Source: https://patents.google.com/patent/US20080206446A1/en
Timestamp: 2019-01-21 00:34:10
Document Index: 155949309

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Art)\n1']

US20080206446A1 - Recyclable dry-particle based adhesive electrode and methods of making same - Google Patents
Recyclable dry-particle based adhesive electrode and methods of making same Download PDF
US20080206446A1
US20080206446A1 US12042935 US4293508A US2008206446A1 US 20080206446 A1 US20080206446 A1 US 20080206446A1 US 12042935 US12042935 US 12042935 US 4293508 A US4293508 A US 4293508A US 2008206446 A1 US2008206446 A1 US 2008206446A1
US12042935
Xiaomei Xi
The present invention is a divisional of U.S. application Ser. No. 10/817,074, filed Apr. 2, 2004, entitled “Recyclable Dry-Particle Based Adhesive Electrode and Methods of Making Same” which claims priority from commonly assigned Provisional Application No. 60/486,002, filed Jul. 9, 2003; commonly assigned Provisional Application No. 60/486,530, filed Jul. 10, 2003; commonly assigned Provisional Application No. 60/498,346, filed Aug. 26, 2003; commonly assigned Provisional Application No. 60/498,210, filed Aug. 26, 2003; commonly assigned Provisional Application No. 60/511,273, filed Oct. 14, 2003; and commonly assigned Provisional Application No. 60/546,093, filed Feb. 19, 2004. Each of these nonprovisional and provisional applications is incorporated herein by reference in their entirety.
The present invention relates generally to the field of energy storage devices that are used to power modern technology. More particularly, the present invention relates to recyclable structures and methods for making dry particle based adhesive electrode films for use in capacitor products.
Although, double-layer capacitors can theoretically be operated at voltages as high as 4.0 volts and possibly higher, current double-layer capacitor manufacturing technologies limit nominal operating voltages of double-layer capacitors to about 2.5 to 2.7 volts. Higher operating voltages are possible, but at such voltages undesirable destructive breakdown begins to occur, which in part may be due to interactions with impurities and residues that can be introduced into, or attach themselves to, electrodes during manufacture. For example, undesirable destructive breakdown of double-layer capacitors is seen to appear at voltages between about 2.7 to 3.0 volts.
In the prior art process of forming an extruded conductive electrode layer, binder and carbon particles are blended together with one or more additive. The resulting material has dough-like properties that allow the material to be introduced into an extruder apparatus. The extruder apparatus fibrillates the binder and provides an extruded film, which is subsequently dried to remove most, but as discussed below, typically not all of the additive(s). When fibrillated, the binder acts as a matrix to support the carbon particles. The extruded film may be calendared many times to produce an electrode film of desired thickness and density.
Known methods for attaching additive/solvent based extruded electrode films and/or coated slurries to a current collector include the aforementioned precoating of a slurry of adhesive/binder. Pre-coated slurry layers of adhesive/binder are used in the capacitor prior arts to promote electrical and physical contact with current collectors, and the current collectors themselves provide a physical electrical contact point.
In the prior art, the resulting additive based extruded product can be subsequently processed in a high-pressure compactor, dried to remove the additive, shaped into a needed form, and otherwise processed to obtain an end-product for a needed application. For purposes of handling, processing, and durability, desirable properties of the end product typically depend on the consistency and homogeneity of the composition of matter from which the product is made, with good consistency and homogeneity being important requirements. Such desirable properties depend on the degree of fibrillization of the polymer. Tensile strength commonly depends on both the degree of fibrillization of the fibrillizable binder, and the consistency of the fibril lattice formed by the binder within the material. When used as an electrode film, internal resistance of an end product is also important. Internal resistance may depend on bulk resistivity—volume resistivity on large scale—of the material from which the electrode film is fabricated. Bulk resistivity of the material is a function of the material's homogeneity; the better the dispersal of the conductive carbon particles or other conductive filler within the material, the lower the resistivity of the material. When electrode films are used in capacitors, such as, electrochemical double-layer capacitors, capacitance per unit volume is yet another important characteristic for consideration. In double layer capacitors, capacitance increases with the specific surface area of the electrode film used to make a capacitor electrode. Specific surface area is defined as the ratio of (1) the surface area of electrode film exposed to an electrolytic solution when the electrode material is immersed in the solution, and (2) the volume of the electrode film. An electrode film's specific surface area and capacitance per unit volume are believed to improve with improvement in consistency and homogeneity.
In both the coating and extrusion processes, once an electrode film is created, if a problem arises or is found to have occurred during a process step, the film is typically discarded.
A need thus exists for new methods of producing inexpensive and reliable capacitor electrode materials with one or more of the following qualities: improved consistency and homogeneity of distribution of binder and active particles on microscopic and macroscopic scales; improved tensile strength of electrode film produced from the materials; decreased resistivity; and increased specific surface area. Yet another need exists for capacitor electrodes fabricated from recycled materials with these qualities. A further need is to provide capacitors and capacitor electrodes without the use of processing additives.
The present invention provides a high yield method for making inexpensive, durable, and highly reliable dry electrode films and associated structures for use in energy storage devices.
In one embodiment, an energy storage device product comprises a mix of recyclable carbon and binder particles. At least some of the mix may be dry fibrillized. The mix may comprise no processing additive.
In one embodiment, an energy storage device product, may comprise a film, the film including a mix of particles, wherein at least some of the particles are recycled particles. The particles may be fibrillized. The recycled particles may be fibrillized. The film may be a self-supporting film. The film may comprise a thickness of less than 250 microns. The film may comprise a length of at least 1 meter. The film may be coupled directly against a substrate. The film may comprise substantially no processing additive. The substrate may comprise a collector. The product may comprise a collector, and wherein the film is coupled directly against a surface of the collector. The collector may comprise two sides, wherein one film is calendered directly against one side of the collector, wherein a second film is calendered directly against a second side of the collector. The collector may be treated. The collector may be formed to comprise a roll. The roll may be disposed within a sealed aluminum housing. The product of claim 4, wherein at least some of the particles comprise fibrillizable fluoropolymer and carbon particles. The carbon particles comprise activated carbon particles and conductive particles. At least some of the particles may comprise thermoplastic particles.
