WO2022211488A1 - Hydrure et son procédé de préparation - Google Patents

Hydrure et son procédé de préparation Download PDF

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Publication number
WO2022211488A1
WO2022211488A1 PCT/KR2022/004504 KR2022004504W WO2022211488A1 WO 2022211488 A1 WO2022211488 A1 WO 2022211488A1 KR 2022004504 W KR2022004504 W KR 2022004504W WO 2022211488 A1 WO2022211488 A1 WO 2022211488A1
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hydride
formula
hydrogen
dimensional
present application
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PCT/KR2022/004504
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English (en)
Korean (ko)
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김성웅
임동철
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성균관대학교산학협력단
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Priority claimed from KR1020210165300A external-priority patent/KR102639462B1/ko
Application filed by 성균관대학교산학협력단 filed Critical 성균관대학교산학협력단
Publication of WO2022211488A1 publication Critical patent/WO2022211488A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material

Definitions

  • the present application relates to hydrides and methods for their preparation.
  • Electrons are a new concept of material that directly determines the functionality of a material regardless of constituent elements and structural factors, while electrons exist as interstitial electrons in vacancies inside the crystal rather than around the nucleus of an atom. Electron materials have a low work function and can be used as an electron-emitting material, and can be used as a magnetic material such as a ferromagnetic material and a magneto-thermal material due to a high magnetic entropy change, and a catalyst due to high electron transfer efficiency It is a material that can be widely used as a material.
  • An ionic conductor refers to a material in which ions themselves carry an electric charge, unlike an electrical conductor in which electrons carry electric charge. refers to Hydrogen ion conductors with high ionic conductivity can be widely used in gas sensors, water splitting, fuel cells, electrochemical hydrogen compressor technology, and hydrogen ion batteries.
  • Nafion which is widely used as a hydrogen ion conductor in hydrogen fuel cells, etc., is a high molecular material with a very complex molecular structure and exhibits a low hydrogen ion conductivity of about 0.2 S/cm.
  • U.S. Patent No. 10173202 relates to a supported metal catalyst and a method for synthesizing ammonia using the catalyst, but the hydride is not recognized.
  • the present application is to solve the problems of the prior art, and an object of the present application is to provide a hydride based on a low-dimensional electron having high ionic conductivity and a method for manufacturing the same.
  • Another object of the present application is to provide a hydrogen ion conductor including the hydride.
  • the first aspect of the present application is a hydride comprising at least one compound selected from the group consisting of the following Chemical Formulas 1 to 3, wherein the hydride is an electron contained in the electron A hydride is provided, which is substituted with hydrogen:
  • X is Sc, Y, La, Ce, Eu, Gd, Tb, Dy, Ho or Er, and x is 0 ⁇ x ⁇ 3.5);
  • Z is Ti, Zr or Hf
  • W is O, S or Se
  • z is 0 ⁇ z ⁇ 3.5
  • the electron material may include one or more low-dimensional electron materials selected from the group consisting of the following Chemical Formulas 4 to 6, but is not limited thereto:
  • X is Sc, Y, La, Ce, Eu, Gd, Tb, Dy, Ho or Er
  • Y is Ca, Sr, or Ba
  • Z is Ti, Zr or Hf, and W is O, S or Se).
  • electrons included between the lattice structures of the electron oxide selected from the group consisting of Chemical Formulas 4 to 6 may be substituted with hydrogen, but is not limited thereto.
  • one or more compounds selected from the group consisting of Chemical Formulas 4 to 6 are arranged in a two-dimensional shape, and electrons disposed between the two-dimensional shape may be substituted with hydrogen, but It is not limited.
  • hydrogen in the hydride, hydrogen may be bonded to the low-dimensional compound itself selected from the group consisting of Chemical Formulas 4 to 6, but is not limited thereto.
  • the symmetry of the crystal structure of the electron nitride and the symmetry of the crystal structure of the hydride may be different from each other, but the present disclosure is not limited thereto.
  • the hydride may have the form of a single crystal, a polycrystal, or a thin film, but is not limited thereto.
