Patent Grant
11374214
This application is a continuation application of U.S. Pat. No. 10,658,651, entitled “SELF STANDING ELECTRODES AND METHODS FOR MAKING THEREOF,” issued on May 19, 2020, the contents of which is hereby incorporated by reference in its entirety.
The presently claimed invention was made by or on behalf of the below listed parties to a joint research agreement. The joint research agreement was in effect on or before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the joint research agreement. The parties to the joint research agreement are 1) Honda Research Institute USA, Inc.; and 2) NanoSynthesis Plus, Ltd.
Single walled carbon nanotubes (SWNTs) as additives in various matrices has become one of the most intensively studied areas for applications, owing to their excellent electrical and mechanical properties and high aspect ratio, which is crucial for composite materials. Among various applications, the exploitation of SWNTs as an additive material for performance enhancement of battery electrodes is very promising. The core of mixing technologies is based on liquid process and includes five required steps: a) synthesis of nanotubes, b) dispersion of nanotubes in the proper solvent (de-aggregation), c) functionalization of the nanotube surfaces (protecting against aggregation), d) mixing with binder and e) mixing with active material (preparing slurry). These processes not only are expensive, but also degrade nanotube properties, e.g. dispersion by ball milling, sonication etc., which leads to inevitable reduction of aspect ratio and the introduction of defects and as a result, requires more nanotube loading (wt %) for improved performance.
In some embodiments, the present disclosure is directed to a method of producing a self-standing electrode. The method includes providing an aerosolized mixture of nanotubes and an electrode active material powder, and collecting the mixture on a porous substrate to form the self-standing electrode.
In some embodiments, the present disclosure is directed to a method of producing a self-standing electrode. The method comprises providing an aerosolized mixture of nanotubes and an electrode active material powder, providing at least a first porous substrate, directing the aerosolized mixture toward the first porous substrate, and collecting the mixture on the first porous substrate to form the self-standing electrode, wherein the self-standing electrode is free of binder and metal-based current collector.
In some embodiments, the present disclosure is directed to a method of producing a self-standing electrode, the method comprising: aerosolizing an electrode active material to produce an aerosolized electrode active material powder; contacting the aerosolized electrode active material powder with single-walled carbon nanotubes in a carrier gas to form a mixture of the single-walled carbon nanotubes and the aerosolized electrode active material powder; collecting the mixture on a surface; and removing the carrier gas, to form the self-standing electrode material that is a composite of single-walled carbon nanotubes and the electrode active material, wherein the self-standing electrode is free of binder and metal-based current collector.
In some embodiments, the present disclosure is directed to an apparatus for producing a self-standing electrode, comprising: a single-walled carbon nanotube synthesis reactor which produces single-walled carbon nanotubes; an aerosolizing reactor configured to aerosolize an electrode active material into an aerosolized electrode active material powder and connected to the carbon nanotube synthesis reactor such that the aerosolized electrode active material powder is contacted with the single-walled carbon nanotubes in a carrier gas to form a mixture of the single-walled carbon nanotubes and the aerosolized electrode active material powder; and a collection chamber having a surface configured to collect the mixture and remove the carrier gas so as to form the self-standing electrode material that is a composite of the single-walled carbon nanotubes and the electrode active material.
In some embodiments, the present disclosure is directed to a self-standing electrode, comprising a composite of an electrode active material and single-walled carbon nanotubes; wherein the self-standing electrode does not contain binder material or a metal-based current collector material.
The present disclosure provides methods and apparatuses for the production of self-standing electrodes. Also provided are self-standing electrodes comprising a mixture of nanotubes and electrode active materials.
In an embodiment, a self-standing electrode is prepared by providing an aerosolized mixture of nanotubes and electrode active materials, and directing the aerosolized mixture to a porous substrate to form a self-standing electrode thereon comprising the mixed carbon nanotubes and the electrode active materials.
In some embodiments, the present disclosure is directed to a method of producing a self-standing electrode, the method comprising: aerosolizing an electrode active material to produce an aerosolized electrode active material powder; contacting the aerosolized electrode active material powder with single-walled carbon nanotubes in a carrier gas to form a mixture of the single-walled carbon nanotubes and the aerosolized electrode active material powder; collecting the mixture on a surface; and removing the carrier gas, to form the self-standing electrode material that is a composite of single-walled carbon nanotubes and the electrode active material.
As used herein, “electrode active material” refers to the conductive material in an electrode. The term “electrode” refers to an electrical conductor where ions and electrons are exchanged with an electrolyte and an outer circuit. “Positive electrode” and “cathode” are used synonymously in the present description and refer to the electrode having the higher electrode potential in an electrochemical cell (i.e. higher than the negative electrode). “Negative electrode” and “anode” are used synonymously in the present description and refer to the electrode having the lower electrode potential in an electrochemical cell (i.e. lower than the positive electrode). Cathodic reduction refers to a gain of electron(s) of a chemical species, and anodic oxidation refers to the loss of electron(s) of a chemical species.
