In Situ Electrochemical Atomic Force Microscopy: From Interfaces to Interphases.

The electrochemical interface formed between an electrode and an electrolyte significantly affects the rate and mechanism of the electrode reaction through its structure and properties, which vary across the interface. The scope of the interface has been expanded, along with the development of energy electrochemistry, where a solid-electrolyte interphase may form on the electrode and the active materials change properties near the surface region. Developing a comprehensive understanding of electrochemical interfaces and interphases necessitates three-dimensional spatial resolution characterization. Atomic force microscopy (AFM) offers advantages of imaging and long-range force measurements. Here we assess the capabilities of AFM by comparing the force curves of different regimes and various imaging modes for in situ characterizing of electrochemical interfaces and interphases. Selected examples of progress on work related to the structures and processes of electrode surfaces, electrical double layers, and lithium battery systems are subsequently illustrated. Finally, this review provides perspectives on the future development of electrochemical AFM.

Highly Stable Lithium Metal Batteries Enabled by Tuning the Molecular Polarity of Diluents in Localized High-Concentration Electrolytes.

Electrolyte plays a crucial role in ensuring stable operation of lithium metal batteries (LMBs). Localized high-concentration electrolytes (LHCEs) have the potential to form a robust solid-electrolyte interphase (SEI) and mitigate Li dendrite growth, making them a highly promising electrolyte option. However, the principles governing the selection of diluents, a crucial component in LHCE, have not been clearly determined, hampering the advancement of such a type of electrolyte systems. Herein, the diluents from the perspective of molecular polarity are rationally designed and developed. A moderately fluorinated solvent, 1-(1,1,2,2-tetrafluoroethoxy)propane (TNE), is employed as a diluent to create a novel LHCE. The unique molecular structure of TNE enhances the intrinsic dipole moment, thereby altering solvent interactions and the coordination environment of Li-ions in LHCE. The achieved solvation structure not only enhances the bulk properties of LHCE, but also facilitates the formation of more stable anion-derived SEIs featured with a higher proportion of inorganic species. Consequently, the corresponding full cells of both Li||LiFePO4 and Li||LiNi0.8 Co0.1 Mn0.1 O2 cells utilizing Li thin-film anodes exhibit extended long-term stability with significantly improved average Coulombic efficiency. This work offers new insights into the functions of diluents in LHCEs and provides direction for further optimizing the LHCEs for LMBs.

Unraveling the Mechanism of Very Initial Dendritic Growth Under Lithium Ion Transport Control in Lithium Metal Anodes.

Lithium metal deposition is strongly affected by the intrinsic properties of the solid-electrolyte interphase (SEI) and working electrolyte, but a relevant understanding is far from complete. Here, by employing multiple electrochemical techniques and the design of SEI and electrolyte, we elucidate the electrochemistry of Li deposition under mass transport control. It is discovered that SEIs with a lower Li ion transference number and/or conductivity induce a distinctive current transition even under moderate potentiostatic polarization, which is associated with the control regime transition of Li ion transport from the SEI to the electrolyte. Furthermore, our findings help reveal the creation of a space-charge layer at the electrode/SEI interface due to the involvement of the diffusion process of Li ions through the SEI, which promotes the formation of dendrite embryos that develop and eventually trigger SEI breakage and the control regime transition of Li ion transport. Our insight into the very initial dendritic growth mechanism offers a bridge toward design and control for superior SEIs.

Correlation between the Humidity-Dependent Surface Microstructure and Macroconductivity of Anion Exchange Membranes.

Anion exchange membrane (AEM) fuel cells have gained significant interest in recent years due to their promising applications in cost-effective and environmentally friendly energy conversion. Among various factors that affect their performance, water content plays an important role in the conductivity and stability of AEMs. However, the effect of the hydration level on the microstructure of AEMs and the correlation between the microstructure and macroconductivity have not been systematically investigated. In this work, four AEMs, quaternary ammonia polysulfone, quaternary ammonia poly(N-methyl-piperidine-co-p-terphenyl) (QAPPT), and bromoalkyl-tethered poly(biphenyl alkylene)s PBPA and PBPA-co-BPP, have been studied by atomic force microscopy and electrochemical impedance spectroscopy to elucidate the correlation between the humidity-dependent surface microstructure and macroconductivity of the AEMs. We obtained phase images by atomic force microscopy and identified hydrophilic and hydrophobic domains by fitting the distribution curve of phase images, which reasonably distinguishes hydrophilic domains from hydrophobic domains of the membrane surface, and thus, the surface hydrophilic area ratio and average size could be quantitatively analyzed. The conductivities of the membranes were then measured by electrochemical impedance spectroscopy at various humidities. The joint results from atomic force microscopy and electrochemical measurements help clarify the effect of the hydration level on the microphase separation and ionic conduction of the membranes.

