bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modeling Mesoporous 3D-Printed Lattice Electrodes for Energy Storage
Authors: Huddy Julia Elizabeth , Tiwari Anand P , Scheideler William Joseph 
Published: September 2023

3D printing could offer the versatility to design and manufacture energy storage devices on demand. The precision and material flexibility of 3D printing is ideal for integrating porous electrodes that can enhance electrochemical performance[1]. This work analyzes the electrical conductivity of 3D-printed mesoscale strut lattices at the 100 μm – 1 mm scale with 40 – 90 % volumetric porosity to develop optimal electrodes for energy storage devices. We use a graph-theory-based model[2] to compute the conductivity of multiple 3D lattice types with either solid conducting struts or struts coated with conductive material. These structures show 3 – 5X higher conductivity than random conductive foams that lack an internal periodic mesostructure[3]. Using microstereolithography, we 3D print samples with high-resolution struts (< 70 µm) that maintain their shape and achieve high conductivity after carbonization at 700 ˚C. By tuning the lattice architecture, we manipulate the tradeoff between conductivity, weight, and porosity, validating our simulations with experimental measurements. These results demonstrate that that body-centered cubic (BCC) strut lattices have optimal conductivity per weight compared with other lattice types.
Implementing these 3D-printed conductive lattices as supercapacitor electrodes, we see that the lattice architecture impacts the gravimetric capacitance of the devices as well as the mechanical strength, with octet structures outperforming both cubic and BCC lattices. Electrochemical impedance spectroscopy (EIS) shows that 3D-printed electrodes with higher porosity exhibit higher gravimetric double layer capacitance and lower charge transfer resistance, making them ideal candidates for use in supercapacitor electrodes as free-standing 3D hosts for active materials. CV characterization of the electrodes also illustrates how our graph theory-based model for 3D lattices can predict the optimal structure for energy storage. This model can also serve to predict electrode performance and tailor design for integration of higher surface area nanoporous materials on these conductive 3D printed scaffolds. This allows us to guide the design of 3D printed electrodes to minimize charge transfer resistance and achieve an optimal balance between gravimetric and volumetric energy density for device applications.
[1] J. Zhao, Y. Zhang, X. Zhao, R. Wang, J. Xie, C. Yang, J. Wang, Q. Zhang, L. Li, C. Lu, Y. Yao, Advanced Functional Materials
2019, 29, 1900809.
[2] J. E. Huddy, M. S. Rahman, A. B. Hamlin, Y. Ye, W. J. Scheideler, Cell Reports Physical Science
2022, 3, 100786.
[3] F. G. Cuevas, J. M. Montes, J. Cintas, P. Urban, J Porous Mater
2008, 16, 675.

Figure showing (a) designed octet (blue), cubic (orange), and BCC (red) lattice types as well as (b) SEM images of their experimental 3D-printed counterparts and (c) measured electrical resistance.

Figure 1
Electrochemical Applications of Porous Materials Derived from Coal
Authors: Paul Abigail , Magee Regan , Wichert Nathan , Wilczewski Warren , Trembly Jason , Garrick Taylor R. , Staser John A. 
Published: September 2023

As the world shifts from the use of coal to alternatives for electricity generation, including renewable energy, interest arises in developing alternative uses for coal. There are vast U.S. coal reserves, much of which are in historically underrepresented or economically depressed regions. This has created environmental concerns in these regions, especially related to legacy impoundments and other waste coal issues. Finding alternative uses for that coal could create new job opportunities in these regions while also addressing climate change. Currently, there are very few applications for coal outside of its traditional use for electricity production.
This group has been developing alternative uses for coal, including uses in energy storage applications. This presentation will discuss the development of macroporous coal materials that then can be further processed into micron or nanometer size particles for porous materials. The characterization of these porous materials will be presented. Graphitized materials for use in lithium ion battery electrodes will be presented. Nanoscale materials such as graphene and carbon quantum dots derived from coal will be presented, along with their application in porous electrodes for batteries and capacitors.
Development of a New Type of Electrochemical Reactor for Low Temperature Lime and Cement Production
Authors: Loudeche Maxime , Rouxhet Rémy , Proost Joris 
Published: September 2023

