Solid-state polymer-particle hybrid electrolytes: Structure and electrochemical properties.

Solid-state electrolytes (SSEs) are challenged by complex interfacial chemistry and poor ion transport through the interfaces they form with battery electrodes. Here, we investigate a class of SSE composed of micrometer-sized lithium oxide (Li2O) particles dispersed in a polymerizable 1,3-dioxolane (DOL) liquid. Ring-opening polymerization (ROP) of the DOL by Lewis acid salts inside a battery cell produces polymer-inorganic hybrid electrolytes with gradient properties on both the particle and battery cell length scales. These electrolytes sustain stable charge-discharge behavior in Li||NCM811 and anode-free Cu||NCM811 electrochemical cells. On the particle length scale, Li2O retards ROP, facilitating efficient ion transport in a fluid-like region near the particle surface. On battery cell length scales, gravity-assisted settling creates physical and electrochemical gradients in the hybrid electrolytes. By means of electrochemical and spectroscopic analyses, we find that Li2O particles participate in a reversible redox reaction that increases the effective CE in anode-free cells to values approaching 100%, enhancing battery cycle life.

A nonsolvolytic fluorine/LiNO3-containing electrolyte for stabilizing dynamic interfaces in Li||LiMn2O4 batteries.

Mn-based high voltage cathodes, e.g., spinel LiMn2O4, are considered among the most promising materials for cost-effective, next generation energy storage. When paired with a Li metal anode, secondary batteries based on Li||LiMn2O4 in principle offer a straightforward, scalable approach for achieving cost-effective and high energy density storage demanded in applications. In practice, however, such batteries fail to live up to their promise. Rapid capacity fading caused by irreversible Mn dissolution at the cathode coupled with mossy/dendritic Li deposition at the anode limit their useful life. In this study, we report on the design of electrolytes based on a binary blend of two widely available salts, LiNO3 and LiTFSI, in ethylene carbonate (EC), which simultaneously overcome failure modes at both the cathode and anode of Li||LiMn2O4 batteries. The electrolyte design is motivated by a recent finding that compared with their linear counterparts (e.g., dimethyl carbonate), cyclic carbonates like EC dissolve considerably larger amount of LiNO3, which markedly improves anode reversibility. On the other hand, it is known that nonsolvolytic fluorine-containing Li salts like LiTFSI, lowers the electrolyte's susceptibility to solvolysis, which generates HF species responsible for Mn leaching at the cathode. In particular, we report instead that fluorine groups in the TFSI salt, promote formation of a favorable, fluorine-rich interphase on the Li metal anode. Electrochemical measurements show that the electrolytes enable remarkably improved charge-discharge cycling stability (>1000 charge-discharge cycles) of Li||LiMn2O4 batteries. In-depth atomic-resolution electron microscopy and X-ray/synchrotron diffraction experiments reveal the fundamental source of the improvements. The measurements show that crystallographic degradation of Mn-based cathodes (e.g., surface Mn leaching and bulk defect generation) upon cycling in conventional electrolytes is dramatically lowered in the LiNO3 + LiTFSI/EC electrolyte system. It is shown further that the reduction of Mn dissolution not only improves the cathode stability but improves the reversibility of the Li metal anode via a unique re-deposition mechanism in which Li and Mn co-deposit on the anode. Taken together, our findings show that the LiNO3 + LiTFSI/EC electrolyte system holds promise for accelerating progress towards practical Li||LiMn2O4 batteries because it stabilizes the dynamic interfaces required for long-term stability at both the Li anode and the LiMn2O4 cathode.

Solid-Adsorbed Polymer-Electrolyte Interphases for Stabilizing Metal Anodes in Aqueous Zn and Non-Aqueous Li Batteries.

