Improved pseudocapacitive charge storage in highly ordered mesoporous TiO2/carbon nanocomposites as high-performance Li-ion hybrid supercapacitor anodes

A Li-ion hybrid supercapacitor (Li-HSCs), an integrated system of a Li-ion battery and a supercapacitor, is an important energy-storage device because of its outstanding energy and power as well as long-term cycle life. In this work, we propose an attractive material (a mesoporous anatase titanium dioxide/carbon hybrid material, m-TiO₂-C) as a rapid and stable Li⁺ storage anode material for Li-HSCs. m-TiO₂-C exhibits high specific capacity (∼198 mA h g⁻¹ at 0.05 A g⁻¹) and promising rate performance (∼90 mA h g⁻¹ at 5 A g⁻¹) with stable cyclability, resulting from the well-designed porous structure with nanocrystalline anatase TiO₂ and conductive carbon. Thereby, it is demonstrated that a Li-HSC system using a m-TiO₂-C anode provides high energy and power (∼63 W h kg⁻¹, and ∼4044 W kg⁻¹).

A mesoporous TiO₂/carbon nanocomposite prepared by block copolymer self-assembly improves pseudocapacitive behavior and achieves high energy/power density Li-ion hybrid supercapacitors.     

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.     

Synthesis of hierarchical Sn/SnO nanosheets assembled by carbon-coated hollow nanospheres as anode materials for lithium/sodium ion batteries

Tin-based anode materials have aroused interest due to their high capacities. Nevertheless, the volume expansion problem during lithium insertion/extraction processes has severely hindered their practical application. In particular, nano–micro hierarchical structure is attractive with the integrated advantages of nano-effect and high thermal stability of the microstructure. Herein, hierarchical Sn/SnO nanosheets assembled by carbon-coated hollow nanospheres were successfully synthesized by a facile glucose-assisted hydrothermal method, in which the glucose served as both morphology-control agent and carbon source. The hierarchical Sn/SnO nanosheets exhibit excellent electrochemical performances owing to the unique configuration and carbon coating. Specifically, a reversible high capacity of 2072.2 mA h g⁻¹ was observed at 100 mA g⁻¹. Further, 964.1 mA h g⁻¹ after 100 cycles at 100 mA g⁻¹ and 820.4 mA h g⁻¹ at 1000 mA g⁻¹ after 300 cycles could be obtained. Encouragingly, the Sn/SnO also presents certain sodium ion storage properties. This facile synthetic strategy may provide new insight into fabricating high-performance Sn-based anode materials combining the advantages of both structure and carbon coating.

Hierarchical Sn/SnO nanosheets assembled by carbon-coated hollow nanospheres with promising lithium and sodium storage performances.     

Sodium insertion/extraction investigations into zinc ferrite nanospheres as a high performance anode material

Electrode materials with high fast charging and high capacity are urgently required for the realization of sodium-ion batteries (SIBs). In this work, zinc ferrite (ZnFe₂O₄) nanospheres have been prepared by the simple hydrothermal route and the structural analysis of ZnFe₂O₄ was evaluated by using X-ray diffraction. The morphology and microstructural characterizations are obtained using scanning electron microscopy and transmission electron microscopy. The results indicate that a single phase material was obtained with uniform sphere-like morphology and high crystallinity. The Brunauer–Emmett–Teller method was employed to determine the specific surface area of the ZnFe₂O₄ nanospheres which has been calculated to be 32 m² g⁻¹. The electrochemical results indicate that the composite possesses high sodium storage capability (478 mA h g⁻¹), and good cycling stability (284 mA h g⁻¹ at 100^th cycle) and rate capability (78 mA h g⁻¹ at 2 A g⁻¹). The high sodium storage performance of the ZnFe₂O₄ electrode is ascribed to the mesoporous nature of the ZnFe₂O₄ nanospheres. Further, sodium kinetics and the reaction mechanism in ZnFe₂O₄ nanospheres have been elucidated using electrochemical impedance spectroscopy, galvanostatic intermittent titration technique, ex situ TEM, and XAS. The acquired results indicate sluggish kinetics, reversibility of the material, and the stable structure of ZnFe₂O₄. Therefore, such a structure can be considered to be an attractive contender as a low cost anode for SIBs.

