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2024 - Optimizing Current Collector Interfaces for Efficient “Anode-Free” Lithium Metal Batteries [Articolo su rivista]
Molaiyan, P.; Abdollahifar, M.; Boz, B.; Beutl, A.; Krammer, M.; Zhang, N.; Tron, A.; Romio, M.; Ricci, M.; Adelung, R.; Kwade, A.; Lassi, U.; Paolella, A.

Current lithium (Li)-metal anodes are not sustainable for the mass production of future energy storage devices because they are inherently unsafe, expensive, and environmentally unfriendly. The anode-free concept, in which a current collector (CC) is directly used as the host to plate Li-metal, by using only the Li content coming from the positive electrode, could unlock the development of highly energy-dense and low-cost rechargeable batteries. Unfortunately, dead Li-metal forms during cycling, leading to a progressive and fast capacity loss. Therefore, the optimization of the CC/electrolyte interface and modifications of CC designs are key to producing highly efficient anode-free batteries with liquid and solid-state electrolytes. Lithiophilicity and electronic conductivity must be tuned to optimize the plating process of Li-metal. This review summarizes the recent progress and key findings in the CC design (e.g. 3D structures) and its interaction with electrolytes.

2023 - Biomass-derived carbon–silicon composites (C@Si) as anodes for lithium-ion and sodium-ion batteries: A promising strategy towards long-term cycling stability: A mini review [Articolo su rivista]
dos Reis, G. S.; Molaiyan, P.; Subramaniyam, C. M.; Garcia-Alvarado, F.; Paolella, A.; de Oliveira, H. P.; Lassi, U.

The global need for high energy density and performing rechargeable batteries has led to the development of high-capacity silicon-based anode materials to meet the energy demands imposed to electrify plug-in vehicles to curtail carbon emissions by 2035. Unfortunately, the high theoretical capacity (4200 mA h g−1) of silicon by (de-)alloy mechanism is limited by its severe volume changes (ΔV ∼ 200% − 400%) during cycling for lithium-ion batteries (LIBs), while for sodium-ion batteries (NIBs) remain uncertain, and hence, compositing with carbons (C@Si) represent a promising strategy to enable the aforementioned practical application. The present review outlines the recent progress of biomass-derived Si-carbon composite (C@Si) anodes for LIBs and NIBs. In this perspective, we present different types of biomass precursors, silicon sources, and compositing strategies, and how these impact on the C@Si physicochemical properties and their electrochemical performance are discussed.

2023 - Exploration of Metal Alloys as Zero-Resistance Interfacial Modification Layers for Garnet-Type Solid Electrolytes [Articolo su rivista]
Cui, J.; Kim, J. H.; Yao, S.; Guerfi, A.; Paolella, A.; Goodenough, J. B.; Khani, H.

A solid-state battery with a lithium-metal anode and a garnet-type solid electrolyte has been widely regarded as one of the most promising solutions to boost the safety and energy density of current lithium-ion batteries. However, lithiophobic property of garnet-type solid electrolytes hinders the establishment of a good physical contact with lithium metal, bringing about a large lithium/garnet interfacial resistance that has remained as the greatest issue facing their practical application in solid-state batteries. Herein, a melt-quenching approach is developed by which varieties of interfacial modification layers based on metal alloys can be coated uniformly on the surface of the garnet. It is demonstrated that with an ultrathin, lithiophilic AgSn0.6Bi0.4Ox coating the interfacial resistance can be eliminated, and a dendrite-free lithium plating and stripping on the lithium/garnet interface can be achieved at a high current density of 20 mA cm−2. The results reveal that the uniform coating on the garnet surface and the facile lithium diffusion through the coating layer are two major reasons for the excellent electrochemical performances. The all-solid-state full cell consisting of the surface modified garnet-type solid electrolyte with a LiNi0.8Mn0.1Co0.1O2 cathode and a lithium–metal anode maintains 86% of its initial capacity after 1000 stable cycles at 1 C.

2023 - Film processing of Li6PS5Cl electrolyte using different binders and their combinations [Articolo su rivista]
Tron, A.; Hamid, R.; Zhang, N.; Paolella, A.; Wulfert-Holzmann, P.; Kolotygin, V.; Lopez-Aranguren, P.; Beutl, A.

The development of solid electrolytes has made significant progress in the last decade. Among the most promising materials, sulfide-based electrolytes show high ionic conductivities and low densities, and their precursors are abundant. For industrially relevant battery cells, sulfide electrolytes need to be processed to form thin electrolyte sheets that are either directly applied to the electrodes as coatings or prepared as stand-alone films. Thus, processing of sulfide electrolyte powders has recently drawn much attention as it seems to be one of the major challenges in realizing sulfide-based all-solid-state batteries. In this work, six different binders (NBR, HNBR, PIB, PBMA, SBS, SEBS) were selected for preparation of electrolyte films using Li6PS5Cl as a sulfidic model compound. The influence of the binders on the electrochemical performance as well as on the mechanical properties of the resulting films was investigated. In addition, binder blends were explored as a vial approach to optimize the properties of the electrolyte films. Special focus was put on elucidating the relation between the physico-chemical properties of the binder materials and the resulting electrochemical and mechanical properties of the electrolyte films.

2023 - Gram-scale carbothermic control of LLZO garnet solid electrolyte particle size [Articolo su rivista]
Campanella, D.; Bertoni, G.; Zhu, W.; Trudeau, M.; Girard, G.; Savoie, S.; Clement, D.; Guerfi, A.; Vijh, A.; George, C.; Belanger, D.; Paolella, A.

In recent years, solid electrolytes have become an enticing alternative to liquid electrolytes in lithium based batteries. However, the high synthesis temperatures and difficult optimization of solid-state electrolytes are a significant drawback in a high-scale application. In this work, we demonstrate that the synthesis process of garnet-based Li7La3Zr2O12 (LLZO) electrolyte can be accelerated while reducing the formation temperature of cubic LLZO to about 720 °C from a standard temperature of 780 °C by supplementing the process with a carbon additive. These carbon-rich LLZO samples have a homogeneous particle distribution with a decreased average size, which is influenced by the type of carbon additive itself. The materials with high carbon content show an improved densification after hot-pressing at a low temperature of 800 °C, which is reflected in their electrochemical performance, since LLZO sample with 10% of DENKA carbon additive shows a total ionic conductivity of 5.95 × 10−5 S cm−1, about 40% higher than the one of carbon-free LLZO (3.53 × 10−5 S cm−1).

