KR100282671B1 - ENERGY STORAGE DEVICE AND METHODS OF MANUFACTURE - Google Patents

Abstract

The dry preunit 10 comprises a plurality of cells 110, 112, 114 of true bipolar structure, which are stacked and joined together to form an integrated and unified structure. Each cell 114 includes two electrically conductive electrodes 111A and 111B spaced apart by a predetermined distance. The cell 114 also includes two identical dielectric gaskets 121, 123 sandwiched between the electrodes 111A, 111B to separate and electrically insulate the electrodes. When the electrodes 111A, 111B and the gaskets 121, 123 are joined together, one or more fill gaps 30 are formed for each cell. Each cell 114 also includes a porous and conductive coating layer 119, 120, which is formed on the surface of each electrode. The coating layer 119 includes a set of central microprojections 127 spaced apart from the peripheral microprojections 125 spaced in close proximity to each other. The microprojections 125 and 127 provide structural support for the cell and provide additional insulation between the electrodes. An energy storage device 10A such as a capacitor is formed by filling an electrolyte in the gap 130 of the dry preunit 10 and then sealing the fill port.

Description

[Name of invention]

ENERGY STORAGE DEVICE AND METHODS OF MANUFACTURE

[Background of invention]

[Reference to Related Applications]

This application is directed to US patent application Ser. No. 07 / 947,414, filed 1002, 9, 18, US patent application Ser. No. 07 / 947,294, filed 1992, 9, 18, and US patent application 07 / 947,294, filed 1002, 10, 7. Partial Serial (CIP) applications of 958,506, which are incorporated in their entirety.

[Field of Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to energy storage devices, and more particularly, to bipolar double layer capacitor type energy storage devices and a method of manufacturing the same.

[Description of Related Technology]

[Energy Storage Device]

Much research has been conducted over the years on reliable and useful electrical storage devices such as capacitors or batteries. In general, a battery has a large energy storage capacity but a low power density. In contrast, electrolyte capacitors have a very high power density but limited energy density. In addition, carbon-based double-layer capacitors have a high energy density, but have a high equivalent series resistance (ERS), so that the power capacity of the carbon electrode is low. Therefore, it would be highly desirable to have an electrical storage device with both high energy density and high power density.

J. Electrochem Soc., Vol., Contributed by B. E. Conway. 138 (# 6), P. 1539 (1991, June), discussed the electrochemical energy storage from "supercapacitor" to "battery" and confirmed the performance characteristics of various capacitor devices.

D. Craig, Canadian Patent No. 1,196,683, Nov. 1985, discusses the utility of an oxide ceramic coated electrode and an electrical storage device based on pseudocapacitance. However, attempts to use the one disclosed above have led to inconsistent electrical properties and unreliability of the capacitor.

The device is not charged up to 1.OV per cell and the leakage current is very large. The cycle life of the device is also very low. In addition, the disclosed packaging is inefficient.

U.S. Patent No. 5,121,288 to M. Matroka and R. Hackbart discussed a storage power source based on the Craig patent, but is not preferred for the invention. Although a capacitor form as a power source for a radiotelephone has been described, a proposal for enabling the capacitor has not been described.

US Patent No. 5,053,340 to J. Kalenowsky discussed a storage power source having a charge equalization circuit. The circuit charges each cell with multiple cells without overcharge. The present invention does not require a charge equalization circuit for fully charging a multicell in a stack form without overcharging an intermediate cell.

IEEE Transactions on Magnetics, Vol. 25 (# 1), P 324 (1989, Jan.), IEE Transactions on Magnetics, Vol. (25) (# 1), P 102 (January, 1989) discussed the pulse power characteristics of high-energy oxide ceramics based on double layer capacitors. In this paper, various performance characteristics are discussed without discussing the structural methodology. The present invention provides a reliable device with more efficient packaging.

Based on Rightmire's initial work in US Pat. No. 3,288,641, carbon electrodes based on double layer capacitors have been extensively developed. A. Yoshia et al., IEEE Transactions on Components, Hybrids and Manufacturing Technology, Vol. CHMT-10, # 1, P-100-103 (1987, March) discussed an electrical double layer capacitor consisting of an activated carbon fiber electrode and a water-insoluble electrolyte. In addition, the package length of the double layer capacitor is shown. The device has a volume of 0.4-1 cc and an energy storage capacity of 1-10 J / cc.

T. Suzuki et al., NEC Research and Development, NO. 82, pp. 118-123, 1986, July, showed that the self-discharge characteristics of a carbon-electric double layer capacitor were improved by using a porous separator material having a thickness of 0.004 inches. A potential problem with carbon based electrodes is the low conductivity of the material and hence the low current density supplied from the device.

The second problem is that the structure of the multicell stack is not in the form of a true bipolar electrode. This problem leads to inefficient packaging and low energy and low power density values.

An interesting example is the following.

Solid state micropower states are described in S. Sekido's Soild State Ionice, vol, 9, 10, pp. 777-782 (1983).

M. Pham-Thi et al. Journal of Materials Science Letters, vol. 5, p. 415 (1986) discussed filtration thresholds and interface optimization in carbon-based solid-state double-layer capacitors.

Various publications have discussed the production of oxide coated electrodes and their application in the chlor-alkali industry for the electrochemical generation of choline. This includes US Patent Nos. 5, O55,169 to 1991, 10, 8, V. Hock et al., US Patent Nos. 4,052,271 to 1977, 10, 4, H. Beer, and 1971, 2, 7, A. US Pat. No. 3,562,008 to Martinsons et al. In general, however, the electrodes do not have the large surface area required for efficient double layer capacitor electrodes.

There is a need for a long term reliable electrical storage device and an improved method for mass production thereof. There is also a need for an improved air storage device having an energy density of at least 20-90 J / cc.

[Packaging of Energy Storage]

As mentioned above, important studies have been conducted for many years on high energy and high power density electrical storage devices. Efficient packaging of active materials with a minimum volume is important for achieving the above object. Space separating the two electrodes in the capacitor or battery is required by electrically insulating the two electrodes. However, for efficient packaging, the space or gap should be minimized. Therefore, there is a need for a method that produces a substantially uniform and small dimension (5 mil (0.0127 cm) or less) gap or space separator.

A common method for maintaining interelectrode separation in electrical storage devices (batteries or capacitors) in which an electrolyte is present is to use electrically conductive porous membranes through which ions can permeate. The membrane is generally located between the electrodes, or a porous separator material such as glass is useful for such applications and is used in aluminum electrolytes and double layer capacitors. However, when separating to sizes 1 or 2 mils (0.00254 to 0.00508 cm) or less, the handling of the material is difficult and the material strength of the capacitor is generally very low. In addition, the open cross-sectional area of the conventional porous membrane separator was 50 to 70%.

Ionic permeable porous polymer separators have been used in carbon double layer capacitors, 1982 by Sanada et al. pp. 224-230, 1986, July, NECR Reserarch and Development, NO. 82, pp. Discussed in 118-112. The separator type as described above has a problem in that the open area is small, which increases the electrical resistance.

In order to prevent electrical contact between two electrode layers when used as a cell, a method of filling the gaps of the electrically insulating layer with photoresist has been disclosed in US Pat. No. 4,774,193 to 1988, 9, 27, J. Wilfried. .

A process for making a thin spacer electrolyte capacitor using a photosensitive polymer resin solution is disclosed in US Pat. No. 4,764,181 to 1988, 8, 16, Maruyama et al. The use of the solution application described in porous double layer capacitors is undesirable for filling porous electrodes.

Other reference examples of general interest are U.S. Patent Nos. 3,718,551, 4,052,271, and 5,055,169. All applications, patents, articles, references and basic examples cited in this application are incorporated in their entirety in this specification.

As seen above, it is very useful to have a method for producing reliable small space separation between electrodes in an electrical storage device with a large opening cross section.

[Summary of invention]

The present invention relates to a new electrical storage device having both high energy density and high power density.

It is an object of the present invention to provide a new method by manufacturing a storage device.

Another object of the present invention is to provide a long term reliable electrical storage device and an improved method for producing the same.

Another object of the present invention is to reduce the gap between the anode and the cathode to provide for the packaging of an efficient electrical storage device, in which the ion conductive electrolyte reduces the electrical resistance.

In summary, this object and other clauses are achieved by an energy storage device such as a capacitor comprising a plurality of cells in bipolar form. The cells are stacked and connected together to provide a device of integrated and unified structure.

Each cell includes two electrically conductive electrodes spaced apart by a firing distance. The cell also includes one or more insulating gaskets that intersect with each other between the electrodes to separate and electrically insulate the electrodes.

When the electrodes and gaskets were joined together, one or more filled gaps were formed for each cell. Each cell also includes a large surface area (porous), electrically conductive coating layer formed on one or more sides of each electrode. The coating layer optionally includes a central microprojection that is spatially spaced apart from peripheral microprojections that are spaced apart.

The microprojections are formed by the latest screen printing or photolithographic printing. The microprojections provide structural support to the cell and provide additional insulation between the electrodes.

The ion conductive medium fills the pores and cell gaps of the large area coating.

[Brief Description of Drawings]

With the accompanying drawings and descriptions, these and other features of the invention and methods for obtaining them will become apparent and the invention itself will be better understood.

1 is an external view of a preunit 10 which is a dry energy storage device constructed in accordance with the present invention.

Figure 1a is an external view of the energy storage device filled with the electrolyte of the present invention.

FIG. 2 is a cross sectional view showing a removable cord 117 A in a storage device taken along line 2-2 of FIG.

2A is a cross-sectional view of the storage device taken along line 2A-2A in FIG.

FIG. 3 is a structural diagram showing an exploded view of the FIG. 1 free unit, showing three cells.

4 is a block diagram of a manufacturing step of the storage device 10A.

FIG. 5 is a plan view of the porous coating layer with the microprojections forming the reservoir portion of FIGS.

6 is a flow chart illustrating the same capacitive circuit as the apparatus 10A.

7 is a structural diagram showing a screen printing method for producing a microprojection on a coating layer used as an energy storage device of the present invention.

8 is a structural diagram showing an electrode holder used in the manufacturing method of FIG.

9 is a structural diagram showing a method for forming a microprojection with a photolithoplast according to the present invention.

10 is an isometric view of a pair of hot rollers used to deposit photoresist at an electrode prior to photolithography.

11 is an isometric view of a mask disposed on the photoresist of FIG.

12 is an isometric view of an exposed portion of an unprotected portion of the photoresist of FIGS. 10 and 11;

FIG. 13 is a cross sectional view of an electrode forming part of an energy storage device, taken along line 13-13 of FIG.

