eNargiZinc objetives and impact

eNargiZinc strives to create fresh insights, cutting-edge technology, and commercially viable products in the realm of innovative and cost-effective next-generation Energy Storage Systems (EES) devices. Our focus is on achieving long-term sustainability by leveraging abundant and renewable materials, coupled with environmentally friendly production processes.

A rigorous training-through-research programme for eleven Doctoral Candidates (DCs) —eight DCs funded by the EU and three DCs funded by the UK national funding agency (UKRI)— has been designed, involving studies on all the essential parts needed to develop sodium-ion batteries, zinc-air batteries, and zinc-ion batteries/supercapacitors. The research within eNargiZinc will focus on developing sustainable electrode materials (biomass-derived carbons and their composites, redox-active polymers, hybrid transition metal oxides, and interphases for anode-less concepts), electrolytes (solid-state and gel-polymer types), and, especially, on integrating all the developed components into full cells at an industrially-relevant scale.

Individual Research Projects

D1

D1

Objectives: assessing the role of the hydrothermal carbonisation process pre-treatment on the defect structures of resulting biomass-derived hard carbons (BHCs) for different precursors (pruning residues and enzymatic hydrolysis lignin); to establish relationships between the properties of carbons (porosity, defects, heteroatoms, etc.) and the measured electrochemical performance.

Expected results: to obtain valuable insights into ion diffusion behaviours and interfacial phenomena; to better understand the mechanisms behind Na+ (in SIBs) and Zn2+ and H+ (in ZHSCs) ions storage; to identify the most promising materials for SIB and ZHSC advanced prototypes.

Supervisor: Magda Titirici (ICL)

PhD enrolment: at ICL

Secondment: TBC

D2

D2

Objectives: to establish the best process conditions for physical activation of two pruning residues-derived pyrochars and enzymatic hydrolysis lignin-derived hydrochar in terms of electrochemical performance of the resulting cathodes; to compare the performance of these materials with that of other carbon-based materials produced within and outside the network.

Expected results: to gain insight into the synthesis of N-doped carbon materials having hierarchical porous structures by easily scalable processes; to assess the effect of pore size distribution and surface chemistry on the electrochemical performance of cathodes; to select the most promising materials— in terms of capacity and stability—for ZHSC full-cell prototypes.

Supervisor: Joan J. Manyà (UNIZAR)

PhD enrolment: at UNIZAR

Secondment: at GEYSER (Finland) for 3 months

D3

D3

Objectives: to functionalise BHCs with redox-active inorganic materials with the aim at boosting the capacity of BHC-based electrodes; to get insights on the electrocatalytic reactions involved using advanced ex-situ and in-situ techniques; to understand changes in the catalysts structure and intermediates adsorption.

Expected results: to obtain outstanding active materials with superior capacity (for both SIBs and ZIBs) thanks to the synergistic role of redox-active compounds and the carbon shell, which can buffer volumetric expansions, enhance conductivity and form a more stable SEI; to assess the effect of hydrothermal pre-treatment on the distribution and size of active sites in the resulting composites.

Supervisor: Magda Titirici (ICL)

PhD enrolment: at ICL

Secondment: TBC

D4

D4

INSTM at UNICAM (Italy)

Objectives: to synthesise composite electrocatalysts, based on transition metals and lignin-derived electrospun nanofibers for flexible positive electrodes in ZABs; to find the best synthesis conditions; to train in advanced electrochemical characterisation techniques; to assess electrocatalytic activity and kinetics.

Expected results: to develop lignin-derived carbon electrodes for ZABs with catalytic activity that contain metal catalysts; to gain in-depth understanding of the interactions among the design (2D and 3D), defects structure and heteroatom- and metal transition-doping, and the electrochemical activity of the electrodes; to implement the developed materials in full ZAB cells.

