WO2024014483A1 - Cellule électrochimique - Google Patents

Cellule électrochimique Download PDF

Info

Publication number
WO2024014483A1
WO2024014483A1 PCT/JP2023/025744 JP2023025744W WO2024014483A1 WO 2024014483 A1 WO2024014483 A1 WO 2024014483A1 JP 2023025744 W JP2023025744 W JP 2023025744W WO 2024014483 A1 WO2024014483 A1 WO 2024014483A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon dioxide
counter electrode
working electrode
electrochemical cell
active material
Prior art date
Application number
PCT/JP2023/025744
Other languages
English (en)
Japanese (ja)
Inventor
勝真 石野
淳一 成瀬
Original Assignee
株式会社デンソー
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社デンソー filed Critical 株式会社デンソー
Publication of WO2024014483A1 publication Critical patent/WO2024014483A1/fr

Links

Images

Classifications

    • 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

Definitions

  • the present disclosure relates to electrochemical cells.
  • carbon dioxide recovery systems have been developed that separate carbon dioxide (CO 2 ) from a target gas containing carbon dioxide (CO 2 ) through an electrochemical reaction.
  • a carbon dioxide adsorbent capable of adsorbing carbon dioxide is provided at the working electrode of an electrochemical cell.
  • the adsorbent is an electroactive species, and by changing the potential difference between the working electrode and the counter electrode, the adsorption and release of carbon dioxide by the carbon dioxide adsorbent can be switched.
  • the counter electrode of the electrochemical cell is configured to include an active material that is an auxiliary electroactive species that exchanges electrons with the carbon dioxide adsorbent of the working electrode.
  • an active material for example, a metal complex that can transfer electrons by changing the valence of metal ions can be used.
  • ferrocene (Fc) for example, as such a metal complex has been considered.
  • ferrocene is a small molecule, it easily dissolves into the electrolyte provided between the working electrode and the counter electrode. This may reduce electrode performance.
  • Non-Patent Document 1 discloses a technique using polyvinylferrocene (PVFc) as a counter electrode active material.
  • PVFc polyvinylferrocene
  • Non-Patent Document 1 a mixed gas of carbon dioxide and nitrogen (N 2 ) is used as the gas to be treated. That is, in Non-Patent Document 1, an electrochemical cell is operated in a CO 2 /N 2 atmosphere.
  • Non-Patent Document 1 when the electrochemical cell described in Non-Patent Document 1 is used in a carbon dioxide recovery system that separates carbon dioxide from a gas containing oxygen such as the atmosphere, the active material of the electrode deteriorates due to oxygen. There is a risk. This can reduce the durability of the electrochemical cell.
  • the present disclosure aims to provide an electrochemical cell that can improve electrode performance and durability.
  • an electrochemical cell includes a working electrode that adsorbs and desorbs carbon dioxide from a gas to be treated containing carbon dioxide through an electrochemical reaction; a counter electrode that transfers electrons to and from the working electrode;
  • An electrochemical cell comprising: an electrolyte material covering a working electrode and a counter electrode;
  • the electrolyte material is an ionic liquid,
  • At least one of the working electrode and the counter electrode has an active material and carbon nanotubes, The active material is contained inside the carbon nanotube.
  • FIG. 1 is a conceptual diagram showing the overall configuration of a carbon dioxide recovery system in one embodiment. It is an explanatory view showing a carbon dioxide recovery device in one embodiment.
  • FIG. 2 is a cross-sectional view of an electrochemical cell in one embodiment.
  • FIG. 2 is an explanatory diagram for explaining the configuration of a counter electrode in one embodiment. It is a figure showing a TEM image. It is a figure showing a STEM-ADF image. It is a figure showing an EDX analysis result. It is a figure showing a cyclic voltammogram of an example. It is a figure which shows the cyclic voltammogram of a comparative example.
  • the electrochemical cell of the present disclosure is applied to a carbon dioxide recovery system that separates and recovers carbon dioxide from a gas to be treated containing carbon dioxide.
