Proton transfer across single-layer graphene proceeds with large computed energy barriers and is therefore thought to be unfavourable at room temperature unless nanoscale holes or dopants are introduced, or a potential bias is applied. Here we subject single-layer graphene supported on fused silica to cycles of high and low pH, and show that protons transfer reversibly from the aqueous phase through the graphene to the other side where they undergo acid–base chemistry with the silica hydroxyl groups. After ruling out diffusion through macroscopic pinholes, the protons are found to transfer through rare, naturally occurring atomic defects. Computer simulations reveal low energy barriers of 0.61–0.75 eV for aqueous proton transfer across hydroxyl-terminated atomic defects that participate in a Grotthuss-type relay, while pyrylium-like ether terminations shut down proton exchange. Unfavourable energy barriers to helium and hydrogen transfer indicate the process is selective for aqueous protons.

Over the past few years, in situ transmission electron microscopy (TEM) studies of lithium ion batteries using an open-cell configuration have helped us to gain fundamental insights into the structural and chemical evolution of the electrode materials in real time. In the standard open-cell configuration, the electrolyte is either solid lithium oxide or an ionic liquid, which is point-contacted with the electrode. This cell design is inherently different from a real battery, where liquid electrolyte forms conformal contact with electrode materials. The knowledge learnt from open cells can deviate significantly from the real battery, calling for operando TEM technique with conformal liquid electrolyte contact. In this paper, we developed an operando TEM electrochemical liquid cell to meet this need, providing the configuration of a real battery and in a relevant liquid electrolyte. To demonstrate this novel technique, we studied the lithiation/delithiation behavior of single Si nanowires. Some of lithiation/delithation behaviors of Si obtained using the liquid cell are consistent with the results from the open-cell studies. However, we also discovered new insights different from the open cell configuration-the dynamics of the electrolyte and, potentially, a future quantitative characterization of the solid electrolyte interphase layer formation and structural and chemical evolution.

In this work we explore how an electrolyte additive (fluorinated ethylene carbonate – FEC) mediates the thickness and composition of the solid electrolyte interphase formed over a silicon anode in situ as a function of state-of-charge and cycle. We show the FEC condenses on the surface at open circuit voltage then is reduced to C-O containing polymeric species around 0.9 V (vs. Li/Li+). The resulting film is about 50 Å thick. Upon lithiation the SEI thickens to 70 Å and becomes more organic-like. With delithiation the SEI thins by 13 Å and becomes more inorganic in nature, consistent with the formation of LiF. This thickening/thinning is reversible with cycling and shows the SEI is a dynamic structure. We compare the SEI chemistry and thickness to 280 Å thick SEI layers produced without FEC and provide a mechanism for SEI formation using FEC additives.

With the use of neutron reflectometry, we have determined the thickness and chemistry of the solid-electrolyte interphase (SEI) layer grown on a silicon anode as a function of state of charge and during cycling. We show the chemistry of this SEI layer becomes more LiF like with increasing lithiation and more Li−C−O−F like with delithiation. More importantly, the SEI layer thickness appears to increase (about 250 Å) as the electrode becomes less lithiated and thins to 180 Å with increasing Li content (Li 3.7 Si). We attribute this "breathing" to the continual consumption of electrolyte with cycling.

Understanding of structural, electrical, and gravimetric peculiarities of water vapor interaction with ion-intercalated MXenes led to design of a multimodal humidity sensor. Neutron scattering coupled to molecular dynamics and ab initio calculations showed that a small amount of hydration results in a significant increase in the spacing between MXene layers in the presence of K and Mg intercalants between the layers. Films of K- and Mg-intercalated MXenes exhibited relative humidity (RH) detection thresholds of ∼0.8% RH and showed monotonic RH response in the 0-85% RH range. We found that MXene gravimetric response to water is 10 times faster than their electrical response, suggesting that HO-induced swelling/contraction of channels between MXene sheets results in trapping of HO molecules that act as charge-depleting dopants. The results demonstrate the use of MXenes as humidity sensors and infer potential impact of water on structural and electrical performance of MXene-based devices.