Electrochemical synthesis and lithium storage properties of three-dimensional porous Sn–Co alloy/CNT composite

Three-dimensional (3-D) porous copper with stable pore structure is prepared by electroless plating. 3-D porous Sn–Co alloy/carbon nanotube (CNT) composite is synthesized by electrodeposition using 3-D porous copper as the substrate. The scanning electron microscope results indicate that 3-D porous Sn–Co alloy/CNT composite contains a large amount of interconnected pores with the diameter size of ~3 μm. Upon cycling, the pore structure gradually disappears, but no serious exfoliation appears due to porous structure and reinforcement by CNT. The charge/discharge results demonstrate that the 3-D porous Sn–Co alloy/CNT composite electrode delivers high first reversible specific capacity of 490 mAh g^?1, and remains 441 mAh g^?1 after 60 cycles tested at different current densities. Even at the current density of 3,200 mA g^?1, the reversible specific capacity remains 319 mAh g^?1, which is 65 % of the first specific capacity cycled at the current density of 100 mA g^?1.     

High Rate and Long Cycle Life of a CNT/rGO/Si Nanoparticle Composite Anode for Lithium‐Ion Batteries

Si nanoparticle (Si‐NP) composite anode with high rate and long cycle life is an attractive anode material for lithium‐ion battery (LIB) in hybrid electric vehicle (HEV)/pure electric vehicle (PEV). In this work, a carbon nanotube (CNT)/reduced graphene oxide (rGO)/Si nanoparticle composite with alternated structure as Li‐ion battery anode is prepared. In this structure, rGO completely wraps the entire Si/CNT networks by different layers and CNT networks provide fast electron transport pathways with reduced solid‐state diffusion, so that the stable solid‐electrolyte interphase layer can form on the whole surface of the matrix instead of on single Si nanoparticle, which ensure the high cycle stability to achieve the excellent cycle performance. As a result, the CNT/rGO/Si‐NP anode exhibits high performances with long cycle life (≈455 mAh g^?1 at 15 A g^?1 after 2000 cycles), high specific charge capacity (≈2250 mAh g^?1 at 0.2 A g^?1, ≈650 mAh g^?1 at 15 A g^?1), and fast charge/discharge rates (up to 16 A g^?1). This nanostructure anode with facile and low‐cost synthesis method, as well as excellent electrochemical performances, makes it attractive for the long life cycles at high rate of the next generation LIB applications in HEV/PEV.     

Encapsulation of SnO2/Sn Nanoparticles into Mesoporous Carbon Nanowires and its Excellent Lithium Storage Properties

A peculiar nanostructure of encapsulation of SnO₂/Sn nanoparticles into mesoporous carbon nanowires (CNWs) has been successfully fabricated by a facile strategy and confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high‐resolution TEM (HRTEM), X‐ray diffraction (XRD), BET, energy‐dispersive X‐ray (EDX) spectrometer, and X‐ray photoelectron spectroscopy (XPS) characterizations. The 1D mesoporous CNWs effectively accommodate the strain of volume change, prevent the aggregation and pulverization of nanostructured SnO₂/Sn, and facilitate electron and ion transport throughout the electrode. Moreover, the void space surrounding SnO₂/Sn nanoparticles also provides buffer spaces for the volumetric change of SnO₂/Sn during cycling, thus resulting in excellent cycling performance as potential anode materials for lithium‐ion batteries. Even after 499 cycles, a reversible capacity of 949.4 mAh g^?1 is retained at 800 mA g^?1. Its unique architecture should be responsible for the superior electrochemical performance.     

Advanced LiTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C anode by incorporation of carbon nanotubes for aqueous lithium-ion batteries

Inferior rate capability is a big challenge for LiTi₂(PO₄)₃ anode for aqueous lithium-ion batteries. Herein, to address such issue, we synthesized a high-performance LiTi₂(PO₄)₃/carbon/carbon nanotube (LTP/C/CNT) composite by virtue of high-quality carbon coating and incorporation of good conductive network. The as-prepared LTP/C/CNT composite exhibits excellent rate performance with discharge capacity of 80.1 and 59.1 mAh g^?1 at 10 C and 20 C (based on the mass of anode, 1 C = 150 mA g^?1), much larger than that of the LTP/C composite (53.4 mAh g^?1 at 10 C, and 31.7 mAh g^?1 at 20 C). LTP/C/CNT also demonstrates outstanding cycling stability with capacity retention of 83.3 % after 1000 cycles at 5 C, superior to LTP/C without incorporation of CNTs (60.1 %). As verified, the excellent electrochemical performance of the LTP/C/CNT composite is attributed to the enhanced electrical conductivity, rapid charge transfer, and Li-ion diffusion because of the incorporation of CNTs.     

