Li-ion Battery Cathode Research Articles

Capacity Fade of Graphite/NMC811: Influence of Particle Morphology, Electrolyte, and Charge Voltage

LiNi0.8Mn0.1Co0.1O2 (NMC811) is an important Li-ion battery cathode material; however, there is a tradeoff between delivered capacity and capacity retention. As the charge potential increases the capacity rises but at the expense of capacity retention. The decrease in capacity retention has been ascribed to several factors including particle cracking, surface reconstruction, transition metal dissolution, and electrolyte reactivity. The present study compares 4.1 and 4.3 V charging limits in commercially relevant graphite/NMC811 pouch cells for single crystal (SC) and polycrystalline (PC) NMC811 with ethylene carbonate (EC)-containing or EC-free electrolytes. The electrochemistry is rationalized through analysis of electrochemical impedance spectroscopy, positive electrode X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, X-ray diffraction, and negative electrode mapping by X-ray fluorescence. Graphite/SC-NMC811 cells show high-capacity retention at 4.1 V but exhibit degradation at 4.3 V charging potentials. The EC-free electrolyte cells led to higher capacity fade, especially when charged to 4.3 V. Cathode dissolution and deposition on the negative electrode from PC-NMC811 cells was higher than for samples from SC-NMC811 cells. This study reveals the impact of material type, charge voltage, and electrolyte composition on the reactions at the positive electrode, their influence on the negative electrode, and evolution with cycle number.

Orientation-dependent electronic structure of Li2WO4 films epitaxial grown on LiCoO2 by spontaneous lithiation

Understanding and modulating the properties of materials requires a deep knowledge of their electronic structures. However, analysis of the electronic structure of a single material can be challenging, particularly for modified electrode materials, due to the complexity of mixed interface structures. In this study, we employ pulsed laser deposition (PLD) to epitaxially synthesize Li₂WO₄ (LWO) films on LiCoO₂ (LCO) layers with different orientations. Based on a series of high-resolution synchrotron-based techniques including X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy (XPS), the electronic structure of LWO is carefully scrutinized where a higher main energy level of W5d(eg)-O2p orbitals hybridization in LWO/LCO(104) as compared to LWO/LCO(003) has been observed. This experimental finding is further validated by a comprehensive set of density of states calculations. Furthermore, detailed polarized XAS characterization unveils distinct anisotropy between the two oriented LWO configurations. This comprehensive scientific investigation, harnessing the capabilities of synchrotron-based techniques, provides invaluable insights for future studies, offering guidance for the optimized utilization of LWO as a solid-state electrolyte or modification layer for LCO cathodes in high-powered Li-ion batteries.

Regulating electronic structure of anionic oxygen by Ti4+ doping to stabilize layered Li-rich oxide cathodes for Li-ion batteries

Abstract Layered Li-rich oxide cathodes enable to activate lattice oxygen anions redox in the charge compensation process and provide superior high specific capacity over 250 mAh g−1 due to their unique configuration, and thus attracting great attentions as promising cathode candidates for Li-ion batteries. However, how to better stabilize the bulk lattice oxygen framework and surface structure, and slow down the release of oxygen, is still major bottleneck to develop high performance Li-rich materials. Transition metal ions with outer d0 electronic configuration have distortable configuration, which can accommodate the local structure and chemical environment of the material, and then improve structural stability. Herein this work, the d0 transition metal Ti4+ is used as doping element to improve the chemical and structural stability, capacity retention and lithium ion diffusion kinetics of Li-rich material. The role of Ti in the material modification is revealed through synchrotron-based soft x-ray absorption spectroscopy, XRD, XPS and electrochemical tests. The improvement in structural stability can be attributed to that Ti doping can adjust the hybridization of O2p and TM3d to regulate the local electronic structure of both bulk lattice oxygen and surface oxygen vacancies. It is hoped that this work should shed light on the development of high-performance cathode materials for Li-ion Batteries.

Two-dimensional fused π-conjugated multi-activity covalent organic framework as high-performance cathode for lithium-ion batteries

Electrochemically active covalent organic frameworks (COFs) with robust skeletons and permanent porosity are attracting wide interest as promising electrode materials for Li-ion batteries (LIBs). However, current COF-based electrodes suffer from poor capacity and rate performance due to limited redox-active sites and low conductivity. To address these challenges, combining the advantages of high stability of the macromolecular skeleton and high-density redox-active CO and CN groups, a novel two-dimensional (2D) fused π-conjugated COF (denoted as HAPT-COF) with ultrahigh theoretical capacity is fabricated. In particular, the post-hydrothermal reaction between HAPT-COF and graphene oxide (GO) affords intercalated COF-based nanocomposites (HAPT-COF@rGO), featuring with improved utilization of redox-active sites, electronic conductivity, and structure stability. The CO and CN groups on the walls contribute to reversible 18 Li-ions storage for each HAPT-COF repeating unit across three stages. Owing to these advantages, the HAPT-COF@rGO exhibited an excellent reversible capacity (558 mAh g−1 at 0.1 C), cycling stability (92% capacity retention after 1000 cycles at 10 C), and superior rate performance (318 mAh g−1 at 10 C), ranking the best among reported polymer cathodes in LIBs.

