Tetraethylammonium difluoro(oxalato)borate as electrolyte salt for electrochemical double-layer capacitors

Difluoro(oxalato)borate (ODFB⁻) is a less symmetric borate anion, which makes it possible to increase the solubility of tetraethylammonium (TEA⁺) salt in propylene carbonate (PC) and improve the capacitance of electrochemical double-layer capacitors (EDLCs). The use of TEAODFB with PC solvent in EDLCs was investigated in the paper. The results show that TEAODFB has good solubility in PC, and the conductivity is comparable to TEABF₄/PC electrolyte. When the molar concentration of TEAODFB reaches to 1.6 M, the TEAODFB/PC electrolyte has superior conductivity of 14.46 mS cm⁻¹ and good capacitor characteristics. Despite the less accessible to the electrode and low energy density was achieved, the specific capacitance of 1.6 M TEAODFB/PC electrolyte is 21.4 F g⁻¹ at 1 A g⁻¹, and the energy density and power density were comparable to 1 M TEABF₄/PC electrolyte at 1–5 A g⁻¹. Temperature characteristic was also tested by 3.3 F circular capacitors from −40 to 60 °C, the result demonstrates that capacitors using 1.6 M TEAODFB/PC electrolyte show much higher capacitance and energy density at the investigated temperatures, and the discharge capacitance of capacitors using 1.6 M TEAODFB/PC electrolyte varies with the temperature less than that of 1 M TEABF₄/PC electrolyte.     

The effects of LiBOB additive for stable SEI formation of PP13TFSI-organic mixed electrolyte in lithium ion batteries

A safe electrolyte system is prepared from N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13TFSI), organic electrolyte (1 mol L⁻¹ LiPF₆/EC-DEC) and lithium bis (oxalato) borate (LiBOB). The additive of LiBOB enhances the stability of interface between electrolyte and anode. The LiBOB-containing mixed electrolytes show non-flammability and good compatibility with active materials. The performance of anode for lithium ion battery is successfully improved by LiBOB-containing mixed electrolytes, which shows 200 mA h g⁻¹ reversible capacities at 0.3 C rate. The ionic conductivity and the lithium ion transference number in LiBOB-containing mixed electrolytes system also suits to application for lithium ion battery.     

Aprotic phosphonium-based ionic liquid as electrolyte for high CO2 electroreduction to oxalate

In this study, a new CO₂ electroreduction electrolyte system consisting of tetrabutylphosphonium 4-(methoxycarbonyl) phenol ([P₄₄₄₄][4-MF-PhO]) ionic liquid (IL) and acetonitrile (AcN) was designed to produce oxalate, and the electroreduction mechanism was studied. The results show that using the new IL-based electrolyte, the electroreduction system exhibits 93.8% Faradaic efficiency and 12.6 mA cm⁻² partial current density of oxalate at −2.6 V. The formation rate of oxalate is 234.4 μmol cm⁻² h⁻¹, which is better than those reported in the literature. The mechanism study using density functional theory (DFT) calculations reveals that [P₄₄₄₄][4-MF-PhO] can effectively activate CO₂ molecule through ester and phenoxy double active sites. In addition, in the phosphonium-based ionic environment, the potential barriers of the key intermediates *CO₂⁻ and *C₂O₄²⁻ are reduced by the induced electric field, which greatly facilitates the activation and conversion of CO₂ molecule to oxalate.     

Conversion of methane to syngas in a solid oxide fuel cell with Ni-SDC anode and LSGM electrolyte

A solid oxide fuel cell constructed from Ni-SDC anode and LSGM electrolyte was applied to the partial oxidation of methane to syngas (CO+H₂) at 700-800 °C with the merits of co-generation of electricity and controllable O₂ supply. It was found that the co-generated syngas at H₂/CO ratio of 1.4-2.0 varied with applied current densities, CH₄ flow rates and operating temperatures. The cell voltage at 100 mA cm⁻² and 800 °C was 0.90 V, i.e. about 90 mW cm⁻² power density could be obtained. The cell operating at 50 mA cm⁻² for 24 h almost showed no degradation of the cell performance. The observed carbon deposition seemed mainly taking place by CH₄ cracking reaction.     

