Novel Macroporous PVdF based separators for supercapacitors

La technologie supercondensateur a fait l'objet d'un grand intérêt ces dernières années. Cependant, tandis qu'une grande attention a été donnée aux électrodes, aux électrolytes et aux électrolytes de polymère gélifiée, peu d'études ont été centrées sur l'amélioration des séparateurs macroporeux. Dans le cadre du projet SEPBATT/DURAMAT, les séparateurs macroporeux à base de poly(fluorure de vinylidène) (PVdF) ont été préparés par inversion de phase, pour les supercondensateurs. Nos membranes présentent également une bonne stabilité thermique, en revanche leurs propriétés mécaniques sont significativement plus faibles que celles des membranes commerciales. De plus le séparateur PVdF de porosité 80% rempli par l'électrolyte à base d'AN atteint, à 25°C, 18mS/cm, tandis que dans les mêmes conditions mais avec le séparateur commercial en cellulose, la conductivité n'atteint que 10 mS/cm. Ce travail a été complété par l'étude de techniques de renforcement (addition de composites, réticulation par l'irradiation) appliquées aux membranes précédemment préparées, pour augmenter leur tenue mécanique. Ces membranes ont montré un renforcement des propriétés mécaniques sans nuire aux propriétés de conduction ionique (15 mS/cm).Abstract In recent years a strong interest has been devoted to supercapacitor technology. However, while great attention has been paid to electrodes, electrolytes and gel polymer electrolytes, only few reports have been dedicated to macroporous separators. Hereby, in the frame of project SEPBATT/DURAMAT, macroporous poly(vinylidene fluoride) (PVdF) based separators were prepared by phase inversion technique for applications of supercapacitors. Their mechanical properties are relatively lower than those of commercial membranes nevertheless such membranes exhibit good thermal stability. Whereas commercial cellulose based separators filled with tetraethyl ammonium tetrafluoroborate + CH3CN electrolyte show 10 mS/cm (at 25°C), our PVdF macroporous separators exhibit significantly higher conductivity (18 mS/cm) under the same conditions. This study was completed with application of reinforcement techniques (addition of composites, crosslinking by irradiation) on to previously prepared membranes in order to increase their mechanical strength. Reinforced membranes showed good high mechanical strength whereas the ionic conductivity is almost maintained (15mS/cm)

Séparateurs macroporeux innovants à base de poly(fluorure de vinylidène) pour supercondensateurs

Abstract In recent years a strong interest has been devoted to supercapacitor technology. However, while great attention has been paid to electrodes, electrolytes and gel polymer electrolytes, only few reports have been dedicated to macroporous separators. Hereby, in the frame of project SEPBATT/DURAMAT, macroporous poly(vinylidene fluoride) (PVdF) based separators were prepared by phase inversion technique for applications of supercapacitors. Their mechanical properties are relatively lower than those of commercial membranes nevertheless such membranes exhibit good thermal stability. Whereas commercial cellulose based separators filled with tetraethyl ammonium tetrafluoroborate + CH3CN electrolyte show 10 mS/cm (at 25°C), our PVdF macroporous separators exhibit significantly higher conductivity (18 mS/cm) under the same conditions. This study was completed with application of reinforcement techniques (addition of composites, crosslinking by irradiation) on to previously prepared membranes in order to increase their mechanical strength. Reinforced membranes showed good high mechanical strength whereas the ionic conductivity is almost maintained (15mS/cm).La technologie supercondensateur a fait l'objet d'un grand intérêt ces dernières années. Cependant, tandis qu'une grande attention a été donnée aux électrodes, aux électrolytes et aux électrolytes de polymère gélifiée, peu d'études ont été centrées sur l'amélioration des séparateurs macroporeux. Dans le cadre du projet SEPBATT/DURAMAT, les séparateurs macroporeux à base de poly(fluorure de vinylidène) (PVdF) ont été préparés par inversion de phase, pour les supercondensateurs. Nos membranes présentent également une bonne stabilité thermique, en revanche leurs propriétés mécaniques sont significativement plus faibles que celles des membranes commerciales. De plus le séparateur PVdF de porosité 80% rempli par l'électrolyte à base d'AN atteint, à 25°C, 18mS/cm, tandis que dans les mêmes conditions mais avec le séparateur commercial en cellulose, la conductivité n'atteint que 10 mS/cm. Ce travail a été complété par l'étude de techniques de renforcement (addition de composites, réticulation par l'irradiation) appliquées aux membranes précédemment préparées, pour augmenter leur tenue mécanique. Ces membranes ont montré un renforcement des propriétés mécaniques sans nuire aux propriétés de conduction ionique (15 mS/cm)

Feasible Energy Density Pushes of Li-Metal vs. Li-Ion Cells

Li-metal batteries are attracting a lot of attention nowadays. However, they are merely an attempt to enhance energy densities by employing a negative Li-metal electrode. Usually, when a Li-metal cell is charged, a certain amount of sacrificial lithium must be added, because irreversible losses per cycle add up much more unfavourably compared to conventional Li-ion cells. When liquid electrolytes instead of solid ones are used, additional electrolyte must also be added because both the lithium of the positive electrode and the liquid electrolyte are consumed during each cycle. Solid electrolytes may present a clever solution to the issue of saving sacrificial lithium and electrolyte, but their additional intrinsic weight and volume must be considered. This poses the important question of if and how much energy density can be gained in realistic scenarios if a switch from Li-ion to rechargeable Li-metal cells is anticipated. This paper calculates various scenarios assuming typical losses per cycle and reveals future e-mobility as a potential application of Li-metal cells. The paper discusses the trade-off if, considering only the push for energy density, liquid electrolytes can become a feasible option in large Li-metal batteries vs. the solid-state approach. This also includes the important aspect of cost

