(19)
(11)EP 3 149 754 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
13.07.2022 Bulletin 2022/28

(21)Application number: 15800681.7

(22)Date of filing:  24.05.2015
(51)International Patent Classification (IPC): 
B32B 33/00(2006.01)
H01G 11/04(2013.01)
H01G 11/46(2013.01)
B82Y 10/00(2011.01)
H01M 4/38(2006.01)
H01G 11/84(2013.01)
H01G 11/36(2013.01)
H01G 11/78(2013.01)
B82Y 40/00(2011.01)
(52)Cooperative Patent Classification (CPC):
H01G 11/36; H01G 11/04; H01G 11/46; H01G 11/78; H01G 11/84; H01L 28/90; Y02E 60/13; B82Y 10/00; B82Y 40/00; H01L 29/0673; Y02E 60/10
(86)International application number:
PCT/US2015/032329
(87)International publication number:
WO 2015/183762 (03.12.2015 Gazette  2015/48)

(54)

CHIP-SCALE EMBEDDED CARBON NANOTUBE ELECTROCHEMICAL DOUBLE LAYER SUPERCAPACITOR

EINGEBETTETER ELEKTROCHEMISCHER DOPPELSCHICHTSUPERKONDENSATOR IN CHIP-GRÖSSE AUF KOHLENSTOFFNANORÖHRCHENBASIS

SUPERCONDENSATEUR À DOUBLE COUCHE ÉLECTROCHIMIQUE À NANOTUBES DE CARBONE INCORPORÉS À ÉCHELLE DE PUCE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
MA

(30)Priority: 24.05.2014 US 201462002812 P
05.05.2015 US 201562156977 P

(43)Date of publication of application:
05.04.2017 Bulletin 2017/14

(73)Proprietor: Georgia Tech Research Corporation
Atlanta, GA 30332 (US)

(72)Inventor:
  • READY, William Jud
    Atlanta, GA 30318-1610 (US)

(74)Representative: Griebling, Onno 
Octrooibureau Griebling BV Sportweg 10
5037 AC Tilburg
5037 AC Tilburg (NL)


(56)References cited: : 
EP-A1- 2 207 189
WO-A2-2009/126382
US-A- 5 711 988
US-A1- 2009 059 474
US-A1- 2011 205 688
US-A1- 2013 055 559
US-A1- 2014 139 975
WO-A2-2008/016990
WO-A2-2010/144153
US-A- 5 711 988
US-A1- 2011 205 688
US-A1- 2012 134 071
US-A1- 2014 042 390
US-B1- 8 503 161
  
  • READY, WJ.: 'Application-Specific Research in Nanotechnology.' GEORGIA INSTITUTE OF TECHNOLOGY. PRESENTATION. 28 February 2012, XP055361481 Retrieved from the Internet: <URL:https://smartech.gatech.edu/handle/185 3/43163>> [retrieved on 2015-08-10]
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

CROSS REFERENCE TO RELATED APPLICATIONS



[0001] This application claims priority to U.S. Provisional Patent Application No 62/002,812, filed May 24, 2014, entitled "Chip-Scale Embedded Carbon Nanotube Electrochemical Double Layer Supercapacitor," and U.S. Provisional Patent Application No. 62/156,977, filed May 5, 2015, entitled "Chip-Scale Embedded Carbon Nanotube Electrochemical Double Layer Supercapacitor,".

STATEMENT OF FEDERALLY SPONSORED RESEARCH



[0002] This invention was made with Government support under Grant No. HQ0727-14-P-1426. The U.S. Government has certain rights in this invention.

TECHNICAL FIELD



[0003] Various embodiments of the present invention relate generally to microscale capacitors constructed using paired carbon nanotube structures that creates a supercapacitor. One type of capacitor can be an electrochemical double layer capacitor.

BACKGROUND



[0004] With the rise of microelectronics, conventional circuitry is under constant modification, especially the internal electrical components to fit increasingly tight constraints. Electronics has made a shift from micro to nano-scale devices within the past decade. With the increase in the miniaturization, electrical components, such as resistors, batteries, and transistors have been modified and redeveloped to fit the physical and mechanical characteristics of nano-scale electrical environments. Silicon based printed circuit boards have started to shrink in size, utilizing different methods of integrating these miniscule components. Recently, the integration of electrical components within the board itself has been an area of development. In specific, the need for high-energy capacitors has risen.

[0005] Capacitors have the capability of holding high charge densities and rapid discharges of energy. This holds ample utilizations within circuitry and device development. However, the reduction of device sizes has rendered conventional components null due to the synonymous energy requirements to present electronics. Electrochemical double layer capacitors (ECDL), otherwise known as supercapacitors, allow for higher power and energy than traditional capacitors. Furthermore, carbon nanotube (CNT) based supercapacitors have provided exceeding improvements over ECDLs. Carbon nanotubes have been heavily studied in the development of capacitors. The scale of function of these ECDLs is drastically smaller than conventional capacitors. Furthermore, it has been shown to possess capacitances from 15-200 F/g, depending on the active surface area. This shows great viability for supercapacitor technology using CNTs.

[0006] Most current capacitor designs are based on the traditional coin structure and follow the stack system, as shown in Figure 1A. This system utilizes three dimensional space, building the capacitor in between two metal contacts, such as shown in Figure 1B. Thus, most of current supercapacitor technology has revolved around this cell-based structure, modeling those similar to current capacitor designs.

BRIEF SUMMARY



[0007] The present invention provides an electrochemical double-layer capacitor as recited in independent claim 1.

[0008] The present invention further provides a method of fabricating an electrochemical double-layer capacitor as recited in independent claim 10.

[0009] Further advantageous embodiments are recited in the dependent claims.

[0010] Some embodiments of the electrochemical double-layer capacitors described above can include at least a portion of the first and second plurality of carbon nanotubes being functionalized with a non-faradaic material. Some embodiments of the electrochemical double-layer capacitors described above can include at least a portion of the first and second plurality of carbon nanotubes being functionalized with a faradaic material. Some embodiments of the electrochemical double-layer capacitors described above can include at least a portion of the first and second plurality of carbon nanotubes being functionalized with a both a non-faradaic and a faradaic material. The non-faradaic material can include graphene platelets on the CNTs. The faradaic material can include metal oxides, including metal oxides selected from the group consisting of ruthenium oxides, manganese oxides, iron oxide, tin oxides, vanadium oxides, titanium oxides, iridium dioxides, cobalt oxides, nickel oxides, indium oxides, copper oxides, and zinc oxides. The faradaic material can include titanium oxide or ruthenium oxide.