Polymers are known to adsorb spontaneously from liquid solutions in contact with high-energy substrates to form configurationally complex, but robust phases that often exhibit higher durability than might be expected from the individual physical bonds formed with the substrate. Rational control of the physical, chemical, and transport properties of such interphases has emerged as a fundamental opportunity for scientific and technological advances in energy storage technology but requires in-depth understanding of the conformation states and electrochemical effect of the adsorbed polymers. Here, we analyze the interfacial adsorption of oligomeric polyethylene glycol (PEG) chains of moderate sizes dissolved in protic and aprotic liquid electrolytes and find that there is an optimum polymer molecular weight of approximately 400 Da at which the highest columbic efficiency is achieved for both Zn and Li deposition. These findings point to a simple, versatile approach for extending the lifetime of batteries.

Highly stretchable ionically crosslinked acrylate elastomers inspired by polyelectrolyte complexes.

Dynamic bonds are a powerful approach to tailor the mechanical properties of elastomers and introduce shape-memory, self-healing, and recyclability. Among the library of dynamic crosslinks, electrostatic interactions among oppositely charged ions have been shown to enable tough and resilient elastomers and hydrogels. In this work, we investigate the mechanical properties of ionically crosslinked ethyl acrylate-based elastomers assembled from oppositely charged copolymers. Using both infrared and Raman spectroscopy, we confirm that ionic interactions are established among polymer chains. We find that the glass transition temperature of the complex is in between the two individual copolymers, while the complex demonstrates higher stiffness and more recovery, indicating that ionic bonds can strengthen and enhance recovery of these elastomers. We compare cycles to increasing strain levels at different strain rates, and hypothesize that at fast strain rates ionic bonds dynamically break and reform while entanglements do not have time to slip, and at slow strain rates ionic interactions are disrupted and these entanglements slip significantly. Further, we show that a higher ionic to neutral monomer ratio can increase the stiffness, but its effect on recovery is minimal. Finally, taking advantage of the versatility of acrylates, ethyl acrylate is replaced with the more hydrophilic 2-hydroxyethyl acrylate, and the latter is shown to exhibit better recovery and self-healing at a cost of stiffness and strength. The design principles uncovered for these easy-to-manufacture polyelectrolyte complex-inspired bulk materials can be broadly applied to tailor elastomer stiffness, strength, inelastic recovery, and self-healing for various applications.

Structure and Evolution of Quasi-Solid-State Hybrid Electrolytes Formed Inside Electrochemical Cells.

Solid-state electrolytes (SSEs) formed inside an electrochemical cell by polymerization of a liquid precursor provide a promising strategy for overcoming problems with electrolyte wetting in solid-state batteries. Hybrid solid-state polymer electrolytes (HSPEs) created by in situ polymerization of a conventional liquid precursor containing electrochemically inert nanostructures are of particular interest because they offer a mechanism for selectively reinforcing or adding new functionalities to the electrolyte-removing the need for high degrees of polymerization. The synthesis, structure, chemical kinetics, ion-transport properties and electrochemical characteristics of HSPEs created by Al(OTf)3 -initiated polymerization of 1,3-dioxolane (DOL) containing hairy, nano-sized SiO2  particles are reported. Small-angle X-ray scattering reveals the particles are well-dispersed in liquid DOL. Strong interaction between poly(ethylene glycol) molecules tethered to the SiO2  particles and poly(DOL) lead to co-crystallization-anchoring the nanoparticles in their host It also enables polymerization-depolymerization processes in DOL to be studied and controlled. The utility of the in-situ-formed HSPE, is demonstrated first in Li|HSPE|Cu half cells, which manifest Coulombic efficiencies (CE) values approaching 99%. HSPEs are also demonstrated in solid-state lithium-sulfur-polyacrylonitrile (SPAN) composite full-cell batteries. The in-situ-formed Li|HSPE|SPAN cells show good cycling stability and thus provide a promising path toward all-solid-state batteries.

Upgrading Carbonate Electrolytes for Ultra-stable Practical Lithium Metal Batteries.