Resolving nanostructure and chemistry of solid-electrolyte interphase on lithium anodes by depth-sensitive plasmon-enhanced Raman spectroscopy.

The solid-electrolyte interphase (SEI) plays crucial roles for the reversible operation of lithium metal batteries. However, fundamental understanding of the mechanisms of SEI formation and evolution is still limited. Herein, we develop a depth-sensitive plasmon-enhanced Raman spectroscopy (DS-PERS) method to enable in-situ and nondestructive characterization of the nanostructure and chemistry of SEI, based on synergistic enhancements of localized surface plasmons from nanostructured Cu, shell-isolated Au nanoparticles and Li deposits at different depths. We monitor the sequential formation of SEI in both ether-based and carbonate-based dual-salt electrolytes on a Cu current collector and then on freshly deposited Li, with dramatic chemical reconstruction. The molecular-level insights from the DS-PERS study unravel the profound influences of Li in modifying SEI formation and in turn the roles of SEI in regulating the Li-ion desolvation and the subsequent Li deposition at SEI-coupled interfaces. Last, we develop a cycling protocol that promotes a favorable direct SEI formation route, which significantly enhances the performance of anode-free Li metal batteries.

Plasmon-Mediated Photoelectrochemical Hot-Hole Oxidation Coupling Reactions of Adenine on Nanostructured Silver Electrodes.

Surface-enhanced Raman spectroscopy (SERS) has been widely applied in the identification and characterization of DNA structures with high efficiency. Especially, the SERS signals of the adenine group have exhibited high detection sensitivity in several biomolecular systems. However, there is still no unanimous conclusion regarding the interpretation of some special kinds of SERS signals of adenine and its derivatives on silver colloids and electrodes. This Letter presents a new photochemical azo coupling reaction for adenyl residues, in which the adenine is selectively oxidized to (E)-1,2-di(7H-purin-6-yl) diazene (azopurine) in the presence of silver ions, silver colloids, and electrodes of nanostructures under visible light irradiation. The product, azopurine, is first found to be responsible for the SERS signals. This photoelectrochemical oxidative coupling reaction of adenine and its derivatives is promoted by plasmon-mediated hot holes and is regulated by positive potentials and pH of solutions, which opens up new avenues for studying azo coupling in the photoelectrochemistry of adenine-containing biomolecules on electrode surfaces of plasmonic metal nanostructures.

Morphology-Dictated Mechanism of Efficient Reaction Sites for Li2O2 Decomposition.

In the pursuit of a highly reversible lithium-oxygen (Li-O2) battery, control of reaction sites to maintain stable conversion between O2 and Li2O2 at the cathode side is imperatively desirable. However, the mechanism involving the reaction site during charging remains elusive, which, in turn, imposes challenges in recognition of the origin of overpotential. Herein, via combined investigations by in situ atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS), we propose a universal morphology-dictated mechanism of efficient reaction sites for Li2O2 decomposition. It is found that Li2O2 deposits with different morphologies share similar localized conductivities, much higher than that reported for bulk Li2O2, enabling the reaction site not only at the electrode/Li2O2/electrolyte interface but also at the Li2O2/electrolyte interface. However, while the mass transport process is more enhanced at the former, the charge-transfer resistance at the latter is sensitively related to the surface structure and thus the reactivity of the Li2O2 deposit. Consequently, for compact disk-like deposits, the electrode/Li2O2/electrolyte interface serves as the dominant decomposition site, which causes premature departure of Li2O2 and loss of reversibility; on the contrary, for porous flower-like and film-like Li2O2 deposits bearing a larger surface area and richer surface-active structures, both the interfaces are efficient for decomposition without premature departure of the deposit so that the overpotential arises primarily from the sluggish oxidation kinetics and the decomposition is more reversible. The present work provides instructive insights into the understanding of the mechanism of reaction sites during the charge process, which offers guidance for the design of reversible Li-O2 batteries.

