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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Systematic Evaluation of Carbon Hosts for High-Energy Rechargeable Lithium-Metal Batteries

Rechargeable lithium batteries (RLBs) have attracted wide attention for achieving high energy and low cost, but the poor stability of the Li anode has remained as a large challenge. In the last several years, great efforts have been made to develop carbon anode structures for RLB applications. A wide range of carbon structures as well as many chemical modification strategies have been investigated to improve the Coulombic efficiency and extend the cycle life of the anodes or the cells. However, currently there is no clear conclusion on key factors that determine the performance of such the types of carbon structures due to the wide range of experimental conditions used in such studies. In this study, we systematically evaluated and compared the electrochemical properties of representative carbon anode materials as well as chemically functionalized carbon materials in different electrolytes. We have found that chemical functionalization, metallic loading, and the types of micro or nano-structures all have an effect on Li deposition/stripping process, but by far the most critical factor is the nature of the electrolytes. All carbon materials produced poor Coulombic efficiency and cycle life in conventional carbonate or ether-based electrolytes. However, when a Li metal compatible is used, the average Coulombic efficiency of Li metal deposition on all carbon structures is increased to 99% or higher. This study provides critical lessons on the directions for carbon anodes for RLBs. Based on these findings, we constructed Li metal coin cells using prelithiated hard carbon, LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode, and compatible electrolyte and tested the cells under conditions of lean electrolyte, lean Li metal and high cathode loading required for more than 300 Wh kg-1 specific energy. More than 200 stable cycles were demonstrated with over 80% capacity retention. Furthermore, the existing challenges and potential approaches have been discussed to further extend the cyclability of lithium-metal batteries under practical conditions.

Liu, Yao↗
DOE OSTI2020

Architecture-Based Control of Temperature Gradient-Driven Water Transport in Polymer Electrolyte Fuel Cells

Temperature gradients can move water within the porous media of a polymer electrolyte fuel cell through phase-change-induced (PCI) flow. It is critical to understand PCI flow so that control and distribution of water within a fuel cell can be accomplished. This work investigates the role of architecture, specifically anode land width, on overall cell water content and distribution in the through-plane direction. A specially-designed 4.8 cm 2 fuel cell with precise thermal boundary conditions was imaged with neutrons using two different anode flow field configurations. A new, non-dimensional thermal transport number was developed which quantifies the relative influence of PCI flow on cell water transport. It was found that anode lands larger than the cathode lands cause large thermal gradients that instigate net water flux from the cathode to the anode. An asymmetric configuration with larger anode lands was found to have large changes in water content that were strongly sensitive to cell operating conditions. The thermal transport number developed here enables deduction of the net flux condition based on operating conditions and architecture. This approach enables design of high-performance systems with balanced water management.

25 ENERGY STORAGE↗
DOE OSTI2020

Investigating the Effects of Lithium Deposition on the Abuse Response of Lithium-Ion Batteries

Li deposition at the graphitic anode is widely reported in literature as one of the leading causes of capacity fade in lithium-ion batteries (LIBs). Previous literature has linked Li deposition resulting from low-temperature ageing to diminished safety characteristics, however no current research has probed the effects of Li deposition on the abuse response of well-characterized cells. Using overtemperature testing, a relationship between increased concentrations of Li deposition and exacerbated abuse response in 1 Ah pouch cells has been established. A novel Li deposition technique is also investigated, where cells with n:p < 1 (anode-limiting) have been cycled at a high rate to exploit Li + diffusion limitations at the anode. Scanning Electron Microscopy of harvested anodes indicates substantial Li deposition in low n:p cells after 20 cycles, with intricate networks of Li(s) deposits which hinder Li + intercalation/deintercalation. Peak broadening and decreased amplitude of differential capacity plots further validates a loss of lithium inventory to Li + dissolution, and Powder X-ray Diffraction indicates Li + intercalation with staging in anode interstitial sites as the extent of Li deposition increases. A cradle-to-grave approach is leveraged on cell fabrication and testing to eliminate uncertainty involving the effects of cell additives on Li deposition and other degradation mechanisms.

