Synthesis and electrochemical performance of NaV3O8 nanobelts for Li/Na-ion batteries and aqueous zinc-ion batteries

NaV₃O₈ nanobelts were successfully synthesized for Li/Na-ion batteries and rechargeable aqueous zinc-ion batteries (ZIBs) by a facile hydrothermal reaction and subsequent thermal transformation. Compared to the electrochemical performance of LIBs and NIBs, NaV₃O₈ nanobelt cathode materials in ZIBs have shown excellent electrochemical performance, including high specific capacity of 421 mA h g⁻¹ at 100 mA g⁻¹ and good cycle stability with a capacity retention of 94% over 500 cycles at 5 A g⁻¹. The good diffusion coefficients and high surface capacity of NaV₃O₈ nanobelts in ZIBs were in favor of fast Zn²⁺ intercalation and long-term cycle stability.

Compared to the electrochemical performance for LIBs and NIBs, NaV₃O₈ nanobelts electrode for ZIBs shows excellent electrochemical performance, including high specific capacity of 421 mA h g⁻¹ at 100 mA g⁻¹, good rate performance and cycle performance.     

Preparation and electrochemical performance of VO2(A) hollow spheres as a cathode for aqueous zinc ion batteries

Rechargeable aqueous zinc ion batteries (ZIBs), owing to their low-cost zinc metal, high safety and nontoxic aqueous electrolyte, have the potential to accelerate the development of large-scale energy storage applications. However, the desired development is significantly restricted by cathode materials, which are hampered by the intense charge repulsion of bivalent Zn²⁺. Herein, the as-prepared VO₂(A) hollow spheres via a feasible hydrothermal reaction exhibit superior zinc ion storage performance, large reversible capacity of 357 mA h g⁻¹ at 0.1 A g⁻¹, high rate capability of 165 mA h g⁻¹ at 10 A g⁻¹ and good cycling stability with a capacity retention of 76% over 500 cycles at 5 A g⁻¹. Our study not only provides the possibility of the practical application of ZIBs, but also brings a new prospect of designing high-performance cathode materials.

VO₂(A) hollow spheres exhibit superior zinc ion storage performance, large reversible capacity of 357 mA h g⁻¹ at 0.1 A g⁻¹, and good cycling stability with a capacity retention of 76% over 500 cycles at 5 A g⁻¹     

A comparison study of MnO2 and Mn2O3 as zinc-ion battery cathodes: an experimental and computational investigation

The high specific capacity, low cost and environmental friendliness make manganese dioxide materials promising cathode materials for zinc-ion batteries (ZIBs). In order to understand the difference between the electrochemical behavior of manganese dioxide materials with different valence states, i.e., Mn(iii) and Mn(iv), we investigated and compared the electrochemical properties of pure MnO₂ and Mn₂O₃ as ZIB cathodes via a combined experimental and computational approach. The MnO₂ electrode showed a higher discharging capacity (270.4 mA h g⁻¹ at 0.1 A g⁻¹) and a superior rate performance (125.7 mA h g⁻¹ at 3 A g⁻¹) than the Mn₂O₃ electrode (188.2 mA h g⁻¹ at 0.1 A g⁻¹ and 87 mA h g⁻¹ at 3 A g⁻¹, respectively). The superior performance of the MnO₂ electrode was ascribed to its higher specific surface area, higher electronic conductivity and lower diffusion barrier of Zn²⁺ compared to the Mn₂O₃ electrode. This study provides a detailed picture of the diversity of manganese dioxide electrodes as ZIB cathodes.

MnO₂ and Mn₂O₃ cathodes for zinc ion batteries were experimentally and computationally explored.     

