CROSS-REFERENCE TQ RELATED APPLICATION

This utility Patent Application claims the benefit of priority to U S Provisional Patent Application Number 61/081,998, entitled "Flexible, High Specific Energy Density, Rechargeable Battery," filed on July 18, 2008, which is incorporated by reference The U S Government has a paid-up license in this invention and the right in limited circumstances to require the patent owner to license others on reasonable terms as provided for by the terms of NSA Contract #H9823004CO490 awarded by the NSA

TECHNICAL FIELD This disclosure is directed to electrochemical energy cells Some embodiments may relate to thin, flexible rechargeable battery and/or capacitor cells that can be integrated mto a flexible electronics matrix

Some embodiments may relate to a rechargeable high capacitance battery cell, in which the cell can include a powdery mixture of hydrated ruthenium oxide particles or nanoparticles and activated carbon particles or nanoparticles suspended in an electrolyte

Some embodiments may relate to an electrochemical energy cell that can provide capacitive storage with electrochemical power generation by combining a rechargeable thm flexible battery with a thin, flexible capacitor in a smgle-hybπd system to form a thin, flexible energy cell for various applications, such as for powering a Distributed Networks Node device

BACKGROUND

The operation of a battery can be based on electrochemical reactions m which electrons are produced The electrons can flow from the negative terminal of the battery to the positive terminal, and, if a load is connected between the positive and negative terminals, the electrical current produced by the battery can flow therethrough

A battery can "hold" power for a long period of time when in a dormant state until electrons flow from the negative to the positive terminal The chemical reaction can be launched once an electric load is created between the positive and negative terminals In some batteries, an electrical circuit can be created when one mateπal oxidizes, or gives up electrons, while another mateπal immersed in an electrolyte becomes reduced, or gains electrons Opposingly, when a rechargeable battery is plugged into an electπcal outlet, the flow of electrons can be reversed so that the material that oxidizes during discharge gams electrons, while the other mateπal gives up electrons Rechargeable batteries are widely used in cordless power tools, cell phones, laptop computers, digital cameras, two-way radios, etc , due to their ability to be recharged numerous times

A capacitor can refer to a passive electronic component that stores energy m the form of an electrostatic field In its simplest form, the capacitor can include a pair of conducting plates separated by an insulating mateπal, e g , a dielectric The capacitance can be directly proportional to the surface area of the plates, and can be inversely proportional to the separation between the plates Capacitance of the capacitor may also depend on the dielectric constant of the substance separating the plates

SUMMARY

Some aspects of some embodiments may involve a rechargeable flexible (e g , bendable, twistable) battery that may be integrated in a flexible electronics matrix, and which may be applicable for powering distπbuted networks node devices

Some embodiments involve a rechargeable electrochemical energy cell that has at least one rechargeable battery cell including an anode electrode unit, a cathode electrode unit, and a first electrolyte body sandwiched between the anode and cathode electrode units, in which the cathode electrode unit includes a cathode mateπal having a powder mixture of a powder of hydrated ruthenium oxide (Ruθ ₂ x H ₂ O) with activated carbon (AC) particles or nanoparticles suspended in a second electrolyte body

Some aspects of some embodiments may include thin batteπes requmng low (e g , below 1 25 volts) charge voltages, and which may be safe in use Some aspects of some embodiments may involve a thm rechargeable flexible battery with high capacity that can have a maximized active surface for efficient electrochemical reactions in the cell, which can be attained by using a powdered mixture of hydrated ruthenium oxide particles or nanoparticles and activated carbon particles or nanoparticles suspended in an electrolyte

Some aspects of some embodiments may include a hybπd rechargeable flexible battery/capacitor structure, which can be based on the cathode active mateπal, including a powder mixture of the hydrated ruthenium oxide and activated carbon particles or nanoparticles

Some aspects of some embodiments may involve a stacked cell structure of multiple batteπes cells connected m seπes or parallel, which can have small overall volume, low charge voltage, and which may be contained within a Lexan package that is acid resistant and sealed using its own adhesive layer or withm a flexible plastic package that is acid resistant and easily sealed using its own adhesive layer

Some aspects of some embodiments may include a rechargeable flexible battery/capacitor electrochemical energy cell that can have a simple manufacturing process and can be highly efficient in operation

Some aspects of some embodiments may involve an electrochemical energy cell that may include at least one rechargeable thm flexible battery unit, but which can have any number of the flexible thm battery cells stacked on each other and connected m seπes or parallel The battery cell(s) may also be combined with capacitor(s) in a hybrid unit to intermittently operate in either power producing or power conserving modes, or in different power sourcing modes The connections in such a stack or combination may be internal or external to the packaging

Some aspects of some embodiments may involve a rechargeable battery unit that may include a thm anode electrode unit, and a thin cathode electrode unit with an expanded active surface area, and having an electrolyte body sandwiched between the thm anode and cathode electrode unit

Some embodiments of the thm anode electrode unit can include a layer of an oxidizable metal, such as for example, zinc, aluminum, or lead The oxidizable metal can be either a sheet of the oxidizable metal or may include a sputter-coated metal powder on a flexible backing material

Some embodiments of the cathode electrode unit can include a cathode material having a powder mixture of a powder of hydrated ruthenium oxide particles or nanoparticles with activated carbon particles or nanoparticles mixed in a volumetric relationship The powdered mixture may be suspended in an electrolyte body to form a paste The powder mixture may vary over a wide range of volume ratios between the powder of hydrated ruthenium oxide and the powder of activated carbon, depending on the individual application

In some embodiments, the volume ratio of the powder of RuC> ₂ x H ₂ O and powder of AC m said powder mixture can vary in a range from 0% 100% volume ratio to 100% 0% volume ratio In some embodiments, the volume ratio can be approximately 50% 50% In some embodiments, each of the first and second electrolyte bodies can have a pH in the range of 3 to 6 5 A range of a thickness of the rechargeable electrochemical energy cell can be 1 mm or lower Some embodiments of the electrolyte in which the powder mixture is suspended may include mateπals from a group of materials, in which some embodiments, may include ethylene glycol, bone acid, citric acid and ammonium hydroxide In some embodiments, this solution can be a mixture of approximately 45% of ethylene glycol, 37% bone acid, 18% citnc acid and 0 5 ml ammonium hydroxide per IQO ml of the electrolyte solution Other electrolyte compositions may be utilized as well

