WO2023049952A1 - Battery module for direct air capture of carbon dioxide - Google Patents

Battery module for direct air capture of carbon dioxide Download PDF

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Publication number
WO2023049952A1
WO2023049952A1 PCT/AU2022/050899 AU2022050899W WO2023049952A1 WO 2023049952 A1 WO2023049952 A1 WO 2023049952A1 AU 2022050899 W AU2022050899 W AU 2022050899W WO 2023049952 A1 WO2023049952 A1 WO 2023049952A1
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Prior art keywords
electrodes
battery module
gas diffusion
pair
mof
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PCT/AU2022/050899
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French (fr)
Inventor
Rohan Gillespie
Deanna D’Alessandro
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Southern Green Gas Limited
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Publication date
Priority claimed from AU2021903101A external-priority patent/AU2021903101A0/en
Application filed by Southern Green Gas Limited filed Critical Southern Green Gas Limited
Priority to AU2022354313A priority Critical patent/AU2022354313A1/en
Publication of WO2023049952A1 publication Critical patent/WO2023049952A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0454—Controlling adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C25B11/032—Gas diffusion electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention is broadly directed to a battery module for direct air capture of carbon dioxide (CO2).
  • the invention is also generally directed to a method of fabricating a battery module for direct air capture of CO2 as well as method of directly capturing CO2 from air.
  • Direct air capture (DAC) of CO2 from atmosphere represents a challenging task given its ultra-dilute concentration in air at around 0.04 percent. Separation of CO2 from other components including N2, O2, Ar, H2O etc. thus requires a process that is highly selective with minimal energy cost.
  • Current mechanisms known for separating CO2 from a gaseous mixture such as air include electrical swing adsorption (ESA) which is based on thermal heating of a material in response to an electrical stimulus. It is understood that these current mechanisms are not sufficiently selective in enabling the separation of CO2 from air or other gaseous mixtures.
  • ESA electrical swing adsorption
  • a battery module for direct air capture of carbon dioxide (CO2) comprising: a pair of gas diffusion electrodes each formed of an electroactive metalorganic framework (MOF) structure produced by additive manufacturing; an electrolyte including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes to facilitate ion and charge transfer between said electrodes whereby (i) in an adsorption mode, a predetermined potential applied to the electrodes is effective in the electroactive MOF structure of said electrodes directly adsorbing CO2 from air exposed to the battery module, and (ii) in a desorption mode, a change in the predetermined potential applied to or reversal in the polarity of said electrodes is effective in releasing adsorbed CO2 from the electroactive MOF structure of said electrodes.
  • MOF electroactive metalorganic framework
  • a method of manufacturing a battery module for direct capture of carbon dioxide (CO2) from air comprising the steps of: forming a pair of gas diffusion electrodes by additive manufacturing of an electroactive metal-organic framework (MOF) structure; associating an electrolyte with the pair of gas diffusion electrodes, said electrolyte including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes to facilitate ion and charge transfer between said electrodes whereby (i) in an adsorption mode, a predetermined potential applied to the gas diffusion electrodes is effective in the electroactive MOF structure of said electrodes directly adsorbing CO2 from air exposed to the batter module, and (ii) in a desorption mode, a change in the predetermined potential applied to or reversal in the polarity of said electrodes is effective in releasing adsorbed CO2 from the electroactive MOF structure of said electrodes.
  • MOF electroactive metal-organic framework
  • a method of directly capturing carbon dioxide (CO2) from air comprising the steps of: exposing air to a battery module including (i) a pair of gas diffusion electrodes each formed of an electroactive metal-organic framework (MOF) structure produced by additive manufacturing, and (ii) an electrolyte arranged to cooperate with the pair of electrodes; in an adsorption mode, applying a predetermined potential to the gas diffusion electrodes thereby enabling the electroactive MOF structure of said electrodes to directly adsorb CO2 from the air exposed to the battery module; in a desorption mode, changing the predetermined potential applied to or reversing the polarity of said electrodes thereby enabling release of the adsorbed CO2 from the electroactive MOF structure of said electrodes.