Electrode materials with high fast charging and high capacity are urgently required for the realization of sodium-ion batteries (SIBs).     

Off-stoichiometric Na3−3xV2+x(PO4)3/C nanocomposites as cathode materials for high-performance sodium-ion batteries prepared by high-energy ball milling

Na₃V₂(PO₄)₃ (NVP) is regarded as a promising cathode material for sustainable energy storage applications. Here we present an efficient method to synthesize off-stoichiometric Na_3−3xV_2+x(PO₄)₃/C (x = 0–0.10) nanocomposites with excellent high-rate and long-life performance for sodium-ion batteries by high-energy ball milling. It is found that Na_3−3xV_2+x(PO₄)₃/C nanocomposites with x = 0.05 (NVP-0.05) exhibit the most excellent performance. When cycled at a rate of 1C in the range of 2.3–3.9 V, the initial discharge capacity of NVP-0.05 is 112.4 mA h g⁻¹, which is about 96% of its theoretical value (117.6 mA h g⁻¹). Even at 20C, it still delivers a discharge capacity of 92.3 mA h g⁻¹ (79% of the theoretical capacity). The specific capacity of NVP-0.05 is as high as 100.7 mA h g⁻¹ after 500 cycles at 5C, which maintains 95% of its initial value (106 mA h g⁻¹). The significantly improved electrochemical performance of NVP-0.05 is attributed to the decrease of internal resistance and increase of the Na⁺ ion diffusion coefficient.

Na₃V₂(PO₄)₃ (NVP) is regarded as a promising cathode material for sustainable energy storage applications.     

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     

In situ preparation of an anatase/rutile-TiO2/Ti3C2Tx hybrid electrode for durable sodium ion batteries

Herein, a facile one-step method is developed to in situ prepare crystalline anatase and rutile TiO₂ nanocrystals on Ti₃C₂T_x by regulating the metastable Ti ions. The combination of TiO₂ nanocrystals and Ti₃C₂T_x not only introduces extensive accessible sites for Na⁺ storage, but also promotes the charge transport by efficiently relieving the collapse of Ti₃C₂T_x. Compared with pristine Ti₃C₂T_x, the optimized TiO₂/Ti₃C₂T_x hybrid electrode (anatase/rutile-TiO₂/Ti₃C₂T_x, A/R-TiO₂/Ti₃C₂T_x) exhibits a desirable specific surface area (22.5 m² g⁻¹), an ultralow charge transfer resistance (42.46 Ω) and excellent ion diffusion (4.01 × 10⁻¹⁴). Remarkably, rich oxygen vacancies are produced on TiO₂/Ti₃C₂T_x which is beneficial to enhance the insertion/de-insertion of Na⁺ during the charge/discharge process. As a result, the A/R-TiO₂/Ti₃C₂T_x delivers a high average capacity of 205.4 mA h g⁻¹ at 100 mA g⁻¹ and a desirable capacitance retention rate of 84.7% can be achieved after 600 cycles at 500 mA g⁻¹.

A facile one-step method is developed to in situ prepare crystalline anatase and rutile TiO₂ nanocrystalline on Ti₃C₂T_x by regulating the metastable Ti ions.     

TiO2-decorated porous carbon nanofiber interlayer for Li–S batteries

Lithium–sulfur (Li–S) batteries are the most promising energy storage systems owing to their high energy density. However, shuttling of polysulfides detracts the electrochemical performance of Li–S batteries and thus prevents the commercialization of Li–S batteries. Here, TiO₂@porous carbon nanofibers (TiO₂@PCNFs) are fabricated via combining electrospinning and electrospraying techniques and the resultant TiO₂@PCNFs are evaluated for use as an interlayer in Li–S batteries. TiO₂ nanoparticles on PCNFs are observed from SEM and TEM images. A high initial discharge capacity of 1510 mA h g⁻¹ is achieved owing to the novel approach of electrospinning the carbon precursor and electrospraying TiO₂ nanoparticles simultaneously. In this approach TiO₂ nanoparticles capture polysulfides with strong interaction and the PCNFs with high conductivity recycle and re-use the adsorbed polysulfides, thus leading to high reversible capacity and stable cycling performance. A high reversible capacity of 967 mA h g⁻¹ is reached after 200 cycles at 0.2C. The cell with the TiO₂@PCNF interlayer also delivers a reversible capacity of around 1100 mA h g⁻¹ at 1C, while the cell without the interlayer exhibits a lower capacity of 400 mA h g⁻¹. Therefore, this work presents a novel approach for designing interlayer materials with exceptional electrochemical performance for high performance Li–S batteries.

