Boosting the performance of poly(ethylene oxide)-based solid polymer electrolytes by blending with poly(vinylidene fluoride-co-hexafluoropropylene) for solid-state lithium-ion batteries

To seek a solid polymer electrolyte (SPE) with excellent performance, a novel poly(ethylene oxide) (PEO) based SPE is prepared by blending an appropriate amount of microcrystalline poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) with PEO using a universal solution casting method. Field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) are utilized to analyse the samples. The crystallinity of the blend solid polymer electrolyte is significantly lower than that of the neat PEO-based SPE. The addition of the PVDF-HFP disrupts the segment structure of the PEO crystal region and increases the proportion of the amorphous region, thus boosting the migration of lithium ions. The results show that the electrochemical stability window of the blend solid polymer electrolyte reaches as high as 4.8 V. The initial discharge specific capacity of the solid-state LiFePO₄/SPE/Li battery is 131 mAh g⁻¹ at 0.5 C and 60°C, and the discharge specific capacity is still 110.5 mAh g⁻¹ after 100 cycles. On the basis of the results, the novel SPE has a widespread application prospects in solid-state lithium-ion batteries.     

A poly(3-decyl thiophene)-modified separator with self-actuating overcharge protection mechanism for LiFePO4-based lithium ion battery

A voltage-sensitive separator is prepared simply by impregnating electroactive poly(3-decylthiophene) (P3DT) polymer into a commercial porous separator and tested for a self-actuating control of overcharge voltage of LiFePO₄/C lithium-ion batteries. The experimental results demonstrate that this type of separator can be reversibly p-doped and dedoped to maintain the cell's voltage at a safe value of ≤4 V even at high rate overcharge of 3 C current, effectively protecting the batteries from voltage runaway. Since this P3DT-modified separator has no obvious negative impact on the normal charge-discharge performance of the batteries, it may be adopted for practical application in commercial lithium ion batteries.     

A highly efficient surface modified separator fabricated with atmospheric atomic layer deposition for high temperature lithium ion batteries

A high throughput mass production of separator is proposed using a well-established unique in-house process of roll-to-roll atmospheric atomic layer deposition. An ultra-thin conformal layer of Al₂O₃ is deposited over the commercial Celgard (PE/PP/PE) using multi-slit gas source head. Overall 10 nm increase is incurred in the thickness, while maintaining the porosity to ~48%. The entire process of fabrication was performed at very low temperature of 90°C. The high thermal stability of as-modified separator is achieved at of 180°C. The separator was analyzed using X-ray photoelectron spectrometer, electrochemical impedance spectra, and field emission scanning electron microscope. The as-developed separator showed excellent wettability due to the surface medication in addition to robust flexibility, high conformity, and minimal thermal shrinkage. The Lithium cobalt oxide (LCO)/Graphite cells with atomic layer deposition (ALD) Celgard (Al₂O₃ deposited) separator delivered remarkable discharge capacity with 79.5% capacity retention after 100 cycles at 1 C as compared to the uncoated-separator(Celgard separator), which yielded relatively less retention of ~70%. Moreover, the LCO/Graphite cells with the ALD-Celgard separator delivered the discharge capacity of 140 mAh/g at elevated temperature (up to 80°C).     

High‐performance solid PEO/PPC/LLTO‐nanowires polymer composite electrolyte for solid‐state lithium battery

Solid polymer composite electrolyte (SPCE) with good safety, easy processability, and high ionic conductivity was a promising solution to achieve the development of advanced solid‐state lithium battery. Herein, through electrospinning and subsequent calcination, the Li_0.33La_0.557TiO₃ nanowires (LLTO‐NWs) with high ionic conductivity were synthesized. They were utilized to prepare polymer composite electrolytes which were composed of poly (ethylene oxide) (PEO), poly (propylene carbonate) (PPC), lithium bis (fluorosulfonyl)imide (LiTFSI), and LLTO‐NWs. Their structures, thermal properties, ionic conductivities, ion transference number, electrochemical stability window, as well as their compatibility with lithium metal, were studied. The results displayed that the maximum ionic conductivities of SPCE containing 8 wt.% LLTO‐NWs were 5.66 × 10^?5 S cm^?1 and 4.72 × 10^?4 S cm^?1 at room temperature and 60°C, respectively. The solid‐state LiFePO₄/Li cells assembled with this novel SPCE exhibited an initial reversible discharge capacity of 135 mAh g^?1 and good cycling stability at a charge/discharge current density of 0.5 C at 60°C.     

