Spotte-Smith, Evan W.C.; Blau, Samuel M.; Barter, Daniel; Leon, Noel J.; Hahn, Nathan H.; Redkar, Nikita S.; Zavadil, Kevin R.; Liao, Chen; Persson, Kristin A.
Out-of-equilibrium electrochemical reaction mechanisms are notoriously difficult to characterize. However, such reactions are critical for a range of technological applications. For instance, in metal-ion batteries, spontaneous electrolyte degradation controls electrode passivation and battery cycle life. Here, to improve our ability to elucidate electrochemical reactivity, we for the first time combine computational chemical reaction network (CRN) analysis based on density functional theory (DFT) and differential electrochemical mass spectroscopy (DEMS) to study gas evolution from a model Mg-ion battery electrolyte-magnesium bistriflimide (Mg(TFSI)2) dissolved in diglyme (G2). Automated CRN analysis allows for the facile interpretation of DEMS data, revealing H2O, C2H4, and CH3OH as major products of G2 decomposition. These findings are further explained by identifying elementary mechanisms using DFT. While TFSI-is reactive at Mg electrodes, we find that it does not meaningfully contribute to gas evolution. The combined theoretical-experimental approach developed here provides a means to effectively predict electrolyte decomposition products and pathways when initially unknown.
Practical Mg batteries require electrolytes that are stable both toward reduction by Mg metal and oxidation by high voltage cathodes. State-of-the-art Mg electrolytes based on weakly coordinating Mg salts utilize standard ether-type solvents (usually glymes) due to their reductive stability. However, the oxidative stabilities of these solvents are less than ideal, leading to difficulties in realizing the high oxidative stabilities of recently developed salts. On the other hand, alternative solvents with greater oxidative stability are typically unable to support Mg cycling. In this work, we report a selective solvation approach involving the combination of glyme and hydrofluoroether solvents. Selective solvation of Mg2+ by the glyme solvent component increases the oxidative stability of the glyme while maintaining sufficient reductive stability of the non-coordinating hydrofluoroether. We show that this approach enables the design of electrolytes with greater oxidative stability than glyme-only electrolytes while retaining enough reductive stability to cycle Mg metal. We also relate the influence of various coordination interactions among the solvents and anions with Mg2+ to their electrochemical stabilities to better inform the design of future electrolytes.
Lithium metal is an ideal anode for high energy density batteries, however the implementation of lithium metal anodes remains challenging. Beyond the development of highly efficient electrolytes, degradation processes restrict cycle life and reduce practical energy density. Herein lithium volumetric expansion and degradation pathways are studied in half cells through coupling electrochemical analysis with cross-sectional imaging of the intact electrode stack using a cryogenic laser plasma focused ion beam and scanning electron microscope. We find that the volumetric capacity is compromised as early as the first cycle, at best reaching values only half the theoretical capacity (1033 vs 2045 mAh cm−3). By the 101st electrodeposition, the practical volumetric capacity decreases to values ranging from 143 to 343 mAh cm−3
Sanz-Matias, Ana; Roychoudhury, Subhayan; Feng, Xuefei; Yang, Feipeng; Cheng, Kao L.; Zavadil, Kevin R.; Guo, Jinghua; Prendergast, David
Given their natural abundance and thermodynamic stability, fluoride salts may appear as evolving components of electrochemical interfaces in Li-ion batteries and emergent multivalent ion cells. This is due to the practice of employing electrolytes with fluorine-containing species (salt, solvent, or additives) that electrochemically decompose and deposit on the electrodes. Operando X-ray absorption spectroscopy (XAS) can probe the electrode-electrolyte interface with a single-digit nanometer depth resolution and offers a wealth of insights into the evolution and Coulombic efficiency or degradation of prototype cells, provided that the spectra can be reliably interpreted in terms of local oxidation state, atomic coordination, and electronic structure about the excited atoms. To this end, we explore fluorine K-edge XAS of mono- (Li, Na, and K) and di-valent (Mg, Ca, and Zn) fluoride salts from a theoretical standpoint and discover a surprising level of detailed electronic structure information about these materials despite the relatively predictable oxidation state and ionicity of the fluoride anion and the metal cation. Utilizing a recently developed many-body approach based on the ΔSCF method, we calculate the XAS using density functional theory and experimental spectral profiles are well reproduced despite some experimental discrepancies in energy alignment within the literature, which we can correct for in our simulations. We outline a general methodology to explain shifts in the main XAS peak energies in terms of a simple exciton model and explain line-shape differences resulting from the mixing of core-excited states with metal d character (for K and Ca specifically). Given ultimate applications to evolving interfaces, some understanding of the role of surfaces and their terminations in defining new spectral features is provided to indicate the sensitivity of such measurements to changes in interfacial chemistry.
Achieving practical, high-energy-density calcium batteries requires controlling the stability of Ca2+electrolytes during calcium metal cycling. Because of the highly reactive nature of calcium, most typical electrolyte constituents are unstable, leading to electrode passivation and low Coulombic efficiency. Among various commercially available salts, calcium bis(trifluoromethylsulfonyl)imide (Ca(TFSI)2) is attractive because of its oxidative stability and high solubility in a variety of solvents. However, this salt does not allow for calcium metal plating, and it has been proposed that TFSI-instability induced by Ca2+coordination is to blame. In this work, we test the ability of strongly coordinating Ca2+cosalts such as halides and borohydrides to displace TFSI-from the first coordination shell of Ca2+and thereby stabilize TFSI-based electrolytes to enable calcium plating. Through spectroscopic analysis, we find that the effectiveness of these cosalts at displacing the TFSI-anion is dependent on the solvent's coordination strength toward Ca2+. Surprisingly, electrochemical calcium deposition behavior is not correlated to the population of bound or free TFSI-. Instead, the nature of the coordination interaction between Ca2+and the cosalt anion is more important for determining stability. Our findings indicate that TFSI-anions are inherently unstable during calcium deposition even in the nominally free state. Therefore, strategies aimed at eliminating the interactions of these anions with the electrode surface via interface/interphase design are required.
Li, Chang; Shyamsunder, Abhinandan; Hoane, Alexis G.; Long, Daniel M.; Kwok, Chun Y.; Kotula, Paul G.; Zavadil, Kevin R.; Gewirth, Andrew A.; Nazar, Linda F.