In a non-limiting example as shown in
The apparatus for providing the aerosolized mixture of carbon nanotubes and electrode active materials is not limited in any way. In an illustrative example as shown in
Optionally, the apparatus 5 may include a plurality of porous substrates 40, 41 to allow for the continuous production of self-standing electrodes 60, 61. Although only two porous substrates are shown, it is to be understood than any number of porous substrates may be included in the apparatus 5. In a non-limiting example, when the flow of the mixed aerosolized stream 30 across the porous substrate 40 produces the self-standing electrode 60 of the desired thickness, a valve 33 may be adjusted to transfer the flow of the mixed aerosolized stream 30 to a second porous substrate 41. The self-standing electrode 60 may be removed from the first porous substrate 40 during formation of the self-standing electrode 61 on the porous substrate 41. When the flow of the mixed aerosolized stream 30 across the second porous substrate 41 produces the self-standing electrode 61 of a desired thickness, the valve 33 may be adjusted to transfer the flow of the mixed aerosolized stream 30 back to the first porous substrate 40. The thickness and/or cross-sectional area of the self-standing electrode 61 may be the same, or different, than the cross-sectional area of the self-standing electrode 60. For example, the self-standing electrode 61 may have a greater thickness and/or cross-sectional area than the self-standing electrode 60.
It is to be understood that a variety of different methods may be used for automatically switching the valve 33 to redirect the flow of the mixed aerosolized stream 30 from one porous substrate to the other. Illustrative examples of systems that may be used to adjust the valve 33 to redirect the flow of the mixed aerosolized stream 30 include one or more sensors for detecting the thickness of the self-standing electrodes 60 and 61, one or more pressure sensors for monitoring a pressure drop across the porous substrates 40 and 41 that corresponds to a desired thickness of the self-standing electrodes 60 and 61, a timer that switches the valve 33 after a set time corresponding to a desired thickness of the self-standing electrodes 60 and 61 for a given flow rate of the mixed aerosolized stream 30, and any combination thereof; after the one or more pressure sensors measures a pressure drop associated with the desired thickness of the self-standing electrode 60 or 61 on porous substrate 40 or 41, or after the one or more thickness sensors detect the desired thickness of the self-standing electrode 60 or 61 on porous substrate 40 or 41, or after the timer measures the set time corresponding to the desired thickness of self-standing electrode 60 or 61 on porous substrate 40 or 41, the mixture is redirected from one porous substrate to the other. It is also to be understood that the porous substrates 40 and/or 41 may have a cross-sectional area that matches the desired cross-sectional area required for use in the battery cell to be made with the self-standing electrode 60 and/or 61. Accordingly, the self-standing electrodes 60 and/or 61 would require no further processing of the cross-sectional area, such as cutting, before assembly in the final battery cell.
It is to be understood that the configuration of the vessel 10 is not intended to be limited in any way. In an illustrative example as shown in
As shown in
As shown in
As an alternative to the specific apparatus noted above where the electrode active material is mixed with the nanotubes after the nanotubes are formed, the electrode active material can be mixed in situ in a fluidized bed reactor or chamber with the nanotubes as the nanotubes are formed.
Carrier and fluidizing gases suitable for use with the present disclosure include, but are not limited to, argon, hydrogen, nitrogen, and combinations thereof. Carrier gases may be used at any suitable pressure and at any suitable flow rate to aerosolize the nanotubes and the electrode active materials and transport the aerosolized mixture of the nanotubes and the electrode active materials to the porous substrate at a sufficient velocity to form the self-standing electrode on the surface thereof. In some embodiments, the carrier gas may be argon, hydrogen, helium, or mixtures thereof. In some embodiments, the carrier gas may comprise argon at a flow rate of 850 standard cubic centimeters per minute (sccm) and hydrogen at a flow rate of 300 sccm.
The type of nanotubes used in the present disclosure are not limited. The nanotubes may be entirely carbon, or they made be substituted, that it is, have non-carbon lattice atoms. Carbon nanotubes may be externally derivatized to include one or more functional moieties at a side and/or an end location. In some aspects, carbon and inorganic nanotubes include additional components such as metals or metalloids, incorporated into the structure of the nanotube. In certain aspects, the additional components are a dopant, a surface coating, or are a combination thereof.
Nanotubes may be metallic, semimetallic, or semi-conducting depending on their chirality. A carbon nanotube's chirality is indicated by the double index (n,m), where n and m are integers that describe the cut and wrapping of hexagonal graphite when formed into a tubular structure, as is well known in the art. A nanotube of an (m,n) configuration is insulating. A nanotube of an (n,n), or “arm-chair”, configuration is metallic, and hence highly valued for its electric and thermal conductivity. Carbon nanotubes may have diameters ranging from about 0.6 nm for single-wall carbon nanotubes up to 500 nm or greater for single-wall or multi-wall nanotubes. The nanotubes may range in length from about 50 nm to about 10 cm or greater.
In a non-limiting example, the carbon nanotubes may be synthesized in a reactor or furnace from a carbon source in the presence of a catalyst, at a temperature of about 1000 to about 1500° C., such as about 1300° C.
The present disclosure is not limited to the type or form of catalysts used for the production of carbon nanotubes. In various aspects, the catalyst particles are present as an aerosol. In some aspects, the catalyst materials are supplied as nanoparticles, comprising a transition metal, a lanthanide metal, or an actinide metal. For example, the catalyst may comprise a Group VI transition metal such as chromium (Cr), molybdenum (Mo), and tungsten (W), or a Group VIII transition metal such as iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), Iridium (Ir), and platinum (Pt). In some aspects, a combination of two or more metals are used, for example an iron, nickel, and cobalt mixture or more specifically a 50:50 mixture (by weight) of nickel and cobalt. The catalyst may comprise a pure metal, a metal oxide, a metal carbide, a nitrate salt of a metal, and/or other compounds containing one or more of the metals described herein. The catalyst may be added to the reactor at about 0.1 atom % to about 10 atom %, where atom % indicates the percentage of the number of catalyst atoms with respect to the total number of atoms in the reactor (catalyst and carbon precursor atoms).
