EP3414815A2 - Cellule de stockage d'énergie capacitif, module et système - Google Patents

Cellule de stockage d'énergie capacitif, module et système

Info

Publication number
EP3414815A2
EP3414815A2 EP17750644.1A EP17750644A EP3414815A2 EP 3414815 A2 EP3414815 A2 EP 3414815A2 EP 17750644 A EP17750644 A EP 17750644A EP 3414815 A2 EP3414815 A2 EP 3414815A2
Authority
EP
European Patent Office
Prior art keywords
energy storage
voltage
meta
converter
capacitive energy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17750644.1A
Other languages
German (de)
English (en)
Other versions
EP3414815A4 (fr
Inventor
Ian S.G. KELLY-MORGAN
Matthew R. Robinson
Paul T. FURUTA
Daniel Membreno
Pavel Ivan Lazarev
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Capacitor Sciences Inc
Original Assignee
Capacitor Sciences Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US15/043,209 external-priority patent/US20170236642A1/en
Priority claimed from US15/043,315 external-priority patent/US10305295B2/en
Priority claimed from US15/043,247 external-priority patent/US20170233528A1/en
Priority claimed from US15/043,186 external-priority patent/US20170236641A1/en
Application filed by Capacitor Sciences Inc filed Critical Capacitor Sciences Inc
Publication of EP3414815A2 publication Critical patent/EP3414815A2/fr
Publication of EP3414815A4 publication Critical patent/EP3414815A4/fr
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/0013—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries acting upon several batteries simultaneously or sequentially
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/34—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering
    • H02J7/345—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering using capacitors as storage or buffering devices
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02M—APPARATUS FOR CONVERSION BETWEEN AC AND AC, BETWEEN AC AND DC, OR BETWEEN DC AND DC, AND FOR USE WITH MAINS OR SIMILAR POWER SUPPLY SYSTEMS; CONVERSION OF DC OR AC INPUT POWER INTO SURGE OUTPUT POWER; CONTROL OR REGULATION THEREOF
    • H02M3/00—Conversion of dc power input into dc power output
    • H02M3/02—Conversion of dc power input into dc power output without intermediate conversion into ac
    • H02M3/04—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters
    • H02M3/10—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode
    • H02M3/145—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode using devices of a triode or transistor type requiring continuous application of a control signal
    • H02M3/155—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode using devices of a triode or transistor type requiring continuous application of a control signal using semiconductor devices only
    • H02M3/156—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode using devices of a triode or transistor type requiring continuous application of a control signal using semiconductor devices only with automatic control of output voltage or current, e.g. switching regulators
    • H02M3/158—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode using devices of a triode or transistor type requiring continuous application of a control signal using semiconductor devices only with automatic control of output voltage or current, e.g. switching regulators including plural semiconductor devices as final control devices for a single load
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02M—APPARATUS FOR CONVERSION BETWEEN AC AND AC, BETWEEN AC AND DC, OR BETWEEN DC AND DC, AND FOR USE WITH MAINS OR SIMILAR POWER SUPPLY SYSTEMS; CONVERSION OF DC OR AC INPUT POWER INTO SURGE OUTPUT POWER; CONTROL OR REGULATION THEREOF
    • H02M3/00—Conversion of dc power input into dc power output
    • H02M3/02—Conversion of dc power input into dc power output without intermediate conversion into ac
    • H02M3/04—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters
    • H02M3/10—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode
    • H02M3/145—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode using devices of a triode or transistor type requiring continuous application of a control signal
    • H02M3/155—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode using devices of a triode or transistor type requiring continuous application of a control signal using semiconductor devices only
    • H02M3/156—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode using devices of a triode or transistor type requiring continuous application of a control signal using semiconductor devices only with automatic control of output voltage or current, e.g. switching regulators
    • H02M3/158—Conversion of dc power input into dc power output without intermediate conversion into ac by static converters using discharge tubes with control electrode or semiconductor devices with control electrode using devices of a triode or transistor type requiring continuous application of a control signal using semiconductor devices only with automatic control of output voltage or current, e.g. switching regulators including plural semiconductor devices as final control devices for a single load
    • H02M3/1582—Buck-boost converters

Definitions

  • CAPACITIVE ENERGY STORAGE CELL CAPACITIVE ENERGY STORAGE MODULE, AND CAPACITIVE ENERGY STORAGE SYSTEM
  • the present disclosure relates generally to a modular energy storage system to simultaneously enable multiple applications and more particularly to an energy storage cell comprising at least one capacitive energy storage device and a DC-voltage conversion device.
  • Rechargeable batteries store and release electrical energy through electrochemical reactions.
  • Rechargeable batteries are used for automobile starters, portable consumer devices, light vehicles (such as motorized wheelchairs, golf carts, electric bicycles, and electric forklifts), tools, and uninterruptible power supplies.
  • Emerging applications in hybrid internal combustion-battery and electric vehicles are driving the technology to reduce cost, weight, and size, and increase lifetime.
  • Grid energy storage applications use rechargeable batteries for load-leveling, storing electric energy at times of low demand for use during peak periods, and for renewable energy uses, such as storing power generated from photovoltaic arrays during the day to be used at night. Load-leveling reduces the maximum power which a plant must be able to generate, reducing capital cost and the need for peaking power plants.
  • BMS battery management system
  • Rechargeable batteries have drawbacks due to relatively large weight per unit energy stored, a tendency to self-discharge, susceptibility to damage if too deeply discharged, susceptibility to catastrophic failure if charged too deeply, limited power availability l per unit weight, limited power availability per unit energy, relatively long charging times, and degradation of storage capacity as the number of charge-discharge cycles increases.
  • Capacitors store energy in the form of an electrostatic field between a pair of electrodes separated by a dielectric layer. When a voltage is applied between two electrodes, an electric field is present in the dielectric layer. Unlike batteries, capacitors can be charged relatively quickly, can be deeply discharged without suffering damage, and can undergo a large number of charge discharge cycles without damage. Capacitors are also lower in weight than comparable batteries. Despite improvements in capacitor technology, including the development of ultracapacitors and supercapacitors, rechargeable batteries store more energy per unit volume. One drawback of capacitors compared to batteries is that the terminal voltage drops rapidly during discharge. By contrast, battery systems tend to have a terminal voltage that does not decline rapidly until nearly exhausted.
  • capacitors for energy storage applications typically operate at much higher voltages than batteries. Furthermore, energy is lost if constant current mode is not used during charge and discharge.
  • aspects of the present disclosure address problems with conventional rechargeable electrical energy storage technology by combining a capacitive energy storage device having one or meta-capacitors with a DC-voltage conversion device having one or more switch mode voltage converters coupled to the terminals of the capacitive energy storage device.
  • Meta- capacitors have greater energy storage capacity than conventional ultracapacitors or
  • the DC-voltage conversion device regulates the voltage on the capacitive energy storage device during charging and discharging.
  • a voltage conversion device typically includes a voltage source (an input), one or more active or passively controlled switches, one or more inductive elements (some advanced converters, e.g., charge-pump circuits, do not specifically use inductors per se though there may be parasitic inductance in the circuit board and/or wiring), one or more energy storage elements(e.g., capacitors and/or inductors), some way of sensing output voltage and/or current, and some way of controlling the switches to create a specific output voltage or current, and terminals to connect this device to external inputs and outputs such as various loads.
  • a voltage source an input
  • active or passively controlled switches include a voltage source (an input), one or more active or passively controlled switches, one or more inductive elements (some advanced converters, e.g., charge-pump circuits, do not specifically use inductors per se though there may be parasitic inductance in the circuit board and/or wiring), one or more energy storage elements(e.g., capacitors and/or inductors), some
  • a standard circuit for producing an output voltage V ou t that is less than the input voltage Vi n (V ou t in ⁇ 1) is called a buck converter, and a standard circuit for producing an output voltage that is greater than the input voltage (V ou t in > 1) is called a boost converter.
  • the basic circuit often used to describe buck conversion is a switched LC filter ( Figure 1).
  • the load can be thought of as a resistor that will vary its resistance to achieve a set current moving through it. Effectively, this is an LCR low-pass filter, with the capacitor and resistor in parallel.
  • the reverse voltage generated will be extremely high if the incremental change in current di occurs over a sufficiently short increment of time dt, and this may damage or destroy the switching element SW1. Therefore, it is necessary to provide a path to ground so that current can continue to flow.