Highly crystalline nickel hexacyanoferrate as a long-life cathode material for sodium-ion batteries

Prussian blue analogs (PBAs) are attractive cathode candidates for high energy density, including long life-cycle rechargeable batteries, due to their non-toxicity, facile synthesis techniques and low cost. Nevertheless, traditionally synthesized PBAs tend to have a flawed crystal structure with a large amount of [Fe(CN)₆]⁴⁻ openings and the presence of crystal water in the framework; therefore the specific capacity achieved has continuously been low with poor cycling stability. Herein, we demonstrate low-defect and sodium-enriched nickel hexacyanoferrate nanocrystals synthesized by a facile low-speed co-precipitation technique assisted by a chelating agent to overcome these problems. As a consequence, the prepared high-quality nickel hexacyanoferrate (HQ-NiHCF) exhibited a high specific capacity of 80 mA h g⁻¹ at 15 mA g⁻¹ (with a theoretical capacity of ∼85 mA h g⁻¹), maintaining a notable cycling stability (78 mA h g⁻¹ at 170 mA g⁻¹ current density) without noticeable fading in capacity retention after 1200 cycles. This low-speed synthesis strategy for PBA-based electrode materials could be also extended to other energy storage materials to fabricate high-performance rechargeable batteries.

A low-speed synthesis strategy was designed to fabricate Prussian blue analog based electrode materials for high-performance rechargeable batteries.     

The influence of different Si : C ratios on the electrochemical performance of silicon/carbon layered film anodes for lithium-ion batteries

With a high specific capacity (4200 mA h g⁻¹), silicon based materials have become the most promising anode materials in lithium-ions batteries. However, the large volume expansion makes the capacity reduce rapidly. In this work, a periodic silicon/carbon (Si/C) multilayer thin film was synthesized by magnetron sputtering method on copper foil. The titanium (Ti) film (about 20 nm) as the transition layer was deposited on the copper foil prior to the deposition of the multilayer film. Superior electrochemical lithium storage performance was obtained by the multilayer thin film. The initial discharge and charge specific capacity of the Si (15 nm)/C (5 nm) multilayer film anode are 2640 mA h g⁻¹ and 2560 mA h g⁻¹ with an initial coulombic efficiency of ∼97%. The retention specific capacity is about 2300 mA h g⁻¹ and there is ∼87% capacity retention after 200 cycles.

With a high specific capacity (4200 mA h g⁻¹), silicon based materials have become the most promising anode materials in lithium-ions batteries.     

Exploration of the modification of carbon-based substrate surfaces in aqueous rechargeable zinc ion batteries

The hydrophobic surfaces of carbon-based substrates lead to a huge interface impedance in aqueous rechargeable zinc ion batteries (ZIBs). Herein, we try to regulate the morphology and investigate the effects of polar groups on the substrate surface. With the treated substrate, the cyclic and rate performances of MnO₂ electrodes are improved by ∼42.5% and 97 mA h g⁻¹.

Oxygen-containing groups can be introduced to carbon paper surfaces by acidification. They improve the electrochemical performances and affect the charge-discharge behaviors of the MnO₂/CP cathode by reducing the interface resistance.     

Highly conductive locust bean gum bio-electrolyte for superior long-life quasi-solid-state zinc-ion batteries

Rechargeable aqueous zinc-ion batteries (ZIBs) are promising wearable electronic power sources. However, solid-state electrolytes with high ionic conductivities and long-term stabilities are still challenging to fabricate for high-performance ZIBs. Herein, locust bean gum (LBG) was used as a natural bio-polymer to prepare a free-standing quasi-solid-state ZnSO₄/MnSO₄ electrolyte. The as-obtained LBG electrolyte showed high ionic conductivity reaching 33.57 mS cm⁻¹ at room temperature. This value is so far the highest among the reported quasi-solid-state electrolytes. Besides, the as-obtained LBG electrolyte displayed excellent long-term stability toward a Zn anode. The application of the optimized LBG electrolyte in Zn–MnO₂ batteries achieved a high specific capacity reaching up to 339.4 mA h g⁻¹ at 0.15 A g⁻¹, a superior rate performance of 143.3 mA h g⁻¹ at 6 A g⁻¹, an excellent capacity retention of 100% over 3300 cycles and 93% over 4000 cycles combined with a wide working temperature range (0–40 °C) and good mechanical flexibility (capacity retention of 80.74% after 1000 bending cycles at a bending angle of 90°). In sum, the proposed ZIBs-based LBG electrolyte with high electrochemical performance looks promising for the future development of bio-compatible and environmentally friendly solid-state energy storage devices.

