Conformal Multifunctional Titania Shell on Iron Oxide Nanorod Conversion Electrode Enables High Stability Exceeding 30 000 Cycles in Aqueous Electrolyte

Iron oxide is promising for use in aqueous energy storage devices due to the high capacity, but one of the most challenging problems is cycling instability within the large potential window that results from the complete quasi‐conversion reaction. Herein, a conformal surface coating strategy toward iron oxide via atomic layer deposition (ALD) is presented and an Fe₃O₄@TiO₂ core–shell nanorod array anode is reported that exhibits remarkable cycling performance exceeding 30 000 times within a wide potential window in neutral lithium salt electrolyte. ALD offers a uniform and precisely controllable TiO₂ shell that not only buffers the inner volume expansion of Fe₃O₄, but also contributes extra capacity through Li⁺ intercalation/de‐intercalation and helps to alleviate the water electrolysis. Furthermore, by pairing with a pseduocapacitive cathode of V₂O₃@carbon and using a hydrogel electrolyte of PVA‐LiCl, a unique flexible quasi‐solid‐state hybrid supercapacitor can be assembled. With a high voltage of 2.0 V, the device delivers high volumetric energy and power densities (2.23 mWh cm^?3, 1090 mW cm^?3), surpassing many recently reported flexible supercapacitors. This work highlights the importance of ALD conformal multifunctional shell to instable nanoarray electrodes in aqueous electrolytes and brings new opportunities to design advanced aqueous hybrid energy storage devices.     

Hydrogenated V2O5 Nanosheets for Superior Lithium Storage Properties

V₂O₅ is a promising cathode material for lithium ion batteries boasting a large energy density due to its high capacity as well as abundant source and low cost. However, the poor chemical diffusion of Li⁺, low conductivity, and poor cycling stability limit its practical application. Herein, oxygen‐deficient V₂O₅ nanosheets prepared by hydrogenation at 200 °C with superior lithium storage properties are described. The hydrogenated V₂O₅ (H‐V₂O₅) nanosheets deliver an initial discharge capacity as high as 259 mAh g^?1 and it remains 55% when the current density is increased 20 times from 0.1 to 2 A g^?1. The H‐V₂O₅ electrode has excellent cycling stability with only 0.05% capacity decay per cycle after stabilization. The effects of oxygen defects mainly at bridging O(II) sites on Li⁺ diffusion and overall electrochemical lithium storage performance are revealed. The results reveal here a simple and effective strategy to improve the capacity, rate capability, and cycling stability of V₂O₅ materials which have large potential in energy storage and conversion applications.     

Single‐Crystalline LiMn2O4 Nanotubes Synthesized Via Template‐Engaged Reaction as Cathodes for High‐Power Lithium Ion Batteries

Single‐crystalline nanotubes of spinel LiMn₂O₄ with a diameter of about 600 nm, a wall thickness of about 200 nm and a length of 1–4 μm have been synthesized via a template‐engaged reaction using β‐MnO₂ nanotubes as a self‐sacrifice template. In this fabrication, a minimal structural reorganization can be responsible for the chemical transformation from [001]‐oriented β‐MnO₂ template to [110]‐oriented LiMn₂O₄. Galvanostatic charge/discharge measurements indicate that the nanotubes exhibit superior high‐rate capabilities and good cycling stability. About 70% of its initial capacity can be retained after 1500 cycles at 5 C rate. Importantly, the tubular nanostructures and the single‐crystalline nature of the most LiMn₂O₄ nanotubes are also well preserved after prolonged charge/discharge cycling at a relatively high current density, indicating good structural stability of the single‐crystalline nanotubes during lithium intercalation/deintercalation process. As is confirmed from Raman spectra analyses, no evident microstructural changes occur upon long‐term cycling. These results reveal that single‐crystalline nanotubes of LiMn₂O₄ will be one of the most promising cathode materials for high‐power lithium ion batteries.     