  • a battery module including (i) a pair of gas diffusion electrodes each formed of an electroactive metal-organic framework (MOF) structure produced by additive manufacturing, and (ii) an electrolyte arranged to cooperate with the pair of electrodes; in an adsorption mode, applying
  • the battery module is of an interdigitated configuration wherein one of the pair of gas diffusion electrodes forms an anode structure, and an other of said pair of electrodes forms a cathode structure arranged to cooperate with the anode structure in a meshed relationship.
  • the anode and cathode structures each include a plurality of plates or discs arranged in the meshed relationship.
  • the electrolyte separates the anode and cathode structures to facilitate ion and charge transfer between the pair of gas diffusion electrodes.
  • the MOF structure of the pair of gas diffusion electrodes is zirconium-based and incorporates chemical functionalities for selective and reversible reactions with CO2. More preferably the chemical functionalities include but are not limited to quinone, phenazine, ferrocenyl groups or combinations thereof. Still more preferably the Zr-based MOF structure provides topologically-matched materials for the pair of gas diffusion electrodes thereby ensuring that ion diffusion and charge transfer kinetics are well-matched between the anode and cathode structures.
  • the electroactive MOF structure of the pair of gas diffusion electrodes is 3D printed by robocasting or Direct Ink Writing (DIW) of a composite paste mixture including a MOF compound.
  • the composite paste mixture includes the MOF compound in the form of zirconium clusters together with chemical functionalities for CO2 adsorption, a carbon-based conductive material, binders, and/or plasticizers.
  • the zirconium clusters include UiO- 66, UiO-67, UiO-68, or combinations thereof.
  • the binders are derivatives of bentonite or kaolinite clay, and the plasticizers are selected to modulate the shear modulus of the composite paste mixture.
  • FIG. 1 schematically depicts a battery module of a preferred embodiment of first and second aspects of the invention.
  • Figure 1 also schematically illustrates a method of directly capturing CO2 from air according to a preferred embodiment of a third aspect of the invention.
  • FIG. 1 there is a battery module 10 constructed in accordance with a preferred embodiment of first and second aspects of the invention.
  • the battery module 10 functions in accordance with a preferred embodiment of a third aspect of the invention for directly capturing CO2 from air.
  • the battery module 10 of this embodiment comprises:
  • a pair of gas diffusion electrodes 12 and 14 each formed of an electroactive metal-organic framework (MOF) structure produced by additive manufacturing;
  • an electrolyte 16 including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes 12 and 14 to facilitate ion and charge transfer between said electrodes 12 and 14.
  • the battery module 10 is configured to operate in an adsorption mode where a predetermined potential applied to the electrodes 12/14 is effective in the electroactive MOF structure of the electrodes 12/14 directly adsorbing CO2 from air 18 exposed to the battery module 10.
  • the battery module 10 is also configured to function in a desorption mode where a change in the predetermined potential applied to, or reversal in the polarity of, the electrodes 12/14 is effective in releasing adsorbed CO2 at 22 from the electroactive MOF structure of the electrodes 12/14.
  • the battery module 10 operating in its adsorption mode is depicted on the left hand side of the accompanying figure 1 whereas the same battery module 10 operating in its desorption mode is shown on the right hand side.
  • the battery module 10 is of an interdigitated configuration wherein a first of the pair of gas diffusion electrodes 12 in an adsorption mode functions as an anode structure.
  • the second of the pair of gas diffusion electrodes 14 in the absorption mode functions as a cathode structure arranged to cooperate with the anode structure in a meshed relationship.
  • the first of the pair of gas diffusion electrodes 12 may include a plurality of finger elements such as 12a to 12t extending laterally outward from a common spinal element 20.
  • the plurality of finger elements such as 12a may be formed as a plurality of plates or discs extending outwardly from the common spinal element 20.