Locust bean gum was utilized to prepare a free-standing quasi-solid-state ZnSO₄/MnSO₄ electrolyte. Zinc-ion batteries with locust bean gum electrolyte achieved high energy density and superior lifetime.     

Self-assembled hierarchical porous NiMn2O4 microspheres as high performance Li-ion battery anodes

Hierarchical structured porous NiMn₂O₄ microspheres assembled with nanorods are synthesized through a simple hydrothermal method followed by calcination in air. As anode materials for lithium ion batteries (LIBs), the NiMn₂O₄ microspheres exhibit a high specific capacity. The initial discharge capacity is 1126 mA h g⁻¹. After 1000 cycles, the NiMn₂O₄ demonstrates a reversible capacity of 900 mA h g⁻¹ at a current density of 500 mA g⁻¹. In particular, the porous NiMn₂O₄ microspheres still could deliver a remarkable discharge capacity of 490 mA h g⁻¹ even at a high current density of 2 A g⁻¹, indicating their potential application in Li-ion batteries. This excellent electrochemical performance is ascribed to the unique hierarchical porous structure which can provide sufficient contact for the transfer of Li⁺ ion and area for the volume change of the electrolyte leading to enhanced Li⁺ mobility.

Hierarchical structured porous NiMn₂O₄ microspheres assembled with nanorods are synthesized through a simple hydrothermal method followed by calcination in air.     

Self-supporting S@GO–FWCNTs composite films as positive electrodes for high-performance lithium–sulfur batteries

Although lithium–sulfur (Li–S) batteries are a promising secondary power source, it still faces many technical challenges, such as rapid capacity decay and low sulfur utilization. The loading of sulfur and the weight percentage of sulfur in the cathode usually have a significant influence on the energy density. Herein, we report an easy synthesis of a self-supporting sulfur@graphene oxide-few-wall carbon nanotube (S@GO–FWCNT) composite cathode film, wherein an aluminum foil current collector is replaced by FWCNTs and sulfur particles are uniformly wrapped by graphene oxide along with FWCNTs. The 10 wt% FWCNT matrix through ultrasonication not only provided self-supporting properties without the aid of metallic foil, but also increased the electrical conductivity. The resulting S@GO–FWCNT composite electrode showed high rate performance and cycle stability up to ∼385.7 mA h g_electrode⁻¹ after 500 cycles and close to ∼0.04% specific capacity degradation per cycle, which was better than a S@GO composite electrode (353.1 mA h g_electrode⁻¹). This S@GO–FWCNT composite self-supporting film is a promising cathode material for high energy density rechargeable Li–S batteries.

We report a synthesis of a self-supporting composite cathode film, wherein aluminum foil current collector is replaced by FWCNTs and sulfur particles are uniformly wrapped by graphene oxide along with FWCNTs.     

Rod-like anhydrous V2O5 assembled by tiny nanosheets as a high-performance cathode material for aqueous zinc-ion batteries

Aqueous zinc-ion batteries offer a low-cost and high-safety alternative for next-generation electrochemical energy storage, whereas suitable cathode materials remain to be explored. Herein, rod-like anhydrous V₂O₅ derived from a vanadium-based metal–organic framework is investigated. Interestingly, this material is assembled by tiny nanosheets with a large surface area of 218 m² g⁻¹ and high pore volume of 0.96 cm³ g⁻¹. Benefiting from morphological and structural merits, this material exhibits excellent performances, such as high reversible capacity (449.8 mA h g⁻¹ at 0.1 A g⁻¹), good rate capability (314.3 mA h g⁻¹ at 2 A g⁻¹), and great long-term cyclability (86.8% capacity retention after 2000 cycles at 2 A g⁻¹), which are significantly superior to the control sample. Such great performances are found to derive from high Zn²⁺ ion diffusion coefficient, large contribution of intercalation pseudocapacitance, and fast electrochemical kinetics. The ex situ measurements unveil that the intercalation of Zn²⁺ ion is accompanied by the reversible V⁵⁺ reduction and H₂O incorporation. This work discloses a direction for designing and fabricating high-performance cathode materials for zinc-ion batteries and other advanced energy storage systems.