A New Strategy to Effectively Suppress the Initial Capacity Fading of Iron Oxides by Reacting with LiBH4

In this work, a new facile and scalable strategy to effectively suppress the initial capacity fading of iron oxides is demonstrated by reacting with lithium borohydride (LiBH₄) to form a B‐containing nanocomposite. Multielement, multiphase B‐containing iron oxide nanocomposites are successfully prepared by ball‐milling Fe₂O₃ with LiBH₄, followed by a thermochemical reaction at 25–350 °C. The resulting products exhibit a remarkably superior electrochemical performance as anode materials for Li‐ion batteries (LIBs), including a high reversible capacity, good rate capability, and long cycling durability. When cycling is conducted at 100 mA g^?1, the sample prepared from Fe₂O₃–0.2LiBH₄ delivers an initial discharge capacity of 1387 mAh g^?1. After 200 cycles, the reversible capacity remains at 1148 mAh g^?1, which is significantly higher than that of pristine Fe₂O₃ (525 mAh g^?1) and Fe₃O₄ (552 mAh g^?1). At 2000 mA g^?1, a reversible capacity as high as 660 mAh g^?1 is obtained for the B‐containing nanocomposite. The remarkably improved electrochemical lithium storage performance can mainly be attributed to the enhanced surface reactivity, increased Li⁺ ion diffusivity, stabilized solid‐electrolyte interphase (SEI) film, and depressed particle pulverization and fracture, as measured by a series of compositional, structural, and electrochemical techniques.     

Accessible Li Percolation and Extended Oxygen Oxidation Boundary in Rocksalt-like Cathode Enabled by Initial Li-deficient Nanostructure

Disordered rocksalt cathodes have shown attractive electrochemical performance via oxygen redox, but are limited by a necessary Li-excess level above the percolation threshold (x > 1.09 in Li_xTM_2-xO₂, TM = transition metals) to obtain electrochemical activity. However, a relatively low-Li content is essential to alleviate excessive oxygen charge compensation in rocksalt oxides. Herein, taking the homogeneous Li₂MnO₃ and LiMn₂O₄ as the starting point, disordered rocksalt-like cathodes are prepared with initial Li-deficient nanostructures, cation vacancies, and partial spinel-type structures that provide a solution for the acquisition of fast Li⁺ percolation channels under Li-deficient condition. As a result, the prepared sample exhibits high initial discharge capacity (363 mAh g⁻¹) and energy density (1081 Wh kg⁻¹). Advanced spectroscopy and in situ measurements observe highly reversible charge compensation during electrochemical process and assign coupled Mn- and O-related redox contribution. Theoretical calculations also suggest the novel and chemical reversible trapped molecular O₂ model in the rocksalt structure with vacancies, demonstrating a dual role of Li-deficient structure in promoting cationic oxidation and extending reversible oxygen redox boundary. This work is expected to breakthrough the existing ideas of oxygen oxidation and opens up a higher degree of freedom in the design of disordered rocksalt structures.     

Electrochemical Activation of Manganese‐Based Cathode in Aqueous Zinc‐Ion Electrolyte

Low‐cost and highly safe zinc‐manganese batteries are expected for practical energy storage and grid‐scale application. The electrolyte adjustment is further combined to boost their performance output; however, the mechanism behind the electrochemical contrast caused by electrolyte composition remains unclear, which has held back the development of these systems. Hence, new insight into the electrochemical activation of manganese‐based cathodes, which is induced by the aqueous zinc‐ion electrolyte, is provided. The relationship between the desolvation of Zn²⁺ from [Zn(OH₂)₆]²⁺‐solvation shell and the electrolyte/electrode interfacial reaction to form Zn₄SO₄(OH)₆·4H₂O phase or its analogues is established, which is the key for the electrochemical activation. Further electrolyte optimization promotes the cycling stability of Zn/LiMn₂O₄ battery with a long life span over 2000 cycles. This work illuminates the confused direction in exploring electrolyte for zinc‐manganese batteries.     

