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An electrochemical quartz crystal microbalance study of lithium insertion into thin films of tungsten trioxide. II: Experimental results and comparison with model calculations

Identifieur interne : 01D012 ( Main/Repository ); précédent : 01D011; suivant : 01D013

An electrochemical quartz crystal microbalance study of lithium insertion into thin films of tungsten trioxide. II: Experimental results and comparison with model calculations

Auteurs : RBID : Pascal:95-0555843

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English descriptors

Abstract

Lithium insertion into amorphous thin films of tungsten trioxide (a-WO3) prepared by thermal vacuum evaporation of WO3 powder has been studied experimentally by chronoamperometry, cyclic voltammetry and ac impedance spectroscopy associated with electrochemical quartz crystal microbalance (EQCM). During cathodic polarization of the electrode and at short times two antagonistic processes occur. One is a non faradaic process and is associated with the expulsion of anions from the electrode surface under the effect of the electric field built in the electrolyte when a potential difference is imposed between the electrodes. The other one is the faradaic insertion of non-solvated lithium ions into the oxide. These two processes occur simultaneously. Under application of a cathodic overvoltage the former one leads to a loss of mass of the electrode and the latter one to a gain of mass. These two processes may explain the experimental data. From these data the diffusion coefficient of lithium ions into the oxide is determined and it is shown that it varies as insertion proceeds. A thermodynamic study of lithium insertion into a-WO3 is also performed to solve the equations of the theoretical model proposed in Part I of this paper. This thermodynamic study allowed us to determine the repulsive and/or attractive interactions between the inserted species and the host matrix as insertion occurs and the influence of the electronic term on the potential.