Vertically aligned α-MnO<Subscript>2</Subscript> nanosheets on carbon nanotubes as cathodic materials for aqueous rechargeable magnesium ion battery

In this work, vertically aligned α-MnO₂ nanosheets on carbon nanotubes are synthesized simply by a solution process and the electrochemical performance as host materials of magnesium ion is tested in aqueous solution. Cyclic voltammetry analysis confirms the enhanced electrochemical activity of carbon nanotube-supported samples. Moreover, carbon nanotubes skeleton could reduce the charge transfer resistant of the cathode materials, which is confirmed by electrochemical impedance spectroscopy. Furthermore, when tested as magnesium ion batteries cathodic electrode, the α-MnO₂/carbon nanotube sample registers a prominent discharge capacity of 144.6 mAh g^?1 at current density of 0.5 A g^?1, which is higher than the discharge capacity of α-MnO₂ (87.5 mAh g^?1) due to the synergistic effect of insertion/deinsertion reaction and physical adsorption/desorption process. After the 1000th cycle, a remarkable discharge capacity of 48.3 mAh g^?1 is collected for α-MnO₂/carbon nanotube at current density of 10 A g^?1, which is 85% of the original. It is found that the carbon skeleton not only improved the capacity but also enhanced the cycling performance of the α-MnO₂ electrode significantly. Therefore, α-MnO₂/carbon nanotube is a very promising candidate for further application in environmentally benign magnesium ion batteries.     

One-pot synthesis and electrochemical property of MnO/C hybrid microspheres

In this paper, we reported a one-pot method to synthesize MnO/C hybrid microspheres via solvothermal approach for the first time. Only peaks of MnO could be observed from X-ray diffractometry patterns, indicating that the carbon in the composite was amorphous. Scanning electron microscope and transmission electron microscopy images showed that the surfaces of these as-prepared spheres were relatively smooth and of about 2.2 μm in diameter. Electrochemical property demonstrated that the annealed MnO/C hybrid microspheres possessed higher reversible capacity and cycling stability than that of MnO nanoparticles. The annealed MnO/C hybrid microspheres exhibited a large initial charge capacity of 856 mAh?g^?1, and the stabilized capacity was as high as 601 mAh?g^?1 after 30 cycles. These improvements can be ascribed to the amorphous carbon, which can enhance the conductivity of MnO, suppress the aggregation of active particles, and increase their structural stability during cycling.     

Effect of pyrolytic polyacrylonitrile on electrochemical performance of Si/graphite composite anode for lithium-ion batteries

The silicon/graphite (Si/G) composite was prepared using pyrolytic polyacrylonitrile (PAN) as carbon precursor, which is a nitrogen-doped carbon that provides efficient pathway for electron transfer. The combination of flake graphite and pyrolytic carbon layer accommodates the large volume expansion of Si during discharge-charge process. The Si/G composite was synthesized via cost-effective liquid solidification followed by carbonization process. The effect of PAN content on electrochemical performance of composites was investigated. The composite containing 40 wt% PAN exhibits a relatively better rate capability and cycle performance than others. It exhibits initial reversible specific capacity of 793.6 mAh g^?1 at a current density of 100 mA g^?1. High capacity of 661 mAh g^?1 can be reached after 50 cycles at current density of 500 mA g^?1.     

A novel composite anode for LIB prepared via template-like-directed electrodepositing Cu–Sn alloy process

A novel composite anode material consisted of electrodeposited Cu–Sn alloy dispersing in a conductive micro-porous carbon membrane coated on Cu current collector was investigated. The composite material was prepared by template-like-directed electrodepositing Cu–Sn alloy process and then annealing. The template-like microporous membrane electrode was obtained as follows: (1) casting a polyacrylonitrile (PAN) solution on a copper foil, (2) then immersing the copper foil into deionized water for phase inversion, and (3) drying the membrane electrode. This method provided the composite material with high decentralization of Cu–Sn alloy and supporting medium function of conductive carbon membrane deriving from pyrolysis of PAN. SEM, XRD, and EDS analysis confirmed this structure. The characteristic structure was beneficial to inhibit the aggregation among Cu–Sn microparticles, to relax the volume expansion during cycling, and to improve the cycle ability of electrode. The reversible charge/discharge capacity of the composite material remained more than 426.6 and 445.1 mAh g⁻¹, respectively, after 70 cycles, while that of the electrode prepared by electrodepositing Cu–Sn on a bare Cu foil decreased seriously to only 11.3 mAh g⁻¹. These results show that the novel preparing anode process for LIB is a promising method and can achieve composite materials with larger specific capacity and long cycle life.     