  • This path can be implemented with a diode that operates as a one-way valve, opening automatically when the inductor tries to pull current out of the switching element SW1 (see Figure 2).
  • This is called a non-synchronous buck converter, because the diode is automatically synchronized with the switching of a power transistor, such as a metal oxide semiconductor field effect transistor (MOSFET). Such a converter does not need to be actively synchronized.
  • MOSFET metal oxide semiconductor field effect transistor
  • a possible issue with this type of circuit is that the turn-on voltage of the diode needs to be reached and be maintained while the switching element SW1 is turned off and the diode is active. This means that there will always be a voltage drop of, e.g., -0.6V across the diode due to current flowing through it, and therefore a power loss.
  • This can be improved by implementing a synchronous converter design, where the diode is replaced with a second switch SW2 (see Figure 3) and the controller actively synchronizes the activity of both switches such that they are never on at the same time.
  • the delay between turn-off and turn-on of the MOSFETs in a synchronous design needs to ensure that a shoot-through event does not occur.
  • two separate pulses can be set up with a delay, a better solution would only need a single PWM channel set up and automatically derive the second signal. With a little bit of thought, this can be achieved using digital buffers (or inverters) to introduce a time delay into the switching signals applied to the switches SW1 and SW2 shown in Figure 3.
  • Typical gates have 2-10ns propagation delay, but programmable logic devices such as a complex programmable logic device (CPLD) or field programmable gate array (FPGA) can be programmed with variable propagation delay.
  • CPLD complex programmable logic device
  • FPGA field programmable gate array
  • S is an input PWM input signal.
  • S' is the input signal S delayed by tdeiay- S" is S' delayed by 2*tdelay
  • !S is the inverse of the input signal S
  • !S is the inverse of signal S
  • !S&&! S is the logical AND of
  • Synchronous converters tend to have an advantage in high-ratio conversion. They are also a fundamental building block of the split-pi- bidirectional converter because the extra switches are needed to provide dual-purpose buck or boost.
  • the boost converter delivers the supply voltage directly to the load through the second switch element SW2 in Figure 5.
  • the process of increasing the voltage to the load is started by opening the switching element SW2 and closing the switching element SW1 ( Figure 6). Due to the additional voltage drop on inductor LI, current flowing through inductor LI will increase over time (see, equation (2)).
  • NMOS N-channel MOSFET
  • PMOS P-channel MOSFET
  • push-pull N-channel MOSFET
  • CMOS complementary metal oxide semiconductor
  • the stacked MOSFET is a high-voltage switching circuit.
  • a low-voltage input signal turns on the first MOSFET in a stack of MOSFET devices, and the entire stack of devices is turned on by charge injection through parasitic and inserted capacitances.
  • Voltage division provides both static and dynamic voltage balancing, preventing any device in the circuit from exceeding its nominal operating voltage. The design equations for these topologies are presented. Simulations for a five device stack implemented in Honeywell's 150 nm process verify the static and dynamic voltage balancing of the output signal. The simulated stack is shown to handle five times the nominal operating voltage.
  • MOSFET metal-oxide semiconductor field effect transistors
  • Another voltage switching circuit configuration is based on an Integrated Gate- Commutated Thyristor (IGCT).
  • IGCT Integrated Gate- Commutated Thyristor
  • the integration of a 10-kV-IGCT and a fast diode in one press pack is an attractive solution for Medium Voltage Converters in a voltage range of 6 kV - 7.2 kV if the converter power rating does not exceed about 5 - 6MVA.
  • Sven Tschirley et al. "Design and Characteristics of Reverse Conducting 10-kV-IGCTs", Proceedings of the 39th annual Power Electronics Specialist Conference, pages 92-98, 2008, which is incorporated herein by reference).
  • Tschirley et al describe the design and characterization of the world's first reverse conducting 68mm 10-kV-IGCTs.
  • improvements in one or more of the physical properties of the dielectric material in a capacitor can result in corresponding performance improvements in the capacitor component, usually resulting in performance and lifetime enhancements of the electronics system or product in which it is embedded. Since improvements in capacitor dielectric can directly influence product size, product reliability, and product efficiency, there is a high value associated with such improvements.
  • capacitors are able to store energy with very high power density, i.e. charge/recharge rates, have long shelf life with little degradation, and can be charged and discharged (cycled) hundreds of thousands or millions of times.
  • capacitors often do not store energy in small volume or weight as in case of a battery, or at low energy storage cost, which makes capacitors impractical for some applications, for example electric vehicles.
  • aspects of the present disclosure address problems with conventional rechargeable electrical energy storage technology by combining a capacitive energy storage device having one or more meta-capacitors (further described below) with a DC-voltage conversion device having one or more switch mode voltage converters coupled to the terminals of the capacitive energy storage device.
  • Meta-capacitors have greater energy storage capacity than conventional ultracapacitors or supercapacitors.
  • the DC-voltage conversion device regulates the voltage on the capacitive energy storage device during charging and discharging.
  • a meta-capacitor is a dielectric film capacitor whose dielectric film is a meta-dielectric material, which is disposed between a first electrode and second electrode.
  • said electrodes are flat and planar and positioned parallel to each other.
  • the meta-capacitor comprises two rolled metal electrodes positioned parallel to each other.
  • a meta-dielectric material comprises of Sharp polymers and/or Furuta polymers.
  • the present disclosure provides an energy storage cell comprising a capacitive energy storage device having one or more meta-capacitors and a DC-voltage conversion device having one or more switch mode voltage converters.
  • the power port (consisting of a positive terminal and a negative terminal, or anode and cathode) on the capacitive energy storage device is connected to the capacitor-side power port on the DC-voltage conversion device.
  • the DC- voltage conversion device has one or more other power ports, which may interface to external circuitry.
  • the power ports are intended to convey power with associated current and voltage commiserate to the specification for the cell.
  • Each terminal in the port is a conductive interface.
  • Each cell may include means to monitor and/or control parameters such as voltage, current, temperature, and other important aspects of the DC-voltage conversion device.
  • a capacitive energy storage module may include one or more individual capacitive energy storage cells and one or more power buses consisting of an interconnection system, wherein a power bus connects the power ports of the individual energy storage cells, in parallel or series, to create common module power ports consisting of common anode(s) and common cathode(s) of the capacitive energy storage module.
  • the module may have additional sensors to monitor temperature, module power, voltage and current of the interconnection system, and may include a communication bus and/or communication bus protocol translator to convey these sensor values as well as the values from the individual cells.
  • a capacitive energy storage system may include one or more of the aforementioned capacitive energy storage modules, an interconnection system and a system control computer that monitors, processes, and controls all the values on the aforementioned communication bus.
  • Figure 1 schematically shows the buck conversion device based on the switched LC filter.
  • Figure 2 schematically shows the non-synchronous buck conversion device.
  • Figure 3 schematically shows the synchronous buck conversion device.
  • Figure 4 demonstrates the signal treatment required to generate a pair of signals with the required time delay spacing.
  • Figure 5 schematically shows a boost converter in an "on state”.
  • Figure 6 schematically shows a boost converter in an "off state”.
  • Figure 7A shows a capacitive energy storage device containing a single capacitive element connected to a two terminal port.
  • Figure 7B shows an alternative configuration of a capacitive energy storage device containing multiple elements connected to a two terminal port.
  • Figure 7C shows an alternative configuration of a capacitive energy storage device containing multiple elements connected to a two terminal port.
  • Figure 7D shows an alternative configuration of a capacitive energy storage device containing multiple elements connected to a two terminal port.
  • Figure 8A schematically shows a switch-mode voltage converter implementing a standard boost circuit.
  • Figure 8B schematically shows a switch-mode voltage converter implementing a standard buck circuit.
  • Figure 8C schematically shows a switch-mode voltage converter implementing a standard inverting buck/boost circuit.
  • Figure 8D schematically shows a switch-mode voltage converter implementing a standard non- inverting and bi-directional buck/boost circuit.
  • Figure 9A schematically shows a DC-voltage conversion device having two power ports and separate one or more boost and one or more buck converters for charging a meta-capacitor and separate one or more boost and one or more buck converters for discharging the meta-capacitor.
  • Figure 9B schematically shows an alternative DC-voltage conversion device having two power ports and a one or more buck converters for charging a meta-capacitor and one or more buck boost converter for the discharging the meta-capacitor.
  • Figure 9C schematically shows another alternative DC-voltage conversion device having two power ports and one or more boost converters for the charge and one or more buck converters for discharging a meta-capacitor.
