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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Decoding Li + /Na + Exchange Route Toward High-Performance Mn-Based Layered Cathodes for Li-Ion Batteries

Li + /Na + exchange has been extensively explored as an effective method to prepare high-performance Mn-based layered cathodes for Li-ion batteries, since the first report in 1996 by P. G. Bruce (Nature, 1996. 381, 499–500). Understanding the detailed structural changes during the ion-exchange process is crucial to implement the synthetic control of high-performance layered Mn-based cathodes, but less studied. Herein, in situ synchrotron X-ray diffraction, density functional theory calculations, and electrochemical tests are combined to conduct the systemic studies into the structural changes during the ion-exchange process of an Mn-only layered cathode O3-type Li 0.67 [Li 0.22 Mn 0.78 ]O 2 (LLMO) from the corresponding counterpart P3-type Na 0.67 [Li 0.22 Mn 0.78 ]O 2 (NLMO). The temperature-resolved observations combined with theoretical calculations reveal that the Li + /Na + exchange is favorable thermodynamically and composited with two tandem topotactic phase transitions: 1) from NLMO to a layered intermediate through ≈60% of Li + /Na + exchange. 2) then to the final layered product LLMO through further Li insertion. Moreover, the intermediate-dominate composite is obtained by slowing down the exchange kinetics below room temperature, showing better electrochemical performance than LLMO obtained by the traditional molten-salt method. Finally, the findings provide guides for the synthetic control of high-performance Mn-based cathodes under mild conditions.

25 ENERGY STORAGE↗
DOE OSTI2021

Chemical Modulation of Local Transition Metal Environment Enables Reversible Oxygen Redox in Mn-Based Layered Cathodes

Oxygen redox plays a prominent role in enhancing the energy density of Mn-based layered cathodes. However, understanding the factors affecting the reversibility of oxygen redox is nontrivial due to complicated structural and chemical transformations. Here in this paper, we show that local Mn–O symmetry induced structural/chemical evolutions majorly dictate the reversibility of oxygen redox of Na x Li y Mn 1–y O 2 in Na cells. Na x Li y Mn 1–y O 2 with Jahn–Teller distorted MnO 6 octahedra undergoes severe Mn dissolution during cycling, which destabilizes the transition metal layer resulting in poor Li retention and irreversible oxygen redox. Jahn–Teller distortion of MnO 6 octahedra can be suppressed by modulating the local charge of Mn and Mn–O distance through Mg/Ti dual doping. This leads to reduced Mn dissolution and more reversible oxygen redox. Such stabilization significantly improves the electrochemical performance of Mg/Ti dual doped Na x Li y Mn 1–y O 2 . Through this work, we show that local structural stabilization through local chemical environment modification can promote reversible oxygen redox in layered cathodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Stabilizing Anionic Redox Chemistry in a Mn-Based Layered Oxide Cathode Constructed by Li-Deficient Pristine State

Li-rich cathode materials are of significant interest for coupling anionic redox with cationic redox chemistry to achieve high-energy-density batteries. However, lattice oxygen loss and derived structure distortion would induce serious capacity loss and voltage decay, further hindering its practical application. Herein, a novel Li-rich cathode material, O3-type Li 0.6 [Li 0.2 Mn 0.8 ]O 2 , is developed with the pristine state displaying both a Li excess in the transition metal layer and a deficiency in the alkali metal layer. Benefiting from stable structure evolution and Li migration processes, not only can high reversible capacity (≈329 mAh g -1 ) be harvested but also irreversible/reversible anionic/cationic redox reactions are comprehensively assigned via the combination of in/ex situ spectroscopies. Furthermore, irreversible lattice oxygen loss and structure distortion are effectively restrained, resulting in long-term cycle stability (capacity drop of 0.045% per cycle, 500 cycles). Altogether, tuning the Li state in the alkali metal layer presents a promising way for modification of high-capacity Li-rich cathode candidates.

anionic redox reactions↗
DOE OSTI2024

Regulating the Electron Distribution of Metal-Oxygen for Enhanced Oxygen Stability in Li-rich Layered Cathodes