14 is a cross sectional structural view of two bipolar electrodes with a large porous coating layer on an electrically conductive substrate forming one cell.

15 is a structural diagram of a frame used to support thin support material during a dip coating process.

FIG. 15A is a structural diagram of wire used in the FIG. 15 frame. FIG.

Detailed Description of the Preferred Embodiments

[Justice]

The definitions of the following terms are not in absolute meaning.

"Cord" refers to the thin strip material included in the dry preunit manufacturing method. After the initial heating, removing the cord creates an opening.

"Electrically conductive support material" means an electrically conductive metal or metal alloy, an electrically conductive polymer, an electrically conductive ceramic, an electrically conductive glass, or a compound thereof. Metals and metal alloys are preferred for making stock units. The support material should have a conductivity of at least 10 4 S / cm.

"Second electrically conductive material" (having a large area) means a porous coated electrode made of the same or different composites on each side of the support material. Preferred metal oxides of the present invention are independently from tin, vanadium, ruthenium, tantalum, rhodium, osmium, iridium, iron, cobalt, nickel, copper, molybdenum, niobium, chromium, manganese, lanthanum, or lanthanum-based metal alloys or compounds thereof And selected additives such as calcium to increase the electrical conductivity.

"Electrolyte" means an ionically conductive water-soluble or non-aqueous solution or material that electrically charges a dry preunit.

"Cab-O-Sil "Means silica filler from Cabot Coporation, Illinois. Dimensional variations are possible.

"Epoxy" means a polyepoxide product mixed with an epoxy resin or polyamine curing agent mixed with a special curing agent which is generally a polyamine.

MYLAR Means a polyester called polyethylene terephthalate manufactured by DuPont of Wilmington, Delaware. It is generally commercialized in the form of sheets of varying thickness.

"Metal oxide" means an electrically conductive metal oxide.

"Mixed metal oxide" means an electrically conductive oxide mixed with two or more metal oxides.

"Photoresist" is a photocurable material. In general, this is an epoxide or acrylate or a compound thereof.

"ConforMASK" is a negative advertising molecule that is a product of Dynachem from Tustin, California. The polymer is used in a state where the relative humidity is 50% or less.

[Dry Free Unit Energy Storage Device]

With reference to the drawings of FIGS. 1, 2, and 3, a dry preunit 10 which is an energy storage device constructed in accordance with the present invention has been described. The energy storage device is a dry free unit 10 assembled. After the cell is filled with electrolyte, an electrically charged device 10A is formed.

In general, the device preunit 10 is shown in FIG. 3 in an exploded view of the preunit 10 that exemplarily shows only cells 110, 112, 114 formed, prepared, and stacked in accordance with the present invention. It was. In general, the cell has a similar design and structure, and therefore only cell 114, 112 will be described in detail with respect to the second, 2A, 3, and 13 degrees.

The cell 114 includes an electrically conductive first external electrode or base plate 111 A, and an electrically conductive second bipole and an electrode 111 B. The electrodes 11A and 11B on both sides are spatially separated from the edge by two dielectric or electrically insulating gaskets 121 and 123.

When the first and second electrodes 111A and 111B, the insulating gaskets 121 and 123, and the electrically conductive porous material layers (oxides) 119 and 120 are all combined to form the cell 114, A gap 130 (FIG. 2A) filled with air is formed by the element. In the case where the preunit 10 is used, the gap 130 is filled with an electrolyte (not shown) and an apparatus 10 A is made.

For this purpose, an exemplary access or fill port 122 is shown in FIG. 2A to illustrate this purpose, and between gaskets 121 and 123 to fill the gap 130 with electrolyte. Formed. The mill pot 122 is formed by a tab or cord 117A and is inserted between the gaskets 121 and 123 before melting or bonding the gaskets 121 and 123. When the gaskets 121 and 123 are heated, the cord 117A is surrounded by a reflow gasket material, which outlines the fill port 122. The two gaskets become a molten polymer mass that covers the minimum of the electrically active conductive coating layers 119 and 120.

The electrodes 111A and 111B will be considered in more detail and the manufacturing method thereof will be described later. One difference between the electrode 111A and the electrode 111B is that the electrode 111A optionally includes a tab 160A for connection to a power source (not shown).

Another difference other than the selective distinction between the electrode 1111A and the electrode 111B is that the electrode 111A includes one electrically conductive porous coating layer deposited on the support material or the structure 116, and the bipolar electrode 111B on all surfaces. ) Includes two porous coating layers 120, 131 deposited on either side or on either side of the support material or structure 111B. As such, electrode 111B is a true bipolar electrode. It should be understood that both sides of electrode 111A may be coated with a porous, electrically conductive layer.

Another distinction between the electrodes 111A and 111B lies in the robustness of the support structures 111A, 111B. The electrode 111A, which serves as the outer base plate, preferably has a more rigid structure, and thus plays a sufficient role in making the overall structure of the energy storage device 10A solid. The electrode 111B and another similar electrode need not be as rigid as the external electrode 111A. Nevertheless, an additional support structure is required when the device 10A is large, and the internal electrode 111B is used as an additional support structure. In this case, the firmness of the internal electrode 111B is required.

As a result, the support material 116 is thicker than the support material 118. In a preferred embodiment, the support material 116 has a thickness of about 10 mils (0.0254 cm) and the support material 118 has a thickness of about 1 mils (0.00254 cm). Other values can also be selected.

Without departing from the scope of the present invention, the electrodes 111A, 111B and the remaining electrodes of the storage device are parasized in size and dimension in the preferred application. For example, in one application, the device 10A is minimized for cardiac fibrillation. In another application, the total volume of the device is 1 cubic meter or more, used for electric vehicles.

The size of the electrode forms the total capacity of the storage 10 A.

In a preferred embodiment, the electrodes 111A, 111B are rectangular in shape. However, the electrode and the preunit 10 may be of various other shapes such as circular or rectangular. An important feature of the preunit 10 is its flexibility in its design, which is desirable for various applications.

Considering the coating layers 119 and 120 in more detail, the formation method thereof will be described later. In a preferred embodiment, the coringching 119 includes a plurality of microprojections, and the coating layer 120 does not include such microprojections. However, without departing from the scope of the present invention, the coating layer 120 can be designed similar to the coating layer 119.

5 is a plan view of the coating layer 119, which includes a microprojection arrangement and is deposited on the inner surface of the support material 116 or on a flat side. Coating layer 119 is relatively thin, electrically conductive and of large porosity. The arrangement includes two sets of microprojections. The second set includes a plurality of microprojections 127 located centrally.

In a preferred embodiment, the peripheral and central microprojections 125, 127 are similarly designed and are generally semicircular. However, within the scope of the present invention, other shapes such as squares are possible. Each protrusion 126, 127 is about 6 mils (0.01524 cm) in diameter. In another application of the device 10, the microprojections 125, 127 are designed differently. The distance from the center to the center of the spherical microprojection 125 is about 20 mils (0.0508 cm), and the distance from the center to the center of the central microprojections 127 is about 40 mils (0.1016 cm).

The reason why the density of the peripheral microprojections 125 is made higher is to prevent edge shorting. The reason for lowering the density of the central microprojection 127 is to minimize the masking of the electrode surface and to provide separation between the electrode 111A and the electrode 111B. For this purpose, the gasket 121 covers at least a portion of the microprojection 125, but does not cover the microprojection 127.

The peripheral microprojections 125 are closely arranged along the outer periphery of the coating layer 119. Although only four rows of microprojections have been described, additional rows may be added depending on the size and application of the device 10. The central microprojections 127 are similarly arranged in close alignment in the central region 132 of the coating layer 119. As illustrated in FIG. 5, the central microprojection 127 is surrounded by the spherical microprojection 125.

The microprojections 125 and 127 are formed on the coating layer 119 to provide structural supports added to the first and second electrodes 111A and 111B. For example, when the second electrode 111B starts to bend toward the first electrode 111A, the microprojection 127 prevents contact between the electrodes 111A and 111B.

5 further shows a plurality of spacings 133A to 133G, the cord 117A lying to form the fill port 122. As described, the larger sized concave electrode extends somewhat into the central region 132. The smaller sized concave electrode crosses the electrode envelope as two ends protruding out of the opposite axis, thus forming fill ports 113C and 133D.

In this case, the width of the cord is equal to or smaller than the distance from the middle to the center between the central microprojections 127. However, the cord is larger than the center-to-center spacing between the peripheral microprojections 125 to protect the peripheral microprojections from the pinch, which increases the peripheral microprojection spacing upon removal of the cord. To prevent this.

In other words, the width of the cord is similar to the peripheral microprojection spacing and does not require modification of the microprojections.

In the coating layer 120, it performs a function similar to the coating tablet 119, and is deposited on the side of the electrode 111B facing the inner side of the first electrode 111A. In a preferred embodiment, the coating layer 120 does not include microprojections. In another embodiment of the preunit 10, the coating layers 119, 120 are similarly constructed and comprise a microprojection layer.

The manufacturing method of the gaskets 121 and 123 will be described later. The gaskets 121, 123 are generally the same, each arranged in a marked (adjacent and foldable) manner. In summary, the gasket 121 will be described in more detail.

Gasket 121 includes a solid peripheral zone 143 and a pupil central zone 144.

In a preferred embodiment, the cord 117A or a portion thereof lies between the gaskets 121 and 123, extends across the pupil area 144 of the gasket and protrudes out of the peripheral area 143. In another embodiment, the cord does not extend across the full width of the gasket, with only a portion of the cord nested between the gaskets and extending both sides of one side edge of the gasket.

In FIG. 1, the next closest cell 112 will be briefly described. In general, cell 112 is similar to cell 114 in design and structure. The cell includes a bipolar electrode 111B as its first electrode and a second bipolar electrode 111C. In general, the electrode 111B and the electrode 111C are the same, and are displayed to be spaced apart from each other.

The same porous coating 131 as coating 119 is deposited on the surface of the support material 118 facing the electrode 111C. A coating layer 133 similar to the coating 120 is deposited on the support material or structure 140, which forms part of the electrode 111C.

Cell 112 further includes two gaskets 135, 137 that are identical to each other with the gaskets 121, 123 of cell 114. Cord 117B forms a fill port 142 between gaskets 135 and 137.

Cell 100 is substantially similar to cell 114 and includes a first bipolar electrode 111Y, a second electrode 111Z, two gaskets 157 and 159, a cord 117C, a tab 160, and Port 162. In FIG. 3, the internal electrode 111Y is not shown.

6 shows a diagram of a representative capacitive circuit 200 generally having the same function as the apparatus 10A. The circuit 200 describes a cell 114 that is two capacitors C1, C2, a cell 112 that is two capacitors, and a cell 110 that is two capacitors C5, C6. As a result, the device 10 is generally the same as a plurality of capacitors connected in series.

