A high-capacity cathode based on silicates material for advanced lithium batteries

Silicate materials have been proposed as alternative cathodes for Li-ion battery applications. A novel mixture of silicates, labelled Li₆MnSi₅, based on the molar ratio among the Li/Mn/Si precursors, with promising electrochemical properties as positive electrode material is synthesized through a solid-state reaction. The results indicate the proposed synthetic method as effective for preparation of nanostructured silicate powders with average particle diameter of 30 nm. Structural morphology of the samples was determined using X-ray powder diffraction (XRPD), XPS and FESEM analysis. A joint analysis by XRPD data and by density functional theory (DFT) identified LiHMn₄Si₅O₁₅, Li₂Mn₄Si₅O₁₅, Li₂Si₂O₅ and Li_0.125Mn_0.875SiO₄ as components of Li₆MnSi₅ mixture. The electrochemical performance of Li₆MnSi₅ was evaluated by charge/discharge testing at constant current mode. Li₆MnSi₅ discharge behaviour is characterized by high capacity value of 480 mA h g^?1, although such capacity fades gradually on cycling. Ex situ XPS studies carried out on the electrode in both full charged and discharged states pointed out that Li₂Si₂O₅ is decisive for achieving such high capacity. The discharge/charge plateau is most probably related to the change in the oxidation state of silicon at the surface of the silica material.     

Cation Additive Enabled Rechargeable LiOH-Based Lithium–Oxygen Batteries

Lithium–oxygen (Li–O₂) batteries have attracted extensive research interest due to their high energy density. Other than Li₂O₂ (a typical discharge product in Li–O₂ batteries), LiOH has proved to be electrochemically active as an alternative product. Here we report a simple strategy to achieve a reversible LiOH-based Li–O₂ battery by using a cation additive, sodium ions, to the lithium electrolyte. Without redox mediators in the cell, LiOH is detected as the sole discharge product and it charges at a low charge potential of 3.4 V. A solution-based reaction route is proposed, showing that the competing solvation environment of the catalyst and Li⁺ leads to LiOH precipitation at the cathode. It is critical to tune the cell chemistry of Li–O₂ batteries by designing a simple system to promote LiOH formation/decomposition.     

Core–Shell‐Structured CNT@RuO2 Composite as a High‐Performance Cathode Catalyst for Rechargeable Li–O2 Batteries

A RuO₂ shell was uniformly coated on the surface of core CNTs by a simple sol–gel method, and the resulting composite was used as a catalyst in a rechargeable Li–O₂ battery. This core–shell structure can effectively prevent direct contact between the CNT and the discharge product Li₂O₂, thus avoiding or reducing the formation of Li₂CO₃, which can induce large polarization and lead to charge failure. The battery showed a high round‐trip efficiency (ca. 79 %), with discharge and charge overpotentials of 0.21 and 0.51 V, respectively, at a current of 100 mA g_total^?1. The battery also exhibited excellent rate and cycling performance.     

Utilizing a Photocatalysis Process to Achieve a Cathode with Low Charging Overpotential and High Cycling Durability for a Li-O2 Battery

The practical applications of non-aqueous lithium-oxygen batteries are impeded by large overpotentials and unsatisfactory cycling durability. Reported here is that commonly encountered fatal problems can be efficiently solved by using a carbon- and binder-free electrode of titanium coated with TiO₂ nanotube arrays (TNAs) and gold nanoparticles (AuNPs). Ultraviolet irradiation of the TNAs generates positively charged holes, which efficiently decompose Li₂O₂ and Li₂CO₃ during recharging, thereby reducing the overpotential to one that is near the equilibrium potential for Li₂O₂ formation. The AuNPs promote Li₂O₂ formation, resulting in a large discharge capacity. The electrode exhibits excellent stability with about 100 % coulombic efficiency during continuous cycling of up to 200 cycles, which is due to the carbon- and binder-free composition. This work reveals a new strategy towards the development of highly efficient oxygen electrode materials for lithium-oxygen batteries.     

Identifying Reactive Sites and Transport Limitations of Oxygen Reactions in Aprotic Lithium‐O2 Batteries at the Stage of Sudden Death

Discharging of the aprotic Li‐O₂ battery relies on the O₂ reduction reaction (ORR) forming solid Li₂O₂ in the positive electrode, which is often characterized by a sharp voltage drop (that is, sudden death) at the end of discharge, delivering a capacity far below its theoretical promise. Toward unlocking the energy capabilities of Li‐O₂ batteries, it is crucial to have a fundamental understanding of the origin of sudden death in terms of reactive sites and transport limitations. Herein, a mechanistic study is presented on a model system of Au|Li₂O₂|Li⁺ electrolyte, in which the Au electrode was passivated with a thin Li₂O₂ film by discharging to the state of sudden death. Direct conductivity measurement of the Li₂O₂ film and in situ spectroscopic study of ORR using ¹⁸O₂ for passivation and ¹⁶O₂ for further discharging provide compelling evidence that ORR (and O₂ evolution reaction as well) occurs at the buried interface of Au|Li₂O₂ and is limited by electron instead of Li⁺ and O₂ transport.     

