Wastewater treatment by adsorption with electrochemical regeneration using graphite-based adsorbents

An innovative technology for wastewater treatment using adsorption and electrochemical regeneration has been developed at the University of Manchester. The process uses a low capacity graphitic adsorbent material (a graphite intercalation compound, Nyex^TM 1000) which can be regenerated electrochemically. In this study, we investigate the characteristics of a new, partially porous adsorbent material, Nyex^TM 2000 which offers increased surface area in comparison with Nyex^TM 1000. Nyex^TM 2000 was found to have an adsorption capacity of almost three times that of Nyex^TM 1000. The electrical conductivity of a Nyex^TM 2000 was found to be double that of Nyex^TM 1000, enabling improvements in the electrochemical regeneration characteristics. The removal of an anionic azo dye, acid violet 17, from aqueous solution using Nyex^TM 1000 and 2000 was investigated under various operating conditions. The adsorption of acid violet 17 on Nyex^TM 2000 was found to be comparatively fast with 75 % of the equilibrium capacity being achieved within 5 min. The parameters affecting the regeneration efficiency including the charge passed, current density, treatment time, adsorbent bed thickness, and pH were investigated. An electrochemical regeneration efficiency of around 100 % was achieved for a fully loaded Nyex^TM 2000 in a sequential batch electrochemical cell with a regeneration time of 60 min and a charge passed of 100 C g⁻¹ at a current density of 14 mA cm⁻². The charge required for electrochemical regeneration was found to be approximately equal to theoretical charge required for complete oxidation of the adsorbed acid violet 17, making process design relatively simple. Nyex^TM 2000 was found to be an economic adsorbent with relatively small electrical energy consumption required (31 J mg⁻¹ of acid violet 17 treated, compared to 52 J mg⁻¹ of acid violet 17 for Nyex^TM 1000). Multiple adsorption/regeneration cycles presented no loss in adsorptive capacity and material loses over five adsorption/regeneration cycles.     

Polyaniline as cathodic material for electrochemical energy sources: The role of morphology

Polyaniline layers of different morphologies ranging from open and “sponge-like” structures to compact and “pebble-like” surfaces were synthesized from perchlorate solutions and employed as cathode in the galvanic cell with Zn anode and NH₄Cl/ZnCl₂ electrolyte. Cathodic properties of synthesized layers were investigated by the constant current charging/discharging method in 500 cycles. Specific charge capacities and specific energies obtained form the current-time curves strongly depend on the morphology of investigated layers and discharge conditions. The results unambiguously show that charging/discharging reaction of polyaniline layers is limited to relatively thin layer at polymer/solution boundary. Specific charge capacities are inversely related to both the polymer thickness and the discharge current density. In the limit of zero current densities the specific charge capacity as high as 245 A h kg⁻¹ could be achieved for porous structures of polyaniline layers. Specific capacitance higher than 400 F g⁻¹ obtained at 2 mA cm⁻² current density makes polyaniline a promising material for the application in electrochemical supercapacitors. The electrochemical behaviour of the layers was investigated by cyclic voltammetry and electrochemical impedance spectroscopy before and after 500 cycles of charging/discharging experiments. Both, cyclic voltammetry and electrochemical impedance spectroscopy showed that some polyaniline layers develop an increased charged transfer resistance at the carbon support/polymer interface during charging/discharging process. The increased charge transfer resistance does not affect the overall specific charge of the layers. The low-frequency capacities in impedance spectra are attributed to charging/discharging of polymer/electrolyte interface and seem to be related to the specific charge capacities obtained by extrapolation to zero current density discharge reaction.     

