Ni-MH battery based on plasticized alkaline solid polymer electrolytes

Solid-state nickel metal hydride cells were fabricated using plasticized alkaline solid polymer electrolytes (ASPE) prepared from polyvinyl alcohol (PVA), potassium hydroxide (KOH), alumina (α-Al₂O₃), and propylene carbonate (PC). The ASPE film with PVA/KOH/α-Al₂O₃/PC/H₂O weight ratio of 1.00:0.67:0.09:2.64:1.32 and conductivity of (6.6 ± 1.7) × 10⁻⁴ S cm⁻¹ was used in fabrication of the electrochemical cells. To investigate the electrochemical properties of the plasticized ASPE, cells with the configuration Mg₂Ni/plasticized ASPE/Ni(OH)₂ were fabricated. At the eighth cycle with a current drain of 0.1 mA and plateau voltage of ∼1.1 V, the discharge lasted for 14 h before the cell was considered to have failed. The failure mode of the cell was due to the formation of thin Mg(OH)₂ insulating layers.     

Alkaline poly(vinyl alcohol)/poly(acrylic acid) polymer electrolyte membrane for Ni-MH battery application

Ionics - Alkaline polymer electrolyte membrane with high ionic conductivity of 0.019 S cm−1 at room temperature was prepared from poly(vinyl alcohol) and acrylic acid...     

Self-discharge performance of Ni-MH battery by using electrodes with hydrophilic/hydrophobic surface

The polytetrafluoroethylene (PTFE) and carboxymethyl cellulose (CMC) film is separately coated on the surface of the metal hydride (MH) and Ni(OH)₂ electrodes to obtain the electrodes with hydrophobic or hydrophilic surface. The effects of the surface treatment on the oxygen and hydrogen evolution from the electrodes are studied by using cyclic voltammetry tests. Although the positive and negative active materials of the Ni-MH batteries show a lower self-decomposition rate after the CMC treatment, the self-discharge rate of the batteries show little change. On the contrary, the self-discharge rate of the batteries decreases from 35.9% to 27.1% by using the PTFE-treated Ni(OH)₂ electrodes, which might be related to the suppression of the reaction between NiOOH and H₂ by the hydrophobic film.     

Evolution of the electrode–electrolyte interface in a lithium–polymer battery

Using impedance spectroscopy and in situ optical absorption experiments, we have studied the evolution of a lithium electrode/polymer electrolyte interface during aging and cycling. During a period of 3–5 days after assembling a cell, aging has a detrimental effect on the interface: this effect is observed both on the interface impedance and on the optical properties of the electrolyte. After this initial period, optical absorption measured during cycling a cell reveals a concentration evolution in the electrolyte in agreement with theoretical predictions.     

Performance studies on composite gel polymer electrolytes for rechargeable magnesium battery application

Effect of micron-sized MgO particles dispersion on poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF–HFP) based magnesium-ion (Mg²⁺) conducting gel polymer electrolyte has been studied using various electrical and electrochemical techniques. The composite gel films are free-standing and flexible with enough mechanical strength. The optimized composition with 10 wt% MgO particles offers a maximum electrical conductivity of ∼6×10⁻³ S cm⁻¹ at room temperature (∼25°C). The Mg²⁺ ion conduction in gel film is confirmed from cyclic voltammetry, impedance spectroscopy and transport number measurements. The applicability of the composite gel electrolyte to a rechargeable battery system has been examined by fabricating a prototype cell consisting of Mg (or Mg–MWCNT composite) and V₂O₅ as negative and positive electrodes, respectively. The rechargeability of the cell has been improved, when Mg metal was substituted by Mg–MWCNT composite as negative electrode.     

Electrochemical cell performance studies on all-solid-state battery using nano-composite polymer electrolyte membrane

