Superior Lithium Storage Research Articles

Autocatalysis Surface-Growth of Co0.85se@Carbon Nanotubes on Carbon Nanosheets as Anode Material for Superior Lithium Storage

Autocatalysis Surface-Growth of Co0.85se@Carbon Nanotubes on Carbon Nanosheets as Anode Material for Superior Lithium Storage

Autocatalysis Surface-Growth of Co0.85se@Carbon Nanotubes on Carbon Nanosheets as Anode Material for Superior Lithium Storage

Autocatalysis Surface-Growth of Co0.85se@Carbon Nanotubes on Carbon Nanosheets as Anode Material for Superior Lithium Storage

Achieving superior lithium storage performances of CoMoO4 anode for lithium-ion batteries by Si-doping dual vacancies engineering

Regarded as a promising anode material, CoMoO4 can reveal higher theoretical capacity (980 mAh g−1) in the context of completely reversible electrochemical reaction. Unfortunately, the large volume expansion, low conductivity and inferior cyclic stability are non-negligible, which have greatly limited its further development and application. Herein, a series of CoMo1-xSix/2O4-2x (x = 0, 0.1, 0.15, 0.2 and 0.25) anode materials have been successfully synthesized through a solid-state method. This heterovalent atom doped strategy can not only provide cationic vacancy (Mo vacancy) but also generate anionic vacancy (O vacancy). The results demonstrate that all the Si doped CoMoO4 samples exhibit superior electrochemical performances than that of the pure CoMoO4 although the produce of the dual vacancies has negligible influence on the microstructures of CoMoO4, which should be attributed to the synergistic effect of the Mo vacancy and O vacancy and thus leading to the lower optical band gap, the enhanced conductivity and the faster transport of lithium ions and electron. Particularly, when the content of Si-doping is set as 0.05, the obtained CoMo0.9Si0.05O3.8 sample displays the highest capacity (847.4 mAh g−1) up to 300 cycles at a current density of 200 mA g−1. This work paves an effective strategy for constructing dual vacancies to promote the electrochemical performance of transition metal oxide anode materials.

Ultrafast Universal Fabrication of Metal-Organic Complex Nanosheets by Joule Heating Engineering.

Two-dimensional metal-organic complex (MOC) nanosheets are of great interest in various areas. Current strategies applied to synthesize MOC nanosheets are suffering from low yield, usage of large amounts of environmentally unfriendly organic solvent, are time and energy consuming, and cumbersome steps for 2D nanostructures. In this work, a novel joule heating mechanism is proposed to fabricate MOC nanosheets about 5nm in thickness with tunable metal compositions (i.e. M = Co, CoNi, and CoFe) within 60 s. Small amount of water is used as the only solvent. Under the intense irradiation of the microwave, fast heating via ionic conduction loss is realized, and urea is catalytically condensed into the long-chain organic ligands rich in N atoms that are capable of coordinating with metal ions to form the stubborn MOC framework, which is simultaneously puffed into an ultrathin nanosheet structure by the intensive release of gas. As a proof of concept, the as-synthesized Co-MOC nanosheet exhibits a superior lithium storage performance of 360 and 330mA h g-1 after 1200 and 2300 cycles at a current density of 500 and 1000mA g-1 , respectively.

Pyro-polymerization of organic pigments for superior lithium storage

Design of high energy density lithium storage materials is one of the everlasting issues in energy storage systems to realize a fully clean and sustainable energy grid. Here, 2,9-dimethyl quinacridone was selected as a precursor to prepare carbon-based electrode via low temperature heat-treatment process from 750 °C to 1050 °C. The pyro-polymerization of 2,9-dimethyl quinacridone induced a distinctive morphological transformation from rice husk-shaped 2,9-dimethyl quinacridone to carbon nanofibers. Electrode fabricated from pigment derived carbon nanofibers (PCNF) pyrolyzed at 750 °C maintained 878 mAh g-1 at a current density of 1 A g-1 and good Coulombic efficiency up to 98% after 1000 cycles. Furthermore, it delivered 337 mAh g-1 at a high current density of 25 A g-1. The superior performance was attributed to the stable structure of pristine 2,9-dimethyl quinacridone giving high thermal stability and crystallinity owing to well-defined π-π and hydrogen bonding interactions, thus rendering a stable microstructure with a large d-spacing of (002) plane of 3.580 Å, as well as efficient surface redox reactions. Density functional theory calculations indicated that the large interlayer distance could facilitate fast lithium ion insertion/extraction because of a ∼38% lower energy barrier for lithium ion insertion than compared with graphite.

