Unveiling Atomic-Scale Product Selectivity at the Cocatalyst-TiO2 Interface Using X-Ray Techniques: Insights into Interface Reactivity.

The microstructure at the interface between the cocatalyst and semiconductor plays a vital role in concentrating photo-induced carriers and reactants. However, observing the atomic arrangement of this interface directly using an electron microscope is challenging due to the coverings of the semiconductor and cocatalyst. To address this, multiple metal-semiconductor interfaces on three TiO2 crystal facets (M/TiO2 ─N, where M represents Ag, Au, and Pt, and N represents the 001, 010, and 101 single crystal facets). The identical surface atomic configuration of the TiO2 facets allowed us to investigate the evolution of the microstructure within these constructs using spectroscopies and DFT calculations. For the first time, they observed the transformation of saturated Ti6c ─O bonds into unsaturated Ti5c ─O and Ti6c ─O─Pt bonds on the TiO2 ─010 facet after loading Pt. This transformation have a direct impact on the selectivity of the resulting products, leading to the generation of CO and CH4 at the Ti6c ─O─Pt and Pt sites, respectively. These findings pinpoint the pivotal roles played by the atomic arrangement at the M/TiO2 ─N interfaces and provide valuable insights for the development of new methodologies using conventional lab-grade equipment.

Mesoporous Polyimide Thin Films as Dendrite-Suppressing Separators for Lithium-Metal Batteries.

Lithium-metal batteries require the effective suppression of lithium dendrites to guarantee both high performance and safety. Today's separators have macropores allowing lithium dendrites to traverse, leading to internal short circuits and other catastrophic results. Herein, we report a mesoporous polyimide separator for dendrite suppression. The polyimide separator exhibits mesopores of 21 nm width and a high storage modulus of 1.80 GPa. This mesoporous polyimide separator assists in the electrodeposition to form flat-top protrusions instead of sharp dendrites, therefore, allowing the safe cycling of lithium-metal batteries. This work is expected to advance the development of dendrite-suppressing strategies and contribute to the revival of lithium-metal batteries.

Mechanistic Insights into the Interplay between Ion Intercalation and Water Electrolysis in Aqueous Batteries.

Improving electrolyte stability to suppress water electrolysis represents a basic principle for designing aqueous batteries. Herein, we investigate counterintuitive roles that water electrolysis plays in regulating intercalation chemistry. Using the NaxFe[Fe(CN)6]∥NaTi2(PO4)3 (x < 1) aqueous battery as a platform, we report that high-voltage overcharging can serve as an electrochemical activation approach to achieving concurrent Na-ion intercalation and an electrolytic oxygen evolution reaction. When the cell capacity is intrinsically limited by deficient cyclable Na ions, the electrolytic water oxidation on the cathode allows for extra Na-ion intercalation from the electrolyte to the NaTi2(PO4)3 anode, leading to a major increase in cyclable Na ions and specific capacity. The parasitic oxygen generation and potential transition-metal dissolution, as proved by our synchrotron and imaging tools, can be significantly mitigated with a simple reassembling approach, which enables stable electrochemical performance and sheds light on manipulating ion intercalation and water electrolysis for battery fast charging and recycling.

Resolving Charge Distribution for Compositionally Heterogeneous Battery Cathode Materials.

The isostructural nature of Li-layered cathodes allows for accommodating multiple transition metals (TMs). However, little is known about how the local TM stoichiometry influences the charging behavior of battery particles thus impacting battery performance. Here, we develop heterogeneous compositional distributions in polycrystalline LiNi1-x-yMnxCoyO2 (NMC) particles to investigate the interplay between local stoichiometry and charge distribution. These NMC particles exhibit a broad, continuous distribution of local Ni/Mn/Co stoichiometry, which does not compromise the global layeredness. The local Mn and Ni concentrations in individual NMC particles are positively and negatively correlated with the electrochemically induced Ni oxidation, respectively, whereas the Co concentration does not impose a clear effect on the Ni oxidation. The resulting material delivers excellent reversible capacity, rate capability, and cycle life at high operating voltages. Engineering Ni/Mn/Co distribution in NMC particles may provide a path toward controlling the charge distribution and thus chemomechanical properties of polycrystalline battery particles.