  • Figure 9D schematically shows another alternative DC-voltage conversion device having two power ports and one or more buck/boost converters for charging a meta-capacitor and one or more buck/boost converters for discharging the meta-capacitor.
  • Figure 9E schematically shows yet another DC-voltage conversion device having two power ports and one or more bidirectional boost/buck converters for the charging and discharging a meta-capacitor.
  • Figure 9F schematically shows still another DC-voltage conversion device having three power ports and separate one or more boost and one or more buck converters for charging a meta- capacitor and separate one or more boost and one or more buck converters for discharging the meta-capacitor.
  • Figure 9G schematically shows another DC-voltage conversion device having three power ports and a one or more buck converters for charging a meta-capacitor and one or more buck boost converter for discharging the meta-capacitor.
  • Figure 9H schematically shows another DC-voltage conversion device having three power ports and one or more buck/boost converters for charging a meta-capacitor and one or more buck/boost converters for discharging a meta-capacitor.
  • Figure 91 schematically shows yet another DC-voltage conversion device having three power ports and one or more bidirectional boost/buck converters for the charging and discharging a meta-capacitor.
  • FIG. 10 schematically shows an energy storage cell according to aspects of the present disclosure.
  • Figure 10A schematically shows a meta-capacitor with flat and planar electrodes according to aspects of the present disclosure.
  • Figure 10B schematically shows a meta-capacitor with rolled (circular) electrodes according to aspects of the present disclosure.
  • Figure 1 1 schematically shows an energy storage cell according to an alternative aspect of the present disclosure.
  • Figure 12 schematically shows an energy storage cell according to an alternative aspect of the present disclosure.
  • Figure 13A shows a constant voltage V_i(t) feeding the input of a converter and voltage V_c(t) on the capacitive energy storage device during charge as the converter transitions from buck to boost in accordance with aspects of the present disclosure.
  • Figure 13B shows a constant voltage V_o(t) extracted from the output side of a converter and voltage V_c(t) on the capacitive energy storage device during discharge as the converter transitions from buck to boost in accordance with aspects of the present disclosure.
  • Figure 15A shows an example of a single switch buck-boost converter that may be implemented in a switch-mode voltage converter, which could be selected for use in a DC voltage conversion device in an energy storage cell according to aspects of the present disclosure.
  • Figure 15B shows an example of a four switch buck-boost converter that may be implemented in a switch-mode voltage converter, which could be selected for use in a DC voltage conversion device in an energy storage cell according to aspects of the present disclosure.
  • Figure 16 shows an example of a capacitive energy storage module having two or more networked energy storage cells according to an alternative aspect of the present disclosure.
  • Figure 17 shows an example of a capacitive energy storage system having two or more energy storage networked modules according to an alternative aspect of the present disclosure.
  • FIG. 10 schematically shows a capacitive energy storage cell 1 comprising a capacitive energy storage device 2 that includes one or more meta-capacitors 20 and a DC-voltage conversion device 3, consisting of one or more switch-mode voltage converters 100, e.g. a buck converter, boost converter, buck/boost converter, bi-directional buck/boost (split-pi) converter, Cuk converter, SEPIC converter, inverting buck/boost converter, or four-switch buck/boost converter.
  • switch-mode voltage converters 100 e.g. a buck converter, boost converter, buck/boost converter, bi-directional buck/boost (split-pi) converter, Cuk converter, SEPIC converter, inverting buck/boost converter, or four-switch buck/boost converter.
  • a meta-capacitor is a capacitor comprising of a dielectric film that is a meta-dielectric material, which is disposed between a first electrode and second electrode.
  • said electrodes are flat and planar and positioned parallel to each other as shown in Figure 10A.
  • the meta-capacitor comprises two rolled metal electrodes positioned parallel to each other as shown in Figure 10B.
  • a meta-capacitor may be configured as shown in Figure 10A.
  • the meta-capacitor comprises a first electrode 21 , a second electrode 22, and a meta-dielectric layer 23 disposed between said first and second electrodes.
  • the electrodes 21 and 22 may be made of a metal, such as copper, zinc, or aluminum or other conductive material and are generally planar in shape.
  • the electrodes 21 , 22 may be flat and planar and positioned parallel to each other.
  • the electrodes may be planar and parallel, but not necessarily flat, e.g., they may be coiled, rolled, bent, folded, or otherwise shaped to reduce the overall form factor of the capacitor. It is also possible for the electrodes to be non-flat, non-planar, or non-parallel or some combination of two or more of these.
  • Composite Dielectric Film layer 23 may range from about 100 nm to about 10,000 ⁇ .
  • the maximum voltage Vbd between the electrodes 21, 22 is approximately the product of the breakdown field E bd and the electrode spacing d.
  • the electrodes 21 , 22 may have the same shape as each other, the same dimensions, and the same area A.
  • the area A of each electrode 1021 , 1022 may range from about 0.01 m 2 to about 1000 m 2 .
  • the electrodes may be up to, e.g., 1000 m long and 1 m wide.
  • the capacitance C of the capacitor may be approximated by the formula:
  • the energy storage capacity U is determined by the dielectric constant ⁇ , the area A, and the breakdown field E bd .
  • a capacitor or capacitor bank may be designed to have any desired energy storage capacity U.
  • a capacitor in accordance with aspects of the present disclosure may have an energy storage capacity U ranging from about 500 Joules to about 2X10 16 Joules.
  • a capacitor of the type described herein may have a specific energy capacity per unit mass ranging from about 10 W-h/kg up to about 100,000 W-h/kg, though implementations are not so limited.
  • Aspects of the present disclosure include the use of meta-capacitors that are coiled, e.g., as depicted in Figure 10B.
  • a meta-capacitor 20 comprises a first electrode 21, a second electrode 22, and a meta-dielectric material layer 23 of one or more of the types described hereinabove disposed between said first and second electrodes.
  • the electrodes 21, 22 may be made of a metal, such as copper, zinc, or aluminum or other conductive material and are generally planar in shape.
  • the electrodes and meta-dielectric material layer 23 are in the form of long strips of material that are sandwiched together and wound into a coil along with an insulating material, e.g., a plastic film such as polypropylene or polyester to prevent electrical shorting between the electrodes 21, 22. Examples of such coiled capacitor energy storage devices are described in detail in commonly-assigned U. S. Patent Application Number 14/752,600, filed June 26, 2015, which has been published as U.S. Patent Application Publication Number 2016/0379757, the entire contents of which are incorporated herein by reference.
  • Said meta-dielectric materials are comprised of composite molecules having supra- structures formed from polymers.
  • polymers include so-called Sharp polymers and so-called Furuta co-polymers and so-called para-Furuta polymers as described in detail in commonly-assigned US Patent Application Numbers 15/043,247 (Attorney Docket No. CSI-046 and 15/043,186 (Attorney Docket No. CSI-019A), and 15/043,209 (Attorney Docket No. CSI- 019B), respectively, all filed February 12, 2016, the entire contents of which are incorporated herein by reference. Furuta co-polymers and para-Furuta polymers are referred to collectively as Furuta polymers.
  • Sharp polymers are composites of a polarizable core inside an envelope of hydrocarbon (saturated and/or unsaturated), fluorocarbon, chlorocarbon, siloxane, and/or polyethylene glycol as linear or branched chain oligomers covalently bonded to the polarizable core that act to insulate the polarizable cores from each other, which favorably allows discrete polarization of the cores with limited or no dissipation of the polarization moments in the cores.
  • the polarizable core has hyperelectronic or ionic type polarizability.
  • “Hyperelectronic polarization may be considered due to the pliant interaction of charge pairs of excitons, localized temporarily on long, highly polarizable molecules, with an external electric field [.] (Roger D. Hartman and Herbert A. Pohl, "Hyper-electronic Polarization in Macromolecular Solids", Journal of Polymer Science: Part A-l Vol. 6, pp. 1135-1152 (1968)).” Ionic type polarization can be achieved by limited mobility of ionic parts of the core molecular fragment.
  • a Sharp polymer has a general structural formula:
  • Core is an aromatic polycyclic conjugated molecule comprising rylene fragments. This molecule has flat anisometric form and self-assembles by pi-pi stacking in a column-like supramolecule.
  • the substitute Rl provides solubility of the organic compound in a solvent.
  • the parameter n is number of substitutes Rl , which is equal to 0, 1 , 2, 3, 4, 5, 6, 7 or 8.
