Alberto Varzi

ZnFe2O4-C/LiFePO4-CNT: A Novel High-Power Lithium-Ion Battery with Excellent Cycling Performance.

An innovative and environmentally friendly battery chemistry is proposed for high power applications. A carbon-coated ZnFe2O4 nanoparticle-based anode and a LiFePO4-multiwalled carbon nanotube-based cathode, both aqueous processed with Na-carboxymethyl cellulose, are combined, for the first time, in a Li-ion full cell with exceptional electrochemical performance. Such novel battery shows remarkable rate capabilities, delivering 50% of its nominal capacity at currents corresponding to ≈20C (with respect to the limiting cathode). Furthermore, the pre-lithiation of the negative electrode offers the possibility of tuning the cell potential and, therefore, achieving remarkable gravimetric energy and power density values of 202 Wh kg−1 and 3.72 W kg−1, respectively, in addition to grant a lithium reservoir. The high reversibility of the system enables sustaining more than 10 000 cycles at elevated C-rates (≈10C with respect to the LiFePO4 cathode), while retaining up to 85% of its initial capacity.

Challenges and prospects of the role of solid electrolytes in the revitalization of lithium metal batteries

The scientific community is continuously committed to the search for new high energy electrochemical storage devices. In this regard, lithium metal batteries, due to their very high electrochemical energy storage capacity, appear to be a highly appealing choice. Unfortunately, the use of lithium metal as the anode may lead to some safety hazards due to its uneven deposition upon charging, resulting in dendrite growth and eventual shorting of the battery. This issue may be successfully addressed by using intrinsically safer electrolytes capable of establishing a physical barrier at the electrode interface. The most promising candidates are solid electrolytes, either polymeric or inorganic. The main purpose of this review is to describe the present status of worldwide research on these electrolyte materials together with a critical discussion of their transport properties and compatibility with metallic lithium, hoping to provide some general guidelines for the development of innovative and safe lithium metal batteries.

Boosting the power performance of multilayer graphene as lithium-ion battery anode via unconventional doping with in-situ formed Fe nanoparticles

Graphene is extensively investigated and promoted as a viable replacement for graphite, the state-of-the-art material for lithium-ion battery (LIB) anodes, although no clear evidence is available about improvements in terms of cycling stability, delithiation voltage and volumetric capacity. Here we report the microwave-assisted synthesis of a novel graphene-based material in ionic liquid (i.e., carved multilayer graphene with nested Fe3O4 nanoparticles), together with its extensive characterization via several physical and chemical techniques. When such a composite material is used as LIB anode, the carved paths traced by the Fe3O4 nanoparticles, and the unconverted metallic iron formed in-situ upon the 1st lithiation, result in enhanced rate capability and, especially at high specific currents (i.e., 5 A g−1), remarkable cycling stability (99% of specific capacity retention after 180 cycles), low average delithiation voltage (0.244 V) and a substantially increased volumetric capacity with respect to commercial graphite (58.8 Ah L−1 vs. 9.6 Ah L−1).

Modeling nucleation and growth of zinc oxide during discharge of primary zinc-air batteries

Metal-air batteries are among the most promising next-generation energy storage devices. Relying on abundant materials and offering high energy densities, potential applications lie in the fields of electro-mobility, portable electronics, and stationary grid applications. Now, research on secondary zinc-air batteries is revived, which are commercialized as primary hearing aid batteries. One of the main obstacles for making zinc-air batteries rechargeable is their poor lifetime due to the degradation of alkaline electrolyte in contact with atmospheric carbon dioxide. In this article, we present a continuum theory of a commercial Varta PowerOne button cell. Our model contains dissolution of zinc and nucleation and growth of zinc oxide in the anode, thermodynamically consistent electrolyte transport in porous media, and multi-phase coexistance in the gas diffusion electrode. We perform electrochemical measurements and validate our model. Excellent agreement between theory and experiment is found and novel insights into the role of zinc oxide nucleation and growth and carbon dioxide dissolution for discharge and lifetime is presented. We demonstrate the implications of our work for the development of rechargeable zinc-air batteries.

Ultrafast Ionic Liquid-Assisted Microwave Synthesis of SnO Microflowers and Their Superior Sodium-Ion Storage Performance

Tin oxide (SnO) is considered one of the most promising metal oxides for utilization as anode material in sodium ion batteries (SIBs), because of its ease of synthesis, high specific gravimetric capacity, and satisfactory cycling performance. However, to aim at practical applications, the Coulombic efficiency during cycling needs to be further improved, which requires a deeper knowledge of its working mechanism. Here, a microflower-shaped SnO material is synthesized by means of an ultrafast ionic liquid-assisted microwave method. The as-prepared SnO anode active material exhibits excellent cycling performance, good Coulombic efficiency as well as a large capacity delivered at low potential, which is fundamental to maximize the energy output of SIBs. These overall merits were never reported before for pure SnO anodes (i.e., not in a composite with, for example, graphene). Additionally, by combining ex situ XRD and XPS, it is clearly demonstrated for the first time that the Sn-Na alloy, which is formed during the initial sodium sodiation, desodiates in two successive but fully separated steps. Totally different from the previous report, the pristine SnO phase is not regenerated upon desodiation up to 3 V vs Na/Na+. The newly disclosed reaction route provides an alternative view of the complex reaction mechanism of these families of metal oxides for sodium ion batteries.

