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Prof. Philippe KNAUTH
Aix-Marseille University

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0 energy materials
0 nanomaterials for energy and environment
0 Solid state ionic conductors
0 Electrochemical Energy Storage
0 Ionomers

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Solid state ionic conductors
Electrochemical Energy Storage

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Aix Marseille University

Institute, Department or Faculty Head

01 January 2017 - 31 August 2021




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Original research
Published: 30 July 2021 in Journal of Nanostructure in Chemistry
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Carbon quantum dots (CQD) were prepared from three different precursors and by three bottom-up synthesis methods: classical pyrolysis of citric acid (CAP), microwave irradiation of glucose (GM), and hydrothermal treatment of glucosamine hydrochloride (GAH). CQD were further functionalized using various nitrogen-containing compounds: 6-aminohexanoic acid, 1,6-diaminohexane, N-octylamine, dimethylamine, and tryptophan. Special attention was dedicated to investigate how the combination of synthetic method and starting material affected the nature and properties of CQD. The analysis indicated that CAP were good candidates for covalent post-functionalization, GM allowed an easy passivation, and GAH permitted the direct introduction of nitrogen into the core. The size distribution showed a core–shell structure for CQD functionalized with an aminoacid by microwave irradiation, whereas the thermal decomposition evidenced the degradation of functionalizing molecules and the presence of pyridinic and pyrrolic nitrogen after hydrothermal synthesis. Photoluminescence spectra revealed important differences between the synthesis techniques, related to the occurrence of surface states, and the highest fluorescence quantum yield for hydrothermally prepared CQD. These approaches led to CQD with properties that can be exploited in many fields from energy conversion to sensing.

ACS Style

A. R. Nallayagari; E. Sgreccia; R. Pizzoferrato; M. Cabibbo; S. Kaciulis; E. Bolli; L. Pasquini; P. Knauth; M. L. Di Vona. Tuneable properties of carbon quantum dots by different synthetic methods. Journal of Nanostructure in Chemistry 2021, 1 -16.

AMA Style

A. R. Nallayagari, E. Sgreccia, R. Pizzoferrato, M. Cabibbo, S. Kaciulis, E. Bolli, L. Pasquini, P. Knauth, M. L. Di Vona. Tuneable properties of carbon quantum dots by different synthetic methods. Journal of Nanostructure in Chemistry. 2021; ():1-16.

Chicago/Turabian Style

A. R. Nallayagari; E. Sgreccia; R. Pizzoferrato; M. Cabibbo; S. Kaciulis; E. Bolli; L. Pasquini; P. Knauth; M. L. Di Vona. 2021. "Tuneable properties of carbon quantum dots by different synthetic methods." Journal of Nanostructure in Chemistry , no. : 1-16.

Review
Published: 04 June 2021 in Polymers
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This short review summarizes the literature on composite anion exchange membranes (AEM) containing an organo-silica network formed by sol–gel chemistry. The article covers AEM for diffusion dialysis (DD), for electrochemical energy technologies including fuel cells and redox flow batteries, and for electrodialysis. By applying a vast variety of organically modified silica compounds (ORMOSIL), many composite AEM reported in the last 15 years are based on poly (vinylalcohol) (PVA) or poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) used as polymer matrix. The most stringent requirements are high permselectivity and water flux for DD membranes, while high ionic conductivity is essential for electrochemical applications. Furthermore, the alkaline stability of AEM for fuel cell applications remains a challenging problem that is not yet solved. Possible future topics of investigation on composite AEM containing an organo-silica network are also discussed.

ACS Style

Emanuela Sgreccia; Riccardo Narducci; Philippe Knauth; Maria Di Vona. Silica Containing Composite Anion Exchange Membranes by Sol–Gel Synthesis: A Short Review. Polymers 2021, 13, 1874 .

AMA Style

Emanuela Sgreccia, Riccardo Narducci, Philippe Knauth, Maria Di Vona. Silica Containing Composite Anion Exchange Membranes by Sol–Gel Synthesis: A Short Review. Polymers. 2021; 13 (11):1874.

Chicago/Turabian Style

Emanuela Sgreccia; Riccardo Narducci; Philippe Knauth; Maria Di Vona. 2021. "Silica Containing Composite Anion Exchange Membranes by Sol–Gel Synthesis: A Short Review." Polymers 13, no. 11: 1874.

Journal article
Published: 04 April 2021 in Membranes
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Nanocomposite anion exchange membranes were synthesized based on poly(sulfone trimethylammonium) chloride. A hybrid semi-interpenetrating silica network containing a large amount of quaternary ammonium groups was prepared by two sol–gel routes, in situ with a single precursor, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride (TMSP), or ex situ mixing two precursors, TMSP and 3-(2-aminoethylamino)propyldimethoxy-methylsilane (AEAPS). The properties of these hybrid composites and their degradation after immersion in 1 M KOH at 60 °C were studied. The degradation is reduced in the composite materials with a lower decrease in the ion exchange capacity. FTIR spectra showed that a main degradation mechanism with a single precursor TMSP is the dissolution of the hybrid silica network in KOH, whereas it is stable with the mixture of TMSP/AEASP. This conclusion is in agreement with the thermogravimetric analysis. The mechanical properties show a better ductility with a single precursor and higher stiffness and strength, but less ductility, by the ex situ route. The activation energy was between 0.25 and 0.14 eV for Cl and OH ion conduction, respectively, consistent with the migration mechanism.

