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DOE OSTI2023

The Role of Transition Metals on Chemo-Mechanical Instabilities in Prussian Blue Analogues For K-Ion Batteries: The Case Study on KNHCF Versus KMHCF

Prussian blue analogues (PBAs) cathodes can host diverse monovalent and multivalent metal ions due to their tunable structure. However, their electrochemical performance suffers from poor cycle life associated with chemo-mechanical instabilities. This study investigates the driving forces behind chemo-mechanical instabilities in Ni- and Mn-based PBAs cathodes for K-ion batteries by combining electrochemical analysis, digital image correlation, and spectroscopy techniques. Capacity retention in Ni-based PBA is 96% whereas it is 91.5% for Mn-based PBA after 100 cycles at C/5 rate. During charge, the potassium nickel hexacyanoferrate (KNHCF) electrode experiences a positive strain generation whereas the potassium manganese hexacyanoferrate (KMHCF) electrode undergoes initially positive strain generation followed by a reduction in strains at a higher state of charge. Overall, both cathodes undergo similar reversible electrochemical strains in each charge–discharge cycle. There is ~0.80% irreversible strain generation in both cathodes after 5 cycles. XPS studies indicated richer organic layer compounds in the cathode-electrolyte interface (CEI) layer formed on KMHCF cathodes compared to the KNHCF ones. Faster capacity fades in Mn-based PBA, compared to Ni-based ones, is attributed to the formation of richer organic compounds in CEI layers, rather than mechanical deformations. In conclusion, understanding the driving forces behind instabilities provides a guideline to develop material-based strategies for better electrochemical performance.

25 ENERGY STORAGE↗

DOE OSTI2023

A Systematic Study on the Effects of Solvating Solvents and Additives in Localized High‐Concentration Electrolytes over Electrochemical Performance of Lithium‐Ion Batteries

Abstract Localized high‐concentration electrolytes (LHCEs) based on five different types of solvents were systematically studied and compared in lithium (Li)‐ion batteries (LIBs). The unique solvation structure of LHCEs promotes the participation of Li salt in forming solid electrolyte interphase (SEI) on graphite (Gr) anode, which enables solvents previously considered incompatible with Gr to achieve reversible lithiation/delithiation. However, the long cyclability of LIBs is still subject to the intrinsic properties of the solvent species in LHCEs. Such issue can be readily resolved by introducing a small amount of additive into LHCEs. The synergetic decompositions of Li salt, solvating solvent and additive yield effective SEIs and cathode electrolyte interphases (CEIs) in most of the studied LHCEs. This study reveals that both the structure and the composition of solvation sheaths in LHCEs have significant effect on SEI and CEI, and consequently, the cycle life of energetically dense LIBs.

Jia, Hao↗

DOE OSTI2023

A Systematic Study on the Effects of Solvating Solvents and Additives in Localized High‐Concentration Electrolytes over Electrochemical Performance of Lithium‐Ion Batteries

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Understanding Discharge‐Driven Growth of Cathode Impedance in Ni‐Rich NMC Cathodes

Degradation of LiNi x Mn y Co 1-x-y O 2 (NMC)-based lithium-ion batteries depends strongly on cut-off voltage ranges. In addition to the high upper cut-off voltage, a high depth of discharge (i.e., lower cut-off voltage) significantly worsens cathode impedance growth and capacity fade during long-term cycling. However, there is currently no consensus on the mechanism behind the negative role of a deep discharge. Here, this phenomenon was investigated in graphite||NMC cells with single-crystal cathodes (LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NMC622) or LiNi 0.76 Co 0.14 Mn 0.10 O 2 (NMC76)) using targeted aging protocols (constant high-voltage holds vs. charge–discharge cycling), while monitoring transition-metal (TM) dissolution, cathode-electrolyte interface (CEI) impedance, and NMC surface composition. We demonstrate a correlation between discharge-driven CEI impedance growth and increased TM dissolution. Furthermore, this degradation pathway is more pronounced in lower-Ni NMC622 than in higher-Ni (NMC76) under comparable delithiation states at charge, with both compositions undergoing the H2→H3 phase transition. X-ray photoelectron spectroscopy (XPS) reveals NMC composition-dependent evolution of surface lattice oxygen and restructured surface layer composition between charged and discharged states. These findings add mechanistic depth to the role of discharge as an active driver of interfacial degradation and provide new insights into its composition dependence.