Lithium–sulfur (Li–S) batteries are the most promising energy storage systems owing to their high energy density.     

Porous carbon-confined CoxSy nanoparticles derived from ZIF-67 for boosting lithium-ion storage

Reasonable regulation and synthesis of hollow nanostructure materials can provide a promising electrode material for lithium-ion batteries (LIBs). In this work, utilizing a metal–organic framework (MOF, ZIF-67) as the raw material and template, a composite of Co_xS_y with a carbon shell is successfully formed through a hydrothermal vulcanization and a subsequent high temperature sintering process. The as-obtained Co_xS_y(700) material sintered at 700 °C has a large specific surface area, and at the same time possesses a hollow carbon shell structure. Benefiting from unique structural advantages, the volume change during the electrochemical reaction can be well alleviated, and thus the structural stability is greatly improved. The presence of the carbon matrix can also offer sufficient ion/electron transfer channels, contributing to the enhanced electrochemical performance. As a result, the Co_xS_y(700) electrode can deliver an excellent capacity of 875.6 mA h g⁻¹ at a current density of 100 mA g⁻¹. Additionally, a high-capacity retention of 88% is achieved after 1000 cycles when the current density is increased to 500 mA g⁻¹, and exhibiting a prominent rate capability of 526.5 mA h g⁻¹, simultaneously. The novel synthesis route and considerable electrochemical properties presented by this study can afford guidance for the exploration of high-performance cobalt sulfide anodes in LIBs.

A composite of Co_xS_y and carbon shell is successfully formed, and as a result it can well alleviate volume change as well as offer sufficient ions/electrons transfer channels, contributing to enhance electrochemical performance.     

Homojunction and defect synergy-mediated electron–hole separation for solar-driven mesoporous rutile/anatase TiO2 microsphere photocatalysts

The photocatalytic hydrogen evolution of TiO₂ is deemed to be one of the most promising ways of converting solar energy to chemical energy; however, it is a challenge to improve the photo-generated charge separation efficiency and enhance solar utilization. Herein, black mesoporous rutile/anatase TiO₂ microspheres with a homojunction and surface defects have been successfully synthesized by an evaporation-induced self-assembly, solvothermal and high-temperature surface hydrogenation method. The H500-BMR/ATM (HX-BMR/ATM, where X means the different hydrogen calcination temperatures) materials not only possess a mesoporous structure and relatively high specific surface area of 39.2 m² g⁻¹, but also have a narrow bandgap (∼2.87 eV), which could extend the photoresponse to the visible light region. They exhibit high photocatalytic hydrogen production (6.4 mmol h⁻¹ g⁻¹), which is much higher (approximately 1.8 times) than that of pristine mesoporous rutile/anatase TiO₂ microspheres (3.58 mmol h⁻¹ g⁻¹). This enhanced photocatalytic hydrogen production property is attributed to the synergistic effect of the homojunction and surface defects in improving efficient electron–hole separation and high utilization of solar light. This work proposes a new approach to improve the performance of photocatalytic hydrogen production and probably offers a new insight into fabricating other high-performance photocatalysts.

Mesoporous rutile/anatase TiO₂ microspheres with surface defects are fabricated and exhibit excellent solar-driven photocatalytic performance due to synergistic effect of the homojunction and surface defects favoring efficient e–h separation.     