ACS Style

Emanuela Sgreccia; Maria Di Vona; Simonetta Antonaroli; Gianfranco Ercolani; Marco Sette; Luca Pasquini; Philippe Knauth. Nanocomposite Anion Exchange Membranes with a Conductive Semi-Interpenetrating Silica Network. Membranes 2021, 11, 260 .

AMA Style

Emanuela Sgreccia, Maria Di Vona, Simonetta Antonaroli, Gianfranco Ercolani, Marco Sette, Luca Pasquini, Philippe Knauth. Nanocomposite Anion Exchange Membranes with a Conductive Semi-Interpenetrating Silica Network. Membranes. 2021; 11 (4):260.

Chicago/Turabian Style

Emanuela Sgreccia; Maria Di Vona; Simonetta Antonaroli; Gianfranco Ercolani; Marco Sette; Luca Pasquini; Philippe Knauth. 2021. "Nanocomposite Anion Exchange Membranes with a Conductive Semi-Interpenetrating Silica Network." Membranes 11, no. 4: 260.

Article
Published: 09 February 2021 in ChemElectroChem
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Thin‐films of cation‐conducting poly(styrene sulfonate) (PSS) and anion‐conducting poly(N‐vinyl‐N‐benzyl‐N,N,N‐trimethylammonium chloride) (PVBTMA) were electrochemically deposited. A low film thickness can be obtained, because the electrodepostion is a self‐limiting process. Various cases were explored: i) the deposition of a single ionomer layer on various substrates, ii) the sequential deposition of the ionomers giving a bipolar membrane, and iii) the co‐deposition of the ionomers giving an ampholytic membrane. The structure and microstructure of the thin films were investigated by NMR spectroscopy and optical and Scanning Electron Microscopy (SEM). Impedance spectroscopy in through‐plane configuration revealed a large resistance of the bipolar membrane, due to the ionic blocking interface between the ionomers. The ampholytic membrane showed also a low conductivity, probably due to the loss of ionic carrier pairs that can leave the ionomer without break of electroneutrality.

ACS Style

Luca Pasquini; Maria Luisa Di Vona; Emanuela Sgreccia; Olim Ruzimuradov; Philippe Knauth. Ionomer Thin‐Films by Electrochemical Synthesis: Bipolar and Ampholytic Membranes. ChemElectroChem 2021, 8, 1493 -1499.

AMA Style

Luca Pasquini, Maria Luisa Di Vona, Emanuela Sgreccia, Olim Ruzimuradov, Philippe Knauth. Ionomer Thin‐Films by Electrochemical Synthesis: Bipolar and Ampholytic Membranes. ChemElectroChem. 2021; 8 (8):1493-1499.

Chicago/Turabian Style

Luca Pasquini; Maria Luisa Di Vona; Emanuela Sgreccia; Olim Ruzimuradov; Philippe Knauth. 2021. "Ionomer Thin‐Films by Electrochemical Synthesis: Bipolar and Ampholytic Membranes." ChemElectroChem 8, no. 8: 1493-1499.

Journal article
Published: 02 February 2021 in Polymers
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Proton-conducting ionomers are widespread materials for application in electrochemical energy storage devices. However, their properties depend strongly on operating conditions. In bio-fuel cells with a separator membrane, the swelling behavior as well as the conductivity need to be optimized with regard to the use of buffer solutions for the stability of the enzyme catalyst. This work presents a study of the hydrolytic stability, conductivity and mechanical behavior of different proton exchange membranes based on sulfonated poly(ether ether ketone) (SPEEK) and sulfonated poly(phenyl sulfone) (SPPSU) ionomers in phosphate buffer solution. The results show that the membrane stability can be adapted by changing the casting solvent (DMSO, water or ethanol) and procedures, including a crosslinking heat treatment, or by blending the two ionomers. A comparison with NafionTM shows the different behavior of this ionomer versus SPEEK membranes.

ACS Style

Luca Pasquini; Botagoz Zhakisheva; Emanuela Sgreccia; Riccardo Narducci; Maria Di Vona; Philippe Knauth. Stability of Proton Exchange Membranes in Phosphate Buffer for Enzymatic Fuel Cell Application: Hydration, Conductivity and Mechanical Properties. Polymers 2021, 13, 475 .

AMA Style

Luca Pasquini, Botagoz Zhakisheva, Emanuela Sgreccia, Riccardo Narducci, Maria Di Vona, Philippe Knauth. Stability of Proton Exchange Membranes in Phosphate Buffer for Enzymatic Fuel Cell Application: Hydration, Conductivity and Mechanical Properties. Polymers. 2021; 13 (3):475.

Chicago/Turabian Style

Luca Pasquini; Botagoz Zhakisheva; Emanuela Sgreccia; Riccardo Narducci; Maria Di Vona; Philippe Knauth. 2021. "Stability of Proton Exchange Membranes in Phosphate Buffer for Enzymatic Fuel Cell Application: Hydration, Conductivity and Mechanical Properties." Polymers 13, no. 3: 475.