The Stabilization Effect of CO2 in Lithium–Oxygen/CO2 Batteries

The lithium (Li)–air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O₂), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O₂^?, and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li‐air battery. Even worse, the water and/or CO₂ in air bring parasitic reactions and safety issues. Therefore, applying such systems in open‐air environment is challenging. Herein, contrary to previous assertions, we have found that CO₂ can improve the stability of both anode and electrolyte, and a high‐performance rechargeable Li–O₂/CO₂ battery is developed. The CO₂ not only facilitates the in situ formation of a passivated protective Li₂CO₃ film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O₂^?. Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li₂CO₃. The Li–O₂/CO₂ battery achieves a full discharge capacity of 6628 mAh g^?1 and a long life of 715 cycles, which is even better than those of pure Li–O₂ batteries.     

The Stabilization Effect of CO2 in Lithium–Oxygen/CO2 Batteries

The lithium (Li)–air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O₂), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O₂⁻, and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li-air battery. Even worse, the water and/or CO₂ in air bring parasitic reactions and safety issues. Therefore, applying such systems in open-air environment is challenging. Herein, contrary to previous assertions, we have found that CO₂ can improve the stability of both anode and electrolyte, and a high-performance rechargeable Li–O₂/CO₂ battery is developed. The CO₂ not only facilitates the in situ formation of a passivated protective Li₂CO₃ film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O₂⁻. Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li₂CO₃. The Li–O₂/CO₂ battery achieves a full discharge capacity of 6628 mAh g⁻¹ and a long life of 715 cycles, which is even better than those of pure Li–O₂ batteries.     

An Illumination‐Assisted Flexible Self‐Powered Energy System Based on a Li–O2 Battery

The flexible Li‐O₂ battery is suitable to satisfy the requirements of a self‐powered energy system, thanks to environmental friendliness, low cost, and high theoretical energy density. Herein, a flexible porous bifunctional electrode with both electrocatalytic and photocatalytic activity was synthesized and introduced as a cathode to assemble a high‐performance Li‐O₂ battery that achieved an overpotential of 0.19 V by charging with the aid of solar energy. As a proof‐of‐concept application, a flexible Li‐O₂ battery was constructed and integrated with a solar cell via a scalable encapsulate method to fabricate a flexible self‐powered energy system with excellent flexibility and mechanical stability. Moreover, by exploring the evolution of the electrode morphology and discharge products (Li₂O₂), the charging process of the Li‐O₂ battery powered by solar energy and solar cell was demonstrated.     

Preparation and characterization of LiMn2O4/Li1.3Al0.3Ti1.7(PO4)3/LiMn2O4 thin-film battery by spray technique

Solid-state thin-film lithium-ion battery of LiMn₂O₄/Li_1.3Al_0.3Ti_1.7(PO₄)₃/LiMn₂O₄ is prepared by spray technique using Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellet as both electrolyte and substrate. The thin-film battery is heat-treated by rapid thermal annealing. Phase identification, morphology and electrochemical properties of the sintered pellets and thin-film battery are investigated by X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge experiments, respectively. The results show that LiMn₂O₄ films with some pores are well deposited on the surface of Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellet. The discharge current density and temperature have considerable effect on discharge capacity of the thin-film battery. LiMn₂O₄/Li_1.3Al_0.3Ti_1.7(PO₄)₃/LiMn₂O₄ thin-film battery can be easily cycled with a capacity loss of 0.213% per cycle when 50 cycles are carried out.     

Lithium‐Rich Layered Oxide Li1.18Ni0.15Co0.15Mn0.52O2 as the Cathode Material for Hybrid Sodium‐Ion Batteries

Li‐rich layered oxide Li_1.18Ni_0.15Co_0.15Mn_0.52O₂ (LNCM) is, for the first time, examined as the positive electrode for hybrid sodium‐ion battery and its Na⁺ storage properties are comprehensively studied in terms of galvanostatic charge–discharge curves, cyclic voltammetry and rate capability. LNCM in the proposed sodium‐ion battery demonstrates good rate capability whose discharge capacity reaches about 90 mA h g^?1 at 10 C rate and excellent cycle stability with specific capacity of about 105 mA h g^?1 for 200 cycles at 5 C rate. Moreover, ex situ ICP‐OES suggests interesting mixed‐ions migration processes: In the initial two cycles, only Li⁺ can intercalate into the LNCM cathode, whereas both Li⁺ and Na⁺ work together as the electrochemical cycles increase. Also the structural evolution of LNCM is examined in terms of ex situ XRD pattern at the end of various charge–discharge scans. The strong insight obtained from this study could be beneficial to the design of new layered cathode materials for future rechargeable sodium‐ion batteries.     