The cement industry is responsible for more than 8% of the global CO2 emissions, making it one of the largest contributors to global warming. Two-thirds of these emissions are coming from unavoidable process gases caused by the calcination reaction of limestone (CaCO3). The remaining emissions are mainly coming from the combustion of fossil fuels. Due to the high temperature requirement (≈1500°C), direct electrification is difficult to consider. For these two reasons, the cement industry is therefore known as a challenging sector to decarbonize.
A new electrochemical pathway for cement production has gained prominence in the scientific literature in recent years [1]. This technology has the potential to electrify the cement and lime production while producing at the same time valuable gases (O2, CO2, H2). It is based on a new type of hybrid electrolyser capable of working with solid, liquid and gaseous phases. Thanks to the acidity generated by water oxidation at the anode, the solid limestone feed, precursor of cement, is being dissolved. This dissolution produces pure CO2 which is mixed with pure O2 generated by electrolysis and which is easily captured for later use. The calcium ions are then migrating towards the cathode under the effect of the electric field. The OH- hydroxyl ions, produced at the cathode by water reduction, meet the calcium ions to form the final solid product, hydrated lime (Ca(OH)2). This lime can be used as such or converted into cement by additional steps.
In this research, a laboratory-scale setup has been developed to study the feasibility of such a process. Different geometries have been tested and the main operational parameters affecting the different steps of the process have been investigated. Our results show first of all the formation and stabilization of a pH gradient within the electrolyser, which allows at the same time for the complete dissolution of CaCO3 in the acidic anodic environment while producing a white precipitate of Ca(OH)2 at the cathode. The setup also presents ideal faradaic efficiencies when using an IrO2 coated titanium anode and a nickel cathode in a 1M NaClO4 electrolyte. Alternative electrode materials, including a 316L stainless steel anode and an Inconel 718 cathode, have been considered as well. Finally, it was shown that the energetic efficiency can be further improved by pushing the kinetics of the dissolution and precipitation reactions through increasing the mobility of calcium ions, using Ca-based electrolytes, like Ca(ClO4)2. Based on our results, all the elementary concepts behind the hybrid electrolyser have been established, and a first blueprint of a continuous industrial process will be proposed.
[1] - L. D. Ellis, et al. (2019). Toward electrochemical synthesis of cement—An electrolyzer-based process for decarbonating CaCO3 while producing useful gas streams. PNAS
, 117, 12584-12591.

Figure 1
Alternating Current Electrolytic Extraction of Transition Metals from NMC532 using Rotating Disc Cyclic Voltammetry in Dilute Chloride Solution
Authors: Watson Bryce , Carlson Brett , Smirnova Alevtina 
Published: September 2023

The rising application of portable electric devices has led to the rapid accumulation of electronic wastes such as lithium-ion batteries. These wastes pose significant environmental threats when improperly disposed of and contain valuable metals that could supplement the supply chain and reduce the need for certain conflict minerals. Recycling methods that limit the potential for environmental damage and improve separation of transition metals are vital to the sustainability of battery based electrical storage. Conventional aqueous recycling of lithium battery electrode materials utilizes oxidizing acids and a chemical reducing agent. This study investigates if chemical oxidizing and reducing agents may be aided or replaced by the application of an alternating electric field to reduce surface metal oxides and subsequently accelerate reoxidation with a solubilizing anion. The electrolytic leaching mechanics of commercial battery cathode material (NMC532) in dilute hydrochloric acid were investigated using rotating disc cyclic voltammetry (RDE-CV), solution analysis with inductively coupled plasma mass spectrometry (ICP-MS), and residue analysis with scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS). We found evidence that applying an alternating electric field allows for adjustment of leaching rates for different transition metals based on electrochemical cell parameters. By applying up to one volt oscillating between reducing and oxidizing polarity, the relative molar leaching rate of nickel and manganese drastically increased while that of cobalt slightly decreased. Future research will be required to determine how this effect translates to different leaching systems and its applicability to an industrial scale process.
The authors acknowledge financial support from the NSF IUCRC program for the “Center for solid-state electric power storage” (#2052631) and support from the South Dakota Board of Regents for the “Governor’s Research Center (GRC) for electrochemical energy storage”.
Rapid and Reversible Lithium Insertion with Multielectron Redox in the Wadsley-Roth Compound NaNb13O33
Authors: Patterson Ashlea , Elizalde Segovia Rodrigo , Wyckoff Kira , Zohar Arava , Narayan Sri , Clement Raphaele J , Seshadri Ram , Griffith Kent 
Published: September 2023