In one embodiment, an energy storage product, may comprise a dry mix of recyclable dry binder and dry carbon particles, the particles formed into a continuous self-supporting electrode film without the substantial use of any processing additives. The processing additive not used may include hydrocarbons, high boiling point solvents, antifoaming agents, surfactants, dispersion aids, water, pyrrolidone, mineral spirits, ketones, naphtha, acetates, alcohols, glycols, toluene, xylene, and Isopars™. At least some of the dry binder may comprise a fibrillized dry binder. The binder may be fibrillized by a high-pressure gas. The high-pressure may comprise a pressure of more than 60 PSI. The gas may comprise a water content of less than about 20 PPM.
In one embodiment, a method of making an energy storage device electrode comprises the steps of forming an electrode film from a plurality of particles; and reusing one or more of the plurality of particles to form the film. The plurality of particles may be dry fibrillized. The method may comprise a step of coupling a first side of the film to a collector. The step of reusing may comprise a step of fibrillizing the particles after the particles are used to make the electrode film. The binder may comprise a fluoropolymer. The carbon particles may comprise conductive carbon particles. The film may be self supporting. The particles may comprise conductive carbon particles and activated carbon particles. The film may be a heated dry film. The film may comprise a density of about 0.50 to 0.70 gm/cm2. The method may comprise between about 80% to 95% activated carbon, between about 0% to 15% conductive carbon, and between about 3% to 15% fibrillizable fluoropolymer. The film may comprise a thermoplastic.
In one embodiment, a capacitor comprises a plurality of dry processed particles, the dry processed particles including recycled binder and conductive particles. At least some of the dry processed particles may be formed as a self supporting dry electrode film. The capacitor may comprise a current collector, wherein the dry processed particles are bonded to the current collector, wherein the current collector comprises aluminum. The capacitor may comprise separator, wherein the dry processed particles are bonded to the separator. The separator may comprise paper. The capacitor may be rated to operate at a maximum voltage of 3.0 volts or less. The dry electrode film may comprise a density of about 0.50 to 0.70 gm/cm2. The dry processed particles may be compacted into a dry self-supporting electrode film by a single pass compaction device. The capacitor may comprise a sealed aluminum housing, wherein the dry processed particles are disposed within the housing. The capacitor may comprise a sealed aluminum housing, wherein the current collector is coupled to the housing by a laser weld. The capacitor may comprise a jellyroll type electrode.
In one embodiment, a capacitor comprises a plurality of reusable particles; a collector; the collector having two sides; and two electrode film layers, the two electrode film layers comprised of the reusable particles, wherein a first electrode film layer is bonded directly onto a first surface of the collector, and wherein a second electrode film layer is bonded directly onto a second surface of the collector. The two electrode film layers may comprise substantially no processing additives. The two electrode layers may comprise dry fibrillized particles. The film layers may comprise substantially zero residues as determined by a chemical analysis of the layers before impregnation by an electrolyte. The energy storage device may comprise one or more continuous self supporting intermixed film structure comprised of reused carbon particles dry binder particles, the film structure consisting of about zero parts per million processing additive. The additive may be selected from hydrocarbons, high boiling point solvents, antifoaming agents, surfactants, dispersion aids, water, pyrrolidone, mineral spirits, ketones, naphtha, acetates, alcohols, glycols, toluene, xylene, and Isopars™. The intermixed film structure may be an electrode film. The electrode film may be an energy storage device electrode film. The electrode film may comprise a capacitor electrode film.
In one embodiment, an energy storage device comprises a housing; a collector, the collector having an exposed surface; an electrolyte, the electrolyte disposed within the housing; and an electrode film, the electrode comprised of recycled particles, wherein the electrode film is impregnated with the electrolyte, and wherein the electrode film is coupled directly to the exposed surface. The electrode film may be substantially insoluble in the electrolyte. The electrode may comprise a dry binder, wherein the binder is substantially insoluble in the electrolyte. The binder may comprise a thermoplastic, wherein the thermoplastic couples the electrode film to the collector. The electrolyte may be an acetonitrile type of electrolyte.
In one embodiment, an energy storage device structure comprises one or more recyclable electrode film, wherein the one or more recyclable electrode film is both conductive and adhesive, and wherein the one or more recyclable electrode film is coupled directly to a current collector.
In one embodiment, an energy storage device structure comprises one or more self-supporting recyclable dry process based electrode film. The film may comprise conductive and adhesive particles. The adhesive particles may comprise a thermoplastic. The electrode may be a capacitor electrode.
In one embodiment, an electrode comprises a collector; and a dry process based electrode film, wherein the electrode film is coupled to the collector, wherein the electrode film comprises conductive particles and binder particles, and wherein between the collector and the electrode film there exists only one distinct interface. The binder particles may comprise a thermoplastic. The conductive particles may comprise conductive carbon. The electrode film may comprise activated carbon. The conductive particles may comprise a metal.
In one embodiment, an energy storage device structure comprises a plurality of intermixed recyclable dry processed carbon and binder particles formed as an electrode, wherein as compared to an electrode formed of a plurality of the same carbon and binder particles processed with a processing additive, the intermixed dry processed carbon and binder particles comprises less residue.
In one embodiment, a capacitor comprises a continuous compacted self supporting recyclable dry electrode film comprised of a dry mix of dry binder and dry carbon particles, the film coupled to a collector, the collector shaped into a roll disposed within a sealed aluminum housing. The dry electrode film may comprise substantially no processing additive.
In one embodiment, an energy storage device comprises dry process recyclable electrode means for providing electrode functionality in an energy storage device.
FIG. 1 a is a block diagram illustrating a method for making an energy storage device electrode film.
FIG. 1 b is a high-level front view of a jet-mill assembly used to fibrillize binder within a dry carbon particle mixture.
FIG. 1 c is a high-level side view of a jet-mill assembly shown in FIG. 1 b;
FIG. 1 d is a high-level top view of the jet-mill assembly shown in FIGS. 1 b and 1 c.
FIG. 1 e is a high-level front view of a compressor and a compressed air storage tank used to supply compressed air to a jet-mill assembly.
FIG. 1 g is a high-level front view of the jet-mill assembly of FIGS. 1 b-d in combination with a dust collector and a collection container.