25 ENERGY STORAGE↗
DOE OSTI2021

The Impact of Different Substituents in Fluorinated Cyclic Carbonates in the Performance of High Voltage Lithium-Ion Battery Electrolyte

Ethylene carbonate (EC) has been used as the Solid-Electrolyte Interphase (SEI) former in the conventional electrolyte for decades. However, its low anodic stability leads to severe capacity decay during cycling under high voltage operation. Therefore, finding a viable electrolyte with high anodic stability and the ability to form robust SEI for high voltage lithium-ion batteries is of primary importance. In this study, a series of electrolytes containing various fluorinated cyclic carbonates as the SEI former have been designed, synthesized and evaluated. Linear sweep voltammetry study suggested that fluorinated cyclic carbonates generally possess higher anodic stability than EC. Based on the cycling performance of LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NMC532)/ graphite full cells, the electrolyte with DFEC/FEMC (1.0 M LiPF 6 ) inhibited the oxidation side reaction on the cathode and forms a vigorous SEI on the anode. The high voltage NMC532/Graphite cell utilizing the novel electrolyte exhibits excellent cycling durability under both room and elevated temperature. The superior performance of the DFEC based electrolyte was further unveiled by SEM, EDAX and XRD. Both the anode and cathode of the full cell employing DFEC based electrolyte retained their intrinsic structures after cycling while the electrodes cycled in conventional electrolyte showed severe degradation.

25 ENERGY STORAGE↗
DOE OSTI2022

Difluorophosphoric Acid Generation and Crossover Reactions in LiNixCoyMnzO 2 Cathodes Operating at High Voltage

Cycling lithiated metal oxides to high potential (>4.5 V vs Li) is of significant interest for the next generation of lithium ion batteries as this significantly increases the capacity and energy of cells. However, cells cycled to high potential suffer from rapid capacity fade due to a combination of thickening of the anode solid electrolyte interphase (SEI) and impedance growth on the cathode. While transition metal catalysed degradation of the anode SEI has been widely proposed as a primary source of capacity loss, a related acid induced degradation of the anode SEI is proposed. A systematic investigation of LiNi 0.5 Co 0.2 Mn 0.3 O 2 , and LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes cycled to 4.2 and 4.6 V has been conducted and the oxidative generation of the strong acid difluorophosphoric acid (F 2 PO 2 H) has been quantified by solution Nuclear Magnetic Resonance (NMR) spectroscopy. Ex-situ surface analysis of the electrodes with X-ray Photo Electron spectroscopy (XPS) suggests that the generation of F 2 PO 2 H correlates with a thickening of the anode SEI and an increase in the fluorophosphate content of the SEI. Changes to the LiNi 0.8 Co 0.1 Mn 0.1 O 2 surface for cells cycled to 4.6 V are also consistent with the generation of acidic species. There is good correlation between the concentration F 2 PO 2 H, anode SEI degradation and the capacity loss of the cells.

25 ENERGY STORAGE↗
DOE OSTI2022

Analytical and Numerical Analysis of Lithium Plating Onset in Single and Bilayer Graphite Electrodes during Fast Charging

Lithium plating is commonly observed in anodes charged at fast rates, and can lead to capacity loss and battery safety issues. The increased risk of plating has been attributed to transport limitations, and architectured electrodes may reduce plating risk. However, while theoretical studies have shown that reaction non-uniformity arises due to interplay of transport limitations, anode open circuit voltage behavior and reaction kinetics, its effect on lithium plating has not been studied. We use analytic and numerical simulations to predict onset of plating in graphite anode half-cells at high C-rates and demonstrate how anodes with layered porosities can delay plating. Simplified analytical models identify trends for plating onset and predictions are calibrated against numerical models. A calibrated numerical model of graphite demonstrates qualitative agreement with analytical model predictions. This reaction inhomogeneity mechanism occurs in the absence of lithium ion depletion, indicating that these mechanisms may contribute to capacity loss independently or simultaneously. A bilayer model of graphite exhibits delayed plating onset, and an optimization procedure is presented. This theoretical work presents quantitative and mechanistic insight on how reaction inhomogenity affects lithium metal plating onset and can be used as a guide to engineer anodes resistant to lithium plating.

