Rapid synthesis of layered KxMnO2 cathodes from metal–organic frameworks for potassium-ion batteries

Layered transition metal oxides (LTMOs) are a kind of promising cathode materials for potassium-ion batteries because of their abundant raw materials and high theoretical capacities. However, their synthesis always involves long time calcination at a high temperature, leading to low synthesis efficiency and high energy consumption. Herein, an ultra-fast synthesis strategy of Mn-based LTMOs in minutes is developed directly from alkali-transition metal based-metal–organic frameworks (MOFs). The phase transformation from the MOF to LTMO is systematically investigated by thermogravimetric analysis, variable temperature optical microscopy and X-ray diffraction, and the results reveal that the uniform distribution of K and Mn ions in MOFs promotes fast phase transformation. As a cathode in potassium-ion batteries, the fast-synthesized Mn-based LTMO demonstrates an excellent electrochemical performance with 119 mA h g⁻¹ and good cycling stability, highlighting the high production efficiency of LTMOs for future large-scale manufacturing and application of potassium-ion batteries.

An ultra-fast synthesis method for layered transition metal oxide cathodes (K_xMnO₂) was developed via minute calcination of metal–organic frameworks for potassium-ion batteries.     

K0.67Ni0.17Co0.17Mn0.66O2: A cathode material for potassium-ion battery

A novel layered ternary material K_0.67Ni_0.17Co_0.17Mn_0.66O₂ has been fabricated via a co-precipitation assisted solid-phase method and further evaluated as a cathode for potassium-ion batteries for the first time. Highly reversible K⁺ intercalation/deintercalation is demonstrated in this material. It delivers a reversible capacity of 76.5 mAh/g with average voltage of 3.1 V and shows good cycling performance with capacity retention of 87% after 100 cycles at 20 mA/g. This work may give a new insight into developing cathode materials for potassium-ion batteries.     

Strategies for constructing manganese-based oxide electrode materials for aqueous rechargeable zinc-ion batteries

Commercial lithium-ion batteries(LIBs) have been widely used in various energy storage systems. However, many unfavorable factors of LIBs have prompted researchers to turn their attention to the development of emerging secondary batteries. Aqueous zinc ion batteries(AZIBs) present some prominent advantages with environmental friendliness, low cost and convenient operation feature. Mn O2electrode is the first to be discovered as promising cathode material. So far, manganese-based oxides have made...     

Molybdenum Substitution for Improving the Charge Compensation and Activity of Li2MnO3

Lithium‐rich layer‐structured oxides xLi₂MnO₃? (1?x)LiMO₂ (0<x<1, M=Mn, Ni, Co, etc.) are interesting and potential cathode materials for high energy‐density lithium ion batteries. However, the characteristic charge compensation contributed by O^2? in Li₂MnO₃ leads to the evolution of oxygen during the initial Li⁺ ion extraction at high voltage and voltage fading in subsequent cycling, resulting in a safety hazard and poor cycling performance of the battery. Molybdenum substitution was performed in this work to provide another electron donor and to enhance the electrochemical activity of Li₂MnO₃‐based cathode materials. X‐ray diffraction and adsorption studies indicated that Mo⁵⁺ substitution expands the unit cell in the crystal lattice and weakens the Li?O and Mn?O bonds, as well as enhancing the activity of Li₂MnO₃ by lowering its delithiation potential and suppressing the release of oxygen. In addition, the chemical environment of O^2? ions in molybdenum‐substituted Li₂MnO₃ is more reversible than in the unsubstituted sample during cycling. Therefore molybdenum substitution is expected to improve the performances of the Li₂MnO₃‐based lithium‐rich cathode materials.     

Research progress of tunnel-type sodium manganese oxide cathodes for SIBs

Among the large energy storage batteries, the sodium ion batteries（SIBs） are attracted huge interest due to the fact of its abundant raw materials and low cost, and has become the most promising secondary battery. Tunnel-type sodium manganese oxides（TMOs） are industrialized cathode materials because of their simple synthesis method and proficient electrochemical performance. Na_0.44MnO₂（NMO） is considered the best candidate material for all tunnel-type structural materials. ...     