  • the gas to be treated is a carbon dioxide-containing gas containing carbon dioxide.
  • the gas to be treated also contains gases other than carbon dioxide.
  • the carbon dioxide-containing gas contains oxygen (O 2 ) as a gas other than carbon dioxide.
  • the gas to be treated is the atmosphere or a highly concentrated gas containing carbon dioxide at a higher concentration than the atmosphere. Highly concentrated gases are emitted from internal combustion engines and factories, for example.
  • the gas to be processed in this embodiment is the atmosphere.
  • the carbon dioxide recovery system 10 of this embodiment is provided with a compressor 11, a carbon dioxide recovery device 100, a flow path switching valve 12, a carbon dioxide utilization device 13, and a control device 14.
  • the compressor 11 pumps atmospheric air, which is a carbon dioxide-containing gas, to the carbon dioxide recovery device 100.
  • the compressor 11 is provided on the downstream side of the carbon dioxide recovery device 100 in the gas flow direction.
  • the carbon dioxide recovery device 100 is a device that separates and recovers carbon dioxide from a carbon dioxide-containing gas.
  • the carbon dioxide recovery device 100 discharges carbon dioxide removed gas after carbon dioxide has been recovered from the carbon dioxide-containing gas, or carbon dioxide recovered from the carbon dioxide-containing gas.
  • the configuration of carbon dioxide recovery device 100 will be described in detail later.
  • the flow path switching valve 12 is a three-way valve that switches the flow path of the exhaust gas of the carbon dioxide recovery device 100.
  • the flow path switching valve 12 switches the flow path of the exhaust gas to the atmosphere side when carbon dioxide removal gas is discharged from the carbon dioxide recovery device 100, and switches the flow path of the exhaust gas to the atmosphere side when carbon dioxide is discharged from the carbon dioxide recovery device 100.
  • the exhaust gas flow path is switched to the carbon dioxide utilization device 13 side.
  • the carbon dioxide utilization device 13 is a device that utilizes carbon dioxide.
  • a storage tank that stores carbon dioxide or a conversion device that converts carbon dioxide into fuel can be used.
  • a conversion device a device that converts carbon dioxide into hydrocarbon fuel such as methane can be used.
  • the hydrocarbon fuel may be a gaseous fuel at normal temperature and normal pressure, or may be a liquid fuel at normal temperature and normal pressure.
  • the control device 14 is composed of a well-known microcomputer including a CPU, ROM, RAM, etc., and its peripheral circuits.
  • the control device 14 performs various calculations and processes based on a control program stored in the ROM, and controls the operations of various devices to be controlled.
  • the control device 14 of this embodiment performs operation control of the compressor 11, operation control of the carbon dioxide recovery device 100, flow path switching control of the flow path switching valve 12, and the like.
  • Electrochemical cell 101 has a working electrode 130, a counter electrode 140, and a separator 150.
  • the working electrode 130, the counter electrode 140, and the separator 150 are each formed into a plate shape.
  • the working electrode 130, the counter electrode 140, and the separator 150 are shown spaced apart from each other in FIG. 2, these components are actually arranged so as to be in contact with each other.
  • the electrochemical cell 101 may be housed in a container (not shown).
  • the container can be provided with a gas inlet that allows the carbon dioxide-containing gas to flow into the container, and a gas outlet that allows the carbon dioxide removal gas and carbon dioxide to flow out of the container.
  • the carbon dioxide recovery device 100 adsorbs and desorbs carbon dioxide through an electrochemical reaction, and separates and recovers carbon dioxide from a carbon dioxide-containing gas.
  • the carbon dioxide recovery device 100 is provided with a control power source 120 that applies a predetermined voltage to the working electrode 130 and the counter electrode 140, and can change the potential difference between the working electrode 130 and the counter electrode 140.
  • Working electrode 130 is a negative electrode
