U.S. patent application number 17/493700 was filed with the patent office on 2022-02-03 for electrodes and currents through the use of organic and organometallic high dielectric constant materials in energy storage devices and associated methods.
The applicant listed for this patent is Cleanvolt Energy, Inc.. Invention is credited to James Elliott Clayton, Zakaryae Fathi, John James Felten.
Application Number | 20220037086 17/493700 |
Document ID | / |
Family ID | |
Filed Date | 2022-02-03 |
United States Patent
Application |
20220037086 |
Kind Code |
A1 |
Fathi; Zakaryae ; et
al. |
February 3, 2022 |
ELECTRODES AND CURRENTS THROUGH THE USE OF ORGANIC AND
ORGANOMETALLIC HIGH DIELECTRIC CONSTANT MATERIALS IN ENERGY STORAGE
DEVICES AND ASSOCIATED METHODS
Abstract
Improved electrodes and currents through the use of organic and
organometallic high dielectric constant materials containing
dispersed conductive particles in energy storage devices and
associated methods are disclosed. According to an aspect, a
dielectric material includes at least one layer of a substantially
continuous phase material comprising a combination of
organometallic having delocalized electrons, organic compositions
and containing metal particles in dispersed form, in another
aspect, the novel material is used with a porous electrode to
further increase charge and discharge currents.
Inventors: |
Fathi; Zakaryae; (Raleigh,
NC) ; Felten; John James; (Chapel Hill, NC) ;
Clayton; James Elliott; (Raleigh, NC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Cleanvolt Energy, Inc. |
Research Triange Park |
NC |
US |
|
|
Appl. No.: |
17/493700 |
Filed: |
October 4, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16010741 |
Jun 18, 2018 |
11139118 |
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17493700 |
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14215890 |
Mar 17, 2014 |
10102978 |
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16010741 |
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61801064 |
Mar 15, 2013 |
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International
Class: |
H01G 4/14 20060101
H01G004/14; H01G 4/33 20060101 H01G004/33; H01G 4/12 20060101
H01G004/12; H01G 4/38 20060101 H01G004/38 |
Claims
1. A dielectric material comprising: at least one layer of a
substantially continuous phase material comprising a combination of
organometallic having delocalized electrons, organic compositions
and containing metal particles in dispersed form.
2. The dielectric material of claim 1, wherein the organometallic
is Metal-Phthalocyanine.
3. The dielectric material of claim 2, wherein the
Metal-Phthalocyanine is selected from the group consisting of
Copper-Phthalocyanine, Zinc-Phthalocyanine,
Magnesium-Phthalocyanine, Nickel-Phthalocyanine,
Iron-Phthalocyanine, and combinations thereof.
4. The dielectric material of claim 1, wherein the organometallic
materials are in particulate form having an average particle size
between 0.05 and 10 micron and are dispersed in organic
compositions.
6. The dielectric material of claim 5, wherein one of the organic
compositions include organic components selected from the group
consisting of ethyl cellulose, polymethylmethacrylate, epoxies,
silicones, polyurethane, acrylates, isocyantes, tripropylene
glycol, glycerol, phthalate esters, Phthalocyanine, and
combinations thereof.
7. The dielectric material of claim 6, wherein the organic
compositions further comprise a solvent.
8. The dielectric material of claim 1, wherein the metal particles
are from a group consisting of Copper, Titanium, Chromium,
Manganese, Iron, Cobalt, Nickel, Zinc, Aluminum, Zirconium,
Molybdenum, Silver, Gold, Tungsten and combinations thereof and/or
alloys thereof.
9. The dielectric material of claim 1, wherein the metal particles
are in powder form having an average particle size between 0.05 and
!Omicron and dispersed in the organic compositions from a group
consisting of Copper, Titanium, Chromium, Manganese, Iron, Cobalt,
Nickel, Zinc, Aluminum, Zirconium, Molybdenum, Silver, Gold,
Tungsten and combinations thereof and/or alloys thereof.
10. The dielectric material of claim 1, wherein the continuous
phase material comprises a second dielectric material in dispersed
form.
11. The dielectric material of claim 10, wherein the second
dielectric material is selected from the group consisting of
BaTiO3, Ferroelectric, relaxor dielectric, alumina, silica,
activated silica, aluminosilicates, alkali aluminosilicates,
alkaline aluminosilicates, Zeolites, and combinations thereof.
12. The dielectric material of claim 1, wherein the dielectric
material comprises at least two layers disposed one on top of the
other, each of the layers being formed of a material selected from
the group consisting of organic compositions, organometallic having
delocalized electrons, and metal particles in dispersed form and
combinations thereof.
13. The dielectric material of claim 11, wherein the dielectric
material contains at least two layers, each layer formed of
material from the group consisting of organic, organometallic
having delocalized electrons, and metal powders in dispersed form
and combinations thereof, and further comprises an inner layer
disposed between each of the at least two layers.
