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This work is part of ongoing and systematic investigations by our groups on the synthesis, electrochemical behavior, structural investigations, and computational modeling of the Ni-rich materials Li[NixCoyMnz]O2 (x+y+z=1; x≥0.8) for advanced lithium-ion batteries. This study focuses on the LiNi0.85Co0.10Mn0.05O2 (NCM85) material and its improvement upon doping with B3+ cations. The data demonstrate the substantial improvement of the doped electrodes in terms of cycling performance, lower voltage hysteresis and reduced self-discharge upon high temperature storage. The electronic structure of the undoped and B-doped material was modelled using density functional theory (DFT), which identified interstitial positions as the preferential location of the dopant. DFT models were also used to shed light on the influence of boron on surface segregation, surface stability, and oxygen binding energy in NCM85 material. Experimental evidence supports the suggestion that the boron segregates at the surface, effectively reducing the surface energy and increasing the oxygen binding energy, and possibly, as a result, inhibiting oxygen release. Additionally, the presence of borate species near the surface can reduce the nucleophilicity of surface oxygens. Cycling of the Li-cells did not cause noticeable changes in the microstructure of the B-doped materials, whereas significant microstructural changes, like a propagating network of cracks, was observed across all grains in the cycled undoped NCM85 cathodes. Analysis by high-resolution microscopy and 6Li and 11B solid-state nuclear magnetic resonance (ss NMR) allowed for the correlation of capacity fade and degradation of the different NCM85 materials with their structural characteristics.

The newly emerging demand for ‘beyond-lithium’ electrochemical energy storage systems necessitates the development of alternative options in providing sustainable cost-effective storage capabilities. In pursuit of discovering such a solution, the intercalation of bisulfate anions into graphite in 17 ​M ​H2SO4 solutions has been revaluated. Although the insertion process of bisulfate into graphite was extensively studied many years ago, only poor electrochemical performance has been demonstrated. In this work, we discovered the superior performance of the graphite bisulfate system, associated with the electrodes’ fabrication method which presents a high energy density of more than 80 ​mW ​h/g and a surprising rate capability (75 ​mW ​h/g was obtained at 15 ​C) alongside impressive long-term stability of more than 1500 cycles with only 5% capacity fading. Potentiostatic intermittent titration technique followed by slow-scan-rate cyclic voltammetry (SSCV) was used to shed light on the bisulfate intercalation process. Combining the bisulfate intercalation into the graphite with a highly reversible proton insertion process into Ti3C2 MXene in such a concentrated acidic environment allows the development of a dual-ion device composed of graphite positive electrode (cathode) and MXene negative electrode (anode). This asymmetric system shows a high energy density of 35 ​mW ​h/g, good cyclability and an extended potential window of 1.5 ​V, demonstrating new opportunities for further developments of intercalation electrodes for large energy storage.

Li and Mn-rich Li1+xNiyCozMnwO2 (LMR-NMC, 0 0.5) materials remain commercially relevant owing to their high specific capacity. Due to this stoichiometry, their synthesis forms always at least two phases: monoclinic Li2MnO3 and rhombohedral LiNiaCobMncO2 (a = b = c = 1) layered moieties. However, a complete understanding of their complex crystal structure has not yet been fully realized. The monoclinic phase may become electrochemically active only at high potentials (>4.6 V vs. Li). To complicate matters even more, it has been shown that the electrochemical performance of these materials, having formally the same stoichiometry, can vary with the chosen method of material synthesis. Identification of the chemical and/or structural reasons for these variations in performance is crucial to ensure the promotion of these important cathode materials towards a practical use. Yet most methods of analysis cannot distinguish the subtle, localized variations that account for such differences. Here, solid state 6,7Li NMR was found to be successful in identifying several distinctions between compounds with identical chemical formulae. Many distinctions can be made, and even suggested to account for some of the differences in the electrochemical behaviors noted for the differently prepared materials.