The development of high-performing battery materials is critical to meet the ever-increasing demand for portable energy storage for electronics and electric vehicles. Owing to their exceptionally high-rate capabilities, high volumetric capacities and long lifetimes, Wadsley-Roth compounds are promising lithium anode materials for fast-charging and high-powered devices. This study comprises an in-depth structural and initial electrochemical investigation of the Wadsley-Roth phase NaNb13O33 phase. To our knowledge, this is the first alkali-containing Wadsley-Roth compound tested for lithium insertion.
Here, we report structural insights obtained from combined neutron and synchrotron diffraction as well as solid-state nuclear magnetic resonance (ss-NMR). We find that a variety of simple, solid-state methods reliably produce a ReO6-like base structure with periodic, ”shear” planes of edge-sharing NbO6 octahedra separating 5 x 3 octahedral blocks with square-planar Na+ occupying block corners. Through ss-NMR, we reveal the presence of sodium cations in block interior sites as well as square-planar block sites.
Through combined experimental and computational studies, we demonstrate and rationalize the high-rate performance of this new anode material in lithium-ion half cells. Using X-ray photoelectron spectroscopy (XPS), we show the multi-electron redox of Nb, which enables capacities of 225 mA h g−1 at slow rates and anodic potentials. Without down-sizing or nano-scaling, 100 mA h g−1 of this capacity is retained at 20 C in micrometer-scale particles. By combining bond-valence mapping and DFT, we show that such excellent rate performance results from facile, multi-channel lithium diffusion down octahedral block interiors and from high electronic conductivity within shear planes. Finally, we utilize differential capacity analysis to identify optimal long-term cycling rates and achieve 80% capacity retention over 600 cycles with 30-minute charging and discharging intervals.
Without optimization, these results place NaNb13O33 in the ranks of promising new high-rate lithium anode materials and warrant further research.
Low Temperature Niobium Tungsten Oxides as Anodes for Fast Charging Li-Ion Batteries
Authors: Nagendran Supreeth , Grey Clare P. 
Published: September 2023

The development of fast-charging Li-ion batteries is one of the important steps in building electric vehicles that need high power and fast charging. The reduction in the particle size to the nanometre length scale drastically improves the charging rate by increasing the surface area but lowers the volumetric energy density and can potentially result in more rapid degradation of the electrolyte via electrode-catalysed reactions. Recent reports show that niobium tungsten oxides (NbWOs) with µm sized particles serve as good anode materials for Li-ion batteries having high volumetric capacity with good cyclability at high rates while avoiding solid electrolyte interphase formation (SEI). The high rate performance of NbWOs is attributed to the topochemical charge storage mechanism that exhibits (i) minimal, highly reversible structural changes during the charge-discharge cycles, (ii) high Li-ion diffusion coefficients due to the presence of fast conducting tunnels, and (iii) high electronic conductivity upon lithiation.1,2 The NbWOs are known to crystallize into two families of different crystal structures depending on the composition and synthesis conditions. The NbWOs phases can either have tungsten bronze-type structures or block-type structures (commonly referred to as Wadsley-Roth phases). Different NbWO phases are reported in the literature3 which could serve as potential anode materials with better performance.
In this work, a series of new NbWO phases have been synthesized at reduced annealing temperatures and the structure of these phases has been established using X-ray and neutron diffraction data. The electrochemical properties of NbWO/Li half cells were examined through a series of galvanostatic (dis)charge tests at varying current rates ranging from 0.2 C to 20 C. The NbWO phases delivers a high reversible capacity of 200 and 130 mAh/g at 0.2C and 10 C respectively vs. Li metal. Here we use operando powder X-ray diffraction to investigate the structural changes occurring at the anode during the charge-discharge process in the newly synthesised NbWO phases.