Electrochemical properties of TiOx/rGO composite as an electrode for supercapacitors

Transition metal oxides are known as the active materials for capacitors. As a class of transition metal oxide, Magnéli phase TiO_x is particularly attractive because of its excellent conductivity. This work investigated the electrochemical characteristics of TiO_x and its composite with reduced graphene oxide (rGO). Two types of TiO_x, i.e. low and high reduction extent, were employed in this research. Electrochemical impedance spectroscopy revealed that TiO_x with lower reduction extent delivered higher electro-activity and charge transfer resistance at the same time. However, combining 10% of low-reduction state TiO_x and rGO using a simple mixing process delivered a high specific capacitance (98.8 F g⁻¹), which was higher than that of standalone rGO (49.5 F g⁻¹). A further improvement in the specific capacitance (102.6 F g⁻¹) was given by adding PEDOT:PSS conductive polymer. Results of this research gave a basic understanding in the electrochemical behavior of Magnéli phase TiO_x for the utilization of this material as supercapacitor in the future.

This work investigated the electrochemical characteristics of TiO_x and its composite with reduced graphene oxide.     

Dendritic nanostructured FeS2-based high stability and capacity Li-ion cathodes

Here we show that dendritic architectures are attractive as the basis of hierarchically structured battery electrodes. Dendritically structured FeS₂, synthesized via simple thermal sulfidation of electrodeposited dendritic α-Fe, was formed into an electrode and cycled vs. lithium. The reversible capacities of the dendritic FeS₂ cathode were 560 mA h g⁻¹ at 0.5C and 533 mA h g⁻¹ at 1.0C after 50 cycles over 0.7–3.0 V. Over 0.7–2.4 V, where the electrode is more stable, the reversible capacities are 348 mA h g⁻¹ at 0.2C and 179 mA h g⁻¹ at 1.0C after 150 cycles. The good cycling performance and high specific capacities of the dendritic FeS₂ cathodes are attributed to the ability of a dendritic structure to provide good ion and electron conducting pathways, and a large surface area. Importantly, the dendritic structure appears capable of accommodating volume changes imposed by the lithiation and delithiation process. The presence of a Li_2−xFeS₂ phase is indicated for the first time by high-resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy (STEM) electron energy loss spectroscopy (EELS). We suspect this phase is what enables electrochemical cycling to possess high reversibility over 0.7–2.4 V.

High performance dendritically structured FeS₂ cathodes are systemically studied. The dendritic structure is resistant to volume changes during cycling, increasing cyclability. The presence of Li_2–xFeS₂, which also enhances cyclability, is confirmed.     

Facile synthesis of mesoporous NixCo9−xS8 hollow spheres for high-performance supercapacitors and aqueous Ni/Co–Zn batteries

Porous micro/nanostructure electrode materials have always contributed to outstanding electrochemical energy storage performances. Co₉S₈ is an ideal model electrode material with high theoretical specific capacity due to its intrinsic two crystallographic sites of cobalt ions. In order to improve the conductivity and specific capacitance of Co₉S₈, nickel ions were introduced to tune the electronic structure of Co₉S₈. The morphology design of the mesoporous hollow sphere structure guarantees cycle stability and ion diffusion. In this work, Ni_xCo_9−xS₈ mesoporous hollow spheres were synthesized via a facile partial ion-exchange of Co₉S₈ mesoporous hollow spheres without using a template, boosting the capacitance to 1300 F g⁻¹ at the current density of 1 A g⁻¹. Compared with the pure Co₉S₈ and Ni-Co₉S₈-30%, Ni-Co₉S₈-60% exhibited the best supercapacitor performance, which was ascribed to the maximum Ni ion doping with morphology and structure retention, enhanced conductivity and stabilization of Co³⁺ in the structure. Therefore, Ni/Co–Zn batteries were fabricated by using a Zn plate as the anode and Ni-Co₉S₈-60% as the cathode, which deliver a high energy density of 256.5 W h kg⁻¹ at the power density of 1.69 kW kg⁻¹. Furthermore, the Ni/Co–Zn batteries exhibit a stable cycling after 3000 repeated cycles with capacitance retention of 69% at 4 A g⁻¹. This encouranging result might provide a new perspective to optimize Co₉S₈-based electrodes with superior supercapacitor and Ni/Co–Zn battery performances.

Mesoporous NiCo₉S₈-0.6 hollow spheres as a high-performance supercapacitor and aqueous Ni/Co–Zn battery.     

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.     