25 ENERGY STORAGE↗

DOE OSTI2022

Garnet solid electrolyte blended LiNi 0.6 Mn 0.2 Co 0.2 O 2 as high-voltage stable cathodes for advanced lithium-ion batteries

Ni-rich LiNi 1-x Co x/2 Mn x/2 O 2 layered materials have been widely adopted as cathodes for current electric vehicles (EVs) due to their high gravimetric and volumetric energy densities. However, their high-voltage instability (e.g., > 4.3 V vsLi ) limited their usable capacities corresponding to about 60 – 70 % of theoretical capacities. The major problems of high-voltage operation stem from instability of Ni 3+/4+ at cathode-electrolyte interphase (CEI) in contact with electrolytes. Here we propose garnet-type Li 6.7 La 3 Zr 1.7 Ta 0.3 O 12 (LLZT) solid-electrolyte-blended LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC) as high-voltage stable cathodes. The LLZT not only passivates the CEI but scavenges protons and moisture in electrolytes. From well-balanced ionic and electronic transport properties, 5 wt% LLZT blended NMC cathodes delivered enhanced electrochemical performances in full-cells. Unlike other complicated coating processes, our proposed solid-electrolyte blending approach can be readily implementable in commercial Li-ion batteries due to its manufacturing friendliness, energy saving, and cost effectiveness.

33 ADVANCED PROPULSION SYSTEMS↗

DOE OSTI2020

New Synthesis Strategies to Improve Co-Free LiNi0.5Mn0.5O2 Cathodes: Early Transition Metal d0 Dopants and Manganese Pyrophosphate Coating

In this work, we report solution-based doping and coating strategies to improve the electrochemical performance of the Co-free layered oxide cathode LiNi0.5Mn0.5O2 (LNMO). Small amounts of d0 dopants (e.g., Mo6+and Ti4+, 0.5-1 at. %) increase the cathode’s specific capacity, cycling stability, and rate capability. More specifically, a Mo-doped cathode with the nominal composition LiNi0.495Mn0.495Mo0.01O2 achieves a high reversible capacity of 180 mAh/g at 20 mA/g with good retention at higher rates (e.g., 120 mAh/g at 100 mA/g). Effects of 1 at.% Mo dopant on the cathode structure were studied using a suite of characterization tools including X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). These measurements demonstrate that Mo6+ reduces Li+/Ni2+cation mixing and mitigates undesirable phase transformations near the cathode surface during cycling. This work also reports the use of an inorganic Mn2P2O7 coating which enhances cycling stability, presumably through formation of a stable cathode electrolyte interphase (CEI) layer. Overall, the synthesis approaches reported herein are quite general and can potentially be expanded to other high voltage LIB cathodes.

Co-free cathodes, d0 cation, pyrophosphate coating↗

DOE OSTI2022

Synergy of carbonyl and azo chemistries for wide-temperature-range rechargeable aluminum organic batteries

Rechargeable aluminum organic batteries (RAOBs) are promising for developing cost-effective and sustainable energy storage devices due to the low cost, abundance, and high sustainability of aluminum and organic resources. In this study, we designed and synthesized a redox-active polymer bearing carbonyl and azo groups as a cathode material for RAOBs. The polymeric cathode exhibits a high reversible specific capacity, superior cyclic stability, fast charging capability, and a wide operation temperature range (₋40°C to 100°C). X-ray photoelectron spectroscopy (XPS), pair distribution function (PDF) analysis, and soft X-ray absorption near edge structure (XANES) were employed to gain fundamental insight into the carbonyl and azo chemistries in RAOBs, as well as the cathode electrolyte interphase (CEI) structure. We demonstrated a step-by-step alumination/de-alumination reaction for carbonyl and azo groups in the polymer cathode and unraveled a Al 2 O 3⁻ and AlN-rich CEI, which is critical for the impressive performance of RAOBs.

