Low-cost SiO-based anode using green binders for lithium ion batteries

The influence of environmentally friendly aqueous binders and carbon coating on the electrochemical performance of SiO powder anodes for lithium ion batteries has been investigated in detail. The SiO anode with sodium alginate (Alg), styrene butadiene rubber/sodium carboxymethyl cellulose (SCMC) or polyacrylic acid binder exhibits fairly good cycling stability. However, use of polyvinyl alcohol as binder results in rapid capacity loss during cycling. The positive effect of the former binders could be attributed to the amorphous structures and ester-like bond, which were detected by X-ray diffraction and Fourier transform infrared. The cycling performance is further enhanced by carbon coating on the surface of the SiO. The reversible capacity of SiO/C electrode with either Alg or SCMC can retain ca. 940 mAh g^?1 after 100 cycles. In particular, a long-term cycling stability can be achieved for SiO/C electrode using SCMC binder. Additionally, the high irreversibility of SiO/C electrode at the first cycle can be completely compensated by a simple pretreatment.     

Highly porous disk-like shape of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> as an anode material for lithium ion batteries

A novel disk-like shape of Co₃O₄ with high porosity was synthesized by a facile hydrothermal approach followed by calcination at 485 °C for 2 h. In order to further confirm the crystal structure, morphology, particle size, surface area, and porosity of the sample, a series of corresponding characterization techniques were used. The disk-like shape of Co₃O₄ as an anode delivered excellent rate capability such as 510.5 mAh g^?1 at 4.0 C, which is much higher than the theoretical capacity of commercial graphite anode (372 mAh g^?1). However, the electrode could not recover the high capacity during the long-term cycling at various higher current rates due to the deformation of the structure as confirmed by the ex situ studies. It is believed that the obtained remarkable structural feature with numerous void pores within the structure may be helpful for short-term cycling due to the large contact areas between the electrode and the electrolyte and a shorter diffusion length for lithium ion insertion but unable to act as a buffer to relax the volume expansion/contraction and alleviate the structural damage of the electrode during long-term cycling.     

Hierarchical SnO2 with double carbon coating composites as anode materials for lithium ion batteries

Hierarchical SnO₂ with double carbon coating (polypyrrole-derived carbon and reduced graphene oxide in order) composites have been successfully synthesized as anode materials for lithium ion batteries. The composites were characterized and examined by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, cyclic voltammetry, and galvanostatic discharge/charge tests. Such a novel nanostructure can not only provide a high conductivity but also prevent aggregation of SnO₂ nanoparticles, leading to the improvement of the cycling performance. Comparing with pure hierarchical SnO₂ and polypyrrole-derived carbon-coated hierarchical SnO₂, hierarchical SnO₂ with double carbon coating composite exhibits higher lithium storage capacities and better cycling performance, 554.8 mAh g^?1 after 50 cycles at a current density of 250 mA g^?1. In addition, the rate performance of hierarchical SnO₂ with double carbon coating composite is also very well. For all the improved performances, this double carbon coating architecture may provide some references for other electrode materials of lithium ion batteries.     

SnO2 sheet/graphite composite as anode material with improved electrochemical performance for lithium-ion batteries

The SnO₂ sheet/graphite composite was synthesized by a hydrothermal method for high-capacity lithium storage. The microstructures of products were characterized by XRD and FE-SEM. The electrochemical performance of SnO₂ sheet/graphite composite was measured by galvanostatic charge/discharge cycling and EIS. The first discharge and charge capacities are 1,072 and 735 mAh g^?1 with coulombic efficiency of 68.6 %. After 40 cycles, the reversible discharge capacity is still maintained at 477 mAh g^?1. The results show that the SnO₂ sheet/graphite composite displays superior Li-battery performance with large reversible capacity and good cyclic performance.     

