LiCoO2 Research Articles

Regulated Li+ Solvation via Competitive Coordination Mechanism of Organic Cations for High Voltage and Fast Charging Lithium Metal Batteries.

Li+ solvation exerted a decisive effect on electrolyte physicochemical properties. Suitable tuning for Li+ solvation enabled batteries to achieve unexpected performance. Here, we introduced inert organic cations to compete with Li+ for combining electrolyte molecules to modulate Li+ coordination in the electrolyte. The relevance between the number of cationic sites in organic cations and the competitive solvation ability was explored. The organic cations with multiple cationic sites attracted solvent molecules and anions away from Li+ to form new solvated shell, improving the Li+ transport kinetics and desolvation process in electrolyte while enhancing electrolyte oxidation tolerance. Moreover, electrostatic shielding provided by organic cations and anion-derived robust SEI promoted uniform and rapid Li+ deposition on Li electrodes. With the positive effect of organic cations, Li||LiCoO2 (LCO) batteries showed high specific capacity (136.46 mAh g-1) at high charge/discharge rate (10 C). Furthermore, Li||LCO batteries exhibited good capacity retention (70% after 500 cycles) at 4.6 V charge cut-off voltage. This work provides fresh insights for the optimization of electrolytes and battery performance.

Organic Cathode Electrolyte Interphase Achieving 4.8 V LiCoO2.

Developing high-voltage electrolytes to stabilize LiCoO2 (LCO) cycling remains a challenge in lithium-ion batteries. Constructing a high-quality cathode electrolyte interface (CEI) is essential to mitigate adverse reactions at high voltages. However, conventional inorganic CEIs dominated by LiF have shown limited performance for high-voltage LCO. Here, we propose an ionic liquid electrolyte (ILE) with a high donor number additive, enabling Li//LCO cells to achieve a high cut-off voltage of 4.7 V/4.8 V and a high-capacity retention of 86.9%/74.2% after 100 cycles at 0.5 C. During this process, a groundbreaking phenomenon was discovered: the construction of a stable organic CEI rich in C-F bonds by the high donor number additive under high voltage. These strong polar C-F bonds exhibit excellent electrochemical inertness and film-forming properties, resulting in optimal passivation of the cathode. This organic C-F bond-dominated CEI significantly suppresses phase transitions, cobalt dissolution, and gas evolution in LCO at high voltage. Additionally, the 4.8 V-class Li//LiNi0.6Co0.2Mn0.2O2 and 4.95 V-class Li//LiNi0.5Mn1.5O4 cells also demonstrate outstanding cycling stability. Even at 60 °C, the ILE-constructed organic CEI maintains superior performance. Our findings highlight the potential of organic CEI to enhance high-voltage cathode stability, paving the way for more efficient lithium-ion batteries.

Lattice-Engineering modulated band structure facilitates enhanced stability of high-voltage LiCoO2 at 4.6 V

Lithium cobalt oxide (LCO) cathode materials could exceed 210 mAh g−1 with excellent volumetric energy density, when operated at voltages above 4.5 V. However, the progress in the advancement of high-voltage LCO cathodes is impeded by unstable lattice oxygen loss and rapid structural degradation. Herein, we propose a modification strategy to modulate the band structure and stabilize the crystal structure of LCO through Zr/Ti dual-doping. The modified Zr/Ti-LCO demonstrates stable cycling performance at elevated cut-off voltage of 4.6 V. Uniform co-doping with zirconium and titanium suppresses the severe H1-3/O1 deleterious phase transition of LCO. By fine-tuning TM-O interactions and modulated band structure mitigate oxygen release reactivity at high voltage, achieving a delicate balance between structural integrity and electrochemical stability. Consequently, the modified Zr/Ti-LCO half-cell achieves superb capacity retention of 87.7 % after 300 cycles at 3.0–4.6 V, while the Zr/Ti-LCO||graphite pouch full-cell retains up to 85.8 % capacity after 500 cycles at 3.0–4.5 V. This study offers critical perspectives for advancing the design of high-voltage LCO cathodes.

Superionic conducting vacancy-rich β-Li3N electrolyte for stable cycling of all-solid-state lithium metal batteries.

