All-day solar cell system integrating high capacity photochromic storage and discharge

Abstract

The invention provides an all-day solar cell system that is capable of simultaneously generating and storing electricity, which allows efficient photocharge during the day and discharge at night.

Claims

1. A solar cell system, consisting essentially of: a dye-sensitized photochromic semiconductor (SC) adapted to serve as a photoelectrode (PE) and a negative electrode (−); a layer of a fluoropolymer partially or completed coating the dye-sensitized photochromic semiconductor; a positive electrode (+); and an aqueous environment comprising a dissolved redox shuttle pair Ox/Re, selected from the group consisting of Vanadium, benzoquinone and anthraquinone, wherein the dye-sensitized photochromic semiconductor comprises: a Ruthenium dye having a light absorption band in the range from about 380 nm to about 750 nm, and WO.sub.3 treated with TiCl.sub.4.

2. The solar cell system of claim 1, wherein the dye is N-719 dye having the structural formula of ##STR00002##

3. The solar cell system of claim 1, wherein the photochromic semiconductor comprises TiO.sub.2—WO.sub.3 hybrid electrodes.

4. The solar cell system of claim 1, wherein the photochromic semiconductor comprises nanoparticles of WO.sub.3 fused together by the TiCl.sub.4 treatment and a high-temperature sintering process.

5. The solar cell system of claim 4, wherein the redox couple is Vanadium in a supporting electrolyte comprising H.sub.2SO.sub.4.

6. The solar cell system of claim 5, wherein the fluoropolymer comprises Nafion (sulfonated tetrafluoroethylene based fluoropolymer-copolymer).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1. Schematic comparison between (FIG. 1a) a conventional solar storage device and the disclosed unconventional ADSC system (FIG. 1b) in Light Mode and (FIG. 1c) Dark Mode. In FIG. 1b and FIG. 1c, the red and blue arrows indicate charge transfer processes and redox reactions, respectively. The thickness of the arrows denotes the relative rates of the charge transfer/reaction processes. HOMO and LUMO in (FIG. 1b) refer to highest occupied molecular orbital and lowest unoccupied molecular orbital of the dye, respectively.

(2) FIG. 2. Fabricated WO.sub.3-based photoelectrodes with (FIG. 2A, right) and without (FIG. 2B, left) TiCl.sub.4 treatment. TiCl.sub.4 treatment has been widely utilized in literature and it was discovered in this work that applying TiCl.sub.4 to the photoelectrodes seems to increase electrode durability and dye (N719 dye) adsorption.

(3) FIG. 3. Picture showing N-719 dye adsorption onto an immersed WO.sub.3-based photoelectrode in a Petri dish.

(4) FIG. 4. SEM Images of a typical WO.sub.3-based photoanode at different resolutions: (FIG. 4A, left)×2,000 and (FIG. 4B, right)×100,000.

(5) FIG. 5. Exemplary all-day solar cell under testing using 0.1 M Ferrocene with 0.05 M TBAF.sub.6 in acetonitrile (FIG. 1A, left) and 0.01M vanadium (V.sup.4+) in 3 M H.sub.2SO.sub.4 (FIG. 1B, right). The simulated light illumination (from a solar simulator) and electric cable connections are shown.

(6) FIG. 6. Exemplary compact all-day solar cell under testing using vanadium (V.sup.4+) electrolytes.

(7) FIG. 7. Dark currents after illumination for 5 min, 10 min, and 15 min under open-circuit condition. The WO3-based photoanode was in contact with 0.1M ferrocene (Fc) in Acetonitrile. 0.01 M TBAPF.sub.6 was used as the supporting electrolyte.

(8) FIG. 8. (FIG. 8A, top) Short-circuit photocurrents under AM1.5 for the ADSCs using 0.1M vanadium redox couple (V.sup.4+) at different concentrations of the H.sub.2SO.sub.4 supporting electrolyte. (FIG. 8B, bottom) Short-circuit discharge current under dark for the ADSCs using 0.01M vanadium redox couple (V.sup.4+) at different concentrations of the H.sub.2SO.sub.4 supporting electrolyte.

(9) FIG. 9. Image of the WO.sub.3-based photoanode after testing. The blue-black colored appearance of the electrode is due to the formed hydrogen tungsten bronze because of electron storage due to the following reaction under light: WO.sub.3+H.sup.++e−.fwdarw.H.sub.xWO.sub.3.

