Neutral state colorless electrochromic polymer networks: Spacer effect on electrochromic performance

A series of carbazole-based monomers and their corresponding polymers with various spacer units were synthesized and coated onto ITO-glass surface via an electrochemical cross-linking process. All carbazole-based polymers exhibited multi-electrochromic behavior thanks to two separate oxidation processes. All materials were characterized by FT-IR, ¹H NMR, GPC, DSC, UV–vis, Florescence and CV. In addition, electrochromic properties of the cross-linked polymer films were investigated via spectro-electrochemical measurements. The colorless films were converted to yellowish green and greenish blue colors at the anodic regime. The results indicate that the spacer unit between the carbazole unit and the polymer backbone has a great impact on the optical and electrochemical properties and also on the electrochromic performance of these polymers. PVBEC with benzyloxy based spacer exhibits a high contrast ratio (ΔT% = 55 at 690 nm), a faster response time of about 2.1 s, a higher coloration efficiency (331 cm² C⁻¹) and a better stability (retains its performance by 94.3% even after 1000 cycles).     

A new processable donor–acceptor polymer displaying neutral state yellow electrochromism

We report here the synthesis of a new solution processable neutral state yellow polymeric electrochromic material containing 2,5-bis-dithienyl-1H-pyrrole (SNS)-donor and 1,8 naphthalimide-acceptor (SNS–NI) as a subunit. The electrochemical and optical properties were investigated via cyclic voltammetry (CV), UV–Vis absorption and fluorescence emission measurements, respectively. Besides, electrochromic performance of poly(SNS–NI) has been compared to the both the film preparation method and poly(1-phenyl-2,5-dithiophen-2-ylpyrrole) [poly(SNS–P)] as a standard polymer. In the poly(SNS–NI), yellow color of the polymer film at neutral state converted to green and then dark blue upon the polymer film fully oxidized in the positive regime. SNS–NI polymer film prepared via spin casting process exhibits a high contrast ratio in the near-IR region (ΔT% = 56% at 890 nm), a response time of about 1 s, high coloration efficiency (299 cm² C⁻¹) and retained its performance by 98.6% even after 5000 cycles. Finally, the results clearly indicate that both electronic nature of the molecule and film preparation method have a major impact on electrochromic performance of these polymers.     

Electropolymerization of high quality electrochromic poly(3-alkyl-thiophene)s via a room temperature ionic liquid

Electrochemical polymerization in a room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF₆), has been used to prepare electrochromic poly(3-methylthiophene) (PMeT) and its more attractive derivatives: poly(3-hexylthiophene) (PHexT) and poly(3-octylthiophene) (POcT). Spectroelectrochemistry and electrochromic properties of the resulting polymers were characterized using various experiment techniques in [BMIM]PF₆/CH₃CN (1:1, v/v) solution. The thin films were bright red, orange red and orange yellow at its fully reduced state for PMeT, PHexT and POcT, respectively. After oxidization of these undoped polymers, the films underwent reversible change to the bright blue, blue or black blue form. These poly(3-alkylthiophene)s (PMeT, PHexT and POcT) films exhibit high chromatic contrast (46, 45 or 39%), comparative switching times (1.1, 1.4 or 1.9 s), great electrochromic efficiency (250, 220 and 230 cm² C⁻¹) and long-term switching stability. High quality electrochromic polymers were provided for the use of commercially available thiophene monomers, avoiding the use of other custom synthesized monomers.     

Synthesis of high-performance electrochromic thin films by a low-cost method

Metal-doping is an effective method to adjust the physical and chemical properties of semiconductor metal oxides. This work adopts a simple solvothermal method to synthesize Mo-doped tungsten oxide nanoparticles. The high-performance electrochromic films can be homogenously formed on ITO glass without post-annealing. Compared with pure WO₃ films, the optimized Mo-doped WO₃ films show improved electrochromic properties with significant optical contrast (68.3% at 633 nm), the short response time (6.3 s and 3.9 s for coloring and bleaching, respectively), and excellent coloration efficiency (107.2 cm² C^?1). The improved electrochromic behavior is mainly due to the increasing diffusion rate of Li⁺ in Mo-doped WO₃ films (increased 20% than that of pure WO₃ films). The porous surface of Mo-doped WO₃ film shortens the diffusion path of Li⁺. Besides, Mo doping reduces the resistance and improves conductivity. Furthermore, 2at% Mo-doped WO₃ films indicate satisfactory energy-storage properties (the specific capacitance is 73.8 F g^?1), resulting from the enhanced electrochemical activity and fast electrical conductivity. This work presents a practical and economical way of developing high-performance active materials for bifunctional electrochromic devices.     