  • the ionic conductivity of the hydride may be 0.1 S/cm to 3 S/cm, but is not limited thereto.
  • a second aspect of the present application comprises the steps of preparing one or more low-dimensional electron materials selected from the group consisting of the following Chemical Formulas 4 to 6; And to a method for producing a hydride comprising the step of heat-treating the low-dimensional electron hydrate in a hydrogen gas atmosphere:
  • X is Sc, Y, La, Ce, Eu, Gd, Tb, Dy, Ho or Er
  • Y is Ca, Sr, or Ba
  • Z is Ti, Zr or Hf, and W is O, S or Se).
  • the step of heat-treating the low-dimensional electron material in a hydrogen gas atmosphere electrons disposed between the lattice structure of the low-dimensional electron material are replaced with hydrogen, or the low-dimensional electron material and hydrogen may be combined, but is not limited thereto.
  • the hydrogen gas atmosphere may further include an inert gas, but is not limited thereto.
  • the heat treatment may be performed at 100° C. to 1,500° C., but is not limited thereto.
  • a third aspect of the present application relates to a hydrogen ion conductor comprising the hydride according to the first aspect.
  • the hydride according to the present application has a structure of a solid inorganic compound while having a high hydrogen ion conductivity, unlike the conventional hydride having a complex structure and weak mechanical properties, thereby storing hydrogen And it can be applied to various fields requiring movement.
  • a hydrogen ion conductor can be used in a fuel cell such as a hydrogen fuel cell when it has high ionic conductivity.
  • the hydrogen fuel cell including the hydrogen ion conductor may be operated at 500° C. to 700° C., but has a disadvantage in that it operates at a high temperature and has low stability.
  • a hydrogen ion conductor comprising a hydride according to the present disclosure may have a high ionic conductivity near about 200°C. That is, the hydrogen fuel cell including the hydrogen ion conductor according to the present application may have a lower operating temperature compared to the conventional hydrogen fuel cell, and by having a lower operating temperature, it may be operated for a long time, and stability may be increased.
  • the hydride according to the present application can be prepared by heat-treating a low-dimensional electron oxide in a hydrogen atmosphere, so that a high-performance hydrogen ion conductor can be manufactured by a simple process.
  • FIG. 1 is a schematic diagram of a hydride according to an embodiment of the present application.
  • FIG. 2 is a schematic diagram of a device for measuring hydrogen ion conductivity of hydride according to an embodiment of the present application.
  • FIG. 3 is a photograph of a hydride according to an embodiment of the present application.
  • FIG. 4 is a photograph of a device for measuring hydrogen ion conductivity of hydride according to an embodiment of the present application.
  • 5 is a graph of the result of thermal desorption spectroscopy measurement of the amount of hydrogen contained in the hydride according to an embodiment of the present application.
  • FIG. 6 is a graph showing a result of X-ray diffraction analysis of a crystal structure change before and after hydrogen injection of a hydride according to an embodiment of the present application.
  • FIG. 7 shows the ionic conductivity of a hydride according to an embodiment of the present application.
  • the first aspect of the present application is a hydride comprising at least one compound selected from the group consisting of the following Chemical Formulas 1 to 3, wherein the hydride is an electron contained in the electron A hydride is provided, which is substituted with hydrogen:
  • X is Sc, Y, La, Ce, Eu, Gd, Tb, Dy, Ho or Er, and x is 0 ⁇ x ⁇ 3.5);
  • Z is Ti, Zr or Hf
  • W is O, S or Se
  • z is 0 ⁇ z ⁇ 3.5
  • the electron cargo according to the present application refers to a material in which electrons exist as an interstitial electron state in an empty space inside a crystal of a material instead of around an atomic nucleus, thereby directly determining the functionality of a material regardless of components and structural factors.
  • the hydride according to the present application includes hydrogen disposed between the lattice structure of the electronized material by replacing electrons in the lattice structure of the electronized material with hydrogen, and at the same time, the cation of the electronized material (eg, Formulas 1 to 3) of X, Y, and Z) and H - means that they are bonded.
