Cross-Linked Gel Electrolytes with Self-Healing Functionalities for Smart Lithium Batteries.

Next-generation Li-ion batteries must guarantee improved durability, quality, reliability, and safety to satisfy the stringent technical requirements of crucial sectors such as e-mobility. One breakthrough strategy to overcome the degradation phenomena affecting the battery performance is the development of advanced materials integrating smart functionalities, such as self-healing units. Herein, we propose a gel electrolyte based on a uniform and highly cross-linked network, hosting a high amount of liquid electrolyte, with multiple advantages: (i) autonomous, fast self-healing, and a promising PF5-scavenging role; (ii) solid-like mechanical stability despite the large fraction of entrapped liquid; and (iii) good Li+ transport. It is shown that such a gel electrolyte has very good conductivity (>1.0 mS cm-1 at 40 °C) with low activation energy (0.25 eV) for the ion transport. The transport properties are easily restored in the case of physical damages, thanks to the outstanding capability of the polymer to intrinsically repair severe cracks or fractures. The good elastic modulus of the cross-linked network, combined with the high fraction of anions immobilized within the polymer backbone, guarantees stable Li electrodeposition, disfavoring the formation of mossy dendrites with the Li metal anode. We demonstrate the electrolyte performance in a full-cell configuration with a LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode, obtaining good cycling performance and stability.

Autonomous Self-Healing Strategy for Stable Sodium-Ion Battery: A Case Study of Black Phosphorus Anodes.

Autonomic self-healing (SH), namely, the ability to repair damages from mechanical stress spontaneously, is polarizing attention in the field of new-generation electrochemical devices. This property is highly attractive to enhance the durability of rechargeable Li-ion batteries (LIBs) or Na-ion batteries (SIBs), where high-performing anode active materials (silicon, phosphorus, etc.) are strongly affected by volume expansion and phase changes upon ion insertion. Here, we applied a SH strategy, based on the dynamic quadruple hydrogen bonding, to nanosized black phosphorus (BP) anodes for Na-ion cells. The goal is to overcome drastic capacity decay and short lifetime, resulting from mechanical damages induced by the volumetric expansion/contraction upon sodiation/desodiation. Specifically, we developed novel ureidopyrimidinone (UPy)-telechelic systems and related blends with poly(ethylene oxide) as novel and green binders alternative to the more conventional ones, such as polyacrylic acid and carboxymethylcellulose, which are typically used in SIBs. BP anodes show impressively improved (more than 6 times) capacity retention when employing the new SH polymeric blend. In particular, the SH electrode still works at a current density higher than 3.5 A g-1, whereas the standard BP electrode exhibits very poor performances already at current densities lower than 0.5 A g-1. This is the result of better adhesion, buffering properties, and spontaneous damage reparation.

Solution microstructures of the micellar phase of Pluronic L64/SDS/water system.

Here we report on a study dealing with a self-assembling ethylene oxide-propylene oxide-ethylene oxide triblock copolymer (Pluronic L64) and an anionic surfactant, sodium dodecyl sulfate (SDS), that in water at 25 degrees C form an interesting micellar region (L-phase). We have investigated the sequence of micelle structures in this L-phase across a wide interval of copolymer concentrations using phase diagram determination, steady shear, and NMR self-diffusion (pulsed gradient spin-echo, PGSE) experiments. In solutions which have been prepared at moderately low copolymer concentrations (ca. 20wt.% L64) we report on a transition from discrete micelles to bicontinuous aggregates on the addition of SDS. This change was mainly inferred from self-diffusion coefficient patterns (i.e., the variation of copolymers and surfactant diffusivity vs. SDS content). At midrange and at higher polymer concentrations (i.e., in the interval from 50 to 80wt.% L64) the L-phase occurred with a bicontinuous structure which was not modified by the progressive addition of SDS. Such a bicontinuous structure was identified by the comparison of self-diffusion coefficients of both cosolutes and the bulk viscosity (i.e., the behavior of zero-shear viscosity vs. SDS).

N,N'-Hexadecanoyl l-2-diaminomethyl-18-crown-6 surfactant: synthesis and aggregation features in aqueous solution.

Bolas surfactants can be inserted into bi-layers and may operate as permanent holes in such membranes. Significant synthetic work and an exhaustive characterisation of their properties in the bulk was performed. On this purpose, the phase diagram of the system composed by water and 1,16-hexadecanoyl-bis-(2-aminomethyl)-18-crown-6 (termed Bola A16) was investigated in a wide temperature and concentration range. No liquid crystalline phases were observed and a large micellar solution was present, up to about 50 surfactant wt%. Surface tension experiments defined adsorption and micelle formation. The low observed cmc value is important for pharmacological applications, in fact, considering intravenous administration, only micelles with low cmc value can exist in blood. Nuclear magnetic resonance experiments determined both water and surfactant self-diffusion. According to the aforementioned experiments, slight, if any, modifications in the structure of micelles were inferred on increasing Bola A16 content. Dynamic rheological experiments probed the solution micro-structure. The observed rheological behaviour is newtonian. The solution viscosity and the shear relaxation processes were rationalized assuming the presence of spherical aggregates, occurring up to high surfactant content. The viscometric behaviour was rationalised in terms of a former theory of flow as a cooperative phenomenon. The number of micelles coordinated each other during the viscous flow and the interaction strength between them was obtained as a function of Bola A16 concentration. Such value is close to unity and practically independent of surfactant content in the whole concentration range we investigated. This behaviour points out that little, or none, interactions among micellar aggregates occur. The absence of shear induced changes in the aggregate shape implies no change in drug delivery properties under flow, this is useful in the pharmaco-dynamics field, since drug delivery usually operates in mechanically stressed conditions. Thanks to the above properties, the material results particularly suitable for application in pharmaceutical field, may solubilize lipid membranes and selectively transport ions across them. Ancillary effects, such as the uptake of counter-ions in the crown ether, are to be considered.