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At least 163 records · Page 9

Improved interfacial li-ion transport in composite polymer electrolytes via surface modification of LLZO

Composite polymer electrolytes that incorporate ceramic fillers in a polymer matrix offer mechanical strength and flexibility as solid electrolytes for lithium metal batteries. However, fast Li + transport between polymer and Li + -conductive filler phases is not a simple achievement due to high barriers for Li + exchange across the interphase. This study demonstrates how modification of Li 7 La 3 Zr 2 O 12 (LLZO) nanofiller surfaces with silane chemistries influences Li + transport at local and global electrolyte scales. Anhydrous reactions covalently link amine-functionalized silanes [(3-aminopropyl)triethoxysilane (APTES)] to LLZO nanoparticles, which protects LLZO in air. APTES functionalization lowers the poly (ethylene oxide) (PEO)-LLZO interphase resistance to half that of unmodified LLZO and increases effective Li + transference number, while insulating Al 2 O 3 completely blocks ion exchange and lowers transference number and conductivity in PEO-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-LLZO composites. Modeling an inner resistive interphase between LLZO and PEO surrounded by an outer conductive interphase explains non-linear conductivity trends. Solid-state 7 Li & 6 Li nuclear magnetic resonance shows Li + only exchanges between PEO-LiTFSI and some LLZO interphase, with no appreciable Li + transport through bulk LLZO. Surface functionalization is a promising path toward lowering the polymer-ceramic interphase resistance. This work demonstrates that local changes in Li + transport affect macroscopic performance, highlighting the intricate relationships between all interfaces in inherently heterogeneous composite polymer electrolytes.

25 ENERGY STORAGE↗

Unraveling the Nature of Excellent Potassium Storage in Small-Molecule Se@Peapod-Like N-Doped Carbon Nanofibers

The potassium-selenium (K-Se) battery is considered as an alternative solution for stationary energy storage because of abundant resource of K. However, the detailed mechanism of the energy storage process is yet to be unraveled. In this work, the findings in probing the working mechanism of the K-ion storage in Se cathode are reported using both experimental and computational approaches. A flexible K-Se battery is prepared by employing the small-molecule Se embedded in freestanding N -doped porous carbon nanofibers thin film (Se@NPCFs) as cathode. The reaction mechanisms are elucidated by identifying the existence of short-chain molecular Se encapsulated inside the microporous host, which transforms to K 2 Se by a two-step conversion reaction via an "all-solid-state" electrochemical process in the carbonate electrolyte system. Through the whole reaction, the generation of polyselenides (K 2 Se n , 3 ≤ n ≤ 8) is effectively suppressed by electrochemical reaction dominated by Se-2 molecules, thus significantly enhancing the utilization of Se and effecting the voltage platform of the K-Se battery. This work offers a practical pathway to optimize the K-Se battery performance through structure engineering and manipulation of selenium chemistry for the formation of selective species and reveal its internal reaction mechanism in the carbonate electrolyte.

25 ENERGY STORAGE↗

Effect of Propagating Dopant Reactivity on Lattice Oxygen Loss in LLZO Solid Electrolyte Contacted with Lithium Metal

Lithium lanthanum zirconium oxide (LLZO) is widely known as the most stable solid electrolyte against lithium metal electrodes. This thermodynamic stability can be lost by the presence of dopants which are required to stabilize the cubic phase of LLZO and can be reduced by lithium metal. However, the role of oxygen in such reactions is taken for granted. In this work, the reduction of Nb-substituted LLZO (Nb-LLZO) is explored by Li metal and shows that interfacial reactions propagate and lead to the decomposition with substantial Nb 5+ reduction deep into the bulk electrolyte. Scanning Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy and thermogravimetric analyses show much of the reduction is due to oxygen vacancies formed, leading to increased electronic conductivity mapped with conductive Atomic Force Microscopy. Density functional theory calculations indicate oxygen release is favored by increased excess lithiation of Nb-LLZO. Electrochemical impedance of polycrystalline Nb-LLZO shows the continuous evolution of ionically resistive interphases near the lithium metal interface with Nb-LLZO while single crystals show little reactivity at room temperature and self-limiting reduction at 60°C. This work underlines the role of grain boundaries in propagating destructive solid electrolyte reactions and highlights previously unseen mechanisms involving lattice oxygen in LLZO.

