Designing high-capacity cathode materials for sodium-ion batteries

Na-rich layered oxides as cathode materials for sodium-ion batteries were designed using an electrochemical method based on Li-rich layered oxides. The materials show high specific capacity that can reach 234 mAh/g at a current of 5 mA/g. The energy density of this material (644 Wh/kg) is even higher than those of commercial cathodes for lithium-ion batteries, such as LiFePO₄ and LiMn₂O₄. Kinetic analysis of Na⁺ insertion/extraction into/from the Na-rich layered oxide reveals that the Na⁺ diffusion coefficient is about 10^− 14 cm²/s.     

NiCo2O4 nanosheets supported on Ni foam for rechargeable nonaqueous sodium–air batteries

NiCo₂O₄ nanosheets supported on Ni foam were synthesized by a solvothermal method. A composite of NiCo₂O₄ nanosheets/Ni as a carbon-free and binder-free air cathode exhibited an initial discharge capacity of 1762 mAh g^− 1 with a low polarization of 0.96 V at 20 mA g^− 1 for sodium–air batteries. Na₂O₂ nanosheets were firstly observed as the discharged product in sodium–air battery. High electrocatalytic activity of NiCo₂O₄ nanosheets/Ni made it a promising air electrode for rechargeable sodium–air batteries.     

High-capacity LiV3O8 thin-film cathode with a mixed amorphous–nanocrystalline microstructure prepared by RF magnetron sputtering

LiV₃O₈ thin films with a mixed amorphous–nanocrystalline microstructure were deposited on stainless steel substrates using radio-frequency (RF) magnetron sputtering for the first time. The films exhibited good performance as a cathode material for lithium ion batteries. Results indicate that the film electrodes had a smooth surface and consisted mainly of an amorphous structure containing nanocrystalline zones dispersed within it. Depending on its microstructure, the films delivered an initial discharge capacity as high as 382 mAh/g and exhibited good capacity retention, with discharge capacity of 301 mAh/g after 100 cycles representing a loss rate of 0.21% per cycle.     

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.     

High capacity Li[Li0.2Mn0.54Ni0.13Co0.13]O2–V2O5 composite cathodes with low irreversible capacity loss for lithium ion batteries

With an aim to suppress the huge irreversible capacity loss encountered in high capacity layered oxide solid solutions between Li₂MnO₃ and LiMO₂ (M = Mn, Ni, and Co), layered Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂–V₂O₅ composite cathodes with various V₂O₅ contents have been investigated. The irreversible capacity loss decreases from 68 mAh/g at 100% Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ to 0 mAh/g around 89 wt.% Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂–11 wt.% V₂O₅ as the lithium-free V₂O₅ serves as an insertion host to accommodate the lithium ions that could not be inserted back into the layered lattice after the first charge. The Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂–V₂O₅ composite cathodes with about 10–12 wt.% V₂O₅ exhibit an attractive discharge capacity of close to 300 mAh/g with little irreversible capacity loss and good cyclability.     

Enhancing the rate capability of high capacity xLi2MnO3 · (1 − x)LiMO2 (M = Mn,Ni, Co) electrodes by Li–Ni–PO4 treatment

The rate capability of high capacity xLi₂MnO₃ · (1 ? x)LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries has been significantly enhanced by stabilizing the electrode surface by reaction with a Li–Ni–PO₄ solution, followed by a heat-treatment step. Reversible capacities of 250 mAh/g at a C/11 rate, 225 mAh/g at C/2 and 200 mAh/g at C/1 have been obtained from 0.5Li₂MnO₃ · 0.5LiNi_0.44Co_0.25Mn_0.31O₂ electrodes between 4.6 and 2.0 V. The data bode well for their implementation in batteries that meet the 40-mile range requirement for plug-in hybrid vehicles.     