  • the substitute R2 is an electrically resistive substitute located in terminal positions, which provides resistivity to electric current and comprises hydrocarbon (saturated and/or unsaturated), fiuorocarbon, siloxane, and/or polyethyleneglycol as linear or branched chains.
  • the substitutes R3 and R4 are substitutes located on side (lateral) positions (terminal and/or bay positions) comprising one or more ionic groups from a class of ionic compounds that are used in ionic liquids connected to the aromatic polycyclic conjugated molecule (Core), either directly, e.g., with direct bound SP2-SP3 carbons, or via a connecting group.
  • the parameter m is a number of the aromatic polycyclic conjugated molecules in the column-like supramolecule, which is in a range from 3 to 100 000.
  • the aromatic polycyclic conjugated molecule comprises an electro-conductive oligomer, such as a phenylene, thiophene, or polyacene quinine radical oligomer or combinations of two or more of these.
  • the electro-conductive oligomer is selected from phenylene, thiophene, or substituted and/or unsubstituted polyacene quinine radical oligomer of lengths ranging from 2 to 12. or combination of two or more of these.
  • substitutions of ring hydrogens by O, S or NR5 is selected from the group consisting of unsubstituted or substituted Ci-Cigalkyl, unsubstituted or substituted C2-Ci 8 alkenyl,
  • the substitute providing solubility (Rl) of the composite organic compound is CxQ2x+i, where X > 1 and Q is hydrogen (H), fluorine (F), or chlorine (CI).
  • the substitute providing solubility (Rl) of the composite organic compound is independently selected from alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl, branched and complex fluorinated alkyl, branched and complex chlorinated alkyl groups, and any combination thereof, and wherein the alkyl group is selected from methyl, ethyl, propyl, butyl, zso-butyl and fert-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups or siloxane, and/or polyethylene glycol as linear or branched chains.
  • At least one electrically resistive substitute (R2) of the composite organic compound is Cx(3 ⁇ 4x + i, where X > 1 and Q is hydrogen (H), fluorine (F), or chlorine (CI).
  • at least one electrically resistive substitute (R2) is selected from the list comprising -(CH2) n -CH3, -CH((CH2) n CH3)2) (where n >1), alkyl, aryl, substituted alkyl, substituted aryl, branched alkyl, branched aryl, and any combination thereof and wherein the alkyl group is selected from methyl, ethyl, propyl, butyl, iso- butyl and fert-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups.
  • the composite organic compound is Cx(3 ⁇ 4x + i, where X > 1 and Q is hydrogen (H), fluorine (F), or chlorine (CI).
  • the substitute Rl and/or R2 is connected to the aromatic polycyclic conjugated molecule (Core) via at least one connecting group.
  • the at least one connecting group may be selected from the list comprising the following structures: ether, amine, ester, amide, substituted amide, alkenyl, alkynyl, sulfonyl, sulfonate, sulfonamide, or substituted sulfonamide.
  • the substitute R3 and/or R4 may be connected to the aromatic polycyclic conjugated molecule (Core) via at least one connecting group.
  • the at least one connecting group may be selected from the list comprising CH2, CF2, S1R2O, CH2CH2O, wherein R is selected from the list comprising H, alkyl, and fluorine.
  • the one or more ionic groups include at least one ionic group selected from the list comprising [NR 4 ] + , [PR 4 ] + as cation and [-C0 2 ] ⁇ , [-SO 3 ] ⁇ , [-SRs] ⁇ , [- PO 3 R] , [-PR 5 ] as anion, wherein R is selected from the list comprising H, alkyl, and fluorine.
  • one aspect of the present disclosure provides a Sharp polymer in the form of a composite organic compound.
  • the aromatic polycyclic conjugated molecule comprises rylene fragments.
  • the rylene fragments are selected from structures 1 to 21 as given in Table 1.
  • the aromatic polycyclic conjugated molecule comprises an electro-conductive oligomer, such as a phenylene, thiophene, or polyacene quinine radical oligomer or combinations of two or more of these.
  • the substitute providing solubility (Rl) of the composite organic compound is CXQ2X+1 , where X > 1 and Q is hydrogen (H), fluorine (F), or chlorine (CI).
  • the substitute providing solubility (Rl) of the composite organic compound is independently selected from alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl, branched and complex fluorinated alkyl, branched and complex chlorinated alkyl groups, and any combination thereof, and wherein the alkyl group is selected from methyl, ethyl, propyl, butyl, iso-butyl and tert-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups or siloxane, and/or polyethyleneglycol as linear or branched chains.
  • the solvent is selected from benzene, toluene, xylenes, acetone, acetic acid, methylethylketone, hydrocarbons, chloroform, carbontetrachloride, methylenechloride, dichlorethane, chlorobenzene, alcohols, nitromethan, acetonitrile, dimethylforamide, 1 ,4-dioxane, tetrahydrofuran (THF), methyl cyclohexane (MCH), and any combination thereof.
  • At least one electrically resistive substitute (R2) of the composite organic compound is CXQ2X+1 , where X > 1 and Q is hydrogen (H), fluorine (F), or chlorine (CI).
  • at least one electrically resistive substitute (R2) is selected from the list comprising -(CH2)n-CH3, - CH((CH ⁇ '-'2)-'nCH3)2) (where n >1), alkyl, aryl, substituted alkyl, substituted aryl, branched alkyl, branched aryl, and any combination thereof and wherein the alkyl group is selected from methyl, ethyl, propyl, butyl, I- butyl and t-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups.
  • the substitute Rl and/or R2 is connected to the aromatic poly cyclic conjugated molecule (Core) via at least one connecting group.
  • the at least one connecting group may be selected from the list comprising the following structures: 31 -41 as given in Table 3, where W is hydrogen (H) or an alkyl group. Table 3. Examples of the connecting group
  • the substitute R3 and/or R4 may be connected to the aromatic polycyclic conjugated molecule (Core) via at least one connecting group.
  • the at least one connecting group may be selected from the list comprising CH2, CF2, SiR20, CH2CH20, wherein R is selected from the list comprising H, alkyl, and fluorine.
  • the one or more ionic groups include at least one ionic group selected from the list comprising [NR4]+, [PR4]+ as cation and [-C02]-, [-S03]-, [-SR5]-, [- P03R]-, [-"-PR5]- as anion, wherein R is selected from the list comprising H, alkyl, and fluorine.
  • the Sharp polymers have hyperelectronic or ionic type polarizability.
  • "Hyperelectronic polarization may be considered due to the pliant interaction of charge pairs of excitons, localized temporarily on long, highly polarizable molecules, with an external electric field [.] (Roger D. Hartman and Herbert A. Pohl, "Hyper-electronic Polarization in Macromolecular Solids", Journal of Polymer Science: Part A-l Vol. 6, pp. 1135-1152 (1968)).
  • Ionic type polarization can be achieved by limited mobility of ionic parts of the tethered/partially immobilized ionic liquid or zwitterion (Q).
  • a meta-dielectric is a dielectric that includes one or more Sharp polymers in the form of a composite organic compound characterized by polarizability and resistivity.
  • characteristics of meta-dielectrics include a relative permittivity greater than or equal to 1 ,000 and resistivity greater than or equal to 10 13 ohm/cm.
  • the Sharp Polymers in a meta-dielectric may form column like supramolecular structures by pi-pi interaction. Said supramolecules of Sharp polymers allow formation of crystal structures of the meta-dielectric material.
  • polarization units are incorporated to provide the molecular material with high dielectric permeability. There are several mechanisms of polarization such as dipole polarization, ionic polarization, and hyper- electronic polarization of molecules, monomers and polymers possessing metal conductivity.
  • Sharp polymers are composite materials which incorporate an envelope of insulating substituent groups that electrically isolate the supramolecules from each other in the dielectric crystal layer and provide high breakdown voltage of the energy storage molecular material.
  • Said insulating substituent groups are resistive alkyl or fluro-alkyl chains covalently bonded to a polarizable core, forming the resistive envelope.
  • Anhydride 1 (60.0 g, 0.15 mol, 1.0 eq), amine 2 (114.4 g, 0.34 mol, 2.2 eq) and imidazole (686.0 g, 10.2 mol, 30 eq to 2) were mixed well into a 500 mL of round-bottom flask equipped with a bump-guarder. The mixture was degassed three times, stirred at 160 °C for 3 hr, 180 °C for 3hr, and cooled to rt. The reaction mixture was crushed into water (1000 mL) with stirring. Precipitate was collected with filtration, washed with water (2x500 mL), methanol (2x300 mL) and dried on high vacuum.
