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1. Manipulating ionic conductivity through chemical modifications in solid-state electrolytes prepared with binderless laser powder bed fusion processing

   https://doi.org/10.1088/2515-7655/ad249a  

   Acord, Katherine A. ; Dupuy, Alexander D. ; Chen, Qian Nataly ; Schoenung, Julie M. ( February 2024 , Journal of Physics: Energy)

   Additive manufacturing of solid-state batteries is advantageous for improving the power density by increasing the geometric complexity of battery components, such as electrodes and electrolytes. In the present study, bulk three-dimensional Li_1+xAl_xTi_2−x(PO₄)₃(LATP) electrolyte samples were prepared using the laser powder bed fusion (L-PBF) additive manufacturing method. Li₃PO₄(LPO) was added to LATP to compensate for lithium vaporization during processing. Chemical compositions included 0, 1, 3, and 5 wt. % LPO. Resulting ionic conductivity values ranged from 1.4 × 10⁻⁶–6.4 × 10⁻⁸S cm⁻¹, with the highest value for the sample with a chemical composition of 3 wt. % LPO. Microstructural features were carefully measured for each chemical composition and correlated with each other and with ionic conductivity. These features and their corresponding ranges include: porosity (ranging from 5% to 19%), crack density (0.09–0.15 mm mm⁻²), concentration of residual LPO (0%–16%), and concentration and Feret diameter of secondary phases, AlPO4 (11%–18%, 0.40–0.61µm) and TiO2 (9%–11%, 0.50–0.78). Correlations between the microstructural features and ionic conductivity ranged from −0.88 to 0.99. The strongest negative correlation was between crack density and ionic conductivity (−0.88), confirming the important role that processing defects play in limiting the performance of bulk solid-state electrolytes. The strongest positive correlation was between the concentration of AlPO4 and ionic conductivity (0.99), which is attributed to AlPO4 acting as a sintering aid and the role it plays in reducing the crack density. Our results indicate that additions of LPO can be used to balance competing microstructural features to design bulk three-dimensional LATP samples with improved ionic conductivity. As such, refinement of the chemical composition offers a promising approach to improving the processability and performance of functional ceramics prepared using binderless, laser-based additive manufacturing for solid-state battery applications.

    

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2. Measured and simulated thermoelectric properties of FeAs 2−x Se x ( x = 0.30–1.0): from marcasite to arsenopyrite structure

   https://doi.org/10.1039/d0ma00371a  

   Perez, Christopher J. ; Devlin, Kasey P. ; Skaggs, Callista M. ; Tan, Xiaoyan ; Frank, Corey E. ; Badger, Jackson R. ; Kang, Chang-Jong ; Emge, Thomas J. ; Kauzlarich, Susan M. ; Taufour, Valentin ; et al ( August 2020 , Materials Advances)

   null (Ed.)

   FeAs 2−x Se x ( x = 0.30–1.0) samples were synthesized as phase pure powders by conventional solid-state techniques and as single crystals ( x = 0.50) from chemical vapor transport. The composition of the crystals was determined to be Fe 1.025(3) As 1.55(3) Se 0.42(3) , crystallizing in the marcasite structure type, Pnnm space group. FeAs 2−x Se x (0 < x < 1) was found to undergo a marcasite-to-arsenopyrite ( P 2 1 / c space group) structural phase transition at x ∼ 0.65. The structures are similar, with the marcasite structure best described as a solid solution of As/Se, whereas the arsenopyrite has ordered anion sites. Magnetic susceptibility and thermoelectric property measurements from 300–2 K were performed on single crystals, FeAs 1.50 Se 0.50 . Paramagnetic behavior is observed from 300 to 17 K and a Seebeck coefficient of −33 μV K −1 , an electrical resistivity of 4.07 mΩ cm, and a very low κ l of 0.22 W m −1 K −1 at 300 K are observed. In order to determine the impact of the structural transition on the high-temperature thermoelectric properties, polycrystalline FeAs 2−x Se x ( x = 0.30, 0.75, 0.85, 1.0) samples were consolidated into dense pellets for measurements of thermoelectric properties. The x = 0.85 sample shows the best thermoelectric performance. The electronic structure of FeAsSe was calculated with DFT and transport properties were approximately modeled above 500 K. 

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3. (Digital Presentation) Activating the Ion Transmission at the Cathode-Electrolyte Interface in All-Solid-State Batteries

   https://doi.org/10.1149/MA2022-012384mtgabs  

   Zhang, Yuxuan ; Kivevele, Thomas ; Song, Han Wook ; Lee, Sunghwan ( July 2022 , ECS Meeting Abstracts)

