Patent Application
20210273230
The present invention relates to substrates comprising largely vertically oriented carbon nanotubes that are, in a plane along the substrate, formed as a connected structure. Such a structure is e.g. known for use as an electrode.
For example, WO2017011052A2 discloses vertically aligned carbon nanotubes in a connected structure covering a large area of a substrate. Lithium is deposited onto these vertically aligned carbon nanotubes to form an electrode. The deposition of lithium results in an agglomeration of these nanotubes and an associated loss of orientation, resulting in bending, curling, cracking and falling over of tubes. It is an aspect of the present invention to provide a connected structure of carbon nanotubes absent of such loss of orientation.
US20170214083A1 also describes the use of a connected structure of vertically aligned carbon nanotubes. The described connected structures of carbon nanotubes are used as a scaffold in the assembly of interlaced or interleaved finger-shaped electrodes for use in 3D-batteries. The electrodes are described to have a length of approximately 1.44 cm and a width in a range from typically less than 100 μm, down to preferably 30 μm. Finger-shaped structures of nanotubes are grown using a physical vapor deposition (PVD) process from a substrate provided with a pattern of suitable catalyst. Subsequently, suitable electrode materials are deposited onto the carbon nanotube structures. The document specifies this cannot be done on a single substrate, since each electrode material requires a different deposition process. Therefore, each electrode is separately cut out of its substrate and processed individually. At a later stage, the anode and cathode must be assembled at a gap, and the gap filled with a suitable electrolyte to form a 3D-battery.
Thin-film battery structures of known type are disclosed e.g. in WO2010032159, the contents of which are included by reference, wherein for example all-solid state compositions are deposited on 3D micro-patterned structures. In this respect, where early battery structures utilize liquid electrolytes, all-solid state compositions utilize electrolytes of a solid state type, which are inherently safer in use. In these structures a large variety of materials are and have been used for the respective electrodes for example as disclosed in US 20110117417. In discharging battery mode, the anode is the “negative electrode” to which the positive current flows, from the cathode, being the “positive electrode”. During charge these functions are reversed. Irrespective charging mode, the electrochemical relationship may be characterized by charge exchange between a negative electrode material and a positive electrode material, the negative electrode material having a workfunction or redox potential that is lower than the workfunction or redox potential of the positive electrode material.
For example, known negative electrode (anode) materials are Lithium metal, Li4Ti6O12 (Titanate); LiC6 (Graphite); Li4.4 Si (Silicon) and Li4.4Ge (Germanium) known positive electrode (cathode) materials are LiCOO2 (LCO), LiCoPO4, (doped) LiMn2O4 (LMO), LiMnPO4, LiFePO4 (LFP), LiFePO4F(LFPF) or LiCO1/3Ni1/3Mn1/3O2 (LCNMO).
Known (solid state) electrolytes might include lithium iodide (LiI), lithium phosphate (Li3PO4) and lithium phosphorus oxynitride (UPON). In addition, lithium salts, such as LiPF6, LiBF4 or LiClO4 in an organic solvent, such as ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate are known to have a typical conductivity of about 10 mS/cm at RT. The electrolyte decomposes on initial charging and forms a solid layer called the solid electrolyte interphase (SET).
Solid polymer separators may also be included, such polymers like polyethylene oxide (PEO) having transport capacity often due to having a lithium salt like LiTFS1 or LiFSI disposed therein as known in the state of the art. In addition, gel polymers include an aprotic solvent like PC, EC or DMC or ionic liquid like Pyr13LiTFS1 or Pyr14LiTFS1. The invention is not limited to the specific chemistry of the battery; alternatively sodium materials can be used e.g.: Anode materials comprising Na, Na—Sn, Na2Ti3O7; Cathode materials comprising Na2S, TiS2, Na0.67Ni0.33Mn0.67O2, Na3V2(PO4)3, NaFePO4 and electrolytes comprising Solid: Na3PS4, Na-ß/ß″-alumina NaSiCON, Na2S-P2S5
In order to maximize power density of 3D-batteries it is, in general terms, desirable to increase interface areas between cathode and anode and/or to reduce ion- and electron-diffusion distances. For US20170214083A1 it is not feasible to further improve these parameters by further minimizing the finger dimensions, nor by providing additional microstructuring on said fingers since US20170214083A1 requires that electrodes must be cut out as well as physically handled. This leads to a limitation that the carbon nanotube scaffold has rather large minimal dimensions; 30 μm appears to be a minimum width for electrodes whereas 25 μm is given as minimal gap distance.
It is an aspect of the present invention to provide a solution for said problems by providing a connected structure of largely vertically oriented carbon nanotubes that provides large surface areas and high aspect ratio elements and enables further processing steps on a single substrate.
A substrate comprises carbon nanotubes, oriented largely parallel in a direction away from the substrate. In a plane along a surface of said substrate carbon nanotubes are formed in first cells formed by one or more connected structures of carbon nanotubes. Said first cells are nested within a structure of second cells. The connected structure comprises at least one opening, without carbon nanotubes, to provide access to the surface of the substrate. Connected structures between second cells are separated from each other by a trench to prevent carbon nanotubes of a second cell from contacting carbon nanotubes of another second cell across a first gap formed by said trench. The trench provides access to the substrate between connected first structures of carbon nanotubes. Said first gap formed by said trench separates nanotubes across said first gap by a distance between 200 inn and 20 μm. Capillary forces are prevented to propagate to neighboring cells. In this way, cracking of the connected structures is prevented
The invention will further be elucidated on the basis of exemplary embodiments which are represented in a drawing. The exemplary embodiments are given by way of non-limitative illustration. It is noted that schematic representations of embodiments of the invention that are given by way of non-limiting example.
In the drawings:
a) and b) depict scanning electron micrographs of a composite material on a substrate;
a) and b) schematically depicts a top-views of a fourth and fifth exemplary embodiment of a connected structure;
a), b) and c) schematically depicts top-views of a fifth exemplary embodiment of a connected structure;
Objects of the present invention include provision of a high surface area scaffold structure that may advantageously be applied in applications particularly benefiting from a high surfaces area. The scaffold or the invention are formed by one or more connected structures of carbon nanotubes on a substrate. The carbon nanotubes are oriented largely parallel in a direction away from the substrate. The one or more connected structures of carbon nanotubes may be used as scaffold in a variety of subsequent processes to manufacture a variety of items and products. Such items and products include, but are not limited to 3D-batteries and 3D-electrode structures. For example, 3D batteries may be manufacture using the provided one or more structures of connected carbon nanotubes as scaffold, e.g. the walls of the scaffold, for the deposition of various layer of active materials comprised in a battery. Such layers include but are not limited to electrode materials, electrolyte materials and/or current collection materials. Said layers may be provided onto the scaffold, in spaces/opening between the scaffold, and/or in pores within the connected structure of carbon nanotubes. Such process may be referred to as impregnation.