Li-rich Mn-based layered oxides (LLO) hold great promise as cathode materials for lithium-ion batteries (LIBs) due to their unique oxygen redox (OR) chemistry, which enables additional capacity. However, the LLOs face challenges related to the instability of their OR process due to the weak transition metal (TM)-oxygen bond, leading to oxygen loss and irreversible phase transition that results in severe capacity and voltage decay. Herein, a synergistic electronic regulation strategy of surface and interior structures to enhance oxygen stability is proposed. In the interior of the materials, the local electrons around TM and O atoms may be delocalized by surrounding Mo atoms, facilitating the formation of stronger TM—O bonds at high voltages. Besides, on the surface, the highly reactive O atoms with lone pairs of electrons are passivated by additional TM atoms, which provides a more stable TM—O framework. Hence, this strategy stabilizes the oxygen and hinders TM migration, which enhances the reversibility in structural evolution, leading to increased capacity and voltage retention. This work presents an efficient approach to enhance the performance of LLOs through surface-to-interior electronic structure modulation, while also contributing to a deeper understanding of their redox reaction.

25 ENERGY STORAGE↗
DOE OSTI2025

Minimizing Inter‐Lattice Strain to Stabilize Li‐Rich Cathode by Order–Disorder Control

Li-rich Mn-based layered (LMR) cathodes with anionic redox chemistry show great potential for next-generation sustainable Li-ion battery (LIB) applications due to the low cost and high energy density. However, the asynchronous structural evolutions with cycling in the heterogeneous composite structure of LMR lead to serious lattice strain and thus fast electrochemical decay, which hinders the commercialization of LMR cathodes. Here, in this study, an order–disorder coherent LMR cathode is demonstrated that exhibits a higher average voltage (by 0.25 V), negligible voltage decay (97.6% voltage retention after 100 cycles at 100 mA g −1 ), and enhanced cycling stability (98% capacity retention after 200 cycles at 100 mA g −1 ) compared to its layered oxide counterparts. It is proposed that this order–disorder coherent structure design can promote a more synchronous and homogeneous structure evolution during charge and discharge, thus minimizing lattice strain, which significantly prevents layer collapse and collective degradation at high voltage, improving the electrochemical stability. The study displays the feasibility of optimizing the performance of Li-rich cathode materials through a dedicated order–disorder structure control for sustainable energy storage.

Xu, Shenyang [Peking University, Shenzhen (China)]↗
DOE OSTI2023

Promoting reversibility of layered potassium cathode through interstitial doping

With the increasing needs for large-scale and low-cost energy storage devices, Mn-based layered oxide cathodes have achieved considerable researching interests for potassium-ion batteries owing to their high energy density, abundant resource and low toxicity. However, their developments are challenged by the absence of suitable cathode materials to tolerate large-sized K-ion insertion/extraction and the presence of Jahn-Teller distortion of Mn 3+ . To address this issue, here we present a strategy of embedding boron into interstitial tetrahedral sites to obtain a P3-K 0.5 Mn 0.8 Co 0.2 B 0.1 O 2 cathode. Strong B-O covalent bonds facilitate the construction of robust orthorhombic framework and alleviate the undesired elongation of Mn-O bonds, contributing to excellent electrochemical performance. In addition, boron ions are verified to promote the formation of a homogeneous cathode electrolyte interphase layer, improving interfacial stability and realizing highly reversible cycling in a wide voltage range (1.4-4.3 V). This strategy provides a new pathway towards the development of high-performance cathode materials for potassium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Tailoring the Reaction Heterogeneity for Robust Li‐Rich Cathodes

