Ni-rich Layered Oxide Research Articles

Surface-to-bulk synergistic modification enables stable interface of Ni-rich oxide cathode for all-solid-state lithium batteries

All-solid-state lithium batteries (ASSLBs) are supposed to a highly forward-looking battery technology by reason of their conspicuous energy density and excellent safety. Ni-rich layered oxide cathodes have been extensively studied in ASSLB systems with sulfide electrolytes owing to their high voltage and preeminent specific capacity. However, the electrochemical performance of ASSLBs is severely degraded due to the interfacial physical contact failure, space charge layer effect, and chemical/electrochemical side reactions between sulfide electrolytes and Ni-rich oxide cathodes. In this work, the surface of LiNi0.92Co0.04Mn0.04O2 (NCM92) is coated with a nano-level CeO2 buffer layer and is simultaneously doped with Ce element (NCM92–1%Ce) by one-step wet chemical method. Ce doping is beneficial for maintaining structural stability and suppressing irreversible phase transition. The CeO2 buffer layer can efficaciously avoid the oxidation and decomposition phenomenon at the interface between NCM92 and sulfide electrolyte. As expected, NCM92–1%Ce cathode shows the discharge specific capacity of 141.46 mAh g−1 after 80 cycles at 0.2C with 79.32% capacity retention rate, which is much higher than that of the unmodified NCM92 cathode. The results indicate that the surface-to-bulk synergistic modification strategy can successfully improve the structure toughness and interface stability of Ni-rich oxide cathode for ASSLBs with sulfide electrolytes.

High Safety Electrolyte Design for Enabling High Energy-Density System of LiNi0.8Co0.1Mn0.1O2//Phosphorus by Simultaneously Adjusting Dual Electrode/Electrolyte Interfaces.

The demand for state-of-the-art high-energy-density lithium-ion batteries is increasing. However, the low specific capacity of electrode materials in conventional full-cell systems cannot meet the requirements. Ni-rich layered oxide cathodes such as Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) have a high theoretical specific capacity of 200 mAh g-1, but it is always accompanied by side reactions on the electrode/electrolyte interface. Phosphorus anode possesses a high theoretical specific capacity of 2596 mAh g-1, but it has a huge volume expansion (≈300%). Herein, a highly compatible and secure electrolyte is reported via introducing an additive with a narrow electrochemical window, Lithium difluoro(oxalato)borate (LiDFOB), into 1m LiPF6 EC/DMC with tris (2,2,2-trifluoroethyl) phosphate (TFEP) as a cosolvent. LiDFOB participates in the formation of organic/inorganic hybrid electrode/electrolyte interface layers at both the cathode and anode sides. The side reactions on the surface of the NCM811 cathode and the volume expansion of the phosphorus anode are effectively alleviated. The NCM811//RP full cell in this electrolyte shows high capacity retention of 82% after 150 cycles at a 0.5C rate. Meanwhile, the electrolyte shows non-flammability. This work highlights the importance of manipulating the electrode/electrolyte interface layers for the design of lithium-ion batteries with high energy density.

Organic coating strategy with oxidized oxygen anion capture to suppress lattice oxygen evolution of Ni-rich cathode materials at high voltage

Ni-rich layered oxide has attracted widespread attention due to its high capacity of over 200 mAh·g−1 at 4.5 V. However, how to solve its lattice oxygen evolution problem during high-voltage cycling remains the major challenge nowadays. It is still important to design stable and efficient Ni-rich layered oxides. Herein, an organic coating strategy was proposed for this challenge. Specifically, (C3H3N)n (PAN) was employed as a proof-of-concept organic coating with better electro-negativity on LiNi0.8Co0.1Mn0.1O2 to inhibit the lattice oxygen evolution. The CN functional groups in the PAN coating can adsorb Oα− (α < 2) and provide it with electrons for its reduction to stable O2−, thus inhibiting the continuous outward migration. As expected, in a voltage range of 2.7–4.5 V, the modified Ni-rich electrode displayed a high-capacity retention of 86.3 % after 200 cycles at 1C, 75.1 % after 350 cycles at 5C, and 83.1 % after 100 cycles at 1C and 55 °C. Furthermore, it also exhibited a high discharge specific capacity of 235.3 mAh·g−1 with a capacity retention of 75.5 % after 200 cycles under a cut-off voltage of 4.7 V. This innovative organic coating strategy presents new insights into suppressing the lattice oxygen evolution under high-voltage cycling by manipulating the surface chemistry of Ni-rich materials.