[0011] Some embodiments of the electrochemical double-layer capacitors described above can include at least one of the bottom substrate and the top substrate having a filling port. The bottom substrate and the top substrate can also include a gasket proximate the filling port. The gasket can be polylactic acid. In some embodiments, the capacitor can include an electrolyte disposed on at least a portion of the electrochemical double-layer capacitor. The electrolyte can be an ionic liquid, preferably a room temperature ionic liquid.

[0012] Some embodiments of the electrochemical double-layer capacitors described above can have a gravimetric energy density of the active materials of the unpackaged capacitor that is from about 100 Whr/kg to about 1000 Whr/kg. The gravimetric energy density can be at least about 95 Whr/kg, at least about 100 Whr/kg, at least about 110 Whr/kg, at least about 120 Whr/kg, at least about 140 Whr/kg.

[0013] In some embodiments, the method can further include functionalizing the first and second plurality of substantially aligned carbon nanotubes with at least one of a faradaic and non-faradaic material. The method can further also include filling an electrolyte into the capacitor. The electrolyte can be filled through a filling port. And the filling port can be located in at least one of the bottom and top substrates. The method also further includes disposing a gasket proximate the filling port, and the electrolyte can be disposed through the filling port via vacuum filling.

BRIEF DESCRIPTION OF THE FIGURES



[0014] 

Figures 1A and 1B illustrate a coin-cell capacitor typical in the prior art.

Figure 2 illustrates a generic structure of a carbon nanotube based ECDL analogous to some embodiments of the disclosure.

Figures 3A, 3B and 3C illustrate SEM images of materials produced using methods associated with construction of the disclosed supercapacitors, in accordance with some embodiments of the disclosure.

Figures 4A and 4B illustrate SEM images of uncoated and TiO2-coated CNTs, in accordance with some embodiments of the disclosure.

Figure 5 illustrates a general process for preparing a half of a ECDL capacitor, in accordance with some embodiments of the disclosure.

Figure 6 illustrates an ECDL capacitor, in accordance with some embodiments of the disclosure.

Figure 7 illustrates an electrochemical interdigitated capacitor.

Figures 8A, 8B, and 8C illustrate SEM images of CNTs that can be controlled and grown in the electrochemical supercapacitors, in accordance with some embodiments of the disclosure.

Figure 9 presents a table of increasing specific capacitance for atomic layer deposition of TiO2 on CNTs, in accordance with some embodiments of the disclosure.

Figures 10A-10N illustrate detailed process steps for preparing an ECDL capacitor, in accordance with some embodiments of the disclosure.

Figures 11A-11E illustrate detailed process steps for filling the capacitor with electrolyte and sealing the fill holes, in accordance with some embodiments of the disclosure.

Figure 12 illustrates a Si wafer used to prepare electrodes for ECDL capacitors, in accordance with some embodiments of the disclosure.

Figures 13A and 13B illustrate the top and backside of a single Si-CNT electrode, in accordance with some embodiments of the disclosure.

Figures 14A and 14B illustrate a crossectional SEM image of an Si-CNT electrode, in accordance with some embodiments of the disclosure.

Figure 15 illustrates an SEM image of the top-side of an Si-CNT electrode, in accordance with some embodiments of the disclosure.

Figures 16A-16D illustrate enlarged views of the SEM image of Figure 15, in accordance with some embodiments of the disclosure.

Figures 17A-17E illustrate SEM images of substantially aligned CNTs, including graphenated and coated version of the substantially aligned CNTs, in accordance with some embodiments of the disclosure.

Figure 18 illustrates the current-voltage graph of an unmodified CNT ECDL capacitor, in accordance with some embodiments of the disclosure.

Figure 19 illustrates the current-voltage graph of a graphene-modified CNT ECDL capacitor, in accordance with some embodiments of the disclosure.

Figure 20 illustrates the current-voltage graph of a TiO2-coated CNT ECDL capacitor, in accordance with some embodiments of the disclosure.

Figure 21 illustrates the current-voltage graph of a graphene-modified TiO2-coated CNT ECDL capacitor, in accordance with some embodiments of the disclosure.

Figure 22 illustrates an ECDL capacitor embedded in a mold compound, in accordance with some embodiments of the disclosure.

Figure 23 illustrates an ECDL capacitor mounted in a separate structure, in accordance with some embodiments of the disclosure.


DETAILED DESCRIPTION



[0015] Although preferred embodiments of the disclosure are explained in detail, it is to be understood that other embodiments are contemplated. Accordingly, it is not intended that the disclosure is limited in its scope to the details of construction and arrangement of components set forth in the following description or illustrated in the drawings. The disclosure is capable of other embodiments and of being practiced or carried out in various ways. Also, in describing the preferred embodiments, specific terminology will be resorted to for the sake of clarity.

[0016] It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise.

[0017] Also, in describing the preferred embodiments, terminology will be resorted to for the sake of clarity. It is intended that each term contemplates its broadest meaning as understood by those skilled in the art and includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.

[0018] Ranges may be expressed herein as from "about" or "approximately" one particular value and/or to "about" or "approximately" another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value.

[0019] By "comprising" or "containing" or "including" is meant that at least the named compound, element, particle, or method step is present in the composition or article or method, but does not exclude the presence of other compounds, materials, particles, method steps, even if the other such compounds, material, particles, method steps have the same function as what is named.

[0020] It is also to be understood that the mention of one or more method steps does not preclude the presence of additional method steps or intervening method steps between those steps expressly identified. Similarly, it is also to be understood that the mention of one or more components in a device or system does not preclude the presence of additional components or intervening components between those components expressly identified.

[0021] As used herein, the height of a capacitor refers to the direction parallel to the substantially aligned carbon nanotubes, as disclosed herein, and width and length are directions in-plane with the first and second substrates in the electrochemical capacitors.

[0022] Described herein are electrochemical double-layer (ECDL) capacitors, or supercapacitors, that have tremendous potential as high-power delivery energy storage elements in low-volume and low-weight microelectronics systems, and can rival conventional batteries in terms of energy capacities. Traditional ECDL approaches utilizing activated carbon have limitations imposed by the structure of their pores. ECDL electrodes as described herein, based on nanostructured carbon, offer improved performance due to their high surface area, high-conductivity, increased porosity, and options for functionalization that enhance surface area and pseudocapacitance. Nanostructured ECDL capacitors have the potential to achieve performance levels applicable to the large-scale energy needs of electric vehicles, electromechanical actuators, and portable power supplies, as well smaller scale needs in microelectronics systems including pulsed wireless communication, embedded sensors, smart structures, wearable electronics and smart textiles. To realize their potential, ECDL technologies need to be miniaturized while simultaneously improving upon performance issues such as volumetric energy density and charge leakage. Fabrication options are also required that are compatible with conventional microelectronics fabrication to realize microelectronics components with integrated energy storage. Methods and devices that achieve these benefits are disclosed herein.