Significant effects of poly(3,4-ethylenedioxythiophene) additive on redox responses of poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene) cathode for rechargeable Li batteries

Redox behaviors of the poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene) (PDBM)-coated electrodes composited with carbon black (CB) or poly(3,4-ethylenedioxy-thiophene) (PEDOT) are presented. Effects of PEDOT additive on the redox activity of PDBM were investigated to apply their composite materials as candidates of cathodes for rechargeable lithium batteries. The film having a PEDOT/PDBM with weight ratio of 1/1 shows a gravimetric capacity of 129 mAh g⁻¹ (corresponding to 188 mAh g⁻¹ for PDBM and 70 mAh g⁻¹ for PEDOT). The highest energy density observed was 140 mAh g⁻¹ (406 mWh g⁻¹) for the composite cathode. Good cycle-ability over 100 cycles was attained with a PEDOT/PDBM composite cathode.     

Polypropylene-supported and nano-Al2O3 doped poly(ethylene oxide)-poly(vinylidene fluoride-hexafluoropropylene)-based gel electrolyte for lithium ion batteries

A new gel polymer electrolyte (GPE) is reported in this paper. In this GPE, blending polymer of poly(ethylene oxide) (PEO) with poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP)), doped with nano-Al₂O₃ and supported by polypropylene (PP), is used as polymer matrix, namely PEO-P(VdF-HFP)-Al₂O₃/PP. The performances of the PEO-P(VdF-HFP)-Al₂O₃/PP membrane and the corresponding GPE are characterized with mechanical test, CA, EIS, TGA and charge-discharge test. It is found that the performances of the membrane and the GPE depend to a great extent on the content of doped nano-Al₂O₃. With doping 10 wt.% nano-Al₂O₃ in PEO-P(VdF-HFP), the mechanical strength from 9.3 MPa to 14.3 MPa, the porosity of the membrane increases from 42% to 49%, the electrolyte uptake from 176% to 273%, the thermal decomposition temperature from 225 °C to 355 °C, and the ionic conductivity of corresponding GPE is improved from 2.7 × 10⁻³ S cm⁻¹ to 3.8 × 10⁻³ S cm⁻¹. The lithium ion battery using this GPE exhibits good rate and cycle performances.     

Preparation and characterization of electrospun poly(acrylonitrile) fibrous membrane based gel polymer electrolytes for lithium-ion batteries

Electrospun, non-woven membrane of high molecular weight poly(acrylonitrile) (PAN) is demonstrated as an efficient host matrix for the preparation of gel polymer electrolytes for lithium-ion batteries. Electrospinning process parameters are optimized to get a fibrous membrane of PAN consisting of bead-free, uniformly dispersed thin fibers with diameter in the range 880-1260 nm. The membrane with good mechanical strength and porosity exhibits high uptake when activated with the liquid electrolyte of 1 M LiPF₆ in a mixture of organic solvents and the gel polymer electrolyte shows ionic conductivity of 1.7 × 10⁻⁵ S cm⁻¹ at 20 °C. Electrochemical performance of the gel polymer electrolyte at 20 °C is evaluated in lithium-ion cell with lithium cobalt oxide cathode and graphite anode. Good performance with a low capacity fading on charge-discharge cycling is demonstrated.     

Porous NiO/poly(3,4-ethylenedioxythiophene) films as anode materials for lithium ion batteries

NiO/poly(3,4-ethylenedioxythiophene) (PEDOT) films are prepared by chemical bath deposition and electrodeposition techniques using nickel foam as the substrate. These composite films are porous, and constructed by many interconnected nanoflakes. As anode materials for lithium ion batteries, the NiO/PEDOT films exhibit weaker polarization and better cycling performance as compared to the bare NiO film. Among these composite films, the NiO/PEDOT film deposited after 2 CV cycles has the best cycling performance, and its specific capacity after 50 cycles at the current density of 2 C is 520 mAh g⁻¹. The improvements of these electrochemical properties are attributed to the PEDOT, a highly conductive polymer, which covers on the surfaces of the NiO nanoflakes, forming a conductive network and thus enhances the electrical conduction of the electrode.     