Lithium-Storage Performance and Mechanism of a (Ni0.5Co0.5)9S8@NC Hollow Nanocube Composite as an Advanced Anode

In this work, the lithium-storage performance and mechanism of a designed (Ni0.5Co0.5)9S8@NC hollow nanocube composite as a rechargeable lithium-ion battery (LIB) anode are investigated. The nanocomposite is composed of a bimetallic sulfide (Ni0.5Co0.5)9S8 core and a surrounding nitrogen-doped carbon shell. It displays a superior electrochemical reactivity with an appealing specific capacity of 724 mAh g–1 at a specific current of 0.5 A g–1 cycled 80 times, as well as attractive stability and rate capability. The quantitative kinetic analysis reveals that the advanced lithium-storage performance is partly derived from the pseudocapacitive contributions. In situ X-ray diffraction (XRD) demonstrates the formation of Ni, Co, and Li2S in the conversion reaction during the initial cycling. Ex situ transmission electron microscopy (TEM) and scanning electron microscopy (SEM) demonstrate the volume expansion of the core (Ni0.5Co0.5)9S8 active material with the essential preservation of the complete (Ni0.5Co0.5)9S8@NC hollow nanocube structure during repeating cycling. Namely, the synergistic effect of the N-doped carbon coating, the rigid hollow nanostructure, and the multiple-electron-transfer conversion reaction of the bimetallic sulfide contributes to the superior lithium-storage performance of the nanocomposite.

Two-dimensional sandwich-like silica@carbon@silica nanosheets for superior lithium storage

A novel two-dimensional porous sandwich-like SiO2@SCNs@SiO2 nanosheet is designed and successfully fabricated as anode for superior lithium storage, where a mesoporous silica nanofilm grows on the two sides of sulfur-doped carbon nanosheets (SCNs). The SiO2@SCNs@SiO2 composite delivers a reversible specific capacity of 775.5 mA h g−1 at 0.2 A g−1 after 100 cycles and 326.7 mA h g−1 at 4 A g−1 after 500 cycles. The lithium storage mechanism of the composite is mainly dominated by the surface capacitive behavior. This SiO2@SCNs@SiO2 has potential to be a high performance anode material.

Core-shell nanostructured SiO2@a-TiO2@Ag composite with high capacity and safety for Li-ion battery anode

Smarting surface coatings have been shown to be good examples to cope with the drastic volume change and poor conductivity of SiO2 anode. Herein, we successfully synthesize the SiO2@a-TiO2@Ag composite with core–shell structure via a facile sol-gel method. The designed structure, in which a-TiO2 layer show elastic behavior, can alleviate the expansion of electrode, and provide more diffusion channels for lithium-ion. In addition, Ag nanoparticles are good conductor of electricity. The resulting materials used as lithium-ion batteries anode with superior lithium storage properties in terms of high initial capacity (1320 m Ah g−1 at 0.1 A g−1), good rate capability (425 m Ah g−1 at 2 A g−1), and excellent cycling stability (712 m Ah g−1 was retained over 300 cycles at 0.1 A g−1).

Efficient vapor-solid fluorination synthesis of MOF-derived MnF2/C for superior lithium storage with boosted kinetics

Transition metal fluorides have attracted widespread interest in recent years on account of their high energy density. However, their low conductivity and poor cyclability limit their development in next-generation power batteries. Herein, two methods (vapor-solid method and traditional calcination fluorination method) were used to successfully synthesize the manganese fluoride nanoparticle anode material attached on in-situ multi-vacancy carbon. Experimental data shows that vapor-solid method can provide more additional active sites, better electrical conductivity and more space to relieve volume expansion when compared to calcined fluorination. Pseudocapacitance analysis show their exceeding theoretical capacity phenomenon. By comparison, it is found that the spherical hollow manganese fluoride nanoparticles embedded carbon anode material obtained by the vapor-solid method exhibits excellent long cycle performance (450 loops at 1 A g−1, and a capacity of up to 864 mAh g−1, at a current density of 2 A g−1 1700 cycles with a capacity of up to 519 mAh g−1).