Some embodiments may include a permeable electncally insulating separator layer saturated with the electrolyte, and sandwiched between the anode and cathode electrode units contiguous to the cathode matenal and a matenal of the anode electrode unit The separator layer can be a matenal that is porous to ions in liquid and is electncally non-conductive The separator layer may be formed from a matenal including glass fiber filter paper, cleanroom- grade tissue paper, styrene-grafted fluoπnated ethylene polypropylene, etc

Some embodiments of the structure may include a flexible backing layer of conductive graphite, which backs the cathode matenal spread thereon m a predetermined active area The surface of the graphite foil may have corrugations, serrations, grooves, holes, etc , to further expand and maximize the active area of the electrochemical cell Positive and negative lead contacts can be electrically connected to the cathode electrode unit and the anode electrode unit, respectively

In some hybnd implementations of the electrochemical energy cell, a capacitor cell can be packaged together with the battery cell m a battery capacitor hybnd structure, where connections can be made to integrate the capacitor in parallel with the battery The capacitor cell may include a pair of flexible graphite layers, and a paste containing a powder mixture of the powder of hydrated ruthenium oxide particles or nanoparticles with activated carbon particles or nanoparticles (or alternatively, just activated carbon powder) suspended in the electrolyte The paste may be dispersed on a predetermined active area of each flexible graphite layer An insulator layer (e g , a dielectnc layer) can be sandwiched between the graphite layers The capacitor cell may include first and second contacts, each of which may be electncally coupled to a respective one of the pair of flexible graphite layers The capacitor cell may be constructed with asymmetncal electrodes, with the paste used on only one of the two electrodes

Some aspects of some embodiments may involve a method of fabncatmg a flexible thin rechargeable electrochemical cell The method may involve forming a graphite backing layer of predetermined dimensions from a flexible graphite foil (corrugations may be formed on the surface of the graphite foil), identifying a predetermined active area on a respective surface of the graphite layer, and mixing a powder mixture from a predetermined quantity of a powder of hydrated ruthenium oxide and a powder of activated carbon The method may involve prepaπng a paste from the powder mixture and an electrolyte, depositing the paste on the active area on the backing graphite layer, thereby forming a cathode electrode unit The method may involve forming a metal anode electrode layer, forming a separator layer of predetermined dimensions from a permeable electrical insulating material, positioning the separator layer on the cathode electrode unit contiguous to the paste dispersed on the active area, impregnating the separator layer with the electrolyte, and attaching the metal anode electrode layer to the cathode electrode unit with the separator layer sandwiched therebetween

Some aspects of some embodiments may involve a first contact strip attached between the bottom of the graphite backing layer and the bottom seal layer, with an end of the first contact strip extending beyond an edge thereof A second contact strip can be attached between a top seal layer and the metal anode electrode layer, with an end of the second contact strip extending beyond an edge of the top seal layer The top and bottom seal layers can be adhered each to the other at the peπmeter of the cell, thus forming a sealing package enveloping the cell

Some aspects of some embodiments may involve a method for forming negative and positive contact leads The method can involve cutting a contact hole m a bottom seal layer and m a top seal layer, fixing the bottom seal layer to the graphite backing layer, adhering the top seal layer to the metal anode layer, and attaching first and second contact leads to the graphite backing layer and the metal anode electrode layer through contact holes formed therein, respectively The first and second contact leads can extend in different directions

Some aspects of some embodiments involve a method of manufacturing a rechargeable electrochemical energy cell The method involves forming at least one battery cell by cutting a contact hole in a bottom seal layer and in a top seal layer, forming a graphite backing layer of predetermined dimensions from a graphite foil, defining an active area on a respective surface of the graphite backing layer, and prepaπng a powdered mixture from predetermined quantities of a powder of hydrated ruthenium oxide (R11O ₂ x H ₂ O) particles or nanoparticles and a powder of activated carbon (AC) particles or nanoparticles The method also involves preparing a paste from the powdered mixture and an electrolyte, depositing the paste on the active area of the backing graphite layer, thereby forming a cathode electrode unit, forming a metal anode electrode layer, forming a separator layer of predetermined dimensions from a permeable electrically insulating material, positioning the separator layer on the cathode electrode unit m contiguous contact with the paste dispersed on the active area, and impregnating the separator layer with the electrolyte The method involves attaching the metal anode electrode layer to the cathode electrode unit with the separator layer sandwiched therebetween, adhenng the bottom seal layer to the graphite backing layer, adhenng the top seal layer to the metal anode electrode layer, and filling the contact holes with a conductive epoxy material

Some aspects of some embodiments may involve a method for production of hybrid structure The method can involve forming a capacitor cell by sandwiching a dielectric separator layer between a pair of flexible graphite layers with the paste deposited thereon (corrugations may be formed on the surface of each graphite layer underlying the paste), and attaching the capacitor cell with internal or external contacts in parallel to the flexible battery cell, thereby forming a hybπd battery/capacitor structure

Some embodiments can involve an electrochemical cell that includes an anode electrode layer, a cathode electrode layer, and a first electrolyte body sandwiched between the anode and the electrode layers In these embodiments, the cathode electrode layer includes a cathode mateπal having at least a powder mixture of a powder of an oxide with activated carbon (AC) particles or nanoparticles suspended m a second electrolyte body The electrochemical cell is bendable and twistable to form a non-planar shape, and the electrochemical cell is configured for a reduction-oxidation (redox) reaction to generate power at a surface of one of the electrode layers

In these embodiments, the electrochemical cell can be 1 mm or less in thickness, and/or be less than 4 grams The first electrolyte body can be approximately PH-neutral (~7) The oxide can include hydrated ruthenium oxide (RuCh x HO) or manganese oxide At least one of the electrodes can include lead (Pb) The first electrolyte body can include citric acid The anode electrode layer can include aluminum (Al) The electrochemical cell can include a separator layer sandwiched between the anode and cathode electrode layers, m which the separator layer can include a mateπal that is porous to ions in liquid and is electrically non- conductive A shape of the electrochemical cell and positions of the electrode layers on the electrochemical cell can be configured for stacking with another electrochemical cell to electrically form a seπal or parallel connection with the other electrochemical cell upon stacking The electrochemical cell can be non-toxic and noncombustible

