WO2019070523A1 - Confirmation de défauts induits par le chargement de gaz par spectroscopie d'impédance complexe - Google Patents

Confirmation de défauts induits par le chargement de gaz par spectroscopie d'impédance complexe Download PDF

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Publication number
WO2019070523A1
WO2019070523A1 PCT/US2018/053368 US2018053368W WO2019070523A1 WO 2019070523 A1 WO2019070523 A1 WO 2019070523A1 US 2018053368 W US2018053368 W US 2018053368W WO 2019070523 A1 WO2019070523 A1 WO 2019070523A1
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WO
WIPO (PCT)
Prior art keywords
sample
complex impedance
conduction
activation energy
impedance spectrum
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Application number
PCT/US2018/053368
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English (en)
Inventor
Darren R. BURGESS
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Ih Ip Holdings Limited
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Publication of WO2019070523A1 publication Critical patent/WO2019070523A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/026—Dielectric impedance spectroscopy

Definitions

  • the loading of hydrogen, any isotope thereof, into a solid material is an important technology for hydrogen fuel cells and other exothermic reaction devices.
  • the loading of methane into metal-organic frameworks is an important, emerging technology to increase the storage capacity of this fuel source.
  • the loading process must be controllable, quantifiable and sustainable to be repeatable and production-worthy.
  • the primary previously existing modalities for measuring such loading are mass change, pressure change, and/or some means of calculating the number of gas molecules which are no longer in the gas phase and therefore adsorbed on or absorbed into a solid sample. Changes in resistance are occasionally used after the resistance has been calibrated against mass change.
  • a method of determining whether a conduction mode is present in a sample by complex impedance spectroscopy includes: setting a sample at a first temperature; establishing a first steady state of the sample at the first temperature; obtaining a first complex impedance spectrum; calculating one or more first resistance value from the first complex impedance spectrum; setting the sample at a second temperature; establishing a second steady state of the sample at the second temperature; obtaining a second complex impedance spectrum; calculating one or more second resistance value from the second complex impedance spectrum; determining a function that relates the first and second resistance values to the first and second temperatures respectively; calculating at least one slope of the determined function; calculating at least one activation energy using the at least one calculated slope; determining whether a conduction mode is present in the sample based on the calculated activation energy.
  • Establishing a first steady state of the sample at the first temperature may include establishing an isothermal and isobaric state.
  • the first resistance value may be determined by determining at least one axis intercept in the first complex impedance spectrum.
  • the second resistance value may be determined by determining at least one axis intercept in the second complex impedance spectrum.
  • Determining a function that relates the first and second resistance values to the first and second temperatures may include determining ln(l/R) as a function of 1/T, wherein R is resistance and T is the absolute temperature of the sample.
  • R is resistance
  • T is the absolute temperature of the sample.
  • E c is the activation energy of conductance (eV);
  • Calculating at least one activation energy using the at least one calculated slope may include relying on ln(l/R) as a function of 1/T having a slope of -E c /k.
  • Determining whether a conduction mode is present in the sample based on the calculated activation energy may include detecting electronic conduction along grain boundaries.
  • the sample may be a defect free sample.
  • Determining whether a conduction mode is present in the sample based on the calculated activation energy may include detecting electronic conduction through bulk grains in the sample.
  • Determining whether a conduction mode is present in the sample based on the calculated activation energy may include detecting ionic conduction of hydrogen or deuterium ions along grain boundaries in the sample.
  • Determining whether a conduction mode is present in the sample based on the calculated activation energy may include detecting ionic conduction of hydrogen or deuterium ions through the bulk grains.
  • the method may include detecting effects of the number of hydrogen or deuterium atoms loaded into a defect free lattice on electronic and ionic conduction.
  • the method may include detecting effects of single atom or multi-atom defects on electronic and ionic conduction.
  • the method may include detecting the effects density or proximity of single atom or multi-atom defects on electronic and ionic conduction.
  • the method may include detecting effects of the number of hydrogen or deuterium atoms loaded into a multi-atom defect on electron and ionic conduction.
  • Obtaining a first complex impedance spectrum comprises obtaining electrical measurements using electrodes in electrical communication with the sample.
  • the electrodes may be placed on opposite sides of the sample.
  • the electrodes may be placed on a same side of the sample to minimize a physical distance of a surface conduction path.
  • Obtaining a first complex impedance spectrum may include applying alternating current perturbations to the sample over a frequency range.
  • the frequency range may be about from 1 Hz to at least 10 MHz.
  • FIG. 1 is a schematic representation of a measurement apparatus for determining electrical impedance parameters of a crystal structure sample.
  • FIG. 2 is a plot for demonstration purposes of an expected complex impedance spectra of the crystal structure represented in FIG. 1.
  • FIG. 3 is a diagram of an electric circuit model equivalent to the complex impedance spectra of FIG. 2.
  • FIG. 4 is another plot of complex impedance spectra for demonstration purposes.
  • FIG. 5 is a flowchart representing a method, according to at least one embodiment, for using CIS to confirm the presence of a defect by detecting a correlated conduction mode.
  • complex impedance spectroscopy is used to probe an electrochemical system with a small AC -perturbation over a range of frequencies. This non-destructive approach enables measurement of the impedance of different conduction paths and conducting species in a material. After being calibrated with the presence of a desirable conduction path or species, complex impedance is used as a confirmation or quality control tool.
  • CIS Two aspects of CIS are of use for measurement of gas loading in solids in embodiments described herein: the measurement of impedance for both ionic and electronic conduction; the measurement of impedance to ions and electrons conducting along different paths.
  • a crystal defect is defined as any irregularity in the crystal structure. Grain boundaries are defects since they represent a discontinuity between grains of continuous crystal structure. The term defect is also used to describe a missing atom in a crystal structure. Missing atoms represent openings in a crystal structure by which an ion could "hop" from one to another thereby permitting conduction through a crystal. Thus, each characterized defect can have a correlated conduction mode that can potentially be discerned by CIS.