(10) FIG. 10. Variation of short-circuit discharge current under dark for the ADSCs using 0.01M vanadium redox couple (V.sup.4+) after under illumination for 5, 10, 15, and 20 min. The photoelectrode was N-719 sensitized WO.sub.3 with TiCl.sub.4 treatment. The electrolyte was 0.01 M vanadium (V.sup.4+) balanced with 0.1M H.sub.2SO.sub.4.

(11) FIG. 11. (FIG. 11A, top) WO.sub.3-based hybrid photoelectrode showing the electrode surface and individual particle of TiO.sub.2 with decorated WO.sub.3 islands; (FIG. 11B, bottom) short-circuit discharge currents under dark for a TiO.sub.2—WO.sub.3 hybrid electrode. The photoelectrode was sensitized with N-719 dye. The electrolyte was 0.01 M vanadium (V.sup.4+) balanced with 0.1M H.sub.2SO.sub.4.

(12) FIG. 12. Pictures showing the impact of Nafoin coating to prevent dye (N-719) loss from the photoelectrode. The electrode on the left (#8) was coated with Nafion while the one on the right (#7) was without the coating.

DETAILED DESCRIPTION OF THE INVENTION

(13) The invention provides a high-capacity electricity generation and storage system with an integrated solar cell that undergoes reversible photochromic switching, a redox process, allowing for efficient photocharge during the day and a multi-hour long discharge at night. The ADSC system allows multiple hours of electricity generation, use and simultaneous storage followed by multiple hours of discharge.

(14) The disclosed invention circumvents the problems associated with the state-of-the-art solar energy storage systems centers on a high-capacity photochromic electrode in a dye-sensitized solar cell construction, which results in a robust, multi-functional, low-cost, and efficient device.

(15) For example, the disclosed invention improves over the recently reported all-vanadium photoelectrochemical (PEC) cell, which resembles a solar-powered redox flow battery. (Liu, et al. Electrochimica Acta, 136, (2014): 435-41; Liu, e al. ACS Catalysis, 5, no. 4 (2015): 2632-39.) In that system, the photochromic property of WO.sub.3 and the reversible charge and discharge of photoinduced electrons in a hybrid WO.sub.3/TiO.sub.2 photoelectrode were utilized.

(16) The present invention features a more advantageous device and a different approach, i.e., the integration of dye-sensitization and high-capacity photochromic materials in an ADSC. This novel construct allows for a low-cost solar cell with built-in energy storage capability while capable of providing all-day power supply.

(17) A schematic illustration is provided in FIG. 1 comparing between the conventional solar storage device (FIG. 1a) and the disclosed unconventional ADSC system in the light mode (FIG. 1b) and (c) the dark mode (FIG. 1b).

(18) As shown in FIG. 1a, to directly integrate storage capability into solar cells, the conventional approach is to simply add a solar power component to a typical storage device, such as a battery, supercapacitor, thermoelectric generator, H.sub.2 fuel cell, etc. To accommodate this combination, smart load switch controllers (S1 and S2 in FIG. 1a) must be employed in the cell module to allow photocharge and discharge under different conditions (light and dark). This approach, however, are accompanied by major disadvantages and limitations, for example, high fabrication cost, increased complexity in system operation, slow and delayed response to dynamic shift of demand, and poor efficiency.

(19) The ADSC system of the invention, in contrast, integrates a dye-sensitized photoelectrode (PE) and negative electrode (−) into a single component, i.e., dye-sensitized photochromic semiconductor (SC). In light mode, as illustrated in FIG. 1b, the photogenerated electrons from the dye are injected to the conduction band (CB) of an exemplary SC of WO.sub.3 (c). Part of the electrons contribute to the photocurrent (e) and the rest will be stored within the photochromic SC (d). The electrons are stored in the form of H.sub.xWO.sub.3 (c), as a result of the photochromic reaction: WO.sub.3+xe.sup.−+xH.sup.+.fwdarw.H.sub.xWO.sub.3. Redox reactions of a dissolved redox shuttle pair Ox/Re with the positive electrode (+) (g) and the dye molecules (f) help to complete the circuit.