Docking MOF crystals on graphene support for highly selective electrocatalytic peroxide production.

Tailoring the reaction kinetics is the central theme of designer electrocatalysts, which enables the selective conversion of abundant and inert atmospheric species into useful products. Here we show a supporting effect in tuning the electrocatalytic kinetics of oxygen reduction reaction (ORR) from four-electron to two-electron mechanism by docking metalloporphyrin-based metal-organic frameworks (MOFs) crystals on graphene support, leading to highly selective peroxide production with faradaic efficiency as high as 93.4%. A magic angle of 38.1° tilting for the co-facial alignment was uncovered by electron diffraction tomography, which is attributed to the maximization of π-π interaction for mitigating the lattice and symmetry mismatch between MOF and graphene. The facilitated electron migration and oxygen chemisorption could be ascribed to the supportive effect of graphene that disperses of the electron state of the active center, and ultimately regulates rate-determining step. ELECTRONIC SUPPLEMENTARY MATERIAL: Supplementary material (synthesis protocols for control samples, morphological and structural characterizations, porosity, electrochemical properties and activities including SEM, TEM, XPS, Raman, AFM investigations) is available in the online version of this article at 10.1007/s12274-021-3382-3.

X-ray Nanoimaging of Crystal Defects in Single Grains of Solid-State Electrolyte Li7-3xAlxLa3Zr2O12.

All-solid-state lithium batteries promise significant improvements in energy density and safety over traditional liquid electrolyte batteries. The Al-doped Li7La3Zr2O12 (LLZO) solid-state electrolyte shows excellent potential given its high ionic conductivity and good thermal, chemical, and electrochemical stability. Nevertheless, further improvements on electrochemical and mechanical properties of LLZO call for an in-depth understanding of its local microstructure. Here, we employ Bragg coherent diffractive imaging to investigate the atomic displacements inside single grains of LLZO with various Al-doping concentrations, resulting in cubic, tetragonal, and cubic-tetragonal mixed structures. We observe coexisting domains of different crystallographic orientations in the tetragonal structure. We further show that Al doping leads to crystal defects such as dislocations and phase boundaries in the mixed- and cubic-phase grain. This study addresses the effect of Al doping on the nanoscale structure within individual grains of LLZO, which is informative for the future development of solid-state batteries.

Defect and structural evolution under high-energy ion irradiation informs battery materials design for extreme environments.

Understanding defect evolution and structural transformations constitutes a prominent research frontier for ultimately controlling the electrochemical properties of advanced battery materials. Herein, for the first time, we utilize in situ high-energy Kr ion irradiation with transmission electron microscopy to monitor how defects and microstructures evolve in Na- and Li-layered cathodes with 3d transition metals. Our experimental and theoretical analyses reveal that Li-layered cathodes are more resistant to radiation-induced structural transformations, such as amorphization than Na-layered cathodes. The underlying mechanism is the facile formation of Li-transition metal antisite defects in Li-layered cathodes. The quantitative mathematical analysis of the dynamic bright-field imaging shows that defect clusters preferentially align along the Na/Li ion diffusion channels (a-b planes), which is likely governed by the formation of dislocation loops. Our study provides critical insights into designing battery materials for extreme irradiation environments and understanding fundamental defect dynamics in layered oxides.

Machine-learning-revealed statistics of the particle-carbon/binder detachment in lithium-ion battery cathodes.

The microstructure of a composite electrode determines how individual battery particles are charged and discharged in a lithium-ion battery. It is a frontier challenge to experimentally visualize and, subsequently, to understand the electrochemical consequences of battery particles' evolving (de)attachment with the conductive matrix. Herein, we tackle this issue with a unique combination of multiscale experimental approaches, machine-learning-assisted statistical analysis, and experiment-informed mathematical modeling. Our results suggest that the degree of particle detachment is positively correlated with the charging rate and that smaller particles exhibit a higher degree of uncertainty in their detachment from the carbon/binder matrix. We further explore the feasibility and limitation of utilizing the reconstructed electron density as a proxy for the state-of-charge. Our findings highlight the importance of precisely quantifying the evolving nature of the battery electrode's microstructure with statistical confidence, which is a key to maximize the utility of active particles towards higher battery capacity.