2023 - Hexavalent Ions Insertion in Garnet Li7La3Zr2O12 Toward a Low Temperature Densification Reaction [Articolo su rivista]
Campanella, D.; Zhu, W.; Girard, G.; Savoie, S.; Kaboli, S.; Feng, Z.; Guerfi, A.; Romio, M.; Molaiyan, P.; Belanger, D.; Paolella, A.

Nowadays, solid electrolytes are considered the main alternative to conventional liquid electrolytes in lithium batteries. The fabrication of these materials is however limited by the strict synthesis conditions, requiring high temperatures which can negatively impact the final performances. Here, it is shown that a modification of garnet-based Li7La3Zr2O12 (LLZO) and the incorporation of tellurium can accelerate the synthesis process by lowering the formation temperature of cubic LLZO at temperatures below 700 °C. Optimized synthesis at 750 °C showed a decrease in particle size and cell parameter for samples with higher amounts of Te and the evaluation of electrochemical performances reported for LLZO Te0.25 a value of ionic conductivity of 5,15×10−5 S cm−1 after hot-pressing at 700 °C, two orders of magnitude higher than commercial Al-LLZO undergoing the same working conditions, and the highest value at this densification temperature. Partial segregation of Te-rich phases occurs for high-temperature densification. Our study shows the advantages of Te insertion on the sintering process of LLZO garnet and demonstrates the achievement of highly conductive LLZO with a low-temperature treatment.

2023 - New Insights of Infiltration Process of Argyrodite Li6PS5Cl Solid Electrolyte into Conventional Lithium-Ion Electrodes for Solid-State Batteries [Articolo su rivista]
Tron, A.; Paolella, A.; Beutl, A.

All-solid-state lithium-ion batteries based on solid electrolytes are attractive for electric applications due to their potential high energy density and safety. The sulfide solid electrolyte (e.g., argyrodite) shows a high ionic conductivity (10−3 S cm−1). There is an open question related to the sulfide electrode’s fabrication by simply infiltrating methods applied for conventional lithium-ion battery electrodes via homogeneous solid electrolyte solutions, the structure of electrolytes after drying, chemical stability of binders and electrolyte, the surface morphology of electrolyte, and the deepening of the infiltrated electrolyte into the active materials to provide better contact between the active material and electrolyte and favorable lithium ionic conduction. However, due to the high reactivity of sulfide-based solid electrolytes, unwanted side reactions between sulfide electrolytes and polar solvents may occur. In this work, we explore the chemical and electrochemical properties of the argyrodite-based film produced by infiltration mode by combining electrochemical and structural characterizations.

2023 - Understanding the Origin of Lithiophilicity Toward Molten Li-Metal Using In-situ Scanning Electron Microscopy (SEM) [Articolo su rivista]
Kaboli, S.; Zhu, W.; Clement, D.; Dontigny, M.; Gendron, F.; Amouzegar, K.; Vijh, A.; Guerfi, A.; Trudeau, M. L.; Paolella, A.

2023 - Unraveling the Origin of Lithiophilicity toward a Molten Li Metal: Zn Metal as Trojan Horse [Articolo su rivista]
Kaboli, S.; Zhu, W.; Clement, D.; Dontigny, M.; Gendron, F.; Amouzegar, K.; Guerfi, A.; Vijh, A.; Trudeau, M. L.; Paolella, A.

In this work, we investigated the origin of lithiophilicity of a Cu foil substrate modified by a sputtered Zn thin film (Cu@Zn) in contact with a molten Li metal to understand the reaction mechanism between Li and Cu@Zn. We studied the reaction between the molten Li metal and the Cu surface during Li solidification via in situ scanning electron microscopy (SEM), subsequently performed post-mortem energy dispersive spectroscopy (EDS) and Grazing Incidence X-ray Diffraction (GIXRD) on the coatings to analyze the chemistry of the reaction products, and compared the results for different thicknesses of nanometric Zn films (5-50 nm). For the first time in the literature, we report the existence of a metastable ternary Li-Cu-Zn alloy at 300 °C after the reaction of Cu@Zn with the molten Li metal. We also report the segregation of Cu and Zn by formation of Cu-Zn intermetallic compounds during the cooling down step. The results of our in situ study are pivotal to clarify the interfacial reactions occurring between a lithiophilic current collector and a molten Li metal and have utmost importance for designing advanced anode materials for future solid-state battery applications.

2022 - Influence of AlPO4 Impurity on the Electrochemical Properties of NASICON-Type Li1.5Al0.5Ti1.5(PO4)3 Solid Electrolyte [Articolo su rivista]
Campanella, D.; Krachkovskiy, S.; Faure, C.; Zhu, W.; Feng, Z.; Savoie, S.; Girard, G.; Demers, H.; Vijh, A.; George, C.; Armand, M.; Belanger, D.; Paolella, A.

Densification of ceramic electrolytes is a key enabler in producing electrolyte pellets for solid-state batteries. This requires understanding the correlation between the starting grain size of electrolytes, chemical phase evolution and degree of compaction which determine ion conductivity and chemical stability of solid electrolytes. In our work we were able to optimize the densification process of LATP at 700 °C with a high total ionic conductivity of 3.45×10−4 S cm−1 after hot pressing, balancing pristine LATP crystallite size and AlPO4 impurity formation. By combining several techniques such as in situ heating X-ray diffraction (XRD), scanning electron microscopy (SEM) and nuclear magnetic resonance (NMR), we explored the formation mechanism of AlPO4 during the synthesis process of NASICON-type Li1.5Al0.5Ti1.5(PO4)3 (LATP) electrolyte and we showed the effects of the annealing temperature on the crystal size of the material. Density functional theory (DFT) calculations on the chemical stability of the electrolyte imply a metastable behaviour of LATP furtherly enhanced by particle nano-structuring at high temperature. Our results point to facile manufacturing of ceramic electrolytes towards energy dense and safe solid-state battery technology.