  • counter electrode 140 is a positive electrode.
  • the electrochemical cell 101 operates by changing the potential difference between the working electrode 130 and the counter electrode 140 to switch between a recovery mode in which carbon dioxide is recovered at the working electrode 130 and a release mode in which carbon dioxide is released from the working electrode 130. I can do it.
  • the recovery mode is a charging mode in which the electrochemical cell 101 is charged
  • the discharge mode is a discharging mode in which the electrochemical cell 101 is discharged.
  • the first voltage V1 is applied between the working electrode 130 and the counter electrode 140, and electrons are supplied from the counter electrode 140 to the working electrode 130.
  • working electrode potential At the first voltage V1, working electrode potential ⁇ counter electrode potential.
  • the first voltage V1 can be within a range of 0.5 to 2.0V, for example.
  • a second voltage V2 lower than the first voltage V1 is applied between the working electrode 130 and the counter electrode 140, and electrons are supplied from the working electrode 130 to the counter electrode 140.
  • the second voltage V2 only needs to be a voltage lower than the first voltage V1, and the magnitude relationship between the working electrode potential and the counter electrode potential is not limited. That is, in the release mode, the working electrode potential may be less than the counter electrode potential, the working electrode potential may be equal to the counter electrode potential, or the working electrode potential may be greater than the counter electrode potential.
  • the working electrode 130 in the electrochemical cell 101 has a working electrode side current collector 131 and a working electrode side electrode film 132.
  • the working electrode side current collector 131 is connected to the control power source 120 and is a porous conductive member through which carbon dioxide-containing gas can pass.
  • the working electrode side current collector 131 for example, a carbonaceous material or a metal material can be used.
  • a carbonaceous material constituting the working electrode side current collector 131 for example, carbon paper, carbon cloth, nonwoven carbon mat, porous gas diffusion layer (GDL), etc. can be used.
  • GDL porous gas diffusion layer
  • the metal material constituting the working electrode side current collector 131 a structure made of a metal such as Al, Ni, or SUS in a mesh shape can be used, for example.
  • the working electrode side electrode film 132 adsorbs and desorbs carbon dioxide from a carbon dioxide-containing gas through an electrochemical reaction.
  • the working electrode side electrode film 132 includes a carbon dioxide adsorbent, a working electrode side conductive agent, and a working electrode side binder.
  • a carbon dioxide adsorbent is an electroactive species (i.e., an active material) that adsorbs carbon dioxide by receiving electrons and desorbs the adsorbed carbon dioxide by releasing electrons.
  • an electroactive species i.e., an active material
  • carbon dioxide adsorbent for example, carbon materials, metal oxides, polyanthraquinone, etc. can be used.
  • the working electrode side conductive agent is a conductive material that forms a conductive path to the carbon dioxide adsorbent.
  • carbon materials such as carbon nanotubes, carbon black, and graphene can be used, for example.
  • the working electrode side binder holds the carbon dioxide adsorbent and the working electrode side conductive agent on the working electrode side current collector 131. Specifically, a mixture of the carbon dioxide adsorbent, the working electrode side conductive agent, and the working electrode side binder is formed, and the mixture is adhered to the working electrode side current collector 131. The carbon dioxide adsorbent and the working electrode side conductive agent are held inside the working electrode side binder.
  • a conductive resin As the binder on the working electrode side, for example, a conductive resin can be used.
  • a conductive resin an epoxy resin containing Ag or the like as a conductive filler, a fluororesin such as PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), etc. can be used.
  • the counter electrode 140 has a counter electrode current collector 141 and a counter electrode film 142.
