Electrochemical characterization of blend polymer electrolytes based on poly(oligo[oxyethylene]oxyterephthaloyl) for rechargeable lithium metal polymer batteries

Solid polymer electrolytes composed of poly(ethylene oxide)(PEO), poly(oligo[oxyethylene]oxyterephthaloyl) and lithium perchlorate have been prepared and characterized. Addition of poly(oligo[oxyethylene]oxyterephthaloyl) to PEO/LiClO₄ reduced the degree of crystallinity and improved the ambient temperature ionic conductivity. The blend polymer electrolyte containing 40 wt.% of poly(oligo[oxyethylene]oxyterephthaloyl) showed an ionic conductivity of 2.0 × 10⁻⁵ S cm⁻¹ at room temperature and a sufficient electrochemical stability to allow application in the lithium batteries. By using the blend polymer electrolytes, the lithium metal polymer cells composed of lithium anode and LiCoO₂ cathode were assembled and their cycling performances were evaluated at 40 °C.     

Electrochemical behavior of polyamides with cyclic disulfide structure and their application to positive active material for lithium secondary battery

Polyamides (DTA-I, DTA-II, and DTA-III) containing cyclic disulfide structure were prepared by condensation between 1,2-dithiane-3,6-dicarboxylic acid (DTA) and alkyl diamine, NH₂–(CH₂)_n–NH₂ (DTA-I; n=4, DTA-II; n=6, DTA-III; n=8) and their application to positive active material for lithium secondary batteries was investigated. Cyclic voltammetry (CV) measurements under slow sweep rate (0.5 mV s⁻¹) with a carbon paste electrode containing the polyamide (DTA-I, DTA-II, or DTA-III) were performed. The results indicated that the polyamides were electroactive in the organic electrolyte solution (propylene carbonate (PC)-1,2-dimethoxyethane (DME), 1:1 by volume containing lithium salt, such as LiClO₄). The responses based on the redox of the disulfide bonds in the polyamide were observed.Test cells, Li/PC-DME (1:1. by volume) with 1 mol dm⁻³ LiClO₄/the polyamide cathode, were constructed and their performance was tested under constant current charge/discharge condition. The average capacity of the test cells with the DTA-III cathode was 64.3 Ah kg⁻¹ of cathode (135 Wh kg⁻¹ of cathode, capacity (Ah kg⁻¹) of the cathode×average cell voltage (2.10 V)). Performance of the cell with linear polyamide containing disulfide bond (–CO–(CH₂)₂–S–S–(CH₂)₂–CONH–(CH₂)₈–NH–, GTA-III) was also investigated and the average capacity was 56.8 Ah kg⁻¹ of cathode (100 Wh kg⁻¹ of cathode, capacity (Ah kg⁻¹) of the cathode×average cell voltage (1.76 V)). Cycle efficiency of the test cell with the DTA-III cathode was higher than that with the GTA-III cathode.     

Solid-state Li/LiFePO4 polymer electrolyte batteries incorporating an ionic liquid cycled at 40 °C

The cycle behaviour and rate performance of solid-state Li/LiFePO₄ polymer electrolyte batteries incorporating the N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₃TFSI) room temperature ionic liquid (IL) into the P(EO)₂₀LiTFSI electrolyte and the cathode have been investigated at 40 °C. The ionic conductivity of the P(EO)₂₀LiTFSI + PYR₁₃TFSI polymer electrolyte was about 6 × 10⁻⁴ S cm⁻¹ at 40 °C for a PYR₁₃⁺/Li⁺ mole ratio of 1.73. Li/LiFePO₄ batteries retained about 86% of their initial discharge capacity (127 mAh g⁻¹) after 240 continuous cycles and showed excellent reversible cyclability with a capacity fade lower than 0.06% per cycle over about 500 cycles at various current densities. In addition, the Li/LiFePO₄ batteries exhibited some discharge capability at high currents up to 1.52 mA cm⁻² (2 C) at 40 °C which is very significant for a lithium metal-polymer electrolyte (solvent-free) battery systems. The addition of the IL to lithium metal-polymer electrolyte batteries has resulted in a very promising improvement in performance at moderate temperatures.     