1-Alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids as highly safe electrolyte for Li/LiFePO4 battery

Several 1-alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids (alkyl-DMimTFSI) were prepared by changing carbon chain lengths and configuration of the alkyl group, and their electrochemical properties and compatibility with Li/LiFePO₄ battery electrodes were investigated in detail. Experiments indicated the type of ionic liquid has a wide electrochemical window (−0.16 to 5.2 V vs. Li⁺/Li) and are theoretically feasible as an electrolyte for batteries with metallic lithium as anode. Addition of vinylene carbonate (VC) improves the compatibility of alkyl-DMimTFSI-based electrolytes towards lithium anode and LiFePO₄ cathode, and enhanced the formation of solid electrolyte interface to protect lithium anodes from corrosion. The electrochemical properties of the ionic liquids obviously depend on carbon chain length and configuration of the alkyl, including ionic conductivity, viscosity, and charge/discharge capacity etc. Among five alkyl-DMimTFSI-LiTFSI-VC electrolytes, Li/LiFePO₄ battery with the electrolyte-based on amyl-DMimTFSI shows best charge/discharge capacity and reversibility due to relatively high conductivity and low viscosity, its initial discharge capacity is about 152.6 mAh g⁻¹, which the value is near to theoretical specific capacity (170 mAh g⁻¹). Although the battery with electrolyte-based isooctyl-DMimTFSI has lowest initial discharge capacity (8.1 mAh g⁻¹) due to relatively poor conductivity and high viscosity, the value will be dramatically added to 129.6 mAh g⁻¹ when 10% propylene carbonate was introduced into the ternary electrolyte as diluent. These results clearly indicates this type of ionic liquids have fine application prospect for lithium batteries as highly safety electrolytes in the future.     

A novel nickel-based mixed rare-earth oxide/activated carbon supercapacitor using room temperature ionic liquid electrolyte

Mesopore nickel-based mixed rare-earth oxide (NMRO) and activated carbon (AC) with rich oxygen-contained groups were prepared as electrode materials in a supercapacitor using room temperature ionic liquid (RTIL) electrolyte. These electrode materials were characterized by XPS, XRD, N₂ adsorption, SEM as well as various electrochemical techniques, and showed good properties and operated well with RTIL electrolyte. A 3 V asymmetrical supercapacitor was fabricated, which delivered a real power density of 458 W kg⁻¹ as well as a real energy density of 50 Wh kg⁻¹, and during a 500-cycle galvanostatic charge/discharge measurement, no capacity decay was visible. Such promising energy-storage performance was to a large extent ascribed to nonvolatile RTIL electrolyte with wide electrochemical windows and high stable abilities worked with both electrode materials.     

Study of electrochemical hydrogen charge/discharge properties of FePO4 for application as negative electrodes in hydrogen batteries

We report the electrochemical hydrogen charge/discharge properties of electrodes containing crystalline and amorphous FePO₄ as active material in KOH electrolyte. Crystalline and amorphous FePO₄ were synthesized by an alcohol-assisted precipitation method, and the powders obtained were characterized by X-ray diffraction. X-ray photoelectron spectroscopy is used to investigate the mechanism of hydrogen charge/discharge behavior of FePO₄. The electrochemical hydrogen charge/discharge properties of electrodes containing crystalline and amorphous FePO₄ were investigated for potential application as negative electrodes in rechargeable hydrogen batteries. In galvanostatic discharge/charge mode at 25 °C, the crystalline FePO₄ showed a maximum discharge capacity of 109 mA h g⁻¹, while the amorphous FePO₄ showed a maximum discharge capacity of 81.4 mA h g⁻¹. The electrochemical kinetic properties, exchange current density, and proton diffusivity were calculated using linear polarization measurement and the potential-step method.     

Electrochemical study of NiO nanoparticles electrode for application in rechargeable lithium-ion batteries

Nickel oxide nanoparticles were synthesized via a simple and inexpensive microwave-assisted synthesis method within a fast reaction time of less than 20 min. The calcination of as-prepared precursor at 600 °C produces single phase nickel oxide. The lattice structure and morphology of the sample were investigated by X-ray diffraction, field-emission scanning electron microscopy and field-emission transmission electron microscopy. The particle size range of the nickel oxide nanoparticles varied from 50 to 60 nm. Nickel oxide nanoparticles exhibited good electrochemical performances as an anode material for lithium-ion batteries. The prepared nickel oxide anode revealed a large initial discharge capacity of 1111.08 mAh g⁻¹ at 0.03 C rate and retained 80% of initial capacity (884.30 mAh g⁻¹) after 20 cycles. Furthermore, at elevated rate of 3.7 C, the charge capacity of the nickel oxide electrode was as high as 253.1 mAh g⁻¹, which was 35% greater than that of commercial bulk nickel oxide (188 mAh g⁻¹). The enhancement of the electrochemical performance was attributed to the high specific surface area, good electric contact among the particles and easier lithium ion diffusion.     