Accelerated discovery of novel high-performance zinc-ion battery cathode materials by combining high-throughput screening and experiments

Aqueous zinc ion batteries (AZIBs) have attracted much attention in recent years due to their high safety, low cost, and decent electrochemical performance. However, the traditional electrodes development process requires tedious synthesis and testing procedures, which reduces the efficiency of developing high-performance battery devices. Here, we proposed a high-throughput screening strategy based on first-principles calculations to aid the experimental development of high-performance spinel cathode materials for AZIBs. We obtained 14 spinel materials from 12,047 Mn/Zn-O based materials by examining their structures and whether they satisfy the basic properties of electrodes. Then their band structures and density of states, open circuit voltage and volume expansion rate, ionic diffusion coefficient and energy barrier were further evaluated by first-principles calculations, resulting in five potential candidates. One of the promising candidates identified, Mg₂MnO₄, was experimentally synthesized, characterized and integrated into an AZIB based cell to verify its performance as a cathode. The Mg₂MnO₄ cathode exhibits excellent cycling stability, which is consistent with the theoretically predicted low volume expansion. Moreover, at high current density, the Mg₂MnO₄ cathode still exhibits high reversible capacity and excellent rate performance, indicating that it is an excellent cathode material for AZIBs. Our work provides a new approach to accelerate the development of high-performance cathodes for AZIBs and other ion batteries.     

Effects of microwave irradiation on the electrochemical performance of manganese-based cathode materials for lithium-ion batteries

Microwave-assisted synthesis has continued to be adopted for the preparation of high-performance manganese-based cathode materials for lithium-ion batteries. The technique is fast, energy-efficient and has significant positive impacts on the general physico-chemical properties of the cathode materials: LiMn₂O₄, LiMn_1.5Ni_0.5O₄, and lithium nickel manganese cobalt oxides. Despite the advantages of microwave-assisted synthesis, this review reveals that the application is still limited. In our opinion, increased basic knowledge of the microwave process and availability of safe and reliable instrumentation could be a great opportunity for the commercial realization of low-cost and energy-dense Mn-based cathode materials for the next-generation lithium-ion batteries.     

Proton Intercalation/De-intercalation Chemistry in Phenazine-based Anode for Hydronium-ion Batteries

Hydronium-ion batteries have received significant attention owing to the merits of extraordinary sustainability and excellent rate abilities. However, achieving high-performance hydronium-ion batteries remains a challenge due to the inferior properties of anode materials in strong acid electrolyte. Herein, a hydronium-ion battery is constructed which is based on a diquinoxalino [2,3-a:2’,3’-c] phenazine (HATN) anode and a MnO₂@graphite felt cathode in a hybrid acidic electrolyte. The fast kinetics of hydronium-ion insertion/extraction into HATN electrode endows the HATN//MnO₂@GF battery with enhanced electrochemical performance. This battery exhibits an excellent rate performance (266 mAh g⁻¹ at 0.5 A g⁻¹, 97 mAh g⁻¹ at 50 A g⁻¹), attractive energy density (182.1 Wh kg⁻¹) and power density (31.2 kW kg⁻¹), along with long-term cycle stability. These results shed light on the development of advanced hydronium-ion batteries.     

Thermal processes in the systems with Li-battery cathode materials and LiPF6 -based organic solutions

Thermodynamic instability of positive electrodes (cathodes) in Li-ion batteries in humid air and battery solutions results in capacity fading and batteries degradation, especially at elevated temperatures. In this work, we studied thermal interactions between cathode materials Li₂MnO₃, xLi₂MnO₃ ^.(1???x)Li(MnNiCo)O₂,LiNi_0.33Mn_0.33Co_0.33O₂, LiNi_0.4Mn_0.4Co_0.2O₂, LiNi_0.8Co_0.15Al_0.05O₂ LiMn_1.5Ni_0.5O₄, LiMn(or Fe)PO₄, and battery solutions containing ethylene carbonate (EC) or propylene carbonate (PC), dimethyl carbonate (DMC) or ethylmethyl carbonate (EMC) and LiPF₆ salt in the temperature range of 40–400 °C. It was found that these materials are stable chemically and well performing in LiPF₆-based solutions up to 60 °C. The thermal decomposition of the electrolyte solutions starts >180 °C. The macro-structural transformations of cathode materials upon exothermic reactions were studied by transmission electron microscopy (TEM), X-ray difraction (XRD) and Raman spectroscopy. Differential scanning calorimetry (DSC) studies have shown that the exothermic reactions in the temperature range of 60–140 °C lead to partial decomposition of both the cathode material and electrolyte solution. The systems thus formed consisted of partially decomposed solutions and partially chemically delithiated cathode materials covered by reactions products. Thermal reactions terminate and this system reaches equilibrium at about 120 °C. It remains stable up to the beginning of the solution decomposition at about 180 °C. The increased content of surface Li₂CO₃ is found to significantly affect the thermal processes at high temperature range due to extensive exothermic decomposition at low temperatures.     