Li metal, solid-state electrolytes↗

Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn 2 O 4 Lithium-Ion Battery Cathodes

Protective coatings have been shown to effectively suppress Mn ion dissolution from the spinel LiMn 2 O 4 lithium-ion battery cathode by stabilizing the surface against undesired side reactions with the electrolyte. In spite of extensive study, however, there remains a lack of atomic-scale understanding of how such coatings are deposited, and no molecular-level descriptor to predict trends in deposition mechanisms has been identified. We have recently shown that Al 2 O 3 coatings grown by atomic layer deposition (ALD) with alternating trimethylaluminum (TMA) and water exposures exhibit submonolayer growth because of precursor decomposition on the lithium manganate spinel (LMO) surface during early ALD pulses. In the present work, we elucidate the underlying mechanisms of this Al 2 O 3 ALD process using density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) experiments, and we introduce a generalized descriptor-based framework to understand the resulting trends across a spectrum of surface structures and functionalities. We demonstrate that all decomposition products, including CH 3 -aluminum adducts and dissociated CH 3 groups, are Lewis bases and are coordinated to oxygen atoms on the LMO surface, leading to charge transfer to Lewis acidic Mn 3d states. Inert-transfer XPS supports these theoretical predictions, showing an increase in near-surface Mn 3+ content following TMA exposure and shifts in C is spectra consistent with C-O bond formation. We extend the DFT studies to various low- and high-index LMO surface facets, as a proxy for tuning the Lewis acid-base interactions between surface-bound CH 3 * and near-surface Mn ions. The thermochemistry for TMA reactions on these chemically distinct LMO surfaces demonstrates that ALD is structure-sensitive and that there is higher reactivity for TMA decomposition and Al 2 O 3 nucleation near LMO steps and defects. Motivated by the Lewis basic character of the decomposition products, we introduce the oxygen vacancy formation energy as a descriptor for decomposition energetics, and we demonstrate that all energetics are correlated to this quantity through the number of electrons that are transferred along the reaction coordinate. Finally, based on these findings, we hypothesize that improved electrochemical cycling with only 1-2 ALD cycles may be due to selective passivation of defect sites on the LMO surface that are more susceptible to Mn dissolution, and we suggest that similar descriptor-based analyses could be useful for the study of other ALD coatings on oxide substrates.

25 ENERGY STORAGE↗

Unraveling the convoluted and dynamic interphasial mechanisms on Li metal anode

Accurate understanding of the chemistry of solid-electrolyte interphase (SEI) is key to developing new electrolytes for high-energy batteries using lithium metal (Li-0) anodes(1). SEI is generally believed to be formed by the reactions between Li-0 and electrolyte(2,3). However, our new study shows this is not the whole story. Through synchrotron-based X-ray diffraction and pair distribution function analysis, we reveal a much more convoluted formation mechanism of SEI, which receives considerable contributions from electrolyte, cathode, moisture and native surface species on Li-0, with highly dynamic nature during cycling. Using isotope labelling, we traced the origin of LiH to electrolyte solvent, moisture and a new source: the native surface species (LiOH) on pristine Li-0. When lithium accessibility is very limited as in the case of anode-free cells, LiOH develops into plate-shaped large crystals during cycling. Alternatively, when the lithium source is abundant, as in the case of Li||NMC811 cells, LiOH reacts with Li-0 to form LiH and Li2O. While the desired anion-derived LiF-rich SEI is typically found in the concentrated electrolytes or their derivatives, we found it can also be formed in low-concentration electrolyte via the crosstalk effect, emphasizing the importance of formation cycle protocol and opening up opportunities for low-cost electrolyte development.