The Role of Water Content of Deep Eutectic Solvent Ethaline in the Anodic Process of Gold Electrode.

Traditional coupling of ligands for gold wet etching makes large-scale applications problematic. Deep eutectic solvents (DESs) are a new class of environment-friendly solvents, which could possibly overcome the shortcomings. In this work, the effect of water content on the Au anodic process in DES ethaline was investigated by combining linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Meanwhile, we employed atomic force microscopy (AFM) to image the evolution of the surface morphology of the Au electrode during its dissolution and passivation process. The obtained AFM data help to explain the observations about the effect of water content on the Au anodic process from the microscopic perspective. High water contents make the occurrence of anodic dissolution of gold at higher potential, but enhances the rate of the electron transfer and gold dissolution. AFM results reveal the occurrence of massive exfoliation, which confirms that the gold dissolution reaction is more violent in ethaline with higher water contents. In addition, AFM results illustrate that the passive film and its average roughness could be tailored by changing the water content of ethaline.

Building K-C Anode with Ultrahigh Self-Diffusion Coefficient for Solid State Potassium Metal Batteries Operating at -20 to 120 °C.

Solid state potassium (K) metal batteries are intriguing in grid-scale energy storage, benefiting from the low cost, safety, and high energy density. However, their practical applications are impeded by poor K/solid electrolyte (SE) interfacial contact and limited capacity caused by the low K self-diffusion coefficient, dendrite growth, and intrinsically low melting point/soft features of metallic K. Herein, a fused-modeling strategy using potassiophilic carbon allotropes molted with K is demonstrated that can enhance the electrochemical performance/stability of the system via promoting K diffusion kinetics (2.37 × 10-8 cm2 s-1 ), creating a low interfacial resistance (≈1.3 Ω cm2 ), suppressing dendrite growth, and maintaining mechanical/thermal stability at 200 °C. A homogeneous/stable K stripping/plating is consequently implemented with a high current density of 2.8 mA cm-2 (at 25 °C) and a record-high areal capacity of 11.86 mAh cm-2 (at 0.2 mA cm-2 ). The enhanced K diffusion kinetics contribute to sustaining intimate interfacial contact, stabilizing the stripping/plating at high current densities. Full cells coupling ultrathin K-C composite anodes (≈50 µm) with Prussian blue cathodes and ß/ß″-Al2 O3 SEs deliver a high energy density of 389 Wh kg-1 with a retention of 94.4% after 150 cycles and fantastic performances at -20 to 120 °C.

Defect Passivation by a Multifunctional Phosphate Additive toward Improvements of Efficiency and Stability of Perovskite Solar Cells.

The quality of perovskite films plays a crucial role in the performance of the corresponding devices. However, the commonly employed perovskite polycrystalline films often contain a high density of defects created during film production and cell operation, including unsaturated coordinated Pb2+ and Pb0, which can act as nonradiative recombination centers, thus reducing open-circuit voltage. Effectively eliminating both kinds of defects is an important subject of research to improve the power conversion efficiency (PCE). Here, we employ hydrogen octylphosphonate potassium (KHOP) as a multifunctional additive to passivate defects. The molecule is introduced into perovskite precursor solution to regulate the perovskite film growth process by coordinating with Pb, which can not only passivate the Pb2+ defect but also effectively inhibit the production of Pb0; at the same time, the presence of K+ reduces device hysteresis by inhibiting I- migration and finally realizes double passivation of Pb2+ and I--based defects. Moreover, the moderate hydrophobic alkyl chain in the molecule improves the moisture stability. Ultimately, the optimal efficiency can reach 22.21%.

Revealing the Interaction of Charge Carrier-Phonon Coupling by Quantification of Electronic Properties at the SrTiO3/TiO2 Heterointerface.

Oxide heterointerfaces with high carrier density can interact strongly with the lattice phonons, generating considerable plasmon-phonon coupling and thereby perturbing the fascinating optical and electronic properties, such as two-dimensional electron gas, ferromagnetism, and superconductivity. Here we use infrared-spectroscopic nanoimaging based on scattering-type scanning near-field optical microscopy (s-SNOM) to quantify the interaction of electron-phonon coupling and the spatial distribution of local charge carriers at the SrTiO3/TiO2 interface. We found an increased high-frequency dielectric constant (ε∞ = 7.1-9.0) and charge carrier density (n = 6.5 × 1019 to 1.5 × 1020 cm-3) near the heterointerface. Moreover, quantitative information between the charge carrier density and extension thickness across the heterointerface has been extracted by monochromatic near-field imaging. A direct evaluation of the relationship between the thickness and the interaction of charge carrier-phonon coupling of the heterointerface would provide valuable information for the development of oxide-based electronic devices.