Hierarchical core/shell titanium dioxide/molybdenum disulfide nanosheets coupled with carbon architecture for superior lithium/sodium ion storage

The peculiar core/shell structure with abundant interfaces is favorable for Li+/Na+ storage, which can elevate the efficiency of energy storage and conversion. Herein, a unique core/shell structure composite with diverse interfaces was successfully designed and fabricated via a facile coordination reaction combined with thermal treatment. Specially, well-crystallized TiO2 nanoparticles were encapsulated and embedded in carbon nanospheres wrapped with MoS2 nanosheets, leading to abundant interfacial structure and boundaries. Benefitting from the synergistic effect between numerous interfaces and distinctive hierarchal core/shell structure, such a hybrid material possesses fascinating features including ultrafast ion diffusion, plentiful storage active sites and prominent electric conductivity. As a proof of concept, as-prepared samples demonstrated superior reversible lithium storage capacity and hybrid lithium-ion capacitor. What is more, when the material was acted as anode material for SIBs, the discharge capacity maintained at a high capacity of 267.2 mA h g−1 after 1000 cycles at 2.0 A g−1. This work highlights a convenient strategy to synthesize other hybrid materials for electrode materials of energy storage and conversion applications.

Metal-organic framework-derived LiFePO4 cathode encapsulated in O,F-codoped carbon matrix towards superior lithium storage

LiFePO4 renders as a prevailing commercialized cathode material for lithium-ion batteries (LIBs). However, due to its intrinsic inferior electronic conductivity and sluggish diffusion kinetics, it necessitates orchestrated efforts to surmount the suppressed rate capability. Herein, a metal-organic framework (MOF)-derived synthetic methodology for LiFePO4 microparticles encapsulated in O,F-codoped carbon matrix (LFP@OFC) via solid-state sintering is proposed as a versatile cathode material for LIBs. Enlightened by experimental investigation and theoretical calculation, the porous carbon matrix with O,F-codoped functionalities is energetically preferable for superior adsorption capability coupled with decreased diffusion barriers of Li, further conferring extra active sites, boosted electronic conductivity, and expedited diffusion aisles. Exceedingly, the LFP@OFC achieves pre-eminent electrochemical performance with exceptional specific capacity (169.9 mAh g−1 at 0.1 C), fabulous rate capacity (85.6 mAh g−1 even at 16.2 C), and distinguished long-term cyclability (160.9 mAh g−1 over 500 loops at 1 C). This work envisions an insightful construction of MOF-derived carbonaceous cathode materials in prospect of outstanding rate and cycling performance for prospective application and development.

Polyvinylpyrrolidone regulated synthesis of mesoporous titanium niobium oxide as high-performance anode for lithium-ion batteries

TiNb2O7 (TNO) as a promising candidate anode for lithium-ion batteries (LIBs) shows obvious advantages in terms of specific capacity and safety, but which undergoes the intrinsic poor electrical and ionic conductivity. Herein, we propose a simple synthesis strategy of mesoporous TNO via a polymeric surfactant-mediated evaporation-induced sol-gel method, using polyvinylpyrrolidone (PVP) with different molecular weights (average Mw: 10000/58000/1300000) as the regulating agent, which greatly affects the lithium storage performance of the as-prepared TNO. The optimized TNO (i.e., PVP of 58000) delivers a high reversible capacity of 303.1 mAh/g at 1 C, with a retention rate of 73.4% (222.5 mAh/g) after 300 cycles. Even at 5 C, a high reversible capacity of 185.6 mAh/g can be achieved, with a retention rate of 72.3% after 1000 cycles. The superior lithium storage behavior is attributed to the fine mesoporous framework consisting of interconnected TNO nanocrystallites with high specific surface area and high mesoporosity, which greatly increases the active sites, improves the Li+ diffusion kinetics and alleviates volume fluctuation induced by the repetitive Li+ insertion-extraction processes.