High-Ni-rich layered oxides [e.g., LiNi

Li-rich cathode materials of the formula xLi2MnO3·yLiNiaCobMncO2 (x + y = 1, a + b + c = 1) boast very high discharge capacity, ca. 250 mAh/g. Yet, they suffer capacity decrease and average voltage fade during cycling in Li-ion batteries that prohibit their commercialization. Treatment of the materials with NH3(g) at high temperatures produces improved electrodes with higher stability of capacity and average voltage. The present study follows the changes occurring in the materials upon treatment with ammonia gas, through 6Li and 7Li solid-state NMR investigations of the untreated and ammonia treated 0.35Li2MnO3·0.65LiNi0.35Mn0.45Co0.20O2 as well as its constituent phases, Li2MnO3 and LiNi0.4Co0.2Mn0.4O2. The NMR analysis demonstrates the biphasic nature of these materials. Furthermore, it shows that the Li2MnO3 component phase in the integrated material is the phase mostly being affected by the gas treatment. A thickening of a protective surface film in the integrated material, with the right exposure tim...

Development of advanced high energy density lithium ion batteries is important for promoting electromobility. Making electric vehicles attractive and competitive compared to conventional automobiles depends on the availability of reliable, safe, high power, and highly energetic batteries whose components are abundant and cost effective. Nickel rich Li[NixCoyMn1−x−y]O2 layered cathode materials (x > 0.5) are of interest because they can provide very high specific capacity without pushing charging potentials to levels that oxidize the electrolyte solutions. However, these cathode materials suffer from stability problems. We discovered that doping these materials with tungsten (1 mol%) remarkably increases their stability due to a partial layered to cubic (rock salt) phase transition. We demonstrate herein highly stable Li ion battery prototypes consisting of tungsten-stabilized Ni rich cathode materials (x > 0.9) with specific capacities >220 mA h g-1. This development can increase the energy density of Li ion batteries more than 30% above the state of the art without compromising durability.

This research sheds light on the intriguing phenomena of structural transformations that take place in spinel LiMn2O4 (space group Fd3m) when charged to high anodic potentials (4.3 to 5.1 V) in lithium cells. It was established from the XRD and electron diffraction analyses that the orthorhombic o-LiMnO2 (space group Pnma) is formed due to the partial transformation of spinel starting at 4.7 V. The Raman spectroscopy measurements of the LiMn2O4 samples charged to 5.1 V also provided evidence of o-LiMnO2, although its band overlaps with the delithiated spinel species. An additional important finding is that some layered-type LiMnO2 is formed upon cycling of the spinel material to 4.5 V, even upon the first charge. LiMnO2 exists as a stable component of the solid electrolyte interphase developed on these electrodes. We also concluded the formation of the layered LiMnO2 structure via solid-state 7Li NMR. The analysis of those results further indicated that the onset of the creation of the intermediate spinel...

One of the many challenges in the study of chiral nanosurfaces and nanofilms is the design of accurate and controlled nanoscale films with enantioselective activity. Controlled design of chiral nanofilms creates the opportunity to develop chiral materials with nanostructured architecture. Molecular layer deposition (MLD) is an advanced surface-engineering strategy for the preparation of hybrid inorganic-organic thin films, with a desired embedded property; in our study this is chirality. Previous attempts to grow enantioselective thin films were mostly focused on self-assembled monolayers or template-assisted synthesis, followed by removal of the chiral template. Here, we report a method to prepare chiral hybrid inorganic-organic nanoscale thin films with controlled thickness and impressive enantioselective properties. We present the use of an MLD reactor for sequenced vapor deposition to produce enantioselective thin films, by embedding the chirality of chiral building blocks into thin films. The prepared thin films demonstrate enantioselectivity of ∼20% and enantiomeric excess of up to 50%. We show that our controlled synthesis of chiral thin films generates opportunities for enantioselective coatings over various templates and 3D membranes.

Atomic deposition of a thin layer of alumina on amorphous carbon materials was recently established to improve their electrochemical properties as anodes in sodium-ion batteries. It is shown that the highest performance for these materials can be achieved by pre-sodiation of the electrode before coating it. The basis for the enhanced performance is illuminated by 13C and 23Na MAS NMR analysis showing that this specific procedure diminishes parasitic reactions and preserves reversible access to active sodiation sites.

