Nanocomposite polymer electrolytes of sodium alginate and montmorillonite clay

Nanocomposite polymer electrolytes (NPEs) were synthesized using sodium alginate (Alg) and either sodium (SCa-3-Na+)- or lithium (SCa-3-Li+)-modified montmorillonite clays. The samples were characterized by structural, optical, and electrical properties. SCa-3-Na+ and SCa-3-Li+ clays’ X-ray structural analyses revealed peaks at 2θ = 7.2° and 6.7° that corresponded to the interlamellar distances of 12.3 and 12.8 Å, respectively. Alg-based NPEs X-ray diffractograms showed exfoliated structures for samples with low clay percentages. The increase of clay content promoted the formation of intercalated structures. Electrochemical Impedance Spectroscopy revealed that Alg-based NPEs with 5 wt% of SCa-3-Na+ clay presented the highest conductivity of 1.96 × 10−2 S/cm2, and Alg with 10 wt% of SCa-3-Li+ showed conductivity of 1.30 × 10−2 S/cm2, both measured at 70 °C. From UV-Vis spectroscopy, it was possible to infer that increasing concentration of clay promoted a decrease of the samples’ transmittance and, consequently, an increase of their reflectance.This research was partially founded by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES)—Finance Code 001 (proc. PNPD20131739-33002045017P6, F. Sentanin fellowship no. 1573926)

Development of eletrochromic windows

Este trabalho apresenta os resultados do preparo e caracterização de janelas eletrocrômicas (ECD) contendo filmes finos de WO3 como camada eletrocrômica, CeO2-TiO2 como contra-eletrodo e eletrólitos a base de polímeros naturais plastificados. Os filmes finos de CeO2-TiO2 e WO3 foram preparados pelo processo sol-gel e usados para montagem de dispositivos (janelas) eletrocrômicas com variados eletrólitos poliméricos. Os filmes finos e as janelas foram caracterizados através de medidas de densidade de carga, voltametria cíclica e transmitância. Os filmes de CeO2-TiO2 e WO3 apresentaram respectivamente, valores de densidade de carga de 11,8 e 27,8 mC/cm2, e razão de carga anódica/catódica de 0,98 e 0,85. As análises voltamétricas dos filmes finos revelaram picos característicos dos processos de oxidação e redução e as análises espectroscópicas a transmitância de 80 e 78 %, respectivamente. Foram preparadas e caracterizadas janelas com eletrólitos a base de gelatina com ácido acético; gelatina com LiI/I2; gelatina com agar; gelatina com líquidos iônicos; gelatina com líquidos iônicos e triflato de európio; poli(vinil butirato) (PVB) com LiI/I2; PVB com LiClO4; agar com LiClO4; agar com líquidos iônicos; DNA; DNA com LiClO4; DNA-cloreto de hexadeciltrimetilamônio (DNA-CTMA) com azul da Prússia; DNA com PEDOT:PSS (poli(3,4-etilenodioxitiofeno):poli(sulfonato de estireno)); DNA-CTMA com PEDOT:PSS. Os melhores resultados de densidade de carga de 5,4 e 6,0 mC/cm2 foram obtidas para os dispositivos com eletrólitos de gelatina com agar e