   All-solid-state batteries (ASSBs) have garnered increasing attention due to the enhanced safety, featuring nonflammable solid electrolytes as well as the potential to achieve high energy density. 1 The advancement of the ASSBs is expected to provide, arguably, the most straightforward path towards practical, high-energy, and rechargeable batteries based on metallic anodes. 1 However, the sluggish ion transmission at the cathode-electrolyte (solid/solid) interface would result in the high resistant at the contact and limit the practical implementation of these all solid-state materials in real world batteries. 2 Several methods were suggested to enhance the kinetic condition of the ion migration between the cathode and the solid electrolyte (SE). 3 A composite strategy that mixes active materials and SEs for the cathode is a general way to decrease the ion transmission barrier at the cathode-electrolyte interface. 3 The active material concentration in the cathode is reduced as much as the SE portion increases by which the energy density of the ASSB is restricted. In addition, the mixing approach generally accompanies lattice mismatches between the cathode active materials and the SE, thus providing only limited improvements, which is imputed by random contacts between the cathode active materials and the SE during the mixing process. Implementing high-pressure for the electrode and electrolyte of ASSB in the assembling process has been verified is a but effective way to boost the ion transmission ability between the cathode active materials and the SE by decreasing the grain boundary impedance. Whereas the short-circuit of the battery would be induced by the mechanical deformation of the electrolyte under high pressure. 4 Herein, we demonstrate a novel way to address the ion transmission problem at the cathode-electrolyte interface in ASSBs. Starting from the cathode configuration, the finite element method (FEM) was employed to evaluate the current concentration and the distribution of the space charge layer at the cathode-electrolyte interface. Hierarchical three-dimensional (HTD) structures are found to have a higher Li + transfer number (t Li+ ), fewer free anions, and the weaker space-charge layer at the cathode-electrolyte interface in the resulting FEM simulation. To take advantage of the HTD structure, stereolithography is adopted as a manufacturing technique and single-crystalline Ni-rich (SCN) materials are selected as the active materials. Next, the manufactured HTD cathode is sintered at 600 °C in an N 2 atmosphere for the carbonization of the resin, which induces sufficient electronic conductivity for the cathode. Then, the gel-like Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP) precursor is synthesized and filled into the voids of the HTD structure cathode sufficiently. And the filled HTD structure cathodes are sintered at 900 °C to achieve the crystallization of the LATP gel. Scanning transmission electron microscopy (STEM) is used to unveil the morphology of the cathode-electrolyte interface between the sintered HTD cathode and the in-situ generated electrolyte (LATP). A transient phase has been found generated at the interface and matched with both lattices of the SCN and the SE, accelerating the transmission of the Li-ions, which is further verified by density functional theory calculations. In addition, Electron Energy Loss Spectroscopy demonstrates the preserved interface between HTD cathode and SEs. Atomic force microscopy is employed to measure the potential image of the cross-sectional interface by the peak force tapping mode. The average potential of modified samples is lower than the sample that mix SCN and SEs simply in the 2D planar structure, which confirms a weakened space charge layer by the enhanced contact capability as well as the ion transmission ability. To see if the demonstrated method is universally applicable, LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is selected as the cathode active material and manufactured in the same way as the SCN. The HTD cathode based on NCM811 exhibits higher electrochemical performance compared with the reference sample based on the 2D planar mixing-type cathode. We believe such a demonstrated universal strategy provides a new guideline to engineer the cathode/electrolyte interface by revolutionizing electrode structures that can be applicable to all-solid-state batteries. Figure 1. Schematic of comparing of traditional 2D planar cathode and HTD cathode in ASSB Tikekar, M. D. , et al. , Nature Energy (2016) 1 (9), 16114 Banerjee, A. , et al. , Chem Rev (2020) 120 (14), 6878 Chen, R. , et al. , Chem Rev (2020) 120 (14), 6820 Cheng, X. , et al. , Advanced Energy Materials (2018) 8 (7) Figure 1 

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4. Synthetic versatility, reaction pathway, and thermal stability of tetrahedrite nanoparticles

   https://doi.org/10.1039/d0tc03599h  

   Fasana, Christine D. ; Jensen, Mitchel S. ; García Ponte, Graciela E. ; MacAlister, Tyler R. ; Kunkel, Grace E. ; Rogers, John P. ; Ochs, Andrew M. ; Stevens, Daniel L. ; Weller, Daniel P. ; Morelli, Donald T. ; et al ( October 2020 , Journal of Materials Chemistry C)

   null (Ed.)

   Copper-antimony-sulfide compounds have desirable earth-abundant compositions for application in renewable energy technologies, such as solar energy and waste heat recycling. These compounds can be synthesized by bottom-up, solution-phase techniques that are more energy and time efficient than conventional solid-state methods. Solution-phase methods typically produce nanostructured materials, which adds another dimension to control optical, electrical, and thermal material properties. This study focuses on a modified-polyol, solution-phase synthesis for tetrahedrite (Cu 12 Sb 4 S 13 ), a promising thermoelectric material with potential also for photovoltaic applications. To dope the tetrahedrite and tune material properties, the utility of the modified polyol synthetic approach has been demonstrated as a strategy to produce phase-pure tetrahedrite that incorporates transition metal (Fe, Co, Ni, Zn, Ag) dopants for Cu, Te dopant for Sb, and Se for S. Six of these reported tetrahedrite compounds have not previously been made by solution-phase methods. For the bottom-up formation of the tetrahedrite nanomaterials, the evolution of the chemical phases has been determined by an investigation of the reaction progress as a function of temperature and time. Digenite (Cu 1.8 S), covellite (CuS), and famatinite (Cu 3 SbS 4 ) are identified as key intermediates and are consistently observed for both undoped and doped tetrahedrites. The effect of nanostructuring and doping tetrahedrite on thermal properties has been investigated. It was found that nanostructured undoped tetrahedrite has reduced thermal stability relative to samples made by solid-state methods, while the addition of dopants for Cu increased the thermal stability of the material. Crystallinity, composition, and nanostructure of products and intermediates were characterized by powder X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy, and transmission electron microscopy. Thermal properties were investigated by differential scanning calorimetry and thermal gravimetric analysis. This synthetic study with thermal property analysis demonstrates the potential of the modified polyol method to produce tetrahedrite and other copper-antimony-sulfide compounds for thermoelectric and photovoltaic applications. 