Formation sequence of solid electrolyte interphases and impacts on lithium deposition and dissolution on copper: an in situ atomic force microscopic study.

Copper is the most widely used substrate for Li deposition and dissolution in lithium metal anodes, which is complicated by the formation of solid electrolyte interphases (SEIs), whose physical and chemical properties can affect Li deposition and dissolution significantly. However, initial Li nucleation and growth on bare Cu creates Li nuclei that only partially cover the Cu surface so that SEI formation could proceed not only on Li nuclei but also on the bare region of the Cu surface with different kinetics, which may affect the follow-up processes distinctively. In this paper, we employ in situ atomic force microscopy (AFM), together with X-ray photoelectron spectroscopy (XPS), to investigate how SEIs formed on a Cu surface, without Li participation, and on the surface of growing Li nuclei, with Li participation, affect the components and structures of the SEIs, and how the formation sequence of the two kinds of SEIs, along with Li deposition, affect subsequent dissolution and re-deposition processes in a pyrrolidinium-based ionic liquid electrolyte containing a small amount of water. Nanoscale in situ AFM observations show that sphere-like Li deposits may have differently conditioned SEI-shells, depending on whether Li nucleation is preceded by the formation of the SEI on Cu. Models of integrated-SEI shells and segmented-SEI shells are proposed to describe SEI shells formed on Li nuclei and SEI shells sequentially formed on Cu and then on Li nuclei, respectively. "Top-dissolution" is observed for both types of shelled Li deposits, but the integrated-SEI shells only show wrinkles, which can be recovered upon Li re-deposition, while the segmented-SEI shells are apparently top-opened due to mechanical stresses introduced at the junctions of the top regions and become "dead" SEIs, which forces subsequent Li nucleation and growth in the interstice of the dead SEIs. Our work provides insights into the impact mechanism of SEIs on the initial stage Li deposition and dissolution on foreign substrates, revealing that SEIs could be more influential on Li dissolution and that the spatial integration of SEI shells on Li deposits is important to improving the reversibility of deposition and dissolution cycling.

Quantification of electron accumulation at grain boundaries in perovskite polycrystalline films by correlative infrared-spectroscopic nanoimaging and Kelvin probe force microscopy.

Organic-inorganic halide perovskites are emerging materials for photovoltaic applications with certified power conversion efficiencies (PCEs) over 25%. Generally, the microstructures of the perovskite materials are critical to the performances of PCEs. However, the role of the nanometer-sized grain boundaries (GBs) that universally existing in polycrystalline perovskite films could be benign or detrimental to solar cell performance, still remains controversial. Thus, nanometer-resolved quantification of charge carrier distribution to elucidate the role of GBs is highly desirable. Here, we employ correlative infrared-spectroscopic nanoimaging by the scattering-type scanning near-field optical microscopy with 20 nm spatial resolution and Kelvin probe force microscopy to quantify the density of electrons accumulated at the GBs in perovskite polycrystalline thin films. It is found that the electron accumulations are enhanced at the GBs and the electron density is increased from 6 × 1019 cm-3 in the dark to 8 × 1019 cm-3 under 10 min illumination with 532 nm light. Our results reveal that the electron accumulations are enhanced at the GBs especially under light illumination, featuring downward band bending toward the GBs, which would assist in electron-hole separation and thus be benign to the solar cell performance. Correlative infrared-spectroscopic nanoimaging by the scattering-type scanning near-field optical microscopy and Kelvin probe force microscopy quantitatively reveal the accumulated electrons at GBs in perovskite polycrystalline thin films.

z-Piezo Pulse-Modulated STM Break Junction: Toward Single-Molecule Rectifiers with Dissimilar Metal Electrodes.