Synthesis and properties of a lithium-organic coordination compound as lithium-inserted material for lithium ion batteries

A lithium-organic coordination compound based on an aromatic carbonyl derivative, [Li₂(C₁₄H₆O₄)], was synthesized by the dehydration of [Li₂(C₁₄H₆O₄)·H₂O], and used as a novel lithium-inserted material for lithium ion batteries. The synthesized material has initial discharge capacity of 126 and 115 mAh/g at current densities of 22 and 111 mAh/g, corresponding to the columbic efficiency of 99.2% and 98.3% at the first cycle, and its capacity fading is only 5% and 13% after 50 cycles, respectively, showing that this compound is a promising candidate as lithium-inserted material for lithium ion batteries.     

High-energy and high-power Li-rich nickel manganese oxide electrode materials

A lithium-rich nickel-manganese oxide compound Li_x(Ni_0.25Mn_0.75)O_y (x > 1) was synthesized from layered Na_0.9Li_0.3Ni_0.25Mn_0.75O_δ precursor using a lithium ion-exchange reaction. The electrochemical behavior of the material as a cathode for lithium batteries, and a preliminary discussion of its structure are reported. The product Li_1.32Na_0.02Ni_0.25Mn_0.75O_y (IE-LNMO) shows broad X-ray diffraction peaks, but possesses a high intensity sharp (003) layering peak and multiple peaks with intensity in the 20–23° 2θ region which suggest Ni–Mn ordering in the transition metal layer (TM). Li/IE-LNMO cells demonstrate very stable reversible capacities of 220 mAh/g @ 15 mA/g and possess extremely high power of 150 mAh/g @ 1500 mA/g (15C). The Li/IE-LNMO cell dQ/dV plot exhibits three reversible electrochemical processes due to Ni/Mn redox behavior in a layered component, and Mn redox exchange in a spinel component. No alteration in the dQ/dV curves and no detectable change in the voltage profiles over 40 cycles were observed, thus indicating a stable structure for lithium insertion/extraction. This new material is attractive for demanding Li-ion battery applications.     

V-MOF@graphene derived two-dimensional hierarchical V2O5@graphene as high-performance cathode for aqueous zinc-ion batteries

Rechargeable aqueous zinc-ion batteries (ZIBs) are attracting growing attention in the field of grid-scale energy storage systems due to their reliable safety and low cost. However, it is still hindered by the limited choices of suitable cathode materials with high performance for aqueous ZIBs. Herein, we developed a V-MOF@graphene derived two-dimensional hierarchical V₂O₅@graphene for the first time, where the porous V₂O₅ nanosheets are homogeneously attached to the 2D graphene substrate. Benefiting from the unique 2D composite structure with excellent electronic and ionic conductivity, adequate active sites, as well as the synergistic effect between the ultrathin V₂O₅ nanosheets and graphene, the V₂O₅@graphene here exhibits outstanding electrochemical performance in aqueous ZIBs. Particularly, it delivered an ultrahigh reversible capacity of 378 mAh/g at a current density of 2 A/g. What is more, a high specific capacity of 305 mAh/g after 100 cycles at 0.1 A/g and 200 mAh/g after 1,000 cycles at 1 A/g can be achieved. These ideal results suggest that the V₂O₅@graphene cathode hold great promise for high-performance aqueous zinc-ion batteries.     

Uniform hematite nanocapsules based on an anode material for lithium ion batteries

Uniform α-Fe₂O₃ nanocapsules with a high surface area were synthesized by a novel wrap–bake–peel approach consisting of silica coating, heat treatment and finally the removal of the silica coating layer. The length, diameter and shell thickness of the hematite nanocapsules were about 65, 15 and 5 nm, respectively. The electrochemical properties of the α-Fe₂O₃ nanocapsules were investigated by cyclic voltammetry and charge/discharge measurements. The α-Fe₂O₃ nanocapsules showed a high reversible capacity of 888 mAh/g in the initial cycle and 740 mAh/g after 30 cycles as well as good capacity retention. This excellent electrochemical performance was attributed to the high surface area, thin shell and volume space of the hollow structure.     