In continuation of the work on the stabilization of the electrochemical performance of Li and Mn‐rich LixNiyCozMnwO2 (HE‐NCM, x > 1, w > 0.5, x + y + z + w = 2) cathode materials via atomic layer deposition (ALD) surface coatings, herein, the active role of aluminum oxides‐based coatings, during prolonged cycling in battery prototypes with graphite anodes, is discussed. Notable progress in electrochemical cycling and rate performance of Na‐aluminate‐coated Li1.142Mn0.513Ni0.230Co0.115O2 cathode material is established. These coated electrodes delivered a stable discharge capacity of 145 mAh g−1 (66% retention), compared to only 118 mAh g−1 (55% retention) for the uncoated sample at a 1.0 C rate after 400 cycles. Steady average discharge potential, lower voltage hysteresis, and stable energy density profiles are the noteworthy achievements for the coated material during cycling. Significant improvement in the coated material's thermal stability compared with the uncoated one has also been confirmed. The present study also enlightens about the Na‐aluminate coating's orientation and distribution on HE‐NCM material's surface. 23Na and 27Al solid‐state nuclear magnetic resonance (NMR) studies reveal the Na‐aluminate coating's crystalline constituent's disappearance upon cycling. The partial dissolution of Na5AlO4 coating, followed by forming a secondary disordered edge‐site phase that remains even after long‐term cycling, is disclosed.

Aluminum doped mixed metal oxides are popular positive electrode materials for Li-ion batteries. They are used extensively in many applications, yet their operation and limitations are not entirely understood. This work shows the advantage of using solid-state 7Li and 27Al NMR for monitoring the electrochemical properties of the doped nickel–cobalt oxide cathode material, LiNi0.8Co0.15Al0.05O2 (NCA), particularly during the first few charge/discharge cycles. The changes in the state of the material as lithium ions are intercalated and deintercalated during discharge and charge, respectively, are highlighted via the Li nuclei as a dynamic reporter and the Al nuclei as a static, material-embedded reporter. In particular, the NMR view of the cyclic change of Ni ions between paramagnetic and diamagnetic oxidation states is enhanced by monitoring both nuclei. Two protocols of cycling the NCA electrode are compared: one employing a smaller voltage window, cycled against graphite as anode, and one using a wider ...

This study investigates the organic components of the solid electrolyte interphase (SEI) on the carbonaceous anodic electrode in LiCoO2 batteries using solid-state nuclear magnetic resonance (NMR) techniques. The electrolyte solvents, ethylene carbonate and diethyl carbonate, were enriched on the carbonyl carbon prior to cell assembly and conditioning in an attempt to trace the breakdown pathways of these components. A strong signal was seen, demonstrating that the carbonyl carbons of both electrolytes survive in some reasonable quantity as insoluble breakdown products on the rinsed electrode surface. This confirms that the fate of these carbons as consumed in the formation of CO2 is either not unique, or not as final product. Furthermore the central carbonyl carbon survives, not as an intact carbonyl species, but instead in the form of compounds in which the carbon-oxygen double bond has been disrupted. Formation of this class of species is likely initiated by a nucleophilic attack on the carbonyl carbon by one or more radical, alkoxy, carbanion or fluorine-containing ionic species formed from solvent and/or salt breakdown. These results suggest a new family of electrolyte breakdown products, predominantly consisting of binary, tertiary and/or quaternary ether-type compounds (i.e., orthocarbonates and orthoesters), as well as fluorine-containing alkoxy compounds.

A straightforward method is presented for characterizing the quality of carbon nanotube (CNT) dispersions using scanning electron microscopy (SEM) imaging of samples prepared using a unique procedure, which successfully prevents re-coagulation of the CNTs during the evaporation of the dispersant. The images obtained more accurately reflect the status of the bulk dispersion in the liquid state. This method can be used to comparatively analyze the degree of disaggregation and the extent of tube breakage following a dispersion protocol in either aqueous or non-aqueous solutions, with or without surfactants, and regardless of the original condition of the CNTs.

Li-rich electrode materials of the family xLi2MnO3·(1−x)LiNiaCobMncO2 (a + b + c = 1) suffer a voltage fade upon cycling that limits their utilization in commercial batteries despite their extremely high discharge capacity, ≈250 mA h g−1. Li-rich, 0.35Li2MnO3·0.65LiNi0.35Mn0.45Co0.20O2, is exposed to NH3 at 400 °C, producing materials with improved characteristics: enhanced electrode capacity and a limited average voltage fade during 100 cycles in half cells versus Li. Three main changes caused by NH3 treatment are established. First, a general bulk reduction of Co and Mn is observed via X-ray photoelectron spectroscopy and X-ray absorption near edge structure. Next, a structural rearrangement lowers the coordination number of CoO and MnO bonds, as well as formation of a surface spinel-like structure. Additionally, Li+ removal from the bulk causes the formation of surface LiOH, Li2CO3, and Li2O. These structural and surface changes can enhance the voltage and capacity stability of the Li-rich material electrodes after moderate NH3 treatment times of 1–2 h.