agar com LiClO4. A razão de carga anódica/catódica desses dispositivos foi de 0,98 e 0,99. Os voltamogramas cíclicos das amostras estudadas revelaram picos anódicos e catódicos referentes à extração e inserção de íons lítio e elétrons no filme de WO3. As análises de transmitância em 550 nm entre o estado colorido e descolorido das janelas mostrou os valores de 28% para a janela contendo eletrólito a base de PVB com LiI/I2. Além disso, também foi verificada a estabilidade dos dispositivos revelando a duração entre 100 a 400 ciclos cronoamperometricos, dependendo do eletrólito usado. Os resultados obtidos mostram que as janelas estudadas são potenciais candidatas às aplicações práticas.This work presents the results of the preparation and characterization of electrochromic windows (ECD) containing thin films of WO3 as electrochromic layer, CeO2-TiO2 as the counter electrode and natural polymer-based electrolytes. Thin films of CeO2-TiO2 and WO3 were prepared by the sol-gel process and used to assembly the electrochromic devices (windows) with different polymer electrolytes. The thin films and windows samples were characterized by charge density, cyclic voltammetry and transmittance measurements. CeO2-TiO2 and WO3 thin films revealed charge density values of 11.8 and 27.8 mC/cm2, and anodic/cathodic charge relation of 0.98 and 0.85, respectively. The cyclic voltammograms revealed the peaks characteristic of the processes of oxidation and reduction and the spectroscopic analysis the transmittance of 80 and 78%, respectively. Electrochromic windows were assembled with electrolytes based on gelatin with acetic acid; gelatina with LiI/I2, gelatin with agar, gelatin with ionic liquids, gelatin with ionic liquids and europium triflate, PVB (poly (vinyl butyrate)) with LiI/I2; PVB with LiClO4; agar with LiClO4, agar with ionic liquids; DNA, DNA with LiClO4; DNA-CTMA (hexadecyltrimethylammonium chloride) with Prussian Blue; DNA with PEDOT:PSS (poly (3,4-ethylenedioxythiophene) poly(styrene sulfonate) ) and DNA-CTMA with PEDOT: PSS. The best results of charge density of 5.4 and 6.0 mC/cm2 and anodic/cathodic charge relations of 0.98 and 0.99 were obtained for the samples containing electrolytes based on gelatin with agar and agar with LiClO4, respectively. The cyclic voltammograms of the electrochromic windows showed cathodic and anodic peaks related to the insertion and extraction of lithium ions and electrons in the film of WO3. The transmittance measurements at 550 nm revealed 28% between the colored and discolored state of the windows with PVB-LiI/I2 electrolyte. Moreover, the stability measurements showed that the ECD remain their transmittance difference during of 100 to 400 of chronoaperometric cycling, depending on the electrolyte used. The obtained results indicate the possibility of use the naturalmacromolecules-based electrolytes in practical electrochromic windows