Sol–gel processing and electrochemical characterization of monoclinic Li3FeF6

To find new cathode materials for future applications in lithium-ion batteries, lithium transition metal fluorides represent an interesting class of materials. In principle the Li intercalation voltage can be increased by replacing oxygen in the cathode host structure with the more electronegative fluorine. A facile pyrolytic sol–gel process with trifluoroacetic acid as fluorine source was established to synthesize monoclinic Li₃FeF₆ using nontoxic chemicals. The acicular Li₃FeF₆ powder was characterized with X-ray diffraction and a detailed structure model was calculated by Rietveld analysis. For the preparation of cathode films to cycle versus lithium monoclinic Li₃FeF₆ was ball milled with carbon and binder down to nanoscale. After 100 cycles galvanostatic cycling (C/20) 47 % fully reversible capacity of the initial capacity (129 mAh/g) could be retained. To the best of our knowledge the results presented in this work include the first rate performance test for monoclinic Li₃FeF₆ up to 1 C maintaining a capacity of 71 mAh/g. The redox reaction involving Fe³⁺/Fe²⁺ during Li insertion/extraction was confirmed by post-mortem XPS and cyclic voltammetry.     

Comparative performance of LiMn2O4 spinel compositions with carbon nanotubes and graphite in Li prototype battery

We reported previously the superiority of electrochemical characteristics of the mechanical mixtures of micrometer LiMn₂O₄ spinel with multiwall carbon nanotubes (MCNT) over those of spinel compositions with natural graphite in the prototypes of the Li-ion batteries. In the presented work, we extended the investigation of the kinetic and interfacial characteristics of the spinel in the redox reaction with the Li ion. Slow-rate scan cyclic voltammetry and impedance spectroscopy were used. Carbon electroconductive fillers, their nature, and particle sizes play the key role in the efficiency of the electrochemical transformation of spinel in Li-ion batteries. Electrodes based on the composition of the spinel and MCNT show a good cycling stability and efficiency at the discharge rate of 2C. Chemical diffusion coefficients of Li ion, which were determined in spinel composite with MCNT and graphite near potentials of peak activity in deintercalation/intercalation processes, change within one order of 10^?12 cm² s^?1. The value of this chemical diffusion coefficient for the composition of the spinel with MCNT and with graphite change within one order of 10^?12 cm² s^?1. The data of the impedance spectroscopy shows that the resistance of surface films on the spinel (R _s) is low and does not considerably differ from R _s in composites of the spinel with MCNT and graphite. The investigation shows that the resistance of charge transport (R _ct) through the boundary of surface film/spinel composite is dependent on the conductive filler. Value of R _ct in spinel electrode decreases by the factor of thousand in the presence of carbon filler. Exchange current of spinel electrode increases from the order of 10^?7 to 10^?4 A cm^?2 under the influence of MCNT. At the potentials of maximum activity in deintercalation processes, exchange current of spinel composite electrode with MCNT is 2.2–3.0 times more than one of the composite with graphite. Determining role of the resistance of charge transport in electrode processes of spinel is established. The value of R _ct is dependent on the resistance in contacts between spinel particles and also between particles and current collectors. Contact resistance decreases under the influence of MCNT with more efficiency than under the influence of graphite EUZ-M because of small the size of its particles with high surface area of the MCNT.     

Electrochemical properties of all-solid-state lithium batteries with amorphous titanium sulfide electrodes prepared by mechanical milling

Amorphous titanium trisulfide (TiS₃) active materials were prepared by ball milling of an equimolar mixture of crystalline titanium disulfide (TiS₂) and sulfur. A high-resolution transmission electron microscope image revealed no periodic lattice fringes on the amorphous TiS₃. The all-solid-state lithium secondary batteries using a sulfide solid electrolyte and the amorphous TiS₃ electrode showed high capacity of greater than 300 mAh g^?1 for 10 cycles. The amorphous TiS₃ had a higher capacity than the mixture of crystalline TiS₂ and S, which was used as the starting material of amorphous TiS₃. The X-ray diffraction patterns and the Raman spectra of the amorphous TiS₃ electrode after the first and tenth charge–discharge measurements were similar to those before the measurement. The amorphous structure of TiS₃ did not change greatly during the first few cycles. The all-solid-state cells with the amorphous TiS₃ electrode showed higher initial coulombic efficiency because the amorphous TiS₃ active material retained its structure during the initial electrochemical test.     

