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.     

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.     

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.     

Dandelion-like mesoporous Co<Subscript>3</Subscript>O<Subscript>4</Subscript> as anode materials for lithium ion batteries

A dandelion-like mesoporous Co₃O₄ was fabricated and employed as anode materials of lithium ion batteries (LIBs). The architecture and electrochemical performance of dandelion-like mesoporous Co₃O₄ were investigated through structure characterization and galvanostatic charge/discharge test. The as-prepared dandelion-like mesoporous Co₃O₄ consisted of well-distributed nanoneedles (about 40 nm in width and about 5 μm in length) with rich micropores. Electrochemical experiments illustrated that the as-prepared dandelion-like mesoporous Co₃O₄ as anode materials of LIBs exhibited high reversible specific capacity of 1430.0 mA h g^?1 and 1013.4 mA h g^?1 at the current density of 0.2 A g^?1 for the first and 100th cycle, respectively. The outstanding lithium storage properties of the as-prepared dandelion-like mesoporous Co₃O₄ might be attributed to its dandelion-like mesoporous nanostructure together with an open space between adjacent nanoneedle networks promoting the intercalation/deintercalation of lithium ions and the charge transfer on the electrode. The enhanced capacity as well as its high-rate capability made the as-prepared dandelion-like mesoporous Co₃O₄ to be a good candidate as a high-performance anode material for LIBs.     

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.     

Carbon‐Coated Supraballs of Randomly Packed LiFePO4 Nanoplates for High Rate and Stable Cycling of Li‐Ion Batteries

One of the key strategies used to obtain high‐rate Li‐ion battery is the reduction of the Li‐ion path length inside the active materials and the enhancement of the ionic diffusion outside the active materials. It is demonstrated that electrochemical performance can be improved significantly at high C‐rates using carbon‐coated spherical aggregates or “supraballs” of randomly packed olivine LiFePO₄ (LFP) nanoplates as cathode active materials. 258 nm LFP nanoplates with 30 nm thickness are synthesized through a high‐temperature solvothermal method, in which short lithium‐ion channels are formed perpendicular to the top or bottom planes. These thin nanoplates are formed into carbon‐coated “supraballs” through a spray‐drying and thermal annealing process, in which nanoplates are not stacked but randomly packed due to relatively fast drying. Internal and external nanoplate ion diffusion is therefore enhanced simultaneously due to the optimal molecular crystalline structure and interparticle pore structures of the nanoplates. Indeed, the initial capacity of the carbon‐coated supraballs is 162 mAh g^?1 (173.34 mAh cm^?3) at 0.1 C and more than 80% is retained (≈130.91 mAh g^?1) at 50 C. Furthermore, they offer durable cycling stability (>500 cycles) at 1 C without compromising their capacity.     

Effect of carbon coating on electrochemical performance of LiFePO<Subscript>4</Subscript> cathode material for Li-ion battery

Pristine LiFePO₄ (LFP) and carbon-coated LiFePO₄ (LFP/C) are synthesized by sol-gel process using citric acid as a carbon precursor. LFP/C is prepared with three different stoichiometric ratios of metal ions and citric acid, namely 1:0.5, 1:1, and 1:2. Prepared LFP and LFP/C powder samples are characterized by X-ray diffractometer, field emission scanning electron microscope, transmission electron microscope, and Raman spectrophotometer. Electrochemical performances of pristine and carbon-coated LFP are investigated by charge-discharge and cyclic voltammetry technique. The results show that LFP/C (1:1) with an optimum thickness of 4.2 nm and higher graphitic carbon coating has the highest discharge capacity of 148.2 mA h g^?1 at 0.1 C rate and 113.1 mA h g^?1 at a high rate of 5 C among all four samples prepared. The sample LFP/C (1:1) shows 96% capacity retention after 300 cycles at 1 C rate. The decrease in discharge capacity (141.4and 105.9 mA h g^?1 at 0.1 and 5 C, respectively) is observed for the sample LFP/C (1:2). Whereas, pristine LFP shows the lowest discharge capacity of 111.1 mA h g^?1 at 0.1 C and capacity was decreased very fast and work only up to 147 cycles. Moreover, cyclic voltammetry has also revealed the lowest polarization of 0.19 V for LFP/C (1:1) and the highest 0.4 V for pristine LFP.     

