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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Unveiling the parasitic-reaction-driven surface reconstruction in Ni-rich cathode and the electrochemical role of Li 2 CO 3

Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energy-density lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cathodes is accompanied by substantial safety and cycle-life obstacles. The major issues of Ni-rich cathodes at high working potentials are originated from the unstable cathode-electrolyte interface, while the underlying mechanism of parasitic reactions towards surface reconstructions of cathode materials is not well understood. In this work, we controlled the Li 2 CO 3 impurity content on LiNi 0.83 Mn 0.1 Co 0.07 O 2 cathodes using air, tank-air, and O 2 synthesis environments. Home-built high-precision leakage current and on-line electrochemical mass spectroscopy experiments verify that Li 2 CO 3 impurity is a significant promoter of parasitic reactions on Ni-rich cathodes. The rate of parasitic reactions is strongly correlated to Li 2 CO 3 content and severe performance deterioration of Ni83 cathodes. The post-mortem characterizations via high-resolution transition electron microscope and X-ray photoelectron spectroscopy depth profiles reveal that parasitic reactions promote more Ni reduction and O deficiency and even rock-salt phase transformation at the surface of cathode materials. Here, our observation suggests that surface reconstructions have a strong affiliation to parasitic reactions that create chemically acidic environment to etch away the lattice oxygen and offer the electrical charge to reduce the valence state of transition metal. Thus, this study advances our understanding on surface reconstructions of Ni-rich cathodes and prepares us for searching for rational strategies.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Ion-Pair Dissociation on α-MoO 3 Surfaces: Focus on the Electrolyte–Cathode Compatibility Issue in Mg Batteries

Nanosizing has been explored as one option to enhance typically sluggish Mg ion mobility in cathode materials. Here, we explore the effects of the surfaces of α-MoO3 in facilitating or hindering Mg ion desolvation at the electrolyte–cathode interface. It is well-known in the Mg battery community that Mg–anion contact ion pairs may form in the electrolyte and thus the insertion of Mg into the cathode must involve desolvation and dissociation, where Mg is detached from the counterion at the cathode surface. Here we compare two representative Mg–anion pairs, i.e., (Mg–Cl)+ and (Mg–TFSI)+ (TFSI–, bis(trifluoromethanesulfonyl)imide), differentiated according to the size and polarizability of the anion, and examine their dissociations on different α-MoO3 surfaces. We find that (Mg–Cl)+ requires a higher dissociation energy than (Mg–TFSI)+, which implies that the Mg–TFSI-type electrolyte is more suitable to be integrated with the MoO3 cathode when creating an electrochemical cell. The dissociation of (Mg–TFSI)+ occurs, however, not on the lowest energy (010) surface where the van der Waals (vdW) gap opens, but on the hydroxyl-terminated (001) surface. Therefore, to optimize the performance of α-MoO3 toward (Mg–TFSI)+ dissociation, preferential growth of the hydroxyl-terminated (001) surface is required.

Wan, Liwen F.↗
DOE OSTI2024

Alumina – Stabilized SEI and CEI in Potassium Metal Batteries

Aluminum oxide (Al 2 O 3 ) nanopowder is spin-coated onto both sides of commercial polypropene separator to create artificial solid-electrolyte interphase (SEI) and artificial cathode electrolyte interface (CEI) in potassium metal batteries (KMBs). Here, this significantly enhances the stability, including of KMBs with Prussian Blue (PB) cathodes. For example, symmetric cells are stable after 1,000 cycles at 0.5 mA/cm 2 –0.5 mAh/cm 2 and 3.0 mA/cm 2 –0.5 mAh/cm 2 . Alumina modified separators promote electrolyte wetting and increase ionic conductivity (0.59 vs. 0.2 mS/cm) and transference number (0.81 vs. 0.23). Cryo-stage focused ion beam (cryo-FIB) analysis of cycled modified anode demonstrates dense and planar electrodeposits, versus unmodified baseline consisting of metal filaments (dendrites) interspersed with pores and SEI. Alumina-modified CEI also suppresses elemental Fe crossover and reduces cathode cracking. Mesoscale modeling of metal – SEI interactions captures crucial role of intrinsic heterogeneities, illustrating how artificial SEI affects reaction current distribution, conductivity and morphological stability.