The scaffolds according to the invention are dimensioned to simultaneously optimize manufacturability and/or stability of the scaffold itself while at the same time optimizing the surface area of the scaffold, e.g. surface area of the walls formed by the connected structure of carbon nanotubes, and/or to optimize the space between opposing connected structures of carbon nanotubes (e.g. space between walls of the scaffold). The dimensioning of the scaffold further ensures processability of the scaffold during subsequent manufacturing processes, e.g. allowing conformal coverage along a scaffold wall during a subsequent vapor deposition step. In case of battery applications, dimensioning the space between connected structures of nanotubes may be used to tune properties of a battery formed with the scaffold. For example, increasingly large separations between opposing walls may leave increasingly more volume that may be filled with electrode materials which accordingly may improve overall battery capacity. At the same time, increasingly large separations between opposing walls may increase diffusion distances of active species during battery operation which may accordingly increase internal resistance and/or reduce attainable charging and/or discharging rates.
In other words, the scaffolds according to the invention are dimensioned to optimize manufacturability and stability of the scaffold, while simultaneously optimizing dimensions of the scaffold to ensure stability and processability of the scaffold during subsequent processes to manufacture functional items/products.
Inventors found that the advantages relating to the above described dimensioned scaffolds of connected structures of carbon nanotubes can not be achieved with trivial connected structures of carbon nanotubes like individual pillars on a substrate, e.g. as described Adv. Mater. 2016, 28, p 6705-6710 by Shahab Ahmad et al. For example, structures of individual pillars provide comparatively less usable vertical surface area per unit area of substrate. Further, the pillars are comparatively spaced out further, allowing improvement of attainable energy density (charging and/or discharging rates) in batteries formed with such scaffold. Aspects pertaining to the dimensioning of the scaffold will be explained in more detail herein below.
In some exemplary embodiments, a structure of carbon nanotubes is provided, wherein said openings within the connected structure of carbon nanotubes in first cells form one or more channels providing access to said trench separating said second cells, and wherein a second gap formed by said channel separates nanotubes across said channel by a minimum distance. Such a distance may be about 0.5 μm or more, e.g. 10 micrometer or 50 micrometer. By forming one or more channels from openings in the first cells to provide access to said trenches separating said second cells one or more connected network of channels and trenches is formed. These networks may form a perfusion network for process gasses and liquids in the process of manufacturing in a direction along the substrate and provide access to said substrate.
In another aspect, a structure of carbon nanotubes comprises one or more channels providing access to said trench separating said second cells, wherein said channels and/or said trenches have a preferential orientation in a direction along the substrate. This preferential direction may for example be along a direction a substrate is moved during fabrication or processing of the structure of carbon nanotube. In case the substrate is flexible, the preferential direction may also be defined according to a preferred bending direction, to prevent carbon nanotubes separated by said channels and trenches from contacting each other.
Preferably a constant distance is maintained between the terminal ends, i.e. upper ends, away from the substrate, of said carbon nanotubes by providing a structure of carbon nanotubes. To this end, a top layer may be provided to connected structures of carbon nanotubes. A top layer links terminal ends of carbon nanotubes and thus helps in controlled agglomeration or collapse of said carbon nanotubes which effectively increases potential room for providing additional composite layers to the connected structures. Agglomeration or collapse can be described as a densification process of closely packed nanotubes due to capillary interaction by a liquid, when the liquid is extracted (dried) which will be further explained in the remainder. The top layer may be formed from a single material or may comprise multiple materials, forming a composite top layer. Suitable materials include, but are not limited to, oxides, for example aluminum oxide, titanium oxide, zinc oxide, vanadium oxide, indium oxide, or a combination thereof. Depending on process conditions, the presence of a trench or other larger openings, and their dimension and orientation, the top layer may also be deposited on the substrate. Suitable deposition methods include, but are not limited, to sputtering methods. Optionally, the part of the top layer deposited on the substrate, i.e. between the carbon nanotube structures, could be electrically conductive. This electrically conductive layer contributes to providing an electrically conductive connection between substrate and carbon nanotube structures. A suitable thickness of such layer would be 5 μm. In another aspect a structure is provided of carbon nanotubes that is further processed to form a composite material comprising the structure carbon nanotubes and at least a second material. A process for the production of a composite material comprises the steps of; preparing a structure of carbon nanotubes, and deposition of at least a second material using a fluid processing step wherein the fluid processing step comprises one or more of sputtering and chemical vapor deposition (CVD), PVD, and ALD and spatial ALD (BALD) and wet liquid deposition methods, such as wet chemical deposition methods, wherein the wet chemical liquid deposition methods comprise methods as hydrothermal growth, chemical bath, sol-gel, chemical solution deposition, combustion synthesis, electrodeposition, and liquid source misted chemical deposition (LSMCD).
Vertically aligned carbon nanotubes on substrates may be obtained using a suitable catalyst with controlled growth process like CVD. The carbon nanotubes may be single-walled or multi-walled carbon nanotubes or a combination thereof. The catalyst may be present as an integral part of the substrate or may be provided separately on a substrate of choice. Substrates may be rigid or flexible.
By growing the carbon nanotubes from a surface a connected structure of carbon nanotubes is formed. It is believed that within a connected structure the presence of nearby carbon nanotubes enables parallel growth of nanotubes. Using a suitable process, carbon nanotubes may be grown with a length of 10, 25 μm, 50 μm, 75 μm, 100 μm, 200 μm, 500 μm or values in between.
Structured or patterned structure of vertically aligned carbon nanotubes on a substrate may be obtained starting from a substrate that is uniformly covered with a structure of carbon nanotubes. These structures may be shaped, for example, by removal of part of the carbon nanotubes according to a desired pattern in a separate patterning or lithographic step. Alternatively, connected structures of vertically aligned carbon nanotubes may be obtained by growing the carbon nanotubes to a desired length using a substrate coated with a suitable catalysts that is provided in a desired pattern. In such event the carbon nanotubes will only grown on regions of the substrate where the catalyst is present.
Schematic representations offering a top-view of exemplary embodiments of structures of carbon nanotubes may be interpreted as top-views of said structures of carbon nanotube. Alternatively, these representations may be interpreted as substrates comprising a suitable catalyst layer in the corresponding design.