13. The inner layer having an organic vehicle containing conductive
particles disposed therein.
14. The dielectric material of any claim 12, wherein at least one
of the at least two layers contains a dispersed dielectric material
in dispersed form, wherein the dielectric material is selected from
the group consisting of BaTiO3, alumina, silica, active silica
aluminosilicates, alkali aluminosilicates, alkaline
aluminosilicates, Zeolites or an organic such as
Bismaleimide-Triazine, cyanate ester, epoxy, silicones,
polystyrenes and combinations thereof.
15. The dielectric material of claim 1, wherein the material is
applied between a pair of spaced-apart porous or solid electrodes
to form a charge storage device.
16. The dielectric material of claim 15, wherein the electrodes
comprise conductive materials selected from the group consisting of
metals, metal alloys, carbon base conductors, graphene, activated
carbon, carbon-nano-tubes, conductive polymers, and organic
polymers doped with carbon base conductors and metals, and
combinations thereof to form solid or porous electrodes.
17. A method for producing a dielectric material, comprising at
least one layer of a substantially continuous phase material
comprising a combination of organometallic having delocalized
electrons, organic compositions and metal particles in dispersed
form.
18. The method of claim 17, comprising partially sintering under
heat and/or pressure the layer containing substantially continuous
phase material comprising a combination of organometallic having
delocalized electrons, organic compositions and metal particles in
dispersed form.
19. A method for stacking multiple charge storage devices in claim
15 device comprising dielectric material, comprising at least one
layer of a substantially continuous phase material comprising a
combination of organometallic having delocalized electrons, organic
compositions and metal particles in dispersed form.
20. A method of claim 19, comprising partially sintering under heat
and/or pressure at least two charge storage devices.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Utility patent
application Ser. No. 16/010,741, filed Jun. 18, 2018, which claims
the benefit of U.S. Utility patent application Ser. No. 14/215,890,
filed Mar. 17, 2014 (now issued as U.S. Pat. No. 10,102,978, which
claims the benefit of U.S. Provisional Patent Application No.
61/801,064, filed Mar. 15, 2013; the contents of which are hereby
incorporated herein by reference in their entireties. This
application is related to U.S. patent application Ser. No.
13/747,441, filed Jan. 22, 2013, and U.S. Provisional Patent
Application No. 61/366,333, filed Jul. 21, 2010; the contents of
which are hereby incorporated by reference in their entireties.
TECHNICAL FIELD
[0002] The present disclosure relates to the use of metallic
dispersions inside organometallics particulates along with organic
vehicles to achieve ultra-high charge capacity dielectric material
(UHCC-dielectric material), and includes novel organometallic based
flexible electrodes to form energy storage devices, associated
fabrication methods, and applications of the dielectric material
and fabrication methods of the electrode and the dielectric. The
dielectric material and the combination of the dielectric material
and the novel electrodes enables superior energy storage per unit
mass or per surface area given a fixed thickness compared to
existing state of the art materials.
BACKGROUND
[0003] Electrical energy has been used for providing energy to
automobiles. Among the advantages of electrical propulsion are its
cleanliness and lack of emissions during driving, high efficiency,
quietness, and reliability. During the early years of automotive
development electrical propulsion was a formidable competitor to
the internal combustion engine.
[0004] The internal combustion engine had a decided advantage over
electric motors because of the greater onboard energy storage
afforded by liquid fuel, especially petroleum distillates and
gasoline. Early electric automobiles had only a short range,
typically less than 40 miles, followed by a lengthy charging cycle.
By comparison, fossil fuel powered vehicles can travel hundreds of
miles and need only a quick refueling in order to go another
several hundred miles.
[0005] The significant drawback of electrically propelled
automobiles has been the low energy density of the batteries used
as a power source. Early batteries were usually lead acid type,
which were very heavy and added to the weight of the vehicle. Over
the years, improvements have been made in battery technology to
reduce the weight penalty, but progress has not been sufficient to
radically change the relative range of electrically powered
automobiles versus their gasoline powered counterparts.
[0006] Recently, lithium ion batteries have been introduced which
reduce the weight and increase the driving range of electric
automobiles, but they are very expensive so that their most
promising application is in hybrid automobiles where a smaller
battery is sufficient. The small battery means that the primary
energy source is still a gasoline powered engine.
[0007] Capacitors store electric energy. A capacitor usually
includes a pair of electrodes that are configured on each side of a
dielectric material to increase energy storage. The amount of
energy stored by the capacitor is directly proportional to the
dielectric constant. Thus, the higher the dielectric constant, the
greater the energy storage. Accordingly, efforts are being
undertaken to develop dielectric materials with higher dielectric
constants so that capacitors and related devices can be used for
energy storage for powering devices and machinery including as
automobiles.
