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Size-exclusion polymer electrolytes are promising charge carriers to diminish the crossover and allowing commercially available low-cost porous membranes in redox flow batteries. Boosting the solubility in water and maximizing the number of redox sites to enhance the capacity of these polymeric systems is challenging. New highly water dispersed amphiphilic diblock copolymers are reported here, with an average concentration value of 1.7 10 mmol of Ferrocene (Fc)-linked moieties per mg of polymer, determined by total X-ray reflection fluorescence. These redox amphiphilic block copolymers are stabilized in water as spherical nanoparticles (20 nm) by using a simple phase solvent inversion procedure. We evidence a maximum polymer dispersibility value of 6 g/L in water, for long-term stable polymer nanoparticle suspensions, yielding a theoretical capacity value of 4.78 mAh at 10.5 mM Fc. Further adjustment of the ionic conductivity and pH of these stable redox block copolymer suspensions has rendered a conductivity value of 44.5 mS/cm at pH values close to a neutral one, by adding a variety of salt supports. Studies using a 3-electrode configuration cell reveal an efficient charge transport between each of the Fc motifs in the polymer nanoparticle. A capacity value of 3.1 mAh with no transient of the polymer nanoparticles crosswise the cheap porous membrane is evidenced when cycled as polycatholyte material in a Zn hybrid aqueous redox flow battery. The particle size and electronic changes of these novel amphiphilic redox block copolymer electrolytes during consecutive redox cycles have also been monitored by dynamic light scattering and ultraviolet-visible spectroscopy, respectively. The analysis of the results enables the understanding of the main mechanisms behind their non-fully reversible capacity. Among them, aggregation and sedimentation, along with retention inside the graphite felt electrode acting the latter as a filter. These insights will aid the design of fut

Los electrolitos basados en biopolímeros están despertando un gran interés, ya que son en potencia componentes cruciales para el desarrollo de dispositivos de almacenamiento de energía de bajo coste, escalables, sostenibles y ecológicos. En este artículo se analizan diferentes desarrollos de electrolitos poliméricos conductores de iones basados en biopolímeros, así como sus propiedades electroquímicas cuando se implementan en supercondensadores y baterías. Esta es área de investigación emergente, todavía poco explorada, pero con un gran interés industrial, pues los materiales empleados como base de estos materiales avanzados son abundantes, disminuyendo los costes finales de los sistemas de almacenamiento de energía, Biopolymer-based electrolytes are attracting great interest, as they are potentially components for the development of low-cost, scalable, sustainable and environmentally friendly energy storage devices. In this article, different developments of biopolymer-based ion-conducting polymer electrolytes and their electrochemical properties when implemented in supercapacitors and batteries are discussed. This is an emerging area of research, still little explored but with a great industrial interest, as the materials used as the basis of these advanced materials are abundant, decreasing the final costs of energy storage systems

Green and scalable materials are essential to fulfill the need of electrification for transitioning into a fossil-fuels free society, and sustainability is a requirement for all new technologies. Rechargeable batteries are one of the most important elements for electrification, enabling the transition to mobile electronics, electrical vehicles and grid storage. We here report synthesis and characterization of polyelectrolyte complexes of alginate and chitosan, both biopolymers deriving from the sea, for transport of zinc ions in hydrogel electrolytes. We have used vibrational spectroscopy, thermal measurements and microscopy, as well as transport measurements with ohmic or blocking contacts. The transference number for zinc ions is close to 1, the conductivity is ≈10 mS/cm, with stability at Zn interfaces seen through 7000 cycles in symmetric zinc//zinc cell.