An Electrolytic Zn–MnO2 Battery for High‐Voltage and Scalable Energy Storage

Zinc‐based electrochemistry is attracting significant attention for practical energy storage owing to its uniqueness in terms of low cost and high safety. However, the grid‐scale application is plagued by limited output voltage and inadequate energy density when compared with more conventional Li‐ion batteries. Herein, we propose a latent high‐voltage MnO₂ electrolysis process in a conventional Zn‐ion battery, and report a new electrolytic Zn–MnO₂ system, via enabled proton and electron dynamics, that maximizes the electrolysis process. Compared with other Zn‐based electrochemical devices, this new electrolytic Zn–MnO₂ battery has a record‐high output voltage of 1.95 V and an imposing gravimetric capacity of about 570 mAh g^?1, together with a record energy density of approximately 409 Wh kg^?1 when both anode and cathode active materials are taken into consideration. The cost was conservatively estimated at <US$ 10 per kWh. This result opens a new opportunity for the development of Zn‐based batteries, and should be of immediate benefit for low‐cost practical energy storage and grid‐scale applications.     

Understanding High-Rate K+-Solvent Co-Intercalation in Natural Graphite for Potassium-Ion Batteries

Graphite shows great potential as an anode material for rechargeable metal-ion batteries because of its high abundance and low cost. However, the electrochemical performance of graphite anode materials for rechargeable potassium-ion batteries needs to be further improved. Reported herein is a natural graphite with superior rate performance and cycling stability obtained through a unique K⁺-solvent co-intercalation mechanism in a 1 m KCF₃SO₃ diethylene glycol dimethyl ether electrolyte. The co-intercalation mechanism was demonstrated by ex situ Fourier transform infrared spectroscopy and in situ X-ray diffraction. Moreover, the structure of the [K-solvent]⁺ complexes intercalated with the graphite and the conditions for reversible K⁺-solvent co-intercalation into graphite are proposed based on the experimental results and first-principles calculations. This work provides important insights into the design of natural graphite for high-performance rechargeable potassium-ion batteries.     

Synthesis of micro and nanostructured MnO2 and their comparative study in lithium battery

Micro and nanostructured ??-MnO₂ are synthesized to investigate the size effect of cathode active materials in battery performance. MnSO₄ and (NH₄)₂S₂O₈ were used as starting materials to prepare micro and nanostructured samples in the presence of stirring and ultrasonic irradiation, respectively. Structure optimization is done by changing values for temperature and manganese sulphate concentration. The MnO₂ micro and nanoparticles are characterized by scanning electron microscopy and X-ray diffraction (XRD). The XRD results reveal that only ??-MnO₂ is formed under the reaction conditions. Under the optimized conditions, manganese dioxide nanoparticles, with an average particle size of 56?nm, are obtained. Both micro and nanostructured MnO₂ is used as the cathode active material in Li/MnO₂ battery. Discharge profiles of stirrer-based cathode material (micro) and ultrasonic instrument-based one (nano) compared with each other in constant discharge currents of 50 and 100?mA?g^?1. The results demonstrated that nanosized materials show higher specific capacities and energies. Electrochemical impedance spectroscopy is used to investigate the size effect of cathode material on battery resistance and the results show a copious decrease in total resistance.     

