Cycling Stability of Lithium-Ion Batteries Based on Fe-Ti-Doped LiNi0.5 Mn1.5 O4 Cathodes, Graphite Anodes, and the Cathode-Additive Li3 PO4.

This study addresses the improved cycling stability of Li-ion batteries based on Fe-Ti-doped LiNi0.5 Mn1.5 O4 (LNMO) high-voltage cathode active material and graphite anodes. By using 1 wt% Li3 PO4 as cathode additive, over 90% capacity retention for 1000 charge-discharge cycles and remaining capacities of 109 mAh g-1 are reached in a cell with an areal capacity of 2.3 mAh cm- 2 (potential range: 3.5-4.9 V). Cells without the additive, in contrast, suffer from accelerated capacity loss and increase polarization, resulting in capacity retention of only 78% over 1000 cycles. An electrolyte consisting of ethylene carbonate, dimethyl carbonate, and LiPF6 is used without additional additives. The significantly improved cycling stability of the full cells is mainly due to two factors, namely, the low MnIII content of the Fe-Ti-doped LNMO active material and the use of the cathode-additive Li3 PO4 . Crystalline Li3 PO4 yields a drastic reduction of transition metal deposition on the graphite anode and prevents Li loss and the propagation of cell polarization. Li3 PO4 is added to the cathode slurry that makes it a very simple and scalable process, first reported herein. The positive effects of crystalline Li3 PO4 as electrode additive, however, should apply to other cell chemistries as well.

Systematic Study of the Multiple Variables Involved in V2AlC Acid-Based Etching Processes, a Key Step in MXene Synthesis.

The realization of the broad range of application of MXenes relies on the successful and reproducible synthesis of quality materials of tailored properties. To date, most MXenes have been produced making use of acid-based etching methods, yet an in-depth understanding of etching processes is lacking. Herein, we have engaged in a comprehensive study of the multiple variables involved in the synthesis of V2CTx with focus on the properties of etched materials. Two main sets of experiments were considered, each using a different V2AlC precursor and a range of synthesis variables including reaction time and temperature, mixing rate, and type of acid. Correlations of synthesis conditions-materials properties were investigated using a broad range of characterization techniques including analytical methods, scanning and transmission electron microscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Findings indicated the crucial relevance of properties of the MAX precursor such as elemental composition, particle size, and crystal structure on etching processes and properties of etched materials. Particularly, depending on the MAX precursor, two etching patterns were identified, core-shell and plate-by-plate, the latter describing a more efficient etching. Combined studies of elemental composition, crystal structure, and yield quantification allowed us to evaluate the effectiveness of etching processes. XRD studies revealed key crystal-structure-type of acid correlations showing advantages of using a HF/HCl mix over only HF. Analytical methods XRD and XPS delivered insights into undergoing chemical processes and their influence on bulk and surface chemistry of etched materials. The relevance for reaction kinetics of highly correlated variables such as reaction vessel dimensions, mixing efficiency, and reaction temperature was recognized. For the first time, a MXene synthesis has been investigated comprehensively highlighting its multivariable nature and the high variable intercorrelation, opening up venues for further investigation on MAX and MXene synthesis.

Impurities in commercial titanium dental implants - A mass and optical emission spectrometry elemental analysis.

OBJECTIVE: Titanium (Ti) is considered bioinert and is still regarded as the "gold standard" material for dental implants. However, even 'commercial pure' Ti will contain minor fractions of elemental impurities. Evidence demonstrating the release of Ti ions and particles from 'passive' implant surfaces is increasing and has been attributed to biocorrosion processes which may provoke immunological reactions. However, Ti observed in peri-implant tissues has been shown to be co-located with elements considered impurities in biomedical alloys. Accordingly, this study aimed to quantify the composition of impurities in commercial Ti dental implants. METHODS: Fifteen commercial titanium dental implant systems were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS) and optical emission spectrometry (ICP-OES). RESULTS: The elemental composition of implants manufactured from commercially pure grades of Ti, Ti-6Al-4V, and the TiZr alloy (Roxolid) conformed to the respective ISO/ASTM standards or manufacturers´ data (TiZr/Roxolid). However, all implants investigated included exogenous metal contaminants including Ni, Cr, Sb, and Nb to a variable extent. Other contaminants detected in a fraction of implants included As and the radionuclides U-238 and Th-232. SIGNIFICANCE: Although all Ti implant studies conformed with their standard compositions, potentially allergenic, noxious metals and even radionuclides were detected. Since there are differences in the degree of contamination between the implant systems, a certain impurity fraction seems technically avoidable. The clinical relevance of these findings must be further investigated, and an adaptation of industry standards should be discussed.