Physical and electrochemical characterization of CuO-doped activated carbon in ionic liquid

A series of CuO-doped activated carbons (CDACs) were prepared by chemical deposition. The electrochemical behavior of CDACs was investigated in electrochemical capacitors based on ionic liquid 1-ethyl-3-methylimidazolium thiocyanate ([EMIm]SCN) as electrolyte. The results indicated that a diffusion-controlling, reversible redox reaction of CuO particles happened in ionic liquid and porous carbon. When the amount of CuO-doped activated carbon with a specific surface area of 2460 m² g⁻¹ reached 2%, the single electrode average specific capacitance can reach the maximal value of 210 F g⁻¹, about 20% higher than the one used pure activated carbon as electrode material.     

Pre-treatment of adsorbents for waste water treatment using adsorption coupled-with electrochemical regeneration

With the aim to address waste water treatment problems, a novel and economic water treatment technology was introduced at the University of Manchester. It comprised of a unique combination of adsorption and electrochemical regeneration in a single unit. This process successfully eliminated a number of organic pollutants by using an electrically conducting adsorbent material called Nyex? which was a modified form of synthetic graphite. To expand the scope of other graphite types in waste water treatment applications, natural vein and recycled vein graphite materials were selected for electrochemical surface treatment (pre-treatment) in order to evaluate their adsorptive and electrical properties. New graphite based adsorbents were developed and characterized using a laser diffraction particle size analyser, BET surface area, SEM analysis, X-ray (EDS) elemental analysis, X-ray powder diffraction, Boehm surface titration, Zeta potential electrical bed conductivity and bulk density measurements. Boehm surface titration and EDS (X-ray) elemental analysis showed a significant increase in oxygen containing surface functional groups. Although, no significant improvement in bed electrical conductivity was found to occur after electrochemical surface treatment, however, natural vein and recycled vein graphite materials presented highest bed electrical conductivity amongst competing graphite materials. Aqueous solution of acid violet 17 as a standard pollutant was used to evaluate the comparative performance of these adsorbents. The investigations revealed that electrochemical surface treatment contributed to an increase in the adsorption capacity by a factor of two only for natural vein graphite. Un-treated recycled vein graphite adsorbent delivered the same adsorptive capacity (3.0 mg g^?1) to that of electrochemically treated natural vein graphite. The electrochemical regeneration efficiency at around 100% was obtained using a treatment time of 60 and 30 min, current density of 14 mA cm^?2, charge passed of 36 and 18 C g^?1 for synthetic graphite, natural and recycled vein graphite materials respectively. Relatively a small consumption of electrical energy, 24 J g^?1 for regenerating natural vein graphite adsorbent versus 36 J g^?1 for synthetic graphite adsorbent, was found to be required for destruction/oxidation of adsorbed acid violet 17. Multiple adsorption/regeneration cycles presented no loss in adsorptive capacity over 5 adsorption/regeneration cycles. The use of natural and recycled vein graphite adsorbents offered some advantages over graphite intercalation based adsorbents with reduced electrical energy consumption during regeneration and simpler separation of particulate adsorbent.     

Porous polythiophene as a cathode material for lithium batteries with high capacity and good cycling stability

Polythiophene (PTh) has been synthesized by chemical oxidative polymerization and used as an active cathode material in lithium batteries. The lithium batteries are characterized by cyclic voltammetry (CV), galvanostatic charge/discharge cycling and electrochemical impedance spectroscopic studies (EIS). The lithium battery with the PTh cathode exhibits a discharge voltage of 3.7 V compared to Li⁺/Li and excellent electrochemical performance. PTh can provide large discharge capacities above 50 mA h g⁻¹ and good cycle stability at a high current density 900 mA g⁻¹. After 500 cycles, the discharge capacity is maintained at 50.6 mA h g⁻¹. PTh is a promising candidate for high-voltage power sources with excellent electrochemical performance.     