  • the second of the gas diffusion electrodes may be formed in a plurality of finger elements such as 14a to 14t extending inwardly of a common shell 22.
  • the finger elements such as 14a of the second of the pair of gas diffusion electrodes 14 may also take the form of a plurality of plates or discs each of an annular configuration designed to mesh with finger elements such as 12a and 12b of the first of the pair of gas diffusion electrodes 12.
  • the battery module 10 of the preferred construction includes the electrolyte 16 in the form of the ionic or polyionic liquid separating the anode and cathode structures such as 12 and 14 operating in an adsorption mode. It will be understood that the electrolyte 16 facilitates ion and charge transfer between the pair of gas diffusion electrodes 12 and 14 in permitting and controlling selective and reversible electrochemical-chemical reactions between CO2 and the electroactive MOF structures of the pair of gas diffusion electrodes 12 and 14.
  • the electroactive MOF structure of the pair of gas diffusion electrodes 12 and 14 is zirconium-based and incorporates chemical functionalities for selective and reversible reactions with CO2.
  • the chemical functionality of this example is a quinone compound although it is to be understood that the chemical functionalities may extend to phenazine, ferrocenyl groups, or combinations thereof.
  • the Zr-based MOF structure provides topologically-matched materials for the pair of gas diffusion electrodes 12 and 14. This topological matching of the additively manufactured electroactive MOF structure is understood to ensure that ion diffusion and charge transfer kinetics are well-matched between the anode and cathode structures.
  • the electroactive MOF structure of the pair of gas diffusion electrodes 12 and 14 is 3D printed by robocasting or Direct Ink Writing (DIW) of a composite paste mixture.
  • the composite paste mixture of this example includes:
  • MOF compound typically in the form of a zirconium cluster at approximately 50-70% w/w;
  • one or more chemical functionalities such as a quinone compound for CO2 adsorption at approximately 5-25% w/w;
  • binders typically being derivatives of bentonite or kaolinite clay at approximately 5-15% w/w;
  • the zirconium clusters of the selected MOF compound from which the pair of gas diffusion electrodes 12 and 14 are additively manufactured include but are not limited to UiO-66, UiO-67, UiO-68, or combinations thereof. It is to be understood that the composition of the composite paste mixture from which the electroactive MOF structure is 3D printed will be tuned depending on a range of functional considerations including:
  • conductivity versus heat where the heat generated may be dependent on electrode potentials which are expected to be relatively low at for example one (1) Volt or less.
  • a battery module 10 for direct air capture of CO2 from air there is a method of manufacturing a battery module 10 for direct air capture of CO2 from air.
  • the method broadly comprises the steps of:
  • a pair of gas diffusion electrodes such as 12 and 14 by additive manufacturing of an electroactive metal-organic framework (MOF) structure
  • the electrolyte 16 including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes 12 and 14 to facilitate ion and charge transfer between said electrodes 12/14.
  • this method broadly comprises the steps of :
  • the predetermined potential applied to the gas diffusion electrodes 12/14 will be relatively low, typically around 1 V or less.
  • the desorption mode it is expected that either by changing the predetermined potential applied to, or reversing the polarity of, said electrodes 12/14 the applied electrode potentials will remain relatively low.
  • the battery module enables selective separation of CO2 from air with minimal energy costs relative to traditional methods such amine-impregnated MOFs that are based on temperature swing mechanisms for adsorption and desorption;
  • electrochemical swing adsorption exploits the redox activity (also called “electroactivity”) of electroactive MOF structures of gas diffusion electrodes in the adsorption and desorption of CO2;
  • ECSA is enabled by additive printing of gas diffusion electrodes of an electroactive MOF structure providing free-standing electrodes which permit selective and reversible electrochemical-chemical reactions between CO2 and chemical functionalities within the electroactive MOF structure;
  • the battery module provides relatively high CO2 adsorption capacity where volumetric capacity is particularly relevant and practical for stationary applications;
  • the battery module and other aspects of the technology provide relatively easy electrochemical regeneration conditions at relatively low energy costs
  • the battery module provides high tolerance to humidity in terms of both the framework stability and adsorption performance of the associated gas diffusion electrodes reducing atmospheric water competition with CO2 adsorption.