SUMMARY
[0008] This Summary is provided to introduce a selection of
concepts in a simplified form that are further described below in
the Detailed Description. This Summary is not intended to identify
key features or essential features of the claimed subject matter,
nor is it intended to be used to limit the scope of the claimed
subject matter. Considerable work has been done on thin films of
copper phthalocyanine which were prepared by sputtering or
evaporation. There are several problems with using thin films,
among which are a low breakdown voltage due to the thinness of
films, and limited ability to make composite films.
[0009] Improved electrodes and currents through the use of organic
and organometallic high dielectric constant materials with
dispersed conductive particles in energy storage devices and
associated methods are disclosed. According to an aspect, a
dielectric material includes at least one layer of a substantially
continuous phase material comprising a combination of
organometallic having delocalized electrons, organic compositions
and containing metal particles in dispersed form.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0010] FIG. 1 is a graph showing resistance versus capacitance of
an example system;
[0011] FIG. 2 are structures showing electrostatic binding forces
formed between copper phthalocyanine crystallites and low molecular
weight species;
[0012] FIG. 3 shows dielectric relaxation measurements that yield
the real and imaginary components of the dielectric constant for
the dielectric material;
[0013] FIG. 4 shows a structure of a building block of the metal
phthalocyanine chemistries enabling high capacitance;
[0014] FIG. 5 is a graph showing battery like behavior that stems
from permanent polarization;
[0015] FIG. 6 is a graph showing discharge of a device using Kovar
electrodes of 1 cm.times.1 cm and containing a dielectric layer in
the range of 35 microns;
[0016] FIG. 7 is a graph showing data plotted over a period of
9,000 hours;
[0017] FIG. 8 is a graph showing real data and the fitted data
based on an example model;
[0018] FIG. 9 is a graph showing that material that was charged at
high temperature (+54 C) and discharged at room temp was more
difficult to fit;
[0019] FIG. 10 is a graph showing that current measured for a
single layer device containing dispersed silver particles and the
current for two devices each containing dispersed silver particles
that were stacked on top of one another;
[0020] FIG. 11 is a graph showing that resistance measured for a
single layer device containing dispersed silver particles and the
current for two devices each containing silver particles that were
stacked on top of one another;
[0021] FIGS. 12 and 13 are graphs showing performance of integrated
currents in mA-sec; and
[0022] FIG. 14 is a graph showing the merger of the graphs.
DETAILED DESCRIPTION
[0023] In accordance with embodiments, one or more experiments and
investigations disclosed herein investigated thick film structures
with phthalocyanine, therefore, and successfully developed methods
of making thick films that would act as capacitors with the ability
to store charge hence ultra-high charge capacitors having capacitor
like and battery like attributes.
[0024] Disclosed herein is the use of the combination of metal
particles along with copper phthalocyanine particulates embedded
within organic vehicles to form an ultra high dielectric constant
k, and capacitors with ultra high capacitance and the ability to
hold charge for long periods of time. The addition of metal
dispersions contributes to a significant charging and discharging
currents. One or more capacitors disclosed herein may be made by
dispersing copper particles and copper phthalocyanine and/or silver
particles and copper phthalocyanine particulates in a solvents and
mixing the dispersion in a printing vehicle to form a copper
phthalocyanine dielectric. The copper phthalocyanine dielectric
with dispersed metal particles is applied over a conductive solid
electrode or a porous electrode of a capacitor to form a thick
film. The thick film copper phthalocyanine with dispersed metal
particles can also be applied over a novel electrode made of copper
phthalocyanine with dispersed metal particles for improved charging
currents and discharging currents. The green dielectric layers can
be dried from room temperature to 60 to 80.degree. C. and
optionally sintered at 150 to 200.degree. C. to form a continuous
layer. The preparation steps are repeated if necessary. A top
electrode is applied over the bottom phthalocyanine dielectric
structure. This method has the advantage that large thickness
dielectric layers can be applied, enhancing the charge storage
capability and increasing the resistance of the dielectric, whereas
conventional methods of creating a copper phthalocyanine dielectric
were limited when using an extremely thin dielectric layers
prohibiting a large scale polarization and charge storage and not
allowing the addition of metallic dispersions. The addition of
metallic particles to form a copper phthalocyanine based electrode
is also novel and the novel electrode is flexible and allows the
film to be cut and stacked to form higher voltage devices.
[0025] The copper phthalocyanine material has a behavior that is
representative of the metal-phthalocyanine chemistry platform from
which high dielectric constants films and devices can be built.
Various metal phthalocyanine chemistries were used. An example mode
focuses on Cu, Fe and zinc phthalocyanine based chemistries.
[0026] The plasticizers and solvents that were used impact the
orientation of the crystallite during the coating and drying
process. Good voltage discharge results are obtained with ethyl
cellulose, poly-methyl-methacrylate and acrylate resin as the
organic vehicle. Better metal phthalocyanine particulates alignment
was observed using Decalin solvent. Also, the addition of
tripropylene glycol in the appropriate amount enables the
activation of more dipoles and hence higher capacitance. The
addition of metal particles in dispersed form enables the
achievement of higher charging current. A novel porous electrode
film can influence the current intake by virtue of the surface area
that increase the effective charge storage capability. The metal
phthalocyanine film was co applied with the electrode film on top
of a release film. The co-applied film can be die-cut, stacked and
thermally compression bonded to form multilayered charge storage
devices.