Facial synthesis of carbon-coated ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphene and their enhanced lithium storage properties

Carbon-coated ZnFe₂O₄ spheres with sizes of ~110–180 nm anchored on graphene nanosheets (ZF@C/G) are successfully prepared and applied as anode materials for lithium ion batteries (LIBs). The obtained ZF@C/G presents an initial discharge capacity of 1235 mAh g^?1 and maintains a reversible capacity of 775 mAh g^?1 after 150 cycles at a current density of 500 mA g^?1. After being tested at 2 A g^?1 for 700 cycles, the capacity still retains 617 mAh g^?1. The enhanced electrochemical performances can be attributed to the synergetic role of graphene and uniform carbon coating (~3–6 nm), which can inhibit the volume expansion, prevent the pulverization/aggregation upon prolonged cycling, and facilitate the electron transfer between carbon-coated ZnFe₂O₄ spheres. The electrochemical results suggest that the synthesized ZF@C/G nanostructures are promising electrode materials for high-performance lithium ion batteries.

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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.     

Synthesis and electrochemical performance of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C by organic solvent replacement drying method

A series of Li₃V₂(PO₄)₃/C composite cathodes have been prepared by the organic solvent replacement drying method. Five kinds of organic solvent including ethyl alcohol, butyl alcohol, 2-methoxyethanol, 1,2-propylene glycol, and ethylene glycol were used in the drying process to replace the water respectively. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge tests were employed to analyze the crystal structure, morphology, and electrochemical properties of the as-prepared materials. The results show that the organic solvent has a great influence on the secondary particle size of the as-synthesized materials. Special emphasis is placed on the sample prepared with 1,2-propylene glycol, which has the smallest average particle size and uniform distribution, thus leading to the best high rate performance and long-term cycling stability. The electrode exhibits average specific discharge capacities of 127.6, 128.3, 127.7, 126.7, 125.5, 124.4, 121.9, and 117.0 mAh g^?1 at 0.1, 0.2, 0.5, 1, 3, 5, 10, and 20C, respectively. More encouragingly, this sample delivers an outstanding cycle life with capacity retention of up to 94.68% even after 1000 cycles at 20C. Moreover, EIS results demonstrate that this sample has the minimum resistance and the largest apparent lithium ion diffusion coefficient (1.569 × 10^?7 cm² s^?1) which can facilitate to the Li⁺ diffusion during the charge/discharge process. Our results indicate that this preparation strategy can be facile and versatile for the synthesis of other high-rate and high-capacity intercalation materials.     

Electrochemical behavior of carbonic precursor with Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>nanostructured material in hybrid battery system

The nanostructured Na₃V₂(PO₄)₃ (NVP) cathode material has been synthesized using the sol-gel route for different molar fractions of citric acid as a carbon source during the synthesis. The nanostructured NVP as cores with carbonic shell structures are fabricated with two different citric acid molar ratios. The thermal treatment has been optimized to convert the amorphous carbon shell into graphitic carbon to realize the better electrical conductivity and thus effective electron transfer during the electrochemical charge transfer process. The X-ray diffraction measurements confirmed the rhombohedral crystallographic phase (space group R-3c) with average crystallite size ~28 ± 5 nm. The coin cells are assembled in a hybrid rechargeable electrochemical cell configuration with lithium as a counter electrode and LiPF₆-EC:DEC:DMC (1:1:1 ratio) as the electrolyte. The electrochemical charge/discharge measurements are carried out at C/10 and C/20 rates and the measured specific capacities are 80 and 120 mAhg^?1 for samples with lower and higher citric acid molar ratios, respectively. The studies suggest that NVP can be used as an effective cathode material in hybrid electrochemical cells, and a higher concentration of citric acid may result in the effective carbonic shell for optimal electron transfer and thus enhanced electrochemical performance.     

Epitaxial Growth of Urchin‐Like CoSe2 Nanorods from Electrospun Co‐Embedded Porous Carbon Nanofibers and Their Superior Lithium Storage Properties

A facile synthesis of porous graphitic carbon nanofibers (CNFs) with encapsulated Co nanoparticles (denote as Co@CNFs) via electrospinning and subsequent annealing is reported. The in situ generated Co nanoparticles (NPs) promote the CNF graphitization under a low temperature of 700 °C, which simultaneously results in the porous structure of the Co@CNFs with a large surface area (416 m² g^?1). Furthermore, urchin‐like CoSe₂ nanorods are epitaxially grown from the Co@CNFs via a facile hydrothermal selenation, in which the embedded Co NPs serve as directing seeds and sacrificial Co‐source, and CoSe₂ nanorods are rooted into the CNFs (denote as CoSe₂@CNFs). When used as anode materials for lithium ion batteries, the CoSe₂@CNFs demonstrate superior lithium storage properties, delivering a high reversible capacity of 1405 mA h g^?1 after 300 cycles at a current density of 200 mA g^?1. The enhanced lithium storage performance can be attributed to the novel hybrid structure, namely, the porous and graphitic CNFs can not only facilitate the charge/ion transfer but also buffer the volume changes of the electrode during lithiation/delithiation processes. More importantly, a general strategy is provided to graphitize amorphous carbon materials via the use of in situ generated transition metal nanoparticles as catalyst.     