[0023] Decreasing size of the capacitor allows for capacitor-dependent devices to drastically shrink. By using ECDLs, not only does the size of capacitor decrease, but also the number of capacitors due to the large capacitance of a supercapacitor. A planar supercapacitor design has the potential to be largely incorporated within PCBs and other devices. In one design, vertically-grown, interlocking CNT forests have shown to have success utilizing a Si base. Not only does the design prove the concept of planar capacitors, but it also allows for the integration of these capacitors using silicon wafers. Furthermore, it has been shown that conventional capacitors can be developed on the surface of integrated circuits. Most stacks are generally constructed on the top silicon wafers rather than incorporated. Further studies have also suggested the idea of using highly doped silicon covered with graphene as electrode material in itself. Similarly, it has been shown that graphene based supercapacitors can hold the equivalent energy of a lithium battery.

[0024] The combination of concepts mentioned above leads to the creation of a capacitor implemented within the etched pits of a Si wafer, as disclosed herein. Not only does this allow integration of nano-scale capacitors within the wafer, but also allows for the space utilization and size reduction of these wafers while holding massive amounts of charge. Moreover, this design can be implemented within printed circuit board technologies, leading to unique ways of capacitor development.

[0025] A typical "coin cell" version of a capacitor, relying on non-aligned CNTs, can be assembled as shown in Figure 1B. A mat of tangled carbon nanotubes is first placed into the coin cell on top of the bottom ("outer") electrode. A separator sheet, such as polypropylene and polyethylene barriers, is then added, followed by a second mat of tangled CNT material. Electrolyte is then poured into the cell. Issues such as the size of the pores in the electrodes and the wettability of the electrolyte factor into the ion diffusion characteristics of the resulting capacitor. Finally, the top ("inner") electrode is placed within the cell and clamped to seal against a gasket.

[0026] While the performance of the coin-cell format of this simple tangled mat CNT ECDL is promising, achieving over 3 Wh/kg, miniaturizing the structure for application in microelectronics and printed circuit boards represents significant challenges. In particular, the use of a tangled mat of CNT material makes attaining desirable levels of volumetric and gravimetric density challenging. In addition, the processes used to make CNT-based coin cell ECDL components are not immediately amenable to microelectronics fabrication. Thermal CVD growth parameters require high-temperature processing at over 600°C. Recent advances in Plasma Enhanced deposition have reduced those temperatures to as low as 400°C, making the process potentially compatible with microelectronics and some flexible substrates Localized heating has also been employed to increase compatibility. Furthermore, functionalization and pseudocapacitive coatings can realize significant gains in capacity.

[0027] Initial efforts in this disclosure demonstrated a variety of ECDL structures based on carbon nanotube approaches. Specific gravimetric densities up to 91 Wh/kg have been achieved in a coin cell format using a combination of carbon nanotube (CNT) growth, functionalization, and coating techniques. The generic structure of a carbon nanotube based ECDL is shown in Figure 2. The two electrodes are composed of nanostructured carbon material placed in direct contact with an electrical conductor. In this initial example, an ion permeable separating membrane keeps the electrodes from short circuiting while also allowing ion diffusion through electrolyte encapsulated within an external casing.

[0028] Miniaturization of the ECDL can, therefore, be achieved using a combination of several different options, including micropattemed and vertically-aligned carbon nanotube sheets that replace tangled CNT mats and provide higher surface areas and porosity; three-dimensional nanotube architectures that reduce intrinsic inactive features; graphene-functionalized nanotubes that dramatically increase total surface area; pseudocapacitive coatings that add to the total capacitance of ECDL electrodes; low-temperature plasma-enhanced chemical vapor deposition (PECVD) CNT growth that provides potential process compatibility with microelectronics components; and microfluidic techniques that incorporate liquid electrolyte into a microfabricated chip.

[0029] A variety of techniques can be used to grow patterned forests of vertically-aligned functionalized nanotubes in 3-dimensional arrangements, such as in Figures 3A, 3B and 3C. Vertically-aligned towers of CNT's can be grown and patterned, through standard photolithography processes, at specific locations on a substrate, allowing electrochemical supercapacitor architectures. As shown in Figure 3A, advanced CNT growth, patterning, and functionalization approaches enables the miniaturization of ECDL components while increasing performance specifications. Nanotubes can be functionalized with a variety of groups that can increase pseudocapacitance and/or surface area. Figure 3B shows graphene functionalized carbon nanotubes, a functionalization approach that dramatically increases the surface area of the electrode. In addition, aligned CNTs can now also be grown within etched cavities of silicon wafers, enabling three dimensional ECDL architectures (Figure 3C, with enlarged section for individual pit.)

[0030] In addition, oxidation and reduction reactions achieved through pseudocapacitive coatings or nanotube functionalization can yield a substantial increase in ECDL performance. As an example, through atomic layer deposition (ALD), vertically-aligned CNT forests have been coated with titania (uncoated, Figure 4A; coated, Figure 4B.) After adding 8nm of uniform coating, the gravimetric energy density increased to over 91 Wh/kg, with a series resistance of only 1.11 Ohms.

[0031] These advanced fabrication approaches enabled miniaturization of the ECDL capacitor while improving volumetric and gravimetric density. High capacity low weight supercapacitors are now accessible, which utilize CNTs structures and ionic liquid electrolytes to achieve these high capacitance and large gravimetric energy densities. Moreover, due to the nature of these structures and the techniques involved, the supercapacitors will have increased applicability and integration into microelectronics, which were often hampered by the lack of miniaturization of capacitors. The goal of 100+Wh/kg is now attainable, using Si wafer embedded technology, vertically aligned carbon nanotubes, some combination of faradaic and/or non-faradaic functionalization, and ionic liquids as electrolytes.

