Layered Oxide Cathode Materials Research Articles

Aging Mechanisms of Lithium-ion Batteries

<p>Modern society is making numerous efforts to reduce reliance on carbon-based energy systems. A notable solution in this transition is the adoption of lithium-ion batteries (LIBs) as potent energy sources, owing to their high energy and power densities. Driven by growing environmental challenges, the application scope of LIBs has expanded from their initial prevalence in portable electronic devices to include electric vehicles (EVs) and energy storage systems (ESSs). Accordingly, LIBs must exhibit long-lasting cyclability and high energy storage capacities to facilitate prolonged device usage, thereby offering a potential alternative to conventional sources like fossil fuels. Enhancing the durability of LIBs hinges on a comprehensive understanding of the reasons behind their performance decline. Therefore, comprehending the degradation mechanism, which includes detrimental chemical and mechanical phenomena in the components of LIBs, is an essential step in resolving cycle life issues. The LIB systems presently being commercialized and developed predominantly employ graphite anode and layered oxide cathode materials. A significant portion of the degradation process in LIB systems takes place during the electrochemical reactions involving these electrodes. In this review, we explore and organize the aging mechanisms of LIBs, especially those with graphite anodes and layered oxide cathodes.</p>

Facilitating the high voltage stability of NFM via transition metal slabs high-entropy configuration strategy

Sodium ion batteries, which is viewed as the potential candidate of Li-ion batteries, are now at the edge of wildly application. The layered oxide cathode materials, represented by NaNi1/3Fe1/3Mn1/3O2 (NFM), inherits the experience of success from LIBs are now promising of commercialization. Yet, the relative low operation voltage of NFM causing by the existence of Fe migration above 4.2 V hinder its further application nowadays. Herein, high-entropy O3-type NaMg0.08Cu0.12Ni0.2Fe0.2Mn0.2Ti0.2O2(HNFM) was proposed addressing working voltage at 4.3 V with the inhibition of large amount of Fe migration. Electrochemical test showed a specific capacity of 131 mAh g−1 was achieved within the voltage range from 2.0 to 4.3 V at current density of 0.2 C which boosted an energy density of up to 425 Wh kg−1. After 200 cycles at a 1 C current density, the capacity retention remains at 84 %. In-situ XRD analysis revealed that HNFM alleviated phase transition at high voltage compared to NFM thus it can withstand a wide operating voltage range of 2–4.3 V. DFT calculations demonstrated that transition metal slabs with high-entropy configurations could effectively suppress the migration of Fe ions from the transition metal slabs to the Na layer, thereby further enhancing the material's stability during cycling. These research findings shed light on the high-voltage operating for the layered oxide materials which provide the novel insight of the material design and inspire the commercialization of sodium ion batteries.

Insights into the Jahn‐Teller Effect in Layered Oxide Cathode Materials for Potassium‐Ion Batteries

AbstractPotassium‐ion batteries (PIBs) have attracted increasing interest as promising alternatives to lithium‐ion batteries (LIBs) in large‐scale electrical energy storage systems due to the potential price advantages, abundant availability of potassium resources, and low standard redox potential of potassium. However, the pursuit of suitable cathode materials that exhibit desirable characteristics such as voltage platforms, high capacity, and long cycling stability is of utmost importance. Recently, layered transition‐metal oxides for PIBs offer great potential due to their high theoretical capacity, suitable voltage range, and eco‐friendliness. Nevertheless, the progress of KxMO2 cathodes in PIBs faces obstacles due to the detrimental effects of structural disorder and irreversible phase transitions caused by the Jahn‐Teller effect. This review provides a brief description of the origin and mechanism of the Jahn‐Teller effect, accompanied by the proposed principles to mitigate this phenomenon. In particular, the current status of KxMO2 cathodes for PIBs, is summarized highlighting the challenges posed by the Jahn‐Teller effect. Furthermore, promising strategies, such as composition modulation, synthesis approaches, and surface modification, are proposed to alleviate and suppress the Jahn‐Teller effect. These strategies offer valuable insights into the prospects of innovative cathode materials and provide a foundation for future research in the field of PIBs.