Electrochemical performance of flowerlike CaSnO3 as high capacity anode material for lithium-ion batteries

Nanosized CaSnO₃ is synthesized by a hydrothermal process and characterized by X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM). The SEM observation shows the sample has a porous flowerlike morphology. The electrochemical results exhibit that the stable and reversible capacity of 547 mAh g⁻¹ is obtained after 50 cycles at 60 mA g⁻¹ (0.1 C) and the corresponding charge capacity is determined to be 316 mAh g⁻¹ at the current density of 2.5 C. Cyclic voltammetry and electrochemical impedance spectroscopy data are analyzed to complement the galvanostatic results. The observed excellent performance is attributed to the porous structure and large surface area of flowerlike CaSnO₃.     

Nano/micro-hybrid NiS cathodes for lithium ion batteries

The present study highlights a low temperature process by which 1D stacked 3D microstructures of nickel sulfide comprised of nanospikes have been synthesized and assembled as cathodes for lithium chalcogenide batteries. These micro/nano-clusters were synthesized hydrothermally under different conditions. These clusters exhibited a surface area of 15 m² g⁻¹. The present study also provides the first reports on the electrochemical performance of these NiS microclusters as cathode materials in lithium fluoro-Tris-sulfonimide electrolyte for lithium ion batteries. A detailed study has been performed to elucidate how surface morphology and redox reaction behaviors underlying these electrodes impact the cyclic behavior and specific capacity. This electrode−electrolyte combination showed minimal dissolution of the electrode in the electrolyte which was confirmed by inductively coupled plasma atomic emission spectroscopy. From the electrochemical analysis performed an intrinsic correlation between the capacity, self-discharge property and the surface morphology has been deduced and explained on the basis of relative contributions from the redox reactions of nickel sulfide in lithium fluoro-Tris-sulfonimide electrolyte. A working model of lithium battery in a coin cell form is also shown exhibiting a specific capacity of 550 mAh g⁻¹.     

Removal of Tartrazine From Water by Adsorption with Electrochemical Regeneration

An innovative process has been developed at University of the Manchester in order to remove organic contaminants from wastewater using graphite intercalation compounds (GICs) as adsorbents with electrochemical regeneration. The present study has demonstrated the removal of tartrazine, from water by adsorption and electrochemical regeneration. The adsorption of tartrazine onto GIC adsorbent was shown to be a quick process, however, with extremely low adsorption capacity compared to porous adsorbents. Low adsorption capacity of the adsorbent is being compensated by rapid electrochemical regeneration associated with low energy consumption that makes the process cost-effective. Regeneration efficiency of around 100% could be obtained in an electrochemical cell by passing a charge of 18 C g^?1 for 18 min through a 10-mm thick adsorbent bed. A series of adsorption and regeneration cycles showed that there was little loss in adsorbent capacity, demonstrating that tartrazine loaded GIC adsorbent could be effectively regenerated electrochemically.     

Large reversible capacity of high quality graphene sheets as an anode material for lithium-ion batteries

High quality graphene sheets were prepared from graphite powder through oxidation followed by rapid thermal expansion in nitrogen atmosphere. The preparation process was systematically investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and Brunauer-Emmett-Teller (BET) measurements. The morphology and structure of graphene sheets were characterized by scanning electron microscope (SEM) and high-resolution transmission electron microscopy (HRTEM). The electrochemical performances were evaluated in coin-type cells versus metallic lithium. It is found that the graphene sheets possess a curled morphology consisting of a thin wrinkled paper-like structure, fewer layers (∼4 layers) and large specific surface area (492.5 m² g⁻¹). The first reversible specific capacity of the prepared graphene sheets was as high as 1264 mA h g⁻¹ at a current density of 100 mA g⁻¹. Even at a high current density of 500 mA g⁻¹, the reversible specific capacity remained at 718 mA h g⁻¹. After 40 cycles, the reversible capacity was still kept at 848 mA h g⁻¹ at the current density of 100 mA g⁻¹. These results indicate that the prepared high quality graphene sheets possess excellent electrochemical performances for lithium storage.     