An electrically conductive coating 119 coupled with an ion conductive medium (not shown) in the cell 114 forms the capacitor C1. The ion conductive medium and coating 120 form a capacitor C2. The ion conductive medium and the coating 131 in the cell 112 form a capacitor C3. The ion conductive medium and the coating 133 in the cell 112 form a capacitor C4. Similarly, cell 110 is represented by capacitors C5 and C6.

An important aspect of the invention is the bipolar form of an energy storage device. Like electrode 111B for forming two back-to-back capacitors (such as C2 and C3), the use of a single electrode results in a bipolar electrode (B).

Unless limited by theory, the description of the operation of the capacitive energy storage device helps to understand the enormous value of the electrical double layer at the molecular level. In summary, by explaining FIG. 14, FIG. 3 can be used for reference, where the same number is used (and the porous material is a mixed metal oxide).

14 is a structural sectional view showing enlarged edges of the electrically conductive coating layers 120, 131, 133, and 133B and the supports 118 & 148A.

Although the central support 188 has been described as metal, other materials with electrical conductivity are possible and provide support for the coating. Coatings having large areas provide structures and configurations for energy storage. In FIG. 14, the layer 120 has a large area, a microhole, a central hole, and a large gap discontinuous surface.

Accordingly, the porous coatings 120 and 131 are coated on the support 118 to form the bipolar electrode 111B, and the coatings 133 and 133B are coated on the support 148A to form the bipolar electrode 111C. Form. After the preunit 10 is assembled, the pull tab is removed to form a fill port, the preunit 10 is filled with the electrolyte 190, and the fill port 117D is united so that the apparatus 10A To form.

The device 10A is electrically charged to produce the following results simultaneously.

The coating 120 is negatively filled. Thus, the electrically conductive support 118 conducts electrons. Thus the porous coating 131 is positively filled. Thus, the ion conductive electrolyte transfers ions. An electrical double layer is formed at the electrode-electrolyte interface that forms each capacitance of the circuit 200. Therefore, the surface of the coating portion 133 is negatively filled, and the surface of the coating portion 133B is positively filled. Since porous large area oxides make the effective area of the electrode very wide, the electrical storage capacity of the corresponding device increases dramatically.

In Figures 1 to 5, the preferred description is listed by making a dry preunit 10 which is an energy storage device 10A.

(A) Support material preparation

The support material is selectively etched or cleaned by various conventional pickling and cleaning procedures.

In certain embodiments it is too smooth if the metal surface is not etched. The smooth side sometimes results in improper attachment of the porous coating. The etching forms a moderately rough surface.

1. Wet etching—The preferred procedure is to contact the metal support with a water-soluble inorganic strong acid such as hydrochloric acid, hydrofluoric acid, nitric acid, perchloric acid or a combination thereof. In general, the etching is carried out at a temperature of 50 ° C. to 95 ° C. (preferably 75 ° C.) for 0.1 to 5 hours (preferably 0.5 hour) and washed with water. Acid etching at room temperature is possible. Alkaline etching or hydroxyl etching may be used.

2. Dry etching-roughened support surfaces are obtained by sputtering, plasma treatment, and / or ion milling. A preferred procedure is an Ar RF sputter etch between 0.001 and 1 torr with 1 KeV energy at 13.5 Mhz. Generally, a power density of 0.1 to 10 W / cm 2 is used for 1 to 60 minutes to clean and roughen the surface. Another procedure is to plasmid etch the support with a reactive gas such as oxygen, tetrafluoromethane, and / or sulfur hexafluoride in the vicinity of 0.1-30 Torr for 1-60 minutes.

3. Electrochemical Etching—An electrochemical oxidation treatment in chloride or fluoride solution yields a rough surface.

(B) coating of support material

The coating (ie oxide) is porous and consists of micropores. A large crack (diameter <17 mm) in width of 0.1-1 mu m protrudes to the thickness of the coating portion and exists on the surface. However, an area of 99% larger than the surface area is made from the micropores. The average diameter of the micropores is about 6-12 mm 3.

After various post treatments, the hole structure can be varied to increase the average hole size. For example, steam aftertreatment produces a dual pore distribution. In the micropores, a narrow distribution of micropores having a diameter of about 35 mm 3 (diameter <17 to 1000 mm 3) is formed. The treated active coating has an area of 85-95% resulting from the micropore structure.

As another electrode construction method, the pore size distribution can be varied. The effective large area of the coating is monolith, which is 1000, 10, 000, 100, 000 times wider than the scanning area of the electrode. Pore size, distribution, and area are controlled as the temperature and / or hot water treatment of pyrolysis. In addition, the use of surfactants to make other organic structures or colloidal particles in the coating solution increases the average pore size by approximately 100 to 200 mm 3 with only 5-10% of the surface of the micropore.

In FIG. 13, electrode 111A includes a porous and conductive coating layer 119 formed on one or more surfaces of support material 116. The support material 116 is electrically conductive, strong enough to support the coating layer 119, and maintains the structural rigidity layered on the device 10.

One object of the present invention is to optimize the energy density and power density of the device 10. This object is possible by reducing the thickness of the support material 116 and also by maximizing the surface area of the coating layer 119. The power density of the device 10 can be further optimized by maintaining a low bottom.

The surface area of the coating layer 119 is formed by the BET method known in the art. The surface enhancement showing the surface area optimization of the coating layer 119 is determined by the following equation.

Surface increase = (BET surface area / scanning surface area)

In the present invention, the surface enhancement may be as large as 10,000 to 100,000.

Coating 119 is porous and its porosity is in the range of about 5% to 95%. Exemplary porosity above for efficient energy storage is within 20% to 25%.

In a conventional double layer capacitor, the main resistance of the device is due to the carbon coating layer. In the present invention, most of the device resistance is due to the electrolyte, which has a greater resistance than the porous conductive coating layer.

When the preunit apparatus 10 is filled with the electrolyte, the preparation for filling is completed and the apparatus 10A is formed. The main criterion as an electrolyte is whether it is ion conductive and bipolar. The interface or interface region between the electrode and the electrolyte is represented by a bilayer and is used to describe the electrolytic arrangement within this region. A more detailed explanation of the bilayer theory is given in "Modern Electrochemistry" (Bockris volume 2, 6th edition, chapter 7 (1977)).

The surface area of the coating layer affects the capacity of the device 10A. For example, if the surface enhancement factor is between 1,000 and 20,000, and the bilayer capacity and density are between approximately 10 to 500 μF / cm 2 of the interface area (ie, BET surface area) of the interface, the surface enhancement capacity density is about 0.1 to 10 F / cm 2.

Although the bilayer theory has been described, it will be appreciated that other theories or models, such as the partial injection model, may also be used.

A large area (porous) electrically conductive coating material is applied on the support material.

1. Dissolution Method-Porous coating material is derived from reactive precursors or sol-gel mixtures in solution.

Various methods of application of the precursor mixture are possible, but are not limited to the following. Curing, hydrolysis and / or pyrolysis processes are performed to form a coating on the support. Pyrolysis of metal salts is carried out in an atmosphere (nitrogen, oxygen, water, and / or other inert and oxidizing gases) controlled by a furnace and / or an infrared source.

(a) Dip Coating—The electrode or support is dip into solution or sol-gel, the support is coated with a precursor, and is substantially cured by pyrolysis and other methods. Optionally, the method can be repeated to increase the layer thickness. A preferred treatment procedure is to thermally decompose between 200 and 500 ° C. for 5-20 minutes in an oxygen atmosphere of 5-100% after the support metal is dip into the metal chloride / alcohol solution.

The process is repeated until a certain mass is obtained in the coating. The final pyrolysis treatment is carried out at 250 to 450 ° C. for 1 to 10 hours. Conventionally, the coating part of 1-30 mg / cm <2> is deposited on a support part, and a capacity density is about 1-10 F / cm <2>. Another procedure is to generate a sol-gel solution as ruthenium, silicon, titanium, and / or other metal oxides and to corrode the support as above. By adjusting the pH, water concentration, solvent, and / or additives such as hydroxyl, formamide, and / or surface active agent, the discharge frequency characteristics of the coating can be adjusted.

High relative humidity is maintained during the pyrolysis step to change the starting material to oxide at low temperatures, and pyrolysis treatment at about 300 ° C. in the absence of control of humidity. However, an additional procedure is to maintain at least 50% relative humidity at temperatures below 350 ° C. during pyrolysis.

A preferred method by deep coding a thin (ie 1 mil) support structure is to use the wire frame structure 300 to hold the support material 118 under tension. (Figure 15, 15a)

The wire framing structure 300 includes two or more wires 301, 301A that are greater in length than the width of the support material 118. Each wire 301, 301A is roughly coiled at each end to form two coils 302, 303, the end of which is about 1 cm above the wire plane. Coils 302 and 303 are provided through holes 304 and 305 in the support material. The holes 304, 305 are located at two corners on adjacent sides of the support material.

Two additional wires 301B, 301C may be used on the remaining side of the support material to provide additional support.

(b) Spray Coating—The coating solution is treated on the support by a spray method, cured to increase thickness and optionally repeating the method. A preferred procedure is to treat the substrate with a coating solution at a temperature of 0 to 150 ° C. as an ultrasonic or other spray nozzle with a carrier gas consisting of nitrogen, oxygen, and / or other reactive and inert gases at a flow rate of 0.5 to 5 ml / min. . The coating properties can be controlled by the partial pressure of oxygen and other active gases.

(c) Roll coating—The precursor coating is treated by the roll coating method, cured and optionally countered to increase thickness. It can also be used for the dip coating described above.

(d) Spin Coating-The spin coating method is a conventional technique used for the precursor coating process and is optionally repeated.

(e) Doctor Blading-The Doctor Blading method is used for the precursor coating process and is optionally repeated.

2. Electrophoretic Deposition—Porous or precursor coatings are applied to the support by electrophoretic deposition techniques and are optionally repeated.

3. Chemical Vapor Deposition-Porous coatings or precursor coatings are handled by compatible vapor deposition techniques known in the art.

(C) Electrode Pretreatment

Many pretreatments (conditions) or combinations thereof are known to be useful for improving the electrical properties of a coating (ie, electrochemical inertness, conductivity, performance properties, etc.). The processing includes the following.

Steam-controlled hot water or steam treatment in the atmosphere can be used to reduce leakage currents. The procedure is to contact the coated electrode with steam saturated with water in a closed vessel at a temperature between 150 and 325 ° C. for 1 to 6 hours under autonomous pressure.