Aqueous zinc-metal batteries are plagued by poor Zn reversibility owing to zinc dendrite and layered double hydroxide (LDH) formation. Here, we introduce a novel additive—N,N-dimethylformamidium trifluoromethanesulfonate (DOTf)—in a low-cost aqueous electrolyte that can very effectively address these issues. The initial water-assisted dissociation of DOTf into triflic superacid creates a robust nanostructured solid-electrolyte interface (SEI)—revealed by operando spectroscopy and cryomicroscopy—which excludes water and enables dense Zn deposition. We demonstrate excellent Zn plating/stripping in a Zn||Cu asymmetric cell for more than 3,500 cycles. Furthermore, near 100% CE is realized at a combined high current density of 4 mA cm−2 and an areal capacity of 4 mAh cm−2 over long-term cycling. Zn||Zn0.25V2O5·nH2O full cells retain ∼83% of their capacity after 1,000 cycles with mass-limited Zn anodes. By restricting the depth of discharge, the cathodes exhibit less proton intercalation and LDH formation with an extended lifetime of 2,000 cycles.
Hu, Jian Z.; Jaegers, Nicholas R.; Hahn, Nathan H.; Hu, Wenda; Han, Kee S.; Chen, Ying; Sears, Jesse A.; Murugesan, Vijayakumar; Zavadil, Kevin R.; Mueller, Karl T.
Efforts to expand the technological capability of batteries have generated increased interest in divalent cationic systems. Electrolytes used for these electrochemical applications often incorporate cyclic ethers as electrolyte solvents; however, the detailed solvation environments within such systems are not well-understood. To foster insights into the solvation structures of such electrolytes, Ca(TFSI)2and Zn(TFSI)2dissolved in tetrahydrofuran (THF) and 2-methyl-tetrahydrofuran were investigated through multi-nuclear magnetic resonance spectroscopy (17O, 43Ca, and 67Zn NMR) combined with quantum chemistry modeling of NMR chemical shifts. NMR provides spectroscopic fingerprints that readily couple with quantum chemistry to identify a set of most probable solvation structures based on the best agreement between the theoretically predicted and experimentally measured values of chemical shifts. The multi-nuclear approach significantly enhances confidence that the correct solvation structures are identified due to the required simultaneous agreement between theory and experiment for multiple nuclear spins. Furthermore, quantum chemistry modeling provides a comparison of the solvation cluster formation energetics, allowing further refinement of the preferred solvation structures. It is shown that a range of solvation structures coexist in most of these electrolytes, with significant molecular motion and dynamic exchange among the structures. This level of solvation diversity correlates with the solubility of the electrolyte, with Zn(TFSI)2/THF exhibiting the lowest degree of each. Comparisons of analogous Ca2+and Zn2+solvation structures reveal a significant cation size effect that is manifested in significantly reduced cation-solvent bond lengths and thus stronger solvent bonding for Zn2+relative to Ca2+. The strength of this bonding is further reduced by methylation of the cyclic ether ring. Solvation shells containing anions are energetically preferred in all the studied electrolytes, leading to significant quantities of contact ion pairs and consequently neutrally charged clusters. It is likely that the transport and interfacial de-solvation/re-solvation properties of these electrolytes are directed by these anion interactions. These insights into the detailed solvation structures, cation size, and solvent effects, including the molecular dynamics, are fundamentally important for the rational design of electrolytes in multivalent battery electrolyte systems.
Hahn, Nathan H.; Self, Julian; Driscoll, Darren M.; Dandu, Naveen; Han, Kee S.; Murugesan, Vijayakumar; Mueller, Karl T.; Curtiss, Larry A.; Balasubramanian, Mahalingam; Persson, Kristin A.; Zavadil, Kevin R.
Ion interactions strongly determine the solvation environments of multivalent electrolytes even at concentrations below that required for practical battery-based energy storage. This statement is particularly true of electrolytes utilizing ethereal solvents due to their low dielectric constants. These solvents are among the most commonly used for multivalent batteries based on reactive metals (Mg, Ca) due to their reductive stability. Recent developments in multivalent electrolyte design have produced a variety of new salts for Mg2+ and Ca2+ that test the limits of weak coordination strength and oxidative stability. Such electrolytes have great potential for enabling full-cell cycling of batteries based on these working ions. However, the ion interactions in these electrolytes exhibit significant and non-intuitive concentration relationships. In this work, we investigate a promising exemplar, calcium tetrakis(hexafluoroisopropoxy)borate (Ca(BHFIP)2), in the ethereal solvents 1,2-dimethoxyethane (DME) and tetrahydrofuran (THF) across a concentration range of several orders of magnitude. Surprisingly, we find that effective salt dissociation is lower at relatively dilute concentrations (e.g. 0.01 M) than at higher concentrations (e.g. 0.2 M). Combined experimental and computational dielectric and X-ray spectroscopic analyses of the changes occurring in the Ca2+ solvation environment across these concentration regimes reveals a progressive transition from well-defined solvent-separated ion pairs to de-correlated free ions. This transition in ion correlation results in improvements in both conductivity and calcium cycling stability with increased salt concentration. Comparison with previous findings involving more strongly associating salts highlights the generality of this phenomenon, leading to important insight into controlling ion interactions in ether-based multivalent battery electrolytes.
The dramatic 50% improvement in energy density that Li-metal anodes offer in comparison to graphite anodes in conventional lithium (Li)-ion batteries cannot be realized with current cell designs because of cell failure after a few cycles. Often, failure is caused by Li dendrites that grow through the separator, leading to short circuits. Here, we used a new characterization technique, cryogenic femtosecond laser cross sectioning and subsequent scanning electron microscopy, to observe the electroplated Li-metal morphology and the accompanying solid electrolyte interphase (SEI) into and through the intact coin cell battery's separator, gradually opening pathways for soft-short circuits that cause failure. We found that separator penetration by the SEI guided the growth of Li dendrites through the cell. A short-circuit mechanism via SEI growth at high current density within the separator is provided. These results will inform future efforts for separator and electrolyte design for Li-metal anodes.
Multivalent batteries represent an important beyond Li-ion energy storage concept. The prospect of calcium batteries, in particular, has emerged recently due to novel electrolyte demonstrations, especially that of a ground-breaking combination of the borohydride salt Ca(BH4)2 dissolved in tetrahydrofuran. Recent analysis of magnesium and calcium versions of this electrolyte led to the identification of divergent speciation pathways for Mg2+ and Ca2+ despite identical anions and solvents, owing to differences in cation size and attendant flexibility of coordination. To test these proposed speciation equilibria and develop a more quantitative understanding thereof, we have applied pulsed-field-gradient nuclear magnetic resonance and dielectric relaxation spectroscopy to study these electrolytes. Concentration-dependent variation in anion diffusivities and solution dipole relaxations, interpreted with the aid of molecular dynamics simulations, confirms these divergent Mg2+ and Ca2+ speciation pathways. These results provide a more quantitative description of the electroactive species populations. We find that these species are present in relatively small quantities, even in the highly active Ca(BH4)2/tetrahydrofuran electrolyte. This finding helps interpret previous characterizations of metal deposition efficiency and morphology control and thus provides important fundamental insight into the dynamic properties of multivalent electrolytes for next-generation batteries.
