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.     

Hollow Silica Spheres Embedded in a Porous Carbon Matrix and Its Superior Performance as the Anode for Lithium‐Ion Batteries

Silica (SiO₂) is regarded as one of the most promising anode materials for lithium‐ion batteries due to the high theoretical specific capacity and extremely low cost. However, the low intrinsic electrical conductivity and the big volume change during charge/discharge cycles result in a poor electrochemical performance. Here, hollow silica spheres embedded in porous carbon (HSS–C) composites are synthesized and investigated as an anode material for lithium‐ion batteries. The HSS–C composites demonstrate a high specific capacity of about 910 mA h g^?1 at a rate of 200 mA g^?1 after 150 cycles and exhibit good rate capability. The porous carbon with a large surface area and void space filled both inside and outside of the hollow silica spheres acts as an excellent conductive layer to enhance the overall conductivity of the electrode, shortens the diffusion path length for the transport of lithium ions, and also buffers the volume change accompanied with lithium‐ion insertion/extraction processes.     

Enhanced rate performance of polypyrrole-coated sulfur/MWCNT cathode material: a kinetic study by electrochemical impedance spectroscopy

Lithium-sulfur batteries have a poor cyclability and inferior rate capability due to the shuttle effect of lithium polysulfides. To solve these problems, a sulfur-coated MWCNT composite (S/MWCNT) was coated with conductive polypyrrole (PPy) to trap the polysulfides and facilitate charge and lithium ion transport. From the contact angle measurement, it is found that the PPy coating improves the wettability of the S/MWCNT composite. Compared with the bare S/MWCNT composite, the PPy-coated S/MWCNT composite cathode exhibited improved cycle stability and high-rate performance. A reversible discharge capacity of 671 mAh g^?1 was maintained after 50 cycles at 3 C for the PPy-coated composite. The effect of PPy coating on kinetic property was investigated by electrochemical impedance spectroscopy (EIS). The electrolyte resistance, surface film resistance, charge transfer resistance, lithium ion diffusion coefficient, and exchange current density were evaluated from the EIS measurements. The EIS results reveal that the PPy coating increases both Li ion diffusion into the cathode and exchange current density. The as-prepared PPy-coated S/MWCNT composite can be considered to be a promising candidate for high capacity and high-rate performance cathode material.     

Synthesis and elevated temperature performance of a polypyrrole-sulfur-multi-walled carbon nanotube composite cathode for lithium sulfur batteries

A sulfur-multi-walled carbon nanotube composite (S/MWCNT) was prepared using a two-step procedure of liquid-phase infiltration and melt diffusion. Polypyrrole (PPy) conductive polymer was coated on the surface of the as-prepared S/MWCNT composite by in situ polymerization of pyrrole monomer to obtain PPy/S/MWCNT composite. The composite materials were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The electrochemical performance of the as-prepared cathode material was investigated at 25, 40, and 70 °C at various rates. It was found that temperature has dual effects on the performance of Li/S cells. Increasing the temperature, on one hand, facilitates the lithium ion transport through the cathode and, on the other hand, leads to faster dissolution of active material into the electrolyte. The PPy coating can effectively trap polysulfides in its porous structure, even at elevated temperatures, leading to the improvement of the discharge capacity, the cycle stability, and the coulombic efficiency. The electrochemical impedance spectroscopy (EIS) results reveal that the PPy coating reduces the formation of passive layer on the cathode surface, even at high temperatures, resulting in a better elevated temperature performance. A high reversible capacity of 945 mAh g^?1 was maintained after 50 cycles for the PPy/S/MWCNT composite at 70 °C at a rate of 0.5 C.     