FIG. 1 h is a high-level top view of the combination of FIGS. 1 f and 1 g.
FIGS. 1 i, 1 j, and 1 k illustrate effects of variations in feed rate, grind pressure, and feed pressure on tensile strength in length, tensile strength in width, and dry resistivity of electrode materials.
FIG. 1 m illustrates effects of variations in feed rate, grind pressure, and feed pressure on internal resistance.
FIG. 4 illustrates a method for recycling/reusing dry particles and structures made therefrom.
FIG. 5 a is a side representation of one embodiment of a structure of an energy storage device electrode.
FIG. 5 b is a top representation of one embodiment of an electrode.
FIG. 6 is a side representation of a rolled electrode coupled internally to a housing.
FIG. 7 a illustrates capacitance vs. number of full charge/discharge charge cycles.
FIG. 7 b illustrates resistance vs. number of full charge/discharge charge cycles.
FIG. 7 c illustrates effects of electrolyte on specimens of electrodes.
Reference will now be made in detail to several embodiments of the invention that are illustrated in the accompanying drawings. Wherever possible, same or similar reference numerals are used to refer to the same or similar elements, or steps and/or elements used therein.
In accordance with embodiments of the present invention, an inexpensive, long lasting, reliable dry particle capacitor, capacitor electrode, and one or more recycled/recyclable structures thereof, as well as methods for making the same are described. The present invention provides distinct advantages when compared to those of the additive-based coating/extruder devices of the prior art, which include the ability to utilize structures that, if needed, can be reused.
The energy storage devices and methods associated with the present invention do not use the one or more prior art processing aides or additives associated with coating and extrusion based processes (hereafter referred throughout as “processing additive” or “additive”), including: added solvents, liquids, lubricants, plasticizers, and the like. As well, one or more associated additive removal steps, post coating treatments such as curing or cross-linking, drying step(s) and apparatus associated therewith, and the like, are eliminated. Because additives are not used during manufacture, a final electrode product is not subject to chemical interactions that may occur between the aforementioned prior art residues of such additives and a subsequently used electrolyte. Because binders that are dissolvable by additives do not need to be used with present invention, a wider class of or selection of binders may be used than in the prior art. Such binders can be selected to be completely or substantially insoluble and nonswellable in typically used electrolytes, an advantage, which when combined with a lack of additive based impurities or residues such electrolytes can react to, allows that a much more reliable and durable energy storage device may be provided. A high throughput method for making more durable and more reliable energy storage devices is thus provided.
Referring now to FIG. 7 a, there are seen capacitance vs. number of full charge/discharge charge cycles tests for both a prior art energy storage device 5 manufactured using processing additives and an embodiment of an energy storage device 6 comprising structures manufactured using no processing additives according to one or more of the principles described further herein.
Device 5 incorporates in its design a prior art processing additive-based electrode available from W.L Gore & Associates, Inc. 401 Airport Rd., Elkton, Md. 21922, 410-392-444, under the EXCELLERATOR™ brand of electrode. The EXCELLERATOR™ brand of electrode was configured in a jellyroll configuration within an aluminum housing to comprise a double-layer capacitor. Device 6 was also configured as a similar Farad double-layer capacitor in a similar form factor housing, but using instead a dry electrode film 33 (as referenced in FIG. 2 g described below).
The dry electrode film 33 was adhered to a collector by an adhesive coating sold under the trade name Electrodag® EB-012 by Acheson Colloids Company, 1600 Washington Ave., Port Huron, Mich. 48060, Telephone 1-800-984-5581. Dry film 33 was manufactured utilizing no processing additives in a manner described further herein.
In the FIGS. 7 a and 7 b embodiments, both devices 5 and 6 were tested without any preconditioning. The initial starting capacitance of devices 5 and 6 was about 2800 Farad. The test conditions were such that at room temperature, both devices 5 and 6 were full cycle charged at 100 amps to 2.5 volts and then discharged to 1.25 volts. Both devices were charged and discharged in this manner continuously. The test was performed for approximately 70,000 cycles for the prior art device 5, and for approximately 120,000 cycles for the device 6. Those skilled in the art will identify that such test conditions are considered to be high stress conditions that capacitor products are not typically expected to be subject to, but were nevertheless conducted to demonstrate the durability of device 6. As indicated by the results, the prior art device 5 experienced a drop of about 30% in capacitance by the time 70,000 full charge cycles occurred, whereas at 70,000 and 120,000 cycles device 6 experienced only a drop of about 15% and 16%, respectively. Device 6 is shown to experience a predictable decrease in capacitance that can be modeled to indicate that cycling of the capacitor up to about 0.5 million, 1 million, and 1.5 million cycles can be achieved under the specific conditions with respective drops of 21%, 23%, and 24% in capacitance. At 70,000 cycles it is shown that device 6 made according to one or more of the embodiments disclosed herein experienced about 50% less in capacitance drop than a processing additive based prior art device 5 (about 15% vs. 30%, respectively). At about 120,000 cycles it is shown that device 6 made according to one or more embodiments disclosed herein experienced only about 17% capacitance drop. At 1 million cycles it is envisioned that device 6 will experience less than 25% drop from its initial capacitance.
Referring now to FIG. 7 b, there are seen resistance vs. number of full charge/discharge charge cycles tests for both a prior art energy storage device 5 manufactured using processing additives and an embodiment of an energy storage device 6. As indicated by the results, the prior art device 5 experienced an increase in resistance over that of device 6. As seen, device 6 experiences a minimal increase in resistance (less than 10% over 100,000 cycles) as compared to device 5 (100% increase over 75,000 cycles).
Referring now to FIG. 7 c, there are seen physical specimens of electrode obtained from devices 5, 6, and 7 shown after one week and 1 month of immersion in 1.5 M tetramethylammonium or tetrafluoroborate in acetonitrile electrolyte at a temperature of 85 degrees centigrade. The electrode sample from device 5 comprises the processing additive based EXCELLERATOR™ brand of electrode film discussed above, and the electrode sample of device 7 comprises a processing additive based electrode film obtained from a 5 Farad NESCAP double-layer capacitor product, Wonchun-Dong 29-9, Paldal-Ku, Suwon, Kyonggi, 442-380, Korea, Telephone: +82 31 219 0682. As seen, electrodes from devices 5 and 7 show damage after 1 week and substantial damage after 1 month immersion in acetonitrile electrolyte. In contrast, an electrode from a device 6 made of one or more of the embodiments described further herein shows no visual damage, even after one year (physical specimen not shown) of immersion in acetonitrile electrolyte.