Some embodiments may involve an electrochemical cell that includes a battery cell and a capacitor cell The battery cell includes an anode electrode layer, a cathode electrode layer, and a first electrolyte body sandwiched between the anode and the electrode layers, in which the cathode electrode layer includes a cathode material having a first powder mixture of an oxide with activated carbon (AC) particles or nanoparticles suspended m a second electrolyte body The capacitor cell is electrically coupled to the battery cell The capacitor cell includes a pair of graphite layers, an insulator layer sandwiched between the graphite layers, and a paste having a second powder mixture of the oxide with the activated carbon particles or nanoparticles suspended in a third electrolyte body, in which the paste is dispersed on a predetermined area of each of the graphite layers The electrochemical cell can be a hybrid battery/capacitor structure, where a thickness of the electrochemical cell can be lmm or less, and the electrochemical cell can be bendable and twistable to form a non- planar shape

In some embodiments, a single or multiple cell electrochemical energy cell structure including stacked battery cells may be created by the present method depending on the application and the power needed for powering the electronics

Embodiments can include a miniature device that offers capacitive storage (capacitor) along with power generation (battery) in a single battery/capacitor hybπd implementation

Some embodiments involve electrochemical energy cells that can provide an environmentally safe, thm flexible energy cell that has a charge voltage at or below 1 25 volts, and may not impose a danger of explosion duπng their operation

The details of one or more implementations are set forth in the accompanying drawings and the description below Other features will be apparent from the description and drawings, and from the claims

BRIEF DESCRIPTION OF THE DRAWINGS

FIG 1 is a simplified schematic representation of an example of a cross-section of the battery cell,

FIG 2 is a top and/or bottom view of an example of the electrochemical energy cell, FIG 3 is a diagram of an example of a thm flexible electrochemical energy cell, FIG 4 is a schematic representation of an example of the basic battery cell on a large scale, FIG 5 is an exploded view of an example of a capacitor cell,

FIG 6 is a structure of an example of a double stacked battery cell, FIG 7 is a simplified schematic representation of an example of a cross-section of the battery/capacitor hybπd cell,

FIG 8 is an exploded view of an example of the battery cell constituents, FIGS 9A-9J represent a sequence of operations of an example method,

FIGS 10A-10D represent a sequence of operations of an example method,

FIG 11 is a diagram representing an example of the cell potential during constant 100 JUA current charging, FIG 12 is a diagram representing an example of a discharge of a single graphite/zinc cell with 100 kOhm load,

FIG 13 is a diagram representing an example of a discharge of a single graphite/zmc cell with 10 kOhm load,

FIG 14 is a diagram representing an example of a discharge of a double stacked graphite/zmc cell with 100 kOhm load,

FIG 15 is a diagram representing an example of a discharge of a double stacked graphite/zmc cell with 5 kOhm load,

FIG 16 is a diagram representing an example of a discharge curve of a hybrid battery/capacitor cell , and FIG 17 is a schematic representation of an example of the IC module (electronic matrix) with the electrochemical energy cell attached thereto

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

In the following description, for the purposes of explanation, numerous specific details are set forth m order to provide a thorough understanding of vaπous example embodiments It will be apparent, however, that some of these embodiments may be practiced without these specific details The details of one or more embodiments are set forth in the accompanying drawings and the description below Other features, objects, and aspects are apparent from the description and drawings, and from the claims Recent advancements m the energy cell design, e g , thm film battery technology, is a promising development that provides not only thin, but also flexible batteries which are sufficiently small so as to enable implementations of numerous applications having volume constraints, such as embedded sensors and wireless sensor networks The disclosed embodiments descπbe thin film batteries that can provide an extremely small and thm physical size, which may aid in "energy harvesting"

In "energy harvesting" applications, energy can be captured and/or stored, m which the energy may be generated by other sources, such as solar, wind, water, vibrational, radio wave, or thermal energy sources In some cases, when combined with "energy harvesting" features, thm film batteries may allow the device they are poweπng to remain m the field almost indefinitely or at least outlive the application The disclosed thm film batteries can be operational throughout a broad range of temperature ranges, making them ideal for many ruggedized applications and environments The disclosed thin film batteries may have little to no toxic effects to the environment, and may be nonexplosive and nonflammable Some embodiments of the disclosed batteries may also operate at a voltage of around IV

Referring to FIGS 1-7, a flexible thm electrochemical cell 10 is presented which may be implemented either as a flexible thin rechargeable battery cell 12 shown m FIGS 1, 4, 6, and 8, as a capacitor unit 14 shown in FIG ₅ , or as a battery/capacitor hybπd structure 16, one example of which is shown m FIG 7 The electrochemical energy cell 10 is a flexible, thm rechargeable energy device, and can be used m low-power, low-maintenance applications, which may be substantially planar as shown m FIG 2, or may be flexibly bent and deformed, as shown m FIG 3, depending on the needs of a particular application The thm electrochemical energy cell 10 can include one or more of the following features a A low voltage requirement (below 1 2 ₅ V) for recharging, which when compared to a larger voltage requirement (e g , 3-4V) can make it easier to recharge the battery remotely using microwatt-level incident RF power b A flexible mechanical design, which can allow batteries to be designed to fit in non-planar contours of specified applications The flexible design can allow the battery to be wrapped around mateπals and devices for applications, such as energy harvesting or changing the thermal characteristics c A flexible chemical design, which can allow the designer several choices m trading off between design factors, such as the open circuit potential, internal resistivity, battery capacity, and sourced current level d A use of hydrated ruthenium oxide as a cathode material m a secondary galvanic cell Ruthenium oxide can be used m a chemical reaction (e g , a reduction- oxidation reaction, or a redox reaction) for battery operation A small amount of ruthenium oxide may be required in the cell The cell is not limited to utilizing only ruthenium oxide Other mateπals (e g , manganese oxide), which can be deposited as a surface layer and capable of a redox reaction, may be formed in a battery with the disclosed techniques e The cell can have flexible applicability, where the battery in the hybπd cell can be suited for sustained power supply, while the capacitor can be useful for rapid deployment of a high power which may be used for poweπng distributed network node devices where it may be required to keep a system running at the maintenance/sleep power level for long peπods of time, while allowing for a high power draw during short periods of "activity" or "on" time peπods An example of systems that can operate in this manner include ad-hoc wireless sensor network nodes In some cases, member nodes of these networks remain in the "listen/sleep" mode, only "waking up" a small percentage of the time to communicate their data or take instruction from other nodes in the network In some embodiments that use a battery withm remote sensors that records environmental conditions, the capacitor can charge quickly with a charging source and the battery may charge slowly, in which the capacitor can trickle charge the battery when the charging source is removed f Activated carbon nanoparticle compounding can be used In some embodiments, nanoparticles can be spread onto a sheet The various particulate structures (e g , cubic, hexagonal) may create non-uniformity spread the ruthenium oxide in the resultant matrix g Embodiments of the cell may have a long operational life The chemical reaction m the cell may not dissolve away mateπal m the battery that would reduce battery life In some embodiments, the reaction may involve a chemical rearrangement, not dissolution, and hence, there may be no byproduct loss, and there can be a long battery life h A redox reaction can be utilized In some embodiments, the battery can utilize a redox reaction, and may not rely on utilizing capacitance Some embodiments can utilize a surface phenomena for charge storage instead of a volume based phenomena i Vaπous types of substrate materials can be used j Zinc can be used to minimize the thickness of the anode and cathode Zinc can be used to reduce weight, lower the thickness of the battery, and increase the energy storage density Zinc can be applied as a nanoparticulate material, and may be inexpensive, thin, and flexible k Two or more layers can be stacked on top of one another In some embodiments, four layers may provide a flexible structure that can be connected m various configurations and have a desired voltage Embodiments may have direct stacking without requiπng full separation on both sides of the cell In some embodiments, the stacking may involve a film with several cells atop of it prior to next film, such that the desired battery voltage can be achieved

