Furuta and para-Furuta polymer formulations and capacitors

Abstract

An organic polymeric compound called a Furuta or para-Furuta polymer is characterized by polarizability and resistivity has repeating units of a general structural formula: ##STR00001##
P1 may be acrylate, methacrylate, polypropylene, polyethylene, polyamide, polyaramid, polyester, siloxane, or polyethylene terephthalate. Tail is a resistive substitute. L is a linker group attached to an ionic functional group Q; j, a number of ionic functional groups Q, ranges from 1 to 5; n and m independently range from 3 to about 1000. Q is an ionic liquid ion, zwitterion, or polymeric acid. The number t ranges from 6 to 200,000. B is a counter ion, that can supply an opposite charge to balance a charge of the organic polymeric compound; s is a number of counter ions B. A plasticizer increases mobility of the polymers within the compound.

Claims

1. A metadielectric layer comprising a mixture of organic, polarizable, resistive, polymeric compounds consisting of repeating units of one of the following repeating unit: ##STR00024## wherein P1 is a monomer unit of polyacrylate, polymethacrylate, polypropylene (PP), polyethylene (PE), polyamide, polyaramid, polyester, siloxane, or polyethylene terephthalate; wherein Tail is independently selected from alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, and chlorinated alkyl; wherein j is a number of ionic functional groups Q ranging from 1 to 5; wherein n and m are independently in the range from 3 to about 1000; wherein Q.sup.+ is a cationic functional group and Q.sup. is an anionic functional group; wherein L is a linker group attached to one or more of Q.sup.+ and Q.sup.; wherein t is a number of polymeric repeats of the structure from 6 to 200,000; wherein P2 is a monomer unit of polyacrylate, polymethacrylate, polypropylene (PP), polyethylene (PE), polyamide, polyaramid, polyester, siloxane, polyethylene terephthalate; and wherein P2 and P1 polymerically repeat independently; and at least one plasticizer to increase supramolecular order of the metadielectric for increased resistivity is included in the medielectric layer.

2. A composite metacapacitor comprising two metal electrodes and a metadielectric layer between the two electrodes, wherein the metadielectric layer is as defined in claim 1.

3. The metadielectric layer of claim 1, wherein the organic, polarizable, resistive, polymeric compound has a HOMO-LUMO gap of no less than 4 eV.

4. The metadielectric layer of claim 3, wherein the HOMO-LUMO gap is no less than 5 eV.

5. The metadielectric layer of claim 1, wherein the linker group L is selected from structures 1 to 7: ##STR00025##

6. The metadielectric layer of claim 1, wherein the linker group L is selected from structures 8 to 17: ##STR00026##

7. The metadielectric layer of claim 1, wherein the linker group L is selected from the list consisting of: CH, CF.sub.2, SiR.sub.2O, CH.sub.2CH.sub.2O, wherein R is selected from the list comprising H, alkyl, and fluorine.

8. The metadielectric layer of claim 1, wherein an energy interaction of the ionic liquid ions is less than kT, where k is Boltzmann's constant and T is a temperature of an environment.

9. The metadielectric layer of claim 1, wherein the organic, polarizable, resistive, polymeric compounds can form ordered or semi-ordered structures via hydrophobic-hydrophilic interactions and ionic interactions.

10. The metadielectric layer of claim 1, wherein the mixture of organic, polarizable, resistive polymeric compounds is electrically neutral.

11. The metadielectric layer of claim 1, wherein the layer's relative permittivity is greater than or equal to 1000.

12. The metadielectric layer of claim 1, wherein the layer's resistivity is greater than or equal to 10.sup.15 ohm-cm.

13. The organic polymeric dielectric formulation of claim 2 where in the plasticizer is a high boiling point aprotic solvent.

14. The organic polymeric dielectric formulation of claim 13 wherein the plasticizer is selected from: NMP, DMSO, and Propylene carbonate.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1A schematically shows the disclosed capacitor with flat and planar electrodes.