As will be explained herein below, inventors found that parallel growth conditions (also known also referred to as straight or upright growth) may constrain the shape as the dimensioning of the connected structure of carbon nanotubes. including the number and dimension of holes and/or trenches in the scaffold as well as the span or wall thicknesses of connected structures of carbon nanotubes.
Within the connected structure the carbon nanotubes are present at a small distance from one another ranging e.g. between 10 nanometer-1 micrometer. This may leave space between the carbon nanotubes which can be filled with a second material resulting in the formation of a composite material.
Materials may be deposited on carbon nanotube structures using vacuum based deposition methods like CVD, PVD, ALD or sALD. This results in the formation of a coating on and between the carbon nanotubes resulting in impregnation of the connected carbon nanotube structures. The amount of material that is deposited may be controlled by process parameters of the corresponding methods. These process parameter include, for example precursor source, precursor concentration or pressure, substrate temperature, and deposition time. For substrates comprising a structure of carbon nanotubes, wherein the carbon nanotubes are patterned in a structure of cells comprising an opening that provides access to the substrate, material may also be deposited on said substrate at locations of said openings. The homogeneity and/or resulting presence of a conformal coating along the sidewalls of carbon nanotubes structures comprising said openings as well as on the substrate at the bottom of said openings also depends on the accessibility of the substrate and these sidewalls to the corresponding vapors under given process conditions. Accessibility is influenced by the dimension of said openings and the length of the carbon nanotubes; in other words the aspect ratio. Wider openings and/or shorter carbon nanotubes result in improved conformal coverage of a material to be deposited along the sidewalls as well as at the bottom of said openings.
It is an aspect of the present invention to provide structures of connected carbon nanotube comprising holes and/or trenches that can be coated and/or impregnated with an additional material using vapor based deposition methods. Important aspects determining the quality of a coating provided using vapor-based methods include the homogeneity and conformity of a formed coating along the side walls of connected carbon nanotube structures as well as on the substrate openings provide access to. Typically, obtaining good conformal coating is more difficult in structures comprising narrow deep openings, i.e. high aspect ratio holes than in wider openings or elongated openings such as trenches.
It is an aspect of the present invention to improve the quality of coatings added onto provided structures on carbon nanotubes by providing a structure of carbon nanotubes, wherein said openings within the first cells form one or more channels providing access to said trench separating said second cells. By forming one or more channels from openings in the first cells to provide access to said trenches separating said second cells one or more connected networks of channels and trenches is formed. These networks form a perfusion network in a direction along the substrate and provide access to said substrate. This perfusion network improves accessibility throughout the structure of carbon nanotubes as well as to the substrate for of materials to be deposited in vacuum based deposition methods. In order to achieve said desired effect, it was found that said second gap, formed by said channel, separates nanotubes across said channel by a minimum distance of 1 μm.
Deposition of materials in vapor based methods in which vapor perfusion contains an anisotropic component may be improved by proving a perfusion network in the carbon nanotube structure along oriented along a preferred direction. Spatial ALD, or sALD, in which a substrate to be processed is continuously moved under a processes element, is a typical example in which anisotropic perfusion of process gasses is an important aspect. With sALD a drag flow, caused by substrate movement influences perfusion of vapor species. By orienting the channels and trenches provided in a structure of carbon nanotubes on a substrate along a directing along the direction of movement of said substrate, coating quality at the substrate level and along the walls defining openings will be improved.
It is an aspect of the present invention to provide a structure of carbon nanotubes, wherein said one or more openings have a preferential orientation in a direction along the substrate. It was found that for structures comprising oriented channels and trenches straight growth of carbon nanotubes, with a length in excess of 50 μm, was obtainable if the oriented connected channels and trenches are designed to be under 500 μm long and comprise a maximum of 10 trenches that form interconnects between adjacent parallel connected channels and trenches.
Not all materials can be deposited by vacuum based deposition methods. Reasons include for example, limited precursor availability, diffusion restrictions or a lack of precursor stability. In addition, multi-material compounds such as many layered oxide structure structures (such as LiCoO2, LiMn1/3Ni1/3Co1/3O2 which may typically be used in Li-ion batteries) pose a major challenge, especially from a cost perspective.
Therefore, solution processing or a combination of vapor and solution processing of vertically aligned carbon nanotubes is of great interest, for example for the production 3D-thin film all-solid-state Li-ion batteries.
The presence of liquids in combination with connected structures of vertically aligned carbon nanotubes comprising openings, results in the occurrence of large capillary forces. Under the influence of capillary forces, high aspect ratio nanostructures, including structures comprising carbon nanotubes, are known to agglomerate, bend and/or deform as a result of these strong capillary forces. More specifically, in an effort to reduce the strong capillary forces acting on the nanostructures, the structures bend at the cost of an increase in elastic bending energy. Hence, this phenomenon is referred to as ‘elastocapillary’ action.
Both WO2017011052A2 and US20170214083A1 teach the use of substrates covered over large areas with vertically aligned carbon nanotubes. After deposition of an additional material on to the carbon nanotubes, the carbon nanotubes agglomerate in an uncontrolled way resulting in bending, curling, cracking and falling over of tubes.
Uncontrolled agglomeration of vertically aligned carbon nanotube structures on a substrate may be prevented by stabilizing the structures of nanotubes by connecting the terminal ends of said tubes at a fixed distance from one another. This effect may, for example, be achieved by addition of a top layer onto a structure of vertically aligned carbon nanotubes on a substrate. This layer may, for example, be deposited as a film of an additional material located on top of the structure of nanotubes. Suitable deposition methods include, but are not limited, to sputtering methods. Suitable materials include, but are not limited to, oxides, for example aluminum oxide.
It is an aspect of the present invention to stabilize structures of largely vertically oriented carbon nanotubes by further providing the structures with a top layer connecting the terminal ends of said carbon nanotubes in order to maintain a constant distance between the terminal ends of said carbon nanotubes.
On surfaces provided with nanostructures of suitable length in suitable patterns, agglomeration can be controlled and a hierarchical assembly of structures can be achieved. U.S. Pat. No. 9,221,684 and US20120126449A1 describe methods for the shaping of nanostructure arrays using controlled agglomeration processes. Said documents present design rules for a broad range of attainable architectures on surfaces including: pillars, tubes, as well as sheets, all in a number of upright, bended, twisted or folded variations.
Upon controlled agglomeration of the carbon nanotubes, present in the connected structure, individual carbon nanotubes may agglomerate and form dense solid bundles. This densification results in a lateral reduction in size of the loose carbon nanotube structures. Thick walls are reduced to thinner more dense walls of carbon nanotubes. Densification of structures of carbon nanotube provided with openings results in an increased dimension of said openings. Trenches and gaps widen as a result of controlled agglomeration. Free standing pillar-shaped structures of carbon nanotubes density into free standing pillar-shaped structures with reduced diameter.
