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Replacement of Electrochemical Batteries PDF Print E-mail
Written by Greg Allen   
Monday, 01 October 2007

I have had several people request for me to post the EEStor patent here on the site... so here it is:

United States Patent # 7,033,406 - Electrical-Energy-Storage Unit (EESU) Utilizing Ceramic and Integrated-Circuit Technologies for Replacement of Electrochemical Batteries

Ultra-Capacitor batteryWeir, Richard D. (Cedar Park, TX); Nelson, Carl W. (Austin, TX)  April 25, 2006

US Cl. 29/623.5 ; 29/623.1
Intl. Cl. H01M 6/00 (20060101)

Abstract

An electrical-energy-storage unit (EESU) has as a basis material a high-permittivity composition-modified barium titanate ceramic powder. This powder is double coated with the first coating being aluminum oxide and the second coating calcium magnesium aluminosilicate glass. The components of the EESU are manufactured with the use of classical ceramic fabrication techniques which include screen printing alternating multilayers of nickel electrodes and high-permittivitiy composition-modified barium titanate powder, sintering to a closed-pore porous body, followed by hot-isostatic pressing to a void-free body. The components are configured into a multilayer array with the use of a solder-bump technique as the enabling technology so as to provide a parallel configuration of components that has the capability to store electrical energy in the range of 52 kWh. The total weight of an EESU with this range of electrical energy storage is about 336 pounds.

References Cited:

U.S. Patent Documents: 5711988 ~ 5738919 ~ 5744258 ~ 5797971 ~ 5800857 ~ 5850113 ~ 5850113 ~ 5867363 ~ 5973913 ~ 6005764 ~ 6078494 ~ 6243254 ~ 6268054

Foreign Patent Documents: JP11147716 ~ WO 93/16012

Other References:   SA. Bruno, D.K. Swanson & I. Burns, High-Performance Multilayer Capacitor Dielectric from Chemically Prepared Powders J. Am. Ceram Soc 76, 1233 (1993). cited by other.  J. Kuwata et al, "Electrical Properties of Perovskite-Type Oxide Thin-Films Prepared by RFSputtering" Jpn J. cited by other.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to energy-storage devices, and relates more particularly to high-permittivity ceramic components utilized in an array configuration for application in ultrahigh-electrical-energy storage devices.

2. Description of the Relevant Art

The internal-combustion-engine (ICE) powered vehicles have as their electrical energy sources a generator and battery system. This electrical system powers the vehicle accessories, which include the radio, lights, heating, and air conditioning. The generator is driven by a belt and pulley system and some of its power is also used to recharge the battery when the ICE is in operation. The battery initially provides the required electrical power to operate an electrical motor that is used to turn the ICE during the starting operation and the ignition system. The most common batteries in use today are flooded lead-acid, sealed gel lead-acid, Nickel-Cadmium (Ni-Cad), Nickel Metal Hydride (NiMH), and Nickel-Zinc (Ni-Z). References on the subject of electrolchemical batteries include the following: Guardian, Inc., "Product Specification": Feb. 2, 2001; K. A. Nishimura, "NiCd Battery", Science Electronics FAQ V1.00: Nov. 20, 1996; Ovonics, Inc., "Product Data Sheet": no date; Evercel, Inc., "Battery Data Sheet--Model 100": no date; S. R. Ovshinsky et al., "Ovonics NiMH Batteries: The Enabling Technology for Heavy-Duty Electrical and Hybrid Electric Vehicles", Ovonics publication 2000-01-3108: Nov. 5, 1999; B. Dickinson et al., "Issues and Benefits with Fast Charging Industrial Batteries", AeroVeronment, Inc. article: no date.