(20) FIG. 1b shows that the output voltage of the ADSC is determined by the energy difference between the redox shuttle potential and the quasi-Fermi level of the photochromic SC material. To achieve an optimum power for the device, the desired redox shuttle must have redox potential close to the HOMO energy of the dye, but has to be reactive enough to allow efficient charge transfer between the dye molecules (process a, FIG. 1b). Suitable materials include that are widely available WO.sub.3 and Ru-based dye.

(21) The reverse reaction (h), occurring in the dark mode as illustrated in FIG. 1c, releases the stored electrons and continues the electric current. Discharge of the photochromic SC (h) continues the electric current, while reduction of the redox shuttle (i) occurs at the (+) electrode. The discharge voltage is determined by the energy difference between the Ox/Re redox potential and the quasi-Fermi level of electrons in the SC electrode (close to its CB edge).

(22) In one aspect, the invention generally relates to a solar cell system, which includes: a dye-sensitized photochromic semiconductor (SC) adapted to serve as a photoelectrode (PE) and a negative electrode (−); a positive electrode (+); and an aqueous environment comprising a dissolved redox shuttle pair Ox/Re.

(23) In certain embodiments of the solar cell system, the dye-sensitized photochromic semiconductor includes a dye molecule having a light absorption band in the range from about 380 nm to about 750 nm (e.g., from about 420 nm to about 750 nm, from about 450 nm to about 750 nm, from about 520 nm to about 750 nm, from about 600 nm to about 750 nm, from about 380 nm to about 650 nm, from about 380 nm to about 550 nm, from about 380 nm to about 450 nm), and a photochromic semiconductor.

(24) Any suitable photochromic semiconductor materials may be used, for example, one or more selected from the group consisting of WO.sub.3, MoO.sub.3, hexacyanoferrates, Prussian blue, conjugated conducting polymers, viologens, and other metal oxides and complexes.

(25) In certain embodiments of the solar cell system, the photochromic semiconductor is WO.sub.3. In certain embodiments of the solar cell system, the photochromic semiconductor comprises TiO.sub.2—WO.sub.3 hybrid electrodes.

(26) In certain embodiments of the solar cell system, the photochromic semiconductor is TiCl.sub.4-treated, where the photochromic semiconductor comprises nanoparticles of WO.sub.3 fused together by the TiCl.sub.4 treatment and a high-temperature sintering process.

(27) In certain embodiments of the solar cell system, the photochromic semiconductor is partially or completed coated with a layer of a fluoropolymer, for example, Nafion (sulfonated tetrafluoroethylene based fluoropolymer-copolymer) or other ion-conducting polymers such as sulfonated polysulfone.

(28) Any suitable dyes may be used, for example, those characterized by a light absorption band in the range from about 380 nm to about 750 nm (e.g., from about 420 nm to about 750 nm, from about 450 nm to about 750 nm, from about 520 nm to about 750 nm, from about 600 nm to about 750 nm, from about 380 nm to about 650 nm, from about 380 nm to about 550 nm, from about 380 nm to about 450 nm). Exemplary dyes include Ru-polypyridyl-complex dyes, such as N719 and N3 dyes, and metal-free organic dyes including indolic dyes, coumarin-based dyes, triarylamines, carbazoles, fluorenes, thiophenes and oligothiophenes.

(29) In certain embodiments of the solar cell system, the dye is a Ruthenium dye, for example, N-719 dye having the structural formula of:

(30) ##STR00001##

(31) Any suitable redox couple may be employed, for example, one selected from the group consisting of Vanadium, Ferrocene, benzoquinone, iron, anthraquinone, ferrocyanide, and others that are commonly used in redox flow batteries.

(32) In certain embodiments of the solar cell system, the redox couple Ox/Re is Vanadium (V.sup.4+/V.sup.5+) in a supporting electrolyte comprising H.sub.2SO.sub.4.

(33) In certain embodiments, the solar cell system allows multiple hours, for example, from about 1 to about 12 hours (e.g., from about 1 to about 10 hours, from about 1 to about 8 hours, from about 1 to about 6 hours, from about 1 to about 4 hours, from about 2 to about 12 hours, from about 4 to about 12 hours, from about 6 to about 12 hours, from about 8 to about 12 hours) of electricity generation, use and simultaneous storage followed by multiple hours, for example, from about 1 to about 12 hours (e.g., from about 1 to about 10 hours, from about 1 to about 8 hours, from about 1 to about 6 hours, from about 1 to about 4 hours, from about 2 to about 12 hours, from about 4 to about 12 hours, from about 6 to about 12 hours, from about 8 to about 12 hours) of discharge.