Characterisation of activated nanoporous carbon for supercapacitor electrode materials

Commercial nanoporous carbon RP-20 was activated with water vapor in the temperature range from 950 °C to 1150 °C. The XRD analysis was carried out on nanoporous carbon powder samples to investigate the structural changes (graphitisation) in modified carbon that occurred at activation temperatures T ? 1150 °C. The first-order Raman spectra showed the absorption peak at 1582 cm⁻¹ and the disorder (D) peak at 1350 cm⁻¹. The low-temperature N₂ adsorption experiments were performed at −196 °C and a specific surface area up to 2240 m²g⁻¹ for carbon activated at T = 1050 °C was measured. The cell capacitance for two electrode activated nanoporous carbon system advanced up to 60 F g⁻¹ giving the specific capacitance ∼240 F g⁻¹ to one electrode nanoporous carbon ∣1.2 M (C₂H₅)₃CH₃NBF₄ + acetonitrile solution interface. A very wide region of ideal polarisability for two electrode system (∼3.2 V) was achieved. The low frequency limiting specific capacitance very weakly increases with the rise of specific area explained by the mass transfer limitations in the nanoporous carbon electrodes. The electrochemical characteristics obtained show that some of these materials under discussion can be used for compilation of high energy density and power density non-aqueous electrolyte supercapacitors with higher power densities than aqueous supercapacitors.     

A new high-performance cathode material for rechargeable lithium-ion batteries: Polypyrrole/vanadium oxide nanotubes

Polypyrrole/vanadium oxide nanotubes (PPy/VOx-NTs) as a new high-performance cathode material for rechargeable lithium-ion batteries are synthesized by a combination of hydrothermal treatment and cationic exchange technique. The morphologies and structures of the as-prepared samples are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry and differential scanning calorimeter (TG-DSC) and X-ray powder diffraction (XRD). The results indicate that the organic templates are mainly substituted by the conducting polymer polypyrrole without destroying the previous nanotube structure. Their electrochemical properties are evaluated via galvanostatic charge/discharge cycling, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is found that PPy/VOx-NTs exhibit high discharge capacity and excellent cycling performance at different current densities compared to vanadium oxide nanotubes (VOx-NTs). After 20 cycles, the reversible capacity of PPy/VOx-NTs (159.5 mAh g⁻¹) at the current density of 80 mA g⁻¹ is about four times of magnitude higher than that of VOx-NTs (37.5 mAh g⁻¹). The improved electrochemical performance could be attributed to the enhanced electronic conductivity and the improved structural flexibility resulted from the incorporation of the conducting polymer polypyrrole.     

Correlations between surface properties of graphite and the first cycle specific charge loss in lithium-ion batteries

We report the influence of two surface parameters, the active surface area (ASA) and the surface chemistry (oxygen functional groups) on the first electrochemical reduction of graphite. The experimental results highlight two important points. One, the ASA is the determining parameter which controls the exfoliation during the first electrochemical cycle. An ASA limit (ca. 0.2 m² g⁻¹) above which the exfoliation is suppressed was experimentally found. Below or above this limit, the specific charge loss remains almost constant even if the ASA changes. Two, for a sample having an ASA value higher than 0.2 m² g⁻¹, it is shown that the presence of oxygen groups at the surface is critical for the formation of an efficient solid electrolyte interphase (SEI) layer. The lack of oxygen groups during the first electrochemical reduction cycle hinders the electrolyte reduction process, and consequently increases the specific charge loss via exfoliation of the graphite electrode. This was confirmed by TPD measurement where significant release of CO gas occured above 400 °C, suggesting the presence of high-thermal-stable surface oxygen-containing groups of different natures in the as-received - SLX50 sample. Finally, it was found that H₂ treatment avoids the formation of oxygen-containing groups during air contact leading to exfoliation of the graphite sample.     

