The polymer binders used in most lithium-ion batteries (LIBs) serve only a structural role, but there are exciting opportunities to increase performance by using polymers with combined electronic and ionic conductivity. To this end, here we examine dihexyl-substituted poly(3,4-propylenedioxythiophene) (PProDOT-Hx2) as an electrochemically stable π-conjugated polymer that becomes electrically conductive (up to 0.1 S cm–1) upon electrochemical doping in the potential range of 3.2 to 4.5 V (vs Li/Li+). Because this family of polymers is easy to functionalize, can be effectively fabricated into electrodes, and shows mixed electronic and ionic conductivity, PProDOT-Hx2 shows promise for replacing the insulating polyvinylidene fluoride (PVDF) commonly used in commercial LIBs. A combined experimental and theoretical study is presented here to establish the fundamental mixed ionic and electronic conductivity of PProDOT-Hx2. Electrochemical kinetics and electron spin resonance are first used to verify that the polymer can be readily electrochemically doped and is chemically stable in a potential range of interest for most cathode materials. A novel impedance method is then used to directly follow the evolution of both the electronic and ionic conductivity as a function of potential. Both values increase with electrochemical doping and stay high across the potential range of interest. A combination of optical ellipsometry and grazing incidence wide angle X-ray scattering is used to characterize both solvent swelling and structural changes that occur during electrochemical doping. These experimental results are used to calibrate molecular dynamics simulations, which show improved ionic conductivity upon solvent swelling. Simulations further attribute the improved ionic conductivity of PProDOT-Hx2 to its open morphology and the increased solvation is possible because of the oxygen-containing propylenedioxythiophene backbone. Finally, the performance of PProDOT-Hx2 as a conductive binder for the well-known cathode LiNi0.8Co0.15Al0.05O2 relative to PVDF is presented. PProDOT-Hx2-based cells display a fivefold increase in capacity at high rates of discharge compared to PVDF-based electrodes at high rates and also show improved long-term cycling stability. The increased rate capability and cycling stability demonstrate the benefits of using binders such as PProDOT-Hx2, which show good electronic and ionic conductivity, combined with electrochemical stability over the potential range for standard cathode operation.
Molecular charge transfer dopants either oxidize or reduce the polymeric backbone through accepting or donating an electron. In such cases, the neutralizing counter-ion to the charge carrier on the polymer is the dopant molecule. [1] Protonating the polymer backbone with a Brønsted acid provides a similar effect with the proton donor acting as the counter-ion. [2,3] Electrochemical methods can be used to supply, or remove, electrons if the polymer is supported by a conductive substrate with infiltration of a counter-ion from an electrolyte. [4] These methods effectively tune the electrical conductivity in polymeric semiconductors for emerging applications including bioelectronics [5] and thermoelectrics. [6] For all doping mechanisms, the interactions that exist between a conjugated polymer, a charge carrier, and its corresponding counter-ion are difficult to ascertain. Our lack of understanding stems from a multitude of complications that arise from doping polymers. The morphology of thin films can evolve upon infiltration of dopants, which convolutes the effects of morphology and carrier concentration on the resulting electrical properties. [7] The use of dopants of varying molecular sizes simultaneously changes steric interactions and the energetics of charge transfer, along with the additional possibility of the formation of charge transfer complexes. [8-10] These confounding factors make simple relationships, like how the degree of interaction between the dopant counter-ion and charge carrier impacts the electronic mobility, challenging to determine. A recent formalism to elucidate the importance of interactions between charge carriers and their associated counterions in semiconducting polymers was developed through examining their spectroscopic signatures in the infrared region. The optical properties of polaronic charge carriers in semiconducting polymers are affected by factors such as electronic/vibrational coupling between chains, coulombic interactions, and disorder. [11,12] One model, developed by Spano and coworkers, rationalizes the optical transitions of polaronic carriers in poly(3-hexylthiophene) (P3HT) using a Holstein Hamiltonian modified to incorporate disorder that is present in crystallites of polymers. [13] Both the predicted energies of the optical transitions and their intensities were in good agreement with experimental observations of field-induced charge carriers Since doped polymers require a charge-neutralizing counter-ion to maintain charge neutrality, tailored and high degrees of doping in organic semiconductors requires an understanding of the coupling between ionic and electronic carrier motion. A method of counter-ion exchange is utilized using the polymeric semiconductor poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b] thiophene]-C 14 to deconvolute the effects of ionic/polaronic interactions with the electrical properties of doped semiconducting polymers. In particular, exchanging the counter-ions of the dopant nitrosonium hexafluorophosphate enables investigation into the...