Structural and Electrochemical Impacts of Mg/Mn Dual Dopants on the LiNiO2 Cathode in Li-Metal Batteries.

Doping chemistry has been regarded as an efficient strategy to overcome some fundamental challenges facing the "no-cobalt" LiNiO2 cathode materials. By utilizing the doping chemistry, we evaluate the battery performance and structural/chemical reversibility of a new no-cobalt cathode material (Mg/Mn-LiNiO2). The unique dual dopants drive Mg and Mn to occupy the Li site and Ni site, respectively. The Mg/Mn-LiNiO2 cathode delivers smooth voltage profiles, enhanced structural stability, elevated self-discharge resistance, and inhibited nickel dissolution. As a result, the Mg/Mn-LiNiO2 cathode enables improved cycling stability in lithium metal batteries with the conventional carbonate electrolyte: 80% capacity retention after 350 cycles at C/3, and 67% capacity retention after 500 cycles at 2C (22 °C). We then take the Mg/Mn-LiNiO2 as the platform to investigate the local structural and chemical reversibility, where we identify that the irreversibility takes place starting from the very first cycle. The highly reactive surface induces the surface oxygen loss, metal reduction reaching the subsurface, and metal dissolution. Our data demonstrate that the dual dopants can, to some degree, mitigate the irreversibility and improve the cycling stability of LiNiO2, but more efforts are needed to eliminate the key challenges of these materials for battery operation in the conventional carbonate electrolyte.

Targeted Surface Doping with Reversible Local Environment Improves Oxygen Stability at the Electrochemical Interfaces of Nickel-Rich Cathode Materials.

Elemental doping represents a prominent strategy to improve interfacial chemistry in battery materials. Manipulating the dopant spatial distribution and understanding the dynamic evolution of the dopants at the atomic scale can inform better design of the doping chemistry for batteries. In this work, we create a targeted hierarchical distribution of Ti4+, a popular doping element for oxide cathode materials, in LiNi0.8Mn0.1Co0.1O2 primary particles. We apply multiscale synchrotron/electron spectroscopy and imaging techniques as well as theoretical calculations to investigate the dynamic evolution of the doping chemical environment. The Ti4+ dopant is fully incorporated into the TMO6 octahedral coordination and is targeted to be enriched at the surface. Ti4+ in the TMO6 octahedral coordination increases the TM-O bond length and reduces the covalency between (Ni, Mn, Co) and O. The excellent reversibility of Ti4+ chemical environment gives rise to superior oxygen reversibility at the cathode-electrolyte interphase and in the bulk particles, leading to improved stability in capacity, energy, and voltage. Our work directly probes the chemical environment of doping elements and helps rationalize the doping strategy for high-voltage layered cathodes.

Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials.

Redox phase transformations are relevant to a number of metrics pertaining to the electrochemical performance of batteries. These phase transformations deviate from and are more complicated than the conventional theory of phase nucleation and propagation, owing to simultaneous changes of cationic and anionic valence states as well as the polycrystalline nature of battery materials. Herein, we propose an integrative approach of mapping valence states and constructing chemical topographies to investigate the redox phase transformation in polycrystalline layered oxide cathode materials under thermal abuse conditions. We discover that, in addition to the three-dimensional heterogeneous phase transformation, there is a mesoscale evolution of local valence curvatures in valence state topographies. The relative probability of negative and positive local valence curvatures alternates during the layered-to-spinel/rocksalt phase transformation. The implementation of our method can potentially provide a universal approach to study phase transformation behaviors in battery materials and beyond.

Accelerated Evolution of Surface Chemistry Determined by Temperature and Cycling History in Nickel-Rich Layered Cathode Materials.

Nickel-rich layered cathode materials have the potential to enable cheaper and higher energy lithium ion batteries. However, these materials face major challenges (e.g., surface reconstruction, microcracking, potential oxygen evolution) that can hinder the safety and cycle life of lithium ion batteries. Many studies of nickel-rich materials have focused on ways to improve performance. Understanding the effects of temperature and cycling on the chemical and structural transformations is essential to assess the performance and suitability of these materials for practical battery applications. The present study is focused on the spectroscopic analysis of surface changes within a strong performing LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode material. We found that surface chemical and structural transformations (e.g., gradient metal reduction, oxygen loss, reconstruction, dissolution) occurred quicker and deeper than expected at higher temperatures. Even at lower temperatures, the degradation occurred rapidly and eventually matched the degradation at high temperatures. Despite these transformations, our performance results showed that a better performing nickel-rich NMC is possible. Establishing relationships between the atomic, structural, chemical, and physical properties of cathode materials and their behavior during cycling, as we have done here for NMC811, opens the possibility of developing lithium ion batteries with higher performance and longer life. Finally, our study also suggests that a separate, systematic, and elaborate study of surface chemistry is necessary for each NMC composition and electrolyte environment.