Design and synthesis of a novel 3D hierarchical mesocarbon microbead as anodes for lithium ion batteries and sodium ion batteries

This work presents a feasible route for the facile synthesis of three-dimensional (3D) hierarchical mesocarbon microbead (MCMB) as anodes for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). The MCMB is oxidized by modified hummers method, and then the precursor is treated by hydrogen reduction to form the HMCMB. The HMCMB with graphene-like architecture has high specific surface, sufficient pore volume, and increased interlayer spacing, which can provide more active insertion/extraction sites and reduce the Li⁺/Na⁺ diffusion resistance. When employed as anode materials for LIBs and SIBs, HMCMB anodes exhibit improved lithium and sodium storage capability. The HMCMB delivers a higher reversible capacity (471.1 and 177.5 mAh g^?1 at 100 mA g^?1 after 100 cycles) and a good rate performance (250 and 121 mAh g^?1 even at 1000 mA g^?1) for LIBs and SIBs, respectively.     

A facile synthesis of heteroatom-doped carbon framework anchored with TiO<Subscript>2</Subscript> nanoparticles for high performance lithium ion battery anodes

Titanium dioxide (TiO₂)-based materials have been well studied because of the high safety and excellent cycling performance when employed as anode materials for lithium ion batteries (LIBs), whereas, the relatively low theoretical capacity (only 335 mAh g^?1) and serious kinetic problems such as poor electrical conductivity (~?10^?13S cm^?1) and low lithium diffusion coefficient (~?10^?9 to 10^?13 cm² s^?1) hinder the development of the TiO₂-based anode materials. To overcome these drawbacks, we present a facile strategy to synthesize N/S dual-doping carbon framework anchored with TiO₂ nanoparticles (NSC@TiO₂) as LIBs anode. Typically, TiO₂ nanoparticles are anchored into the porous graphene-based sheets with N, S dual doping feature, which is produced by carbonization and KOH activation process. The as-obtained NSC@TiO₂ electrode exhibits a high specific capacity of 250 mAh g^?1 with a coulombic efficiency of 99% after 500 cycles at 200 mA g^?1 and excellent rate performance, indicating its promising as anode material for LIBs.     

Nitrogen-doped carbon nanofiber decorated LiFePO<Subscript>4</Subscript> composites with superior performance for lithium-ion batteries

Nitrogen-doped carbon nanofiber (NCNF) decorated LiFePO₄ (LFP) composites are synthesized via an in situ hydrothermal growth method. Electrochemical performance results show that the embedded NCNF can improve electron and ion transfer, thereby resulting in excellent cycling performance. The as-prepared LFP and NCNF composites exhibit excellent electrochemical properties with discharge capacities of 188.9 mAh g^?1 (at 0.2 C) maintained at 167.9 mAh g^?1 even after 200 charge/discharge cycles. The electrode also presents a good rate capability of 10 C and a reversible specific capacity as high as 95.7 mAh g^?1. LFP composites are a potential alternative high-performing anode material for lithium ion batteries.     

Conductive TiN thin layer-coated nitrogen-doped anatase TiO<Subscript>2</Subscript> as high-performance anode materials for sodium-ion batteries

Nitrogen-doped anatase titanium oxide (N-TiO₂) with enhanced electronic conductivity induced by titanium nitride (TiN) thin layer coating was employed as high-performance anode material for sodium-ion batteries. The TiN thin layer can not only dramatically increase the electronic conductivity among crystal grains but also alleviate the volume expansion to consolidate the structure during long-term sodiation and desodiation process. The composite exhibits an excellent electrochemical performance, delivering a high specific capacity of 226.9 mA h g^?1 at 0.1 C and owning excellent rate capability of 158.3 mA h g^?1 at 10 C high rate. Moreover, the composite has no obvious capacity decay after 500 cycles at 1 C, showing its superior cycling performance. The enhancement of electrochemical performance may be attributed to the faster kinetics of sodium ion sodiation/desodiation, which could be a result of enhanced electronic conductivity due to the formation of TiN thin layer coating.     