V₂O₅ with intriguing micro/nano-hierarchical structure is fabricated via the pyrolysis of MIL-47 (a MOF material) and displays great performances as the cathode material for aqueous zinc-ion batteries.     

Ultradispersed titanium dioxide nanoparticles embedded in a three-dimensional graphene aerogel for high performance sulfur cathodes

Lithium–sulfur (Li–S) batteries are regarded as one of the most promising energy storage technologies, however, their practical application is greatly limited by a series of sulfur cathode challenges such as the notorious “shuttle effect”, low conductivity and large volume change. Here, we develop a facile hydrothermal method for the large scale synthesis of sulfur hosts consisting of three-dimensional graphene aerogel with tiny TiO₂ nanoparticles (5–10 nm) uniformly dispersed on the graphene sheet (GA–TiO₂). The obtained GA–TiO₂ composites have a high surface area of ∼360 m² g⁻¹ and a hierarchical porous structure, which facilitates the encapsulation of sulfur in the carbon matrix. The resultant GA–TiO₂/S composites exhibit a high initial discharge capacity of 810 mA h g⁻¹ with an ultralow capacity fading of 0.054% per cycle over 700 cycles at 2C, and a high rate (5C) performance (396 mA h g⁻¹). Such architecture design paves a new way to synthesize well-defined sulfur hosts to tackle the challenges for high performance Li–S batteries.

GA–TiO₂ composites as a cathode material realize an excellent electrochemical performance in Li–S batteries.     

The study of zirconium vanadate as a cathode material for lithium ion batteries

The electrochemical properties of ZrV₂O₇ (ZVO) and ZVO@C were investigated in lithium ion batteries. The first charge (or discharge) specific capacity of ZVO and ZVO@C are 279 mA h g⁻¹, 392 mA h g⁻¹, 208 mA h g⁻¹ and 180 mA h g⁻¹ for 0%, 3%, 5% and 9% of carbon, respectively. The capacity retention rates (with 0% 3%, 5% and 9% carbon content) are 33.0%, 52.5%, 56.4% and 76.1% after ten cycles, respectively. The low inner resistance relates to the good contact of the electrode rather than the high content of carbon, and the specific capacity retention rate increases with the increase of the carbon content.

The carbon content in the electrode is not the only factor that determines the internal resistance. The high capacity of lithium ion batteries is related to high conductivity. The lattice is stable (expect for shrinkage) when Li ions insert into ZVO.     

Preparation and lithium storage of core–shell honeycomb-like Co3O4@C microspheres

Core–shell honeycomb-like Co₃O₄@C microspheres were synthesized via a facile solvothermal method and subsequent annealing treatment under an argon atmosphere. Owing to the core–shell honeycomb-like structure, a long cycling life was achieved (a high reversible specific capacity of 318.9 mA h g⁻¹ was maintained at 5C after 1000 cycles). Benefiting from the coated carbon layers, excellent rate capability was realized (a reversible specific capacity as high as 332.6 mA h g⁻¹ was still retained at 10C). The design of core–shell honeycomb-like microspheres provides a new idea for the development of anode materials for high-performance lithium-ion batteries.

The reversible specific capacity of CSHCo₃O₄@C microspheres was as high as 332.6 mA h g⁻¹ at 10C, which was significantly higher than that of SCo₃O₄ microspheres (68.7 mA h g⁻¹).     