Structure Design and Performance of LiNixCoyMn1‐x‐yO2 Cathode Materials for Lithium‐ion Batteries: A Review

Lithium‐ion batteries are now considered to be the technology of choice for future hybrid electric and full electric vehicles to address global warming. One of the challenges for improving the performance of lithium ion batteries to meet increasingly demanding requirements for energy storage is the development of suitable cathode materials. The recent advancement of lithium nickel cobalt manganese oxides are investigated as advanced positive cathode materials for lithium‐ion batteries. This review aims at providing the reader with an understanding of the critical scientific challenges facing the development of LiNi_xCo_yMn_1‐x‐yO₂ materials, the latest developments in crystal structure, synthesis methods, and structure designs to unravel the mechanisms of charge and mass transport processes associated with battery performance, and the outlook for future‐generation batteries that exploit gradient structures materials for significantly improved performance to meet the ever‐increasing demands of emerging technologies.     

The Development of Vanadyl Phosphate Cathode Materials for Energy Storage Systems: A Review

Various cathode materials have been proposed for high-performance rechargeable batteries. Vanadyl phosphate is an important member of the polyanion cathode family. VOPO₄ has seven known crystal polymorphs with tunneled or layered frameworks, which allow facile cation (de)intercalations. Two-electron transfer per formula unit can be realized by using V^V/V^IV and V^IV/V^III redox couples. The electrochemical performance is closely related to the structures of VOPO₄ and the types of inserted cations. This Review outlines the crystal structures of VOPO₄ polymorphs and their lithiated phases. The research progress of vanadyl phosphate cathode materials for different energy storage systems, including lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, multivalent batteries, and supercapacitors, as well as the related mechanism investigations are summarized. It is hoped that this Review will help with future directions of using vanadyl phosphate materials for energy storage.     

Success and serendipity on achieving high energy density for rechargeable batteries

Rechargeable lithium batteries that use non-aqueous electrolytes may not be suitable for electric vehicle applications, which require safe, inexpensive, and high energy density. In this paper, we showed that reversible lithium intercalation can occur in MnO₂ cathode coupled with Zn anode while using LiOH aqueous electrolyte. This new Zn|LiOH|MnO₂ aqueous rechargeable cell could operate around 1.5 V for multiple cycles and possibly be used in battery packs, are of low cost, and environmentally benign. However, higher energy density, power density, and cycling life of the Zn|LiOH|MnO₂ system are required for exploiting this technology to better compete with the lithium battery counterparts. Serendipitously, high energy density (270 Wh/Kg) that was achieved with physically mixed additives (Bi₂O₃ and TiB₂) on MnO₂ is reported. Physically modified cathode containing multiple additives is shown to be superior in energy density and capacity retention compared to that of the additive-free MnO₂ or carbon-coated MnO₂ using polyvinylpyrrolidone as the source. The role of the additives (Bi₂O₃ and Bi₂O₃?+?TiB₂) in the MnO₂ electrode is found to avoid the formation of unwanted (non-rechargeable) products and to decrease the polarization of the electrode.     

Carbon Electrode Materials for Advanced Potassium-Ion Storage

Tremendous progress has been made in the field of electrochemical energy storage devices that rely on potassium-ions as charge carriers due to their abundant resources and excellent ion transport properties. Nevertheless, future practical developments not only count on advanced electrode materials with superior electrochemical performance, but also on competitive costs of electrodes for scalable production. In the past few decades, advanced carbon materials have attracted great interest due to their low cost, high selectivity, and structural suitability and have been widely investigated as functional materials for potassium-ion storage. This article provides an up-to-date overview of this rapidly developing field, focusing on recent advanced and mechanistic understanding of carbon-based electrode materials for potassium-ion batteries. In addition, we also discuss recent achievements of dual-ion batteries and conversion-type K−X (X=O₂, CO₂, S, Se, I₂) batteries towards potential practical applications as high-voltage and high-power devices, and summarize carbon-based materials as the host for K-metal protection and possible directions for the development of potassium energy-related devices as well. Based on this, we bridge the gaps between various carbon-based functional materials structure and the related potassium-ion storage performance, especially provide guidance on carbon material design principles for next-generation potassium-ion storage devices.     

Surface analysis on discharged MnO2 cathode using XPS and SIMS techniques

Manganese dioxide (MnO₂) appears to be an effective cathode material for a battery system. No studies on lithium insertion in aqueous media are known to the best of our knowledge. However, in one of our previous papers we reported that lithium could be intercalated into a MnO₂ host compound using an aqueous LiOH electrolyte; however simple chemistry suggests that it should not. It is found that a battery with LiOH electrolyte functions quite differently from the cell that uses Li₂SO₄. This paper describes the surface modifications that accompany the electrochemical behavior of MnO₂ during redox (discharge) processes in the lithium hydroxide and sulfate media. XPS and SIMS techniques were used to study the resultant surface of the MnO₂ cathode and the spectra reveal that the formation of an insoluble layer of Li₂CO₃ precedes the process of reduction. SEM was used to study the microstructure of the MnO₂ cathode. Copyright © 2008 John Wiley & Sons, Ltd.     