Polzin, Bryant J.↗

Stabilized Lithium, Manganese-Rich Layered Cathode Materials Enabled by Integrating Co-Doping and Nanocoating

While lithium, manganese-rich (LMR) layered oxide cathode materials offer high energy density (>900 Wh kg –1 ) and low cost, LMR is susceptible to continuous capacity and voltage decay from the oxygen migration and side reaction with aqueous electrolyte at high voltage. Herein, the integration of Na/F co-doping (CD) and AlF 3 coating on LMR is achieved without the need of complex atomic layer deposition. Akin to pristine and CD samples, CD with 1 wt % AlF 3 (CD-1.0 wt %) shows excellent electrochemical performance with the capacity and voltage retentions of 93 and 91% after 150 cycles at 0.5C, respectively, and increased ionic conductivity. Spectroscopic analysis indicates that the coating mainly influences the Co distribution, where Co is enriched on the surface, and partial diffusion of Al 3+ ions toward the bulk, leading to a slight change of transition-metal (TM) valence states at the nanometer scale and the formation of a stable Li x (CoAl)O y phase. Post-cycling analysis reveals that CD-1.0 wt % can alleviate the formation of rock-salt structure and Mn dissolution. Besides, little to no metal segregation is detected for the cycled CD-1.0 wt % sample. This finding presents the first instance to apply co-doping and AlF 3 coating as a new strategy to enhance the structural homogeneity and takes another step toward their commercial viability.

25 ENERGY STORAGE↗

Co 2 P-Pt Heterostructure Interfaces for Electrocatalytic Hydrogen Evolution

Pt-based electrocatalysts are effective for the hydrogen evolution reaction (HER); however, their limited ability to facilitate water dissociation and suboptimal hydrogen binding energy (H BE ) in alkaline electrolytes result in slow reaction kinetics, which hinders their cost-efficiency and practical applications. This study reports the synthesis of Co 2 P-Pt heterostructure nanorods using a seed-mediated growth method, producing a high density of Co 2 P-Pt interfacial sites. Density functional theory (DFT) calculations indicate that electronic interactions at these interfaces optimize H BE on Pt, while the interfacial sites promote water dissociation. The Co 2 P-Pt nanorods demonstrate an overpotential of 14 mV at 10 mA cm −2 for the HER, highlighting the potential of precisely engineered metal-metal phosphide interfaces for enhancing electrocatalytic efficiency.

36 MATERIALS SCIENCE↗

Intrinsic chemical reactivity of solid-electrolyte interphase components in silicon–lithium alloy anode batteries probed by FTIR spectroscopy

Herein we report the solid reaction products from the chemical reaction of aprotic battery electrolyte and three purported components of the Si-based anode SEI : SiO 2 nanoparticles (NPs), lithium silicate (Li x SiO y ) powders, and Si NPs. We use FTIR and classical molecular dynamics/density functional perturbation theory to assess the solid products remaining with these model materials after exposure to electrolyte. The absence of electrochemical bias provides a view of the chemical speciation resulting from early-stage chemical reactivity during battery assembly as well as under open circuit storage conditions. We believe these species represent the initial stages of SEI growth and predict they likely drive subsequent chemical and electrochemical reactions by controlling molecular interactons at the Si active material interface. We find that nominally equivalent materials react differently even before any electrochemistry is performed (e.g., acidic SiO 2 dissolves whereas alkaline SiO 2 is relatively robust), and derive new understanding of the chemical species that could and could not form stable SEI components in Si-based anodes. These results can be used to inform how to passivate Si anode surfaces and potentially generate an artificially engineered SEI that would be stable and enable next-generation battery anodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Synthesis of Graphene-Coated Silicon Monoxide Anodes from Coa-Derived Humic Acid for High-Performance Lithium-Ion Batteries