Garnet to hydrogarnet: effect of post synthesis treatment on cation substituted LLZO solid electrolyte and its effect on Li ion conductivity.

We investigated why commercial Li7La3Zr2O12 (LLZO) with Nb- and Ta substitution shows very low mobility on a local scale, as observed with temperature-dependent NMR techniques, compared to Al and W substituted samples, although impedance spectroscopy on sintered pellets suggests something else: conductivity values do not show a strong dependence on the type of substituting cation. We observed that mechanical treatment of these materials causes a symmetry reduction from garnet to hydrogarnet structure. To understand the impact of this lower symmetric structure in detail and its effect on the Li ion conductivity, neutron powder diffraction and 6Li NMR were utilized. Despite the finding that, in some materials, disorder can be beneficial with respect to ionic conductivity, pulsed-field gradient NMR measurements of the long-range transport indicate a higher Li+ diffusion barrier in the lower symmetric hydrogarnet structure. The symmetry reduction can be reversed back to the higher symmetric garnet structure by annealing at 1100 °C. This unintended phase transition and thus a reduction in conductivity is crucial for the processing of LLZO materials in the fabrication of all-solid state batteries.

Lithium containing layered high entropy oxide structures.

Layered Delafossite-type Lix(M1M2M3M4M5…Mn)O2 materials, a new class of high-entropy oxides, were synthesized by nebulized spray pyrolysis and subsequent high-temperature annealing. Various metal species (M = Ni, Co, Mn, Al, Fe, Zn, Cr, Ti, Zr, Cu) could be incorporated into this structure type, and in most cases, single-phase oxides were obtained. Delafossite structures are well known and the related materials are used in different fields of application, especially in electrochemical energy storage (e.g., LiNixCoyMnzO2 [NCM]). The transfer of the high-entropy concept to this type of materials and the successful structural replication enabled the preparation of novel compounds with unprecedented properties. Here, we report on the characterization of a series of Delafossite-type high-entropy oxides by means of TEM, SEM, XPS, ICP-OES, Mössbauer spectroscopy, XRD including Rietveld refinement analysis, SAED and STEM mapping and discuss about the role of entropy stabilization. Our experimental data indicate the formation of uniform solid-solution structures with some Li/M mixing.

Synthesis and Characterization of a Multication Doped Mn Spinel, LiNi0.3Cu0.1Fe0.2Mn1.4O4, as 5 V Positive Electrode Material.

The suitability of multication doping to stabilize the disordered Fd3̅m structure in a spinel is reported here. In this work, LiNi0.3Cu0.1Fe0.2Mn1.4O4 was synthesized via a sol-gel route at a calcination temperature of 850 °C. LiNi0.3Cu0.1Fe0.2Mn1.4O4 is evaluated as positive electrode material in a voltage range between 3.5 and 5.3 V (vs Li+/Li) with an initial specific discharge capacity of 126 mAh g-1 at a rate of C/2. This material shows good cycling stability with a capacity retention of 89% after 200 cycles and an excellent rate capability with the discharge capacity reaching 78 mAh g-1 at a rate of 20C. In operando X-ray diffraction (XRD) measurements with a laboratory X-ray source between 3.5 and 5.3 V at a rate of C/10 reveal that the (de)lithiation occurs via a solid-solution mechanism where a local variation of lithium content is observed. A simplified estimation based on the in operando XRD analysis suggests that around 17-31 mAh g-1 of discharge capacity in the first cycle is used for a reductive parasitic reaction, hindering a full lithiation of the positive electrode at the end of the first discharge.