1 Embodiments of the battery may be non-flammable Because the battery may not start a fire, it can be useful for hazardous environments, such as dangerous chemical plants or places that can explode, and may be used for vaπous applications including firefighting, military, manufactuπng, chemical, and refinement activities m The batteries can be configurable for various current or voltage requirements by having various parallel/series combinations

The battery/capacitor hybrid provided in the present system can be suited to these applications at least because (1) the battery can maintain the energy requirement for the long "sleep" peπods, (2) the capacitor can provide a large current rapidly over the short peπods of time when the system is consuming a high power, and (3) the (low) requirements for recharging can allow the battery/capacitor hybπd structure to be easily recharged at a distance

Some embodiments of the thm flexible electrochemical cell presented herein can be easily integrated mto a general flexible electronics matrix and may utilize some of the following concepts a Some embodiments of the electrodes of the electrochemical energy cell 10 can have a maximized active surface area, e g , an expanded surface area duπng power generation at the electrode surface This can be achieved through the use of the powdered nano-particulate or particulate R.UO ₂ XH ₂ O or another material, such as manganese oxide, as an ingredient m the cathode material The permeability of the R.UO ₂ XH ₂ O paste may be assured by compounding it with graphite (activated carbon) particles or nanoparticles This approach may also lower the internal resistance of the cell when compared to implementing the cell without the composition The compound may form a screenable conducting paste that can be applied as an extremely thm layer over a flexible substrate, for example polypropylene, to assure a simple manufacturing and thm profile structure b In some embodiments, the electrolyte may be near pH neutral or mildly acidic (pH 3-6 5) to prevent rapid dissolution of the electrode mateπals or package sealing materials This requirement may be accomplished through the use of an ethylene glycol base and weakly acidic solution, or of an ethylene glycol base to which a buffered HNO ₃ solution is added The buffeπng and dilution process can create a pH = 5 mixture This electrolyte can be applied as droplets over the Ruθ ₂ xH ₂ θ/achvated carbon, thus forming a gel-like mixture A counter-electrode made from either Zn, Al, or Pb, or another oxidizable metal, can be pressed over the gel paste The RuO _∑ xH _∑ O /activated carbon /electrolyte/metal foil cell may have an electrochemistry that is close to that of a lead-acid battery and the redox (reduction- oxidation) reaction responsible for power generation, which is close to equilibrium, and allowing for electricity driven recharging c The reaction chemistry may proceed close to equilibrium to allow electrically driven reversibility (recharging), which may be satisfied by the chemical and mechanical structure discussed above d Regarding manufacturing, the electrochemical cell can have a light weight and a low volume As will be presented in detail in further paragraphs, a second plastic sheet can be placed over the entire assemblage and the assemblage can be sealed AU the materials used in the electrochemical energy cell 10 can be flexible and extremely thm so that the resulting Ruθ ₂ xH ₂ O/activated carbon/electrolyte/metal foil cell may be as thm as 0 5 mm and possibly lower A typical zmc anode cell with a surface area of 4 cm may have a weight less than 4 grams, so that a goal of having a light weight for the subject electrochemical energy cell can be attained

Referring to Figures 1, 2 and 4, the thin flexible rechargeable battery cell 12, which may be a single battery cell (FIG 1), a stacked battery cell (FIG 6), or the battery/capacitor hybπd cell 16 (FIG 7), includes a anode electrode unit 20, a cathode electrode unit 22, a separator layer 24 sandwiched between the anode and cathode electrode units 20 and 22, an electrolyte body 26 throughout positioned on and impregnating the separator layer 24, a positive contact terminal 28 in contact with the cathode electrode unit 22, a negative contact terminal 30 m contact with the metal anode electrode unit 20, and the sealing package 32

(e g , Lexan)enveloping the electrochemical energy cell therewithm In some embodiments, there may be a permeable electncally-insulating separator layer 24 saturated with the electrolyte body 26

The thin flexible cells may be manufactured to have a wide range of sizes depending on their intended use In a contemplated embodiment, the active surface area ranges from

0 25 cm to as wide and long as material availability permits The cell thickness may be limited by the thickness of the layers m use, and it is possible to construct a cell having a thickness less than 0 5 mm in some embodiments

Cells may be stacked one to another with seπes or parallel connections to form an expanded cell with higher current-driving capabilities, higher specific capacity, or higher open-circuit potential as required for particular applications Stacking may be achieved by electncal connections constructed internal or external to sealing package In the stacked implementation, shown for example m FIGS 6 and 7, the thickness of the resulting structure can increase commensurately with the number of stacked cells