In general, because both the prior art and embodiments of the present invention obtain base particles and materials from similar manufacturers, and because they may be exposed to similar pre-process environments, measurable amounts of prior art pre-process residues and impurities may be similar in magnitude to those of embodiments of the present invention, although variations may occur due to differences in pre-processes, environmental effects, etc. In the prior art, the magnitude of such pre-process residues and impurities is smaller than that of the residues and impurities that remain and that can be measured after processing additives are used. This measurable amount of processing additive based residues and impurities can be used as an indicator that processing additives have been used in a prior art energy storage device product. The lack of such measurable amounts of processing additive can as well be used to distinguish the non-use of processing additives in embodiments of the present invention.
Table 1 indicates the results of a chemical analysis of a prior art electrode film and an embodiment of a dry electrode film made in accordance with principles disclosed further herein. The chemical analysis was conducted by Chemir Analytical Services, 2672 Metro Blvd., Maryland Heights, Mo. 63043, Phone 314-291-6620. Two samples were analyzed with a first sample (Chemir 533572) comprised of finely ground powder obtained from a prior art additive based electrode film sold under the EXCELLERATOR™ brand of electrode film by W.L Gore & Associates, Inc. 401 Airport Rd., Elkton, Md. 21922, 410-392-444. A second sample (Chemir 533571) comprised a thin black sheet of material cut into ⅛ to 1 inch sided irregularly shaped pieces obtained from a dry film 33 (as discussed in FIG. 2 g below). The second sample (Chemir 533571) comprised a particle mixture of about 80% to 90% activated carbon, about 0% to 15% conductive carbon, and about 3% to 15% PTFE binder by weight. Suitable carbon powders are available from a variety of sources, including YP-17 activated carbon particles sold by Kuraray Chemical Co., LTD, Shin-hankyu Bldg. 9F Blvd. C-237, 1-12-39 Umeda, Kiata-ku, Osaka 530-8611, Japan; and BP 2000 conductive particles sold by Cabot Corp. 157 Concord Road, P.O. Box 7001, Billerica, Mass. 01821-7001, Phone: 978 663-3455. A tared portion of prior art sample Chemir 53372 was transferred to a quartz pyrolysis tube. The tube with its contents was placed inside of a pyrolysis probe. The probe was then inserted into a valved inlet of a gas chromatograph. The effluent of the column was plumbed directly into a mass spectrometer that served as a detector. This configuration allowed the sample in the probe to be heated to a predetermined temperature causing volatile analytes to be swept by a stream of helium gas into the gas into the gas chromatograph and through the analytical column, and to be detected by the mass spectrometer. The pyrolysis probe was flash heated from ambient temperature at a rate of 5 degrees C./millisecond to 250 degrees C. and held constant for 30 seconds. The gas chromatograph was equipped with a 30 meter Agilent. DB-5 analytical column. The gas chromatograph oven temperature was as follows: the initial temperature was held at 45 degrees C. for 5 minutes and then was ramped at 20 degrees C. to 300 degrees C. and held constant for 12.5 minutes. A similar procedure was conducted for sample 53371 of a dry film 33. Long chain branched hydrocarbon olefins were detected in both samples, with 2086 parts per million (PPM) detected in the prior art sample, and with 493 PPM detected in dry film 33. Analytes dimethylamine and a substituted alkyl propanoate were detected in sample Chemir 53372 with 337 PPM and were not detected in sample Chemir 53371. It is envisioned that future analysis of other prior art additive based electrode films will provide similar results with which prior art use of processing additives, or equivalently, the non-use of additives of embodiments described herein, can be identified and distinguished.
Retention Chemir 53372
Time in Minutes Chemir 53371 (Prior Art)
1.65 0 PPM 0 PPM
12.3 0 PPM 0 PPM
13.6 0 PPM Butylated hydroxyl toluene
20.3 0 PPM 0 PPM
20.6 A long chain A long chain branched
branched hydrocarbon hydrocarbon olefin
493 PPM 2086 PPM
Referring to now to FIGS. 1 b, 1 c, and 1 d, there is seen, respectively, front, side, and top views of a jet-mill assembly 100 used to perform a dry fibrillization step 20. For convenience, the jet-mill assembly 100 is installed on a movable auxiliary equipment table 105, and includes indicators 110 for displaying various temperatures and gas pressures that arise during operation. A gas input connector 115 receives compressed air from an external supply and routes the compressed air through internal tubing (not shown) to a feed air hose 120 and a grind air hose 125, which both lead and are connected to a jet-mill 130. The jet-mill 130 includes: (1) a funnel-like material receptacle device 135 that receives compressed feed air from the feed air hose 120, and the blended carbon-binder mixture of step 18 from a feeder 140; (2) an internal grinding chamber where the carbon-binder mixture material is processed; and (3) an output connection 145 for removing the processed material. In the illustrated embodiment, the jet-mill 130 is a 4-inch Micronizer® model available from Sturtevant, Inc., 348 Circuit Street, Hanover, Mass. 02339; telephone number (781) 829-6501. The feeder 140 is an AccuRate® feeder with a digital dial indicator model 302M, available from Schenck AccuRate®, 746 E. Milwaukee Street, P.O. Box 208, Whitewater, Wis. 53190; telephone number (888) 742-1249. The feeder includes the following components: a 0.33 cubic ft. internal hopper; an external paddle agitation flow aid; a 1.0-inch, full pitch, open flight feed screw; a % hp, 90VDC, 1,800 rpm, TENV electric motor drive; an internal mount controller with a variable speed, 50:1 turndown ratio; and a 110 Volt, single-phase, 60 Hz power supply with a power cord. The feeder 140 dispenses the carbon-binder mixture provided by step 18 at a preset rate. The rate is set using the digital dial, which is capable of settings between 0 and 999, linearly controlling the feeder operation. The highest setting of the feeder dial corresponds to a feeder output of about 12 kg per hour.