High energy and high voltage integrated photo-electrochemical double layer capacitor

A novel, monolithic harvesting–storage (HS) device composed of a dye-sensitized solar cell (DSSC)-based module and a high voltage supercapacitor with impressive discharge capacity after photocharging is herein proposed. Both the harvesting and the storage sections are fabricated onto conductive glass substrates, paving the way to a smart and easy integration in window facades for energy self-sustainable buildings. In addition, the HS device can also be integrated in portable electronics or drive remote, off-grid sensor networks requiring high power intermittent electrical energy. The harvesting photovoltaic section is constituted by a series of four DSSCs integrated in a single W-type module while the storage section consists of an activated carbon-based supercapacitor (SC) utilizing Pyr14TFSI ionic liquid as the electrolyte. The testing of the two separated sections as well as of the integrated system is reported here. In particular, the integration is evaluated through photo-charge and subsequent discharge protocols performed at different galvanostatic currents, showing that the SC handles photo-charges up to 2.45 V while delivering discharge capacities exceeding 1.8 mA h (0.1 mA h cm−2) upon 1 mA discharge current. To the best of our knowledge this is a never reported before, absolute record value, for stable and reliable integrated HS devices.

Portable High Voltage Integrated Harvesting-Storage Device Employing Dye-Sensitized Solar Module and All-Solid-State Electrochemical Double Layer Capacitor

A dye-sensitized solar module (DSSM) and a high voltage all-solid-state electrochemical double layer capacitor (EDLC) are, for the first time, implemented in a compact Harvesting-Storage (HS) device. Conductive glass is employed as current collecting substrate for both DSSM and EDLC, leading to a robust and portable final structure. The photovoltaic section is constituted by a 4 series cells W-type module, while in the storage section an EDLC employing an ionic liquid-based polymeric electrolyte (a mixture of polyethylene oxide and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, PEO-Pyr14TFSI) and activated carbon electrodes is used. The solid state EDLC is first characterized individually to determine its electrochemical performance before successfully proving the integration with the DSSM. The harvesting-storage properties of the integrated photo-capacitor are evaluated through photo-charge and subsequent discharge protocols performed at two different discharge currents, showing that in this configuration the EDLC unit can be effectively charged up to 2.45 V.

Enabling Reversible (De-)lithiation of Aluminum via the Use of Bis(fluorosulfonyl)imide-based Electrolytes

Aluminum, a cost-effective and abundant metal capable of alloying with Li up to around 1000 mAh g-1 , is a very appealing anode material for high energy density lithium-ion batteries (LIBs). However, despite repeated efforts in the past three decades, reports presenting stable cycling performance are extremely rare. This study concerns recent findings on the highly reversible (de)lithiation of a micro-sized Al anode (m-Al) by using bis(fluorosulfonyl)imide (FSI)-based electrolytes. By using this kind of electrolyte, m-Al can deliver a specific capacity over 900 mAh g-1 and superior Coulombic efficiency (96.8 %) to traditional carbonate- and glyme-based electrolytes (87.8 % and 88.1 %, respectively), which represents the best performance ever obtained for an Al anode without sophisticated structure design. The significantly improved electrochemical performance, which paves the way to realizing high-performance Al-based high energy density LIBs, can be attributed the peculiar solid-electrolyte interphase (SEI) formed by the FSI-containing electrolyte.

Cobalt Disulfide Nanoparticles Embedded in Porous Carbonaceous Micro-Polyhedrons Interlinked by Carbon Nanotubes for Superior Lithium and Sodium Storage

Transition metal sulfides are appealing electrode materials for lithium and sodium batteries owing to their high theoretical capacity. However, they are commonly characterized by rather poor cycling stability and low rate capability. Herein, we investigate CoS2, serving as a model compound. We synthesized a porous CoS2/C micro-polyhedron composite entangled in a carbon-nanotube-based network (CoS2-C/CNT), starting from zeolitic imidazolate frameworks-67 as a single precursor. Following an efficient two-step synthesis strategy, the obtained CoS2 nanoparticles are uniformly embedded in porous carbonaceous micro-polyhedrons, interwoven with CNTs to ensure high electronic conductivity. The CoS2-C/CNT nanocomposite provides excellent bifunctional energy storage performance, delivering 1030 mAh g-1 after 120 cycles and 403 mAh g-1 after 200 cycles (at 100 mA g-1) as electrode for lithium-ion (LIBs) and sodium-ion batteries (SIBs), respectively. In addition to these high capacities, the electrodes show outstanding rate capability and excellent long-term cycling stability with a capacity retention of 80% after 500 cycles for LIBs and 90% after 200 cycles for SIBs. In situ X-ray diffraction reveals a significant contribution of the partially graphitized carbon to the lithium and at least in part also for the sodium storage and the report of a two-step conversion reaction mechanism of CoS2, eventually forming metallic Co and Li2S/Na2S. Particularly the lithium storage capability at elevated (dis-)charge rates, however, appears to be substantially pseudocapacitive, thus benefiting from the highly porous nature of the nanocomposite.

Study of Carbon Nanotubes for Lithium-Ion Batteries Application

The potential use of multi-walled carbon nanotubes (MWCNTs) produced by chemical vapour deposition (CVD) as a conductive agent for electrodes in Li-ion batteries has been investigated. LiNi0.33Co0.33Mn0.33O2 (NCM) has been chosen as active material for positive electrodes, and a nano-sized TiO2-rutile for the negative electrodes. The electrochemical performances of the electrodes were studied by galvanostatic techniques and especially the influence of the nanotubes on the rate capability and cycling stability has been evaluated. The addition of MWCNTs significantly enhanced the rate performances of both positive and negative electrodes and improved the capacity retention upon cycling. The obtained results demonstrated that the addition of MWCNTs in low amounts to the electrode composition enables an increase in both energy and power density of a Li-ion battery.