Each specific type of battery has characteristics, which make it either more or less desirable to use in a specific application. Cost is always a major factor and the NiMH battery tops the list in price with the flooded lead-acid battery being the most inexpensive. Evercel manufactures the Ni-Z battery and by a patented process, with the claim to have the highest power-per-pound ratio of any battery. See Table 1 below for comparisons among the various batteries. What is lost in the cost translation is the fact that NiMH batteries yield nearly twice the performance (energy density per weight of the battery) than do conventional lead-acid batteries. A major drawback to the NiMH battery is the very high self-discharge rate of approximately 5 to 10% per day. This would make the battery useless in a few weeks. The Ni-Cad battery as does the lead-acid battery also has self-discharge but it is in the range of about 1% per day and both contain hazardous materials such as acid or highly toxic cadmium. The Ni-Z and the NiMH batteries contain potassium hydroxide and this electrolyte in moderate and high concentrations is very caustic and will cause severe burns to tissue and corrosion to many metals such as beryllium, magnesium, aluminum, zinc, and tin.

Another factor that must be considered when making a battery comparison is the recharge time. Lead-acid batteries require a very long recharge period, as long as 6 to 8 hours. Lead-acid batteries, because of their chemical makeup, cannot sustain high current or voltage continuously during charging. The lead plates within the battery heat rapidly and cool very slowly. Too much heat results in a condition known as "gassing" where hydrogen and oxygen gases are released from the battery's vent cap. Over time, gassing reduces the effectiveness of the battery and also increases the need for battery maintenance, i.e., requiring periodic deionized or distilled water addition. Batteries such as Ni-Cad and NiMH are not as susceptible to heat and can be recharged in less time, allowing for high current or voltage changes which can bring the battery from a 20% state of charge to an 80% state of charge in as quick as 20 minutes. The time to fully recharge these batteries can take longer than an hour. Common to all present day batteries is a finite life and if they are fully discharged and recharged on a regular basis their life is reduced considerably.

SUMMARY OF THE INVENTION  (continued)

In accordance with the illustrated preferred embodiment, the present invention provides a unique electrical-energy-storage unit that has the capability to store ultrahigh amounts of energy.

One aspect of the present invention is that the materials used to produce the energy-storage unit, EESU, are not explosive, corrosive, or hazardous. The basis material, a high-permittivity calcined composition-modified barium titanate powder is an inert powder and is described in the following references: S. A. Bruno, D. K. Swanson, and I. Burn, J. Am Ceram. Soc. 76, 1233 (1993); P. Hansen, U.S. Pat. No. 6,078,494, issued Jun. 20, 2000. The most cost-effective metal that can be used for the conduction paths is nickel. Nickel as a metal is not hazardous and only becomes a problem if it is in solution such as in deposition of electroless nickel. None of the EESU materials will explode when being recharged or impacted. Thus the EESU is a safe product when used in electric vehicles, buses, bicycles, tractors, or any device that is used for transportation or to perform work. It could also be used for storing electrical power generated from solar voltaic cells or other alternative sources for residential, commercial, or industrial applications. The EESU will also allow power averaging of power plants utilizing SPVC or wind technology and will have the capability to provide this function by storing sufficient electrical energy so that when the sun is not shinning or the wind is not blowing they can meet the energy requirements of residential, commercial, and industrial sites.

Another aspect of the present invention is that the EESU initial specifications will not degrade due to being fully discharged or recharged. Deep cycling the EESU through the life of any commercial product that may use it will not cause the EESU specifications to be degraded. The EESU can also be rapidly charged without damaging the material or reducing its life. The cycle time to fully charge a 52 kWh EESU would be in the range of 4 to 6 minutes with sufficient cooling of the power cables and connections. This and the ability of a bank of EESUs to store sufficient energy to supply 400 electric vehicles or more with a single charge will allow electrical energy stations that have the same features as the present day gasoline stations for the ICE cars. The bank of EESUs will store the energy being delivered to it from the present day utility power grid during the night when demand is low and then deliver the energy when the demand hits a peak. The EESU energy bank will be charging during the peak times but at a rate that is sufficient to provide a full charge of the bank over a 24-hour period or less. This method of electrical power averaging would reduce the number of power generating stations required and the charging energy could also come from alternative sources. These electrical-energy-delivery stations will not have the hazards of the explosive gasoline.