Elemental analysis of commercial zirconia dental implants - Is "metal-free" devoid of metals?

OBJECTIVES: The interest in ceramic dental implants made of yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) or alumina toughened zirconia (ATZ) has increased in recent years. However, in the light of aging, corrosion, and potential impurities of zirconia ceramics, the material composition of these implants and the associated term "metal-free" is persistently questioned. Thus, the present study aimed to conduct an elemental analysis of commercial zirconia dental implants to specify their elemental composition and to identify contaminants. METHODS: Nine commercial zirconia dental implant systems and corresponding material samples were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS) and optical emission spectrometry (ICP-OES). RESULTS: While the elemental composition was dominated by the main components Zr, Y and Al (in ATZ samples), all investigated samples contained impurities with Hf and contamination with alkali and alkali earth elements (Na, K, Mg, Ca), essential trace elements (e.g. Fe, Cu, Zn) but also potentially noxious metal elements (e.g. Ni, Cr). Furthermore, ultra-trace level contamination with the radionuclides U-238 and Th-232 was found in the majority of samples. SIGNIFICANCE: The results indicate that, although all the investigated Y-TZP and ATZ dental implants meet the currently relevant ISO standards and manufacturer's specifications, from an elemental point of view, they are not devoid of metals. Due to the lack of a universal definition and thresholds for the term "metal-free", the question of whether the examined zirconia dental implants can be holistically classified as "metal-free" or not remains a controversial, philosophical one.

Syntheses, Crystal Structure, Electrocatalytic, and Magnetic Properties of the Monolanthanide-Containing Germanotungstates [Ln(H2O) n GeW11O39]5- (Ln = Dy, Er, n = 4,3).

Two monolanthanide-containing polyanions based on monolacunary Keggin germanotungstates [Ln(H2O) n GeW11O39]5- (Ln = Dy, Er, n = 4,3) have been synthesized in simple one-pot synthetic procedure and compositionally characterized in solid state by single-crystal X-ray diffraction, powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and elemental analysis. Electronic absorption and emission spectra of the title compounds in solution were also studied. The [DyIII(H2O)4GeW11O39]5- Keggin POM exhibits a slow relaxation of magnetization. The cyclic voltammetry measurements and mass spectrometry were carried out to check the stability of the compounds in solution. Both polyanions prove efficient in the electrocatalytic reduction of nitrite. To our knowledge, this observation establishes the first example of electrocatalysis of nitrite reduction by all inorganic monolanthanide-containing germanotungstates family.

Characterization of Nanoparticle Batch-To-Batch Variability.

A central challenge for the safe design of nanomaterials (NMs) is the inherent variability of NM properties, both as produced and as they interact with and evolve in, their surroundings. This has led to uncertainty in the literature regarding whether the biological and toxicological effects reported for NMs are related to specific NM properties themselves, or rather to the presence of impurities or physical effects such as agglomeration of particles. Thus, there is a strong need for systematic evaluation of the synthesis and processing parameters that lead to potential variability of different NM batches and the reproducible production of commonly utilized NMs. The work described here represents over three years of effort across 14 European laboratories to assess the reproducibility of nanoparticle properties produced by the same and modified synthesis routes for four of the OECD priority NMs (silica dioxide, zinc oxide, cerium dioxide and titanium dioxide) as well as amine-modified polystyrene NMs, which are frequently employed as positive controls for nanotoxicity studies. For 46 different batches of the selected NMs, all physicochemical descriptors as prioritized by the OECD have been fully characterized. The study represents the most complete assessment of NMs batch-to-batch variability performed to date and provides numerous important insights into the potential sources of variability of NMs and how these might be reduced.

Molecular Surface Modification of NCM622 Cathode Material Using Organophosphates for Improved Li-Ion Battery Full-Cells.