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials.

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. We observe that the mechanical breakdown of charged Li1- xNi0.4Mn0.4Co0.2O2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformations from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles, i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to the formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.

Unraveling the storage mechanism in organic carbonyl electrodes for sodium-ion batteries.

Organic carbonyl compounds represent a promising class of electrode materials for secondary batteries; however, the storage mechanism still remains unclear. We take Na2C6H2O4 as an example to unravel the mechanism. It consists of alternating Na-O octahedral inorganic layer and π-stacked benzene organic layer in spatial separation, delivering a high reversible capacity and first coulombic efficiency. The experiment and calculation results reveal that the Na-O inorganic layer provides both Na(+) ion transport pathway and storage site, whereas the benzene organic layer provides electron transport pathway and redox center. Our contribution provides a brand-new insight in understanding the storage mechanism in inorganic-organic layered host and opens up a new exciting direction for designing new materials for secondary batteries.

Prototype Sodium-Ion Batteries Using an Air-Stable and Co/Ni-Free O3-Layered Metal Oxide Cathode.

A prototype rechargeable sodium-ion battery using an O3-Na0.90[Cu0.22 Fe0.30 Mn0.48]O2 cathode and a hard carbon anode is demonstrated to show an energy density of 210 W h kg(-1) , a round-trip energy efficiency of 90%, a high rate capability (up to 6C rate), and excellent cycling stability.

Superior Na-Storage Performance of Low-Temperature-Synthesized Na3(VO(1-x)PO4)2F(1+2x) (0≤x≤1) Nanoparticles for Na-Ion Batteries.

Na-ion batteries are becoming comparable to Li-ion batteries because of their similar chemical characteristics and abundant sources of sodium. However, the materials production should be cost-effective in order to meet the demand for large-scale application. Here, a series of nanosized high-performance cathode materials, Na3(VO(1-x)PO4)2F(1+2x) (0≤x≤1), has been synthesized by a solvothermal low-temperature (60-120 °C) strategy without the use of organic ligands or surfactants. The as-synthesized Na3(VOPO4)2F nanoparticles show the best Na-storage performance reported so far in terms of both high rate capability (up to 10 C rate) and long cycle stability over 1200 cycles. To the best of our knowledge, the current developed synthetic strategy for Na3(VO(1-x)PO4)2F(1+2x) is by far one of the least expensive and energy-consuming methods, much superior to the conventional high-temperature solid-state method.

A phase-transfer assisted solvo-thermal strategy for low-temperature synthesis of Na3(VO1-xPO4)2F1+2x cathodes for sodium-ion batteries.

We demonstrate that a series of high-performance cathode materials, sodium vanadium polyanionic compounds, Na3(VO1-xPO4)2F1+2x (x = 0, 0.5 and 1), can be synthesized by a phase-transfer assisted solvo-thermal strategy at a rather low temperature (80-140 °C) in one simple step, exhibiting a high Na storage capacity of ca. 120 mA h g(-1) and excellent cycling performance. This study makes a significant step to extend this strategy to the synthesis of functional materials from simple binary to complex multicomponent compounds.

Air-Stable Copper-Based P2-Na7/9Cu2/9Fe1/9Mn2/3O2 as a New Positive Electrode Material for Sodium-Ion Batteries.

An air-stable copper-based P2-Na7/9Cu2/9Fe1/9Mn2/3O2 is designed and synthesized by a simple solid-state method and investigated as a positive electrode material for sodium-ion batteries. The attractive long cycling stability is demonstrated by the capacity retention of 85% after 150 cycles at 1 C rate without phase transformation. The reversible Cu2+/Cu3+ redox couple in P2 phase oxides is proved for the first time.