Positron unveiling high mobility graphene stack interfaces in Li-ion cathodes

Carbon-based coatings in Li-ion battery cathodes improve electron conductivity and enable rapid charging. However, the mechanism is not well understood. Here, we address this question by using positrons as non-destructive probes to investigate nano-interfaces within cathodes. We calculate the positron annihilation lifetime in a graphene stack LiCoO2 heterojunction using an ab initio method with a non-local density approximation to accurately describe the electron-positron correlation. This ideal heterostructure represents the standard carbon-based coating performed on cathode nanoparticles to improve the conduction properties of the cathode. We characterize the interface between LiCoO2 and graphene as a p-type Schottky junction and find positron surface states. The intensity of the lifetime component for these positron surface states serves as a descriptor for positive ion ultra-fast mobility. Consequently, optimizing the carbon layer by enhancing this intensity and by analogizing Li-ion adatoms on graphene layers with positrons at surfaces can improve the design of fast-charging channels.

Recycling and Reutilization of Metals Aided by Deep Eutectic Solvents: from NMC Cathodes of Spent Li-ion Batteries to Electrolytes for Supercapacitors.

With the rapidly increasing demand for lithium ion batteries (LIBs), recycling the metals found in spent cathodes is mandatory to both alleviate shortages resulting from the mining of natural metal ores and manage the disposal of spent LIBs. The use of deep eutectic solvents (DESs) for metals recovery from spent cathodes of LIBs (e. g., LCO and NMC types) offers a sustainable yet efficient alternative to conventional hydrometallurgical processes. Nonetheless, g efforts are required to use milder temperatures and higher mass loadings, thus ensuring cost-effectiveness. In this latter regard, addressing the reutilization of DESs in subsequent stages of metal extraction, and streamlining or eliminating the chemical procedures employed for metal separation, is even more crucial to guarantee the economic feasibility of the recycling process. Herein, we have prepared a DES that provides extraction efficiencies of ca. 100 % for every metal of NMC cathodes even at mild experimental conditions (e. g., 60 °C) and for loadings as high as 70 mgNMC/gDES. Moreover, we have pioneered the direct use of leachates containing DESs and metals as electrolytes for supercapacitors. This approach enables the reintroduction of DESs and the recovered metals into the value chain with a minimal economic and environmental impact.

Photothermal Enhancement of Prussian Blue Cathodes for Li-Ion Batteries.

Photoenhanced batteries, where light improves the electrochemical performance of batteries, have gained much interest. Recent reports suggest that light-to-heat conversion can also play an important role. In this work, we study Prussian blue analogues (PBAs), which are known to have a high photothermal heating efficiency and can be used as cathodes for Li-ion batteries. PBAs were synthesized directly on a carbon collector electrode and tested under different thermally controlled conditions to show the effect of photothermal heating on battery performance. Our PBA electrodes reach temperatures that are 14% higher than reference electrodes using a blue LED, and a capacity enhancement of 38% was achieved at a current density of 1600 mA g-1. Additionally, these batteries show excellent cycling stability with a capacity retention of 96.6% in dark conditions and 94.8% in light over 100 cycles. Overall, this work shows new insights into the effects leading to improved battery performance in photobatteries.

Nitrogen-based redox couple regulated anionic redox to long-term cycling stability of Li and Mn-rich layered oxide cathode for Li-ion batteries

Lithium and manganese-rich layered oxides (LMROs) have attracted extensive attention and are promising cathode materials for next-generation lithium ion batteries due to their high capacities and high energy densities. However, LMRO cathode suffers from severe capacity and voltage fading originating from irreversible surface oxygen evolution. Herein, we propose a facile redox couple strategy by introducing nitroxyl radicals species to regulate the surface anionic redox reaction of LMRO cathode. Differential electrochemical mass spectroscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analyses demonstrate that during charge process, the peroxide ion O22− on the surface generated from the oxidation of lattice O2− could be reduced back to stable O2− by redox couple in time, thus avoiding oxygen evolution and structure degradation, as well as enhancing bulk oxygen redox activity. The enhanced LMRO electrode delivers a high capacity of 220.3 mAh g−1 at 1 C. An excellent cycling stability with a capacity retention of 94.4 % is achieved after 500 cycles, as well as a suppressed voltage decay with only 1.12 mV per cycle.