Aqueous Lithium‐ion Battery LiTi2(PO4)3/LiMn2O4 with High Power and Energy Densities as well as Superior Cycling Stability**

Porous, highly crystalline Nasicon‐type phase LiTi₂(PO₄)₃ has been prepared by a novel poly(vinyl alcohol)‐assisted sol–gel route and coated by a uniform and continuous nanometers‐thick carbon thin film using chemical vapor deposition technology. The as‐prepared LiTi₂(PO₄)₃ exhibits excellent electrochemical performance both in organic and aqueous electrolytes, and especially shows good cycling stability in aqueous electrolytes. An aqueous lithium‐ion battery consisting of a combination of LiMn₂O₄ cathode, LiTi₂(PO₄)₃ anode, and a 1 M Li₂SO₄ electrolyte has been constructed. The cell delivers a capacity of 40 mA h g^–1 and a specific energy of 60 W h kg^–1 with an output voltage of 1.5 V based on the total weight of the active electrode materials. It also exhibits an excellent cycling stability with a capacity retention of 82 % over 200 charge/discharge cycles, which is much better than any aqueous lithium‐ion battery reported.     

Enabling Stable Cycling of 4.2 V High‐Voltage All‐Solid‐State Batteries with PEO‐Based Solid Electrolyte

Poly(ethylene oxide) (PEO)‐based solid electrolytes are expected to be exploited in solid‐state batteries with high safety. Its narrow electrochemical window, however, limits the potential for high voltage and high energy density applications. Herein the electrochemical oxidation behavior of PEO and the failure mechanisms of LiCoO₂‐PEO solid‐state batteries are studied. It is found that although for pure PEO it starts to oxidize at a voltage of above 3.9 V versus Li/Li⁺, the decomposition products have appropriate Li⁺ conductivity that unexpectedly form a relatively stable cathode electrolyte interphase (CEI) layer at the PEO and electrode interface. The performance degradation of the LiCoO₂‐PEO battery originates from the strong oxidizing ability of LiCoO₂ after delithiation at high voltages, which accelerates the decomposition of PEO and drives the self‐oxygen‐release of LiCoO₂, leading to the unceasing growth of CEI and the destruction of the LiCoO₂ surface. When LiCoO₂ is well coated or a stable cathode LiMn_0.7Fe_0.3PO₄ is used, a substantially improved electrochemical performance can be achieved, with 88.6% capacity retention after 50 cycles for Li_1.4Al_0.4Ti_1.6(PO₄)₃ coated LiCoO₂ and 90.3% capacity retention after 100 cycles for LiMn_0.7Fe_0.3PO₄. The results suggest that, when paired with stable cathodes, the PEO‐based solid polymer electrolytes could be compatible with high voltage operation.     

High Voltage,Transition Metal Complex Enables Efficient Electrochemical Energy Storage in a Li‐Ion Battery Full Cell

Efficient energy storage systems impact profoundly the renewable energy future. The performance of current electrical energy storage technologies falls well short of requirements for using electrical energy efficiently in transportation, commercial, and residential applications. This paper explores the possibility by using transition‐metal‐based complexes as active materials in a Li‐ion battery full cell that synergizes the concept of both lithium‐ion batteries and redox flow batteries. A cathode made from transition metal complex, [Fe(bpy)₃](BF₄)₂, exhibits high discharge voltage approaching 4 V (vs Li/Li⁺). When coupled with a Li₄Ti₅O₁₂ anode, the Li‐ion full battery exhibits a cell voltage exceeding 2.2 V and decent cycling efficiencies with Coulombic efficiency and energy/voltage efficiencies above 99% and 92%/93%, respectively. Such a Li‐ion battery full cell offers distinct features such as low cost and flexibility in molecular structure design. The result reveals a generic design route toward iron‐based complexes as cathode materials with good electrochemical performances.     