(34) In certain embodiments, the solar cell system provides a photocurrent in the light mode in the range of about 0.05 A to about 200 A (e.g., about 0.1 A to about 200 A, about 1 A to about 200 A, about 5 A to about 200 A, about 10 A to about 200 A, about 50 A to about 200 A, about 0.05 A to about 100 A, about 0.05 A to about 10 A, about 0.05 A to about 5 A, about 0.05 A to about 1 A, about 0.05 A to about 0.5 A) and a current in the dark mode in the range of about 0.01 A to about 200 A (e.g., about 0.05 A to about 200 A, about 0.1 A to about 200 A, about 1 A to about 200 A, about 10 A to about 200 A, about 20 A to about 200 A, about 100 A to about 200 A, about 0.01 A to about 100 A, about 0.01 A to about 10 A, about 0.01 A to about 5 A, about 0.01 A to about 1 A, about 0.01 A to about 0.5 A, about 0.01 A to about 0.1 A).

(35) In another aspect, the invention generally relates to an article of manufacture comprising the solar cell system disclosed herein.

(36) In yet another aspect, the invention generally relates to a method for fabricating a solar cell. The method includes: providing a photochromic semiconductor (SC); depositing a dye to the photochromic semiconductor; providing a positive electrode (+); positioning the dye-deposited photochromic semiconductor in reference to the positive electrode (+) so as to serve as a negative electrode (−) and a photoelectrode (PE); and providing an aqueous environment comprising a dissolved redox shuttle pair Ox/Re to form a solar cell

(37) In certain embodiments, the method further includes, prior to depositing a dye to the photochromic semiconductor, treating the photochromic semiconductor (SC) with TiCl.sub.4 and a high-temperature sintering process.

(38) In certain embodiments, the method further includes, following depositing a dye to the photochromic semiconductor, coating the dye-deposited photochromic semiconductor with a fluoropolymer.

(39) Exemplary dyes include Ru-polypyridyl-complex dyes, such as N719 and N3 dyes, and metal-free organic dyes including indolic dyes, coumarin-based dyes, triarylamines, carbazoles, fluorenes, thiophenes and oligothiophenes.

(40) Any suitable redox couple may be employed in the method, for example, one selected from the group consisting of Vanadium, Ferrocene, benzoquinone, iron, anthraquinone, ferrocyanide, and others that are commonly used in redox flow batteries. In certain embodiments of the method, the redox couple Ox/Re is Vanadium in a supporting electrolyte comprising H.sub.2SO.sub.4.

(41) In yet another aspect, the invention generally relates to a solar cell produced by a method disclosed herein or an article of manufacture having such a solar cell.

(42) The solar cell system disclosed herein offers unique benefits. The simplified system design allows for low fabrication and maintenance costs, unlike the conventional electrochemical solar devices where specially fabricated dual electrodes and organic solvents are required. The ADSC system is readily scalable and adopted because of its modular panel design that is compatible with the existing PV infrastructure.

(43) The disclosed system also offers operational simplicity and low maintenance. As illustrated in FIG. 1c, the discharge current in the dark mode remains the same as the photocurrent in the light mode, obviating the need for smart switch controllers and dramatically simplifying the operation. At night or under reduced light intensity (e.g., cloudy or rainy conditions), the electron discharge automatically kicks in, providing an instantly responsive and effective energy management solution such as load leveling.

(44) Additionally, the system of the invention employs high-capacity and earth-abundant photochromic materials such as WO.sub.3 or MoO.sub.3 in an aqueous solution. WO.sub.3, for example, as a typical negative electrode material in Li-ion batteries, has capacity 4-times higher than that of state-of-the-art positive counterparts. Another feature is that a much thicker electrode (e.g., LiCoO.sub.2) can be used leading to a much higher storage capacity, which is partially enabled by the chosen electrochemically active redox shuttle that could react through the entire thickness of the PE. The system enjoys a highly efficient DSSC platform with achievable efficiencies in the range of 6% to 19%.