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Pascal:95-0555843

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<title xml:lang="en" level="a">An electrochemical quartz crystal microbalance study of lithium insertion into thin films of tungsten trioxide. II: Experimental results and comparison with model calculations</title>
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<term>Amorphous material</term>
<term>Chronoamperometry</term>
<term>Comparative study</term>
<term>Cyclic voltammetry</term>
<term>Diffusion coefficient</term>
<term>Electrochemical reaction</term>
<term>Electrodes</term>
<term>Experimental study</term>
<term>Indium Oxides</term>
<term>Intercalation compound</term>
<term>Kinetic parameter</term>
<term>Lithium Ions</term>
<term>Lithium Perchlorates</term>
<term>Mathematical model</term>
<term>Modeling</term>
<term>Modified material</term>
<term>Quartz microbalance</term>
<term>Rate constant</term>
<term>Reaction mechanism</term>
<term>Theoretical study</term>
<term>Thermodynamic analysis</term>
<term>Thin film</term>
<term>Tin Oxides</term>
<term>Transfer function</term>
<term>Tungsten VI Oxides</term>
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<term>Etude théorique</term>
<term>Etude expérimentale</term>
<term>Etude comparative</term>
<term>Electrode</term>
<term>Indium Oxyde</term>
<term>Etain Oxyde</term>
<term>Matériau modifié</term>
<term>Tungstène VI Oxyde</term>
<term>Couche mince</term>
<term>Matériau amorphe</term>
<term>Lithium Perchlorate</term>
<term>Chronoampérométrie</term>
<term>Voltammétrie cyclique</term>
<term>Microbalance quartz</term>
<term>Réaction électrochimique</term>
<term>Composé insertion</term>
<term>Lithium Ion</term>
<term>Modélisation</term>
<term>Modèle mathématique</term>
<term>Analyse thermodynamique</term>
<term>Coefficient diffusion</term>
<term>Fonction transfert</term>
<term>Mécanisme réaction</term>
<term>Constante vitesse</term>
<term>Paramètre cinétique</term>
<term>Electrode ITO</term>
<term>1,3-Dioxolan-2-one(méthyl)</term>
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<front>
<div type="abstract" xml:lang="en">Lithium insertion into amorphous thin films of tungsten trioxide (a-WO
<sub>3</sub>
) prepared by thermal vacuum evaporation of WO
<sub>3</sub>
powder has been studied experimentally by chronoamperometry, cyclic voltammetry and ac impedance spectroscopy associated with electrochemical quartz crystal microbalance (EQCM). During cathodic polarization of the electrode and at short times two antagonistic processes occur. One is a non faradaic process and is associated with the expulsion of anions from the electrode surface under the effect of the electric field built in the electrolyte when a potential difference is imposed between the electrodes. The other one is the faradaic insertion of non-solvated lithium ions into the oxide. These two processes occur simultaneously. Under application of a cathodic overvoltage the former one leads to a loss of mass of the electrode and the latter one to a gain of mass. These two processes may explain the experimental data. From these data the diffusion coefficient of lithium ions into the oxide is determined and it is shown that it varies as insertion proceeds. A thermodynamic study of lithium insertion into a-WO
<sub>3</sub>
is also performed to solve the equations of the theoretical model proposed in Part I of this paper. This thermodynamic study allowed us to determine the repulsive and/or attractive interactions between the inserted species and the host matrix as insertion occurs and the influence of the electronic term on the potential.</div>
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<s0>Lithium insertion into amorphous thin films of tungsten trioxide (a-WO
<sub>3</sub>
) prepared by thermal vacuum evaporation of WO
<sub>3</sub>