2022 - Influence of Rutile and Anatase TiO2Precursors on the Synthesis of a Li1.5Al0.5Ti1.5(PO4)3Electrolyte for Solid-State Lithium Batteries [Articolo su rivista]
La Monaca, A.; Zhu, W.; Feng, Z.; Bertoni, G.; Campanella, D.; Girard, G.; Savoie, S.; Nita, A. G.; Clement, D.; Demers, H.; Vijh, A.; Rosei, F.; Paolella, A.

We report the effect of using rutile and anatase TiO2 as precursors in the synthesis of ceramic Li1.3Al0.3Ti1.7(PO4)3 (LATP) NASICON-type electrolyte for solid-state lithium batteries. Anatase TiO2 enables LATP crystallization at lower temperatures while rutile TiO2 leads to a purer and more crystalline LATP phase. We believe these findings are an important contribution towards the development of more effective and less expensive synthesis of Ti-based solid electrolyte materials.

2022 - Influence of TiIV substitution on the properties of a Li1.5Al0.5Ge1.5(PO4)3 nanofiber-based solid electrolyte [Articolo su rivista]
La Monaca, A.; Girard, G.; Savoie, S.; Veillette, R.; Krachkovskiy, S.; Pierini, F.; Vijh, A.; Rosei, F.; Paolella, A.

We report the influence of the partial substitution of Ge with Ti on the properties of NASICON Li1.5Al0.5Ge1.5(PO4)3 (LAGP) nanofibers prepared by electrospinning. Replacing a small amount of Ge (up to 20%) with Ti is advantageous for enhancing both the purity and morphology of LAGP fibers, as observed by X-ray diffraction, electron microscopy and nuclear magnetic resonance spectroscopy. When Ti-substituted LAGP (LAGTP) fibers are used as filler to develop composite polymer electrolytes, the ionic conductivity at 20 °C improves by a factor of 1.5 compared to the plain polymer electrolyte. Additionally, above 40 °C the LAGTP fiber-based composite electrolytes were more conductive than the equivalent LAGP fiber-based one. We believe that these findings can make a substantial contribution to optimizing current methods and developing novel synthesis approaches for NASICON based electrolytes.

2022 - Metastable properties of a garnet type Li5La3Bi2O12 solid electrolyte towards low temperature pressure driven densification [Articolo su rivista]
Campanella, D.; Krachkovskiy, S.; Bertoni, G.; Gazzadi, G. C.; Golozar, M.; Kaboli, S.; Savoie, S.; Girard, G.; Gheorghe Nita, A. C.; Okhotnikov, K.; Feng, Z.; Guerfi, A.; Vijh, A.; Gauvin, R.; Belanger, D.; Paolella, A.

Solid state electrolytes represent an attractive alternative to liquid electrolytes for rechargeable batteries. However, the fabrication of batteries with ceramic materials requires high temperature that could be detrimental to their electrochemical performance. In this work, we show that it's possible to densify a garnet-type Li5La3Bi2O12 solid electrolyte at low temperature (600 °C) with respect to standard high sintering temperature (T > 1000 °C) used for zirconium-based Li7La3Zr2O12 doped garnet. Li5La3Bi2O12 showed a high conductivity (1.2 × 10−4 S cm−1) after hot pressing at 600 °C. The synthesis conditions have been optimized: at 700 °C we observed the presence of the LiLa2O3.5 phase as a consequence of LLBO metastability, and the formation mechanism has been described by density functional theory (DFT) and density functional perturbation theory (DFPT) calculations. Moreover, we have reported the application of small amounts of LLBO as a sintering aid (5-10%) in the densification of LLZTO. Our investigation successfully demonstrated that LLBO introduction positively affects the densification process and global performances of LLZTO garnet, allowing us to obtain an ionic conductivity higher than 10−4 S cm−1 after annealing at 600 °C.

2022 - Monitoring lithium metal plating/stripping in anode free//NMC811 battery by in-situ X-rays diffraction [Articolo su rivista]
Zhu, W.; Demers, H.; Girard, G.; Clement, D.; Zimin, F.; Guerfi, A.; Trudeau, M.; Vijh, A.; Paolella, A.

One of the main limitations to the application of anode free lithium battery is low Coulombic efficiency, this loss of capacity is due to irreversible processes, mainly the formation of dead lithium, the instability of electrolyte, etc. In this work, conventional x-ray diffraction technique was employed to monitor the lithium metal plating and stripping during cycling between 4.3 and 3 V using cells composed of 5 μm thick copper current collector and LiN0.8Co0.1Mn0.1O2 cathode. We have observed that the lithium metal was not completely stripped off from the copper substrate at the end of discharge at a slow cycling rate of C/24 even in the first 2 cycles. In addition, the lithium metal was still seen following a constant voltage period of 3V despite at its reduced amount. The observation of this unreacted lithium metal unveils one of the important degradation mechanisms of anode free lithium battery, thus provides essential information for finding solution to reduce/eliminate “dead” lithium metal and prolonging cycling life.

2022 - NASICON lithium ions conductors: Materials, composites, and batteries [Articolo su rivista]
Paolella, A.; Zhu, W.; Campanella, D.; Kaboli, S.; Feng, Z.; Vijh, A.

In this review, we present the most recent studies about NASICON (LATP, LAGP, LZP) solid electrolytes in Li-metal batteries and show possible structure evolutions and their applications in polymer composites as membranes electrolyte. We describe all the possible interfacial side reactions occurring at the cathode and the lithium (Li) metal electrodes and summarize the possible options that have been proposed in the literature to date to suppress these reactions.

2022 - Unveiling the Cation Exchange Reaction between the NASICON Li1.5Al0.5Ge1.5(PO4)3Solid Electrolyte and the pyr13TFSI Ionic Liquid [Articolo su rivista]
Paolella, A.; Bertoni, G.; Zhu, W.; Campanella, D.; La Monaca, A.; Girard, G.; Demers, H.; Gheorghe Nita, A. C.; Feng, Z.; Vijh, A.; Guerfi, A.; Trudeau, M.; Armand, M.; Krachkovskiy, S. A.