Graphene/poly(ortho-phenylenediamine) nanocomposite material for electrochemical supercapacitor

Reduced graphene oxide was synthesized by simple chemical processing of graphite. Electron microscopy investigations of synthesized graphene showed slightly folded transparent sheets with a few square micrometers dimension. Poly(ortho-phenylenediamine)/graphene/Pt electrode was electrochemically fabricated in a 2.0-M H₂SO₄ solution by means of multiple potential cycling. Due to the catalytic effect of graphene on the oxidative electropolymerization of ortho-phenylenediamine, the ortho-phenylenediamine/graphene (PoPD/GR) nanocomposite showed greatly enhanced electrical properties and excellent capacitive behavior. Electrochemical impedance spectroscopy, galvanostatic charge/discharge curves, and voltammetric investigations revealed that PoPD/GR nanocomposite represented good capacitive behavior with a specific capacitance as high as 308.3 F g^?1 at 0.1 A g^?1. It is almost three times higher than that of pure graphene (111.7 F g^?1). In addition, the nanocomposite electrode retained more than 99 % of the initial capacity after 1,500 cycles at a current density of 1 A g^?1.     

Preparing graphene oxide–copper composite material from spent lithium ion batteries and catalytic performance analysis

The wide use of lithium ion batteries (LIBs) has created much waste, which has become a global issue. It is vital to recycle waste LIBs considering their environmental risks and resource characteristics. Anode graphite from spent LIBs still possess a complete layer structure and contain some oxygen-containing groups between layers, which can be reused to prepare high value-added products. Given the intrinsic defect structure of anode graphite, copper foils in LIB anode electrodes, and excellent properties of graphene, graphene oxide–copper composite material was prepared in this work. Anode graphite was firstly purified to remove organic impurities by calcination and remove lithium. Purified graphite was used to prepare graphene oxide–copper composite material after oxidation to graphite oxide, ultrasonic exfoliation to graphene oxide (GO), and Cu²⁺ adsorption. Compared with natural graphite, preparing graphite oxide using anode graphite consumed 40% less concentrated H₂SO₄ and 28.6% less KMnO₄. Cu²⁺ was well adsorbed by 1.0 mg L^?1 stable GO suspension at pH 5.3 for 120 min. Graphene oxide–copper composite material could be successfully obtained after 6 h absorption, 3 h bonding between GO and Cu²⁺ with 3/100 of GO/CuSO₄ mass ratio. Compared to CuO, graphene oxide–copper composite material had better catalytic photodegradation performance on methylene blue, and the electric field further improved the photodegradation efficiency of the composite material.     

Effect of crystallite size on the intercalation pseudocapacitance of lithium nickel vanadate in aqueous electrolyte

This work describes lithium nickel vanadate (LiNiVO₄) as a pseudocapacitor electrode material for the first time. The micro and nano-sized LiNiVO₄ are synthesized via mechanochemical reaction and hydrothermal reaction followed by calcination, respectively. The phase purity, surface morphology and microstructure of the LiNiVO₄ synthesized by both methods are analysed by X-ray diffraction and scanning electron microscopy techniques. The lithium ion intercalation-extraction behaviour of the LiNiVO₄ electrode material is investigated in 1 M LiOH electrolyte solution. The results demonstrate an improved capacitive performance for nano-sized LiNiVO₄ electrode synthesized via hydrothermal reaction due to the collective effect of small size and additional redox sites. The nanocrystalline LiNiVO₄ electrode exhibits a high specific capacitance of 456.56 F g^?1 at a current density of 0.5 A g^?1. The cycle stability test reveals exceptional capacitance retention of 99.60% even after 1000 cycles owing to the unique structural feature which permit intercalation mechanism. These findings demonstrate the significance of lithium transition metal vanadate-based electrode material in the development of lithium ion intercalation pseudocapacitors.     