Mijailovic, Aleksandar S.↗
DOE OSTI2020

Influence of Proton Activity Gaps between Electrodes on Open-Circuit Potential of H 2 /H 2 and H 2 /Air Cells

Polymer -electrolyte-fuel-cell open-circuit voltages (OCVs) are exactly defined by equation (1), where cathode and anode proton activities [(aH+)cathode and (aH+)anode, respectively] usually are identical, so the third term in the right-hand side of equation (2) is ignored. OCV=E0+RT/2F*ln(a1/2 O2*(a2 H+)cathode/aH2O)-RT/2F*ln((a2 H+)anode/aH2) (1) =E0+RT/2F*ln(a1/2 O2*aH2/aH2O)+RT/2F*ln((a2 H+)cathode/(a2 H+)anode) (2) Water vapor pressure is a colligative property that fundamentally correlates to electrolyte concentrations in aqueous solutions. Proton activity is a function of acid concentration, such as pH, when electrolytes are acids. In polymer-electrolyte membranes, water vapor pressure and acid concentration are understood as relative humidity (RH) and water uptake (λ), respectively, where λ represents number of water molecules per sulfonic acid molecule. Several investigations have reported the relationship between RH and λ, meaning that proton activities and associated water uptakes are intimately related to RH. In actual fuel cell operation, cathode RH is determined by ambient-atmosphere and/or humidifier RH(s), and anode RH depends on hydrogen-circulator RH. Therefore, RH is not always identical at both electrodes, and the difference between electrode RHs is considerable during dry operation of polymer electrolyte fuel cells. Therefore, the third term in the right-hand side of equation (2) may be significant for dry operation. We measured OCVs when hydrogen was supplied to both electrodes at 80°C. One electrode (A) was fixed at 30% RH, while RH at the other electrode (B) was varied (0, 5, 10, 20, and 30%). Measured OCVs varied from 0 to 75 mV. For fuel cell tests, electrode A was supplied with hydrogen at 30% RH; electrode B, oxygen at 0, 5, 10, 20, and 30% RH. OCVs deviated from that measured when RH at electrode B was 30%, increasing from 0 to 60 mV with decreasing RH at electrode B. Results are also shown in Figure 1. Proton activities of both electrodes were thermodynamically calculated. The Gibbs–Duhem relation was applied to obtain molar Gibbs free energies of water and sulfonic acid, and proton activity coefficient was calculated using the Gibbs free energy of sulfonic acid and the relationship between RH and λ1–4, assuming that protons and sulfonic anions show identical ionic-activity coefficients. OCVs were estimated using the third term in the right-hand side of equation (2). Results are shown in Figure 1. Fuel-cell current–voltage performance was poor when RHs at the anode and cathode were 30 and 20%, respectively. To determine kinetic current, we measured the oxygen-reduction reaction (ORR) using a rotating-disk electrode (RDE) in concentrated-acid aqueous solutions, which modeled catalyst-layer ionomers. Kinetic currents decreased with acid concentrations. References T. A. Zawodzinski, Jr., C. Derouin, S. Radzinski, R. J. Sherman, V. T. Smith, T. E. Springer and S. Gottesfeld , J. Electrochem. Soc., 140,1041 (1993) P. K. Das and A. Z. Weber, Proceedings of the ASME 2013 11th Fuel Cell Science, Engineering and Technology Conference, Fuel Cell 18010 (2013) V. A. Sethuraman, J. W. Weidner, A. T. Haug, S. Motupally,b and L. V. Protsailo, J. Electrochem. Soc., 155, B50 (2008) A. Kusoglu and A. Z. Weber, Chem. Rev., 117, 987 (2017) Figure 1

Yoshida, Toshihiko↗
DOE OSTI2021

Ultra low background time projection alpha particle detector ( Phase II Final Scientific/Technical Report)

When alpha particles are emitted into a gas they create an ionization track of gas ions and electrons. In our commercial UltraLo instrument we apply a voltage between a planar sample and an anode, integrate the anode signal as it collects the electrons, and distinguish between alphas emitted from the sample and elsewhere (anode, sidewalls) by the duration and shape of the resultant signal. The major contributors limiting the instrument’s lower detection limit are cosmic rays that pass through the detector close to the sample and Rn decays that produce charge tracks the originate in the gas and end on the sample. In this work we proposed to identify and reject these events by converting the anode into a multi-pixel array and operating in time projection mode. Cosmic rays would be eliminated by generating charge on many pixels, while charge collection asymmetry would distinguish between sample events (Bragg curve up) and Rn events (Bragg curve down). We therefore proposed to modify an UltraLo by pixilating its anode, developing low noise, low power multiplexed electronics to track each pixel’s signal individually, and develop analysis software to make the required discriminations.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Collisional Effects on Electron Trajectories in Crossed-Field Devices

