Differential Electrochemical Mass Spectrometry Research Articles

Ethylene Glycol Co‐Solvent Enables Stable Aqueous Ammonium‐Ion Batteries with Diluted Electrolyte

AbstractAqueous ammonium‐ion batteries (AAIBs) are considered as one of the most promising technologies for large scale energy storage applications, due to their intrinsic safety, environmental friendliness and low cost. Nevertheless, the practical application of AAIBs is impeded by hydrogen evolution reaction (HER) occurring in diluted aqueous electrolyte. Highly concentrated electrolytes can improve electrochemical stability but lead to higher costs and increased hydrolysis of NH4+. In this work ethylene glycol (EG) is proposed as co‐solvent, which can act as H‐bond modulating agent, to increase the stability of AAIBs with diluted electrolytes. The perturbation of water H‐bond network regulated by EG is proved by spectroscopic methods, while the suppressed HER is confirmed by differential electrochemical mass spectrometry (DEMS) results. As a result, full cells with 3,4,9,10‐perylenebis(dicarboximide) (PTCDI) anode and FeFe(CN)6 (FeHCF) cathode and EG‐added electrolyte exhibit stable cycling performance with capacity retention of 77% after 1950 cycles.

Air-Stable and Low-Cost High-Voltage Hydrated Eutectic Electrolyte for High-Performance Aqueous Aluminum-Ion Rechargeable Battery with Wide-Temperature Range.

Aqueous aluminum-ion batteries (AAIBs) are considered as a promising alternative to lithium-ion batteries due to their large theoretical capacity, high safety, and low cost. However, the uneven deposition, hydrogen evolution reaction (HER), and corrosion during cycling impede the development of AAIBs, especially under a harsh environment. Here, a hydrated eutectic electrolyte (AATH40) composed of Al(OTf)3, acetonitrile (AN), triethyl phosphate (TEP), and H2O was designed to improve the electrochemical performance of AAIBs in a wide temperature range. The combination of molecular dynamics simulations and spectroscopy analysis reveals that AATH40 has a less-water-solvated structure [Al(AN)2(TEP)(OTf)2(H2O)]3+, which effectively inhibits side reactions, decreases the freezing point, and extends the electrochemical window of the electrolyte. Furthermore, the formation of a solid electrolyte interface, which effectively inhibits HER and corrosion, has been demonstrated by X-ray photoelectron spectroscopy, X-ray diffraction tests, and in situ differential electrochemical mass spectrometry. Additionally, operando synchrotron Fourier transform infrared spectroscopy and electrochemical quartz crystal microbalance with dissipation monitoring reveal a three-electron storage mechanism for the Al//polyaniline full cells. Consequently, AAIBs with this electrolyte exhibit improved cycling stability within the temperature range of -10-50 °C. This present study introduces a promising methodology for designing electrolytes suitable for low-cost, safe, and stable AAIBs over a wide temperature range.

KIr4O8 Nanowires with Rich Hydroxyl Promote Oxygen Evolution Reaction in Proton Exchange Membrane Water Electrolyzer.

The sluggish kinetics for anodic oxygen evolution reaction (OER) and insufficient catalytic performance over the corresponding Ir-based catalysts are still enormous challenges in proton exchange membrane water electrolyzer (PEMWE). Herein, we report that KIr4O8 nanowires anode catalyst with more exposed active sites and rich hydroxyl achieves a current density of 1.0 A/cm2 at 1.68V and possesses excellent catalytic stability with 1230h in PEMWE. Combining in situ Raman spectroscopy and differential electrochemical mass spectroscopy results, we propose the modified adsorbate evolution mechanism that rich hydroxyl in the inherent structure of KIr4O8 nanowires directly participates in the catalytic process for favoring the OER. Density functional theory calculation results further suggest that the enhanced proximity between Ir (d) and O (p) band center in KIr4O8 can strengthen the covalence of Ir-O, facilitate the electron transfer between adsorbents and active sites, and decrease the energy barrier of rate-determining step from OH* to O* during the OER. This article is protected by copyright. All rights reserved.