Fabricating single-molecule junctions with asymmetric metal electrodes is significant for realizing single-molecule diodes, but it remains a big challenge. Herein, we develop a z-piezo pulse-modulated scanning tunneling microscopy break junction (STM-BJ) technique to construct a robust asymmetric junction with different metal electrodes. The asymmetric Ag/BPY-EE/Au single-molecule junctions exhibit a middle conductance value in between those of the two individual symmetric metal electrode junctions, which is consistent with the order of calculated energy-dependent transmission coefficient T(E) of the asymmetric junctions at EF. Furthermore, the single-molecule conductance of Ag/BPY-EE/Au decreases by about 70% when reversing the bias voltage from 100 to -100 mV, and a clear asymmetric I-V feature at the single-molecule level is observed for these junctions. This rectifying behavior could be ascribed to a different interfacial coupling of molecules at the two end electrodes, which is confirmed by the different displacement of T(E) at the two bias voltages. Other asymmetric junctions exhibit similar rectifying behavior. The current work provides a feasible way to fabricate hybrid junctions based on asymmetric metal electrodes and investigate their electron transport toward the design of molecular rectifiers.

Plasmonic Hot Electron-Mediated Hydrodehalogenation Kinetics on Nanostructured Ag Electrodes.

An attractive field of plasmon-mediated chemical reactions (PMCRs) is developing rapidly, but there is still incomplete understanding of how to control the kinetics of such a reaction related to hot carriers. Here, we chose 8-bromoadenine (8BrAd) as a probe molecule of hot electrons to investigate the influence of the electrode potential, laser wavelength, and power on the PMCR kinetics on silver nanoparticle-modified silver electrodes. Plasmonic hot electron-mediated cleavage of the C-Br bond in 8BrAd has been investigated by combining in situ electrochemical surface-enhanced Raman spectroscopy and density functional theory calculations. The experimental and theoretical results reveal that the energy position of plasmon relaxation-generated hot electrons can be modulated conveniently by applied potentials and laser light. This allows the proposal of a mechanism of modulating the matching energy of the hot electron of plasmon relaxation to promote the efficiency of PMCRs in electrochemical interfaces. Our work will be helpful to design surface plasmon resonance photoelectrochemical reactions on metal electrode surfaces of nanostructures with higher efficiency.

Observation of inhomogeneous plasmonic field distribution in a nanocavity.

The progress of plasmon-based technologies relies on an understanding of the properties of the enhanced electromagnetic fields generated by the coupling nanostrucutres1-6. Plasmon-enhanced applications include advanced spectroscopies7-10, optomechanics11, optomagnetics12 and biosensing13-17. However, precise determination of plasmon field intensity distribution within a nanogap remains challenging. Here, we demonstrate a molecular ruler made from a set of viologen-based, self-assembly monolayers with which we precisely measures field distribution within a plasmon nanocavity with ~2-Å spatial resolution. We observed an unusually large plasmon field intensity inhomogeneity that we attribute to the formation of a plasmonic comb in the nanocavity. As a consequence, we posit that the generally adopted continuous media approximation for molecular monolayers should be used carefully.

Constructing Dual-Molecule Junctions to Probe Intermolecular Crosstalk.

Understanding and controlling charge transport across multiple parallel molecules are fundamental to the creation of innovative functional electronic components, as future molecular devices will likely be multimolecular. The smallest possible molecular ensemble to address this challenge is a dual-molecule junction device, which has potential to unravel the effects of intermolecular crosstalk on electronic transport at the molecular level that cannot be elucidated using either conventional single-molecule or self-assembled monolayer (SAM) techniques. Herein, we demonstrate the fabrication of a scanning tunneling microscopy (STM) dual-molecule junction device, which utilizes noncovalent interactions and allows for direct comparison to the conventional STM single-molecule device. STM-break junction (BJ) measurements reveal a decrease in conductance of 10% per molecule from the dual-molecule to the single-molecule junction device. Quantum transport simulations indicate that this decrease is attributable to intermolecular crosstalk (i.e., intermolecular π-π interactions), with possible contributions from substrate-mediated coupling (i.e., molecule-electrode). This study provides the first experimental evidence to interpret intermolecular crosstalk in electronic transport at the STM-BJ level and translates the experimental observations into meaningful molecular information to enhance our fundamental knowledge of this subject matter. This approach is pertinent to the design and development of future multimolecular electronic components and also to other dual-molecular systems where such crosstalk is mediated by various noncovalent intermolecular interactions (e.g., electrostatic and hydrogen bonding).