Development of eletrochromic windows

Este trabalho apresenta os resultados do preparo e caracterização de janelas eletrocrômicas (ECD) contendo filmes finos de WO3 como camada eletrocrômica, CeO2-TiO2 como contra-eletrodo e eletrólitos a base de polímeros naturais plastificados. Os filmes finos de CeO2-TiO2 e WO3 foram preparados pelo processo sol-gel e usados para montagem de dispositivos (janelas) eletrocrômicas com variados eletrólitos poliméricos. Os filmes finos e as janelas foram caracterizados através de medidas de densidade de carga, voltametria cíclica e transmitância. Os filmes de CeO2-TiO2 e WO3 apresentaram respectivamente, valores de densidade de carga de 11,8 e 27,8 mC/cm2, e razão de carga anódica/catódica de 0,98 e 0,85. As análises voltamétricas dos filmes finos revelaram picos característicos dos processos de oxidação e redução e as análises espectroscópicas a transmitância de 80 e 78 %, respectivamente. Foram preparadas e caracterizadas janelas com eletrólitos a base de gelatina com ácido acético; gelatina com LiI/I2; gelatina com agar; gelatina com líquidos iônicos; gelatina com líquidos iônicos e triflato de európio; poli(vinil butirato) (PVB) com LiI/I2; PVB com LiClO4; agar com LiClO4; agar com líquidos iônicos; DNA; DNA com LiClO4; DNA-cloreto de hexadeciltrimetilamônio (DNA-CTMA) com azul da Prússia; DNA com PEDOT:PSS (poli(3,4-etilenodioxitiofeno):poli(sulfonato de estireno)); DNA-CTMA com PEDOT:PSS. Os melhores resultados de densidade de carga de 5,4 e 6,0 mC/cm2 foram obtidas para os dispositivos com eletrólitos de gelatina com agar e agar com LiClO4. A razão de carga anódica/catódica desses dispositivos foi de 0,98 e 0,99. Os voltamogramas cíclicos das amostras estudadas revelaram picos anódicos e catódicos referentes à extração e inserção de íons lítio e elétrons no filme de WO3. As análises de transmitância em 550 nm entre o estado colorido e descolorido das janelas mostrou os valores de 28% para a janela contendo eletrólito a base de PVB com LiI/I2. Além disso, também foi verificada a estabilidade dos dispositivos revelando a duração entre 100 a 400 ciclos cronoamperometricos, dependendo do eletrólito usado. Os resultados obtidos mostram que as janelas estudadas são potenciais candidatas às aplicações práticas.This work presents the results of the preparation and characterization of electrochromic windows (ECD) containing thin films of WO3 as electrochromic layer, CeO2-TiO2 as the counter electrode and natural polymer-based electrolytes. Thin films of CeO2-TiO2 and WO3 were prepared by the sol-gel process and used to assembly the electrochromic devices (windows) with different polymer electrolytes. The thin films and windows samples were characterized by charge density, cyclic voltammetry and transmittance measurements. CeO2-TiO2 and WO3 thin films revealed charge density values of 11.8 and 27.8 mC/cm2, and anodic/cathodic charge relation of 0.98 and 0.85, respectively. The cyclic voltammograms revealed the peaks characteristic of the processes of oxidation and reduction and the spectroscopic analysis the transmittance of 80 and 78%, respectively. Electrochromic windows were assembled with electrolytes based on gelatin with acetic acid; gelatina with LiI/I2, gelatin with agar, gelatin with ionic liquids, gelatin with ionic liquids and europium triflate, PVB (poly (vinyl butyrate)) with LiI/I2; PVB with LiClO4; agar with LiClO4, agar with ionic liquids; DNA, DNA with LiClO4; DNA-CTMA (hexadecyltrimethylammonium chloride) with Prussian Blue; DNA with PEDOT:PSS (poly (3,4-ethylenedioxythiophene) poly(styrene sulfonate) ) and DNA-CTMA with PEDOT: PSS. The best results of charge density of 5.4 and 6.0 mC/cm2 and anodic/cathodic charge relations of 0.98 and 0.99 were obtained for the samples containing electrolytes based on gelatin with agar and agar with LiClO4, respectively. The cyclic voltammograms of the electrochromic windows showed cathodic and anodic peaks related to the insertion and extraction of lithium ions and electrons in the film of WO3. The transmittance measurements at 550 nm revealed 28% between the colored and discolored state of the windows with PVB-LiI/I2 electrolyte. Moreover, the stability measurements showed that the ECD remain their transmittance difference during of 100 to 400 of chronoaperometric cycling, depending on the electrolyte used. The obtained results indicate the possibility of use the naturalmacromolecules-based electrolytes in practical electrochromic windows

Preparation and characterizations of thin films of SnO2:Sb by sol-gel process.

