HIGH ENERGY DENSITY CAPACITOR SYSTEM AND METHOD

Abstract

A high energy density capacitor comprising a substrate, a positive electrode, a negative electrode, a plurality of intermediate dielectric layers disposed between the positive electrode and negative electrode, and a metal layer deposited on each of the intermediate dielectric layers. Each intermediate dielectric layer comprises sequential layers of a high surface area dielectric material, an electrolyte and a polar organic solvent deposited onto the substrate. The plurality of intermediate dielectric layers and metal layers are arranged in series to form a stack, and at least one an internal passivation layer is disposed between each stack. The positive and negative electrodes extend along a height of the capacitor and have poles in an alternating arrangement around an edge thereof, wherein the positive and negative electrodes are attached to periodic metal layers deposited on each of the intermediate dielectric layers. Dipoles of the intermediate dielectric layers are aligned in an opposite direction of an electric field created between the positive and negative electrodes while charging.

Claims

1. A high energy density capacitor, comprising: a substrate; a positive electrode; a negative electrode; at least one intermediate dielectric layer disposed between the positive electrode and negative electrode, the at least one intermediate dielectric layer comprised of a high surface area dielectric material, an electrolyte and a polar organic solvent; and a metal layer deposited on each of the at least one intermediate dielectric layers.

2. The capacitor according to claim 1 wherein the high surface area dielectric material has a dielectric constant in the range of about 10.sup.9 to about 10.sup.11.

3. The capacitor according to claim 1 wherein the polar organic solvent is a polar protic solvent selected from the group comprising NH.sub.3, (CH.sub.3).sub.3COH, C.sub.3H.sub.8O, C.sub.2H.sub.6O, CH.sub.3OH, CH.sub.3COOH, and H.sub.2O.

4. The capacitor according to claim 1 wherein the polar organic solvent is a polar aprotic solvent selected from the group comprising C.sub.3H.sub.6O, (CH.sub.3).sub.2NCH, CH.sub.3CN, C.sub.2H.sub.6OS, CH.sub.2Cl.sub.2, C.sub.4H.sub.8O, and C.sub.4H.sub.8O.sub.2.

5. The capacitor according to claim 1 wherein the intermediate dielectric layer is formed by depositing sequential layers of the high surface area dielectric material, electrolyte and polar organic solvent onto the substrate using semiconductor fabrication techniques.

6. The capacitor according to claim 1 further comprising: a plurality of intermediate dielectric layers and metal layers arranged in series to form a stack; and at least one an internal passivation layer disposed between each stack.

7. The capacitor according to claim 1 wherein the at least one intermediate dielectric layer is comprised by molar percentage of about 3% to about 20% electrolyte, about 3% to about 20% dielectric material, and about 60% to about 94% polar organic solvent.

8. The capacitor according to claim 1 wherein dipoles of the at least one intermediate dielectric layer align in an opposite direction of an electric field created between the positive and negative electrodes while charging.

9. The capacitor according to claim 1 wherein the positive and negative electrodes extend along a height of the capacitor and have poles in an alternating arrangement around an edge thereof, and wherein the positive and negative electrodes are attached to periodic metal layers deposited on each of the at least one intermediate dielectric layers.

10. A method of forming a high energy density capacitor, comprising: providing a substrate; providing a positive electrode disposed on the substrate; providing a negative electrode opposite the positive electrode; providing at least one intermediate dielectric layer disposed between the positive electrode and negative electrode, the at least one intermediate dielectric layer comprised of a high surface area dielectric material, an electrolyte and a polar organic solvent; and providing a metal layer deposited on each of the at least one intermediate dielectric layers.

11. The method according to claim 10 wherein the step of providing at least one intermediate dielectric layer disposed between the positive electrode and negative electrode further comprises: depositing sequential layers of the high surface area dielectric material, electrolyte and polar organic solvent onto the substrate using semiconductor fabrication techniques.

12. The method according to claim 10 further comprising: providing a plurality of intermediate dielectric layers and metal layers arranged in series to form a stack; and providing at least one an internal passivation layer disposed between each stack.

13. The method according to claim 10 further comprising: aligning dipoles of the at least one intermediate dielectric layer such that the polarized dielectric layer opposes an electric field created between the positive and negative electrodes while charging.

14. The method according to claim 10 further comprising: positioning the positive and negative electrodes to extend along a height of the capacitor such that poles of the electrodes are in an alternating arrangement around an edge thereof; and attaching the positive and negative electrodes to periodic metal layers deposited on each of the at least one intermediate dielectric layers.