Reference
s
:

1 K. J. Griffith, K. M. Wiaderek, G. Cibin, L. E. Marbella and C. P. Grey, Nature, 2018, 559, 556–563.
2 C. P. Koçer, K. J. Griffith, C. P. Grey and A. J. Morris, Chem. Mater., 2020, 32, 3980–3989.
3 N. C. Stephenson, Acta Crystallogr. Sect. B Struct. Crystallogr. Cryst. Chem., 1968, 24, 637–653.

Figure 1
Microwave-Assisted Sol-Gel Synthesis of High-Voltage Ruthenium-Doped LiFePO4 Cathodes for Solid-State Lithium-Ion Batteries
Authors: Rodmyre Collin , Zheng Fan , Smirnova Alevtina 
Published: September 2023

The demand for high voltage and high-capacity energy systems has grown due to increased use of portable electronics, electric vehicles, and grid energy storage systems. LiFePO4 (LFP) shows great promise as a cathode material due to its low cost, structural stability, safety characteristics, and low environmental impact. However, LFP cathodes possess a low Li-ion diffusion coefficient and poor electrical conductivity compared to oxide-based cathodes that are used currently. To make LFP competitive with oxide-based cathodes, LFP was modified to improve its characteristics. Doping of materials is a highly effective method for improving electrochemical characteristics in LFP cathodes. Ruthenium-doping of iron sites within LFP has shown positive effects in the promotion of Li-ion diffusion, reduction in band gap energies, and improved electrical conductivity. Previous studies have shown that ruthenium-doping at 0.01 moles has an increased specific capacity of 162 mAh g-1, better cycling characteristics, and reduced resistance compared to pristine LFP.1 Ruthenium doping levels above 0.02 moles have shown a decrease in specific capacity, cycling characteristics, and an increased resistance due to the formation of ruthenium oxide that disrupts the crystal lattice of LFP. In this study, LiFe1-xRuxPO4 (x= 0.01, 0.0075, and 0.005) and pristine LFP were prepared via microwave-assisted sol-gel synthesis to explore the effects of lower levels of ruthenium-doping on LFP electrochemical characteristics. Microwave synthesis was employed for reduced sintering time, beneficial effects on microstructure, and decreased cost. Samples were characterized via scanning electron microscopy, in-situ/ex-situ X-ray diffraction, energy dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry.
The authors acknowledge financial support from the NSF IUCRC program for the “Center for solid-state electric power storage” (#2052631) and support from the South Dakota Board of Regents for the “Governor’s Research Center (GRC) for electrochemical energy storage”.
1.) Gao, Y.; Xiong, K.; Zhang, H.; Zhu, B. Effect of RU Doping on the Properties of Lifepo4/c Cathode Materials for Lithium-Ion Batteries. ACS Omega
2021, 6 (22), 14122–14129.
Unveiling the Roles of Key Dopant Elements in Tuning Electrochemical, Thermal, and Air Stabilities of High-Nickel Layered Oxide Cathodes
Authors: Cui Zehao , Manthiram Arumugam 
Published: September 2023