The advancement of all-solid-state lithium metal batteries requires breakthroughs in solid-state electrolytes (SSEs) for the suppression of lithium dendrite growth at high current densities and high capacities (>3 mAh cm-2) and innovation of SSEs in terms of crystal structure, ionic conductivity and rigidness. Here we report a superionic conducting, highly lithium-compatible and air-stable vacancy-rich β-Li3N SSE. This vacancy-rich β-Li3N SSE shows a high ionic conductivity of 2.14 × 10-3 S cm-1 at 25 °C and surpasses almost all the reported nitride-based SSEs. A Li- and N-vacancy-mediated fast lithium-ion migration mechanism is unravelled regarding vacancy-triggered reduced activation energy and increased mobile lithium-ion population. All-solid-state lithium symmetric cells using vacancy-rich β-Li3N achieve breakthroughs in high critical current densities up to 45 mA cm-2 and high capacities up to 7.5 mAh cm-2, and ultra-stable lithium stripping and plating processes over 2,000 cycles. The high lithium compatibility mechanism of vacancy-rich β-Li3N is unveiled as intrinsic stability to lithium metal. In addition, β-Li3N possesses excellent air stability through the formation of protection surfaces. All-solid-state lithium metal batteries using the vacancy-rich β-Li3N as SSE interlayers and lithium cobalt oxide (LCO) and Ni-rich LiNi0.83Co0.11Mn0.06O2 (NCM83) cathodes exhibit excellent battery performance. Extremely stable cycling performance is demonstrated with high capacity retentions of 82.05% with 95.2 mAh g-1 over 5,000 cycles at 1.0 C for LCO and 92.5% with 153.6 mAh g-1 over 3,500 cycles at 1.0 C for NCM83. Utilizing the vacancy-rich β-Li3N SSE and NCM83 cathodes, the all-solid-state lithium metal batteries successfully accomplished mild rapid charge and discharge rates up to 5.0 C, retaining 60.47% of the capacity. Notably, these batteries exhibited a high areal capacity, registering approximately 5.0 mAh cm-2 for the compact pellet-type cells and around 2.2 mAh cm-2 for the all-solid-state lithium metal pouch cells.

Citric Acid Leaching Performance at High Solid-to-Liquid Ratios for Lithium-Ion Battery Recycling

AbstractThis study investigated the performance of citric acid as lixiviant for cathode material from end-of-life lithium-ion batteries (LIBs). Black mass containing 84.2 wt% MNC (LiNi0.45Mn0.4Co0.15O2) and 15.8 wt% LCO (LiCoO2) material was leached at solid-to-liquid ratios of 20, 50, and 100 g/L. Leaching with 1.5 M citric acid, 2 vol.% H2O2, and a solid-to-liquid ratio of 20 g/L at 95 °C extracted 90% Co, 95% Li, 94% Mn, and 94% Ni within 20 min. At the highest solid/liquid ratio of 100 g/L with 1.5 M citric acid, 10 vol.% H2O2, and 95 °C, 84% Al, 84% Co, 87% Li, 86% Mn, and 96% Ni were leached after 40 min, producing a leach solution containing 0.68 g/L Al, 20.0 g/L Co, 6.0 g/L Li, 13.6 g/L Mn, and 19.3 g/L Ni. Using stepwise addition of H2O2, instead of initial bulk addition, did not significantly improve the leaching efficiency but did reduce the required leaching time. Temperature control of the reactor was also more manageable with stepwise addition of H2O2 and evolution of gas was less vigorous. It was observed that the leaching efficiencies of Co, Li, and Mn decreased slightly at solid/liquid ratios of 50 g/L and 100 g/L, while the leaching of Ni increased slightly. The solution leached at 20 g/L could be stored for 6 weeks without any spontaneous precipitation. However, solutions leached at 50 g/L and 100 g/L showed changes in concentration after 1 month’s storage, suggesting that processes that have a large material throughput and use high solid-to-liquid ratios around 100 g/L must ensure that the solutions are not stored for extended periods of time.

Integrated optimization design with inherent element behaviors for bulk and surface stability towards 4.7 V LiCoO2 cathode

LiCoO2 (LCO) cathode with higher energy density can be harvested through raising its upper cut-off voltage to 4.7 V (vs. Li+/Li). However, such high-voltage operation exacerbates the bulk and surface instability of LCO, which is responsible for its rapid capacity decay at high voltages. Consequently, to address these issues, an integrated optimization design is reasonably proposed, which involves Mg/F/PO43- cooperative modulation for LCO (LCO-MFP) based on the inherent behaviors of these elements. Specifically, our theoretical calculations reveal the distinct distribution of Mg/F/PO43- (Mg pillaring, F doping and PO43- coating), which is rooted in their innate occupancy propensity. Consistent with our theoretical results, it is experimentally discerned that Mg and F atoms prefer to enter Li layer and O framework of LCO, respectively, whereas PO43- gravitates towards enrichment on the surface, thereby stabilizing bulk structure, hampering the lattice O/Co evolution and enhancing surface stability. The resulting integrated optimized LCO-MFP cathode can achieve an excellent capacity retention of 81.0 % at 4.7 V after 200 cycles. This integrated optimization design is anticipated to pave the way for selecting appropriate modification elements with their intrinsic properties for high-voltage LCO cathode.