Han, Kee S.; Hahn, Nathan H.; Zavadil, Kevin R.; Jaegers, Nicholas R.; Chen, Ying; Hu, Jian Z.; Murugesan, Vijayakumar; Mueller, Karl T.
Most multivalent secondary batteries have employed electrolytes composed of cyclic ether solvents such as tetrahydrofuran or linear glycol ether solvents (glymes) such as 1,2-dimethoxyethane (G1). A robust understanding of multivalent cation solvation tendencies in these classes of solvents provides insight into corresponding structure-property relationships which, in turn, promotes the design and discovery of improved electrolytes. In this work, our goal is to systematically address how electrolyte constituent properties, namely, ether solvent structure and dication size, direct the solvation interactions of divalent electrolytes and their resultant properties. This study utilizes pulsed-field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy in conjunction with Raman spectroscopy and ionic conductivity measurements to elucidate the preferential interactions between multivalent cations, anions, and solvent molecules along with their correlated ion dynamics. These investigations incorporate two representative divalent cations (Ca2+ and Zn2+) as well as two ethereal solvent representatives from both the cyclic ether and glyme structural classes. The results reveal that anions coordinate more readily with divalent cations in cyclic ethers than in glymes. Furthermore, the coordination of the anions with Ca2+, i.e., contact-ion pair (CIP) formation is more pronounced than with Zn2+ in a glyme solvent of limited chain length (G1), providing insight into cation size effects that are important for translating solvation behavior across various multivalent electrolytes. Importantly, we find that specific anion coordination is more strongly controlled by solvent structure than by salt concentration in the practical range of 0.1-0.5 M. However, simply reducing these inner-sphere inter-ionic interactions by changing solvent structure does not necessarily de-correlate ionic motion. Instead, concentration-dependent changes in molar ionic conductivity suggest that second-shell interactions, i.e., solvent separated ion pairs (SSIPs), are prevalent in these electrolytes and that the solution dielectric constant, which is increased by the presence of dipolar ion pairs, is critical for controlling these interactions. These findings thus provide a basis for understanding the physical chemistry of multivalent battery electrolytes.
Driscoll, Darren M.; Dandu, Naveen K.; Hahn, Nathan H.; Seguin, Trevor J.; Persson, Kristin A.; Zavadil, Kevin R.; Curtiss, Larry A.; Balasubramanian, Mahalingam
Ca-ion electrochemical systems have been pushed to the forefront of recent multivalent energy storage advances due to their use of earth-abundant redox materials and their high theoretical specific densities in relation to monovalent or even other more widely explored multivalent-charge carriers. However, significant pitfalls in metal plating and stripping arise from electrolyte decomposition and can be related to the coordination environment around Ca2+ with both the negatively charged anion and the organic-aprotic solvent. In this study, we apply multiple spectroscopic techniques in conjunction with density functional theory to evaluate the coordination environment of Ca2+ across a class of ethereal solvents. Through the combination of X-ray absorption fine structure and time-dependent density functional theory, descriptive measures of the local geometry, coordination, and electronic structure of Ca-ethereal complexes provide distinct structural trends depending on the extent of the Ca2+-solvent interaction. Finally, we correlate these findings with electrochemical measurements of calcium tetrakis(hexafluoroisopropoxy)borate (CaBHFIP2) salts dissolved within this class of solvents to provide insight into the preferred structural configuration of Ca2+ electrolytic solutions for optimized electrochemical plating and stripping.
Wang, Hui; Shao, Yuyan; Pan, Huilin; Feng, Xuefei; Chen, Ying; Liu, Yi S.; Walter, Eric D.; Engelhard, Mark H.; Han, Kee S.; Deng, Tao; Ren, Guoxi; Lu, Dongping; Lu, Xiaochuan; Xu, Wu; Wang, Chunsheng; Feng, Jun; Mueller, Karl T.; Guo, Jinghua; Zavadil, Kevin R.; Zhang, Ji G.
Lithium-sulfur (Li–S) battery is one of the most promising candidates for the next generation energy storage systems. However, several barriers, including polysulfide shuttle effect, the slow solid-solid surface reaction pathway in the lower discharge plateau, and corrosion of Li anode still limit its practical applications, especially under the lean electrolyte condition required for high energy density. Here, we propose a solution-mediated sulfur reduction pathway to improve the capacity and reversibility of the sulfur cathode. With this method, a high coulombic efficiency (99%) and stable cycle life over 100 cycles were achieved under application-relevant conditions (S loading: 6.2 mg cm−2; electrolyte to sulfur ratio: 3 mLE gs−1; sulfur weight ratio: 72 wt%). This result is enabled by a specially designed Li2S4-rich electrolyte, in which Li2S is formed through a chemical disproportionation reaction instead of electrochemical routes. A single diglyme solvent was used to obtain electrolytes with the optimum range of Li2S4 concentration. Operando X-ray absorption spectroscopy confirms the solution pathway in a practical Li–S cell. This solution pathway not only introduces a new electrolyte regime for practical Li–S batteries, but also provides a new perspective for bypassing the inefficient surface pathway for other electrochemical processes.
Hahn, Nathan H.; Driscoll, Darren M.; Yu, Zhou; Sterbinsky, George E.; Cheng, Lei; Balasubramanian, Mahalingam; Zavadil, Kevin R.
The emergence of magnesium and calcium batteries as potential beyond Li ion energy storage technologies has generated significant interest into the fundamental aspects of alkaline earth metal cation coordination in multivalent electrolytes and the impact of coordination on application-critical electrolyte properties such as solubility, transport, and electrochemical stability. Understanding these details in calcium electrolytes is of immediate importance due to recent, unprecedented demonstrations of reversible calcium metal electrodeposition in a limited number of ethereal solvent-based systems. In this work, we provide insight connecting Ca2+ coordination tendencies to important calcium battery electrolyte properties. Our results demonstrate a clear solvent:Ca2+ coordination strength trend across a series of cyclic ether and linear glyme solvents that controls the extent of ion association in solutions of "weakly"coordinating salts. We apply understanding gained from these results to rationalize relative anion:Ca2+ coordination tendencies and attendant Ca2+ coordination structures using two oxidatively stable anions of particular interest for current battery electrolytes. Armed with this understanding of solvent and anion interactions with Ca2+, we demonstrate and interpret differences in electrochemical calcium deposition behavior across several electrolyte exemplars with varying solvent and anion coordination strengths. Our findings demonstrate that solvents exhibiting especially strong coordination to Ca2+, such as triglyme, can inhibit reversible calcium deposition despite effective elimination of anion:Ca2+ coordination while solvents exhibiting more modest coordination strength, such as 1,2-dimethoxyethane, may enable deposition provided anion:Ca2+ coordination is substantially limited. These results reveal that the strength of coordination of both anion and solvent should be considered in the design of electrolytes for calcium batteries.