Crossed-field diodes (CFDs) are used in multiple high-power applications and are characterized by an applied magnetic field orthogonal to the electric field, induced by the applied voltage across the anode-cathode gap. In vacuum, the Hull cutoff magnetic field (HCMF) represents the maximum applied magnetic field for which an electron from the cathode can reach the anode. This study investigates the effects of non-vacuum conditions on electron trajectories by introducing electron mobility, which represents particle collisions. We used numerical solutions of the electron force law and particle-in-cell simulations (XPDP1) to assess electron motion for various electron mobilities. For magnetic fields above the HCMF in vacuum, reducing the electron mobility increases the time for an electron emitted from the cathode to reach the anode. Reducing mobility below 22 C s/kg eliminates the HCMF for any magnetic field, meaning that an emitted electron will always cross the gap. We derived the magnetic field, mobility, and electron transit time corresponding to this condition by solving for the condition when the electron velocity in the direction across the anode-cathode gap going to zero at the anode. A parametric study of these conditions using theory and XPDP1 is performed under different gap distances, voltages, and magnetic fields.

42 ENGINEERING↗
DOE OSTI2026

Fluorinated Glyme Solvents to Extend Lithium-Sulfur Battery Life (Final Technical Report, Unlimited)

This project investigated a number of partially fluorinated glymes (PFGs) as electrolyte cosolvents to improve the performance of lithium-sulfur (Li-S) batteries. A major issue in Li-S cells is the electrochemical reaction of sulfur in the cathode to form lithium polysulfides (LPS) that dissolve in the electrolyte. Those LPS are electrochemically and chemically reactive at the lithium anode, resulting in lithium sulfide deposition on the anode and also electrochemical reaction at both the anode and cathode, leading to a “polysulfide shuttle” and reduced coulombic efficiency (CE) and self-discharge of the cell. PFGs reduce the solubility of LPS while maintaining good solubility of lithium salts such as LiTFSI. By adjusting the amount of PFG as cosolvent in the electrolyte, we showed that the solubility of LPS in the electrolyte can be tuned. (It is not desirable to completely eliminate LPS in the electrolyte, as they facilitate electrochemical reaction of the electrically insulating S 8 and Li 2 S within the cathode by shuttling charge between them and the conductive carbon.) Another issue in Li-S cells is degradation of the Li anode over many cycles of stripping (discharge) and plating (charge). We showed that PFGs have a beneficial effect on the physical morphology of the Li anode, SEI formation, and the CE of a Li-Li cell. Among the many PFGs tested, we found the best performance from PFGs designated PFG2 and PFG5, and these two PFGs were thoroughly studied. A systematic coin-cell study of electrolyte solvents of 90:10, 80:20, or 70:30 DME:PFG (DME = 1,2-dimethoxyethane) revealed some systematic trends: a higher percentage of PFG solvent led to substantially longer cycle life, but at the same time reduced specific capacity (mAh/g(S)) and cell capacity at higher rates. These studies used LiFSI as the electrolyte salt, as it was found to extend cycle life compared to LiTFSI. Finally, the addition of a small amount of 1,3-dioxolane (DOL) to the electrolyte was found to be beneficial. The overall optimal electrolyte solution was found to be 0.6 M LiFSI + 0.5 M LiNO 3 in 75:5:20 DME/DOL/PFG (either PFG2 or PFG5).