Alternatively or in combination, a catalyst precursor may be introduced, wherein the catalyst precursor can be converted to an active catalyst under the reactor's conditions. The catalyst precursor may comprise one or more transition metal salts such as a transition metal nitrate, a transition metal acetate, a transition metal citrate, a transition metal chloride, a transition metal fluoride, a transition metal bromide, a transition metal iodide, or hydrates thereof. For example, the catalyst precursor may be a metallocene, a metal acetylacetonate, a metal phthalocyanine, a metal porphyrin, a metal salt, a metalorganic compound, or a combination thereof. For example, the catalyst precursor may be a ferrocene, nickelocene, cobaltocene, molybdenocene, ruthenocene, iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, molybdenum acetylacetonate, ruthenium acetylacetonate, iron phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine, iron porphyrin, nickel porphyrin, cobalt porphyrin, an iron salt, a nickel salt, cobalt salt, molybdenum salt, ruthenium salt, or a combination thereof. The catalyst precursor may comprise a soluble salt such as Fe(NO3)3, Ni(NO3)2 or Co(NO3)2 dissolved in a liquid such as water. The catalyst precursor may achieve an intermediate catalyst state in the catalyst particle growth zone of the reactor, and subsequently become converted to an active catalyst upon exposure to the nanostructure growth conditions in the nanostructure growth zone of the reactor. For example, the catalyst precursor may be a transition metal salt that is converted into a transition metal oxide in the catalyst particle growth zone, then converted into active catalytic nanoparticles in the nanostructure growth zone.
The catalyst particles may comprise a transition metal, such as a d-block transition metal, an f-block transition metal, or a combination thereof. For example, the catalyst particles may comprise a d-block transition metal such as an iron, nickel, cobalt, gold, silver, or a combination thereof. The catalyst particles may be supported on a catalyst support. In order to have catalyst particles on a catalyst support, the catalyst support material may be introduced into the catalyst material prior to adding the catalyst to the reactor.
The present disclosure is not limited to the type of carbon precursors or carbon sources used to form carbon nanotubes such as one or more carbon-containing gases, one or more hydrocarbon solvents, and mixtures thereof. Examples of carbon precursors include, but are not limited to hydrocarbon gases, such as methane, acetylene, and ethylene; alcohols, such as ethanol and methanol; benzene; toluene; CO; and CO2. A fuel for carbon nanotube synthesis and growth comprises a mixture of one or more carbon precursors or carbon sources and one or more catalysts or catalyst precursors.
The fuel or precursor may be injected at a range of about 0.05 to about 1 ml/min, such as about 0.1 ml/min or about 0.3 ml/min, per injector. In some embodiments, more than one injector may be used, for example at large scale. The gas flow rate may be about 0.1 to about 5 L/min of hydrogen and/or about 0.2 to about 2 L/min helium or argon, such as about 5 L/min hydrogen, or 0.3 L/min hydrogen and about 1 L/min argon. Without wishing to be bound to any particular theory, helium or argon may be included in the carrier gas to dilute the hydrogen concentration, for example to keep the hydrogen concentration below the explosive limit. Selection of a fuel injection rate and/or a gas flow rate may depend, for example, on the reactor volume, as will be apparent to those of ordinary skill in the art. In some embodiments, more than one reactor may be used in conjunction. In some embodiments, the reactor temperature profile consists of a starting low temperature, an increase to a peak or a maximum, and then a decrease, preferably to the starting low temperature. Without wishing to be bound by any particular theory, for a given reactor temperature profile, the injector position inside the reactor should be correlated with the precursor temperature so that the precursor evaporates from the point of injection, without droplet formation or decomposition, as can be determined by those of ordinary skill in the art, considering for example the boiling point and decomposition. In some embodiments, the injector tip may be inserted into the reactor, for example, by about 8 inches. The injection temperature, at the tip of the injector, may depend on the reactor or furnace temperature and upon the depth of insertion of the injector into the reactor or furnace. In some embodiments, the injection temperature at the tip of the injector is about 750° C. In some embodiments, the injector tip is inserted about 8 inches inside the reactor. The carbon nanotube reactor may be run for any suitable length of time to obtain the product composition and thickness desired, as can be determined by those of ordinary skill in the art, for example as long as there are starting materials.