  • the bond between the cation and hydrogen of the electron hydride is a bond made in a two-dimensional or one-dimensional structure, and since it is a weak bond compared to a bond made in a three-dimensional structure, the movement of hydrogen ions in the hydride is similar to that of the conventional hydride. Compared to that, it is free and may require less energy for the movement of hydrogen ions.
  • FIG. 1 is a schematic diagram of a hydride according to an embodiment of the present application, wherein the hydride of FIG. 1 is a schematic diagram of Gd 2 CH x (0 ⁇ x ⁇ 3.5) represented by Chemical Formula 1, but is not limited thereto.
  • the hydride of FIG. 1 is a schematic diagram of Gd 2 CH x (0 ⁇ x ⁇ 3.5) represented by Chemical Formula 1, but is not limited thereto.
  • the Gd 2 CH x it can be confirmed that hydrogen is bonded to Gd 2 C , and hydrogen ions, that is, H ⁇ are disposed between the lattice structure of the two-dimensional Gd 2 CH x instead of electrons.
  • H disposed between the lattice structures of the compound may be a hydrogen anion (H ⁇ ), but is not limited thereto.
  • H ⁇ hydrogen anion
  • all of the hydrogens disposed between the lattice structures of Gd 2 CH x may be H ⁇ .
  • the electron material may include one or more low-dimensional electron materials selected from the group consisting of the following Chemical Formulas 4 to 6, but is not limited thereto:
  • X is Sc, Y, La, Ce, Eu, Gd, Tb, Dy, Ho or Er
  • Y is Ca, Sr, or Ba
  • Z is Ti, Zr or Hf, and W is O, S or Se).
  • the low-dimensional electron material means that the electron material has a one-dimensional or two-dimensional structure, so that interstitial electrons are distributed one-dimensionally or two-dimensionally.
  • the hydride since the interstitial electrons are substituted with hydrogen (specifically H ⁇ ) by heat treatment in a hydrogen atmosphere, the hydride may form a one-dimensional or two-dimensionally distributed hydrogen arrangement, and , due to the hydrogen arrangement, the hydride may have high hydrogen ion conductivity.
  • ordinary hydrogen can be arranged in three dimensions to be relatively strongly bonded to other atoms in the lattice.
  • the hydrogen may be relatively weakly bound to other atoms in the lattice. That is, since the hydride has a one-dimensionally or two-dimensionally distributed hydrogen arrangement, hydrogen disposed between the lattices of the hydride or hydrogen bonded to a metal atom of the electron hydride forms a relatively weak bond with other atoms. It can move easily, and because of this, it can have higher hydrogen ion conductivity than a hydride having a three-dimensional structure because the energy required for movement is low.
  • electrons included between the lattice structures of the electron oxide selected from the group consisting of Chemical Formulas 4 to 6 may be substituted with hydrogen, but is not limited thereto.
  • one or more compounds selected from the group consisting of Chemical Formulas 4 to 6 are arranged in a two-dimensional shape, and electrons disposed between the two-dimensional shape may be substituted with hydrogen, but It is not limited.
  • the electrons and substituted hydrogens disposed between the lattice structure of the electron material, or the electrons and the substituted hydrogens disposed between the two-dimensional shapes must eventually be hydrogen bonded to the electrons, the charge of H ⁇ have a state
  • hydrogen in the hydride, hydrogen may be bonded to the low-dimensional compound itself selected from the group consisting of Chemical Formulas 4 to 6, but is not limited thereto.
  • the metal elements (X, Y, and Z of Formulas 4 to 6) of the low-dimensional compound and a hydrogen ion (H ⁇ ) may be combined.
  • the hydride according to the present application refers to a material in which hydrogen ions of H ⁇ exist in the empty space between the lattice structures and at the same time include a bond with hydrogen.
  • the symmetry of the crystal structure of the electron nitride and the symmetry of the crystal structure of the hydride may be different from each other, but the present disclosure is not limited thereto.
  • the hydride and the hydride may have the same lattice structure on the Bravais lattice, but the hydride is generated by combining the electrons with hydrogen and replacing interstitial electrons with hydrogen at the same time.
  • Silver may have different symmetry with the electron material due to bonding and substitution with the hydrogen.