(45) The disclosed system also offers easy state-of-charge (SoC) monitoring. Precise SoC monitoring is important for energy storage devices. A major virtue of the disclosed invention is that the photochromic material undergoes distinct color change upon photocharge, providing a unique and readily discernable SoC monitoring mechanism.

(46) Furthermore, the unique energy storage mechanism enables a wide range of capabilities. In the light mode (FIG. 1b), the photochromic reaction (d) at the PE is accompanied by Ox/Re redox reactions; however, the reaction rate from Re to Ox (f) is not balanced by its reverse reaction (g) at the (+) electrode (the thickness of the arrows in FIG. 1 denotes the relative rates of charge transfer/reaction processes), resulting in a monotonic rise of the Ox/Re ratio in the solution. This temporary unbalance is annulled by the continued reduction reaction (i) at the (+) electrode in the dark mode. This unique storage mechanism indicates that both the photochromic material and redox shuttle pair, as the storage agents, can be separately optimized without compromising the overall performance.

(47) An important and immediate impact of the disclosed ADSC system is that it significantly increases the utility and value of non-dispatchable solar energy. The ADSC system enables both overall effectiveness and efficiency of energy load management and shorter term bridging power. In particular, addressing daily variations (e.g., mismatches between the time of day when renewable resources produce peak output and peak demand on the grid) requires multiple-hour run time capability, for which there are fewer technology options. The ADSC disclosed here can effectively address the surging need for daily renewable energy supply with the growing market share of solar energy. This will also minimize the need to build and operate spinning-reserve power plants, which is the most common method employed today to close the gaps between power consumption and generation.

(48) The ADSC system also allows exploration of new sustainable energy product solutions, especially small-scale end users who rely on distributed generation—such as homes, schools, hospitals, and corporate office headquarters.

EXAMPLES

(49) Summarized below are certain experiments on materials fabrication, photoelectrode optimization, cell assembly, tests of different combination of materials and redox couples, and evaluation of electric currents under both dark and simulated light, and analysis of storage capacity under dark.

(50) In an exemplary embodiment, an ADSC system was built using vanadium redox species (V.sup.4+) in 0.1 M H.sub.2SO.sub.4 as the supporting electrolyte, and nano-sized WO.sub.3 loaded with N-719 dye and TiCl.sub.4-treated photoelectrode. A photocurrent as high as 1.0 mA was observed and about 1 hour discharge under dark was achieved at around 0.25 mA in a laboratory-scale experimental cell.

(51) The photoelectrode is the key component of the ADSC and its durability and performance are essential to the viability of the ADSC system. In an exemplary fabrication procedure, the following steps are included: mixing storage materials (e.g., WO.sub.3 particles) with polyethylene glycol (PEG) and solvents, coating on a FTO glass, and then sintering at low- and high-temperatures.

(52) FIG. 2 shows the fabricated WO.sub.3-based photoelectrodes with and without TiCl.sub.4 treatment. TiCl.sub.4 treatment was utilized to increase electrode durability and dye (N719 dye) adsorption. FIG. 3 shows an immersed WO.sub.3-based photoelectrode in a Petri dish for adsorption of N-719 dye.

(53) FIG. 4 shows SEM images of the WO.sub.3-based photoanode at different resolutions. FIG. 4A (left) was at ×2,000 while FIG. 4B (right) was at ×100,000.

(54) The results indicated that the photoelectrode was composed of nano-sized WO.sub.3 particles that are fused together by the TiCl.sub.4 treatment and high-temperature sintering. The prepared photoelectrode provides a high surface area that allows for a high dye loading.

(55) The redox couple in the ADSC system is important because not only it helps to regenerate the oxidized dye (e.g., N-719), but also determines the photovoltage of the system. Ferrocene (Fc) and its corresponding oxidized species (Fc.sup.+) were tested. For example, according to the following reaction: Fe(C.sub.5H.sub.5).sub.2.Math.Fe(C.sub.5H.sub.5).sub.2.sup.++e.sup.−, the redox couple sets the electrochemical potential at around 1.2V (vs. NHE) at the counter electrode.

(56) FIG. 5 shows an embodiment of an ADSC under testing using 0.1 M Ferrocene with 0.05 M TBAF.sub.6 in acetonitrile (FIG. 5A, left) and 0.01M vanadium (V.sup.4+) in 3 M H.sub.2SO.sub.4 (FIG. 5B, right). The simulated light illumination (from a solar simulator) and electric cable connections are shown. FIG. 6 shows an embodiment of an ADSC under testing using vanadium (TiCl.sub.4) electrolytes. This design was much thinner than that shown in FIG. 5.