No presente trabalho foram obtidos e caracterizados filmes finos de SnO2 e SnO2:Sb preparados pelo processo sol-gel. Estes filmes foram estudados através da influência do número de camadas nas suas propriedades ótico-eletroquímicas. Foi observado que a densidade de carga para um filme de SnO2:Sb de 5 camadas foi de 40 mC/cm2, tornando-se um excelente candidato como contra-eletrodo para aplicação em janelas eletrocrômicas. Os filmes de SnO2 e SnO2:Sb também foram estudados utilizando técnicas eletroquímicas: cronoamperometria e voltametria cíclica cujo o enfoque na análise foi o de intercalação de lítio em função da carga inserida. As medidas de transmissão ótica na região de ultravioletainfravermelho próximo revelaram que estes filmes possuem leve coloração azul, evidenciadas pela mudança do espectro UV-Vis em 8% entre estado colorido e descolorido; Por espectroscopia no infravermelho dos sóis, foi possível observar bandas características dos grupos de moléculas presentes em alcóxido, confirmando a formação do alcóxido de estanho enquanto dos precipitados apenas evidências da formação do óxido de estanho. As morfologias dos filmes estudadas por Microscopia Eletrônica de Varredura (MEV) e Microscopia de Força Atômica (AFM) demonstraram que o filme apresenta pequenos riscos, provavelmente devido a presença de Sb, e por AFM obtidas informações da rugosidade e do tamanho de grão, sendo estes valores de 100 nm e 104 nm respectivamente. A partir do espectro do filme por EDX foi possível confirmar a presença de estanho e antimônio nos filmes. A estrutura dos xerogéis e dos sóis para deposição dos filmes estudada por difração de raios-X é a casseterite. Por fim Análises Térmicas (DSC/TGA) demonstram que à 60oC um pico endotérmico correspondendo à liberação de água e uma perda da massa de 6,3 %, e na faixa de 450C um pequeno aumento da linha de base no sentido exotérmico atribuído a cristalização do SnO2:Sb na fase casseterite, com perda de massa de 33%.In this study were obtained and characterized thin films of SnO2 and SnO2: Sb prepared by the sol-gel process. These films were studied through the influence of the number of layers in its optical-electrochemical properties. It was observed that the density of charge for a film of SnO2: Sb, 5 layers was 40 mC/cm2, making it an excellent candidate as counter-electrode for use in electrochromic windows. The films of SnO2 and SnO2: Sb also were studied using electrochemical techniques: chronoamperometry and cyclic voltammetry with a focus on analysis of intercalation of lithium according to load inserted. Measures of optical transmission in the ultraviolet region of near-infrared revealed that these films have light blue colour, highlighted by the changing spectrum of UV-Vis by 8% between state and colorful discolour; In the infrared spectroscopy, in solution has been possible to see bands characteristics groups of molecules present in alkoxide, confirming the formation of alkoxide of tin while the precipitated only evidence of the formation formation of tin oxide. The morphologies of the films studied by Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) showed that the film presents little risk, probably because the presence of Sb, and the information obtained by the AFM roughness and the size of grain, and these values of 100 nm and 104 nm respectively. From the spectrum of the film by EDX were unable to confirm the presence of tin and antimony in the films. The structure of xerogel and solution for deposition of films studied by X-rays diffraction is the cassiterite. Finally Thermal Analysis (DSC / TGA) show that the 60oC a peak endothermical corresponding to the release of water and a loss of the mass of 6.3%, and in the 450ºC a small increase from baseline in the sense attributed range of exothermically the crystallization of SnO2:Sb during casseterite, with mass loss of 33%

Solid polymer electrolytes based on chitosan and dy(CF3SO3)3 for electrochromic devices

In the present work, one host natural matrix (chitosan) was doped with glycerol and different amounts of dysprosium triflate salt (Dy(CF3SO3)3). The behaviour of the electrolytes was evaluated by thermal analyses (thermogravimetric analysis – TGA and differential scanning calorimetry – DSC), impedance spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and atomic force microscopy (AFM). Sample with 0.15 g of Dy(CF3SO3)3 showed the best ionic conductivity values of 1.85x10-7 and 9.55x10-6 S cm-1 at 30 and 90 ºC, respectively. The lower values obtained for the other samples may be due to the appearance of aggregates, which corroborates with the XRD and SEM results. The new sample prepared with higher glycerol amount showed the highest conductivity values, namely 1.31x10-5 and 5.05x10-4 Scm-1 at 30 and 90 ºC respectively, so it was used to produce small electrochromic devices, which behaviour was evaluated.Chemistry Research Centre of the University of Minho UID/QUI/00686/2013 and UID/QUI/0686/2016. M.M. Silva and A. Pawlicka acknowledges CNPq for PVE 406617/2013-9, PQ 305029/2013-4, and 152252/2016-9 grants. F. Sentanin acknowledges CAPES for grant 1573926. Finally, the authors, acknowledges FAPESP (grant 2014/17174-4 spectrophotometer Jasco V670).info:eu-repo/semantics/publishedVersio

Improved Conductivity in Gellan Gum and Montmorillonite Nanocomposites Electrolytes