[0032] Supercapacitors as disclosed herein can be based on two potential approaches: a 3-D stacking approach and an interdigitated electrode approach. In the 3-D stacking approach, a single microelectrode can be fabricated, using for example a process as shown in Figure 5. A single electrode can be fabricated with all of the features required of an ECDL, including cavities to hold electrolyte, nanostructured carbon in the form of graphene functionalized vertically-aligned carbon nanotubes, as well as both physical and electrical separation of electrodes. The process can include depositing and patterning an oxide isolation layer and a bond seal ring, etching a cavity into the substrate and depositing the CNT seed layer, growing vertically aligned CNTs and functionalizing with graphene, then applying a pseudocapacitive coating using atomic layer deposition. The CNT forests can be grown in electrically isolated shallow wells within a substrate. In addition, PECVD growth processes for CNTs have moved to lower temperature processing parameters, making CNT growth possible on microelectronics substrates as well as flexible materials. After the fabrication of a single electrode, a full ECDL capacitor can be realized by capping one electrode with a second identical copy, as shown in Figure 6. This structure, with electrodes separated by a well-controlled gap, removes the requirement for a separator sheet, thereby achieving higher levels of volumetric density. It also exhibits high porosity and surface area due to the vertically-aligned graphene-functionalized carbon nanotubes. Furthermore, ALD processes can create conformal pseudocapacitive coatings that greatly increase the overall capacity of the structure. Finally, it is also relatively simple to fabricate using process steps that are compatible with traditional microelectronics approaches and that minimize wasted space that does not contribute to volumetric density.

[0033] In addition to the vertical structure of the ECDL capacitor, a planar structure can be fabricated to create interdigitated arrays of electrodes in a planar configuration, as shown in Figure 7; such interdigitated structure is currently not claimed. In the planar approach, all of the nanostructures are on the same level within the chip, but are interdigitated to yield two electrodes in close proximity. In this approach, capping and electrolyte injection can be significantly simpler, as would incorporation in a flexible substrate. Either of these micro-capacitor configurations could be integrated as either a multichip module with the microelectronics to be powered, or as a component fabricated directly on the same microelectronic substrate.

[0034] An electrolyte is typically required for conductance, but bonding to create cavities can preferably be performed without electrolyte present, as bonding processes can be difficult with liquid material residing in the cavity. Therefore, electrolyte can be placed within the cavity after bonding. The disclosure includes processes for capping microfluidic cavities containing nanostructured material and placing fluid within the cavities after completion. In the process, electrolyte degasification can be achieved through vacuum infiltration and the cavity can be sealed using frit compression of a low-temperature thermoplastic polymer.

[0035] By altering the electrolyte composition and active electrode material attributes, CNT-based supercapacitor performance can be markedly altered. The results from constant current and constant voltage tests include specific capacitance and equivalent series resistance (ESR) determinations. Improved packaging, sealing and manufacturing techniques markedly reduce ESR and leakage current in the product. Specifically, a variety of growth processes have been demonstrated on multiple substrates for patterned, vertically-aligned, and randomly-oriented nanotubes. CNTs can be grown as a random-orientation on carbon fiber (Figure 8A), as patterned vertically-aligned CNTs (Figure 8B), and as ALD-coated CNT forests (Figure 8C). In addition, multiple functionalization approaches for CNT-based ECDL capacitors have been conducted. These have included graphene-functionalized CNT's, which presents a significant advantage in that the surface area is significantly increased. Finally, coatings for CNTs to enhance pseudocapacitive effects have been demonstrated, making significant gains in performance. For example, titania-coated CNT's, through conformal and low-temperature atomic layer deposition processes, has significantly increased capacity through pseudocapacitance, as shown in Figure 9 for atomic layer deposition of pseudocapacitive coatings that increased capacity by a factor of three as measured using cyclic voltammetry.

[0036] Thus, in an embodiment, the disclosure can include an electrochemical double-layer capacitor 600, as shown in Figure 6. The capacitor can include a bottom substrate 601 and a top substrate 602. The bottom substrate can include a first cavity 603, and the top substrate can include a second cavity 604. The substrates 601 and 602 are preferably silicon or other conductive substrate, preferably an n-doped silicon, and each can serve as an electrode for each side of the ECDL capacitor.

[0037] The first cavity and second cavity can face each other, which indicates that the open part of each cavity in the two substrates are directed towards each other, as shown in Figure 6. The top and bottom cavity can also be aligned with each other. By aligned is meant that the two cavities are in alignment in the x-y plane of the two substrates. Alignment of the two cavities need not be perfect, meaning that all of one cavity does not need to align perfectly with the other cavity, nor do the cavities need to be the same size. However, decreases in the capacitance of the device might be observed when less than all of the two cavities are not aligned. Overlap of the two cavities should therefore be at least about 50% of the two dimensional surface area of at least one of the cavities, including at least about 66%, at least about 75%, at least about 80%, or at least about 90%.

[0038] Within the first cavity can be disposed a first plurality of substantially aligned carbon nanotubes 605. By substantially aligned carbon nanotubes is meant that the majority of the carbon nanotubes were grown in the same direction. In contrast to tangled masses or random piles of CNTs, the CNTs of this disclosure are closer to parallel with each other across the length of the CNTs, as can be seen in several figures disclosure herein. Within the second cavity can be disposed a second plurality of substantially aligned carbon nanotubes 606. In each of the first and second cavities, the carbon nanotubes can be vertically disposed within the cavity, as shown in Figure 6. Note that the carbon nanotubes within a cavity need not be a continuous forest or vertical mat of aligned tubes, but could instead be separated into islands of CNTs with intervening stretches of unoccupied surface, such as was shown in Figure 3A. The first and/or second cavity can be at least about 100 microns deep, at least about 110 microns deep, at least about 120 microns deep, or at least about 130 microns deep. The CNTs within the cavity can be about 50 to about 150 microns in height, about 75 microns to about 150 microns, or about 75 microns to about 125 microns. The CNTs can be less than 100% the height of the cavity, less than about 95% the height of the cavity, less than about 90% of the height of the cavity, less than about 80% of the height of the cavity, or less than about 75% of the height of the cavity.

[0039] The capacitor can also include a gap 607 between the first plurality of substantially aligned carbon nanotubes and the second plurality of substantially aligned carbon nanotubes. The gap described herein defines the separation space between the upper ends of the CNTs of the two sides of the capacitor. The gap can be described by a gap height, or separation height between the first and second plurality of CNTs. This gap height prevents contact of any of the first plurality of substantially aligned carbon nanotubes with any of the second plurality of substantially aligned carbon nanotubes. The gap height can be from about 5 microns to about 150 microns, from about 5 microns to about 100 microns, from about 10 microns to about 100 microns, or from about 10 microns to about 50 microns. The gap height can be less than about 125 microns, less than about 100 microns, less than about 75 microns, less than about 50 microns, less than about 40 microns or less than about 30 microns. The gap height can be great than about 2 microns, greater than about 5 microns, or greater than about 10 microns.