Carbon nanotubes synthesized according to the present disclosure may be characterized using any suitable means known in the art, including but not limited to derivative thermogravimetric analysis (DTG) and Raman spectroscopy, such as for calculation of the G/D ratio, as is disclosed in U.S. Patent Application Publication No. 2009/0274609, which is incorporated herein by reference in its entirety. The Raman spectra of SWNTs has three major peaks, which are the G-band at about 1590 cm−1, D-band at about 1350 cm−1, and the Radial breathing mode (RBM) at about 100-300 cm−. RBM frequency is proportional to an inverse of the diameter of SWNTs and can thus be used to calculate the diameter of the SWNT. Normally, a red shift in RBM peak corresponds to an increase in the mean diameter of SWNTs. The tangential mode G-band related to the Raman-allowed phonon mode E2g can be a superposition of two peaks. The double peak at about 1593 and 1568 cm−1 has been assigned to semiconductor SWNTs, while the broad Breit-Wigner-Fano line at about 1550 cm−1 has been assigned to metallic SWNTs. Thus, G-band offers a method for distinguishing between metallic and semiconducting SWNTs. The D-band structure is related to disordered carbon, the presence of amorphous carbon, and other defects due to the sp2-carbon network. The ratio of the G-band to D-band in the Raman spectra (IG:ID or G/D ratio) of SWNTs can be used as an index to determine the purity and quality of the SWNTs produced. Preferably, IG:ID is about 1 to about 500, preferably about 5 to about 400, more preferably greater than about 7. A representative, non-limiting example of DTG of carbon nanotubes synthesized according to the present disclosure is shown in
Collecting the mixture of single-walled carbon nanotubes and aerosolized electrode active material powder on a surface and removing the carrier gas may be carried out by any suitable means. The collecting surface of the porous substrate 40, 41 may be a porous surface, including but not limited to a filter or a frit, where the pores are appropriately sized to retain the mixture of carbon nanotubes and the electrode active material thereon to form the self-standing electrode while permitting passage of the carrier and fluidizing gases. The carrier and fluidizing gases may be removed after passing through the surface and by way of an outlet. In some embodiments, removal of the carrier gas may be facilitated by a vacuum source. With respect to filters, the filters may be in the form of a sheet and may comprise a variety of different materials including woven and non-woven fabrics. Illustrative filter materials include, but are not limited to, cotton, polyolefins, nylons, acrylics, polyesters, fiberglass, and polytetrafluoroethylene (PTFE). To the extent the porous substrate is sensitive to high temperatures, one or more of the streams 25A, 25B, and 30 may be precooled with dilution gases comprising a lower temperature and/or by directing one or more of the streams 25A, 25B and 30 through a heat exchanger prior to contacting the porous substrate.
In some embodiments, the aerosolizing of the electrode active material comprises distributing an aerosolizing gas through a first porous frit and a bed of an electrode active material, in an aerosolizing chamber, to produce the aerosolized electrode active material powder. The aerosolizing chamber may be constructed with an appropriately sized porous material such that gas can pass through to enable aerosolization but that does not permit the active material to fall through the pores. The aerosolizing chamber is not limited to any particular configuration. Suitable aerosolizing gases include, but are not limited to, argon, helium, or nitrogen. In some embodiments, the aerosolizing gas may be the same as the carrier gas.
In some embodiments, the electrode active material is selected from graphite, hard carbon, metal oxides, lithium metal oxides, and lithium iron phosphate. In some embodiments, the electrode active material for the anode may be graphite or hard carbon. In some embodiments, the electrode active material for the cathode may be lithium metal oxides or lithium iron phosphate.
In a non-limiting example, the electrode active material may be any solid, metal oxide powder that is capable of being aerosolized. In an illustrative example, the metal oxide is a material for use in the cathode of the battery. Non-limiting examples of metal oxides include oxides of Ni, Mn, Co, Al, Mg, Ti and any mixture thereof. The metal oxide may be lithiated. In an illustrative example, the metal oxide is lithium nickel manganese cobalt oxide (LiNiMnCoO2). The metal oxide powders can have a particle size defined within a range between about 1 nanometer and about 100 microns. In a non-limiting example, the metal oxide particles have an average particle size of about 1 nanometer to about 10 nanometers.
Metals in lithium metal oxides according to the present disclosure may include but are not limited to one or more alkali metals, alkaline earth metals, transition metals, aluminum, or post-transition metals, and hydrates thereof. In some embodiments, the electrode active material is lithium nickel manganese cobalt oxide (LiNiMnCoO2).
“Alkali metals” are metals in Group I of the periodic table of the elements, such as lithium, sodium, potassium, rubidium, cesium, or francium.
“Alkaline earth metals” are metals in Group II of the periodic table of the elements, such as beryllium, magnesium, calcium, strontium, barium, or radium.
“Transition metals” are metals in the d-block of the periodic table of the elements, including the lanthanide and actinide series. Transition metals include, but are not limited to, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and lawrencium.
“Post-transition metals” include, but are not limited to, gallium, indium, tin, thallium, lead, bismuth, or polonium.
In some embodiments, the method further comprises allowing the mixture of single-walled carbon nanotubes and electrode active material in the carrier gas to flow through one or more tubes connecting the aerosolizing reactor, the carbon nanotube synthesis reactor, and the collection chamber. In some embodiments, the one or more tubes are at least about 0.5″ O.D. stainless tubing.