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5. Investigating the Relationship between Nitrate, Total Dissolved Nitrogen, and Phosphate with Abundance of Pathogenic Vibrios and Harmful Algal Blooms in Rehoboth Bay, Delaware

   https://doi.org/10.1128/aem.00356-22  

   Rosales, Detbra ; Ellett, Ava ; Jacobs, John ; Ozbay, Gulnihal ; Parveen, Salina ; Pitula, Joseph ( July 2022 , Applied and Environmental Microbiology)

   Dozois, Charles M. (Ed.)

   ABSTRACT Vibrio spp. and phytoplankton are naturally abundant in marine environments. Recent studies have suggested that the co-occurrence of phytoplankton and the pathogenic bacterium Vibrio parahaemolyticus is due to shared ecological factors, such as nutrient requirements. We compared these communities at two locations in the Delaware Inland Bays, representing a site with high anthropogenic inputs (Torquay Canal) and a less developed area (Sloan Cove). In 2017 to 2018, using light microscopy, we were able to identify the presence of many bloom-forming algal species, such as Karlodinium veneficum , Dinophysis acuminata , Heterosigma akashiwo , and Chattonella subsalsa . Dinoflagellate biomass was higher at Torquay Canal than that at Sloan Cove. D. acuminata and Chloromorum toxicum were found only at Torquay Canal and were not observed in Sloan Cove. Most probable number real-time PCR revealed V. parahaemolyticus and Vibrio vulnificus in environmental samples. The abundance of vibrios and their virulence genes varied between sites, with a significant association between total dissolved nitrogen (TDN), PO 4 − , total dissolved phosphorus (TDP), and pathogenic markers. A generalized linear model revealed that principal component 1 of environmental factors (temperature, dissolved oxygen, salinity, TDN, PO 4 − , TDP, NO 3 :NO 2 , NO 2 − , and NH 4 + ) was the best at detecting total ( tlh+ ) V. parahaemolyticus , suggesting that they are the prime drivers for the growth and distribution of pathogenic Vibrio spp. IMPORTANCE Vibrio-associated illnesses have been expanding globally over the past several decades (A. Newton, M. Kendall, D. J. Vugia, O. L. Henao, and B. E. Mahon, Clin Infect Dis 54:S391–S395, 2012, https://doi.org/10.1093/cid/cis243 ). Many studies have linked this expansion with an increase in global temperature (J. Martinez-Urtaza, B. C. John, J. Trinanes, and A. DePaola, Food Res Int 43:10, 2010, https://doi.org/10.1016/j.foodres.2010.04.001 ; L. Vezzulli, R. R. Colwell, and C. Pruzzo, Microb Ecol 65:817–825, 2013, https://doi.org/10.1007/s00248-012-0163-2 ; R. N. Paranjpye, W. B. Nilsson, M. Liermann, and E. D. Hilborn, FEMS Microbiol Ecol 91:fiv121, 2015, https://doi.org/10.1093/femsec/fiv121 ). Temperature and salinity are the two major factors affecting the distribution of Vibrio spp. (D. Ceccarelli and R. R. Colwell, Front Microbiol 5:256, 2014, https://doi.org/10.3389/fmicb.2014.00256 ). However, Vibrio sp. abundance can also be affected by nutrient load and marine plankton blooms (V. J. McKenzie and A. R. Townsend, EcoHealth 4:384–396, 2007; L. Vezzulli, C. Pruzzo, A. Huq, and R. R. Colwell, Environ Microbiol Rep 2:27–33, 2010, https://doi.org/10.1111/j.1758-2229.2009.00128.x ; S. Liu, Z. Jiang, Y. Deng, Y. Wu, J. Zhang, et al. Microbiologyopen 7:e00600, 2018, https://doi.org/10.1002/mbo3.600 ). The expansion of Vibrio spp. in marine environments calls for a deeper understanding of the biotic and abiotic factors that play a role in their abundance. We observed that pathogenic Vibrio spp. were most abundant in areas that favor the proliferation of harmful algal bloom (HAB) species. These results can inform managers, researchers, and oyster growers on factors that can influence the growth and distribution of pathogenic Vibrio spp. in the Delaware Inland Bays. 

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