Surface coating is a viable strategy for improving the cyclability of Li1+ x(Ni1- y- zCo yMn z)1- xO2 (NCM) cathode active materials for lithium-ion battery cells. However, both gaining synthetic control over thickness and accurate characterization of the surface shell, which is typically only a few nm thick, are considerably challenging. Here, we report on a new molecular surface modification route for NCM622 (60% Ni) using organophosphates, specifically tris(4-nitrophenyl) phosphate (TNPP) and tris(trimethylsilyl) phosphate. The functionalized NCM622 was thoroughly characterized by state-of-the-art surface and bulk techniques, such as attenuated total reflection infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS), to name a few. The comprehensive ToF-SIMS-based study comprised surface imaging, depth profiling, and three-dimensional visualization. In particular, tomography is a powerful tool to analyze the nature and morphology of thin coatings and is applied, to our knowledge, for the first time, to a practical cathode active material. It provides valuable information about relatively large areas (over several secondary particles) at high lateral and mass resolution. The electrochemical performance of the different NCM622 materials was evaluated in long-term cycling experiments of full-cells with a graphite anode. The effect of surface modification on the transition-metal leaching was studied ex situ via inductively coupled plasma optical emission spectroscopy. TNPP@NCM622 showed reduced transition-metal dissolution and much improved cycling performance. Taken together, with this study, we contribute to optimization of an industrially relevant cathode active material for application in high-energy-density lithium-ion batteries.

Synthesis and Characterization of a Heterometallic Extended Architecture Based on a Manganese(II)-Substituted Sandwich-Type Polyoxotungstate.

The reaction of [α-P2W15O56]12- with MnII and DyIII in an aqueous basic solution led to the isolation of an all inorganic heterometallic aggregate Na10(OH2)42[{Dy(H2O)6}2Mn4P4W30O112(H2O)2]·17H2O (Dy2Mn4-P2W15). Single-crystal X-ray diffraction revealed that Dy2Mn4-P2W15 crystallizes in the triclinic system with space group P 1 ¯ , and consists of a tetranuclear manganese(II)-substituted sandwich-type phosphotungstate [Mn4(H2O)2(P2W15O56)2]16- (Mn4-P2W15), Na, and DyIII cations. Compound Dy2Mn4-P2W15 exhibits a 1D ladder-like chain structure based on sandwich-type segments and dysprosium cations as linkers, which are further connected into a three-dimensional open framework by sodium cations. The title compound was structurally and compositionally characterized in solid state by single-crystal XRD, powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric (TGA), and elemental analyses. Further, the absorption and emission electronic spectra in aqueous solutions of Dy2Mn4-P2W15 and Mn4-P2W15 were studied. Also, magnetic properties were studied and compared with the magnetic behavior of [Mn4(H2O)2(P2W15O56)2]16-.

Performance Improvement of V-Fe-Cr-Ti Solid State Hydrogen Storage Materials in Impure Hydrogen Gas.

Two approaches of engineering surface structures of V-Ti-based solid solution hydrogen storage alloys are presented, which enable improved tolerance toward gaseous oxygen (O2) impurities in hydrogen (H2) gas. Surface modification is achieved through engineering lanthanum (La)- or nickel (Ni)-rich surface layers with enhanced cyclic stability in an H2/O2 mixture. The formation of a Ni-rich surface layer does not improve the cycling stability in H2/O2 mixtures. Mischmetal (Mm, a mixture of La and Ce) agglomerates are observed within the bulk and surface of the alloy when small amounts of this material are added during arc melting synthesis. These agglomerates provide hydrogen-transparent diffusion pathways into the bulk of the V-Ti-Cr-Fe hydrogen storage alloy when the remaining oxidized surface is already nontransparent for hydrogen. Thus, the cycling stability of the alloy is improved in an O2-containing hydrogen environment as compared to the same alloy without addition of Mm. The obtained surface-engineered storage material still absorbs hydrogen after 20 cycles in a hydrogen-oxygen mixture, while the original material is already deactivated after 4 cycles.