In organic mixed ionic-electronic conductors (OMIECs), it is critical to understand the motion of ions in the electrolyte and OMIEC. Generally, the focus is on the movement of net charge during gating, and the motion of neutral anion-cation pairs is seldom considered. Uptake of mobile ion pairs by the semiconductor before electrochemical gating (passive uptake) can be advantageous as this can improve device speed, and both ions can participate in charge compensation during gating. Here, such passive ion pair uptake in high-speed solid-state devices is demonstrated using an ion gel electrolyte. This is compared to a polymerized ionic liquid (PIL) electrolyte to understand how ion pair uptake affects device characteristics. Using X-ray photoelectron spectroscopy, the passive uptake of ion pairs from the ion gel into the OMIEC is detected, whereas no uptake is observed with a PIL electrolyte. This is corroborated by X-ray scattering, which reveals morphological changes to the OMIEC from the uptake of ion pairs. With in situ Raman, a reorganization of both anions and cations is then observed during gating. Finally, the speed and retention of OMIEC-based neuromorphic devices are tuned by controlling the freedom of charge motion in the electrolyte.
Two disparate modes of operation can occur in an electrolyte-gated transistors (EGTs) depending on the permeability of the semiconductor to ions that are opposite in charge to the induced carriers. High permeability to ions promotes volumetric doping whereas a low permeability promotes electric double layer (EDL) formation and field-effect doping at the semiconductor/dielectric interface. Here, we present a generalized method to control the mode of charge accumulation in an EGT with a constant semiconducting layer by gating with anhydrous polymeric ionic liquids (PILs) of opposite polarity. The polarity of the acrylate-based PILs was controlled by tethering ionic units of positive or negative charge to the backbone. In situ optical spectroscopy of EGTs with poly(3-hexylthiophene), P3HT, reveals that selectively tethering either the anion or the cation dictates whether ions infiltrate P3HT. Gating with both dielectric materials results in similar trends in the dependence of the charge carrier mobility on carrier concentration, despite the difference in doping mechanisms. The EDL (interfacial) doping of the anion-tethered PIL leads to higher mobilities at low carrier concentrations in P3HT with lower onset voltages. Optical measurements during gating show that the anion-tethered PIL gate results in a more even distribution of carriers between ordered and less ordered domains, promoting the formation of a percolated network in the film.
Conjugated polyelectrolytes (CPEs), which combine πconjugated backbones with ionic side chains, are intrinsically soluble in polar solvents and have demonstrated tunability with respect to solution processability and optoelectronic performance. However, this class of polymers often suffers from limited solubility in water. Here, we demonstrate how polyelectrolyte coacervation can be utilized for aqueous processing of conjugated polymers at extremely high polymer loading. Sampling various mixing conditions, we identify compositions that enable the formation of complex coacervates of an alkoxysulfonatesubstituted PEDOT (PEDOT-S) with poly(3-methyl-1-propylimidazolylacrylamide) (PA-MPI). The resulting coacervate is a viscous fluid containing 50% w/v polymer and can be readily blade-coated into films of 4 ± 0.5 μm thick. Subsequent acid doping of the film increased the electrical conductivity of the coacervate to twice that of a doped film of neat PEDOT-S. This higher conductivity of the doped coacervate film suggests an enhancement in charge carrier transport along PEDOT-S backbone, in agreement with spectroscopic data, which shows an enhancement in the conjugation length of PEDOT-S upon coacervation. This study illustrates the utilization of electrostatic interactions in aqueous processing of conjugated polymers, which will be useful in large-scale industrial processing of semiconductive materials using limited solvent and with added enhancements to optoelectronic properties.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.