Watkins, Tylan W.; Sarbapalli, Dipobrato; Counihan, Michael J.; Danis, Andrew S.; Zhang, Jingjing; Zhang, Lu; Zavadil, Kevin R.; Rodriguez-Lopez, Joaquin
Redox flow batteries are attractive technologies for grid energy storage since they use solutions of redox-active molecules that enable a superior scalability and the decoupling of power and energy density. However, the reaction mechanisms of the redox active components at RFB electrodes are complex, and there is currently a pressing need to understand how interfacial processes impact the kinetics and operational reversibility of RFB systems. Here, we developed a combined electrochemical imaging methodology rooted in scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM) for exploring the impact of electrode structure and conditioning on the electron transfer properties of model redox-active dialkoxybenzene derivatives, 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (C1) and 2,3-dimethyl-1,4-dialkoxybenzene (C7). Using AFM and secondary-ion mass spectrometry (SIMS), we observed the formation of interfacial films with distinct mechanical properties compared to those of cleaved graphitic surfaces, and exclusively during reduction of electrogenerated radical cations. These films had an impact on the median rate and distribution of the electron transfer rate constant at the basal plane of multilayer and single layer graphene electrodes, displaying kinetically-limited values that did not yield the activation expected per the Butler-Volmer model with a transfer coefficient ∼0.5. These changes were dependent on redoxmer structure: SECM showed strong attenuation of C7 kinetics by a surface layer on MLG and SLG, while C1 kinetics were only affected by SLG. SECM and AFM results together show that these limiting films operate exclusively on the basal plane of graphite, with the edge plane showing a relative insensitivity to cycling and operation potential. This integrated electrochemical imaging methodology creates new opportunities to understand the unique role of interfacial processes on the heterogeneous reactivity of redoxmers at electrodes for RFBs, with a future role in elucidating phenomena at high active concentrations and spatiotemporal variations in electrode dynamics. This journal is
Proceedings of the National Academy of Sciences of the United States of America
Trahey, Lynn; Brushett, Fikile R.; Balsara, Nitash P.; Ceder, Gerbrand; Cheng, Lei; Chiang, Yet M.; Hahn, Nathan H.; J, Ingrambrian; Minteer, Shelley D.; Moore, Jeffrey S.; Mueller, Karl T.; Nazar, Linda F.; Persson, Kristin A.; Siegel, Donald J.; Xu, Kang; Zavadil, Kevin R.; Srinivasan, Venkat; Crabtree, George W.
Energy storage is an integral part of modern society. A contemporary example is the lithium (Li)-ion battery, which enabled the launch of the personal electronics revolution in 1991 and the first commercial electric vehicles in 2010. Most recently, Li-ion batteries have expanded into the electricity grid to firm variable renewable generation, increasing the efficiency and effectiveness of transmission and distribution. Important applications continue to emerge including decarbonization of heavy-duty vehicles, rail, maritime shipping, and aviation and the growth of renewable electricity and storage on the grid. This perspective compares energy storage needs and priorities in 2010 with those now and those emerging over the next few decades. The diversity of demands for energy storage requires a diversity of purpose-built batteries designed to meet disparate applications. Advances in the frontier of battery research to achieve transformative performance spanning energy and power density, capacity, charge/discharge times, cost, lifetime, and safety are highlighted, along with strategic research refinements made by the Joint Center for Energy Storage Research (JCESR) and the broader community to accommodate the changing storage needs and priorities. Innovative experimental tools with higher spatial and temporal resolution, in situ and operando characterization, first-principles simulation, high throughput computation, machine learning, and artificial intelligence work collectively to reveal the origins of the electrochemical phenomena that enable new means of energy storage. This knowledge allows a constructionist approach to materials, chemistries, and architectures, where each atom or molecule plays a prescribed role in realizing batteries with unique performance profiles suitable for emergent demands.
Development of calcium metal batteries has been historically frustrated by a lack of electrolytes capable of supporting reversible calcium electrodeposition. In this paper, we report the study of an electrolyte consisting of Ca(BH4)2 in tetrahydrofuran (THF) to gain important insight into the role of the liquid solvation environment in facilitating the reversible electrodeposition of this highly reactive, divalent metal. Through interrogation of the Ca2+ solvation environment and comparison with Mg2+ analogs, we show that an ability to reversibly electrodeposit metal at reasonable rates is strongly regulated by dication charge density and polarizability. Our results indicate that the greater polarizability of Ca2+ over Mg2+ confers greater configurational flexibility, enabling ionic cluster formation via neutral multimer intermediates. Increased concentration of the proposed electroactive species, CaBH4+, enables rapid and stable delivery of Ca2+ to the electrode interface. This work helps set the stage for future progress in the development of electrolytes for calcium and other divalent metal batteries.
Detailed speciation of electrolytes as a function of chemical system and concentration provides the foundation for understanding bulk transport as well as possible decomposition mechanisms. In particular, multivalent electrolytes have shown a strong coupling between anodic stability and solvation structure. Furthermore, solvents that are found to exhibit reasonable stability against alkaline-earth metals generally exhibit low permittivity, which typically increases the complexity of the electrolyte species. To improve our understanding of ionic population and associated transport in these important classes of electrolytes, the speciation of Mg(TFSI)2 in monoglyme and diglyme systems is studied via a multiscale thermodynamic model using first-principles calculations for ion association and molecular dynamics simulations for dielectric properties. The results are then compared to Raman and dielectric relaxation spectroscopies, which independently confirm the modeling insights. We find that the significant presence of free ions in the low-permittivity glymes in the concentration range from 0.02 to 0.6 M is well-explained by the low-permittivity redissociation hypothesis. Here, salt speciation is largely dictated by long-range electrostatics, which includes permittivity increases due to polar contact ion pairs. The present results suggest that other low-permittivity multivalent electrolytes may also reach high conductivities as a result of redissociation.
