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    • 专利摘要:
    Electrode for capacitive deionization. The present invention relates to an electrode for capacitive deionization comprising a composite material, wherein the composite material comprises carbon nanotube fibers coated with a metal oxide coating. The invention also relates to a method for the preparation of said electrode, to a device for capacitive deionization comprising at least one of said electrodes and to the use of said device for capacitive deionization for water purification. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2694653A1
    申请号:ES201730828
    申请日:2017-06-22
    公开日:2018-12-26
    发明作者:Juan José VILATELA；Cleis SANTOS SANTOS；Enrique GARCÍA-QUISMONDO HERNÁIZ；Jesús PALMA DEL VAL
    申请人:Fundacion Imdea Energia；Fund Imdea Energia；Fundacion Imdea Mat；FUNDACION IMDEA MATERIALES；
    IPC主号:
    专利说明:

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    electrochemical and texture properties to the final performance of the electrode of the present invention.
    In the context of the present invention, the term "carbon nanotube" refers to a structure produced by winding a sheet of graphene to form a cylinder. Depending on the winding angle and the way in which the original graphene sheet is formed, carbon nanotubes of different diameter and internal geometry can be formed. The carbon nanotubes formed by rolling a single sheet forming the cylinder mentioned above, are called "single wall" nanotubes. The carbon nanotubes formed by winding more than one sheet with a structure that resembles a series of concentric cylinders, logically, of increasing diameters from the center to the periphery as matrioska dolls are called "multiple wall" nanotubes.
    In a preferred embodiment, the carbon nanotubes used in the present invention are single wall or multiple wall, more preferably multiple wall, even more preferably carbon nanotubes having between 2 and 5 graphitic layers.
    In another preferred embodiment, the carbon nanotubes used in the present invention are nanotubes with high aspect ratio, preferably between 10 and 10000000, even more preferably between 100 and 10000000. The carbon nanotubes used in the present invention are preferably also highly graphitic
    In the context of the present invention, the term "carbon nanotube fiber" refers to a macroscopic arrangement of agglomerated carbon nanotubes as defined above, wherein the fiber can be used as a single filament or as a flat sheet or film or as woven or non-woven textile material. By grouping carbon nanotubes as fibers, their mechanical properties as well as their electrical conductivity are enhanced. In addition, the carbon nanotube fibers used in the present invention exhibit porosity as a result of gaps formed between the carbon nanotubes due to imperfect packing.
    Therefore, in another preferred embodiment, the carbon nanotube fibers used in the present invention are fibers having a specific surface area of between 50 and 2000 cm3 / g. In the context of the present invention, the term "coating" refers to a structure in which the metal oxide is in the form of particles or forming a layer around the fibers of carbon nanotubes.
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    temperature between 1000 and 1400ºC. In addition to the mixture, a stream of hydrogen is injected into the reactor. Inside the reactor, the reaction between the components of the initial mixture takes place, so that an airgel of carbon nanotubes is generated. In the lower part of the reactor, a rod that causes agglomeration of said carbon nanotube airgel is introduced at the same time that said agglomerate is adhered to the rod and extracted from the reactor in the form of a fiber. As the formed fiber is extracted, it is collected on a substrate. The method allows to obtain a fiber with a long length in a short period of time (figure 1 (2)).
    In addition, the method for preparing the electrode as defined above further comprises step (b) of coating said carbon nanotube fibers with a metal oxide coating.
    In step (b) of the process of the invention, carbon nanotube fibers can be coated using a metal oxide precursor or directly using the metal oxide to form the coating.
    In a particular embodiment, carbon nanotube fibers are coated using a metal oxide precursor. In this particular case, the metal oxide precursor is applied onto the carbon nanotube fibers in the form of a solution containing said precursor, more preferably, in the form of a sol-gel type solution to form the oxide of metal through a "sol-gel" type process in which the primary solid particles contained in the "sol" (ie, the precursor solution) are packaged with a given geometry, resulting in the formation of pores between the particles that are fused in a gel process to evolve to the formation of the "gel", and the particle packing process provides for the formation of the metal oxide and the coating on the fiber of carbon nanotubes.
    Non-limiting examples of metal oxide precursors suitable in the method of the present invention are metal alkoxides, metal nitrates, metal acetates and metal chlorides.
    In a preferred embodiment, the metal oxide precursor is tetraethyl orthosilicate (TEOS), aluminum tri-sec-butoxide (ATSB), titanium isopropoxide (TTIP), zirconium propoxide (NPZ), or a combination thereof .
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    external of the carbon nanotube fibers but also of the inner surface of the carbon nanotube fibers (holes inside the carbon nanotubes leading to pores in the fibers). This kind of coating preserves the high electrical conductivity of carbon nanotube fibers coated with a metal oxide coating while reducing the contact resistance promoted by the incorporation of metal oxides. In addition, the use of a binder is not required to maintain cohesion between the carbon nanotube fibers and the metal oxide coating since the coating forms part of the carbon nanotube fiber network.
    Furthermore, the method of the present invention allows the continuous production of carbon nanotube fibers coated with a metal oxide coating and thus, allowing large quantities of composite material to be manufactured and leading to the scaling of capacitive deionization devices to industrial sizes. . Current methods in the state of the art for the manufacture of electrodes for capacitive deionization devices comprising carbon materials such as carbon nanotubes or graphene, composite materials with metal oxide and activated carbons, do not lend themselves to the continuous production of electrodes nor to their scaling.