Comprehensive Study of Zr-Doped Ni-Rich Cathode Materials Upon Lithiation and Co-Precipitation Synthesis Steps.

Ni-rich layered oxides LiNi1-x-yMnxCoyO2 (NMC811, x = 0.1 and y = 0.1) are considered promising cathode materials in lithium-ion batteries (LiBs) due to their high energy density. However, those suffer a severe capacity loss upon cycling at high delithiated states. The loss of performance over time can be retarded by Zr doping. Herein, a small amount of Zr is added to NMC811 material via two alternative pathways: during the formation of the transition metal (TM) hydroxide precursor at the co-precipitation step (0.1%-Zr-cp) and during the lithiation at the solid-state synthesis step (0.1%-Zr-ss). In this work, the crystallographic Zr uptake in both 0.1%-Zr-ss and 0.1%-Zr-cp is determined and quantified through synchrotron X-ray diffraction and X-ray absorption spectroscopy. We prove that the inclusion of Zr in the TM site for 0.1%-Zr-cp leads to an improvement of both specific capacity (156 vs 149 mAh/g) and capacity retention (85 vs 82%) upon 100 cycles compared to 0.1%-Zr-ss where the Zr does not diffuse into the active material and forms only an extra phase separated from the NMC811 particles.

Double-Salts Super Concentrated Carbonate Electrolyte Boosting Electrochemical Performance of Ni-Rich LiNi0.90Co0.05Mn0.05O2 Lithium Metal Batteries.

Current lithium-ion batteries cannot meet the requirement of higher energy density with further large-scale application of electrical vehicles. Lithium metal batteries combined with Ni-rich layered oxides cathode are expected as the one of promising solutions, while the poor electrode and electrolyte interface impedes the commercial development of lithium metal batteries. A new double-salts super concentrated (DSSC) carbonate electrolyte is proposed to improve the electrochemical performance of LiNi0.90Co0.05Mn0.05O2 (NCM9055)||Li metal battery which exhibits stable cycling performance with the capacity retention of 93.04% and reversible capacity of 173.8 mAh g-1 after 100 cycles at 1 C, while cells with conventional 1m diluted electrolyte remains only 60.55% and capacity of 114.2 mAh g-1. The double salts synergistic effect in super concentrated electrolyte promotes the formation for more balanced stable cathode electrolyte interface (CEI) inorganic compounds of CFx, LiNOx, SOF2, Li2SO4, and less LiF by X-ray photoelectron spectroscopy (XPS)test, and the uniform 2-3nm rock-salt phase protection layer on the cathode surface by transmission electron microscope (TEM) characterization, improving the cycling performance of the Ni-rich NCM9055 layered oxide cathode. The DSSC electrolyte also can relief the Li dendrite growth on Li metal anode, as well as exhibit better flame retardance, promoting the application of more safety Ni-rich NCM9055||Li metal batteries.

Gaining insight into lithium-ion battery degradation by a calorimetric approach

With the growing demand for lithium-ion batteries (LIBs) in transportation and renewable energy sectors, ensuring reliability and mitigating degradation are crucial challenges for their widespread deployment. This study investigates the relationship between thermal characteristics and degradation/reliability by developing an in-situ heat measurement methodology for LIBs operating under grid services. Using adiabatic mode-based calorimetry, we determine the thermal behavior of two commercial cells with distinct cathode chemistries (Ni-rich layered oxide and olivine) before and after two years of peak shaving operation and demonstrate a strong correlation between thermal characteristics and electrochemical performance and its degradation. By further analyzing the heat sources separation and differentiating between irreversible and reversible heat, we disclose the underlying degradation mechanisms of LIBs. These findings emphasize the critical role of thermal characteristics in determining LIB reliability and degradation, while the obtained heat data can aid in the development and calibration of LIB state-of-health models for grid applications.