All-solid-state proton-conducting polymeric batteries have been fabricated in the cell configurations: Zn + ZnSO₄·7H₂O (anode) || polyethylene oxide (PEO):NH₄HSO₄ + SiO₂ || MnO₂ + C (cathode) and Zn + ZnSO₄·7H₂O (anode) || PEO:NH₄HSO₄ + SiO₂ || PbO₂ + V₂O₅ + C (cathode). Nano-composite proton-conducting polymeric membrane in wt.% composition, 92PEO: 8 NH₄HSO₄ + 3 SiO₂, synthesized by solution cast technique, has been used as electrolyte. Dispersal of nanosized (8 nm) fumed-SiO₂ particles resulted into an enhancement in the room temperature conductivity of polymer electrolyte host, 92PEO: 8 NH₄HSO₄ (wt.%), approximately by an order of magnitude with the substantial increase in the mechanical strength of the films. Details on the electrolyte film casting and ion transport characterization studies have been discussed elsewhere in the literature. However, a brief mention has been made for reference. An open circuit voltage in the range 1.5–1.8 V, obtained for both the batteries, is in very good agreement with the value reported. The cell performance has been studied under varying load conditions. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Electrochemical studies on polymer electrolytes based on poly(methyl methacrylate)-grafted natural rubber for lithium polymer battery

MG30 is natural rubber grafted with 30% poly(methyl methacrylate). Gel polymer electrolytes containing MG30–LiCF₃SO₃–X (X = propylene carbonate, ethylene carbonate) are prepared by solution casting technique. The polymer–salt complexes were investigated using Fourier-transformed infrared. The ionic conductivity of the electrolytes are determined by the ac impedance studies over the temperature range of 303–383 K and is observed to obey the Vogel–Tamman–Fulcher (VTF) rule. The Li⁺ transference number obtained using the Bruce and Vincent method is <0.3. The Li/Li⁺ interface stability is established and the electrolytes were found to be able to withstand a voltage of more than 4.2 V.     

Electrochemical characterization of ionic liquid based gel polymer electrolyte for lithium battery application

High molecular weight polymer poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP), ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIMFSI), and salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based free-standing and conducting ionic liquid-based gel polymer electrolytes (ILGPE) have been prepared by solution cast method. Thermal, electrical, and electrochemical properties of 80 wt% IL containing gel polymer electrolyte (GPE) are investigated by thermogravimetric (TGA), impedance spectroscopy, linear sweep voltammetry (LSV), and cyclic voltammetry (CV). The 80 wt% IL containing GPE shows good thermal stability (~?200 °C), ionic conductivity (6.42?×?10^?4 S cm^?1), lithium ion conductivity (1.40?×?10^?4 S cm^?1 at 30 °C), and wide electrochemical stability window (~?4.10 V versus Li/Li⁺ at 30 °C). Furthermore, the surface of LiFePO₄ cathode material was modified by graphene oxide, with smooth and uniform coating layer, as confirmed by scanning electron microscopy (SEM), and with element content, as confirmed by energy dispersive X-ray (EDX) spectrum. The graphene oxide-coated LiFePO₄ cathode shows improved electrochemical performance with a good charge-discharge capacity and cyclic stability up to 50 cycles at 1C rate, as compared with the without coated LiFePO₄. At 30 °C, the discharge capacity reaches a maximum value of 104.50 and 95.0 mAh g^?1 for graphene oxide-coated LiFePO₄ and without coated LiFePO₄ at 1C rate respectively. These results indicated improved electrochemical performance of pristine LiFePO₄ cathode after coating with graphene oxide.     

Ionic conductivity and battery characteristic studies on PEO+NaClO3 polymer electrolyte

Solid polymer electrolyte films based on poly (ethylene oxide) PEO complexed with NaClO₃ have been prepared by a solution-cast technique. The solvation of Na⁺ ion with PEO is confirmed by XRD and IR studies. Measurements of the a.c. conductivity in the temperature range 308 – 378 K and the transference numbers have been carried out to investigate the charge transport in this polymer electrolyte system. Transport number data show that the charge transport in this polymer electrolyte system is predominantly due to ions. The highest conductivity (2.12.10⁻⁴ S/cm) has been observed for the 70:30 composition. Using the polymer electrolyte solid state electrochemical cells have been fabricated. The various cell parameters are evaluated and reported.     

Transport, structural and thermal studies on nanocomposite polymer blend electrolytes for Li-ion battery applications

Nanocomposite polymer electrolytes (NCPEs) composed of poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP) as a host polymer, Poly(vinyl acetate) (PVAc) as an additive, Ethylene Carbonate (EC) as a plasticizer, Lithium Perchlorate as dopant salt and Barium Titanate (BaTiO₃) as a filler were prepared for various concentrations of BaTiO₃ using solvent casting technique. Thermal stability of the sample having maximum ionic conductivity was found using TG/DTA analysis. Nano composite polymer electrolytes were subjected to ac impedance analysis spectra for acquiring the ionic conductivity values at different temperature. Surface structure of the sample was analysed using scanning electron microscope and the complexations of samples were analysed using X-ray diffraction analysis. It was noted that the polymer electrolyte contains 8 wt. % of BaTiO₃ showed maximum ionic conductivity than the other ratios of BaTiO₃.     

