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.
Carrier mobility in doped conjugated polymers is limited by Coulomb interactions with dopant counterions. This complicates studying the effect of the dopant's oxidation potential on carrier generation because different dopants have different Coulomb interactions with polarons on the polymer backbone. Here, dodecaborane (DDB)-based dopants are used, which electrostatically shield counterions from carriers and have tunable redox potentials at constant size and shape. DDB dopants produce mobile carriers due to spatial separation of the counterion, and those with greater energetic offsets produce more carriers. Neutron reflectometry indicates that dopant infiltration into conjugated polymer films is redox-potential-driven. Remarkably, X-ray scattering shows that despite their large 2-nm size, DDBs intercalate into the crystalline polymer lamellae like small molecules, indicating that this is the preferred location for dopants of any size. These findings elucidate why doping conjugated polymers usually produces integer, rather than partial charge transfer: dopant counterions effectively intercalate into the lamellae, far from the polarons on the polymer backbone. Finally, it is shown that the IR spectrum provides a simple way to determine polaron mobility. Overall, higher oxidation potentials lead to higher doping efficiencies, with values reaching 100% for driving forces sufficient to dope poorly crystalline regions of the film.
Mixed electron- and ion-conducting polymers serve as excellent candidates for polymer binders in lithium-ion batteries (LIBs) because of an extension of functionality beyond simple mechanical adhesion. Such dual conduction was observed in our recent report on dihexyl-substituted poly(3,4-propylenedioxythiophene) (PProDOT-Hx2), which showed excellent performance as a cathode binder for LiNi0.8Co0.15Al0.05O2 (NCA). However, ionic conductivity was found to be significantly lower than that of its electronic counterpart. To enhance mixed conduction, here we report a family of synthetically tunable, electrochemically stable, random copolymers based on PProDOT-Hx2, in which the hexyl (Hex) side chains are replaced to varying extents with oligoether (OE) side chains, generating a series of (Hex:OE) PProDOTs. When OE content was varied from 5 to 35%, the resulting copolymers were insoluble in the battery electrolyte and were stable after 100 electrochemical doping/dedoping cycles. Electron paramagnetic resonance and electrochemical kinetics studies were performed to illustrate the reversible and fast electrochemical doping process of (Hex:OE) PProDOTs. Electronic and ionic conductivity measurements as a function of electrochemical potential show a decrease in electronic conductivity and a concurrent increase in ionic conductivity with increasing incorporation of OE side chains. X-ray scattering studies on electrochemically doped polymers indicate a decline in crystalline ordering with the increase in OE content of the (Hex:OE) PProDOTs, suggesting that decreasing crystallinity is responsible for both the increased ionic and reduced electronic conductivity. Compounding these structural changes, swelling studies show a linear mass increase with OE content upon electrolyte exposure, indicating that solvent-induced swelling and electrolyte uptake play a significant role in the ability of these polymers to conduct ions. Finally, rigorous cell testing was performed by employing electrochemical impedance spectroscopy, galvanostatic charge–discharge, rate capability tests, and differential capacity vs voltage analysis, using NCA cathodes to understand the role of these polymers as mixed electron- and Li+-ion-conducting polymer binders in LIBs in comparison to the commonly used polyvinylidene fluoride. It is observed that (75:25) PProDOT containing 25% of OE side chains achieves the highest rate capability and fastest charging and discharging under symmetric testing conditions. The synthetic flexibility to fine-tune electronic and ionic conductivity makes (Hex:OE) PProDOTs a promising new class of mixed conducting polymers for electrochemical energy-storage application.
When an electron is removed from a conjugated polymer, such as poly(3‐hexylthiophene‐2,5‐diyl) (P3HT), the remaining hole and associated change in the polymer backbone structure from aromatic to quinoidal are referred to as a polaron. Bipolarons are created by removing the unpaired electron from an already‐oxidized polymer segment. In electrochemically‐doped P3HT films, polarons, and bipolarons are readily observed, but in chemically‐doped P3HT films, bipolarons rarely form. This is explained by studying the effects of counterion position on the formation of polarons, strongly coupled polarons, and bipolarons using both spectroscopic and X‐ray diffraction experiments and time‐dependent density functional theory calculations. The counterion positions control whether two polarons spin‐pair to form a bipolaron or whether they strongly couple without spin‐pairing are found. When two counterions lie close to the same polymer segment, bipolarons can form, with an absorption spectrum that is blueshifted from that of a single polaron. Otherwise, polarons at high concentrations do not spin‐pair, but instead J‐couple, leading to a redshifted absorption spectrum. The counterion location needed for bipolaron formation is accompanied by a loss of polymer crystallinity. These results explain the observed formation order of single polarons, coupled single polarons, and singlet bipolarons in electrochemically‐ and chemically‐doped conjugated polymers.
Molecular dopants such as 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) can interact with conjugated polymers such as poly(3-hexylthiophene-2,5-diyl) (P3HT) in two different ways: they can undergo integer charge transfer (ICT) or they can form a partial-charge-transfer complex (CTC). Both are seen experimentally, but the CTC has been challenging to characterize, making it difficult to answer questions such as the following. Which polymorph is more stable? Do they have similar barriers for formation? Is there a thermodynamic route to convert one to the other? Here, we study the structure and the thermodynamics of bulk F4TCNQ-doped P3HT with all-atom molecular dynamics simulations, using thermodynamic integration to calculate the relative free energies. We find that the ICT and CTC polymorphs have similar thermodynamic stabilities. The barrier to create the ICT polymorph, however, is lower than that to make the CTC polymorph, because the ICT polymorph has a small critical nucleus, but the critical nucleus for the CTC polymorph is larger than what we can simulate. Moreover, simulated thermal annealing shows that the activation barrier for converting the CTC polymorph to the ICT polymorph is relatively modest. Overall, the simulations explain both the observed structures and the thermodynamics of F4TCNQ-doped P3HT and offer guidelines for targeting the production of a desired polymorph for different applications.
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