Boron- and calcium-interspersed cathode-electrolyte interphases on Ni-rich layered oxide cathodes for advanced performance lithium-ion batteries

Although Ni-rich layered oxides (Ni-rich NCM) have become the preferred cathode materials in the electric vehicle market, their unsustainable cycling behavior arising from the extremely high reactivity at the interface has become a formidable challenge. To alleviate this problem, we propose modifying the cathode-electrolyte interphase (CEI) of Ni-rich L-NCM cathodes by incorporating B/Ca functional groups. Dual-functionalized CEI layers are prepared by heating boric acid (H3BO3) and calcium oxide (CaO) in a one-step process. Islands of B- and Ca-functionalized CEI layer are observed at the Ni-rich L-NCM cathode, and the thickness is controlled to approximately 2.4 nm. The B-functional group not only lowers the concentration of residual lithium but also compensates for the longer Li+ migration distance by providing a desirable pathway based on ion-hopping sites. The Ca functional groups increase the mechanical rigidity of the Ni-rich L-NCM cathode, which inhibits the appearance of microcracks. In terms of its cycling behavior, the capacity retention of the cell with the B/Ca-incorporated Ni-rich L-NCM cathode improves markedly (72.4%), whereas the bare Ni-rich L-NCM material only retains 44.3% of its capacity after 100 cycles.

Origins and Importance of Intragranular Cracking in Layered Lithium Transition Metal Oxide Cathodes.

Li-ion batteries have a pivotal role in the transition toward electric transportation. Ni-rich layered transition metal oxide (LTMO) cathode materials promise high specific capacity and lower cost but exhibit faster degradation compared with lower Ni alternatives. Here, we employ high-resolution electron microscopy and spectroscopy techniques to investigate the nanoscale origins and impact on performance of intragranular cracking (within primary crystals) in Ni-rich LTMOs. We find that intragranular cracking is widespread in charged specimens early in cycle life but uncommon in discharged samples even after cycling. The distribution of intragranular cracking is highly inhomogeneous. We conclude that intragranular cracking is caused by local stresses that can have several independent sources: neighboring particle anisotropic expansion/contraction, Li- and TM-inhomogeneities at the primary and secondary particle levels, and interfacing of electrochemically active and inactive phases. Our results suggest that intragranular cracks can manifest at different points of life of the cathode and can potentially lead to capacity fade and impedance rise of LTMO cathodes through plane gliding and particle detachment that lead to exposure of additional surfaces to the electrolyte and loss of electrical contact.

Revealing the Nanoscopic Corrosive Degradation Mechanism of Nickel-Rich Layered Oxide Cathodes at Low State-of-Charge Levels: Corrosion Cracking and Pitting.

Ni-rich layered oxides have received significant attention as promising cathode materials for Li-ion batteries due to their high reversible capacity. However, intergranular and intragranular cracks form at high state-of-charge (SOC) levels exceeding 4.2 V (vs. Li/Li+), representing a prominent failure mechanism of Ni-rich layered oxides. The nanoscale crack formation at high SOC levels is attributed to a significant volume change resulting from a phase transition between the H2 and H3 phases. Herein, in contrast to the electrochemical crack formation at high SOC levels, another mechanism of chemical crack and pit formation on a nanoscale is directly evidenced in fully lithiated Ni-rich layered oxides (low SOC levels). This mechanism is associated with intergranular stress corrosion cracking, driven by chemical corrosion at elevated temperatures. The nanoscopic chemical corrosion behavior of Ni-rich layered oxides during aging at elevated temperatures is investigated using high-resolution transmission electron microscopy, revealing that microcracks can develop through two distinct mechanisms: electrochemical cycling and chemical corrosion. Notably, chemical corrosion cracks can occur even in a fully discharged state (low SOC levels), whereas electrochemical cracks are observed only at high SOC levels. This finding provides a comprehensive understanding of the complex failure mechanisms of Ni-rich layered oxides and provides an opportunity to improve their electrochemical performance.

Recent Progress and Synthetic Methods for Single-crystalline Cathode in Lithium-ion Batteries

Ni-rich layered transition metal oxides have been regarded as the most feasible way for achieving high energy density of lithium-ion batteries. Conventional Ni-rich cathodes are composed of spherical secondary particles, consisting of numerous primary particles. Unfortunately, the grain boundaries in the polycrystalline structure are vulnerable to the pulverization, leading to microcracks during cycling. The newly exposed surface from the microcrack can induce undesirable side reactions with the electrolyte, which severely deteriorates the battery performance. On the other hand, single-crystalline Ni-rich cathodes have gained significant attention for industrial applications due to their robust mechanical strength, resulting from the elimination of grain boundaries. The improved mechanical properties of single-crystalline cathodes effectively mitigate the interfacial side reactions, thereby attaining superior structural, thermal, and electrochemical performance. Herein, we have introduced various synthetic methods of the single-crystalline cathode, encompassing not only high-temperature sintering and the molten-salt method for the Ni-rich cathode but also the other strategies for different single-crystalline cathode materials. This review aims to provide a comprehensive understanding of single-crystalline cathode synthesis, with implications for the development of high-performance cathode materials.