CRUE-CSIC (Acuerdos Transformativos 2021), The transition to low-carbon emitting technologies provokes an increasing demand in energy conversion and storage systems such as fuel cells, batteries, and supercapacitors, and consequently, the need for their raw materials. The use of new chemistries from earth-abundant precursors instead of scarce, toxic, and nondegradable components existing in current systems must be a priority in future years. Cellulose is the most abundant biopolymer on earth. Their crystalline constituents designated as cellulose nanocrystals (CNC) have been studied as functional materials due to their excellent structural and chemical properties. This review covers a recent collection of works on innocuous CNC-based materials with special attention to the fabrication methodologies of electrodes, electrolytes, membranes, and separators. The implementation of these CNC-derived materials in sustainable energy conversion and storage systems is also discussed., Ministerio de Ciencia e Innovación (MICINN), Ministerio de Economía y Competitividad (MINECO), Comunidad de Madrid, Depto. de Química Inorgánica, Fac. de Ciencias Químicas, TRUE, pub

CRUE-CSIC (Acuerdos Transformativos 2022), Solid polymer electrolytes (SPEs) could play a major role in the transition to safer and high-energy-density potassium-based batteries. However, most polymeric K-ion electrolytes are based on fluorine-containing anions and flammable organic solvents, whose safety is nowadays in question. Herein, we report a facile solvent-free synthesis of a series of several poly(ethylene oxide) (PEO)-based SPE solid solutions with KBPh4 salt as potassium-ion source, including the formation of two crystalline (PEO)n/KBPh4 complexes. The ionic conductivity of these novel K-ion SPEs above and below the melting point of PEO is rationalized in light of their glass-transition temperature and chemical composition. We highlight that below the melting point of PEO, the crystalline complexes may not be intrinsically ionically conducting, but they act as ion sinks preventing the polymer cross-linking and the formation of contact ion pairs and lower the glass-transition temperature leading to a conductivity of 1.1 × 10–4 S cm–1 at 55 °C. A high ionic conductivity of 1.8 × 10–3 S cm–1 is achieved at 80 °C for the optimum (PEO)30/KBPh4 composition (3.2 mol % KBPh4). Besides, the SPE compositions were found to be stable up to 4 V vs K0 metal electrode at 60 °C. The (PEO)30/KBPh4 composite electrolyte employed in an all-solid-state symmetric cell with Prussian Blue electrodes showed reversible K+-ion (de)intercalation, where a reversible capacity of 20 mAh g–1 and low voltage hysteresis were achieved for 20 cycles. Considering the material availability, ease of synthesis, and promising electrochemical properties, this work may encourage future research on fluorine-free polymer electrolytes for K-ion batteries., Ministerio de Ciencia e Innovación (MICINN), Ministerio de Economía y Competitividad (MINECO), Depto. de Química Inorgánica, Fac. de Ciencias Químicas, TRUE, pub

Solid polymer electrolytes (SPEs) could play a major role in the transition to safer and high-energy-density potassium-based batteries. However, most polymeric K-ion electrolytes are based on fluorine-containing anions and flammable organic solvents, whose safety is nowadays in question. Herein, we report a facile solvent-free synthesis of a series of several poly(ethylene oxide) (PEO)-based SPE solid solutions with KBPhsalt as potassium-ion source, including the formation of two crystalline (PEO)/KBPhcomplexes. The ionic conductivity of these novel K-ion SPEs above and below the melting point of PEO is rationalized in light of their glass-transition temperature and chemical composition. We highlight that below the melting point of PEO, the crystalline complexes may not be intrinsically ionically conducting, but they act as ion sinks preventing the polymer cross-linking and the formation of contact ion pairs and lower the glass-transition temperature leading to a conductivity of 1.1 × 10S cmat 55 °C. A high ionic conductivity of 1.8 × 10S cmis achieved at 80 °C for the optimum (PEO)/KBPhcomposition (3.2 mol % KBPh). Besides, the SPE compositions were found to be stable up to 4 V vs Kmetal electrode at 60 °C. The (PEO)/KBPhcomposite electrolyte employed in an all-solid-state symmetric cell with Prussian Blue electrodes showed reversible K-ion (de)intercalation, where a reversible capacity of 20 mAh gand low voltage hysteresis were achieved for 20 cycles. Considering the material availability, ease of synthesis, and promising electrochemical properties, this work may encourage future research on fluorine-free polymer electrolytes for K-ion batteries.

The transition to low-carbon emitting technologies provokes an increasing demand in energy conversion and storage systems such as fuel cells, batteries, and supercapacitors, and consequently, the need for their raw materials. The use of new chemistries from earth-abundant precursors instead of scarce, toxic, and nondegradable components existing in current systems must be a priority in future years. Cellulose is the most abundant biopolymer on earth. Their crystalline constituents designated as cellulose nanocrystals (CNC) have been studied as functional materials due to their excellent structural and chemical properties. This review covers a recent collection of works on innocuous CNC-based materials with special attention to the fabrication methodologies of electrodes, electrolytes, membranes, and separators. The implementation of these CNC-derived materials in sustainable energy conversion and storage systems is also discussed.