Synthesis, Structure, and Electrochemistry of Sm-Modified LiMn2O4 Cathode Materials for Lithium-Ion Batteries

Spinel lithium manganese oxide and a series of Sm/LiMn₂O₄ spinels with different Sm additive contents (x = 0.02%, 0.05%) were prepared for the first time via a coprecipitation method for rechargeable lithium-ion batteries. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive analysis of x-rays (EDAX), infrared (IR), and electron spin resonance spectral studies as well as various electrochemical measurements were used to examine the structural and electrochemical characteristics of LiMn_2?x Sm _x O₄ (x = 0.00%, 0.02%, 0.05%). XRD and SEM studies confirmed the nano materials size for all prepared spinels. From cyclic voltammetry studies, in terms of peak splitting, electrochemical active surface area, and intensity of the peaks, the LiMn_1.98Sm_0.02O₄ sample possesses better electrochemical performance compared with the LiMn_1.95Sm_0.05O₄ sample. Hence, limited addition of a rare-earth dopant is preferable to obtain better efficiency. Direct-current (DC) electrical conductivity measurements indicated that these samples are semiconducting and their activation energies decrease with increasing rare-earth Sm³⁺ content.     

Enhanced Capacitive Energy Storage in Polyoxometalate‐Doped Polypyrrole

High‐performance batteries and supercapacitors require the molecular‐level linkage of charge transport components and charge storage components. This study shows how redox‐tunable Lindqvist‐type molecular metal oxide anions [V_nM _6–n O₁₉]^{(2+n )?} (M = W(VI) or Mo(VI); n = 0, 1, 2) can be incorporated in cationic polypyrrole (PPy) conductive polymer films by means of electrochemical polymerization. Electron microscopy and (spectro‐)electrochemistry show that the electroactivity and morphology of the composites can be tuned by Lindqvist anion incorporation. Reductive electrochemical “activation” of the Lindqvist–PPy composites leads to significantly increased electrical capacitance (range: ≈25–38 F g^?1, increase up to ≈25×), highlighting that this general synthetic route gives access to promising capacitive materials with suitable long‐term stability. Electrochemical, electron microscopic, and Raman spectroscopic analyses together with density functional theory (DFT) calculations provide molecular‐level insight into the effects of Lindqvist anion incorporation in PPy films and their role during reductive activation. The study therefore provides fundamental understanding of the principles governing the bottom‐up integration of molecular components into nanostructured composites for electrochemical energy storage.     

Crystallographic Insight of Reduced Lattice Volume Expansion in Mesoporous Cu2+-Doped TiNb2O7 Microspheres during Li+ Insertion

TiNb₂O₇ represents a promising anode material for lithium-ion batteries (LIBs), but its practical applications are currently hampered by the non-negligible volumetric expansion and contraction during the charge/discharge process and the sluggish ion/electron kinetics. A combination technique is reported by systematically optimizing the porous and spherical morphology, crystal structure, and surface decoration of mesoporous Cu²⁺-doped TiNb₂O₇ microspheres to enhance the electrochemical Li⁺ storage performance and stability simultaneously. The Cu²⁺ dopants preferentially replace Ti⁴⁺ in crystal lattices, which decreases the Li⁺ diffusion barrier and increases the electronic conductivity, as confirmed by density functional theory (DFT) calculation and demonstrated by diverse electrochemical characterizations. The successful Cu²⁺ doping significantly reduces the lattice expansion coefficient from 7.26% to 4.61% after Li⁺ insertion along the b-axis of TiNb₂O₇, as visualized from in situ and ex situ XRD analysis. The optimal 5% Cu²⁺-doped TiNb₂O₇ with surface coating of N-doped carbon exhibits significantly enhanced specific capacity and rate and cyclic performances in both half- and full-cell configurations, demonstrating an excellent electrochemical behavior for fast-charging LIB applications.     