Surface reactivity versus microcracks in Ni-rich layered oxide cathodes: Which is critical for long cycle life？

Capacity fading of Ni-rich cathode is thought to originate from the formation of inactive rock-salt phase induced by surface reactivity and the isolation of active material caused by microcracks due to anisotropic volume contraction of grains. It is generally assumed that inhibiting the formation of microcracks within secondary particle by radially aligned microstructure is a vital aspect for suppressing capacity fading. However, the new researches about reduction of microcracks simply by certain electrolytes call a question on the origin of microcracks and the critical factor for the cycle life of cathodes. Herein, LiNi0.92Co0.04Mn0.04O2 cathodes with different surface characteristic and radially aligned microstructure were synthesized by doping with high valence elements using some hydroxide precursor. The effects of W6+ and/or Mo6+ induced surface phase and microstructure on electrochemical performance were investigated. Despite the inferior radially aligned, size-refined primary grains and higher degree of microcracks, W6+ doped cathode still possesses alleviated parasitic reactions, higher crystal structural stability and capacity retention than Mo6+ doped materials, because of the enhanced cathode-electrolyte interfacial stability. The results contend that the consequence of surface reactivity on determining cycle life of Ni-rich cathodes is more critical than that of microcracks, and efforts relating to constructing intact and uniform stable surface phase will exhibit greater potential to promote the performance of Ni-rich cathodes than microstructural refinement.

Advancements in Addressing Microcrack Formation in Ni–Rich Layered Oxide Cathodes for Lithium–Ion Batteries

AbstractNickel–rich layered oxides of LiNi1–x–yCoxMn(Al)yO2 (where 1–x–y&gt;0.6) are considered promising cathode active materials for lithium‐ion batteries (LIBs) due to their high reversible capacity and energy density. However, the widespread application of NCM(A) is limited by microstructural degradation caused by the anisotropic shrinkage and expansion of primary particles during the H2→H3 phase transition. In this mini–review, we comprehensively discuss the formation of microcracks, subsequent material degradation, and related alleviation strategies in nickel–rich layered NCM(A). Firstly, theories on microcracks′ formation and evolution mechanisms are presented and critically analyzed. Secondly, recent advancements in mitigation strategies to prevent degradation in Ni–rich NCM/NCA are highlighted. These strategies include doping, surface coating, structural optimization, and morphology engineering. Finally, we provide an outlook and perspective to identify promising strategies that may enable the practical application of Ni–rich NCM/NCA in commercial settings.

Effective incorporation of cobalt near surface region for cobalt-free cathodes in lithium-ion batteries

Cobalt-free cathode materials, particularly Ni-rich layered oxide cathode materials, are ideal for electric vehicle Li-ion batteries, offering high energy density and cost-effectiveness. However, high Ni content in high-temperature synthesis leads to issues like increased Li/Ni cation mixing and reduced rate capability, mainly due to the absence of Co. Therefore, this study investigated the utilization of a small amount of Co instead of completely removing it to enhance electrochemical performance. A simple pre-calcination process was used to induce Co substitution beneath the Ni-rich layered oxide cathode materials surface. A coating process was also performed for comparison. The Li/Ni cation mixing in the Co-substituted sample during high-temperature calcination was 2.43%, demonstrating a superior value compared to the Co-coating process. Rate capability tests showed superior performance for Co-substituted sample (164.2 mAh g−1) at 2 C compared to coated sample (151.0 mAh g−1). Moreover, Co substitution improved not only the cycle stability but also the high-temperature stability at an elevated state of charge.This study focuses on the surface modification of cobalt-free cathode, providing direct insight into the effects of Co substitution and typical Co coating and suggests an optimal process that uses small amounts of Co.