Controlled agglomeration of carbon nanotubes by a liquid process can be used to generate large aspect ratio carbon nanotube structures with lateral dimensions beyond minimal lateral dimensions attainable by conventional lithographic methods.
It is an aspect of the present invention to provide substrates comprising structures of largely vertically oriented carbon nanotubes that are designed to form of large aspect ratio bundles of carbon nanotubes using controlled agglomeration and to avoid undesired collapse, bending, curling, cracking or other unwanted loss of structure resulting from contact with liquids.
It is a further aspect of the present invention to increase the aspect ratio of structures of largely vertically oriented carbon nanotubes by controlled agglomeration.
Without the desire of being bound to any theory, it is believed that uncontrolled agglomeration of carbon nanotubes is the result of lateral stress within the connected structure of carbon nanotubes. For example, in case large structures of carbon nanotubes are exposed to a liquids, capillary forces during drying lead to the agglomeration and bundling of carbon nanotubes within the structure. This results in densification and for large structures this may lead to random formation of cracks and thus to poor long-range order.
An effect of providing trenches, separating structures of carbon nanotubes from opposing structures is that lateral forces within a structure are limited and forces are prevented to propagate to neighboring cells. In an embodiment according to the invention structures are provided with trenches to provide controlled agglomeration as a result of contact with liquids and to prevent random cracking. Also carbon nanotubes from structures across the trench are prevented from contacting each other.
By inducing agglomeration by contact with fluids that are mixtures or solutions comprising a suitable precursor, bundles of carbon nanotubes can be prepared that are impregnated with a desired material. Suitable fluid processing methods in which a layer may be deposited onto a scaffold include, but are not limited to: sputtering, CVD, ALD, spatial ALD and wet deposition methods, such as wet chemical deposition methods, wherein the wet chemical deposition methods comprise methods as hydrothermal growth, chemical bath, sol-gel, chemical solution deposition, combustion synthesis, electrodeposition, and liquid source misted chemical deposition (LSMCD).
It is an aspect of the present to provide a patterned nested structure of carbon nanotubes on a surface with in which the patterning enables controlled agglomeration or agglomeration combined with impregnation.
Controlled agglomeration of carbon nanotubes structures may be performed using pure liquids. Controlled agglomeration may be combined with impregnation by using suitable mixtures of solutions comprising a suitable precursor. Controlled agglomeration may also be preceded by a vacuum based impregnation step. A vacuum based deposition step may also follow after a controlled agglomeration step.
It is a further aspect of the present invention to provide a patterned nested structure of carbon nanotubes on a surface which, after densification and impregnation, is suitable for further processing steps including, but not limited to, gas phase functionalization processes as PVD, CVD, ALD and spatial ALD.
By impregnation using vapor-based processing methods or by combined impregnation and densification using wet liquid methods a composite material is formed. Repeated deposition of additional material onto these composites may lead to the formation of multi-layered composite materials.
It is a further aspect of the present invention that provided carbon nanotube structures are used as scaffold for the production of composite materials. These composite materials comprise the carbon nanotube structure and least one additional material. Additional materials may be added by liquid deposition methods, vapor based deposition methods or using combinations of processes. Material may also be deposited on carbon nanotube structures repeatedly, resulting in the formation of multi-layered structures on substrates. In case the carbon nanotube structures are provided with a suitable pattern high aspect ratio structures can be formed using controlled agglomeration. Subsequent deposition of additional layers onto these high aspect ratio carbon nanotube structures, layered structures are formed with an orientation largely perpendicular to the substrate.
In conventional 2D-batteries, two suitable electrode materials, separated by an electrolyte material, are oriented parallel to a substrate. In order to increase the energy storage capacity of such layered 2D-batteries, the thickness of the electrode layers may be increased. Increasing the thickness of the electrode layers results in an increase of electron- and ion-diffusion distances. This results in an increased internal resistance of the battery and is accompanied by poor power density of the battery. By simultaneously increasing the volume and interface area of electrode materials within a battery, while maintaining a short distance between the electrodes, both power and energy density of a battery can be increased.
It is a further aspect of the present invention that the ability to form multi layered structures with a largely perpendicular orientation to a substrate is especially beneficial for energy applications like 3D-batteries and super capacitors.
In energy storage systems volume expansion and shrinkage of electrode materials during operation under discharge and/or charging conditions is a well recognized problem. Expansion and/or shrinkage of electrode materials may lead to formation of cracks and/or other damage to the system, leading to performance degradation. Damage to a system may progressively increase upon repeated charging and discharging cycles, resulting in reduced performance over time. For 3D battery applications these issues are especially relevant.
In an embodiment according to the invention a 3D energy storage system is formed comprising the scaffold structure according to the invention. The scaffold structure provides large aspect ratio structures onto which suitable layers of electrode material and electrolyte are deposited. Layers may be deposited using fluid deposition processes such as the aforementioned vacuum deposition methods and wet chemical deposition methods. Good control over properties of deposited layers such as layer thickness, conformity, and homogeneity is desired. To allow for this control, good access to the large aspect ratio carbon nanotube structures during the deposition process is desired, such that material to be deposited is not only deposited on top of said structures, but material may also be deposited along the side walls of the large aspect ratio structures. The scaffold structure according to the invention provides such access by providing a structure wherein carbon nanotubes are formed in a structure of first cells, nested in a structure of second cells, wherein the first cells comprise at least one opening, without carbon nanotubes, to provide access to the surface of the substrate, and wherein second cells are separated from each other by a trench to prevent carbon nanotubes of a second cell from contacting a carbon nanotube of another second cell across a first gap formed by said trench. By providing suitable openings in cells and by separating cells in the scaffold structure across a gap, a space between adjacent large aspect ratio structures is formed which allows for the desired access to access to the large aspect ratio carbon nanotube structures during subsequent fluid deposition steps.
Layers deposited onto the scaffold may also partly impregnate space between carbon nanotubes within a structure. By only partly filling the space between the carbon nanotubes within a structure a porous structure may remain. Leaving porous regions within the carbon nanotube structure reduces potential damage to an energy storage system resulting from volume changes within the electrode material. Optionally, impregnation may result in the formation of a porosity gradient within the carbon nanotube structure in a direction along the carbon nanotubes. Porosities up to 90% have been achieved, for example with ALD, while still getting a layer thickness in excess of 50 nm
Deposited layers may be provided comprising a gradual and/or step-wise compositional gradient in a direction along the substrate. Alternatively, or additionally, the deposited layers may comprise a compositional gradient in a direction away from the substrate. In this way electrode material comprising large volume changes during operation may desirably be deposited at locations with higher porosity, for example near inner regions of a carbon nanotube structure. Also, electrode material with low volume expansion may, for example, be deposited preferentially near the outer regions of a carbon nanotube structure.