Electrochemical studies of few-layered graphene as an anode material for Li ion batteries

Few-layered graphene (FLG) with specific surface area of only ~8.2 m² g^?1 was synthesized from graphene oxide (GO) using microwave-assisted exfoliation. GO was prepared using modified Hummers method. Few-layered nature of the exfoliated material was confirmed by electron microscopy, X-ray and electron diffraction, and Raman spectroscopy. Coin cells were fabricated using FLG as an anode and lithium metal as a counter electrode. The cells were tested using cyclic voltammetry and galvanostatic cycling techniques. FLG showed reversible capacity values of ~400 and ~250 mAh g^?1 at current rates of 0.1 and 1 C, respectively. Columbic efficiency was more than 98 % while cycle to cycle capacity fading was less than 2 %. Maximum discharge or charging capacity was below 0.3 V, a preferable characteristic for achieving ideal anodic behavior.     

Enhanced high temperature cycling performance of LiMn2O4/graphite cells with methylene methanedisulfonate (MMDS) as electrolyte additive and its acting mechanism

The effects of methylene methanedisulfonate(MMDS) on the high-temperature(~50℃) cycle performance of LiMn_2O_4/graphite cells are investigated.By addition of 2 wt%MMDS into a routine electrolyte,the high-temperature cycling performance of LiMn204/graphite cells can be significantly improved.The analysis of differential capacity curves and energy-dispersive X-ray spectrometry(EDX) indicates that MMDS decomposed on both cathode and anode.The three-electrode system of pouch cell is used to reveal the capacity loss mechanism in the cells.It is shown that the capacity fading of cells without MMDS in the electrolytes is due to irreversible lithium consumption during cycling and irreversible damage of LiMn_2O_4 material,while the capacity fading of cell with 2 wt%MMDS in electrolytes mainly originated from irreversible lithium consumption during cycling.     

Layered LiNi<Subscript>0.80</Subscript>Co<Subscript>0.15</Subscript>Al<Subscript>0.05</Subscript>O<Subscript>2</Subscript> as cathode material for hybrid Li<Superscript>+</Superscript>/Na<Superscript>+</Superscript> batteries

LiNi_0.80Co_0.15Al_0.05O₂ (NCA) is explored to be applied in a hybrid Li⁺/Na⁺ battery for the first time. The cell is constructed with NCA as the positive electrode, sodium metal as the negative electrode, and 1 M NaClO₄ solution as the electrolyte. It is found that during electrochemical cycling both Na⁺ and Li⁺ ions are reversibly intercalated into/de-intercalated from NCA crystal lattice. The detailed electrochemical process is systematically investigated by inductively coupled plasma-optical emission spectrometry, ex situ X-ray diffraction, scanning electron microscopy, cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. The NCA cathode can deliver initially a high capacity up to 174 mAh g^?1 and 95% coulombic efficiency under 0.1 C (1 C?=?120 mA g^?1) current rate between 1.5–4.1 V. It also shows excellent rate capability that reaches 92 mAh g^?1 at 10 C. Furthermore, this hybrid battery displays superior long-term cycle life with a capacity retention of 81% after 300 cycles in the voltage range from 2.0 to 4.0 V, offering a promising application in energy storage.     

Glucose biosensor based on graphite electrodes modified with glucose oxidase and colloidal gold nanoparticles

The electrochemistry of glucose oxidase (GOx) immobilized on a graphite rod electrode modified by gold nanoparticles (Au-NPs) was studied. Two types of amperometric glucose sensors based on GOx immobilized and Au-NPs modified working electrode (Au-NPs/GOx/graphite and GOx/Au-NPs/graphite) were designed and tested in the presence and the absence of N-methylphenazonium methyl sulphate in different buffers. Results were compared to those obtained with similar electrodes not containing Au-NPs (GOx/graphite). This study shows that the application of Au-NPs increases the rate of mediated electron transfer. Major analytical characteristics of the amperometric biosensor based on GOx and 13 nm diameter Au-NPs were determined. The analytical signal was linearly related to glucose concentration in the range from 0.1 to 10 mmol L^?1. The detection limit for glucose was found within 0.1 mmol L^?1 and 0.08 mmol L^?1 and the relative standard deviation in the range of 0.1–100 mol L^?1 was 0.04–0.39%. The τ_1/2 of V _max characterizes the storage stability of sensors: this parameter for the developed GOx/graphite electrode was 49.3 days and for GOx/Au-NPs/graphite electrode was 19.5 days. The sensor might be suitable for determination of glucose in beverages and/or in food.     