25 ENERGY STORAGE↗

DOE OSTI2023

Interphasial engineering for Ni-rich NMC cathode materials

Ni-rich LiNi 1-x-y Mn x CoyO 2 , (NMC: 1-x-y ≥ 0.6) are promising cathode materials for lithium-ion batteries (LIBs) due to high reversible capacity and low cost. However, the fast capacity decay and voltage fading caused by interphasial instability requires improvement. The unstable cathodeelectrolyte interphase (CEI) and transition metal (TM) dissolution at higher voltages can lead to the drastic deterioration of electrochemical performance. In this review, recent approaches to novel electrolyte and additive design, cathode engineering including artificial CEI, and doping/coating on the surface of particles or the whole electrode are comprehensively summarized. In conclusion, the importance of multi-model and multi-scale characterization methods in understanding the effects of interphasial chemistry on battery performance is highlighted.

25 ENERGY STORAGE↗

DOE OSTI2022

Delineating the Roles of Mn, Al, and Co by Comparing Three Layered Oxide Cathodes with the Same Nickel Content of 70% for Lithium-Ion Batteries

High-nickel layered oxides continue to prevail in the energy storage market as the frontmost cathode candidates for next-generation lithium-ion batteries. Demand and development of LiNi 1–x–y Mn x Co y O 2 (NMC) and LiNi 1–x–y Co x Al y O 2 (NCA) cathodes are rampantly increasing, particularly for the electric vehicle (EV) industry. However, the continued presence of cobalt in NMC and NCA cathodes raises global concerns due to geopolitical and ethical issues attributed to Co sourcing. We herein introduce a novel cobalt-free, high-nickel cathode LiNi 0.7 Mn 0.25 Al 0.05 O 2 (NMA70) and benchmark it against Co-containing LiNi 0.7 Mn 0.15 Co 0.15 O 2 (NMC70) as well as Co- and Al-free LiNi 0.7 Mn 0.3 O 2 (NM70) cathodes with equivalent 70% Ni contents that are all synthesized in-house. NMA70 displays a high initial C/10 capacity of 210 mA h g –1 , matching that of NMC70 in half cells with a cutoff voltage of 4.5 V. NMA70 also exhibits an impressive high-voltage full cell cycling performance with a cutoff voltage of 4.4 V with a nearly identical capacity retention of 83% compared to that of 82% for NMC70 after 300 cycles. Postmortem X-ray photoelectron spectroscopy (XPS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and electron energy loss spectroscopy (EELS) analyses indicate a thinner cathode–electrolyte interface (CEI) developed in NMA70 compared to that in NM70 and unveil a more robust solid-electrolyte interface (SEI) passivation on the graphite anode among all samples. The benefits of Al doping are additionally highlighted with enhanced high-voltage CEI and thermal stabilities in NMA70. Furthermore, this work assesses the roles of Mn, Al, and Co to demonstrate both the practicality and feasibility of synthesizing cobalt-free, high-nickel cathodes that are promising alternatives to current NMC- and NCA-based cathodes.

25 ENERGY STORAGE↗

DOE OSTI2023

First-Principles Examination of Multiple Criteria of Organic Solvent Oxidative Stability in Batteries