Yet another aspect of the present invention is that the coating of aluminum oxide and calcium magnesium aluminosilicate glass on calcined composition-modified barium titanate powder provides many enhancement features and manufacturing capabilities to the basis material. These coating materials have exceptional high voltage breakdown and when coated onto the above material will increase the breakdown voltage of ceramics comprised of the coated particles from 3.times.10.sup.6 V/cm of the uncoated basis material to around 5.times.10.sup.6 V/cm or higher. The following reference indicates the dielectirc breakdown strength in V/cm of such materials: J. Kuwata et al., "Electrical Properties of Perovskite-Type Oxide Thin-Films Prepared by RF Sputtering", Jpn. J. Appl. Phys., Part 1, 1985, 24(Suppl. 24-2, Proc. Int. Meet. Ferroelectr., 6.sup.th), 413-15. This very high voltage breakdown assists in allowing the ceramic EESU to store a large amount of energy due to the following: Stored energy E=CV.sup.2/2, Formula 1, as indicated in F. Sears et al., "Capacitance-Properties of Dielectrics", University Physics, Addison-Wesley Publishing Company, Inc.: Dec. 1957: pp 468-486, where C is the capacitance, V is the voltage across the EESU terminals, and E is the stored energy. This indicates that the energy of the EESU increases with the square of the voltage. FIG. 1 indicates that a double array of 2230 energy storage components 9 in a parallel configuration that contain the calcined composition-modified barium titanate powder. Fully densified ceramic components of this powder coated with 100 .ANG. of aluminum oxide as the first coating 8 and a 100 .ANG. of calcium magnesium aluminosilicate glass as the second coating 8 can be safely charged to 3500 V. The number of components used in the double array depends on the electrical energy storage requirements of the application. The components used in the array can vary from 2 to 10,000 or more. The total capacitance of this particular array 9 is 31 F which will allow 52,220 Wh of energy to be stored as derived by Formula 1.

These coatings also assist in significantly lowering the leakage and aging of ceramic components comprised of the calcined composition-modified barium titanate powder to a point where they will not effect the performance of the EESU. In fact, the discharge rate of the ceramic EESU will be lower than 0.1% per 30 days which is approximately an order of magnitude lower than the best electrochemical battery.

A significant advantage of the present invention is that the calcium magnesium aluminosilicate glass coating assists in lowering the sintering and hot-isostatic-pressing temperatures to 800.degree. C. This lower temperature eliminates the need to use expensive platinum, palladium, or palladium-silver alloy as the terminal metal. In fact, this temperature is in a safe range that allows nickel to be used, providing a major cost saving in material expense and also power usage during the hot-isostatic-pressing process. Also, since the glass becomes easily deformable and flowable at these temperatures it will assist in removing the voids from the EESU material during the hot-isostatic-pressing process. The manufacturer of such systems is Flow Autoclave Systems, Inc. For this product to be successful it is mandatory that all voids be removed to assist in ensuring that the high voltage breakdown can be obtained. Also, the method described in this patent of coating the calcium magnesium aluminosilicate glass ensures that the hot-isostatic-pressed double-coated composition-modified barium titanate high-relative-permittivity layer is uniform and homogeneous.

Yet another aspect of the present invention is that each component of the EESU is produced by screen-printing multiple layers of nickel electrodes with screening ink from nickel powder. Interleaved between nickel electrodes are dielectric layers with screening ink from calcined double-coated high-permittivity calcined composition-modified barium titanate powder. A unique independent dual screen-printing and layer-drying system is used for this procedure. Each screening ink contains appropriate plastic resins, surfactants, lubricants, and solvents, resulting in a proper rheology for screen printing. The number of these layers can vary depending on the electrical energy storage requirements. Each layer is dried before the next layer is screen printed. Each nickel electrode layer 12 is alternately preferentially aligned to each of two opposite sides of the component automatically during this process as indicated in FIG. 2. These layers are screen printed on top of one another in a continuous manner. When the specified number of layers is achieved, the component layers are then baked to obtain by further drying sufficient handling strength of the green plastic body. Then the array is cut into individual components to the specified sizes.

