Periodic Reporting for period 1 - MeBattery (MEDIATED BIPHASIC BATTERY)
Periodo di rendicontazione: 2022-05-01 al 2023-04-30
The need for decarbonization is more pressing than ever as global warming continues to have a profound impact on the world's climate. Increasing demand for high-performing and sustainable batteries for applications such as clean energy storage, e-mobility, portable electronics and smart cities is driving research and development globally.
However, the flow and static battery technologies currently considered state-of-the-art (such as All-Vanadium, Zinc-Br2, Na-ion and Li-ion) suffer from significant drawbacks in sustainability, recyclability and energy efficiency. To meet surging energy demands and ambitious climate goals sooner, radically different energy storage concepts are urgently needed.
MeBattery strives to lay the foundations of a next generation battery technology relying on a combination of fundamentally new thermodynamical concepts. These have the potential to overcome the critical limitations of previously developed battery systems across the most crucial performance categories.
The project’s core outcome will be a battery prototype based on the novel MeBattery concept. The innovative prototype is envisioned to be energy-dense, eco-friendly and long-lasting and can pave the way for the next phase of the transition to decarbonised and sustainable energy solutions for society.
The overarching goal of the MeBattery project is to lay the foundations of a next-generation battery technology, which will possess an excellent balance among all the key performance indicators. In detail, the following three objectives will contribute to achieving this goal:
- To increase the energy density of a flowing technology system: 50 Ah L-1.
- To increase the battery cycle life by preventing crossover of dissolved species: 99.25 % per 100 cycles.
- To achieve an energy efficiency value above 75 % at 50 mA cm-2.
However, the flow and static battery technologies currently considered state-of-the-art (such as All-Vanadium, Zinc-Br2, Na-ion and Li-ion) suffer from significant drawbacks in sustainability, recyclability and energy efficiency. To meet surging energy demands and ambitious climate goals sooner, radically different energy storage concepts are urgently needed.
MeBattery strives to lay the foundations of a next generation battery technology relying on a combination of fundamentally new thermodynamical concepts. These have the potential to overcome the critical limitations of previously developed battery systems across the most crucial performance categories.
The project’s core outcome will be a battery prototype based on the novel MeBattery concept. The innovative prototype is envisioned to be energy-dense, eco-friendly and long-lasting and can pave the way for the next phase of the transition to decarbonised and sustainable energy solutions for society.
The overarching goal of the MeBattery project is to lay the foundations of a next-generation battery technology, which will possess an excellent balance among all the key performance indicators. In detail, the following three objectives will contribute to achieving this goal:
- To increase the energy density of a flowing technology system: 50 Ah L-1.
- To increase the battery cycle life by preventing crossover of dissolved species: 99.25 % per 100 cycles.
- To achieve an energy efficiency value above 75 % at 50 mA cm-2.
1-Two computational protocols were developed that can predict partitioning coefficient and redox potentials of redox compounds in aqueous biphasic systems (ABS). A database with redox potentials of ~230 organic compounds was constructed and partitioning coefficient of ~ 28 redox mediator candidates in different ABS was predicted, indicating most promising candidates to avoid cross contamination with catholyte. The two computational methodologies were successfully validated with molecules synthesized in the project.
2- A library of 6 inorganic solid electroactive materials covering a wide range of redox potentials was synthesized and characterized. Synthetic approaches were established that allow controlling size, dispersity and morphology of the solid electroactive materials. In addition, a broad library (41 compounds) of redox mediators for the negative and positive electrolyte were synthesized and extensively characterized.
3- The liquid-liquid equilibria of immiscible systems and the partitioning of organic compounds on them was investigated. Also, the equilibrium potential of developed redox mediators and solid materials was explored to assess the spontaneity of the charge transfer reaction in the solid/liquid interface in the reservoir. Three solid/liquid candidate pairs were identified for the positive compartment of the battery.