Photocured PEO-based solid polymer electrolyte and its application to lithium–polymer batteries

A solid polymer electrolyte (SPE) based on polyethylene oxide (PEO) is prepared by photocuring of polyethylene glycol acrylates. The conductivity is greatly enhanced by adding low molecular weight poly(ethylene glycol) dimethylether (PEGDME). The maximum conducticity is 5.1×10⁻⁴ S cm⁻¹ at 30°C. These electrolytes display oxidation stability up to 4.5 V against a lithium reference electrode. Reversible electrochemical plating/stripping of lithium is observed on a stainless steel electrode. Li/SPE/LiMn₂O₄ as well as C(Li)/SPE/LiCoO₂ cells have been fabricated and tested to demonstrate the applicability of the resulting polymer electrolytes in lithium–polymer batteries.     

All-solid-state lithium secondary batteries using a layer-structured LiNi0.5Mn0.5O2 cathode material

All-solid-state cells of In/LiNi_0.5Mn_0.5O₂ using a superionic oxysulfide glass with high conductivity at room temperature of 10⁻³ S cm⁻¹ as a solid electrolyte were fabricated and the cell performance was investigated. Although a large irreversible capacity was observed at the 1st cycle, the solid-state cells worked as lithium secondary batteries and exhibited excellent cycling performance after the 2nd cycle; the cells kept charge–discharge capacities around 70 mAh g⁻¹ and its efficiency was almost 100%. This is the first case to confirm that all-solid-state cells using manganese-based layer-structured cathode materials work as lithium secondary batteries.     

Effects of addition of TiO2 nanoparticles on mechanical properties and ionic conductivity of solvent-free polymer electrolytes based on porous P(VdF-HFP)/P(EO-EC) membranes

To enhance the performance (i.e., mechanical properties and ionic conductivity) of pore-filling polymer electrolytes, titanium dioxide (TiO₂) nanoparticles are added to both a porous membrane and its included viscous electrolyte, poly(ethylene oxide-co-ethylene carbonate) copolymer (P(EO-EC)). A porous membrane with 10 wt.% TiO₂ shows better performance (e.g., homogeneous distribution, high uptake, and good mechanical properties) than the others studied and is therefore chosen as the matrix to prepare polymer electrolytes. A maximum conductivity of 5.1 × 10⁻⁵ S cm⁻¹ at 25 °C is obtained for a polymer electrolyte containing 1.5 wt.% TiO₂ in a viscous electrolyte, compared with 3.2 × 10⁻⁵ S cm⁻¹ for a polymer electrolyte without TiO₂. The glass transition temperature, T_g is lowered by the addition of TiO₂ (up to 1.5 wt.% in a viscous electrolyte) due to interaction between P(EO-EC) and TiO₂, which weakens the interaction between oxide groups of the P(EO-EC) and lithium cations. The overall results indicate that the sample prepared with 10 wt.% TiO₂ for a porous membrane and 1.5 wt.% TiO₂ for a viscous electrolyte is a promising polymer electrolyte for rechargeable lithium batteries.     

Recent developments and future prospects for lithium rechargeable batteries

Possible future developments of lithium rechargeable batteries are discussed. Lithium ion liquid electrolyte batteries are now well established, with energy densities of up to around 150 Wh kg⁻¹. There are prospects of increases in the energy density to perhaps 200–250 Wh kg⁻¹ by using new cathode materials (lithium nickel cobalt oxide) and light weight construction. High power cells make it possible for these batteries to find new uses, e.g. in military applications. Some new materials could reduce the cost, which might make lithium rechargeable batteries economic for electric vehicles.     

Lithium ion and electronic conductivity in 3-(oligoethylene oxide)thiophene comb-like polymers

The Li-ion and electronic conductivities of a series of p-doped poly(thiophene)s with oligo-ethylene oxide side chains have been determined at room temperature as functions of side-chain length and concentration of LiOTf dissolved in the polymers in order to assess their utility as binders in Li-ion batteries. The lithium triflate concentration was varied from 0.23 to 2.26 mmol LiOTf/g –C₂H₄O– (100 O:Li to 10 O:Li), and the concentration of dissociated Li⁺ was determined from the IR spectra of the polymer solutions. The greatest ionic conductivity, 2 × 10⁻⁴ S cm⁻¹, was attained with intermediate concentrations of added salt that corresponded with the greatest degree of LiOTf dissociation. Li-ion mobilities of 5 × 10⁻⁷ cm² (Vs)⁻¹ were measured for poly(thiophene)s (PT) with short oligo(ethylene oxide) side-chains (E_n), PE₂T and PE₃T, whereas the polymers with longer side chains, PE₇T and PE₁₅T, had Li-ion mobilities about an order of magnitude greater, 5 × 10⁻⁶ cm² (Vs)⁻¹. The electronic conductivity of the polymers heavily doped with NOBF₄ was near 0.1 S cm⁻¹ for PE₂T and PE₃T, but was orders of magnitude smaller for the polymers with longer side-chains. Addition of LiOTf caused the electronic conductivity of PE₂T and PE₃T to drop to that of the longer chain polymers whose conductivities were insensitive to the LiOTf concentration.     