  • the symmetry of the crystal structure refers to a space group.
  • the symmetry of the crystal structure of the electron nitride is R3-m
  • the symmetry of the crystal structure of the hydride may be P3-m1, but is not limited thereto.
  • the hydride may have the form of a single crystal, a polycrystal, or a thin film, but is not limited thereto.
  • the hydride since the hydride has a structure in which electrons having a one-dimensional or two-dimensional structure, and electrons disposed in the lattice structure of the one-dimensional or two-dimensional structure are substituted with hydrogen, the hydride has the above formula
  • a thin film made of one or more compounds selected from the group consisting of 1 to 3 may have a laminated form.
  • the hydride and the electron hydride may be subjected to thermal carbon bonding spectroscopy to determine whether the hydride contains hydrogen.
  • the thermal desorption spectroscopic analysis may analyze hydrogen desorbed from the sample when the sample is heated.
  • the ionic conductivity of the hydride may be 0.1 S/cm to 3 S/cm, but is not limited thereto.
  • the ionic conductivity of the hydride is about 0.1 S/cm to about 3 S/cm, about 0.2 S/cm to about 3 S/cm, about 0.3 S/cm to about 3 S/cm, about 0.4 S /cm to about 3 S/cm, about 0.5 S/cm to about 3 S/cm, about 0.6 S/cm to about 3 S/cm, about 0.7 S/cm to about 3 S/cm, about 0.8 S/cm to about 3 S/cm, from about 0.9 S/cm to about 3 S/cm, from about 1 S/cm to about 3 S/cm, from about 1.25 S/cm to about 3 S/cm, from about 1.5 S/cm to about 3 S/cm, about 1.75 S/cm to about 3 S/cm
  • the ionic conductivity of the conventional electron oxide or hydride is known to be less than 0.5 S/cm, but the ionic conductivity of the hydride according to the present application is 0.1 S/cm to 3 S/cm, which is higher than that of the conventional electron oxide or hydride. can have In this regard, the ionic conductivity of the hydride may increase or decrease depending on the environment in which the hydride is disposed or the temperature of the hydride.
  • a second aspect of the present application comprises the steps of preparing one or more low-dimensional electron materials selected from the group consisting of the following Chemical Formulas 4 to 6; And it relates to a method for producing a hydride comprising the step of heat-treating the low-dimensional electron hydrate in a hydrogen gas atmosphere:
  • X is Sc, Y, La, Ce, Eu, Gd, Tb, Dy, Ho or Er
  • Y is Ca, Sr, or Ba
  • Z is Ti, Zr or Hf, and W is O, S or Se).
  • one or more low-dimensional electron materials selected from the group consisting of Chemical Formulas 4 to 6 are prepared.
  • the low-dimensional electron oxide may be prepared by mixing a metal element (X, Y, or Z) and a non-metal element (C, N, W) in a 2:1 ratio and then melting,
  • a metal element X, Y, or Z
  • a non-metal element C, N, W
  • the present invention is not limited thereto.
  • the low-dimensional electronized material is heat-treated in a hydrogen gas atmosphere.
  • the step of heat-treating the low-dimensional electron material in a hydrogen gas atmosphere electrons disposed between the lattice structure of the low-dimensional electron material are replaced with hydrogen, or the low-dimensional electron material and hydrogen may be combined, but is not limited thereto.
  • the low-dimensional electron oxide is heat-treated in a hydrogen gas atmosphere, so that interstitial electrons are replaced with H ⁇ , and at the same time, hydrogen ions may be bonded to a metal element (X, Y, or Z) of the electron oxide. In this case, the substitution of the electrons and the bonding of the metal element and hydrogen may occur at the same time.
  • a portion of the hydrogen gas may be combined with the metal element of the low-dimensional electron material, and the other portion may be substituted with electrons disposed between the lattice structures of the low-dimensional electron material.
  • the hydrogen gas atmosphere may further include an inert gas, but is not limited thereto.
  • the hydrogen gas atmosphere may include Ar, but is not limited thereto.
  • the hydrogen gas atmosphere may further include an inert gas such as N 2 , but is not limited thereto.