Recently, the formation of the ceramic-ionic liquid composite has attracted huge interest in the scientific community. In this work, we investigated the chemical reactions occurring between NASICON LAGP ceramic electrolyte and ionic liquid pyr13TFSI. This study allowed us to identify the cation exchange reaction pyr13-Li occurring on the LAGP surface, forming a LiTFSI salt that was detected by the nuclear magnetic resonance analysis. In addition, using 6Li foils, we succeeded in demonstrating that both LAGP and LiTFSI:pyr13TFSI participate in the diffusion of Li ions by the formation of an ionic bridge between two species.

2021 - Advanced silicon-based electrodes for high-energy lithium-ion batteries [Capitolo/Saggio]
Leblanc, D.; Guerfi, A.; Cho, M.; Paolella, A.; Wang, Y.; Mauger, A.; Julien, C.; Zaghib, K.

In commercial lithium-ion batteries (LIBs), the negative electrode (conventionally called the anode) is generally fabricated from graphite. For enhanced performance and critical safety considerations, LIBs must be constructed such that the capacity of the negative electrode is higher than that of the positive electrode. This condition imposed by safety concerns implies that substituting for graphite with a material that has a higher specific capacity is desirable to increase the energy density of LIBs. In this chapter, we report on two types of silicon (Si) that can be employed as negative electrodes for lithium-(Li)-ion batteries (LIBs). The first type is based on metallurgical-grade silicon produced by a low-cost mechanical grinding process from ingots to nanostructured particles. The second one, more expansive, involves an induced plasma process that produces homogeneous spherical Si nanoparticles. Moreover, we describe the challenges and solutions of the use of carbon-coated silicone and a graphite-silicone composite in advanced electrodes for high-energy LIBs. To characterize the volume expansion of the silicone particles, we employed in situ transmission electron microscopy for the observation of a typical 200-nm pristine spherical silicon particle synthesized using an induced plasma. When a bias potential of - 2 to -5 V was used to initiate lithiation of the silicon particle, a rapid reaction from the interior of the particle was observed, forming a core-shell structure. The crystalline core was gradually transformed into an amorphous LixSi alloy. An advanced composite Li-ion anode made from this nanometer-size powder was found to have a high reversible capacity of 2400 mAh g-1 and an improved cycling stability compared to micrometer-sized powder. It is proposed that improved battery cycling performance is ascribed to the nanoscale silicon particles which suppresses the volume expansion owing to it is super plasticity.

2021 - Alumina-flame retardant separators toward safe high voltage Li-Ion batteries [Articolo su rivista]
Delaporte, N.; Perea, A.; Paolella, A.; Dube, J.; Vigeant, M. -J.; Demers, H.; Clement, D.; Zhu, W.; Gariepy, V.; Zaghib, K.

In this work, we reported the easy incorporation of high amount of flame retardants in Li-ion batteries without affecting the electrochemical performance through grafting on alumina surface. The strategy consisted to firstly graft halogen- and phosphorus-based molecules on Al2O3 surface and then to incorporate the modified ceramics in the porosity of a thermally stable cellulose separator. The final composite separator was analyzed by thermogravimetric and flame test analyses. The results revealed that the use of flame retardant ceramics in the cellulose matrix was an effective method to increase the thermal stability of the separator and slow down and even avoid its combustion. The electrochemical performance of NMC/graphite Li-ion batteries assembled with the various cellulose separators were similar and even slightly better than those obtained for the cell made with a Celgard separator.

2021 - Beyond garnets, phosphates and phosphosulfides solid electrolytes: New ceramic perspectives for all solid lithium metal batteries [Articolo su rivista]
Campanella, D.; Belanger, D.; Paolella, A.

Lithium-ion battery technology has been steadily approaching its intrinsic limits of energy density and cycling capacity, and solid-state electrolytes offer a more performant solution when compared with traditional organic electrolytes in terms of affinity with Li-metal electrodes and global battery safety. Oxide and sulfide-based solid electrolytes have been abundantly reported in literature owing to their peculiar chemical properties which made them the favourite candidates for practical applications. However, some significant limitations, such as sensitivity against moisture, partial incompatibility with active materials and relatively high costs, lead current research interest towards a series of alternative chemistries and configurations which may overcome their deficiences. Among these new families of Li-superionic conductors halides and hydrides stand out the most for their appealing qualities, including, foremost, values of ionic conductivities above and beyond 10−3 S cm−1 at room temperature. Some of the most promising outcomes in research are reported and discussed in the present review, along with a brief outlook of the crucial challenges to face in the field of solid-state batteries and the future developments prospected for energy storage systems.

2021 - Effect of pressure on the properties of a NASICON Li1.3Al0.3Ti1.7(PO4)3nanofiber solid electrolyte [Articolo su rivista]
La Monaca, A.; Girard, G.; Savoie, S.; Demers, H.; Bertoni, G.; Krachkovskiy, S.; Marras, S.; Mugnaioli, E.; Gemmi, M.; Benetti, D.; Vijh, A.; Rosei, F.; Paolella, A.

We report the effect of pressure on a membrane made of dense electrospun NASICON-like Li1.3Al0.3Ti1.7(PO4)3(LATP). The properties and performance of the pressed LATP nanofibers were investigated and compared with those of pristine LATP nanofibers. While the applied pressure affects the purity and homogeneity of LATP, it is beneficial for ionic transport across the solid electrolyte. The presence of impurity phases as well as the decrease of porosity results in a two order of magnitude higher ionic conductivity at room temperature (3 × 10−5S cm−1) which is promising to replace bulk NASICON materials in energy storage devices.

2021 - Enabling High-Performance NASICON-Based Solid-State Lithium Metal Batteries Towards Practical Conditions [Articolo su rivista]
Paolella, A.; Liu, X.; Daali, A.; Xu, W.; Hwang, I.; Savoie, S.; Girard, G.; Nita, A. G.; Perea, A.; Demers, H.; Zhu, W.; Guerfi, A.; Vijh, A.; Bertoni, G.; Gazzadi, G. C.; Berti, G.; Sun, C.; Ren, Y.; Zaghib, K.; Armand, M.; Kim, C.; Xu, G. -L.; Amine, K.

