Carbon-based hydrogen storage material having autocatalytic capability, production method thereof, and hydrogen adsorbing—storing method, hydrogen releasing method, and hydrogen adsorption—storage device using thereof

Patent metadata

Field	Value
Publication number	US-11072524-B2
Application number	US-201916288252-A
Country	US
Kind code	B2
Filing date	Feb 28, 2019
Priority date	Aug 31, 2016
Publication date	Jul 27, 2021
Grant date	Jul 27, 2021

Abstract

The objective of the present invention is to provide a carbon-based hydrogen storage material having an autocatalytic capability and an atomic vacancy, wherein the hydrogen storage is a hydrocarbon compound which produces a non-endothermic release or an exothermic release of hydrogen adsorbed in the compound. In addition, the present invention provides a method of manufacturing the material comprising: preparing a hydrocarbon compound as the raw material of the carbon-based hydrogen storage material; setting the raw material in a container having a predetermined gas partial pressure; producing the hydrocarbon compound by ion beam irradiation of the raw material; performing annealing treatment under the predetermined conditions; and exposing the product to the hydrogen under the predetermined conditions, wherein the product is a hydrogen storage hydrocarbon compound producing a non-endothermic or an exothermic release of hydrogen adsorbed thereto with autocatalysis activity.

First claim

The invention claimed is:

1. A carbon-based hydrogen storage material with a triply hydrogenated vacancy (V 111 ) structure as a catalytic capability point for adsorbing a hydrogen molecule and dissociated hydrogens therefrom as autocatalysis,
wherein the hydrogen storage material is a hydrocarbon compound which produces a non-endothermic release or an exothermic release of hydrogen adsorbed in the compound,
wherein the hydrogen storage material is manufactured by a method comprising the steps of:
preparing a hydrocarbon compound as a raw material of the carbon-based hydrogen storage material;
setting the raw material in a container having a gas at a partial pressure from 0.5×10 −7 to 0.5×10 2 Pa, wherein the gas has reaction activity with the hydrocarbon compound;
producing the hydrocarbon compound having an atomic vacancy by ion beam irradiation of the hydrocarbon compound, and performing an annealing treatment for 2 to 5 seconds at a temperature from 550 to 650° C.;
activating the hydrogen molecules in the container using an arc-shaped filament producing a temperature from 2000 to 2400° C.;
exposing the hydrocarbon compound having an atomic vacancy to the activated hydrogen from 5 to 10 seconds at a temperature from 800 to 1000° C.,
wherein the hydrocarbon compound adsorbs the hydrogen molecule at a pressure from 0.5×10 −3 to 15 MPa, thereby producing the hydrogen storage material.

2. The carbon-based hydrogen storage material according to claim 1 ,
wherein the hydrogen storage hydrocarbon compound consists of carbon and hydrogen.

3. The carbon-based hydrogen storage material according to claim 1 , wherein the hydrogen storage hydrocarbon compound is a graphene or a nanographene.

4. The carbon-based hydrogen storage material according to claim 3 , wherein the graphene or the nanographene is selected from the group consisting of: a C 59 segment, a C 59 segment having an alkyl group, and a C 131 segment.

5. The carbon-based hydrogen storage material according to claim 1 , wherein a releasing adsorption activation barrier of the hydrogen storage hydrocarbon compound is smaller than 2 eV.

6. The carbon-based hydrogen storage material according to claim 5 , wherein the releasing adsorption activation barrier of the hydrogen storage hydrocarbon compound is 1.3 eV or smaller.

7. The carbon-based hydrogen storage material according to claim 1 , wherein the hydrogen storage hydrocarbon compound releases and/or adsorbs more than two hydrogen molecules per catalytic capability point.

8. A method of manufacturing a carbon-based hydrogen storage material with a triply hydrogenated vacancy (V 111 ) structure as a catalytic capability point for adsorbing a hydrogen molecule and dissociated hydrogens therefrom as autocatalysis, comprising the steps of:
preparing a hydrocarbon compound as a raw material of the carbon-based hydrogen storage material;
setting the raw material in a container having a gas with a partial pressure from 0.5×10 −7 to 0.5×10 2 Pa, wherein the gas has reaction activity with the hydrocarbon compound;
producing the hydrocarbon compound having an atomic vacancy by ion beam irradiation of the hydrocarbon compound, and performing an annealing treatment for 2 to 5 seconds at a temperature from 550 to 650° C.;
activating hydrogen molecules in the container using an arc-shaped filament having the temperature from 2000 to 2400° C.; and
exposing the hydrocarbon compound having an atomic vacancy to the activated hydrogen for 5 to 10 seconds at a temperature from 800 to 1000° C.,
wherein the hydrocarbon compound adsorbs the hydrogen molecule at a pressure from 0.5×10 −3 to 15 MPa, thereby producing the carbon-based hydrogen storage material; and
wherein the carbon-based hydrogen storage material is a hydrocarbon compound which produces a non-endothermic release or an exothermic release of hydrogen adsorbed in the compound.