Oxygen-Incorporated Lithium-Rich Iron Sulfide Cathodes for Li-Ion Batteries with Boosted Material Stability and Electrochemical Performance

Oxygen-Incorporated Lithium-Rich Iron Sulfide Cathodes for Li-Ion Batteries with Boosted Material Stability and Electrochemical Performance

Enhancing the Performance of LiFePO4 Cathodes in Li-ion Batteries: Role of Surface Coating Based on ZIF-8 Particle Size Optimization

Enhancing the Performance of LiFePO4 Cathodes in Li-ion Batteries: Role of Surface Coating Based on ZIF-8 Particle Size Optimization

Synergetic recycling of permanent magnet and Li-ion battery cathode material for metals recovery

Rare earth elements (REEs)-based (NdFeB) magnets and lithium−ion batteries (LIBs) are critical for a low−carbon economy. Their production depends on critical elements like REEs, Li, Co and Ni. Recycling of these products have been explored separately as a potential solution. Conventional methods for recycling NdFeB magnets and LIBs face challenges like high energy consumption, lengthy processing, excessive reagent usage, and waste generation. In this study, a novel synergetic recycling methodology is proposed to minimize these challenges. The idea is based on using waste ferrous sulfate solution generated during magnet leaching as a reducing and leaching reagent for battery recycling thereby eliminating the need for additional reagents for oxidation of iron in NdFeB and reduction of cathode material in LIBs. The magnet is leached in diluted H2SO4 at 70 °C followed by double sulfate precipitation for REEs with Na2SO4. The REE-depleted but acidic ferrous solution is then used for reductive leaching of cathode material at 90 °C. The overall recovery rates of REEs, Li, Co, Ni, and Mn in this process are >95%. The iron from magnet material is recovered as crystalline and easily-filterable iron compound that can be converted to goethite and used as a byproduct. This synergetic approach not only reduces reagent consumption and waste generation aligning with the principles of circular economy but also offers improved efficiency, resource conservation, and environmental sustainability.

Defect-Driven Configurational Entropy in the High-Entropy Oxide Li1.5MO3-δ.

Layered lithiated oxides are promising materials for next generation Li-ion battery cathode materials; however, instability during cycling results in poor performance over time compared to the high capacities theoretically possible with these materials. Here we report the characterizations of a Li1.47Mn0.57Al0.13Fe0.095Co0.105Ni0.095O2.49 high-entropy layered oxide (HELO) with the Li2MO3 structure where M = Mn, Al, Fe, Co, and Ni. Using electron microscopy and X-ray spectroscopy, we identify a homogeneous Li2MO3 structure stabilized by the entropic contribution of oxygen vacancies. This defect-driven entropy would not be attainable in the LiMO2 structure sometimes observed in similar materials as a secondary phase owing to the presence of fewer O sites and a 3+ oxidation state for the metal site; instead, a Li2-γMO3-δ is produced. Beyond Li2MO3, this defect-driven entropy approach to stabilizing novel compositions and phases can be applied to a wide array of future cathode materials including spinel and rock salt structures.

All-Dry Solid-Phase Synthesis of Single-Crystalline Ni-Rich Co-Poor Ternary Cathodes for Li-Ion Batteries

All-Dry Solid-Phase Synthesis of Single-Crystalline Ni-Rich Co-Poor Ternary Cathodes for Li-Ion Batteries

Microwave-accelerated direct regeneration of LiCoO2 cathodes for Li-ion batteries

Microwave-accelerated direct regeneration of LiCoO2 cathodes for Li-ion batteries

Understanding the Role of Imide-Based Salts and Borate-Based Additives for Safe and High-Performance Glyoxal-Based Electrolytes in Ni-Rich NMC811 Cathodes for Li-Ion Batteries.