Tin Tungstate Nanoparticles: A Photosensitizer for Photodynamic Tumor Therapy.

The nanoparticulate inorganic photosensitizer ß-SnWO4 is suggested for photodynamic therapy (PDT) of near-surface tumors via reiterated 5 min blue-light LED illumination. ß-SnWO4 nanoparticles are obtained via water-based synthesis and comprise excellent colloidal stability under physiological conditions and high biocompatibility at low material complexity. Antitumor and antimetastatic effects were investigated with a spontaneously metastasizing (4T1 cells) orthotopic breast cancer BALB/c mouse model. Besides protamine-functionalized ß-SnWO4 (23 mg/kg of body weight, in PBS buffer), chemotherapeutic doxorubicin was used as positive control (2.5 mg/kg of body weight, in PBS buffer) and physiological saline (DPBS) as a negative control. After 21 days, treatment with ß-SnWO4 resulted in a clearly inhibited growth of the primary tumor (all tumor volumes below 3 cm(3)) as compared to the doxorubicin and DPBS control groups (volumes up to 6 cm(3)). Histological evaluations of lymph nodes and lungs as well as the volume of ipsilateral lymph nodes show a remarkable antimetastatic effect being similar to chemotherapeutic doxorubicin but-according to blood counts-at significantly reduced side effects. On the basis of low material complexity, high cytotoxicity under blue-light LED illumination at low dark and long-term toxicity, ß-SnWO4 can be an interesting addition to PDT and the treatment of near-surface tumors, including skin cancer, esophageal/gastric/colon tumors as well as certain types of breast cancer.

Gas Evolution in LiNi0.5Mn1.5O4/Graphite Cells Studied In Operando by a Combination of Differential Electrochemical Mass Spectrometry, Neutron Imaging, and Pressure Measurements.

The cycling performance and in operando gas analysis of LiNi0.5Mn1.5O4 (LNMO)/graphite cells with reasonably high loading, containing a "standard" carbonate-based electrolyte is reported. The gas evolution over the first couple of cycles was thoroughly investigated via differential electrochemical mass spectrometry (DEMS), neutron imaging and pressure measurements. The main oxidation and reduction products were identified as CO2, H2 and C2H4. In different sets of experiments graphite was substituted with delithiated LiFePO4 (LFP) and LNMO with LFP to distinguish between processes occurring at either anode or cathode and gain mechanistic insights. Both C2H4 and H2 were found to be mainly formed at the anode side, while CO2 is generated at the cathode. The results from DEMS analysis further suggest that the Ni redox couples play a profound role in the evolution of CO2 at the LNMO/electrolyte interface. Lastly, it is shown that the cycling stability and capacity retention of LNMO/graphite cells can be considerably improved by a simple cell formation procedure.

Electrolyte Mixtures Based on Ethylene Carbonate and Dimethyl Sulfone for Li-Ion Batteries with Improved Safety Characteristics.

In this study, novel electrolyte mixtures for Li-ion cells are presented with highly improved safety features. The electrolyte formulations are composed of ethylene carbonate/dimethyl sulfone (80:20 wt/wt) as the solvent mixture and LiBF4 , lithium bis(trifluoromethanesulfonyl)azanide, and lithium bis(oxalato)borate as the conducting salts. Initially, the electrolytes are characterized with regard to their physical properties, their lithium transport properties, and their electrochemical stability. The key advantages of the electrolytes are high flash points of >140 °C, which enhance significantly the intrinsic safety of Li-ion cells containing these electrolytes. This has been quantified by measurements in an accelerating rate calorimeter. By using the newly developed electrolytes, which are liquid down to T=-10 °C, it is possible to achieve C-rates of up to 1.5 C with >80 % of the initial specific capacity. During 100 cycles in cell tests (graphite||LiNi1/3 Co1/3 Mn1/3 O2 ), it is proven that the retention of the specific capacity is >98 % of the third discharge cycle with dependence on the conducting salt. The best electrolyte mixture yields a capacity retention of >96 % after 200 cycles in coin cells.