Ever-rising energy demand, fossil fuel dependence, and climate issues have harmful consequences to the society. Exploring clean and renewable energy to diversify the world energy matrix has become an urgent matter. Less explored or unexplored renewable energy sources like the salinity and proton gradient energy are an attractive alternative with great energy potential. This paper discusses important electrochemical systems for energy conversion from natural and artificial concentration gradients, namely capacitive mixing (CapMix), mixing entropy batteries (MEB), and neutralization batteries (NB); the working principle and thermodynamic formalism of these systems; and the materials employed in the assembly of these systems.

Filmes de quitosana/poli(ácido vinilsulfônico) (PVS) foram depositados sobre membranas de Nafion® a partir do método camada por camada (LbL), visando o seu uso em células a combustível de metanol direto (DMFC). Métodos computacionais e espectros de infravermelho com transformada de Fourier (FTIR) sugerem a formação de um par iônico entre o grupo sulfônico do PVS e o grupo amino protonado da quitosana, o qual promove o crescimento dos filmes LbL sobre a membrana de Nafion®, assim como impede parcialmente a passagem de metanol. Experimentos de cronopotenciometria e varredura linear de potencial foram realizados a fim de se investigar a passagem de metanol através das membranas de Nafion® e quitosana/PVS/Nafion® em uma célula a diafragma. Os valores de resistência iônica associada ao transporte de prótons nas membranas de Nafion® e quitosana/PVS/Nafion® são próximos, de acordo com as medidas de impedância elétrica devido à pequena espessura do filme LbL. Assim, espera-se um melhor desempenho da DMFC, uma vez que a resistência do filme automontado é insignificante comparada ao resultado associado à passagem de metanol através das membranas.

Chitosan/poly(vinyl sulfonic acid) (PVS) films have been prepared on Nafion® membranes by the layer-by-layer (LbL) method for use in direct methanol fuel cell (DMFC). Computational methods and Fourier transform infrared (FTIR) spectra suggest that an ionic pair is formed between the sulfonic group of PVS and the protonated amine group of chitosan, thereby promoting the growth of LbL films on the Nafion® membrane as well as partial blocking of methanol. Chronopotentiometry and potential linear scanning experiments have been carried out for investigation of methanol crossover through the Nafion® and chitosan/PVS/Nafion® membranes in a diaphragm diffusion cell. On the basis of electrical impedance measurements, the values of proton resistance of the Nafion® and chitosan/PVS/Nafion® membranes are close due to the small thickness of the LbL film. Thus, it is expected an improved DMFC performance once the additional resistance of the self-assembled film is negligible compared to the result associated with the decrease in the crossover effect.

In this work, composites formed from a mixture of V2O5 and polyaniline (PANI) were investigated, for applications as cathode materials for secondary lithium batteries. Electrochemical quartz crystal microbalance (EQCM) data show that charge compensation in the [PANI]0.3V2O5 nanocomposite is achieved predominantly by Li+ migration. However, the charge compensation in the [PANI]V2O5 microcomposite occurs by Li+ and ClO4- transport. Electrochemical Impedance Spectroscopy (EIS) measurements reveal several benefits of nanohybrid formation, including the achievement of shorter ionic diffusion pathways, the higher diffusion rate of the lithium ion and also the higher electronic conductivity, which are responsible for a synergetic effect of the energy storage properties.

Filmes finos obtidos a partir de xerogel de V2O5 com distintas quantidades de Li+ intercalado eletroquimicamente foram caracterizados utilizando diferentes técnicas in-situ. As mudanças nas propriedades mecânicas foram investigadas utilizando medidas de impedância eletroacústica e estes experimentos indicaram que o processo de intercalação não produz mudanças importantes nas propriedades viscoelásticas do filme; portanto, a equação de Sauerbrey foi utilizada para transformas mudanças de freqüência em mudança de massa. A técnica de microbalança eletroquímica a cristal de quartzo permitiu mostrar a participação do solvente (carbonato de propileno) durante os ciclos de carga/descarga. Diferentes experimentos espectroeletroquímicos permitiram mostrar a influencia das modificações estruturais no processo de eletro-intercalação. Aa mudanças para uma estrutura mais amorfa do material durante o processo de descarga produz uma diminuição na velocidade dos portadores de carga. A simetria local do vanádio no óxido foi estudada utilizando absorção de raios X.

Thin films of V2O5 xerogel were characterized by several in-situ techniques for different amount of intercalated Li+. Changes in the V2O5 mechanical properties were analyzed by electroacoustic impedance data, indicating that lithium intercalation does not produce an important change in the viscoelastic properties. So that, it is possible to use the electrochemical quartz crystal microbalance to measure mass change. Electrogravimetric results showed a significant participation of propylene carbonate molecules during charge/discharge cycles, associated with a significant expansion/contraction of the structure. The ultraviolet-visible spectrophotometry, chronoamperometry and electrochemical impedance spectroscopy data showed the influence of structural modifications on electronic and ionic properties during the intercalation process. The amorphization of the material in the discharged state produces a diminution in the charge carrier rate. Besides this, changes in the local symmetry of the vanadium ion by extended X-ray absorption fine structure experiments, were verified.

In this work, cathodes employed in secondary lithium batteries are reviewed. These cathodes have great technologic and scientific importance, specifically, materials for cathodes as electronic conductor polymers (ECP), transition metal oxides (TMO) and nanocomposites of ECP/TMO. The use of a specific cathodic material is based in some intrinsic characteristics that improve the performance of the battery. Thus, some vantages and disvantages of these insertion compounds are discussed, as lithium insertion capacity, energy density, and the ciclability of these materials.