Mitigation of Jahn–Teller distortion and Na+/vacancy ordering in a distorted manganese oxide cathode material by Li substitution

Layered manganese-based oxides are promising candidates as cathode materials for sodium-ion batteries (SIBs) due to their low cost and high specific capacity. However, the Jahn–Teller distortion from high-spin Mn³⁺ induces detrimental lattice strain and severe structural degradation during sodiation and desodiation. Herein, lithium is introduced to partially substitute manganese ions to form distorted P′2-Na_0.67Li_0.05Mn_0.95O₂, which leads to restrained anisotropic change of Mn–O bond lengths and reinforced bond strength in the [MnO₆] octahedra by mitigation of Jahn–Teller distortion and contraction of MnO₂ layers. This ensures the structural stability during charge and discharge of P′2-Na_0.67Li_0.05Mn_0.95O₂ and Na⁺/vacancy disordering for facile Na⁺ diffusion in the Na layers with a low activation energy barrier of ∼0.53 eV. It exhibits a high specific capacity of 192.2 mA h g⁻¹, good cycling stability (90.3% capacity retention after 100 cycles) and superior rate capability (118.5 mA h g⁻¹ at 1.0 A g⁻¹), as well as smooth charge/discharge profiles. This strategy is effective to tune the crystal structure of layered oxide cathodes for SIBs with high performance.

Li-Substitution in P′2-Na_0.67MnO₂ mitigates the anisotropic change of Mn–O bonds and Na/vacancy ordering, and hence significantly promotes its cycling stability and rate capability as a cathode material for sodium-ion batteries.     

Synergistic effect of additives on electrochemical properties of MnO<Subscript>2</Subscript> cathode in aqueous rechargeable batteries

The synergistic effect of bismuth oxide (Bi₂O₃) + titanium disulphide (TiS₂) additives in different proportions into the MnO₂ cathode material is physically modified and tested in a Zn-MnO₂ battery with aqueous LiOH electrolyte. It is found that these foreign cations stabilized the MnO₂ structure upon multiple cycling and the synergistic effect between two additives enhanced the rechargeability. This class of additive modified MnO₂ may be of interest for high-energy density and safer batteries for applications such as electric vehicles. The cyclability of the material suitable for electric vehicle (EV) applications is established in this report. The incorporation of Bi₂O₃ (3 wt.%) and TiS₂ (2 wt.%) additives into the MnO₂ cathode was found to improve the cell performance, this is partly due to the suppression of proton insertion. The results on cyclic voltammetric and charge–discharge studies describing the redox mechanisms in LiOH electrolyte and the role of additives on those redox reactions are discussed and compared with that of traditional KOH electrolyte.     

A Sodium Manganese Oxide Cathode by Facile Reduction for Sodium Batteries

A nonstoichiometric sodium manganese oxide (Na_xMnO_2+δ) cathode useful for sodium batteries was synthesized by an ambient‐temperature strategy that involved facile reduction of aqueous sodium permanganate in sodium iodide and subsequent heat treatment at 600 °C. Combined powder X‐ray diffraction and synchrotron X‐ray diffraction analyses confirmed the annealed sample to belong to a Na_xMnO₂ phase with a P2‐hexagonal structure. The ICP‐AES results confirmed the stoichiometry of the sample to be Na_0.53MnO_2+δ. Electron microscopy studies revealed the particle size of the electrode to be in the range of a few hundred nanometers. The Na_0.53MnO_2+δ cathode delivered an average discharge capacity of 170 mA h g^?1 with a stable plateau at 2.1 V for the initial 25 cycles versus sodium. Ex situ XANES studies confirmed the reversible intercalation of sodium into Na_0.53MnO_2+δ and suggested the accommodation of over‐stoichiometric Mn⁴⁺ ions to contribute towards the performance of the electrode.