Water-Mediated Surface Engineering Enhances High-Voltage Stability of Fast-Charge LiCoO2 Cathodes.

Maintaining the surface structure stability of LiCoO2 (LCO) during rapid charge-discharge processes (>5C) and under high-voltage conditions (>4.2 V) is challenging due to interfacial side reactions, cobalt dissolution, and oxygen redox activity at deeply delithiated states, all of which contribute to performance degradation. Herein, different from traditional surface coating methods, we report a water-mediated strategy that modifies the surface architecture of LCO, creating a passivating layer to inhibit surface degradation and enhance cycling stability under fast charging conditions. The surface etching of LCO by H2O is accompanied by a concurrent Li+/H+ cation exchange, which passivates surface oxygen with H+ ions, thereby enhancing both the hydrophobicity and structural stability. Consequently, the modified LCO exhibits superior capacity retention, which is 2.5 times that of the pristine LCO, after 100 cycles at a current density of 1000 mA g-1 (∼6C at 4.5 V). Even at an elevated temperature of 45 °C, it maintains impressive cycling stability at a current density of 500 mA g-1 (∼3C), as demonstrated in practical full-cell configurations. Investigation with multiple samples confirmed that the water-mediated strategy demonstrated broad applicability. We emphasize that the water-mediated modification of the surface architecture on cathode materials offers significant insights into enhancing the stability of high-energy-density lithium-ion batteries (LIBs).

Kinetics Enhancement of High‐Voltage LCO via In‐Situ Formed Cyanide‐Rich Polymer Interfaces

AbstractLithium cobalt oxide (LiCoO2) is widely used as cathode material for lithium‐ion batteries due to its high operation voltage and high specific capacity. However, conventional LiCoO2 (LCO) undergoes severe structural phase transitions and compositional changes at high voltage (>4.4 V) leading to failure. Herein, a multifunctional crosslinked polymer interface is insitu formed on LCO particles, which can build a nanoscale conformal coating layer on the interface of LCO, preventing the side reaction with the electrolyte. Moreover, thanks to its high‐voltage talerances and high Li+ conductivity, the in‐situ polymerized interface has excellent high‐voltage stability and Li+ transport kinetics, which significantly improves the electrochemical performances of LCO at 4.55 or 4.6 V. This study confirms the feasibility of in situ polymer modification of LCO, providing new ideas and methods for the structural stabilization and performance enhancement of high‐voltage lithium cobalt oxides.

High-entropy doping for high-voltage LiCoO2 with enhanced electrochemical performances

Lithium cobalt oxide (LiCoO2), as a pioneering layered oxide cathode material for lithium-ion batteries (LIBs), possesses exceptional theoretical specific capacity and cycling stability, positioning it as a leading candidate for commercial LIB applications. Boosting the upper-limit of charge voltage of LiCoO2 is a promising strategy to increase the capacity of batteries, vital for advancing energy storage solutions from portable electronics to electric vehicles. Nevertheless, hybrid redox reactions at high voltages speed up oxygen evolution, electrolyte decomposition, and irreversible phase transitions, ultimately causing rapid capacity fading.To address these challenges, we present a novel approach to enhance the structural stability and electrochemical performances of LiCoO2 cathode via La-Al-Mg-Y high-entropy doping. This strategy significantly improves the high-voltage cycling stability of the cathode material by retaining 72.5 % of its initial capacity after 500 cycles at 5 C under 4.6 V. Furthermore, the structural change caused by the phase transition between the O3 and H1-3 phases is remarkably suppressed. This advancement in LIB cathode technology paves the way for the development of high performance batteries and it is crucial for meeting the growing demand for sustainable energy storage.