Omni-functional simultaneous interfacial treatment for enhancing stability and outgassing suppression of lithium-ion batteries

Ni-rich layered oxides in lithium-ion batteries have problems with gas generation and electrochemical performance reduction due to residual lithium’s reaction on the surface with the electrolyte. To address this issue, in this study, the Acid solvent evaporation (ASE) method has been proposed as a potential method to remove residual lithium while promoting the formation of a new LiNO3-derived coating layer on the cathode surface. The reduction of residual lithium using the ASE method and the construction of a LiNO3-derived coating layer suppresses gas evolution caused by the side effects of the electrolyte, improves electrochemical performance, and improves thermal stability by facilitating the smooth movement of lithium ions. Furthermore, the structural stability and resistance change due to the LiNO3-derived coating layer effects is guaranteed through cycling and DCIR of the pouch cell. As a result, compared to Pristine, the capacity retention of coin cells increased by 8% after 100 cycles, and pouch cells increased by 25% after 160 cycles. In addition, after cycling the pouch cell, CO2 gas has significantly reduced by about 30% compared to Pristine using gas chromatography. The ASE method effectively forms a robust LiNO3-derived coating layer on the cathode active material, which helps minimize electrolyte reactivity, suppress CO2 emissions, enhance surface structure stability, improve thermal stability, and improve overall battery performance.

Chemical modification of nickel-rich layered cathode materials to improve battery life

Mechanical integrity issues of Ni-rich cathode materials are major bottlenecks for their commercial application, stemming from the abrupt anisotropic lattice contraction during H2 ↔ H3 phase transitions. Herein, zirconium is used to modify LiNi0.9Co0.05Mn0.05O2 to solve the mechanical integrity issues. The relationship between the mechanical integrity issues and electrochemical performance is systematically examined to gain insights into the Zr activity-governing mechanisms. Results find that the addition of zirconium not only improves the diffusion ability of lithium ions by providing a rapid channel for diffusion of lithium ions, but also enhances mechanical properties by inhibiting cation mixing. As a result, the optimal LiNi0.9Co0.05Mn0.05O2 achieves superiority capacity retention of 84.12 % after 200 cycles at 5C, higher than that of unmodified LiNi0.9Co0.05Mn0.05O2 74.32 %. This work deeply investigates the information on the bulk structure and interaction mechanism between substitution cations and Ni-rich layered oxides, which provides a new insight to design and construct of advanced high-capacity cathode materials.

Data-driven unlocking volume conservation in single-crystal Ni-rich layered oxides

Our study redefines anisotropic lattice variation through volume conservation (VC) in single-crystal (SC) Ni-rich layered oxides to facilitate long-term cycling stability. Data-driven analysis of the correlation heatmap of the five covariate variables and cycling retention enables precise cut-off voltage modulation for high-energy-density Ni-rich cathodes. We establish the anisotropic variation between a and c lattice constants as critical, leading to interfacial microcracks formation in degrading cycling retention. A balanced use of this variation, verified through computational models, Li1−x[Ni10/12Co1/12Mn1/12]O2 (NCM) and Li1−x[Ni10/12Co1/12Ti1/12]O2 (NCT), creates a volumetric stress free state at the inflection point. Unfortunately, two-scale challenges, namely macroscopic and local structure lattice misfits, which trigger intragranular microcracks, remain unresolved. Formation energy diagrams show biphasic reaction causing macroscopic lattice misfit based on the lattice direction occurring below x = 0.75 in both cathode models. Its effect can be mitigated by doping Ti into the Ni-rich material. Atomistic misfits of in-plane and out-of-plane directions are observed. Furthermore, MO2 and LiO2 slabs anisotropically vary in the complexes for NCM and NCT. Moreover, Ti-doped layered oxide clearly reduces local structural misfits and anisotropy. The proposed VC holds potential as a universal parameter for durable Ni-rich layered oxide fabrication for lithium-ion batteries.