Preparation and electrochemical performance of polyaniline-based carbon nanotubes as electrode material for supercapacitor

Nitrogen-containing carbon nanotubes (CNTs) with open end and low specific surface area were prepared via the carbonization of polyaniline (PANI) nanotubes synthesized by a rapidly mixed reaction. On the basis of analyzing the morphologies and structures of the original and carbonized PANI nanotubes, the electrochemical properties of PANI-based CNTs obtained at different temperatures as electrode materials for supercapacitors using 30 wt.% aqueous solution of KOH as electrolyte were investigated by galvanostatic charge/discharge and cyclic voltammetry. It was found that the carbonized PANI nanotubes at 700 °C exhibit high specific capacitance of 163 F g⁻¹ at a current density of 0.1 A g⁻¹ and excellent rate capability in KOH solution. Using X-ray photoelectron spectroscopy measurement the nitrogen state and content in PANI-CNTs were analysed, which could play important roles for the enhancement of electrochemical performance. When the appropriate content of nitrogen is present, the presence of pyrrole or pyridone and quaternary nitrogen is beneficial for the improvement of electron mobility and the wettability of electrode.     

Electrochemical enhancement of adsorption capacity of activated carbon fibers and their surface physicochemical characterizations

The adsorption of activated carbon fibers (ACFs) and their surface characteristics were investigated before and after electrochemical polarization. The adsorption kinetics of m-cresol showed the dependence on polarized potential, and the adsorption rate constant increased by 77.1%, from 6.38 × 10⁻³ min⁻¹ at open-circuit (OC) to 1.13 × 10⁻² min⁻¹ at polarization of 600 mV. The adsorption isotherms at different potentials were in good agreement with Langmuir isotherm model, and the maximum adsorption capacity increased from 2.28 mmol g⁻¹ at OC to 3.67 mmol g⁻¹ at polarized potential of 600 mV. These indicated that electrochemical polarization could effectively improve the adsorption rate and capacity of ACFs. The surface characteristics of ACFs before and after electrochemical polarization were evaluated by N₂ adsorption-desorption isotherms, scanning electron microscope (SEM), zeta potential and Fourier transform infrared spectroscopy (FTIR). The results showed that the BET specific surface area and pore size increased as the potential rose. However, the surface chemical properties of ACFs hardly changed under electrochemical polarization of less than 600 mV. This study was beneficial to understand the mechanism of electrochemically enhanced adsorption.     

Hydrothermal synthesis of flower-like Zn2SnO4 composites and their performance as anode materials for lithium-ion batteries

Flower-like Zn₂SnO₄ composites had been prepared through a green hydrothermal synthesis. The structural, morphological and electrochemical properties were investigated by means of XRD, BET, SEM, TEM, and electrochemical measurement. The results show that the as-prepared sample is in high purity phase and of good crystallinity; meanwhile it has a particular 3-D structure and large surface area. Electrochemical measurement suggests that flower-like Zn₂SnO₄ composites exhibit better cycling properties and lower initial irreversible capacities than the solid Zn₂SnO₄ cubes. The first discharge and charge capacities of the material are 1750 mA h g⁻¹ and 880 mA h g⁻¹ respectively. A higher reversible capacity of 501 mA h g⁻¹ was obtained after 50 cycles at a current density of 300 mA g⁻¹. The higher reversible capacity and good stability can be related to the special nanostructural features of the material. Such Zn₂SnO₄ structures synthesized by the simple and cheap method are expected to have potential application in energy storage.     

Enhanced electrochemical properties of LiFePO4/C synthesized with two kinds of carbon sources,PEG-4000 (organic) and Super p (inorganic)

Olivine structured LiFePO₄/C cathode was synthesized via a freeze-drying route and followed by microwave heating with two kinds of carbon sources: PEG-4000 (organic) and Super p (inorganic). XRD patterns indicate that the as-prepared sample has an olivine structure and carbon modification does not affect the structure of the sample. Image of SEM shows a uniform and optimized particles size, which greatly improves the electrochemical properties. TEM result reveals the amorphous carbon around the surface of the particles. At a low rate of 0.1 C, the LiFePO₄/C sample presents a high discharge capacity of 157.8 mAh g⁻¹ which is near the theoretical capacity (170 mAh g⁻¹), and it still attains to 149.1 mAh g⁻¹ after 200 cycles. It also exhibits an excellent rate capacity with high discharge capacities of 143.2 mAh g⁻¹, 137.5 mAh g⁻¹, 123.7 mAh g⁻¹ and 101.6 mAh g⁻¹ at 0.5 C, 1.0 C, 2.0 C and 5.0 C, respectively. EIS results indicate that the charge transfer resistance of LiFePO₄ decreases greatly after carbon coating.