4- The capability of an adapted methodology, Scanning Electrochemical Microscopy, to investigate charge transfer rate in an immiscible liquid-liquid system containing redox mediators was demonstrated. Moreover, the feasibility of nano-electrochemistry to assess the kinetics of charge transfer at the liquid.solid interface was successfully proven using a model system.
5- A prototype of flowing half-cell to gather know-how on the two semi-reactions of the battery separately was developed, tested and validated with promising candidate catholyte materials. In addition, a counter-flow cell design was evaluated with ABS containing pre-selected mediator candidates with promising initial performance.
6- The toxicological potential of 7 redox mediators was assessed using representative biological models of human and environmental exposure, showing that small differences in the chemical structure of these molecules can induce drastic changes in their toxicological impact on living organisms and the environment. At least 2 candidates with low toxicological potential were identified.
2- A library of 6 inorganic solid electroactive materials covering a wide range of redox potentials was synthesized and characterized. Synthetic approaches were established that allow controlling size, dispersity and morphology of the solid electroactive materials. In addition, a broad library (41 compounds) of redox mediators for the negative and positive electrolyte were synthesized and extensively characterized.
3- The liquid-liquid equilibria of immiscible systems and the partitioning of organic compounds on them was investigated. Also, the equilibrium potential of developed redox mediators and solid materials was explored to assess the spontaneity of the charge transfer reaction in the solid/liquid interface in the reservoir. Three solid/liquid candidate pairs were identified for the positive compartment of the battery.
4- The capability of an adapted methodology, Scanning Electrochemical Microscopy, to investigate charge transfer rate in an immiscible liquid-liquid system containing redox mediators was demonstrated. Moreover, the feasibility of nano-electrochemistry to assess the kinetics of charge transfer at the liquid.solid interface was successfully proven using a model system.
5- A prototype of flowing half-cell to gather know-how on the two semi-reactions of the battery separately was developed, tested and validated with promising candidate catholyte materials. In addition, a counter-flow cell design was evaluated with ABS containing pre-selected mediator candidates with promising initial performance.
6- The toxicological potential of 7 redox mediators was assessed using representative biological models of human and environmental exposure, showing that small differences in the chemical structure of these molecules can induce drastic changes in their toxicological impact on living organisms and the environment. At least 2 candidates with low toxicological potential were identified.
The main results of the project beyond the state of the art were published as 4 articles in scientific journals. The publications and a summary of the reported results are listed below:
1. A Systematic Study on the Redox Potentials of Phenazine-derivatives in Aqueous Media: A Combined Computational and Experimental Work; Carlos de la Cruz, Roberto Sanz, Anisley Suárez, Edgar Ventosa, Rebeca Marcilla, Andreas Mavrandonakis; ChemSusChem 16 (2023) e202201984.
Phenazines are an emerging class of organic compounds recently utilized in aqueous redox flow batteries, a promising technology for large-scale energy storage. In this publication, a virtual screening based on density functional theory calculations is used to investigate the redox potentials of around 100 phenazine derivatives in aqueous media containing various electron-donating or electron-withdrawing groups at different positions. Calculations identify crucial positions that should be functionalized to design new anolytes. The combined experimental–computational methodology reported guided the development of a new molecule with a record low reversible redox potential as potential anolyte for aqueous redox flow batteries.
2. Addressing Practical Use of Viologen-Derivatives in Redox Flow Batteries through Molecular Engineering; Ruben Rubio-Presa, Lara Lubian, Mario Borlaf, Edgar Ventosa, Roberto Sanz; ACS Materials Lett. 5 (2023) 798.
In practical scenarios, viologen-derivatives face an accelerated degradation in the unavoidable presence of traces of oxygen in large-scale redox flow batteries. In this work, the primary degradation mechanism is confirmed and a straightforward, cheap, and fast method to evaluate the stability of viologen-derivatives toward this degradation is proposed. A new viologen-derivative is designed and synthesized to illustrate how molecular engineering can be used to improve stability.