Facile synthesis of N-doped carbon-coated Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode for application in high-rate lithium ion batteries

A facile sol-gel approach for the synthesis of lithium titanate composite decorated with N-doped carbon material (LTO/NC) is proposed. Urea is used as a nitrogen source in the proposed approach. The LTO/NC exhibits superior electrochemical performances as an electrode material for lithium-ion batteries, delivering a discharge capacity of as high as 103 mAh g^?1 at a high rate of 20 C and retaining a stable reversible capacity of 90 mAh g^?1 after 1000 cycles, corresponding to 100% capacity retention. These excellent electrochemical performances are proved by the nanoscale structure and N-doped carbon coating. NC layers were uniformly dispersed on the surface of LTO, thus preventing agglomeration, favoring the rapid migration of the inserted Li ion, and increasing the Li⁺ diffusion coefficient and electronic conductivity. LTO with the appropriate amount of NC coating is a promising anode material with applications in the development of high-powered and durable lithium-ion batteries.     

Template‐Free Fabrication of Hollow NiO–Carbon Hybrid Nanoparticle Aggregates with Improved Lithium Storage

Hollow NiO–carbon hybrid nanoparticle aggregates are fabricated through an environmental template‐free solvothermal alcoholysis route. Controlled hollow structure is achieved by adjusting the ratio of ethylene glycol to water and reaction time of solvothermal alcoholysis. Amorphous carbon can be loaded on the NiO nanoparticles uniformly in the solvothermal alcoholysis process, and the subsequent calcination results in the formation of hollow NiO–C hybrid nanoparticle aggregates. As anode materials for lithium‐ion batteries, it exhibits a stable reversible capacity of 622 mAh g^?1, and capacity retention keeps over 90.7% after 100 cycles at constant current density of 200 mA g^?1. The NiO–C electrode also exhibits good rate capabilities. The unique hollow structures can shorten the length of Li‐ion diffusion and offer a sufficient void space, which sufficiently alleviates the mechanical stress caused by volume change. The hybrid carbon in the particles renders the electrode having a good electronic conductivity. Here, the hollow NiO‐C hybrid electrode exhibits excellent electrochemical performance.     

An electrochemical and structural investigation of porous composite anode materials for LIB

A porous composite anode for lithium ion battery (LIB) was investigated. The composite anode was prepared by electrodepositing Sn?CSb alloy on a template-like electrode and then annealing it in the atmosphere of N₂, whereas the porous template-like electrode was obtained by forming a sponge-like porous membrane on a copper foil via a mixed phase inversion process, followed by pre-plating Cu through membrane pores in it. SEM and XRD results showed that composite structure of the anode consisted of electrodeposited Sn?CSb alloy dispersed in a PAN-pyrolyzed conjugated conducting polymer gridding, which was tightly connected with the Cu foil through transition alloy layer formed by heat treatment. Due to its relatively reasonable microcosmic structure, the composite anode presented better cycling performance and specific capacity retention during charging and discharging at diverse rates. When cycled between 0 and 2.0?V (vs Li/Li⁺) at 0.5?C rate, the reversible charge/discharge capacity of the composite material remained 415 and 414.8?mAh?g^?1, respectively, after 30 cycles, corresponding to 82.9% of the capacity retention. When charging and discharging at 2?C rate, the composite material electrode showed 71.7% capacity retention at the 30th cycle.     

An improved solid-state reaction route to Mg2+-doped LiFePO4/C cathode material for Li-ion battery

An improved solid-state reaction route has been employed to synthesize Mg²⁺-doped LiFePO₄/C nanocomposite cathode by calcining the precursor obtained via evaporating the mixture of ascorbic acid, LiCH₃COO·2H₂O, Mg(CH₃COO)₂·4H₂O, and amorphous FePO₄ nanoparticles in anhydrous ethanol under continuous stirring. Ascorbic acid used here acted as both reducing agent and carbon source. The amorphous FePO₄ was pre-prepared via a simple and fast oxidic precipitation method. Electrochemical tests showed that the final product exhibited good rate and cycling performance, with discharge capacities of 145.2 mAh g^?1 at 0.2 C, 129.8 mAh g^?1 at 1 C, 107.6mAh g^?1 at 5 C, and 81.4 mAh g^?1 at 20 C, respectively. The Mg²⁺-doped LiFePO₄/C showed enhanced charge–discharge performance compared with undoped LiFePO₄/C, especially at high rates. The enhanced electrochemical performance of the composite could be attributed to a combination result of the fine particle size with narrow particle size distribution, homogeneous carbon coating on the surface of the particles, and magnesium ion doping.     