Cathode material for sodium-ion batteries based on manganese hexacyanoferrate: the role of the binder component

Sodium manganese hexacyanoferrate (NaMnHCF) was synthesized by a hydrothermal method and investigated as a cathode material for sodium-ion batteries. The morphology and the structure of NaMnHCF were investigated by X-ray diffraction, scanning electron microscopy, and EDX analysis. New composition of NaMnHCF cathode material for sodium-ion batteries with eco-friendly water-based binder consisting of conducting polymer poly-3,4-ethylenedioxythiopene/polystyrene sulfonate (PEDOT:PSS) dispersion and carboxymethyl cellulose (СМС) was proposed. The electrochemical properties of NaMnHCF cathode material with conductive polymer binder were investigated by cyclic voltammetry and galvanostatic charge-discharge, and the results were compared with the performance of a conventional PVDF-bound material. It was shown that the initial discharge capacity of electrodes with conductive binder is 130 mAh g⁻¹, whereas the initial discharge capacity of PVDF-bound electrodes was 109 mAh g⁻¹ (both at current density 120 mA g⁻¹, values normalized by NaMnHCF mass). The material with conductive binder also has better rate capability; however, it is losing in cycling capability to the electrode composition with conventional PVDF binder.

     

Characteristics of nanosized LiNi x Fe1−x PO4/C (x = 0.00–0.20) composite material prepared via sol–gel-assisted carbothermal reduction method

Pure LiFePO₄ and LiNi _x Fe_1?x PO₄/C (x?=?0.00–0.20) nanocomposite cathode materials have been synthesized by cheap and convenient sol–gel-assisted carbothermal reduction method. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy, and inductively coupled plasma have been used to study the phase, morphology, and chemical composition of un-doped and Ni-doped materials. XRD patterns display the slight shrinkage in crystal lattice of LiFePO₄ after Ni²⁺ doping. The SEM images have revealed that Ni-doped particles are not agglomerated and the particle sizes are practically homogeneously distributed. The particle size is found between 50 and 100 nm for LiNi_0.20Fe_0.80PO₄/C sample. The discharge capacity at 0.2 C rate has increased up to 155 mAh g^?1 for the LiNi_0.05Fe_0.95PO₄/C sample and good capacity retention of 99.1 % over 100 cycles, while that of the unsubstituted LiFePO₄/C and pure LiFePO₄ has showed only 122 and 89 mAh g^?1, respectively. Doping with Ni has a noticeable effect on improving its electrical conductivity. However, serious electrochemical declension will occur when its doping density is beyond 0.05 mol LiNi_0.20Fe_0.80PO₄/C electrode shows only 118 mAh g^?1, which is less than un-doped LiFePO₄/C sample at 0.2 C. The cycling voltammogram demonstrates that Ni-doped LiNi_0.05Fe_0.95PO₄/C electrode has more stable lattice structure, enhanced conductivity, and diffusion coefficient of Li⁺ ions, in which Ni²⁺ is regarded to act as a column in crystal lattice structure to prevent the collapse during cycling process.     

Synthesis of single-crystal magnesium-doped spinel lithium manganate and its applications for lithium-ion batteries

Single-crystal magnesium-doped spinel lithium manganate cathode materials are prepared by the hydrothermal method followed by the heat treatment. XRD patterns reveal that Mg²⁺ions have already diffused into the Li_1.088Mn_1.912O₄ crystal structure and not affect the Fd3m space group. SEM images demonstrate that the magnesium-doped spinel lithium manganates show uniform polyhedral single crystals with 2–4 μm. Electrochemical performance demonstrates that the optimized composition of Li_1.088Mg_0.070Mn_1.842O₄ electrode exhibits the best electrochemical properties. It delivers 92.0 mAh g^?1 at 8C rates and corresponds to 90.8% capacity retention (vs. 1C), far higher than those of the pristine electrode (70.4 mAh g^?1 and 69.2%). In addition, the Li_1.088Mg_0.070Mn_1.842O₄ electrode also shows 95.5% capacity retention after 100 cycles at 1C, while the pristine electrode only shows 91.0% capacity retention. The excellent electrochemical performances of Li_1.088Mg_0.070Mn_1.842O₄ electrode are ascribed to the suppressed polarization, more stable crystal structure, and better kinetic characteristics.     