The feeder 140 appears in FIGS. 1 b and 1 d, but has been omitted from FIG. 1 c, to prevent obstruction of view of other components of the jet-mill 130. The compressed air used in the jet-mill assembly 100 is provided by a combination 200 of a compressor 205 and a compressed air storage tank 210, illustrated in FIGS. 1 e and 1 f; FIG. 1 e is a front view and FIG. 1 f is a top view of the combination 200. The compressor 205 used in this embodiment is a GA 30-55C model available from Atlas Copco Compressors, Inc., 161 Lower Wesffield Road, Holyoke, Mass. 01040; telephone number (413) 536-0600. The compressor 205 includes the following features and components: air supply capacity of 180 standard cubic feet per minute (“SCFM”) at 125 PSIG; a 40-hp, 3-phase, 60 HZ, 460 VAC premium efficiency motor; a WYE-delta reduced voltage starter; rubber isolation pads; a refrigerated air dryer; air filters and a condensate separator; an air cooler with an outlet 206; and an air control and monitoring panel 207. The 180-SCFM capacity of the compressor 205 is more than sufficient to supply the 4-inch Micronizer® jet-mill 130, which is rated at 55 SCFM. The compressed air storage tank 210 is a 400-gallon receiver tank with a safety valve, an automatic drain valve, and a pressure gauge. The compressor 205 provides compressed air to the tank 205 through a compressed air outlet valve 206, a hose 215, and a tank inlet valve 211.
It is identified that the compressed air provided under high-pressure by compressor 205 is preferably as dry as possible. Thus, in one embodiment, an appropriately placed in-line filter and/or dryer may be added. In one embodiment, a range of acceptable dew point for the air is about −20 to −40 degrees F., and a water content of less than 20 ppm. Although discussed as being effectuated by high-pressure air, it is understood that other sufficiently dry gases are envisioned as being used to fibrillize binder particles utilized in embodiments of the present invention, for example, oxygen, nitrogen, helium, and the like.
(Feed Rate, SAMPLE TENSILE NORMALIZED
Exp. Grind psi, Feed DOE THICKNESS STRENGTH IN TENSILE STRENGTH
No. psi) POINTS (mil) LENGTH (grams) IN LENGTH (g/mil)
1 250/85/60 0/0/0 6.1 123.00 20.164
2 250/85/70 0/0/1 5.5 146.00 26.545
3 250/110/60 0/1/0 6.2 166.00 26.774
4 250/110/70 0/1/1 6.1 108.00 17.705
5 800/85/60 1/0/0 6.0 132.00 22.000
6 800/85/70 1/0/1 5.8 145.00 25.000
7 800/110/60 1/1/0 6.0 135.00 22.500
8 800/110/70 1/1/1 6.2 141.00 22.742
Factors Sample Normalized Tensile
(Feed Rate, DOE Thickness Tensile Strength Strength
Exp. No Grind psi, Feed psi) Points (mil) in Length (grams) in Length (g/mil)
1 250/85/60 0/0/0 6.1 63.00 10.328
2 250/85/70 0/0/1 5.5 66.00 12.000
3 250/110/60 0/1/0 6.2 77.00 12.419
4 250/110/70 0/1/1 6.1 59.00 9.672
5 800/85/60 1/0/0 6.0 58.00 9.667
6 800/85/70 1/0/1 5.8 70.00 12.069
7 800/110/60 1/1/0 6.0 61.00 10.167
8 800/110/70 1/1/1 6.2 63.00 10.161
(Feed Rate, Grind psi, DRY RESISTANCE
Exp. No. Feed psi) DOE Points (Ohms)
1 250/85/60 0/0/0 0.267
2 250/85/70 0/0/1 0.229
3 250/110/60 0/1/0 0.221
4 250/110/70 0/1/1 0.212
5 800/85/60 1/0/0 0.233
6 800/85/70 1/0/1 0.208
7 800/110/60 1/1/0 0.241
8 800/110/70 1/1/1 0.256
In Table 5 below we present data for final capacitances measured in double-layer capacitors utilizing dry electrode films made from dry fibrillized particles as described herein by each of the 8 experiments, averaged over the sample size of each experiment. Note that Cup refers to the capacitances measured when charging double-layer capacitors, while Cup values were measured when discharging the capacitors. As in the case of tensile strength data, the capacitances were normalized to the thickness of the electrode film. In this case, however, the thicknesses have changed, because the dry film has undergone compression in a high-pressure nip during the process of bonding the film to a current collector. It is noted in obtaining the particular results of Table 5, the dry electrode film was bonded to a current collector by an intermediate layer of adhesive. Normalization was carried out to the standard thickness of 0.150 millimeters.