A disordered rock-salt Li-excess cathode material with high capacity and substantial oxygen redox activity: Li1.25Nb0.25Mn0.5O2

A disordered rocksalt Li-excess cathode material, Li_1.25Nb_0.25Mn_0.5O₂, was synthesized and investigated. It shows a large initial discharge capacity of 287 mAh g^− 1 in the first cycle, which is much higher than the theoretical capacity of 146 mAh g^− 1 based on the Mn³⁺/Mn⁴⁺ redox reaction. In situ X-ray diffraction (XRD) demonstrates that the compound remains cation-disordered during the first cycle. Electron energy loss spectroscopy (EELS) suggests that Mn and O are likely to both be redox active, resulting in the large reversible capacity. Our results show that Li_1.25Nb_0.25Mn_0.5O₂ is a promising cathode material for high capacity Li-ion batteries and that reversible oxygen redox in the bulk may be a viable way forward to increase the energy density of lithium-ion batteries.     

Nano-LiCoO2 as cathode material of large capacity and high rate capability for aqueous rechargeable lithium batteries

Crystalline nanoparticles of LiCoO₂ are prepared by a sol–gel method at 550 °C and characterized by X-ray diffraction. Their electrochemical behaviors were characterized by cyclic voltammograms, capacity measurement and cycling performance. Results show that the reversible capacity of the nano-LiCoO₂ can be up to 143 mAh/g at 1000 mA/g and still be 133 mAh/g at 10,000 mA/g (about 70C) in 0.5 mol/l Li₂SO₄ aqueous electrolyte. In addition, their cycling behavior is also very satisfactory, no evident capacity fading during the initial 40 cycles. These data present great promise for the application of aqueous rechargeable lithium batteries.     

Na4Mn9O18 as a positive electrode material for an aqueous electrolyte sodium-ion energy storage device

Here we demonstrate Na₄Mn₉O₁₈ as a sodium intercalation positive electrode material for an aqueous electrolyte energy storage device. A simple solid-state synthesis route was used to produce this material, which was then tested electrochemically in a 1 M Na₂SO₄ electrolyte against an activated carbon counter electrode using cyclic voltammetry and galvanostatic cycling. Optimized Na₄Mn₉O₁₈ was documented as having a specific capacity of 45 mAh/g through a voltage range of 0.5 V, or an equivalent specific capacitance of over 300 F/g. With the proper negative:positive electrode mass ratio, energy storage cells capable of being charged to at least 1.7 V without significant water electrolysis are documented. Cycling data and rate studies indicate promising performance for this unexplored low-cost positive electrode material.     

Preparation and electrochemical lithium storage of flower-like spinel Li4Ti5O12 consisting of nanosheets

In this paper, flower-like spinel Li₄Ti₅O₁₂ consisting of nanosheets was synthesized by a hydrothermal process in glycol solution and following calcination. The as-prepared product was characterized by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction and cyclic voltammetry. The capacity of the sample used as anode material for lithium ion battery was measured. This structured Li₄Ti₅O₁₂ exhibited a high reversible capacity and an excellent rate capability of 165.8 m Ahg⁻¹ at 8 C, indicating potential application for lithium ion batteries with high rate performance and high capacity.     

Synthesis of MXene-supported layered MoS2 with enhanced electrochemical performance for Mg batteries

In this paper, the petal-like MoS₂/MXene composite has been successfully synthesized by one-step hydrothermal method. With the combination of few-layer MoS₂ nanosheets and the high conductive MXene substrate, the composite exhibits enhanced capacities and rate performance as cathode material of Mg batteries.     

Ether-based electrolyte enabled Na/FeS2 rechargeable batteries

We demonstrate for the first time that by simply substituting ether-based electrolyte (1.0 M NaCF₃SO₃ in diglyme) for the commonly used carbonate-based electrolyte, the cyclability of FeS₂ towards sodium storage can be significantly improved. A sodiation capacity over 600 mAh/g and a discharge energy density higher than 750 Wh/kg are obtained for FeS₂ at 20 mA/g. When tested at 60 mA/g, FeS₂ presents a sodiation capacity of 530 mAh/g and retains 450 mAh/g after 100 cycles, much better than the cycling performance of Na/FeS₂ tested in carbonate-based electrolyte.     