2. Corresponding gas—The coated electrode is subjected to a pressurized or reduced pressure once at a temperature between ambient and 300 ° C. with a reactive gas such as oxygen, ozone, hydrogen, peroxide, carbon monoxide, nitrous oxide, nitrogen dioxide, or nitrogen oxide. Contact over. A preferred procedure is to contact the coated electrode with an ozone rate flowing between about 5 to 20 weight percent in air at a temperature between room temperature and 100 ° C. at a pressure of 0.1 to 2000 Torr for 0.1 to 3 hours.

3. Supercritical Fluid—The coated electrode is in contact with a supercritical fluid such as carbon dioxide, organic solvent, and / or water. A preferred procedure is to first increase the pressure, then raise the temperature to supercritical conditions, and then treat with supercritical water or carbon dioxide for 0.1-5 hours.

4. Electrochemical-The coated electrode is placed in a sulfuric acid electrolyte and brought into contact with a sufficient anode current and the next cathode current to release oxygen gas. In one embodiment, the electrode is contacted under conditions of 10 mA / cm 2 in 0.5 M sulfuric acid for 5 minutes to release oxygen gas. The electrode then turns to cathode current and the open circuit potential is between 0.5V-0.75V, preferably between 0.5 and 0.6, more preferably about 0.5V (relative to NHE) to release hydrogen gas.

5. Reactive liquids-The coated electrode is made of torsion peroxide, ozone, sulfoxide, potassium permanganate, sodium perchlorate, chromium (VI) series and / or combinations thereof at temperatures between 100 ° C. and 100 ° C. for 0.1-6 hours Contact with an oxidizing liquid such as an aqueous solution of water. A preferred procedure uses 10-100 mg / l of an aqueous solution of ozone at 20-50 ° C. for 0.5-2 hours, followed by water washing. An additional procedure is to treat the coated electrode in a chromate or dichromate solution.

(D) spacing between electrodes

As various methods, it is possible to know the firing spacing and electrical insulation between the electrodes. The method includes the following.

1. Microprotrusions—Separators 1 25 and 127 between coatings 119 and 120 include mattress-like microprotrusions 127 and 127 of small area and height on the surface of one or more sides of the electrode. The microprojections may be composed of a thermoset, thermoplastic, elastomer, ceramic, or other electrically insulating material.

Some methods applied to the microprojections are listed, but are not limited thereto.

(a) Screen printing—The microprojection is on the electrode surface by conventional screen printing, and screen printing is entitled “SCREN PRINTING” as described below. Various modulus, thermosets, photocured plastics, and thermoplastics are applied to the method. Preferred procedure is acid resistant epoxy or VITON Is to use a solution.

(b) Chemical Vapor Deposition—The microprojections are also placed on the electrode surface by depositing silica, titania and / or other insulating oxides or materials through a mask.

(c) Photolithography-The microprojections are also produced by photolithographic methods entitled "PHOTOLITHOGRAPHIC PRODUCTION OF MICRPROTRUSIONS".

2. Physically thin separator sheet-The separator between the electrodes is a thin, substantially glassy open material. Preferred materials are O.OO1 to 0.005 in (0.00254 to 0.01270 cm) porous glass sheet on Whatman Paper Ltd, located in Clifton, NJ.

3. Separator structure-The separator between porous materials is NAFION Thin castings into substantially open structure films such as polysulfones, or various aero and sol-gels.

4. Air space-The separator between the electrodes is also an air space filled with a water-insoluble or water-soluble electrolyte.

(E) Gasketing

At the edge of the active electrode surface, the materials used for the gaskets 121, 123, 135, 137, 157, 159 contain organic polymers that are stable in the electrical / chemical environment and also in the processing conditions. For example, suitable polymers include polyamide, TEFZEL , Polyelylene (high density and high density), polypropylene, polyolefin, polysulfone, KRATON Other fluorinated or partially fluorinated polymers or combinations thereof.

(F) Cord for Fill Port

The cords 117A, 117B, 117C for forming fill ports (e.g. 122, 142) are of a suitable material with certain special properties, which are different from the gasket material and have a higher melting temperature than the gasket material. And the gasket does not adhere, melt or flow under the heating conditions described herein. Generally, glass, metal, ceramic, and organic polymers or combinations thereof are used.

(G) Stacking

A stack is formed, starting with a gasket material, cord, electrode, gasket, cord electrode, which alternately forms with the base plate before a predetermined number of cells are formed, and finally on the outer top of the stack. The gasket material can be formed.

(H) Assembilng (heating and cooling)

The stick is heated under pressure to cause reflow of the gasket material, the periphery of the electrode material being attached and sealed to adjacent electrodes in the stack, thus forming a stacked unit assembled with the isolated cell. This is done in an inert atmosphere.

(a) Radio Frequency Induction Heating (RFIH) heats the stack causing reflow of gasket material.

(b) Radiant Heating (RH) heats the stack evenly, resulting in reflow of the gasket material. The preferred method is to use 1-100 μm north-rays at 0.5-10 watt / cm 2 for 1-20 minutes.

(c) In the furnace, conductive and / or convective heating, optionally in an inert atmosphere, heats the stack resulting in reflow of the gasket material.

(I) fill port formation

The cord is pulled away from the assembled unit to form a dry preunit with one or more fill ports per cell.

(J) Post-Conditioning

1. Many post-conditioning as reactive gas treatments of stacks or assembled stacks or combinations thereof are useful for improving the overall and long term electrical properties of electrodes and their associated devices. This includes treating pre-step (H) and / or post-step (I) with hydrogen, nitrogen oxides, carbon monoxide, ammonia, and other reducing gases or combinations thereof under reduced pressure or pressure, between room temperature and the temperature of the gasket material. .

2. The second post-conditioning generally done is to adjust the open circuit potential of the electrode after step (F) and to stack the electrode in an inert atmosphere (ie Ar, N ₂ ). This is done using a cathode current without hydrogen evolution.

(K) Filling Dry Free Units

The dry preunit is filled with an aqueous conductive or non-aqueous electrolyte of ion conductivity.

Preferred electrolytes have 30% aqueous sulfuric acid solution and have high conductivity. Water-insoluble electrolytes based on propylene and ethylene carbonate are also used to obtain potentials greater than 1.2 V / cell potential.

The preferred procedure for filling the liquid electrolyte into the dry preunit is to place the preunit in the chamber, place the chamber at a pressure between about 1 torr and 1 μtorr, preferably at 250 mtorr and less than 1 torr, The cell gap is filled with electrolyte.

In other words, the preunit is placed in a vacuum in the electrolyte, so that the gas in the cell gap is removed and replaced by the electrolyte.

In addition, non-liquid electrolytes (poles, solids and polymers) can be used.

In this case, the electrode is coated with electrolyte prior to reflow, and no fill port is required.

(L) Sealing of Fill Port

Fillpots reflow additional polymer films or others onto the opening to seal and form a sealed device. This is generally done by an induction heater that locally heats the film on the pearl pot opening.

(M) Burn-In

Typically the device is fully charged by charging the device in 0.1 V / cell steps at a charge current of about 4 mA / cm 2.

(N) testing

Termination Methods-Several methods for electrical connection to the ultracapacitor bottom plate are used, which will be described later.

1. Bottom tabs 160, 160A-Bottom plates 111A, 1112 are cut to extend beyond the normal gasket periphery. This extension allows for attachment of the wire or ribbon. Typically the extension is a stub from which all oxide material is removed down to the support material and a 5 mil (0.0127 cm) thick nickel ribbon is spot welded to the stub.

2. The silver epoxy-oxide coating is removed from the exposed side of the base plate or the base plate is coated on only one shaft. A clean nickel foil lead or copper plate is electrically connected to the exposed surface, which is possible by bonding them with conductive silver epoxy. Optionally forming an oxide coating.

3. Lugs-Titanium nuts with screws are welded to a thick titanium base plate before coating. The electrical connection of the titanium nuts is by screw attachment.

4. Press Contacts—Before assembling in the device stack, the base plate must be sputtered to clean the surface with the material on its exposed side, ie, titanium, and care must be taken not to overheat the substrate. The clean surface is then sputtered with titanium to form a clean adhesion layer and a gold layer. The gold forms a low contact resistance surface, the electrical contact to which can be made by pressing or wire bonding.

5. Deposit compatible media such as aluminum, gold, silver, etc. by CVD or other means.

The resistance of the device is measured at 1 kHz. The capacity of the device is formed by measuring the chromium required to fully charge the device at a charge rate of about 4 mA / cm 2 relative to the electrode area. Leakage current is measured as the current required to maintain full charge 30 minutes after charging.

The device can modify the structure in accordance with certain applications. By adjusting the thickness of the device, the cell voltage, the electrode area, and / or the ratio of the coating in a rational manner, the device is made as desired and certain conditions are constructed.

The electrode capacitance density (C ′ in units of F / cm 2) is approximately 1 F / cm 2 for coatings of 100 μm overall. Therefore, in order to obtain a large capacity, the thickness of the coating portion is made thicker. The device capacitance C is an urgent electrode area (A having a unit of cm 2) divided by twice the electrode capacitance density and the number of cells (n). (Equation 1)

The leakage current i "is proportional to the electrode area, but the equivalent series resistance ESR is inversely proportional to the electrode area (Equation 2). The general value of i" is not more than 20 A / cm 2.

The total number of cells (n) in the device is equal to the actual voltage (V ') divided by the total device voltage (V) (Equation 3). As the liquid electrolyte, it is possible to increase the cell voltage to 1.2V.

The device height (h) based on the cell gap (h ') and the support thickness (h ") is in cm as in Equation 4 and is determined from the number of cells and the electrode capacitance density.

The ESR of the device is the number of cell get times, the cell gap (h ') and the resistivity (r) of the electrolyte, multiplied by approximately 2 and divided by the area (Equation 5).

The device is configured to meet various applications in consideration of voltage, energy, and resistance conditions. The following examples are not meant to limit the invention.

About 100 KJ to 3 MJ devices in applications to electric vehicles are used. High voltage (about 100 to 1000 V) high energy (1-5 F / cm 2) storage devices have an electrode area of about 100 to 10,000 cm 2.

A device of about 10 to 80 KJ is used to reduce emissions at vehicle start-up in electrically heated livestock applications. The device has an energy of 1-5 F / cm 2, an electrode area of about 100-10000 cm 2 and a precancer of about 12-50V. Optionally, a device configured in parallel with several devices can be configured to meet electrical requirements.

For application to defibrillators, devices with energy of 1-3 F / cm 2, electrode area of 0.5 to 10 cm 2 and voltage of about 200 to 40 OV are used.

Various serial / parallel device structures can be used to apply to a continuous power source.