Silicon monoxide (SiO) is attaining extensive interest amongst silicon-based materials due to its high capacity and long cycle life; however, its low intrinsic electrical conductivity and poor coulombic efficiency strictly limit its commercial applications. Here low-cost coal-derived humic acid (HA) is used as a feedstock to synthesize in-situ graphene-coated disproportionated SiO (D-SiO@G) anode with a facile method. HRTEM and XRD confirm the well-coated graphene layers on an SiO surface. Scanning Transmission X-ray Microscopy (STXM) and X-ray Absorption Near-Edge Structure (XANES) spectra analysis indicate that the graphene coating effectively hinders the side-reactions between the electrolyte and SiO particles . As a result, the D-SiO@G anode presents an initial discharge capacity of 1937.6 mAh g -1 at 0.1 A g -1 and an initial coulombic efficiency (ICE) of 78.2%. High reversible capacity (1023 mAh g -1 at 2.0 A g -1 ), excellent cycling performance ( 72.4% capacity retention after 500 cycles at 2.0 A g -1 ), and rate capability (774 mAh g -1 at 5 A g -1 ) results are substantial. Full coin cells assembled with LiFePO 4 electrodes and D-SiO@G electrodes display impressive rate performance. These results indicate a promising potential for practical use in high-performance lithium-ion batteries.

25 ENERGY STORAGE↗

A Cobalt– and Manganese–Free High–Nickel Layered Oxide Cathode for Long–Life, Safer Lithium–Ion Batteries

High-nickel LiNi 1–x–y Mn x Co y O 2 and LiNi 1–x–y Co x Al y O 2 cathodes are receiving growing attention due to the burgeoning demands on high-energy-density lithium-ion batteries. The presence of both cobalt and manganese in them, however, triggers multiple issues, including high cost, high toxicity, rapid surface deterioration, and severe transition-metal dissolution. Herein, a Co- and Mn-free ultrahigh-nickel LiNi 0.93 Al 0.05 Ti 0.01 Mg 0.01 O 2 (NATM) cathode that exhibits 82% capacity retention over 800 deep cycles in full cells, outperforming two representative high-Ni cathodes LiNi 0.94 Co 0.06 O 2 (NC, 52%) and LiNi 0.90 Mn 0.05 Co 0.05 O 2 (NMC, 60%) is presented. It is demonstrated that a titanium-enriched surface along with aluminum and magnesium as the stabilizing ions in NATM not only ameliorates unwanted side reactions with the electrolyte and structural disintegrity, but also mitigates transition-metal dissolution and active lithium loss on the graphite anode. As a result, the graphite anode paired with NATM displays an ultrathin (≈8 nm), monolayer anode-electrolyte interphase architecture after extensive cycling. Furthermore, NATM displays considerably enhanced thermal stability with an elevated exothermic temperature (213 °C for NATM vs 180 and 190 °C for NC and NMC, respectively) and remarkably reduced heat release. This work sheds light on rational compositional design to adopt ultrahigh-Ni cathodes in lithium-based batteries with low cost, long service life, and improved thermal stability.

25 ENERGY STORAGE↗

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Abstract Gas evolution from high‐nickel layered oxide cathodes (>90% Ni) remains a major issue for their practical application. Gaseous species, such as CO 2 , O 2 , and CO, that are evolved at high states of charge (SOC) worsen the overall safety of batteries, as pressure build‐up within the cell may lead to cell rupture. Since these gasses are produced during cathode degradation, tracking the formation of gasses is also important in diagnosing cathode failure. Online electrochemical mass spectrometry (OEMS) is a powerful in situ technique to study gas evolution from the cathode during high‐voltage charge. However, the differences in the OEMS experimental setups between different groups make it challenging to compare results between groups. In this perspective, the various factors that influence gas evolution based on the OEMS results collected in this group are presented. The focus is on the conditions that lead to gas release, with a particular emphasis on reactive oxygen formation and subsequent chemical reactions with the electrolyte. Promising strategies, such as electrolytes, compositional tuning, and surface coatings that are effective at suppressing gas evolution from the cathode are highlighted. Critical insights into mitigating cathode degradation and gas evolution are provided to guide the development of safer, high‐energy batteries.