  • Furuta co-polymers and para-Furuta polymers are polymeric compounds with insulating tails, and linked/tethered/partially immobilized polarizable ionic groups.
  • the insulating tails are hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol linear or branched chains covalently bonded to the co-polymer backbone.
  • the tails act to insulate the polarizable tethered/partially immobilized ionic molecular components and ionic pairs from other ionic groups and ionic group pairs on the same or parallel co-polymers, which favorably allows discrete polarization of counter ionic liquid pairs or counter Q groups (i.e. polarization of cationic liquid and anionic liquid tethered/partially immobilized to parallel Furuta polymers) with limited or no interaction of ionic fields or polarization moments of other counter ionic group pairs partially immobilized on the same or parallel co-polymer chains.
  • the insulating tails electrically insulate supra-structures of Furuta polymers from each other.
  • Parallel Furuta polymers may arrange or be arranged such that counter ionic groups (i.e.
  • tethered/partially immobilized ionic groups (Qs) of cation and anion types are aligned opposite from one another.
  • a Furuta co-polymer has the following general structural formula:
  • backbone structure of the co-polymer comprises structural units of first type PI and structural units of second type P2 both of which randomly repeat and are independently selected from the list comprising acrylic acid, methacrylate, repeat units of polypropylene (-[CH2- CH(CH 3 )]-), repeat units of polyethylene (-[CH 2 ]-), siloxane, or repeat units of polyethylene terephthalate (sometimes written poly(ethylene terephthalate)) for which the repeat unit may be expressed as -CH 2 -CH 2 -0-CO-C 6 H 4 -CO-0-.
  • n is the number of the PI structural units in the backbone structure which is in the range from 3 to 100 000 and m is number of the P2 structural units in the backbone structure which is in the range from 3 to 100 000.
  • the first type structural unit (PI) has a resistive substitute Tail which is oligomers of polymeric material with HOMO-LUMO gap no less than 2 eV.
  • the second type of structural units (P2) has an ionic functional group Q which is connected to P2 via a linker group L.
  • the parameter j is a number of functional groups Q attached to the linker group L, which may range from 0 to 5.
  • the ionic functional group Q comprises one or more ionic liquid ions (from the class of ionic compounds that are used in ionic liquids), zwitterions, or polymeric acids.
  • an energy interaction of the ionic Q groups may be less than kT, where k is Boltzmann constant and T is the temperature of environment.
  • parameter B is a counter ion which is a molecule or molecules or oligomers that can supply the opposite charge to balance the charge of the co-polymer.
  • s is the number of the counter ions.
  • the resistive substitute Tails are independently selected from the list comprising oligomers of polypropylene (PP), oligomers of polyethylene terephthalate (PET), oligomers of polyphenylene sulfide (PPS), oligomers of polyethylene naphthalate (PEN), oligomers of polycarbonate (PP), polystyrene (PS), and oligomers of polytetrafluoroethylene (PTFE).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PPS polyphenylene sulfide
  • PEN oligomers of polyethylene naphthalate
  • PP polycarbonate
  • PS polystyrene
  • PTFE polytetrafluoroethylene
  • the resistive substitutes Tail are independently selected from alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl, branched and complex fluorinated alkyl, branched and complex chlorinated alkyl groups, and any combination thereof, and wherein the alkyl group is selected from methyl, ethyl, propyl, butyl, iso- butyl and fert-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups.
  • the resistive substitute Tail may be added after polymerization.
  • the HOMO-LUMO gap is no less than 4 eV. In still another aspect of the present disclosure, it is even more preferable that the HOMO-LUMO gap is no less than 5 eV.
  • the ionic functional group Q comprises one or more ionic liquid ions from the class of ionic compounds that are used in ionic liquids, zwitterions, or polymeric acids.
  • the energy of interaction between Q group ions on discrete P2 structural units may be less than kT, where k is Boltzmann constant and T is the temperature of environment.
  • the temperature of environment may be in range between - 60C of and 150 C.
  • the preferable range of temperatures is between-40 C and lOOC.
  • At least one ionic liquid ion is selected from the list comprising [NR t ] + , [PP ] + as cation and [-C0 2 ] ⁇ , [-SO3] ⁇ , [-SRs] ⁇ , [-PO3R] , [-PR5] as anion, wherein R is selected from the list comprising H, alkyl, and fluorine.
  • the functional group Q may be charged after or before polymerization.
  • the linker group L is oligomer selected from structures 42 to 47 as given in Table 4.
  • the linker group L is selected from structures 48 to 57 as given in Table 5.
  • the linker group L may be selected from the list comprising C3 ⁇ 4, CF2, S1R2O, and CH2CH20, wherein R is selected from the list comprising H, alkyl, and fluorine.
  • the ionic functional group Q and the linker groups L may be added after polymerization.
  • the present disclosure provides a dielectric material (sometimes called a meta-dielectric) comprising of one or more of the class of Furuta polymers comprising protected or hindered ions of zwitterion, cation, anion, or polymeric acid types described hereinabove.
  • the meta-dielectric material may be a mixture of zwitterion type Furuta polymers, or positively charged (cation) Furuta polymers and negatively charged (anion) Furuta polymers, polymeric acid Furuta polymers, or any combination thereof.
  • the mixture of Furuta polymers may form or be induced to form supra-structures via hydrophobic and ionic interactions.
  • the cation on a positively charged Furuta polymer replaces the B counter ions of the anion on a negatively charged Furuta polymer parallel to the positively charged Furuta polymer and vice versa; and the resistive Tails of neighboring Furuta polymers further encourages stacking via van der Waals forces, which increases ionic group isolation.
  • Meta-dielectrics comprising both cationic and anionic Furuta polymers have a 1 : 1 ratio of cationic and anionic Furuta polymers.
  • the Tails of hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol linear or branched act to insulate linked/tethered/partially immobilized polarizable ionic liquids, zwitterions, or polymeric acids (ionic Q groups).
  • the Tails insulate the ionic Q groups from other ionic Q groups on the same or parallel Furuta polymer via steric hindrance of the ionic Q groups' energy of interaction, which favorably allows discrete polarization of the ionic Q groups (i.e. polarization of cationic liquid and anionic liquid tethered/partially immobilized to parallel Furuta polymers).
  • Tails insulate the ionic groups of supra-structures from each other.
  • Parallel Furuta polymers may arrange or be arranged such that counter ionic liquids (i.e. tethered/partially immobilized ionic liquids (Qs) of cation and anion types) are aligned opposite from one another (sometimes known as cationic Furuta polymers and anionic Furuta polymers).
  • Qs tethered/partially immobilized ionic liquids
  • the Furuta polymers have hyperelectronic or ionic type polarizability.
  • “Hyperelectronic polarization may be considered due to the pliant interaction of charge pairs of excitons, localized temporarily on long, highly polarizable molecules, with an external electric field [.] (Roger D. Hartman and Herbert A. Pohl, "Hyper-electronic Polarization in Macromolecular Solids", Journal of Polymer Science: Part A-l Vol. 6, pp. 1135-1152 (1968)).
  • Ionic type polarization can be achieved by limited mobility of ionic parts of the tethered/partially immobilized ionic liquid or zwitterion (Q). Additionally, other mechanisms of polarization such as dipole polarization and monomers and polymers possessing metal conductivity may be used independently or in combination with hyper-electronic and ionic polarization in aspects of the present disclosure.
  • a meta-dielectric layer may be comprised of one or more types of zwitterion Furuta polymer and/or selected from the anionic Q + group types and cationic Q " group types and/or polymeric acids, having the general configuration of Furuta polymers: m m
  • Carboxylic acid co-polymer P002 To a solution of 1.02g (1 1.81 mmol) of methacrylic acid and 4.00g (1 1.81 mmol) of stearylmethacrylate in 2.0g isopropanol was added a solution of 0.030g 2,2'-azobis(2-methylpropionitrile) (AIBN) in 5.0g of toluene. The resulting solution was heated to 80 C for 20 hours in a sealed vial, after which it became noticeably viscous. NMR shows ⁇ 2%remaining monomer. The solution was used without further purification in film formulations and other mixtures.
  • AIBN 2,2'-azobis(2-methylpropionitrile)
  • Example 4 Amine co-polymer P011. To a solution of 2.52g (11.79 mmol) of 2-(diisopropylamino)ethyl methacrylate and 3.00g (11.79 mmol) of laurylmethacrylate in 2.0g toluene was added a solution of 0.030g 2,2'-azobis(2-methylpropionitrile) (AIBN) in 4.0g of toluene. The resulting solution was heated to 80 C for 20 hours in a sealed vial, after which it became noticeably viscous. NMR shows ⁇ 2%remaining monomer. The solution was used without further purification in film formulations and other mixtures.