Efficient direct repairing of lithium- and manganese-rich cathodes by concentrated solar radiation

Lithium- and manganese-rich layered oxide cathode materials have attracted extensive interest because of their high energy density. However, the rapid capacity fading and serve voltage decay over cycling make the waste management and recycling of key components indispensable. Herein, we report a facile concentrated solar radiation strategy for the direct recycling of Lithium- and manganese-rich cathodes, which enables the recovery of capacity and effectively improves its electrochemical stability. The phase change from layered to spinel on the particle surface and metastable state structure of cycled material provides the precondition for photocatalytic reaction and thermal reconstruction during concentrated solar radiation processing. The inducement of partial inverse spinel phase is identified after concentrated solar radiation treatment, which strongly enhances the redox activity of transition metal cations and oxygen anion, and reversibility of lattice structure. This study sheds new light on the reparation of spent cathode materials and designing high-performance compositions to mitigate structural degradation.

Inhibiting phase conversion and improving cyclic stability of Ni-rich layered oxide by high-valence element concentration gradient doping

Nickel (Ni)-rich layered oxide cathodes are believed to be one of the crucial materials for the development of high-energy density power batteries. However, accompanied by the Ni content of layered cathodes increases, it encounters some awkward issues such as sensitivity to moisture, side reactions, and gas production. Herein, by using a high-valency elements Tellurium (Te) doping strategy, we successfully design and fabricate the layered oxide cathode material Li[(Ni0.90Co0.10)0.99Te0.01]O2 (1.0 Te-NC90) with a high capacity of 231.36 mAh g−1 at 0.1C, which has high cycling stability of 95.01 % after 100 cycles at 0.5C, good thermal stability of 205 °C and high Li+ diffusion rate of 8.12 × 10−10 cm2 s−1. It has been found that the (003) interplanar spacing of 1.0 Te-NC90 cathode will increase from 0.472 nm to 0.491 nm due to the concentration gradient Te-doping strategy, which can promote Li+ diffusion. Besides, it can refine the grain structure and transform the primary particles from bulk-grained to rod-grained morphology, and these elongated and closely packed particles radiate from the center to the surface with a spoke-like arrangement, which effectively dissipates lattice strain generated during deeply charging states and suppresses the abrupt lattice transformation associated with the H2 → H3 phase, thereby avoiding the development of microcracks during cycling. In the meantime, robust Te-O bonds can keep the material lattice stable to prevent oxygen loss and TM ion movement. Therefore, this study reveals the significant role of trace Te-doping in enhancing crystal structure and electrochemical stability through microstructural engineering for the control of primary particle morphology.

P2/O3 Biphasic Cathode Material through Magnesium Substitution for Sodium-Ion Batteries.

P2-type Fe-Mn-based oxides offer excellent discharge specific capacity and are as affordable as typical layered oxide cathode materials for sodium-ion batteries (SIBs). After Cu modification, though they can improve the cycling performance and air stability, the discharge specific capacity will be reduced. Considering the complementary nature of biphasic phases in electrochemistry, hybridizing P2/O3 hybrid phases can enhance both the storage performance of the battery and specific capacity. Herein, a hybrid phase composite with high capacity and good cycle performance is deliberately designed and successfully prepared by controlling the amount of Mg doping in the layered oxide. It has been found that the introduction of Mg can activate anion redox in the oxide layer, resulting in a significant increase in the specific discharge capacity of the material. Meanwhile, the dual-phase structure can produce an interlocking effect, thus effectively alleviating structure strain. The degradation of cycling performance caused by structural damage during the high-voltage charging and discharging process is clearly mitigated. The results show that the specific discharge capacity of Na0.67Cu0.2Mg0.1Fe0.2Mn0.5O2 is as high as 212.0 mAh g-1 at 0.1C rate and 186.2 mAh g-1 at 0.2C rate. After 80 cycles, the capacity can still maintain 88.1%. Moreover, the capacity and cycle performance as well as the stability can still remain stable even in the high-voltage window. Therefore, this work offers an insightful exploration for the development of composite cathode materials for SIBs.