Polymer Electrolytes Based on Polymeric Ionic Liquid Poly(methyl 2-(3-vinylimidazolidin-1-yl)acetate bis(trifluoromethane sulfonyl)imide)

A new kind of ionic liquid monomer methyl 2-(3-vinylimidazolidin-1-yl)acetate bromide (MVIm-Br) and polymeric ionic liquid (PIL), poly(methyl 2-(3-vinylimidazolidin-1-yl)acetate bis(trifluoromethanesulfonyl)imide) (PMVIm-TFSI), were synthesized and characterized. Different compositions of polymer electrolytes were prepared by blending PMVIm-TFSI and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) with poly(methylmethacrylate-co-vinyl acetate) (P(MMA-VAc)). The thermal stability and ionic conductivity improved significantly when PMVIm-TFSI was added into P(MMA-VAc)/LiTFSI polymer. For the polymer electrolytes obtained, the highest ionic conductivity at 30 °C is 4.71 × 10⁻⁴ S cm⁻¹ and the corresponding decomposition temperature is ca. 308 °C. Moreover, P(MMA-VAc)/PMVIm-TFSI/LiTFSI electrolyte membrane (transmittance ≥90%) can be used as the ion-conductive layer material for electrochromic devices, which reveal excellent electrochromic performance.     

Design and fabrication of MoSe2/WO3 thin films for the construction of electrochromic devices on indium tin oxide based glass and flexible substrates

Electrochromic devices (ECDs) have the ability to block the heat generated by sunlight, making them ideal for use in smart windows. Herein, we report the fabrication of ECDs using MoSe₂/WO₃ (MSW) as the electrochromic material, for smart windows applications. A solvothermal method was used for the synthesis of MoSe₂, while WO₃ was synthesized using a sol-gel approach. Subsequently, MoSe₂/WO₃ (MSW) hybrids with different wt% of MoSe₂ (0.05 wt%, 0.2 wt%, 0.5 wt%) were synthesized using an ultra-sonication approach. The physicochemical features of these MSW hybrids herein termed as MSW 0.05, MSW 0.2 and MSW 0.5, were investigated using X-ray diffraction (XRD), X-ray photon electron spectroscopic (XPS), scanning electron microscope (SEM), and EDS techniques and compared with pristine MoSe₂ and WO₃. The ECDs synthesized using MSW 0.05 showed increased coloration efficiency (62 cm^2 C-1) with an applied potential range of 0 to −1.5 V. Subsequently, the ECDs based on indium tin oxide (ITO) and MSW 0.05 demonstrated excellent electrochromic performance and stability for 10,000 cycles. The enhanced electrochromic performance of the MSW-based ECDs may be attributed to the conductive nature as well as the synergistic effects between MoSe₂ and WO₃ when compared to the WO₃-based ECDs. The synthesized MSW also showed promise as an electrochromic material in flexible ECDs for smart windows applications.     

Solvothermally grown WO3·H2O film and annealed WO3 film for wide-spectrum tunable electrochromic applications