25 ENERGY STORAGE↗
DOE OSTI2025

Balancing solvation: stabilizing lithium metal batteries via optimized cosolvents for ionic-liquid electrolytes

In this study, we examined three cosolvents with distinct solvation capabilities for ionic-liquid electrolytes based on 1-methyl-1-propyl pyrrolidinium bis(fluorosulfonyl)imide (Py13FSI). We demonstrate that 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG) notably enhances the cycle life of Py13FSI-based electrolytes, outperforming 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropylether (TTE) and diglyme (DG). Electrochemical and surface analyses showed that this improvement could be attributed to the formation of a favorable cathode interphase, promoting efficient Li+ transport with reduced overpotential. Spectroscopic techniques (FTIR, Raman, and NMR spectroscopy) and molecular dynamics simulations revealed that cosolvents with varying solvation abilities can influence the solvation structures in Py13FSI-based electrolytes. The mild solvating strength and lithium stability of FDG are key contributors to its effectiveness. Conversely, DG, a strong solvating solvent, destabilized the Py13FSI-DG electrolyte at the lithium metal anode, while TTE, a non-solvating solvent, failed to enhance lithium transport or form a stable cathode interphase. Our findings highlight that balanced solvation exerted by the cosolvents is critical for forming a stable electrolyte–cathode interface, potentially through FSI decomposition. This study offers valuable insights into the development of durable ionic-liquid electrolytes, emphasizing the importance of selecting cosolvents with optimal solvation properties.

Li, Xinlin [Argonne National Laboratory (ANL), Arg↗
DOE OSTI2023

Modifying Surface Chemistry to Enhance the Electrochemical Stability of Nickel‐Rich Cathode Materials

Residual impurities such as lithium carbonate and hydroxide are a major concern for accelerating parasitic reactions at the cathode electrolyte interface of lithium-ion batteries. Removal of these lithium-bearing species becomes a necessity for high-performance nickel-rich cathode materials. Instead of directly removing these impurities through washing steps, a wet impregnation process is employed to convert these detrimental surface impurities into beneficial surface coating on nickel-rich cathode materials. Specifically, the pristine cathode material is treated with Al(H 2 PO 4 ) 3 solution to convert undesired compounds into Li 3 PO 4 and AlPO 4 , both of which are considered positive surface coating materials for high-voltage cathodes. It is found that the introduced modification greatly suppresses the interfacial impedance hike and improves the capacity retention of the cathode material after repeating charging/discharging. It is believed that these benefits are realized through the modification of the surface chemistry of the cathode material, which helps to slow down the parasitic reactions and reduce the damage to the cathode material.

25 ENERGY STORAGE↗
DOE OSTI2019

Dopant Distribution in Co-Free High-Energy Layered Cathode Materials

The practical implementation of Co-free, LiNiO 2 -derived cathodes has been prohibited by their poor cycle life and thermal stability, concluded from the structural instability, phase transformations, reactive surfaces, and chemomechanical breakdown. With the hierarchical distribution of Mg/Ti dual dopants in LiNiO 2 , we report a Co-free layered oxide that exhibits enhanced bulk and surface stability. Ti shows a gradient distribution and is enriched at the surface, whereas Mg distributes homogeneously throughout the primary particles. The resulting Mg/Ti codoped LiNiO 2 delivers a material-level specific energy of ~780 W h/kg at C/10 with 96% retention after 50 cycles. The specific energy reaches ~680 W h/kg at 1C with 77% retention after 300 cycles. Furthermore, the Mg/Ti dual dopants improve the rate capability, thermal stability, and self-discharge resistance of LiNiO 2 . Our synchrotron X-ray, electron, and electrochemical diagnostics reveal that the Mg/Ti dual dopants mitigate phase transformations, reduce nickel dissolution, and stabilize the cathode–electrolyte interface, thus leading to the favorable battery performance in lithium metal and graphite cells. The current study suggests that engineering the dopant distribution in cathodes may provide an effective path toward lower cost, safer, and higher energy density Co-free lithium batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

Coupling Redox Compensation and Interfacial Stabilization in Low-Ni O3-Type Sodium Layered Oxide Cathodes