(2) FIG. 1B schematically shows the disclosed capacitor with rolled (coiled) electrodes.

DETAILED DESCRIPTION

(3) While various embodiments of the invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions may occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed.

(4) The present disclosure provides an organic polymeric compound. In one embodiment of the organic polymeric compound, 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). In another embodiment of the organic polymeric compound, 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 tert-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups. The resistive substitute Tail may be added after polymerization. In yet another embodiment of the present disclosure, it is preferable that 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. The energy of interactions between Q group ions on discrete P1 or 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 60 and 150 C. The preferable range of temperatures is between 40 and 100 C. The energetic interactions between ions depends on the effective radius of ions. Therefore, by increasing the steric hindrance between ions it is possible to reduce the energy of interactions between ions. In one embodiment of the present invention, at least one ionic liquid ion is selected from the list comprising [NR.sub.4].sup.+, [PR.sub.4].sup.+ as cation and [CO.sub.2].sup., [SO.sub.3].sup., [SR.sub.5].sup., [PO.sub.3R].sup., [PR.sub.5].sup. 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. In another embodiment of the present invention, the linker group L is oligomer selected from structures 1 to 7 as given in Table 1.

(5) TABLE-US-00001 TABLE 1 Examples of the oligomer linker group 1 2 3 4 5 6 0 7
In yet another embodiment of the present invention, the linker group L is selected from structures 8 to 17 as given in Table 2.

(6) TABLE-US-00002 TABLE 2 Examples of the linker group 8 9 10 11 12 13 14 15 16 0 17

(7) In yet another embodiment of the present invention, the linker group L is selected from the list comprising [CH.sub.2].sub.n, [CF.sub.2].sub.n, SiR.sub.2O, and CH2CH2O, wherein n is 1-22 and 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. Further, in yet another embodiment of the present invention, the linker group L is not present and the ionic species Q are attached directly to the backbone.

(8) In another aspect, the present disclosure provides a dielectric material (sometimes called a metadielectric) comprising of one or more of the class of Furuta/para-Furuta polymers comprising protected or hindered ions of zwitterion, cationic liquid ions, anionic liquid ions, or polymeric acid types described hereinabove. The metadielectric material may be a mixture of zwitterion type Furuta/para-Furuta polymers, or positively charged (cation) Furuta/para-Furuta polymers and negatively charged (anion) Furuta/para-Furuta polymers, polymeric acid Furuta/para-Furuta polymers, or any combination thereof. The mixture of Furuta/para-Furuta polymers may form or be induced to form supra-structures via hydrophobic and ionic interactions. By way of example, but not limiting in scope, the cation(s) on a positively charged Furuta/para-Furuta polymer replaces the B counter ions of the anion(s) on a negatively charged Furuta/para-Furuta polymer parallel to the positively charged Furuta/para-Furuta polymer and vice versa; and the resistive Tails of neighboring Furuta/para-Furuta polymers further encourages stacking via van der Waals forces, which increases ionic group isolation. Metadielectrics comprising both cationic and anionic Furuta/para-Furuta polymers preferably have a 1:1 ratio of cationic and anionic Furuta/para-Furuta polymers.

(9) The tails of hydrocarbon (saturated and/or unsaturated), fluorocarbon, siloxane, and/or polyethylene glycol linear or branched act to insulate the 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/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 Furuta/para-Furuta polymers). Further, the tails insulate the ionic groups of supra-structures from each other. Parallel Furuta/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 Furuta/para-Furuta polymers and anionic Furuta/para-Furuta polymers).

(10) The Furuta/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 Macromolecular Solids, Journal of Polymer Science: Part A-1 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.

(11) Further, a metadielectric layer may be comprised of one or more types of zwitterion Furuta/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 Furuta/para-Furuta polymers:

(12) ##STR00021##

(13) In yet another aspect, the present disclosure provides a meta-capacitor, an example of which is shown schematically in FIG. 1A. The meta-capacitor comprises a first electrode 1, a second electrode 2, and a metadielectric layer 3 disposed between said first and second electrodes. The electrodes 1 and 2 may be made of a metal, such as copper, zinc, or aluminum or other conductive material and are generally planar in shape.