Stabilizing High-Nickel Cathodes with High-Voltage Electrolytes

Electrolytes connect the two electrodes in a lithium battery by providing Li⁺ transport channels between them. Advanced electrolytes are being explored with high-nickel cathodes and the lithium-metal anode to meet the high energy density and cycle life goals, but the origin of the performance differences with different electrolytes is not fully understood. Here, the mechanisms involved in protecting the high-capacity, cobalt-free cathode LiNiO₂ with a model high-voltage electrolyte (HVE) are delineated. The kinetic barrier posed by a thick surface degradation layer with poor Li⁺-ion transport is found to be the major contributor to the fast capacity fade of LiNiO₂ with the conventional carbonate electrolyte. In contrast, HVE reduces the side reactions between the electrolyte and the electrodes, leading to a thinner nano-interphase layer comprised of more beneficial species. Crucially, the HVE leads to a different surface reorganization pathway involving the formation of a thinner nanoscale LiNi₂O₄ spinel phase on the LiNiO₂ surface. With a high 3D Li⁺-ion and electronic conductivity, the spinel LiNi₂O₄ reorganization nanolayer preserves fast Li⁺ transport across the cathode–electrolyte interface, reduces reaction heterogeneity in the electrode and alleviates intergranular cracking within secondary particles, resulting in superior long-term cycle life.     

Gallium Sulfide–Single‐Walled Carbon Nanotube Composites: High‐Performance Anodes for Lithium‐Ion Batteries

Metal sulfides are an important class of functional materials possessing exceptional electrochemical performance and thus hold great promise for rechargeable secondary batteries. In this work, we deposited gallium sulfide (GaS_x, x = 1.2) thin films by atomic layer deposition (ALD) onto single‐walled carbon nanotube (SWCNT) powders. The ALD GaS_x was performed at 150 °C, and produced uniform and conformal amorphous films. The resulting core‐shell, nanostructured SWCNT‐GaS_x composite exhibited excellent electrochemical performance as an anode material for lithium‐ion batteries (LIBs), yielding a stable capacity of ≈575 mA g^–1 at a current density of 120 mA g^–1 in the voltage window of 0.01–2 V, and an exceptional columbic efficiency of >99.7%. The GaS_x component of the composite produced a specific capacity of 766 mA g^–1, a value two times that of conventional graphite anodes. We attribute the excellent electrochemical performance of the composite to four synergistic effects: 1) the uniform and conformal ALD GaS_x coating offers short electronic and Li‐ion pathways during cycling; 2) the amorphous structure of the ALD GaS_x accommodates stress during lithiation‐delithiation processes; 3) the mechanically robust SWCNT framework also accommodates stress from cycling; 4) the SWCNT matrix provides a continuous, high conductivity network.     

Manipulating the Electronic Structure of Li‐Rich Manganese‐Based Oxide Using Polyanions: Towards Better Electrochemical Performance

Lithium‐rich manganese‐based layered oxides show great potential as high‐capacity cathode materials for lithium ion batteries, but usually exhibit a poor cycle life, gradual voltage drop during cycling, and low thermal stability in the highly delithiated state. Herein, a strategy to promote the electrochemical performance of this material by manipulating the electronic structure through incorporation of boracic polyanions is developed. As‐prepared Li[Li_0.2Ni_0.13Co_0.13Mn_0.54](BO₄)_0.015(BO₃)_0.005O_1.925 shows a decreased M‐O covalency and a lowered O 2p band top compared with pristine Li[Li_0.2Ni_0.13Co_0.13Mn_0.54]O₂. As a result, the modified cathode exhibits a superior reversible capacity of 300 mA h g^?1 after 80 cycles, excellent cycling stability with a capacity retention of 89% within 300 cycles, higher thermal stability, and enhanced redox couple potentials. The improvements are correlated to the enhanced oxygen stability that originates from the tuned electronic structure. This facile strategy may further be extended to other high capacity electrode systems.     