powder has been studied experimentally by chronoamperometry, cyclic voltammetry and ac impedance spectroscopy associated with electrochemical quartz crystal microbalance (EQCM). During cathodic polarization of the electrode and at short times two antagonistic processes occur. One is a non faradaic process and is associated with the expulsion of anions from the electrode surface under the effect of the electric field built in the electrolyte when a potential difference is imposed between the electrodes. The other one is the faradaic insertion of non-solvated lithium ions into the oxide. These two processes occur simultaneously. Under application of a cathodic overvoltage the former one leads to a loss of mass of the electrode and the latter one to a gain of mass. These two processes may explain the experimental data. From these data the diffusion coefficient of lithium ions into the oxide is determined and it is shown that it varies as insertion proceeds. A thermodynamic study of lithium insertion into a-WO
<sub>3</sub>
is also performed to solve the equations of the theoretical model proposed in Part I of this paper. This thermodynamic study allowed us to determine the repulsive and/or attractive interactions between the inserted species and the host matrix as insertion occurs and the influence of the electronic term on the potential.</s0>
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<s5>01</s5>
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<s5>02</s5>
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<s5>02</s5>
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<s0>Estudio experimental</s0>
<s5>02</s5>
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<s5>03</s5>
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<s0>Comparative study</s0>
<s5>03</s5>
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<s0>Vergleich</s0>
<s5>03</s5>
</fC03>
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<s0>Estudio comparativo</s0>
<s5>03</s5>
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<fC03 i1="04" i2="X" l="FRE">
<s0>Electrode</s0>
<s5>05</s5>
</fC03>
<fC03 i1="04" i2="X" l="ENG">
<s0>Electrodes</s0>
<s5>05</s5>
</fC03>
<fC03 i1="04" i2="X" l="GER">
<s0>Elektrode</s0>
<s5>05</s5>
</fC03>
<fC03 i1="04" i2="X" l="SPA">
<s0>Electrodo</s0>
<s5>05</s5>
</fC03>
<fC03 i1="05" i2="X" l="FRE">
<s0>Indium Oxyde</s0>
<s1>ACT</s1>
<s2>NC</s2>
<s2>NA</s2>
<s5>06</s5>
</fC03>
<fC03 i1="05" i2="X" l="ENG">
<s0>Indium Oxides</s0>
<s1>ACT</s1>
<s2>NC</s2>
<s2>NA</s2>
<s5>06</s5>
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<fC03 i1="05" i2="X" l="SPA">
<s0>Indio Óxido</s0>
<s1>ACT</s1>
<s2>NC</s2>
<s2>NA</s2>
<s5>06</s5>
</fC03>
<fC03 i1="06" i2="X" l="FRE">
<s0>Etain Oxyde</s0>
<s1>ACT</s1>
<s2>NC</s2>
<s2>FX</s2>
<s2>NA</s2>
<s5>07</s5>
</fC03>
<fC03 i1="06" i2="X" l="ENG">
<s0>Tin Oxides</s0>
<s1>ACT</s1>
<s2>NC</s2>
<s2>FX</s2>
<s2>NA</s2>
<s5>07</s5>
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<fC03 i1="06" i2="X" l="SPA">
<s0>Estaño Óxido</s0>
<s1>ACT</s1>
<s2>NC</s2>
<s2>FX</s2>
<s2>NA</s2>
<s5>07</s5>
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<s0>Matériau modifié</s0>
<s5>08</s5>
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<s0>Modified material</s0>
<s5>08</s5>
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<s0>Material modificado</s0>
<s5>08</s5>
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<fC03 i1="08" i2="X" l="FRE">
<s0>Tungstène VI Oxyde</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>09</s5>
<s6>Tungstène «VI» Oxyde</s6>
</fC03>
<fC03 i1="08" i2="X" l="ENG">
<s0>Tungsten VI Oxides</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>09</s5>
<s6>Tungsten «VI» Oxides</s6>
</fC03>
<fC03 i1="08" i2="X" l="SPA">
<s0>Wolframio VI Óxido</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>09</s5>
<s6>Wolframio «VI» Óxido</s6>
</fC03>
<fC03 i1="09" i2="X" l="FRE">
<s0>Couche mince</s0>
<s5>10</s5>
</fC03>
<fC03 i1="09" i2="X" l="ENG">
<s0>Thin film</s0>
<s5>10</s5>
</fC03>
<fC03 i1="09" i2="X" l="GER">
<s0>Duennschicht</s0>
<s5>10</s5>
</fC03>
<fC03 i1="09" i2="X" l="SPA">
<s0>Capa fina</s0>
<s5>10</s5>
</fC03>
<fC03 i1="10" i2="X" l="FRE">
<s0>Matériau amorphe</s0>
<s5>11</s5>
</fC03>
<fC03 i1="10" i2="X" l="ENG">
<s0>Amorphous material</s0>
<s5>11</s5>
</fC03>
<fC03 i1="10" i2="X" l="SPA">
<s0>Material amorfo</s0>
<s5>11</s5>
</fC03>
<fC03 i1="11" i2="X" l="FRE">
<s0>Lithium Perchlorate</s0>
<s1>SOL</s1>
<s2>NC</s2>
<s2>NA</s2>
<s5>12</s5>
</fC03>
<fC03 i1="11" i2="X" l="ENG">
<s0>Lithium Perchlorates</s0>
<s1>SOL</s1>