In the screen printing method 250 of FIGS. 7 and 8, the focus of the method is to make the microprojections 125, 127 in series on the surface of the coating layer, which is a capacitor or a battery, and in particular a dry preunit energy storage device. In an electrical storage device such as (10), it acts as a space separator.

The substrate is usually of a thin metal such as titanium, zirconium, or an alloy thereof. In general, as in conventional capacitor technology, the substrate is in the form of a thin metal plate.

On one or both sides of the substrate is coated with a porous carbon compound or a porous oxide coating. This step is accomplished by a prior art method. The oxide coating acts as the charge resistance of the device.

Optionally, it may be made of a stacked set of electrolyte capacitor electrodes (ie aluminum and tantalum) or battery electrodes (ie lead).

The flat surfaces of the electrodes or adjacent coated substrates shall not be in contact with each other and shall be spaced at even intervals. The epoxy microprojections are made at predetermined uniform intervals.

Sample Holding—Thin coated flat substrates must be seated, and thus forming microprojections on the flat surface of the substrate must be precise and accurate. Of particular importance is the electrode holder 275 at a thin metal sheet (0.1 to 5 mil (0.000254 to 0.0127 cm), especially about 1 mil (0.00254 cm)). When a strong vacuum is applied to a thin sheet, reverse dimples are often formed in the thin sheet, which causes undesirable changes in the physical and electrical properties of the final device.

Electrode holder 275 includes a porous ceramic holder 276, which is useful because the pore size is small enough that no dimples will occur upon application of a moderate or very strong vacuum. The flat ceramic surface of the ceramic holder 276 is in intimate contact with the surface of the electrode 111A, and in this case it should not deform the metal or rupture the coating present. The vacuum using porous ceramics is at least 25 mercury. Preferably the vacuum should be between about 25 and 30, in particular between 26 and 29.

In addition, in order to make the projection of the epoxy even through the screen opening, the ceramic substrate must be made to have the surface and lifetime of the predetermined mechanical holder. The horizontal means that the flat surface of the holder and the surface of the coating for electrical storage are staggered by a deviation of about ± 5 mils (0.0127 cm) or less.

In addition, the electrode holder 275 includes a metal frame 277, which should also be as horizontal as possible, so that a protrusion of uniform size is formed from one end to the other end of the electrode.

Electrode holders 275 are available from many commercial products from Ceramicon Designs, Golden, Colorado. In addition, the sample holder Z76 may be made of a commercially available metal, alloy or sample holder 276 using a commercially available metal, alloy or ceramic.

Generally, sheet electrodes are formed that are 5 in. (12.7 cm) and 7 in. (17.78 cm) coated horizontally and vertically, respectively.

The metal holder 277 has a plurality of pins strategically located, such as three pins 278, 279, 280, which uses a plurality of corresponding holes 281, 282, 283 to connect the electrode 111A. Used to align and position. The holes 281, 282, 283 are generally proximate to the peripheral edge of the electrode 111A in order to preserve the useful electrode surface. In addition, unclean holes are used, and pins are used to align the electrode edges.

A stencil (not shown) with a predetermined open pattern is stretched and seated in a conventional screen print frame (not shown). The screen mesh was removed.

Epoxy elements are mixed and a liquid epoxy is placed on the surface of the stencil and then spread evenly by coating. This is done by using a pressure bar, doctor bar or squeegee.

In general, constant temperature and humidity are important to ensure uniform coating.

Carefully remove the stencil leaving the liquid epoxy protrusions on the oxide surface. Next, the epoxidized protrusions are cured using normal temperature or a high temperature heated temperature of 100 ° C. to 150 ° C. or light rays.

Next, the electrode having the microprojections is combined with other electrodes and assembled in a well process or a dry process.

If dry porosity is used, if dry unit 10 is to be charged, dry unit 10 is back fill as electrolyte.

It is important that the cured epoxy does not react with the liquid electrolyte used in the assembly of the capacitor with the multilayer electrode.

The cured microprojections perform their functions by keeping the spacing between the electrodes constant.

In FIG. 6, the flat surface edges across the country have protrusions 125, which are closer to each other than protrusions 127 in the active or central region of the electrode. The protrusion 125 increases the support at the edges to maintain a constant spacing.

Rods can also be used.

From the above, it is clear that the following points are possible.

Increasing or decreasing the substrate electrode thickness may enable an increase or decrease in the microprojection spacing due to a change in support rigidity.

Other thermosets, thermoelastic polymers, or photocurable epoxy or epoxy derivatives in the prior art can be used.

Other microprojection pattern elements such as square, linear, cross, etc. may be used. In particular, the rod on the perimeter serves as a mechanical support.

If it is necessary to maintain the flowable epoxy resin at a temperature when the viscosity of the flowable epoxy resin becomes suitable for painting in a short time, the screen will be selectively heated.

The heating step following screen printing as a flowable epoxy resin has to be carried out quickly, since the epoxy operating time decreases very quickly.

The electrical storage device produced to have the micro protrusions 125 and 127 is usefully used as a battery, a capacitor, and the like.

The method focuses on fabricating microprojections in series on the alloy or surface of the electrode substrate in relation to the tenth, eleven and twelfth degrees using photolithography. As in the conventional capacitor technology, the substrate is generally in the shape of a thin metal plate.

The photoresist film (1) is allowed to pass through the photoresist film 381 and the electrode 111A through a vacuum lamination using a commercial Dynachem ConforMASK film applicator and Dynachem vacuum model name 724/730, or through a pair of heated rollers 384, 385. 381 is applied to the surface of the electrode 111A.

The exposure is done using a standard 1-7 kW UV exposure source such as mercury vacuum lamp 389.

The ConforMask film applicator is developed using standard conditions, such as 0.5 to 1.0% sodium or potassium carbonate monohydrate, in a developing tank or conveyor equipped water-soluble developer. Optionally, after development, the electrode with microprojections is neutralized in diluted 10% sulfuric acid solution. This removes all of the undesirable nonreactive films leaving only reactive microprojections attached to the electrode surface.

In order to achieve the best physical and electrical performance properties, the material is subjected to a final curing process involving UV irradiation and heat treatment using conventional UV curing equipment and air convection ovens.

In order to manufacture the above-mentioned capacitor and the like, the multilayer electrode is assembled.

[Commercial application]

The energy storage 10 A has various applications such as essential or emergency power, and / or capacitors. The size is 0.1 to 100,00 V or 0.1 to 10 6 cm 3. Conventional voltage ranges include both automotive and other applications.

Examples of such applications include:

To achieve the desired performance, multi-layer devices are arranged in series and / or in parallel in certain embodiments.

The following examples are presented by way of example only. It should not be considered limited in any way.

Example 1

[Production of Dry Free Unit]

(A) Coating method

The support structure is prepared by etching a 1 mil (0.00254 cm) titanium sheet with 35% HNO ₃ /15% / HF at 60 ° C. for 5 minutes. Base plate is 5 mil (0.0127 cm) of titanium.

Oxide coating solutions are 0.2M rudennium trichloride trihydrate and 0.2M niobium contaminant in T-butanol.

The etched Ti sheet is placed and dipcoated in the solution under normal conditions. The coated sheet is removed after 1 second in the solution.

After each coating, the oxide is dried at 70 ° C. for 10 minutes, pyrolyzed at 350 ° C. for 10 minutes, and removed to cool at normal ambient temperature.

The dip toting step repeats coating about 10 times (or a predetermined number of times) while rotating the Ti sheet to alternately dip both shaft portions. A thickness of about 10 μm is obtained.

The fully coated sheet is finally heat treated at 350 ° C. for 3 hours at room temperature.

(B) pretreatment

The coated electrode is contacted with saturated salt in a hermetically sealed container at 280 ° C. for 3 hours under magnetic pressure.

(C) spacing

The microprojections are screen printed on one side of the electrode, named "SCREEN PRINTING" as described below. Screen print on one side of epoxy. The epoxy compound is EP 21 AR from Masterbond, Hackensack, NJ.

The epoxy protrusions set at 150 ° C. for 4 hours in air. The coated electrode is then die stamped to the desired shape.

(D) gasket

An excised high density polyethylene (HDPE, improved pore resistance and adhesion) with an outer periphery is the same as for the electrode and is 1.5 mil (0.00381 cm) thick and 30 mil (0.0762 cm) wide and is located on the electrode on the same side as the microprojection. It is instantaneously heated and laminated. The HDPE is Philips-Joana's PJX 2242 from Illinois Ward rod.

(E) code

One cord 0.9 mil (0.00229 cm) wide and 10 mil (0.0254 cm) wide (Dupont T ² TEFZEL with slit in the machining direction) Film 90 ZM) lies across the narrow dimensions of the gasket and the electrode surface and is arranged between the microprojections. The position of the cord is one of the three positions of the center, the left side of the center, and the right side of the center.

The second HDPE gasket rests on the first gasket and nests the cord between the two gaskets.

The second gasket is instantaneously heated to attach to the first gasket and to hold the cord in place.

(F) stacking

Electrodes / Microprotrusions / Gaskets / Cords / Gasket Units are nonmetallic (ceramic) arrays starting from 5 mil (0.0127 cm) base plate up to a specified number of cells and ending with a 5 mil (0.0127 cm) base plate with cord arrangement Stacked as fixtures, so they are stacked on the left, center, and right in repeating cycles of three units. Low pressure is applied to the top of the stack through the ceramic piston block to maintain uniform alignment and to contact the entire stack.

(G) reflow

A radio frequency induction heater (2.5 kW) is used to heat the stack. The stack is centered with three turns of 3 in (7.62 cm) diameter coils and heated for 90 seconds at a 32% power setting. The molten unit is cooled at room temperature.

(H) code removal

Remove the cord by carefully pulling the exposed end of the cord to leave the open fill port open.

Example 2

Another manufacture of dry preunit

(A) Coating method

The support structure is made by etching a 1 mil (0.00254 cm) titanium sheet at 75 ° C. with 50% HCl for 30 minutes.

Oxide coating solutions are 0.3 ruthenium trichloride trihydrate and 0.2 M tantalum contaminants in isopropanol.

The etched Ti sheet is dip-coated in the solution under normal conditions. The coated sheet is removed after 1 second in the solution.

After each coating, the oxide is dried for 10 minutes at 70 ° C. in a normal atmosphere, and a flow of 50% oxygen and 50% nitrogen is pyrroled at 330 ° C. for 15 minutes at 3 cubic feet per hour, and at normal temperature to normal temperature. Cooled and removed

The dip coating step is repeated about 30 times (or a predetermined number of times) while firing the Ti sheet to alternately dip both sides.