15. The method according to claim 10 wherein the polar organic solvent is a polar protic solvent selected from the group comprising NH.sub.3, (CH.sub.3).sub.3COH, C.sub.3H.sub.8O, C.sub.2H.sub.6O, CH.sub.3OH, CH.sub.3COOH, and H.sub.2O.

16. The method according to claim 10 wherein the polar organic solvent is a polar aprotic solvent selected from the group comprising C.sub.3H.sub.6O, (CH.sub.3).sub.2NCH, CH.sub.3CN, C.sub.2H.sub.6OS, CH.sub.2Cl.sub.2, C.sub.4H.sub.8O, and C.sub.4H.sub.8O.sub.2.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The features of the invention believed to be novel and the elements characteristic of the invention are set forth with particularity in the appended claims. The figures are for illustration purposes only and are not drawn to scale. The invention itself, however, both as to organization and method of operation, may best be understood by reference to the detailed description which follows taken in conjunction with the accompanying drawings in which:

[0020] FIG. 1 depicts a wafer or panel with layers of metal and dielectric layers, in accordance with disclosed embodiments of the present invention.

[0021] FIG. 2 depicts the capacitors of the present invention in serial parallel arrays, in accordance with disclosed embodiments.

[0022] FIG. 3 depicts the capacitors of the present invention having an alternating anode and cathode pole arrangement around the edge of the device in order to get the charge in and out quickly with minimal effective series resistance (ESR).

[0023] FIG. 4 depicts the dielectric surface area of a capacitor in accordance with embodiments of the present invention, wherein surface area A is a three dimensional (3D) surface area, as opposed to two dimensional (2D).

[0024] FIG. 5 depicts the capacitor layer anatomy of a capacitor in accordance with disclosed embodiments of the present invention.

[0025] FIG. 6 depicts a deposition chamber used in an exemplary process for forming a capacitor in accordance with embodiments of the present invention.

[0026] FIG. 7 depicts a deposition chamber used in a second exemplary process for forming a capacitor in accordance with embodiments of the present invention.

DESCRIPTION OF THE EMBODIMENT(S)

[0027] In describing the embodiments of the present invention, reference will be made herein to FIGS. 1-7 of the drawings in which like numerals refer to like features of the invention.

[0028] The high energy density capacitor of the present invention provides a solution for replacing slow charging, short-life batteries with quick charging, long-life capacitors. The method of forming the capacitor(s) of the present invention utilizes atomic layer deposition (ALD), metal oxide chemical vapor deposition (MOCVD), Electrospray, Sputtering, 3D printing and other semiconducting fabrication equipment to produce sub-micron thin layers and the capability for at least twelve (12) inch wafers and/or rectangular substrates, like those used for LED panels, which are available in a wide variety of generations and sizes. Wafers may also be sawed into any shape or size and stacked to any height.

[0029] The instant invention takes advantages of these advances by utilizing a large array of ALD machines and other standard semiconducting fabrication machinery, 3D printing and robotic automation to apply up to thousands of layers per day to mass produce the capacitors in any shape or size.

[0030] The primary advantage that batteries currently have over prior art capacitors is energy density. The capacitor of the present invention eliminates this barrier.

[0031] Certain terminology is used herein for convenience only and is not to be taken as a limitation of the invention. For example, words such as upper, lower, left, right, horizontal, vertical, upward, and downward merely describe the configuration shown in the drawings. For purposes of clarity, the same reference numbers may be used in the drawings to identify similar elements.

[0032] Additionally, in the subject description, the word exemplary is used to mean serving as an example, instance or illustration. Any aspect or design described herein as exemplary is not necessarily intended to be construed as preferred or advantageous over other aspects or design. Rather, the use of the word exemplary is merely intended to present concepts in a concrete fashion.

[0033] Referring now to FIG. 1, an exemplary high energy density capacitor of the present invention is shown. The capacitor includes a wafer or substrate upon which is deposited alternating layers of metal and dielectric layers, and further includes a positive electrode 100, a negative electrode 101, and a stack of five (5) capacitors 102, which makes a 25 volt stack at one-fifth (?.sup.th) the capacitance of a single instantiation, since the five are in series. It should be understood by those skilled in the art that a stack of five capacitors is being shown for exemplary purposes only, and that any number of capacitors may be implemented, in series, in order to achieve the desired voltage per design requirements, as will be described below. A passivation layer 103 or insulator isolates the stacks 102. A metal layer 104, an ultra-dielectric material (UDM) layer 105, and the substrate or wafer 106 complete the assembly, in accordance with disclosed embodiments of the present invention.