The intricate roles of Al2O3 on the structure and electrochemical performances of LiNi0.5Co0.2Mn0.3O2 cathode materials

Severe capacity fading of in NCM layered oxide cathode materials has hampered their practical adoption. This problem can be effectively alleviated by the introduction of Al3+. Previous studies have shown that when Al3+ is introduced into the lattice to partially replace the transition metals, it acts as a structural stabilizer and inter-Al3+ does not participate in the redox reactions. However, the reaction of an aluminum source with lithium salts has not attracted enough attention in the synthesis of Al3+doped cathode materials. In this paper, Al2O3-modified LiNi0.5Co0.2Mn0.3O2 cathode materials are revisited by the solid-state reaction methods. Combined with XRD results, SEM and mapping analysis, it is found that during the heattreatment process, a part of Al3+ ions are doped into the lattice of the cathode material, and it is proved that most parts of Al2O3 react with LiOH⋅H2O to form α-LiAlO2, which is coated on the surface of the cathode material. Considering that lithium will be consumed because of the reaction between Al2O3 and LiOH⋅H2O, we systematically adjusted the lithium amount. It is found that because LiOH reacts preferentially with Al2O3, the amount of lithium reacting with the Ni0.5Co0.2Mn0.3(OH)2 precursor is reduced, which will reduce the electrochemical performance of the cathode material. The deterioration of the electrochemical properties of LiNi0.5Co0.2Mn0.3O2 cathode materials with insufficient lithium is mainly due to the transition of the material structure from a layered structure to a spinel structure. Moreover, the lithium supplemented samples show higher initial charge and discharge capacities, rate capabilities and cycling performances than the lithium un-supplemented samples.

Unravelling the peculiar role of Co and Al in highly Ni-rich layered oxide cathode materials

Currently, the limited availability of cobalt resources has had a negative impact on the progress of commercial batteries, prompting the development of cobalt-free Ni-rich cathodes. However, the complete replacement of cobalt has faced challenges due to the lack of understanding the influence of dopants on cathode material performance. In this study, we aimed to address this knowledge gap by designing and preparing LiNi0.95Co0.05-xAlxO2 (x = 0.00, 0.01, 0.02, 0.03, 0.04, and 0.05) cathode materials. The impact of cobalt and aluminum doping on the morphology, crystallographic structure and electrothermal performance of Ni-rich cathode materials has been systematically investigated. Our findings confirmed the significant role of cobalt in increasing energy density and mitigating cationic disordering. However, it is found that cobalt doping contributes to the release of lattice oxygen during cycling, leading to rapid capacity fading. Conversely, aluminum doping could stabilize the crystal structure of the cathode material, resulting in slower capacity degradation. Furthermore, the substitution of aluminum effectively mitigates the crystal growth during the synthesis of highly Ni-rich cathode materials, leading to a reduced Li+ diffusion length and thereby excellent rate performance. Specifically, LiNi0.95Al0.05O2 could deliver a high discharge capacity of around 163 mAh g−1 at 10C. This study provides valuable insights for the design of cobalt-free Ni-rich cathodes and sheds light on the possibility of cobalt elimination.

Structural Insight into Protective Alumina Coatings for Layered Li-Ion Cathode Materials by Solid-State NMR Spectroscopy.

Layered transition metal oxide cathode materials can exhibit high energy densities in Li-ion batteries, in particular, those with high Ni contents such as LiNiO2. However, the stability of these Ni-rich materials often decreases with increased nickel content, leading to capacity fade and a decrease in the resulting electrochemical performance. Thin alumina coatings have the potential to improve the longevity of LiNiO2 cathodes by providing a protective interface to stabilize the cathode surface. The structures of alumina coatings and the chemistry of the coating-cathode interface are not fully understood and remain the subject of investigation. Greater structural understanding could help to minimize excess coating, maximize conductive pathways, and maintain high capacity and rate capability while improving capacity retention. Here, solid-state nuclear magnetic resonance (NMR) spectroscopy, paired with powder X-ray diffraction and electron microscopy, is used to provide insight into the structures of the Al2O3 coatings on LiNiO2. To do this, we performed a systematic study as a function of coating thickness and used LiCoO2, a diamagnetic model, and the material of interest, LiNiO2. 27Al magic-angle spinning (MAS) NMR spectra acquired for thick 10 wt % coatings on LiCoO2 and LiNiO2 suggest that in both cases, the coatings consist of disordered four- and six-coordinate Al-O environments. However, 27Al MAS NMR spectra acquired for thinner 0.2 wt % coatings on LiCoO2 identify additional phases believed to be LiCo1-xAlxO2 and LiAlO2 at the coating-cathode interface. 6,7Li MAS NMR and T1 measurements suggest that similar mixing takes place near the interface for Al2O3 on LiNiO2. Furthermore, reproducibility studies have been undertaken to investigate the effect of the coating method on the local structure, as well as the role of the substrate.