Lychee-like TiO2@TiN dual-function composite material for lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries are promising candidates for next generation rechargeable batteries because of their high energy density of 2600 W h kg⁻¹. However, the insulating nature of sulfur and Li₂S, the “shuttle effect” of lithium polysulfides (LiPSs), and the volumetric change of sulfur electrodes limit the practical application of Li–S batteries. Here, lychee-like TiO₂@TiN hollow spheres (LTTHS) have been developed that combine the advantages of high adsorption TiO₂ and high conductivity TiN to achieve smooth adsorption/spread/conversion of LiPSs and use them as a sulfur host material in Li–S batteries for the first time. The cathode exhibits an initial specific capacity of 1254 mA h g⁻¹ and a reversible capacity of 533 mA h g⁻¹ after 500 cycles at 0.2C, which corresponds to an average coulombic efficiency up to 99%. The cell with the LTTHS@S cathode achieved an extended lifespan of over 1000 cycles. Such good performance can be assigned to the good adsorption and catalysis of the dual-function TiO₂@TiN composite. This work proved that the TiO₂@TiN composite can be an attractive matrix for sulfur cathodes.

Lithium–sulfur (Li–S) batteries are promising candidates for next generation rechargeable batteries because of their high energy density of 2600 W h kg⁻¹.     

A new approach to improve the electrochemical performance of ZnMn2O4 through a charge compensation mechanism using the substitution of Al3+ for Zn2+

ZnMn₂O₄ and Zn_1−xAl_xMn₂O₄ were synthesized by a spray drying process followed by an annealing treatment. Their structural and electrochemical characteristics were investigated by SEM, XRD, XPS, charge–discharge tests and EIS. XPS data indicate that the substitution of Al³⁺ for Zn²⁺ causes manganese to be in a mixed valence state by a charge compensation mechanism. Moreover, the presence of this charge compensation significantly improves the electrochemical performance of Zn_1−xAl_xMn₂O₄, such as increasing the initial coulombic efficiency, stabilizing the cycleability as well as improving the rate capability. The sample with 2% Al doping shows the best performance, with a first cycle coulombic efficiency of 69.6% and a reversible capacity of 597.7 mA h g⁻¹ after 100 cycles. Even at the high current density of 1600 mA g⁻¹, it still retained a capacity of 558 mA h g⁻¹.

This work reports the nonequivalent substitution of ZnMn₂O₄. This is a new approach to improve the electrochemical performance of ZnMn₂O₄ through a charge compensation mechanism using the substitution of Al³⁺ for Zn²⁺.     

Mesoporous TiO2 coating on carbon–sulfur cathode for high capacity Li–sulfur battery

In this paper, a meso-porous TiO₂ (titania) coating is shown to effectively protect a carbon–sulfur composite cathode from polysulfide dissolution. The cathode consisted of a sulfur impregnated carbon support coated with a few microns thick mesoporous titania layer. The carbon–sulfur cathode is made using activated carbon powder (ACP) derived from biomass. The mesoporous titania coated carbon–sulfur cathodes exhibit a retention capacity after 100 cycles at C/3 rate (433 mA g ⁻¹) and stabilized at a capacity around 980 mA h g⁻¹. The electrochemical impedance spectroscopy (EIS) of the sulfur cathodes suggests that the charge transfer resistance at the anode, (R_act) is stable for the titania coated sulfur electrode in comparison to a continuous increase in R_act for the uncoated electrode implying mitigation of polysulfide shuttling for the protected cathode. Stability in the cyclic voltammetry (CV) data for the first 5 cycles further confirms the polysulfide containment in the titania coated cathode while the uncoated sulfur electrode shows significant irreversibility in the CV with considerable shifting of the voltage peak positions. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) studies confirm the adsorption of soluble polysulfides by mesoporous titania.

Mesoporous TiO₂ coating on carbon–sulfur cathode with simple electrical contact for high capacity Li–S battery.     