Improved Li-storage performance of CNTs-decorated LiVPO4F/C cathode material for electrochemical energy storage

Lithium vanadium fluorophosphate (LiVPO₄F) has been attracted increasing attention as an advanced cathode for Li-ion batteries because of its excellent thermal stability and high operating voltage. Nevertheless, the pure LiVPO₄F possesses a low electrical conductivity which prevents its usage for practical application in energy storage. In this work, the CNTs-decorated LiVPO₄F/C (CNTs@LiVPO₄F/C) nanocomposite has been prepared via a conventional sol-gel approach. The XRD results reveal that all the diffraction peaks obtained for CNTs@LiVPO₄F/C are indexed to the triclinic structure. TEM images show that the conductive CNTs are distributed homogeneously over the LiVPO₄F/C particles. Benefiting from the enhanced conductivity, the as-prepared CNTs@LiVPO₄F/C electrode exhibits outstanding electrochemical performance with high reversible capacity of 121.1 mAh g^?1 at a high current rate of 10 C. Therefore, the novel CNTs@LiVPO₄F/C cathode material developed from this investigation with superior Li-storage performance has promising practical applications in electrochemical energy storage systems.     

Thermal battery cells utilizing molten nitrates as the electrolyte and oxidizer

The Ca/LiNO₃-LiCl-KCl (50-25-25 mol%) thermal battery cell can be activated at 160° C and operated over a temperature range of 250–450° C to produce 2.5–2.8 V at open-circuit and initial operating voltages above 2 V at 10 mA cm^–2. At operating temperatures between 250 and 350° C, this system shows promise for applications requiring a sixty-minute thermal battery. Cell lifetimes decrease at higher temperatures due to the accelerating reaction of calcium with the molten nitrate salt to form gaseous products. An experimental energy density value of 142 Whkg^–1 was obtained at 300° C during constant current discharge at 10 mAcm^–2. Effects of applied face pressure on cell discharge characteristics were small. At current densities above 20–30 mA cm^–2, the cell performance deteriorates due to polarization at the anode. This is probably caused by the precipitation of CaO which blocks the active sites at the anode.     

A rechargeable redox battery utilizing ruthenium complexes with non-aqueous organic electrolyte

A new-type redox battery has been developed. Some ruthenium complexes in organic electrolyte solution were utilized as the electrode active materials. A single cell consisting of [Ru(bpy)₃]²⁺ complex in acetonitrile solution had an open circuit voltage of 2.6 V and a discharge current of 5 mA cm^–2 (at a smooth carbon electrode). The characteristics of this type of cell were much influenced by such factors as the diaphragm material and the concentration of the complex. A cell with flowing electrolyte was also constructed and its charge-discharge performance was examined.     

Sulfur–carbon composite electrode for all-solid-state Li/S battery with Li2S–P2S5 solid electrolyte

All-solid-state Li/S batteries with Li₂S–P₂S₅ glass–ceramic electrolytes were fabricated and their electrochemical performance was examined. Sulfur–carbon composite electrodes were prepared by grinding with a mortar and milling with a planetary ball-mill apparatus. Milling of a mixture of sulfur, acetylene black and the Li₂S–P₂S₅ glass–ceramic electrolyte resulted in the amorphization of sulfur and a reduction in the particle size of the mixture. The charge–discharge properties of all-solid-state cells with the composite electrode were investigated at temperatures from −20 °C to 80 °C. The cells retained a reversible capacity higher than 850 mAh g⁻¹ for 200 cycles under 1.3 mA cm⁻² (333 mA g⁻¹) at 25 °C. The cell performance was influenced by the crystallinity of sulfur and the particle size of the electrode material, whereby improved contact among the electrode components achieved by milling contributed to enhancement of the capacity of an all-solid-state Li/S cell.     

Electrochemical performance for the electro-oxidation of ethylene glycol on a carbon-supported platinum catalyst at intermediate temperature

To determine the kinetic performance of the electro-oxidation of a polyalcohol operating at relatively high temperatures, direct electrochemical oxidation of ethylene glycol on a carbon supported platinum catalyst (Pt/C) was investigated at intermediate temperatures (235–255 °C) using a single cell fabricated with a proton-conducting solid electrolyte, CsH₂PO₄, which has high proton conductivity (>10⁻² S cm⁻¹) in the intermediate temperature region. A high oxidation current density was observed, comparable to that for methanol electro-oxidation and also higher than that for ethanol electro-oxidation. The main products of ethylene glycol electro-oxidation were H₂, CO₂, CO and a small amount of CH₄ formation was also observed. On the other hand, the amounts of C₂ products such as acetaldehyde, acetic acid and glycolaldehyde were quite small and were lower by about two orders of magnitude than the gaseous reaction products. This clearly shows that C–C bond dissociation proceeds almost to completion at intermediate temperatures and the dissociation ratio reached a value above 95%. The present observations and kinetic analysis suggest the effective application of direct alcohol fuel cells operating at intermediate temperatures and indicate the possibility of total oxidation of alcohol fuels.     