The practical application of Li-rich Mn-based layered oxides (LLO) cathode is hindered by severe capacity and voltage degradation resulting from severe oxygen release and irreversible phase transition. In this work, the reaction heterogeneity, which describes the spatially resolved electrochemical divergence within individual cathode particles, is engineered through compositional gradient design to couple Li + transport kinetics and the anion redox activity between particle interiors and surfaces. It is revealed that Co/Mn concentration gradient within particles creates heterogeneous phase content distribution and structural ordering, inducing surface-bulk reaction heterogeneity that significantly impacts the overall electrochemical performance. Specifically, Li 2 MnO 3 -poor and Co-enriched surface effectively mitigates the oxygen loss and enhances electrochemical reaction kinetics, benefited from the reduced surface redox reactivity and induced highly ordered intra-layered cationic arrangement. Meanwhile, the Li 2 MnO 3 -enriched core with slight Li/Ni intermixing provides high reversible capacity and strong mechanical stability. Consequently, the greatly enhanced anion redox reversibility, Li + diffusion dynamics, and structure stability endow LLO with exceptional electrochemical properties, showing a capacity retention of 86.0% and a reduced voltage decay of 0.518 mV per cycle after 500 cycles at 1 C. This work provides a valuable strategy to tailor the redox chemistry and achieve robust LLO.

25 ENERGY STORAGE↗
DOE OSTI2025

A Quasi-Ordered Mn-Rich Cathode with Highly Reversible Oxygen Anion Redox Chemistry

Anionic oxygen redox chemistry in Li-rich Mn-based layer oxide cathodes represents a transformative approach for boosting the energy density of next-generation lithium-ion batteries. However, conventional oxygen redox reactions often induce oxygen dimerization at high voltages, leading to irreversible lattice oxygen loss and a rapid voltage fade. Herein, we achieve highly reversible oxygen redox chemistry through a new quasi-ordered structural design that incorporates both intra- and interlayer cation disorder configurations. This unique structure significantly enhances lattice oxygen stability, effectively stabilizes oxidized oxygen, and inhibits the formation of peroxo- or superoxol-like species, thereby enabling anionic redox reactions to proceed reversibly even at deep delithiation states. The quasi-ordered design mitigates irreversible phase transitions and preserves the structural integrity throughout extended cycling. Consequently, the proposed cathode demonstrates exceptional cyclability with negligible capacity and voltage fade, retaining 99% capacity and 98% average voltage after long-term cycling. Finally this work provides fresh insights into addressing issues related to lattice oxygen instabilities and reforming strategies for developing long-life, high-energy-density anionic redox cathode materials for advanced batteries.

chemical structure↗
DOE OSTI2023

Regulating Anionic Redox via Mg Substitution in Mn-Rich Layered Oxide Cathodes Enabling High Electrochemical Stability for Sodium-Ion Batteries

Here, with the limited resources and high cost of lithium-ion batteries (LIBs) and the ever-increasing market demands, sodium-ion batteries (SIBs) gain much interest due to their economical sustainability, and similar chemistry and manufacturing processes to LIBs. As cathodes play a vital role in determining the energy density of SIBs, Mn-based layered oxides are promising cathodes due to their low cost, environmental friendliness, and high theoretical capacity. However, the main challenge is structural instability upon cycling at high voltage. Herein, Mg is introduced into the P2-type Na 0.62 Ni 0.25 Mn 0.75 O 2 cathode to enhance electrochemical stability. By combining electrochemical testing and material characterizations, it is found that substituting 10 mol% Mg can effectively alleviate the P2–O2 phase transition, Jahn-Teller distortion, and irreversible oxygen redox. Moreover, structural integrity is greatly improved. These lead to enhanced electrochemical performances. With the optimized sample, a remarkable capacity retention of 92% in the half cell after 100 cycles and 95% in the full cell after 170 cycles can be achieved. Altogether, this work provides an alternative way to stabilize P2-type Mn-based layer oxide cathodes, which in turn, put forward the development of this material for the next-generation SIBs.