(14) The electrodes 1, 2 may be flat and planar and positioned parallel to each other. Alternatively, 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, while maintaining an approximately constant spacing d between the electrodes 1, 2. It is also possible for the electrodes 1, 2, to be non-flat, non-planar, or non-parallel or some combination of two or more of these. By way of example and not by way of limitation, a spacing d between the electrodes 1, 2, which may correspond to the thickness of the Composite Dielectric Film layer 3, may range from about 100 nm to about 15 m with a preferred range of between 1 m and 10 m. It should be noted that thicknesses of greater than 15 m are possible and may be chosen to provide a mechanical advantage to the capacitor such as improving the rigidity. As noted in Equation (2) below, the maximum voltage V.sub.bd between the electrodes 1, 2 is approximately the product of the breakdown field E.sub.bd and the electrode spacing d.
V.sub.bd=E.sub.bdd(2)

(15) For example, if, E.sub.bd=0.1 V/nm and the spacing d between the electrodes 1, 2 is 10 microns (10,000 nm), the maximum voltage V.sub.bd would be 1,000 volts.

(16) The electrodes 1, 2 may have the same shape as each other, the same dimensions, and the same area A. By way of example, and not by way of limitation, the area A of each electrode 1, 2 may range from about 0.01 m.sup.2 to about 1000 m.sup.2. By way of example and not by way of limitation, for rolled capacitors, the electrodes may be up to, e.g., 1000 m long and 1 m wide.

(17) These ranges are non-limiting. Other ranges of the electrode spacing d and area A are within the scope of the aspects of the present disclosure.

(18) If the spacing d is small compared to the characteristic linear dimensions of electrodes (e.g., length and/or width), the capacitance C of the capacitor may be approximated by the formula:
C=.sub.oA/d,(3)
where .sub.o is the permittivity of free space (8.8510.sup.12 Coulombs.sup.2/(Newton.Math.meter.sup.2)) and is the dielectric constant of the dielectric layer. The energy storage capacity U of the capacitor may be approximated as:
U=CV.sub.bd.sup.2(4)
which may be rewritten using equations (2) and (3) as:
U=.sub.oAE.sub.bd.sup.2d(5)

(19) The energy storage capacity U is determined by the dielectric constant K, the area A, and the breakdown field E.sub.bd. By appropriate engineering, a capacitor or capacitor bank may be designed to have any desired energy storage capacity U. By way of example, and not by way of limitation, given the above ranges for the dielectric constant K, electrode area A, and breakdown field E.sub.bd a capacitor in accordance with aspects of the present disclosure may have an energy storage capacity U ranging from about 500 Joules to about 210.sup.16 Joules.

(20) For a dielectric constant K ranging, e.g., from about 100 to about 1,000,000 and constant breakdown field E.sub.bd between, e.g., about 0.1 and 0.5 V/nm, a capacitor of the type described herein may have a specific energy capacity per unit mass ranging from about 10 W.Math.h/kg up to about 100,000 W.Math.h/kg, though implementations are not so limited.

(21) Aspects of the present disclosure include meta-capacitors that are coiled, e.g., as depicted in FIG. 1B. In this example, a meta-capacitor 20 comprises a first electrode 21, a second electrode 22, and a metadielectric material layer 23 of the type 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. In one implementation, the electrodes and metadielectric 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 Ser. No. 14/752,600, filed Jun. 26, 2015, the entire contents of which are incorporated herein by reference.

(22) A 4 kg meta-capacitor cell with a specific energy of 250 Wh/kg may be comprised of a metadielectric film 120 nm thick and an area 19000 m.sup.2. Alternatively, a 4 kg meta-capacitor cell with a specific energy of 250 Wh/kg may be comprised of a metadielectric film 10.05 m thick and a surface area 140 m.sup.2.