[0034] FIG. 2 depicts how a plurality of capacitors are organized in serial parallel arrays, in accordance with disclosed embodiments. Capacitor 201 is a single capacitor formed with UDM and metal layers. Stack 202 depicts a stack of five (5) capacitors in series. Putting capacitors in series lowers the capacitance, but it is necessary to increase the voltage. By way of example herein, each capacitor 201 is rated at 5 volts, therefore the stack 202 is rated up to 25 volts, albeit at one-fifth (?.sup.th) the capacitance of a single capacitor. The total capacitance is increased by arranging an array of stacks in parallel, because capacitors in parallel sum. Up to n stacks 203 may be created until the desired level of energy storage is achieved.

[0035] Capacitance is defined as:

C=(k?.sub.0A)/d

where:

[0036] C=Capacitance (Farads)

[0037] k=Dielectric multiplier

[0038] ?.sub.0=permittivity constant

[0039] A=Area of the plates (m.sup.2)

[0040] d=distance between plates (?m)

[0041] The present invention produces a high capacitance EDLC-type electrochemical capacitor by substantially increasing the dielectric constant k, while shrinking the distance between the plates.

[0042] Referring now to FIG. 3, the capacitors' alternating anode 300 and cathode 301 pole arrangement around the edge of the capacitor device is shown. Alternating poles in such a way allows the charge in and out quickly with minimal effective series resistance (ESR). In larger capacitors, additional positive and negative electrodes may be dispersed intermittently in the interior of the capacitor device, and may be arranged around the center of the device. As shown in the side view of FIG. 3, the electrodes extend along the full height of the capacitor array, even though these poles only attach to the metal layers periodically. In one embodiment, the electrodes 301 are attached to every fifth layer (as depicted in FIG. 1), in order to achieve 25 volt stacks. The unconnected layers may be masked to create a gap between the metal layers 501 and the electrodes 300, 301.

[0043] FIG. 4 depicts the dielectric surface area of an embodiment of a capacitor of the present invention. Of particular note is that surface area A is a three dimensional (3D) surface area, not 2D. The atomic layer of conducting atoms snuggle in around the dielectric atoms, forming a three dimensional structure which yields a much higher surface area than just the 2D. It's the 3D surface area which in this case is the surface area for a bunch of half spheres, i.e. ?*(4?r.sup.2) multiplied by the number of atoms or molecules in the length by width area.

[0044] FIG. 5 depicts the capacitor layer anatomy of one embodiment of the capacitor of the present invention, comprising anode and cathode metal layers 501, with layers of high surface area dielectric material (such as silica) and positive and negative atomic layers disposed therebetween. FIG. 5 illustrates how the dipoles 502 in the dielectric layer 500 align with the electric field 503 of the capacitor, but in the opposite direction, which leads to a reduction in the total field, and an increase in the total quantity of charge that the capacitor can hold for a given voltage/applied field. As a result, more charge can build up on the positive and negative electrodes 501. The k in physics is determined by the degree of polarization that the dielectric layers 500 can undergo, in other words, how many dipoles 502 are available inside the N-type and P-type atomic layers to reduce the applied field across the capacitor, thereby allowing more charge to be stored on the plates.

[0045] The metal atoms with their conduction band and free electrons snuggle in around the hemispherical surfaces of the top of the dielectric layer (FIG. 4). Using pairs of high voltage plates to align the dipoles, as will be described in more detail below, the dielectric layers become electrets, equivalent to magnets; however, instead of aligning magnetic domains, the high energy density capacitor of the present invention comprises aligning electric dipole domains.

[0046] The present invention optimizes energy density by maximizing the operating voltage. Some polar organic solvents have breakdown voltages three (3) to four (4) times higher than distilled water, and some are in the 5V range at micron thicknesses. By contrast, distilled water breakdown voltage limits the operating voltage to 0.8 to 1.2 volts per cell. The present invention also encompasses replacing the polar protic solvents with electric dipole materials, electrets, that are deposited and aligned to oppose the main electric field created when the capacitor is charging.

[0047] One advantage of the present invention is that each capacitor may have a thickness of much less than 1 micron (?m) to optimize energy density while increasing capacitance.