Se4P4 nanoparticles confined within porous carbon as a lithium-ion battery anode with superior electrochemical performance

The exploration of advanced anode materials through rational structure/phase design is the key to developing high-performance rechargeable batteries. Herein, tetraphosphorus tetraselenide (Se4P4) nanoparticles confined within porous carbon (named SeP@C) are developed for lithium-ion batteries. The designed SeP@C shows a set of structural/compositional advantages as lithium-ion battery anodes including high electrical conductivity, low ion diffusion barrier, and relieved lithiation stress. Consequently, the SeP@C electrode displays superior comprehensive lithium storage performance, e.g., high reversible capacity (640.8 mA h g−1 at 0.1 A g−1), excellent cycling stability (500 cycles with respective capacity retention of over or nearly 100%), and good rate capability, representing a comparable lithium storage performance in reported phosphide-based anodes. More significantly, it shows excellent energy storage properties in lithium-ion full cells which can light up 85 red LEDs for over 3.2 h. This work offers an advanced electrode construction guidance of phosphorous-based anodes for the development of high-performance energy storage devices.

Solvothermal synthesis of FeMnO3 nanobelts with excellent electrochemical performances for lithium-ions batteries and supercapacitors

One-dimensional nanobelt with inner nanopores has been considered as an ideal electrode material for electric energy storage. Herein iron manganese trioxide (FeMnO3) nanobelts have been prepared by a facile solvothermal approach. The phase, composition, structure and morphology of the as-synthesized sample are characterized by several techniques. Benefiting from the unique structure, the as-prepared FeMnO3 nanobelts achieve a superior lithium storage capacity with 635.7 mAh g−1 after 200 cycles, excellent cyclability and good kinetic properties, as well as a high specific capacitance of 209 F g−1 after 2000 cycles for supercapacitor. These results show a great application in large-scale energy storage.

Abnormally High‐Lithium Storage in Pure Crystalline C60 Nanoparticles (Adv. Mater. 43/2021)

Lithium-Ion Batteries In article number 2104763, Dong-Hwa Seo, Chae-Ryong Cho, and co-workers demonstrate superior reversible lithium storage of pure face-centered-cubic C60 nanoparticles with uniform morphology and a new phase transformation of LixC60 during the lithiation/de-lithiation process both experimentally and theoretically. A full-cell showing the transport of Li ions between C60 anode and LiFePO4 cathode is represented in the cover image.

Oxygen Vacancies Enhance Lithium‐Ion Storage Properties of TiO2 Hierarchical Spheres

AbstractTitanium dioxide (TiO2) is a promising electrode material for reversible lithium storage. However, the poor electronic conductivity, sluggish diffusivity, and intrinsic kinetics limit hinder its fast lithium storage capability. Here we present that the oxygen‐deficient TiO2 hierarchical spheres can address the issues for high capacity, long‐term lithium‐ion battery anode. First‐principles calculations show that introducing oxygen vacancies to anatase TiO2 can reduce the bandgap, thus improving the electronic conductivity and further the lithium storage properties of TiO2. By annealing TiO2/H2Ti5O11⋅3H2O hierarchical spheres precursor in nitrogen, accompanying with the phase transfer process, the growth of TiO2 crystallites is restricted due to the generation of residual carbon species, resulting in a well maintained hierarchical spherical structure. Rich oxygen vacancies are generated in the oxygen‐deficient environment and evidenced by EPR, XPS, and UV‐Vis spectra, which enable the TiO2 hierarchical spheres reduced bandgap. The oxygen vacancies in the as‐obtained TiO2 hierarchical spheres together with the high structural integrity of the hierarchical spheres gives rise to superior lithium storage properties including a high specific capacity of 282 mAh g−1 at 200 mA g−1, and long‐term cycling stability with a capacity retention of 85.2 % at 4 A g−1 over 10000 cycles.

A Novel Salen-based Porous Framework Polymer as Durable Anode for Lithium-Ion Storage.

Organic electrode materials with abundant resources, environmental friendliness and recyclability play a crucial role in rechargeable lithium-ion batteries (LIBs). However, the inferior electrical conductivity and unsatisfactory long-term cycling performance seriously impede their large-scale application in LIBs. Herein, a novel salen-based porous framework polymer (SPP) with a large conjugated skeleton was constructed and utilized as anode for LIBs. Owing to its unique architecture with a large conjugated skeleton facilitating the electron transport, rich pores accelerating the organic electrolyte infiltration, and stable skeleton structure improving the long-term cycling performance, SPP delivered a high specific capacity of 337 mA h g-1 at 0.1 C (1 C=250 mA g-1 ) after 100 cycles, and robust rate capacity of 95.5 mA h g-1 at 32 C. Importantly, an impressive long-term cycling performance with a storage capacity of 155.7 mA h g-1 at 8 C after 4000 cycles was obtained, showing a durable cyclic stability of SPP. Furthermore, the lithium storage mechanism of SPP was evaluated by ex-situ X-ray photoelectron spectroscopy, manifesting that the multiple active sites of C=N, -OH, and benzene ring were responsible for the superior lithium storage performance. The novel SPP presented in this work should be a promising organic electrode for energy storage applications.