A poly(ethylene glycol)-based smart phase change material

A shape memory thermoplastic polyurethane (PU) as a phase change material (PCM) was synthesized by employing poly(ethylene glycol) (PEG) as the soft segment via bulk polymerization. Its phase separation structure, crystalline morphology, phase change behaviors, dynamic mechanical properties and melt-processing ability were investigated using polarizing optical microscopy, atomic force microscopy, differential scanning calorimetry, dynamic mechanical analysis, thermogravimetry and melt flow index. A well-formed phase separation structure in the PEG-based polyurethane (PEGPU) was found which accounts for most of the material phase change properties and shape memory effect. The PEG soft segment phase transition between crystalline and amorphous states resulted in heat storage and release of the PEGPU. Due to the hydrogen bonded hard segment phase serving as “physical cross-linking” restricted the free movement of the soft segments, at temperature above the PEG phase melting transition, the PEGPU was still solid. The differential scanning calorimetry results indicated that the PEGPU had high latent heat storage capacity of more than 100 J/g. The dynamic mechanical analysis results showed that it had a plateau elastic modulus about 40 MPa in the region above the PEG phase melting transition while below 150 °C. The thermogravimetry results suggested that the PEGPU had a much broader applicable temperature range compared with pure PEG. The melt flow index results indicated that the material had a good melt-processing ability. The material shape fixity ratio was more than 84% and shape recovery ratio up to 93.7% obtained from thermomechanical cyclic tensile testing.     

Macroporous poly(vinylidene fluoride) membrane as a separator for lithium-ion batteries with high charge rate capacity

The performance of PVdF macroporous separators used in lithium battery at high charge rates was evaluated using Li₄Ti₅O₁₂ and LiMn₂O₄ as negative and positive electrodes respectively. The effects of the non-solvent used, the PVdF concentration in the good solvent and the thickness of the swelled membrane on membrane porosity and on the conductivity of the separator + liquid electrolyte were evaluated. The conductivity decrease, induced by the porous separator introduction and separator thickness influence notably battery performance for high charge rate.     

Sulfonated poly(ether sulfone)-based silica nanocomposite membranes for high temperature polymer electrolyte fuel cell applications

Fuel Cell operation at high temperature (e.g. 120 °C) and low relative humidity (e.g. 50%) remains challenging due to creep (in the case of Nafion^®) and membrane dehydration. We approached this problem by filling PES 70, a sulfonated poly(ether sulfone) with a T_g of 235 ± 5 °C and a theoretical IEC of 1.68 mmol g⁻¹, with 5-20% silica nano particles of 7 nm diameter and 390 ± 40 m² g⁻¹ surface area. While simple stirring of particles and polymer solutions led to hazy, strongly anisotropic (air/glass side) and sometimes irregular shaped membranes, good membranes were obtained by ball milling. SEM analysis showed reduced anisotropy and TEM analysis proved that the nanoparticles are well embedded in the polymer matrix. The separation length between the ion-rich domains was determined by SAXS to be 2.8, 2.9 and 3.0 nm for PES 70, PES 70-S05 and Nafion^® NRE 212, respectively. Tensile strength and Young’s modulus increase with the amount of silica. Ex-situ in-plane proton conductivity showed a maximum for PES 70-S05 (2 mS cm⁻¹). In the fuel cell (H₂/air, 120 °C, <50%), it showed a current density of 173 mA cm⁻² at 0.7 V, which is 3.4 times higher than for PES 70.     

Sulfonated poly(arylene ether nitrile)-based hybrid membranes containing amine-functionalized GO for constructing long-range ionic nanochannels

To simultaneously balance proton conduction and methanol diffusion, the acid-base hybrid membranes based on sulfonated poly(arylene ether nitrile) (SPEN) with 3-aminopropyltriethoxysilane functionalized graphene oxide (NGO) are prepared by solution-casting method. The loading of NGO is varied to explore the influence on cross-sectional morphology, dimensional stability, proton conductivity and methanol permeability of composite membranes. In this way, the interfacial ionic nanochannels are established at the interface of NGO and SPEN, constructing the long-range ionic nanochannels to provide fast proton transfer. Meanwhile, the formation of more zigzag transportation channels could effectively prevent methanol diffusion. The improved properties of the composite membranes can be attributed to the excellent interfacial interactions induced by acid-base and hydrogen bonding interactions. The composite membrane with 1 wt% NGO shows high proton conductivity (0.104 S·cm^?1 at 20 °C) and low methanol permeability (1.74 × 10^?7 cm²·s^?1 at 20 °C), exhibiting higher selectivity (5.977 × 10⁵ S cm^?3s) compared with pure SPEN and Nafion 117 membranes. Therefore, it will provide a feasible pathway to conquer the trade-off effect between proton conductivity and methanol resistance for direct methanol fuel cells (DMFC) applications.     