25 ENERGY STORAGE↗
DOE OSTI2026

Cathodic Protection Modeling for Hanford Underground Double-Shell Tank Farms

Hanford stores millions of gallons of radioactive and chemically hazardous waste from the production of weapon materials in tank farms consisting of underground carbon-steel storage tanks surrounded by reinforced concrete. Six of these Hanford tank farms use double-shell storage tanks (DSTs). The DST farms were constructed from 1968 to 1986 with a planned 40–50 year design life, so some are already operating beyond their initial life expectancy. Ultrasonic testing (UT) has indicated significant thinning on the bottom of the secondary (outer) liner of these tanks, believed to arise from groundwater intrusion driving concrete side corrosion. There is no direct access to the steel/concrete interface between the tank and the concrete pad, making it difficult to apply a chemical-based mitigation strategy or to conduct repairs, but cathodic protection (CP) is a possible method to inhibit further concrete-side corrosion. Hanford already uses CP to protect below grade steel piping within the tank farms and connected to the tanks, but this system was not designed to protect the tank bottoms. CP design must account for the structures surrounding the DSTs, including the steel reinforcing bars (rebar) within the concrete pad and vault, various process lines, and the existing CP system. In this study, finite element analysis (FEA) modeling was carried out to simulate CP protection of 1) a single tank and CP anode to develop options for modeling the rebar and to compare to a simpler circuit model and 2) the entire Hanford AN tank farm as a representative example consisting of seven tanks, associated piping, and both existing and new CP anodes. Both circuit and FEA models predict that significant protective current could be delivered to the bottoms of the tanks with the addition of tank-protection anodes below the depth of the tanks. Simulations with only the existing pipe-protection anodes active confirmed that only a very small current to the tank bottoms is predicted under present conditions. Multiple simplified representations of the dome and wall rebar were tested to reduce the computational complexity of the tank-farm simulations, resulting in modeling the rebar as edge elements with a prescribed effective circumference that matches the real rebar surface area. The geometry of the rebar is also simplified into horizontal hoops around the tank walls and radial rebar over the dome with increased effective circumference to retain the target surface area. This simplification was found to greatly reduce the complexity and solution time of the models without large changes in current distributions, especially to the tank bottom. A range of values were tested for model parameters such as soil and concrete resistivities and polarization resistance to investigate their impact on the current and electric potential distributions. Depending on the parameters used, FEA simulations predict some risk of overprotection, particularly on the piping system; since overprotection can also lead to surface damage associated with hydrogen gas generation at the interface (e.g. hydrogen embrittlement or damage to coatings), this needs to be considered when refining the design of the new CP system. Comparison between the FEA models and the circuit model representation demonstrated that the circuit model could not match the predicted FEA current distribution, even when using the exact same surface areas. This discrepancy appeared to be at least partly attributable to the impact of the relative positions of the tank components and anodes to each other and to the ground surface. The FEA model accounts for the relative positions since it solves the governing equations in three dimensions, but the circuit model cannot account for the positioning. In particular, the circuit model underpredicts the current to the tank bottom and overpredicts the current to the dome compared to FEA for the baseline geometry. The FEA models omitted the electrically isolated rebar in the bottom concrete slab. However, a circuit based stray current model estimated that only 2.1% of the total current through the slab would stray into the rebar, corresponding to ~0.21 A for a target current density of 2 mA/ft2 to the tank bottom. The estimated corrosion driven by this amount of stray current is predicted to yield a lifetime of >400 years for the minimum rebar diameter, assuming an acceptable cross-section area loss of 10%.

d'Entremont, Anna [Savannah River National Laborat↗
DOE OSTI2022

Neutron tomography of porous aluminum electrodes used in electrocoagulation of groundwater

In this work, neutron computed tomography (CT) is employed to investigate the dissolution of porous aluminum electrodes during electrocoagulation (EC). Porous electrodes were chosen in efforts to reduce electric power requirements by using larger surface-area electrodes, having both inner and outer surface, for the EC process. Neutron CT allowed 3D reconstruction of the porous electrodes, and image analysis provided the volume of each electrode vs. thickness, which can indicate whether the inner surface is effectively involved in EC reactions. For the anode, the volume decreased uniformly throughout the thickness of the electrode, indicating that both the outer and inner surface participated in electrochemical dissolution, while the volume of the cathode increased uniformly vs. thickness, indicating deposition of material on both the outer and inner surface. The attenuation coefficient vs. thickness, increased for both anode and cathode, indicating surface chemistry changes. For the anode, the attenuation coefficient increased slightly but uniformly, probably due to aluminum oxide formation on the surface of the anode. For the cathode, the attenuation coefficient increased more than for the anode and nonuniformly. The higher increase in the attenuation coefficient for the cathode is due to precipitation of aluminum hydroxide on the electrode surface, which added hydrogen. Image analysis also showed that, although the attenuation coefficient increased throughout the thickness of the electrode, most of the hydroxide deposition occurred on the outer surface. Energy analysis showed that porous electrodes can be used to reduce process energy requirements by as much as 4 times compared to solid electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Al 2 O 3 Thin Films on Magnesium: Assessing the Impact of an Artificial Solid Electrolyte Interphase