[0040] The capacitor can also include a micropackage 608 located between the bottom substrate 601 and the top substrate 602, wherein a top end of the micropackage is proximate a bottom end of the top substrate and a bottom end of the micropackage is proximate a top end of the bottom substrate. This configuration places the micropackage within the area where the gap or gap height is presented, and where a separator would typically be found. In the capacitor, the height of the first plurality of carbon nanotubes 605 would typically not exceed the bottom end of the micropackage and wherein a height of the second plurality of carbon nanotubes 606 would typically not exceed the top end of the micropackage.

[0041] The capacitors in this disclosure do not require a separator between two sides of the capacitor. The absence of a separator can allow for several advantages, including for example simpler construction, less material, faster response times and higher overall capacitance. The space between the two sides of the capacitor includes at least a portion of open space that is not occupied by a separator. In some embodiments, the separator can be completely absent. In some alternate embodiments, a separator could still be included, but a portion of the space still unoccupied by a separator.

[0042] As shown in Figure 6, the two halves of the ECDL capacitor are about equal height, and exhibit a rough symmetry between the two halves. In an embodiment, the capacitor can be approximately symmetric across the two halves, meaning that the differences in dimensions and shapes of the two halves are less than 10%. This symmetry can be preferred, at least in part because the manufacturing of the two halves can be achieved with the same process parameters. For example, a pair of substrates can be prepared that each have a cavity and a plurality of substantially aligned carbon nanotubes vertically disposed in the cavity, then one of the pair is flipped and placed atop the other substrate to form the capacitor. However, other embodiments could be considered wherein the height of the two halves could be unequal, even when the width and length are approximately the same. The ratio of the heights of the two halves can be greater than about 1:1. The ratio of the heights of the two halves can be less than about 1.1:1, less than about 1.2:1, less than about 1.5:1, less than about 2:1, less than about 2.5:1 or less than about 3:1, or less than about 5:1. Preferably, the ratio of the two halves can be about 1:1.

[0043] The capacitor can include in at least one of the substrates a filling port through which the electrolyte can be added. The capacitor can also include a gasket proximate the filling port to seal the port once the electrolyte has been added. The gasket can be any material suitable for this use, including for example polylactic acid.

[0044] As noted above, the capacitor of the current disclosure can include an electrolyte in the space between the two substrates that is occupied by the cavities and carbon nanotubes. The electrolyte can be any electrolyte compatible with the substrates and carbon nanotubes. In an embodiment, the electrolyte is an ionic liquid, or a room temperature ionic liquid. Examples of ionic liquids includes benzyldimethylpropylammonium aluminum tetrachlorate, benzyldimethyl ammonium imide, dimethylethyl ammonium imide, ethylmethyl ammonium bisulfate, 1-butyl-3-methylimidazolium tetraflouroborate.

[0045] As discussed above, at least a portion of the carbon nanotubes can be further functionalized to increase performance. The carbon nanotubes can include a non-faradaic material to improve the performance. The non-faradaic material can include graphene platelets, which can dramatically increase the surface area of the material. The carbon nanotubes can also be functionalized with a faradaic material. The faradaic material can be metal oxides, including for example, ruthenium oxides, manganese oxides, iron oxide, tin oxides, vanadium oxides, titanium oxides, iridium dioxides, cobalt oxides, nickel oxides, indium oxides, copper oxides, and zinc oxides. The faradaic material can preferably include titanium oxide or ruthenium oxide, preferably titanium oxide. The carbon nanotubes can include both of a faradaic material and a non-faradaic material, and each can include the examples cited above.

[0046] As discussed above, a planar structure can have an interdigitated arrays of electrodes, as was shown in Figure 7. In an example not claimed, an electrochemical interdigitated capacitor 700 can include a substrate 701 having a cavity 702 therein, and a first electrode 703 and a second electrode 704 within the cavity. The first electrode can include a first plurality of substantially aligned carbon nanotubes 705 disposed thereon, and the second electrode can include a second plurality of substantially aligned carbon nanotubes 706 disposed thereon. The first and the second electrodes can be separated by a separation distance such that the first electrode does not contact the second electrode, and a positioned in a planar arrangement relative to the cavity. The capacitor can include a series of alternating first and second electrodes across the bottom the cavity, and a microelectronics section 709 that can provide a connection point to the series of first and second electrodes.

[0047] The separation distance of the interdigitated capacitor, between the first electrode and the second electrode, can be from about 3 to about 30 microns, or from about 5 micron to about 20 micron, or from about 5 to about 10 microns. The separation distance can be greater than about 3 microns or greater than about 5 microns, and less than about 30 microns, less than about 20 microns, less than about 15 micron, or less than about 10 microns.

[0048] The interdigitated capacitor can include a micropackage 707, and can further include a lid 708 disposed on the micropackage. The top end of the micropackage can be proximate the lid and the height of the first and second plurality of substantially aligned carbon nanotubes would typically not exceed a bottom end of the micropackage. Preferably, none of the first and second plurality of substantially aligned carbon nanotubes contact the lid.

[0049] As with the electrochemical double-layer capacitor described above, at least a portion of the first and second plurality of carbon nanotubes can be functionalized with a non-faradaic material, or can be functionalized with a faradaic material, or can be functionalized with both non-faradaic and faradaic material. The faradaic and non-faradaic materials are as described above. Additionally, as with the electrochemical double-layer capacitor above, the interdigitated capacitor can include a filling port in at least one of the lid or the substrate, and can include a gasket proximate the filling port. The interdigitated capacitor can include an electrolyte disposed on at least a portion of the interdigitated capacitor, and that electrolyte can include an ionic liquid, preferably a room temperature ionic liquid.

[0050] The supercapacitor of the invention can have a gravimetric energy density of at least about 95 Whr/kg and/or a volumetric energy density of at least about 300 Whr/L. The gravimetric energy density can be at least about 95 Whr/kg, at least about 100 Whr/kg, at least about 110 Whr/kg, at least about 120 Whr/kg, at least about 140 Whr/kg. The gravimetric energy density can be up to about 1000 Whr/kg, up to about 750 Whr/kg, or up to about 600 Whr/kg. The volumetric energy density can be at least about 300 Whr/L, at least about 350 Whr/L, at least about 400 Whr/L, at least about 450 Whr/L, or at least about 500 Whr/L. The volumetric energy density can be up to about 4000 Whr/L. The supercapacitor can also achieve specific capacitance of at least about 75 F/g, at least about 80 F/g, at least about 90 F/g, or at least about 100 F/g.