Preparation of SnO2–graphene from SnS–graphene oxide for enhanced reversible lithium ion storage

SnO₂–graphene nanocomposites (SnO₂–GNS) have been prepared through a simple hydrothermal reaction with SnS–graphene oxide composites as the precursor. The composite material as prepared was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller analysis, and thermogravimetric analysis. The results indicate that SnO₂ nanoparticles possess a good dispersion on the surface of graphene. Electrochemical tests demonstrate the high reversible lithium ion storage properties of SnO₂–GNS. The nanocomposites retained a reversible capacity of 503 mAh?g^?1 after 40 cycles. Moreover, the composite material exhibited higher capacity and better cyclic performance compared to free SnO₂ nanoparticles physically mixed with graphene in the relative weight ratio. The results suggest that the combination of SnO₂ and graphene leads to synergistic performance, which enhances lithium ion storage properties of the overall system.     

Silicon/carbon nanocomposites used as anode materials for lithium-ion batteries

Silicon/carbon nanocomposites are prepared by dispersing nano-sized silicon in mesophase pitch and a subsequent pyrolysis process. In the nanocomposites, silicon nanoparticles are homogeneously distributed in the carbon networks derived from the mesophase pitch. The silicon/carbon nanocomposite delivers a high reversible capacity of 841 mAh g^?1 at the current density of 100 mA g^?1 at the first cycle, high capacity retention of 98 % over 30 cycles, and good rate performance. The superior electrochemical performance of nanocomposite is attributed to the carbon networks with turbostratic structure, which enhance the conductivity and alleviate the volume change of silicon.     

Preparation of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> hollow microsphere/graphene/carbon nanotube flexible film as a binder-free anode material for lithium-ion batteries

A flexible Co₃O₄ hollow microsphere/graphene/carbon nanotube hybrid film is successfully prepared through a facile filtration strategy and a subsequent thermally treated process. The composition, morphology, and structure of the as-prepared film are characterized by X-ray diffraction, X-ray photoelectron spectrometer, scanning electron microscopy, and transmission electron microscopy. Based on the morphology characterizations on the hybrid film, the Co₃O₄ hollow microspheres are uniformly and closely attached on three-dimensional (3D) graphene/carbon nanotubes (GR/CNTs) network, which decreases the agglomeration of Co₃O₄ microspheres effectively. In this hybrid film, the 3D GR/CNT network which enhances conductance as well as prevents aggregation is a benefit to help Co₃O₄ to exert its lithium storage capabilities sufficiently. When used as a binder-free anode material for lithium-ion batteries, the hybrid film delivers excellent electrochemical properties involving reversible capacity (863 mAh g^?1 at a current density of 100 mA g^?1) and rate performance (185 mAh g^?1 at a current density of 1600 mA g^?1).     

Graphene‐Based Phosphorus‐Doped Carbon as Anode Material for High‐Performance Sodium‐Ion Batteries

Graphene‐based phosphorus‐doped carbon (GPC) is prepared through a facile and scalable thermal annealing method by triphenylphosphine and graphite oxide as precursor. The P atoms are successfully doped into few layer graphene with two forms of P–O and P–C bands. The GPC used as anode material for Na‐ion batteries delivers a high charge capacity 284.8 mAh g^?1 at a current density of 50 mA g^?1 after 60 cycles. Superior cycling performance is also shown at high charge?discharge rate: a stable charge capacity 145.6 mAh g^?1 can be achieved at the current density of 500 mA g^?1 after 600 cycles. The result demonstrates that the GPC electrode exhibits good electrochemical performance (higher reversible charge capacity, super rate capability, and long‐term cycling stability). The excellent electrochemical performance originated from the large interlayer distance, large amount of defects, vacancies, and active site caused by P atoms doping. The relationship of P atoms doping amount with the Na storage properties is also discussed. This superior sodium storage performance of GPC makes it as a promising alternative anode material for sodium‐ion batteries.     