  • the battery module may in its construction involve post synthetic modification to incorporate the required chemical functionalities for selective and reversible reactions with CO2.
  • the “chemistry” of the electroactive MOF structure may vary from the preferred embodiment provided it lends itself to additive manufacturing and is effective in both adsorption and desorption of CO2 utilising ECSA.

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Abstract

The present invention is broadly directed to a battery module (10) comprising: 1. a pair of gas diffusion electrodes (12) and (14) each formed of an electroactive metal-organic framework (MOF) structure produced by additive manufacturing; 2. an electrolyte (16) including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes (12) and (14) to facilitate ion and charge transfer between said electrodes (12) and (14).

Description

BATTERY MODULE FOR DIRECT AIR CAPTURE OF CARBON DIOXIDE
Technical Field
[0001 ] The present invention is broadly directed to a battery module for direct air capture of carbon dioxide (CO2). The invention is also generally directed to a method of fabricating a battery module for direct air capture of CO2 as well as method of directly capturing CO2 from air.
Background
[0002] Direct air capture (DAC) of CO2 from atmosphere represents a challenging task given its ultra-dilute concentration in air at around 0.04 percent. Separation of CO2 from other components including N2, O2, Ar, H2O etc. thus requires a process that is highly selective with minimal energy cost. Current mechanisms known for separating CO2 from a gaseous mixture such as air include electrical swing adsorption (ESA) which is based on thermal heating of a material in response to an electrical stimulus. It is understood that these current mechanisms are not sufficiently selective in enabling the separation of CO2 from air or other gaseous mixtures.
Summary of Invention
[0003] According to a first aspect of the present invention there is provided a battery module for direct air capture of carbon dioxide (CO2), said module comprising: a pair of gas diffusion electrodes each formed of an electroactive metalorganic framework (MOF) structure produced by additive manufacturing; an electrolyte including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes to facilitate ion and charge transfer between said electrodes whereby (i) in an adsorption mode, a predetermined potential applied to the electrodes is effective in the electroactive MOF structure of said electrodes directly adsorbing CO2 from air exposed to the battery module, and (ii) in a desorption mode, a change in the predetermined potential applied to or reversal in the polarity of said electrodes is effective in releasing adsorbed CO2 from the electroactive MOF structure of said electrodes. [0004] According to a second aspect of the invention there is provided a method of manufacturing a battery module for direct capture of carbon dioxide (CO2) from air, said method comprising the steps of: forming a pair of gas diffusion electrodes by additive manufacturing of an electroactive metal-organic framework (MOF) structure; associating an electrolyte with the pair of gas diffusion electrodes, said electrolyte including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes to facilitate ion and charge transfer between said electrodes whereby (i) in an adsorption mode, a predetermined potential applied to the gas diffusion electrodes is effective in the electroactive MOF structure of said electrodes directly adsorbing CO2 from air exposed to the batter module, and (ii) in a desorption mode, a change in the predetermined potential applied to or reversal in the polarity of said electrodes is effective in releasing adsorbed CO2 from the electroactive MOF structure of said electrodes.
[0005] According to a third aspect of the invention there is provided a method of directly capturing carbon dioxide (CO2) from air, said method comprising the steps of: exposing air to a battery module including (i) a pair of gas diffusion electrodes each formed of an electroactive metal-organic framework (MOF) structure produced by additive manufacturing, and (ii) an electrolyte arranged to cooperate with the pair of electrodes; in an adsorption mode, applying a predetermined potential to the gas diffusion electrodes thereby enabling the electroactive MOF structure of said electrodes to directly adsorb CO2 from the air exposed to the battery module; in a desorption mode, changing the predetermined potential applied to or reversing the polarity of said electrodes thereby enabling release of the adsorbed CO2 from the electroactive MOF structure of said electrodes.