Introduction and Relevance:
[0027] A set of chemistries based on metal-phthalocyanine and
related devices that are capable of storing extremely high amounts
of charge (far surpassing what is commercially available or
published in the literature). The materials are stable and
non-hazardous. The processing methods are reliable and devices with
ultra high capacitance can be reproduced (from small to large
scale). Devices with surface areas from 1 cm.times.1 cm to 30
cm.times.10 cm have been built. The application methods are
continuous and amenable to scale up via reel to reel techniques.
Devices from one layer to 27 layers have been fabricated. The
chemistries can be tailored to have devices exhibiting capacitor
like behavior or to have dual capacitor and battery like behaviors
can be fabricated.
[0028] The patent literature reported the use of
metal-phthalocyanine material chemistries in discontinuous phases
and at high frequencies. Devices containing phthalocyanine in a
discontinuous phase cannot build up very high capacitance. Also,
the phthalocyanine chemistries do not effectively store charge at
high frequencies due to the nature and the relaxation times
involved in these chemistries. In other words many of the
relaxation mechanisms are frozen in place at high frequency. For
this reason, phthalocyanines are not capable of very high
dielectric constants or ultra high charge storage once the
frequencies are elevated.
[0029] Test devices built using metal-phthalocyanine material
chemistries stored as much as 15 farads in a 4''.times.12'' device.
More typically, 4 to 8 farads in a 3''.times.3'' coupon, and have
achieved a maximum of over 60 volts peak. Charge retention is about
2 volts after one hour decay, and we have achieved 1.2 volts after
a day. This is from a single layer about 2 to 4 mils in
thickness.
[0030] Another set of metal-phthalocyanine material chemistries
managed to store charge and maintain 0.23 Volts in a single later
in 4 mills for a period of 12 months. The metal phthalocyanine
material chemistries offer a path for ultra high charge storage.
The charging rates and the discharge rates were identified as the
area of improvement. The improvements were obtained not by making
thinner films but by making thicker films and the non-linear
improvements were obtained by adding metal dispersions and also
tuning the porosity of the electrodes for improved performance. The
discharge rate was increased using porous electrodes that match our
dielectric materials to control the behavior at the electrode
region.
[0031] The academic literature addressed the fundamental
conductivity mechanisms of thin film phthalocyanine materials
deposited using known semiconductor techniques (among others). The
academic studies resolved some of the mechanisms but fell short in
terms of achieving neither the high capacitance nor the charge
storage that was achieved in the present invention, the main reason
being that most people followed conventional wisdom which is that
the thinner the dielectric films the higher the capacitance. This
is simply not true with the phthalocyanine materials. In fact it is
the opposite.
[0032] In accordance with embodiments, techniques are provided
based on the combination of chemistries and surface treatments
combined with thick film techniques. These novel approaches led to
the fabrication of phthalocyanine films that far surpass what has
been reported in the open and patent literature. The dielectric
behavior of films did better in terms of charge build up from 5
microns to 250 microns in thickness. These thicknesses allowed us
to tolerate minor defects and variations in the applications
methods (including drawing, spraying, dip coating and others).
Surprisingly, the phthalocyanine crystallites have to be in
electrical continuity, the materials can be in a continuous phase,
the thickness of the film is preferably in microns (not-submicron),
multi-layering of sufficiently different phthalocyanine chemistries
helps elongate halflife (such is the case of having one layer being
copper phthalocyanine and the second layer being zinc
phthalocyanine or iron phthalocyanine) and processing techniques
are necessary to increase capacitance and maintain charge storage.
Some of the relaxation mechanisms that can be activated are
chemistry and additives dependent. Controlled vs. uncontrolled
atmosphere (oxidation of the particulates and the copper metal
particles) has an impact on conductivity and the buildup of
capacitance. Also in general, we observed that resistance can be
increased depending the chemistry. However, capacitance decreased
as resistance increased according to the following general behavior
described in FIG. 1. The observable trend for resistance decreases
with increasing voltage and the capacitance increases with
increasing voltage.
Dielectric Materials
[0033] Dielectric materials are insulators and exhibit little or no
free electron conductivity. Their structure contains molecules,
atoms or ions and bound electrons. In complex materials the atoms
or molecules may be grouped in ordered or crystal structures. If
free electrons can be created at room temperature, their
concentrations are very small.
[0034] Under an applied external electric field or a voltage, the
dielectric material will polarize in an attempt to reduce the net
internal field. The rate of polarization will depend on the
mobility of the polarizing species or their ability to re-orient to
form dipoles. Several different species can contribute to the
polarization.