Conventional electrolytes made by mixing simple Mg2+ salts and aprotic solvents, analogous to those in Li-ion batteries, are incompatible with Mg anodes because Mg metal readily reacts with such electrolytes, producing a passivation layer that blocks Mg2+ transport. In this paper, we report that, through tuning a conventional electrolyte—Mg(TFSI)2 (TFSI– is N(SO2CF3)2–)—with an Mg(BH4)2 cosalt, highly reversible Mg plating/stripping with a high Coulombic efficiency is achieved by neutralizing the first solvation shell of Mg cationic clusters between Mg2+ and TFSI– and enhanced reductive stability of free TFSI–. A critical adsorption step between Mg0 atoms and active Mg cation clusters involving BH4– anions is identified to be the key enabler for reversible Mg plating/stripping through analysis of the distribution of relaxation times (DRT) from operando electrochemical impedance spectroscopy (EIS), operando electrochemical X-ray absorption spectroscopy (XAS), nuclear magnetic resonance (NMR), and density functional theory (DFT) calculations.
Engineered solid-liquid interfaces will play an important role in the development of future energy storage and conversion (ESC) devices. In the present study, defective graphene oxide (GO) and reduced graphene oxide (rGO) structures were used as engineered interfaces to tune the selectivity and activity of Pt disk electrodes. GO was deposited on Pt electrodes via the Langmuir-Blodgett technique, which provided compact and uniform GO films, and these films were subsequently converted to rGO by thermal reduction. Electrochemical measurements revealed that both GO and rGO interfaces on Pt electrodes exhibit selectivity toward the oxygen reduction reaction (ORR), but they do not have an impact on the activity of the hydrogen oxidation reaction in acidic environments. Scanning transmission electron microscopy at atomic resolution, along with Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), revealed possible diffusion sites for H2 and O2 gas molecules and functional groups relevant to the selectivity and activity of these surfaces. Based on these insights, rGO interfaces are further demonstrated to exhibit enhanced activity for the ORR in nonaqueous environments and demonstrate the power of our ex situ engineering approach for the development of next-generation ESC devices.
To suppress dendrite formation in lithium metal batteries, high cation transference number electrolytes that reduce electrode polarization are highly desirable, but rarely available using conventional liquid electrolytes. Here, we show that liquid electrolytes increase their cation transference numbers (e.g., ∼0.2 to >0.70) when confined to a structurally rigid polymer host whose pores are on a similar length scale (0.5-2 nm) as the Debye screening length in the electrolyte, which results in a diffuse electrolyte double layer at the polymer-electrolyte interface that retains counterions and reject co-ions from the electrolyte due to their larger size. Lithium anodes coated with ∼1 μm thick overlayers of the polymer host exhibit both a low area-specific resistance and clear dendrite-suppressing character, as evident from their performance in Li-Li and Li-Cu cells as well as in post-mortem analysis of the anode's morphology after cycling. High areal capacity Li-S cells (4.9 mg cm -2 8.2 mAh cm -2 ) implementing these high transference number polymer-hosted liquid electrolytes were remarkably stable, considering ∼24 μm of lithium was electroreversibly deposited in each cycle at a C-rate of 0.2. We further identified a scalable manufacturing path for these polymer-coated lithium electrodes, which are drop-in components for lithium metal battery manufacturing.
This quarter, we have focused on characterizing the electrochemical response, both through cyclic voltammetry and through constant current charge/discharge characterization of the silicon samples coated with silicates containing varying amounts of Li in the SiOx layer. These studies were performed using a standard Gen-2 electrolyte without FEC. We also performed electrochemical impedance spectroscopy on samples exposed to the Gen-2 electrolyte continually, and collected EIS spectra as a function of time and temperature.
Seguin, Trevor J.; Hahn, Nathan T.; Zavadil, Kevin R.; Persson, Kristin A.
Rational design of novel electrolytes with enhanced functionality requires fundamental molecular-level understanding of structure-property relationships. Here we examine the suitability of a range of organic solvents for non-aqueous electrolytes in secondary magnesium batteries using density functional theory (DFT) calculations as well as experimental probes such as cyclic voltammetry and Raman spectroscopy. The solvents considered include ethereal solvents (e.g., glymes) sulfones (e.g., tetramethylene sulfone), and acetonitrile. Computed reduction potentials show that all solvents considered are stable against reduction by Mg metal. Additional computations were carried out to assess the stability of solvents in contact with partially reduced Mg cations (Mg 2+ → Mg + ) formed during cycling (e.g., deposition) by identifying reaction profiles of decomposition pathways. Most solvents, including some proposed for secondary Mg energy storage applications, exhibit decomposition pathways that are surprisingly exergonic. Interestingly, the stability of these solvents is largely dictated by magnitude of the kinetic barrier to decomposition. This insight should be valuable toward rational design of improved Mg electrolytes.
Future energy applications rely on our ability to tune liquid intermolecular interactions and achieve designer electrolytes with highly optimized properties. In this work, we demonstrate rational, combined experimental-computational design of a new carba-closo-dodecaborate-based salt with enhanced anodic stability for Mg energy storage applications. We first establish, through a careful examination using a range of solvents, the anodic oxidation of a parent anion, the carba-closo-dodecaborate anion at 4.6 V vs Mg0/2+ (2.0 vs Fc0/+), a value lower than that projected for this anion in organic solvent-based electrolytes and lower than weakly associating bis(trifluoromethylsulfonyl)imide and tetrafluoroborate anions. Solvents such as acetonitrile, 3-methylsulfolane, and 1,1,1,3,3,3-hexafluoroisopropanol are shown to enable the direct measurement of carba-closo-dodecaborate oxidation, where the resultant neutral radical drives passive film formation on the electrode. Second, we employ computational screening to evaluate the impact of functionalization of the parent anion on its stability and find that replacement of the carbon-vertex proton with a more electronegative fluorine or trifluoromethyl ligand increases the oxidative stability and decreases the contact-ion pair formation energy while maintaining reductive stability. This predicted expansion of the electrochemical window for fluorocarba-closo-dodecaborate is experimentally validated. Future work includes evaluation of the viability of these derivative anions as efficient and stable carriers for energy storage as a function of the ionic transport through the resulting surface films formed on candidate cathodes.