Journal article
Published: 15 August 2020 in Journal of Membrane Science
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The effective mobility of hydroxide, chloride and fluoride ions is reported in various anion exchange membranes (AEM) with a backbone of polysulfone (PSU) or poly (2,6-dimethyl-1,4-phenylene)oxide (PPO). The concentration dependence of the effective mobility is used to derive the porosity (π), tortuosity (τ), and percolation thresholds and to plot the ionic conductivity vs the hydration number. Semi-logarithmic plots of the effective ion mobility u(i) vs the square root of concentration √c(i) for hydroxide, fluoride and chloride ions in various PSU- and PPO-based ionomers at 25 and 60 °C show linear relations, from which the ratio π/τ can be determined. This existence of linear u(i) = f(√c(i)) plots is related to the very particular boundary conditions experienced by mobile ions, migrating in close vicinity to the immobile grafted counter-ions placed at the interfaces between polymer domains and electrolyte solution. The π/τ values for PSU-QA (0.29) and PPO-QA (0.38) are consistent with a relatively low hydrophilic-hydrophobic nanophase separation, which leads to channels with low diameter and high tortuosity. The tortuosity determined from a Bruggeman-type relation is 1.9 for PSU-QA and 1.6 for PPO-QA. The percolation thresholds ϕH2O,p, determined from the universal percolation equation near and above ϕH2O,p, are at a water volume fraction of 0.07 for PSU-TMA and 0.03 for PPO-QA indicating that these AEM have a two-dimensional structure of the hydrated domains. The prefactor, which should represent a good indication as to the maximum achievable ionic conductivity, is slightly below 100 mS/cm for both PSU-TMA and PPO-based ionomers. Plots of experimental and computed hydroxide and chloride ion conductivities as function of the hydration number (λ) show a maximum ionic conductivity for a value of the hydration number around 60, corresponding to optimal hydration conditions. At λ = 100, the ratio of conductivity between PSU-QA (OH− form) and PPO-QA (Cl− form) indicates that the degree of dissociation of ion pairs is about 30% lower for hydroxide than for chloride ions, which is consistent with the effective ionic radii of Cl− and OH−.

ACS Style

P. Knauth; L. Pasquini; R. Narducci; E. Sgreccia; R.-A. Becerra-Arciniegas; M.L. Di Vona. Effective ion mobility in anion exchange ionomers: Relations with hydration, porosity, tortuosity, and percolation. Journal of Membrane Science 2020, 617, 118622 .

AMA Style

P. Knauth, L. Pasquini, R. Narducci, E. Sgreccia, R.-A. Becerra-Arciniegas, M.L. Di Vona. Effective ion mobility in anion exchange ionomers: Relations with hydration, porosity, tortuosity, and percolation. Journal of Membrane Science. 2020; 617 ():118622.

Chicago/Turabian Style

P. Knauth; L. Pasquini; R. Narducci; E. Sgreccia; R.-A. Becerra-Arciniegas; M.L. Di Vona. 2020. "Effective ion mobility in anion exchange ionomers: Relations with hydration, porosity, tortuosity, and percolation." Journal of Membrane Science 617, no. : 118622.

Article
Published: 26 May 2020 in ChemElectroChem
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We studied composite anion exchange membranes made from poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) with grafted 1,4‐diazabicyclo[2.2.2]octane (DABCO) and Mg/Al lamellar double hydroxide particles as inorganic filler. The mechanical and conductivity properties were measured in fully humidified conditions. The activation energy for conductivity amounts to (0.20 ± 0.01) eV. The degradation of the anion exchange membrane in 2 M NaOH at 60 °C was investigated during 168 h following the ionic conductivity, water uptake and ion exchange capacity as function of the alkaline treatment time. The degradation is rapid within the first hours and then slows down. The degradation was also studied by thermogravimetric analysis and FTIR spectroscopy, showing the various decomposition phenomena of the composite.

ACS Style

Luca Pasquini; Raul‐Andres Becerra‐Arciniegas; Riccardo Narducci; Emanuela Sgreccia; Vincent Gressel; Maria‐Luisa Di Vona; Philippe Knauth. Properties and Alkaline Stability of Composite Anion Conducting Ionomers Based on Poly(phenylene oxide) Grafted with DABCO and Mg/Al Lamellar Double Hydroxide. ChemElectroChem 2020, 7, 2917 -2924.

AMA Style

Luca Pasquini, Raul‐Andres Becerra‐Arciniegas, Riccardo Narducci, Emanuela Sgreccia, Vincent Gressel, Maria‐Luisa Di Vona, Philippe Knauth. Properties and Alkaline Stability of Composite Anion Conducting Ionomers Based on Poly(phenylene oxide) Grafted with DABCO and Mg/Al Lamellar Double Hydroxide. ChemElectroChem. 2020; 7 (13):2917-2924.

Chicago/Turabian Style

Luca Pasquini; Raul‐Andres Becerra‐Arciniegas; Riccardo Narducci; Emanuela Sgreccia; Vincent Gressel; Maria‐Luisa Di Vona; Philippe Knauth. 2020. "Properties and Alkaline Stability of Composite Anion Conducting Ionomers Based on Poly(phenylene oxide) Grafted with DABCO and Mg/Al Lamellar Double Hydroxide." ChemElectroChem 7, no. 13: 2917-2924.