<s2>NC</s2>
<s2>NA</s2>
<s5>12</s5>
</fC03>
<fC03 i1="11" i2="X" l="SPA">
<s0>Litio Perclorato</s0>
<s1>SOL</s1>
<s2>NC</s2>
<s2>NA</s2>
<s5>12</s5>
</fC03>
<fC03 i1="12" i2="X" l="FRE">
<s0>Chronoampérométrie</s0>
<s5>13</s5>
</fC03>
<fC03 i1="12" i2="X" l="ENG">
<s0>Chronoamperometry</s0>
<s5>13</s5>
</fC03>
<fC03 i1="12" i2="X" l="GER">
<s0>Chronoamperometrie</s0>
<s5>13</s5>
</fC03>
<fC03 i1="12" i2="X" l="SPA">
<s0>Cronoamperimetría</s0>
<s5>13</s5>
</fC03>
<fC03 i1="13" i2="X" l="FRE">
<s0>Voltammétrie cyclique</s0>
<s5>14</s5>
</fC03>
<fC03 i1="13" i2="X" l="ENG">
<s0>Cyclic voltammetry</s0>
<s5>14</s5>
</fC03>
<fC03 i1="13" i2="X" l="SPA">
<s0>Voltametría cíclica</s0>
<s5>14</s5>
</fC03>
<fC03 i1="14" i2="X" l="FRE">
<s0>Microbalance quartz</s0>
<s5>15</s5>
</fC03>
<fC03 i1="14" i2="X" l="ENG">
<s0>Quartz microbalance</s0>
<s5>15</s5>
</fC03>
<fC03 i1="14" i2="X" l="SPA">
<s0>Microbalanza cuarzo</s0>
<s5>15</s5>
</fC03>
<fC03 i1="15" i2="X" l="FRE">
<s0>Réaction électrochimique</s0>
<s5>16</s5>
</fC03>
<fC03 i1="15" i2="X" l="ENG">
<s0>Electrochemical reaction</s0>
<s5>16</s5>
</fC03>
<fC03 i1="15" i2="X" l="SPA">
<s0>Reacción electroquímica</s0>
<s5>16</s5>
</fC03>
<fC03 i1="16" i2="X" l="FRE">
<s0>Composé insertion</s0>
<s5>17</s5>
</fC03>
<fC03 i1="16" i2="X" l="ENG">
<s0>Intercalation compound</s0>
<s5>17</s5>
</fC03>
<fC03 i1="16" i2="X" l="SPA">
<s0>Compuesto inserción</s0>
<s5>17</s5>
</fC03>
<fC03 i1="17" i2="X" l="FRE">
<s0>Lithium Ion</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>18</s5>
</fC03>
<fC03 i1="17" i2="X" l="ENG">
<s0>Lithium Ions</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>18</s5>
</fC03>
<fC03 i1="17" i2="X" l="SPA">
<s0>Litio Ión</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>18</s5>
</fC03>
<fC03 i1="18" i2="X" l="FRE">
<s0>Modélisation</s0>
<s5>19</s5>
</fC03>
<fC03 i1="18" i2="X" l="ENG">
<s0>Modeling</s0>
<s5>19</s5>
</fC03>
<fC03 i1="18" i2="X" l="SPA">
<s0>Modelización</s0>
<s5>19</s5>
</fC03>
<fC03 i1="19" i2="X" l="FRE">
<s0>Modèle mathématique</s0>
<s5>20</s5>
</fC03>
<fC03 i1="19" i2="X" l="ENG">
<s0>Mathematical model</s0>
<s5>20</s5>
</fC03>
<fC03 i1="19" i2="X" l="GER">
<s0>Mathematisches Modell</s0>
<s5>20</s5>
</fC03>
<fC03 i1="19" i2="X" l="SPA">
<s0>Modelo matemático</s0>
<s5>20</s5>
</fC03>
<fC03 i1="20" i2="X" l="FRE">
<s0>Analyse thermodynamique</s0>
<s5>21</s5>
</fC03>
<fC03 i1="20" i2="X" l="ENG">
<s0>Thermodynamic analysis</s0>
<s5>21</s5>
</fC03>
<fC03 i1="20" i2="X" l="SPA">
<s0>Análisis termodinámico</s0>
<s5>21</s5>
</fC03>
<fC03 i1="21" i2="X" l="FRE">
<s0>Coefficient diffusion</s0>
<s5>22</s5>
</fC03>
<fC03 i1="21" i2="X" l="ENG">
<s0>Diffusion coefficient</s0>
<s5>22</s5>
</fC03>
<fC03 i1="21" i2="X" l="GER">
<s0>Diffusionskoeffizient</s0>
<s5>22</s5>
</fC03>
<fC03 i1="21" i2="X" l="SPA">
<s0>Coeficiente difusión</s0>
<s5>22</s5>
</fC03>
<fC03 i1="22" i2="X" l="FRE">
<s0>Fonction transfert</s0>
<s5>23</s5>
</fC03>
<fC03 i1="22" i2="X" l="ENG">
<s0>Transfer function</s0>
<s5>23</s5>
</fC03>
<fC03 i1="22" i2="X" l="GER">
<s0>Uebertragungsfunktion</s0>
<s5>23</s5>
</fC03>
<fC03 i1="22" i2="X" l="SPA">
<s0>Función traspaso</s0>
<s5>23</s5>
</fC03>
<fC03 i1="23" i2="X" l="FRE">
<s0>Mécanisme réaction</s0>
<s5>24</s5>
</fC03>
<fC03 i1="23" i2="X" l="ENG">
<s0>Reaction mechanism</s0>
<s5>24</s5>
</fC03>
<fC03 i1="23" i2="X" l="SPA">
<s0>Mecanismo reacción</s0>
<s5>24</s5>
</fC03>
<fC03 i1="24" i2="X" l="FRE">
<s0>Constante vitesse</s0>
<s5>25</s5>
</fC03>
<fC03 i1="24" i2="X" l="ENG">
<s0>Rate constant</s0>
<s5>25</s5>
</fC03>
<fC03 i1="24" i2="X" l="SPA">
<s0>Constante velocidad</s0>
<s5>25</s5>
</fC03>
<fC03 i1="25" i2="X" l="FRE">
<s0>Paramètre cinétique</s0>
<s5>26</s5>
</fC03>
<fC03 i1="25" i2="X" l="ENG">
<s0>Kinetic parameter</s0>
<s5>26</s5>
</fC03>
<fC03 i1="25" i2="X" l="SPA">
<s0>Parámetro cinético</s0>
<s5>26</s5>
</fC03>
<fC03 i1="26" i2="X" l="FRE">
<s0>Electrode ITO</s0>
<s4>INC</s4>
<s5>62</s5>
</fC03>
<fC03 i1="27" i2="X" l="FRE">
<s0>1,3-Dioxolan-2-one(méthyl)</s0>
<s1>SOL</s1>
<s2>NK</s2>
<s4>INC</s4>
<s5>63</s5>
</fC03>
<fN21>
<s1>317</s1>
</fN21>
</pA>
</standard>
</inist>
</record>

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