[0006] Preferably the battery module is of an interdigitated configuration wherein one of the pair of gas diffusion electrodes forms an anode structure, and an other of said pair of electrodes forms a cathode structure arranged to cooperate with the anode structure in a meshed relationship. More preferably the anode and cathode structures each include a plurality of plates or discs arranged in the meshed relationship. In each of these embodiments the electrolyte separates the anode and cathode structures to facilitate ion and charge transfer between the pair of gas diffusion electrodes.
[0007] Preferably the MOF structure of the pair of gas diffusion electrodes is zirconium-based and incorporates chemical functionalities for selective and reversible reactions with CO2. More preferably the chemical functionalities include but are not limited to quinone, phenazine, ferrocenyl groups or combinations thereof. Still more preferably the Zr-based MOF structure provides topologically-matched materials for the pair of gas diffusion electrodes thereby ensuring that ion diffusion and charge transfer kinetics are well-matched between the anode and cathode structures.
[0008] Preferably the electroactive MOF structure of the pair of gas diffusion electrodes is 3D printed by robocasting or Direct Ink Writing (DIW) of a composite paste mixture including a MOF compound. More preferably the composite paste mixture includes the MOF compound in the form of zirconium clusters together with chemical functionalities for CO2 adsorption, a carbon-based conductive material, binders, and/or plasticizers. Even more preferably the zirconium clusters include UiO- 66, UiO-67, UiO-68, or combinations thereof. Still more preferably the binders are derivatives of bentonite or kaolinite clay, and the plasticizers are selected to modulate the shear modulus of the composite paste mixture.
Brief Description of Drawings
[0009] In order to achieve a better understanding of the nature of the present invention a preferred embodiment of a battery module for direct air capture of carbon dioxide (CO2) together with other aspects of the technology will now be described, by way of example only. The accompanying figure 1 schematically depicts a battery module of a preferred embodiment of first and second aspects of the invention.
Figure 1 also schematically illustrates a method of directly capturing CO2 from air according to a preferred embodiment of a third aspect of the invention.
Detailed Description
[0010] As seen in figure 1 , there is a battery module 10 constructed in accordance with a preferred embodiment of first and second aspects of the invention. The battery module 10 functions in accordance with a preferred embodiment of a third aspect of the invention for directly capturing CO2 from air.
[0011 ] The battery module 10 of this embodiment comprises:
1 . a pair of gas diffusion electrodes 12 and 14 each formed of an electroactive metal-organic framework (MOF) structure produced by additive manufacturing;
2. an electrolyte 16 including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes 12 and 14 to facilitate ion and charge transfer between said electrodes 12 and 14.
[0012] The battery module 10 is configured to operate in an adsorption mode where a predetermined potential applied to the electrodes 12/14 is effective in the electroactive MOF structure of the electrodes 12/14 directly adsorbing CO2 from air 18 exposed to the battery module 10. The battery module 10 is also configured to function in a desorption mode where a change in the predetermined potential applied to, or reversal in the polarity of, the electrodes 12/14 is effective in releasing adsorbed CO2 at 22 from the electroactive MOF structure of the electrodes 12/14. The battery module 10 operating in its adsorption mode is depicted on the left hand side of the accompanying figure 1 whereas the same battery module 10 operating in its desorption mode is shown on the right hand side.
[0013] In this embodiment the battery module 10 is of an interdigitated configuration wherein a first of the pair of gas diffusion electrodes 12 in an adsorption mode functions as an anode structure. The second of the pair of gas diffusion electrodes 14 in the absorption mode functions as a cathode structure arranged to cooperate with the anode structure in a meshed relationship. The first of the pair of gas diffusion electrodes 12 may include a plurality of finger elements such as 12a to 12t extending laterally outward from a common spinal element 20. The plurality of finger elements such as 12a may be formed as a plurality of plates or discs extending outwardly from the common spinal element 20. The second of the gas diffusion electrodes may be formed in a plurality of finger elements such as 14a to 14t extending inwardly of a common shell 22. The finger elements such as 14a of the second of the pair of gas diffusion electrodes 14 may also take the form of a plurality of plates or discs each of an annular configuration designed to mesh with finger elements such as 12a and 12b of the first of the pair of gas diffusion electrodes 12.