Research article
Published: 20 December 2019 in The Journal of Physical Chemistry C
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The stability of anion exchange membranes is paramount for the use in alkaline fuel cells. Long chain ionomers are supposed to be more alkaline-resistant with respect to short chain isomers. In this paper the synthesis, properties and stability of ionomers with a long side chain are investigated. Poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) is chosen as backbone, due to its reported stability in alkaline conditions. The functional group is pentyl-ammonium with trimethylamine (TMA) or 1,4-diazabicyclo[2.2.2]octane (DABCO) as model amines. The synthesis is carried out via metalation reaction and is optimized as a function of temperature and time. The water uptake is relatively low, in accordance with the large hydrophobicity of the PPO backbone. The through-plane ionic conductivity is consistent with literature data; it amounts to 15.3 mS/cm at 80 °C for the TMA derivative. The mechanical properties are typical of ionomers below the glass transition temperature (for the TMA derivative at ambient humidity: Young Modulus = 1310 ± 30 MPa). The stability in alkaline conditions, studied by thermogravimetric analysis and measurements of ionic conductivity and ion exchange capacity, is higher than that of short-side chain ionomers with the same basic group. The decrease of ionic conductivity (57 vs 22% residual conductivity after 72 h in 2 M NaOH at 80 °C) and IEC is monitored showing that the degradation is fast in the first hours and may by described by second order kinetics. These results help in selecting high performance anion exchange membranes for electrochemical energy technologies.

ACS Style

Raul Andres Becerra Arciniegas; Riccardo Narducci; Gianfranco Ercolani; Emanuela Sgreccia; Luca Pasquini; Maria Luisa Di Vona; Philippe C Knauth. Model Long Side-Chain PPO-Based Anion Exchange Ionomers: Properties and Alkaline Stability. The Journal of Physical Chemistry C 2019, 124, 1309 -1316.

AMA Style

Raul Andres Becerra Arciniegas, Riccardo Narducci, Gianfranco Ercolani, Emanuela Sgreccia, Luca Pasquini, Maria Luisa Di Vona, Philippe C Knauth. Model Long Side-Chain PPO-Based Anion Exchange Ionomers: Properties and Alkaline Stability. The Journal of Physical Chemistry C. 2019; 124 (2):1309-1316.

Chicago/Turabian Style

Raul Andres Becerra Arciniegas; Riccardo Narducci; Gianfranco Ercolani; Emanuela Sgreccia; Luca Pasquini; Maria Luisa Di Vona; Philippe C Knauth. 2019. "Model Long Side-Chain PPO-Based Anion Exchange Ionomers: Properties and Alkaline Stability." The Journal of Physical Chemistry C 124, no. 2: 1309-1316.

Journal article
Published: 17 October 2019 in Membranes
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We investigated the possibility to increase the working temperature and endurance of proton exchange membranes for fuel cells and water electrolyzers by thermal annealing of short side chain perfluorosulfonic acid (SSC-PFSA) Aquivion® membranes. The Ionomer nc Analysis (INCA method), based on nc/T plots where nc is a counter elastic force index, was applied to SSC-PFSA in order to evaluate ionomer thermo-mechanical properties and to probe the increase of crystallinity during the annealing procedure. The enhanced thermal and mechanical stability of extruded Aquivion® 870 (equivalent weight, EW = 870 g·mol−1) was related to an increase of long-range order. Complementary differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) measurements confirmed the increase of polymer stiffness by the annealing treatment with an enhancement of the storage modulus over the whole range of temperature. The main thermomechanical relaxation temperature is also enhanced. DSC measurements showed slight base line changes after annealing, attributable to the glass transition and melting of a small amount of crystalline phase. The difference between the glass transition and melting temperatures derived from INCA plots and the ionic-cluster transition temperature derived from DMA measurements is consistent with the different experimental conditions, especially the dry atmosphere in DMA. Finally, the annealing procedure was also successfully applied for the first time to an un-crystallized cast membrane (EW = 830 g·mol−1) resulting in a remarkable mechanical and thermal stabilization.

ACS Style

Stefano Giancola; Raul Andres Becerra Arciniegas; Armand Fahs; Jean-Franҫois Chailan; Maria Luisa Di Vona; Philippe Knauth; Riccardo Narducci. Study of Annealed Aquivion® Ionomers with the INCA Method †. Membranes 2019, 9, 134 .

AMA Style

Stefano Giancola, Raul Andres Becerra Arciniegas, Armand Fahs, Jean-Franҫois Chailan, Maria Luisa Di Vona, Philippe Knauth, Riccardo Narducci. Study of Annealed Aquivion® Ionomers with the INCA Method †. Membranes. 2019; 9 (10):134.

Chicago/Turabian Style

Stefano Giancola; Raul Andres Becerra Arciniegas; Armand Fahs; Jean-Franҫois Chailan; Maria Luisa Di Vona; Philippe Knauth; Riccardo Narducci. 2019. "Study of Annealed Aquivion® Ionomers with the INCA Method †." Membranes 9, no. 10: 134.

Journal article
Published: 29 April 2019 in Membranes
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We synthesized anion exchange polymers by a reaction of chloromethylated poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) with strongly basic 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). TBD contains secondary and tertiary amine groups in the guanidine portion. To favor the functionalization with the secondary amine, TBD was activated with butyl lithium. The yield of amine formation via the reaction of the benzyl chloride moiety with TBD was 85%. Furthermore, we prepared polymers with quaternary ammonium groups by the reaction of PPO-TBD with CH3I. The synthesis pathways and ionomer structure were investigated by NMR spectroscopy. The thermal decomposition of both ionomers, studied by thermogravimetry, started above 200 °C, corresponding to the loss of the basic group. The ion exchange capacities, water uptake and volumetric swelling are also reported. The “intrinsic” anion conductivity of PPO-TBD due to the dissociation of grafted TBD was in the order of 1 mS/cm (Cl form). The quaternized ionomer (PPO-TBD-Me) showed an even larger ionic conductivity, above 10 mS/cm at 80 °C in fully humidified conditions.