Reversible Lithium Storage with High Mobility at Structural Defects in Amorphous Molybdenum Dioxide Electrode

This work demonstrates that structural defects in amorphous metal oxide electrodes can serve as a reversible Li⁺ storage site for lithium secondary batteries. For instance, molybdenum dioxide electrode in amorphous form (a‐MoO₂) exhibits an unexpectedly high Li⁺ storage capacity (up to four Li per MoO₂ unit), which is larger by a factor of four than that for the crystalline counterpart. The conversion‐type lithiation is discarded for this electrode from the absence of Mo metal and lithium oxide (Li₂O) in the lithiated a‐MoO₂ electrode and the retention of local structural framework. The sloping voltage profile in a wide potential range suggests that Li⁺ ions are inserted into the structural defects that are electrochemically nonequivalent. This electrode also shows an excellent cycle stability and rate capability. The latter feature is seemingly due to a rather opened Li⁺ diffusion pathway provided by the structural defects. A high Li⁺ mobility is confirmed from nuclear magnetic resonance study.     

Fe3O4 Nanoparticles Confined in Mesocellular Carbon Foam for High Performance Anode Materials for Lithium‐Ion Batteries

Fe₃O₄ nanocrystals confined in mesocellular carbon foam (MSU‐F‐C) are synthesized by a “ host–guest ” approach and tested as an anode material for lithium‐ion batteries (LIBs). Briefly, an iron oxide precursor, Fe(NO₃)₃·9H₂O, is impregnated in MSU‐F‐C having uniform cellular pores ～30 nm in dia­meter, followed by heat‐treatment at 400 °C for 4 h under Ar. Magnetite Fe₃O₄ nanocrystals with sizes between 13–27 nm are then successfully fabricated inside the pores of the MSU‐F‐C, as confirmed by transmission electron microscopy (TEM), dark‐field scanning transmission electron microscopy (STEM), energy dispersive X‐ray spectroscopy (EDS), X‐ray diffraction (XRD), and nitrogen sorption isotherms. The presence of the carbon most likely allows for reduction of some of the Fe³⁺ ions to Fe²⁺ ions via a carbothermoreduction process. A Fe₃O₄/MSU‐F‐C nanocomposite with 45 wt% Fe₃O₄ exhibited a first charge capacity of 1007 mA h g^?1 (Li⁺ extraction) at 0.1 A g^?1 (～0.1 C rate) with 111% capacity retention at the 150^th cycle, and retained 37% capacity at 7 A g^?1 (～7 C rate). Because the three dimensionally interconnected open pores are larger than the average nanosized Fe₃O₄ particles, the large volume expansion of Fe₃O₄ upon Li‐insertion is easily accommodated inside the pores, resulting in excellent electrochemical performance as a LIB anode. Furthermore, when an ultrathin Al₂O₃ layer (<4 Å) was deposited on the composite anode using atomic layer deposition (ALD), the durability, rate capability and undesirable side reactions are significantly improved.     

Combined First‐Principle Calculations and Experimental Study on Multi‐Component Olivine Cathode for Lithium Rechargeable Batteries

The electrochemical properties and phase stability of the multi‐component olivine compound LiMn_1/3Fe_1/3Co_1/3PO₄ are studied experimentally and with first‐principles calculation. The formation of a solid solution between LiMnPO₄, LiFePO₄, and LiCoPO₄ at this composition is confirmed by XRD patterns and the calculated energy. The experimental and first‐principle results indicate that there are three distinct regions in the electrochemical profile at quasi‐open‐circuit potentials of ～3.5 V, ～4.1 V, and ～4.7 V, which are attributed to Fe³⁺/Fe²⁺, Mn³⁺/Mn²⁺, and Co³⁺/Co²⁺ redox couples, respectively. However, exceptionally large polarization is observed only for the region near 4.1 V of Mn³⁺/Mn²⁺ redox couples, implying an intrinsic charge transfer problem. An ex situ XRD study reveals that the reversible one‐phase reaction of Li extraction/insertion mechanism prevails, unexpectedly, for all lithium compositions of Li_xMn_1/3Fe_1/3Co_1/3PO₄ (0 ≤ x ≤ 1) at room temperature. This is the first demonstration that the well‐ordered, non‐nanocrystalline (less than 1% Li–M disorder and a few hundred nanometer size particle) olivine electrode can be operated solely in a one‐phase mode.     