Nanocomposite polymer electrolytes (NPEs) were obtained using gellan gum (GG) and 1 to 40 wt.% of montmorillonite (Na+SYN-1) clay. The NPEs were crosslinked with formaldehyde, plasticized with glycerol, and contained LiClO4. The samples were characterized by impedance spectroscopy, thermal analyses (TGA and DSC), UV-vis transmittance and reflectance, X-ray diffraction (XRD), and continuous-wave electron paramagnetic resonance (CW-EPR). The NPEs of GG and 40 wt.% LiClO4 showed the highest conductivity of 2.14 × 10−6 and 3.10 × 10−4 S/cm at 30 and 80 °C, respectively. The samples with 10 wt.% Na+SYN-1 had a conductivity of 1.86 × 10−5 and 3.74 × 10−4 S/cm at 30 and 80 °C, respectively. TGA analyses revealed that the samples are thermally stable up to 190 °C and this did not change with clay addition. The transparency of the samples decreased with the increase in the clay content and at the same time their reflectance increased. Finally, CW-EPR was performed to identify the coordination environment of Cu2+ ions in the GG NPEs. The samples doped with the lowest copper concentration exhibit the typical EPR spectra due to isolated Cu2+ ions in axially distorted sites. At high concentrations, the spectra become isotropic because of dipolar and exchange magnetic effects. In summary, GG/clay NPEs presented good ionic conductivity results, which qualifies them for electrochemical device applications

Gellan Gum-Montmorillonite Nanocomposites for Electrochromic Devices

The present paper shows the results of nanocomposite polymer electrolytes (SPEs) of montmorillonite (MMT; Na+SYN-1) and gellan gum obtained by the solution casting method. The membrane samples were characterized by ATR-FTIR, time-domain nuclear magnetic resonance (TD-NMR), and scanning electron microscopy (SEM). Then, two samples were chosen and applied in small electrochromic devices (ECDs). The ATR-FTIR revealed shifts in bands of acetate and glycosidic bonds at 1032 and 1611 cm−1, respectively, indicating an interaction between the gellan gum and Na+SYN-1. The spin–lattice relaxation time of the proton nuclei (T1) suggests the poor dispersion of MMT in the matrix, especially above 20 wt.%. However, SEM pictures pointed to a more homogeneous surface of the nanocomposite containing 40 wt.% Na+SYN-1 when compared to the sample without clay. NPEs with 10 and 40 wt.% Na+SYN-1 were applied in ECDs, and the voltammograms showed a decrease in anodic and cathodic peaks after 2519 chronocoulometric cycles for the sample with 10 wt.% Na+SYN-1 and after 420 cycles for the sample with 40 wt.% Na+SYN-1. There was also a decrease in the charge density in both ECDs and an oscillating difference in transmittance between the colored/discolored states during the chronocoulometric cycles of the ECD with GG-MMT10. Further studies may reveal more property improvements in gellan gum nanocomposites

Effect of the alkyl chain length of the ionic liquid anion on polymer electrolytes properties

New polymer electrolytes (PEs) based on chitosan and three ionic liquid (IL) families ([C2mim][CnSO3], [C2mim][CnSO4] and [C2mim][diCnPO4]) were synthesized by the solvent casting method. The effect of the length of the alkyl chain of the IL anion on the thermal, morphological and electrochemical properties of the PEs was studied. The solid polymer electrolytes (SPE) membranes were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), polarized optical microscopy (POM), atomic force microscopy (AFM), complex impedance spectroscopy (ionic conductivity) and cyclic voltammetry (CV). The obtained results evidenced an influence of the alkyl chain length of the IL anion on the temperature of degradation, birefringence, surface roughness and ionic conductivity of the membranes. The DSC, XRD and CV results showed independency from the length of the IL-anion-alkyl chain. The PEs displayed an predominantly amorphous morphology, a minimum temperature of degradation of 135 °C, a room temperature (T = 25 °C) ionic conductivity of 7.78 × 10−4 S cm−1 and a wide electrochemical window of ∼ 4.0 V.This work was supported by FEDER through the COMPETE Program and by Fundação para a Ciência e a Tecnologia (FCT) in the framework of the Strategic Projects PEST-C/QUI/UI0686/2013, PEst-OE/SAU/UI0709/2014 and UID/Multi/00709/2013, UID/Multi/04551/2013, projects PTDC/QUI/117340/2010 and COST Action MP1202 “Rational design of hybrids organic inorganic interfaces”, grants SRFH/BD/90366/2012 (R.L.) and SFRH/BPD/63152/2009 (S.C. Nunes) and FCT Investigator contract (J.M.S.S.E.). The authors are also indebted to CNPq, FAPESP and CAPES for the financial support given to this research. M.M. Silva acknowledges Fundação Luso- Americana (FLAD) and CNPq (PVE grant 406617/2013-9), for the mobility grant provided by these institutions