Tungsten trioxide (WO₃) is a classical electrochromic (EC) material with advantages of abundant reserves, high coloration efficiency and cyclic stability. However, WO₃ films are often accompanied by a narrow spectrum of modulation due to a single-color change from transparent to blue. In this work, we report a wide-spectrum tunable WO₃·H₂O nanosheets EC film solvothermally grown on fluorine-doped tin oxide (FTO) glass. Interestingly, the crystalline WO₃·H₂O nanosheets film is transformed into amorphous WO₃ after annealing at 250 °C for 1 h. The amorphous film can be transformed into crystalline WO₃ film by increasing the annealing temperature to 450 °C. After annealing at 250 °C, the WO₃ film exhibits an optical modulation of 75.8% in a broad solar spectrum range of 380–1400 nm and blocks 88.9% of solar irradiance. Fast switching responses of 4.9 s for coloration and 6.0 s for bleaching, and a coloration efficiency of 86.4 cm² C⁻¹ are also achieved. Additionally, the WO₃ film annealed at 250 °C also demonstrates an excellent cyclic stability, where 99.6% of the initial optical modulation can be retained after 1500 cycles. This simple and mild solvothermal method used in this work provides a new idea for the preparation of wide-spectrum tunable WO₃ EC films.     

Electrochromism of novel triphenylamine-containing polyamide polymers

A series of novel polymers (coded as BCT-1 to BCT-6 (BTC is block triphenylamine)) based on N¹-(4-aminophenyl)-N¹-phenyl benzene-1,4-diamine, pyridine-2,6-dicarboxylic acid, 4,4′-(phenyl azanediyl)dibenzoic acid (PDA), and different diamine compounds were synthesized successfully through a polymer condensation reaction. For comparison, model polymers, BCT–2,6-pyridine dicarboxylic acid (PA) and BCT–PDA, were synthesized as well. The electrochromic properties of the BCTs were determined via an electrochemical workstation and a UV–visible spectrophotometer. Through electrooxidation, the polymer films showed reversible redox processes and steady color changes. In a comparision of the electrochromic characteristics of the BCTs, almost all the novel polymer films showed a better electrochromism stability, a higher electrochromic coloration efficiency (CE), and a more rapid switching time than BCT–PA and BCT–PDA. Among these polymers, BCT-1 exhibited the highest CE of 266.7 cm²/C, and BCT-4 showed the most rapid switching time (color switching time = 3.08 s and bleaching time = 2.01 s). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47264.     

Conjugated opto/electroactive ethynylene-carbazole polymers with TTF as pendant group

Three conjugated ethynylene-carbazole polymers with Tetrathiafulvalene (TTF) as pendant group (P1–P3) were synthesized by using sonogashira coupling reaction and characterized by ¹H NMR, GPC, CV, UV–Vis, FL, and TGA. CV and UV–Vis spectra showed that an intramoleular interaction existed between the electron-rich moiety TTF and electron-deficient moiety polyethynylcarbazole of the polymers. A strong fluorescence quench (ca. 99%) could be observed, compared to the polyethynylene-carbazole without TTF units, which could be ascribed to the photo-induced electron transfer (PET) interaction from TTF moiety to the polyethynylene-carbazole backbone. The observed onset decomposition temperatures (T _d) for P1–P3 varied from 256 to 298 °C. The polymers mentioned above exhibited good thermal properties and higher conductivity (neutral conductivity ~7–11 × 10⁻⁷ S cm⁻¹; doped conductivity ~6–11 × 10⁻⁴ S cm⁻¹).     

A soluble conducting polymer: 1-Phenyl-2,5-di(2-thienyl)-1H-pyrrole and its electrochromic application

A thiophene-functionalized monomer 1-phenyl-2,5-di(2-thienyl)-1H-pyrrole (PTP) was synthesized. The chemical polymerization of PTP (CPTP) was realized by using FeCl₃ as the oxidant. The structures of both the monomer and the soluble polymer (CPTP) were investigated by Nuclear Magnetic Resonance (¹H and ¹³C NMR) and Fourier Transform Infrared (FTIR). The average molecular weight of the chemically synthesized polymer was determined by gel permeation chromatography (GPC) as Mn = 7.2 × 10³. The electrochemical oxidative polymerization of PTP was carried out via constant-potential electrolysis. Characterizations of the resulting polymer were done by cyclic voltammetry (CV), FTIR, Scanning Electron Microscopy (SEM) and UV-vis Spectroscopy. The conductivity of sample was measured by four-probe technique. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. Spectroelectrochemical analysis of P(PTP) revealed electronic transitions at 413, 577 and 884 nm corresponding to π-π^* transition, polaron, and bipolaron band formations, respectively. Kinetic studies evaluated the switching ability of the P(PTP); the percent transmittance T% was found as 27%. The homopolymer of PTP was used to construct dual-type polymer electrochromic devices (ECDs) against poly(3,4-ethylenedioxythiophene) (PEDOT). Spectroelectrochemistry, electrochromic switching and open circuit stability of the devices were investigated.     