  • the configuration of counter electrode 140 will be explained in detail later.
  • the separator 150 is arranged between the working electrode film 132 and the counter electrode film 142.
  • the separator 150 separates the working electrode film 132 and the counter electrode film 142. That is, the separator 150 prevents physical contact between the working electrode film 132 and the counter electrode film 142. Moreover, the separator 150 suppresses electrical short circuit between the working electrode side electrode film 132 and the counter electrode side electrode film 142.
  • separator 150 a separator made of a cellulose membrane, a polymer, a composite material of polymer and ceramic, etc. can be used.
  • separator 150 a porous separator may be used.
  • An electrolyte material 160 (see FIG. 4 described later) is provided between the working electrode film 132 and the separator 150 and between the counter electrode film 142 and the separator 150.
  • Working electrode 130 and counter electrode 140 are covered with electrolyte material 160.
  • the electrolyte material 160 promotes electrical conduction to the carbon dioxide adsorbent.
  • an ionic liquid is used as the electrolyte material 160.
  • Ionic liquids are liquid salts that are nonvolatile at room temperature and pressure.
  • the ionic liquid used as the electrolyte material 160 has a cation containing at least one of imidazole and ammonium, and an anion containing TFSI (trifluoromethanesulfonylimide).
  • the counter electrode side current collector material 141 in the counter electrode 140 is a conductive member connected to the control power source 120.
  • the counter electrode side current collector material 141 may be made of the same material as the working electrode side current collector material 131, or may be made of a different material.
  • the counter electrode film 142 of the counter electrode 140 exchanges electrons with the working electrode film 132.
  • the counter electrode film 142 includes a counter active material 143, a counter conductive agent 144, and a counter binder (not shown).
  • the counter electrode active material 143 is an auxiliary electroactive species that exchanges electrons with the carbon dioxide adsorbent.
  • the counter electrode side active material 143 is a material that can transfer electrons in and out by changing the valence of the metal and transferring charges into and out of the ⁇ electron cloud.
  • a metal complex that enables transfer of electrons by changing the valence of metal ions can be used.
  • metal complexes include cyclopentadienyl metal complexes such as ferrocene, nickelocene, and cobaltocene, and porphyrin metal complexes. These metal complexes may be polymers or monomers.
  • a compound having a ferrocene skeleton may be used.
  • the counter electrode side active material 143 may include a substance that undergoes a redox reaction within a potential range of ⁇ 1.1 V to +0.5 V with respect to the redox potential of ferrocene.
  • the counter electrode active material 143 may contain at least one of ferrocene, ferrocene derivatives, metallocene, and phenothiazine. In this embodiment, ferrocene is used as the counter electrode side active material 143.
  • the counter electrode conductive aid 144 is a conductive material that forms a conductive path to the counter electrode active material 143.
  • the counter electrode side conductive agent 144 is used in combination with the counter electrode side active material 143.
  • carbon nanotubes are used as the counter electrode conductive aid 144.
  • the counter electrode binder is a material that can hold the counter electrode active material 143 and the counter electrode conductive agent 144 on the counter electrode current collector 141 and has electrical conductivity.
  • the binder on the opposite electrode side may be made of the same material as the binder on the working electrode side, or may be made of a different material. In this embodiment, PVDF is used as the opposite binder.
  • the counter electrode side active material 143 is contained inside the carbon nanotube as the counter electrode side conductive agent 144.
  • the present inventors conducted a TEM-EDX analysis to confirm the encapsulation state of ferrocene, which is the counter electrode side active material 143, in the carbon nanotubes.