Solid-state lithium metal batteries (SSLMBs) are promising next-generation high-energy rechargeable batteries. However, the practical energy densities of the reported SSLMBs have been significantly overstated due to the use of thick solid-state electrolytes, thick lithium (Li) anodes, and thin cathodes. Here, a high-performance NASICON-based SSLMB using a thin (60 µm) Li1.5Al0.5Ge1.5(PO4)3 (LAGP) electrolyte, ultrathin (36 µm) Li metal, and high-loading (8 mg cm−2) LiFePO4 (LFP) cathode is reported. The thin and dense LAGP electrolyte prepared by hot-pressing exhibits a high Li ionic conductivity of 1 × 10−3 S cm−1 at 80 °C. The assembled SSLMB can thus deliver an increased areal capacity of ≈1 mAh cm−2 at C/5 with a high capacity retention of ≈96% after 50 cycles under 80 °C. Furthermore, it is revealed by synchrotron X-ray absorption spectroscopy and in situ high-energy X-ray diffraction that the side reactions between LAGP electrolyte and LFP cathode are significantly suppressed, while rational surface protection is required for Ni-rich layered cathodes. This study provides valuable insights and guidelines for the development of high-energy SSLMBs towards practical conditions.

2021 - Synthesis of electrospun NASICON Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte nanofibers by control of germanium hydrolysis [Articolo su rivista]
la Monaca, A.; Girard, G.; Savoie, S.; Bertoni, G.; Krachkovskiy, S.; Vijh, A.; Pierini, F.; Rosei, F.; Paolella, A.

We report the synthesis of ceramic Li1.5Al0.5Ge1.5(PO4)3 (LAGP) nanofibers by combining sol–gel and electrospinning techniques. A homogeneous and stable precursor solution based on chlorides was achieved by controlling Ge hydrolysis. Subsequent electrospinning and heat treatment resulted in highly porous nanostructured NASICON pellets. After a full chemical-physical characterization, various amounts of LAGP nanofibers were used as a filler to develop polyethylene oxide (PEO)-based composite electrolytes. The addition of 10% LAGP nanofibers has allowed doubling the ionic conductivity of the plain polymer electrolyte, by providing longer ion-conductive paths and reducing PEO crystallinity. These findings are promising towards developing solution-based synthesis approaches featuring Ge precursors. In addition, the achieved LAGP nanofibers proved to be a promising nanofiller candidate to develop composite electrolytes for next-generation solid-state batteries.

2021 - Synthesis of one-dimensional metal oxide–based crystals as energy storage materials [Capitolo/Saggio]
La Monaca, A.; Campanella, D.; Paolella, A.

2021 - Thermal evolution of NASICON type solid-state electrolytes with lithium at high temperaturevia in situscanning electron microscopy [Articolo su rivista]
Kaboli, S.; Girard, G.; Zhu, W.; Gheorghe Nita, A.; Vijh, A.; George, C.; Trudeau, M. L.; Paolella, A.

We present the thermal evolution of two NASICON-type ceramics namely LATP (Li1+xAlxTi2−x(PO4)3) and LAGP (Li1+xAlxGe2−x(PO4)3) by monitoring the electrode-electrolyte interfaces (i.e., Li/LATP and Li/LAGP) at temperatures up to 330 °Cvia in situscanning electron microscopy, post-mortem energy-dispersive spectroscopy, and X-ray diffraction. Upon melting of Li and contacting electrolytes, LAGP decomposes completely to form Li based alloys, while LATP is partially decomposed without alloying.

2020 - A sustainable light-chargeable two-electrode energy storage system based on aqueous sodium-ion photo-intercalation [Articolo su rivista]
Wang, Z.; Chiu, H. -C.; Paolella, A.; Gauvin, R.; Zaghib, K.; Demopoulos, G. P.

Direct photo-to-chemical energy conversion realized through photocatalysis could provide the ultimate solution to the intermittency problem of solar energy. Among different designs of photocatalytic solar energy storage systems, the two-electrode system offers the simplest configuration for enabling highly integrated solar energy conversion and storage in one electrode and on-demand electrocatalytic discharge in the other. In this study, a novel type of visible light chargeable two-electrode Na-ion energy storage system has been developed, to the best of our knowledge, for the first time. It consists of a WO3-(TiO2)-CdS photo absorbing, energy storing bi-functional electrode, a Pt foil counter electrode, and a sacrificial hole scavenging electrolyte. This device delivered a discharge capacity of 12.3 μA h cm-2 (or 18.1 mA h g-1) after 10 min light charging without exhibiting signs of photo/chemical corrosion on the chalcogenide sensitizer. Further by controlling the working voltage window, structure distortion due to overcharging was avoided, thereby leading to an improvement of cyclability (discharge capacity retention after 5 working cycles) from 36% to 64%, and this was eventually elevated to ∼90% upon optimizing the discharging rate. A stable overall solar-to-electrical energy efficiency of ∼0.3% has been achieved for the system. Moreover, a modified photo-rechargeable two-electrode system was developed by replacing the sacrificial hole scavenger and Pt with polysulfide aqueous electrolyte and Cu2S electrocatalytic electrode, respectively. In this way the issue of non-regenerable hole scavenger consumption and instability of Pt in sulfide electrolyte was resolved, establishing a new design, highly promising towards the development of an all-sustainable photo-rechargeable system.

2020 - Behavior of Solid Electrolyte in Li-Polymer Battery with NMC Cathode via in-situ Scanning Electron Microscopy [Articolo su rivista]
Shirin, Kaboli; Hendrix, Demers; Paolella, A; Ali, Darwiche; Martin, Dontigny; Daniel, Clement; Abdelbast, Guerfi; Michel, L Trudeau; John, B Goodenough; Karim, Zaghib

2020 - Brief history of early lithium-battery development [Articolo su rivista]
Reddy, M. V.; Mauger, A.; Julien, C. M.; Paolella, A.; Zaghib, K.

Lithium batteries are electrochemical devices that are widely used as power sources. This history of their development focuses on the original development of lithium-ion batteries. In particular, we highlight the contributions of Professor Michel Armand related to the electrodes and electrolytes for lithium-ion batteries.