LixV2O5 nanobelts for high capacity lithium-ion battery cathodes

5–10 μm long, typically 200–300 nm wide, and several nanometers thick Li_xV₂O₅ (× ～ 0.8) nanobelts with the δ-type crystal structure were synthesized by a hydrothermal treatment of Li⁺-exchanged V₂O₅ gel. When dried at 200 °C under vacuum prior to electrochemical testing, the as-prepared nanobelts underwent the well-known δ → ε → γ-phase transition giving a mixture of ε and γ phases as a nanocomposite electrode material. Such a simple preparation procedure guarantees a yield of material with drastically enhanced initial discharge specific capacity of 490 mAh/g and great cyclability. The enhanced electrochemical performance is attributed to the complex of experimental procedures including post-synthesis treatment of the single-crystalline Li_xV₂O₅ nanobelts.     

Anomalous capacity and cycling stability of xLi2MnO3 · (1 − x)LiMO2 electrodes (M = Mn,Ni, Co) in lithium batteries at 50 °C

Transition metal oxides with composite xLi₂MnO₃ ·  (1 − x)LiMO₂ rocksalt structures (M = Mn, Ni, Co) are of interest as a new generation of cathode materials for high energy density lithium-ion batteries. After electrochemical activation to 4.6 or 4.8 V (vs. Li⁰) at 50 °C, xLi₂MnO₃ · (1 − x)LiMn_0.33Ni_0.33Co_0.33O₂ (x = 0.5, 0.7) electrodes deliver initial discharge capacities (>300 mAh/g) at a low current rate (0.05 mA/cm²) that exceed the theoretical values for lithiation back to the rocksalt stoichiometry (240–260 mAh/g), at least during the early charge/discharge cycles of the cells. Attention is drawn to previous reports of similar, but unaccounted and unexplained anomalous behavior of these types of electrode materials. Possible reasons for this anomalous capacity are suggested. Indications are that electrodes in which M = Mn, Ni and Co do not cycle with the same stability at 50 °C as those without cobalt.     

Tremella-like molybdenum dioxide consisting of nanosheets as an anode material for lithium ion battery

Tremella-like structured MoO₂ consisting of nanosheets was obtained via a Fe₂O₃-assisted hydrothermal reduction of MoO₃ in ethylenediamine aqueous solution. The as-prepared product was characterized and tested with scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and capacity measurement as anode material for lithium ion batteries. This structured MoO₂ shows very high reversible capacity (>600 mA h g⁻¹), good rate capability and cycling performance, presenting potential application as anode material for lithium ion batteries with high rate capability and high capacity.     

A Co(OH)2−graphene nanosheets composite as a high performance anode material for rechargeable lithium batteries

A Co(OH)₂?graphene nanosheets (Co(OH)₂?GNS) composite as a high performance anode material was firstly prepared through a simultaneous hydrothermal method. The structure, morphology and electrochemical performance of the obtained samples were systematically investigated by X-ray diffraction (XRD), transmission electron microscope (TEM) and electrochemical measurements. According to the TEM analysis, the surface of the Co(OH)₂ is surrounded with GNS in the Co(OH)₂?GNS composite. The specific discharge (lithiation) and charge (delithiation) capacities of Co(OH)₂?GNS attain to 1599 and 1120 mAh/g at a current density of 200 mA/g in the first cycle, respectively. After 30 cycles, the reversible capacity of Co(OH)₂?GNS is still 910 mAh/g with the retention of 82%. The particular structure of Co(OH)₂ particles surrounded by the GNS could limit the volume change during cycling and provide an excellent electronic conduction pathway, which could be the main reason for the remarkable improvement of electrochemical performance.