[0014] The battery module 10 of the preferred construction includes the electrolyte 16 in the form of the ionic or polyionic liquid separating the anode and cathode structures such as 12 and 14 operating in an adsorption mode. It will be understood that the electrolyte 16 facilitates ion and charge transfer between the pair of gas diffusion electrodes 12 and 14 in permitting and controlling selective and reversible electrochemical-chemical reactions between CO2 and the electroactive MOF structures of the pair of gas diffusion electrodes 12 and 14.
[0015] In this embodiment the electroactive MOF structure of the pair of gas diffusion electrodes 12 and 14 is zirconium-based and incorporates chemical functionalities for selective and reversible reactions with CO2. The chemical functionality of this example is a quinone compound although it is to be understood that the chemical functionalities may extend to phenazine, ferrocenyl groups, or combinations thereof. The Zr-based MOF structure provides topologically-matched materials for the pair of gas diffusion electrodes 12 and 14. This topological matching of the additively manufactured electroactive MOF structure is understood to ensure that ion diffusion and charge transfer kinetics are well-matched between the anode and cathode structures.
[0016] In this embodiment the electroactive MOF structure of the pair of gas diffusion electrodes 12 and 14 is 3D printed by robocasting or Direct Ink Writing (DIW) of a composite paste mixture. The composite paste mixture of this example includes:
1 . a MOF compound typically in the form of a zirconium cluster at approximately 50-70% w/w;
2. one or more chemical functionalities such as a quinone compound for CO2 adsorption at approximately 5-25% w/w;
3. a carbon-based conductive material at approximately 0-10% w/w;
4. binders typically being derivatives of bentonite or kaolinite clay at approximately 5-15% w/w;
5. plasticisers typically selected to modulate the shear modulus of the composite paste mixture at approximately 5-10% w/w. [0017] In this embodiment the zirconium clusters of the selected MOF compound from which the pair of gas diffusion electrodes 12 and 14 are additively manufactured include but are not limited to UiO-66, UiO-67, UiO-68, or combinations thereof. It is to be understood that the composition of the composite paste mixture from which the electroactive MOF structure is 3D printed will be tuned depending on a range of functional considerations including:
1 . redox potentials suitable for effective operation of the battery module in its adsorption mode together with a change in the redox potential, or reversal in polarity, for operation of the battery module in its desorption mode;
2. reactant/product in the form of CO2 evolution as a function of time;
3. conductivity versus heat where the heat generated may be dependent on electrode potentials which are expected to be relatively low at for example one (1) Volt or less.
[0018] In a second aspect of the invention and in the context of the preferred embodiment, there is a method of manufacturing a battery module 10 for direct air capture of CO2 from air. The method broadly comprises the steps of:
1 . forming a pair of gas diffusion electrodes such as 12 and 14 by additive manufacturing of an electroactive metal-organic framework (MOF) structure;
2. associating an electrolyte 16 with the pair of gas diffusion electrodes 12 and 14, the electrolyte 16 including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes 12 and 14 to facilitate ion and charge transfer between said electrodes 12/14.
[0019] In a third aspect of the invention there is a method of directly capturing CO2 from air. In the context of the preferred embodiment, this method broadly comprises the steps of :
1 . exposing air at 18 to a battery module at 10;
2. in an adsorption mode (left hand side of the accompanying figure 1 ), applying a predetermined potential to the gas diffusion electrodes 12 and 14 thereby enabling the electroactive MOF structure of said electrodes 12/14 to directly adsorb CO2 from the air; 3. in a desorption mode (right hand side of the accompanying figure 1 ), changing the predetermined potential (or reversing the polarity) of said electrodes 12/14 thereby enabling release of the adsorbed CO2 at 22 from the electroactive MOF structure of the electrodes 12/14.