2020 - Direct observation of lithium metal dendrites with ceramic solid electrolyte [Articolo su rivista]
Golozar, M.; Paolella, A.; Demers, H.; Savoie, S.; Girard, G.; Delaporte, N.; Gauvin, R.; Guerfi, A.; Lorrmann, H.; Zaghib, K.

Dendrite formation, which could cause a battery short circuit, occurs in batteries that contain lithium metal anodes. In order to suppress dendrite growth, the use of electrolytes with a high shear modulus is suggested as an ionic conductive separator in batteries. One promising candidate for this application is Li7La3Zr2O12 (LLZO) because it has excellent mechanical properties and chemical stability. In this work, in situ scanning electron microscopy (SEM) technique was employed to monitor the interface behavior between lithium metal and LLZO electrolyte during cycling with pressure. Using the obtained SEM images, videos were created that show the inhomogeneous dissolution and deposition of lithium, which induce dendrite growth. The energy dispersive spectroscopy analyses of dendrites indicate the presence of Li, C, and O elements. Moreover, the cross-section mapping comparison of the LLZO shows the inhomogeneous distribution of La, Zr, and C after cycling that was caused by lithium loss near the Li electrode and possible side reactions. This work demonstrates the morphological and chemical evolution that occurs during cycling in a symmetrical Li–Li cell that contains LLZO. Although the superior mechanical properties of LLZO make it an excellent electrolyte candidate for batteries, the further improvement of the electrochemical stabilization of the garnet–lithium metal interface is suggested.

2020 - Discovering the influence of lithium loss on Garnet Li7La3Zr2O12 Electrolyte Phase Stability [Articolo su rivista]
Paolella, A; Wen, Zhu; Giovanni, Bertoni; Sylvio, Savoie; Zimin, Feng; Hendrix, Demers; Vincent, Gariepy; Gabriel, Girard; Etienne, Rivard; Nicolas, Delaporte; Abdelbast, Guerfi; Henning, Lorrmann; Chandramohan, George; Karim, Zaghib

2020 - On high-temperature evolution of passivation layer in Li–10 wt % Mg alloy via in situ SEM-EBSD [Articolo su rivista]
Kaboli, S.; Noel, P.; Clement, D.; Demers, H.; Paolella, A.; Bouchard, P.; Trudeau, M. L.; Goodenough, J. B.; Zaghib, K.

Li–10 wt % Mg alloy (Li–10 Mg) is used as an anode material for a solid-state battery with excellent electrochemical performance and no evidence of dendrite formation during cycling. Thermal treatment of Li metal during manufacturing improves the interfacial contact between a Li metal electrode and solid electrolyte to achieve an all solid-state battery with increased performance. To understand the properties of the alloy passivation layer, this paper presents the first direct observation of its evolution at elevated temperatures (up to 325°C) by in situ scanning electron microscopy. We found that the morphology of the surface passivation layer was unchanged above the alloy melting point, while the bulk of the material below the surface was melted at the expected melting point, as confirmed by in situ electron backscatter diffraction. In situ heat treatment of Li-based materials could be a key method to improve battery performance.

2020 - Review-Li-Ion Photo-Batteries: Challenges and Opportunities [Articolo su rivista]
Paolella, A.; Vijh, A.; Guerfi, A.; Zaghib, K.; Faure, C.

Humanity's greatest challenge in the 21st century consists in transitioning from fossil fuels towards renewable energy technologies. Since all renewable are intermittent, the common challenge for all renewables is storage. In this context, designing and realizing hybrid devices that combine energy conversion with storage represents a major opportunity. Among renewables, solar energy is particularly important, because in one hour the Sun sends towards us enough energy to power the whole planet for one year; nevertheless, our current global use of solar energy is only about 1%, The aim of this short review is to describe the current state of the art and perspectives in the emerging area of photo-rechargeable batteries. This hybrid device consists in a photo-electrochemical system that combines solar energy conversion with electrochemical storage, storing energy during the day and allowing release at night. While the opportunity of combining solar and battery technologies into a single system is promising, major challenges are yet to be overcome. Here we summarize the most promising architectures developed so far and potential research directions in this exciting area of technology.

2020 - Toward an all-ceramic cathode–electrolyte interface with low-temperature pressed NASICON Li1+xAlxGe2-x(PO4)3 electrolyte [Articolo su rivista]
Paolella, A; Wen, Zhu; Giovanni, Bertoni; Alexis, Perea; Hendrix, Demers; Sylvio, Savoie; Gabriel, Girard; Nicolas, Delaporte; Abdelbast, Guerfi; Mathias, Rumpel; Henning, Lorrmann; George P., Demopoulos; and Karim, Zaghib

2020 - Understanding the Reactivity of a Thin Li1.5Al0.5Ge1.5(PO4)3 Solid-State Electrolyte toward Metallic Lithium Anode [Articolo su rivista]
Paolella, A.; Zhu, W.; Xu, G. -L.; La Monaca, A.; Savoie, S.; Girard, G.; Vijh, A.; Demers, H.; Perea, A.; Delaporte, N.; Guerfi, A.; Liu, X.; Ren, Y.; Sun, C. -J.; Lu, J.; Amine, K.; Zaghib, K.

The thickness of solid-state electrolytes (SSEs) significantly affects the energy density and safety performance of all-solid-state lithium batteries. However, a sufficient understanding of the reactivity toward lithium metal of ultrathin SSEs (<100 µm) based on NASICON remains lacking. Herein, for the first time, a self-standing and ultrathin (70 µm) NASICON-type Li1.5Al0.5Ge1.5(PO4)3 (LAGP) electrolyte via a scalable solution process is developed, and X-ray photoelectron spectroscopy reveals that changes in LAGP at the metastable Li–LAGP interface during battery operation is temperature dependent. Severe germanium reduction and decrease in LAGP particle size are detected at the Li–LAGP interface at elevated temperature. Oriented plating of lithium metal on its preferred (110) face occurs during in situ X-ray diffraction cycling.