ACS Style

Riccardo Narducci; Gianfranco Ercolani; Raul Becerra-Arciniegas; Luca Pasquini; Philippe Knauth; Maria Di Vona. “Intrinsic” Anion Exchange Polymers through the Dissociation of Strong Basic Groups: PPO with Grafted Bicyclic Guanidines. Membranes 2019, 9, 57 .

AMA Style

Riccardo Narducci, Gianfranco Ercolani, Raul Becerra-Arciniegas, Luca Pasquini, Philippe Knauth, Maria Di Vona. “Intrinsic” Anion Exchange Polymers through the Dissociation of Strong Basic Groups: PPO with Grafted Bicyclic Guanidines. Membranes. 2019; 9 (5):57.

Chicago/Turabian Style

Riccardo Narducci; Gianfranco Ercolani; Raul Becerra-Arciniegas; Luca Pasquini; Philippe Knauth; Maria Di Vona. 2019. "“Intrinsic” Anion Exchange Polymers through the Dissociation of Strong Basic Groups: PPO with Grafted Bicyclic Guanidines." Membranes 9, no. 5: 57.

Journal article
Published: 04 December 2018 in Advanced Materials Letters
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ACS Style

Philippe Knauth; Maria Luisa; Di Vona. Electrochemical synthesis of conformal, thin and dense ionomer separators for energy storage and conversion devices. Advanced Materials Letters 2018, 9, 855 -860.

AMA Style

Philippe Knauth, Maria Luisa, Di Vona. Electrochemical synthesis of conformal, thin and dense ionomer separators for energy storage and conversion devices. Advanced Materials Letters. 2018; 9 (12):855-860.

Chicago/Turabian Style

Philippe Knauth; Maria Luisa; Di Vona. 2018. "Electrochemical synthesis of conformal, thin and dense ionomer separators for energy storage and conversion devices." Advanced Materials Letters 9, no. 12: 855-860.

Research article
Published: 16 November 2018 in The Journal of Physical Chemistry B
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We studied the gravimetric and volumetric water uptake and ionic conductivity of two model ionomers, cation-conducting sulfonated poly(ether ether ketone) (SPEEK) and anion-conducting polysulfone-trimethylammonium chloride (PSU-TMA), after immersion in phosphate, acetate and citrate buffer solutions. The equilibrium swelling of SPEEK and PSU-TMA ionomer networks was determined as a function of pH and buffer composition. The hydration data can be interpreted using the osmotic swelling pressure dependence on the ion exchange capacity of the ionomers and the concentration of the electrolyte solutions. In the case of SPEEK, anisotropic swelling is observed in diluted buffer solutions, where the swelling pressure is higher. A large water uptake is observed for citrate ions, due to the large hydration of this bulky anion. The ionic conductivity is related to the conducting ions and, in the case of SPEEK, to sorbed excess electrolyte. The highest ionic conductivity is observed after immersion in phosphate buffers. Ionic cross-linking is for the first time observed in the case of an anion-conducting ionomer in presence of divalent citrate ions, which limits the volumetric swelling and decreases the ionic conductivity of PSU-TMA.

ACS Style

Luca Pasquini; Oceane Wacrenier; Maria Luisa Di Vona; Philippe C Knauth. Hydration and Ionic Conductivity of Model Cation and Anion-Conducting Ionomers in Buffer Solutions (Phosphate, Acetate, Citrate). The Journal of Physical Chemistry B 2018, 122, 12009 -12016.

AMA Style

Luca Pasquini, Oceane Wacrenier, Maria Luisa Di Vona, Philippe C Knauth. Hydration and Ionic Conductivity of Model Cation and Anion-Conducting Ionomers in Buffer Solutions (Phosphate, Acetate, Citrate). The Journal of Physical Chemistry B. 2018; 122 (50):12009-12016.

Chicago/Turabian Style

Luca Pasquini; Oceane Wacrenier; Maria Luisa Di Vona; Philippe C Knauth. 2018. "Hydration and Ionic Conductivity of Model Cation and Anion-Conducting Ionomers in Buffer Solutions (Phosphate, Acetate, Citrate)." The Journal of Physical Chemistry B 122, no. 50: 12009-12016.

Article
Published: 23 July 2018 in ChemElectroChem
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Zinc‐aluminium layered double hydroxide (LDH) containing an ionic liquid, 1‐butyl‐3‐methylimidazolium hydrogen sulphate (BmimSO4), has been synthesized by the co‐precipitation method. This strategy enabled the intercalation of the ionic liquid (IL) into the interlamellar space of LDH with the aim of increasing the ionic conductivity and reducing its dependence on the water content. Pure and IL‐intercalated LDHs have been characterized by Fourier‐Transform Infrared (FTIR) spectroscopy and X‐ray diffraction. Electrochemical Impedance Spectroscopy (EIS) measurements showed that the addition of IL enhanced the ionic conductivity of LDH by a factor of 15 at low humidity and by a factor of 9 at high humidity conditions. As a possible application, LDHs were dispersed as a guest filler in a composite anion exchange membrane (AEM) based on polysulfone‐DABCO. In this case, the addition of IL remarkably improved the ionic conductivity of the membrane from 1.0 10‐9 to 2.4 10‐7 S/cm at low humidity. At high humidity, the membranes reached a conductivity of 25 mS/cm at 25 °C in OH form. Stability tests of composite AEM confirmed the positive effect of LDH nanoparticles.

