Isothermal microcalorimetry as a tool to study solid-electrolyte interphase formation in lithium-ion cells.

Isothermal microcalorimetry can be used in conjunction with electrochemical measurements to study solid-electrolyte interphase (SEI) formation reactions as they occur in a Li-ion cell. The heat flow was measured in wound cells that contained no electrolyte additives and in cells prepared with four additives that are known to produce an SEI at the negative electrode surface: vinylene carbonate (VC), fluoroethylene carbonate (FEC), pyridine boron trifluoride (PBF), and prop-1-ene-1,3-sultone (PES). For VC, two distinct features in the differential capacity (dQ/dV vs. Q) plot that align with overlapping peaks in the heat flow plot do not agree with a simple one-electron reduction followed by anionic polymerization. For FEC, three distinct differential capacity and calorimetric peaks are observed. Heat flow measurements at multiple PBF concentrations show that PBF reduction does not significantly affect the reduction of EC at higher cell voltage. The total heat flow during SEI formation in PBF- and PES-containing cells match the calculated energies in recently published reaction pathways. It is concluded that IMC may be used to study the underlying chemistry of SEI formation, especially when paired with computational studies.

Mechanism of action of ethylene sulfite and vinylene carbonate electrolyte additives in LiNi1/3Mn1/3Co1/3O2/graphite pouch cells: electrochemical, GC-MS and XPS analysis.

The role of ethylene sulfite used either alone or in combination with VC in LiNi1/3Mn1/3Co1/3O2 (NMC)/graphite pouch cells was studied by correlating data from differential capacity (dQ/dV) analysis, gas chromatography/mass spectroscopy (GC-MS), theoretical calculations, ultrahigh precision coulometry, storage experiments and X-ray photoelectron spectroscopy. For cells containing VC alone, the electrochemical performance and gas production were greatly improved, compared to cells without VC, due to the formation of more stable and protective SEI films at both electrode surfaces by a polymer of VC. For cells with ES alone, a vigorous reactivity was observed due to preferential reduction that also generated large amounts of gas during formation. The dramatic decrease in electrochemical performance as well as the continuous production of gas during cycling in cells with ES was explained by the formation of a very thin and ineffective SEI film at the NMC surface. The suppression of the vigorous reaction of ES in cells with both ES and VC occurred because the solvation energy of Li(+) by VC is smaller than that of EC so VC is reduced first during formation. During charge-discharge cycling, a slow consumption of ES occurred and different sulfur species were observed on the electrodes when VC was combined with ES. SEI film formation processes and SEI composition were therefore dominated by VC and the electrochemical performance of cells with both VC and ES were similar compared to those of cells with VC alone.

Rechargeable lithium batteries with aqueous electrolytes.

Rechargeable lithium-ion batteries that use an aqueous electrolyte have been developed. Cells with LiMn(2)O(4) and VO(2)(B) as electrodes and 5 M LiNO(3) in water as the electrolyte provide a fundamentally safe and cost-effective technology that can compete with nickelcadmium and lead-acid batteries on the basis of stored energy per unit of weight.

New Chemical Insights into the Beneficial Role of Al2O3 Cathode Coatings in Lithium-ion Cells.

Inorganic surface coatings such as Al2O3 are commonly applied on positive electrode materials to improve the cycling stability and lifetime of lithium-ion cells. The beneficial effects are typically attributed to the chemical scavenging of corrosive HF and the physical blockage of electrolyte components from reaching the electrode surface. The present work combines published thermochemistry data with new density functional theory calculations to propose a new mechanism of action: the spontaneous reaction of the LiPF6 electrolyte salt with Al2O3-based surface coatings. Using 19F and 31P solution nuclear magnetic resonance spectroscopy, it is demonstrated that the storage of LiPF6-containing electrolyte solution with Al2O3 produces LiPO2F2, a well-known electrolyte additive. The production of LiPO2F2 is also observed for electrolyte solutions that were stored for 14 days at 40 °C with Al2O3-coated LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNi0.8Co0.15Al0.05O2 (NCA) materials. Given the beneficial nature of this species for the lifetime and stability of lithium-ion cells, this reaction is here proposed to similarly benefit the performance of cells that use Al2O3-coated cathode materials.