Synthesis and properties of new highly soluble poly(amide-ester-imide)s containing poly(ethylene glycol) as a soft segment

In this study, a new class of highly soluble poly(amide-ester-imide)s (PAEI)s contains poly(ethyleneglycol) (PEG) as hydrophilic and soft segment were prepared. Poly(ethylene glycol)-bis-(N-trimellitylimido-4-phenyl carboxylic acid) (3) as a novel diacid monomer was synthesized via two step. The reaction of poly(ethylene glycol) (PEG 6000) with trimellitic anhydride chloride yield poly(ethylene glycol)-bis-trimellitic anhydride (1). The reaction of dianhydride 1 with p-aminobenzoic acid (2) produces novel diacid monomer 3. The direct polycondensation technique of the diacid 1 with several aromatic diamines was carried out in pyridine/N-methyl-2-pyrrolidone/triphenylphosphite/CaCl₂ as condensing agent. The resulting novel PAEIs with inherent viscosities ranging between 0.21 and 0.42 dl g⁻¹, were obtained in good yield. This group of polymers exhibit excellent solubility in a variety of organic solvents and water. All of these polymers were characterized with FT-IR spectroscopy. Thermal properties, ¹H-NMR and XRD study of these PAEIs were also reported. The results demonstrate that this polymers show crystalline structure as well as high thermal stability. In addition the effect of PEG length on solubility and thermal properties of the polymers were also studied.     

SrTiO3-modified Bi0.5Na0.47Li0.03Ti0.99Sn0.01O3 relaxor ferroelectric ceramics with high energy storage performance

(1 − x)Bi_0.5Na_0.47Li_0.03Ti_0.99Sn_0.01O₃–xSrTiO₃ (BNLST–xST) lead-free ceramics were synthesized by traditional solid phase sintering. When x = 0.4, the ceramic achieves a high energy storage density W_rec of 3.78 J/cm³ as well as a superior efficiency η of 90.3% under 360 kV/cm. The charge–discharge curves related to temperature and cycle show that the 0.6BNLST–0.4ST sample has good temperature stability (20–180°C) and cycling reliability (variation of W_D < 5%). Moreover, a fast discharge rate (t_0.9 = 0.219 μs) and a large discharge energy density (W_D = 1.89 J/cm³) are achieved at 220 kV/cm. The results show that BNLST–xST energy storage ceramics are promising materials for devices with pulsed power capacitor.     

Synthesis and structure of Mu-33, a new layered aluminophosphate

Mu-33, a new layered aluminophosphate with an Al/P ratio of 0.66, was obtained from a quasi non-aqueous synthesis in which tert-butylformamide (tBF) was the main solvent and only limited amounts of water were present. During the synthesis, tBF decomposed and the resulting protonated tert-butylamine is occluded in the as-synthesized material. The approximate structure was determined from data collected on a microcrystal (200 × 25 × 5 μm³) at the European Synchrotron Radiation Facility (ESRF) in Grenoble, but the quality of these data did not allow satisfactory refinement. Therefore the structure was refined using high-resolution powder diffraction data, also collected at the ESRF. The structure (P2₁/c, a = 9.8922(6) Å, b = 26.180(2) Å, c = 16.729(1) Å and β = 90.4(1)°) consists of anionic aluminophosphate layers that can be described as a six-ring honeycomb of alternating corner-sharing AlO₄ and PO₄ tetrahedra with additional P-atoms above and below the honeycomb layer bridging between Al-atoms. The tert-butylammonium ions and water molecules located in the interlayer spacing interact via hydrogen-bonds with the terminal oxygens of the P-atoms. The characterization of this new aluminophosphate by ¹³C, ³¹P, ¹H–³¹P heteronuclear correlation (HETCOR) and ²⁷Al 3QMAS solid state NMR spectroscopy is also reported.     