[0035] The metal-phthalocyanine family exhibits delocalized n
electrons. When the crystallites of the copper phthalocyanine (for
example) enter into contact the electrons can move over large
distances to result in the formation of a net dipole the magnitude
of which depends of the vectorial summation of all the smaller
dipoles residing within the aggregates forming the crystallites or
the particulates. This mechanism can contribute to a significant
portion of the stored energy. However its relaxation time is rapid
and the phenomenon is short lived. This behavior is desirable in
transportation applications for instance if/when high voltages are
required. Special chemistries can be designed for a very rapid
voltage drop with little current flow.
[0036] In general, the charge built up on the electrode by charging
currents freezes the internal and surface polarization effects in
the dielectric. When the electrodes are connected across a load,
current can flow only as fast as the polarization of the dielectric
discharges internally.
[0037] In most instances, the dielectric material will be in
contact with metal electrodes. In such a case, if the electrodes
are reversing electrodes, it means that they conduct using carrier
species that will enter the dielectric and will diffuse far into
its structure. If the electrodes are blocking, as is most often the
case, their electron carriers cannot diffuse into the insulating
dielectric and an additional "electrode polarization" will occur.
This is typical of dielectric-filled capacitors. However, the
metal-phthalocyanine family can carry (intrinsically or by
deliberate additions) additional chemical species that contribute
to a large electrode polarization with charge species that are not
electronic in nature. The mobility of these conductive ionic and
anionic species is low and results in a slow decay of the charge
build up at the electrode. In effect, the coercive field (inside
the dielectric) is strengthened and the electrode polarization
effect (also known as space charge polarization) can be enhanced
and used advantageously in this case.
[0038] Space charge polarization can take place other than at the
electrodes. Space charge polarization results from the cumulative
charge build up at the interface between dielectric layers having
contrasting conductive species. Space charge polarization can be an
effective charge storage mechanism. Some of the ultra-capacitors we
build are multilayered having at least 2 layers with contrasting
phthalocyanine layers with conductive species that do not readily
pass from one layer to the next. For example one layer can be
copper phthalocyanine rich and the other layer can be zinc
phthalocyanine or iron phthalocyanine rich. This effect can further
be improved if conductive chemical species (with low mobility) are
deliberately added to these metal Pc layers.
[0039] Furthermore, the chemical species can be deliberately varied
to add to the net polarization mechanisms and these added
chemistries can be ions, anions, low molecular weight ionic or
anionic species. The polarization, the mobility and the relaxation
of each of the species can be tailored by design. What is to be
appreciated is that the relaxation mechanisms can be drastically
different and therefore can be rendered from rapid to slow
depending on the intended use.
[0040] The capacitance is written in terms of the dielectric
constant of the dielectric material which polarizes under the field
generated by the charged capacitor plates, and the area and
separation of the capacitor plates.
[0041] The response rate of a dielectric capacitor depends on the
rate at which the various components of the polarization will decay
in the dielectric material. The leakage rate of a dielectric
capacitor will depend on any leakage currents that may exist in the
dielectric.
[0042] The electrostatic binding forces formed between copper
phthalocyanine crystallites and low molecular weight species
illustrated in FIG. 2. Further increase the storage capacity and
further mobilize localized orientations the relaxation of which can
be slowed down by the steric hindrance of the surrounding
material.
Measurements
[0043] Dielectric relaxation measurements yield the real and
imaginary components of the dielectric constant for the dielectric
material as illustrated in FIG. 3. The measurements reveal the
presence of the different polarizing species. However, due to the
limited frequency range of the instruments available, only a part
of each relaxation can be studied at a time. Since the response
rate of most, but not all, polarizing species can be slowed by
decreased temperature, many studies measure the change in
polarizability or dielectric constant as a function of frequency
and temperature to evaluate a greater portion of the polarization
mechanisms.
[0044] Lowering the temperature allows an examination of the higher
frequency range of the dielectric polarization. Raising the
temperature shows the lower frequency region of the relaxation.
[0045] This approach works if the polarization rates are not
dependent on temperature. However, if the polarization rates are
dependent on temperature, as is most often the case, then the
results can be ambiguous and difficult to interpret.
[0046] Finally, in order to study the critical very slow
polarization processes in dielectrics, it is necessary to have
instruments that can record data at frequencies well below 1 Hz.
This is not often accurate and the measurements are not as useful
as one would hope. Some devices can go to 0.01 Hz with reasonable
accuracy, but this can still be too high a frequency to measure the
diffusion processes and electrode polarization processes.
[0047] The best measurement method simulates the performance of the
dielectric when in use and it consists of measuring the charging
and discharging currents on the dielectric-filled capacitor. The
variations in charging and discharging currents with time are then
fitted with a variety of exponential functions to account for
various relaxation processes. The results give an indication of the
rates of response of the various polarization processes active
during charging and discharging of the capacitor. The measurements
also yield energy storage factors and rate of energy discharge
(ramp rate) for the storage function. The method, however, can only
give the magnitude of the very fast (sub-second) processes and not
their decay rate or relaxation time.