[EN] The application of batteries coupled to renewable energy conversion systems in cities will greatly help to overcome some of the technological challenges for grid electrification and transport, such as difficult accessibility to charging points, and cost, by improving their technical capabilities and making the energy system globally more sustainable. Furthermore, its implementation will have an immediate effect on citizens’ health due to the reduction of greenhouse gas emissions into the atmosphere, as well as other pollutants. Below is a review of recent efforts to develop new advanced technologies for future sustainable batteries. We will also highlight current battery recycling strategies that are being implemented towards a zero-carbon future based on the concept of the circular economy., [ES] La aplicación de baterías acopladas a sistemas de conversión de energía renovable en las ciudades ayudará en gran medida a superar algunos de los retos tecnológicos para la electrificación de la red y el transporte, como la difícil accesibilidad a puntos de carga, y de coste, mejorando sus capacidades técnicas y haciendo que el sistema energético a nivel global sea más sostenible. Además, su aplicación tendrá un efecto inmediato en la salud de los ciudadanos debido a la disminución de las emisiones de gases de efecto invernadero a la atmósfera, así como otros contaminantes. A continuación, presentamos una revisión de los esfuerzos recientes para desarrollar nuevas tecnologías avanzados para las futuras baterías sostenibles. También destacaremos las estrategias actuales de reciclado de baterías que se aplican hacia un futuro con cero emisiones de carbono y basado en el concepto de economía circular.

In this communication, a novel two-dimensional polymer network (DAPT-TFP) has been synthesized based on pyrenetetraone moieties connected through robust enamine functional groups. Results show that DAPT-TFP exhibit high thermal and chemical stability, even after subjecting the material to a basic or acidic media for certain time (1 M HSO or 1 M NaOH, respectively). An application to conductive additive-free electrode is detailed, as a proof of the ideal interaction between the ions of the neutral aqueous electrolyte and the molecular polymer nanostructure activated by simple acidic treatment. Thus, the study indicates that the redox properties of new organic electrode materials exhibiting limited electroactive properties can be boosted by a straightforward acidic treatment.

[EN] The present invention relates to an electrochemically active nanoparticulate polymer material comprising methylcellulose, sulfonated lignin and polypyrrole with a hierarchical structure and method of obtaining thereof, for use as an electrochemical material dispersed in an aqueous medium. The present invention belongs to the field of sustainable electrochemical systems mainly for converting and storing energy from renewable sources and capturing and transporting CO2 gas from the combustion of fossil fuels in the industry sector, [FR] La présente invention concerne un matériau polymère nanoparticulaire électrochimiquement actif comprenant de la méthylcellulose, de la lignine sulfonée et du polypyrrole avec une structure hiérarchique et son procédé d'obtention, destiné à être utilisé en tant que matériau électrochimique dispersé dans un milieu aqueux. La présente invention concerne le domaine des systèmes électrochimiques durables principalement pour convertir et stocker de l'énergie provenant de sources renouvelables et capturer et transporter du CO2 gazeux issu de la combustion de combustibles fossiles dans le secteur de l'industrie

Highly water-dispersible, redox-active 1D coordination polymers (CPs) have been synthesized using low-cost precursors. These CPs, containing chloranilic acid as organic ligand and a transition element, such as Fe and Mn as a metal center, form long-term stable slurries containing up to 100 g/L solid particles in aqueous media (0.5 M NaCl, 1 mg carbon nanotubes). Voltammetry studies showed that the iron-based particulate slurries exhibited three different redox stages with no metal plating. However, the suspensions with manganese-based coordination polymers experienced a metal plating process in the same potential window range as for the iron-based CPs. Moreover, the particulate suspension of iron-CPs shown longer-term stability than their isostructural analogs based on manganese. The 1D Fe-CPs were used as catholyte and anolyte in a symmetrical cell with a low-cost size exclusion cellulose membrane acting as a separator. The cell experienced a reversible capacity value of 45 mAh/g (225 mAh/L) at a current density value of 20 mA/g for 50 cycles (~12 days) at neutral pH. This study opens the possibility of using inexpensive coordination polymers as single bifunctional electrolyte material in aqueous batteries and other sustainable energy storage-related systems.