  • AIBN 2,2'-azobis(2-methylpropionitrile)
  • Carboxylic acid co-polymer and amine co-polymer mixture 1.50g of a 42wt % by solids solution of P002 was added to 1.24g of a 56wt% solution of P011 with lg of isopropanol and mixed at 40 C for 30 minutes. The solution was used without further purification.
  • a para-Furuta polymer has repeat units of the following general structural formula:
  • a structural unit P comprises a backbone of the copolymer, which is independently selected from the list comprising acrylic acid, methacrylate, repeat units for polypropylene (PP) (-[CH 2 -CH(CH 3 )]-), repeat units for polyethylene (PE) (-[CH 2 ]-), , siloxane, or repeat units of polyethylene terephthalate (sometimes written poly( ethylene terephthalate)) for which the repeat unit may be expressed as -CH2-CH2-O-CO-C6H4-CO-O-.
  • the first type of repeat unit (Tail) is a resistive substitute in the form of an oligomer of a polymeric material.
  • the resistive substitute preferably has a HOMO-LUMO gap no less than 2 eV.
  • the parameter n is a number of Tail repeat units on the backbone P structural unit, and is in the range from 3 to 100 000.
  • the second type of repeat units (-L-Q) include an ionic functional group Q which is connected to the structural backbone unit (P) via a linker group L, and m is number of the -L-Q repeat units in the backbone structure which is in the range from 3 to 100 000.
  • the ionic functional group Q comprises one or more ionic liquid ions (from the class of ionic compounds that are used in ionic liquids), zwitterions, or polymeric acids.
  • An energy of interaction of the ionic Q groups may be less than kT, where k is Boltzmann constant and T is the temperature of environment. Still further, the parameter t is average of para-Furuta polymer repeat units, ranging from 6 to 200 000.
  • B's are counter ions which are molecules or oligomers that can supply the opposite charge to balance the charge of the co-polymer, s is the number of the counter ions.
  • the resistive substitute Tails are independently selected from the list comprising polypropylene (PP), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyethylene naphthalate (PEN), polycarbonate (PP), polystyrene (PS), and polytetrafluoroethylene (PTFE).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PPS polyphenylene sulfide
  • PEN polyethylene naphthalate
  • PP polycarbonate
  • PS polystyrene
  • PTFE polytetrafluoroethylene
  • the resistive substitutes Tail are independently selected from alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl, branched and complex fluorinated alkyl, branched and complex chlorinated alkyl groups, and any combination thereof, and wherein the alkyl group is selected from methyl, ethyl, propyl, butyl, iso- butyl and fert-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups.
  • the resistive substitute Tail may be added after polymerization.
  • the HOMO-LUMO gap is no less than 4 eV. In still another embodiment of the present disclosure, it is even more preferable that the HOMO-LUMO gap is no less than 5 eV.
  • the ionic functional group Q comprises one or more ionic liquid ions from the class of ionic compounds that are used in ionic liquids, zwitterions, or polymeric acids. Energy of interaction between Q group ions on discrete P structural units may be less than kT, where k is Boltzmann constant and T is the temperature of environment. The temperature of environment may be in range between - 60C of and 150 C. The preferable range of temperatures is between-40 C and lOOC.
  • At least one ionic liquid ion is selected from the list comprising [NRt] + , [PP ] + as cation and [-C0 2 ] ⁇ , [- SO3] ⁇ , [-SR5] ⁇ , [-PO3R] , [-PR5] as anion, wherein R is selected from the list comprising H, alkyl, and fluorine.
  • the functional group Q may be charged after or before polymerization.
  • the linker group L is oligomer selected from structures 58 to 63 as given in Table 6.
  • the linker group L is selected from structures 64 to 73 as given in Table 7.
  • the linker group L is selected from the list comprising CH 2 , CF 2 , S1R 2 O, and CH2CH20, wherein R is selected from the list comprising H, alkyl, and fluorine.
  • the ionic functional group Q and the linker groups L may be added after polymerization.
  • the present disclosure provides a dielectric material (sometimes called a meta-dielectric) comprising of one or more of the class of para-Furuta polymers comprising protected or hindered ions of zwitterion, cationic liquid ions, anionic liquid ions, or polymeric acid types described hereinabove.
  • the meta-dielectric material may be a mixture of zwitterion type para-Furuta polymers, or positively charged (cation) para-Furuta polymers and negatively charged (anion) para-Furuta polymers, polymeric acid para-Furuta polymers, or any combination thereof.
  • the mixture of para-Furuta polymers may form or be induced to form supra-structures via hydrophobic and ionic interactions.
  • the cation(s) on a positively charged para-Furuta polymer replaces the B counter ions of the anion(s) on a negatively charged para-Furuta polymer parallel to the positively charged para-Furuta polymer and vice versa; and the resistive Tails of neighboring para-Furuta polymers further encourages stacking via van der Waals forces, which increases ionic group isolation.
  • Meta- dielectrics comprising both cationic and anionic para-Furuta polymers preferably have a 1 : 1 ratio of cationic and anionic para-Furuta polymers.
  • the Tails of hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol linear or branched act to insulate linked/tethered/partially immobilized polarizable ionic liquids, zwitterions, or polymeric acids (ionic Q groups).
  • the Tails insulate the ionic Q groups from other ionic Q groups on the same or parallel para-Furuta polymer via steric hindrance of the ionic Q groups' energy of interaction, which favorably allows discrete polarization of the ionic Q groups (i.e. polarization of cationic liquid and anionic liquid tethered/partially immobilized to parallel para-Furuta polymers).
  • Tails insulate the ionic groups of supra-structures from each other.
  • Parallel para-Furuta polymers may arrange or be arranged such that counter ionic liquids (i.e. tethered/partially immobilized ionic liquids (Qs) of cation and anion types) are aligned opposite from one another (sometimes known as cationic para-Furuta polymers and anionic para-Furuta polymers).
  • the para-Furuta polymers have hyperelectronic or ionic type polarizability.
  • Hyperelectronic polarization may be considered due to the pliant interaction of charge pairs of excitons, localized temporarily on long, highly polarizable molecules, with an external electric field [.] (Roger D. Hartman and Herbert A. Pohl, "Hyper-electronic Polarization in
  • Ionic type polarization can be achieved by limited mobility of ionic parts of the tethered/partially immobilized ionic liquid or zwitterion (Q). Additionally, other mechanisms of polarization such as dipole polarization and monomers and polymers possessing metal conductivity may be used independently or in combination with hyper-electronic and ionic polarization in aspects of the present disclosure.
  • a meta-dielectric layer may be comprised of one or more types of zwitterion para- Furuta polymer and/or selected from the anionic Q group types and cationic Q group types and/or polymeric acids, which may have the following general arrangement of para-Furuta polymers:
  • a meta-dielectric is defined here as a dielectric material comprised of one or more types of structured polymeric materials (SPMs) having a relative permittivity greater than or equal to 1000 and resistivity greater than or equal to 10 13 ohm/cm.
  • SPMs structured polymeric materials
  • the SPMs in a meta- dielectric may form column like supramolecular structures by pi-pi interaction or hydrophilic and hydrophobic interactions. Said supramolecules of SPMs may permit formation of crystal structures of the meta-dielectric material.
  • polarization units are incorporated to provide the molecular material with high dielectric permeability.
  • SPMs are composite materials which incorporate an envelope of insulating substituent groups that electrically isolate the supramolecules from each other in the dielectric layer and provide high breakdown voltage of the energy storage molecular material.
  • Said insulating substituent groups are hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol linear or branched chains covalently bonded to a polarizable core or co-polymer backbone, forming the resistive envelope.
  • each of the one or more meta-capacitors 20 comprises a first electrode 21, a second electrode 22, and a meta- dielectric material layer 23 disposed between said first and second electrodes.
  • the electrodes 21, 22 may be made of a metal, such as copper, zinc, or aluminum or other conductive material and are generally planar in shape.
  • the electrodes and meta-dielectric material layer 23 are in the form of long strips of material that are sandwiched together and wound into a coil along with an insulating material, e.g., a plastic film such as polypropylene or polyester to prevent electrical shorting between the electrodes 21, 22. Examples of such coiled capacitor energy storage devices are described in detail in commonly-assigned U. S.