Theoretical prediction of borophene monolayer as anode materials for high-performance lithium-ion batteries

Three morphologies of two-dimension Boron with metallicity have been successfully synthetized by experiments. To access the potential of β₁₂ borophene (□) and χ₃ borophene monolayer (◇) as anode materials for lithium ion batteries, first-principles calculations based on density functional theory (DFT) are performed. Lithium atom is preferentially absorbed over the center of the hexagonal B atom hollow of β₁₂ and χ₃ borophene monolayer. The fully lithium storage phase of β₁₂ and χ₃ borophene monolayer corresponds to Li₈B₁₀ and Li₈B₁₆ with a theoretical specific capacity of 1983 and 1240 mA h g^?1, respectively, much larger than other two-dimension materials. Interestingly, lithium ion diffusion on β₁₂ borophene (□) monolayer is extremely fast with a low-energy barrier of 41 meV. Meanwhile, lithiated-borophene monolayer shows enhanced metallic conductivity during the whole lithiation process. Compared to the buckled borophene (△), the extremely enhanced lithium adsorption energy of β₁₂ and χ₃ phase with vacancies weakens lithium ion diffusion. Therefore, it is important to control the generation of vacancy in the buckled borophene (△) anode for lithium ion batteries. Borophene is a promising candidate with high capacity and high rate capability for anode material in lithium ion batteries.     

Urea-assisted solvothermal synthesis of monodisperse multiporous hierarchical micro/nanostructured ZnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> microspheres and their lithium storage properties

High-quality monodisperse multiporous hierarchical micro/nanostructured ZnCo₂O₄ microspheres have been fabricated by calcinating the Zn_1/3Co_2/3CO₃ precursor prepared by urea-assisted solvothermal method. The as-prepared products are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and Brunauer-Emmett-Teller (BET) measurement to study the crystal phase and morphology. When tested as anode material for lithium ion batteries, the multiporous ZnCo₂O₄ microspheres exhibit an initial discharge capacity of 1,369 mAh g^?1 (3,244.5 F cm^?3) and retain stable capacity of 800 mAh g^?1 (1,896 F cm^?3) after 30 cycles. It should be noted that the good electrochemical performances can be attributed to the porous structure composed of interconnected nanoscale particles, which can promote electrolyte diffusion and reduce volume change during discharge/charge processes. More importantly, this ZnCo₂O₄ 3D hierarchical structures provide a large number of active surface position for Li⁺ diffusion, which may contribute to the improved electrochemical performance towards lithium storage.     

Performance of developed natural vein graphite as the anode material of rechargeable lithium ion batteries

Electrochemical performance of natural vein graphite as an anode material for the rechargeable Li-ion battery (LIB) was investigated in this study. Natural graphite exhibits many favorable characteristics such as, high reversible capacity, appropriate potential profile, and comparatively low cost, to be an anode material for the LIB. Among the natural graphite varieties, the vein graphite typically possesses very high crystallinity together with extensively high natural purity, which in turn reduces the cost for purification. The developed natural vein graphite variety used for this study, possessed extra high purity with modified surface characteristics. Half-cell testing was carried out using CR 2032 coin cells with natural vein graphite as the active material and 1 M LiPF₆ (EC: DMC; vol. 1:1) as the electrolyte. Galvanostatic charge–discharge, cyclic voltammetry, and impedance analysis revealed a high and stable reversible capacity of 378 mA h g^?1, which is higher than the theoretical capacity (372 mA h g^?1 for LiC₆). Further, the observed low irreversible capacity acquiesces to the high columbic efficiency of over 99.9%. Therefore, this highly crystalline developed natural vein graphite can be presented as a readily usable low-cost anode material for Li-ion rechargeable batteries.     