[0051] As discussed previously, the disclosure also includes a method of fabricating the ECDL capacitor. The method can include providing a bottom substrate, etching a first cavity in to the bottom substrate, and growing a first plurality of substantially aligned carbon nanotubes within the first cavity. The top substrate can then be provided, and a second cavity etched within the top substrate, and then a second plurality of substantially aligned carbon nanotubes can be grown within the second cavity. One of skill in the art would understand that these two steps are interchangeable with respect to which one is conducted first. The next step can include providing a micropackage, wherein a height of the micropackage defines the minimum of a gap between the first plurality of substantially aligned carbon nanotubes and the second plurality of substantially aligned carbon nanotubes such that there is no contact between the first plurality of substantially aligned carbon nanotubes and the second plurality of substantially aligned carbon nanotubes.

[0052] The method can further include functionalizing the first and second plurality of substantially aligned carbon nanotubes with at least one of a faradaic and non-faradaic material. The faradaic and non-faradaic materials are as disclosed above.

[0053] The cavity of the capacitor can be filled with an electrolyte, where the electrolyte is filled through the filling port, located in at least one of the bottom and top substrates, and optionally disposed through the filling port via vacuum filling. A gasket can then be disposed proximate the filling port to seal the capacitor. The electrolyte can be as described above.

[0054] The method for preparing these devices and the technology in the devices themselves can be exemplified in the following nonlimiting example.

[0055] An ECDL capacitor was created according to the following steps, as exemplified in Figures 10A-N. An initial silicon wafer, Figure 10A, had deposited by plasma-enhanced chemical vapor deposition a layer of silicon dioxide on the front side of the silicon wafer, Figure 10B. The positive photoresist SPR220-7 was then spin-coated onto the front-side of the wafer, Figure 10C, and front-side photolithography of the photoresist was conducted to form the initial cavities, Figure 10D. The silicon dioxide was then etched using a buffered oxide etch (BOE), Figure 10E, and then a deep-reactive ion etch (DRIE), such as a Bosch Plasma Etch (BPE) was used to dig cavities of the CNTs in the silicon, Figure 10F. A layer of Fe catalyst for the CNT growth positions was deposited by electron beam deposition in the cavities, Figure 10G.

[0056] A portion of the wafers were then treated backside to create the fill holes for electrolyte infusion. To the back-side of the wafer was spin-coated the positive photoresist SPR220-7, Figure 10H, and back-side photolithography was conducted to position the fill holes, Figure 10I. Deep reactive ion etch in Figure 10J prepared the fill holes for the electrolyte. The remaining photoresist was removed and the wafers cleaned, Figure 10K. CNT growth, functionalization with graphene and/or titania as a pseudocapacitive film, and die separation were conducted, Figure 10L. Two sections were then bonded together, the top one of which contained the fill holes, Figure 10M. The cavities were then filled with room temperature electrolyte and sealed, Figure 10N.

[0057] With respect to the electrolyte fill process, fill ports can be shown at least at two points on a wafer, as in Figure 11A. Polylactic acid connectors can be added to the filling ports, Figure 11B, and would eventually become the gasket that seals the device. The electrolyte can then be added to the capacitor by flowing it in one fill port while the other fill port is placed under vacuum to flow the electrolyte into the cavities of the capacitor, Figure 11C. A contacting plate at 60°C can be pressed against the PLA to form the gaskets, Figure 11D and seal the final capacitor, Figure 11E.

[0058] For the initial devices, a heavily doped silicon wafer was utilized, and the electrolyte initially used was 1-butyl-3-methylimidazolium tetrafluoroborate, (BMIM BF4). Fifty two electrodes per wafer were created, as shown in Figure 12. An individual electrode is shown in Figure 13A, showing the CNT side of the electrode, and Figure 13B, showing the backside of an electrode, having the fill holes.

[0059] SEM images of an individual wafer are shown in Figures 14A-B, 15, and 16A-D. In Figure 14A, a cross-sectional image shows the fill hole (1) in the silicon wafer, the depth of the etch pit (5), and the CNTs (3). A similar image is shown in Figure 14B. Figure 15 reveals the top-down view of the etch pit, including positions where the fill holes are placed. Section A in Figure 15 is expanded in Figure 16A, showing the fill hole, the silicon substrate near the hole, and the forest of CNTs growing around the holes. Figure 16B, 16C and 16D show higher magnifications of that CNT section from Figure 16A.

[0060] For the CNTs on the individual electrodes, samples were prepared having only CNTs, CNTs functionalized with graphene, CNTs functionalized with TiO2, and CNTs functionalized with graphene and TiO2. SEM images of CNTs (Figure 17A and 17B) and CNTs modified with graphene (Figure 17C and 17D) are shown, as is graphene modified CNTs that have been coated with TiO2 (Figure 17E.)

[0061] Current-Voltage graphs were constructed for each of the capacitors constructed using only CNTs (Figure 18), graphene-CNTs (Figure 19), CNTs with TiO2 (Figure 20), and graphene-CNTs with TiO2 (Figure 21), and the energy density for each calculated. The graphs and results are shown together, and the results also listed in Table 1.
TABLE 1
 CNTGraphene-CNTCNT-TiO2Graphene-CNT - TiO2
Capacitance (mF) 6.9 17.3 26.2 42.2
Specific Capacitance (F/g) 18.56 56.8 70.9 114.1
Gravimetric energy density (Whr/kg) 23.2 58.5 88.6 142.6
Volumetric energy density (Whr/L) 48.72 122.9 280.86 452.0


[0062] Based on the disclosure for supercapacitors provided herein, the structures developed can be constructed in any manner suitable for application to microelectronics. For example, an ECDL capacitor can be mounted into a mold compound as shown in Figure 22, where the two electrodes of the capacitor are connected via a wire to a lead on the outside of the mold. Alternatively, the ECDL capacitor can be mounted within a separate structure analogous to a coin-cell structure used previous, as shown in Figure 23.

[0063] The supercapacitors disclosed herein have then achieved gravimetric energy densities of over 100 Wh/kg. The fabrication of the capacitor in a silicon wafer has been achieved. Graphenated-CNTs and pseudocapacitive coatings can significantly increase energy densities. And microfluidics can be used for the electrolyte fill to complete the system.

[0064] It is to be understood that the embodiments disclosed and discussed are given by way of example only and are not intended to limit the invention. Rather, various variations and modifications are possible without departing from the scope of protection as defined in the claims.


