Raphael Zahn

Filling of the electrode and the separator with an electrolyte is a crucial step in the lithium ion battery manufacturing process. Incomplete filling negatively impacts electrochemical performance, cycle life, and safety of cells. Here, we apply concepts from the theory of partial wetting to explain the amount of gas entrapment that occurs during electrolyte infilling and show that this can explain the lower than expected effective transport coefficients that are measured experimentally. We consider a polyethylene separator as a model system. Quasi-static infilling simulations on 3D reconstructions of the separator structure indicate that there can be up to 30% gas entrapment upon infilling due to the geometry of the separator, which results in a reduction of effective transport by >40%. Considering the dynamics of the electrolyte (e.g., viscosity) and the infilling process explains why the residual gas phase is typically less (15%–20%) and why, for electrolytes that wet well, increasing viscosity leads to higher values of gas entrapment, which is observed experimentally as decreased effective electrolyte conductivity. This work highlights the importance of optimizing not only the physiochemical properties of the electrolyte and pore surfaces, but also the 3D structure of the pore space, providing insights how to do so.

Pore space connectivity is a useful metric for describing microstructure of lithium ion battery components.

In this paper, we study how polyolefin separators respond to compressive stress, which can occur during battery operation as active particles lithiate, expand, and push into and deform the separator. We use real microstructures of polyethylene and polypropylene separators acquired with focused ion beam scanning electron microscopic (FIB-SEM) tomography and simulate how these structures deform under compressive strain. After validating our mechanical simulations, we characterize how the microstructural properties of the separators change as a function of compressive strain and simulate the influence these changes in microstructure have on the lithium ion transport through the separator. We find that a given compressive strain negatively impacts the microstructure of polyethylene separator more than that of a polypropylene separator. To understand the origins of the different response to compressive strains in polyethylene and polypropylene separators, we use a network-based analysis to assess the type of mechanical deformations occurring in the separator membrane and show that it is the combination of material properties and structure that are responsible for the greater stability of polypropylene. This work highlights how the structure of a separator plays an important role in its mechanical robustness and prevention of cell degradation.

The microstructure of lithium ion battery separators plays an important role in separator performance; however, here we show that a geometrical analysis falls short in predicting the lithium ion transport in the electrolyte-filled pore space. By systematically modifying the surface chemistry of a commercial polyethylene separator while keeping its microstructure unchanged, we demonstrate that surface chemistry, which alters separator-electrolyte interactions, influences ionic conductivity and lithium ion transference number. Changes in separator surface chemistry, particularly those which increase lithium ion transference numbers can reduce voltage drops across the separator and improve C-rate capability.

The permeability barrier of nuclear pore complexes (NPCs) controls bulk nucleocytoplasmic exchange. It consists of nucleoporin domains rich in phenylalanine-glycine motifs (FG domains). As a bottom-up nanoscale model for the permeability barrier, we have used planar films produced with three different end-grafted FG domains, and quantitatively analyzed the binding of two different nuclear transport receptors (NTRs), NTF2 and Importin β, together with the concomitant film thickness changes. NTR binding caused only moderate changes in film thickness; the binding isotherms showed negative cooperativity and could all be mapped onto a single master curve. This universal NTR binding behavior – a key element for the transport selectivity of the NPC – was quantitatively reproduced by a physical model that treats FG domains as regular, flexible polymers, and NTRs as spherical colloids with a homogeneous surface, ignoring the detailed arrangement of interaction sites along FG domains and on the NTR surface.

Separators play an important role in lithium-ion battery operation; however, no comprehensive studies of their microstructure and its impact exist. To enable such studies, we present a simple method for separator microstructure visualization and quantification based on focused-ion-beam scanning electron microscopic tomography. Here, we use this approach to visualize a sample of commercial polyethylene separator, calculate its directional effective transport parameters, and explain the impact of these values on battery performance. We further extend this technique to visualize metallic deposition within the separator, which could facilitate the study of lithium plating and dendritic growth.

We discuss physicochemical determinants of electrochemical polyelectrolyte multilayer swelling that are relevant to actuator usage. We used electrochemical quartz crystal microbalance with dissipation monitoring (EC-QCM-D) and cyclic voltammetry to compare the electrochemical swelling of two types of ferrocyanide-containing polyelectrolyte multilayers, poly(l-glutamic acid)/poly(allylamine hydrochloride) (PGA/PAH), and carboxymethyl cellulose/poly(diallyldimethylammonium chloride) (CMC/PDDA). We showed that ferrocyanide oxidation causes the swelling of PGA/PAH multilayers whereas it results in the contraction of CMC/PDDA multilayers. This behavior can be attributed to the presence of a positive and a negative Donnan potential in the case of PGA/PAH and CMC/PDDA multilayers, respectively. Using multilayers consisting of PGA and poly(allylamine) ferrocene (PGA/PAH-FC), we applied EC-QCM-D and demonstrated potentiostatic thickness control with nanometer precision and showed that the multilayer’s thickness depends linearly on the applied potential within a certain potential range.