Lithium metal is considered the "holy grail" of next-generation battery anodes. However, severe parasitic reactions at the lithium-electrolyte interface deplete the liquid electrolyte and the uncontrolled formation of high surface area and dendritic lithium during cycling causes rapid capacity fading and battery failure. Engineering a dendrite-free lithium metal anode is therefore critical for the development of long-life batteries using lithium anodes. In this study, we deposit a conformal, organic/inorganic hybrid coating, for the first time, directly on lithium metal using molecular layer deposition (MLD) to alleviate these problems. This hybrid organic/inorganic film with high cross-linking structure can stabilize lithium against dendrite growth and minimize side reactions, as indicated by scanning electron microscopy. We discovered that the alucone coating yielded several times longer cycle life at high current rates compared to the uncoated lithium and achieved a steady Coulombic efficiency of 99.5%, demonstrating that the highly cross-linking structured material with great mechanical properties and good flexibility can effectively suppress dendrite formation. The protected Li was further evaluated in lithium-sulfur (Li-S) batteries with a high sulfur mass loading of ∼5 mg/cm2. After 140 cycles at a high current rate of ∼1 mA/cm2, alucone-coated Li-S batteries delivered a capacity of 657.7 mAh/g, 39.5% better than that of a bare lithium-sulfur battery. These findings suggest that flexible coating with high cross-linking structure by MLD is effective to enable lithium protection and offers a very promising avenue for improved performance in the real applications of Li-S batteries.
To understand the mechanism that controls low-aspect-ratio lithium deposition morphologies for Li-metal anodes in batteries, we conducted direct visualization of Li-metal deposition and stripping behavior through nanoscale in situ electrochemical scanning transmission electron microscopy (EC-STEM) and macroscale-cell electrochemistry experiments in a recently developed and promising solvate electrolyte, 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane. In contrast to published coin cell studies in the same electrolyte, our experiments revealed low Coulombic efficiencies and inhomogeneous Li morphology during in situ observation. We conclude that this discrepancy in Coulombic efficiency and morphology of the Li deposits was dependent on the presence of a compressed lithium separator interface, as we have confirmed through macroscale (not in the transmission electron microscope) electrochemical experiments. Our data suggests that cell compression changed how the solid-electrolyte interphase formed, which is likely responsible for improved morphology and Coulombic efficiency with compression. Furthermore, during the in situ EC-STEM experiments, we observed direct evidence of nanoscale self-discharge in the solvate electrolyte (in the state of electrical isolation). This self-discharge was duplicated in the macroscale, but it was less severe with electrode compression, likely due to a more passivating and corrosion-resistant solid-electrolyte interphase formed in the presence of compression. By combining the solvate electrolyte with a protective LiAl0.3S coating, we show that the Li nucleation density increased during deposition, leading to improved morphological uniformity. Furthermore, self-discharge was suppressed during rest periods in the cycling profile with coatings present, as evidenced through EC-STEM and confirmed with coin cell data.
Electrochemistry is necessarily a science of interfacial processes, and understanding electrode/electrolyte interfaces is essential to controlling electrochemical performance and stability. Undesirable interfacial interactions hinder discovery and development of rational materials combinations. By example, we examine an electrolyte, magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) dissolved in diglyme, next to the Mg metal anode, which is purported to have a wide window of electrochemical stability. However, even in the absence of any bias, using in situ tender X-ray photoelectron spectroscopy, we discovered an intrinsic interfacial chemical instability of both the solvent and salt, further explained using first-principles calculations as driven by Mg2+ dication chelation and nucleophilic attack by hydroxide ions. The proposed mechanism appears general to the chemistry near or on metal surfaces in hygroscopic environments with chelation of hard cations and indicates possible synthetic strategies to overcome chemical instability within this class of electrolytes.
Zavadil, Kevin R.; Cheng, Lei; Curtiss, Larry A.; Gewirth, Andrew A.; Shao, Yuyan; Gallagher, Kevin G.
Moving to lighter and less expensive battery chemistries compared to contemporary lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium-sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry require large excesses of electrolyte to fully solubilize the polysulfide intermediates. Achieving reversible electrochemistry under lean electrolyte operation is the most promising path for Li/S to move beyond niche applications to potentially transformational performance. An emerging Li/S research area is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systems that fundamentally decouple electrolyte volume from sulfur and polysulfide reaction mechanism. This Perspective presents an outlook for sparingly solvating electrolytes as a key path forward for long-lived, high energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.
Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. Here, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge-discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed for the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Our results show that electrochemically induced solid-solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.
A new model of electrodeposition and electrodissolution is developed and applied to the evolution of Mg deposits during anode cycling. The model captures Butler-Volmer kinetics, facet evolution, the spatially varying potential in the electrolyte, and the time-dependent electrolyte concentration. The model utilizes a diffuse interface approach, employing the phase field and smoothed boundary methods. Scanning electron microscope (SEM) images of magnesium deposited on a gold substrate show the formation of faceted deposits, often in the form of hexagonal prisms. Orientation-dependent reaction rate coefficients were parameterized using the experimental SEM images. Three-dimensional simulations of the growth of magnesium deposits yield deposit morphologies consistent with the experimental results. The simulations predict that the deposits become narrower and taller as the current density increases due to the depletion of the electrolyte concentration near the sides of the deposits. Increasing the distance between the deposits leads to increased depletion of the electrolyte surrounding the deposit. Two models relating the orientation-dependence of the deposition and dissolution reactions are presented. The morphology of the Mg deposit after one deposition-dissolution cycle is significantly different between the two orientation-dependence models, providing testable predictions that suggest the underlying physical mechanisms governing morphology evolution during deposition and dissolution.
Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultradry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad···H2O (aqueous solutions) and LiO2···H2O (organic solvents) complexes that place water in a configurationally favorable position for proton transfer to weakly adsorbed intermediates. We also find that, even at low concentrations (<10 ppm), water acts simultaneously as a promoter and as a catalyst in the production of Li2O2, regenerating itself through a sequence of steps that include the formation and recombination of H+ and OH-. We conclude that, although the binding energy between metal surfaces and oxygen intermediates is an important descriptor in electrocatalysis, understanding the role of water as a proton-donor reactant may explain many anomalous features in electrocatalysis at metal-liquid interfaces.