[0048] The ultra-dielectric materials (UDM) utilized in one embodiment comprise a combination of a polar organic solvent from Table 1 below, an electrolyte from Table 2 below, and a high surface area dielectric material from Table 3 below. In an embodiment, polar protic solvents are used for their high dielectric constants and high dipole moments. In other embodiments, polar aprotic solvents work well also, e.g. DMSO, KCl, and SiO.sub.2 or DMSO, NaCl, and SiO.sub.2, and therefore it should be understood by those skilled in the art that the present invention encompasses such alternative compositions which include a polar aprotic solvent in place of a polar protic solvent.

TABLE-US-00001 TABLE 1 Polar Protic/Aprotic Solvents Protic Break or Dielectric Dipole Down Polar Solvents Aprotic Constant Moment Volts.sup.1 Ammonia protic 25 1.40 D t-Butanol protic 12 1.70 D n-Propanol protic 20 1.68 D Ethanol protic 25 1.69 D Methanol protic 33 1.70 D Acetic Acid protic 6.2 1.74 D Water protic 80 1.85 D .8-1.2 Acetone aprotic 25 1.40 D Dimethylformamide (DMF) aprotic 12 1.70 D Acetonitrile (MeCN) aprotic 20 1.68 D Dimethyl Sulfoxide (DMSO) aprotic 25 1.69 D Dichloromethane aprotic 9.1 1.60 D Tetrahydrofuran (THF) aprotic 7.5 1.75 D Ethyl Acetate aprotic 6 1.78 D

TABLE-US-00002 TABLE 2 Electrolyte materials Electrolyte Materials NaCL NH.sub.4CL KCl

TABLE-US-00003 TABLE 3 High Surface Area Dielectric materials High Surface Area Dielectric Materials In situ k Pyrogenic Silica (Fumed Silica) 10.sup.10 to 10.sup.11 Silicon Dioxide (SiO.sub.2) ~10.sup.10 Alumina 10.sup.9 to 10.sup.10

[0049] In one exemplary embodiment, ammonia (NH.sub.3) is used as the polar protic solvent, NH.sub.4CL is the electrolyte, and silicon dioxide is the high surface area dielectric material.

[0050] In an embodiment, these materials are each deposited in sequential layers onto the wafer or substrate to build up a half micron (0.5 ?m) layer of UDM material 105 using semiconductor processing equipment and/or 3D printers. Then a quarter micron (0.25 ?m) layer of metal 104 is deposited on top of the UDM layer 105. This is repeated in an alternating process until five (5) complete UDM/metal sandwich layers are completed, thereby forming a 25 volt stack 102.

[0051] The three UDM compounds are built up sequentially in molar percentages of about three percent (3%) to about twenty percent (20%) electrolyte (Table 2), about three percent (3%) to about twenty percent (20%) dielectric materials (Table 3), and about sixty percent (60%) to about ninety-four percent (94%) polar organic solvent (Table 1).

[0052] These UDM compounds yield dielectric k values in the 10.sup.8 to 10.sup.11 range.

[0053] Table 4 below reveals the high energy density of an embodiment of the capacitor of the present invention using a six (6) inch wafer and assuming k is at the median point of the range of about 10.sup.10. The UDM dielectric layer thickness is 0.5 ?m in this example. Stacks of five layers in series creates a 25 volt capacitor. This embodiment yields 56.1 kWh of capacity with only 100 stacks.

TABLE-US-00004 TABLE 4 A six inch wafer at the median k range k ?.sub.0 A d F/lyr Lyrs F/stk Par Stks F Total J = CV.sup.2/2 kWh 1.00E+10 8.85E?12 0.182415 5.00E?07 3.23E+04 5 6460.5 100 646,055 201,892,084 56.1

[0054] In one embodiment, the Fumed Silica utilized was 7 nm Aldrich powder.

[0055] Capacitors made in accordance with the present invention may have a life cycle of more than 1,000,000 cycles even at deep discharge rates, e.g., eighty percent (80%) depth of discharge (DoD). The charge time for each capacitor may be about 30 seconds for full recharge.

[0056] After the wafers or panels are processed, the capacitors may be sawed in various shapes and sizes and placed into the final packaging using activated carbon, graphene or other type electrodes.

[0057] These capacitors may be used in electric vehicles (EVs) and charged using a Capacitive Wireless Charging System and Method, as described in patent application Ser. No. 62/511,754, filed May 26, 2017, by the same inventor, which may be easily installed in existing service stations. Other applications for the improved high energy density capacitor of the present invention include not only vehicles, but other modes of transportation including planes or trains, backup storage for utilities, windmills, and any other type of electrical facilities.