The fully coated sheet is subjected to a return heat treatment for 3 hours at the above conditions.

(C) spacing

VITON The microprojections are screen printed on one side of the country named "VII. SCREEN PRINTING" as described below.

VITON The protrusions set at 150 ° C. for 30 minutes in air. The coated electrode is then sprouted to the desired shape.

(D) gasket

Modified high density polyethylene (HDPE, improved pore resistance and adhesion), whose outer periphery is the same as for the electrode and has a thickness of 1.0 mil (0.00254) and 20 mil (0.058 cm) wide, is instantaneously heated and laminated on both sides of the electrode. The HDPE is Philips-Joana's PJX 2242 from Rad, Illinois.

(E) code

TEFLON 1 mil (0.00254 cm) in diameter One cord, a tungsten wire coated with, lies across the narrow size of the gasket and the electrode surface and is arranged between the microprojections. The position of the code is one of three positions: center, left of center, and right of center.

(F) stacking

Electrodes / microprotrusions / gaskets / cord / gasket units are stacked on a 2 mil (0.00508 cm) base plate starting with a 2 mil (0.00508 cm) base plate up to the desired number of cells, and thus three units It is located on the left side, the center, and the right side in this repeated cycle.

(G) reflow

The HOPE gasket was reflowed in nitrogen at 125 ° C. for 120 minutes to reflow the thermoplastic.

(H) code removal

The cord is removed by pulling the exposed end of the cord, leaving the open mill port.

Example 3

[Other Manufacturing of Dry Free Units]

(A) Coating method

The magnetic structure is made by etching a 1 mil (0.00254 cm) titanium sheet with 50% HCl at 75 ° C. for 30 minutes. The base plate is 10 mil (0.0254 cm) titanium.

Oxide coating solutions are 0.2M ruthenium trichloride trihydrate and 0.2M tantalum contaminants in isopropanol.

The etched Ti sheet is dip-coated in the solution under normal conditions. The coated sheet is removed after 1 second in the solution.

After each coating, the oxide is dried at 70 ° C. for 10 minutes in normal atmosphere, pyrrolyized at 330 ° C. for 15 minutes, and cooled to normal temperature in normal atmosphere and removed.

In the dip coating step, the coating is repeated about 10 times (or a predetermined number of times) while rotating the Ti sheet to alternately dip both sides.

The fully coated sheet is finally heat treated at 330 ° C. for 3 hours under normal atmosphere.

(B) pretreatment

The coated electrode is in contact with saturated steam in a hermetically sealed vessel at 260 ° C. for 2 hours under magnetic pressure.

(C) spacing

The microprojections are screen printed on one side of an electrode named "SCREEN PRINTING" as described below. The epoxy compound is EP21AR from Hackensack, Master Bond, of New Jersey.

The epoxy protrusions set at 150 ° C. for 4 hours in air. The coated electrode is then sprouted to the desired shape.

(D) gasket

A modified high density polyethylene (HDPE, improved pore resistance and adhesion) of 1.5 mil (0.00381 cm) and 30 mil (0.0762 cm) wide, with the periphery as in the case of the electrode, was instantaneously heated laminated on both sides of the electrode. The HDPE is Philips-Joana's PJX 2242 from Rad, Illinois.

(E) code

One cord (TEFZEL) with a thickness of 1 mil (0.00254 cm) and a width of 10 mil (0.0254 cm) ) Lies across the narrow dimensions of the gasket and the electrode surface and is arranged between the microprojections. The position of the code is one of three positions: center, left of center, and right of center.

2nd HDPE The gasket lies on the first gasket which overlaps the cord between the two gaskets.

The second gasket is instantaneously heated to attach to the first gasket and to fasten the cord immediately.

(F) stacking

Electrodes / microprotrusions / gaskets / cords / gasket units are stacked on top of a 10 mil (0.0254 cm) base plate (0.0254 cm) base plate to the firing number of cells, thus allowing three units to be repeated at left, center and right Stacked in

(G) reflow

The gasket is reflowed in nitrogen at 160 ° C. for 45 minutes to reflow the thermoplastic. The unit is cooled in normal temperature nitrogen.

(H) code removal

Remove the cord by pulling the exposed end of the cord to leave an open fill port.

Example 4

[Other Manufacturing of Dry Free Units]

(A) Coating method

The magnetic structure is prepared by etching 1 mil (0.00254 cm) titanium sheet with 50% HCl at 75 ° C. for 30 minutes. The base is 5 mils (0.0127 cm) of titanium.

Oxide coating solutions are 0.2 M ruthenium trichloride trihydrate in isopropanol and 0.2 M Ti (di-isopropoxide) bis 2,4-pentanedionate in ethanol.

The etched Ti sheet is dip-coated in the solution under normal conditions. The coated sheet is removed after 1 second in the solution.

After each coring, the oxide is dried at 70 ° C. for 10 minutes in normal atmosphere, pyrrolyized at 350 ° C. for 5 minutes, and cooled to normal temperature in normal atmosphere and removed.

In the dip coating step, the coating is repeated about 10 times (or a predetermined number of times) while rotating the Ti sheet to alternately dip both sides.

The fully coated sheet is finally heat treated at 350 ° C. for 3 hours in an oxygen atmosphere.

The microprojections are thermally sprayed through a mask on one side of the electrode. The thermally sprayed material is E. Wilmington, Delaware. children. It is TEFLON of Dupont de Nemesa.

The TEFLON protrusions cure at 300 ° C. for 0.5 hour in air. The coated electrode is then sprouted to the desired shape.

(D) gasket

Modified high density polyethylene (HDPE, improved pore resistance and adhesion), the outer periphery being the same as for the electrode and having a thickness of 1.5 mil (0.00381 cm) and 30 mil (0.0762 cm) wide, was instantaneously heated laminated on both sides of the electrode. The HDPE is Philips-Joana's PJX 2242 from Illinois Ward Rad.

(E) code

One cord (TEFZEL) 1 mil (0.00254 cm) thick and 10 ml (0.0254 cm) wide ) Lies across the narrow dimensions of the gasket and the electrode surface and is arranged between the microprojections. The position of the code is one of three positions: center, left of center, and right of center.

2nd HDPE The gasket lies on the first gasket which overlaps the cord between the two gaskets.

The second gasket is instantaneously heated to attach to the first gasket and to fasten the cord immediately.

(F) stacking

Electrodes / microprotrusions / gaskets / cord / gasket units are stacked on top of a 5 mil (0.0127 cm) base plate starting with a 5 mil (0.0127 cm) base plate unit up to the desired number of cells, and thus three Units are stacked on the left, center, and right sides in repeating cycles.

(G) reflow

The gasket is reflowed in nitrogen at 190 ° C. for 30 minutes to reflow the thermoplastic. The unit is cooled in normal temperature nitrogen.

(H) code removal

Remove the cord by pulling the exposed end of the cord to leave the open fill port.

Example 5

[Other Manufacturing of Dry Free Units]

(A) Coating method

The magnetic structure is made by etching 0.8 mil (0.002032 cm) of zirconium sheet with 1% HF / 20% HNO ₃ at 20 ° C. for 1 minute. The base plate is 2 mil (0.00508 cm) zirconium.

Oxide coating solutions are 0.2M ruthenium trichloride trihydrate and 0.11M tantalum contaminants in isopropanol.

The deposited Ti sheet is put in the solution under ordinary conditions and dip coated. The coated sheet is removed after 1 second in the solution.

After each coating, the oxide is dried at 85 ° C. for 10 minutes in normal atmosphere, pyrrolyized at 310 ° C. for 7 minutes, and cooled to normal temperature in normal atmosphere and removed.

In the dip coating step, the coating is repeated about 10 times (or a predetermined number of times) while rotating the Ti sheet to alternately dip both sides.

The fully coated sheet is finally heat treated at 310 ° C. for 2 hours in a normal atmosphere.

(C) spacing

The microprojections are thermally sprayed through a mask on one side of the electrode. The thermally sprayed material is E. Wilmington, Delaware. children. It is TEFLON of Dupont de Nemesa.

The TEFLON protrusions cure at 310 ° C. for 1 hour in air. The coated electrode is then sprouted to the desired shape.

(D) gasket

Modified high density polyethylene (HDPE, improved pore resistance and adhesion), whose outer periphery is the same as for the electrode and is 1.5 mil (0.00381 cm) thick and 30 mil (0.0762 cm) wide, is instantaneously heated and laminated on both sides of the electrode.

(E) code

1 mil (0.00254 cm) diameter TEFZEL coated with tungsten wire One cord is placed across the narrow size of the gasket and the electrode surface and is arranged between the microprojections. The location of the chord is one of the three location layers: center, left of center, and right axis of center.

The second polypropylene gasket lies on the first gasket which overlaid the cord between the two gaskets.

The second gasket is instantaneously heated to attach to the first gasket and to fasten the cord immediately.

(F) stacking

Electrodes / microprotrusions / gaskets / cord / gasket units are stacked on top of a 2 mil (0.0508 cm) base plate, starting with a 2 mil (0.0508 cm) base plate unit up to the desired number of cells, and thus three Units are stacked on the left, center, and right sides in repeating cycles.

(G) reflow

The gasket is reflowed in nitrogen at 195 ° C. for 60 minutes to reflow the thermoplastic. The unit is cooled in normal temperature nitrogen.

(H) code removal

Remove the cord by pulling the exposed end of the cord to leave an open fill port.

Example 6

[Peeling of Cell Gap Space]

The dry preunit 10 is filled with an electrolyte by the following procedure. Any dry preunit structure may be used.

(H) Back Fill

Remove the cord by hand to open the fill port. The stacked units are placed in the discharge chamber and discharged to 35 mtorr or less for 5 to 60 minutes. The liquid electrolyte 3.8MH ₂ S0 ₄ , with the air drawn out with nitrogen, is introduced into the chamber and fills the discharged space between the electrodes.

(I) sealing of the fill port opening

The preunit filled with electrolyte is removed from the chamber. To remove excess electrolyte, wash with deionized water and dry. An HDPE film (1.5 mil (0.00381 cm thick)) is placed over the fill port opening and the port is heated and sealed.

(J) Conditioning

The device is fully charged starting with 0.1V / cell and increasing by 0.1V / cell until 1V / cell.

(K) test

The device is tested in a conventional manner, with a capacity density of at least about 0.1 F / cm 2 for one cell with 1 V / cell with a leakage current of 25 μmA / cm 2. The height of the 10V device is only 0.05 ", the height of the 40V device is only 0.13" and the 100V device is only 0.27 ".

Performance characteristics for the structure and form of the various devices based on the sulfuric acid electrolyte are shown in Table 1.