Low-Ni O3-type sodium layered oxides are attractive cathodes for cost-robust sodium-ion batteries, yet high-voltage cycling is often limited by Fe-driven degradation, including cation migration/dissolution, irreversible slab gliding with large strain, particle cracking, and accelerated interfacial parasitic reactions. Here, in this study, we introduce a redox-interface codesign strategy using stoichiometric, charge-balanced Cu 2+ /Ti 4+ cosubstitution while preserving full Na stoichiometry, transitioning from NaNi 1/4 Fe 1/2 Mn 1/4 O 2 to NaNi 1/4 Fe 1/5 Mn 1/4 Cu 3/20 Ti 3/20 O 2 . With the cosubstitution, Cu and Ti suppress Fe migration and dissolution and facilitate sustained Fe oxidation at high voltage. Meanwhile, Cu is also shown to be redox-active, providing reversible cationic charge compensation that mitigates the capacity penalty typically associated with reducing Fe participation. Operando diffraction and spectroscopy collectively indicate a more reversible high-voltage structural evolution with suppressed Fe-related irreversibility. Particularly, spontaneous Ti enrichment at surface/grain-boundary regions stabilizes the cathode−electrolyte interface and promotes a more NaF-rich interphase signature. This work establishes a generalizable route to reconcile stability and capacity in low-Ni, Fe-containing O3 sodium layered oxide cathodes via compositionally encoded bulk-interfacial coupling.

25 ENERGY STORAGE↗
DOE OSTI2025

Locally Confined Polysulfide-Reactive Electrolytes for Shuttle-Free Sodium–Sulfur Batteries

Sodium-sulfur batteries promise high-energy-density and sustainable electrochemical energy storage but suffer from uncontrolled polysulfides dissolution and high sodium reactivity. These challenges fundamentally originate from poor electrolyte-electrode compatibility. Current electrolyte research inadequately addresses the trade-off between minimal polysulfides solvation and stabilizing sodium interfaces. Here, we present a locally-confined polysulfide-reactive electrolyte strategy that mediates the polysulfide dissolution dynamics and sodium stability by leveraging an electrophilic solvating species with a localized high-concentration electrolyte. This design enables shuttle-free cell operation by synergistically restricting the global solvating power of the electrolyte through intermolecular interactions and locally scavenging sparingly dissolved polysulfides via electrolyte electrophilicity. The precisely confined surface reaction facilitates a protective cathode-electrolyte interface, realizing a quasi-solid-state sulfur conversion in our liquid ether-based electrolyte, which crucially avoids crossover-induced catastrophic sodium-metal degradation. The proposed electrolyte demonstrates long-term cycling of high-mass-loading sulfur cathodes (> 3 mg S cm −2 with commercial carbon host and 70 wt% sulfur content), which afford 710 mA h g −1 over 400 cycles in coin cells and steady pouch cell operation over 180 cycles. Furthermore, this work establishes a scalable electrolyte design protocol that regulates the reaction chemistry of highly reactive electrodes, offering a pathway toward sustainable renewable energy storage.

25 ENERGY STORAGE↗
DOE OSTI2017

From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes

Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNi x Mn y Co 1–x–y O 2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532) to LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) was found to facilitate the diffusion of surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structural characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Enhanced Electrocatalytic and Cathode‐Electrolyte Interfacial Properties With a Pr‐Based Simple Perovskite/Ruddlesden‐Popper Nanocomposite Cathode in Protonic Ceramic Fuel Cells