Metal–organic framework derived hollow porous CuO–CuCo2O4 dodecahedrons as a cathode catalyst for Li–O2 batteries

Herein, hollow porous CuO–CuCo₂O₄ dodecahedrons are synthesized by using a simple self-sacrificial metal–organic framework (MOF) template, which resulted in dodecahedron morphology with hierarchically porous architecture. When evaluated as a cathodic electrocatalyst in lithium–oxygen batteries, the CuO–CuCo₂O₄ composite exhibits a significantly enhanced electrochemical performance, delivering an initial capacity of 6844 mA h g⁻¹ with a remarkably decreased discharge/charge overpotential to 1.15 V (vs. Li/Li⁺) at a current density of 100 mA g⁻¹ and showing excellent cyclic stability up to 111 charge/discharge cycles under a cut-off capacity of 1000 mA h g⁻¹ at 400 mA g⁻¹. The outstanding electrochemical performance of CuO–CuCo₂O₄ composite can be owing to the intrinsic catalytic activity, unique porous structure and the presence of substantial electrocatalytic sites. The ex situ XRD and SEM are also carried out to reveal the charge/discharge behavior and demonstrate the excellent reversibility of the CuO–CuCo₂O₄ based electrode.

Metal–organic framework derived porous CuO–CuCo₂O₄ dodecahedrons as a cathode catalyst for Li–O₂ batteries with significantly enhanced rate and cyclic performance.     

Preparation of novel two-stage structure MnO micrometer particles as lithium-ion battery anode materials

MnO micrometer particles with a two-stage structure (composed of mass nanoparticles) were produced via a one-step hydrothermal method using histidine and potassium permanganate (KMnO₄) as reagents, with subsequent calcination in a nitrogen (N₂) atmosphere. When the MnO micrometer particles were utilized in lithium-ion batteries (LIBs) as anode materials, the electrode showed a high reversible specific capacity of 747 mA h g⁻¹ at 100 mA g⁻¹ after 100 cycles, meanwhile, the electrode presented excellent rate capability at various current densities from 100 to 2000 mA g⁻¹ (∼203 mA h g⁻¹ at 2000 mA g⁻¹). This study developed a new approach to prepare two-stage structure micrometer MnO particles and the sample can be a promising anode material for lithium-ion batteries.

MnO micrometer particles with a two-stage structure (composed of mass nanoparticles) were produced via a one-step hydrothermal method using histidine and potassium permanganate (KMnO₄) as reagents, with subsequent calcination in a nitrogen (N₂) atmosphere.     

An investigation of Li2TiO3–coke composite anode material for Li-ion batteries

Anode material Li₂TiO₃–coke was prepared and tested for lithium-ion batteries. The as-prepared material exhibits excellent cycling stability and outstanding rate performance. Charge/discharge capacities of 266 mA h g⁻¹ at 0.100 A g⁻¹ and 200 mA h g⁻¹ at 1.000 A g⁻¹ are reached for Li₂TiO₃–coke. A cycling life-time test shows that Li₂TiO₃–coke gives a specific capacity of 264 mA h g⁻¹ at 0.300 A g⁻¹ and a capacity retention of 92% after 1000 cycles of charge/discharge.

Anode material Li₂TiO₃–coke was prepared and tested for lithium-ion batteries. The as-prepared material exhibits excellent cycling stability and outstanding rate performance.     

High electrochemical performance of nanocrystallized carbon-coated LiFePO4 modified by tris(pentafluorophenyl) borane as a cathode material for lithium-ion batteries

Tris(pentafluorophenyl) borane (C₁₈BF₁₅) was first adopted as a boron source, which clearly demonstrated its modification effects. XPS and EDX mapping proved that boron can be successfully doped into a carbon layer. The high number of defects in the carbon induced by boron was demonstrated via Raman spectroscopy and thus, the electric conductivity of LiFePO₄ was greatly enhanced. The boron-doped composite possessed a higher specific discharge capacity and rate capability than the undoped sample. For instance, the reversible specific capacity for the boron-doped cathode reached 165.8 mA h g⁻¹ at 0.5C, which was almost close to its theoretical capacity (166 mA h g⁻¹). Even at a high rate of 5C, it still possessed a high specific capacity of 124.8 mA h g⁻¹. This provides for the possibility that boron-doped carbon-coated LiFePO₄ cathodes may deliver high energy and power density for rechargeable lithium-ion batteries.

C₁₈BF₁₅ was first adopted as a boron source and has demonstrated its clear modification effects, as shown by the high rate capability.     