Synthesis of mesoporous SnO2 spheres via self-assembly and superior lithium storage properties

This paper firstly reported a simple route to prepare SnO₂ mesoporous spheres for lithium ion battery. Mesoporous SnO₂ spheres in range of 100–300 nm were prepared by primary reaction at 353 K for 30 min, and calcination process at 773 K, which could be scaled up for manufacturing. The nano-size effect of the small particle and the 3D mesoporous structure promoted the electrolyte and lithium ion transfer and suppressed the volume changes, which greatly enhanced the cycle performances. As the anode material, it could deliver 761 mAh g⁻¹ capacity after 50 cycles at the current density of 200 mA g⁻¹. Even at 2 A g⁻¹, it retained 480 mAh g⁻¹ after 50 cycles. Furthermore, we suggested that the high stability of the structure was responsible for the improved cycle properties.     

Zinc deposition and dissolution in methanesulfonic acid onto a carbon composite electrode as the negative electrode reactions in a hybrid redox flow battery

Electrodeposition and dissolution of zinc in methanesulfonic acid were studied as the negative electrode reactions in a hybrid redox flow battery. Cyclic voltammetry at a rotating disk electrode was used to characterize the electrochemistry and the effect of process conditions on the deposition and dissolution rate of zinc in aqueous methanesulfonic acid. At a sufficiently high current density, the deposition process became a mass transport controlled reaction. The diffusion coefficient of Zn²⁺ ions was 7.5 × 10⁻⁶ cm² s⁻¹. The performance of the zinc negative electrode in a parallel plate flow cell was also studied as a function of Zn²⁺ ion concentration, methanesulfonic acid concentration, current density, electrolyte flow rate, operating temperature and the addition of electrolytic additives, including potassium sodium tartarate, tetrabutylammonium hydroxide, and indium oxide. The current-, voltage- and energy efficiencies of the zinc-half cell reaction and the morphologies of the zinc deposits are also discussed. The energy efficiency improved from 62% in the absence of additives to 73% upon the addition of 2 × 10⁻³ mol dm⁻³ of indium oxide as a hydrogen suppressant. In aqueous methanesulfonic acid with or without additives, there was no significant dendrite formation after zinc electrodeposition for 4 h at 50 mA cm⁻².     

Electrochemical investigation of LiMn2O4 cathodes in gel electrolyte at various temperatures

A composite lithium battery electrode of LiMn₂O₄ in combination with a gel electrolyte (1 M LiBF₄/24 wt% PMMA/1:1 EC:DEC) has been investigated by galvanostatic cycling experiments and electrochemical impedance spectroscopy (EIS) at various temperatures, i.e. −3<T<56 °C. For analysis of EIS data, a mathematical model taking into account local kinetics and potential distribution in the liquid phase within the porous electrode structure was used. Reasonable values of the double-layer capacitance, the exchange-current density and the solid phase diffusion were found as a function of temperature. The apparent activation energy of the charge-transfer (∼65 kJ mol⁻¹), the solid phase transfer (∼45 kJ mol⁻¹) and of the ionic bulk and effective conductance in the gel phase (∼34 kJ mol⁻¹), respectively, were also determined. The kinetic results related to ambient temperature were compared to those obtained in the corresponding liquid electrolyte. The incorporated PMMA was found to reduce the ionic conductivity of the free electrolyte, and it was concluded that the presence of 24 wt% PMMA does not have a significant influence on the kinetic properties of LiMn₂O₄.     