A Performance and Cost Overview of Selected Solid-State Electrolytes: Race between Polymer Electrolytes and Inorganic Sulfide Electrolytes

Electrolytes are key components in electrochemical storage systems, which provide an ion-transport mechanism between the cathode and anode of a cell. As battery technologies are in continuous development, there has been growing demand for more efficient, reliable and environmentally friendly materials. Solid-state lithium ion batteries (SSLIBs) are considered as next-generation energy storage systems and solid electrolytes (SEs) are the key components for these systems. Compared to liquid electrolytes, SEs are thermally stable (safer), less toxic and provide a more compact (lighter) battery design. However, the main issue is the ionic conductivity, especially at low temperatures. So far, there are two popular types of SEs: (1) inorganic solid electrolytes (InSEs) and (2) polymer electrolytes (PEs). Among InSEs, sulfide-based SEs are providing very high ionic conductivities (up to 10−2 S/cm) and they can easily compete with liquid electrolytes (LEs). On the other hand, they are much more expensive than LEs. PEs can be produced at less cost than InSEs but their conductivities are still not sufficient for higher performances. This paper reviews the most efficient SEs and compares them in terms of their performances and costs. The challenges associated with the current state-of-the-art electrolytes and their cost-reduction potentials are described

Preparation and characterization of alumina-supported iron nanoparticles and its application for the removal of aqueous Cu2+ ions

A composite sorbent of iron nanoparticles and alumina (Al–nZVI) was prepared and applied in the removal of Cu2+ ions from aqueous solutions. Alumina was introduced in a solution of Fe2+ ions, which were then reduced to metallic iron nanoparticles using borohydride ions. The characterization results showed that iron nanoparticles were partially dispersed on alumina surface, with their diameter being in the range 10–80 nm. The uptake experiments were performed at initial Cu2+ concentrations ranging from 10.0 to 500.0 mg/L. The experiments investigated the effects of initial concentration, contact time, and repetitive usage of the Al–nZVI on the extent of removal of Cu2+ ions. The composite sorbent demonstrated fast uptake, and its fixation capacity was 1.50 mmol/g (95.3 mg/g), which is well above that of pure alumina (0.32 mmol/g; 20.3 mg/g)

Radiation-grafted materials for energy conversion and energy storage applications

Polymer electrolyte membranes are key components in electrochemical power sources thatare receiving ever-growing demand for the development of more efficient, reliable and envi-ronmentally friendly energy systems. Ongoing research is focusing on materials with highionic conductivity and stability, at low cost. Among different methods, radiation-inducedgrafting is a universal attractive method for preparation of polymer electrolyte materialswith tunable properties for various energy conversion and energy storage applications.This review addresses recent advances in the application of radiation-induced graftingtechniques for the preparation of polymer electrolyte membranes/separators for emergingelectrochemical devices such as fuel cells, batteries and supercapacitors. The challengesassociated with the current state-of-the-art materials are highlighted, together with newdirections that should be considered for future researc

Tackling xEV Battery Chemistry in View of Raw Material Supply Shortfalls

The growing number of Electric Vehicles poses a serious challenge at the end-of-life for battery manufacturers and recyclers. Manufacturers need access to strategic or critical materials for the production of a battery system. Recycling of end-of-life electric vehicle batteries may ensure a constant supply of critical materials, thereby closing the material cycle in the context of a circular economy. However, the resource-use per cell and thus its chemistry is constantly changing, due to supply disruption or sharply rising costs of certain raw materials along with higher performance expectations from electric vehicle-batteries. It is vital to further explore the nickel-rich cathodes, as they promise to overcome the resource and cost problems. With this study, we aim to analyze the expected development of dominant cell chemistries of Lithium-Ion Batteries until 2030, followed by an analysis of the raw materials availability. This is accomplished with the help of research studies and additional experts’ survey which defines the scenarios to estimate the battery chemistry evolution and the effect it has on a circular economy. In our results, we will discuss the annual demand for global e-mobility by 2030 and the impact of Nickel-Manganese-Cobalt based cathode chemistries on a sustainable economy. Estimations beyond 2030 are subject to high uncertainty due to the potential market penetration of innovative technologies that are currently under research (e.g. solid-state Lithium-Ion and/or sodium-based batteries)

SODIUM-BASED BATTERIES: IN SEARCH OF THE BEST COMPROMISE BETWEEN SUSTAINABILITY AND MAXIMIZATION OF ELECTRIC PERFORMANCE

Till 2020 the predominant key success factors of battery development have been overwhelmingly energy density, power density, lifetime, safety, and costs per kWh. That is why there is a high expectation on energy storage systems such as lithium-air (Li-O2) and lithium sulfur (Li-S) systems, especially for mobile applications. These systems have high theoretical specific energy densities compared to conventional Li-ion systems. If the challenges such as practical implementation, low energy efficiency, and cycle life are handled, these systems could provide an interesting energy source for EVs. However, various raw materials are increasingly under critical discussion. Though only 3 wt% of metallic lithium is present in a modern Li-ion cell, absolute high amounts of lithium demand will rise due to the fast-growing market for traction and stationary batteries. Moreover, many lithium sources are not available without compromising environmental aspects. Therefore, there is a growing focus on alternative technologies such as Na-ion and Zn-ion batteries. On a view of Na-ion batteries, especially the combination with carbons derived from food waste as negative electrodes may generate a promising overall cost structure, though energy densities are not as favorable as for Li-ion batteries. Within the scope of this work, the future potential of sodium-based batteries will be discussed in view of sustainability and abundance vs. maximization of electric performance. The major directions of cathode materials development are reviewed and the tendency towards designing high-performance systems is discussed. This paper provides an outlook on the potential of sodium-based batteries in the future battery market of mobile and stationary application