Three types of fluorinated carbon, all in their original form and upon sequential chemical lithiations via n-butyllithium, were investigated by (13)C and (19)F solid-state NMR methods. The three starting CF(x) materials [where x = 1 (nominally)] were fiber based, graphite based, and petroleum coke based. The aim of the current study was to identify, at the atomic/molecular structural level, factors that might account for differences in electrochemical performance among the different kinds of CF(x). Differences were noted in the covalent F character among the starting compounds and in the details of LiF production among the lithiated samples.

Intensive studies of an advanced energy material are reported and lithium polyacrylate (LiPAA) is proven to be a surprisingly unique, multifunctional binder for high-voltage Li-ion batteries. The absence of effective passivation at the interface of high-voltage cathodes in Li-ion batteries may negatively affect their electrochemical performance, due to detrimental phenomena such as electrolyte solution oxidation and dissolution of transition metal cations. A strategy is introduced to build a stable cathode–electrolyte solution interphase for LiNi0.5Mn1.5O4 (LNMO) spinel high-voltage cathodes during the electrode fabrication process by simply using LiPAA as the cathode binder. LiPAA is a superb binder due to unique adhesion, cohesion, and wetting properties. It forms a uniform thin passivating film on LNMO and conducting carbon particles in composite cathodes and also compensates Li-ion loss in full Li-ion batteries by acting as an extra Li source. It is shown that these positive roles of LiPAA lead to a significant improvement in the electrochemical performance (e.g., cycle life, cell impedance, and rate capability) of LNMO/graphite battery prototypes, compared with that obtained using traditional polyvinylidene fluoride (PVdF) binder for LNMO cathodes. In addition, replacing PVdF with LiPAA binder for LNMO cathodes offers better adhesion, lower cost, and clear environmental advantages.

Background Pyrite, the most abundant metal sulphide on Earth, is known to spontaneously form hydrogen peroxide when exposed to water. In this study the hypothesis that pyrite-induced hydrogen peroxide is transformed to hydroxyl radicals is tested. Results Using a combination of electron spin resonance (ESR) spin-trapping techniques and scavenging reactions involving nucleic acids, the formation of hydroxyl radicals in pyrite/aqueous suspensions is demonstrated. The addition of EDTA to pyrite slurries inhibits the hydrogen peroxide-to-hydroxyl radical conversion, but does not inhibit the formation of hydrogen peroxide. Given the stability of EDTA chelation with both ferrous and ferric iron, this suggests that the addition of the EDTA prevents the transformation by chelation of dissolved iron species. Conclusion While the exact mechanism or mechanisms of the hydrogen peroxide-to-hydroxyl radical conversion cannot be resolved on the basis of the experiments reported in this study, it is clear that the pyrite surface promotes the reaction. The formation of hydroxyl radicals is significant because they react nearly instantaneously with most organic molecules. This suggests that the presence of pyrite in natural, engineered, or physiological aqueous systems may induce the transformation of a wide range of organic molecules. This finding has implications for the role pyrite may play in aquatic environments and raises the question whether inhalation of pyrite dust contributes to the development of lung diseases.

Presented herein is a discussion of the forefront in research and development of advanced electrode materials and electrolyte solutions for the next generation of lithium ion batteries. The main challenge of the field today is in meeting the demands necessary to make the electric vehicle fully commercially viable. This requires high energy and power densities with no compromise in safety. Three families of advanced cathode materials (the limiting factor for energy density in the Li battery systems) are discussed in detail: LiMn1.5Ni0.5O4 high voltage spinel compounds, Li2MnO3–LiMO2 high capacity composite layered compounds, and LiMPO4, where M = Fe, Mn. Graphite, Si, LixTOy, and MO (conversion reactions) are discussed as anode materials. The electrolyte is a key component that determines the ability to use high voltage cathodes and low voltage anodes in the same system. Electrode–solution interactions and passivation phenomena on both electrodes in Li-ion batteries also play significant roles in determining stability, cycle life and safety features. This presentation is aimed at providing an overall picture of the road map necessary for the future development of advanced high energy density Li-ion batteries for EV applications.