Hierarchical porous ZnMnO3 yolk–shell microspheres with superior lithium storage properties enabled by a unique one-step conversion mechanism

ZnMnO₃ has attracted enormous attention as a novel anode material for rechargeable lithium-ion batteries due to its high theoretical capacity. However, it suffers from capacity fading because of the large volumetric change during cycling. Here, porous ZnMnO₃ yolk–shell microspheres are developed through a facile and scalable synthesis approach. This ZnMnO₃ can effectively accommodate the large volume change upon cycling, leading to an excellent cycling stability. When applying this ZnMnO₃ as the anode in lithium-ion batteries, it shows a remarkable reversible capacity (400 mA h g⁻¹ at a current density of 400 mA g⁻¹ and 200 mA h g⁻¹ at 6400 mA g⁻¹) and excellent cycling performance (540 mA h g⁻¹ after 300 cycles at 400 mA g⁻¹) due to its unique structure. Furthermore, a novel conversion reaction mechanism of the ZnMnO₃ is revealed: ZnMnO₃ is first converted into intermediate phases of ZnO and MnO, after which MnO is further reduced to metallic Mn while ZnO remains stable, avoiding the serious pulverization of the electrode brought about by lithiation of ZnO.

ZnMnO₃ has attracted enormous attention as a novel anode material for rechargeable lithium-ion batteries due to its high theoretical capacity.     

Role of polyvinylpyrrolidone in the electrochemical performance of Li2MnO3 cathode for lithium-ion batteries

While Li₂MnO₃ as an over-lithiated layered oxide (OLO) shows a significantly high reversible capacity of 250 mA h g⁻¹ in lithium-ion batteries (LIBs), it has critical issues of poor cycling performance and deteriorated high rate performance. In this study, modified OLO cathode materials for improved LIB performance were obtained by heating the as-prepared OLO at different temperatures (400, 500, and 600 °C) in the presence of polyvinylpyrrolidone (PVP) under an N₂ atmosphere. Compared to the as-prepared OLO, the OLO sample heated at 500 °C with PVP exhibited a high initial discharge capacity of 206 mA h g⁻¹ and high rate capability of 111 mA h g⁻¹ at 100 mA g⁻¹. The superior performance of the OLO sample heated at 500 °C with PVP is attributed to an improved electronic conductivity and Li⁺ ionic motion, resulting from the formation of the graphitic carbon structure and increased Mn³⁺ ratio during the decomposition of PVP.

The modified OLO cathode materials for improved LIB performance were obtained by heating the as-prepared OLO in the presence of polyvinylpyrrolidone (PVP) under an N₂ atmosphere.     

Suppressing self-discharge of Li–B/CoS2 thermal batteries by using a carbon-coated CoS2 cathode

Thermal batteries with molten salt electrolytes are used for many military applications, primarily as power sources for guided missiles. The Li–B/CoS₂ couple is designed for high-power, high-voltage thermal batteries. However, their capacity and safe properties are influenced by acute self-discharge that results from the dissolved lithium anode in molten salt electrolytes. To solve those problems, in this paper, carbon coated CoS₂ was prepared by pyrolysis reaction of sucrose at 400 °C. The carbon coating as a physical barrier can protect CoS₂ particles from damage by dissolved lithium and reduce the self-discharge reaction. Therefore, both the discharge efficiency and safety of Li–B/CoS₂ thermal batteries are increased remarkably. Discharge results show that the specific capacity of the first discharge plateau of carbon-coated CoS₂ is 243 mA h g⁻¹ which is 50 mA h g⁻¹ higher than that of pristine CoS₂ at a current density of 100 mA cm⁻². The specific capacity of the first discharge plateau at 500 mA cm⁻² for carbon-coated CoS₂ and pristine CoS₂ are 283 mA h g⁻¹ and 258 mA h g⁻¹ respectively. The characterizations by XRD and DSC indicate that the carbonization process has no noticeable influence on the intrinsic crystal structure and thermal stability of pristine CoS₂.

Suppressing self-discharge of Li–B/CoS₂ thermal batteries through modifying the CoS₂ cathode with a protective carbon coating layer.