Referring to FIGS 1-4, 8, as well as 9A-9J, the battery cell 12 can be manufactured from one or more of the following elements a Two squares of flexible adhesive material cut and prepared to form the bottom seal layer 34 and top seal layer 36 In some embodiments, the bottom seal and top seal layers 34, 36 are squares with the edge about 10 cm (for a battery cell 12 with an active area of 4cm x 4cm), which can be formed from non-permeable self-adhesive plastic b Two squares of flexible adhesive material are cut and prepared to become the inner seal frame layers 38 and 40 In each of the inner seal frame layers 38 and 40, a square cutout 42 or 44 is formed in a central region The dimension of the inner seal frame layer 38 and 40 may coincide with dimensions of the bottom and top seal layers 34, 36 The size of the square cutout 42, 44 can define the active area of the electrochemical energy cell 10 c One square flexible graphite foil is cut and prepared to become the graphite backing layer 46 The graphite foil thickness may be about 0 005 inch The dimension of the graphite backing layer square may be larger than the edge of the cutout 42, 44 formed in the inner seal frame layers 38, 40 and smaller than the bottom seal and top seal layers 34, 36 For a battery with 4x4 cm ² active area the graphite backing layer 46 can have a dimension around 6x6 cm ² d A single square of filter paper or other separator mateπal is cut and prepared to become the separator layer 24 The separator layer may be slightly larger than the dimensions of the cutouts 42 and 44 formed m the inner seal frame layers 38, 40 For example, for a battery with 4x4 cm ² active area, the dimensions of the separator layer 24 may be around 4 25x4 25 cm ² The separator 24 may be formed of glass fiber filter paper, standard cleanroom-grade tissue paper, or styrene-grafted fluoπnated ethylene polypropylene among others e A square of the anode metal foil is cut and prepared to become the metal anode layer 52 The dimensions of the metal anode layer 52 can be approximately the same as the graphite backing layer 46, e g , 5x5 to 6x6 cm ² for a battery with 4x4 cm ² active area The anode metal can be formed from zinc foil with a thickness of approximately 0 003 inches

Different oxidizable metals may be used m the system to generate different open- circuit potentials to the galvanic reaction For example, Zn, Al, and Pb may be considered for metal anode layer 52 In addition to sheets of such metals, the use of sputter coated metal powders on flexible backing mateπal are withm the scope Zinc may be used for the metal anode layer Aluminum may be an option for a lower- voltage cell, which may be recharged with a very low (smaller than 1 volt) charging potential f Two strips of the anode metal foil are cut and prepared to become the contact strips 54, 56 The dimensions of the contact strips may be in the approximate range of lcm x 7cm g The powdered cathode material ₅ 8 can be a mixture of a powder of hydra ted ruthenium oxide (note that the chemical composition Ruθ ₂ xH ₂ O, sometimes be referred to and abbreviated in this disclosure as RuOx), particles or nanoparticles and activated (chemical composition C) nanoparticles The volume ratios of the mateπals m the mixture may vary from 0% 10Q% to 100% 0%, depending on the requirements for battery/capacitor and current sourcmg capabilities The battery/capacitor hybπd nature of the device is adaptable by modifying this ratio For example, the activated carbon to hydrated ruthenium oxide volume ratio may change between 10 1 and 1 10 This corresponds to a weight ratio between approximately 16 1 RuOx AC and 1 6 3 RuOx AC In cases, such as for a capacitor design, only activated carbon without hydrated ruthenium oxide may be used Additionally, for a battery/capacitor hybπd design, the volume ratio may be 50% 50% The total weight of the powder mixture used to create the paste may be less than a gram per cm ² of active battery/capacitor area For example, m some embodiments the total weight of the powder mixture used to create the paste may be less than 0 25 gram per cm ² of active battery/capacitor area h The electrolyte may be a mixture of ethylene glycol, bone acid, citric acid, and ammonium hydroxide Other electrolyte compositions can be implemented (e g , ammonium hydroxide and/or citric acid may not be added to the composition in some embodiments) The mixture in the range of pH3 to pH7 (e g , in the range of pH3-pH6 5) is used m the subject cell As an example, the bone acid may be prepared with 5 gram of bone acid that is dissolved in 100 cc of water The citnc acid may be prepared with 40 mg of citnc acid crystals dissolved m 100 cc of water The volume percentages of the components in the electrolyte may be as follows ethylene glycol (0%-50%), bone acid (30%- 100%), and citnc acid (0%-20%), to make up the volume Ammonium hydroxide may be added m trace amount (less than 5mL per 100 mL of electrolyte)

One possible mode of electrolyte is to use the following volume ratios 45% ethylene glycol, 37% bone acid, 18% citnc acid, and 0 5 ml of ammonium hydroxide per 100 mL solution

Ethylene glycol, when present, can be particularly useful for its high viscosity, which may allow cathode particles to be suspended in the solution and present a high surface area available for chemical and Faradaic reactions as well as for double-layer capacitance effects The cells may have layers with other sizes and shapes that are different from the shapes and sizes descnbed herein For example, some cells may have layers that are several feet long and/or wide In some embodiments, a method for prepanng an electrolyte recipe EOl, for example, may be as follows

1 Measure ₅ g of bone acid powder

2 Measure 100 mL of de-ionized DI water 3 Mix the bone acid crystals into the water, and stir well

4 Measure 04 g of citric acid powder

5 Measure 10O mL of DI water

6 Mix the citπc acid powder into the water, and stir well

7 Measure 4 ₅ mL of ethylene glycol 8 Measure 37 mL of mixed bone acid, add to the ethylene glycol and mix

9 Measure 18 mL of mixed citπc acid, add to the ethylene glycol and mix

10 Measure the pH of the mixture

11 If the pH is less than 5, add a predetermined quantity of ammonium hydroxide (NH ₃ or NH ₄ OH), and mix If the pH is still less than ₅ , add further NH ₃ however no more than 0 ₅ mL (e g , approximately three drops) of NH ₃ should be added

12 Mark the EOl bottle and the acid bottles

In an alternative implementation, the electrolyte recipe EGBA may be prepared by the following sequence of operations

1,2,3 Prepare bone acid as in steps 1-3 for the EOl electrolyte 4 Measure 5O mL of ethylene glycol