Herein, the design of novel and safe electrolyte formulations for high-voltage Ni-rich cathodes is reported. The solvent mixture comprising 1,1,2,2-tetraethoxyethane and propylene carbonate not only displays good transport properties, but also greatly enhances the overall safety of the cell thanks to its low flammability. The influence of the conducting salts, that is, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), and of the additives lithium bis(oxalato)borate (LiBOB) and lithium difluoro(oxalato)borate (LiDFOB) is examined. Molecular dynamics simulations are carried out to gain insights into the local structure of the different electrolytes and the lithium-ion coordination. Furthermore, special emphasis is placed on the film-forming abilities of the salts to suppress the anodic dissolution of the aluminum current collector and to create a stable cathode electrolyte interphase (CEI). In this regard, the borate-based additives significantly alleviate the intrinsic challenges associated with the use of LiTFSI and LiFSI salts. It is worth remarking that a superior cathode performance is achieved by using the LiFSI/LiDFOB electrolyte, displaying a high specific capacity of 164mAhg-1 at 6C and ca. 95% capacity retention after 100 cycles at 1C. This is attributed to the rich chemistry of the generated CEI layer, as confirmed by ex situ X-ray photoelectron spectroscopy.

Quantification and chemical fluctuation in NMC Li-ion battery cathode materials analyzed using APT

Quantification and chemical fluctuation in NMC Li-ion battery cathode materials analyzed using APT

Oxidative decolorization of indigo carmine dye using spent cathode of Li-ion batteries

Oxidative decolorization of indigo carmine dye using spent cathode of Li-ion batteries

Enhancing Orbital Interaction in Spinel LiNi0.5Mn1.5O4 Cathode for High-Voltage and High-Rate Li-Ion Batteries.

High voltage cobalt-free spinel LiNi0.5Mn1.5O4 (LNMO) is well organized as a high-power cathode material for lithium (Li)-ion batteries, however, the weak interaction between the 3d orbital of the transition metal (TM) ions and the 2p orbital of oxygen (O) leads to the instability of crystal structural, hindering the long-term stable cycling of LNMO cathode especially at high temperatures. Here, a design strategy of orbital interaction is initiated to strengthen TM 3d-O 2p framework in P-doped LNMO (P-LNMO) by choosing phytic acid as P dopant, which can realize more uniform doping compared to regular phosphate. The results show that the enhancement of TM 3d-O 2p orbital interaction in P-LNMO can suppress the Jahn-Teller effect and subsequent dissolution of Mn, as well as lowers the energy barrier for Li ion insertion/extraction kinetics. As a result, superior electrochemical performances including high discharge capacity, stable cycling behavior and enhanced rate capability of P-LNMO are obtained. Significantly, the P-LNMO pouch cell shows great cycling stability with 97.4% capacity retention after 100 cycles.

Unlocking iron metal as a cathode for sustainable Li-ion batteries by an anion solid solution.

Traditional cathode chemistry of Li-ion batteries relies on the transport of Li-ions within the solid structures, with the transition metal ions and anions acting as the static components. Here, we demonstrate that a solid solution of F- and PO43- facilitates the reversible conversion of a fine mixture of iron powder, LiF, and Li3PO4 into iron salts. Notably, in its fully lithiated state, we use commercial iron metal powder in this cathode, departing from electrodes that begin with iron salts, such as FeF3. Our results show that Fe-cations and anions of F- and PO43- act as charge carriers in addition to Li-ions during the conversion from iron metal to a solid solution of iron salts. This composite electrode delivers a reversible capacity of up to 368 mAh/g and a specific energy of 940 Wh/kg. Our study underscores the potential of amorphous composites comprising lithium salts as high-energy battery electrodes.

Molecular design of highly Li-ion conductive cathode-electrolyte interface enabling excellent rate performance for lithium-ion batteries

The structural stability and ionic conductivity of the cathode electrolyte interface (CEI) film at high voltages are crucial to the nickel-rich layered cathode in Li-ion batteries (LIBs). These characteristics are largely determined by electrolyte components. Herein, an air-stable organic cyclophosphate salt named lithium 1, 3, 2-dioxaphosphinan-2-olate-2-oxide (LiDOP) is designed and synthesized as a CEI forming additive. It preferentially oxidizes and undergoes opening-ring polymerization under charging to form an organic–inorganic hybrid polymers with –LiPO4 segments and –(CH2)3– alternately connected on the cathode surface. Such a structure endows CEI film with high ionic conductivity, flexibility and mechanical strength, which can ameliorate the structure phase transformation, suppress the transition metal ion dissolution and enhance the interfacial stability at high cut-off voltage. The electrolyte with 0.2 wt% LiDOP endows 4.3 V-charged Li||LiNi0.8Co0.1Mn0.1O2 battery with 83.2 % capacity retention after 200 cycles at 5C rate. The graphite||NCM811 pouch cell shows a capacity retention of 85.6 % after 150 cycles under a 4.5 V voltage, while the cell without LiDOP shows only 23.5 %. Our work demonstrates the effectiveness of covalently coupled P-O-Li compounds as CEI film in stabilizing the interface, which provides a guidance for the electrolyte design in high-voltage LIBs.