As mentioned above inventors found that parallel growth conditions may constrain the design (e.g. shape) and/or dimensioning of the scaffold. To provide a connected structure that grows sufficiently straight, inventers found that the connected structure preferably has a minimum wall thickness. Wall thickness may be understood as the shortest distance from an opening or trench providing access to the substrate to an adjacent opening or trench or in other words as the smallest distance between two outer walls of the connected structure of carbon nanotubes. For example it was found that in order to achieved straight growth of carbon nanotubes with a length in excess of 100 μm (i.e. form a connected structure with a thickness in excess of 100 μm), a wall thickness (tmin) of 1 μm or more is preferred. Table 1 lists experimentally derived values for tmin categorized for specific ranges of carbon nanotube height .
Irrespective of the actual pattern, inventors found experimentally that, the connected structure of carbon nanotubes preferably has a minimal lateral dimension Dmin of at least 8/100 times the length of the carbon nanotubes in that structure (i.e. the height of the connected structure of carbon nanotubes). In other words, for a scaffold with a desired height of 100 μm (carbon nanotube length of 100 μm), the connected structure preferably has a minimal lateral dimension in a direction along the plane of the substrate of at least 8 μm. The smallest lateral dimension along the plane of the substrate may be understood to be a smallest spanning diameter of a connected carbon nanotube structure i.e. a dimension of a minimum first bounding box (B1—see
Inventors found that similar to the preferred minimum wall thickness (tmin) the minimum value for the lateral dimension (Drain) of the connected carbon nanotube structure also scales with carbon nanotube length. Increasingly longer tubes require increasingly longer distances (spans) over which tubes feel the presence of neighboring tubes in order to grow straight. Inventors further experimentally derived that the minimum value for the lateral dimension (Drain) also depends on the number, and size of pores and trenches within the structure, i.e. a covering ratio P within the connected structure.
Table 2 lists experimentally derived values for the preferred minimum lateral dimension (Dmin) of the connected carbon nanotube structure categorized for specific ranges of carbon nanotube heights and covering ratio P defined as the fraction of substrate covered with the connected structure of carbon nanotubes. A covering ratio of 0 provides full open access to the underlying substrate surface in the region of the connected structure; whereas a covering ratio of 100 provides no access. The covering ratio includes surrounding open channels/trenches (i.e. within a second bounding box (B2—see
wherein Dmin is the smallest lateral dimension of a minimum first bounding box (B1—see is the height of the connected structure of carbon nanotubes, e.g. the length of the carbon nanotubes, and wherein P is a local covering ratio, defined as the fraction of substrate covered with the connected structure of carbon nanotubes that provides open access to the underlying substrate surface in the region of the connected structure including surrounding open channels/trenches (i.e. within a second bounding box (B2—see
For a graphical representation of Dmin, B1, B2, reference is made to the connected structure depicted in
Accordingly, for a 100 μm high structure of connected carbon nanotubes with a local covering ratio of 0.5 (50% open structure), the smallest dimension (e.g. diameter) of the connected carbon nanotube structure is preferably in excess of 16 μm. Note that the exemplary structures shown in the overview electron micrograph of
The specified dimensioning of Dmin ensures that scaffolds with complex designs as described herein below, e.g. nested designs, e.g. scaffold designs with lateral openings (side-feeds), side-wall patterning, and/or zig-zag patterns, grow at least as straight as structures formed with patterns of trivial geometric shapes as squares, circles, or straight lines.
As explained above, inventors further found that carbon nanotubes separated from each other across a gap/trench should be separated by a distance of al least 200 nm By separating carbon nanotubes across a gap by at least 200 nm intermixing of tubes across said gap is prevented.
Further, inventors found that that portions of the connected structure of carbon nanotubes connecting carbon nanotube structures with a larger size preferably have a minimum width (i.e. wall thickness) of 500 nm. For example, with reference to
Additionally, the connected structure may be defined by a cover ratio PCS<0.2, wherein PCS is defined as the ratio of underlying substrate covered by carbon nanotubes within its respective bounding box B1.
A further set of dimensioning constraints relates to the dimensioning of trenches and channels. Inventors found that the channels and/or trenches, which not necessarily need to be straight, preferably have a width in a range between about 500 nm up to about 20 μm. This specified width allows that materials, e.g. active chemicals, may be supplied throughout the complete scaffold (from top to substrate) during subsequent processing steps such as gas phase deposition steps and/or wet chemical processing steps. For example, a trench with a width of 500 or 1000 nm may be sufficient to allow conformal coverage of the scaffold side walls with an electrode material using a known vapor deposition procedure.
The above provided constrains for minimal dimensioning of the connected structure of carbon nanotubes (e.g. Dmin and tmin) contribute to proper parallel alignment of carbon nanotubes forming the scaffold. In combination with the herein disclosed specification of openings, trenches and optional channels connecting the openings, a scaffold comprising a percolation network may be provided with improved surface area onto which further functional materials may be deposited during subsequent vapor and/or liquid deposition processes, while providing accessibility to allow deposition of materials along the height of the scaffold and/or onto the substrate, all while the scaffold is further dimensioned to allow controlled agglomeration of the carbon nanotubes in the connected structure following by contact with a liquid.
Inventors found that substrates provided with connected structures of carbon nanotubes with a lateral dimension in excess of 500 micrometer negatively affect handling, e.g. flexibility, of the substrate. Accordingly a maximum dimension (span) of the connected structure of carbon nanotubes in a direction along the substrate, e.g. a dimension (span) of the second cells, preferably does not exceed 500 μm.
At the same time, a further set of dimensioning constraints may be defined which relates to the envisioned application that is to formed with, e.g. on, the scaffold. These applications include for example. 3D electrodes and 3D batteries. For both battery and electrode applications the length of the carbon nanotubes (height of the scaffold) is preferably in a range from 20 μm up to 500 μm.