5 Measure 50 mL of mixed bone acid, add to ethylene glycol and mix Bone acid used for the EOl and EGBA recipe was a 5 g per 100 mL mixture This is a saturated mixture, as the solubility of bone acid is 4 9 g/ 100 mL at 20 ⁰ C The saturation to be used m the electrolyte (EOl) may range between 0 5 g per 100 mL to 5 g per 100 mL The citnc acid used was a 0 4 g/100 mL mixture This is a weak mixture, as the solubility of citric acid is 133 g/100 mL at 22 ⁰ C The saturation used in the electrolyte (EOl as well as EGBA) may range between 0 1 g/100 mL to 40 g/100 mL

EOl electrolyte can have the volume ratios of 45% ethylene glycol, 37% bone acid, 18% citnc acid, and trace amounts of ammonium hydroxide which may be considered to be desired amounts in some embodiments However, other ratios of the constituents are also contemplated in the present disclosure For example, a The volume share of ethylene glycol may vary between 0% to 70%, b The volume share of bone acid may vary between 0% to 100%, but if it is 0% the citric acid is to be at least 30%, c The volume share of citric acid may vary between 0% to 100%, but if it is 0%, the bone acid is to be at least 30%, so that the total amount of all three liquids by volume adds to 100%

As a vaπant of the EOl electrolyte with the bone acid at 50% and citric acid at 0%, 5 the EGBA electrolyte can have volume ratios of bone acid and ethylene glycol of 50 50

Other electrolytic matenals may be considered, including organic acids, phosphoric acid and sulphunc acid

Although the desired pH level for EOl or EGBA, or any other devised electrolyte may be 5, the resulting pH of the electrolyte mixture may vary between 3 and 6 5

10 Other matenals, which may be needed for the assembly of the electrochemical energy cell, may include conductive epoxy matenal, which may be a commercial conductive epoxy material mixed in accordance with instructions from a manufacturer

Refernng further to FIGS 9A-9J the assemblage of the electrochemical energy cell 10

, specifically of the battery cell 12 is shown Refernng to FIG 9A, the bottom seal layer

15 (also referred to herein as the bottom frame layer) 34 is placed on a level surface with the adhesive 60 facing upwardly A contact stnp 54 is placed on the bottom frame layer 34 with a end section 62 of it placed on the central area of the layer 34 to be covered by the graphite backing layer 46 An end 64 of the contact stnp 54 extends beyond the edge of the bottom seal layer 34 The contact stnp 54 thus is securely adhered to the adhesive surface 60 of the

20 bottom seal layer 34 Further, an epoxy layer 66 is spread on the end section 62 of the contact stnp 54

Further, refernng to FIG 9B, the graphite backing layer 46 is placed on the center of the bottom frame layer 34 to cover the end section 62 of the contact stnp 54 and is adhered thereto through epoxy layer 66

25 Refernng to FIG 9C, the inner seal frame layer 38 is placed on the graphite backing layer 46 so that the cutout 42 thereof is centered with the graphite backing layer 46 The self- adhesive surface 68 of the inner seal frame layer 38 faces upwardly The cathode electrode 70 shown in FIG 9C is thus formed

Refernng to FIG 9D, the top seal layer 36 is placed on a level surface with adhesive 30 72 of the top seal layer 36 facing upwardly Next, the second contact stnp 56 is placed on the top seal layer 36 with the end 74 m contact with the central area of the top seal layer 36 An end 76 of the contact stnp 56 extends beyond the edge of the top seal layer 36 in a direction opposite to that of the end 64 of the contact stnp 54 as presented m FIGS 2 and 9J The epoxy layer 78 is spread on the end 74 of the contact stnp 56, and the metal anode layer 52 is placed thereon m the manner identical to the placement of the graphite backing layer 46 of the cathode electrode 70 Further, as shown m FIG 9E, the inner seal frame layer 40 is placed on the metal anode layer ₅ 2 to result in the anode electrode unit 20

Further, as shown in FIG 9F, 4 drops (0 2 mL) of the electrolyte 26 are mixed with 0 5 g of the powder mixture ₅ 8 to form a paste 80 which is considered a cathode material paste A pipette may be used to measure the amount of the electrolyte If any powder remains dry, additional electrolyte may be added

Referring to FIG 9G, the paste 80 is deposited onto the active area of the graphite backing layer 46 exposed withm the cutout 42 of the inner seal frame layer 38 The paste 80 is spread throughout the exposed active area of the graphite backing layer 46 to create an even and thm layer This completes the construction of the cathode electrode unit 22 with the active cathode matenal 80 thereon

Referring to FIG 9H, the separator layer 24 is placed on the cathode electrode unit 22 so as to cover the cutout 42 with the cathode matenal paste 80 therewithin The separator 24 is pressed against the cathode electrode to assure even contact Excessive pressing is avoided in order to prevent the paste underneath the separator layer from having an uneven distribution Referring to FIG 91, the separator layer 24 is impregnated with the electrolyte

26 liquid mostly near the center The consumption of electrolyte 26 for this purpose may be approximately 1 6 mL for a battery cell 12 with an active area of 4 cm x 4 cm Further, referring to FIG 9J, the anode electrode unit 20 is turned so that the adhesive surface 72 thereof faces downwardly, and the top seal surface 36 faces up, and is placed on the cathode electrode unit 22 to sandwich the separator 24 therebetween The protruding ends 64 and 76 of the contact strips 54 and 56, respectively, face in opposite directions and extend external the structure The entire structure is pressed tightly around the edges, as shown by arrows A-A and B-B, to ensure adhesion and a complete seal to form the sealing package The entire battery cell is gently pressed throughout the entire surface to ensure full contact of the mateπals

FIG 2 shows the resulting structure (plan view) of the structured formed by the techniques presented in FIGS 9A-9J Heat sealing or tape-sealing may be performed along the perimeter of the structure