[0048] Dielectric constants from dielectric films made with
crystallites of metal phthalocyanine according to the present
invention have been measured to be in the millions. The highest
determined in experimental results exceeds 1 billion. Table 1 below
provides an example of a dielectric film with a dielectric constant
of eight million (8.times.10+.sup.6) This is quite remarkable.
TABLE-US-00001 TABLE 1 k Dielectric Constant C 8.33E-04 Farads
(capacitance with material) Co 9.58E-11 Farads (capacitance in air)
Eo 8.80E-12 -- air permitivity LI 1.65E-02 (Length) L2 1.65E-02 m2
(width) D 2.50E-05 m2 (Thickness) Formula dielectric 8.70E+06
Calculation constant Using dielectric 8.70E+06 C/C0 constant
Metal Phthalocyanine Material Chemistries
[0049] Copper phthalocyanine material chemistries have been
reported (Patent Application No. 61/366,333 filed on Jul. 21, 2010)
to enable the achievement of high dielectric constants. The
attribute of most relevance in the phthalocyanine chemistries is
the delocalized molecular orbitals innate to this family of
chemistries. However, the delocalized molecular orbitals are a
necessary but not sufficient condition to the achievement of the
ultra high dielectric constants with long relaxation times and
ultimately energy storage. The building block of the metal
phthalocyanine chemistries enabling high capacitance is illustrated
in FIG. 4.
[0050] In addition to the delocalized molecular orbitals nature of
the copper phthalocyanine (for example), it was determined that
there are some techniques (solvents, organic vehicles, inert
atmosphere, chemical additives, treatment processes (like biasing),
and surface area of the electrodes) that have to be utilized for
the reliable fabrication of ultra high capacitors exhibiting
battery like behavior to be achieved. The battery like behavior
stems from the permanent polarization that can be imparted to the
film, which limits the current output but maintains a steady stream
of charge flow over a long period of time as illustrated in FIG.
5.
[0051] The discharge of a device using Kovar electrodes of 1
cm.times.1 cm and containing a dielectric layer in the range of 35
microns is shown in FIG. 6. The organic Vehicle was ethyl
cellulose.
Permanent Polarization (Long Term Storage in One Chemistry)
[0052] The discharge of a 1 cm by 1 cm device built using a copper
phthalocyanine material chemistry using Decalin as a solvent. This
solvent is known for wetting metal phthalocyanine pigments very
well by virtue of the ring currents that are inherent to its
chemistry. The thickness was 40 microns. The film was applied by
drawing. The discharge of a 1 cm by 1 cm device built using a
copper phthalocyanine material chemistry using Decalin as a
solvent. A 60 micron device allowed the charge storage for 12
months. The data plotted over a period of 9,000 hours is shown in
FIG. 7. The voltage after 15 months was 0.23V.
[0053] There appears to be a recovery of voltage with time. This is
most likely due to the charge depletion around the electrode. So
that further charge build up is gated by the slow reorientation of
some dipoles in combination with diffusion of conductive species
contributing to charge build up.
[0054] The plasticizers and solvents that were used impact the
orientation of the crystallite during the coating and drying
process. Better voltage discharge results are obtained with ethyl
cellulose as the organic vehicle. Better metal phthalocyanine
particulates alignment was observed using Decalin solvent. Also the
addition of tripropylene glycol in the appropriate amount enables
the activation of more dipoles and hence higher capacitance. Lastly
the addition of metal particles in dispersed form enables the
achievement of higher charging current. And lastly the porosity of
the electrode can influence the current intake by virtue of the
surface area that increases the effective charge storage
capability.
Relaxation Time Example
[0055] In one example from one of our early chemistries, prior to
adding species that increase permanent voltage and lower leakage
rate, the data for voltage relaxation was fitted to the following
equation:
V(t)=Vai exp(t1-r,)T4i.sub.2 exp(t1-r,)JLi;
where Table 2 shows the results. The real data and the fitted data
based on the model is provided in FIG. 8. The data for the
(+27.degree. C.), the data from the (-27.degree. C.) are shown and
modeled. This is interesting result because there is a permanent
residual voltage of 0.33 volts at room temperature and 0.9 volts at
low temperature. This proves that the capacitor has a battery like
behavior from this residual voltage.
[0056] The material that was charged at high temperature (+54 C)
and discharged at room temp was more difficult to fit as is
illustrated in FIG. 9.
[0057] The fast process has: [0058] T.sup.1=4 seconds Vo1=0.5
volts
[0059] The mid process seems to have broken up into two processes:
[0060] T.sup.2.sub.a=100 seconds Vo2=0.4 volts [0061]
T.sup.2.sub.b=2,500 seconds Vo2b=1.1 volts In effect, another
relaxation mechanism was triggered by the high temperature
treatment during charging and then frozen at room temperature
during the discharge.
