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.

Based on cosmochemistry evidence and element partitioning experiments, phosphorus is thought to be present in the iron‐rich cores of Earth and Moon. Phosphorus has a similar effect as silicon and sulfur on the electrical and thermal transport properties of iron at core conditions. However, the magnitude of the impurity scattering caused by phosphorus, the temperature dependence of iron phosphorus compounds, and the change across melting all have not been intensively investigated. We measured the electrical resistivity of Fe3P, Fe2P, and FeP using a four‐wire method at 1.3 to 3.2 GPa and temperatures up to 1800 K. We also identify the melting temperatures of FeP, Fe2P, and Fe3P by sudden changes in resistivity upon heating. The present experimental results demonstrate that phosphorus can enhance the electrical resistivity of iron more effectively than silicon. The resistivity of iron phosphides decreases with increasing pressures and decreasing phosphorus content. The resistivity of Fe‐P alloys obeys the Matthiessen's rule, which describes the positive linear correlation between resistivity and phosphorus content. This finding is comparable to previously observed atomic order‐disorder in Fe‐Si and Fe‐C systems. Furthermore, the resistivity of liquid Fe2P and Fe3P shows a negative linear correlation with temperatures. Different from pure iron, the calculated thermal conductivity of Fe3P increases by 33% upon melting. It is speculated that the thermal conductivity of the lunar solid inner core may be much lower than that of the liquid outer core when ordered iron light element compounds (e.g., Fe3C and Fe3P) are present in the solid core.

The Wadsley-Roth compound PNb 9 O 25 is a promising fast charging lithium ion battery anode material with high operating voltage to prevent solid electrolyte interface formation.Here, we present potentiometric entropy measurements featuring signatures of semiconductorto-metal transition and intralayer ordering upon lithiation in the anode material PNb 9 O 25 that could not be observed with in situ X-ray diffraction. In addition, the instantaneous heat generation rates at the PNb 9 O 25 working electrode and at the lithium metal counter electrode during galvanostatic cycling were measured individually for the first time by operando isothermal calorimetry. The heat generation rate decreased at the PNb 9 O 25 electrode upon lithiation due to the decrease in electrical resitivity caused by the semiconductor-to-metal transition observed in potentiometric entropy measurements. Furthermore, the heat generation rate at the lithium metal electrode was positive during delithiation due to the exothermic plating of Li + ions on the lithium metal counter electrode associated with dendrite formation. Furthermore, calorimetric measurements established that the entropy change dominated the reversible heat generation rate at each electrode. Finally, the contribution of enthalpy of mixing was relatively small even at high C-rates thanks to the high Li + ion mobility in Pnb 9 O 25 confirming its promises as a fast charging anode material.