Referring to FIGS 10A-10D, providing an alternative method of formulation the electrochemical energy cell 10 of the present concept, the top and bottom seal layers 34' and 36' are prepared with the center of each of these layers having a cutout 82 and 84, as shown in FIG 1OA, for contact terminals 28 and 30 The cutout 82, 84 may be formed as squares with the dimensions approximately 1x1 cm Further, as presented in FIG 1OB, the graphite backing layer 46 is adhered onto the bottom seal layer 34' The paste 80 made of the powdered cathode material and the electrolyte is spread over the active area formed on the graphite backing layer similar to the step shown in FIG 9C (For the formation of this active area, an inner seal layer may be used in manner similar to the step shown in FIG 9C The inner seal frame layer 38 is placed on the graphite backing layer 46 so that the cutout 42 thereof is centered with the graphite backing layer 46 The self-adhesive surface 68 of the inner seal frame layer 38 faces upwardly This is not shown in FIG lOB-D ) When the cathode electrode unit 22 and anode electrode unit 20 are prepared as shown in FIG 1OB, the separator layer 24 is impregnated with the electrolyte body 26 and sandwiched therebetween, as shown in FIG 1 OC The contact holes 82 and 84 are filled with conductive epoxy to form the negative and positive contact leads 86 and 88 to which the contact strips 54, 56 may be glued, as shown m FIG 1OD Alternatively, the contact strips may be replaced with conductive wires The entire structure is further sealed along its periphery by pressing the edges as shown by arrows A-A and B-B Heat sealing or tape-sealing may be performed along the peπmeter of the structure

FIG 1 shows the cross-section of the resulting structure formed by techniques presented m FIGS 10A-10D The plan view in this case may look similar to FIG 2, however the contacts originate from the center of the cell instead of the edges The ranges for the dimensions of the design elements specified in the assemblage procedures described in the previous paragraphs, may be as follows

1 For the top and bottom seal layers, the square edge size depends on the active area edge A margin of at least 2 cm (and at most 5 cm) may be left around the active area on each side of the top and bottom seal layers For a 4x4 active area battery, the square edge may range between 8 cm to 14 cm

2 In some embodiments, the outer square edge of the inner seal frame layers has to be in the similar size range as for the top and bottom seal layers If a stacked cell structure, such as that depicted in FIG 6, is built, this outer square edge may be smaller than the top and bottom seal layers The cutout edge can define the active area, which has dimensions specified by a particular application requirement

3 The graphite backing layer thickness can depend on available raw materials, and 0 005 inch (0 127 mm) or less may be desirable in some embodiments The edge size of the graphite backing may range between the cutout (active area) edge size and top seal edge size, and is determined thereby 4 The separator layer thickness can depend on the available raw mateπal and 0 015 inch (0 38 mm) or less may be desirable in some embodiments The edge size may range between the cutout (active area) edge size and the graphite backing edge size

5 The metal anode thickness depends on the available raw material 0 003 inch (0 0762 mm) or less may be desirable m some embodiments The edge size may range between the cutout (active layer) edge size and top seal edge size

6 The size of the contact strips are wide enough to provide a sufficient conductive area and long enough to overshoot the margin of the top and bottom seal layers

The form factor may be different from the form factor shown and described above For example, the form factor may differ from square cells in some embodiments, and may be rectangular m shape If a form factor other than a square is to be utilized, the shapes and planar dimensions of the cell layers may be adjusted accordingly

The amount of powder mixture for a 4 cm x 4 cm active area may vary between 0 1 g to 0 5 g The amount can be determined by the size of the surface area The amount of the electrolyte with which the powder mixture is mixed can be scaled from the weight of the powder mixture and should be sufficient to wet the entire amount of powder mixture The amount of electrolyte used to dampen the separator for a 4 cm x 4 cm active area may vary between 02 mL to 4 mL The amount used can be sufficient to dampen the entire separator layer while ensuring that the electrolyte does not leak from the saturated separator Although the inner seal layers 38, 40 are not shown m Figs 10B- 10D, and an alternative process is descπbed for forming the contact terminals, the various structures and fabπcation processes descπbed with respect to Figs 9C-9J may be applied with respect to the configurations shown by Figs lOB-lOD, including the same or similar design elements and manufacturing steps Referring to FIGS 5 and 7, the electrochemical energy cell m the form of capacitor unit 14 may be prepared which includes a pair of graphite sheets 90, 92 with a paste 81 covered thereon The paste 81 may be formed of the powdered mixture containing hydrated ruthenium oxide particles or nanoparticles and activated carbon particles or nanoparticles mixed with the electrolyte (as discussed in previous paragraphs) or, alternatively, may include only a powder of activated carbon particles or nanoparticles suspended in the electrolyte Two graphite sheets with the conductive paste 81 formed thereon sandwich a cellulose porous insulator layer 94 therebetween to form in combination a thm flexible capacitor cell 14 The design presented in FIG 5 yields an electrochemical capacitor of arbitrary geometry to meet energy storage specifications for low-power ad hoc distributed networks The capacitor cell 14 may utilize an active surface enhancement through the use of corrugations 95 formed on the graphite sheets 90, 92 The corrugations 95 may be formed through etching and may be used to increase the effective surface area The corrugations may be formed as square holes, or parallel trenches, or in any shape permitted by etching or other corrugation methods

Similar corrugations may be formed on the surface of the graphite backing layer 46 underlying the paste 80 m the battery cell 12 for the purposes of active surface enhancement The capacitor cell 14 is implemented with an ultra-thm dielectric paste 81 based on hydrated RuO _∑ xH _∑ O mixed with activated carbon (AC) particles or nanoparticles (or just powder of AC) in combination with acid to form a double-layer capacitor 14 The paste 81 is applied on the corrugated (or not corrugated) graphite sheets 90, 92 and dπed

The acid-resistant (for example, cellulous) porous insulator filter paper layer 94 is fitted on the graphite layer 90 or 92 with the paste 81 dπed thereon, and a few drops of the electrolyte 2 ₆ are used to wet the layer 94 The electrolyte 26 includes ethylene glycol, bone acid, citric acid, and ammonium hydroxide combined m proportions similar to those used for preparation of the battery cell 12 The second graphite sheet 92 or 90 is then attached to the sub-assembly to sandwich the insulator layer 94 therebetween, and the edges of the structure are sealed each to the other Although not shown m FIG 5, it may be understood by a person skilled in the art, that two seal layers may be adhered to the graphite sheets 90, 92, so that when pressed together along the periphery thereof, they form the sealing package similar to the Lexan or flexible plastic package 32 of the battery cell 12 shown in FIG 1 to seal the capacitor cell 14 therein The thickness of the cell 14 may be less than 0 5 mm The capacitor cell 14 is perfectly applicable for a "stackable" design with other capacitor cells 14 or with battery cells 19