[0020] It is expected that in the adsorption mode the predetermined potential applied to the gas diffusion electrodes 12/14 will be relatively low, typically around 1 V or less. In the desorption mode it is expected that either by changing the predetermined potential applied to, or reversing the polarity of, said electrodes 12/14 the applied electrode potentials will remain relatively low.
[0021 ] Now that a preferred embodiment of the various aspects of the technology have been described it will be apparent to those skilled in the art that they have at least the following advantages:
1 . the battery module enables selective separation of CO2 from air with minimal energy costs relative to traditional methods such amine-impregnated MOFs that are based on temperature swing mechanisms for adsorption and desorption;
2. electrochemical swing adsorption (ECSA) exploits the redox activity (also called “electroactivity”) of electroactive MOF structures of gas diffusion electrodes in the adsorption and desorption of CO2;
3. ECSA is enabled by additive printing of gas diffusion electrodes of an electroactive MOF structure providing free-standing electrodes which permit selective and reversible electrochemical-chemical reactions between CO2 and chemical functionalities within the electroactive MOF structure;
4. the battery module provides relatively high CO2 adsorption capacity where volumetric capacity is particularly relevant and practical for stationary applications;
5. the battery module and other aspects of the technology provide relatively easy electrochemical regeneration conditions at relatively low energy costs;
6. the battery module provides high tolerance to humidity in terms of both the framework stability and adsorption performance of the associated gas diffusion electrodes reducing atmospheric water competition with CO2 adsorption. [0022] Those skilled in the art will appreciate that the invention as described herein is susceptible to variations and modifications other than those specifically described. For example, the battery module may in its construction involve post synthetic modification to incorporate the required chemical functionalities for selective and reversible reactions with CO2. The “chemistry” of the electroactive MOF structure may vary from the preferred embodiment provided it lends itself to additive manufacturing and is effective in both adsorption and desorption of CO2 utilising ECSA.
[0023] All such variations and modifications are to be considered within the scope of the present invention the nature of which is to be determined from the foregoing description.

Claims

9 Claims
1 . A battery module for direct air capture of carbon dioxide (CO2), said module comprising: a pair of gas diffusion electrodes each formed of an electroactive metal-organic framework (MOF) structure produced by additive manufacturing; an electrolyte including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes to facilitate ion and charge transfer between said electrodes whereby (i) in an adsorption mode, a predetermined potential applied to the electrodes is effective in the electroactive MOF structure of said electrodes directly adsorbing CO2 from air exposed to the battery module, and (ii) in a desorption mode, a change in the predetermined potential applied to or reversal in the polarity of said electrodes is effective in releasing adsorbed CO2 from the electroactive MOF structure of said electrodes.
2. A battery module as claimed in claim 1 being of an interdigitated configuration wherein one of the pair of gas diffusion electrodes forms an anode structure, and an other of said pair of electrodes forms a cathode structure arranged to cooperate with the anode structure in a meshed relationship.
3. A battery module as claimed in claim 2 wherein the anode and cathode structures each include a plurality of plates or discs arranged in the meshed relationship.
4. A battery module as claimed in either of claims 2 or 3 wherein the electrolyte separates the anode and cathode structures to facilitate ion and charge transfer between the pair of gas diffusion electrodes.
5. A battery module as claimed in any one of the preceding claims wherein the MOF structure of the pair of gas diffusion electrodes is zirconium-based and incorporates chemical functionalities for selective and reversible reactions with CO2.
6. A battery module as claimed in claim 5 wherein the chemical functionalities include but are not limited to quinone, phenazine, ferrocenyl groups or combinations thereof.
7. A battery module as claimed in either of claims 5 or 6 wherein the Zr-based MOF structure provides topologically-matched materials for the pair of gas diffusion electrodes thereby ensuring that ion diffusion and charge transfer kinetics are well- matched between the anode and cathode structures.