Cup and Cdown
(Feed Rate, Sample
Exp. Grind psi, DOE Thickness Cup Normalized Cdown NORMALIZED
No. Feed psi) Points (mm) (Farads) Cup (Farads) (Farads) Cdown (Farads)
1 250/85/60 0/0/0 0.149 1.09 1.097 1.08 1.087
2 250/85/70 0/0/1 0.133 0.98 1.105 0.97 1.094
3 250/110/60 0/1/0 0.153 1.12 1.098 1.11 1.088
4 250/110/70 0/1/1 0.147 1.08 1.102 1.07 1.092
5 800/85/60 1/0/0 0.148 1.07 1.084 1.06 1.074
6 800/85/70 1/0/1 0.135 1.00 1.111 0.99 1.100
7 800/110/60 1/1/0 0.150 1.08 1.080 1.07 1.070
8 800/110/70 1/1/1 0.153 1.14 1.118 1.14 1.118
Rup and Rdown
Factors Sample Electrode Resistance
Exp. (Feed Rate, Grind DOE Thickness Resistance Rdown
No. psi, Feed psi) Points (mm) Rup (Ohms) (Ohms)
1 250/85/60 0/0/0 0.149 1.73 1.16
2 250/85/70 0/0/1 0.133 1.67 1.04
3 250/110/60 0/1/0 0.153 1.63 1.07
4 250/110/70 0/1/1 0.147 1.64 1.07
5 800/85/60 1/0/0 0.148 1.68 1.11
6 800/85/70 1/0/1 0.135 1.60 1.03
7 800/110/60 1/1/0 0.150 1.80 1.25
8 800/110/70 1/1/1 0.153 1.54 1.05
Referring back to FIG. 1 a, the illustrated process also includes steps 21 and 23, wherein dry conductive particles 21 and dry binder 23 are blended in a dry blend step 19. Step 19, as well as added step 26, also do not utilize additives before, during, or after the steps. In one embodiment, dry conductive particles 21 comprise conductive carbon particles. In one embodiment, dry conductive particles 21 comprise conductive graphite particles. In one embodiment, it is envisioned that conductive particles may comprise a metal powder of the like. In one embodiment, dry binder 23 comprises a dry thermoplastic material. In one embodiment, the dry binder comprises non-fibrillizable fluoropolymer. In one embodiment, dry binder 23 comprises polyethylene particles. In one embodiment, dry binder 23 comprises polypropylene or polypropylene oxide particles. In one embodiment, the thermoplastic material is selected from polyolefin classes of thermoplastic known to those skilled in the art. Other thermoplastics of interest and envisioned for potential use include homo and copolymers, olefinic oxides, rubbers, butadiene rubbers, nitrile rubbers, polyisobutylene, poly(vinylesters), poly(vinylacetates), polyacrylate, fluorocarbon polymers, with a choice of thermoplastic dictated by its melting point, metal adhesion, and electrochemical and solvent stability in the presence of a subsequently used electrolyte. In other embodiments, thermoset and/or radiation set type binders are envisioned as being useful. The present invention, therefore, should not be limited by the disclosed and suggested binders, but only by the claims that follow.
In FIG. 2 g, container 19 is disposed to provide dry particles 19 onto a dry film 33. In FIG. 2 g, container 20 comprises dry particles 12, 14, and 16, which are dry fibrillized and provided in accordance with principles described above. A dry free flowing mixture from container 20 may be compacted to provide the dry film 33 to be self-supporting after one pass through a compacting apparatus, for example roll-mill 32. The self-supporting continuous dry film 33 can be stored and rolled for later use as an energy device electrode film, or may be used in combination with dry particles provided by container 19. For example, as in FIG. 2 g, dry adhesive/binder particles comprising a free flowing mixture of dry conductive carbon 21 and dry binder 23 from container 19 may be fed towards dry film 33. In one embodiment, scatter coating equipment similar to that used in textile and non-woven fabric industries is contemplated for dispersion of the dry particles onto dry film 33. In one embodiment, the dry film 33 is formed from dry particles 12, 14, and 16 as provided by container 20. The dry particles from container 19 may be compacted and/or calendared against and within the dry film 33 to form a subsequent dry film 34, wherein the dry particles are embedded and intermixed within the dry film 34. Through choice of location of containers 19 and 20, separating blade 35, powder feed-rate, roll speed ratios, and/or surface of rolls, it is identified that the interface between dry particles provided to form a dry particle based electrode film may be appropriately varied. An embedded/intermixed dry film 34 may be subsequently attached to a collector or wound onto a storage roll 48 for subsequent use.
Referring to FIG. 3, and preceding Figures as needed, there is seen an apparatus used to bond a dry film to a current collector. In step 28, a dry film 34 is bonded to a current collector 50. In one embodiment, the current collector comprises an etched or roughened aluminum sheet, foil, mesh, screen, porous substrate, or the like. In one embodiment, the current collector comprises a metal, for example, copper, aluminum, silver, gold, and the like. In one embodiment, current collector comprises a thickness of about 30 microns. Those skilled in the art will recognize that if the electrochemical potential allows, other metals could also be used as a collector 50.
In one embodiment, a current collector 50 and two dry film(s) 34 are fed from storage rolls 48 into a heated roll-mill 52 such that the current collector 50 is positioned between two self-supporting dry films 34. In one embodiment, the current collector 50 may be pre-heated by a heater 79. The temperature of the heated roll-mill 52 may be used to heat and soften the dry binder 23 within the two intermixed dry films 34 such that good adhesion of the dry films to the collector 50 is effectuated. In one embodiment, a roll-mill 52 temperature of at the nip of the roll is between 100° C. and 300° C. In one embodiment, the nip pressure is selected between 50 pounds per linear inch (PLI) and 1000 PLI. Each intermixed dry film 34 becomes calendared and bonded to a side of the current collector 50. The two dry intermixed films 34 are fed into the hot roll nip 52 from storage roll(s) 48 in a manner that positions the peak of the gradients formed by the dry particles from container 19 directly against the current collector 50 (i.e. right side of a dry film 34 illustrated in FIG. 2 b). After exiting the hot roll nip 52, it is identified that the resulting calendared dry film and collector product can be provided as a dry electrode 54 for use in an energy storage device, for example, as a double-layer capacitor electrode. In one embodiment, the dry electrode 54 can be S-wrapped over chill rolls 56 to set the dry film 34 onto the collector 50. The resulting dry electrode 54 can then be collected onto another storage roll 58. Tension control systems 51 can also be employed by the system shown in FIG. 3.
Referring to FIG. 4, and preceding Figures as needed, there is seen a block diagram illustrating a method for reusing/recycling dry particles and structures made therefrom. It has been identified that problems may arise during one or more of the process steps described herein, for example, if various process parameters vary outside a desired specification during a process step. It is identified, according to embodiments described further herein, that dry particles 12, 14, 16, 21, 23, dry films 33 and 34, and one or more structures formed therefrom may be reused/recycled despite such problems arise, if so desired or needed. Because of use of additives, prior art process are unable provide such reuse/recycle process steps. In general, because one or more of the embodiments described herein do not utilize processing additives, the properties of the dry particles 12, 14, 16, 21, and/or 23 are not adversely altered ensuing process steps. Because solvent, lubricants, or other liquids are not used, impurities and residues associated therewith do not degrade the quality of the dry particles 12, 14, 16, 21, and/or 23, allowing the particles to be reused one or more times. Because minimal or nor drying times are needed, dry particles 12, 14, 16, 21, and/or 23 may be reused quickly without adversely affecting throughput of the dry process. Compared against the prior art, it has been identified that the dry particles and/or dry structures formed therefrom may be reused/recycled such that overall process yield and cost can be reduced without affecting overall quality.