(57) FIG. 7 shows dark currents after illumination for 5 min, 10 min, and 15 min under open-circuit condition. The WO.sub.3-based photoanode was in contact with 0.1 M ferrocene in acetonitrile. 0.01 M TBAPF.sub.6 was used as the supporting electrolyte.

(58) Vanadium redox couples were tested in the ADSC. 0.01 M V.sup.4+ balanced with different H.sub.2SO.sub.4 concentrations was studied. The redox couple has the electrochemical potential at around 1.0 V (vs. NHE), yielding an open circuit potential of ˜1.1 V. FIG. 8 depicts the short-circuit currents under both illumination and dark. In addition, high photocurrents were found to yield high dark currents. This was because more photo-generated charges are created due to facilitated photoelectrochemical reactions, which contribute to both the photocurrent and electron storage under illumination. The stored charges were released under dark forming the dark-condition discharge current (bottom, FIG. 8B). The mechanism can be explained through the reversible intercalation/deintercalation of electrons and H.sup.+ ions into/out of WO.sub.3 to form hydrogen tungsten bronze, H.sub.xWO.sub.3. It was observed from the appearance of the electrode after the photoelectrochemical experiment (FIG. 9). The blue-black colored hydrogen tungsten bronze (confirmed by X-ray diffraction) appears on the electrode after AM1.5 irradiation due to the following reaction under light: WO.sub.3+H.sup.++e.sup.−.fwdarw.H.sub.xWO.sub.3.

(59) The impact of light illumination period was also studied. As shown in FIG. 10, the WO.sub.3 photoelectrode was tested under different light illumination periods including 10 and 20 min. A two-stage discharge profile was observed in FIG. 10, where the dark currents first dropped promptly and then appeared to reach saturation/stabilization eventually. Integrated area under the discharge curves in FIG. 10 was found to be irrelevant to the light illumination time, indicating that the photocharging process (i.e., forming the H.sub.xWO.sub.3) was fast and is nearly completed even with 5-min light illumination.

(60) To increase durability of the ADSC, a TiO.sub.2—WO.sub.3 hybrid electrode was fabricated, as shown in FIG. 11. Results showed that (i) TiO.sub.2 does not contribute to electron storage and (ii) it may render as the barricade to prevent electron transfer.

(61) Additionally, coatings of the dye-sensitized photoelectrode were tested, for example fluoropolymers such as Nafion (sulfonated tetrafluoroethylene based fluoropolymer-copolymer), were shown to prevent dye loss from the photoelectrode (FIG. 12).

(62) Applicant's disclosure is described herein in preferred embodiments with reference to the Figures, in which like numbers represent the same or similar elements. Reference throughout this specification to “one embodiment,” “an embodiment,” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.

(63) The described features, structures, or characteristics of Applicant's disclosure may be combined in any suitable manner in one or more embodiments. In the description, herein, numerous specific details are recited to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that Applicant's composition and/or method may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the disclosure.

(64) In this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural reference, unless the context clearly dictates otherwise.

(65) Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. Methods recited herein may be carried out in any order that is logically possible, in addition to a particular order disclosed.

INCORPORATION BY REFERENCE

(66) References and citations to other documents, such as patents, patent applications, patent publications, journals, books, papers, web contents, have been made in this disclosure. All such documents are hereby incorporated herein by reference in their entirety for all purposes. Any material, or portion thereof, that is said to be incorporated by reference herein, but which conflicts with existing definitions, statements, or other disclosure material explicitly set forth herein is only incorporated to the extent that no conflict arises between that incorporated material and the present disclosure material. In the event of a conflict, the conflict is to be resolved in favor of the present disclosure as the preferred disclosure.

EQUIVALENTS

(67) The representative examples are intended to help illustrate the invention, and are not intended to, nor should they be construed to, limit the scope of the invention. Indeed, various modifications of the invention and many further embodiments thereof, in addition to those shown and described herein, will become apparent to those skilled in the art from the full contents of this document, including the examples and the references to the scientific and patent literature included herein. The examples contain important additional information, exemplification and guidance that can be adapted to the practice of this invention in its various embodiments and equivalents thereof.