A novel flame retardant and film-forming electrolyte additive for lithium ion batteries

Allyl tris(2,2,2-trifluoroethyl) carbonate (ATFEC) was synthesized as a bi-functional additive of flame retardant and film former in electrolytes for lithium ion batteries (LIBs). The flame retardancy of the additive was characterized with differential scanning calorimetry (DSC) and self-extinguishing time (SET). It is shown that adding 1 vol.% ATFEC in 1 M LiPF₆/propylene carbonate (PC) can effectively enhance the thermal stability of the electrolyte and suppress the co-intercalation of PC into the graphitic anode. Further evaluation indicates that the additive hardly affect the conductivity of electrolyte. These support the feasibility of using ATFEC as an additive on formulating an electrolyte with multiple functions such as film-forming enhancement, high thermal stability and high ionic conductivity.     

Synthesis and characterization of a novel poly (vinyl alcohol)-based zinc oxide (PVA-ZnO) composite proton exchange membrane for DMFC

Electrolyte polymeric membranes were synthesized by impregnating zinc oxide (ZnO) nanoparticles (NPs) in a cross-linked PVA matrix for Direct Methanol Fuel Cell (DMFC) applications. The novel membranes consist of PVA as the support while zinc oxide nanoparticles serve as inorganic ion exchangers. The fabricated composite proton exchange membranes exhibit a wide variety of advantages which include good thermal and chemical stability. The synthesized membranes demonstrate a high percentage of water uptake (85%–105%) and a low percentage of methanol uptake (17%–21%). Other important properties such as transport number (0.88) and ion exchange capacity (0.78 meq.g^?1) were also determined, and they were found comparable to Nafion®117. Ionic conductivity (3.9 mS/cm) of the composite membranes was determined and found comparable to other PVA based composite membranes reported in literature. Characterization of the membranes was carried out using Fourier-Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), Scanning Electron Microscope (SEM), Energy-dispersive X-ray Spectroscopy (EDX) and Thermogravimetric analysis (TGA). These characterizations revealed the structural interaction between the support and the ion exchanger, crystalline nature, surface morphology, elemental analysis and the thermal stability (upto 280 °C) of the membranes, respectively. The mechanical characterization of the membranes was also carried out on a Universal Testing Machine (UTM), revealing satisfactory mechanical stability. The results demonstrate the possibility of synthesis of a low-cost proton exchange membrane for DMFC applications.     

Novel poly(carbazole-butanedione) anion exchange membranes constructed by obvious microphase separation for fuel cells

To develop anion exchange membranes with excellent chemical stability and high performance. A series of quaternary ammonium functionalized (hydrophilic) hydrophobic rigid poly (carbazole-butanedione) (HOCB-TMA-x) anion exchange membranes were prepared, where x represents the percentage content of hydrophobic unit octylcarbazole (OCB). Due to the introduction of hydrophobic rigid unit octylcarbazole and hexyl flexible side chain, the hydrophilic-hydrophobic microstructure of AEMs was developed. The AEMs exhibit excellent overall performance, specifically the low swelling ratio HOCB-TMA-30 membrane exhibits the highest OH^? conductivity of 152.9 mS/cm at 80 °C. Furthermore, the ionic conductivity of AEM decreased by only 9.5% after 2250 h of immersion in 1 M NaOH. The maximum peak power density of a single cell with a current density of 4.38 A/cm² at 80 °C was 1.85 W/cm².     

Inorganic-organic polymer electrolytes based on poly(vinyl alcohol) and borane/poly(ethylene glycol) monomethyl ether for Li-ion batteries

In this study, poly(vinyl alcohol) (PVA) was modified with poly(ethylene glycol) monomethyl ether (PEGME) using borane-tetrahydrofuran (BH₃/THF) complex. Molecular weights of both PVA and PEGME were varied prior to reaction. Boron containing comb-branched copolymers were produced and abbreviated as PVA1PEGMEX and PVA2PEGMEX. Then polymer electrolytes were successfully prepared by doping of the host matrix with CF₃SO₃Li at several stoichiomeric ratios with respect to EO to Li. The materials were characterized via nuclear magnetic resonance (¹H NMR and ¹¹B NMR), Fourier transform infrared spectroscopy (FT-IR), Thermogravimetry (TG) and differential scanning calorimeter (DSC). The ionic conductivity of these novel polymer electrolytes were studied by dielectric-impedance spectroscopy. Li-ion conductivity of these polymer electrolytes depends on the length of the side units as well as the doping ratio. Such electrolytes possess satisfactory ambient temperature ionic conductivity (>10⁻⁴ S cm⁻¹). Cyclic voltammetry results illustrated that the electrochemical stability domain extends over 4 V.     