Three‐Dimensional Multilayer Assemblies of MoS2/Reduced Graphene Oxide for High‐Performance Lithium Ion Batteries

Three‐dimensional (3D) multilayer molybdenum disulfide (MoS₂)/reduced graphene oxide (RGO) nanocomposites are prepared by a solution‐processed self‐assembly based on the interaction using different sizes of MoS₂ and GO nanosheets followed by in situ chemical reduction. 3D multilayer assemblies with MoS₂ wrapped by large RGO nanosheets and good interface are observed by transmission electron microscopy. The interaction of Na⁺ ions with oxygen‐containing groups of GO is also investigated. The measurement of lithium ion batteries (LIBs) shows that MoS₂/RGO anode nanocomposite with a weight ratio of MoS₂ to GO of 3:1 exhibits an excellent rate performance of 750 mAh g^?1 at 3 A g^?1 outperforming many previous studies and a high reversible capacity up to ≈1180 mAh g^?1 after 80 cycles at 100 mA g^?1. Good rate performance and high capacity of MoS₂/RGO with 3D unique layered‐structures are attributed to the combined effects of continuous conductive networks of RGO, good interface facilitating charge transfer, and strong RGO sheets preventing the volume expansion. Results indicate that 3D multilayer MoS₂/RGO prepared by a facile solution‐processed assembly can be developed to be an excellent nanoarchitecture for high‐performance LIBs.     

Nanoporous carbon microspheres as matrix of sulfur to prepare sulfur/carbon cathode material for lithium–sulfur battery

A high specific surface area (2798.8 m² g^?1) of nanoporous carbon microsphere (NPCM) is prepared by activated carbon microsphere in hot CO₂ atmosphere, which is used as matrix material of sulfur to prepare NPCM/sulfur composite cathode material by a melt-diffusion method. The NPCM/sulfur composite cathode material with the sulfur content of 53.5% shows high discharge capacity; the initial discharge capacity is 1274 mAh g^?1 which maintains as high as 776.4 mAh g^?1 after 50 cycles at 0.1 C current. At high current density of 1 C, the NPCM/sulfur cathode material still shows initial discharge capacity of 830.3 mAh g^?1, and the reversible capacity retention is 78% after 50 cycles. To study the influence of different sulfur content of NPCM/sulfur cathode material to the performance of Li–S battery, the different sulfur content of NPCM/sulfur composite cathode materials is prepared by changing the thermal diffusion time and the ratio of sulfur powder to NPCM. The performance of NPCM/sulfur cathode material with different sulfur content is studied at a current of 0.1 C, which will be very important to the preparation of high-performance sulfur/carbon cathode material with appropriate sulfur content.     

Distinctive slit-shaped porous carbon encapsulating phosphorus as a promising anode material for lithium batteries

A distinctive structure of carbon materials for Li-ion batteries is proposed for the preparation of red phosphorus-carbon composites. The slit-shaped porous carbon is observed with aggregation of plate-like particles, whose isotherm belongs to the H3 of type IV. The density functional theory (DFT) method reveals the presence of micro-mesopores in the 0.5–5 nm size range. The unique size distribution plays an important role in adsorbing phosphorus and electrochemical performance. The phosphorus-slit-shaped porous carbon composite shows initial capacity of 2588 mAh g^?1, reversible capacity of 1359 mAh g^?1 at a current density of 100 mA g^?1. It shows an excellent coulombic efficiency of ～99 % after 50 cycles.     

Cu-supported carbon networks containing SnO<Subscript>2</Subscript> as three-dimensional anodes for lithium-ion batteries

Cu-supported SnO₂@C composite coatings constructed by interconnected carbon-based porous branches were fabricated by annealing Cu foils with films formed by knife coating DMF solution containing SnCl₂, polyacrylonitrile (PAN), and poly(methyl methacrylate) (PMMA) on their surface in vacuum. The carbon-based porous branches consist of amorphous carbon matrices, SnO₂ nanoparticles with a size of 30–100 nm mainly encapsulated inside, and many micropores with a size of 1–5 nm. The three-dimensional (3D) porous network structures of the SnO₂@C composite were achieved by volatilization of PMMA and pyrolysis of SnCl₂. The SnO₂@C composite coatings demonstrate good cyclic performance with a high reversible capacity of 642 mA h g^?1 after 100 cycles at a current density of 50 mA g^?1 without apparent capacity fading during cycling and excellent rate performance with a capacity of 276 mA h g^?1 at a high current density up to 10 A g^?1.