25 ENERGY STORAGE↗
DOE OSTI2021

A highly-stable layered Fe/Mn-based cathode with ultralow strain for advanced sodium-ion batteries

Sodium-ion batteries (SIBs) with iron- and manganese-based cathode electrodes have exhibited great promise in the grid-scale energy storage systems, on the basis of the satisfactory theoretical capacity, as well as huge abundance, low price and non-toxicity of raw materials. However, the inferior cycle life of cathode materials originating from their poor structural stability remains a formidable challenge towards practical applications. In this study, an efficient strategy of improving the structure durability is demonstrated in iron- and manganese-based cathodes by dual heteroatom doping. The as-obtained P2-type Na 0.65 Li 0.08 Cu 0.08 Fe 0.24 Mn 0.6 O 2 cathode delivers superior cyclability (88.2% capacity retention for 500 cycles at 2C), fabulous rate capability (76% capacity retention at 5C compared to 0.1C), and a useable reversible capacity of around 85 mAh g -1 at 0.1C. Through in-depth characterizations, the underlying structure-property relationship is established, revealing that the complete solid-solution reaction during cycling ensures the ultralow volume variation (as small as 0.7%) and excellent electrochemical performance. These results highlight the significance of fabricating a stable host for the design and development of advanced SIBs with long life.

25 ENERGY STORAGE↗
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 OSTI2020

Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a Li x TM 3-x O 4 -type spinel shell

The poor long-term cycling stability, including the fast capacity fade and the severe voltage decay, has become the main concern hindering the practical application of Li-rich layered oxides, a promising cathode for high- energy-density Li-ion battery. Herein, we design and electrochemically construct a ~10 nm-thick Li x TM 3-x O 4 - type (TM ¼Ni, Co, Mn, 0 3 O 4 -type spinel phase and the good Liþconductivity of LiMn 2 O 4 -type spinel phase. Systemic structural and electrochemical analysis demonstrate that, it slows down the activation rate of Li 2 MnO 3 component and efficiently alleviates the lattice O loss at high voltage (>4.5 V) and Mn dissolution, thereby suppressing the structural degradation from the layered phase to the spinel phase in the bulk, eventually significantly enhancing the long-term cycling stability. This study adds richness into the Mn-based spinel phase system and provides a new heterostructure design strategy to improve the electrochemical performance of Li-rich layered cathodes and beyond.

25 ENERGY STORAGE↗
DOE OSTI2024

Co-free gradient lithium-rich cathode for high-energy batteries with optimized cyclability

Lithium-rich layered oxides (LLOs) hold the promise for high-energy battery cathodes. However, its application has been hindered by voltage decay associated with irreversible reactions at high voltages despite decades of intensive efforts. Here, we first theoretically studied the molecular orbitals of Mn-based Li-rich configurations. We found that the π-bond ring formed within the LiMn 6 structure could participate in stable redox reactions as one unit, but Co could disrupt its symmetry. We thus designed and synthesized Co-free concentration-gradient LLOs (CF-CG-LLOs) materials. The combination of concentration gradient and Co removal leads to exceptional capacity retention without any fading over 100 cycles of the pouch cell. More importantly, it exhibits an extraordinarily low voltage decay of 0.15 mV/cycle, accompanied by a high Coulombic efficiency of 99.86%. This concept and demonstration of CF-CG-LLO cathodes reveal a viable avenue toward low-cost, high-energy-density battery cathodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Building interface bonding and shield for stable Li-rich Mn-based oxide cathode

Implementation of Li-rich Mn-based oxide cathode with high-energy-density has been restrained by capacity/voltage degradation that results from irreversible lattice oxygen loss and structure rearrangements. To resolve these challenges, in this work, Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 encapsulated by amorphous Co x B (CB-LRM) is rationally designed via autocatalytic plating for highly reversible cationic/anionic hybrid cathode material. Band coherency is ingeniously evoked by interface-reconstruction between bulk structure and amorphous coating layer, which lower the energy of O $2p$ states. Furthermore, this is associated with strengthened orbital hybridization of O $2p$-Mn $3d$ and increased formation energy of oxygen vacancy, which mitigates the lattice oxygen loss considerably. Additionally, interface shielding effects that protect electrode against electrolyte corrosion and the reduction of surface oxygen are also present with fully coverage of amorphous Co x B coating layer. As a result, the as-designed CBLRM cathode exhibits excellent cycle stability after 100 loops with only 0.154% per cycle capacity fade and improved voltage degradation. Given this, this work provides a potential avenue for rational design of lattice oxygen-based electrode materials with high-energy-density.