Enhancing Charge–Discharge Speed of Li-Ion Batteries with BaTiO3-Coated LiCoO2

Lithium-ion batteries experience a decrease in capacity as the charge–discharge speed increases. To enhance the charge–discharge speed characteristics, the surface of the LiCoO2 (LCO) cathode material was coated with ferroelectric BaTiO3 (BT) nanodots. The electric field concentration phenomenon occurs at the triple-phase interface of LCO-BT-electrolyte due to the polarizing characteristics of the ferroelectric system. BT coated on the LCO surface acts as a protective layer and promotes the insertion and extraction of Li ions, resulting in a discharge capacity of 131.9 mAh g−1 at 10 C. This value is approximately 333% higher than that of bare LCO, and it enables stable cycling of LCO even at a cut-off voltage of 4.5 V. The study’s findings suggest that coating LCO with BT nanodots can significantly improve the charge–discharge performance of lithium-ion batteries, making them more efficient for high-speed charging applications in portable electronics and electric vehicles.

Recommended Practices for the Electrochemical Recovery of Cobalt from Lithium Cobalt Oxide: A Case Study of the Choline Chloride:Ethylene Glycol Deep Eutectic Solvent.

We recommend best practices for the recovery of cobalt from LiCoO2 (LCO) lithium-ion battery (LIB) cathodes by (i) leaching using green deep eutectic solvents (DES) and (ii) subsequent electrodeposition, through a case study of the choline chloride (ChCl):ethylene glycol (EG) DES. DES physical properties (conductivity, viscosity, and surface tension) were tailored by varying the composition between mole ratios of 1 : 2 and 1 : 5 (ChCl:EG). Examined along with leaching process parameters (temperature, duration), increasing the fraction of hydrogen bond donors (HBDs) decreased DES surface tension and enhanced leaching. Complete Co recovery was achieved using 1 : 5 ChCl:EG DES at 160 °C and 48 h. Leaching temperatures >160 °C are discouraged due to DES thermal degradation. The electrodeposition process was optimized for selective Co recovery with high faradaic efficiency. The leaching ability of the DES was antithetical to the stability of electrodeposition cell components and required operational parameter adjustment to minimize degradation. The optimized system (copper cathode and stainless-steel anode) employing 1 : 5 DES leachate exhibited a faradaic efficiency of ~80 %, specific Co recovery of ~0.8 mg hr<M-1 cm-1 at 50 °C and evidence of uniform deposition. DES surface tension is a key descriptor of metal recovery, and guidelines are presented to maximize selective Co recovery.

Robust polymer electrolytes with fast ion-transport nanochannels constructed by carbon dots for long lifespan Li metal batteries

As an anode material in energy storage systems, Li metal has exceptional merits, including high specific capacity, low density, and low redox potential. However, challenges such as lithium dendrites and unstable solid electrolyte interphase (SEI) hinder the practical application of lithium metal batteries (LMBs). Solid polymer electrolytes (SPEs), notably PVDF-HFP, are expected to overcome the above problems because of their mechanical merits and safe features, but their limited ion transportation behaviors result in insufficient ionic conductivity at room temperature. Herein, we invent an approach to prepare high performance electrolytes composed by porous PVDF-HFP and functionalized carbon dots (CDs). Such porous PVDF-HFP polymer membranes are created by a subtle phase inversion process, possessing a sponge-like structure, vertical lithium-ion transport channels and CDs decorated surfaces, thus able to uptake the liquid electrolyte (LE) to form gel polymer electrolytes (GPEs). The CDs fillers are produced in large scale with adjustable surface states, which can enhance Li salts disassociation to release free Li ions. As a result, the optimal conductivity of the as-prepared GPEs at room temperature is up to 8.7 mS cm−1 and the lithium transference number reaches 0.64. Our GPEs endow Li symmetric batteries with very stable SEI and long cycling life over 2200 h, and help realize high capacities and retention rates of the LMBs using LiFePO4(LFP) or LiCoO2(LCO) cathodes.

Directly Regenerating of Spent LiCoO2 with Gradient F-Doped Subsurface towards Ultra-Stable Storage Properties.