Synthesis of Spherical Carbon‐Coated CoP Nanoparticles for High‐Performance Lithium‐Ion Batteries

Transition metal phosphides are emerging as potential anode materials for lithium‐ion batteries (LIBs) due to their high theoretical capacity and good thermal stability, but the severe volume changes during the charge/discharge process and low electrical conductivity have hampered their practical application. Herein, the facile synthesis of carbon‐coated CoP nanoparticles (CoP@C) with uniform spherical morphology is demonstrated through the solvothermal method followed by annealing and phosphating treatments, in which an interesting precursor, the Co–gluconate complex, is prepared as the Co/C sources. When used as the LIB anode, the CoP@C electrode displays excellent cycling stability with a reversible capacity of 483.4 mA h g−1 upon 1000 cycles at 0.5 A g−1. The superior lithium storage performance is attributed to the unique composite structure of CoP@C with the nanosized CoP particles wrapped into the carbon matrices, which can enhance the electrical conductivity, provide sufficient reaction sites, shorten the Li+ transport path, and buffer the volume changes of the electrode upon lithiation/delithiation. More importantly, the strategy of generating gluconate–metal complex as the metal‐ and carbon‐containing precursor can be widely applied in the synthesis of various functional materials for energy‐related applications.

Multiple anionic Ni(SO4)0.3(OH)1.4 nanobelts/reduced graphene oxide enabled by enhanced multielectron reactions with superior lithium storage capacity

The multielectron reaction materials for lithium-ion batteries are interesting charge storage hosts for next-generation high-energy–density anodes. As a class of multiple-anion transition metal compounds (MATMCs), the layered Nickel hydroxide sulfate (NiSH) nanobelts integrate positive-charged cations and intercalated anions, can be expected to construct the advanced high-energy–density materials, but have not yet reported. Herein, the layered NiSH nanobelts grafting on the 3D porous reduced Graphene oxide (rGO) nanosheets were fabricated for the first time as the negative electrode of lithium-ion battery (denoted as NiSH@rGO) by a one-pot hydrothermal approach. As expected, the NiSH@rGO composite delivers a superior initial discharge capacity (1060 mAh g−1 at 200 mA g−1 after 230 cycles) and an exceptional rate capacity (991 mA g−1 at 2000 mA g−1). Through in-situ XRD, ex-situ SEM and TEM, we showed that the outstanding performance of NiSH@rGO anode originate from multielectron reaction mechanism and prominent structural, which render expose more active sites for charge storage, increase the surface wettability of anode, accelerate electron/ion diffusion and ensure the stability of the structure. Above that, it showed excellent lithium storage capacity and high-rate performance. Furthermore, a full cell composed of the NiSH@rGO anode and LiFePO4 cathode displays an impressive capacitance and low-capacity decay rate. Our findings fundamentally and experimentally provide insights into the multi-anionic compounds for markedly enhancing the performance of the multi-electron anodes for advanced high-capacity lithium-ion battery.

Oxygen-deficient and orderly mesoporous cobalt oxide nanospheres for superior lithium storage

Lithium-ion batteries (LIBs) dominate the current electrical and electronic markets. However, the energy density that approaches the theoretical limit for conventional LIBs struggles to meet the future energy demand. Herein,5 oxygen-deficient cobalt oxide nanospheres in three-dimensional ordered mesoporous architecture (3DOM Co3O4−X) are developed via a simple nanocasting method, which serve as advanced anode materials for superior lithium storage. The unique highly porous and robust construction facilitates the mass transfer, restrains the volume expansion, and exposes vast interfaces for reversible lithiation/delithiation, while the oxygen vacancies in Co3O4−X lattice promote the electron/ion conductions and enrich the active sites for conversion reactions. Benefiting from these synergistic attributes, the 3DOM Co3O4−X electrodes retain a highly reversible capacity of 629.1 mA h g−1 after 1000 cycles at 2 A g−1, which significantly outperform the Co3O4 nanoparticle counterpart. This work demonstrates a highly promising material advancement combining architecture and defect engineering towards high-performance LIBs.