Electochemical characteristics of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> battery with conducting polymeric binder

Lithium-ion battery based on LiMn₂O₄/Li₄Ti₅O₁₂ materials was assembled for the first time. The cathode and anode of this battery are prepared with the aqueous combined binder poly-3,4-ethylenedioxythiophene: polystyrene sulfonate/carboxymethylcellulose (without polyvinylidene fluoride). The capacity of the LiMn₂O₄/Li₄Ti₅O₁₂ battery was found to be 75 mA h g^–1 at 0.1 C and 55 mA h g^–1 at 1 C. A 95% capacity was retained after 100 charge-discharge cycles. The batteries demonstrated a high Coulombic efficiency close to 100%. Scanning electron microscopy demonstrated that using the conducting binder poly-3,4-ethylenedioxythiophene: polystyrene sulfonate/carboxymethylcellulose provides formation of dense compact layers of electrode materials with good adhesion to the substrate. The electrode structure remains maintained after 100 charge-discharge cycles.     

Porous nanostructured V2O5 film electrode with excellent Li-ion intercalation properties

Porous nanostructured V₂O₅ films were prepared by electrodeposition from V₂O₅ sol with the addition of block copolymer Pluoronic P123, and they can be readily applied as Li-ion battery cathode without adding any polymer binder or conductive additives. SEM images showed an ideal morphology for Li⁺ intercalation favored charge transfer kinetics, which is a combination of homogeneously distributed nano-pores and V₂O₅ nanoparticles. Electrochemical measurements revealed that, the porous nanostructured V₂O₅ films have a high discharge capacity of 160 mAh/g at 9 A/g, and maintain 240 mAh/g after 40 cycles at 300 mA/g. The excellent Li⁺ intercalation property could be ascribed to the high surface area, sufficient contact between electrode materials and electrolyte, short Li⁺ diffusion path, as well as the good accommodation for volume change which are benefited from homogeneously distributed nano-pores and V₂O₅ nanoparticles.     

A New Perspective on Li–SO2 Batteries for Rechargeable Systems

Primary Li–SO₂ batteries offer a high energy density in a wide operating temperature range with exceptionally long shelf life and have thus been frequently used in military and aerospace applications. Although these batteries have never been demonstrated as a rechargeable system, herein, we show that the reversible formation of Li₂S₂O₄, the major discharge product of Li–SO₂ battery, is possible with a remarkably smaller charging polarization than that of a Li–O₂ battery without the use of catalysts. The rechargeable Li–SO₂ battery can deliver approximately 5400 mAh g^?1 at 3.1 V, which is slightly higher than the performance of a Li–O₂ battery. In addition, the Li–SO₂ battery can be operated with the aid of a redox mediator, exhibiting an overall polarization of less than 0.3 V, which results in one of the highest energy efficiencies achieved for Li–gas battery systems.     

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O₂ batteries, and are believed to form and decompose reversibly in metal‐O₂/CO₂ cells. In these cathodes, Li₂CO₃ decomposes to CO₂ when exposed to potentials above 3.8 V vs. Li/Li⁺. However, O₂ evolution, as would be expected according to the decomposition reaction 2 Li₂CO₃→4 Li⁺+4 e^?+2 CO₂+O₂, is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen (¹O₂) forms upon oxidizing Li₂CO₃ in an aprotic electrolyte and therefore does not evolve as O₂. These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding ¹O₂ in metal‐O₂ batteries, question the possibility of a reversible metal‐O₂/CO₂ battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li₂CO₃.     

Intermittent operation of the aprotic Li-O2 battery: the mass recovery process upon discharge interval

The intermittent operation of the aprotic Li-O₂ battery is systematically studied in this paper. A combined study of the battery charge retention and the electrolyte stability to O₂ suggests a low self-discharge rate of the Li-O₂ battery, which is a prerequisite to achieve desirable intermittent discharge performance. The battery under intermittent operation exhibits significantly improved discharge performance as compared to the continuously discharged one. It is found that the capacity output is directly associated with the time interval between two discharge steps and with the capacity limit for each discharge step. The open-circuit potential and linear scan voltammetry analyses confirm that a “mass recovery” process, corresponding to the concentration relaxation of the oxygen which is available at the cathode, proceed during the discharge intervals. In the “mass recovery” process, an increased amount of O₂ homogeneously redistributes at the electrolyte/carbon interface at both sides of the electrode, which relieves the O₂ transport limit, enhances the availability of O₂ and the utilization of carbon material for the cathode, and thus significantly improves the discharge performance of the aprotic Li-O₂ battery.     