Supervisor: Francesco Nobili (INSTM)

PhD enrolment: at UNICAM

Secondment: at CICE (Spain) for 4 months

D5

D5

KIT (Germany)

Objectives: to develop long-term cycling sodium cathode material made by earth crust abundant elements; to synthesise hybrid solid-state electrolytes with good compatibility with the electrodes for safe sodium-ion batteries; to understand the electrode and solid-state electrolyte interphases formation and their properties.

Expected results: to gain knowledge on scalable and reproducible synthesis methods to develop hybrid O/P-type sodium layered oxides with improved cycling stability with respect to the state-of-the-art of single-type layered oxides; to correlate the microstructure/morphology with the electrochemical performance via deep physicochemical and electrochemical characterisation of sodium cathode material; to identify the optimal properties of hybrid solid-state electrolytes for improving the interfacial resistance; to select the most promising hybrid sodium layered oxides and polymer/inorganic solid-state electrolytes for SIB full-cell assembly.

Supervisor: Maider Zarrabeitia (KIT)

PhD enrolment: at KIT

Secondment: at GAZ (Germany) for 6 months

D6

D6

KIT and VARTA (Germany)

Objectives: to identify the optimal interphase composition for homogeneous and dendrite-free Na metal electrodeposition on the anode current collector; to correlate the properties of the artificial interphase with the electrochemical behaviour in half-cell; to implement such anode-free concepts in zero-excess Na full cells using industrially relevant formats.

Expected results: easy and scalable process for preparing and applying the artificial interphase on the current collector; insights on the conduction mechanism of Na ions though the interphase and relationship with the morphology of electroplated Na metal; know-how on pre-sodiation additives and methods for reducing initial irreversible capacity; highly efficient Na plating/stripping at loading of practical interest (up to 5-6 mA h cm–2); long and stable cycling of anode-free full sodium-ion cells with zero Na metal excess.

Supervisor: Alberto Varzi (KIT)

PhD enrolment: at KIT

Secondment: at VARTA (Germany) for 12 months (employed by VARTA during the third year)

D7

D7

Objectives: to develop novel redox-active polymers (RAPs) and their hybrids, including conjugated porous polymers with a large surface area and redox-active groups; to explore the preparation of electrode hybrids by promoting in-situ polymerisation of RAPs in presence of nanocarbons or conducting polymers; to improve the long-term cyclability, the capacity and the transport properties of the electrodes.

Expected results: to optimise the molar mass, morphology and size of RAPs and their hybrids as well as other macromolecular properties (e.g., conductivity and flexibility); to obtain hybrid polymer materials with two distinct functionalities: a functionality able to undergo fast and reversible redox reactions and a conducting functionality to ensure efficient charge collection; to implement tailor-made RAPs into the SIB and ZIB prototypes; to combine RAPs with the best-performing bifunctional ORR/OER catalysts towards innovative polymer-air batteries.

Supervisor: Rebeca Marcilla (IME)

PhD enrolment: at UNIZAR

Secondment: at MIDAC (Italy) for 3 months

D8

D8

Objectives: to establish processing methods and optimisation of sodium-ion battery materials for their implementation in full-cell prototypes.

Expected results: to develop aqueous processing methods for TMOs-based and RAPs-based cathodes; to establish manufacturing methods towards integration of hybrid inorganic/polymeric and solid-state NASICON-type electrolytes in composite electrodes; to integrate the final optimised cell components in real-world cell prototypes; to validate the performance of prototypes and compare it with the state-of-the-art technology (lead acid and Li-ion) used on the MIDAC’s industrial and stationary fields.

Supervisor: Ivana Hasa (WMG)

PhD enrolment: at WMG

Secondment: at MIDAC (Italy) for 3 months

D9

D9

Objectives: to develop an alkaline gel electrolyte based on naturally occurring biopolymers and optimised liquid electrolyte formulation to obtain a crosslinked solid electrolyte with high ionic conductivity, high mechanical resistance, superior water retention, optimal electrode/electrolyte interaction, and enhanced reversibility to be integrated in rechargeable ZABs with high performance electrodes, aiming superior cyclability, total DoD (> 60%), and energy density (> 150–200 W h kg–1).