  • CIS methods described herein are able to access the various conduction modes in a crystal structure by AC perturbations over a large frequency range, for example from 1 Hz to at least 10 MHz in at least one embodiment.
  • FIG. 1 is a schematic representation of a measurement apparatus 100 for determining electrical impedance parameters of simple crystal structure sample 150 having multiple grains 152. Electrodes 102 and 104 may be placed on opposite sides of the sample 150 as represented in FIG. 1 or on the same side of a sample in other embodiments. Depending upon the size of a sample, having the electrodes on the same side may be advantageous for minimizing the physical distance of the surface conduction path. Note as described above, different frequencies probe different conduction paths. Lower frequencies measure the impedance to conduction along the grain boundaries 154. Higher frequencies measure the impedance to conduction through the grains 152. Respective conducting lines 112 and 114 represent electrical connections to the electrodes 102 and 104 by which voltage and current can be applied and passed across the sample 150 and measurements thereof taken.
  • the apparatus 100 may include a housing 110 defining a chamber for containing, isolating, and or pressurizing the sample 150 and electrode arrangement.
  • the chamber may be thermally controlled, for example by way of a thermal element 116, and thus may be thermally isolated from the exterior conditions such that the sample temperature can be set or varied by a controller.
  • One or more fluidic ports may be included for use in establishing gaseous, pressured, or vacuum conditions in the chamber.
  • One or more sensors 118 may be included in pressure and/or thermal communication or other coupling with the sample so chamber and sample conditions can be monitored and controlled.
  • the one or more sensors 118 can include sensors that monitor temperature, pressure, IR and other light ranges, and chemical species or conditions.
  • a controller 120 is shown in electrical communication with each of the electrodes 102 and 104 by way of the respective conducting lines 112 and 114.
  • the controller 120 is configured to apply voltage and current across the sample 150 and conduct measurements thereof, for example particularly for CIS, in which a small AC-perturbation is used over a range of frequencies.
  • the controller may also be operatively coupled to the thermal element 116, and the one or more sensors 118, and may be in control of any fluidic ports by which the conditions about the sample 150 are established and controlled.
  • FIG. 2 is a plot of an expected complex impedance spectra of the crystal structure of
  • Intercepts along the Z' axis represent resistances determined by the plot.
  • the first intercept R b along the Z' axis is bulk grain resistance
  • the second intercept is R b +R gb , in which R gb is a grain boundary resistance.
  • FIG. 3 An electric circuit model 300 approximately equivalent to the complex impedance spectra of FIG. 2 is shown in FIG. 3. Crystalline solids typically fit a parallel capacitor and resistor circuit model.
  • R b bulk grain resistance (as in FIG. 2)
  • C b bulk grain capacitance
  • R gb grain boundary resistance (as in FIG. 2)
  • C gb grain boundary capacitance.
  • the resistance (R) of a conduction path can be taken from the lower frequency by taking the difference between the higher and lower intercepts of the semi-circular spectra with the real impedance ( ⁇ ') axis.
  • the intercepts along the Z' axis of a measured spectra are RA, RB and Rc as shown in FIG. 4.
  • the resistance value which most likely corresponds to the surface or grain boundary resistance (R gb ) is calculated by taking the difference between the values Rc and RB along the Z' axis at the intercepts.
  • the resistance value which most likely corresponds to the bulk resistance (R b ) of the crystalline grains is calculated by taking the difference between RB and RA-
  • Ec is the activation energy of conductance (eV)
  • T is the absolute temperature (K)
  • FIG. 5 is a flowchart representing a method 500, according to at least one embodiment, for using CIS to confirm the presence of a defect in sample, of which the sample 150 can serve as a non-limiting example for description and illustration purposes.
  • a sample temperature is set.
  • the temperature of the sample 150 may be set and controlled by use of the thermal element 116 operatively coupled to the controller 120.
  • step 504 the sample is allowed to reach steady state.
  • the sample may be monitored to confirm that a steady state has been established.
  • Monitoring of the sample 150 in FIG. 1, for example, can be conducted by way of the one or more sensors 118.
  • Steady state conditions can include stasis in temperature, pressure, chemical species and/or other conditions.
  • steady state can refer to an isothermal state and/or an isobaric state, and other stabilized or relatively non-varying conditions as well.
  • step 506 a complex impedance spectrum (CIS) is obtained, examples of which are shown in FIGS. 2 and 4.
  • the controller 120 may apply voltage and current across the sample 150 and conduct measurements thereof, according to CIS techniques, in which a small AC- perturbation is used over a range of frequencies, for example from 1 Hz to at least 10 MHz in at least one embodiment.
  • step 508 resistance values are calculated from the obtained spectrum, for example by determining intercepts as described above in descriptions of FIGS. 2 and 4.
  • step 510 whether resistance values have been obtained at multiple temperatures is determined. As the resistance varies as a function of temperature, multiple temperatures are to established, and respective measurements taken thereof, so as to calculate activation energy by which the defects or sample phenomena of interest are to be discerned.
  • step 512 if resistance values have not been obtained at multiple temperatures as determined in step 510 ("No"), the sample temperature is increased, and further process of the method 500 returns to step 504. Iterations from step 504 to step 510 repeat (loop) until the determination in step 510 renders an affirmative.
  • ln(l/R) as a function of l/T(absolute temperature in K) for analogous sets of resistance values is determined and may be plotted.
  • step 516 the slope of the determined function and/or plot is calculated.
  • step 518 activation energy is calculated from the slope(s).
  • activation energy (E c ) can be calculated by way of ln(l/R) as a function of 1/T, which has a slope of -E c /k, thereby allowing calculation of E c .
  • step 520 a determination is made as to whether the activation energy values suggest the presence of conduction modes and thus the correlated defects, some of which may be desired. Because activation energy can be matched with an observed sample behavior, through experimentation and other analyses such as electron microscopy and other investigation techniques, the nature or presence of defects can be matched or mapped via activation energy determinations so as to confirm the presence of a certain types of conduction modes and their correlated defects.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