ACS Style

Roberto Pizzoferrato; Erica Ciotta; Ivan Vito Ferrari; Riccardo Narducci; Luca Pasquini; Alessandra Varone; Maria Richetta; Simonetta Antonaroli; Michele Braglia; Philippe Knauth; Maria Luisa Di Vona. Layered Double Hydroxides Containing an Ionic Liquid: Ionic Conductivity and Use in Composite Anion Exchange Membranes. ChemElectroChem 2018, 5, 2781 -2788.

AMA Style

Roberto Pizzoferrato, Erica Ciotta, Ivan Vito Ferrari, Riccardo Narducci, Luca Pasquini, Alessandra Varone, Maria Richetta, Simonetta Antonaroli, Michele Braglia, Philippe Knauth, Maria Luisa Di Vona. Layered Double Hydroxides Containing an Ionic Liquid: Ionic Conductivity and Use in Composite Anion Exchange Membranes. ChemElectroChem. 2018; 5 (19):2781-2788.

Chicago/Turabian Style

Roberto Pizzoferrato; Erica Ciotta; Ivan Vito Ferrari; Riccardo Narducci; Luca Pasquini; Alessandra Varone; Maria Richetta; Simonetta Antonaroli; Michele Braglia; Philippe Knauth; Maria Luisa Di Vona. 2018. "Layered Double Hydroxides Containing an Ionic Liquid: Ionic Conductivity and Use in Composite Anion Exchange Membranes." ChemElectroChem 5, no. 19: 2781-2788.

Original paper
Published: 07 July 2018 in Journal of Solid State Electrochemistry
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A nanocomposite solid ion conductor was prepared by infiltrating zirconia or titania nanotube arrays, made by electrochemical anodization of Zr or Ti metal, with proton-conducting sulfonated poly(ether-ether-ketone) (SPEEK) ionomer. The resulting material was characterized using scanning electron microscopy, X-ray diffraction, and infrared spectroscopy showing the successful filling of the nanotubular matrix with the ionomer. Impedance spectroscopy revealed a conductivity increase by several orders of magnitude after infiltration; furthermore, the impedance of the TiO2nt-SPEEK nanocomposite is very sensitive to the relative humidity. Possible applications of these ionic conducting nanocomposites include solid-state humidity sensors or heterogeneous catalytic materials.

ACS Style

O. Ruzimuradov; M. Braglia; F. Vacandio; P. Knauth. A humidity-sensitive nanocomposite solid ion conductor: sulfonated poly-ether-ether-ketone in nanotubular TiO2 or ZrO2 matrix. Journal of Solid State Electrochemistry 2018, 22, 3255 -3260.

AMA Style

O. Ruzimuradov, M. Braglia, F. Vacandio, P. Knauth. A humidity-sensitive nanocomposite solid ion conductor: sulfonated poly-ether-ether-ketone in nanotubular TiO2 or ZrO2 matrix. Journal of Solid State Electrochemistry. 2018; 22 (10):3255-3260.

Chicago/Turabian Style

O. Ruzimuradov; M. Braglia; F. Vacandio; P. Knauth. 2018. "A humidity-sensitive nanocomposite solid ion conductor: sulfonated poly-ether-ether-ketone in nanotubular TiO2 or ZrO2 matrix." Journal of Solid State Electrochemistry 22, no. 10: 3255-3260.

Article
Published: 09 January 2018 in ChemistrySelect
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We report the electrochemical performance of amorphous LiCuPO4 thin films obtained by radio frequency sputtering as a cathode material for Li-ion microbatteries. The thin films were characterized by X-ray diffraction, scanning electron microscopy, profilometry and electrochemical techniques. Charge/discharge profiles and cycling performance were evaluated in lithium electrochemical test cells. Cyclic voltammogram of the LiCuPO4 film shows the typical redox reaction peak at ∼ 1.9 V vs. Li/Li+. A discharge capacity of 160 mAh g−1 (50 μAh cm−2) is attained for the first cycle at C/10 to reach a stable capacity of 70 mAh g−1 (22 μAh cm−2) with good stability over 160 cycles. For comparison, the electrochemical performance of a crystalline LiCuPO4 film was investigated. The first discharge could deliver a high capacity of around 375 mAh g−1 at C/10, but the capacity decayed quickly to a low capacity of 11 mAh g−1 over 50 cycles. The results show that the LiCuPO4 amorphous materials can be considered as the exciting cathode candidate for Li-ion microbatteries.

ACS Style

Vinsensia Ade Sugiawati; Florence Vacandio; Philippe Knauth; Thierry Djenizian. Sputter-Deposited Amorphous LiCuPO4 Thin Film as Cathode Material for Li-ion Microbatteries. ChemistrySelect 2018, 3, 405 -409.