Ammonia, cyclohexane, nitrogen and water adsorption capacities of an activated carbon impregnated with increasing amounts of ZnCl(2), and designed to chemisorb gaseous NH(3) from an air stream.

The adsorption capacity of ZnCl(2)-impregnated activated carbon (AC) for NH(3) is reported in terms of stoichiometric ratio of reaction (NH(3) per ZnCl(2)). This ratio depends on the testing conditions used. Compared to the ratio obtained under dry conditions, the ratio is higher under humid conditions or increased NH(3) concentrations. The linear increase of the NH(3) capacity with increasing loading of ZnCl(2) breaks down at about 3.5 mmol ZnCl(2)/g AC. This behavior is explained in terms of preferential adsorption of a monolayer of salt followed by aggregation of the impregnant once a monolayer is completed. The effect of increasing the loading of ZnCl(2) on the capacity for gases for which the impregnants are not intended, namely cyclohexane, nitrogen, and water vapor, is also discussed. A break in the linear relationship between water capacity and impregnant loading at about 3.5 mmol ZnCl(2) seems to correspond to a full monolayer coverage of ZnCl(2) on AC. The monolayer of ZnCl(2) is shown to reduce the uptake of water into AC, while the ZnCl(2) aggregates are shown to be hydrophilic.

Role of CuO in improving NH3 and SO2 capture on nanoporous Fe2O3 sorbents.

In this work, mixed Fe/Cu oxides as sorbents for SO2 and NH3 removal were investigated. Nanoporous iron oxide mixed with 10, 20 and 30 at.% CuO were prepared by thermal decomposition of the corresponding oxalates at 250 °C for 5 h in air. The mixed Fe/Cu oxalates were obtained from the co-precipitation of iron/copper sulfate and ammonium oxalate during ultrasonication. The physical properties of the oxalate precursors and the resulting mixed Fe/Cu oxides were characterized with SEM, TGA-DSC, FTIR, powder XRD and Mössbauer spectroscopy. The porosity was studied by N2 adsorption-desorption isotherms and small angle X-ray scattering. Evenly dispersed CuO hindered the crystallization of Fe2O3, which significantly increased the specific BET surface area from 211 m2/g for Fe2O3 to 354 m2/g for Fe0.8Cu0.2Ox. As a result, SO2 and NH3 adsorption on Fe0.8Cu0.2Ox were enhanced by about 70% compared to Fe2O3. Compared to Fe2O3-impregnated activated carbons, nanoporous Fe0.8Cu0.2Ox could capture five times more SO2 per unit weight, which will be attractive for applications in respirators with lower weight and smaller size.

An automated system for performing continuous viscosity versus temperature measurements of fluids using an Ostwald viscometer.

An automated system was developed to measure the viscosity of fluids as a function of temperature using image analysis tracking software. An Ostwald viscometer was placed in a three-wall dewar in which ethylene glycol was circulated using a thermal bath. The system collected continuous measurements during both heating and cooling cycles exhibiting no hysteresis. The use of video tracking analysis software greatly reduced the measurement errors associated with measuring the time required for the meniscus to pass through the markings on the viscometer. The stability of the system was assessed by performing 38 consecutive measurements of water at 42.50 ± 0.05 °C giving an average flow time of 87.7 ± 0.3 s. A device was also implemented to repeatedly deliver a constant volume of liquid of 11.00 ± 0.03 ml leading to an average error in the viscosity of 0.04%. As an application, the system was used to measure the viscosity of two Li-ion battery electrolyte solvents from approximately 10 to 40 °C with results showing excellent agreement with viscosity values calculated using Gering's Advanced Electrolyte Model (AEM).

Novel nanoporous MnOx (x=∼1.75) sorbent for the removal of SO2 and NH3 made from MnC2O4·2H2O.