LiPON as a protective layer on graphite anode to extend the storage life of Li-ion battery at elevated temperature

A thin-film lithium phosphorous oxynitride (LiPON) layer on the top of a graphite anode is synthesized via radio frequency magnetron sputtering, whereas the thickness of the film is about 0.3 ~ 1.3 μm. The field emission scanning electron microscopy on the samples confirms the even-coated layer on the anode, while the thickness of layer is reconfirmed by weighing the area density of sputtered anode. The storage experiment at elevated temperature of LiNi_0.8Co_0.15Al_0.05O₂/graphite cells with and without a LiPON layer on anode reveals that the LiPON layer on the anode would restrain the capacity loss when compared with bare anode. Moreover, it is found that a thicker LiPON layer on anode would provide better capacity retention during storage aging. Meanwhile, the electrochemical impedance spectroscopy is recorded during aging and its equivalent circuit simulation is proposed. Also, the anode surface morphology with and without a LiPON layer is observed before and after aging. Based on these investigations and analysis, we conclude that the LiPON layer on the top of the anode would act as a protective layer and improve the capacity retention during storage aging at elevated temperature.     

Improvement in rate capability of lithium-rich cathode material Li[Li<Subscript>0.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>]O<Subscript>2</Subscript> by Mo substitution

Lithium-rich cathode material Li[Li_0.2Ni_0.13Co_0.13Mn_0.54]O₂ doped with trace Mo is successfully synthesized by a sol-gel method. The X-ray diffraction patterns show that trace Mo substitution increases the inter-layer space of the material, of which is benefiting to lithium ion insertion/extraction among the electrode materials. The (CV) tests demonstrate the decrease of polarization, and on the other hand, the lithium ion diffusion coefficient (D _Li) of the modified material turns out to be larger, which indicates a faster electrochemical process. As a result, the Mo doped material possesses high rate performance and good cycling stability, and the initial discharge capacity reaches 149.3 mAh g^?1 at a current density of 5.0 °C, and the residual capacity is 144.0 mAh g^?1 after 50 cycles with capacity retention of 96.5 % in the potential range of 2.0–4.8 V at room temperature.     

Sulfur/microporous carbon composites for Li-S battery

A commercial carbon black with microporous framework is used as carbon matrix to prepare sulfur/microporous carbon (S/MC) composites for the cathode of lithium sulfur (Li-S) battery. The S/MC composites with 50, 60, and 72 wt.% sulfur loading are prepared by a facile heat treatment method. Electrochemical performance of the as-prepared S/MC composites are measured by galvanostatic charge/discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), with carbonate-based electrolyte of 1.0 M LiPF₆/(PC-EC-DEC). The composite with 50 wt.% sulfur presents the optimized electrochemical performance, including the utilization of active sulfur, discharge capacity, and cycling stability. At the current density of 50 mA g^?1, it can demonstrate a high initial discharge capacity of 1624.5 mAh g^?1. Even at the current density of 800 mA g^?1, the initial capacity of 1288.6 mAh g^?1 can be obtained, and the capacity can still maintain at 522.8 mAh g^?1 after 180 cycles. The remarkably improved electrochemical performance of the S/MC composite with 50 wt.% sulfur are attributed to the carbon matrix with microporous structure, which can effectively enhance the electrical conductivity of the sulfur cathode, suppress the loss of active material during charge/discharge processes, and restrain the migration of polysulfide ions to the lithium anode.     

DTT-doped MWCNT coating for checking shuttle effect of lithium-sulfur battery

In order to improve the rate and reversible capacity of lithium-sulfur (Li-S) battery, a reagent of dithiothreitol (DTT) was utilized to check the dissolution and shuttle of long-chain lithium polysulfides (LiPSs) by cutting the disulfide bond (–S–S– bonds) in them. The slurry of DTT-doped multi-walled carbon nanotubes (MWCNTs) was coated on the surface of sulfur cathode as a shield to slice the long-chain LiPSs to short-chain ones for checking the dissolution and migration of LiPSs to lithium anode. The morphology and structure of the electrodes were observed by scanning electron microscopy (SEM). The electrochemical performance was tested by galvanostatic charge-discharge, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The initial discharge capacity of S-DTT- carbon nanotube paper (CNTP) electrode reached 1670 and 949 mAh/g at 0.05 and 2 C respectively with a coulombic efficiency of over 99%. The electrode maintained a reversible specific capacity of 949 mAh/g after 45 cycles at 2 C. This suggested that the DTT-doped MWCNT coating can restrain shuttle effect and improve the rate and capacity of Li-S battery. The S-DTT-CNTP electrode not only accommodates the volume expansion but also provides stable electronics and ions channels.     