As great potential recycling strategy, the direct regeneration of spent LiCoO2 (LCO) is beneficial for lowering environmental pollutions and promoting global sustainability. However, owing to the using of binder and electrolyte, some fluorine impurities would be remained into spent materials. Considering the doping behaviors of F-elements, their suitable content introducing would facilitate the energy-storage abilities of regenerated LCO. Herein, through the tailored introduction of F-elements, spent LCO are successfully regenerated with physical-chemical evolutions. Benefitting from the existed oxygen vacancies, the diffusion energy-barrier of F-elements is reduced from 1.73 eV to 0.61 eV, facilitating the establishment of gradient F-doped subsurface, along with the formation of rigid CoO5F. Meanwhile, excess F-elements (1 wt %, as a threshold) lead to the formation of LiF passivation layer on the surface. Thus, the as-optimized sample displays a considerable capacity of 154.4 mAh g-1 even at 5.0 C, with retention rate (88.3 %) in 3.0-4.5 V. Supported by detailed electrochemical and kinetic analysis, the structural advantages are confirmed to boost the improved redox activity of Co-ions and the alleviating of irreversible oxygen-release. Give this, the work is anticipated to reveal the evolutions of regenerated LCO with the introduced F-elements, whilst providing the practical regeneration strategies toward excellent high-voltage properties.

Directly Regenerating of Spent LiCoO2 with Gradient F‐Doped Subsurface towards Ultra‐Stable Storage Properties

AbstractAs great potential recycling strategy, the direct regeneration of spent LiCoO2 (LCO) is beneficial for lowering environmental pollutions and promoting global sustainability. However, owing to the using of binder and electrolyte, some fluorine impurities would be remained into spent materials. Considering the doping behaviors of F‐elements, their suitable content introducing would facilitate the energy‐storage abilities of regenerated LCO. Herein, through the tailored introduction of F‐elements, spent LCO are successfully regenerated with physical‐chemical evolutions. Benefitting from the existed oxygen vacancies, the diffusion energy‐barrier of F‐elements is reduced from 1.73 eV to 0.61 eV, facilitating the establishment of gradient F‐doped subsurface, along with the formation of rigid CoO5F. Meanwhile, excess F‐elements (1 wt %, as a threshold) lead to the formation of LiF passivation layer on the surface. Thus, the as‐optimized sample displays a considerable capacity of 154.4 mAh g−1 even at 5.0 C, with retention rate (88.3 %) in 3.0–4.5 V. Supported by detailed electrochemical and kinetic analysis, the structural advantages are confirmed to boost the improved redox activity of Co‐ions and the alleviating of irreversible oxygen‐release. Give this, the work is anticipated to reveal the evolutions of regenerated LCO with the introduced F‐elements, whilst providing the practical regeneration strategies toward excellent high‐voltage properties.

Surface Engineering via Rare Earth Oxide Composite Coating to Enhance the High-Voltage Stability of the LiCoO2 Cathode.

The commercial application of high-voltage LiCoO2 (LCO) faces significant challenges due to rapid capacity decay, primarily attributed to an unstable interface and structure at deeply delithiated states. Herein, a unique rare earth oxide composite coating comprising La2O3, Y2O3, and LaYO3 has been prepared to stabilize LCO at high voltage. The synergistic effect between these rare earth oxides significantly reinforces the protective capabilities of the coating, effectively enhancing the interfacial/structural stability of LCO. When tested at 4.6 V, the coated LCO exhibits an excellent capacity retention of 94.4% after 300 cycles at 1 C. Even after an ultralong charge/discharge test of 700 cycles at 2 C, the coated LCO retains 85.2% of its initial specific capacity, which significantly outperforms the uncoated LCO (6.3%). Moreover, the coated LCO shows enhanced cycling performance at a high temperature of 45 °C, owing to the outstanding thermal stability of the La-Y-O composite. Additionally, the superior cycling stability of the coated LCO at 4.7 V, compared to the uncoated LCO, demonstrated the promising potential of the La-Y-O composite coating in improving electrochemical performance of LCO at higher cutoff voltages. These findings highlight an efficacious strategy to enhance the interfacial/structural stability of high-voltage LCO using rare earth oxides.

In Situ Constructing Robust Interface by Deep Eutectic Polymeric Electrolyte Enables High Performance Lithium Metal Batteries with High-Loading Cathode.