In this work, nanoporous manganese oxides (MnOx) were prepared by thermal decomposition of MnC2O4·2H2O at 225°C for 6h in air. The manganese oxalate dihydrate precipitate was made from manganese sulfate and ammonium oxalate during ultrasonication and stirring. The physical properties of the oxalate precursors and the resulting MnOx samples were characterized with SEM, TGA-DSC, FTIR and powder XRD. The specific surface areas and porosity of MnOx were studied by single-point BET and multi-point N2 adsorption-desorption measurements. The amorphous MnOx from oxalate prepared by sonication showed a specific surface area as large as 499.7m(2)/g. Dynamic SO2 and NH3 flow tests indicated that the adsorption capacity of MnOx, especially for SO2, can be increased by increased surface area. Compared to the best Mn3O4-impregnated activated carbon adsorbent, nanoporous MnOx could remove approximately three times as much SO2 and a comparable amount of NH3 per gram of adsorbent. This could lead to respirators of lower weight and smaller size which will be attractive to users.

Combinatorial Study of the Li-Ni-Mn-Co Oxide Pseudoquaternary System for Use in Li-Ion Battery Materials Research.

Combinatorial synthesis has proven extremely effective in screening for new battery materials for Li-ion battery electrodes. Here, a study in the Li-Ni-Mn-Co-O system is presented, wherein samples with nearly 800 distinct compositions were prepared using a combinatorial and high-throughput method to screen for single-phase materials of high interest as next generation positive electrode materials. X-ray diffraction is used to determine the crystal structure of each sample. The Gibbs' pyramid representing the pseudoquaternary system was studied by making samples within three distinct pseudoternary planes defined at fractional cobalt metal contents of 10%, 20%, and 30% within the Li-Ni-Mn-Co-O system. Two large single-phase regions were observed in the system: the layered region (ordered rocksalt) and cubic spinel region; both of which are of interest for next-generation positive electrodes in lithium-ion batteries. These regions were each found to stretch over a wide range of compositions within the Li-Ni-Mn-Co-O pseudoquaternary system and had complex coexistence regions existing between them. The sample cooling rate was found to have a significant effect on the position of the phase boundaries of the single-phase regions. The results of this work are intended to guide further research by narrowing the composition ranges worthy of study and to illustrate the broad range of applications where solution-based combinatorial synthesis can have significant impact.

Evaluation of the SO(2) and NH(3) gas adsorption properties of CuO/ZnO/Mn(3)O(4) and CuO/ZnO/NiO ternary impregnated activated carbon using combinatorial materials science methods.

Impregnated activated carbons (IAC) are widely used materials for the removal of toxic gases in personal respiratory protection applications. The combinatorial method has been employed to prepare IACs containing different types of metal oxides in various proportions and evaluate their adsorption performance for low molecular weight gases, such as SO(2) and NH(3), under dry conditions. Among the metal oxides used for the study, Mn(3)O(4) was found to have the highest capacity for retaining SO(2) gas under dry conditions. NiO and ZnO were found to have similar NH(3) adsorption capacities which are higher than the NH(3) capacities observed for the other metal oxide impregnants used in the study. Although Cu- or Zn-based impregnants and their combinations have been extensively studied and used as gas adsorbents, neither Mn(3)O(4) nor NiO have been incorporated in the formulations used. In this study, ternary libraries of IACs with various combinations of CuO/ZnO/Mn(3)O(4) and CuO/ZnO/NiO were studied and evaluated for their adsorption of SO(2) and NH(3) gases. Combinations of CuO, ZnO, and Mn(3)O(4) were found to have the potential to be multigas adsorbents compared to formulations that contain NiO.

Fibrinogen and albumin adsorption on titanium nanoroughness gradients.

The influence of nanoscale roughness on protein adsorption has been efficiently studied through the application of Ti roughness gradients. Gradients were prepared by sputter deposition with a length of 76 mm and a range in RMS roughness varying linearly from 1 to 16 nm. They were then exposed to solutions containing either 1 mg/mL of fibrinogen or albumin. The amount of protein that adsorbed as a function of roughness was measured ex situ by electron microprobe analysis and compared to values obtained for smooth Ti films. The adsorption profiles of fibrinogen and albumin along the gradients were found to be highly similar when normalized by their respective amounts from smooth films, each showing a 50% increase in adsorption with roughness. A statistic called the average surface curvature was created to provide a plausible explanation for the similar adsorption behavior and connect findings from random topographies with earlier research on curved substrates like nanoparticles.