Among the many emerging technologies under investigation as alternatives to the successful Lithium-ion battery, the magnesium battery is promising due to the wide availability of magnesium, its high volumetric capacity, and the possibility for safety improvements. One of the largest challenges facing rechargeable magnesium batteries is the formation of a passivation layer at the Mg metal anode interface when reactive species in the electrolyte are reduced at the electrode-electrolyte interface. To control the solid electrolyte interphase in Lithium batteries, protective layers called artificial solid electrolyte interphase (ASEI) layers have been successful in improving Li metal anode performance. The approach of protecting Mg metal anodes from electrolyte degradation has been demonstrated by fewer studies in the literature than Li systems. In this work, we discuss the properties of Al 2 O 3 thin films deposited using atomic layer deposition as an artificial solid electrolyte interphase at the Mg anode. Our results demonstrate that Al 2 O 3 does prevent electrolyte degradation due to the reductive nature of Mg. However, undesirable properties such as defects and layer breakdown lead to Mg growth that causes soft-shorting. The soft-shorting occurs with and without the protection layer, indicating the ALD layer does not prevent it and hinders Al 2 O 3 from being an ideal candidate for a protection layer. Crucial effects of this layer on Mg electrochemistry at the interface were observed, including growth of Mg deposits leading to soft-shorting of the cell whose morphology showed a dependence on the Al 2 O 3 layer. These results may provide guidelines for the future design and development of protective ASEI layers for Mg anodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Flow-regulated growth of nanotubes

A method for growing nanotubes via flow-regulated microfluidic electrochemical anodization, includes providing a microfluidic device having a fluid inlet; a fluid outlet; and a fluidic microchannel connecting the fluid inlet and outlet, wherein the microchannel includes a Pt cathode and a Ti anode separated by an electrical insulator; providing an electrolyte fluid flow through the microchannel; and providing an electrical current across the anode and cathode sufficient to cause electrochemical anodization growth of TiO2 nanotubes in the microchannel on a surface of the anode.

Wan, Jiandi↗
DOE OSTI2021

High efficiency electrolytes for high voltage battery systems

Disclosed herein are embodiments of an electrolyte that is stable and efficient at high voltages. The electrolyte can be used in combination with certain cathodes that exhibit poor activity at such high voltages with other types of electrolytes and can further be used in combination with a variety of anodes. In some embodiments, the electrolyte can be used in battery systems comprising a lithium cobalt oxide cathode and lithium metal anodes, silicon anodes, silicon/graphite composite anodes, graphite anodes, and the like.

Ren, Xiaodi↗
DOE OSTI2021

Vapor phase photo-electrochemical cell

This disclosure provides systems, methods, and apparatus related to a vapor phase photo-electrochemical cell. In one aspect, a device includes a photovoltaic cell, a cathode disposed on the photovoltaic cell, an ionomer membrane disposed on the cathode, and an anode disposed on the ionomer membrane. The cathode includes a cathode catalyst. The ionomer membrane is in contact with the cathode catalyst. The anode includes an anode catalyst. The anode catalyst is in contact with the ionomer membrane. The anode, the ionomer membrane, and the cathode are transmissive to the solar radiation spectrum.

Larson, David M.↗
DOE OSTI2023

Methods and systems for diagnosis of failure mechanisms and for prediction of lifetime of metal batteries

Methods for diagnosing failure mechanisms and for predicting lifetime of metal batteries include monitoring rest voltage and Coulombic Efficiency over relatively few cycles to provide profiles that indicate, by the trends thereof, a particular failure mechanism (e.g., electrolyte depletion, loss of metal inventory, increased cell impedance). The methods also include cycling over relatively few cycles an anode-free cell, having the same cathode and electrolyte as the metal battery, but with a current collector instead of the anode. Discharge capacity is monitored and profiled, and a discharge capacity curve is fitted to the discharge capacity profile to discern a capacity retention per cycle. The lifetime of the metal battery is determined using the capacity retention per cycle discerned from the anode-free cell. Related systems include a metal-based battery and an anode-free cell or a battery cell reconfigurable between a metal-based and an anode-free cell.