New dry and wet Zn-polyaniline bipolar batteries and prediction of voltage and capacity by ANN

Chemically synthesized polyaniline doped with perchlorate ion was used as the electroactive material of the cathode in the construction of bipolar rechargeable batteries based on carbon doped polyethylene (CDPE) as a conductive substrate of the bipolar electrodes. A significant improvement in the originally poor adherence between the polymer foil and electroactive material layer of the anode was achieved by chemical pretreatment (etching) and single-sided metallization of the polymer foil with copper. A thin layer of optalloy was electroplated onto the surface of the copper-coated polymer foil to increase the battery overvoltage. A mixture of 1 wt% electrochemically synthesized optalloy, 92 wt% electrochemically synthesized zinc powder, 2 wt% MgO, 4 wt% ZnO and 1 wt% sodium carboxymethyl cellulose (CMC) was used as the anode mixture. Then, the electroactive mixture of the anode was coated onto the metallized surface of the CDPE. Graphite powder was used to coat the other side of the CDPE at 90 °C at 1 t cm⁻² pressure This side was coated with a cathode mixture containing 80 wt% polyaniline powder, 18 wt% graphite powder and 2 wt% acetylene black. The battery electrolyte contained 1 M Zn(ClO₄)₂ and 0.5 M NH₄ClO₄ and 1.0 × 10⁻⁴ M Triton X-100 at pH 3.2. Both 3.2 V dry and wet bipolar batteries were constructed using a bipolar electrode and tested successfully during 200 charge–discharge cycles. The battery possessed a high capacitance of 130 mAh g⁻¹ and close to 100% columbic efficiency. The loss of capacity during charge–discharge cycles for the wet bipolar battery was less than that for the dry bipolar battery. Self-discharge of the dry and wet batteries during a storage time of 30 days was about 0.64% and 0.45% per day, respectively. An artificial neural network (ANN) was used to model the voltage and battery available capacity (BAC) only for the dry bipolar battery at different currents and different times of discharge.     

Electrochemical properties of the Li-ion polymer batteries with P(VdF-co-HFP)-based gel polymer electrolyte

Gel polymer electrolytes consisting of 25 wt.% P(VdF-co-HFP), 65 wt.% ethylene carbonate + propylene carbonate and 10 wt.% LiN(CF₃SO₂)₂ are prepared using by a solvent-casting technique. The electrodes are for use in lithium-ion polymer batteries. The electrochemical characteristics of the gel polymer electrolytes are evaluated by means of ac impedance and cyclic voltammetry. The charge–discharge performance of lithium polymer and lithium-ion polymer batteries is examined. A LiCoO₂ | gel polymer electrolyte (GPE) | mesocarbon microbeads (MCMB) cell delivers a discharge capacity of 146.8 and 144.5 mAh g⁻¹ on the first and the 20th cycle, respectively. The specific discharge capacity is greater than 140 mAh g⁻¹ for up to 20 cycle at all the current densities examined.     

Electrochemical lithium insertion into amorphous MoO3·2H2O

Following the route of synthesis of β-MoO₃ through soft chemistry methods a new amorphous material with composition MoO₃·2H₂O has been detected. The hydrated molybdenum oxide showed the capacity for electrochemical lithium insertion. The maximum amount of lithium incorporated in this material (∼3.3 Li/Mo) leads to a specific capacity of 490 Ah kg⁻¹. The charge–discharge curve showed a good reversibility in the potential range from 3.2 to 1.1 V versus Li⁺/Li⁰ where the cell voltage decreased monotonously as a function of the degree of lithium inserted. The electrochemical features of amorphous MoO₃·2H₂O suggest that it can be considered as a possible cathode candidate in rechargeable lithium batteries.     