It is identified that dry particles 12, 14, 16, 21, and/or 23 may be reused/recycled after being processed by a particular dry process step 19, 20, 22, 24, 26, 28, and/or 29. For example, in one embodiment, after dry process step 18 or 20, if it is determined that a defect in dry particles 12, 14, 16, and/or a structure formed thereform is present, the resulting material may be collected in a dry process step 25 for reuse or recycling. In one embodiment, dry particles 12, 14, and 16 may be returned and reprocessed without addition of any other dry particles, or may be returned and added to fresh new additional particles 12, 14, and/or 16. Dry particles provided for recycling by step 25 may be reblended by dry blend step 18, and further processed according to one or more embodiments described herein. In one embodiment, a dry film 33 comprised of dry particles 12, 14, and 16 as described above in FIG. 2 g, and provided as a self-supporting film 33 by step 24, may be recycled in step 25. In one embodiment, after dry process step 19, 26, or 29, if it is determined that a defect in dry particles 21, 23, or a structure formed therefrom is present, the resulting material may be collected in a dry process step 25 and returned for recycling. In one embodiment, dry particles 21 and 23 may be returned and reprocessed without addition of any other dry particles, or may be returned and added to fresh additional particles 21 or 23. Dry particles provided for recycling by step 25 may be reblended by dry blend step 19, and further processed according to one or more embodiments described herein. In one embodiment, dry particles 12, 14, 16, 21, and 23 as provided as a self-supporting film 34 by step 24 may be recycled in step 25. Prior to reuse, the dry film 33 or 34 can be sliced, chopped, or other wise be reduced in size so as to be more easily blended, by itself, or in combination with additional new dry particles 12, 14, 16, 21, and/or 23.
If after bonding dry film 34 to a collector, a defect in the resulting electrode is found, it is envisioned that the combination of dry film and bonded collector could also be sliced chopped, or otherwise reduced in size so as to be easily blended. Because the collector may comprise a conductor, it is envisioned that the collector portion of the recycled electrode could provide similar functionality to that provided by the dry conductive particles. It is envisioned that the recycled/reused dry film 34 and collector mixture could be used in combination with additional new dry particles 12, 14, 16, 21, and/or 23.
In one embodiment, it is envisioned that a certain percentage of dry reused/recycled dry material provided by step 25 could be mixed with a certain percentage of fresh dry particles 12, 14, 16, 21, and/or 23. In one embodiment a mix of fresh particles 12, 14, 16, 21, and/or 23; and dry reused/recycled material resulting from step 25 comprises a 50/50 mix. Other mixtures of new and old dry structures are also within the scope of the invention. In one embodiment, over all particle percentages by weight, after recycle/reuse steps described herein, may comprise percentages previously described herein, or other percentages as needed. In contrast to embodiments of intermixed film 34 discussed above, those skilled in the art will identify that a dry film 34 comprising one or more recycled structures may, (depending on what particular point a recycle/use step was performed), comprise a dry film with less, or even no, particle distribution gradients (i.e. an evenly intermixed dry film).
Referring now to FIGS. 5 a and 5 b, and preceding Figures as needed, there are seen structures of an energy storage device. In FIG. 5 a, there are shown cross-sections of four intermixed dry films 34, which are bonded to a respective current collector 50 according to one or more embodiments described previously herein. First surfaces of each of the dry films 34 are coupled to a respective current collector 50 in a configuration that is shown as a top dry electrode 54 and a bottom dry electrode 54. According to one or more of the embodiments discussed previously herein, the top and bottom dry electrodes 54 are formed from a blend of dry particles without use of any additives. In one embodiment, the top and bottom dry electrodes 54 are separated by a separator 70. In one embodiment, separator 70 comprises a porous paper sheet of about 30 microns in thickness. Extending ends of respective current collectors 50 are used to provide a point at which electrical contact can be effectuated. In one embodiment, the two dry electrodes 54 and separators 70 are subsequently rolled together in an offset manner that allows an exposed end of a respective collector 50 of the top electrode 54 to extend in one direction and an exposed end of a collector 50 of the bottom electrode 54 to extend in a second direction. The resulting geometry is known to those skilled in the art as a jellyroll and is illustrated in a top view by FIG. 5 b.
Referring now to FIG. 5 b, and preceding Figures as needed, first and second electrodes 54, and two separators 70 are rolled about a central axis to form a rolled energy storage device electrode 200. In one embodiment, the electrode 200 comprises two dry films 34, each dry film comprising a width and a length. In one embodiment, one square meter of a 150 micron thick dry film 34 weighs about 0.1 kilogram. In one embodiment, the dry films 34 comprise a thickness of about 80 to 260 microns. In one embodiment, a width of the dry films comprises between about 10 to 300 mm. In one embodiment, a length is about 0.1 to 5000 meters and the width is between 30 and 150 mm. Other particular dimensions may be may be determined by a required final energy storage device storage parameter. In one embodiment, the storage parameter includes values between 1 and 5000 Farads. With appropriate changes and adjustments, other dry film 34 dimensions and other capacitance are within the scope of the invention. Those skilled in the art will understand that offset exposed current collectors 50 (shown in FIG. 5 a) extend from the roll, such that one collector extends from one end of the roll in one direction and another collector extends from an end of the roll in another direction. In one embodiment, the collectors 50 may be used to make electric contact with internal opposing ends of a sealed housing, which can include corresponding external terminals at each opposing end for completing an electrical contact.