Stabilized heteropolyacid/Nafion composite membranes for elevated temperature/low relative humidity PEFC operation

Organic/inorganic composite membranes with different inorganic heteropolyacid (HPA) additives maintain sufficient proton conductivities for atmospheric pressure elevated temperature (>100 °C) polymer electrolyte fuel cell (PEFC) operation. However, membrane and membrane electrode assembly (MEA) processing is severely curtailed because of the solubility of the HPA additives in aqueous media. Composite membranes with the HPA (phosphotungstic acid; PTA) additive rendered insoluble by ion exchanging protons with larger cations such as Cs⁺, NH₄⁺, Rb⁺ and Tl⁺ were fabricated. The additive loss in aqueous media was lowered from nearly 100% (unmodified HPA) to about 5% (modified HPA). The membranes were robust, and demonstrated low H₂ crossover currents of around 2 mA/cm² for a 28 μm thick membrane. All membranes were evaluated at high temperatures and low relative humidities in an operating fuel cell. The conductivities of the composite membranes at 120 °C and 35% relative humidity were on the order of 1.6 × 10⁻² S/cm.     

Hollow CuFe2O4 spheres encapsulated in carbon shells as an anode material for rechargeable lithium-ion batteries

We report here a polymer-templated hydrothermal growth method and subsequent calcination to achieve carbon coated hollow CuFe₂O₄ spheres (H–CuFe₂O₄@C). This material, when used as anode for Li-ion battery, retains a high specific capacity of 550 mAh g⁻¹ even after the 70th cycle, which is much higher than those of both CuFe₂O₄@C (∼300 mAh g⁻¹) and H–CuFe₂O₄ (∼120 mAh g⁻¹). And galvanostatic cycling at different current densities reveals that a capacity of 480 mAh g⁻¹, 91% recovery of the specific capacity cycling at 100 mA g⁻¹, can be obtained even after 50 cycles running from 100 to 1600 mA g⁻¹. The significantly enhanced electrochemical performances of H–CuFe₂O₄@C with regard to Li-ion storage are ascribed to the following factors: (1) the hollow void, which could mitigate the pulverization of electrode and facilitate the lithium-ion, electron and electrolyte transport; (2) the conductive carbon coating, which could enhance the conductivity, alleviate the agglomeration problem, prevent the formation of an overly thick SEI film and buffer the electrode. Such a structural motif of H–CuFe₂O₄@C is promising, for electrode materials of LIBs, and points out a general strategy for creating other hollow-shell electrode materials with improved electrochemical performances.     

Polyterthiophene/CNT composite as a cathode material for lithium batteries employing an ionic liquid electrolyte

A polyterthiophene (PTTh)/multi-walled carbon nanotube (CNT) composite was synthesised by in situ chemical polymerisation and used as an active cathode material in lithium cells assembled with an ionic liquid (IL) or conventional liquid electrolyte, LiBF₄/EC-DMC-DEC. The IL electrolyte consisted of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF₄) containing LiBF₄ and a small amount of vinylene carbonate (VC). The lithium cells were characterised by cyclic voltammetry (CV) and galvanostatic charge/discharge cycling. The specific capacity of the cells with IL and conventional liquid electrolytes after the 1st cycle was 50 and 47 mAh g⁻¹ (based on PTTh weight), respectively at the C/5 rate. The capacity retention after the 100th cycle was 78% and 53%, respectively. The lithium cell assembled with a PTTh/CNT composite cathode and a non-flammable IL electrolyte exhibited a mean discharge voltage of 3.8 V vs Li⁺/Li and is a promising candidate for high-voltage power sources with enhanced safety.     

Room temperature molten salts as lithium battery electrolyte

In the present study, are reported investigations obtained with the room temperature molten salt (RTMS) ethyl-methyl-imidazolium bis-(trifluoromethanesulfonyl)-imide (EMI-TFSI) in order to use it as solvent in lithium battery. The thermal stability, viscosity, conductivity and electrochemical properties are presented. A solution of 1m lithium bis-(trifluoromethanesulfonyl)-imide (LiTFSI) in EMI-TFSI has been used to test the electrolyte in a battery with LiCoO₂ and Li₄Ti₅O₁₂ as respectively cathode and anode materials. Cycling and power measurements have been obtained. The results have been compared with those obtained with a molten salt formulated with a different anion, BF₄⁻ and with a conventional liquid organic solvent EC/DMC containing LiTFSI. The 1m LiTFSI/EMI-TFSI electrolyte provides the best cycling performance: a capacity up to 106 mAh g⁻¹ is still delivered after 200 cycles, with 1C rate at 25 °C.     