  • TEM is a transmission electron microscope.
  • EDX is Energy Dispersive X-ray Spectroscope.
  • the following samples were prepared. First, 20 mg of carbon nanotubes were heat-treated at 350° C. in an air atmosphere. Next, 100 mg of ferrocene was encapsulated in the carbon nanotubes under an Ar atmosphere and heated at 270° C. for 48 hours to create a mixture. Thereafter, the mixture was washed with ethanol multiple times and air-dried to obtain a sample.
  • TEM-EDX analysis was performed on the sample.
  • a sample was processed into a thin section using an FIB (Focused Ion Beam System), and then a TEM image was observed. In the TEM image shown in FIG. 5, it was confirmed that some substance was contained inside the carbon nanotube.
  • an ADF (Annular Dark Field) image of the sample was observed using a STEM (Scanning Transmission Electron Microscope). Note that in this specification, an ADF image observed using STEM may be referred to as a STEM-ADF image. In the STEM-ADF image shown in FIG. 6, it was confirmed that the substance present inside the carbon nanotube appeared bright.
  • CV cyclic voltammetry
  • a three-electrode system was used, including an electrode film/glassy carbon substrate containing ferrocene inside carbon nanotubes as a working electrode, an Ag/Ag + electrode as a reference electrode, and Pt as a counter electrode.
  • the peak current value of the ferrocene oxidation wave after 20 cycles is 11% compared to the peak current value of the ferrocene oxidation wave after the first cycle. % increase.
  • the electrode film according to the comparative example was used, the peak current value of the ferrocene oxidation wave after 20 cycles was reduced by 29% compared to the peak current value of the ferrocene oxidation wave after the first cycle.
  • the peak current did not decrease.
  • the electrode film according to the comparative example was used, the peak current decreased.
  • the counter electrode side active material 143 is contained inside the carbon nanotube as the counter electrode side conductive agent 144. According to this, the counter electrode active material 143 can be protected by the carbon nanotubes. Therefore, elution of the counter electrode side active material 143 into the ionic liquid that is the electrolyte material 160 can be suppressed, so that the electrode performance of the counter electrode 140 can be improved. Further, since it is possible to suppress deterioration of the counter electrode side active material 143 due to oxygen contained in the atmosphere, durability can be improved.
  • the counter electrode side active material 143 was contained inside the carbon nanotube as the counter electrode side conductive agent 144, but the present invention is not limited to this embodiment.
  • carbon nanotubes may be used as the conductive agent on the working electrode side, and a carbon dioxide adsorbent, which is the active material of the working electrode 130, may be contained inside the carbon nanotubes.
  • an ionic liquid was used as the electrolyte material 160, but the present invention is not limited to this embodiment.
  • an ionic liquid gel obtained by gelling an ionic liquid may be used as the electrolyte material 160. According to this, it is possible to suppress the electrolyte material 160 from being eluted from the electrochemical cell 101.
  • double-walled carbon nanotubes are shown as carbon nanotubes in the TEM image shown in FIG. 5, but carbon nanotubes are not limited to double-walled carbon nanotubes.
  • the carbon nanotube a single-walled carbon nanotube or a three- or more-walled carbon nanotube may be used.
  • the characteristics of the electrochemical cell disclosed herein are as follows.
  • a working electrode (130) that adsorbs and desorbs carbon dioxide from a gas to be treated containing carbon dioxide through an electrochemical reaction
  • a counter electrode (140) that exchanges electrons with the working electrode
  • An electrochemical cell comprising an electrolyte material (160) covering the working electrode and the counter electrode,
  • the electrolyte material is an ionic liquid
  • At least one of the working electrode and the counter electrode has an active material (143) and carbon nanotubes, An electrochemical cell in which the active material is contained inside the carbon nanotube.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