2019 - A platinum nanolayer on lithium metal as an interfacial barrier to shuttle effect in Li-S batteries [Articolo su rivista]
Paolella, A; Hendrix, Demers; Pascale, Chevallier; Catherine, Gagnon; Gabriel, Girard; Nicolas, Delaporte; Wen, Zhu; Ashok, Vijh; Abdelbast Guerfi and Karim, Zaghib

2019 - Building better batteries in the solid state: a review [Articolo su rivista]
Alain, Mauger; Christian, Julien; Paolella, A; Michel, Armand; Karim, Zaghib

2019 - Diffusion Control of Organic Cathode Materials in Lithium Metal Battery [Articolo su rivista]
Rachel L., Belanger; Basile, Commarieu; Paolella, A; Jean Christophe, Daigle; Stéphanie, Bessette; Ashok, Vijh; Jerome Claverie and Karim, Zaghib

2019 - Electrospun Ceramic Nanofibers as 1D Solid Electrolytes for Lithium Batteries [Articolo su rivista]
Andrea La, Monaca; Paolella, A; Abdelbast, Guerfi; Federico, Rosei; Karim, Zaghib

2019 - Facile Protection of Lithium Metal for All-Solid-State Batteries [Articolo su rivista]
Nicolas, Delaporte; Abdelbast, Guerfi; Hendrix, Demers; Henning, Lorrmann; Paolella, A; Karim, Zaghib

2019 - In situ observation of solid electrolyte interphase evolution in a lithium metal battery [Articolo su rivista]
Maryam, Golozar; Paolella, A; Hendrix, Demers; Stephanie, Bessette; Martin, Lagacé; Patrick, Bouchard; Abdelbast, Guerfi; Raynald, Gauvin; Karim, Zaghib

2019 - Lithium Photo‐Intercalation of CdS‐Sensitized WO₃ Anode for Energy Storage and Photoelectrochromic Applications [Articolo su rivista]
Zhuoran, Wang; Hsien-Chieh, Chiu; Paolella, A; Karim, Zaghib; George, Demopoulo

2019 - Mechanochemically-tuned structural annealing: a new pathway to enhancing Li-ion intercalation activity in nanosized βII Li2FeSiO4 [Articolo su rivista]
Majid, Rasool; Hsien-Chieh, Chiu; Xia, Lu; Frédéric, Voisard; Raynald, Gauvin; Jiang, D. T.; Paolella, A; Karim Zaghib and George P, P Demopoulos

2019 - Recent Progress on Organic Electrodes Materials for Rechargeable Batteries and Supercapacitors [Articolo su rivista]
Alain, Mauger; Christian, Julien; Paolella, A; Michel, Armand; Karim, Zaghib

2019 - Solid-to-liquid transition of polycarbonate solid electrolyte in Li-metal batteries [Articolo su rivista]
Basile, Commarieu; Paolella, A; Steve, Collin-Martin; Catherine, Gagnon; Ashok, Vijh; Abdelbast, Guerfi; Karim, Zaghib

2018 - A comprehensive review of lithium salts and beyond for rechargeable batteries: Progress and perspectives [Articolo su rivista]
Alain, Mauger; Christian, Julien; Paolella, A; Michel, Armand; Karim, Zaghib

2018 - Application of operando X-ray diffraction and Raman spectroscopies in elucidating the behavior of cathode in lithium-ion batteries [Articolo su rivista]
Wen, Zhu; Dongqiang, Liu; Paolella, A; Catherine, Gagnon; Vincent, Gariepy; Ashok, Vijh; Karim, Zaghib

2018 - In-situ SEM detection of carbide dendrites in Li-Polymer Batteries [Articolo su rivista]
Maryam, Golozar; Pierre, Hovington; Paolella, A; Stephanie, Bessette; Marin, Lagace; Patrick, Bouchard; Hendrix, Demers; Raynald, Gauvin; Karim, Zaghib

2018 - Nanoscale Lithium Quantification in LixNiyCowMnzO2 as Cathode for Rechargeable Batteries [Articolo su rivista]
Stéphanie, Bessette; Paolella, A; Chisu, Kim; Wen, Zhu; Pierre, Hovington; Raynald, Gauvin; Karim, Zaghib

2018 - State of charge influence on thermal reactions and abuse tests in commercial lithium-ion cells [Articolo su rivista]
Alexis, Perea; Paolella, A; Joël, Dubé; Dominique, Champagne; Alain, Mauger; Karim, Zaghib

2018 - The role of metal disulfide interlayer in Li-S batteries [Articolo su rivista]
Paolella, A; Dharminder, Laul; Vladimir, Timoshevskii; Wen, Zhu; Sergio, Marras; Giovanni, Bertoni; Alexander Sean, Wahba; Gabriel, Girard; Catherine, Gagnon; Lisa, Rodrigue; Basile, Commarieu; Abdelbast, Guerfi; Raynald, Gauvin; Michel, L Trudeau; Ashok, Vijh; Michel, Armand; Karim, Zaghib

2018 - Toward high lithium conduction in solid polymer and polymer-ceramic batteries [Articolo su rivista]
Basile, Commarieu; Paolella, A; Jean-Christophe, Daigle; Karim, Zaghib

2017 - A review on hexacyanoferrate-based materials for energy storage and smart windows: challenges and perspectives [Articolo su rivista]
Paolella, A; Cyril, Faure; Vladimir, Timochevskii; Sergio, Marras; Giovanni, Bertoni; Guerfi, Abdelbast; Ashok, Vijh; Michel, Armand; Karim, Zaghib

2017 - Investigation of the reaction mechanism of lithium sulfur batteries in different electrolyte systems by in situ Raman spectroscopy and in situ X-ray diffraction [Articolo su rivista]
W, Zhu; Paolella, A; C-S, Kim; D, Liu; Z, Feng; C, Gagnon; J, Trottier; A, Vijh; A, Guerfi; A, Mauger; Cm, Julien; M, Armand; K, Zaghib

2017 - Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries [Articolo su rivista]
Paolella, A; Cyril, Faure; Giovanni, Bertoni; Sergio, Marras; Abdelbast, Guerfi; Ali, Darwiche; Pierre, Hovington; Basile, Commarieu; Zhuoran, Wang; Mirko, Prato; Massimo, Colombo; Simone, Monaco; Wen, Zhu; Zimin, Feng; Ashok, Vijh; Chandramohan, George; George, P Demopoulos; Michel, Armand; Karim, Zaghib

