Maider Zarrabeitia

Bio: Maider Zarrabeitia is an academic researcher from Karlsruhe Institute of Technology. The author has contributed to research in topics: Electrolyte & Materials science. The author has an hindex of 12, co-authored 26 publications receiving 483 citations. Previous affiliations of Maider Zarrabeitia include University of the Basque Country.

Composition and evolution of the solid-electrolyte interphase in Na2Ti3O7 electrodes for Na-ion batteries: XPS and Auger parameter analysis.

Abstract: Na2Ti3O7 is considered a promising negative electrode for Na-ion batteries; however, poor capacity retention has been reported and the stability of the solid-electrolyte interphase (SEI) could be one of the main actors of this underperformance. The composition and evolution of the SEI in Na2Ti3O7 electrodes is hereby studied by means of X-ray photoelectron spectroscopy (XPS). To overcome typical XPS limitations in the photoelectron energy assignments, the analysis of the Auger parameter is here proposed for the first time in battery materials characterization. We have found that the electrode/electrolyte interface formed upon discharge, mostly composed by carbonates and semicarbonates (Na2CO3, NaCO3R), fluorides (NaF), chlorides (NaCl) and poly(ethylene oxide)s, is unstable upon electrochemical cycling. Additionally, solid state nuclear magnetic resonance (NMR) studies prove the reaction of the polyvinylidene difluoride (PVdF) binder with sodium. The powerful approach used in this work, namely Auger param...

Operando pH Measurements Decipher H+/Zn2+ Intercalation Chemistry in High-Performance Aqueous Zn/δ-V2O5 Batteries

Abstract: Vanadium oxides have been recognized to be among the most promising positive electrode materials for aqueous zinc metal batteries (AZMBs). However, their underlying intercalation mechanisms are sti...

Toward Safe and Sustainable Batteries: Na4Fe3(PO4)2P2O7 as a Low-Cost Cathode for Rechargeable Aqueous Na-Ion Batteries

Abstract: The electrochemical properties of Na4Fe3(PO4)2P2O7 in aqueous and organic electrolyte are compared under similar conditions. Na4Fe3(PO4)2P2O7 is able to deliver almost the same capacity in both types of electrolytes despite the smaller electrochemical window entailed by the aqueous one. As shown by electrochemical impedance spectroscopy (EIS), this is possible thanks to the lower overpotential that this material exhibits in aqueous electrolyte. It is shown here that the main contribution to overpotential in organic electrolyte mainly originates from a SPI (Solid Permeable Interphase) layer formed below 3.5 V vs Na+/Na that acts as a blocking layer and hinders Na+ diffusion and that is absent in aqueous electrolyte. Overall, the obtained results highlight the positive attributes of using low-cost and environmentally friendly aqueous electrolytes and the challenges to be overcome in terms of air and moisture stability of the studied material.

Structure of H2Ti3O7 and its evolution during sodium insertion as anode for Na ion batteries

Abstract: H2Ti3O7 was prepared as a single phase material by ionic exchange from Na2Ti3O7. The complete ionic exchange was confirmed by 1H and 23Na solid state Nuclear Magnetic Resonance (NMR). The atomic positions of H2Ti3O7 were obtained from the Rietveld refinement of powder X-ray diffraction (PXRD) and neutron diffraction experimental data, the latter collected at two different wavelengths to precisely determine the hydrogen atomic positions in the structure. All H+ cations are hydrogen bonded to two adjacent [Ti3O7]2− layers leading to the gliding of the layers and lattice centring with respect to the parent Na2Ti3O7. In contrast with a previous report where protons were located in two different positions of H2Ti3O7, 3 types of proton positions were found. Two of the three types of proton are bonded to the only oxygen linked to a single titanium atom forming an H–O–H angle close to that of the water molecule. H2Ti3O7 is able to electrochemically insert Na+. The electrochemical insertion of sodium into H2Ti3O7 starts with a solid solution regime of the C-centred phase. Then, between 0.6 and 1.2 inserted Na+ the reaction proceeds through a two phase reaction and a plateau at 1.3 V vs. Na+/Na is observed in the voltage–composition curve. The second phase resembles the primitive Na2Ti3O7 cell as detected by in situ PXRD. Upon oxidation, from 0.9 to 2.2 V, the PXRD pattern remains mostly unchanged probably due to H+ removal instead of Na+, with the capacity quickly fading upon cycling. Conditioning H2Ti3O7 for two cycles at 0.9–2.2 V before cycling in the 0.05–1.6 V range yields similar specific capacity and better retention than the original Na2Ti3O7 in the same voltage range.