L'invention concerne une cellule électrochimique comprenant une électrode de travail (130), une contre-électrode (140) et un matériau d'électrolyte (160). L'électrode de travail (130), par des réactions électrochimiques, adsorbe le dioxyde de carbone d'un gaz contenant du dioxyde de carbone à traiter et désorbe le dioxyde de carbone. La contre-électrode (140) effectue des transferts d'électrons entre elle-même et l'électrode de travail. Le matériau d'électrolyte (160) recouvre l'électrode de travail (130) et la contre-électrode (140). Le matériau d'électrolyte (160) est un liquide ionique. L'électrode de travail (130) et/ou la contre-électrode (140) comprend un matériau actif (143) et des nanotubes de carbone. Le matériau actif (143) est contenu à l'intérieur des nanotubes de carbone.
PCT/JP2023/025744 2022-07-15 2023-07-12 Cellule électrochimique WO2024014483A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022114039A JP2024011776A (ja) 2022-07-15 2022-07-15 電気化学セル
JP2022-114039 2022-07-15

Publications (1)

Publication Number Publication Date
WO2024014483A1 true WO2024014483A1 (fr) 2024-01-18

Family

ID=89536762

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/025744 WO2024014483A1 (fr) 2022-07-15 2023-07-12 Cellule électrochimique

Country Status (2)

Country Link
JP (1) JP2024011776A (fr)
WO (1) WO2024014483A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022025699A (ja) * 2020-07-29 2022-02-10 株式会社日立製作所 ガス分離装置およびガスシステム

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022025699A (ja) * 2020-07-29 2022-02-10 株式会社日立製作所 ガス分離装置およびガスシステム

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUAN, L. SHI, Z. LI, M. GU, Z.: "Ferrocene-filled single-walled carbon nanotubes", CARBON, ELSEVIER OXFORD, GB, vol. 43, no. 13, 1 November 2005 (2005-11-01), GB , pages 2780 - 2785, XP005004228, ISSN: 0008-6223, DOI: 10.1016/j.carbon.2005.05.025 *
VOSKIAN SAHAG, HATTON T. ALAN: "Faradaic electro-swing reactive adsorption for CO 2 capture", ENERGY & ENVIRONMENTAL SCIENCE, RSC PUBL., CAMBRIDGE, vol. 12, no. 12, 4 December 2019 (2019-12-04), Cambridge , pages 3530 - 3547, XP055941462, ISSN: 1754-5692, DOI: 10.1039/C9EE02412C *

Also Published As

Publication number Publication date
JP2024011776A (ja) 2024-01-25

Similar Documents

Publication Publication Date Title
Shi et al. A shorted membrane electrochemical cell powered by hydrogen to remove CO2 from the air feed of hydroxide exchange membrane fuel cells
CN114432849B (zh) 二氧化碳回收系统和工作电极
JP2007287415A (ja) 燃料電池
JP5792567B2 (ja) 酸素還元能を有する電極触媒
Hu et al. Synthesis of anti-poisoning spinel Mn–Co–C as cathode catalysts for low-temperature anion exchange membrane direct ammonia fuel cells
GB2439690A (en) Particle containing carbon particle platinum and ruthenium oxide and method for producing same
Jindal et al. Excellent oxygen reduction reaction performance in self-assembled amyloid-β/platinum nanoparticle hybrids with effective platinum–nitrogen bond formation
US20240149215A1 (en) Carbon dioxide recovery system
Chaparro Oxygen reduction limited by surface diffusion at a rotating ring-disk electrode
WO2024014483A1 (fr) Cellule électrochimique
US20140178794A1 (en) Fuel electrode catalyst for fuel cell, electrode/membrane assembly, and fuel cell and fuel cell system provided with the electrode/membrane assembly
US20170149079A1 (en) Nanocomposite electrode material for proton conducting electrochemical devices
JP6727264B2 (ja) 燃料電池用アノード触媒層及びそれを用いた燃料電池
EP4091701A1 (fr) Système de récupération de dioxyde de carbone
JP2006209999A (ja) 固体高分子形燃料電池用電極およびその製造方法
CN114342129A (zh) 用于燃料电池的催化剂、制备该催化剂的方法和包含该催化剂的膜-电极组件
US10381656B2 (en) Nanocomposite electrode material for proton conducting fuel cell
WO2024009858A1 (fr) Cellule électrochimique
US20230383429A1 (en) Carbon dioxide recovery system
US20230381715A1 (en) Carbon dioxide recovery system
JP2007250214A (ja) 電極触媒とその製造方法
JP2024008535A (ja) 電気化学セルおよびその製造方法
US20230387425A1 (en) Electrochemical cell, gas recovery system equipped with electrochemical cell, and method of manufacturing electrochemical cell
CN115020724B (zh) 电极催化剂
US20240216859A1 (en) Gas recovery system

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23839655

Country of ref document: EP

Kind code of ref document: A1