Polymeric gel electrolytes reinforced with glass-fibre cloth for lithium secondary batteries

Polymeric gel electrolytes (PGE), based on polyacrylonitrile blended with poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-co-HFP)), which are reinforced with glass-fibre cloth (GFC) to increase the mechanical strength, are prepared for the practical use in lithium secondary batteries. The resulting electrolytes exhibit electrochemical stability at 4.5 V against lithium metal and a conductivity value of (2.0–2.1)×10⁻³ S cm⁻¹ at room temperature. The GFC–PGE electrolytes show excellent strength and flexibility when used in batteries even if they contain a plasticiser. A test cell with LiCoO₂ as a positive electrode and mesophase pich-based carbon fibre (MCF) as a negative electrode display a capacity of 110 mAh g⁻¹ based on the positive electrode weight at the 0.2 C rate at room temperature. Over 80% of the initial capacity is retained after 400 cycles. This indicates that GFC is suitable as a reinforcing material to increase the mechanical strength of gel-based electrolytes for lithium secondary batteries.     

Structure and performance of porous polymer electrolytes based on P(VDF-HFP) for lithium ion batteries

In order to develop polymer electrolyte for lithium ion batteries, highly porous P(VDF-HFP) membranes were prepared by using phase inversion method, then they were immerged in 1 mol kg⁻¹ solution of LiClO₄-EC/PC(1:1) to form porous polymer electrolytes. Conductivity of the polymer electrolytes was found to be as high as 10⁻³ S cm⁻¹. Structures of the porous membranes were observed with SEM. Porous membranes with different structure, porosity and pore diameter were prepared by changing the processing conditions. There are two kinds of typical structure, one is honeycomb-like (type I), and the other is network-like (type II). Membrane structures were found to be important to the performance of the porous polymer electrolytes. Small pore diameter with narrow distribution is needed to prevent solution leakage and high porosity is needed to achieve high conductivity. The type II membranes can meet the requirements. The model lithium ion batteries made of the resulting porous polymer electrolytes have good cycleablity.     

Preparation of LiMn2O4 at the low temperature of 250 °C using eutectic self-mixing method

Spinel LiMn₂O₄ as a cathode material for lithium rechargeable batteries is prepared at the low temperature of 250 °C without any artificial mixing procedures of reactants. The phase transitions of lithium manganese oxide are found three times on heating at 250 °C. The prepared material exhibits the initial discharge capacity of 85.5 mAh g⁻¹ and the discharge capacity retention of 91.5% after 50 cycles.     

Further development of lithium/polycarbon monofluoride envelope cells

Lithium primary cells in a light weight plastic envelope format have been made using carbon monofluoride (CF_x) as cathode material, because previous work showed that this cathode material has the highest energy density in lithium primary batteries. Energy densities of around 650 Wh kg⁻¹ were obtained in an envelope cell. Different electrolytes have been examined for high rate and low temperature performance.     

Electrochemical characteristics of room temperature Li/FeS2 batteries with natural pyrite cathode

Electrochemical characteristics of Li/FeS₂ batteries having natural pyrite as cathode and liquid electrolytes have been studied at room temperature. The organic electrolytes used were 1 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in tetra(ethylene glycol) dimethyl ether (TEGDME) or a mixture of TEGDME and 1,3-dioxolane (DOX), and 1 M LiPF₆ in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC). The pyrite powder and FeS₂ cathode were characterized by SEM, EDS, XRD and charge/discharge cycling. The discharge capacities of Li/FeS₂ cells with 1 M LiTFSI dissolved in TEGDME were 772 mAh g⁻¹ at the 1st cycle and 313 mAh g⁻¹ at the 25th cycle at 0.1C. The cycling performance could be improved by using a mixture of TEGDME and DOX as the electrolyte. It was found that TEGDME contributed to high initial discharge capacity, whereas, DOX contributed to better stabilization of the performance. The first discharge capacities of Li/FeS₂ cells showed a decreasing trend with higher current densities (615 and 534 mAh g⁻¹, respectively, at 0.5C and 1.0C). Li/FeS₂ cells with the battery grade electrolyte 1 M LiPF₆ in EC/DMC had lower initial discharge capacity and cycling capability compared to the TEGDME system. The natural pyrite cathode with 1 M LiTFSI dissolved in a mixture of TEGDME and DOX showed reasonably good first discharge capacity and overall cycling performance, suitable for application in room temperature lithium batteries.     