  • the capacitive energy storage device 2 may include multiple meta-capacitors 20 connected in parallel, as in FIG. 7B, to provide a desired amount of energy storage capacity that scales roughly with the number of meta- capacitors in parallel.
  • the capacitive energy storage device 2 may include two or more meta-capacitors connected in series to accommodate a desired voltage level, as in FIG. 7C.
  • the capacitive energy storage device 2 may include combinations of three or more meta-capacitors in a capacitor network involving various series and parallel combinations, as in FIG. 7D.
  • the meta-dielectric material 23 may be characterized by a dielectric constant ⁇ greater than about 100 and a breakdown field E bd greater than or equal to about 0.01 volts (V)/nanometer (mn).
  • the dielectric constant ⁇ may be greater than or equal to about 100, 200, 300, 400, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10,000, or 100,000.
  • the breakdown field may be greater than about 0.01 V/nm, 0.05 V/nm, 0.1 V/nm, 0.2 V/nm, 0.3 V/nm, 0.4 V/nm, 0.5 V/nm, 1 V/nm, or 10 V/nm.
  • the meta- dielectric material 23 may be characterized by a dielectric constant ⁇ between about 100 and about 1,000,000 and a breakdown field Ebd between about 0.01 V/nm and about 2.0 V/nm.
  • the capacitive energy storage devices may comprise more than one of the meta-capacitors connected in series or parallel.
  • the capacitive energy storage device may further comprise a cooling mechanism 30.
  • the cooling can be passive, e.g., using radiative cooling fins on the capacitive energy storage device 2 and DC-voltage conversion device 3.
  • a fluid such as air, water or ethylene glycol can be used as a coolant in an active cooling system.
  • the cooling system 30 may include conduits in thermal contact with the capacitive energy storage device 2 and DC-voltage conversion device 3. The conduits are filled with a heat exchange medium, which may be a solid, liquid or gas.
  • the cooling mechanism may include a heat exchanger configured to extract heat from the heat exchange medium.
  • the cooling mechanism 30 may include conduits in the form of cooling fins on the capacitive energy storage device 2 and DC- voltage conversion device 3 and the heat exchange medium is air that is blown over the cooling fins, e.g., by a fan.
  • the heat exchanger 32 may include a phase-change heat pipe configured to carry out cooling. The cooling carried out by the phase-change heat pipe may involve a solid to liquid phase change (e.g., using melting of ice or other solid) or liquid to gas phase change (e.g., by evaporation of water or alcohol) of a phase change material.
  • the conduits or heat exchanger 32 may include a reservoir containing a solid to liquid phase change material, such as paraffin wax.
  • the DC-voltage conversion device 3 may include a buck converter for applications in which Vout ⁇ Vi n , a boost converter for applications in which or a bidirectional buck/boost converter for applications in which Vout ⁇ Vi n in certain situations and Vout>Vi n in other situations.
  • the DC-voltage conversion device 3 may be connected to a control board 4 containing suitable logic circuitry, e.g., microprocessor, microcontroller, application specific integrated circuit (ASIC), field programmable gate array (FPGA), a complex programmable logic device (CPLD), capable of implementing closed loop control processes 90 and (optionally) a communication interface 5, as well as an analog to digital converter coupled to sensors on the DC-voltage conversion device 3, e.g., voltage sensors V for the input voltage Vi Marie and the output voltage V ou t, current sensors A for current I SIJ to/from the capacitive energy storage device 2 and/or current I vc to/from the DC- voltage conversion device 3, temperature sensors T on the capacitive energy storage device and/or DC-voltage conversion device.
  • suitable logic circuitry e.g., microprocessor, microcontroller, application specific integrated circuit (ASIC), field programmable gate array (FPGA), a complex programmable logic device (CPLD), capable of implementing closed loop control processes 90 and (optionally)
  • control board 4 may be integrated into the DC-voltage conversion device 3.
  • the conversion device 3 may contain a buck regulator, a boost regulator, buck and boost regulators with separate input/outputs, a bidirectional boost/buck regulator, or a split-pi converter and the control board 4 may be configured to maintain a constant output voltage V ou t from the DC-voltage conversion device during discharge, and/or charge the capacitor at a more-or-less constant current while maintaining a stable input voltage.
  • control board 4 may be based on a controller for a bidirectional buck/boost converter.
  • control board 4 stabilizes the output voltage of the DC-voltage conversion device according to the following algorithm forming the control loop 90: a) determining a target output voltage level for the energy storage system,
  • a bidirectional buck/boost converter configuring a bidirectional buck/boost converter to buck down the voltage and direct current in the input direction IF the voltage on the capacitive energy storage device is lower than the desired input voltage and the desired outcome is to charge the device
  • a bidirectional buck/boost converter configuring a bidirectional buck/boost converter to boost up the voltage and direct current in the input direction IF the voltage on the capacitive energy storage device is higher than the desired output voltage and the desired outcome is to charge the device
  • a buck/boost converter may be a single switch converter of the type shown in FIG. 15A.
  • This type of converter includes a high-side switch SW having an input side coupled to the input voltage Vicute and an output side coupled to one side of an inductor L, the other side of which is connected to the ground or common voltage (-).
  • a capacitor C is coupled across the output voltage Vout.
  • a pulsed switching signal S turns the switch on and off. The output voltage depends on the duty cycle of the switching signal S.
  • the switches may be implanted as gated switch devices, e.g., MOSFET devices, stacked MOSFET devices, IGCT devices, high drain- source voltage SiC MOSFET devices, and the like depending on the voltage and/or current requirements of the DC-voltage converter for the energy storage cell.
  • the control board provides the signals to the gate terminals of the switching devices.
  • the control board 4 can configure this type of buck/boost converter to buck or boost by adjusting the duty cycle of the switching signal S.
  • Figure 15B shows an alternative four-switch buck/boost converter.
  • a first switch SW1 is connected between the high side (+) of the input voltage ViRIC and an input side of the inductor L
  • a second switch SW2 is connected between an output side of the inductor L and the common voltage (-)
  • a third switch SW3 is connected between the input side of the inductor L and the common voltage
  • a fourth switch SW4 is connected between the output side of the inductor and the high side (+) of the output voltage V ou t-
  • An input capacitor C- in may be coupled across the input voltage Vi Marie and an output capacitor C ou t may be coupled across the output voltage V ou t-
  • the switches SW1, SW2, SW3, and SW4 change between open (non-conducting) and closed (conducting) states in response to switching signals from the control board 4.
  • the second switch SW2 is open and the fourth switch SW4 closed and pulsed buck mode switching signals are applied to the first switch SW1 and third switch SW3, e.g., as described above with respect to Figure 3 and Figure 4.
  • the control board 4 can adjust the output voltage Vout in buck mode by adjusting the duty cycle signal of the switching signals SI and S3.
  • the first switch SW1 is open, the third switch SW3 is closed and pulsed boost mode switching signals are applied to the second switch SW2 and fourth switch SW4, e.g., as described above with respect to Figure 5 and Figure 6.
  • the control board 4 can adjust the output voltage V ou t in boost mode by adjusting the duty cycle signal of the switching signals S2 and S4.
  • the DC-voltage conversion device 3 as depicted in figure 9A, 9B, 9C, 9D, 9E, 9F, 9G, 9H, 91 may include one or more switch-mode voltage converters 100, arranged to boost/or buck the input output voltages as necessary to achieve the charge and discharge modalities depicted in figures 13A, 13B, 14A and 14B corresponding to the voltage labels v_c(t), v_i(t) and v_o(t) on the capacitive energy storage cell 3 of figures 11 and 12.
  • the input/output port may be split into a separate input and output. These separate inputs and outputs may have different bus voltages.
  • the switch-mode voltage converters 100 may have circuitry selected from the following list: a buck converter (as show in figure 8B), boost converter (as show in figure 8A), buck/boost converter, bi-directional buck/boost (split-pi) converter (as show in figure 8D), Cuk converter, single-ended primary inductor converter (SEPIC), inverting buck/boost converter (as show in figure 8C), or four- switch buck/boost converters.
  • the switch mode voltage converters 100 are connected to power ports 101, by an interconnect system 102.
  • the power ports 101 include a positive terminal and negative terminal intended to work together to transmit power in either direction.
  • a power port can be an input, output or bidirectional.
  • a control interface 104 is connected to all of the control interfaces on the switch mode voltage converters 100 through a control network 103.