AMA Style

Vinsensia Ade Sugiawati, Florence Vacandio, Philippe Knauth, Thierry Djenizian. Sputter-Deposited Amorphous LiCuPO4 Thin Film as Cathode Material for Li-ion Microbatteries. ChemistrySelect. 2018; 3 (2):405-409.

Chicago/Turabian Style

Vinsensia Ade Sugiawati; Florence Vacandio; Philippe Knauth; Thierry Djenizian. 2018. "Sputter-Deposited Amorphous LiCuPO4 Thin Film as Cathode Material for Li-ion Microbatteries." ChemistrySelect 3, no. 2: 405-409.

Article
Published: 20 December 2017 in Advanced Materials Technologies
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Self-supported titanium dioxide nanotube is explored as a potential negative electrode for 3D Li-ion (micro) batteries. Apart from the direct contact of the nanotubes with the substrate, the 1D porous structure effectively facilitates the flow of electrolyte into the bulk, alleviates any volume expansion during cycling, and provides a short lithium-ion diffusion length. The fabrication of self-supported Nb rich titanium dioxide nanotubes by electrochemical anodization of Ti–Nb alloys is reported. The structure, morphology, and the composition of the Nb alloyed TiO2 nanotubes are studied using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The electrochemical behavior of the alloyed and the pristine TiO2 nanotubes is investigated by cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy. The electrochemical performance of the pristine and the alloyed titania nanotubes reveals that as the niobium concentration increases the capacity increases. The titania nanotubes containing 10 wt% of Nb deliver a higher capacity, with good capacity retention and coulombic efficiency. Electrochemical impedance spectroscopy analysis shows that Nb alloying can decrease the overall cell impedance by reducing the charge transfer resistance.

ACS Style

Girish D. Salian; Bon Min Koo; Christophe Lefevre; Thomas Cottineau; Chrystelle Lebouin; Alexander T. Tesfaye; Philippe Knauth; Valerie Keller; Thierry Djenizian. Niobium Alloying of Self‐Organized TiO 2 Nanotubes as an Anode for Lithium‐Ion Microbatteries. Advanced Materials Technologies 2017, 3, 1 .

AMA Style

Girish D. Salian, Bon Min Koo, Christophe Lefevre, Thomas Cottineau, Chrystelle Lebouin, Alexander T. Tesfaye, Philippe Knauth, Valerie Keller, Thierry Djenizian. Niobium Alloying of Self‐Organized TiO 2 Nanotubes as an Anode for Lithium‐Ion Microbatteries. Advanced Materials Technologies. 2017; 3 (3):1.

Chicago/Turabian Style

Girish D. Salian; Bon Min Koo; Christophe Lefevre; Thomas Cottineau; Chrystelle Lebouin; Alexander T. Tesfaye; Philippe Knauth; Valerie Keller; Thierry Djenizian. 2017. "Niobium Alloying of Self‐Organized TiO 2 Nanotubes as an Anode for Lithium‐Ion Microbatteries." Advanced Materials Technologies 3, no. 3: 1.

Original paper
Published: 06 July 2017 in Ionics
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In this study, ZnO thin films have been electrodeposited from zinc nitrate solution without using any catalyst, additive, or seed layer on two kinds of substrates (Si and ITO glass). Using cyclic voltammetry and chronoamperometry, it was shown that the mechanism of ZnO deposition strongly depends on the substrate used and its overpotential for nitrate reduction. On Si, the nitrate reduction into nitrite occurs before that of Zn2+. This reaction induces an increase of the local pH leading to ZnO precipitation. In contrast on ITO, the Zn2+ reduction brings first metallic Zn deposition, which is then chemically oxidized by nitrate into ZnO phase. The effect of deposition time on morphology, structure, and photoluminescence properties was studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) measurements. The chemical nature of the substrate has no influence on the orientation of nanorods, but really impacts their morphology and the optical emission properties. X-ray diffraction analysis always revealed ZnO wurtzite phase with a (002) preferential orientation enhanced with increasing deposition time. A well-defined ZnO morphology was generated under −1.4 V for 60 min on Si and ITO glass. ZnO nanorods that composed the nanoflowers grown on ITO glass tend to be shorter, wider, and with higher aspect ratio than on Si. ZnO nanostructures prepared on ITO showed an intense UV emission without spreading in the visible region, thus demonstrating the formation of a defect free structure.

ACS Style

N. Ait Ahmed; H. Hammache; M. Eyraud; C. Chassigneux; L. Makhloufi; N. Gabouze; P. Knauth; A. Lahreche. Morphological and optical properties of ZnO thin films grown on Si and ITO glass substrates. Ionics 2017, 24, 1 .

AMA Style

N. Ait Ahmed, H. Hammache, M. Eyraud, C. Chassigneux, L. Makhloufi, N. Gabouze, P. Knauth, A. Lahreche. Morphological and optical properties of ZnO thin films grown on Si and ITO glass substrates. Ionics. 2017; 24 (1):1.

Chicago/Turabian Style

N. Ait Ahmed; H. Hammache; M. Eyraud; C. Chassigneux; L. Makhloufi; N. Gabouze; P. Knauth; A. Lahreche. 2017. "Morphological and optical properties of ZnO thin films grown on Si and ITO glass substrates." Ionics 24, no. 1: 1.