Alternatively, the dielectric powder is prepared by blending with plastic binders, surfactants, lubricants, and solvents to obtain a slurry with the proper rheology for tape casting. In tape casting, the powder-binder mixture is extruded by pressure through a narrow slit of appropriate aperture height for the thickness desired of the green plastic ceramic layer onto a moving plastic-tape carrier, known as a doctor-blade web coater. After drying to develop sufficient handling strength of the green plastic ceramic layer this layer is peeled away from the plastic-tape carrier. The green plastic ceramic layer is cut into sheets to fit the screen-printing frame in which the electrode pattern is applied with nickel ink. After drying of the electrode pattern, the sheets are stacked and then pressed together to assure a well-bonded lamination. The laminate is then cut into components of the desired shape and size.

The components are treated for the binder-burnout and sintering steps. The furnace temperature is slowly ramped up to 350.degree. C. and held for a specified length of time. This heating is accomplished over a period of several hours so as to avoid any cracking and delamination of the body. Then the temperature is ramped up to 850.degree. C. and held for a specified length of time. After this process is completed the components are then properly prepared for the hot isostatic pressing at 700.degree. C. and the specified pressure. This process will eliminate voids. After this process the components are then side lapped on the connection side to expose the preferentially aligned nickel electrodes 12. Then these sides are dipped into ink from nickel powder that has been prepared to have the desired rheology. Then side conductors of nickel 14 are dipped into the same ink and then are clamped onto each side of the components 15 that have been dipped into the nickel powder ink. The components are then fired at 800.degree. C. for 20 minutes to bond the nickel bars to the components as indicated in FIG. 3. The components are then assembled into a first-level array, FIG. 3, with the use of the proper tooling and solder-bump technology. Then the first-level arrays are assembled into a second-level array, FIG. 4, by stacking the first array layers on top of one another in a preferential mode. Then nickel bars 18 are attached on each side of the second array as indicated in FIG. 4. Then the EESU is packaged into its final assembly.

The features of this patent indicate that the ceramic EESU, as indicated in Table 1, outperforms the electrochemical battery in every parameter. This technology will provide mission-critical capability to many sections of the energy-storage industry.

This EESU will have the potential to revolutionize the electric vehicle (EV) industry, the storage and use of electrical energy generated from alternative sources with the present utility grid system as a backup source for residential, commercial, and industrial sites, and the electric energy point of sales to EVs. The EESU will replace the electrochemical battery in any of the applications that are associated with the above business areas or in any business area where its features are required.

The features and advantages described in the specifications are not all inclusive, and particularly, many additional features and advantages will be apparent to one of ordinary skill in the art in view of the description, specification and claims hereof. Moreover, it should be noted that the language used in the specification has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter, resort to the claims being necessary to determine such inventive subject matter.

Readers have left 3 comments.
 No.1  DR
Look's Very good.
Can you provide complete technical specifications ?
What is the capacity ?
How suitable is the battery for Solar Installations ?
Where can you buy it ?
How much will it cost ?
Guest Anthonius F. Slamet (Unregistered) • 2008-01-19 01:02:55
 No.2  Untitled
is it www.eestor.us? What is their official website?
So far as I know,Eestor is subsidiary company of Lockheed Martin Corporation? Then should we contact to this company for barium titinate capacitors?
bariumsalt (Registered) • 2008-05-04 00:53:48
 No.3  dajavue
sounds exactly like altiarnano (nanosafe)in reno Nevada allready shipping these batteries to select oems only
Guest (Unregistered) • 2008-05-17 10:51:38
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