Expected results: comprehensive analysis of gel electrolyte capabilities (conductivity, chemical structure, thermal degradation, water adsorption/release capability) and electrochemical behaviour and stability over time; analysis of overall cell integration: influence of operating (current, cycling time), environmental (temperature, humidity), and component (area, thickness, mass) parameters on full cell performance for the design of enhanced sandwich format cells; mechanism’s understanding from both experimental data (EIS) and molecular dynamics simulation (electrolyte level).

Supervisor: Nagore Ortiz-Vitoriano (CICE)

PhD enrolment: at UPV/EHU

Secondment: at BCare (Spain) for 3 months

D10

D10

INSTM at PoliTO (Italy)

Objectives: to develop specific gel-polymer electrolytes with high compatibility with both anode and cathode environments for ZIBs and ZHSCs; to develop PBA-based cathodes for ZIBs; to integrate the innovative components at full-cell level.

Expected results: development of a tailor-made electrolyte able to guarantee compatibility with electrode materials and protection from dendrite growth and Zn passivation, including functional additives; development of PBA-based cathodes; coupling of GPEs with anodes and cathodes developed within the network; integration at full-cell level of the innovative components developed.

Supervisor: Claudio Gerbaldi (INSTM)

PhD enrolment: at PoliTO

Secondment: at IME (Spain) for 3 months

D11

D11

INSTM at UNIMIB (Italy)

Objectives: to develop specific ceramic-polymeric composite electrolytes with high compatibility with both anode and cathode environments for SIBs, also including autonomous self-healing moieties; to validate the approach at low TRL half-cell level and to integrate the electrolytes at high TRL full-cell level.

Expected results: development of functionalised ceramic fillers with surface modification; development of core-shell nano/microspheres with self-healing capabilities; development of composite electrolytes able to protect from dendrite growth in SIBs; coupling of composite electrolytes with metallic Na or anode-less approaches and positive electrodes developed within the network; integration at full-cell level of the innovative electrolytes.

Supervisor: Riccardo Ruffo (INSTM)

PhD enrolment: at UNIMIB

Secondment: at WMG (UK) for 3 months

Work packages (WPs)

WP1

Network management

Lead Beneficiary: UNIZAR

Objectives: To ensure the DN achieves the deliverables within the budget and time frame of the project; to implement and update the risk assessment and data management plans; to provide the legal and ethical framework for the project through the Consortium Agreement.

WP2

Career development

Lead Beneficiary: UNIZAR

Objectives: To provide the DCs with the knowledge and skills required for a successful career in industry or academia based on the training-through-research programme.

WP3

Dissemination and exploitation of results

Lead Beneficiary: UNIZAR

Objectives: To ensure the dissemination of knowledge and technology to the research community and related industrial sectors; to address IP right issues and guarantee the terms of the IP agreement; to stimulate and supervise the transfer of knowledge among the partners; to implement the communication and public engagement strategy in an open science framework.

WP4

Development of sustainable electrode materials

Lead Beneficiary: KIT

Objectives: To ensure the dissemination of knowledge and technology to the research community and related industrial sectors; to address IP right issues and guarantee the terms of the IP agreement; to stimulate and supervise the transfer of knowledge among the partners; to implement the communication and public engagement strategy in an open science framework.

WP5

Engineered and eco-friendly electrolytes

Lead Beneficiary: INSTM

Objectives: To develop engineered electrolyte formulations aimed at increasing the performance of the full cell, reducing their cost and increasing their safety: inorganic NASICON-type solid-state electrolytes (and their composites with organic polymers) for SIBs, alkaline gel-biopolymer electrolyte formulations for ZAB purposes, and novel gel-type polymer electrolyte formulations for ZIB/ZHSC full cells.

WP6

Integration into full-cell prototypes

Lead Beneficiary: INSTM

Objectives: To design, assemble and test full-cell prototypes for SIBs, ZIBs and ZHSCs as well as ZABs. The prototypes will include and validate materials produced within WPs 4 and 5.