The loading or weight % of carbon nanotubes in the composite self-standing electrode product is based on the relative amounts of the nanotubes (or carbon source used to form the nanotubes) and the electrode active material. It is within the level of ordinary skill in the art to determine the relative starting amounts of carbon source, catalyst/catalyst precursor, and electrode active material that will afford a given loading or weight % of carbon nanotubes in the composite self-standing electrode product. In a non-limiting example, the self-standing electrode may comprise from 0.1% to 4% by weight carbon nanotubes, and the balance the electrode active material and optionally one or more additives. Optionally, the self-standing electrode may comprise from 0.2% to 3% by weight carbon nanotubes, and the balance the electrode active material and optionally one or more additives. Optionally, the self-standing electrode may comprise from 0.75% to 2% by weight carbon nanotubes, and the balance the electrode active material and optionally one or more additives. Additives and/or dopants may be present for each range in an amount of 0 to 5% by weight. In a non-limiting example, the self-standing electrode consists essentially of the carbon nanotubes and the electrode active material powder. In a non-limiting example, the self-standing electrode consists of the carbon nanotubes and the electrode active material powder. For each of the ranges, the self-standing electrode may be free of any binders. The lack of a binder results in a self-standing electrode with improved flexibility. Further, it has been discovered that a higher carbon nanotube content increases the flexibility of the self-standing electrode. Without being bound to any particular theory, this is likely due to the webbed morphology of the self-standing electrode in which there is a webbed arrangement of carbon nanotubes with the electrode active material contained or embedded within the web.
In a non-limiting example, the self-standing electrode may comprise a density of 0.9 to 1.75 g/cc. Optionally, the self-standing electrode may comprise a density of 0.95 to 1.25 g/cc. Optionally, the self-standing electrode may comprise a density of 0.75 to 2.0 g/cc. Optionally, the self-standing electrode may comprise a density of 0.95 to 1.60 g/cc.
In a non-limiting example, the self-standing electrode may comprise a thickness of up to 750 μm following collection on the porous substrate. Optionally, the self-standing electrode may comprise a thickness of 50 μm to 500 μm following collection on the porous substrate. Optionally, the self-standing electrode may comprise a thickness of from 100 μm to 450 μm following collection on the porous substrate. Optionally, the self-standing electrode may comprise a thickness of from 175 μm to 250 μm following collection on the porous substrate.
In some embodiments, the method of the present disclosure may further comprise treating the composite or self-standing electrode, including but not limited to pressing the composite or self-standing electrode. Without wishing to be bound to any particular theory, pressing may increase the density and/or lower the thickness of the self-standing electrode, which may improve such properties as rate performance, energy density, and battery life. Pressing of the self-standing electrodes may be carried out by applying a force to achieve a desired thickness and/or density, such as by using a rolling press or calendaring machine, platen press, or other suitable means, as will be known to those of ordinary skill in the art. Any suitable force may be applied, to achieve a desired thickness, and/or density, and/or impedance, such as but not limited to a force of about 1 ton, about 2 tons, about 3 tons, about 4 tons, about 5 tons, about 6 tons, about 7 tons, about 8 tons, about 9 tons, about 10 tons, about 15 tons, or any integer or range in between, such as between about 7 tons and about 10 tons. In some embodiments, pressing may be limited to pressing to a thickness of about 20 microns, about 30 microns, about 40 microns, about 50 microns, about 60 microns, about 70 microns, about 80 microns, about 90 microns, about 100 microns, about 150 microns, about 200 microns, about 250 microns, about 300 microns, about 350 microns, about 400 microns, or any integer or range in between. Without wishing to be bound by any particular theory, too thick of an electrode may be slow to produce energy or may not be suitably flexible. In some embodiments, it may be desirable to obtain an electrode foil that is flexible without formation of oxide or cracks. If the electrode is too thin, energy production may be rapid but it may be the case that not enough energy is produced. In addition, it may be desirable to regulate the distance between the rolls or rollers in a rolling press or calendaring machine, or between the plates of a platen press, by any suitable means known to those of ordinary skill in the art.
Determination of a suitable amount of pressing is within the level of ordinary skill in the art. As will be known to those of ordinary skill in the art, excessive pressing may cause the electrolyte to penetrate the electrode too much, as determined by measuring impedance and/or resistance to diffusion. As will be evident to those of ordinary skill in the art, it may be of interest to minimize the electrolyte diffusion resistance or coefficient for a given electrolyte, as measured by impedance. In a non-limiting example, the thickness of the self-standing electrode following pressing may be from 40% to 75% of the thickness of the untreated self-standing electrode, or the self-standing electrode following collection on the porous substrate. Optionally, the thickness of the self-standing electrode following pressing may be from 45% to 60% of the thickness of the untreated self-standing electrode, or the self-standing electrode following collection on the porous substrate.
In a non-limiting example, the density of the self-standing electrode following pressing is increased by 40% to 125% of the density of the untreated self-standing electrode, or the self-standing electrode following collection on the porous substrate. Optionally, the density of the self-standing electrode following pressing is increased by 45% to 90% of the density of the untreated self-standing electrode, or the self-standing electrode following collection on the porous substrate.
In some embodiments, the present disclosure is directed to an apparatus for producing a self-standing electrode, comprising: a single-walled carbon nanotube synthesis reactor which produces single-walled carbon nanotubes; an aerosolizing reactor configured to aerosolize an electrode active material into an aerosolized electrode active material powder and connected to the carbon nanotube synthesis reactor such that the aerosolized electrode active material powder is contacted with the single-walled carbon nanotubes in a carrier gas to form a mixture of the single-walled carbon nanotubes and the aerosolized electrode active material powder; and a collection chamber having a surface configured to collect the mixture and remove the carrier gas so as to form the self-standing electrode material that is a composite of the single-walled carbon nanotubes and the electrode active material. All embodiments described for the method apply with equal force to the apparatus.