This work reports the synthesis of poly (monomethyl itaconate) grafted multi-layer graphene oxide (PMMI-g-GO) by atom transfer radical polymerization using activators regenerated by electron transfer (ARGET-ATRP). PMMI-g-GO presents outstanding properties, such as a high electrical conductivity (5.04 S m), low number of stacked graphene layers (6) and I/I ratio of 2.05 estimated from Raman spectrum, which indicates the high quality of PMMI-g-GO as a graphenic material. In addition, polymer brushes based on PMMI represent a new green alternative for the development of polymer composite materials, since the monomer used for their production is obtained from a renewable source. Interestingly, the PMMI-g-GO nanomaterial is also capable of storing Li ions without the need of using electron conductive additives that are usually employed in the electrode's composition of conventional lithium ion batteries.

The implementation of sustainable batteries coupled to renewable energy conversion systems in off-grid, poor and remote communities will overcome some of the technological challenges for electrification, such as the difficult geographical and cost accessibility, improving their modest technical capabilities and making the full system ecofriendly. Besides, their application to power off-grid "structures and facilities"requiring a large amount of energy (>50 kW) such as heavyweight carriers (e.g. boats and trucks) and for instance those located far away from the main grid such as small-size islands and mines, will have an immediate impact on the decrease of greenhouse gas emissions to the atmosphere. Herein we present an overview of recent efforts to develop green and advanced electrode and electrolyte materials for future sustainable batteries. Further, we will also highlight both current second-life and end-of-life battery disposal sustainable strategies that are applied towards a zero-carbon future. This journal is

The creation of flexible and high strength hydrogel materials from natural polymers as low cost and safe solid electrolytes is an area of intense research nowadays. We present a novel approach for the preparation of gelatin and chondroitin sulfate hydrogel complexes by using a simple centrifugation process. The innovative dual-bio-gel-network is able to swell and shrink upon changes on the pH and NaCl concentration. The solid bio-gels sandwiched between two macroporous carbon electrode materials are assembled in symmetric cells and their electrochemical properties are evaluated by cyclic voltammetry, galvanostatic, and impedance spectroscopy measurements. The cells exhibit areal capacitance values up to 2.74 mF cm¿2 (3.1 F g¿1) and a low resistance value of 12 Ohm cm2 for graphene electrode materials. These properties are the consequence of the successful infiltration of the solid gel inside the porous structure of the carbon electrode that boosts the charge transfer at the biopolymer/carbon electrode interphase. The results obtained may provide additional inspiration in the emerging field of bioelectronics, where biocompatible and powered systems are of the utmost importance.

Herein, we present a multigram scale-up route for the preparation of novel polymer composite nanoparticles as potential multifunctional rechargeable material for future, sustainable batteries. The nanoparticles (20 nm) comprise three innocuous yet functional interpenetrated macromolecular networks: polypyrrole, methylcellulose, and lignin. They are uniquely assembled in strands or chains (~200 nm) such as necklace beads and show long-term stability as water dispersion. We find that an aqueous suspension of this hierarchical nanomaterial shows two sets of reversible redox peaks, separated by ~600 mV, originating from the catechol moieties present in the lignin biopolymer. Remarkably, the addition of carbon dioxide increased the capacity of one of the redox processes by 500%. Importantly, the three redox stages occur in the presence of the same nanostructured polymer so being a potentially bifunctional material to be used in advanced electrochemical systems. The new properties are attributed to an intrinsic chemical and electronic coupling at the nanoscale among the different building blocks of the metal-free polymer composite and the structural rearrangement of the interpenetrated polymer network by the incorporation of CO. We have provided both a new electrochemically multifunctional hierarchically structured material and a facile route that could lead to novel sustainable energy applications.