A thermal and electrochemical properties research on gel polymer electrolyte membrane of lithium ion battery

N-methyl-N-propyl-piperidin-bis(trifluoromethylsulfonyl)imide/bis(trifluoromethylsulfonyl) imide lithium base/polymethyl methacrylate(PP₁₃TFSI/LiTFSI/PMMA) gel polymer electrolyte (GPE) membrane was prepared by in situ polymerization. The physical and chemical properties were comprehensively discussed. The decomposition characteristics were emphasized by thermogravimetric (TG-DTG) method in the nitrogen atmosphere at the different heating rates of 5, 10, 15 and 20 °C min⁻¹, respectively. The activation energy was calculated with the iso-conversional methods of Ozawa and Kissinger, Friedman, respectively, and the Coats-Redfern methods were adopted to employ the detailed mechanism of the electrolyte membrane. The equation f(α)=3/2[(1−α)^1/3−1] was quite an appropriate kinetic mechanisms to describe the thermal decomposition process with an activation energy (E_α) of 184 kJ/mol and a pre-exponential factor (A) of 1.894×10¹¹ were obtained.     

Synthesis of LiCoPO4 as a cathode material for lithium-ion battery by a polymer method

A polymer method has been used to synthesize high operation voltage LiCoPO₄ cathode material. Thermogravimetric analysis and differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM),galvanostatic charge–discharge test and cyclic voltammetry (CV) are used to study the LiCoPO ₄ . The results show LiCoPO₄ has a well-crystallized olivine structure with submicron size. In the range of 3.0–5.1 V, the initial discharge capacities of polymer material are 97.3, 91.5, and 86.5 mAh g^?1 at 0.1, 0.2. and 1 C, respectively. Thus, the polymer method has a great potential in preparing electrode materials for lithium-ion batteries.     

New polymer electrolyte based on (PVA–PAN) blend for Li-ion battery applications

A polymer blend electrolyte based on polyvinyl alcohol (PVA) and polyacrylonitrile (PAN) was prepared by a simple solvent casting technique in different compositions. The ionic conductivity of polymer blend electrolytes was investigated by varying the PAN content in the PVA matrix. The ionic conductivity of polymer blend electrolyte increased with the increase of PAN content. The effect of lithium salt concentrations was also studied for the polymer blend electrolyte of high ionic conductivity system. A maximum ionic conductivity of 3.76×10⁻³ S/cm was obtained in 3 M LiClO₄ electrolyte solution. The effect of ionic conductivity of polymer blend electrolyte was measured by varying the temperature ranging from 298 to 353 K. Linear sweep voltammetry and DC polarization studies were carried out to find out the stability and lithium transference number of the polymer blend electrolyte. Finally, a prototype cell was assembled with graphite as anode, LiMn₂O₄ as cathode, and polymer blend electrolyte as the electrolyte as well as separator, which showed good compatibility and electrochemical stability up to 4.7 V.     

A novel and shortcut method to prepare ionic liquid gel polymer electrolyte membranes for lithium-ion battery

The ionic liquid polymer electrolyte (IL-PE) membrane is prepared by ultraviolet (UV) cross-linking technology with polyurethane acrylate (PUA), methyl methacrylate (MMA), ionic liquid (Py₁₃TFSI), lithium salt (LiTFSI), ethylene glycol dimethacrylate (EGDMA), and benzoyl peroxide (BPO). N-methyl-N-propyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py₁₃TFSI) ionic liquid is synthesized by mixing N-methyl-N-propyl pyrrolidinium bromide (Py₁₃Br) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The addition of Py₁₃TFSI to polymer electrolyte membranes leads to network structures by the chain cross-linking. The resultant electrolyte membranes display the room temperature ionic conductivity of 1.37 × 10^?3 S cm^?1 and the lithium ions transference number of 0.22. The electrochemical stability window of IL-PE is about 4.8 V (vs. Li⁺/Li), indicating sufficient electrochemical stability. The interfacial resistances between the IL-PE and the electrodes have the less change after 10 cycles than before 10 cycles. IL-PE has better compatibility with the LiFePO₄ electrode and the Li electrode after 10 cycles. The first discharge performance of Li/IL-PE/LiFePO₄ half-cell shows a capacity of 151.9 mAh g^?1 and coulombic efficiency of 87.9%. The discharge capacity is 131.9 mAh g^?1 with 95.5% coulombic efficiency after 80 cycles. Therefore, the battery using the IL-PE exhibits a good cycle and rate performance.     