The surface may be configured to collect the mixture and remove the carrier gas by any suitable means. The collecting surface may be a porous surface, including but not limited to a filter or a frit, where the pores are appropriately sized to permit passage of the carrier gas but not the mixture of carbon nanotubes and electrode active material. The carrier gas may be removed after passing through the surface and by way of an outlet. In some embodiments, removal of the carrier gas may be facilitated by a vacuum source.
In some embodiments, the aerosolizing reactor comprises a vertical shaker, one or more gas inlets, one or more outlets, and a first porous frit.
In some embodiments, the aerosolizing reactor is downstream of the carbon nanotube synthesis reactor and upstream of the collection chamber.
In some embodiments, the aerosolizing reactor is upstream of the carbon nanotube synthesis reactor and upstream of the collection chamber.
In some embodiments, the aerosolizing reactor is coincident with the carbon nanotube synthesis reactor and upstream of the collection chamber.
In some embodiments, the present disclosure is directed to a self-standing electrode, comprising a composite of an electrode active material and single-walled carbon nanotubes; wherein the self-standing electrode does not contain binder material or a metal-based current collector material.
In some embodiments, the self-standing electrode comprises a webbed morphology or a net. In some embodiments, a webbed morphology or a net is a webbed arrangement of carbon nanotubes with the electrode active material contained or embedded within the carbon nanotube web or net.
While the aspects described herein have been described in conjunction with the example aspects outlined above, various alternatives, modifications, variations, improvements, and/or substantial equivalents, whether known or that are or may be presently unforeseen, may become apparent to those having at least ordinary skill in the art. Accordingly, the example aspects, as set forth above, are intended to be illustrative, not limiting. Various changes may be made without departing from the spirit and scope of the disclosure. Therefore, the disclosure is intended to embrace all known or later-developed alternatives, modifications, variations, improvements, and/or substantial equivalents.
Thus, the claims are not intended to be limited to the aspects shown herein, but are to be accorded the full scope consistent with the language of the claims, wherein reference to an element in the singular is not intended to mean “one and only one” unless specifically so stated, but rather “one or more.” All structural and functional equivalents to the elements of the various aspects described throughout this disclosure that are known or later come to be known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the claims. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims. No claim element is to be construed as a means plus function unless the element is expressly recited using the phrase “means for.”
Further, the word “example” is used herein to mean “serving as an example, instance, or illustration.” Any aspect described herein as “example” is not necessarily to be construed as preferred or advantageous over other aspects. Unless specifically stated otherwise, the term “some” refers to one or more. Combinations such as “at least one of A, B, or C,” “at least one of A, B, and C,” and “A, B, C, or any combination thereof” include any combination of A, B, and/or C, and may include multiples of A, multiples of B, or multiples of C. Specifically, combinations such as “at least one of A, B, or C,” “at least one of A, B, and C,” and “A, B, C, or any combination thereof” may be A only, B only, C only, A and B, A and C, B and C, or A and B and C, where any such combinations may contain one or more member or members of A, B, or C. Nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims.
Moreover, all references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference.
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the present invention, and are not intended to limit the scope of what the inventors regard as their invention nor are they intended to represent that the experiments below are all or the only experiments performed. Efforts have been made to ensure accuracy with respect to numbers used (e.g. amounts, dimensions, etc.) but some experimental errors and deviations should be accounted for.
Production of flexible self-standing electrodes. The following self-standing electrode examples set forth in
A quartz tube having dimensions of 25 mm OD×22 mm ID×760 mm length was provided as the carbon nanotube reactor 10A for the apparatus 5 (
Reactor 10A was heated to a temperature of 1300° C. The carrier gas 20A included a mixture of 850 sccm Ar and 300 sccm H2 and was provided to the reactor 10A via inlet 128. The catalyst precursor 130 composition was 80% ethanol, 20% methanol, 0.18% ferrocene, and 0.375% thiophene. The ethanol functioned both as a solvent for the ferrocene and as the carbon source for growing the nanotubes. The catalyst precursor 130 solution was injected at a rate of 0.3 ml/min via inlet 132 into the reactor carbon nanotube growth zone, where the ferrocene decomposed to iron catalyst particles and the ethanol was converted to a carbon source for the growth of single-walled nanotubes on the iron catalysts. The carrier gas 20A transported the single-walled nanotubes through reactor outlet 175 and into tube 412 as the first aerosolized stream 25A.
Lithium nickel manganese cobalt oxide (LiNiMnCoO2) particles were used as the electrode active material 106 and were loaded into aerosolizing chamber 10B on frit 407 to a height of about 5 mm, loading about 50 g. The carrier/aerosolizing gas 20B, argon, was provided at a rate of about 2 L/min Ar through porous frit 407 via inlet 408 (1 L/min; bottom up) and inlets 409, 410 (1 L/min; tangential flows) in combination. Aerosolized suspended LiNiMnCoO2 exits aerosolizing chamber 10B as the second aerosolized stream 25B via tube 413 and combines with the first aerosolized stream 25A comprising the synthesized carbon nanotubes traveling through tube 412 at the junction 27, forming a mixture 30 of aerosolized, suspended LiNiMnCoO2 and carbon nanotubes in the carrier gases. The mixture 30 travels through tube 416 into collection chamber 170 via an inlet 418. The mixture 30 of LiNiMnCoO2 and carbon nanotubes deposits on the porous substrate 40, in this case a porous frit, as a composite self-standing electrode 60, as the carrier gases 50 pass through frit 40 and out an exhaust 420.