25 ENERGY STORAGE↗
DOE OSTI2023

Ultrahigh-Capacity Rocksalt Cathodes Enabled by Cycling-Activated Structural Changes

Mn-redox-based oxides and oxyfluorides are considered the most promising earth-abundant high-energy cathode materials for next-generation lithium-ion batteries. While high capacities are obtained in high-Mn content cathodes such as Li- and Mn-rich layered and spinel-type materials, local structure changes and structural distortions ( often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn-rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. Here, it is shown that upon cycling of a cation-disordered rocksalt (DRX) cathode (Li 1.1 Mn 0.8 Ti 0.1 O 1.9 F 0.1 , an ultrahigh capacity of ≈320 mAh g –1 (energy density of ≈900 Wh kg –1 ) can be obtained through dynamic structural rearrangements upon cycling , along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn 4+ and Li + vacancies promotes local cation ordering, leading to the formation of domains of a “δ phase” within the disordered framework. On deep discharge, Mn 4+ reduction, along with Li + insertion transform the structure to a partially ordered DRX phase with a β'-LiFeO 2 -type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high-Mn DRXbut also provide guidance for the future development of Mn-based, high-energy density oxide, and oxyfluoride cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2022

Achieving High Stability and Performance in P2-Type Mn-Based Layered Oxides with Tetravalent Cations for Sodium-Ion Batteries

We report P2-type sodium-manganese-based layered cathodes, owing to their high capacity from both cationic and anionic redox, are a potential candidate for Na-ion batteries to replace Li-ion technology in certain applications. Still, the structure instability originates from irreversible oxygen redox at high voltage remains a challenge. Here, a high sustainability cobalt-free P2- Na 0.72 Mn 0.75 Li 0.24 X 0.01 O 2 (X= Ti/Si) cathode is developed. The outstanding capacity retention and voltage retention after 150 cycles are obtained in Na half-cells. Our finding shows Ti locates on the surface while Si diffuses to the bulk of the particles. Thus, Ti can act as protective layer that alleviate side reactions in carbonate-based electrolyte. Meanwhile, Si can regulate the local electronic structure and suppress oxygen redox activities. Notably, full-cells with hard carbon (≈300-335 Whkg -1 based on the cathode mass) deliver the capacity retention of 83% for P2- Na 0.72 Mn 0.75 Li 0.24 Si 0.01 O 2 and 66% for P2-Na 0.72 Mn 0.75 Li 0.24 Ti 0.01 O 2 after 500 cycles; this electrochemical stability is the best compared to other reported cathodes based on oxygen redox at present. The superior cycle performance also stems from the ability to inhibit microcracking and planar gliding within the particles. Altogether, this finding offers new composition towards developing high performance low-cost cathodes for Na-ion batteries and highlights the unique role of Ti/Si ions.

25 ENERGY STORAGE↗
DOE OSTI2023

Constructing uniform oxygen defect engineering on primary particle level for high-stability lithium-rich cathode materials

Lithium-rich layered cathode materials are considered to be research focus of cathode candidates for next generation lithium-ion batteries due to their high specific capacity and low cost. However, lattice deoxidation associated with elemental migration and internal local shrinkage usually results in deteriorated cyclic performance and notorious voltage attenuation, severely limiting its application. In this paper, we have successfully injected uniform oxygen defects into surface region of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 primary particles under the high-pressure and weak carbonate environment. Various experimental investigations indicate that the injected robust oxygen defects can not only mitigate detrimental interfacial reactions but also suppress unfavorable lattice variation and particle breakage. More importantly, theoretical calculations unravel the critical roles of oxygen defects in regulating energy band structure for strengthened anionic reversibility. Owing to stabilization effects of unique oxygen defect engineering, the modified Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 cathode has harvested dramatically enhanced electrochemical performance including a high initial coulombic efficiency of 96.6%, an outstanding capacity retention of 91.96% (1C, 200 cycles) and suppressed voltage decay of only 1.62 mV per cycle. Therefore, this facile and effective defect engineering strategy could establish new guidance for promoting practical application of Li-rich Mn-based cathode material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