8. A method of manufacturing a battery module for direct capture of carbon dioxide (CO2) from air, said method comprising the steps of: forming a pair of gas diffusion electrodes by additive manufacturing of an electroactive metal-organic framework (MOF) structure; associating an electrolyte with the pair of gas diffusion electrodes, said electrolyte including an ionic or polyionic liquid arranged to cooperate with the pair of gas diffusion electrodes to facilitate ion and charge transfer between said electrodes whereby (i) in an adsorption mode, a predetermined potential applied to the gas diffusion electrodes is effective in the electroactive MOF structure of said electrodes directly adsorbing CO2 from air exposed to the batter module, and (ii) in a desorption mode, a change in the predetermined potential applied to or reversal in the polarity of said electrodes is effective in releasing adsorbed CO2 from the electroactive MOF structure of said electrodes.
9. A method of manufacturing a battery module as claimed in claim 8 wherein the electroactive MOF structure of the pair of gas diffusion electrodes is 3D printed by robocasting or Direct Ink Writing (DIW) of a composite paste mixture including a MOF compound.
10. A method of manufacturing a battery module as claimed in claim 9 wherein the composite paste mixture includes the MOF compound in the form of zirconium clusters together with chemical functionalities for CO2 adsorption, a carbon-based conductive material, binders, and/or plasticizers.
11. A method of manufacturing a battery module as claimed in claim 10 wherein the zirconium clusters include UiO-66, UiO-67, UiO-68, or combinations thereof.
12. A method of manufacturing a battery module as claimed in either of claims 10 or 11 wherein the binders are derivatives of bentonite or kaolinite clay, and the 1 1 plasticizers are selected to modulate the shear modulus of the composite paste mixture.
13. A method of directly capturing carbon dioxide (CO2) from air, said method comprising the steps of: exposing air to a battery module including (i) a pair of gas diffusion electrodes each formed of an electroactive metal-organic framework (MOF) structure produced by additive manufacturing, and (ii) an electrolyte arranged to cooperate with the pair of electrodes; in an adsorption mode, applying a predetermined potential to the gas diffusion electrodes thereby enabling the electroactive MOF structure of said electrodes to directly adsorb CO2 from the air exposed to the battery module; in a desorption mode, changing the predetermined potential applied to or reversing the polarity of said electrodes thereby enabling release of the adsorbed CO2 from the electroactive MOF structure of said electrodes.
PCT/AU2022/050899 2021-09-28 2022-08-16 Battery module for direct air capture of carbon dioxide WO2023049952A1 (en)

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Citations (5)

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US20180085703A1 (en) * 2016-09-23 2018-03-29 Lehigh University Gas separation apparatus and methods using same
CN106861634B (en) * 2017-03-14 2020-03-31 潍坊学院 Metal-organic framework compound @ mesoporous material composite material and preparation method and application thereof
WO2021041732A1 (en) * 2019-08-28 2021-03-04 Massachusetts Institute Of Technology Electrochemically mediated gas capture, including from low concentration streams
WO2021180564A1 (en) * 2020-03-10 2021-09-16 University Of Exeter Metal organic framework material
EP3991827A1 (en) * 2020-10-30 2022-05-04 Denso Corporation Carbon dioxide recovery system and working electrode

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180085703A1 (en) * 2016-09-23 2018-03-29 Lehigh University Gas separation apparatus and methods using same
CN106861634B (en) * 2017-03-14 2020-03-31 潍坊学院 Metal-organic framework compound @ mesoporous material composite material and preparation method and application thereof
WO2021041732A1 (en) * 2019-08-28 2021-03-04 Massachusetts Institute Of Technology Electrochemically mediated gas capture, including from low concentration streams
WO2021180564A1 (en) * 2020-03-10 2021-09-16 University Of Exeter Metal organic framework material
EP3991827A1 (en) * 2020-10-30 2022-05-04 Denso Corporation Carbon dioxide recovery system and working electrode

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