Li, Bin↗
DOE OSTI2025

Examples of X-Ray Characterization Techniques in Energy Storage Research

Lithium-ion batteries have revolutionized the portable electronics and transportation sectors. Their performance is often critically dependent on the crystal structures of the anode and cathode electrode materials, which must enable the transport and reversible storage of lithium ions into and out of the lattice. Because lithium is a low-Z element, characterization of materials for lithium-ion batteries can be particularly challenging. Regardless, X-ray techniques enable analysis of material structures to better understand how battery materials perform and degrade, particularly when combined with other materials characterization and electrochemical characterization techniques. While X-ray techniques are most often used in battery research for phase identification of crystal structures, X-ray characterization techniques are also used for a wide variety of other purposes. I will discuss several examples from my research with various collaborators on several projects that highlight the impact that X-ray characterization techniques can have on battery research. The first example will focus on low-temperature microwave-assisted solvothermal synthesis of vanadium-doped LiFePO4 cathode materials for lithium-ion batteries. (1,2) Through a combination of electrochemical and materials characterization, we determined that low temperature synthesis resulted in metastable phases that enabled incorporation of higher dopant levels than resulting from high-temperature synthesis of thermodynamically stable phases. Rietveld refinement of X-ray diffraction data enabled understanding of how lattice parameters changed with doping levels and synthesis temperature. X-ray absorption near edge spectroscopy enabled understanding of the vanadium and iron oxidation states to confirm how vacancies in the structure caused by doping were charge compensated. This was important to understand because the literature suggests doping can improve LiFePO4 electrical conductivity, which improves battery charge and discharge rates. The second example will focus on understanding residual strain in lithium metal anodes. Lithium-ion batteries typically use graphite anodes, but the charge-storage capacity can be theoretically improved ~10x by using lithium metal as the anode material instead. However, lithium anodes suffer from growth of high-aspect-ratio features, such as dendrites, that can pierce nanoporous polymer separators and lead to short circuits and fires. External pressure is commonly applied to cells to enable better morphological control. We hypothesized that applied pressure may promote strain and possibly work hardening during electrochemical cycling, which motivated us to look for evidence of residual strain in lithium metal cycled under applied pressure using X-ray diffraction and sin2(..psi..) analysis. We found that lithium electrodeposited under high pressure exhibited in-plane compressive strain and that that lithium electrodeposited under low pressure did not. (3) The residual strain that accompanies electrodeposition under high pressure may lead to work hardening, which may explain how a soft metal like lithium can puncture separators and why higher pressure does not always decrease short circuits. (4-6) References: 1) Harrison, K. L.; Manthiram, A. Microwave-Assisted Solvothermal Synthesis and Characterization of Metastable LiFe1- x (VO) x PO4 Cathodes. Inorganic chemistry 2011, 50(8), 3613-3620. 2) Harrison, K. L.; Bridges, C. A.; Paranthaman, M. P.; Segre, C. U.; Katsoudas, J.; Maroni, V. A.; Idrobo, J. C.; Goodenough, J. B.; Manthiram, A. Temperature Dependence of Aliovalent-Vanadium Doping in LiFePO4 Cathodes. Chemistry of Materials 2013, 25(5), 768-781. 3) Rodriguez, M. A.; Harrison, K. L.; Goriparti, S.; Griego, J. J.; Boyce, B. L.; Perdue, B. R. Use of a Be-Dome Holder for Texture and Strain Characterization of Li Metal Thin Films via Sin2 (..psi..) Methodology. Powder Diffraction 2020, 35(2), 89-97. 4) Jungjohann, K. L.; Gannon, R. N.; Goriparti, S.; Randolph, S. J.; Merrill, L. C.; Johnson, D. C.; Zavadil, K. R.; Harris, S. J.; Harrison, K. L. Cryogenic Laser Ablation Reveals Short-Circuit Mechanism in Lithium Metal Batteries. ACS Energy Letters 2021, 6(6), 2138-2144. 5) Harrison, K. L.; Merrill, L. C.; Long, D. M.; Randolph, S. J.; Goriparti, S.; Christian, J.; Warren, B.; Roberts, S. A.; Harris, S. J.; Perry, D. L. Cryogenic Electron Microscopy Reveals That Applied Pressure Promotes Short Circuits in Li Batteries. Iscience 2021, 24(12). 6) Harrison, K. L.; Goriparti, S.; Merrill, L. C.; Long, D. M.; Warren, B.; Roberts, S. A.; Perdue, B. R.; Casias, Z.; Cuillier, P.; Boyce, B. L. Effects of Applied Interfacial Pressure on Li-Metal Cycling Performance and Morphology in 4 M LiFSI in DME. ACS Applied Materials & Interfaces 2021, 13(27), 31668-31679.

batteries↗