3- Operando Scanning Electrochemical Probe Microscopy during Electrocatalysis; Carla Santana Santos, Bright Nsolebna Jaato, Ignacio Sanjuán, Wolfgang Schuhmann, Corina Andronescu; Chem. Rev. 123 (2023) 4972.
This review article focuses in the recent progress in operando scanning electrochemical probe microscopy (SEPM) measurements during electrocatalysis. SEPM techniques can disclose the local electrochemical reactivity of interfaces in single-entity and sub-entity studies. The powerful operando SEPM measurements can correlate electrochemical activity with changes in surface properties as well as provide insight into reaction mechanisms.
4- A neutral pH aqueous biphasic system applied to both static and flow membrane-free battery; Paula Navalpotro, Santiago E. Ibañez, Eduardo Pedraza, Rebeca Marcilla; Energy Storage Materials 56 (2023) 403.
In this publication, a new aqueous biphasic electrolyte system with near neutral pH and low cost is prepared. Battery performance shows high efficiency, capacity utilization and stability. Thus, results reported in this work represent a breakthrough in the membrane-free battery field since it ceases to just be a promising idea demonstrated only in static conditions and becomes real in a flow battery.
1. A Systematic Study on the Redox Potentials of Phenazine-derivatives in Aqueous Media: A Combined Computational and Experimental Work; Carlos de la Cruz, Roberto Sanz, Anisley Suárez, Edgar Ventosa, Rebeca Marcilla, Andreas Mavrandonakis; ChemSusChem 16 (2023) e202201984.
Phenazines are an emerging class of organic compounds recently utilized in aqueous redox flow batteries, a promising technology for large-scale energy storage. In this publication, a virtual screening based on density functional theory calculations is used to investigate the redox potentials of around 100 phenazine derivatives in aqueous media containing various electron-donating or electron-withdrawing groups at different positions. Calculations identify crucial positions that should be functionalized to design new anolytes. The combined experimental–computational methodology reported guided the development of a new molecule with a record low reversible redox potential as potential anolyte for aqueous redox flow batteries.
2. Addressing Practical Use of Viologen-Derivatives in Redox Flow Batteries through Molecular Engineering; Ruben Rubio-Presa, Lara Lubian, Mario Borlaf, Edgar Ventosa, Roberto Sanz; ACS Materials Lett. 5 (2023) 798.
In practical scenarios, viologen-derivatives face an accelerated degradation in the unavoidable presence of traces of oxygen in large-scale redox flow batteries. In this work, the primary degradation mechanism is confirmed and a straightforward, cheap, and fast method to evaluate the stability of viologen-derivatives toward this degradation is proposed. A new viologen-derivative is designed and synthesized to illustrate how molecular engineering can be used to improve stability.
3- Operando Scanning Electrochemical Probe Microscopy during Electrocatalysis; Carla Santana Santos, Bright Nsolebna Jaato, Ignacio Sanjuán, Wolfgang Schuhmann, Corina Andronescu; Chem. Rev. 123 (2023) 4972.
This review article focuses in the recent progress in operando scanning electrochemical probe microscopy (SEPM) measurements during electrocatalysis. SEPM techniques can disclose the local electrochemical reactivity of interfaces in single-entity and sub-entity studies. The powerful operando SEPM measurements can correlate electrochemical activity with changes in surface properties as well as provide insight into reaction mechanisms.
4- A neutral pH aqueous biphasic system applied to both static and flow membrane-free battery; Paula Navalpotro, Santiago E. Ibañez, Eduardo Pedraza, Rebeca Marcilla; Energy Storage Materials 56 (2023) 403.
In this publication, a new aqueous biphasic electrolyte system with near neutral pH and low cost is prepared. Battery performance shows high efficiency, capacity utilization and stability. Thus, results reported in this work represent a breakthrough in the membrane-free battery field since it ceases to just be a promising idea demonstrated only in static conditions and becomes real in a flow battery.