ion polymer conductors (SIPCs) with exceptional selectivity for Li‐ion conduction (Li‐ion transference number up to 0.93), high room‐temperature ionic conductivity of about 10−4 S cm−1, and a wide electrochemical stability window (>4.5 V, vs Li/Li+) are prepared by precisely regulating the ion–dipole interactions between Li+ and carbonyl/cyano groups. The resulting SIPCs show an excellent electrochemical stability with Li metal during long‐term cycling at room temperature and 60 °C. LiFePO4‐based solid‐state cells containing the SIPCs exhibit good rate and cycling performance in a wide temperature range from −20 to 90 °C. By the same way of ion–dipole interaction regulation, sodium‐ and potassium‐based SIPCs with both high ionic conductivity and high cationic transference numbers are also prepared. The findings in this work provide guidance for the development of high‐performance SIPCs and other metal‐ion systems beyond Li+.

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Design of ionic liquid like monomers towards easy-accessible single-ion conducting polymer electrolytes

Cited by 39 publications

References 38 publications

Expanding the chemistry of single‐ion conducting poly(ionic liquid)s with polyhedral boron anions

Expanding the chemistry of single‐ion conducting poly(ionic liquid)s with polyhedral boron anions

Ultra‐Stretchable, Ionic Conducting, Pressure‐Sensitive Adhesive with Dual Role for Stable Li‐Metal Batteries

Ion–Dipole Interaction Regulation Enables High‐Performance Single‐Ion Polymer Conductors for Solid‐State Batteries

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