Journal article
Published: 01 July 2017 in International Journal of Hydrogen Energy
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Composite anion exchange membranes based on polysulfone with grafted 1,4-diazabicyclo [2.2.2]octane (DABCO) and surface functionalized TiO2 nanoparticles were prepared and characterized. Tri(hydroxymethyl)propane (TMP) was used for hydrophilic and polymethyl-hydrosiloxane (PMHS) for hydrophobic surface functionalization. Thermal analysis (TGA and DSC) showed water loss, the loss of quaternary ammonium groups around 300 degrees C and the backbone decomposition above 400 degrees C starting from the quaternary carbon. The decompositions were confirmed by temperature-dependent FTIR spectroscopy. The thermomechanical study (DMA) showed a secondary relaxation, probably due to DABCO side groups motions, around 130 degrees C followed by the glass transition around 250 degrees C and by a partial crystallization of the polymer, which is also observed by DSC. The increase of storage modulus observed for the composites is consistent with their reduced hydration, which is confirmed by water uptake measurements. Atomic Force Microscopy observations show a more homogeneous dispersion of hydrophobic TiO2 nanoparticles, which are also well embedded in the polymer, whereas agglomeration is evident for hydrophilic surface treatment. The contact angle with water decreases strongly in composites with TMP-TiO2. The ionic conductivity is higher for PMHS-TiO2, probably related to the more homogeneous filler distribution with lower agglomeratio

ACS Style

Z. Derbali; A. Fahs; J.-F. Chailan; I.V. Ferrari; M.L. Di Vona; P. Knauth. Composite anion exchange membranes with functionalized hydrophilic or hydrophobic titanium dioxide. International Journal of Hydrogen Energy 2017, 42, 19178 -19189.

AMA Style

Z. Derbali, A. Fahs, J.-F. Chailan, I.V. Ferrari, M.L. Di Vona, P. Knauth. Composite anion exchange membranes with functionalized hydrophilic or hydrophobic titanium dioxide. International Journal of Hydrogen Energy. 2017; 42 (30):19178-19189.

Chicago/Turabian Style

Z. Derbali; A. Fahs; J.-F. Chailan; I.V. Ferrari; M.L. Di Vona; P. Knauth. 2017. "Composite anion exchange membranes with functionalized hydrophilic or hydrophobic titanium dioxide." International Journal of Hydrogen Energy 42, no. 30: 19178-19189.

Research article
Published: 28 June 2017 in ACS Applied Materials & Interfaces
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The cathodic deposition of poly(styrene sulfonate) on nanoarchitectured TiO2 electrodes is explored by cyclic voltammetry and potentiostatic and galvanostatic experiments, showing a diffusion-controlled deposition described by Cottrell’s law. The structure and composition of the polymer is evidenced by various spectroscopic techniques, including nuclear magnetic resonance, Fourier transform infrared, and X-ray photoelectron spectroscopy, and its morphology is studied by scanning electron microscopy. The average chain length can be estimated from the NMR spectra. The electropolymerization mechanism initiates by radical anion formation. The cycling behavior in half-cell batteries against Li metal is excellent, especially at high rates explored up to 10 C. The areal insertion capacity is above recent literature results, up to 80 μA h cm–2. The combination of normalized areal power density and areal energy density is one of the best reported in the literature.

ACS Style

Michele Braglia; Ivan Vito Ferrari; Thierry Djenizian; Saulius Kaciulis; Peiman Soltani; Maria Luisa Di Vona; Philippe Knauth. Bottom-Up Electrochemical Deposition of Poly(styrene sulfonate) on Nanoarchitectured Electrodes. ACS Applied Materials & Interfaces 2017, 9, 22902 -22910.

AMA Style

Michele Braglia, Ivan Vito Ferrari, Thierry Djenizian, Saulius Kaciulis, Peiman Soltani, Maria Luisa Di Vona, Philippe Knauth. Bottom-Up Electrochemical Deposition of Poly(styrene sulfonate) on Nanoarchitectured Electrodes. ACS Applied Materials & Interfaces. 2017; 9 (27):22902-22910.

Chicago/Turabian Style

Michele Braglia; Ivan Vito Ferrari; Thierry Djenizian; Saulius Kaciulis; Peiman Soltani; Maria Luisa Di Vona; Philippe Knauth. 2017. "Bottom-Up Electrochemical Deposition of Poly(styrene sulfonate) on Nanoarchitectured Electrodes." ACS Applied Materials & Interfaces 9, no. 27: 22902-22910.

Journal article
Published: 01 June 2017 in Journal of Power Sources
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ACS Style

I.V. Ferrari; M. Braglia; T. Djenizian; Philippe Knauth; M.L. Di Vona. Electrochemically engineered single Li-ion conducting solid polymer electrolyte on titania nanotubes for microbatteries. Journal of Power Sources 2017, 353, 95 -103.

AMA Style

I.V. Ferrari, M. Braglia, T. Djenizian, Philippe Knauth, M.L. Di Vona. Electrochemically engineered single Li-ion conducting solid polymer electrolyte on titania nanotubes for microbatteries. Journal of Power Sources. 2017; 353 ():95-103.

Chicago/Turabian Style

I.V. Ferrari; M. Braglia; T. Djenizian; Philippe Knauth; M.L. Di Vona. 2017. "Electrochemically engineered single Li-ion conducting solid polymer electrolyte on titania nanotubes for microbatteries." Journal of Power Sources 353, no. : 95-103.