Boosting the Proton Intercalation via Crystal Plane Optimization of TiS2 for Cycling‐Stable Aqueous Zn‐Ion Batteries

AbstractTiS2 has received significant attention as a promising anode for “Rocking‐Chair”‐type aqueous Zn‐ion batteries due to the large interlayer spacing and low discharge plateau. However, the structural distortion caused by the embedding of divalent Zn2+ as well as the undesirable hydrogen evolution reaction (HER) severely affects their cycling stability. Herein, a facet‐dependent mechanism is first deeply investigated to understand charge storage behaviors of TiS2 via differential electrochemical mass spectrometry, in situ electrochemical quartz crystal microbalance, and in situ X‐ray diffraction characterizations. By regulating the exposed crystal facets of TiS2 from (001) (TS (001)) to (011) (TS(011)), HER can be effectively inhibited, and the charge storage mechanism is transformed from Zn2+ insertion/extraction dominating to H+ insertion/extraction dominating, resulting in faster charge transfer kinetics and strong structure stability during long‐term cycling. Hence, TS(011) delivers a higher reversible capacity of 212.9 mAh g−1 at 0.1 A g−1 and a strong cycling stability of 74% capacity retention over 1000 cycles, much better than that of TS (001) with a reversible capacity of 164.7 mAh g−1 at 0.1 A g−1, a capacity retention of 17% after 1000 cycles. These new findings can provide deep insight into the rational design of high‐performance intercalation‐type electrode materials for energy storage applications.

Experimental screening of intermetallic alloys for electrochemical CO2 reduction

In this study, we experimentally screen a promising class of intermetallic alloys for the electrochemical reduction of CO2 toward hydrocarbon products. Based on previous DFT-based screening papers, combinations of strongly CO-binding metals such as iron, cobalt, and nickel with weakly CO-binding metals such as gallium, aluminium or zinc were selected as potentially promising catalytic materials. Despite the challenging production of these alloys, we report a general two-step synthesis method for intermetallic alloys and discuss the specific synthesis conditions that must be taken into account when synthesising these materials. After their synthesis, we use a recently developed differential electrochemical mass spectrometry (DEMS) setup to rapidly quantify the CO2 reduction products over a range of potentials. Almost all newly developed intermetallic catalysts are shown to produce methane and ethylene, while the CoSn catalyst showed higher selectivity towards formate production. However, all tested catalysts mostly produced hydrogen and only reduce CO2 to a small extent, despite the favourable computational screening results. We discuss possible reasons for this discrepancy and outline a more holistic approach for linking future DFT studies with experiments.

Dual-ion regulation of coordination chemistry for high-voltage stabilized P2-type cathode

P2-Na2/3Ni1/3Mn2/3O2 has shown great potential as cathode material for sodium-ion batteries with its high theoretical capacity and energy density. However, severe structural changes are induced by charging P2-Na2/3Ni1/3Mn2/3O2 above 4.2 V, resulting in rapid capacity decay and poor kinetic capability. In this study, we propose a Zn/Ti synergistic modification strategy to stabilize the P2-type cathode under high voltage. It is found that the P2-O2 phase transition with large volume change is replaced by a milder P2-Z phase transition with the noteworthy improvement in structural stability and Na+ diffusion kinetics, due to the disordered Na+/vacancy and the suppressed of the sliding of transition metal layers, as disclosed by density functional theory calculations and in-situ X-ray diffraction. Concurrently, The phenomenon of Ni and O reductive coupling is inhibited by regulating local O coordination owing to the incorporation of a strong Ti−O covalence bond, leading to the more reversible charge compensation mechanism and the inhibited lattice O evolution, as clearly revealed by ex-situ X-ray absorption spectroscopy and Differential Electrochemical Mass Spectrometry. Consequently, we obtained a stable P2-Na0.67Zn0.05Ni0.28Mn0.52Ti0.15O2 cathode, achieving an average discharge voltage of 3.62 V at 0.1 C and a capacity retention of 80% after 500 cycles at 2 C. This research provides valuable insights into the enhancement of sodium-ion battery cathode materials by utilizing different functional ions in synergy.

Suppressed Electrolyte Decomposition Behavior to Improve Cycling Performance of LiCoO2 under 4.6V through the Regulation of Interfacial Adsorption Forces.