As shown in
As shown below in Table 1, several additional self-standing electrodes were prepared using the same method with differing amounts of single-walled nanotubes (the balance of the self-standing electrode being LiNiMnCoO2 particles), as well as different thicknesses (as collected from the porous substrate). The self-standing electrodes of samples 7-11 were treated following collection from the porous substrate by pressing to increase the density. Pressing of the self-standing electrodes also resulted in a thickness reduction.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3513034 | Fischbach et al. | May 1970 | A |
| 3772084 | Scholle | Nov 1973 | A |
| 5985175 | Fan et al. | Nov 1999 | A |
| 7094385 | Beguin et al. | Aug 2006 | B2 |
| 7288870 | Mitcham et al. | Oct 2007 | B2 |
| 7348101 | Gozdz et al. | Mar 2008 | B2 |
| 7622059 | Bordere et al. | Nov 2009 | B2 |
| 7999028 | Lin et al. | Aug 2011 | B2 |
| 8083905 | Choi et al. | Dec 2011 | B2 |
| 8084158 | Chu et al. | Dec 2011 | B2 |
| 8293204 | Khodadadi et al. | Oct 2012 | B2 |
| 8435676 | Zhamu et al. | May 2013 | B2 |
| 8465871 | Juzkow et al. | Jun 2013 | B2 |
| 8628747 | Zachariah et al. | Jan 2014 | B2 |
| 8703092 | Ziegler | Apr 2014 | B2 |
| 8787001 | Fleischer et al. | Jul 2014 | B2 |
| 8825178 | Feng et al. | Sep 2014 | B2 |
| 8883113 | Richter et al. | Nov 2014 | B2 |
| 8974960 | Manthiram et al. | Mar 2015 | B2 |
| 8986872 | Lev et al. | Mar 2015 | B2 |
| 9034421 | Mikhaylik et al. | May 2015 | B2 |
| 9167736 | Shah et al. | Oct 2015 | B2 |
| 9396829 | Mann et al. | Jul 2016 | B2 |
| 9406985 | Amaratunga et al. | Aug 2016 | B2 |
| 9450266 | Hosaka et al. | Sep 2016 | B2 |
| 9502734 | Lim et al. | Nov 2016 | B1 |
| 9615473 | Kim | Apr 2017 | B2 |
| 9692056 | Liu et al. | Jun 2017 | B1 |
| 9711763 | Sohn et al. | Jul 2017 | B2 |
| 9782082 | Gannon et al. | Oct 2017 | B2 |
| 9786872 | Suh et al. | Oct 2017 | B2 |
| 9807876 | Catchpole | Oct 2017 | B2 |
| 9812681 | Heo | Nov 2017 | B2 |
| 9859586 | Suh et al. | Jan 2018 | B2 |
| 9887644 | Kim et al. | Feb 2018 | B2 |
| 9941492 | Suh et al. | Apr 2018 | B2 |
| 9972868 | Choi et al. | May 2018 | B2 |
| 9979225 | Bernhard | May 2018 | B2 |
| 10033031 | Wang et al. | Jul 2018 | B2 |
| 10090556 | Rho et al. | Oct 2018 | B2 |
| 10096803 | Iseri et al. | Oct 2018 | B2 |
| 10122010 | Tajima et al. | Nov 2018 | B2 |
| 10147915 | Song et al. | Dec 2018 | B2 |
| 10199851 | Hiroki et al. | Feb 2019 | B2 |
| 10217971 | Takahashi et al. | Feb 2019 | B2 |
| 10957939 | Zhi et al. | Mar 2021 | B2 |
| 20030084847 | Wood et al. | May 2003 | A1 |
| 20030099883 | Ochoa et al. | May 2003 | A1 |
| 20040086783 | Fong et al. | May 2004 | A1 |
| 20040234445 | Serp et al. | Nov 2004 | A1 |
| 20050008778 | Utsugi et al. | Jan 2005 | A1 |
| 20050063891 | Shaffer et al. | Mar 2005 | A1 |
| 20050148887 | Reiter et al. | Jul 2005 | A1 |
| 20050209392 | Luo et al. | Sep 2005 | A1 |
| 20050221185 | Sakata et al. | Oct 2005 | A1 |
| 20060039849 | Resasco et al. | Feb 2006 | A1 |
| 20060078489 | Harutyunyan et al. | Apr 2006 | A1 |
| 20060116443 | Probst et al. | Jun 2006 | A1 |
| 20060151318 | Park et al. | Jul 2006 | A1 |
| 20060245996 | Xie et al. | Nov 2006 | A1 |
| 20070224106 | Sakakibara et al. | Sep 2007 | A1 |
| 20070274899 | Wolf et al. | Nov 2007 | A1 |
| 20080131351 | Wang et al. | Jun 2008 | A1 |
| 20080210550 | Walther et al. | Sep 2008 | A1 |
| 20080233402 | Carlson et al. | Sep 2008 | A1 |
| 20080258117 | Sakakibara et al. | Oct 2008 | A1 |
| 20090117026 | Shimazu et al. | May 2009 | A1 |
| 20090142659 | Lai et al. | Jun 2009 | A1 |
| 20090208708 | Wei et al. | Aug 2009 | A1 |