  • the heat treatment may be performed at 100° C. to 1,500° C., but is not limited thereto.
  • the heat treatment may include about 100°C to about 1,500°C, about 200°C to about 1,500°C, about 300°C to about 1,500°C, about 400°C to about 1,500°C, about 500°C to about 1,500°C, about 600°C to about 1,500°C, about 700°C to about 1,500°C, about 800°C to about 1,500°C, about 900°C to about 1,500°C, about 1,000°C to about 1,500°C, about 1,100°C to about 1,500°C, about 1,200°C to about 1,500 °C, about 1,300 °C to about 1,500 °C, about 1,400 °C to about 1,500 °C, about 100 °C to about 200 °C, about 100 °C to about 300 °C, about 100 °C to about 400 °C, about 100 °C to about 500°C,
  • the low-dimensional electrons are thermally decomposed by high energy, or the amount of hydrogen injected into the low-dimensional electrons exits to the outside of the low-dimensional electrons. Problems such as an increase in the amount of hydrogen may occur.
  • the temperature of the heat treatment is less than 100° C., the interstitial electrons may not be replaced with hydrogen because the thermal energy is low, so that hydrogen is not injected into the low-dimensional electronic material.
  • a third aspect of the present application relates to a hydrogen ion conductor comprising the hydride according to the first aspect.
  • the hydrogen ion conductor may be selected from the group consisting of a hydrogen sensor, a water decomposition system, a fuel cell, a hydrogen ion battery, a hydrogen compressor, and combinations thereof, but is not limited thereto. .
  • the hydride has a higher hydrogen ion conductivity than a conventional electron oxide or hydride, it is suitable for devices that need to transfer, generate, or store hydrogen or hydrogen ions.
  • a two-dimensional Gd 2 C electronic material was prepared by melting and synthesizing raw materials quantitatively mixed with Gd and C at a molar ratio of 2 : 1 at a high temperature using an electric furnace for high temperature of 1000° C. or higher, and cooling the mixture. At this time, the synthesis atmosphere was conducted in an inert gas or a vacuum atmosphere having a pressure of 10 -1 Torr or less.
  • the synthesized electron material was processed into pellets in a glove box in an argon gas atmosphere to prepare a sample. Then, the prepared sample was loaded into a tubular electric furnace, and heated at a temperature of 300° C. for 24 hours while flowing a hydrogen/argon mixed gas, and hydrogen was injected into the two-dimensional Gd 2 C electron material.
  • FIG 3 is a photograph of a hydride according to an embodiment of the present application, Gd 2 CH x is taken, and Figure 4 is a photograph taken of a facility for measuring the ionic conductivity of the Gd 2 CH x .
  • a raw material prepared by quantitatively mixing Ca and Ca 3 N 2 in a molar ratio of 1:1 was reacted in an electric furnace for high temperature of 800° C. or higher, and then cooled to prepare Ca 2 N electronized material.
  • the Ca 2 N was carried out under an inert gas or a pressure of 10 -3 Torr or less.
  • the synthesized electron material is processed into pellets in a glove box in an argon gas atmosphere to prepare a sample, and then the prepared sample is loaded into a tubular electric furnace, and a hydrogen and argon mixed gas is flowed thereto for 24 hours at a temperature of 300°C. Hydrogen was injected into the interior of the two-dimensional Ca 2 N electrons by heating during
  • Hf and S were mixed at a molar ratio of 2: 1, pelletized, vacuum sealed in a silica tube, and then sintered at 500° C. for 50 to 70 hours in an electric furnace. Then, the heat-treated mixture was put into an arc melting facility, and melted and cooled at a temperature of 1,000° C. or higher under an argon atmosphere to prepare a two-dimensional Hf 2 S electride.
  • the synthesized electron material was processed into pellets in a glove box in an argon gas atmosphere to prepare a sample. Then, the prepared sample was loaded into a tubular electric furnace, and heated at a temperature of 300° C. for 24 hours while flowing a hydrogen/argon mixed gas, and hydrogen was injected into the two-dimensional Hf 2 S electron material.