SO2 and NH3 gas adsorption on a ternary ZnO/CuO/CuCl2 impregnated activated carbon evaluated using combinatorial methods.

Ternary libraries of 64 ZnO/CuO/CuCl(2) impregnated activated carbon samples were prepared on untreated or HNO(3)-treated carbon and evaluated for their SO(2) and NH(3) gas adsorption properties gravimetrically using a combinatorial method. CuCl(2) is shown to be a viable substitute for HNO(3) and some compositions of ternary ZnO/CuO/CuCl(2) impregnated carbon samples prepared on untreated carbon provided comparable SO(2) and NH(3) gas removal capacities to the materials prepared on HNO(3)-treated carbon. Through combinatorial methods, it was determined that the use of HNO(3) in this multigas adsorbent formulation can be avoided.

The effect of co-impregnated acids on the performance of Zn-based broad spectrum respirator carbons.

Impregnated activated carbons (IACs) that are used in multi-gas respirator applications usually contain copper and/or zinc impregnants. Co-impregnating with properly selected acids can improve the distribution of the metallic impregnant on the carbon and improve the gas adsorption capacity of the IAC. In this work a comparative study of some common acids co-impregnated with a zinc nitrate (Zn(NO(3))(2)) precursor is performed. The IACs were heated in an inert atmosphere at temperatures which promoted the thermal decomposition of Zn(NO(3))(2) to zinc oxide (ZnO). The gas adsorption properties of the IACs were tested using ammonia (NH(3)), sulphur dioxide (SO(2)) and hydrogen cyanide (HCN) challenge gases. Powder X-ray diffraction (XRD) was used to identify the impregnant species present after heating and to study impregnant distribution. Gravimetric analysis was used to determine the impregnant loading, and help to identify the impregnant species after heating. The interactions between the co-impregnated acid and Zn(NO(3))(2) precursor during heating are discussed. The relationship between impregnant species and gas adsorption capacity is discussed.

Combinatorial synthesis of mixed transition metal oxides for lithium-ion batteries.

Many methods exist for the synthesis of lithium metal oxides for use as positive electrode materials in lithium-ion batteries; however, no such method to date is both combinatorial (able to process broad ranges of compositional space quickly and efficiently) and well-studied to ensure confidence in the procedure. This study develops a procedure for microliter-scale solution-processing synthesis using a combinatorial solutions-processing robot. Two compositional systems (LiNi(x)Mn(2-x)O(4) and Li-Al-Mn oxide) were synthesized to compare the method to existing syntheses to ensure confidence in the procedure. Samples produced by this new synthetic procedure have crystal structures and lattice constants that closely match those of bulk-prepared samples found in the literature.

The effect of heating temperature and nitric acid treatments on the performance of Cu- and Zn-based broad spectrum respirator carbons.

Impregnated activated carbons (IACs) that are used in broad spectrum gas mask applications have historically contained copper and/or zinc impregnants. The addition of an oxidizing agent, such as nitric acid (HNO(3)) can be useful in distributing the metallic impregnants uniformly on the activated carbon substrate. In this work, we study IACs prepared from copper nitrate (Cu(NO(3))(2)) and zinc nitrate (Zn(NO(3))(2)) precursors as a function of HNO(3) content present in the impregnating solution and as a function of heating temperature. The gas adsorption capacity of the IACs was determined by dynamic flow testing using sulfur dioxide (SO(2)), ammonia (NH(3)), hydrogen cyanide (HCN) and cyclohexane (C(6)H(12)) challenge gases under dry and humid conditions. The thermal decomposition and distribution of the impregnant on the activated carbon substrate is studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermal analysis techniques. Relationships between gas adsorption capacity, impregnant distribution and the species of surface impregnants are discussed.

A combinatorial approach to screening carbon based materials for respiratory protection.