Competing Mechanisms Determine Oxygen Redox in Doped Ni-Mn Based Layered Oxides for Na-Ion Batteries.

Cation doping is an effective strategy for improving the cyclability of layered oxide cathode materials through suppression of phase transitions in the high voltage region. In this study, Mg and Sc are chosen as dopants in P2-Na0.67Ni0.33Mn0.67O2, and both have found topositively impact the cycling stability, but influence the high voltage regime in different ways. Through a combination of synchrotron-based methods and theoretical calculations it is shown that it is more than just suppression of the P2 to O2 phase transition that is critical for promoting the favorable properties, and that the interplay between Ni and O activity is also a critical aspect that dictates the performance. With Mg doping, the Ni activity can be enhanced while simultaneously suppressing the O activity. This is surprising because it is in contrast to what has been reported in other Mn-based layered oxides where Mg is known to trigger oxygen redox. This contradiction is addressed by proposing a competing mechanism between Ni and Mg that impacts differences in O activity in Na0.67MgxNi0.33- xMn0.67O2 (x<0<0.33). These findings provide a new direction in understanding the effects of cation doping on the electrochemical behavior of layered oxides.

Why the Synthesis Affects Performance of Layered Transition Metal Oxide Cathode Materials for Li-Ion Batteries.

The limited cyclability of high-specific-energy layered transition metal oxide (LiTMO2) cathode materials poses a significant challenge to the industrialization of batteries incorporating these materials. This limitation can be attributed to various factors, with the intrinsic behavior of the crystal structure during the cycle process being a key contributor. These factors include phase transition induced cracks, reduced Li active sites due to Li/Ni mixing, and slower Li+ migration. In addition, the presence of synthesis-induced heterogeneous phases and lattice defects cannot be disregarded as they also contribute to the degradation in performance. Therefore, gaining a profound understanding of the intricate relationship among material synthesis, structure, and performance is imperative for the development of LiTMO2. This paper highlights the pivotal role of structural play in LiTMO2 materials and provides a comprehensive overview of how various control factors influence the specific pathways of structural evolution during the synthesis process. In addition, it summarizes the scientific challenges associated with diverse modification approaches currently employed to address the cyclic failure of materials. The overarching goal is to provide readers with profound insights into the study of LiTMO2.

Negative Lattice Expansion in an O3-Type Transition-Metal Oxide Cathode for Highly Stable Sodium-Ion Batteries.

The sodium extraction/insertion in layered transition-metal oxide (TMO) cathode materials are typically accompanied by slab sliding and lattice changes, leading to microstructure destruction and capacity decay. Herein, negative lattice expansion is observed in an O3 type Ni-based layered cathode of Na0.9 Ni0.32 Zn0.08 Fe0.1 Mn0.3 Ti0.2 O2 upon Na+ extraction. It is attributed to the weak Zn2+ -O2- orbital hybridization and increased electron density of the surrounding oxygen for reinforced interlayer O-O repulsive force. This enables gliding of TMO slabs for the intergrowth phase transition of P3→OP2 to alleviate lattice strain with moderate lattice shrinkage, which exhibits general interslab spacings and volume changes as low as 2.4 % and 1.9 %, respectively. The strong Ti-O bonds accommodate the internal distortion of TMO6 octahedra due to the flexibility of TiO6 octahedra during cycling. These endow a high specific capacity of 144.9 mAh g-1 and excellent cycling performance of pouch-type sodium-ion batteries with 93 % capacity retention after 3600 cycles.

Optimizing O3-type cathode materials for sodium-ion batteries: Insights from precursor-based structural control and particle sizing strategies

Utilization of secondary spherical structures derived from metal hydroxides as precursor materials is one of the most promising approaches in terms of energy density and industrial viability for sodium-ion batteries. However, the understanding of how the particle size and arrangement of these secondary spherical structures influence electrochemical performance remains limited. Herein, a series of O3-type layered oxide cathode materials with various sizes (6, 8, 10, and 12 μm) and internal structures (hollow and radial arrangements) were tailored based on precursor-based structural control and particle sizing strategies. The relation in precursor size/structure, cathode characteristics, crystal microstress, structural stability, and electrochemical performance was established through a combination of structure, morphology, and electrochemical characterization. Notably, the size of secondary spherical particles exerted influence on microstress, leading to consequential changes in the c-axis. Elevated microstress levels induced compression of the unit cell along the c-axis, hampering sodium ion migration and undermining the stability of secondary spherical particles during cyclic charge-discharge processes. The optimized NaNi1/3Fe1/3Mn1/3O2-10 material exhibits the least micro stress and significant layer distance, delivers a capacity of 110 mAh g−1, and maintains an impressive capacity retention rate of 91.8% after 100 cycles at 10 C. This work offers valuable insights in energy-density cathode materials in sodium ion batteries.