Electrochromic properties of a novel low band gap conjugated copolymer based on 1,4-bis(2-thienyl)-naphthalene and 3,4-ethylenedioxythiophene

1,4-Bis(2-thienyl)-naphthalene (BTN) monomer is successfully synthesized via coupling reaction. A novel copolymer based on 1,4-bis(2-thienyl)-naphthalene (BTN) and 3,4-ethylenedioxythiophene (EDOT) is electrochemically synthesized and characterized. Characterizations of the resulting copolymer P(BTN-co-EDOT) are performed by cyclic voltammetry (CV), UV–vis spectroscopy, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and thermogravimetry (TG). At the neutral state of the copolymer, the π–π* transition absorption peak is located at 515 nm and the optical band gap (E_g) is calculated as 1.73 eV. Spectroelectrochemical analysis reveals that the copolymer film has distinct electrochromic properties from that of the BTN homopolymer film and shows six different colors under various potentials. The copolymer film shows a maximum optical contrast (ΔT%) of 48.4% at 504 nm with a response time of 0.88 s and of 45.2% at 770 nm with a response time of 0.84 s. An electrochromic device (ECD) based on P(BTN-co-EDOT) and poly(3,4-ethylenedioxythiophene) (PEDOT) is constructed and characterized. The optical contrast (ΔT%) at 645 nm is found to be 21.1% and response time is measured as 0.41 s. The coloration efficiency (CE) of the device is calculated to be 154 cm² C⁻¹ at 645 nm.     

Syntheses, Crystal Structures and Photophysical Properties of a Series of LnIII (Ln?=?Sm, Tb, Pr) Coordination Polymers

Four new lanthanide(Ш) coordination polymers, [Ln(p-aminobenzoate)₂(DMF)(HCOO) (H₂O)]_n (Ln = Sm 1, Tb 2, Pr 3) and {[Pr(2,5-dcp)(CH₃COO)(H₂O)]·1.5H₂O}_n (4) (DMF = N,N-dimethylformamide, 2,5-dcp = pyridine-2,5-dicarboxylate), have been synthesized by hydrothermal method. The structures are determined by the single-crystal X-ray diffraction. The four polymers all crystallize in the monoclinic space group P2₁/n. Polymers 1 and 2 are isostructural; both Sm^III ion of polymer 1 and Tb^III ion of polymer 2 are eight-coordinate. Although polymer 3 possesses the same asymmetric unit as polymers 1 and 2, the three are not isomorphous. The Pr^III ions in polymers 3 and 4 are nine-coordinate. In polymers 1, 2 and 3 the neighboring units are bridged by formyloxy and extend into infinite chains, which are connected by hydrogen bonds to form a hydrogen bond network. However, polymer 4 is bridged by pyridine-2,5-dicarboxylate and acetates to form an infinite 3D network. At room temperature, the IR, UV–Vis–NIR and emission spectra of the four polymers were measured and analyzed. The four polymers emit in the visible or NIR region. The luminescent properties are discussed.     

Luminescence properties of novel Eu3+-doped tantalate NaCaTiTaO6 red-emitting phosphors for solid-state lighting

A novel tantalate red-emitting phosphors NaCa_1-xEu_xTiTaO₆ (x = 0.02-0.50) is synthesized via the traditional solid-state reaction sintering. The photoluminescence properties, X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermal stability are characterized in detail. Photoluminescence spectra show strong red emission monitored at 614 nm at λ_ex = 395 nm. The spectral properties exhibit excellent color purity and chromaticity coordinate (CIE) characteristics. White light-emitting diodes (w-LEDs) device are fabricated by the prepared phosphors and show high quality of color-rendering index. The investigated results suggest that the Eu³⁺-doped NaCaTiTaO₆ phosphors can be as potential substitute red phosphors for w-LEDs.     

