Structural batteries and supercapacitors combine energy storage and structural functionalities in a single unit, leading to lighter and more efficient electric vehicles. However, conventional electrodes for batteries and supercapacitors are optimized for high energy storage and suffer from poor mechanical properties. More specifically, commercial lithium-ion battery anodes and cathodes demonstrate tensile strength values <4 MPa and Young’s modulus of <1 GPa. Here, we show that using branched aramid nanofibers (BANFs) or nanoscale Kevlar fibers as a binder leads to mechanically stronger lithium-ion battery electrodes. BANFs are combined with lithium iron phosphate (LFP, cathode) or silicon (Si, anode) particles and reduced graphene oxide (rGO). Hydrogen-bonding interactions between rGO and BANFs are harnessed to accommodate load transfer within the nanocomposite electrodes. Overall, we obtained up to 2 orders of magnitude improvements in Young’s modulus and tensile strength compared to commercial battery electrodes while maintaining good energy storage capabilities. This work demonstrates an efficient route for designing structural lithium-ion battery cathodes and anodes with enhanced mechanical properties using BANFs as a binder.

Reduced graphene oxide/aramid nanofiber (rGO/ANF) supercapacitor electrodes have a good combination of energy storage and mechanical properties, but ion transport remains an issue toward achieving higher energy densities at high current because of the tightly packed electrode structure. Herein, carbon nanotubes (CNTs) are introduced to prevent rGO flake stacking to improve the rate capability of the rGO/ANF structural supercapacitor. The effect of CNTs on the rGO/ANF composite electrode’s mechanical and electrochemical properties is investigated by varying the composition. The addition of 20 wt % CNTs led to an increase in Young’s modulus up to 10.3 ± 1.8 GPa, while a maximum in ultimate strain and strength of 1.3 ± 0.14% and 55 ± 6.8 MPa, respectively, was found at a loading of 2.5 wt % CNTs. At low specific currents, the electrodes performed similarly (160–170 F g–1), but at high specific currents (5 A g–1), the addition of 20 wt % CNTs led to a significantly higher capacitance (76 F g–1) as compared to that of rGO/ANF electrodes without CNTs (26 F g–1). In addition, the energy density also improved significantly at high power from 1.4 to 5.1 W h L–1 with the addition of CNTs. The improvement in mechanical properties is attributed to the introduction of additional hydrogen-bonding and π–π interactions from the carboxylic acid-functionalized CNTs. The increase in capacitance at higher discharge rates is due to improved ion transport from the CNTs. Finally, in situ electrochemomechanical testing examines how capacitance varies with strain in these structural electrodes for the first time.

Water existing within thin polyelectrolyte multilayer (PEM) films has significant influence on their physical, chemical, and thermal properties, having implications for applications including energy storage, smart coatings, and biomedical systems. Ionic strength, salt type, and terminating layer are known to influence PEM swelling. However, knowledge of water's microenvironment within a PEM, whether that water is affiliated with intrinsic or extrinsic ion pairs, remains lacking. Here, we examine the influence of both assembly and post-assembly conditions on the water−ion pair interactions of poly(styrene sulfonate)/ poly(diallyldimethylammonium) (PSS/PDADMA) PEMs in NaCl and KBr. This is accomplished by developing a methodology in which quartz crystal microbalance with dissipation monitoring is applied to estimate the number of water molecules affiliated with an ion pair (i), as well as the hydration coefficient,. PSS/PDADMA PEMs are assembled in varying ionic strengths of either NaCl and KBr and then exposed post-assembly to increasing ionic strengths of matching salt type. A linear relationship between the total amount of water per intrinsic ion pair and the post-assembly salt concentration was obtained at post-assembly salt concentrations >0.5 M, yielding estimates for both i and π salt H 2 O . We observe higher values of i and π salt H 2 O in KBr-assembled PEMs due to KBr being more effective in doping the assembly because of KBr's more chaotropic nature as compared to NaCl. Lastly, when PSS is the terminating layer, i decreases in value due to PSS's hydrophobic nature. Classical and ab initio molecular dynamics provide a microstructural view as to how NaCl and KBr interact with individual polyelectrolytes and the involved water shells. Put together, this study provides further insight into the understanding of existing water microenvironments in PEMs and the effects of both assembly and post-assembly conditions.

Ionically conducting, porous separator membranes with submicrometer size pores play an important role in governing the outcome of lithium-ion batteries (LIBs) in terms of life, safety, and effective transport of ions. Though the polyolefin membranes have dominated the commercial segment for the past few decades, to develop next-generation batteries with high-energy density, high capacity, and enhanced safety, there is a need to develop advanced separators with superior thermal stability, electrolyte interfacial capabilities, high melting temperature, and mechanical stability at elevated temperatures. Here, aramid nanofiber separators with enhanced mechanical and thermal stability dried at the critical point are processed and tested for mechanical strength, wettability, electrochemical performance, and thermal safety aspects in LIBs. These separators outperform Celgard polypropylene in all aspects such as delivering a high Young’s modulus of 6.9 ± 1.1 GPa, and ultimate tensile strength of 170 ± 25 MPa. At 40 and 25 °C, stable 200 and 300 cycles with 10% and 11% capacity fade were obtained at 1 C rate, respectively. Multimode calorimetry, specially designed to study thermal safety aspects of LIB coin cells, demonstrates low exothermicity for critical-point-dried aramid nanofiber separators, and post-diagnosis illustrates preservation of structural integrity up to 300 °C, depicting possibilities of developing advanced safer, high-performance LIBs.

Zinc-ion batteries address common environmental and safety concerns by using nontoxic and abundant metals in conjunction with aqueous electrolytes. Nonetheless, for applications such as structural energy storage, where a multifunctional system aims to replace both the structural and energy storage subsystems of an electric vehicle, safe but mechanically strong components are desired. MnO 2 , a typical cathode material for Zn-ion batteries, however, exhibits poor mechanical performance. Therefore, a lack of knowledge remains for mechanically strong cathodes for safe, structural Zn-ion batteries. Here, we combine branched aramid nanofibers (BANFs) with MnO 2 particles and reduced graphene oxide (rGO) to fabricate mechanically improved cathodes for Znion batteries. The addition of BANFs allows for an increase in the MnO 2 loading and significantly improved electrochemical properties (up to 190% increase of capacity). Additionally, hydrogen bonding between BANFs and rGO notably improved the mechanical properties (up to 51% increase in ultimate tensile strength and up to 593% increase in ultimate strain). Electrochemo-mechanical tests were also performed to assess coupling, showing that applied strain decreases the capacity, but no measurable internal stresses develop during electrochemical cycling. This work combines the multifunctionality of structural electrodes with the inherent safety of Zn-ion batteries.