Unraveling the role of Ti in the stability of positive layered oxide electrodes for rechargeable Na-ion batteries

Abstract: The many advantages of Na-ion batteries (NIBs) in terms of availability and cost of raw materials compared with Li-ion batteries (LIBs) are hindered by the stability of Na-based electrodes. The most promising NIB positive electrodes are Co- and Ni-free sodium manganese rich layered oxides with the general formula (y < 0.33, TM = transition metal/s). Although their stability is greatly improved when doped with electrochemically inactive species such as Mg or Ti, the rationale behind this has not been understood to date. Here, we demonstrate how a given degree of TiIV doping (z = 0.1) helps to stabilize the crystal structure of sodium manganese rich layered oxides by absorbing electrochemically induced strain; a remarkable step forward on the quest of finding the best NIB positive electrode. In this case, any Mn–Ti substitution below z = 0.1 will not be enough to absorb the strain and substitutions above this value will increase the amount of Jahn–Teller active MnIII leading to destabilization of the crystal structure with poor electrochemical performance. The possibility of controlling structural and electrochemical properties by TM substitution is the starting point towards the design of electrode materials that will ultimately lead towards competitive Na-ion batteries.

Sodium-ion batteries: present and future

Abstract: Energy production and storage technologies have attracted a great deal of attention for day-to-day applications. In recent decades, advances in lithium-ion battery (LIB) technology have improved living conditions around the globe. LIBs are used in most mobile electronic devices as well as in zero-emission electronic vehicles. However, there are increasing concerns regarding load leveling of renewable energy sources and the smart grid as well as the sustainability of lithium sources due to their limited availability and consequent expected price increase. Therefore, whether LIBs alone can satisfy the rising demand for small- and/or mid-to-large-format energy storage applications remains unclear. To mitigate these issues, recent research has focused on alternative energy storage systems. Sodium-ion batteries (SIBs) are considered as the best candidate power sources because sodium is widely available and exhibits similar chemistry to that of LIBs; therefore, SIBs are promising next-generation alternatives. Recently, sodiated layer transition metal oxides, phosphates and organic compounds have been introduced as cathode materials for SIBs. Simultaneously, recent developments have been facilitated by the use of select carbonaceous materials, transition metal oxides (or sulfides), and intermetallic and organic compounds as anodes for SIBs. Apart from electrode materials, suitable electrolytes, additives, and binders are equally important for the development of practical SIBs. Despite developments in electrode materials and other components, there remain several challenges, including cell design and electrode balancing, in the application of sodium ion cells. In this article, we summarize and discuss current research on materials and propose future directions for SIBs. This will provide important insights into scientific and practical issues in the development of SIBs.

From Lithium-Ion to Sodium-Ion Batteries: Advantages, Challenges, and Surprises.

Abstract: Mobile and stationary energy storage by rechargeable batteries is a topic of broad societal and economical relevance. Lithium-ion battery (LIB) technology is at the forefront of the development, but a massively growing market will likely put severe pressure on resources and supply chains. Recently, sodium-ion batteries (SIBs) have been reconsidered with the aim of providing a lower-cost alternative that is less susceptible to resource and supply risks. On paper, the replacement of lithium by sodium in a battery seems straightforward at first, but unpredictable surprises are often found in practice. What happens when replacing lithium by sodium in electrode reactions? This review provides a state-of-the art overview on the redox behavior of materials when used as electrodes in lithium-ion and sodium-ion batteries, respectively. Advantages and challenges related to the use of sodium instead of lithium are discussed.