Multi-strategies interface and structure design of Li- and Mn-rich layered oxide for all-solid-state lithium batteries

Li- and Mn-rich layered oxide (LMRO) cathode materials is highly potential for next generation lithium-ion batteries as its extremely high energy density. However, the oxygen release and the interfacial side reactions against liquid electrolytes cause severe capacity fading and their practical applications are highly impeded. Herein, all-solid-state lithium-ion batteries (ASSLIBs) are demonstrated to be a promising solution towards practical application of LMROs. For the sulfide electrolyte of Li6PS5Cl, a highly compatible interface of LMRO to the electrolyte can be constructed with extra content of Li2MnO3 in LMRO, which prevents significantly side reaction between the LMRO and electrolyte. Moreover, the Li6PS5Cl electrolyte can provide S2-/SO32- redox couple to suppress the oxygen release of LMROs. Combining a further modification in composition with a few amounts of the LiNiO2, the ionic and electronic conductivities of LMRO are evidently improved, where the highly compatible interface is preserved. As results, a superiorly high capacity of 256 mAh g−1 and an energy density of 874 Wh kg−1 at 0.1 C, meanwhile the superior capacity retention as high as 87% for 1000 cycles at 0.5 C are achieved for ASSLIBs. The result is hopefully of great helpful on realizing the practical applications of LMROs in sulfide-based ASSLIBs.

Regulation of Coordination Chemistry for Ultrastable Layered Oxide Cathode Materials of Sodium-Ion Batteries.

Layered transition-metal (TM) oxide cathodes have attracted growing attention in sodium-ion batteries (SIBs). However, their practical implementation is plagued by Jahn-Teller distortion and irreversible cation migration, leading to severe voltage decay and structure instability. Herein, O3-Na0.898K0.058Ni0.396Fe0.098Mn0.396Ti0.092O2 (KT-NFM) is reported as an ultrastable cathode material via multisite substitution with rigid KO6 pillars and flexible TiO6 octahedra. The K pillars induce contracted TMO2 slabs and their strong Coulombic repulsion to inhibit Ni/Fe migration; and Ti incorporation reinforces the hybridization of Ni(3deg*)-O(2p) to mitigate the undesired O3-O'3 phase transition. These enable the reversible redox of Ni2+↔Ni3 . 20+ and Fe3+↔Fe3.69+ for 138.6 mAh g-1 and ultrastable cycles with >90% capacity retention after 2000 cycles in a pouch cell of KT-NFM||hard carbon. This will provide insights into the design of ultrastable layered cathode materials of sodium-ion batteries and beyond.

Moderate active Fe3+ doping enables improved cationic and anionic redox reactions for wide-voltage-range sodium storage

Layered metal oxides are promising cathode materials for sodium-ion batteries (SIBs) due to their high theoretical specific capacity and wide Na+ diffusion channels. However, the irreversible phase transitions and cationic/anionic redoxes cause fast capacity decay. Herein, P2-type Na0.67Mg0.1Mn0.8Fe0.1O2 (NMMF-1) cathode material with moderate active Fe3+ doping has been designed for sodium storage. Uneven Mn3+/Mn4+distribution is observed in NMMF-1 and the introduction of Fe3+ is beneficial for reducing the Mn3+ contents both at the surface and in the bulk to alleviate the Jahn–Teller effect. The moderate Fe3+/Fe4+ redox can realize the best tradeoff between capacity and cyclability. Therefore, the NMMF-1 demonstrates a high capacity (174.7 mAh g−1 at 20 mA g−1) and improved cyclability (78.5% over 100 cycles) in a wide-voltage range of 1.5–4.5 V (vs. Na+/Na). In-situ X-ray diffraction reveals a complete solid-solution reaction with a small volume change of 1.7% during charge/discharge processes and the charge compensation is disclosed in detail. This study will provide new insights into designing high-capacity and stable layered oxide cathode materials for SIBs.