[0062] There are at least two relaxation times indicating a fast
and slow process. The relaxation time of the fast process seems to
be temperature independent. The slow process has a measurable
temperature dependence (activation energy of about 125 kcal/mol)
which is similar to diffusion processes.
[0063] The differences in amplitudes with V.sub.01 being much
greater at room temperature from the same charging condition
indicates that the three processes leak into each other. (i.e., the
permanent or long time voltage can be reduced by the diffusion
process and both can be reduced or short circuited by the
polarization or electronic process.)
[0064] In other chemistries we have added chemistries that forced
three and four relaxation mechanisms. These examples are a few on
how we can engineer a high dielectric constant with a discharge
that can be relaxation dependent and each of the additives can have
distinct characteristics in terms of altering the internal leakage
as well as enhancing the polarization and the net observable
capacitance. The addition of tripropylene glycol in the appropriate
amount enables the activation of more dipoles and hence higher
capacitance.
Charge and Current Measurements in the Metal Phthalocyanine Based
Chemistries Having Metal Particles Dispersed in the Dielectric
[0065] The metal phthalocyanine based chemistries lead to charge
storage devices that are neither a battery nor a capacitor but can
exhibit attributes of battery like and capacitor like behavior. The
metal phthalocyanine based chemistries first of a new class of
charge storage devices, the extension of either capacitor or
battery technology is not a linear extension, nor is it
intuitive.
[0066] The metal-phthalocyanine based chemistries materials exhibit
higher resistance at lower voltages. The addition of metal
particles in a dispersion format inside the dielectric of metal
creates field gradients inside the dielectric. The externally
imposed field is broken into sections of lower gradients. The field
gradient between metal particles is lower than the main field
applied to the external electrodes. In effect the dispersed powders
act as miniature electrodes inside the dielectric and increases the
resistance of the dielectric material between particles.
[0067] If one were to add the same metal powder particles in a
BaTiO3 dielectric, the capacitance would drop by virtue of lowering
the field gradients. However, the addition of the dispersed metal
powders results in lowering the gradients and increasing the
effective resistance between two metal powder sites is quite
beneficial to the metal phthalocyanine based chemistries. This is
quite counter-intuitive. For this reason, the performance of charge
storage devices based on metal phthalocyanine chemistries is
enhanced not impaired. The devices based on metal-phthalocyanine
were prepared by adding silver as a dispersed material inside the
dielectric as is illustrated in the table. This composition
exhibited enhanced current intake and discharge. Table 2 below
illustrates a metal phthalocyanine crystallites along with a metal
dispersion.
TABLE-US-00002 TABLE 2 1/o after evaporation Weight Weight Solid
Solid Solid (grams) W3/4 Voume V3/4 of solids W3/4 V V3/4 Ag 0.64
2.53% 0.062 0.23% 0.64 4.54% 0.062 1.03% BaTiO3 0.29 1.16% 0.053
0.19% 0.29 2.08% 0.053 0.88% CPC 0.98 3.87% 0.615 2.26% 0.98 6.95%
0.615 10.28% ZPC 0.49 1.94% 0.307 1.13% 0.49 3.47% 0.307 5.14%
Elvacite 0.75 2.96% 0.537 1.97% 0.75 5.30% 0.537 8.97% tripropylene
2.09 8.22% 2.088 7.67% 6.00 42.36% 2.088 34.91% glycol Texanol 2.09
8.22% 2.320 8.52% 5.00 35.30% 2.320 38.79% Isopropanol 18.06 71.10%
21.246 78.03% 0.00 0.00% 0.000 0.00% Total W 25.40 100% 27.228 100%
14.16 100.00% 5.98 100.00% indicates data missing or illegible when
filed
[0068] In this chemistry, the current was measured for a single
layer and the current for two devices that were stacked on top of
one another as is illustrated in FIG. 10. This is a much higher
current compared to dielectric compositions not containing the
metal particles. The behavior exhibited here is different than
stacking two capacitors together or connecting them in series.
[0069] Example for Non-Linear Behavior
[0070] If one were to connect ten of the metal phthalocyanine
devices of the present disclosure in series, along with ten
batteries and ten super-capacitors for comparison purposes, our
device would hold one hundred times the energy of a single device,
the battery would hold ten times the energy of a single battery,
and the super capacitor would contain no more energy than a single
device (but 10.times. the voltage). Thus, as voltage is ramped up,
the advantage of the metal phthalocyanine based chemistries becomes
more pronounced in terms of energy storage and power delivery.
[0071] As an example of charge storage, three identical devices
were stacked in a serial manner. Each device had one dielectric
layer of about 50 microns in thickness. The usable area for storage
in these devices was 3 in.times.3 in.
[0072] The devices were clamped together (which is optional) and
then charged using a power supply set at 12V. The current was
measured while the capacitors were charging. The current and the
time were then tabulated (see Table 3 below) to calculate the
charge.