Liquid-phase transfer of graphene oxide (GO) and reduced graphene oxide (RGO) monolayers is investigated from the perspective of the mechanical properties of these films. Monolayers are assembled in a Langmuir-Blodgett trough, and oscillatory barrier measurements are used to characterize the resulting compressive and shear moduli as a function of surface pressure. GO monolayers are shown to develop a significant shear modulus (10-25 mN/m) at relevant surface pressures while RGO monolayers do not. The existence of a shear modulus indicates that GO is acting as a two-dimensional solid driven by strong interaction between the individual GO sheets. The absence of such behavior in RGO is attributed to the decrease in oxygen moieties on the sheet basal plane, permitting RGO sheets to slide across one another with minimum energy dissipation. Knowledge of this two-dimensional solid behavior is exploited to successfully transfer large-area, continuous GO films to hydrophobic Au substrates. The key to successful transfer is the use of shallow-angle dipping designed to minimize tensile stress present during the insertion or extraction of the substrate. A shallow dip angle on hydrophobic Au does not impart a beneficial effect for RGO monolayers, as these monolayers do not behave as two-dimensional solids and do not remain coherent during the transfer process. We hypothesize that this observed correlation between monolayer mechanical properties and continuous film transfer success is more universally applicable across substrate hydrophobicities and could be exploited to control the transfer of films composed of two-dimensional materials.
The impact of surface film formation on Mg is explored during electrodeposition and electrodissolution in two high activity, aprotic electrolytes: the all phenyl complex (APC) and the magnesium aluminum chloride complex (MACC). Where past studies have argued such films are benign, results show that interfacial films are responsible for controlling the Mg deposit structure when deposition and dissolution are conducted at the rates required for practical Mg batteries. Chronopotentiometry is shown to provide clear signatures of the impact of interfacial films on deposition and dissolution. The particular combination of cycling punctuated by periods of open circuit equilibration is shown to yield a noticeable decrease in coulombic efficiency over a 50 cycle sequence. High resolution electron imaging shows that cycling results in porosity development and accumulation of electrolyte constituents within the deposit. Reduced coulombic efficiency signaling Mg loss appears related to progressive isolation of a fraction of the deposit. Mg and electrolyte loss must be compensated for in a practical cell through the introduction of excess inventory and resulting in a reduced energy density of the system.
Zavadil, Kevin R.; Hahn, Nathan H.; Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T.; Meng, Yifei; Vieker, Henning; Golzhauser, Armin; Zuo, Jian M.; Gewirth, Andrew A.; Nuzzo, Ralph G.
Although rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. The passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte. (Figure Presented).
Sandia journal manuscript; Not yet accepted for publication
Zavadil, Kevin R.; Sa, Niya; Proffit, Danielle L.; Lipson, Albert L.; Liu, Miao; Gautam, Gopalakrishnan S.; Hahn, Nathan H.; Feng, Zhenxing; Fister, Timothy T.; Ren, Yang; Sun, Cheng-Jun; Vaughey, John T.; Liao, Chen; Fenter, Paul A.; Ceder, Gerbrand; Burrell, Anthony K.
A major roadblock for magnesium ion battery development is the availability of an electrolyte that can deposit Mg reversibly and at the same time is compatible with a high voltage cathode. We report a prospective full magnesium cell utilizing a simple, non-aqueous electrolyte composed of high concentration magnesium bis(trifluoromethane sulfonyl)imide in diglyme, which is compatible with a high voltage vanadium pentoxide (V2O5) cathode and a Mg metal anode. For this system, plating and stripping of Mg metal can be achieved with magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolyte over a wide concentration range, however, reversible insertion of Mg into V2O5 cathode can only be attained at high electrolyte concentrations. Reversible intercalation of Mg into V2O5 is characterized and confirmed by X-ray diffraction, X-ray absorption near edge spectroscopy and energy dispersive spectroscopy.
Zavadil, Kevin R.; Kundu, Dipan; Black, Robert; Adams, Brian; Harrison, Katharine; Nazar, Linda F.
The development of nonaqueous Li-oxygen batteries, which relies on the reversible reaction of Li + O2 to give lithium peroxide (Li2O2), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li2O2 oxidation on a passivated nanostructured metallic carbide (Mo2C), carbon-free cathode host. Online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the LixMoO3-passivated conductive interface formed on the carbide, owing to their close redox potentials. The process rejuvenates the surface on each cycle upon electrochemical charge by releasing LixMoO3 into the electrolyte, explaining the low charging potential.
Multivalent (MV) battery architectures based on pairing a Mg metal anode with a high-voltage (∼3 V) intercalation cathode offer a realistic design pathway toward significantly surpassing the energy storage performance of traditional Li-ion-based batteries, but there are currently only few electrolyte systems that support reversible Mg deposition. Using both static first-principles calculations and ab initio molecular dynamics, we perform a comprehensive adsorption study of several salt and solvent species at the interface of Mg metal with an electrolyte of Mg2+ and Cl- dissolved in liquid tetrahydrofuran (THF). Our findings not only provide a picture of the stable species at the interface but also explain how this system can support reversible Mg deposition, and as such, we provide insights in how to design other electrolytes for Mg plating and stripping. The active depositing species are identified to be (MgCl)+ monomers coordinated by THF, which exhibit preferential adsorption on Mg compared to possible passivating species (such as THF solvent or neutral MgCl2 complexes). Upon deposition, the energy to desolvate these adsorbed complexes and facilitate charge transfer is shown to be small (∼61-46.2 kJ mol-1 to remove three THF from the strongest adsorbing complex), and the stable orientations of the adsorbed but desolvated (MgCl)+ complexes appear to be favorable for charge transfer. Finally, observations of Mg-Cl dissociation at the Mg surface at very low THF coordinations (0 and 1) suggest that deleterious Cl incorporation in the anode may occur upon plating. In the stripping process, this is beneficial by further facilitating the Mg removal reaction.
Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm2 leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. The effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. We discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.
This report documents work that was performed under the Laboratory Directed Research and Development project, Science of Battery Degradation. The focus of this work was on the creation of new experimental and theoretical approaches to understand atomistic mechanisms of degradation in battery electrodes that result in loss of electrical energy storage capacity. Several unique approaches were developed during the course of the project, including the invention of a technique based on ultramicrotoming to cross-section commercial scale battery electrodes, the demonstration of scanning transmission x-ray microscopy (STXM) to probe lithium transport mechanisms within Li-ion battery electrodes, the creation of in-situ liquid cells to observe electrochemical reactions in real-time using both transmission electron microscopy (TEM) and STXM, the creation of an in-situ optical cell utilizing Raman spectroscopy and the application of the cell for analyzing redox flow batteries, the invention of an approach for performing ab initio simulation of electrochemical reactions under potential control and its application for the study of electrolyte degradation, and the development of an electrochemical entropy technique combined with x-ray based structural measurements for understanding origins of battery degradation. These approaches led to a number of scientific discoveries. Using STXM we learned that lithium iron phosphate battery cathodes display unexpected behavior during lithiation wherein lithium transport is controlled by nucleation of a lithiated phase, leading to high heterogeneity in lithium content at each particle and a surprising invariance of local current density with the overall electrode charging current. We discovered using in-situ transmission electron microscopy that there is a size limit to lithiation of silicon anode particles above which particle fracture controls electrode degradation. From electrochemical entropy measurements, we discovered that entropy changes little with degradation but the origin of degradation in cathodes is kinetic in nature, i.e. lower rate cycling recovers lost capacity. Finally, our modeling of electrode-electrolyte interfaces revealed that electrolyte degradation may occur by either a single or double electron transfer process depending on thickness of the solid-electrolyte-interphase layer, and this cross-over can be modeled and predicted.