Enabling High-Performance Layered Li-Rich Oxide Cathodes by Regulating the Formation of Integrated Cation-Disordered Domains.

Layered Li-rich oxide cathode materials are capable of offering high energy density due to their cumulative cationic and anionic redox mechanism during (de)lithiation process. However, the structural instability of the layered Li-rich oxide cathode materials, especially in the deeply delitiated state, results in severe capacity and voltage degradation. Considering the minimal isotropic structural evolution of disordered rock salt oxide cathode during cycling, cation-disordered nano-domains have been controllably introduced into layered Li-rich oxides by co-doping of d0-TM and alkali ions. Combining electrochemical and synchrotron-based advanced characterizations, the incorporation of the phase-compatible cation-disordered domains can not only hinder the oxygen framework collapse along the c axis of layered Li-rich cathode under high operation voltage but also promote the Mn and anionic activities as well as Li+ (de)intercalation kinetics, leading to remarkable improvement in rate capability and mitigation of capacity and voltage decay. With this unique layered/rocksalt intergrown structure, the intergrown cathode yields an ultrahigh capacity of 288.4mAhg-1 at 0.1C, and outstanding capacity retention of ≈90.0% with obviously suppressed voltage decay after 100 cycles at 0.5, 1, and 2C rate. This work provides a new direction toward advanced cathode materials for next-generation Li-ion batteries.

Enhancing the long-term cycling stability of Ni-rich cathodes via regulating the length/width ratio of primary particle

Ni-rich layered oxide cathode materials are promising candidates for high-specific-energy battery systems owing to their high reversible capacity. However, their widespread application is still severely impeded by severe capacity loss upon long-term cycling. It has been proven that the cyclic stability of Ni-rich cathode materials is closely related to their microstructure and morphology. Despite this, the influence of the microstructure of primary particles on the fatigue mechanism of Ni-rich cathode materials during prolonged cycling has not been fully understood. Here, two Ni-rich layered spherical agglomerate oxides consisting of the primary particle with different length/width ratios are successfully synthesized. It is found that the long-term structural stability of both materials strongly depends on the microstructure of primary crystallites, although there is no significant difference between the electrochemical and crystalline characteristics during the initial cycle. A higher primary particle length/width ratio could effectively inhibit the accumulation of microcracks and chemical degradation during long-term cycling, thereby promoting the electrochemical performance of the cathode materials (80% capacity retention after 200 cycles at 1 C compared to the 55% of the counterpart with a lower primary particle length/width ratio). This study highlights the structure-activity relationship between the primary particle microstructure and fatigue mechanisms during long-term cycling, thereby advancing the development of Ni-rich cathode materials.

Insights into the capacity fading and failure mechanism of an O3-NaNi1/3Fe1/3Mn1/3O2 layered oxide cathode material for sodium-ion batteries

Low-cost sodium-ion batteries hold great potential for large-scale energy storage owing to the abundance of sodium reserves.

Cobalt-Free Oxide Cathode Material with Phase Composition Control to High Electrochemical Performance in Li-Ion Batteries

Cobalt-free layered oxide cathode material (LiMn0.5Ni0.5O2) was obtained via a two-step synthesis method. Firstly, hydrothermal synthesis of MnOOH with nanorod morphology was achieved and then a co-precipitation process to obtain the LiMn0.5Ni0.5O2 active layered material was performed. Structural and morphological characterization revealed a promising disordered layered structure obtained at 800 °C with improved electrochemical performance. The thermal treatment performed on the active materials resulted in a controlled balance between the monoclinic and rhombohedral phase leading to good phases formation ratio in a cobalt-free layer cathode. It was found that the controlled mixing of structural phases plays an important role in improving the electrochemical performance of the active cathodic layer material, resulting in an adequate balance between high discharge capacity and electrochemical stability during the charge/discharge cycling. The morphological analysis showed two kinds of particles that played a crucial role in the structural stability and electrochemical performance. The active material thermally treated at 800 °C displayed outstanding discharge capacity of 235.05 mAh g−1 at 20 mA g−1 in CCCV (Current Constant-Constant Voltage) mode. While, in CC (Current Constant) mode showed the highest discharge capacity, of 178.95 mAh g−1 at 20 mA g−1 and good capacity retention (87.2% after 100 cycles).