Claims

1. An electrochemical double-layer capacitor (600) comprising:

a bottom substrate (601) having a first cavity (603);

a first plurality of substantially aligned carbon nanotubes (605) vertically disposed within the first cavity (603);

a top substrate (602) having a second cavity (604) facing the first cavity (603);

a second plurality of substantially aligned carbon nanotubes (606) vertically disposed within the second cavity (604); and

a micropackage (608), wherein the micropackage (608) defines a gap (607) between the first plurality of substantially aligned carbon nanotubes (605) and the second plurality of substantially aligned carbon nanotubes (606), the gap (607) having a gap height that prevents contact between the first plurality of substantially aligned carbon nanotubes (605) and the second plurality of substantially aligned carbon nanotubes (606), wherein the gap height is from about 10 microns to about 50 microns; wherein the space between the two sides of the capacitor includes at least a portion of open space not occupied by a separator.
 
2. The electrochemical double-layer capacitor of claim 1, wherein at least a portion of the first and second plurality of carbon nanotubes (605, 606) are functionalized with a non-faradaic material.
 
3. The electrochemical double-layer capacitor as in any one of claims 1 and 2, wherein at least a portion of the first and second plurality of carbon nanotubes (605, 606) are functionalized with a faradaic material.
 
4. The electrochemical double-layer capacitor as in claims 1, 2, or 3, further comprising an electrolyte disposed on at least a portion of the electrochemical double-layer capacitor (600).
 
5. The electrochemical double-layer capacitor as in one of claims 1-4, wherein the micropackage (608) is located between the bottom substrate (601) and the top substrate (602), wherein a top end of the micropackage (608) is proximate a bottom end of the top substrate (602) and a bottom end of the micropackage (608) is proximate a top end of the bottom substrate (601).
 
6. The electrochemical double-layer capacitor as in one of claims 1-5, wherein a height of the first plurality of carbon nanotubes (605) does not exceed the bottom end of the micropackage (608); and
wherein a height of the second plurality of carbon nanotubes (606) does not exceed the top end of the micropackage (608).
 
7. The electrochemical double-layer capacitor as in one of claims 1-7, wherein the capacitor is symmetric.
 
8. A method of fabricating an electrochemical double-layer capacitor comprising:

providing a bottom substrate;

etching a first cavity within the bottom substrate;

growing a first plurality of substantially aligned carbon nanotubes within the first cavity;

providing a top substrate;

etching a second cavity within the top substrate;

growing a second plurality of substantially aligned carbon nanotubes within the second cavity; and

providing a micropackage, wherein the micropackage defines a gap between the first plurality of substantially aligned carbon nanotubes and the second plurality of substantially aligned carbon nanotubes, the gap having a gap height that prevents contact between the first plurality of substantially aligned carbon nanotubes and the second plurality of substantially aligned carbon nanotubes, wherein the gap height is from about 10 microns to about 50 microns, and wherein the space between the two sides of the capacitor includes at least a portion of open space not occupied by a separator.


 
9. The method of claim 8, further comprising functionalizing the first and second plurality of substantially aligned carbon nanotubes with at least one of a faradaic and a non-faradaic material.
 
10. The method as in any one of claims 8 and 9, further comprising filling the first and second cavities with an electrolyte through a filling port.
 
11. The method as in claim 10, wherein the electrolyte is disposed through the filling port via vacuum filling.
 
12. The method as in one of claims 8 -11, wherein the electrolyte comprises a room temperature ionic liquid.
 
13. The method as in one of claims 8 -12, wherein a gravimetric energy density of the active materials of the capacitor is from about 100 Whr/kg to about 1000 Whr/kg.
 


Ansprüche

1. Elektrochemischer Doppelschichtkondensator (600), umfassend:

ein unteres Substrat (601) mit einem ersten Hohlraum (603);

eine erste Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen (605), die vertikal innerhalb des ersten Hohlraums (603) angeordnet sind;

ein oberes Substrat (602) mit einem zweiten Hohlraum (604), der dem ersten Hohlraum (603) zugewandt ist;

eine zweite Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen (606), die vertikal innerhalb des zweiten Hohlraums (604) angeordnet sind; und

ein Mikro-Package (608), wobei das Mikro-Package (608) einen Spalt (607) zwischen der ersten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen (605) und der zweiten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen (606) definiert, wobei der Spalt (607) eine Spalthöhe aufweist, die einen Kontakt zwischen der ersten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen (605) und der zweiten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen (606) verhindert, wobei die Spalthöhe von etwa 10 Mikrometer bis etwa 50 Mikrometer beträgt; wobei der Raum zwischen den beiden Seiten des Kondensators mindestens einen Anteil offenen Raum umfasst, der nicht von einem Separator besetzt ist.
 
2. Elektrochemischer Doppelschichtkondensator nach Anspruch 1, wobei mindestens ein Anteil der ersten und zweiten Vielzahl von Kohlenstoff-Nanoröhrchen (605, 606) mit einem nicht-faradayschen Material funktionalisiert ist.
 
3. Elektrochemischer Doppelschichtkondensator nach einem der Ansprüche 1 und 2, wobei mindestens ein Anteil der ersten und zweiten Vielzahl von Kohlenstoff-Nanoröhrchen (605, 606) mit einem faradayschen Material funktionalisiert ist.
 
4. Elektrochemischer Doppelschichtkondensator nach Anspruch 1, 2 oder 3, ferner umfassend einen Elektrolyten, der an mindestens einem Abschnitt des elektrochemischen Doppelschichtkondensators (600) eingebracht ist.
 
5. Elektrochemischer Doppelschichtkondensator nach einem der Ansprüche 1-4, wobei das Mikro-Package (608) zwischen dem unteren Substrat (601) und dem oberen Substrat (602) angeordnet ist, wobei ein oberes Ende des Mikro-Package (608) in der Nähe eines unteren Endes des oberen Substrats (602) liegt und ein unteres Ende des Mikro-Package (608) in der Nähe eines oberen Endes des unteren Substrats (601) liegt.
 
6. Elektrochemischer Doppelschichtkondensator nach einem der Ansprüche 1-5, wobei eine Höhe der ersten Vielzahl von Kohlenstoff-Nanoröhrchen (605) nicht über das untere Ende des Mikro-Package (608) hinausgeht; und
wobei eine Höhe der zweiten Vielzahl von Kohlenstoff-Nanoröhrchen (606) nicht über das obere Ende des Mikro-Package (608) hinausgeht.
 