[0073] This is quite remarkable in that the series of capacitors
acts like a battery rather than 3 capacitors in series. The
voltages are additive between the 3 capacitors. Each capacitor
exhibits a net intake of 9.5 F per layer.
TABLE-US-00003 TABLE 3 Time Charge F = ( )*T (sec) I (mA) (sec) 1
40.8 0.041 15 32 0.587 30 27 1.472 45 23.7 2.613 60 20.7 3.945 120
15.5 6.117 180 10.2 8.43 240 8.5 10.674 300 7.38 13.056 600 4.8
16.71 1200 3.23 21.528 2700 2.12 28.75 indicates data missing or
illegible when filed
Current Integrals: Contrast Between an Electrolytic Capacitor and
Metal Phthalocyanine Capacitor
[0074] An electrolytic capacitor having 1000 mF was charged and
discharged through a load. The integrated currents in mA-sec were
collected for both devices and contrasted in FIG. 12 and FIG. 13.
When the two graphs are merged as is the case of FIG. 14. The graph
that is obtained shows the contrast of the large charge storage
capability of the devices made with pigments or crystalline metal
phthalocyanine chemistries according to the teaching of the present
disclosure.
Porous Electrode
[0075] A dielectric composition having a metal dispersed within was
used according to the recipe in Table 4 below. A copper porous
electrode was made using either PMMA or Ethyl cellulose following
the composition in Table 5 below.
TABLE-US-00004 TABLE 4 Dielectric (composition-A) Weight % Copper
Pthalocyanine 7.55% Zinc Pthalocyanine 3.78% polymethylmethacrylate
5.67% Tripropylene Glycol 0.35% Dioctyl Phthalatc 18.42% Copper
powder 7.55% Acetone 56.67%
TABLE-US-00005 TABLE 5 Electrode (composition-B) Weight % Copper
49.07% polymethylmethacrylate 1.80% Acetone 49.13%
[0076] The porous electrode was applied to a 2 mil copper foil and
then dried. Subsequently the dielectric composition was applied on
top of the film and dried. A storage device was built using this
method. The current intake and discharge can be significant
depending on the pores and the interaction between the dielectric
and the electrode material.
[0077] In other methods the material of the electrode is applied to
a silicone treated mylar. The electrode material is deposited and
dried. Subsequently the dielectric composition was applied on top
of the film and dried. Then the co-applied films are released from
the silicone treated mylar. The dried film is then cut and stacked
to make multilayered devices. The polymethylmethacrylate allows the
flow under heat and as such, when the co-applied films are stacked,
they undergo a thermal compression bonding during which the
polymethylmethacrylate flows to allow electrical communication
between the various layers in the stack. A device having 4 to 20
layers was built using this method.
[0078] In one embodiment, the electrode material was a mixture of
the two chemistries A and B where by 90% of composition-B and 10%
of composition-A were mixed together and applied as the electrode
film. In a similar way the film were die cut and multilayered
charge storage devices were built.
[0079] Many modifications and other embodiments of the present
disclosure set forth herein will come to mind to one skilled in the
art to which the present disclosed subject matter pertains having
the benefit of the teachings presented in the foregoing
descriptions and the associated drawings. Therefore, it is to be
understood that the present subject matter is not to be limited to
the specific embodiments disclosed and that modifications and other
embodiments are intended to be included within the scope of the
appended claims. Although specific terms are employed herein, they
are used in a generic and descriptive sense only and not for
purposes of limitation.
[0080] It will be understood that various details of the presently
disclosed subject matter may be changed without departing from the
scope of the presently disclosed subject matter. Furthermore, the
foregoing description is for the purpose of illustration only, and
not for the purpose of limitation.
[0081] The novel dielectric materials used in the present invention
was made using the following industrially available materials:
pigment grade copper phthalocyanine Heliogen Blue L 6955 from BASF
located in Vandalia, Ill. Pigment grade copper phthalocyanine
Heliogen Blue L 6905 from BASF located in Vandalia, Ill. Pigment
grade copper phthalocyanine Heliogen Blue L 7101 from BASF located
in Vandalia, Ill. Copper phthalocyanine due content ca 95% from
Acros Organics. Copper metal powder with size 2 microns from Culox
Technologies Inc. Iron phthalocyanine and Zinc phthalocyanine from
Acros Organics. Triprpylene Glycol from Alfa Aesar (a Johnson
Mathey company located in Ward Hill, Mass.). Silver powder from
Technic Inc (the engineered powders division). Elvacite Acrylic
resin from Lucite International located in Cordova, Tenn. Barium
Titanate powder from Atlantic Equipment Engineering located in
Bergenfield N.J. Dioctyl phthalate, 99% from Acros Organics.
Texanol Ester Alcohol from Eastman in Kingsport Tenn. Isopropanol
from LabChem Inc located in Pittsburgh, Pa.
* * * * *