(23) In some embodiments, a 1 kg meta-capacitor cell with a specific energy of 1000 Wh/kg may be comprised of a metadielectric film 120 nm thick and an area 4700 m.sup.2. Alternatively, a 1 kg meta-capacitor cell with a specific energy of 1000 Wh/kg may be comprised of a metadielectric film 10.05 m thick and a surface area of 35 m.sup.2.

(24) In order that the invention may be more readily understood, reference is made to the following examples, which are intended to be illustrative of the invention, but are not intended to be limiting the scope.

Example 1

(25) ##STR00022##
Co-Polymer 1 (poly(stearylmethacrylate-co-methacrylic acid). To a solution of 1.02 g (11.81 mmol) of methacrylic acid and 4.00 g (11.81 mmol) of stearylmethacrylate in 2.0 g isopropanol was added a solution of 0.030 g 2,2-azobis(2-methylpropionitrile) (AIBN) in 5.0 g 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.

Example 2

(26) ##STR00023##
Co-Polymer 2 (poly(lauryl methacrylate-co-2-(Diisopropylamino)ethyl methacrylate). To a solution of 2.52 g (11.79 mmol) of 2-(diisopropylamino)ethyl methacrylate and 3.00 g (11.79 mmol) of laurylmethacrylate in 2.0 g toluene was added a solution of 0.030 g 2,2-azobis(2-methylpropionitrile) (AIBN) in 4.0 g 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.

Example 3

(27) Co-Polymer 1 and Co-Polymer 2 mixture (poly(stearylmethacrylate-co-methacrylic acid and poly(lauryl methacrylate-co-2-(Diisopropylamino)ethyl methacrylate mixture). 1.50 g of a 42 wt % by solids solution of co-polymer 1 was added to 1.24 g of a 56 wt % solution of co-polymer 2 with 1 g of isopropanol and mixed at 40 C for 30 minutes. The solution was used without further purification.

(28) To any of the embodiments of the polymeric species, a plasticizer is added. The work of Kamlesh Pandey in Effect of Plasticizers on Structural and Dielectric Behaviour of [PEO+(NH4)2C4H8(COO)2] Polymer Electrolyte, Journal of Polymers, 2013 Article ID 752596 teaches that plasticizers can increase the ion mobility in electrolytic polymers. A plasticizer should therefore allow the polar ionic fractions of the polymer to increase mobility in their local pocket, the polar plasticizers should congregate in the polar areas of the polymer, and not be attracted to the tail phases. The plasticizer should thereby increase the mobility of the polymer while simultaneously thermally treating the final film product. The presence of a plasticizer can increase the tail phase alignment and create polar pockets for the ionic groups. Use of plasticizers can thereby improve the material's resistivity by assisting in supramolecular alignment of tail phases and ionic (polar) phases to smooth out an external electric field

(29) Preferred, non-limiting, plasticizers are selected from high boiling point aprotic solvents such as propylene carbonate, NMP (boiling point 202 C.), and DMSO (boiling point 189 C.).

(30) While the above is a complete description of the preferred embodiment of the present invention, it is possible to use various alternatives, modifications and equivalents. Therefore, the scope of the present invention should be determined not with reference to the above description but should, instead, be determined with reference to the appended claims, along with their full scope of equivalents. Any feature described herein, whether preferred or not, may be combined with any other feature described herein, whether preferred or not. In the claims that follow, the indefinite article A, or An refers to a quantity of one or more of the item following the article, except where expressly stated otherwise. As used herein, in a listing of elements in the alternative, the word or is used in the logical inclusive sense, e.g., X or Y covers X alone, Y alone, or both X and Y together, except where expressly stated otherwise. Two or more elements listed as alternatives may be combined together. The appended claims are not to be interpreted as including means-plus-function limitations, unless such a limitation is explicitly recited in a given claim using the phrase means for.