The sluggish kinetics and poor stability of the oxygen reduction reaction (ORR) remain the primary bottleneck for achieving high performance in protonic ceramic fuel cells (PCFCs) at intermediate temperatures (400–650°C). In this work, a Pr-based nanocomposite cathode comprised of simple perovskite phase (PrNi 0.7 Co 0.3 O 3-δ ) and Ruddlesden-Popper phase (Co-doped Pr 4 Ni 3 O 10+δ ) is developed. Although PrNi 0.7 Co 0.3 O 3-δ solely stands as a good cathode with facile proton transfer, combining the superior catalytic activity against oxygen on the Ruddlesden-Popper phase boosts the ORR performance further. The designed nanocomposite cathode outperforms the simple perovskite cathode, attributed to enhanced oxygen absorption and surface diffusion with the Ruddlesden-Popper phase. A precursor-based cathode deposition technique is also developed to achieve cathode grain sizes of ∼100 nm. A single cell with the nanocomposite cathode delivers a peak power density of 1.38 W cm −2 at 650°C, among the highest in reported PCFCs with Pr-based cathodes, with a small degradation rate of 0.145 mV h −1 during 250 h stability test. Further investigation of cathode-electrolyte interface revealed interfacial PrO 2 phase formation, promoted by abundant Pr 6 O 11 in the nanocomposite precursor powder, thereby improving both ohmic resistance and stability. These findings highlight the effectiveness of the nanocomposite cathode and underscore its advantages on interfacial properties.

08 - HYDROGEN↗
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 OSTI2019

Building ultraconformal protective layers on both secondary and primary particles of layered lithium transition metal oxide cathodes

Despite their relatively high capacity, layered lithium transition metal oxides suffer from crystal and interfacial structural instability under aggressive electrochemical and thermal driving forces, leading to rapid performance degradation and severe safety concerns. In this paper, we report a transformative approach using an oxidative chemical vapour deposition technique to build a protective conductive polymer (poly(3,4-ethylenedioxythiophene)) skin on layered oxide cathode materials. The ultraconformal poly(3,4-ethylenedioxythiophene) skin facilitates the transport of lithium ions and electrons, significantly suppresses the undesired layered to spinel/rock-salt phase transformation and the associated oxygen loss, mitigates intergranular and intragranular mechanical cracking, and effectively stabilizes the cathode-electrolyte interface. This approach remarkably enhances the capacity and thermal stability under high-voltage operation. Building a protective skin at both secondary and primary particle levels of layered oxides offers a promising design strategy for Ni-rich cathodes towards high-energy, long-life and safe lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2019

Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi 0.8 Co 0.2-y Al y O 2 Cathodes

Aluminum is a common dopant across oxide cathodes for improving the bulk and cathode-electrolyte interface (CEI) stability. Aluminum in the bulk is known to enhance structural and thermal stability, yet the exact influence of aluminum at the CEI remains unclear. To address this, we utilized a combination of X-ray photoelectron and absorption spectroscopy to identify aluminum surface environments and extent of transition metal reduction for Ni-rich LiNi 0.8 Co 0.2-y Al y O 2 (0%, 5%, or 20% Al) layered oxide cathodes tested at 4.75 V under thermal stress (60 °C). For these tests, we compared the conventional LiPF6 salt with the more thermally stable LiBF 4 salt. The CEI layers are inherently different between these two electrolyte salts, particularly for the highest level of Al-doping (20%) where a thicker (thinner) CEI layer is found for LiPF 6 (LiBF 4 ). Focusing on the aluminum environment, we reveal the type of surface aluminum species are dependent on the electrolyte salt, as Al-O-F- and Al-F-like species form when using LiPF 6 and LiBF 4 , respectively. In both cases, we find cathode-electrolyte reactions drive the formation of a protective Al-F-like barrier at the CEI in Al-doped oxide cathodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Insight Into Sulfur‐Containing Additive to Boost Anti‐Oxidation Ability of the Ether‐Based Electrolyte for Sodium‐Ion Full Batteries

Ether-based electrolytes are considered as promising candidates for sodium-ion batteries (SIBs) due to their high ionic conductivity and good compatibility with hard carbon (HC) anode. However, they suffer from poor anti-oxidative ability with unstable cathode electrolyte interface, inducing successive electrolyte decomposition and rapid capacity fading. Herein, the sulfur-containing additive (1,3-propanediol cyclic sulfate, PCS) is introduced to boost the stability of the electrode-electrolyte interface (EEI) in ether-based electrolyte. PCS largely participates in the inner Na + sheath, causing more diglyme (G2) molecules and fewer PF 6 - anions to occupy the inner Na + solvation sheath, avoiding the decomposition of G2 molecules at high operation voltage. Moreover, PCS is beneficial for simultaneously constructing thin and robust sulfur-containing EEI on both Prussian blue (PB) cathode and HC anode, maintaining the structural stability of PB and alleviating the dissolution of transition metals. These enable PB||HC pouch cells to deliver a capacity retention of 60.3% after 400 cycles, significantly higher than the 32.1% in PCS-free electrolytes. In conclusion, this work discloses the underlying mechanism of PCS to evoke the anti-oxidation ability of ether-based electrolyte and provides a promising method for realizing advanced sodium-ion full cells.