Zavadil, Kevin R.; Barile, Christopher J.; Barile, Elizabeth C.; Nuzzo, Ralph G.; Gewirth, Andrew A.
We describe in this report the electrochemistry of Mg deposition and dissolution from the magnesium aluminum chloride complex (MACC). The results define the requirements for reversible Mg deposition and definitively establish that voltammetric cycling of the electrolyte significantly alters its composition and performance. Elemental analysis, scanning electron microscopy, and energy-dispersive X-ray spectroscopy (SEM-EDS) results demonstrate that irreversible Mg and Al deposits form during early cycles. Electrospray ionization mass spectrometry (ESI-MS) data show that inhibitory oligomers develop in THF-based solutions. These oligomers form via the well-established mechanism of a cationic ring-opening polymerization of THF during the initial synthesis of the MACC and under resting conditions. In contrast, MACC solutions in 1,2-dimethoxyethane (DME), an acyclic solvent, do not evolve as dramatically at open circuit potential. From these results, we propose a mechanism describing how the conditioning process of the MACC in THF improves its performance by both tuning the Mg:Al stoichiometry and eliminating oligomers.
The integration and stability of electrocatalytic nanostructures, which represent one level of porosity in a hierarchical structural scheme when combined with a three-dimensional support scaffold, has been studied using a combination of synthetic processes, characterization techniques, and computational methods. Dendritic platinum nanostructures have been covalently linked to common electrode surfaces using a newly developed chemical route; a chemical route equally applicable to a range of metals, oxides, and semiconductive materials. Characterization of the resulting bound nanostructure system confirms successful binding, while electrochemistry and microscopy demonstrate the viability of these electroactive particles. Scanning tunneling microscopy has been used to image and validate the short-term stability of several electrode-bound platinum dendritic sheet structures toward Oswald ripening. Kinetic Monte Carlo methods have been applied to develop an understanding of the stability of the basic nano-scale porous platinum sheets as they transform from an initial dendrite to hole containing sheets. Alternate synthetic strategies were pursued to grow dendritic platinum structures directly onto subunits (graphitic particles) of the electrode scaffold. A two-step photocatalytic seeding process proved successful at generating desirable nano-scale porous structures. Growth in-place is an alternate strategy to the covalent linking of the electrocatalytic nanostructures.
The Proliferation Assessment (program area - Things Thin) within the Defense Systems and Assessment Investment Area desires high energy density and long-lived power sources with moderate currents (mA) that can be used as building blocks in platforms for the continuous monitoring of chemical, biological, and radiological agents. Fuel cells can be an optimum choice for a power source because of the high energy densities that are possible with liquid fuels. Additionally, power generation and fuel storage can be decoupled in a fuel cell for independent control of energy and power density for customized, application-driven power solutions. Direct methanol fuel cells (DMFC) are explored as a possible concept to develop into ultrathin or two-dimensional power sources. New developments in nanotechnology, advanced fabrication techniques, and materials science are exploited to create a planar DMFC that could be co-located with electronics in a chip format. Carbon nanotubes and pyrolyzed polymers are used as building block electrodes - porous, mechanically compliant current collectors. Directed assembly methods including surface functionalization and layer-by-layer deposition with polyelectrolytes are used to pattern, build, and add functionality to these electrodes. These same techniques are used to incorporate nanoscale selective electrocatalyst into the carbon electrodes to provide a high density of active electron transfer sites for the methanol oxidation and oxygen reduction reactions. The resulting electrodes are characterized in terms of their physical properties, electrocatalytic function, and selectivity to better understand how processing impacts their performance attributes. The basic function of a membrane electrode assembly is demonstrated for several prototype devices.
Advances in electrochemical energy storage science require the development of new or the refinement of existing in situ probes that can be used to establish structure - activity relationships for technologically relevant materials. The drive to develop reversible, high capacity electrodes from nanoscale building blocks creates an additional requirement for high spatial resolution probes to yield information of local structural, compositional, and electronic property changes as a function of the storage state of a material. In this paper, we describe a method for deconstructing a lithium ion battery positive electrode into its basic constituents of ion insertion host particles and a carbon current collector. This model system is then probed in an electrochemical environment using a combination of atomic force microscopy and tunneling spectroscopy to correlate local activity with morphological and electronic configurational changes. Cubic spinel Li{sub 1+x}Mn{sub 2-x}O{sub 4} nanoparticles are grown on graphite surfaces using vacuum deposition methods. The structure and composition of these particles are determined using transmission electron microscopy and Auger microprobe analysis. The response of these particles to initial de-lithiation, along with subsequent electrochemical cycling, is tracked using scanning probe microscopy techniques in polar aprotic electrolytes (lithium hexafluorophosphate in ethylene carbonate:diethylcarbonate). The relationship between nanoparticle size and reversible ion insertion activity will be a specific focus of this paper.
Erbium is known to effectively load with hydrogen when held at high temperature in a hydrogen atmosphere. To make the storage of hydrogen kinetically feasible, a thermal activation step is required. Activation is a routine practice, but very little is known about the physical, chemical, and/or electronic processes that occur during Activation. This work presents in situ characterization of erbium Activation using variable energy photoelectron spectroscopy at various stages of the Activation process. Modification of the passive surface oxide plays a significant role in Activation. The chemical and electronic changes observed from core-level and valence band spectra will be discussed along with corroborating ion scattering spectroscopy measurements.
Erbium is known to effectively load with hydrogen when held at high temperature in a hydrogen atmosphere. To make the storage of hydrogen kinetically feasible, a thermal activation step is required. Activation is a routine practice, but very little is known about the physical, chemical, and/or electronic processes that occur during Activation. This work presents in situ characterization of erbium Activation using variable energy photoelectron spectroscopy at various stages of the Activation process. Modification of the passive surface oxide plays a significant role in Activation. The chemical and electronic changes observed from core-level and valence band spectra will be discussed along with corroborating ion scattering spectroscopy measurements.