For 3D electrodes the covering ratio is preferably between 50% and 80% (i.e. preferably 0.5≤P≤0.8) Further, the maximum distance from a position within the connected structure of carbon nanotubes to a position on a wall surface of the structure is preferably below 15 μm. It was found that the combination of these constraints ensures processability of the connected structure in a subsequent processing step involving gas phase and/or wet chemical deposition process (i.e. processability without uncontrolled agglomeration). Said combination further improves functionality in applications wherein the 3D-electrode is combined with a liquid electrolyte (e.g. power density in 3D batteries). By limiting the maximum distance from a position within the connected structure of carbon nanotubes to a position on a wall surface (where an electrolyte would contact the electrode) ion transport times may be shortened by minimizing diffusion distances, e.g. tortuosity.
Optimization of the surface area of the scaffold enables improving properties such as capacity and/or energy density for 3D batteries. With regard to 3D batteries inventors found that:
A
W≥10·AS;
wherein AW is the outer area of the one or more connected structures of carbon nanotubes (i.e. the area of the walls of the scaffold) and AS is the total area of the substrate covered by the scaffold (i.e. the area of the substrate covered by connected structures of carbon nanotubes including the openings, gaps and trenches). Like for 3D electrodes, for 3D batteries the maximum distance from a position within the connected structure of carbon nanotubes to a position on a wall surface of the structure is preferably below 15 μm. Inventors found that for 3D batteries wherein the scaffold is to be completely filled with electrode material the maximum distance is preferably below 5 μm. For scaffolds for 3D batteries, the covering ratio P is preferably between 20% and 70% (i.e. 0.2≤P≤0.7). Inventors found that this combination of constraints ensures stability of a scaffold provided with an electrode layer (forming a 3D electrode) during further processing steps (i.e. improves processability) to cover the 3D-electrode. In particular, it was found that the constraints allow a gas phase and/or a wet chemical deposition process for depositing an electrolyte to cover the 3D electrode surface. Further, the constraints limit a remaining volume after such steps needed to be filled with a top electrode material in the remaining structure.
On the other hand, connected structures with increasingly large dimension in a lateral direction (along a substrate) are increasingly prone to uncontrolled agglomeration and/or to formation of random cracks in the connected carbon nanotube structure upon contact with a liquid, as demonstrated in the continuous array of connected tubes shown in
Without wishing to be bound to theory inventors found that there exists a minimum inter-distance between separated cells, i.e. a minimum distance between carbon nanotubes separated across a gap, which arises from growth conditions. With respect to the scaffolds of the present invention, inventors found that carbon nanotubes in structures separated by at least 200 nm, more preferably by at least 500 nm can grow separately without intermixing with carbon nanotubes from adjacent cells. Inventors found experimentally that in order to allow carbon nanotubes in adjacent structures to grow separately, e.g. without intermixing, the minimum separation distance (up to a distance of 3 μm) may be described by the relation: separation distance=0.5 μm+0.001 times h; wherein h is the height of the connected structure of carbon nanotubes in nanometer, e.g. the length of the carbon nanotubes. Accordingly, a 100 μm high structure of connected carbon nanotubes may grow independently of an adjacent structure if it is separated therefrom by 0.6 μm. Note that the correlation was confirmed for separation distances up to 3 μm. An exact value for a maximum separation is hard to provide. In the present context a maximum of about 20 μm may be preferred in view of a general desired to maximize surface area of the scaffold, and thus minimize the trench area.
It was experimentally found that long range order remains present after agglomeration of carbon nanotubes due to contact with liquid, for honeycomb-shaped structures with a up to 3 holes per side having walls with a dimension ranging from 0.5 μm to 5 μm and having holes with a diameter ranging between 2 μm and 10 μm.
It will be appreciated that although the first exemplary embodiment comprises circular openings, arranged in hexagonal packing forming a honeycomb shape with 2 holes per side, the disclosure thereof is not to be understood as limiting. Other embodiments comprising, for example, different shape openings, different number of openings, arrangements in honeycomb-shaped structures with a different number of openings per side, and/or packing in a non-hexagonal way, for example square, are also envisioned.
It is an aspect of the second exemplary embodiment to avoid uncontrolled collapse of the carbon nanotube structure resulting from contact with liquids. Within the second exemplary embodiment first cells may have a diameter ranging between 2 urn and 30 μm, interconnects may have a width ranging from 50 nm to 90% of the dimension of the first cell and interconnects may have a length ranging from 50 nm to 100% of the dimension of the first cell. The distance between adjacent second cells may be between 50 nm and 20% of the dimension of the second cell.
It will be appreciated that although the second exemplary embodiment comprises 7 interconnected circular first cells, arranged in flower-shaped second cell, the disclosure thereof is not to be understood as limiting. Other embodiments comprising, for example, different shape first cells, second cells comprising a different number of interconnected first cells, are also envisioned.
The scaffold structure of
In a variation of the described embodiments a pillar structure is provided with additional openings along an outer perimeter of the pillar the form of short trenches. In accordance with the hollow pillar-shaped connected structures shown in the third exemplary embodiment, a minimum dimension of 15 μm was found to be sufficient to support parallel growth of carbon nanotubes with a length in excess of 100 μm.
a) and b) depict scanning electron micrographs of a composite material on a substrate. The composite is made by depositing a layer of ZnO using ALD onto a connected structure of vertically aligned carbon nanotubes in a structure of first cells, nested in a structure of second cells, wherein the first cells comprise openings (62, 63), without carbon nanotubes, to provide access to the surface of the substrate, and wherein second cells 64 are separated from each other by a trench 61.
a) provides an overview of a structure 5a of carbon nanotubes onto which ZnO is deposited. The honeycomb-shaped structure of carbon nanotubes 64 is similar to the embodiment depicted in
On the right an electron micrograph (5b) is depicted, which provides a close-up view of a ZnO-coated structure of carbon nanotubes 65 at a position adjacent a trench. To facilitate recording the region of the carbon nanotube structure near the substrate, part of the structure of carbon nanotubes was removed. The location 68 were the carbon nanotubes were removed remains visible. In the micrograph bright locations 66 on the remaining carbon nanotube structure is indicative of the presence of ZnO along the length of the carbon nanotubes up to the level of the substrate, whereas dark regions 67 indicate the absence of ZnO. In the presented structure, two classes of openings within the honeycomb-shaped structure are discerned; a first type adjacent the trench (62, 66), and a second type in a more central location, at least one row of holes away from the trench (63, 67). ZnO was found to be present on the substrate in areas corresponding to the first type of openings. ZnO was also found to be present at the bottom of the trenches (not shown). In order for ZnO to cover the substrate, its vapor precursor species have to perfuse all the way down the openings. In the present case no conformal ZnO coating was observed at the bottom of openings of the second type. It is believed that perfusion of precursor vapor species through high aspect ratio openings is insufficient to cover the substrate at locations distant from the trench. The observed presence of a thin layer of ZnO at the bottom of openings adjacent the trench, is believed to be facilitated by a partial permeability of the wall separating the hole and the trench.