Ultrafast-charging and long cycle-life anode materials of TiO2-bronze/nitrogen-doped graphene nanocomposites for high-performance lithium-ion batteries

Emerging technologies demand a new generation of lithium-ion batteries that are high in power density, fast-charging, safe to use, and have long cycle lives. This work reports charging rates and specific capacities of TiO₂(B)/N-doped graphene (TNG) composites. The TNG composites were prepared by the hydrothermal method in various reaction times (3, 6, 9, 12, and 24 h), while the N-doped graphene was synthesized using the modified Hummer''s method followed by a heat-treatment process. The different morphologies of TiO₂ dispersed on the N-doped graphene sheet were confirmed as anatase-nanoparticles (3, 6 h), TiO₂(B)-nanotubes (9 h), and TiO₂(B)-nanorods (12, 24 h) by XRD, TEM, and EELS. In electrochemical studies, the best battery performance was obtained with the nanorods TiO₂(B)/N-doped graphene (TNG-24h) electrode, with a relatively high specific capacity of 500 mA h g⁻¹ at 1C (539.5 mA g⁻¹). In long-term cycling, excellent stability was observed. The capacity retention of 150 mA h g⁻¹ was observed after 7000 cycles, at an ultrahigh current of 50C (27.0 A g⁻¹). The synthesized composites have the potential for fast-charging and have high stability, showing potential as an anode material in advanced power batteries for next-generation applications.

The TiO₂-bronze/nitrogen-doped graphene nanocomposites have the potential for fast-charging and have high stability, showing potential as an anode material in advanced power batteries for next-generation applications.     

Rapid fabrication of porous silicon/carbon microtube composites as anode materials for lithium-ion batteries

Herein, we present a simple and rapid method to synthesize porous silicon/carbon microtube composites (PoSi/CMTs) by adopting a unique configuration of acid etching solution. The CMTs can act as both conductive agent and buffer for Si volume change during the charge and discharge process. The highly reversible capacity and excellent rate capability can be ascribed to the structure, where porous silicon powders are wrapped by a network of interwoven carbon microtubes. The composites show specific capacities of more than 1712 mA h g⁻¹ at a current density of 100 mA g⁻¹, 1566 mA h g⁻¹ at 200 mA g⁻¹, 1407 mA h g⁻¹ at 400 mA g⁻¹, 1177 mA h g⁻¹ at 800 mA g⁻¹, 1107 mA h g⁻¹ at 1000 mA g⁻¹, 798 mA hg⁻¹ at 2000 mA g⁻¹, and 581 mA h g⁻¹ at 3000 mA g⁻¹ and maintain a value of 1127 mA h g⁻¹ after 100 cycles at a current density of 200 mA g⁻¹. Electrochemical impedance spectroscopy (EIS) measurements prove that charge transfer resistance of PoSi/CMT composites is smaller than that of pure PoSi. In this study, we propose a quick, economical and feasible method to prepare silicon-based anode materials for lithium-ion batteries.

We added additives to the acid etching solution and prepared the silicon/carbon microtubes composites using a simple and fast method.     

Chitosan-grafted-poly(aniline-co-anthranilic acid) as a water soluble binder to form 3D structures for Si anodes

We graft an electrically conductive poly(aniline-co-anthranilic acid) (PAAA) polymer capable of interacting with Si particles onto chitosan, a natural hydrophilic polymer, to form a chitosan-grafted-PAAA (CS-g-PAAA) copolymer, and use it as a new water soluble polymeric binder for Si anodes to relieve the physical stress resulting from Si volume change during charge/discharge cycles. The carboxylic acid functional groups within the PAAA structure, as well as the chitosan functional groups, bind to silicon particles to form a stable 3D network, resulting in high adhesion. Because the binder is conductive, the electrode using the CS-g-PAAA-8 : 1 with an optimal composition ratio of CS to PAAA of 8 : 1 shows a high initial capacity of 2785.6 mA h g⁻¹, and maintains a high capacity of 1301.0 mA h g⁻¹ after 300 cycles. We also extract chitosan directly from crab shells, and fabricate a Si@ECS-g-PAAA electrode by grafting PAAA onto the extracted-chitosan (ECS). This electrode records an initial capacity of 3057.3 mA h g⁻¹, and maintains a high capacity of 1408.8 mA h g⁻¹ with 51.4% retention after 300 cycles. Overall, we develop a polymeric binder with outstanding cell properties, ease of fabrication, and high water solubility for Si anodes by grafting a conductive PAAA onto chitosan.

We develop a polymeric binder with outstanding cell properties, and high water solubility for Si anodes by grafting a conductive PAAA onto chitosan.