Ion transport and battery discharge characteristics of polymer electrolyte based on PEO complexed with NaFeF4 salt

Ion-conducting solvent-free solid polymer electrolytes based on polyethylene oxide (PEO) complexed with sodium ferric tetrafluoride (NaFeF₄) were prepared using a solution casting technique. The complexation of the films was investigated through X-ray diffraction and Fourier transform infrared spectroscopic studies. Measurements of DC conductivity in the temperature range 300–370 K and the transference numbers were carried out to investigate the nature of charge transport in the polymer electrolyte system. Transference number data shows that the charge transport in this system is found to be predominantly due to ions. Using these polymer electrolytes, electrochemical cells were fabricated with the configuration of Na/(PEO+NaFeF₄)/(I₂+C+electrolyte). Various cell parameters, such as open circuit voltage, short circuit current, power density, and energy density of the device were evaluated and reported.     

A polymer electrolyte based on poly(vinylidene fluoride-hexafluoropylene)/hydroxypropyl methyl cellulose blending for lithium-ion battery

A polymer electrolyte based on the blending of poly(vinylidene fluoride-hexafluoropylene) (PVDF-HFP) and hydroxypropyl methyl cellulose (HPMC) was prepared for the first time. The structure and performance of the gel polymer electrolyte were characterized and measured by X-ray diffraction, Fourier transform infrared, thermogravimetric analysis, scanning electron microscopy, electrochemical impedance spectroscopy, linear sweep voltammetry, and by a charge/discharge test. The results show that the gel polymer electrolyte has the best performance when PVDF-HFP/HPMC ratio (w/w) is 4:1. At room temperature, the ionic conductivity can reach 0.38?×?10^?3 S cm^?1, the electrochemical stable window is up to 5.0 V (vs. Li/Li⁺), and the half cell of Li/GPE/LiMn₂O₄ shows high-discharge-specific capacity and good cycling performance.     

Electrochemical properties of modified negative electrode for Ni-MH cell

This study discusses the influence of different composition of negative electrode material on the performance of Ni-MH cells. Two major groups of multicomponent alloys were used during the experiments: AB₅ and AB₂ types. The best capacity was observed for the AB₅-type alloy with the highest content of Co in its structure. The presence of Co in the alloy increased the capacity of the negative electrode most likely as a result of hydriding/dehydriding processes or Faradaic reaction following the dissolution-precipitation mechanism. The influence of different amounts of nickel (0–20 wt%) was determined. The presence of nickel in the electrode materials increased the current density as well as the diffusion of hydrogen into the bulk of alloys. Moreover, the carbon materials have been used as an additive for negative electrode grains in order to increase the conductivity and hydrogen sorption properties.     

Electrodeposition study of simulated and dissolution solutions of the positive electrode of a spent Ni-MH battery using the electrochemical quartz crystal microbalance and inductively coupled plasma optical emission spectrometry

Ionics - The use of electrochemical quartz crystal microbalance (EQCM) and inductively coupled plasma optical emission spectrometry (ICP-OES) as well as potentiodynamic and potentiostatic methods...     

Study on ionic conductivity of polymer electrolyte plasticized with PEG–aluminate ester for rechargeable lithium ion battery

We have synthesized poly(ethylene glycol) (PEG)-aluminate ester as a plasticizer for solid polymer electrolytes. The thermal stability, ionic conductivity and electrochemical stability of the polymer electrolyte which consist of poly(ethylene oxide) (PEO)-based copolymer, PEG–aluminate ester and lithium bis-trifluoromethanesulfonimide (LiTFSI) were investigated. Addition of PEG–aluminate ester increased the ionic conductivity of the polymer electrolyte, showing greater than 10^− 4 S cm^− 1 at 30 °C. The polymer electrolyte containing PEG–aluminate ester retained thermal stability of the non-additive polymer electrolyte and exhibited electrochemical stability up to 4.5 V vs. Li⁺/Li at 30 °C.