TABLE 1

Example 17

Another Backfill of the Dry Free Unit

The dry preunit 10 is filled with an electrolyte through the following process. Any dry preunit structure may be used.

(H) Backfill

The code is removed to open the fill port. The stacked units are placed in the discharge chamber and discharged up to 35 mtorr for 5 to 60 minutes. 0.5 M KPF ₆ of a liquid non-aqueous electrolyte of propylene carbonate with air removed as nitrogen is introduced into the chamber and fills the exhaust space between the electrodes.

(I) sealing of the fill port opening

The prefilled electrolyte is removed from the chamber and excess electrolyte is removed. An HDPE film (1.5 mil (0.00381 cm thick)) is placed over the fillport opening and the port is momentarily heated to seal.

(J) Conditioning

The device is fully charged starting with 0.1V / cell and increasing by 0.1V / cell until 1.5V / cell.

(K) test

The device is tested in a conventional manner with a leakage current of about 100 μA / cm 2 and 1.5 V / cell, with a capacity density of about 4 Mf / cm 2 for 10 cell devices.

Example 8

[Post-processing conditions of the device]

In order to control the stop potential of the electrode, using the post-conditional technique as various gases, the electrode properties of the device (Table 3) are shown as follows. It is possible to charge the multi-cell device filled with 46M sulfuric acid electrolyte to 1V / cell or more. And a decrease in leakage current was observed. This treatment has been done before, during, and after the reflow of the gasket material. In the gas treatment used to reflow the gasket at low temperatures, the atmosphere is replaced with an inert gas such as nitrogen or argon during the reflow. In order to process after reflow of the gasket material, the tab is removed before processing. During the treatment the air is vented and the reactive gas is periodically filled.

TABLE 3

[Formation of micro protrusions by screen printing]

Example 9

[Application of Epoxy Microprojection by Screen Printing on Porous Coating on Thin Substrate]

(A) Screen preparation-325 mesh stainless steel is spread on a standard screen printing frame. On the screen is a (Eexter Epoxy 608 clear) edge bonded to a 1-15 mil (0.00254 to 0.00381 cm) thick brass sheet having holes or etched holes (diameter 6.3 mil (0.016 cm) in a predetermined pattern). The screen mesh is removed from the area covered by the brass sheet, leaving the brass sheet edge attached to the screen mesh attached to the frame.

(B) Sample Holding—Vacuum was applied on a porous alumina holding plate with an average pore diameter of 10 μm and used to support the coated porous oxide material with a thickness of 1 mil (0.00254 cm) during printing.

(C) Epoxy-Two component epoxy Master Bond EP21AR is modified to have a predetermined viscosity (thixotropic, 300,000 to 400,000 cps) by addition of a silica filter. Epoxy filled to the desired viscosity can be ordered from Master Bond, Hackensak, New Jersey. The epoxy is prepared in one order. Useful life as a flowable liquid is about 30 minutes.

(D) screen printer parameters

Squeegee Speed 1-2 in / s

Snap off 20-30 mil (0.0508 to 0.0762 cm)

Constant temperature and humidity of the epoxy is important in forming a flat coated coating. Conventional conditions were at a relative humidity of about 40 to 70% and a temperature of about 20 to 25 ° C.

(E) Printed Epoxy Pattern—Epoxy bumps were constructed that were substantially 1 mil (0.00254 cm) in height and approximately 75 mil (0.019 cm) in diameter. The conventional electrode pattern is composed of microprojections arranged at 40 mil (0.1016 cm) spaced from center to center. In addition, the microprojectile density at the electrode periphery was increased by reducing the center-to-center spacing to 20 mils (0.508 cm). Screen printed epoxy compositions are cured at 150 ° C. for a minimum of 4 hours.

Example 10

[Screen Print Formation of Epoxy Microprojection]

(A) Screen Preparation—Without emulsion on the surface, 230 or 325 meshed screens (8 × 10 stainless steel) mounted on a standard printing frame are used as the base piece. Etched, drilled or perforated stencils (60 x 85 molybdenum) are edges glued to the back of the screen using the Dexter Epoxy 608 Clear on Nexter. MYLAR Is placed on a stencil-screen unit and pressure is applied to purchase the epoxy in a uniform layer.

The screen is then flipped, epoxy is applied to the top side of the screen, MYLAR The sheet is placed over the area and the epoxy is smoothed. Next, MYLAR on the upper side of the screen Is removed. The screen-stencil assembly is then concentrated in an oven at 120 ° C. to cure the epoxy for 5 minutes with normal air. It is also possible to cure the epoxy for 30 to 60 minutes at normal temperature.

MYLAR on the rear axle after removing the screen-stencil from the oven Carefully peels off immediately. Next, the mesh screen on the upper side is cut with a sharp edge, which must be done carefully to prevent the stencil from being cut. When removing the mesh on the stencil pattern, a thermally stable thermoset adhesive (ie epoxy resin) is MYLAR The cut mesh is covered with a stencil periphery and the epoxy is smoothed so that the screen is sharply attached to the stencil. The epoxy is cured in the oven for 5 minutes. The result is a stencil spread taut by the screen, ready for printing.

(B) Sample holding—porous ceramic holding (ie, FIG. 8) plate having a pore diameter of 4.5-6 μm and porosity of 36.5% (possible 30-60% porosity) (Ceramicon Designs, Golden, Colorado, P − 6-C material is used to hold a 1 mil (0.00254 cm) thick porous oxide coated material during printing by applying a vacuum through the porous ceramic plate. The ceramic plate is cut into predetermined dimensions (size and shape of the substrate to be printed). The ceramic plate is then inserted into an aluminum (steel or the like) frame 277 and an epoxy or other adhesive that can be mounted to a screen printer. The ceramic is then ground flushed to the metal frame as smoothly as possible. Next, pins 278, 279, and 280 are positioned in the holes 281, 282, and 283 to hold the substrate at a predetermined position.

(C) Epoxy-Master Bond EP 21 ART (Component epoxy with a thickness of 150,000 to 600,000 cps (33 weight percent polyaminehardner, 67 weight percent liquid epoxy resin)).

The epoxy is made to order and prepared. Useful life as a flowable liquid is about 30 minutes.

(D) screen printing parameters

Squeegee Speed 1-2 in / s (depending on epoxy viscosity)

Snap off 20-30 mil (0.0050 to 0.0076 cm) (adjusted relative to screen tension)

(E) Printed Epoxy Patterns—Epoxy bumps were constructed that were substantially about 1 to 1.25 mil (0.00254 to 0.00316 cm) in height and about 7.5 mil (0.019 cm) in diameter. The conventional electrode pattern is composed of microprojections arranged at 40 mil (0.1 cm) spaced from center to center. In addition, the microprojection density at the electrode periphery was increased by reducing the distance from center to center to 20 mil (0.0508 cm). Screen printed epoxy compositions are usually cured at 150 ° C. for 4-12 hours in air.

Example 11

[Another Screen Printing Parameter]

(A) Separator Bump-Separator bumps have a height of 0.01 to 0.004 in (0.00254 to 0.01016 cm) and a width of 0.006 to 0.012 in (0.01524 to 0.03038 cm). The separator bumps are formed by dots, squares, squares, or a combination of these shapes. The width of the bump increases as the bump height increases.

(B) Separator Patterns-Two patterns, an active field area and a bounding border area, have separator bumps located at 0.040 and 0.040 in (0.1016 cm) horizontally and vertically on an electrode substrate, and are generally dot-shaped. The BBA has an increased bump density with a center-to-center spacing of O.O 2 O and O.O 2 O in (0.0508 cm), respectively. The horizontal lines of the rectangles alternate between the array of dots.

(C) Screen preparation-The design of the separator configuration is performed by CAD system. CAD electronic data is converted into a "Gerber polt file". In order to produce a stencil having a predetermined thickness for a screen printer, the screen preparation particles use the plot data. The screen can be used from Screen Manufacturing Technologies of Santa Clara, California.

(D) electrode vacuum plate (Warkholder)

Porous ceramic plates (Ceramicon Designs, Golden, Colorade, P-6-C materical), which are 0.050 smaller than the electrode periphery, are installed and the bottom face is ground flash and parallel for screen printer installation. Multi-layered pins are inserted in the center electrode edge portion forming the corner stop for electrode substrate placement.

(E) Epoxy-Two component epoxy Master Bond EP21AR is transformed to the viscosity of firing (thixotropic, 300,000 to 400,000 cps) by the addition of a silica filter. Epoxy with the desired viscosity is ordered from Master Bond, Hackensak, New Jersey. The epoxy is prepared by order. The useful life of the flowable liquid is about 30 minutes.

(F) screen printing parameters

[Formation of micro protrusions by photolithography]

Example 12

Fabrication by hot roller photolithography of micro protrusions

(A) Highly applicable solder mask Confer MASK with thickness of 1.5 mil (0.0038 cm) 2000 is cut to the same size as the electrode.

(B) Confer MASK on electrode material surface 111A. After the film was placed to apply the photoresist film 381, the release sheet 382 between the photoresist film 381 and the electrode 111A was removed, and the laminate was heated at 150 ° F. for the rollers 384 and 385. Through, the photoresist film 381 is attached to the electrode surface 111A. Next, the polyester cover sheet 382 A is removed on the outer side of the photoresist film.

(C) A dark field mask 387 including horizontally-transparent transparent holes (openings 388) is placed on the photoresist 381. The conventional pattern is a high density (central to center 20 mil (0.0508 cm) with three horizontal lines on the periphery of the electrode, 6 mils (0.0212 cm) in diameter and 40 mils (0.1 cm) from center to center. It is made by arranging alone.

(D) The film 381 is exposed to a conventional UV light source, that is, a mercury layer lamp 389, for about 20 seconds through the hole 388 and the mask 387. Next, remove the mask.

(E) The unexposed area of the photoresist is developed or stripped in a rank of 1% potassium carbonate for 15 minutes.

(F) Next, the electrode surface with the microprojections is washed with deionized water, placed in a 10% sulfuric acid tank for 1.5 minutes, and finally with deionized water.

(G) At first, the microprojections 13 are exposed to UV light. Final hardening of the microprojections is done in an air convection oven at 300 ° F. for 1 hour.

The final electrode 111A is used directly or treated as above.

Example 13

[Vacuum Lamination of Photoresist]

(A) Highly applicable solder mask Confer MASK with thickness of 2.3 mil (0.0058 cm) 2000 is cut slightly larger than the electrode.

(B) Photoresist film 381 was fabricated on the backing plate of the electrode 11 A and the support backing plate at 160 ° C, 0.3 mbars using a Dynachem vacuum applicator model 724, 730 Vacuum laminated on. The polyester cover sheet 382 A is removed.