Sulfonated poly(propylene oxide) oligomers/Nafion acid-base blend membranes for DMFC

A novel functional poly(propylene oxide)-backboned diamine of M_w 400 (abbreviated as D400) was grafted with sulfonic acid (abbreviated as D400-PS) to improve the performance of Nafion^® membranes in direct methanol fuel cells (DMFCs). The interaction of the D400-PS with Nafion^® was studied by Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC). The performance of the blend Nafion^®/D400-PS membranes was evaluated in terms of methanol permeability, proton conductivity and cell performance. The proton conductivity of the blend membrane was slightly reduced by rendering proton conductivity to D400 by functionalized with an organic sulfonic acid. The methanol permeability of the blend membrane decreased with increasing of D400-PS content. The methanol permeability of the blend Nafion^®/D400-PS with the composition 3/1 (–SO₃H/–NH₂) was 1.02 × 10⁻⁶ cm² S⁻¹, which was reduced 50% compared to that of pristine Nafion^®. The current densities that were measured with Nafion^®/D400-PS blend membranes in the ratio 1/0 and 5/1 (–SO₃H/–NH₂), were 51 and 72 mA cm⁻², respectively, at a potential of 0.2 V. Consequently, the blend Nafion^®/D400-PS membranes critically improved the single-cell performance of DMFC.     

A novel crosslinking strategy for preparing poly(vinyl alcohol)-based proton-conducting membranes with high sulfonation

This study synthesizes poly(vinyl alcohol) (PVA)-based polymer electrolyte membranes by a two-step crosslinking process involving esterization and acetal ring formation reactions. This work also uses sulfosuccinic acid (SSA) as the first crosslinking agent to form an inter-crosslinked structure and a promoting sulfonating agent. Glutaraldehyde (GA) as the second crosslinking agent, reacts with the spare OH group of PVA and forms, not only a dense structure at the outer membrane surface, but also a hydrophobic protective layer. Compared with membranes prepared by a traditional one-step crosslinking process, membranes prepared by the two-step crosslinking process exhibit excellent dissolution resistance in water. The membranes become water-insoluble even at a molar ratio of SO₃H/PVA-OH as high as 0.45. Moreover, the synthesized membranes also exhibit high proton conductivities and high methanol permeability resistance. The current study measures highest proton conductivity of 5.3 × 10⁻² S cm⁻¹ at room temperature from one of the synthesized membranes, higher than that of the Nafion^® membrane. Methanol permeability of the synthesized membranes measures about 1 × 10⁻⁷ cm² S⁻¹, about one order of magnitude lower than that of the Nafion^® membrane.     

A facile,effective thermal crosslinking to balance stability and proton conduction for proton exchange membranes based on blend sulfonated poly(ether ether ketone)/sulfonated poly(arylene ether sulfone)

The development of hydrocarbon polymer electrolyte membranes with high proton conductivities and good stability as alternatives to perfluorosulfonic acid membranes is an ongoing research effort. A facile and effective thermal crosslinking method was carried out on the blended sulfonated poly (ether ether ketone)/poly (aryl ether sulfone) (SPEEK/SPAES) system. Two SPEEK polymers with ion exchange capacities (IECs) of 1.6 and 2.0 mmol g^?1 and one SPAES polymer (2.0 mmol g^?1) were selected to create different blends. The effect of thermal crosslinking on the fundamental properties of the membranes, especially their physicochemical stability and electrochemical performance, were investigated in detail. The homogeneous and flexible thermally-crosslinked SPEEK/SPAES membranes displayed excellent mechanical toughness (27–46 Mpa), suitable water uptake (<60%), high dimensional stability (swelling ratio < 15%) and large proton conductivity (>120 mS cm^?1) at 80 °C. The thermal crosslinking membranes also show significantly enhanced hydrolytic (<2.5%) and oxidative stability (<2%). Fuel cell with t-SPEEK/SPAES (1:2:2) membrane achieves a power density of 665 mW cm^?2 at 80 °C.