Chemistry↗

Halogen Thermochemistry Assessed with Density Functional Theory: Systematic Errors, Swift Corrections and Effects on Electrochemistry

Abstract Despite its sizable errors, density functional theory (DFT) is extensively used to evaluate thermochemical properties of gases, liquids and their interfaces with solids. As numerous halogen‐containing compounds appear as reactants, products and/or electrolytes in electrochemical reactions, and ionic effects are currently an active area of research, it is important to evaluate the accuracy of DFT for halogen thermochemistry. Herein, we assess the formation energies of interhalogens, hydrogen halides, diatomic and atomic halogens and their ions using six widespread functionals at the GGA, meta‐GGA and hybrid levels. We observe that DFT errors with respect to experiments are correlated with the electronegativity of the species and there are systematic trends across functionals, such that swift corrections were devised. Specifically, the average of the mean absolute errors for the six functionals decreased from 0.19 eV before the corrections to 0.08 eV after them. Besides, the overall maximum absolute error (MAX) decreased from 0.76 to 0.44 eV and the average of the MAXs decreased from 0.51 to 0.24 eV. Finally, we illustrate the qualitative and quantitative impact of gas‐phase errors on the predictions of surface Pourbaix diagrams.

Chemistry↗

Development of a universal method for high yield of furfural and hydrogen from raw lignocellulosic biomass

In order to develop a universal method for the co-production of furfural and hydrogen from raw lignocellulosic biomass, three types of substrates (maple wood, wheat straw, and tall fescue) were investigated, integrating chemical and electrochemical technologies. The results show both furfural and pure hydrogen were produced from all the biomass substrates, and the substrate type, composition, concentration, and size all affected furfural and hydrogen production. The highest furfural production of 154 mg g -1 substrate was achieved from wheat straw. The highest conversion rate of 67% for the waste furfural residue was realized, and 335 ml pure hydrogen per gram of furfural residue with a Faradaic efficiency of 99.3% was obtained with a new electrolytic cell. A reaction mechanism for hydrogen evolution from furfural residue and a rule for co-production of furfural and hydrogen from raw biomass were proposed. The facts show that a promising universal method for the co-production of furfural and hydrogen from lignocellulosic biomass has been developed.

08 HYDROGEN↗

Characterizing Complex Gas–Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe–N–C Catalysts

Electrocatalysts for the oxygen reduction reaction within polymer electrolyte membrane fuel cells based on iron, nitrogen, and carbon elements (Fe–N–C) are receiving significant research attention as they offer an inexpensive alternative to catalysts based on platinum-group metals. Although both the performance and the fundamental understanding of Fe–N–C catalysts have improved over the past decade, there remains a need to differentiate the relative activity of different active sites. Toward this goal, our study is focused on characterizing the interactions between O 2 and a set of five structurally different Fe–N–C materials. Detailed characterization of the Fe speciation was performed with 57 Fe Mössbauer spectroscopy and soft X-ray absorption spectroscopy of the Fe L 3,2 -edge, whereas nitrogen chemical states were investigated with X-ray photoelectron spectroscopy (XPS). In addition to initial sXAS and XPS measurements performed in ultra-high vacuum (UHV), measurements were also performed (at the identical location) in an atmosphere of 100 mTorr of O 2 at 80 °C (O 2 -rich). XPS and sXAS results reveal the presence of several types of FeNxCy adsorption sites. FeNxCy sites that are proposed as the most active ones do not show significant change (based on the techniques used in this study) when their environment is changed from UHV to O 2 -rich. Correlation with Mössbauer and sXAS results suggests that this is most likely due to the persistence of strongly adsorbed O 2 molecules from their previous exposure to air. However, other species do show spectroscopic changes from UHV conditions to O 2 -rich. This implies that these sites have a weaker interaction with O 2 that results in their desorption in vacuum conditions and re-adsorption when exposed to the O 2 -rich environment. The nature of these weakly and strongly O 2 -adsorbing FeN x C y sites is discussed in the context of different synthetic and processing parameters employed to fabricate each of these five Fe–N–C materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale Compositional Mapping of Commercial LiNi 0.8 Co 0.15 Al 0.05 O 2 Cathodes Using Atom Probe Tomography