LiNO3 is a widely used salt-additive that markedly improves the stability of ether-based electrolytes at a Li metal anode but is generally regarded as incompatible with alkyl carbonates. Here we find that contrary to common wisdom, cyclic carbonate solvents such as ethylene carbonate can dissolve up to 0.7 M LiNO3 without any additives, largely improving the anode reversibility. We demonstrate the significance of our findings by upgrading various state-of-the-art carbonate electrolytes with LiNO3 , which provides large improvements in batteries composed of thin lithium (50 µm) anode and high voltage cathodes. Capacity retentions of 90.5 % after 600 cycles and 92.5 % after 200 cycles are reported for LiNi0.6 Mn0.2 Co0.2 O2 (2 mAh cm-2 , 0.5 C) and LiNi0.8 Mn0.1 Co0.1 O2 cathode (4 mAh cm-2 , 0.2 C), respectively. 1 Ah pouch cells (≈300 Wh kg-1 ) retain more than 87.9 % after 100 cycles at 0.5 C. This work illustrates that reforming traditional carbonate electrolytes provides a scalable, cost-effective approach towards practical LMBs.

On the crystallography and reversibility of lithium electrodeposits at ultrahigh capacity.

Lithium metal is a promising anode for energy-dense batteries but is hindered by poor reversibility caused by continuous chemical and electrochemical degradation. Here we find that by increasing the Li plating capacity to high values (e.g., 10-50 mAh cm-2), Li deposits undergo a morphological transition to produce dense structures, composed of large grains with dominantly (110)Li crystallographic facets. The resultant Li metal electrodes manifest fast kinetics for lithium stripping/plating processes with higher exchange current density, but simultaneously exhibit elevated electrochemical stability towards the electrolyte. Detailed analysis of these findings reveal that parasitic electrochemical reactions are the major reason for poor Li reversibility, and that the degradation rate from parasitic electroreduction of electrolyte components is about an order of magnitude faster than from chemical reactions. The high-capacity Li electrodes provide a straightforward strategy for interrogating the solid electrolyte interphase (SEI) on Li -with unprecedented, high signal to noise. We find that an inorganic rich SEI is formed and is primarily concentrated around the edges of lithium particles. Our findings provide straightforward, but powerful approaches for enhancing the reversibility of Li and for fundamental studies of the interphases formed in liquid and solid-state electrolytes using readily accessible analytical tools.

Chain dynamics and glass transition of dry native cellulose solutions in ionic liquids.

Dry native cellulose solutions in 1-butyl-3-methylimidazolium methylphosphonate (EMImMPO3H), 1-butyl-3-methylimidazolium acetate (EMImAc), and 1-butyl-3-methylimidazolium chloride (BMImCl) ionic liquids (IL) were investigated using subambient linear viscoelastic oscillatory shear. Glass transition temperatures (Tg) of solutions with various cellulose concentrations up to 8.0 wt% were observed as the peaks of loss tangent tan(δ) and loss modulus G'' in descending temperature sweeps at 1 rad s-1. Cellulose/IL solutions showed a minimum in Tg at ∼2.0 wt% cellulose content before increasing with cellulose concentration, suggesting a perturbation of the strongly structured IL solvents by the cellulose chains. Isothermal frequency sweeps in the vicinity of Tg were used to construct time-temperature-superposition master curves. The angular frequency shift factor aT as a function of temperature indicates Arrhenius behavior within a 9 K range near Tg, allowing calculation of fragility, which was found to be constant up to 8.0 wt% cellulose concentration. This result implied that increasing cellulose concentration initially decreases Tg due to disrupted ionic regularity of ILs, but does not seem to change their fragility.

The Effect of Water on Rheology of Native Cellulose/Ionic Liquids Solutions.

Cellulose coagulates upon adding water to its solutions in ionic liquids. Although cellulose remains in solution with much higher water contents, here we report the effect of 0-3 wt % water on solution rheology of cellulose in 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium acetate. Fourier transform infrared spectroscopy, thermal gravimetric analysis, and polarized light microscopy were also used to study water absorbance to the solutions. Tiny amounts of water (0.25 wt %) can significantly affect the rheological properties of the solutions, imparting a yield stress, while dry solutions appear to be ordinary viscoelastic liquids. The yield stress grows linearly with water content and saturates at a level that increases with the square of cellulose content. Annealing the solutions containing small amounts of water at 80 °C for 20 min transforms the samples to the fully dissolved "dry" state.