A multi-cell battery structure or a battery/capacitor hybrid structure may be formed by stacking battery cells 12 and/or capacitor cells 14 each to the other As an example, a double stacked cell structure 10 is shown in FIG 6, while an example of a hybπd battery /capacitor structure 16 is shown m FIG 7 It will be understood by those skilled in the art that FIGS 6 and 7 represent only a specific design example, but any number of electrochemical cells may form the stacked battery structure and/or the hybπd structure, e g , any number of battery cells 12 and/or capacitor units 14 in any order may be stackable in accordance to the pπnciples of the present system Furthermore, the physical placement of the capacitor units and battery cells or of the multiple battery cells integrated together in the same package as shown FIGS 6 and 7 represent only a specific design example, and the physical placement of the capacitor units and battery cells integrated within the same package may vary

Shown in FIG 6, as an example only, but not to limit the scope of the protection available for the present stacked battery cell, the thm flexible electrochemical energy cell 10 includes two stacked battery cells 12 sealed in a single sealing (Lexan or other plastic) package 100 Each battery cell 12 includes the graphite layer 46 with the paste 80 deposited thereon, the separator layer 24 impregnated with the electrolyte 26, and the anode electrode 20 The paste 80 is a powdered mixture containing hydrated ruthenium oxide particles or nanoparticles and activated carbon particles or nanoparticles suspended in the electrolyte 26 The positive contact terminal 28 and negative terminal 30 are attached to the cathode 22 and anode 20 of the respective battery cells The battery cells 12 may be interconnected in parallel and/or seπes by internal and/or external conductors (not shown in the Drawings)

Referring to FIG 7, a particular design example of the hybπd battery/capacitor cell 16 is shown, which shows the battery cell 12 stacked with the capacitor cell 14 The structure serves as an example, and any number of the cells 12 and 14, as well as various arrangements of interconnections therebetween is also contemplated in the present concept As shown m FIG 7, the hybrid cell 16 may include the battery cell 12 stacked with the capacitor cell 14 and interconnected by internal or external connectors (not shown) in parallel and/or seπes, as dictated by a particular application The battery cell 12 includes the graphite layer 46 with the paste 80 dispersed thereon, the separator layer 24 wetted with the electrolyte, and the anode electrode 20 Positive and negative leads 28, 30 are coupled to the cathode 22 and anode 20 The capacitor 14 portion of the hybrid cell 16 includes a pair of graphite layers 90, 92 with the paste 81 deposited on each of them The dielectric layer 94 impregnated with the electrolyte is sandwiched between the graphite sheets 90 and 92 Contact terminals 91, 93 are formed on the graphite sheets 90, 92 The entire stacked structure is enveloped in the sealing package 102 While not shown m the drawing of FIG 7, the inner seal frame layers 38 and 40 may be used in a manner similar to described above and depicted in FIG 9

Multiple samples of the single, double stacked, and hybπd electrochemical energy cells have been fabπcated and subjected to the following tests a Cell charging, for which a constant current was applied to the cell and the voltage across the cell was monitored For an ideal capacitor, the voltage first increased linearly before saturating at its working potential, b Cell charging, for which a constant voltage was applied to the cell, o Load discharge, for which a load was attached across the cell and the potential was monitored This was done with fresh cells just fabπcated, cycled cells which were previously load discharged, and charged cells (current charged), d Self discharge, for which the potential across the cell was measured periodically with no load attached This test was conducted with fresh cells, cycled cells, and charged cells

The potential obtained from the cell self-discharge of the cells over multiple weeks is presented in Table 1

Table 1

In Table 1, the "not tested before" single cell is a cell that was not subjected to any load discharge or current charging, while the "tested" cells have been subjected multiple times to both current charging and load discharges The potential across each cell is seen to remain stable over multiple weeks

FIG 11 illustrates the cell potential during constant 100 μA charging The cell capacitance was estimated to be about 4 5 F

The 100 kOhm load discharge of a single cell is presented m Figure 12 The initial voltage of the cell was 1 2V and the cell potential duπng the discharge was monitored for 2 5 hours The result of a similar test conducted with a 10 kOhm load is plotted in FIG 13 In both tests, after discharging the cell, self-charging was observed In FIG 12 the potential across the cell drops below 0 8V dunng discharge and with the load still connected, the potential πses and remains around 0 8V for more than one hour The same behavior is displayed in FIG 13 under 10 kOhm load discharge

The double stacked cell was also discharged with 100 kOhm load and 5 kOhm load The recorded cell discharge potentials are shown m FIGS 14 and 15, respectively In FIG 14, the discharge was conducted after 100 μA current charging duπng 60 seconds Duπng current charging, the potential across the cell increased to 1 8V Once the 100 kOhm load is connected, the cell potential stays above 1 6V (internal potential presented in Table 1) and then decreases For the diagram shown in FIG I ₅ , no prior current charging of the cell was conducted The initial voltage of the cell was 1 δV The stacked structure stored 30J/cm ³ while the single graphite/zmc cells stored 22J/cm ³

5 FIG 16 shows a diagram representing discharge curve of the battery /capacitor cell presenting a long term discharge which "holds" for over 15 days

FIG 17 shows one particular application of the flexible thm electrochemical energy cell 10 for the IC matrix The cell film 10 is glued to the wafer 96 with IC circuitry 98 formed thereon The electrochemical energy cell 10 is electrically coupled to the IC circuitry

10 98 for poweπng the structure

The description above is intended to illustrate possible implementations and is not restrictive Many variations, modifications and alternatives will become apparent to the skilled artisan upon review of the disclosure For example, method steps equivalent to those shown and descπbed may be substituted therefore, elements and methods individually

15 descπbed may be combined, and methodologies descπbed as discrete may be distributed across many algonthm techniques While this disclosure contains many specifics, these should not be construed as limitations or of what may be claimed, but rather as descπptions of features specific to particular embodiments Certain features that are descπbed in this specification m the context of separate embodiments can also be implemented in combination 0 in a single embodiment Conversely, vaπous features that are descπbed in the context of a single embodiment can also be implemented in multiple embodiments separately or m any suitable subcombmation Moreover, although features may be descπbed above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can m some cases be excised from the combination, and the claimed 5 combination may be directed to a subcombmation or vaπation of a subcombmation Similarly, while operations are depicted in the drawings in a particular order, this should not be understood as requiπng that such operations be performed in the particular order shown or m sequential order, or that all illustrated operations be performed, to achieve desirable results The scope of the disclosure should therefore be determined not with reference to only the 0 particular descnptions above, but also with reference to the appended Claims, along with their full range of equivalence