In the
a)-c) schematically illustrate three stages of a production process of a 3D-battery, wherein an exemplary structure of carbon nanotubes is used as scaffold for the fabrication of a multi layered composite. The process starts in
The ingress structure 103a can be formed by trenches 103 separating the cells, but can also be formed by channels of wider dimensions, e.g. dimensions more than 10 times the width of a trench 103, e.g. more than 30 micrometer. The ingress structure 103a is preferably patterned pattern outside an overlap area of the cathode 11, to provide a uniform electric condition in the liquid electrolyte.
It will be appreciated that the visualized stages of an exemplary production process of an energy application is not limited to the exemplary process, nor to the used materials and/or depicted carbon nanotube structure. Other production processes, for example, starting from carbon nanotubes structures other than the exemplary structures presented here, or processes using other materials, or process using different deposition processes, and/or processes further comprising steps for the deposition of additional layers or materials are also envisioned.
Accordingly, the present application further relates to a patterned 3D electrode comprising the scaffold structure according to the invention. In a preferred embodiment, the scaffold is provided, e.g. grown, on a current collector foil. In another or further preferred embodiment, the scaffold is provided with, e.g. impregnated and/or covered, one or more of the of electrode materials (e.g. anode materials comprising Li, Sn, SnO2, ZnO, Si or cathode materials, such as LixMyOz (with M representing one or more transition metals), Air, or Sulphur, but also the high-volume expansion electrode materials such as the materials listed above).
By impregnating and/or covering the scaffold with electrode materials an electrode may be obtained for a battery application with improved energy density per unit area compared to thin film batteries and/or 3D batteries applications using a less porous (e.g. scaffolds with less openings per unit volume).
These materials may also be lithiated, e.g. using a chemical bath. Hereby partly filling the pores 134 between the carbon nanotubes forming the connected carbon nanotube structure. In exemplary embodiment 13 the material is deposited such that a gradient is formed in a direction along the substrate wherein a more dense filling is obtained in directions away from the center of the carbon nanotube structure or vice versa. Providing a gradient in a vertical direction, i.e. along the length of the carbon nanotubes, may be conveniently achieved on account of the parts of openings in the scaffold due being nearer to the substrate requiring having longer diffusion distances than parts of the scaffold being closer to a (vapor) deposition tool.
Generally speaking, it is found that a layer thickness between 10-100 nm of the material deposited on CNTs is favorable for battery performance. This may provide the effect of preventing cracks in the inner parts of the connected structure of carbon nanotubes, affecting the integrity of it. Additionally, lithium metal may plate in the pore structure formed after partly filling the pores with electrode material 132. This leads to a hybrid anode of both lithium metal and electrode material 132. Lithium deposition may also been processed in later stages of the battery fabrication, and eventually in-operando, i.e. during the first formation cycles of a full battery including cathode material. Additionally or alternatively, a continuous layer of electrode material is deposited on the top and sidewall of the carbon nanotube structure and in regions next to these structures, which may be formed from openings and or trenches provided to the connected structure of carbon nanotubes. The thickness of the closing electrode layer is preferably between 50 nm-1000 nm. The continuous layer may be of different electrode material than the first electrode material partly impregnating into the carbon nanotube structure. For example using materials with low expansion upon lithiation as continuous layer may improve cycling performance of the 3D electrode, whilst the impregnated electrode material has higher expansion providing more capacity. The inner material expands into the tuned porosity, whilst the outer surface of the 3D electrode material keeps minimal expansion/contraction upon cycling. Providing the electrode materials onto the connected structure of carbon nanotubes in a gradient may advantageously be used to provide higher density of electrode materials near the openings, trenches, and/or channels, e.g. closer to the pores. By providing the electrode materials in greater density at locations closer to pores the expansion and/or contraction of said electrode materials during charging and/or discharging cycles is less likely to result in degradation, e.g. formation of cracks.
In some preferred embodiments, the carbon nanotube structures forming the scaffold are first coated with a wetting layer. The wetting layer may improve the impregnation and/or conformal coating of scaffold with the electrode material. If Lithium metal is used as the electrode material, such a wetting layer may include for instance ZnO, SnO2, or doped versions thereof that show affinity towards Lithium metal.
Further to the above, the connected carbon nanotubes structures may be first capped on top with a layer that is electrically insulating or optionally ionically conducting. Inventors found that such layer may help in homogenous impregnation of the connected carbon nanotubes structures with electrode materials, be it using vapor phase, wet-chemical, diffusion-based, and/or electrodeposition-based deposition methods. Moreover, such a layer will also prevent Li-ion intercalation or plating on top of the CNTs when the battery is operated. Such a layer may also be deposited in the microspaces, e.g. the bottom of the trenches, channels, and/or openings, e.g. holes in or between the connected carbon nanotubes structures forming the scaffold.
Such capping layer could be electrically insulating or optionally ionically conducting. Said capping layer could, in a device comprising lithium, prevent stress that, in use, could be built by plating Lithium metal in the axial direction by isolating part of the structure (e.g. pillar top) with a resistive thin layer of substantial resistivity, e.g. formed by Al2O3, in order to block a direct conduction pathway between the structure, e.g. pillar top, and a topstrate current collector, which could cause Lithium ions to migrate in axial direction. Accordingly, there is provided a 3D electrode and/or energy storage application comprising an electrode layer covering the scaffold according to the invention, wherein the electrode is shielded from an apposing conductive structure by an insulator covering a part of electrode layer adjacent an end side (e.g. pillar top) thereof to, in use, prevent an conductive ion transport path between the electrode and counter electrode, thereby mitigating stress build up near the end side of the covered scaffold, improving stability & cycle life of and/or improving interfacial contact, between layers in a device comprising said capping layer. For further details reference is made to WO2017222378 describing a method of manufacturing a battery with a substrate current collector, which is hereby incorporated by reference.
Further to the above 3D electrodes, the present application relates to a 3D electrode that is covered, preferably conformally covered, with a layer of a solid-state electrolyte. In a preferred embodiment, the solid state electrolyte comprises an inorganic electrolyte, a polymer, or a mixture thereof, e.g. a composite solid state electrolyte material. Inorganic solid state electrolytes include, but are not limited to, ceramics like UPON, oxides, and sulphides. Suitable polymeric materials include polyethers such as polyethylene oxide (PEO). Optionally, or additionally, said electrolyte may be a hybrid of multiple electrolyte layer types forming a laminate. This will be beneficial for interfacial stability against different kinds of positive and negative electrode materials.