  • 5 is a graph of the result of thermal desorption spectroscopy measurement of the amount of hydrogen contained in the hydride according to an embodiment of the present application.
  • thermal desorption spectroscopy analysis was performed. At this time, when the heat treatment temperature is 300 °C, it can be confirmed that the hydrogen injection degree is higher than when the heat treatment at 700 °C. It was confirmed that hydrogen was actually injected into the low-dimensional electrons through the heat treatment in a hydrogen atmosphere, and it was confirmed that the amount of hydrogen contained in the sample was changed according to the heat treatment temperature in the hydrogen atmosphere.
  • FIG. 6 is a graph showing a result of X-ray diffraction analysis of a crystal structure change before and after hydrogen injection of a hydride according to an embodiment of the present application.
  • the XRD peak is changed by heat treatment of Gd 2 C in a hydrogen gas atmosphere, it can be confirmed that Gd 2 CH x and Gd 2 C have different symmetric structures.
  • FIG. 7 shows the ionic conductivity of a hydride according to an embodiment of the present application.
  • the ionic conductivity of the hydride Gd 2 CH x is ⁇ 2.5 S/cm at 200° C., which means that it has a significantly larger value than the previously reported conductivity of hydrogen ion conductors.

Abstract

La présente invention concerne un hydrure comprenant au moins un composé choisi dans le groupe constitué par les formules chimiques 1 à 3, un électron contenu dans un électrure étant substitué par de l'hydrogène.
PCT/KR2022/004504 2021-04-01 2022-03-30 Hydrure et son procédé de préparation WO2022211488A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2021-0042497 2021-04-01
KR20210042497 2021-04-01
KR10-2021-0165300 2021-11-26
KR1020210165300A KR102639462B1 (ko) 2021-04-01 2021-11-26 수소화물 및 이의 제조 방법

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160361712A1 (en) * 2014-02-27 2016-12-15 Japan Science And Technology Agency Supported metal catalyst and method of synthesizing ammonia using the same
KR20200060284A (ko) * 2018-11-21 2020-05-29 성균관대학교산학협력단 이차원 페리자성 전자화물 및 이의 제조방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160361712A1 (en) * 2014-02-27 2016-12-15 Japan Science And Technology Agency Supported metal catalyst and method of synthesizing ammonia using the same
KR20200060284A (ko) * 2018-11-21 2020-05-29 성균관대학교산학협력단 이차원 페리자성 전자화물 및 이의 제조방법

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ALTORFER, F. ; BUHRER, W. ; WINKLER, B. ; CODDENS, G. ; ESSMANN, R. ; JACOBS, H.: "H^--jump diffusion in barium-nitride-hydride Ba"2NH", SOLID STATE IONICS, NORTH HOLLAND PUB. COMPANY. AMSTERDAM; NL, NL, vol. 70-71, 1 May 1994 (1994-05-01), NL , pages 272 - 277, XP024657337, ISSN: 0167-2738, DOI: 10.1016/0167-2738(94)90322-0 *
BAI QIANG, HE XINGFENG, ZHU YIZHOU, MO YIFEI: "First-Principles Study of Oxyhydride H – Ion Conductors: Toward Facile Anion Conduction in Oxide-Based Materials", ACS APPLIED ENERGY MATERIALS, vol. 1, no. 4, 23 April 2018 (2018-04-23), pages 1626 - 1634, XP055972265, ISSN: 2574-0962, DOI: 10.1021/acsaem.8b00077 *
KURA CHIHARU, FUJIMOTO SHO, KUNISADA YUJI, KOWALSKI DAMIAN, TSUJI ETSUSHI, ZHU CHUNYU, HABAZAKI HIROKI, AOKI YOSHITAKA: "Enhanced hydrogen permeability of hafnium nitride nanocrystalline membranes by interfacial hydride conduction", JOURNAL OF MATERIALS CHEMISTRY A, ROYAL SOCIETY OF CHEMISTRY, GB, vol. 6, no. 6, 1 January 2018 (2018-01-01), GB , pages 2730 - 2741, XP055972262, ISSN: 2050-7488, DOI: 10.1039/C7TA10253D *

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