(C) The dark field mask 387 including the horizontally-transparent transparent holes 388 is placed on the photoresist film 381. The conventional pattern is dense (20 mil (0.0054 cm) from center to center) with three horizontal lines on the periphery of the electrode, 6 mil (0.0015 cm) orthogonal, and 40 mil (0.102 cm) from center to center. ) Is made by arranging alone.

(D) The film is exposed for 20 to 40 seconds in an untargeted UV light source of 3-7 KW power.

(E) The unexposed area of the photoresist film is developed or stripped with 0.5% potassium carbonate in a conveyor spray developing apparatus, washed with deionized water and dried in a turbine.

(F) The final hardening of the microprojections is carried out in a two step process. Initially, the microprojections are exposed to the UV light of the Dynachem UVCS 933 apparatus and then placed in a forced inlet air oven at 300-310 ° F. for 75 minutes. The final electrode is either used directly or further processed as above.

Example 14

Surfactant for Porosity Control

32 g of cetyltrimethyl ammonium bromide is added to 1 L of iso-propanol, which is stirred and subjected to some heat. After about 1 hour 73 g TaCl ₅ and 47 g RuCl ₃ H ₂ O are added to the clear solution. The standard coating process is carried out as intepy pyrrolisis at 300 ° C. for 5 minutes and final pyrrolisis at 300 ° C. for 3 hours. The average pore diameter of the coating is increased to about 45 mm 3. After workup in steam at 680 psi, 260 ° C. for 2 hours, the average pore diameter increases to 120 mm 3.

In order to modify the pore diameter of the resulting coating, 25% by weight aqueous solution of cetyltrimethyl ammonium chloride can be used.

Example 15

Thermal elastomeric gaskets between thermal elastomeric gaskets (ie KRATION ) Is inserted. The characteristics of the device are similar to those described above.

Example 16

[Including Second Material to Control Electrolyte Volume Increase]

Because of the increase in temperature, a porous hydrophobic material is added to each cell to control the increase in the desired volume of electrolyte. As a disk, it is placed in a cell.

Typically 1-3 mils thick W. L. Gore & Associates, Inc. PTFE material is used. Preferably, the PTFF material has a molar purchase pressure of 20 to 10 psi.

Example 17

[Another Pretreatment of Electrodes]

After the electrode has a microprojection, a gasket, and a pull card (after step E), the electrode is placed in 1 M sulfuric acid and the open circuit potential is adjusted to about 0.5V, which is the cathode without hydrogen evolution. Regulated using current. The electrode is placed in deionized water, dried and assembled in an inert atmosphere (ie Ar).

Although certain embodiments of the present invention have been presented and described, there is an improved method of fabricating an electrical storage device, such as a battery or capacitor, with increased lifetime and charge / discharge characteristics, low leakage current, without departing from the spirit and scope of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made thereto. All such modifications and variations are intended to be made within the scope of the appended claims.

Claims (11)

An improved method for producing a dry preunit, which is an electrical storage device for charge storage in the state of having an electrode surface in contact with a water-insoluble or water-soluble electrolyte, (a) tin, lead, vanadium, titanium, ruthenium, tantalum, rhodium, osmium, iridium, iron, cobalt, nickel, copper, molybdenum, niobium, chromium, manganese, lanthanum or lanthanum based metals or alloys or combinations thereof; A thickness of 0, coated on each flat surface with a thin porous layer of one or more metal oxides having a large surface area independently selected from the group of metal oxides containing small proportions of additives to improve electrical conductivity Take a thin, flat metal sheet support, selected from titanium, zirconium, iron, copper, lead, tin, nickel, zinc, or a combination, on the order of .1 to 10 mils, wherein the thickness of the thin metal oxide layer is about 0.1 to 100 microns, (b) (i) a substantially uniform electrically insulating discrete microprojection that is stable for water-soluble or non-aqueous electrolytes having a thickness of about 0.1 to 10 mils on the surface of one or both sides of the porous thin metal oxide layer. To be deposited in an array (ii) placing a thinly cut ionically permeable electrically insulating separator (a separator) having a thickness of about 0.1 to 10 mils on a flat surface of the metal oxide layer, (iii) constructing an ionically or semipermeable separator having a thickness of about 0.1 to 10 mils on at least one surface of the second electrically conductive material, (iv) forming a thin air space as a separator, To form a stable ion-permeable spatial separator for the selected water-soluble or water-insoluble electrolyte, (c) Polyamide, TEFZEL as gasket material , KRATION , Polyethylene At least one thin synthetic organic polymer layer selected from polypropylene, other polyolefins, polysulfones, fluorinated or partially fluorinated polymers or combinations thereof, on one or both sides of the thin electrically conductive sheet of step (b) In contact with the surface of the peripheral edge of the (d) one or more thin cords of unusual material having a higher melting temperature (Tm) than the polymeric gasket material, optionally traversing a thin, flat sheet and placed on or in the gasket material, the cord being excited here Does not adhere to, melt, or flow on the material under the process conditions described in (e) a method of assembling the separator fabricated in step (d), in which the stack repeatedly stacked with thin and flat sheet pieces coated with metal oxide and only one side selectively has a sheet end formed from a coating and / or thicker support material. and, (f) the stacked stack of step (e) is heated to a temperature greater than the temperature of the gasket material Tm at 0 to 10O &lt; 0 &gt; C so that the gasket material flows to the edges of the stacked stack to attach and seal, and the stack is integrated with the aggregated polymer body. A method of forming an integrated stacked solid stack of sheets and separators for selectively encapsulating and sealing; (g) cooling the aggregated solid stack of step (f) to ambient temperature in an inert atmosphere, (h) removing one or more thin cords between each layer forming one or more small openings in a pencil positioned between the porous electrode layers. The method of claim 1, wherein in step (b), the array of uniform microprojections is (a) takes an electrically insulating material that is substantially inert to the electrolyte state to produce a thixotropic composition between atmospheric pressure and about 75 ° C. ambient temperature, (b) having a thin, flat electrically conductive metal sheet coated at the center on one or both sides with electrically conductive carbon, porous metal oxide, mixed porous metal oxide or other porous coating, and fixing the flat electrode to a stable holder, Take thin electrode material, (c) placing a thin flat screen or stencil having a small opening on the thin flat electrode; (d) in the case of bringing a squeegee across the screen surface to contact the screen and the electrode surface, the contacting of the flowable composition of step (a) with the outer top of the thin screen surface causes the small portion of the composition to Protrudes through, contacts the outer surface of the thin electrode, optionally penetrates the outer surface of the porous electrode coating, (e) removing the sample from the screen printer, (f) curing the applied applied material such that the separated microprotrusions maintain their shape and size substantially. The method of claim 1, In step (a) the support has a second electrically conductive material on the peripheral edge surface, In step (b) the microprojection is on the surface of the second electrically conductive material, In step (c) the gasket material is thermoplastic, In step (e) the bottomsheet is a thicker support material, In paragraph (f) the gasket material is redundant to form a suture that is collected continuously, In step (g) the stack is cooled to room temperature, And wherein in step (h) the cord consists of a metal, a ceramic, an organic polymer or a combination thereof. An energy storage device obtained by filling an empty fill gap region with an electrolyte, sealing a fill port opening, and electrically charging using a preunit manufactured by the method according to claim 1, wherein the energy storage device includes: It is included in the computer memory shut-down or the periodic lighting power of the orbital satellite while the electricity is weak, provided by means of continuous use of power, and used when the additional power and power required for the shutdown for a predetermined period are discontinuous. To provide power, Provides pulsed power when high current and / or energy is required, which requires a power source to heat the catalyst or to power a defibrillator or other heart rate control device, or an electric vehicle battery Supplying pulsed power to the internal combustion engine for recharging, It is required for a surge tool without an electrical cord, which supplies power when the recharge is fast and the discharge is slow, An energy storage device, characterized in that it is used as an electrical power source for a purpose independently selected from providing portable power for devices and communication equipment. As a dry free unit for energy storage device, One or more first cells for storing energy, the first cells, a. A first electrically conductive electrode, b. A second electrically conductive electrode and the first and second electrodes are spaced apart by a predetermined first distance, c. Combining first dielectric gasket means sandwiched between the first and second electrodes to separate and electrically insulate the first and second electrodes, d. A large surface area first electrically conductive coating layer formed on one surface of the first electrode, and the first coating layer is located between the first electrode and the gasket means, e. A large surface area of the second electrically conductive coating layer formed on one surface of the second electrode, and the second coating layer is located between the first electrode and the first gasket means, f. By further comprising a layer comprising a plurality of protrusions on the first coating layer, the second coating layer, or a combination thereof, When the first electrode, the second electrode, and the first gasket means having the centrally located opening are joined together to form the first cell, an air filled fill gap is formed therebetween, Wherein the first coating layer of the first electrode and the first and second coating layers of the second electrode are selected from the group consisting of metal oxides, mixed metal oxides, metal nitrides, and polymers. unit. The method of claim 1, wherein the porous electrode in step (a) is (a) contacting steam at a temperature between about 150 and 300 ° C. between about 0.5 to 4 hours or (b) contacting the reactive gas or the reactive liquid at a temperature between about 0.2 to 2 hours and between about 80 to 140 ° C. (c) is formed under conditions in contact with an anode current sufficient to evacuate oxygen for about 1 to 60 minutes, And then contacting the cathode current without hydrogen gas emissions until the open circuit potential is adjusted to within the range of about 0.5 to 0.75 V (relative to the imaginary hydrogen electrode). The method of claim 1, wherein between (d) and (e), the porous coating is brought into contact with the cathode current until the open circuit potential is adjusted within the range of about 0.5V to 0.75V (relative to normal hydrogen electrode). How to feature. A wide surface area electrically conductive porous coating layer for use in the dry preunit of claim 5, wherein the porous layer is a metal having a large effective surface area substantially consisting of micropores and mesopores, coated on a support. A coating layer comprising an oxide or a mixed metal oxide. A method of storing energy in accordance with the dry preunit according to claim 5, wherein the preunit is filled with a subsequent conductive electrolyte, sealed and electrically charged. An energy storage device, wherein the inside of the cell gap of the dry preunit of claim 5 is filled with an ion conductive medium, and the fill port is sealed. In an improved method for manufacturing an electrical storage device for charge storage, Exhausting the dry preunit according to claim 5, For a time sufficient to backfill the space between the support sheets using the fill port, an electrolyte selected from an ionically conductive water-soluble inorganic acid or a non-aqueous organic medium is contacted with the evacuated dry preunit, Remove electrolyte from a given outer surface, Sealing the opening of the fill port and sealing the method.