Recent Progress in Electrode Materials for Sodium-Ion Batteries

Abstract: Grid-scale energy storage systems (ESSs) that can connect to sustainable energy resources have received great attention in an effort to satisfy ever-growing energy demands. Although recent advances in Li-ion battery (LIB) technology have increased the energy density to a level applicable to grid-scale ESSs, the high cost of Li and transition metals have led to a search for lower-cost battery system alternatives. Based on the abundance and accessibility of Na and its similar electrochemistry to the well-established LIB technology, Na-ion batteries (NIBs) have attracted significant attention as an ideal candidate for grid-scale ESSs. Since research on NIB chemistry resurged in 2010, various positive and negative electrode materials have been synthesized and evaluated for NIBs. Nonetheless, studies on NIB chemistry are still in their infancy compared with LIB technology, and further improvements are required in terms of energy, power density, and electrochemical stability for commercialization. Most recent progress on electrode materials for NIBs, including the discovery of new electrode materials and their Na storage mechanisms, is briefly reviewed. In addition, efforts to enhance the electrochemical properties of NIB electrode materials as well as the challenges and perspectives involving these materials are discussed.

Review of Hybrid Ion Capacitors: From Aqueous to Lithium to Sodium.

Abstract: In this critical Review we focus on the evolution of the hybrid ion capacitor (HIC) from its early embodiments to its modern form, focusing on the key outstanding scientific and technological questions that necessitate further in-depth study. It may be argued that HICs began as aqueous systems, based on a Faradaic oxide positive electrode (e.g., Co3O4, RuOx) and an activated carbon ion-adsorption negative electrode. In these early embodiments HICs were meant to compete directly with electrical double layer capacitors (EDLCs), rather than with the much higher energy secondary batteries. The HIC design then evolved to be based on a wide voltage (∼4.2 V) carbonate-based battery electrolyte, using an insertion titanium oxide compound anode (Li4Ti5O12, LixTi5O12) versus a Li ion adsorption porous carbon cathode. The modern Na and Li architectures contain a diverse range of nanostructured materials in both electrodes, including TiO2, Li7Ti5O12, Li4Ti5O12, Na6LiTi5O12, Na2Ti3O7, graphene, hard carbon, soft carbo...

Observation of Pseudocapacitive Effect and Fast Ion Diffusion in Bimetallic Sulfides as an Advanced Sodium-Ion Battery Anode

Abstract: Lithium-ion batteries (LIBs) have permeated energy storage market from portable electronics to electric vehicles in view of their high energy density and long cycle life.[1] Nevertheless, it is still expensive to scale up due to the limited Li sources.[2] In contrast, sodium-ion batteries (SIBs), with similar energy Sodium-ion batteries (SIBs) are promising next-generation alternatives due to the low cost and abundance of sodium sources. Yet developmental electrodes in SIBs such as transition metal sulfides have huge volume expansion, sluggish Na+ diffusion kinetics, and poor electrical conductivity. Here bimetallic sulfide (Co9S8/ZnS) nanocrystals embedded in hollow nitrogen-doped carbon nanosheets are demonstrated with a high sodium diffusion coefficient, pseudocapacitive effect, and excellent reversibility. Such a unique composite structure is designed and synthesized via a facile sulfidation of the CoZn-MOFs followed by calcination and is highly dependant on the reaction time and temperature. The optimized Co1Zn1-S(600) electrode exhibits excellent sodium storage performance, including a high capacity of 542 mA h g−1 at 0.1 A g−1, good rate capability at 10 A g−1, and excellent cyclic stability up to 500 cycles for half-cell. It also shows potential in full-cell configuration. Such capabilities will accelerate the adoption of sodium-ion batteries for electrical energy applications.