Large-scale energy storage is becoming increasingly critical to balancing renewable energy production and consumption. Organic redox flow batteries, made from inexpensive and sustainable redox-active materials, are promising storage technologies that are cheaper and less environmentally hazardous than vanadium-based batteries, but they have shorter lifetimes and lower energy density. Thus, fundamental insight at the molecular level is required to improve performance. Here we report two in situ nuclear magnetic resonance (NMR) methods of studying redox flow batteries, which are applied to two redox-active electrolytes: 2,6-dihydroxyanthraquinone (DHAQ) and 4,4′-((9,10-anthraquinone-2,6-diyl)dioxy) dibutyrate (DBEAQ). In the first method, we monitor the changes in the H NMR shift of the liquid electrolyte as it flows out of the electrochemical cell. In the second method, we observe the changes that occur simultaneously in the positive and negative electrodes in the full electrochemical cell. Using the bulk magnetization changes (observed via the H NMR shift of the water resonance) and the line broadening of the H shifts of the quinone resonances as a function of the state of charge, we measure the potential differences of the two single-electron couples, identify and quantify the rate of electron transfer between the reduced and oxidized species, and determine the extent of electron delocalization of the unpaired spins over the radical anions. These NMR techniques enable electrolyte decomposition and battery self-discharge to be explored in real time, and show that DHAQ is decomposed electrochemically via a reaction that can be minimized by limiting the voltage used on charging. We foresee applications of these NMR methods in understanding a wide range of redox processes in flow and other electrochemical systems.

The lithium ion storage properties of a series of metal-organic frameworks (MOFs) with formula {[M(L)(HO)]HO}n and [M(CA)(Pyz)]n (where L refers to the tetraoxolene ligands: CA = chloranilate and DHBQ = dihydroxybenzoquinone; Pyz = pyrazine; M = Fe and Mn) and exhibiting a 1D and 2D structure, respectively, have been studied. The 1D MOFs ({[M(L)(HO)]HO}n) show higher reversible capacity values for lithium ion insertion with respect to 2D structures containing two organic ligands (M(CA)(Pyz)]n). The gravimetric capacity for the 1D Fe-CA MOF is 75 mAh/g at 2.16 mA/g (∼ 1 lithium atom per formula unit) higher than for the Mn complexes which is 65 mAh/g at 2.12 mA/g, though isostructural. Lithium ion insertion in the 1D Mn-CA chains takes place at 2.4 V vs. Li/Li which is ∼700 mV higher than what is recorded for the Fe analogue. This result is most probably due to much more stable d electronic configuration of Mn than d of Fe in its isostructural Fe-based framework analogue of the final reduced phases. The 1D Fe-DHBQ capacity is higher than its manganese analogue 75 mAh/g at 2.5 mA/g (0.8 lithiums) against 40 mAh/g. In general, the high voltages of reaction in these 1D MOFs suggest that they involve the participation of the ligand on the redox processes along with the reduction of the transition metal if any. In fact, the potential of ion insertion changed depending on the metal. This fact along with the absence of evidence of conversion reaction by x-ray diffraction of cycled electrodes suggests that the charge delocalization may be all along the metal-ligand molecular framework participating as a whole hybrid unit in the lithium storage.

En este libro se recogen los trabajos de investigación llevados a cabo en el campo de los polímeros por jóvenes investigadores de toda España. En estos trabajos se tratan varias áreas de conocimiento dentro de la Ciencia de Materiales, como son polímeros con aplicaciones avanzadas que van desde redes poliméricas de alta porosidad, copolímeros electroactivos para el almacenamiento sostenible de energía, polímeros sensibles al medio para aplicaciones farmacéuticas y biomédicas, hasta redes epoxi auto curables. También se presentan trabajos orientados al estudio, síntesis y caracterización de nuevos polímeros como la síntesis de poliéteres alifáticos organocatalizada a partir de dioles, aerogeles de poliuretano o copolímeros tribloque con capacidad de autoensamblado. Se presentan también trabajos en los que se estudia las propiedades de membranas densas con capacidad sensora a distintas sustancias de interés, así como la utilización de fibras recubiertas de aramidas para la detección de aminas biógenas. Este libro ofrece de forma rápida y sencilla una visión general de las nuevas tendencias en investigación en el campo de los polímeros con aplicaciones avanzadas