Alleviating the decomposition of the electrolyte is of great significance to improving the cycle stability of cathodes, especially for LiCoO2 (LCO), its volumetric energy density can be effectively promoted by increasing the charge cutoff voltage to 4.6V, thereby supporting the large-scale application of clean energy. However, the rapid decomposition of the electrolyte under 4.6V conditions not only loses the transport carrier for lithium ion, but also produces HF and insulators that destroy the interface of LCO and increase impedance. In this work, the decomposition of electrolyte is effectively suppressed by changing the adsorption force between LCO interface and EC. Density functional theory illustrates the LCO coated with lower electronegativity elements has a weaker adsorption force with the electrolyte, the adsorption energy between LCO@Mg and EC (0.49eV) is weaker than that of LCO@Ti (0.73eV). Meanwhile, based on the results of time of flight secondary ion mass spectrometry, conductivity-atomic force microscopy, in situ differential electrochemical mass spectrometry, soft X-ray absorption spectroscopy, and nuclear magnetic resonance, as the adsorption force increases, the electrolyte decomposes more seriously. This work provides a new perspective on the interaction between electrolyte and the interface of cathode and further improves the understanding of electrolyte decomposition.

Highly Active W2C-Based Composites for the HER in Alkaline Solution: the Role of Surface Oxide Species.

The hydrogen evolution reaction (HER) is a crucial electrochemical process for the proposed hydrogen economy since it has the potential to provide pure hydrogen for fuel cells. Nowadays, hydrogen electroproduction is considerably expensive, so promoting the development of new non-noble catalysts for the cathode of alkaline electrolyzers appears as a suitable way to reduce the costs of this technology. In this sense, a series of tungsten-based carbide materials have been synthesized by the urea-glass route as candidates to improve the HER in alkaline media. Moreover, two different pyridinium-based ionic liquids were employed to modify the surface of the carbide grains and control the amount and nature of their surface species. The main results indicate that the catalyst surface composition is modified in the hybrid materials, which are then distinguished by the appearance of tungsten suboxide structures. This implies the action of ionic liquids as reducing agents. Consequently, differential electrochemical mass spectrometry (DEMS) is used to precisely determine the onset potentials and rate-determining steps (RDS) for the HER in alkaline media. Remarkably, the modified surfaces show high catalytic performance (overpotentials between 45 and 60 mV) and RDS changes from Heyrovsky-Volmer to Heyrovsky as the surface oxide structures get reduced. H2O molecule reduction is then faster at tungsten suboxide, which allows the formation of the adsorbed hydrogen at the surface, boosting the catalytic activity and the kinetics of the alkaline HER.

Stabilizing Lattice Oxygen through Mn Doping in NiCo2O4-δ Spinel Electrocatalysts for Efficient and Durable Acid Oxygen Evolution.

Design the electrocatalysts without noble metal is still a challenge for oxygen evolution reaction (OER) in acid media. Herein, we reported the manganese (Mn) doping method to decrease the concentration of oxygen vacancy (VO) and form the Mn-O structure adjacent octahedral sites in spinel NiCo2O4-δ (NiMn1.5Co3O4-δ), which highly enhanced the activity and stability of spinel NiCo2O4-δ with a low overpotential (η) of 280 mV at j=10 mA cm-2 and long-term stability of 80 h in acid media. The isotopic labelling experiment based on differential electrochemical mass spectrometry (DEMS) clearly demonstrated the lattice oxygen in NiMn1.5Co3O4-δ is more stable due to strong Mn-O bond and shows synergetic adsorbate evolution mechanism (SAEM) for acid OER. Density functional theory (DFT) calculations reveal highly increased oxygen vacancy formation energy (EVO) of NiCo2O4-δ after Mn doping. More importantly, the highly hydrogen bonding between Mn-O and *OOH adsorbed on adjacent Co octahedral sites promote the formation of *OO from *OOH due to the greatly enhanced charge density of O in Mn substituted sites.

Sub-2nm IrRuNiMoCo High-Entropy Alloy with Iridium-Rich Medium-Entropy Oxide Shell to Boost Acidic Oxygen Evolution.