    In another particular embodiment, the method of the present invention may optionally comprise an additional step (d) of chemically functionalizing carbon nanotube fibers resulting from step (b) or (c). Said fibers can be functionalized by gas phase, liquid phase, sintering or irradiation processes that modify the surface chemistry of the carbon nanotube fibers so that their interaction with the metal oxide or metal oxide precursors is improved, as well as electrolytes in the capacitive deionization process.
    As a non-limiting example, carbon nanotube fibers can be functionalized by partial oxidation of their surface through the use of an oxygen plasma. Said treatment produces a plurality of surface functional groups, such as carboxylic groups, which increase the hydrophilicity of the final electrode and, therefore, improves the infiltration of water ions in its pore structure. Said functional groups can also lead to the formation of chemical bonds with the metal oxide, which leads to a low electrical resistance of the capacitive deionization device.
    The use of carbon nanotube fibers and the elimination of the need for conventional metallic or graphitic current collectors such as graphite, stainless steel or titanium,


    they increase the flexibility of the composite material and, therefore, allow the electrode of the present invention to be produced in a wide variety of conformations and, therefore, increase the design versatility of the capacitive deionization devices.
    The non-limiting examples of conformations suitable for the electrode of the present invention are woven and flat electrodes with high curvature, electrodes with conformations adapted to cylindrical structures, configurations of spiral windings, or polygonal structural architectures adapted for a direct flow configuration and continuous flow.
    Electrodes of a specific geometry or configuration can be produced, for example, by winding filaments, whereby the carbon nanotube fibers are collected on a preform of the desired shape while simultaneously integrating the metal oxide into the structure of pores of the nanotube fibers of
    15 carbon.
    In another aspect, the present invention relates to a device for capacitive deionization comprising at least one electrode as defined above.
    20 Capacitive deionization devices are essentially capacitors or electric charge storage devices. These devices store electrical energy in the form of an electric field generated in the space between two electrodes of opposite charge, separated.
    In a preferred embodiment, the capacitive deionization device of the present invention comprises two electrodes as defined above, one as a cathode
    or anode and the other facing the anode or the cathode.
    In a more preferred embodiment, the capacitive deionization device of the present invention comprises:
    - an electrode comprising a composite material comprising carbon nanotube fibers coated with a silica coating, and
    35 - an electrode comprising a composite material comprising carbon nanotube fibers coated with an alumina coating.
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    Direct flow, are essentially capacitors designed to provide a flow path for water that may comprise the electrodes as defined above.
    Therefore, in a particular embodiment, the device for capacitive deionization of the present invention is an electrochemical cell. A plurality of electrochemical cells can also be used as a capacitive deionization device allowing for voltage sharing.
    The non-limiting examples of geometries of suitable electrochemical cells in the capacitive deionization devices of the present invention are capacitors of cylindrical structure, electric double layer capacitors with facing electrodes which may include spiral winding, stacked disc, flat plate or bundles of polygonal electrodes. These capacitors may differ in terms of the fluid path through
    15 of the device. Generally, however, the ionic species are removed perpendicular to the fluid flow path or are introduced into the electrode.
    Still another object of the present invention provides the use of the capacitive deionization device as defined above for water purification.
    The term "water purification" refers to the removal of salt ions from saline water, the removal of ionic contaminants such as species rich in nitrogen, phosphorus or sulfur, or other materials such as heavy metals.
    In a particular embodiment, the device for capacitive deionization is used for the removal of water sulfates.
    In another particular embodiment, the device for capacitive deionization is used for the removal of heavy metals, B, Li, Pb, As or mixtures thereof from water.
    The purification of water takes place by applying an electrical potential to the electrodes of the capacitive deionization device that can cause the hydrated ions in the water to be electrostatically attracted to the electrodes based on the electrical potential of the ions. For example, a salt such as sodium chloride ("ΝaCl") is
    It hydrates when mixed with water to produce the dissociation of the sodium cation from the chloride anion. The positively charged sodium cation is electrostatically attracted to the plate
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    权利要求:
    Claims (1)
    [1]
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    类似技术:
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    Tang et al.2019|Carbon–metal compound composite electrodes for capacitive deionization: synthesis, development and applications
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    Pu et al.2014|Fe3O4@ C core–shell microspheres: synthesis, characterization, and application as supercapacitor electrodes
    CN104694989A|2015-06-10|Preparation method of graphene-base metal composite material
    Du et al.2017|A Three‐Layer All‐In‐One Flexible Graphene Film Used as an Integrated Supercapacitor
    Kumar et al.2020|In situ carbon-supported titanium dioxide | as an electrode material for high performance supercapacitors
    同族专利:
    公开号 | 公开日
    ES2694653B2|2019-05-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20160326026A1|2011-01-26|2016-11-10|Indian Institute Of Technology Madras|Methods and systems for separating ions from fluids|
    法律状态:
    2018-12-26| BA2A| Patent application published|Ref document number: 2694653 Country of ref document: ES Kind code of ref document: A1 Effective date: 20181226 |
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201730828A|ES2694653B2|2017-06-22|2017-06-22|Electrode for capacitive deionization|ES201730828A| ES2694653B2|2017-06-22|2017-06-22|Electrode for capacitive deionization|
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