7. Elektrochemischer Doppelschichtkondensator nach einem der Ansprüche 1-7, wobei der Kondensator symmetrisch ist.
 
8. Verfahren zur Herstellung eines elektrochemischen Doppelschichtkondensators, umfassend:

Bereitstellen eines unteren Substrats;

Ätzen eines ersten Hohlraums innerhalb des unteren Substrats;

Züchten einer ersten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen innerhalb des ersten Hohlraums;

Bereitstellen eines oberen Substrats;

Ätzen eines zweiten Hohlraums innerhalb des oberen Substrats;

Züchten einer zweiten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen innerhalb des zweiten Hohlraums; und

Bereitstellen eines Mikro-Package, wobei das Mikro-Package einen Spalt zwischen der ersten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen und der zweiten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen definiert, wobei der Spalt eine Spalthöhe aufweist, die einen Kontakt zwischen der ersten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen und der zweiten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen verhindert, wobei die Spalthöhe von etwa 10 Mikrometer bis etwa 50 Mikrometer beträgt, und wobei der Raum zwischen den beiden Seiten des Kondensators mindestens einen Anteil offenen Raum umfasst, der nicht von einem Separator besetzt ist.


 
9. Verfahren nach Anspruch 8, ferner umfassend Funktionalisieren der ersten und zweiten Vielzahl von im Wesentlichen ausgerichteten Kohlenstoff-Nanoröhrchen mit mindestens einem von einem faradayschen und einem nicht-faradayschen Material.
 
10. Verfahren nach einem der Ansprüche 8 und 9, ferner umfassend Füllen des ersten und zweiten Hohlraums mit einem Elektrolyten über eine Einfüllöffnung.
 
11. Verfahren nach Anspruch 10, wobei der Elektrolyt durch die Einfüllöffnung mittels Vakuumfüllung eingebracht wird.
 
12. Verfahren nach einem der Ansprüche 8-11, wobei der Elektrolyt eine ionische Flüssigkeit bei Raumtemperatur umfasst.
 
13. Verfahren nach einem der Ansprüche 8-12, wobei die gravimetrische Energiedichte der aktiven Materialien des Kondensators zwischen etwa 100 Whr/kg und etwa 1000 Whr/kg liegt.
 


Revendications

1. Condensateur électrochimique double couche (600) comprenant :

un substrat inférieur (601) comportant une première cavité (603) ;

une première pluralité de nanotubes de carbone sensiblement alignés (605) disposés verticalement dans la première cavité (603) ;

un substrat supérieur (602) comportant une seconde cavité (604) faisant face à la première cavité (603) ;

une seconde pluralité de nanotubes de carbone sensiblement alignés (606) disposés verticalement dans la seconde cavité (604) ; et

un micro-emballage (608), dans lequel le micro-emballage (608) définit un interstice (607) entre la première pluralité de nanotubes de carbone sensiblement alignés (605) et la seconde pluralité de nanotubes de carbone sensiblement alignés (606), l'interstice (607) ayant une hauteur d'interstice qui empêche le contact entre la première pluralité de nanotubes de carbone sensiblement alignés (605) et la seconde pluralité de nanotubes de carbone sensiblement alignés (606), dans lequel la hauteur d'interstice est d'environ 10 microns à environ 50 microns ;

dans lequel l'interstice entre les deux côtés du condensateur inclut au moins une partie d'espace ouvert non occupé par un séparateur.


 
2. Condensateur électrochimique double couche selon la revendication 1, dans lequel au moins une partie des première et seconde pluralités de nanotubes de carbone sensiblement alignés (605, 606) sont fonctionnalisées avec un matériau non faradique.
 
3. Condensateur électrochimique double couche selon l'une quelconque des revendications 1 et 2, dans lequel au moins une partie des première et seconde pluralités de nanotubes de carbone sensiblement alignés (605, 606) sont fonctionnalisées avec un matériau faradique.
 
4. Condensateur électrochimique double couche selon l'une quelconque des revendications 1, 2, ou 3, comprenant en outre un électrolyte disposé sur au moins une partie du condensateur électrochimique double couche (600).
 
5. Condensateur électrochimique double couche selon l'une quelconque des revendications 1-4, dans lequel le micro-emballage (608) est situé entre le substrat inférieur (601) et le substrat supérieur (602), dans lequel une extrémité supérieure du micro-emballage (608) est proche d'une extrémité inférieure du substrat supérieur (602) et une extrémité inférieure du micro-emballage (608) est proche d'une extrémité supérieure du substrat inférieur (601).
 
6. Condensateur électrochimique double couche selon l'une quelconque des revendications 1-5, dans lequel une hauteur de la première pluralité de nanotubes de carbone (605) ne dépasse pas l'extrémité inférieure du micro-emballage (608) ; et
dans lequel une hauteur de la seconde pluralité de nanotubes de carbone (606) ne dépasse pas l'extrémité supérieure du micro-emballage (608).
 
7. Condensateur électrochimique double couche selon l'une quelconque des revendications 1-7, dans lequel le condensateur est symétrique.
 
8. Procédé de fabrication d'un condensateur électrochimique double couche comprenant :

de fournir un substrat inférieur ;

de graver une première cavité dans le substrat inférieur ;

de faire croître une première pluralité de nanotubes de carbone sensiblement alignés dans la première cavité ;

de fournir un substrat supérieur ;

de graver une seconde cavité dans le substrat supérieur ;

de faire croître une seconde pluralité de nanotubes de carbone sensiblement alignés dans la seconde cavité ; et

de fournir un micro-emballage, dans lequel le micro-emballage définit un interstice entre la première pluralité de nanotubes de carbone sensiblement alignés et la seconde pluralité de nanotubes de carbone sensiblement alignés, l'interstice ayant une hauteur d'interstice qui empêche le contact entre la première pluralité de nanotubes de carbone sensiblement alignés et la seconde pluralité de nanotubes de carbone sensiblement alignés, dans lequel la hauteur d'interstice est d'environ 10 microns à environ 50 microns, et dans lequel l'interstice entre les deux côtés du condensateur inclut au moins une partie d'espace ouvert non occupé par un séparateur.


 
9. Procédé selon la revendication 8, comprenant en outre de fonctionnaliser les première et seconde pluralités de nanotubes de carbone sensiblement alignés (605, 606) avec au moins un d'un matériau faradique et non faradique.
 
10. Procédé selon l'une quelconque des revendications 8 et 9, comprenant en outre de remplir les première et seconde cavités avec un électrolyte par un orifice de remplissage.
 
11. Procédé selon la revendication 10, dans lequel l'électrolyte est disposé à travers l'orifice de remplissage par remplissage par vide.
 
12. Procédé selon l'une quelconque des revendications 8-11, dans lequel l'électrolyte comprend un liquide ionique à température ambiante.
 
13. Procédé selon l'une quelconque des revendications 8-12, dans lequel une densité d'énergie gravimétrique des matériaux actifs du condensateur est d'environ 100 Whr/kg à environ 1000 Whr/kg.
 




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Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description