Exfoliation-induced nanoribbon formation of poly(3,4-ethylene dioxythiophene) PEDOT between MoS2 layers as cathode material for lithium batteries

A new type of layered nanocomposite synthesized by delaminated MoS₂ nanosheets and poly(3,4-ethylenedioxythiophene) (PEDOT) are restacked to produce alternate polymer nanoribbons between layers of MoS₂ with an interlayer distance of ∼1.38 nm. The unique properties of resulting nanocomposite are investigated by powder XRD, XPS, SEM, TEM, and four-probe conductivity measurements. The obtained nanocomposite can be used as a cathode material for a small power rechargeable lithium battery as demonstrated by the electrochemical insertion of lithium into the PEDOT/MoS₂ nanocomposite. A significant enhancement in the discharge capacity (100 mAh g⁻¹) is observed compared with that (40 mAh g⁻¹) for MoS₂.     

Effect of (Al,Mg) substitution in LiNiO2 electrode for lithium batteries

Stabilized lithium nickelate is receiving increased attention as a low-cost alternative to the LiCoO₂ cathode now used in rechargeable lithium batteries. Layered LiNi_1−x−yM_xM_yO₂ samples (M_x = Al³⁺ and M_y = Mg²⁺, where x = 0.05, 0.10 and y = 0.02, 0.05) are prepared by the refluxing method using acetic acid at 750 °C under an oxygen stream, and are subsequently subjected to powder X-ray diffraction analysis and coin-cell tests. The co-doped LiNi_1−x−yAl_xMg_yO₂ samples show good structural stability and electrochemical performance. The LiNiAl_0.05Mg_0.05O₂, cathode material exhibits a reversible capacity of 180 mA h g⁻¹ after extended cycling. These results suggest that the threshold concentration for aluminum and magnesium substitution is of the order of 5%. The co-substitution of magnesium and aluminium into lithium nickelate is considered to yield a promising cathode material.     

Effect of ball milling on structural and electrochemical properties of (PEO)nLiX (LiX = LiCF3SO3 and LiBF4) polymer electrolytes

Polymer electrolytes consisting of poly(ethylene oxide) (PEO) and lithium salts, such as LiCF₃SO₃ and LiBF₄ are prepared by the ball-milling method. This is performed at various times (2, 4, 8, 12 h) with ball:sample ratio of 400:1. The electrochemical and thermal characteristics of the electrolytes are evaluated. The structure and morphology of PEO–LiX polymer electrolyte is changed to amorphous and smaller spherulite texture by ball milling. The ionic conductivity of the PEO–LiX polymer electrolytes increases by about one order of magnitude than that of electrolytes prepared without ball milling. Also, the ball milled electrolytes have remarkably higher ionic conductivity at low temperature. Maximum ionic conductivity is found for the PEO–LiX prepared by ball milling for 12 h, viz. 2.52×10⁻⁴ S cm⁻¹ for LiCF₃SO₃ and 4.99×10⁻⁴ S cm⁻¹ for LiBF₄ at 90 °C. The first discharge capacity of Li/S cells increases with increasing ball milling time. (PEO)₁₀LiCF₃SO₃ polymer electrolyte prepared by ball milling show the typical two plateau discharge curves in a Li/S battery. The upper voltage plateau for the polymer electrolyte containing LiBF₄ differs markedly from the typical shape.     

Effect of synthesis conditions on the properties of LiFePO4 for secondary lithium batteries

LiFePO₄ is one of the promising materials for cathode of secondary lithium batteries due to its high energy density, low cost, environmental friendliness and safety. However, LiFePO₄ has very poor electronic conductivity (∼10⁻⁹ S cm⁻¹) and Li-ion diffusion coefficient (∼1.8 × 10⁻¹⁴ cm² s⁻¹) at room temperature. In an attempt to improve electrochemical properties, Li_XFePO₄ with various amounts of Li contents were investigated in this study. Li_XFePO₄ (X = 0.7–1.1) samples were synthesized by solid-state reaction. High resolution X-ray diffraction, Rietveld analysis, BET, scanning electron microscopy, and hall effect measurement system were used to characterize these samples. Electronic conductivities of the samples with Li-deficient and Li-excess in Li_xFePO₄ were 10⁻³ to 10⁻¹ S cm⁻¹. Discharge capacities and rate capabilities of the samples with Li-deficient and Li-excess in Li_XFePO₄ were higher than those of stoichiometric LiFePO₄ sample. Li_0.9FePO₄ samples fired at 700 °C had discharge capacity of 156 and 140 mAh g⁻¹ at 0.1 C- and 2 C-rate, respectively.