[0058] In another embodiment, the wafers or substrates may be twelve (12) inch (?300 mm), but any size wafer or even rectangular LED panels will work in ALD, MOCVD and other semiconductor or 3D printing systems. Up to 370 mm?470 mm panels may be used to make rectangular capacitors. It is further contemplated by the present invention that larger panels may be used as they become available in the future.

[0059] In one embodiment according to the present invention is a two solvent mixture of ethylene glycol and a polar organic cosolvent from Table 1. Boric acid is dissolved in this mixture with a carboxylic acid.

[0060] A deposition chamber used in an exemplary solid state process for forming a capacitor in accordance with embodiments of the present invention is shown in FIG. 6. Dipoles structures in each dielectric layer are fabricated by depositing a layer of polarized dielectric material and aligning the dipoles using high voltage plates. This process requires minimal layers per capacitor.

[0061] Capacitive plates are placed above and below the deposition chamber external to the chamber and a high voltage DC is applied. One capacitive plate takes on a high positive Voltage and the other a high negative Voltage, to ensure that the dipoles remain aligned while applying each subsequent layer. During ion deposition, the small dipoles in the Oxide layer align in the opposite direction of the Electric Field. After each layer is completed, the dipoles will remain aligned after the external Electric Field is removed. Consequently, the dielectric k value increases by several orders of magnitude and the breakdown voltages increase by an order of magnitude or more over what is conventionally expected. An advantage of this solid state deposition process is that many layers may be built up to make very large capacitors.

[0062] Referring now to FIG. 7, an atomic layer deposition (ALD) chamber used in a second, different solid state process for forming a high energy density capacitor of the present invention is shown. In this process, the dipole structures are fabricated in a sandwich of alternating layers of ions and dielectric by first depositing a layer of dielectric 605 disposed above the p-Electrode 606, then a layer of n-ions 604, another layer of dielectric 603, a layer of p-ions 602, and another layer of dielectric 601 to insulate the p-ions from the n-Electrode 600. This process requires more layers per capacitor.

[0063] As shown in FIG. 7, a wafer or substrate is placed at the bottom of the deposition chamber, and aligned with the positive electrode or p-Electrode. The first layer of ions is deposited by filling the chamber with ionic gas and placing a High Voltage plate inside the chamber beneath the substrate or wafer, as well as placing a High Voltage plate having an opposite voltage above and external to the chamber, to create a strong Electric Field by applying a DC Voltage. The stronger the Electric field applied, the more densely the layer of ions is able to be packed. Next, the chamber is cleared, and a dielectric layer is applied to hold the ions (up to five atomic layers may be required), before removing the Electric field. The chamber is then flooded with a positive ion gas and the voltage on the plates is reversed. As the Positive ions get close to the dielectric layer, the Negative ions underneath the dielectric layer attract the Positive ions and align them overhead, creating smaller dipoles. On each successive layer, the process of reversing the chamber plate Voltage is repeated, selecting the other ionizing tip, as necessary. It is further contemplated by the present invention that the positive and negative ions may instead be replaced by a mixture of bare electrons and protons. In another embodiment, electrospray may be used to deposit the ion layers.

[0064] It is contemplated that other low cost, high fidelity methods may be used to deposit the dielectric layer. For example, technologies that may be suitable for producing dielectric layers of appropriate thickness include spin-coating, spray-coating, or screen printing. Generally, roll-to-roll coating methods are considered suitable.

[0065] Thus, the present invention achieves one or more of the following advantages. The capacitor of the present invention provides a solution for replacing slow charging, short-life batteries with quick charging, long-life capacitors having a significant higher energy density than prior art capacitors. The method of forming the capacitor(s) of the present invention utilizes atomic layer deposition (ALD), metal oxide chemical vapor deposition (MOCVD), 3D printing and other semiconducting fabrication equipment to produce sub-micron thin layers and the capability for 12 inch wafers and/or rectangular substrates, like those used for LED panels, which are available in a wide variety of generations and sizes. Wafers may also be sawed into any shape or size and stacked to any height. The instant invention takes advantage of these advances by utilizing a large array of ALD machines and other standard semiconducting fabrication machinery, 3D printing and robotic automation to apply up to thousands of layers per day to mass produce the capacitors of the present invention in any shape or size.

[0066] While the present invention has been particularly described, in conjunction with specific embodiments, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. It is therefore contemplated that the appended claims will embrace any such alternatives, modifications and variations as falling within the true scope and spirit of the present invention.