The low Li+ transport and poor interface have consistently been two major impediments to practical applications of Polyacrylonitrile (PAN)-based composite solid-state electrolytes (PCPE). In this work, a polymerizable deep eutectic electrolyte is meticulously designed with high fluidity which consists of Poly (Ethylene Glycol) Diacrylate (PEGDA), Fluoroethylene Carbonate (FEC), Succinonitrile (SN) and dual salts (LiTFSI/LiDFOB) to promote Li+ transport and ameliorate the interface of PCPE. Inclusion of PEGDA monomers and FEC alters the crystallinity of SN, enhancing the wettability of thick electrode, and formation of polymeric 3D network from polymerization of PEGDA can anchor SN and suppress the side reactions between SN and lithium metal. Consequently, the modified PCPE exhibit an enhanced conductivity of 4.47×10-4Scm-1 with Li-ion transference number of 0.60, and show an excellent lithium stability. LiCoO2(LCO)/SP-PCPE/Li batteries with higher loading (3-4.4V, 6mgcm-2) can work for over 300 cycles at 0.5 C. Even with an ultra-high loading of 16mgcm-2, LCO/SP-PCPE/Li batteries achieve an excellent cycling performance. This work provides new insights into how to construct a robust interface for solid-state batteries with high-loading cathode.

Imaging in-operando LiCoO2 nanocrystallites with Bragg coherent X-ray diffraction

Although the LiCoO2 (LCO) cathode material has been widely used in commercial lithium ion batteries (LIB) and shows high stability, LIB’s improvements have several challenges that still need to be overcome. In this paper, we have studied the in-operando structural properties of LCO within battery cells using Bragg Coherent X-ray Diffraction Imaging to identify ways to optimise the LCO batteries’ cycling. We have successfully reconstructed the X-ray scattering phase variation (a fingerprint of atomic displacement) within a ≈ (1.6 × 1.4 × 1.3) μm3 LCO nanocrystal across a charge/discharge cycle. Reconstructions indicate strained domains forming, expanding, and fragmenting near the surface of the nanocrystal during charging, with a determined maximum relative lattice displacements of 0.467 Å. While discharging, all domains replicate in reverse the effects observed from the charging states, but with a lower maximum relative lattice displacements of 0.226 Å. These findings show the inefficiency-increasing domain dynamics within LCO lattices during cycling.

High-fidelity reconstruction of porous cathode microstructures from FIB-SEM data with deep learning

Accurate modeling of lithium-ion battery (LIB) electrode microstructures provides essential references for understanding degradation mechanisms and optimizing materials. Traditional segmentation methods often struggle to accurately capture the complex microstructures of porous LIB electrodes in focused ion beam scanning electron microscopy (FIB-SEM) data. In this work, we develop a deep learning model based on the Swin Transformer to segment FIB-SEM data of a lithium cobalt oxide electrode, utilizing fused secondary and backscattered electron images. The proposed approach outperforms other deep learning methods, enabling the acquirement of 3D microstructure with reduced particle elongated artifacts. Analyses of the segmented microstructures reveal improved electrode tortuosity and pore connectivity crucial for ion and electron transport, emphasizing the necessity of accurate 3D modeling for reliable battery performance predictions. These results suggest a path toward voxel-level degradation analysis through more sensible battery simulation on high-fidelity microstructure models directly twinned from real porous electrodes.

Recycling spent battery components into highly efficient hydrogen and oxygen evolution electro-nano-catalysts

Inspired by the 'waste-to-resource' strategic theme for environmental recovery, here we present the recycling of spent dry cells and spent Lithium-ion batteries aiming to achieve the preparation of cheap and efficient electrocatalysts for Proton Exchange membrane electrolyzers instead of the precious-based electrocatalysts. Graphite doped with manganese (IV) oxide nanoparticles, graphite doped with manganese (IV) oxide and aluminum oxide nanoparticles, lithium cobalt oxide doped with copper oxide nanoparticles, and lithium cobalt oxide doped with copper oxide and zinc oxide nanoparticles synthesis procedures are done via hydrothermal method at a pressure of 4.5 Mpa at 180 °C. Electrochemical characterization is done to determine overpotential, tafel slope, and electrocatalytic stability via a three-electrode system. The optimum results are observed by the graphite doped with manganese (IV) oxide nanoparticles, which show -55.06 mV and -41.33 mV/dec as overpotential and tafel slope at -10 mA/cm2 for hydrogen evolution reaction with surface area of 40.87 m2/g and 21.05 nm as crystal size and Graphite doped with manganese oxide and aluminum oxide nanoparticles, which show 321.58 mV and 174.14 mV/dec as overpotential and Tafel slope for oxygen evolution reaction at 10 mA/cm2 with surface area of 7.64 m2/g and 44.43 nm as crystal size.

Chemo-mechanical instabilities in lithium cobalt oxide at higher state-of-charge in Li-Ion batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.