Nickel-rich cathodes provide improved specific capacity that lead to higher gravimetric energy density, critical for electric vehicles. However, poor long-term capacity retention at elevated temperatures/high C-rates (the rate of charge and discharge on a battery) stem from material issues: surface phase changes, corrosive side reactions with the electrolyte, ion dissolution and propagation of cracks. Introducing dopants, developing nanoscale surface coatings and graded core-shell structures have all improved the electrochemical performance of nickel-rich cathodes. However, a material level understanding on the effect of Li composition and distribution in Ni-rich cathodes is limited, due to a lack of characterization methods available that can directly image Li at the nanoscale. Hence, it is critical to establish methods such as atom probe tomography (APT), having both nanometer scale spatial resolution and high compositional sensitivity to quantitatively analyze battery cathodes. To fully realize its potential as a method for quantitative compositional analysis of commercial Li-ion batteries, we provide a comprehensive description of the challenges in sample preparation and analyze the dependency of the analysis parameters, specifically laser pulse energy on the measured stoichiometry of elements in a high Ni content cathode material; LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA). In this work, our findings show the stoichiometry variations cannot be explained by charge state ratios or Ga implantation damage alone during FIB preparation, indicating that additional factors such as crystallographic orientation may need to be considered to achieve quantitative nanoscale compositional analysis of such battery cathodes using APT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uncovering the Relationship between Aging and Cycling on Lithium Metal Battery Self-Discharge

Lithium metal is considered the “holy grail” material to replace typical Li-ion anodes due to the absence of a host structure coupled with a high theoretical capacity. The absence of a host structure results in large volumetric changes when lithium is electrodeposited/dissolved, making the lithium prone to stranding and parasitic reactions with the electrolyte. Lithium research is focused on enabling highly reversible lithium electrodeposition/dissolution, which is important to achieving long cycle life. Understanding the various mechanisms of self-discharge is also critical for realizing practical lithium metal batteries but is often overlooked. In contrast to previous work, it is shown here that self-discharge via galvanic corrosion is negligible, particularly when lithium is cycled to relevant capacities. Rather, the continued electrochemical cycling of lithium metal results in self-discharge when periodic rest is applied during cycling. The extent of self-discharge can be controlled by increasing the capacity of plated lithium, tuning electrolyte chemistry, incorporating regular rest, or introducing lithiophilic materials. Finally, the Coulombic losses that occur during periodic rest are largely reversible, suggesting that the dominant self-discharge mechanism in this work is not an irreversible chemical process but rather a morphological process.

25 ENERGY STORAGE↗

Effects of Ball Milling on the Electrochemical Capacity and Interfacial Stability of Li 2 MnO 3 Cathode Materials

The cycling mechanism of Li 2 MnO 3 cathode materials synthesized by conventional solid-state methods at high temperatures (800-900 °C) has been intensively investigated. Previous studies showed that CO 2 and O 2 gas evolution accounts for most of the charge capacity, followed by some Mn reduction during discharge. In this work, we analyze the effects of ball milling on the structure, surface contaminant, and electrochemical capacity of Li 2 MnO 3 cathode material, with or without a graphitic fluoride (C-F) additive. At the same time, C-F is added to form a protective coating layer that reduces unwanted reactions with the electrolyte during later electrochemical cycling. We find that the C-F ball-milled material shows Li 2 MnO 3 /LiMnO 2 composite phases, while the purely ball-milled material shows a single Li 2 MnO 3 phase. Furthermore, we characterize surface species and gas evolution during the first cycle, which reveals the decomposition of Li 2 CO 3 and the carbonate electrolyte during the first charge, especially during the high potential region (>4.4 V), and the electrochemical reduction of only a small fraction of the evolved gas on the first discharge (<2.75 V). The appearance further demonstrates the repetitive nature of this process during charge and disappearance during discharge of Mn 2p 3/2 X-ray photoelectron spectroscopy (XPS) spectra signals during the first two cycles. These processes result in first discharge specific capacities of only 155 and 170 mAh/g after first charge specific capacities of 210 and 320 mAh/g for the pure ball-milled and ball-milled with C-F materials, respectively. These studies demonstrate the interfacial instability introduced by ball milling. However, the electrochemical capacity is significantly increased, necessitating further investigation to determine whether ball milling can activate Mn-containing cathode materials.

25 ENERGY STORAGE↗