Oxidative instability of the liquid electrolyte at or near battery cathode oxide surfaces has significant detrimental effects on batteries. Organic solvent molecules are often the fuel and precursors of such degradation processes, releasing electrons and protons that react with cathode oxides and electrolyte anions. These reactions contribute to cathode–electrolyte interphase (CEI) film formation, transition-metal ion dissolution, and phase transformation of the surface regions of the cathode. Here we apply density functional theory calculations to examine four criteria of oxidative stability (oxidation potential, hydrogen removal energies, and initial reactivity on two types of oxide facets) using four different solvent/additive molecules (ethylene carbonate, fluoroethylene carbonate, 1,3-dioxolane, and dimethyl ether). The ranking of molecular stability differs with each criterion. Surprisingly, the all-oxygen-terminated basal planes of layered oxides exhibit lower reaction barriers than spinel surface facets with exposed transition-metal cations, especially for ether solvents; the calculations also suggest basal planes contribute to the dissolution of transition-metal ions. Further, the structure–degradation relation complexity underscores the challenge of understanding the function of the CEI but also offers a guide to future degradation-mitigation strategies including facet engineering. Our predictions and models help establish a framework for future studies relevant to high-voltage conditions.

25 ENERGY STORAGE↗

DOE OSTI2019

Toward Long-Life, Ultrahigh-Nickel Layered Oxide Cathodes for Lithium-Ion Batteries: Optimizing the Interphase Chemistry with a Dual-Functional Polymer

Boosting the Ni content in LiMO 2 (M = Ni, Co, Mn, etc.) layered oxides is a promising way to establish high-energydensity, low-cost cathodes, but the poor cathode surface stability is a daunting challenge for their practical viability. Herein, by constructing a dual-functional binder framework with a conductive polymer - polyaniline (PANI), the ultrahigh-Ni layered oxide cathode (LiNi 0.94 Co 0.06 O 2 ) exhibits significantly improved cyclability, with a capacity retention greatly increased from 47% to 81% over 1,000 cycles in full cells. It is demonstrated that the acidic species (e.g. HF) in the electrolyte can be efficiently scavenged through a protonation process of PANI, hence the cathode surface reactivity is greatly suppressed and the rock-salt phase propagation into bulk structure is considerably alleviated. Furthermore, the PANI binder system effectively prevents both the cathode-electrolyte interphase (CEI) and anode-electrolyte interphase (AEI) from degrading to a thick “triple-layer” architecture upon extensive cycling, resulting in more robust, thinner CEI and AEI with regulated interphasial chemistry. Moreover, the delocalized π-conjugated electrons along the backbone of PANI facilitate fast electron transfer and promote rate capability even at low temperatures (-20 °C). Finally, this work sheds light on rational binder engineering for developing high-energy-density lithium-ion batteries with acceptable cycle life.

25 ENERGY STORAGE↗

DOE OSTI2026

Imaging Three-Dimensional Molecular Structure and Dynamics with Multiparticle Covariance and Cumulant Coulomb Explosion Analysis

Coulomb explosion imaging (CEI) provides a direct means of imaging molecular geometry by correlating fragment ion momenta following the fragmentation of a molecular polycation. Here, we demonstrate the use of three-body covariance and four-body cumulant analysis to extract three-dimensional (3D) structural information from the X-ray-induced Coulomb explosion of tert-butyl iodide (C4H9I). Site-selective ionization at the iodine 4d edge with intense femtosecond soft X-ray pulses from an X-ray free-electron laser (XFEL) enables rapid charge buildup and molecular breakup. By correlating ionic fragments in the molecular frame, we isolate complete dissociation channels and reveal subtle structural changes, such as umbrella-type motion of the branched alkyl chain, during the ionization process. Comparison with point-charge simulations of the Coulomb explosion shows close agreement, validating the approach. Furthermore, these results establish covariance/cumulant mapping as a powerful strategy for imaging complex three-dimensional molecular structures and point the way toward time-resolved CEI using both XFEL and tabletop sources for capturing ultrafast structural dynamics.