2017 - Measuring spatially resolved collective ionic transport on lithium battery cathodes using atomic force microscopy [Articolo su rivista]
Aaron, Mascaro; Zi, Wang; Pierre, Hovington; Yoichi, Miyahara; Paolella, A; Vincent, Gariepy; Zimin, Feng; Tyler, Enright; Connor, Aiken; Karim, Zaghib; Kirk, H Bevan; Peter, Grutter

2016 - Accelerated removal of Fe-antisite defects while nanosizing hydrothermal LiFePO4 with Ca2+ [Articolo su rivista]
Paolella, A; Stuart, Turner; Giovanni, Bertoni; Pierre, Hovington; Roxana, Flacau; Chad, Boyer; Zimin, Feng; Massimo, Colombo; Sergio, Marras; Mirko, Prato; Liberato, Manna; Abdelbast, Guerfi; George, P Demopoulos; Michel, Armand; Karim, Zaghib

2016 - In operando scanning electron microscopy and ultraviolet–visible spectroscopy studies of lithium/sulfur cells using all solid-state polymer electrolyte [Articolo su rivista]
Hugues, Marceau; Chi-Su, Kim; Paolella, A; Sébastien, Ladouceur; Marin, Lagacé; Mohamed, Chaker; Ashok, Vijh; Abdelbast, Guerfi; Christian, M Julien; Alain, Mauger; Michel, Armand; Pierre, Hovington; Karim, Zaghib

2016 - Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes [Articolo su rivista]
Lin, Chen; Enrico, Dilena; Paolella, A; Giovanni, Bertoni; Alberto, Ansaldo; Massimo, Colombo; Sergio, Marras; Bruno, Scrosati; Liberato, Manna; Simone, Monaco

2016 - Transient existence of crystalline lithium disulfide Li 2 S 2 in a lithium-sulfur battery [Articolo su rivista]
Paolella, A; Wen, Zhu; Hugues, Marceau; Chi-su, Kim; Zimin, Feng; Dongqiang, Liu; Catherine, Gagnon; Julie, Trottier; Guerfi, Abdelbast; Pierre, Hovington; Ashok, Vijh; George, P Demopoulos; Michel, Armand; Karim, Zaghib

2015 - Cation exchange mediated elimination of the Fe-antisites in the hydrothermal synthesis of LiFePO 4 [Articolo su rivista]
Paolella, A; Giovanni, Bertoni; Pierre, Hovington; Zimin, Feng; Roxana, Flacau; Mirko, Prato; Massimo, Colombo; Sergio, Marras; Liberato, Manna; Stuart, Turner; Gustaaf Van, Tendeloo; Abdelbast, Guerfi; George, P Demopoulos; Karim, Zaghib

2015 - Composés de type olivine : procédé de préparation et utilisation dans des matériaux de cathode pour batteries sodium-ion [Brevetto]
Montse GALCERAN, Mestres; Montse, CASAS-CABANAS; Abdelbast, Guerfi; Michel, Armand; Teofilo, Rojo; Karim, Zaghib; Paolella, A

Paolella, A; Cyril, Faure; Abdelbast, Guerfi; Pierre, Hovington; Karim, Zaghib

2014 - Etched colloidal LiFePO4 nanoplatelets toward high-rate capable Li-ion battery electrodes [Articolo su rivista]
Paolella, A; Giovanni, Bertoni; Sergio, Marras; Enrico, Dilena; Massimo, Colombo; Mirko, Prato; Andreas, Riedinger; Mauro, Povia; Alberto, Ansaldo; Karim, Zaghib; Liberato, Manna; Chandramohan, George

2014 - Redox Centers Evolution in Phospho-Olivine Type (LiFe0. 5Mn0. 5 PO4) Nanoplatelets with Uniform Cation Distribution [Articolo su rivista]
Paolella, A; Giovanni, Bertoni; Enrico, Dilena; Sergio, Marras; Alberto, Ansaldo; Liberato, Manna; Chandramohan, George

2013 - Colloidal synthesis of cuprite (Cu2O) octahedral nanocrystals and their electrochemical lithiation [Articolo su rivista]
Paolella, A; Rosaria, Brescia; Mirko, Prato; Mauro, Povia; Sergio, Marras; Luca De, Trizio; Andrea, Falqui; Liberato, Manna; Chandramohan, George

2013 - CuIn x Ga1–x S2 Nanocrystals with Tunable Composition and Band Gap Synthesized via a Phosphine-Free and Scalable Procedure [Articolo su rivista]
Enrico, Dilena; Yi, Xie; Rosaria, Brescia; Mirko, Prato; Lorenzo, Maserati; Roman, Krahne; Paolella, A; Giovanni, Bertoni; Mauro, Povia; Iwan, Moreels; Liberato, Manna

2012 - Colloidal Synthesis of Cuprite Nanocrystals for Lithium Ion Battery [Poster]
Paolella, A; Chandramohan, George

2012 - Process for the colloidal synthesis of lithium iron phosphate [Brevetto]
Paolella, A; George, Chandramohan; Mirko, Prato; Mauro, Povia; Alessandro, Genovese; Liberato, Manna; Roberto, Cingolani

2011 - Charge transport and electrochemical properties of colloidal greigite (Fe3S4) nanoplatelets [Articolo su rivista]
Paolella, A; Chandramohan, George; Mauro, Povia; Yang, Zhang; Roman, Krahne; Marti, Gich; Alessandro, Genovese; Andrea, Falqui; Maria, Longobardi; Pablo, Guardia; Teresa, Pellegrino; Liberato, Manna

Room-temperature superparamagnetic greigite nanoplatelets were synthesized using 3-methyl catechol as growth moderator and phase-control agent, in the presence of sulfur, thiosulfate, octadecylamine, and Fe2+. Dense films of nanoplatelets showed ohmic behavior in the 10–300 K range. In as-deposited films the resistivity increased with decreasing temperature (as for semiconductors), while in hydrazine-treated films it decreased with decreasing temperature, as for metals. The electrochemical properties of as-prepared greigite nanoplatelets upon lithiation/de-lithiation have been followed by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electrodes containing greigite nanoplatelets were found to be active in the lithiation/delithiation processes.