9. The method according to claim 8 , wherein the hydrocarbon compound is graphene or its analog.

10. The method according to claim 8 ,
wherein the ion beam is selected from the group consisting of: an Argon ion beam, a Helium ion beam, a Krypton ion beam, and a Xenon ion beam.

11. The method according to claim 10 ,
wherein the Argon ion beam is irradiated, thus having an irradiation time from 2 to 5 seconds at an irradiation power from 80 to 110 eV.

12. A method of storing hydrogen, comprising storing hydrogen to the carbon-based hydrogen storage material according to claim 1 at a pressure from 0.5×10 −3 to 15 MPa.

13. A method of releasing hydrogen from a carbon-based hydrogen storage material, comprising heating the carbon-based hydrogen storage material having a V 111 structure as a catalytic capability point for adsorbing a hydrogen molecule and dissociated hydrogens therefrom as autocatalysis, wherein the hydrogen storage material is a hydrocarbon compound which produces a non-endothermic release or an exothermic release of hydrogen adsorbed in the compound for releasing hydrogen at a pressure from 0.5×10 −3 to 15 MPa, the heating time being from 0.5×10 −9 to 0.5×10 3 seconds at a temperature from 0.5×10 2 to 0.5×10 3 ° C.

14. A hydrogen storage device comprising:
a container including: a hydrogen storage element constituted by the carbon-based hydrogen storage material having a V 111 structure as a catalytic capability point for adsorbing a hydrogen molecule and dissociated hydrogens therefrom as autocatalysis, wherein the hydrogen storage material is a hydrocarbon compound which produces a non-endothermic release or an exothermic release of hydrogen adsorbed in the compound and a hydrogen supply/outlet port, forming a sealed internal space in a condition that the hydrogen storage element is accommodated;
a pressure control device controlling a pressure in the container; and
a temperature control device controlling a temperature in the container,
wherein the hydrogen supply/outlet port has a safety valve.

15. The hydrogen storage device according to claim 14 ,
wherein hydrogen is stored in the hydrogen storage element through a temperature control of the container by the temperature control device in addition to a pressurization control by the pressure control device.

16. The hydrogen storage device according to claim 14 ,
wherein the pressure control device gives an atmospheric pressure in the container, and in addition, a heating controlling of an inside of the container starts a release of hydrogen adsorbed in the hydrogen storage device, and after the start of the release, the temperature control device controls a temperature of the inside of the container and also controls a speed of releasing hydrogen adsorbed in the carbon-based hydrogen storage material.

17. The hydrogen storage device according to claim 14 , further comprising a voltage applying device applying a voltage to both sides of a plate type member consisting of the carbon-based hydrogen storage material and substrate material,
wherein the voltage applying device can reverse the polarity of the applied voltage.

18. The hydrogen storage device according to claim 17 , further comprising a vibration device vibrating the plate type member.

19. The hydrogen storage device according to claim 18 , further comprising a lighting device accelerating the hydrogen release by irradiating the plate type member, wherein the plate type member is selected from the group consisting of: an electromagnetic wave, an ultrasonic wave, and a particle beam.

Assignees

• Univ Osaka
• Fukuoka Institute Of Tech
• Univ Hosei

Inventors

• Kusakabe Koichi
• SUNNARDIANTO Gagus Ketut
• Enoki Toshiaki
• Maruyama Isao
• Takai Kazuyuki

Classifications

• Y02E60/32

  Hydrogen storage · CPC title

• C01B32/184

  Preparation · CPC title

• C01B3/0021 Primary

  Elemental carbon, e.g. active carbon, carbon nanotubes or fullerenes · CPC title

• F17C11/00

  Use of gas-solvents or gas-sorbents in vessels {(absorbing compositions for acetylene C10L3/04; absorbing compositions for hydrogen C01B3/0005)} · CPC title

• Y02P90/45

  Hydrogen technologies in production processes · CPC title