Ensuring high catalytic activity and durability at low iridium(Ir)usage is still a big challenge for the development of electrocatalysts toward oxygen evolution reaction (OER) in proton exchange membrane water electrolysis (PEMWE). Here, a rapid liquid-reduction combined with surface galvanic replacement strategy is reported to synthesize the sub 2nm high-entropy alloy (HEA) nanoparticles featured with Ir-rich IrRuNiMo medium-entropy oxide shell (Ir-MEO) and a IrRuCoNiMo HEA core (HEA@Ir-MEO). Advanced spectroscopies reveal that the Ir-rich MEO shell inhibits the severe structural evolution of transition metals upon the OER, thus guaranteeing the structural stability. In situ differential electrochemical mass spectrometry, activation energy analysis and theoretical calculations unveil that the OER on HEA@Ir-MEO follows an adsorbate evolution mechanism pathway, where the energy barrier of rate-determining step is substantially lowered. The optimized catalyst delivers the excellent performance (1.85V/3.0 A cm-2@80°C), long-term stability (>500 h@1.0 Acm-2), and low energy consumption (3.98kWh Nm-3 H2 @1.0 A cm-2) in PEMWE with low Ir usage of ≈0.4 mg cm-2, realizing the dramatical reduction of hydrogen (H2) production cost to 0.88 dollarper kg (H2).

Rationally coordinating polymer enabling effective Li-ion percolation network in composite electrolyte for solid-state Li-metal batteries

The sluggish lithium-ion mobility and inferior electrolyte/electrode interfacial compatibility of composite solid electrolytes greatly hinder the practical application of solid-state lithium-metal batteries. Here, a novel composite polymer electrolyte (CPE) with effective Li+ percolation network is synthesized based on single-ion conductive polymer lithiated polyvinyl formal (LiPVFM) and garnet Li6.4La3Zr2Ga0.2O12 (LLZGO) nanoparticles. The supramolecular interaction between the branched hydroxyl in LiPVFM and the lattice oxygen in LLZGO fillers endows CPE with a continuous percolation structure and improved toughness. Meanwhile, the rational O-Li+ coordination in the LiPVFM random polymer significantly enhances Li+ transfer within the percolation network. Therefore, this as-prepared CPE presents a lithium-ion transference number of 0.75 and an ionic conductivity of 0.527 mS cm−1 at 30 °C, alongside an electrochemical stability window of 4.6 V and a substantial suppression of Li dendrite growth. In addition, ultra-stable interfaces between this CPE and high-voltage LiNi0.6Mn0.2Co0.2O2 (NMC) cathode during cycling can be determined by in-situ electrochemical impedance spectroscopy and in-situ differential electrochemical mass spectrometry characterization. This work is a new exploration for the structural design of CPEs and highlights the importance of “rational coordination” of alkali cation in solid batteries.

In-situ differential electrochemical mass spectrometry study on the effects of negative/positive ratios on gas evolution in lithium-ion full batteries

In-situ differential electrochemical mass spectrometry study on the effects of negative/positive ratios on gas evolution in lithium-ion full batteries

Electrochemical oxidation of glucose in alkaline environment—A comparative study of Ni and Au electrodes

The glucose oxidation reaction (GOR) was studied on Au and Ni electrodes by cyclic voltammetry (CV), rotating disk electrode (RDE) measurements coupled with Koutecky–Levich analysis, Differential Electrochemical Mass Spectrometry (DEMS), in situ Fourier Transform Infrared spectroscopy (FTIRS) and High Performance Liquid Chromatography (HPLC) analysis of the reaction products after electrolysis in potentiostatic mode under continuous flow conditions. This study allowed to identify the reaction products and propose tentative reaction mechanisms. On gold, glucose is adsorbed on metallic sites through its anomeric function (C1) resulting in the formation of gluconate as the main GOR product at potentials close to 0.6 V vs. RHE, with a selectivity towards gluconate close to 100% and a projected faradaic efficiency of ca. 70%. The conversion rate is rather low, close to 20%, due to poisoning of the surface, leading to a strong deactivation. At potentials above 0.7 V vs. RHE, the selectivity towards gluconate decreases and non-selective GOR oxidation proceeds through CC bond cleavage. On nickel, the GOR occurs at high potentials (close to 1.2 V vs. RHE) on Ni(OH)2 and NiOOH sites, and proceeds through C1C2 bond breaking, resulting in arabinose and formate. At higher potentials, the selectivity towards arabinose decreases, formate being the main reaction product.