Li6ALa2Ta2O12 (A = Sr, Ba): Novel Garnet‐Like Oxides for Fast Lithium Ion Conduction

Oxides with the nominal chemical formula Li₆ALa₂Ta₂O₁₂ (A = Sr, Ba) have been prepared via a solid‐state reaction in air using high purity La₂O₃, LiOH·H₂O, Sr(NO₃)₂, Ba(NO₃)₂, and Ta₂O₅ and are characterized by powder X‐ray diffraction (XRD) in order to identify the phase formation and AC impedance to determine the lithium ion conductivity. The powder XRD data of Li₆ALa₂Ta₂O₁₂ show that they are isostructural with the parent garnet‐like compound Li₅La₃Ta₂O₁₂. The cubic lattice parameter was found to increase with increasing ionic size of the alkaline earth ions (Li₆SrLa₂Ta₂O₁₂: 12.808(2) Å; Li₆BaLa₂Ta₂O₁₂: 12.946(3) Å). AC impedance results show that both the strontium and barium members exhibit mainly a bulk contribution with a rather small grain‐boundary contribution. The ionic conductivity increases with increasing ionic radius of the alkaline earth elements. The barium compound, Li₆BaLa₂Ta₂O₁₂, shows the highest ionic conductivity, 4.0×10^–5 S cm^–1 at 22 °C with an activation energy of 0.40 eV, which is comparable to other lithium ion conductors, especially with the presently employed solid electrolyte lithium phosphorus oxynitride (Lipon) for all‐solid‐state lithium ion batteries. DC electrical measurements using lithium‐ion‐blocking and reversible electrodes revealed that the electronic conductivity is very small, and a high electrochemical stability (&#62; 6 V/Li) was exhibited at room temperature. Interestingly, Li₆ALa₂Ta₂O₁₂ was found to be chemically stable with molten metallic lithium.     

Ultrathin Amorphous Silica Membrane Enhances Proton Transfer across Solid‐to‐Solid Interfaces of Stacked Metal Oxide Nanolayers while Blocking Oxygen

A large jump of proton transfer rates across solid‐to‐solid interfaces by inserting an ultrathin amorphous silica layer into stacked metal oxide nanolayers is discovered using electrochemical impedance spectroscopy and Fourier‐transform infrared reflection absorption spectroscopy (FT‐IRRAS). The triple stacked nanolayers of Co₃O₄, SiO₂, and TiO₂ prepared by atomic layer deposition (ALD) enable a proton flux of 2400 ± 60 s^?1 nm^?2 (pH 4, room temperature), while a single TiO₂ (5 nm) layer exhibits a threefold lower flux of 830 s^?1 nm^?2. Based on FT‐IRRAS measurements, this remarkable enhancement is proposed to originate from the sandwiched silica layer forming interfacial SiOTi and SiOCo linkages to TiO₂ and Co₃O₄ nanolayers, respectively, with the O bridges providing fast H⁺ hopping pathways across the solid‐to‐solid interfaces. Together with the complete O₂ impermeability of a 2 nm ALD‐grown SiO₂ layer, the high flux for proton transport across multi‐stack metal oxide layers opens up the integration of incompatible catalytic environments to form functional nanoscale assemblies such as artificial photosystems for CO₂ reduction by H₂O.