Synthesis of highly conjugated poly(3,9-carbazolyleneethynylenearylene)s emitting variously colored fluorescence

Novel conjugated polymers P1–P7 containing 3,9-linked carbazole units in the main chain were synthesized by the polycondensation of 3-ethynyl-9-(4-ethynylphenyl)carbazole (EEPCz) and dihaloarenes, and their optical and electrical properties were studied. Polymers with weight-average molecular weights of 4100–48,000 were obtained in 24–92% yields by the Sonogashira coupling polycondensation in tetrahydrofuran (THF)/Et₃N at 30 or 50 °C for 48 h. All the polymers absorbed light around 350 nm. The polymers with electron-accepter units exhibited absorption bands originating from charge transfer. The polymers except the one containing azobenzenes emitted variously colored fluorescence with moderate quantum yields upon excitation at the absorption maxima. P1–P3 were oxidized around 0.6 V, and then reduced around 0.5 V. The conductivity of P3 was 1.1 × 10⁻¹⁴ S/cm at 10³ V/cm.     

Hydrogen reduced graphene oxide/metal grid hybrid film: towards high performance transparent conductive electrode for flexible electrochromic devices

The metal grid and reduced graphene oxide (RGO) are both promising transparent conductive materials for replacing the indium tin oxide (ITO) in flexible optoelectronics. However, the large empty area that exists in the grid together with the relatively high sheet resistance of RGO hinder both the materials for practical applications. In this work, we report for the first time a novel strategy for efficient combination of the metal grid and RGO by using a newly developed room-temperature reduction technique. The obtained RGO/metal grid hybrid films not only overcome the shortcomings of individual components but exhibit enhanced optical and electrical performances (R_s = 18 Ω sq⁻¹ and T = 80%) and excellent flexural endurance. With this hybrid film as the window electrode, a highly flexible electrochromic device with excellent stability and ultra-fast response shorter than 60 ms has been successfully fabricated. Considering its high efficiency, high quality, low cost and large area, the strategy would be particularly useful for economically fabricating various metal grid/RGO films which are quite promising high performance transparent and conductive materials for next generation optoelectronic devices.     

Effect of argon-oxygen ratio on dielectric and energy storage properties of Ba(Zr0.35Ti0.65)O3 thin films

Lead-free Ba(Zr_0.35Ti_0.65)O₃(short as BZT35) ferroelectric thin films are prepared by RF magnetron sputtering on Pt/Ti/SiO₂/Si substrates. Effects of argon-to-oxygen (short as Ar/O₂) ratios on phase transition, dielectric and energy storage properties are studied. The research found that all thin films are perovskite structures. With the decrease of Ar/O₂, the oxygen vacancies (OVs) in the film are effectively suppressed, which promotes the film to obtain a larger dielectric constant, smaller dielectric loss, and lower leakage current density. The BZT35 film prepared under Ar/O₂ = 40:10 has excellent energy storage density (48.03 J/cm³) and efficiency (87.7%) because of its elongated hysteresis loop, the largest polarization difference (ΔP = 22.91 μC/cm²), higher breakdown field strength (E_b = 4.50 MV/cm) and lower leakage current density (J = 2.3 × 10^?5 A/cm²) and high power density of 7.94 MW/cm³. In addition, the BZT35 film also has excellent frequency stability (500 Hz-20 kHz). These excellent properties show that BZT35 has very broad application prospects in energy storage.     

Novel soluble carbazole‐based poly(aryl ethers): Preparation,properties, and application for dispersing multiwalled carbon nanotubes

Effectively dispersing of carbon nanotubes (CNTs) is the key to producing high performance CNTs/poly(aryl ethers) (PAEs) composite materials. Here, a series of novel soluble carbazole‐based PAEs with different alkyl side‐chains were synthesized corresponding polymers P1, P2, P3, and P4, and characterized clearly by ¹H NMR and IR. All the polymers exhibited good mechanical properties and thermostabilities (T_g ～ 128–212 °C, T_d5% ～ 450–499 °C) as PAEs. Due to containing lots of large π‐conjugated carbazole derivative units and possess suitable solubility, these non‐conjugated polymers can wrap and disperse MWNTs well (238–416 mg/L) in CHCl₃, and the similar work has been reported rarely. This excellent property makes these polymers become a promising and ideal type solubilizer for CNTs/PAEs composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46250.