Regulating interfacial chemistry and kinetic behaviors of F/Mo co-doping Ni-rich layered oxide cathode for long-cycling lithium-ion batteries over −20 °C–60 °C

Ni-rich layered oxide cathodes have shown promise for high-energy lithium-ion batteries (LIBs) but are usually limited to mild environments because of their rapid performance degradation under extreme temperature conditions (below 0 °C and above 50 °C). Here, we report the design of F/Mo co-doped LiNi0.8Co0.1Mn0.1O2 (FMNCM) cathode for high-performance LIBs from −20 to 60 °C. F– doping with high electronegativity into the cathode surface is found to enhance the stability of surface lattice structure and protect the interface from side reactions with the electrolyte by generating a LiF-rich surface layer. Concurrently, the Mo6+ doping suppresses phase transition, which blocks Li+/Ni2+ mixing, and stabilizes lithium-ion diffusion pathway. Remarkably, the FMNCM cathode demonstrates excellent cycling stability at a high cutoff voltage of 4.4 V, even at 60 °C, maintaining 90.6% capacity retention at 3 C after 150 cycles. Additionally, at temperatures as low as −20 °C, it retains 77.1% of its room temperature capacity, achieving an impressive 97.5% capacity retention after 500 cycles. Such stable operation under wide temperatures has been further validated in practical Ah-level pouch-cells. This study sheds light on both fundamental mechanisms and practical implications for the design of advanced cathode materials for wide-temperature LIBs, presenting a promising path towards high-energy and long-cycling LIBs with temperature adaptability.

Improving the electrochemical cycle stability of LiNi0.8Co0.1Mn0.1O2 via Al(H2PO4)3 treatment on its precursor

Ni-rich layered transition-metal oxides are important cathodes for lithium-ion batteries (LIBs). Unfortunately, they still suffer from capacity fading arising from structure transformation and side reactions. Cation doping and surface coating with a protective layer can alleviate the problem. Herein, a synergistic strategy of Al3+ doping near the surface and Li3PO4-LiAlO2 coating is adopted to modify LiNi0.8Co0.1Mn0.1O2 (NCM811), and it is carried out by using a simple Al(H2PO4)3 wet deposition method on its precursor. Structure and surface analysis show that Li3PO4-LiAlO2 is formed on the NCM surface and some Al3+ ions enter the near-surface lattice of cathode particles. Compared to NCM811, the modified-NCM811 exhibits slower impedance growth and better capacity retention (from 55.55 % to 75.09 % after 100 cycles) during cycling, which shows the strategy can effectively stabilize the interface and crystal structure.

In situ and Real-time Monitoring the Chemical and Thermal Evolution of Lithium-ion Batteries with Single-crystalline Ni-rich Layered Oxide Cathode.

High-capacity Ni-rich layered oxides are promising cathode materials for fabrication of lithium-ion batteries (LIBs) with high energy density. However, thermal runaway of LIBs with these cathodes leads to great safety concerns. In this study, single crystalline LiNi0.9Co0.05Mn0.05O2 (NCM-SC) has been prepared and a flexible optical fiber was buried inside the pouch-type LIBs with NCM-SC cathode to in situ study its real-time temperature evolution during charge/discharge process. NCM-SC exhibits an enhanced Li+ ions transportation efficiency and electrode reaction kinetics, which can effectively reduce the generation of polarization heat and mitigate the internal temperature rise of the pouch-type battery. Meanwhile, solid-electrolyte interface (SEI) film decomposition and gas accumulation are effectively alleviated, due to the enhanced thermal stability of SEI film formed on NCM-SC. Moreover, the single crystal architecture can effectively retard layered to spinal and rock-salt phase transition, mitigate the crack formation and structural collapse. Consequently, NCM-SC exhibits an excellent electrochemical performance and enhanced thermal stability.

Recycling of protective layer of Ni rich layered oxide material in Li ion batteries

We investigated the recycling of protective layer of Ni rich layered oxide–material used in Li ion batteries. Decreasing electrochemical performance of the cathode powder while leaving the powder in air was confirmed by various analyses and was found to be due to the formation of lithium residuals. The surface of the protective layer of Ni rich layered oxide was covered by the lithium residuals and that led to the cancellation of the coating effect. The residual lithium decreased and the cell performance was recovered by following a recycling process in this work. After the recycling process, the performance of the protective layer became similar to that of the layer immediately after the initial coating, and the coating layer showed a resurgence, which was confirmed by SEM and TEM images. The capacity of the initial coated Ni rich NCM and the sample after recycling was 209 and 206 mAh/g at 1C, respectively. The cycle retention for the initial coated Ni rich NCM and the sample after recycling was 93.4 and 92.6 % after 50 cycles at 1C, respectively. It is concluded that the coating layer and the electrochemical performance were recovered by the recycling process.