High-nickel (Ni) layered oxides, LiNixM1–xO2 (M = Mn, Co, Al, etc.), are regarded as promising cathode candidates for next-generation lithium-based batteries in electric vehicles. Current successfully adopted LiNi0.8Mn0.1Co0.1O2 and LiNi0.8Co0.15Al0.05O2 cathodes with an energy density of nearly 750 Wh kg–1 will be inadequate for easing the driving range anxiety of customers in the foreseeable future. Increasing the Ni content further to > 90% is deemed as a feasible solution as it can simultaneously provide more energy density and reduce the raw material cost. Unfortunately, as the Ni content increases, structural, interfacial, thermal, and air stabilities of high-Ni cathodes become significantly worse, hindering their practical applications.1 In this regard, a rational compositional design with a precise use of dopant elements and their concentrations is needed to achieve the best stabilities of a high-Ni cathode. Evidently, this cannot be realized without a clear understanding of the roles of key dopant elements, such as Co, Mn, and Al, in tuning the stabilities of high-Ni cathodes.
In this work, three cathode materials with a 5% single-element doping, viz., LiNi0.95Co0.05O2 (NC), LiNi0.95Mn0.05O2 (NM), and LiNi0.95Al0.05O2 (NA), along with undoped LiNiO2 (LNO) are synthesized in-house to systematically examine the influences of Co, Mn, and Al on cycle, thermal, and air stabilities of high-Ni cathodes. From the aspect of cycle stability, it is unveiled that a critical role of dopants is regulating the state-of-charge and, more importantly, the extent of H2-H3 phase transition, which have a dominate role in dictating the cycle stability. In addition, Co offers important benefits of reducing irreversible capacity/energy loss and facilitating Li+ diffusivity. With respect to thermal stability, although Co, Mn, and Al doping can all mitigate the heat release of thermal runaway reactions, only Al doping can effectively delay the onset of thermal runaway reactions. Furthermore, Al doping can also delay the onset of outgassing (mainly O2 and CO2) at deep charge due to its ability to perturb long-range metal-metal interaction and make the metal-O bonds more ionic and stronger.2 Finally, in terms of air stability, compared to Co and Al, Mn doping can more effectively reduce the formation and accumulation of surface residual Li species (LiOH and Li2CO3) due to a higher concentration of stable Ni2+ in NM counterbalancing Mn4+. Our systematic investigation into the roles of key dopant elements can help precisely predict the most effective high-Ni cathode compositions according to the specific application requirements.

References

W. Li, E. M. Erickson, and A. Manthiram, Nat. Energy, 5, 26 (2020).

A. Manthiram, Nat. Commun., 11, 1550 (2020).
SECM as a Direct Method to Track Changes in Silicon Passivation
Authors: McBrayer Josefine , Harrison Katharine L , Fenton Kyle , Minteer Shelley 
Published: September 2023

Silicon is a promising next-generation anode to increase energy density over current state of the art graphite anodes. Despite much progress in improving the cycling of silicon electrodes, the calendar life is still problematic. In this work, scanning electrochemical microscopy (SECM) was used to track the reactivity of the surface of a silicon thin film over time to better understand the role of the solid electrolyte interphase (SEI) during calendar aging. The passivation of silicon was found to decrease with increasing time and potential relative to Li/Li+. Along with the decrease in passivation with time, the homogeneity of passivation decreases. Despite some local “hot spots” of reactivity, within resolution limits (tip radius of 12.5 μm), the changes in passivation seemed to be global SEI failure rather than local (for example, cracking). In all cases, the delithiated silicon was less passivated than the lithiated silicon. When delithiated up to 1.5 V versus Li/Li+ the surface was found to be more reactive than the pristine silicon surface. This could potentially be the result of destabilization of the surface by SEI oxidation. When the cell was only delithiated up to 0.75 V versus Li/Li+, the surface was still passivating, but still less so than the lithiated surface. This indicates that the potential of the anode should be kept at or below ∼ 0.75 V Li/Li+ for half cell and full cell cycling to prevent decreasing SEI passivation.
This research was supported by the U.S. Department of Energy’s Vehicle Technologies Office under the Silicon Consortium Project, directed by Brian Cunningham, and managed by Anthony Burrell. This work was conducted in part by the Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Sandia National Laboratories is a multimission Laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.