A bimetal strategy for suppressing oxygen release of 4.6V high-voltage single-crystal high-nickel cathode

High-voltage cathode materials, such as single-crystal high-nickel layered oxide materials, are a necessary condition for achieving high energy density lithium-ion batteries, but they have to be accompanied by the structural instability and irreversible release of lattice oxygen during operation, posing serious safety hazards. Here, to solve the lattice oxygen release issue of single-crystal high-nickel cathode, we propose an improved strategy for overall cathode by synchronously addressing interface and lattice instability, ensuring stable operation at a high voltage up to 4.6 V. By Al-doping, in the bulk phase, we intensify the charge transfer between transition metals and oxygen, and the columnar effect caused by doped atoms effectively alleviates internal strain, thereby significantly limiting lattice shrinkage and then suppressing oxygen release. On the other hand, the protective layer of LiNbO3 as the fast ion conductor formed at the cathode interface suppresses parasitic reactions and hinders lattice oxygen loss caused by dissolution of transition metals. Therefore, after 200 cycles at a cut-off voltage of 4.6 V, our cathode material still maintains a capacity retention rate of 89.1%. Density functional theory (DFT) calculations predict the effective suppression of oxygen release for the modified cathode materials, which has been further confirmed by differential electrochemical mass spectrometry (DEMS) tests. This work provides a new perspective for solving the problem of oxygen release under high cut-off voltage conditions for single crystal high nickel cathode.

Locking the lattice oxygen in RuO2 to stabilize highly active Ru sites in acidic water oxidation

Ruthenium dioxide is presently the most active catalyst for the oxygen evolution reaction (OER) in acidic media but suffers from severe Ru dissolution resulting from the high covalency of Ru-O bonds triggering lattice oxygen oxidation. Here, we report an interstitial silicon-doping strategy to stabilize the highly active Ru sites of RuO2 while suppressing lattice oxygen oxidation. The representative Si-RuO2−0.1 catalyst exhibits high activity and stability in acid with a negligible degradation rate of ~52 μV h−1 in an 800 h test and an overpotential of 226 mV at 10 mA cm−2. Differential electrochemical mass spectrometry (DEMS) results demonstrate that the lattice oxygen oxidation pathway of the Si-RuO2−0.1 was suppressed by ∼95% compared to that of commercial RuO2, which is highly responsible for the extraordinary stability. This work supplied a unique mentality to guide future developments on Ru-based oxide catalysts’ stability in an acidic environment.

Stabilizing Lattice Oxygen through Mn Doping in NiCo2O4−d Spinel Electrocatalysts for Efficient and Durable Acid Oxygen Evolution

Design the electrocatalysts without noble metal is still a challenge for oxygen evolution reaction (OER) in acid media. Herein, we reported the manganese doping method to decrease the concentration of oxygen vacancy (Vo) and form the Mn−O structure adjacent octahedral sites in spinel NiCo2O4−δ (NiMn1.5Co3O4−δ), which highly enhanced the activity and stability of spinel NiCo2O4−δ with a low overpotential (η) of 280 mV at j = 10 mA cm−2 and long‐term stability of 80 h in acid media. The isotopic labelling experiment based on differential electrochemical mass spectrometry (DEMS) clearly demonstrated the lattice oxygen in NiMn1.5Co3O4−δ is more stable due to strong Mn‐O bond and synergetic adsorbate evolution mechanism (SAEM) for acid OER. Density functional theory (DFT) calculations reveal highly increased oxygen vacancy formation energy (EVO) of NiCo2O4−δ after Mn doping. More importantly, the highly hydrogen bonding between Mn−O and *OOH adsorbed on adjacent Co octahedral sites promote the formation of *OO from *OOH due to the greatly enhanced charge density of O in Mn substituted sites.

New approach to produce cubic-WC at low temperature for hydrogen evolution reaction

A novel catalyst, a nanostructured cubic-WC (c-WC) flat film, is introduced for the hydrogen evolution reaction (HER) using a specialized magnetron sputtering system. This method results in over 94% crystalline c-WC0.95 formation at room temperature, featuring high-density stacking faults and twin defects. The catalytic performance of the c-WC film for HER is investigated through theoretical simulations and experimental studies. Density-functional theory (DFT) suggests that the c-WC (100) surface exhibits faster reaction kinetics than c-WC (111) surface, approaching the efficiency of Pt (111) surfaces. Experimentally, the c-WC0.95 film exhibits a high electrochemical surface area and increased active sites due to surface defects. Differential electrochemical mass spectrometry (DEMS) confirms an onset potential for HER of −50.0 mV for c-WC0.95 films and establishes electrodesorption as the rate-determining step. Overall, the c-WC film emerges as a cost-effective and efficient catalyst for green hydrogen production, showcasing excellent reproducibility and electrochemical stability.