A combinatorial materials science approach for the discovery of an impregnated activated carbon that can adsorb a wide variety of toxic gases (i.e. a multi-gas carbon) has been developed. This approach presently allows for the parallel preparation and investigation of 64-100 IAC samples at once increasing the rate of discovery of viable multi-gas carbons. Multi-gas carbons were prepared using a solutions handling robot and screened gravimetrically for their effectiveness as gas adsorbents. The method was validated using known gas adsorbent materials such as ZnCl(2), K(2)CO(3) and CuO-impregnated carbons. The calculated adsorption capacities and stoichiometric ratios of reactions for these known gas adsorbent materials, when evaluated using the combinatorial approach, was comparable to the values obtained using traditional methods of analysis. A library of samples prepared by combining various amounts of CuO and ZnO impregnants showed the expected decreasing trend in the calculated stoichiometric ratio of reaction with respect to increasing amount of impregnants added. The method is now ready to use to explore new systems of impregnated activated carbons.

Investigation of copper oxide impregnants prepared from various precursors for respirator carbons.

Copper oxide impregnated activated carbon was prepared by three methods and studied as a respirator carbon. Using techniques such as dynamic flow testing, X-ray diffraction (XRD), thermal analysis, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX), copper oxide impregnants, derived from different sources such as basic copper carbonate (Cu(2)CO(3)(OH)(2)), copper nitrate (Cu(NO(3))(2)) and copper chloride (CuCl(2)) reacted with sodium hydroxide (NaOH), have been studied. Dynamic flow tests performed using sulfur dioxide (SO(2)), ammonia (NH(3)) and hydrogen cyanide (HCN) challenge gases allow the determination of the stoichiometric ratio of reaction (SRR) between challenge gas and impregnant. Thermal gravimetric analysis experiments showed that an inert heating environment was required when thermally decomposing the Cu(NO(3))(2) impregnant to CuO to avoid damaging the activated carbon substrate. SEM has been used to investigate dispersal and particle size of the impregnant on the activated carbon. XRD permits the identification of crystalline and amorphous phases as well as the grain size of the impregnant. XRD analysis of samples before and after exposure to SO(2) has allowed the active impregnant in SO(2) adsorption to be identified. The relationship between SRR, impregnant loading and grain size is discussed. Methods to improve impregnant distribution are presented and their impact discussed.

Surface characteristics and protein adsorption on combinatorial binary Ti-M (Cr, Al, Ni) and Al-M (Ta, Zr) library films.

Systematic studies of protein adsorption onto metallic biomaterial surfaces are generally lacking. Here, combinatorial binary library films with compositional gradients of Ti(1-x)Cr(x), Ti(1-x)Al(x), Ti(1-x)Ni(x) and Al(1-x)Ta(x), (0

An in situ study of protein adsorption on combinatorial Cu-Al films using spectroscopic ellipsometry.

An approach to quantifying adsorbed protein layers at the protein/metal interface through spectroscopic ellipsometry using an in situ technique is described. A combinatorial binary Cu(1-x)Al(x) (0

The investigation of copper-based impregnated activated carbons prepared from water-soluble materials for broad spectrum respirator applications.

The preparation of impregnated activated carbons (IACs) from aqueous, copper-containing solutions for broad spectrum gas filtration applications is studied here. Several samples were studied to determine the effect that impregnant loading, impregnant distribution and impregnant recipe had on the overall performance. Dynamic flow testing was used to determine the gas filtration capacity of the IAC samples versus a variety of challenge gases. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) were used to characterize the impregnant distribution on the carbon as a function of impregnant loading. Oven tests were performed to determine the thermal stability of the IAC samples exposed to elevated temperatures. The role impregnant distribution plays in gas filtration capacity and the overall performance of the IAC samples is discussed. The IAC samples prepared in this work were found to have gas filtration capacities as good as or better than broad spectrum respirator carbon samples prepared from the patent literature. IACs impregnated with an aqueous 2.4 M Cu(NO(3))(2)/0.04 M H(3)PO(4).12MoO(3)/4M HNO(3) solution that were heated to 200 degrees C under argon were found to have the best overall performance of the samples studied in this work.