Imaging↗

DOE OSTI2025

LiNi0.8Mn0.1Co0.1O2 Thin Films Prepared by Polymer-Assisted Deposition for the Study of Cathode-Electrolyte Interphases in Lithium-Ion Batteries

High-nickel layered oxide cathodes such as LiNi0.8Mn0.1Co0.1O2 (NMC811) are critical for next-generation lithium-ion batteries (LIBs) due to their superior energy density and reduced reliance on cobalt. However, many Ni-rich cathodes suffer from rapid capacity fade and structural instability originating from complex interfacial reactions at the cathode-electrolyte interface. Traditional composite electrodes exhibit degradation mechanisms that are challenging to quantitatively understand due to additives, including binders and carbon black. In this study, we demonstrate a new synthesis approach for binder- and additive-free NMC811 thin films using polymer-assisted deposition (PAD). PAD-NMC811 are model thin-film cathodes for investigating interfacial phenomena that can be obscured in composite cathodes. Structural and chemical characterization by X-ray diffraction, soft X-ray absorption spectroscopy, and atomic force microscopy show that PAD-NMC811 films possess high phase purity, crystallinity, chemical homogeneity, and morphological uniformity. Electrochemical analyses using cyclic voltammetry and galvanostatic cycling revealed electrochemical behavior consistent with that of composite electrodes, along with a moderate capacity fade indicative of cathode-electrolyte interphase (CEI) formation. Our findings illustrate the effectiveness of PAD synthesis of thin films tailored for detailed mechanistic studies, which offer critical insights into CEI evolution and cathode degradation pathways.

25 ENERGY STORAGE↗

DOE OSTI2021

Understanding the Roles of the Electrode/Electrolyte Interface for Enabling Stable Li∥Sulfurized Polyacrylonitrile Batteries

Sulfurized polyacrylonitrile (SPAN) is a promising high-capacity cathode material. Here, we use spatially resolved X-ray absorption spectroscopy combined with X-ray fluorescence (XRF) microscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy to examine the structural transformation of SPAN and the critical role of a robust cathode–electrolyte interface (CEI) on the electrode. LiS x species forms during the cycling of SPAN. However, in carbonate-based electrolytes and ether-based electrolytes with LiNO 3 additives, these species are well protected by the CEI and do not dissolve into the electrolytes. In contrast, in an ether-based electrolyte without the LiNO 3 additive, LiS x species dissolve into the electrolyte, resulting in the shuttle effect and capacity loss. Examination of the Li anode by XRF and SEM reveals dense spherical Li morphology in ether-based electrolytes, but sulfur is present in the absence of the LiNO 3 additive. In contrast, porous dendritic Li is found in the carbonate electrolyte. These analyses established that an ether-based electrolyte with LiNO 3 is a superior choice that enables stable cycling of both electrodes. Based on these insights, we successfully demonstrate the stable cycling of high areal loading SPAN cathode (>6.5 mA h cm –2 ) with lean electrolyte amounts, showing promising Li∥SPAN cell performance under practical conditions.

25 ENERGY STORAGE↗

DOE OSTI2024

A Coordinated-Anion-Enriched Electrolyte for Lean-Electrolyte Li–S Batteries

The solid electrolyte interphase (SEI) on Li and cathode electrolyte interphase (CEI) at sulfurized polyacrylonitrile (SPAN) formed in the commonly used liquid electrolytes cannot accommodate the large volume change of both Li anode and SPAN cathode, resulting in severe electrolyte and Li consumption and fast capacity decay under high mass loading and lean electrolyte condition. Herein, a LiF-rich SEI and a LiF-Li x N y O z co-enriched CEI are simultaneously formed by adding ionic liquid (Py 13 TFSI) in the localized high-concentration electrolyte (LHCE), which forms a coordinated-anion-enriched solvation structure. In this study, the LiF-rich interphase results in less stress/strain during large volume changes of Li and SPAN and therefore achieving obviously improved stability even at a high areal capacity. Consequently, Li (50 μm)||SPAN (6 mg cm -2 ) pouch cells under the lean electrolyte condition (E/S ratio of 5 mL g SPAN -1 ) delivers a stable cycle life of 120 cycles with 79.2% capacity retention, demonstrating great promise for high-energy-density lithium-sulfur batteries.