Un procédé de détermination du fait qu'un mode de conduction est présent dans un échantillon par spectroscopie d'impédance complexe consistant à : régler un échantillon à une première température; établir un premier état stable de l'échantillon à la première température; obtenir un premier spectre d'impédance complexe; calculer une ou plusieurs premières valeurs de résistance à partir du premier spectre d'impédance complexe; régler l'échantillon à une seconde température; établir un second état stable de l'échantillon à la seconde température; obtenir un second spectre d'impédance complexe; calculer une ou plusieurs secondes valeurs de résistance à partir du second spectre d'impédance complexe; déterminer une fonction qui relie les première et seconde valeurs de résistance respectivement aux première et seconde températures; calculer au moins une pente de la fonction déterminée; calculer au moins une énergie d'activation à l'aide de l'adite au moins une pente calculée; déterminer si un mode de conduction est présent dans l'échantillon sur la base de l'énergie d'activation calculée.
PCT/US2018/053368 2017-10-04 2018-09-28 Confirmation de défauts induits par le chargement de gaz par spectroscopie d'impédance complexe WO2019070523A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6125529A (en) * 1996-06-17 2000-10-03 Thermometrics, Inc. Method of making wafer based sensors and wafer chip sensors
US20100077840A1 (en) * 2008-06-27 2010-04-01 Northwestern University Light induced gas sensing at room temprature
WO2013057574A1 (fr) * 2011-10-21 2013-04-25 Uniwersytet Warszawski Cellule et procédé pour effectuer des mesures électriques d'échantillons liquides ou en poudre hautement réactifs
WO2015157848A1 (fr) * 2014-04-15 2015-10-22 Simon Fraser University Ionènes stables aux hydroxydes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6125529A (en) * 1996-06-17 2000-10-03 Thermometrics, Inc. Method of making wafer based sensors and wafer chip sensors
US20100077840A1 (en) * 2008-06-27 2010-04-01 Northwestern University Light induced gas sensing at room temprature
WO2013057574A1 (fr) * 2011-10-21 2013-04-25 Uniwersytet Warszawski Cellule et procédé pour effectuer des mesures électriques d'échantillons liquides ou en poudre hautement réactifs
WO2015157848A1 (fr) * 2014-04-15 2015-10-22 Simon Fraser University Ionènes stables aux hydroxydes

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