Besides being advantageous for application in energy storage application, authors further envision application of 3D electrodes comprising the scaffold according to the invention in other electrochemical cells and devices, including but not limited to fuel cells, sensors, liquid (water) filtration devices, and any other application benefitting from a 3D electrode comprising a scaffold according to the invention.
In exemplary embodiment 14 of
It will be appreciated that the depicted exemplary 3D electrode are not indented as limiting examples. Layers of other materials or combinations of materials are also envisioned. Depicted gradients may be formed by variations in one or more of: density, layer thickness, composition or combinations thereof. Gradients may be gradual, step-wise or combinations thereof. Layers may be provided with gradients oriented in directions along and/or away from the substrate.
It will be appreciated that 3D energy storage systems according to the invention, e.g. 3D battery foils, may be stacked and electrically connected and/or packaged into a battery cell for improved capacity and/or for protection against the environment respectively.
Optionally a dual-conductor could be deposited between electrode and counter electrode layers. For example, a layer of a dual-conductor material could e.g. filled in before filling in a second electrode material. A dual conductor can be understood to be a good ion- and electron conducting material. As such, the dual conductor may improve in electronic and ionic conductivity particularly when insulating electrode materials like Sulphur or Lithium peroxide are used. Accordingly, in one embodiment there is provided an energy storage structure comprising the scaffold according to the invention wherein a dual-conductor is provided between the first and second electrode layers.
Optionally, or in additionally, the second electrode material could be deposited as a mixture of a binder, an electronic conductor, an ionic conductor, and a electrode material. The particle size of the active material could range from 10 nm up to 5 microns, preferably from 100 nm up to 500 nm.
In some embodiments, the second electrode material composite may optionally further comprises a gel or semi-solid electrolyte. Addition of a non-solid material to the second electrode may improve good ionic conductivity within the electrode.
In a preferred embodiment, the second electrode material composite may be partially porous, e.g. comprise porous material. Said material preferably provides at least 5%, preferably 10%, or more e.g. 15% up to 30% of porosity to the second electrode. Providing a partially porous electrode may accommodate the volume expansion of the electrode material, e.g. during cycling, and may accordingly, improve stability and/or life-time of an energy storage device.
Optionally or in addition, the porous material may be comprise hollow beads, e.g. hollow latex beads, that may compress to, in use, accommodate a the volume expansion of the electrode. Reference is made to patent application EP 18210849.8 which discloses a rechargeable battery cell comprising a compressible elastic composite material and which is hereby incorporated by reference.
It will be appreciated that the scaffolds of present application are particularly suitable for application in 3D energy storage applications, e.g. batteries. In addition to improving the energy density per unit area, as described above, the openings, trenches and/or channels in and between the connected carbon nanotube structures provide space to accommodate not only an electrode material but also an electrolyte material and/or or counter electrode material (i.e. a complete stack of electrochemically active materials). By providing the openings, trenches and channels defined by the scaffold with a complete stack of electrochemically active materials diffusion lengths may be decreased, resulting in the formation of energy storage applications with lower internal resistance and/or improved power density output. The scaffolds according to the invention are suitably dimensioned to enable the conformal deposition of one or more of the electrode- and electrolyte materials. Further, the connected carbon nanotube structures according to the invention may be suitably dimensioned to tune the dimension of said openings, trenches and/or channels by enabling controlled agglomeration by wet processing steps, resulting in a densification of the connected carbon nanotube structures along with a controlled increase in volume, e.g. widening of the openings, trenches and/or channels in the scaffold, thusly providing additional space for the layers of electrochemically active materials.
A described above the scaffold structure according to the invention may be obtained from a substrate that comprises a suitable patterned layer of catalyst. It is noted that in some preferred embodiments a base buffer layer may be provided between the substrate and the catalyst. A buffer layer may improve interfacial contact, stability & cycle life in devices, e.g. 3D electrodes and/or energy storage systems comprising a scaffold formed with a buffer layer. Suitable buffer layers include thin electrically insulating films such as aluminum oxide.
In a preferred embodiment, the bottom part (base), e.g. the bottom 5 μm, the carbon nanotube structures can be provided/coated (e.g. deposited, electroplated, impregnated) with a conductive material (e.g. metal). By providing the bottom part of the carbon nanotube structures with a conductive material may help bridging the base buffer layer, i.e. improve an electrical conductivity between carbon nanotube structure and underlying substrate. Reference is made to WO2016178571 describing a device and method of manufacturing high aspect ratio structures grown from a substrate with buffer layer and provided with a conductive material that helps bridging the conductive pillars to the conductive substrate. WO2016178571 is hereby incorporated by reference.
In some embodiments, the aforementioned conductive material provided to the base of the carbon nanotube structures to improve the electrical conductivity between structure and substrate could result in a porosity gradient in a direction along or away from the carbon nanotubes of the structure. In other words, the conductive material may partially fill up (nano)spaces/nanoporosities between the carbon nanotubes resulting in the formation of a vertical or lateral porosity gradient within the carbon nanotube structure. As described earlier, (nano)porosity within an energy storage system may advantageously improve life time by mitigating damage, i.e. crack formation, due to expansion of electrode materials.
The presented exemplary sixth embodiment may be interpreted as a variation of the open honeycomb-shaped structure of the fourth embodiment. In stead of directly connecting each hole to a trench, holes are connected to each other, forming a multitude of parallel channels in a preferred orientation. Each channel is separated from an adjacent channel by a wall of connected carbon nanotubes. Each channel is connected 83 to adjacent channels. For walls with a thickness under 5 μm, straight growth of carbon nanotubes with a length well above 100 μm, combined with the absence of closure of channels, was found for structures comprising: a maximum channel length of 500 μm, and a maximum of 10 interconnects between adjacent channels. The scaffold structure of
It will be appreciated that, besides its application in the present embodiment, the concept of providing a network (a network that enables lateral perfusion of gaseous and vapor species within the carbon nanotube structure) is not limited to the exemplary embodiments presented in the present application. The concept can also be applied to other structures of carbon nanotubes or structures comprising holes or trenches with different, shapes, dimensions or orientation.
It will be appreciated that the visualized 3D electrodes and energy storage systems are not limited to the provided exemplary embodiments, nor to the described materials and/or depicted carbon nanotube structure. The invention may advantageously be applied to with carbon nanotubes structures other than the exemplary structures presented here, or systems comprising other and/or additional materials. Also envisioned are material layers provided with gradients in one or more of thickness, density, composition, and a combination thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 18182705.6 | Jul 2018 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/NL2019/050428 | 7/10/2019 | WO | 00 |