A microporous carbon derived from phenol–melamine–formaldehyde resin by K2CO3 activation for lithium ion batteries

A microporous carbon material with large surface area was prepared by carbonizing and activating of phenol–melamine–formaldehyde resin, using K₂CO₃ as activation reagent. The textural characteristics of the carbon materials were characterized by scanning electron microscope, X-ray diffraction, Raman spectra, Brunauer–Emmett–Teller, elemental analyses, respectively. Results showed that the surface area and pore diameter of the activated carbon were 1,610 m² g^?1 and less than 2 nm. Electrochemical lithium insertion properties were also investigated. At a current density of 100 mA g^?1, the activated carbon showed an enormous first-discharge capacity of 2,610 mAh g^?1 and the first charge capacity of 992 mAh g^?1. From the second cycle, the coulombic efficiency went up rapidly to above 95 %. The results indicated it may be a promising candidate as an anode material for lithium secondary batteries.     

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.     

Nanoporous carbon microspheres as anode material for enhanced capacity of lithium ion batteries

Nanoporous carbon microspheres (NCMs) are prepared by a one-step carbonizing and activating resorcinol?formaldehyde polymer spheres (RFs) in inert and CO₂ atmosphere for anode materials of lithium-ion batteries (LIBs). Compared with RFs carbon microspheres (RF-C), after activating with hot CO₂, the NCMs with porous structure and high BET surface area of 2798.8 m² g^?1, which provides abundant lithium-ion storage site as well as stable lithium-ion transport channel. When RF-C and NCM are used to anode material for LIBs, at the same current density of 210 mA g^?1, the initial specific discharge capacity are 482.4 and 2575.992 mA h g^?1, respectively; after 50 cycles, the maintain capacity are 429.379 and 926.654 mA h g^?1, respectively. The porous spherical structure of NCM possesses noticeably lithium-ion storage capability, which exhibits high discharge capacity and excellent cycling stability at different current density. The CO₂ activating carbonaceous materials used in anode materials can tremendously enhance the capacity storage, which provides a promising modification strategy to improve the storage capacity and cyclic stability of carbonaceous anode materials for LIBs.     

Influence of post-calcination treatment on the spinel lithium titanium oxide anode material for lithium ion batteries

The influence of post-calcination treatment on spinel Li₄Ti₅O₁₂ anode material is extensively studied combining with a ball-milling-assisted rheological phase reaction method. The post-calcinated Li₄Ti₅O₁₂ shows a well distribution with expanded gaps between particles, which are beneficial for lithium ion mobility. Electrochemical results exhibit that the post-calcinated Li₄Ti₅O₁₂ delivers an improved specific capacity and rate capability. A high discharge capacity of 172.9 mAh g^?1 and a reversible charge capacity of 171.1 mAh g^?1 can be achieved at 1 C rate, which are very close to its theoretical capacity (175 mAh g^?1). Even at the rate of 20 C, the post-calcinated Li₄Ti₅O₁₂ still delivers a quite high charge capacity of 124.5 mAh g^?1 after 50 cycles, which is much improved over that (43.9 mAh g^?1) of the pure Li₄Ti₅O₁₂ without post-calcination treatment. This excellent electrochemical performance should be ascribed to the post-calcination process, which can greatly improve the lithium ion diffusion coefficient and further enhance the electrochemical kinetics significantly.     

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.