25 ENERGY STORAGE↗

DOE OSTI2025

Visualizing the Three-Dimensional Arrangement of Hydrogen Atoms in Organic Molecules by Coulomb Explosion Imaging

Structure-sensitive methods based on femtosecond light or electron pulses are now making it possible to measure how molecular structures change during light-induced processes. Despite significant progress, high-fidelity imaging of nuclear positions remains a challenge even for relatively small molecular systems and, notably, regarding the positions of hydrogen atoms. As demonstrated in recent work, X-ray-induced Coulomb explosion imaging (CEI) may overcome this obstacle, as its sensitivity does not depend on the mass of the imaged atoms. The photoinduced ring opening of the heterocyclic molecule 2(5 H )-thiophenone has attracted recent interest. Here, in this work, we show that CEI offers a powerful route to imaging the peripheral H atoms in this molecule and thus, more generally, to tracking detailed nuclear motions (e.g., isomerizations) in organic molecules on ultrafast time scales. Specifically, we record momentum-space Coulomb explosion images that report on the three-dimensional positioning of all nuclei within the molecule, for instance, distinguishing H atoms in C–H bonds that lie within or are directed out of the plane defined by the heavy atoms. The prospect of imaging peripheral H atoms to probe photochemical dynamics is explored by coupling ab initio molecular dynamics with classical Coulomb explosion simulations, thereby differentiating potential photoproduct isomers, including those whose structures primarily differ in the position of the hydrogens.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Doubling of U.S. Population Exposure to Climate Extremes by 2050

We quantify historical and projected trends in the population exposure to climate extremes as measured by the United States National Center for Environmental Information Climate Extremes Index (CEI). Based on the analyses of the historical observations, we find that the U.S. has already experienced a rise in the occurrence of aggregated extremes in recent decades, consistent with the climate response to historical increases in radiative forcing. Additionally, we find that exposure can be expected to intensify under the Representative Concentration Pathway 8.5, with all counties permanently exceeding the baseline variability in the occurrence of extreme hot days, warm nights, and drought conditions by 2050. As a result, every county in the U.S. is projected to permanently exceed the historical CEI variability (as measured by one standard deviation during the 1981–2005 period). Based on the current population distribution, this unprecedented change implies a yearly exposure to extreme conditions for one in every three people. We find that the increasing trend in exposure to the aggregated extremes is already detectable over much of the U.S., and particularly in the central and eastern U.S. The high correspondence between the pattern of trends in our simulations and observations increases confidence in the projected amplification of population exposure to unprecedented combinations of extreme climate conditions, should greenhouse gas concentrations continue to escalate along their current trajectory.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Stabilizing LiCoO 2 at 4.6 V by regulating anti-oxidative solvents

For LiCoO 2 (LCO) operating at high voltages (>4.5 V vs. Li/Li + ), the intensive side reactions between LCO and traditional ethylene carbonate (EC)-based electrolytes with LiPF 6 salts can produce plenty of corrosive species (such as HF and HPO 2 F 2 ), causing severe surface degradation. Herein, anti-oxidative fluoroethylene carbonate (FEC) and difluoroethylene carbonate (DFEC) were selected as co-solvents to reduce the generation of corrosive species. Besides, PF 6 − anions enrich the Helmholtz plane of the LCO/electrolyte interface and promote the formation of a robust cathode/electrolyte interphase (CEI) featuring LiF/Li x PO y F z /Li 3 PO 4 inorganics and P-containing organics under the synergy of fluorinated solvents, which significantly inhibits the catalysis of highly oxidative Co 4+ /O n− (0 < n < 2). Benefiting from the reduced corrosive species and reinforced CEI, the layered structure of the LCO surface is well preserved during long-term cycling, with a highly reversible O3/H1-3 phase transition. Consequently, a LCO||graphite pouch cell exhibits a remarkable capacity retention of 85.7% after 500 cycles in 3.0–4.55 V. Furthermore, this work provides a new insight into developing advanced functional electrolytes for high-voltage lithium-ion batteries.

Co/O loss↗