Referring now to FIG. 6, and preceding Figures as needed, during manufacture, a rolled electrode 1200 made according to one or more of the embodiments disclosed herein is inserted into an open end of a housing 2000. An insulator (not shown) is placed along a top periphery of the housing 2000 at the open end, and a cover 2002 is placed on the insulator. During manufacture, the housing 2000, insulator, and cover 2002 may be mechanically curled together to form a tight fit around the periphery of the now sealed end of the housing, which after the curling process is electrically insulated from the cover by the insulator. When disposed in the housing 2000, respective exposed collector extensions 1202 of electrode 1200 make internal contact with the bottom end of the housing 2000 and the cover 2002. In one embodiment, external surfaces of the housing 2000 or cover 2002 may include or be coupled to standardized connections/connectors/terminals to facilitate electrical connection to the rolled electrode 1200 within the housing 2000. Contact between respective collector extensions 1202 and the internal surfaces of the housing 2000 and the cover 2002 may be enhanced by welding, soldering, brazing, conductive adhesive, or the like. In one embodiment, a welding process may be applied to the housing and cover by an externally applied laser welding process. In one embodiment, the housing 2000, cover 2002, and collector extensions 1202 comprise substantially the same metal, for example, aluminum. An electrolyte can be added through a filling/sealing port (not shown) to the sealed housing 1200. In one embodiment, the electrolyte is 1.5 M tetramethylammonium or tetrafluoroborate in acetonitrile solvent. After impregnation and sealing, a finished product is thus made ready for commercial sale and subsequent use.
Although the particular systems and methods herein shown and described in detail are capable of attaining the above described objects of the invention, it is understood that the description and drawings presented herein represent some, but not all, embodiments that are broadly contemplated. Structures and methods that are disclosed may thus comprise configurations, variations, and dimensions other than those disclosed. For example, other classes of energy storage devices that utilize electrodes and adhesives as described herein are within the scope of the present invention, including batteries and fuel cells. Also, different housings may comprise coin-cell type, clamshell type, prismatic, cylindrical type geometries, as well as others as are known to those skilled in the art. For a particular type of housing, it is understood that appropriate changes to electrode geometry may be required, but that such changes would be within the scope of those skilled in the art. It is also contemplated that an energy storage device made according to dry principles described herein may comprise two different electrode films that differ in compositions and/or dimensions (i.e. asymmetric electrodes). Additionally, it is contemplated that principles disclosed herein could be utilized in combination with a carbon cloth type electrode. Thus, the scope of the present invention fully encompasses other embodiments that may become obvious to those skilled in the art and that the scope of the present invention is accordingly limited by nothing other than the appended claims and their equivalents.
1. A method of making an energy storage device electrode, the method comprising:
forming a first electrode film from a plurality of particles;
and reusing one or more of the plurality of particles to form a second film.
2. The method of claim 1, wherein the plurality of particles are dry fibrillized.
3. The method of claim 2, wherein the operation of reusing comprises dry fibrillizing the particles after the particles are used to make the first electrode film.
4. The method of claim 1, further comprising coupling a first side of the second film to a collector.
5. The method of claim 1, wherein the one or more of the plurality of particles reused to form the second film comprise fibrillizable fluoropolymer particles, activated carbon particles, and conductive particles.
6. The method of claim 5, wherein the binder comprises a fluoropolymer.
7. The method of claim 5, wherein the conductive particles comprise conductive carbon particles.
8. The method of claim 1, wherein the first film is self-supporting.
9. The method of claim 1, wherein the second film is self-supporting.
10. The method of claim 1, wherein the plurality of particles comprise conductive carbon particles and activated carbon particles.
11. The method of claim 1, wherein the first and second films are heated dry films.
12. The method of claim 1, wherein the second film comprises a density of about 0.50 to 0.70 gm/cm2.
13. The method of claim 1, wherein the first film comprises between about 80% to 95% activated carbon, between about 0% to 15% conductive carbon, and between about 3% to 15% fibrillizable fluoropolymer.
14. The method of claim 13, wherein the first film further comprises a thermoplastic.
15. The method of claim 1, wherein the second film comprises a length of at least one meter.
16. The method of claim 1, wherein the first film comprises substantially no processing additive.
17. The method of claim 1, wherein reusing operation comprises forming the second film using substantially no processing additive.
18. The method of claim 17, wherein the processing additives include hydrocarbons, high boiling point solvents, antifoaming agents, surfactants, dispersion aids, water, pyrrolidone, mineral spirits, ketones, naphtha, acetates, alcohols, glycols, toluene, xylene, and/or isoparaffinic fluids.
19. The method of claim 1, wherein the one or more of the plurality of particles reused to form the second film comprise dry processed recycled binder particles and conductive particles.
20. The method of claim 1, wherein the second film comprises a self-supporting dry intermixed film structure comprised of reused carbon and binder particles.
21. The method of claim 20, wherein the reusing operation comprises forming the second film comprises with substantially no processing additive.
22. The method of claim 1, wherein the one or more of the plurality of particles reused to form the second film comprise dry processed recycled binder particles and activated carbon particles.
23. The method of claim 22, wherein the second film is both conductive and adhesive.
24. The method of claim 23, wherein the second film is coupled directly to a current collector.
25. A method of making an energy storage device electrode, the method comprising:
dry processing a dry mixture of binder particles, activated carbon particles and recycled conductive particles to form an electrode film.
26. The method of claim 25, wherein the binder particles comprise a thermoplastic.
27. The method of claim 25, wherein electrode film is coupled to a collector.
28. The method of claim 25, wherein the recycled conductive particles comprise recycled conductive carbon particles.
29. The method of claim 25, wherein the dry processing operation comprises fibrillizing the binder particles.
30. The method of claim 25, wherein the binder particles comprise fibrillizable fluoropolymer particles.
31. The method of claim 25, wherein the electrode film comprises a self-supporting film.
32. The method of claim 25, wherein the binder particles are recycled.
33. The method of claim 25, wherein the activated carbon particles are recycled.
34. The method of claim 25, wherein the dry processing operation comprises substantially no processing additive.
35. A method of making an energy storage device electrode, the method comprising:
dry processing a dry mixture of activated carbon particles and recyclable binder particles to form a self-supporting electrode film.
36. The method of claim 35, further comprising coupling the self-supporting electrode film to a collector.
37. The method of claim 35, wherein the electrode film comprises a capacitor electrode film.
38. The method of claim 35, wherein the dry processing operation comprises fibrillizing the recyclable binder particles.
39. The method of claim 35, wherein the recyclable binder particles comprise recyclable fibrillizable fluoropolymer particles.
40. The method of claim 35, wherein the recyclable binder particles are recycled.
41. The method of claim 35, wherein the activated carbon particles are recyclable.
42. The method of claim 41, wherein the recyclable activated carbon particles are recycled.
43. The method of claim 35, wherein the dry processing operation comprises substantially no processing additive.
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