Carbonization and graphitization of pitch applied for anode materials of high power lithium ion batteries

The artificial graphite materials were prepared by carbonizing coal tar pitch using two methods, namely, one- and two-step processes, and all sintered samples were graphitized at 2800 °C. Effects of different heat treatments on the performance of the samples were characterized by scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction, Brunauer–Emmett–Teller, electrochemical impedance spectroscopy (EIS), particle size analysis, polarized light microscopy, and charge–discharge measurements. All samples show a typical graphite crystalline structure; moreover, the degree of graphitization (g factor) and crystallite size along the c-axis (L _c ) were calculated from (002) peak. The polarized light microscopy indicates that the coke with carbonization at 700 °C has an obvious wide domain (D) optical structure, while that with two-step sintering at 400 and 700 °C has a mixed optical structures of wide D, flow domains, and mosaics. TEM analysis revealed a number of irregular graphene layer images which are caused by the defects of graphite. EIS shows that the sample carbonized by two-step has a larger diffusion coefficient than the sample carbonized at 700 °C by one step. Higher carbonization temperature leads to better cycle performance as the temperature increasing from 500 to 700 °C in the one-step route. Specifically, the charge (Li⁺ extraction) capacity at the 50th cycle increases from 318 mA?h?g^?1 to 357 mA?h?g^?1. The results show that the rate performance of the artificial graphite is improved with the addition of the presintering at 400 °C.     

Polymeric membrane and coated graphite electrode based on newly synthesized tetraazamacrocyclic ligand for trace level determination of nickel ion in fruit juices and wine samples

Novel polymeric membrane electrode (PME) and coated graphite electrode (CGE) for nickel ion were prepared based on 2,9-(2-methoxyaniline)₂-4,11-Me₂-[14]-1,4,8,11-tetraene-1,5,8,12-N₄ as a suitable neutral ionophore. The addition of lipophilic anion excluder (NaTPB) and various plasticizers viz o-nitrophenyloctylether (o-NPOE), dioctylphthalate (DOP), dibutylphthalate (DBP), 1-chloronaphthalene (CN) and tri-n-butylphosphate (TBP) have found to improve the performance of the sensors. The best performance was obtained for the membrane sensor having a composition of I:NaTPB:TBP:PVC in the ratio 6:4:100:90 (w/w; mg). The electrodes exhibit Nernstian slopes for Ni²⁺ ions over wide concentration ranges of 4.6 × 10^?7–1.0 × 10^?1 M for PME and 7.7 × 10^?8–1.0 × 10^?1 M for CGE with limits of detection of 2.7 × 10^?7 M for PME and 3.7 × 10^?8 M for CGE. The response time for PME and CGE was found to be 10 and 8 s respectively. The potentiometric responses are independent of the pH of the test solution in the pH range 3.0–8.0. The proposed electrodes revealed good selectivities over a wide variety of other cations including alkali, alkaline earth, transition and heavy metal ions. The coated graphite electrode was used as an indicator electrode in the potentiometric titration of nickel ion with EDTA and in direct determination in different fruit juices and wine samples.     

Natural graphite enhanced the electrochemical performance of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> cathode material for lithium ion batteries

Natural graphite treated by mechanical activation can be directly applied to the preparation of Li₃V₂(PO₄)₃. The carbon-coated Li₃V₂(PO₄)₃ with monoclinic structure was successfully synthesized by using natural graphite as carbon source and reducing agent. The amount of activated graphite is optimized by X-ray diffraction, scanning electron microscope, transmission electron microscope, Raman spectrum, galvanostatic charge/discharge measurements, cyclic voltammetry, and electrochemical impedance spectroscopy tests. Our results show that Li₃V₂(PO₄)₃ (LVP)-10G exhibits the highest initial discharge capacity of 189 mAh g^?1 at 0.1 C and 162.9 mAh g^?1 at 1 C in the voltage range of 3.0–4.8 V. Therefore, natural graphite is a promising carbon source for LVP cathode material in lithium ion batteries.