anti-oxidation ability↗
DOE OSTI2025

Single-Crystallization of O3-Type Layered Oxide Cathode for Na-Ion Battery

The development of high-energy-density Na-ion batteries places significant demands on single-crystal layered oxide cathodes, especially for further high-voltage, solid-state battery scenarios. In the O3-type structure, due to the original sluggish Na ion diffusion kinetics (approximately 1 order of magnitude lower than that of Li-ion), and further hindrance against diffusion kinetics caused by single-crystal architecture, these inherent defects lead to the decline in the electrochemical performance. Herein, we demonstrated that the single crystallization of O3-type NaNi 1/3 Fe 1/3 Mn 1/3 O 2 cathode (d 50 = 5.04 μm) aggravates surface-to-bulk phase inhomogeneity distribution, which is attributed to the uneven Na ions extraction. Moreover, the Na-depletion of the surface/shell region not only aggravates Na ion diffusion resistance but also leads to a higher valence state of transition-metal elements (e.g., Ni/Fe) near the surface of the single-crystal particle, which further compromises the cathode-electrolyte interface stability. Furthermore, not limited to revealing the challenges, tuning the particle size and moderating quasi-single-crystal strategies have been proven to effectively mitigate the negative uneven distributions of Na ions, phases, and valence/oxidative states, resulting in efficient modification for single crystallization of Na-layered oxide cathodes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Stability Enhancement and Microstructural Modification of Ni-Rich Cathodes via Halide Doping

In this study, elemental doping is an effective strategy to modify surface and bulk chemistry in NMC cathode materials. By adding small amounts of lithium halide salts during the calcination process, the Ni-rich NMC811 cathode is doped with Br, Cl, or F halogens. The dopant type has a significant impact on the lithiation process and heavily influences the final cathode porosity and surface morphology. Utilizing a variety of electrochemical, surface, and bulk characterization techniques, it is demonstrated that an initial content of 5 mol % LiBr or LiCl in the lithium source is effective in improving capacity retention while also providing excellent rate performance. The improvements are attributed to a substantial increase in specific surface area, the formation of a stable cathode electrolyte interface (CEI) layer, and suppressed surface reconstruction. In addition, the particle microstructure is better equipped to handle cyclic volume changes with increased values of critical crack lengths. Overall, it is demonstrated that anion doping via the addition of lithium halide salts is a facile approach toward Ni-rich NMC modification for enhanced cathode performance.

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

Stabilizing High–Nickel Cathodes with High–Voltage Electrolytes

Electrolytes connect the two electrodes in a lithium battery by providing Li + transport channels between them. Advanced electrolytes are being explored with high-nickel cathodes and the lithium-metal anode to meet the high energy density and cycle life goals, but the origin of the performance differences with different electrolytes is not fully understood. Here, the mechanisms involved in protecting the high-capacity, cobalt-free cathode LiNiO 2 with a model high-voltage electrolyte (HVE) are delineated. The kinetic barrier posed by a thick surface degradation layer with poor Li + -ion transport is found to be the major contributor to the fast capacity fade of LiNiO 2 with the conventional carbonate electrolyte. In contrast, HVE reduces the side reactions between the electrolyte and the electrodes, leading to a thinner nano-interphase layer comprised of more beneficial species. Crucially, the HVE leads to a different surface reorganization pathway involving the formation of a thinner nanoscale LiNi 2 O 4 spinel phase on the LiNiO 2 surface. Finally, with a high 3D Li + -ion and electronic conductivity, the spinel LiNi 2 O 4 reorganization nanolayer preserves fast Li + transport across the cathode–electrolyte interface, reduces reaction heterogeneity in the electrode and alleviates intergranular cracking within secondary particles, resulting in superior long-term cycle life.

25 ENERGY STORAGE↗