Synthesis of spinel LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> as advanced cathode via a modified oxalate co-precipitation method

Spinel-type LiNi_0.5Mn_1.5O₄ (LNMO) cathode materials for lithium ion batteries have been synthesized via a modified oxalate co-precipitation method. By virtue of the co-precipitation of Li⁺ with transition metal ions, the target materials can be obtained through one-pot reaction without subsequent mixing with lithium salts. What’s more, a uniform distribution between the lithium and transition metal ions at molecular level could be realized, which is beneficial for final electrochemical performances. The physical and electrochemical properties of the material are characterized by XRD, TGA, EDS, FT-IR, SEM, CV, EIS, and charge/discharge tests. The results prove that the as-prepared material owns a cubic spinel structure with a space group of Fd-3m, high crystallinity, uniform particle size, and excellent electrochemical performances. A higher initial capacity and superior rate performance are delivered compared with that of material by conventional co-precipitation method. High capacities of 131.7 and 104.0 mAh g^?1 could be displayed at 0.5 and 10 C, respectively. Excellent cycle stability is also demonstrated with more than 98.5 % capacity retention after 100 cycles at 1 C.     

Facile synthesis of ultrafine SnO<Subscript>2</Subscript> nanoparticles on graphene nanosheets via thermal decomposition of tin-octoate as anode for lithium ion batteries

We demonstrate a facile synthesis of ultrafine SnO₂ nanoparticles within graphene nanosheets (GNSs) via thermal decomposition of tin-octoate, in which tin-octoate is firstly blended with GNSs followed by annealing in air at a low temperature (350 °C) and a short time (1 h). As anode for lithium ion batteries, the SnO₂/GNSs displays superior cycle and rate performance, delivering reversible capacities of 803 and 682 mA h/g at current densities of 200 and 500 mA/g after 120 cycles, respectively, much higher than that of pure SnO₂ and GNSs counterparts (143 and 310 mA h/g at 500 mA/g after 120 cycles, respectively). The enhanced electrochemical performance is attributed to the ultrafine SnO₂ nanoparticle size and introduction of GNSs. GNSs prevent the aggregation of the ultrafine SnO₂ nanoparticles, which alleviate the stress and also provide more electrochemically active sites for lithium insertion and extraction. Moreover, GNSs with large specific surface area (~363 m²/g) act as a good electrical conductor which greatly improves the electrode conductivity and also an excellent buffer matrix to tolerate the severe volume changes originated from the Li-Sn alloying-dealloying. This work provides a straight-forward synthetic approach for the design of novel composite anode materials with superior electrochemical performance.     

A lithium salt additive Li<Subscript>2</Subscript>ZrF<Subscript>6</Subscript> for enhancing the electrochemical performance of high-voltage LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode

In this work, Li₂ZrF₆, a lithium salt additive, is reported to improve the interface stability of LiNi_0.5Mn_1.5O₄ (LNMO)/electrolyte interface under high voltage (4.9 V vs Li/Li⁺). Li₂ZrF₆ is an effective additive to serve as an in situ surface coating material for high-voltage LNMO half cells. A protective SEI layer is formed on the electrode surface due to the involvement of Li₂ZrF₆ during the formation of SEI layer. Charge/discharge tests show that 0.15 mol L^?1 Li₂ZrF₆ is the optimal concentration for the LiNi_0.5Mn_1.5O₄ electrode and it can improve the cycling performance and rate property of LNMO/Li half cells. The results obtained by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) demonstrate that Li₂ZrF₆ can facilitate the formation of a thin, uniform, and stable solid electrolyte interface (SEI) layer. This layer inhibits the oxidation decomposition of the electrolyte and suppresses the dissolution of the cathode materials, resulting in improved electrochemical performances.     

Electrochemical comparison of LiFe<Subscript>0.4</Subscript>Mn<Subscript>0.595</Subscript>Cr<Subscript>0.005</Subscript>PO<Subscript>4</Subscript>/C and LiMnPO<Subscript>4</Subscript>/C cathode materials

A comparison of electrochemical performance between LiFe_0.4Mn_0.595Cr_0.005PO₄/C and LiMnPO₄/C cathode materials was conducted in this paper. The cathode samples were synthesized by a nano-milling-assisted solid-state process using caramel as carbon sources. The prepared samples were investigated by XRD, SEM, TEM, energy-dispersive X-ray spectroscopy (EDAX), powder conductivity test (PCT), carbon-sulfur analysis, electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge cycling. The results showed that LiFe_0.4Mn_0.595Cr_0.005PO₄/C exhibited high specific capacity and high energy density. The initial discharge capacity of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 163.6 mAh g^?1 at 0.1C (1C = 160 mA g^?1), compared to 112.3 mAh g^?1 for LiMnPO₄/C. Moreover, the Fe/Cr-substituted sample showed good cycle stability and rate performance. The capacity retention of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 98.84 % over 100 charge-discharge cycles, while it was only 86.64 % for the pristine LiMnPO₄/C. These results indicated that Fe/Cr substitution enhanced the electronic conductivity for the prepared sample and facilitated the Li⁺ diffusion in the structure. Furthermore, LiFe_0.4Mn_0.595Cr_0.005PO₄/C composite presented high energy density (606 Wh kg^?1) and high power density (574 W kg^?1), thus suggested great potential application in lithium ion batteries (LIBs).     

