Non-solvating, side-chain polymer electrolytes as lithium single-ion conductors: synthesis and ion transport characterization

Liu, Jiacheng; Pickett, Phillip D.; Park, Bumjun; Upadhyay, Sunil P.; Orski, Sara V.; Schaefer, Jennifer L.

doi:10.1039/c9py01035a

Cited by 59 publications

(82 citation statements)

References 44 publications

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“…[ 10 ] For low Li‐salt doping contents, the dense electrostatic attractions within LiPSTFSI and the (dynamic) crosslinking, renders the matrix very rigid and an Arrhenius behavior. [ 33 ] For higher doping contents, there is a delicate balance between increased permittivity which affects redissociation of ion pairs and the formation of triplets and higher aggregates, and the overall decrease in ion mobility. [ 34 ] At this stage, the clusters and agglomerates can arguably be arranged in such a way that continuous Li + conduction pathways are created, percolation threshold is reached, impacting positively the ionic conductivity.…”

Section: Resultsmentioning

confidence: 99%

“…This is also reflected in the hightemperature ionic conductivity data-where the added temperature eases the polymer chain dynamics even more and 50-60 wt% creates a maximum (Figure 8), which has been observed previously for other concentrated systems. [23,25] There is no simple rule as to what ion conduction mechanism is to be preferred or the ideal to achieve the higher ionic conductivities, but recent studies have demonstrated the possibility of decoupling the conductivity from the mechanical motions typically at temperatures approaching the T g , either by creating systems with low T g s and high contents of aggregated ionic domains, [35,38,39] or as Liu et al [33] engineer the local environment by placing different anion groups on the side chains of LiPSTFSI. Indeed, for PS-based SICs/SPEs ion transport occur even when the polymer segmental motions are slow.…”

Section: Ion Transport and Conduction Mechanism(s) Analysismentioning

confidence: 99%

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Li‐Salt Doped Single‐Ion Conducting Polymer Electrolytes for Lithium Battery Application

Loaiza

Johansson

2022

Macro Chemistry & Physics

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Traditionally solid polymer electrolytes (SPEs) for lithium battery application are made by dissolving a Li-salt in a polymer matrix, which renders both the Li + cations, the charge carriers of interest, and the anions, only by-standers, mobile. In contrast, single-ion conductors (SICs), with solely the Li + cation mobile, can be created by grafting the anions onto the polymer backbone. SICs provide the safety, mechanical stability, and flexibility of SPEs, but often suffer in ionic conductivity. Herein an intrinsically synergetic design is suggested and explored; one dopes a promising SIC, LiPSTFSI (poly[(4-styrenesulfonyl) (trifluoromethanesulfonyl)imide]), with a common battery Li-salt, LiTFSI. This way one both increases the Li + concentration and transport. Indeed, systematically exploring doping, it is found that 50-70 wt% of LiTFSI renders materials with considerable improvements in both the (Li + ) dynamics and the ionic conductivity. A deeper analysis allows to address connections between the ion transport mechanism(s) (Arrhenius/VTF), the charge carrier speciation and concentration, and the free volume and glass transition temperature. While no silver bullet is even remotely found, the general findings open paths to be further explored for SPEs in general and Li-salt doped SICs in particular.

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Section: Resultsmentioning

confidence: 99%

Section: Ion Transport and Conduction Mechanism(s) Analysismentioning

confidence: 99%

Li‐Salt Doped Single‐Ion Conducting Polymer Electrolytes for Lithium Battery Application

Loaiza

Johansson

2022

Macro Chemistry & Physics

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“…Here, the curve in the high-frequency region is related to the dielectric relaxation process and the slope at mid-lowfrequency region is related to the electrode polarization (EP) process. Then, the dielectric relaxation time was extracted via fitting ε der ′ ′ to the Havriliak-Negami (HN) equation, which gives the HN relaxation time (τ HN ) [38,39]:…”