  • the control network may carry target voltages, target currents, observed voltages, observed currents, temperatures and other parameters necessary to control the system.
  • the control network 103, control interfaces 104, control board 4, and control loops 90 may or may not be combined in a single discrete physical package. For example, one implementation may have all aforementioned elements distributed throughout a system and another
  • the constant output voltage of the energy storage cell can be a programmable value.
  • the output voltage is made constant by the DC-voltage conversion device selected from the list comprising a buck regulator, a boost regulator, buck and boost regulators with separate input/outputs, bi-directional boost/buck regulator, split-pi converter.
  • the cell 1 includes circuitry configured to enable observation of parameters selected from the following list: the voltage on the meta-capacitor, the current going into or out of the meta-capacitor, the current flowing into or out of the DC-voltage conversion device, the output voltage of the DC-voltage conversion device, the temperature at one or more points within the meta-capacitor, the temperature at one or more points within the DC-voltage conversion device.
  • the energy storage cell further comprises an AC- inverter to create AC output voltage, wherein the DC output voltage of the DC-voltage conversion device is the input voltage of the AC-inverter.
  • energy storage cell further comprises power electronics switches which are based on Si insulated-gate bipolar transistors (IGBTs), SiC MOSFETs, GaN MOSFETs, Graphene or comprising organic molecular switches.
  • the power electronics switches comprise multiple switch elements stacked in series to enable switching of voltages higher than the breakdown voltage of individual switch components.
  • a capacitive energy storage module 40 e.g., as illustrated in FIG. 16.
  • the energy storage module 40 includes two or more energy storage cells 1 of the type described above.
  • Each energy storage cell includes a capacitive energy storage device 2 having one or more meta-capacitors 20 and a DC-voltage converter 3, which may be a buck converter, boost converter, or buck/boost converter.
  • each module may include a control board 4 of the type described above with respect to Figures 10,11,12, and an (optional) cooling mechanism (not shown).
  • the module 40 may further include an interconnection system that connects the anodes and cathodes of the individual energy storage cells to create a common anode and common cathode of the capacitive energy storage module.
  • the interconnection system includes a parameter bus 42 and power switches PSW.
  • Each energy storage cell 1 in the module 40 may be coupled to the parameter bus 42 via the power switches PSW.
  • These switches allow two or more modules to be selectively coupled in parallel or in series via two or more rails that can serve as the common anode and common cathode.
  • the power switches can also allow one or more energy storage cells to be disconnected from the module, e.g., to allow for redundancy and/or maintenance of cells without interrupting operation of the module.
  • the power switches PSW may be based on solid state power switching technology or may be implemented by
  • electromechanical switches e.g., relays
  • electromechanical switches e.g., relays
  • the energy storage module further comprises a power meter 44 to monitor power input or output to the module.
  • the energy storage module further comprises a networked control node 46 configured to control power output from and power input to the module.
  • the networked control node 46 allows each module to talk with a system control computer over a high speed network.
  • the networked control node 46 includes voltage control logic circuitry 50 configured to selectively control the operation of each of voltage controller 3 in each of the energy storage cells 2, e.g., via their respective control boards 4.
  • the control node 46 may also include switch control logic circuitry 52 configured to control operation of the power switches PSW.
  • the control boards 4 and power switches PSW may be connected to the control node 46 via a data bus 48.
  • the voltage control and switching logic circuitry in the networked control node 46 may be implemented by one or more microprocessors, microcontrollers, application specific integrated circuits (ASICs), field programmable gate arrays (FPGAs), or complex programmable logic devices (CPLDs).
  • the control node 46 may include a network interface 54 to facilitate transfer of signals between the voltage control logic circuitry 50 and the control boards 4 on the individual energy storage cells 2 and also to transfer signals between the switching logic circuitry 52 and the power switches PSW, e.g., via the data bus 48.
  • a capacitive energy storage system may include two or more networked capacitive energy storage modules, e.g., of the type shown in Figure 16.
  • One embodiment of such a capacitive energy storage system 60 is shown in Figure 17.
  • the system 60 includes two or more energy storage modules 40 of the type shown in Figure 16.
  • Each capacitive energy storage module 40 includes two or more capacitive energy storage cells 1 , e.g., of the type shown in Figures 10, 11, 12, connected by an interconnection system 42 and controlled by a control node 46.
  • Each capacitive energy storage module may also include a module power meter 44.
  • each control node 46 may include voltage control logic circuitry 50 to control voltage controllers within the individual capacitive energy storage cells 1 and switching logic circuitry 52 to control internal power switches with the module, as described above.
  • each control node 46 includes an internal data bus 48 and a network interface 54, which may be connected as described above.
  • Power to and from capacitive energy storage modules 40 is coupled to a system power bus 62 via system power switches SPSW, which may be based on solid state power switching technology or may be implemented by electromechanical switches (e.g., relays) or some combination of the two.
  • SPSW system power switches
  • the system 60 includes a system controller 66 connected to a system data bus 68.
  • the system controller may include switching control logic 70, voltage control logic 72, and system network interface 74.
  • the voltage control logic 70 may be configured to control the operation of individual DC-voltage controllers within individual cells 1 of individual modules 40.
  • the switching control logic 72 may be configured to control operation of the system power switches SPSW and also the power switches PSW within individual capacitive energy storage modules 40.
  • Voltage control signals may be sent from the voltage control logic 72 to a specific DC- voltage control device 3 within a specific capacitive energy storage cell 1 of a specific capacitive energy storage module through the network interface 74, the system data bus 68, the module network interface 54 of the control node 46 for the specific module, the module data bus 48, and the control board 4 of the individual cell 1.
  • the system controller 66 may be a deterministic controller, an asynchronous controller, or a controller having distributed clock.
  • the system controller 66 may include a distributed clock configured to synchronize several independent voltage conversion devices in one or more capacitive energy storage cells of one or more of the capacitive energy storage modules 40.
  • aspects of the present disclosure allow for electrical energy storage on a much larger scale than possible with conventional electrical energy storage systems.
  • a wide range of energy storage needs can be met by selectively combining one or more meta-capacitors with a DC- voltage conversion devices into a cell, combining two or more cells into a module, or combining two or more modules into systems.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Charge And Discharge Circuits For Batteries Or The Like (AREA)
  • Dc-Dc Converters (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention concerne une cellule de stockage d'énergie qui comprend au moins un dispositif de stockage d'énergie capacitif et un dispositif de conversion de tension continue. Le dispositif de stockage d'énergie capacitif comprend au moins un méta-condensateur. La tension de sortie du dispositif de stockage d'énergie capacitif est la tension d'entrée du dispositif de conversion de tension continue. La présente invention concerne également un module de stockage d'énergie capacitif et un système de stockage d'énergie capacitif.
EP17750644.1A 2016-02-12 2017-02-07 Cellule de stockage d'énergie capacitif, module et système Pending EP3414815A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US15/043,209 US20170236642A1 (en) 2016-02-12 2016-02-12 para-FURUTA POLYMER AND CAPACITOR
US15/043,315 US10305295B2 (en) 2016-02-12 2016-02-12 Energy storage cell, capacitive energy storage module, and capacitive energy storage system
US15/043,247 US20170233528A1 (en) 2016-02-12 2016-02-12 Sharp polymer and capacitor
US15/043,186 US20170236641A1 (en) 2016-02-12 2016-02-12 Furuta co-polymer and capacitor
PCT/US2017/016862 WO2017139284A2 (fr) 2016-02-12 2017-02-07 Cellule de stockage d'énergie capacitif, module de stockage d'énergie capacitif, et système de stockage d'énergie capacitif

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EP3414815A2 true EP3414815A2 (fr) 2018-12-19
EP3414815A4 EP3414815A4 (fr) 2019-11-20

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JP (1) JP6906535B2 (fr)
CN (1) CN109496381A (fr)
CA (1) CA3052242A1 (fr)
TW (1) TWI666846B (fr)
WO (1) WO2017139284A2 (fr)

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JP6906535B2 (ja) 2021-07-21
JP2019506125A (ja) 2019-02-28
CA3052242A1 (fr) 2017-08-17
TW201801438A (zh) 2018-01-01
WO2017139284A2 (fr) 2017-08-17
CN109496381A (zh) 2019-03-19
WO2017139284A9 (fr) 2017-11-23
TWI666846B (zh) 2019-07-21
WO2017139284A3 (fr) 2017-09-28
EP3414815A4 (fr) 2019-11-20

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