Synthesis and characterization of pristine Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript> and Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript>/C cathode materials for lithium ion batteries

The cathode materials, pristine Li₂MnSiO₄ and carbon-coated Li₂MnSiO₄ (Li₂MnSiO₄/C), were synthesized by the sol–gel method. Power X-ray diffraction and scanning electron microscopy analyses show that the presence of carbon during synthesis can weaken the formation of impurities in the final product and decrease the particle size of the final product. The effects of carbon coating on electrochemical characteristics were investigated by galvanostatic cycling test and electrochemical impedance spectroscopy. The galvanostatic cycling test results indicate that Li₂MnSiO₄/C cathode exhibits better electrochemical performance with an initial discharge capacity of 134.4 mAh g⁻¹ and a capacity retention of 63.9 mAh g⁻¹ after 20 cycles. Electrochemical impedance analyses confirm that carbon coating can increase electronic conductivity, which results in good electrochemical performance of Li₂MnSiO₄/C cathode. The two semicircles and the large arc obtained in this study can be attributed to the migration of lithium ions through the solid electrolyte interphase films, the electronic properties of the material, and the charge transfer step, respectively.     

Preparation and characterization of LiTi<Subscript>2</Subscript>O<Subscript>4</Subscript> anode material synthesized by one-step solid-state reaction

LiTi₂O₄ anode material for lithium-ion battery has been prepared by a novel one-step solid-state reaction method using Li₂CO₃, TiO₂, and carbon black as raw materials. X-ray diffraction, scanning electron microscopy, energy-dispersive spectrometry, and the determination of electrochemical properties show that the single phase of LiTi₂O₄ with spinel crystal structure is formed at 850?°C by this new method, and the lattice parameter is about 8.392?Å. The primary particle size of the LiTi₂O₄ powder is about 0.5–1.0 μm and its morphology is similar to a sphere. The lithium ion insertion voltage of LiTi₂O₄ anode material is about 1.50 V versus lithium metal, the initial discharge capacity is about 133.6 mAh g^-1, the charge–discharge voltage plateau is very flat, and no solid electrolyte interface film is formed when working potential is more than 1.0 V. The reaction reversibility and the cycling stability are excellent, and the high rate performance is good.     

Spray pyrolysis-deposited TiO<Subscript>2</Subscript> thin films as high-performance lithium ion battery anodes

Focusing on additive-free electrodes, thin films are of typical interest as electrodes for lithium ion battery application. Herein, we report the fabrication of TiO₂ thin films by spray pyrolysis deposition technique. X-ray diffraction and transmission electron microscopic analysis confirms the formation of anatase TiO₂. Electrochemical evaluation of these sub-micron TiO₂ thin films exhibits high-rate performance and long cycling stability. At 1C rate (1C?=?335 mA/g), the electrode delivered discharge capacity of 247 mAh/g allowing about 0.74 lithium into the structure. The electrodes also delivered specific capacities of 122 and 72 mAh/g at 10 and 30C rates, respectively. Without conductive additives, this excellent performance can be attributed to the nanosize effect of TiO₂ particles combined with the uniform porous architecture of the electrode. Upon cycling at high rates (10 and 30C), the electrode exhibited excellent cycling stability and retention, specifically only <?0.6% capacity loss per cycle over 2500 cycles.     

Synthesis of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>-reduced graphene oxide composite and its application for hybrid supercapacitors

We describe in this paper the synthesis and the characterization of Li₄Ti₅O₁₂-reduced graphene oxide (LTO-RGO) composite and demonstrate their use as hybrid supercapacitor, which is consist of an LTO negative electrode and activate carbon (AC) positive electrode. The LTO-RGO composites were synthesized using a simple, one-step process, in which lithium sources and titanium sources were dissolved in a graphene oxide (GO) suspension and then thermal treated in N₂. The lithium-ion battery with LTO-RGO composite anode electrode revealed higher discharge capacity (167 mAh g^?1 at 0.2 C) and better capacity retention (67%) than the one with pure LTO. Meanwhile, compared with the AC//LTO supercapacitor, the AC//LTO-RGO hybrid supercapacitor exhibits higher energy density and power density. Results show that the LTO-RGO composite is a very promising anode material for hybrid supercapacitor.