Ir Single Atoms Boost Metal-Oxygen Covalency on Selenide-Derived NiOOH for Direct Intramolecular Oxygen Coupling.

This investigation probes the intricate interplay of catalyst dynamics and reaction pathways during the oxygen evolution reaction (OER), highlighting the significance of atomic-level and local ligand structure insights in crafting highly active electrocatalysts. Leveraging a tailored ion exchange reaction followed by electrochemical dynamic reconstruction, we engineered a novel catalytic structure featuring single Ir atoms anchored to NiOOH (Ir1@NiOOH). This novel approach involved the strategic replacement of Fe with Ir, facilitating the transition of selenide precatalysts into active (oxy)hydroxides. This elemental substitution promoted an upward shift in the O 2p band and intensified the metal-oxygen covalency, thereby altering the OER mechanism toward enhanced activity. The shift from a single-metal site mechanism (SMSM) in NiOOH to a dual-metal-site mechanism (DMSM) in Ir1@NiOOH was substantiated by in situ differential electrochemical mass spectrometry (DEMS) and supported by theoretical insights. Remarkably, the Ir1@NiOOH electrode exhibited exceptional electrocatalytic performance, achieving overpotentials as low as 142 and 308 mV at current densities of 10 and 1000 mA cm-2, respectively, setting a new benchmark for the electrocatalysis of OER.

Superhydrophilic Dendritic FeP/Cu3P Electrocatalyst for Urea Splitting via the Intramolecular Mechanism.

The electrocatalytic overall urea splitting can achieve the dual goals of urea treatment and hydrogen energy acquisition. Herein, we exploited the principle of precipitation dissolution equilibrium to obtain bimetallic phosphide FeP/Cu3P/CF for the simultaneous oxidation of urea and reduction of water and comprehensively reveal the inherent molecular thermodynamic mechanisms on the surface of catalysts. The excellent electrochemical performance can be derived from the super water affinity and synergistic effect. Especially, the theoretical calculation unveils that the synergistic effect between FeP and Cu3P can lower the activation energy required for urea electrooxidation, thereby promoting urea splitting. In situ differential electrochemical mass spectrometry (in situ DEMS) measurements further demonstrated that urea oxidation on FeP/Cu3P/CF proceeded according to the intramolecular mechanism. This work has laid the foundation for constructing highly efficient superhydrophilic bifunctional electrocatalysts.

Electrochemical reduction of NO3− to NH3 using defect-rich TiO2 support loaded with CuNi catalysts: differential electrochemical mass spectrometry insights

A promising approach for reducing nitrate (NO3−) in water waste is NO3− reutilization to ammonia (NH3). This work investigates the synergistic effect of Cu40Ni60 catalyst on a defect-rich TiO2 (TNSD) carbon vulcan composite (C-TNSD). The study starts with CuNi metallic content pre-screened over carbon vulcan (C) to identify the most promising CuNi ratios for nitrate reduction reaction (NO3-RR) to NH3. This is the case of Cu 20 wt% and Ni 80 wt% (Cu20Ni80), Cu 40 wt% and Ni 60 wt% (Cu40Ni60), Cu 60 wt% and Ni 40 wt% (Cu60Ni40), and Cu 80 wt%, Ni 20 wt% (Cu80Ni20) and Cu/Ni monometallic catalysts. Among these ratios, Cu40Ni60 resulted in the most promising electrocatalyst when loaded over C-TNSD, whose functionality has been assessed using in situ differential electrochemical mass spectrometry (DEMS). The results indicate that Cu40Ni60/C-TNSD attains a similar NH3 selectivity to Cu40Ni60 supported on TiO2-carbon vulcan composites. However, Cu40Ni60/C-TNSD does not hinder charge transport, making it the most suitable electrocatalyst for NH3 production. A synergistic interaction between Cu40Ni60 and C-TNSD is proposed. The results are supported by structural, (electro)chemical, and morphological characterization. From a broader perspective, defective-rich catalysts can be developed to control the electrochemical reaction sequence during NO3-RR.