Section: Resultsmentioning

confidence: 99%

Ion Coordination and Transport in Magnesium Polymer Electrolytes Based on Polyester-co-Polycarbonate

et al. 2021

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Magnesium-ion-conducting solid polymer electrolytes have been studied for rechargeable Mg metal batteries, one of the beyond-Li-ion systems. In this paper, magnesium polymer electrolytes with magnesium bis(trifluoromethane)sulfonimide (Mg(TFSI)2) salt in poly(ε-caprolactone-co-trimethylene carbonate) (PCL-PTMC) were investigated and compared with the poly(ethylene oxide) (PEO) analogs. Both thermal properties and vibrational spectroscopy indicated that the total ion conduction in the PEO electrolytes was dominated by the anion conduction due to strong polymer coordination with fully dissociated Mg2+. On the other hand, in PCL-PTMC electrolytes, there is relatively weaker polymer–cation coordination and increased anion–cation coordination. Sporadic Mg- and F-rich particles were observed on the Cu electrodes after polarization tests in Cu|Mg cells with PCL-PTMC electrolyte, suggesting that Mg was conducted in the ion complex form (MgxTFSIy) to the copper working electrode to be reduced which resulted in anion decomposition. However, the Mg metal deposition/stripping was not favorable with either Mg(TFSI)2 in PCL-PTMC or Mg(TFSI)2 in PEO, which inhibited quantitative analysis of magnesium conduction. A remaining challenge is thus to accurately assess transport numbers in these systems.

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“…The conductivity of the three decane-tailed materials follows the trend of higher conductivity with lower ionpair binding energy, the same as with our previous findings for a polymer system. 42 In Figure 7, conductivity curves of LiC10TFSI and LiC18TFSI are compared to better understand the effect of the material phase. The faster dynamics of these two molecules not only affected their phase change kinetics but also improved conductivity.…”

Section: Ionic Conductivitymentioning

confidence: 99%

Improved conductivity of single-component, ion-condensed smectic liquid crystalline electrolytes

Liu

Upadhyay

Schaefer

2022

Preprint

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Fast Li+ conductors with enhanced thermal stability are sought for next-generation lithium batteries. Li+ transport within percolated polymeric ionic aggregates has been a novel focus recently due to the possible fast hopping process observed in atomistic and coarse-grained simulations. This fast ion hopping is decoupled from polymer structural relaxations. In this work, we discuss the synthesis and conductivity performance of single-component ionic liquid crystalline (ILC) materials where morphological control via molecular structure variations is more facile than with ionic polymers. A smectic LC phase can be readily achieved with an easily synthesized ILC having a -trifluoromethanesulfonylimide (-TFSI-) head group and an octadecane tail. The smectic ILC with regular ionic aggregate phase has improved (10 to 1000 times) ionic conductivity compared with an isotropic version of a counterpart having decane tail. Through the analysis of the phase behavior and physiochemical properties of ionic liquid molecules having -sulfonylazanide (-SA-) and -sulfonylphenylsulfonylimide (-PSI-) head groups, it is also found that lower electrostatic interaction between ion-pairs and smaller size of anion has a positive influence on conductivity due to faster relaxation of ion pairs.

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Non-solvating, side-chain polymer electrolytes as lithium single-ion conductors: synthesis and ion transport characterization

Abstract: Non-solvating, side-chain polymer electrolytes with more dissociable pendent anion chemistries exhibit a dielectric relaxation dominated lithium ion transport mechanism.

Cited by 59 publications

References 44 publications

Li‐Salt Doped Single‐Ion Conducting Polymer Electrolytes for Lithium Battery Application

Li‐Salt Doped Single‐Ion Conducting Polymer Electrolytes for Lithium Battery Application

Ion Coordination and Transport in Magnesium Polymer Electrolytes Based on Polyester-co-Polycarbonate

Improved conductivity of single-component, ion-condensed smectic liquid crystalline electrolytes

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