Monitoring the phase evolution in LiCoO2 electrodes during battery cycles using in-situ neutron diffraction technique

LiCoO₂ (LCO) with average particle distribution of 8 μm (LCO-A) and 11 μm (LCO-B) exhibit substantial differences in cycle performance. The half-cells have similar first-cycle discharge capacities of 173 and 175 mAh/g at 0.25 C, but after 100 cycles, the discharge capacities are substantially different, that is, 114 and 141 mAh/g for LCO-A and LCO-B, respectively. Operando neutron powder diffraction of full LCO||Li₄Ti₅O₁₂ batteries show differences in the LCO reaction mechanism underpinning the electrochemical behavior. LCO-A follows a purely solid solution reaction during cycling compared to the solid solution and two-phase reaction mechanism in LCO-B. The absence of the two-phase reaction in LCO-A is consistent with a homogeneous distribution of Li throughout the particle. The two-phase reaction in LCO-B reflects two distinguishable distributions of Li within the particles. The faster capacity decay in LCO-A is correlated to an increase in electrode cracking during battery cycles.     

An aqueous rechargeable lithium battery based on doping and intercalation mechanisms

An aqueous rechargeable lithium battery (ARLB) using an electroactive polymer, polypyrrole (PPy), as a negative electrode; a lithium ion intercalation compound LiCoO₂ as a positive electrode; and Li₂SO₄ aqueous solution as an electrolyte and its working mechanism are described. The charge/discharge process is associated with the doping/un-doping of anions at the negative electrode and intercalation/deintercalation of lithium ions at the positive electrode. The average output voltage of the PPy//LiCoO₂ battery is about 0.85 V. This battery exhibits excellent cycling performance. This new technology solves the major problem of poor cycling life of ARLBs and will provide a new strategy to explore advanced energy storage and conversion systems.     

Single-Atom-Mediated Spinel Octahedral Structures for Elevated Performances of Li-Oxygen Batteries

Li-oxygen batteries have attracted much attention due to its ultra-high theoretical specific capacity, but the discharge product Li₂O₂ is easy to accumulate, leading to low battery stability. Here, we demonstrate a series of high-efficiency cathode catalysts of Co₃O₄ loaded with single-atomic metals (M=Ru, Pd, Pt, Au, Ir). The single-atomic metal could substitute the central Co atom in the octahedral coordination structure and maintain the structural stability; benefiting from the electron promoter effect, rendering more highly active Co³⁺ exposed, providing rich nucleation sites for Li₂O₂ deposition. And the loaded M atoms could separate the active Co³⁺ centers, thereby regulating the dispersion of Li₂O₂ to obtained a sheet-like morphology, which could facilitate its decomposition in the subsequent charge cycle. Our work found that the single atoms could effectively modulate the active metal oxide with which it is coordinated, thus collectively boosting the catalytic performance.     

Improving the Electrochemical Performance of the Li4Ti5O12 Electrode in a Rechargeable Magnesium Battery by Lithium–Magnesium Co‐Intercalation

Rechargeable magnesium batteries have attracted recent research attention because of abundant raw materials and their relatively low‐price and high‐safety characteristics. However, the sluggish kinetics of the intercalated Mg²⁺ ions in the electrode materials originates from the high polarizing ability of the Mg²⁺ ion and hinders its electrochemical properties. Here we report a facile approach to improve the electrochemical energy storage capability of the Li₄Ti₅O₁₂ electrode in a Mg battery system by the synergy between Mg²⁺ and Li⁺ ions. By tuning the hybrid electrolyte of Mg²⁺ and Li⁺ ions, both the reversible capacity and the kinetic properties of large Li₄Ti₅O₁₂ nanoparticles attain remarkable improvement.     

Li0.68Ni1.32O2/Ag nanocomposite: A Li-intercalation anode material with higher coulombic efficiency and better cycling performance

NiO, Li_0.68Ni_1.32O₂ and Li_0.68Ni_1.32O₂/Ag composite as anodes for Li-ion batteries are reported. Li_0.68Ni_1.32O₂ decomposed to Ni and Li₂O when discharged to 0.02 V, according to XRD analysis, which was similar to NiO. Increased initial coulombic efficiency was obtained for the Li_0.68Ni_1.32O₂ electrode (73%), higher than that of NiO (64.9%), but its cycling performance became worse because poorer conductive Li₂O formed when the first discharge process was finished. However, the Li_0.68Ni_1.32O₂/Ag electrode exhibited better cycling performance than NiO and Li_0.68Ni_1.32O₂, because the Ag nanoparticles in the composite improved the conductivity of the electrode. The initial coulombic efficiency for Li_0.68Ni_1.32O₂/Ag is still as high as 72%, nearly the same as that of Li_0.68Ni_1.32O₂.