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This study examined the aging mechanisms of layered cathode materials for lithium batteries upon exposure to air and the influence of this aging on the thermal stability and electrochemical performance of these materials composed of solid solutions of LiMO 2 (M = [MnNi] or [MnNiCo]) in Li cells. A unique methodology for the quantitative characterization of surface carbonates on LiMO 2 compounds based on differential scanning calorimeter (DSC) measurements was developed. Correlations were made between the formation of Li 2 CO 3 and other carbonates on the surface of the lithiated metal oxide powders and the changes in the structure and electrochemical performance of the cathode materials. The techniques used included solid-state NMR, X-ray photelectron spectroscopy, Fourier transform IR, high resolution scanning electron microscopy, high resolution transmission electron microscopy and the thermal analysis, DSC, and accelerating rate calorimetry in conjunction with electrochemical measurements. .

We report herein on the synthesis of "layered-layered" integrated xLi 2 Mno 3 ·(1 ― x)LiMn 1/3 Ni 1/3 Co 1/3 O 2 materials (x = 0.3, 0.5, and 0.7) using the self-combustion reaction in solutions containing metal nitrates and sucrose. The nanoparticles of these materials were obtained by further annealing of the as-prepared product in air at 700°C for 1 h and submicrometric particles were obtained by further annealing at 900°C for 22 h. The effect of composition on the electrochemical performance was explored in this work. By a rigorous study with high resolution transmission electron microscopy (HRTEM), it became clear that the syntheses with the above stoichiometries produce two-phase materials comprising nanodomains of both rhombohedral LiNiO 2 -like and monoclinic Li 2 MnO 3 structures, which are closely integrated and interconnected with one another at the atomic level. Stable reversible capacities ∼220 mAh/g were obtained with composite electrodes containing submicrometer particles of 0.5Li 2 MnO 3 ·0.5LiMn 1/3 Ni 1/3 Co 1/3 O 2 . Structural aspects, activation of the monoclinic component, and stabilization mechanisms are thoroughly discussed using Raman spectroscopy, solid-state NMR, HRTEM, and X-ray diffraction (including Rietveld analysis) in conjunction with electrochemical measurements. This work provides a further indication that this family of integrated compounds contains the most promising cathode materials for high energy density Li-ion batteries.

We investigated the magnetic anisotropic parameters and spin-wave relaxation of thin films of the ferromagnetic half-metallic Sr2FeMoO6 by ferromagnetic resonance technique. The resonance field and linewidth were recorded as a function of relative angle between applied magnetic field and crystallographic axes of the sample. The resonance field varies sinusoidally and considerable linewidth broadening occurs when the applied field is rotated parallel to the sample plane. The results are described using higher order components of anisotropy fields. We obtain the values of the cubic anisotropic field, 2K4∥∕M=0.09611T, the effective demagnetization field, 4πM−2K2⊥∕M=0.1216T, and the planar anisotropic field, 2K4⊥∕M=−0.108T. Moreover, we estimated the spin relaxation time (damping factor) from the analysis of the angular dependence of peak-to-peak linewidth, leading to an intrinsic value of α∼0.00025 (Gilbert damping).

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Structural studies have been carried out on Ag{sub 2}V{sub 4}O{sub 11} (silver vanadium oxide, SVO) and Li{sub x}Ag{sub 2}V{sub 4}O{sub 11}, lithiated SVO with x=0.72, 2.13, and 5.59 using nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy (XAS). Lithium-7 NMR indicates the formation of a solid electrolyte interphase layer on the x=0.72 sample and lithium intercalation into both octahedral and tetrahedral sites in the SVO lattice, and that most but not all of the Ag (I) is reduced prior to initiation of V(V) reduction. Vanadium-51 NMR studies of SVO and lithiated SVO show decreased crystallinity with increased lithiation, as previously reported. Silver XAS studies indicate the formation of metallic silver crystallites in all the lithiated samples. A comparison of X-ray absorption near edge spectroscopy spectra for vanadium in these samples with those of reference compounds shows that some reduction of vanadium (V) occurs in the lithiated SVO with x=0.72 and increases with further lithiation leading to the formation of V(IV) and V(III) species. The results of this study indicate that vanadium(V) reduction occurs in parallel with silver (I) reduction during the initial stages of SVO lithiation, leading ultimately to the formation of vanadium (IV) and (III) species with further lithiation.

We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium–fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and 11B nuclear magnetic resonance studies suggest that co-intercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.