Fabrication of all-solid-state battery using Li5La3Ta2O12 ceramic electrolyte

The chemical and electrochemical properties of Li₅La₃Ta₂O₁₂ (LLTa) solid electrolyte were extensively investigated to determine its compatibility with an all-solid-state battery. A well-sintered LLTa pellet with a garnet-like structure was obtained after sintering at 1200 °C for 24 h. Li ion conductivity of the LLTa pellet was estimated to be 1.3×10⁻⁴ S cm⁻¹. The LLTa pellet was stable when in contact with lithium metal. This indicates that Li metal anode, which is the best anode material, can be applied with the LLTa system. A full cell composed of LiCoO₂/LLTa/Li configuration was constructed, and its electrochemical properties were tested. In the resulting cyclic voltammogram, a clear redox couple of LiCoO₂ was observed, implying that the all-solid-state battery with the Li metal anode was successfully operated at room temperature. The redox peaks of the battery were still observed even after one year of storage in an Ar-filled glove-box. It can be concluded that the LLTa electrolyte is a promising candidate for the all-solid-state battery because of its relatively high Li ion conductivity and good stability when in contact with Li metal anode and LiCoO₂ cathode.     

Lithium-polymer battery based on an ionic liquid-polymer electrolyte composite for room temperature applications

A lithium-polymer battery based on an ionic liquid-polymer electrolyte (IL-PE) composite membrane operating at room temperature is described. Utilizing a polypyrrole coated LiV₃O₈ cathode material, the cell delivers >200 mAh g⁻¹ with respect to the mass of the cathode material. Discharge capacity is slightly higher than those observed for this cathode material in standard aprotic electrolytes; it is thought that this is the result of a lower solubility of the LiV₃O₈ material in the IL-PE composite membrane.     

Discharge performance of a primary alkaline CuO cathode material prepared via a novel non-aqueous precipitation method

An amorphous copper oxide material with a large BET surface area (191.9 m² g⁻¹) was prepared via the room temperature conversion of a Cu(OH)₂ intermediate, itself formed via a novel base precipitation technique from an ethylene glycol solvent. The electrochemical discharge rate performance as a primary alkaline cathode material was examined galvanostatically (50 − 2000 mA g⁻¹) in 9.0 mol dm⁻³ KOH electrolyte, and compared to the incumbent primary alkaline cathode material, electrolytic manganese dioxide (EMD). The prepared CuO material performs favourably compared to EMD under high rate discharge conditions (>600 mA g⁻¹), where the material discharges 154 and 135 mA h g⁻¹ capacity at a discharge rate of 1000 and 2000 mA g⁻¹, respectively, compared to 132 and 83 mA h g⁻¹ for EMD under the same conditions.     

Solid-state storage batteries

Investigations were conducted to study the feasibility of a solid-state battery system for storage applications. During the development of various high energy density solid-state batteries we noted that the solid electrolyte material, LiI dispersed in large surface area Al₂O₃, has a high ionic conductivity at elevated temperatures, (for example 0.1^–1 cm^–1 at 300° C) and is suitable for high-rate storage battery applications. In solid-state battery systems both the electrodes and electrolytes are in the solid state under the operating conditions of the battery. The absence of any liquid phase makes the individual cell containers unnecessary in a multicell battery resulting in a simplified battery structure and increased package efficiency. Furthermore, no material compatibility problem is encountered in the system. As a result, the solid-state battery system has excellent charge retention characteristics and a long projected operating life. Solid-state test cells, Li-Si/LiI(Al₂O₃)/TaS₂/Ta, Li-Si/LiI(Al₂O₃/TiS₂/Ti and Li-Si/LiI(Al₂O₃)/TiS₂, Sb₂S₃, Bi were constructed and subjected to discharge-charge cycle tests at 300±10° C, at 13·7 mA cm^–2. Preliminary test results demonstrated that these solid-state battery systems are rechargeable and may be suitable for both load levelling and/or vehicle propulsion. From the considerations of material availability and cost and operational efficiencies it was concluded that the Li-Si/LiI(Al₂O₃)/TiS₂, Sb₂S₃, Bi system is most suitable among the three systems studied for the development of practical storage batteries. Preliminary design studies showed that practical energy densities of 200W h kg^–1 and 520 W h l^–1 can be realized with the Li-Si/TiS₂, Sb₂S₃, Bi storage batteries.