| 20090226704 | Kauppinen et al. | Sep 2009 | A1 |
| 20090274609 | Harutyunyan et al. | Nov 2009 | A1 |
| 20090286675 | Wei et al. | Nov 2009 | A1 |
| 20100000441 | Jang et al. | Jan 2010 | A1 |
| 20100038602 | Plee | Feb 2010 | A1 |
| 20100112443 | Blomgren | May 2010 | A1 |
| 20100140560 | Wang et al. | Jun 2010 | A1 |
| 20100178543 | Gruner et al. | Jul 2010 | A1 |
| 20100221606 | Nalamasu et al. | Sep 2010 | A1 |
| 20100276644 | Wolf et al. | Nov 2010 | A1 |
| 20100285352 | Juzkow et al. | Nov 2010 | A1 |
| 20100285358 | Cui et al. | Nov 2010 | A1 |
| 20110060162 | Tatsuhara et al. | Mar 2011 | A1 |
| 20110111279 | Smithyman et al. | May 2011 | A1 |
| 20110123429 | Bordere et al. | May 2011 | A1 |
| 20110150746 | Khodadadi et al. | Jun 2011 | A1 |
| 20110158892 | Yamaki | Jun 2011 | A1 |
| 20110171398 | Oladeji | Jul 2011 | A1 |
| 20110177393 | Park et al. | Jul 2011 | A1 |
| 20110281156 | Boren et al. | Nov 2011 | A1 |
| 20110311874 | Zhou et al. | Dec 2011 | A1 |
| 20120105370 | Moore | May 2012 | A1 |
| 20120107683 | Kim et al. | May 2012 | A1 |
| 20120132861 | Tamamitsu et al. | May 2012 | A1 |
| 20120138148 | Harutyunyan | Jun 2012 | A1 |
| 20120141864 | Juzkow et al. | Jun 2012 | A1 |
| 20120149824 | Hocke et al. | Jun 2012 | A1 |
| 20120177934 | Vogel et al. | Jul 2012 | A1 |
| 20120193602 | Lieber et al. | Aug 2012 | A1 |
| 20120241666 | Hong et al. | Sep 2012 | A1 |
| 20120282522 | Axelbaum et al. | Nov 2012 | A1 |
| 20120295161 | Wang et al. | Nov 2012 | A1 |
| 20120315539 | Lashmore et al. | Dec 2012 | A1 |
| 20120321911 | Watanabe et al. | Dec 2012 | A1 |
| 20130040229 | Grigorian et al. | Feb 2013 | A1 |
| 20130065130 | Ban et al. | Mar 2013 | A1 |
| 20130106026 | Wang et al. | May 2013 | A1 |
| 20130143077 | Yebka et al. | Jun 2013 | A1 |
| 20130149440 | Pyzik et al. | Jun 2013 | A1 |
| 20130171485 | Kodera et al. | Jul 2013 | A1 |
| 20130189565 | Lashmore et al. | Jul 2013 | A1 |
| 20130224551 | Hiralal et al. | Aug 2013 | A1 |
| 20130256011 | Chang et al. | Oct 2013 | A1 |
| 20130323583 | Phares | Dec 2013 | A1 |
| 20140013588 | Wang et al. | Jan 2014 | A1 |
| 20140021403 | Kim et al. | Jan 2014 | A1 |
| 20140057178 | He et al. | Feb 2014 | A1 |
| 20140065447 | Liu et al. | Mar 2014 | A1 |
| 20140141248 | Noyes | May 2014 | A1 |
| 20140170490 | Izuhara et al. | Jun 2014 | A1 |
| 20140178543 | Russell et al. | Jun 2014 | A1 |
| 20140255782 | Jabbour et al. | Sep 2014 | A1 |
| 20140326181 | Kim | Nov 2014 | A1 |
| 20140370347 | Jung et al. | Dec 2014 | A1 |
| 20150010788 | Aria et al. | Jan 2015 | A1 |
| 20150037239 | Sue et al. | Feb 2015 | A1 |
| 20150044581 | Holme et al. | Feb 2015 | A1 |
| 20150064521 | Watanabe et al. | Mar 2015 | A1 |
| 20150087858 | Ci et al. | Mar 2015 | A1 |
| 20150133569 | Gong et al. | May 2015 | A1 |
| 20150188112 | Adre et al. | Jul 2015 | A1 |
| 20150200417 | Song et al. | Jul 2015 | A1 |
| 20150207143 | Wu et al. | Jul 2015 | A1 |
| 20150207168 | Do et al. | Jul 2015 | A1 |
| 20150233010 | Pan et al. | Aug 2015 | A1 |
| 20150236366 | Chang et al. | Aug 2015 | A1 |
| 20150243451 | Kim et al. | Aug 2015 | A1 |
| 20150243452 | Gruner et al. | Aug 2015 | A1 |
| 20150255828 | Momo et al. | Sep 2015 | A1 |
| 20150279578 | Martini et al. | Oct 2015 | A1 |
| 20150325820 | Sohn et al. | Nov 2015 | A1 |
| 20150333302 | Johns et al. | Nov 2015 | A1 |
| 20150340684 | Voillequin et al. | Nov 2015 | A1 |
| 20150340741 | Kim et al. | Nov 2015 | A1 |
| 20150349325 | Chen et al. | Dec 2015 | A1 |
| 20150364750 | Maheshwari et al. | Dec 2015 | A1 |
| 20150380738 | Zhou et al. | Dec 2015 | A1 |
| 20160013457 | Suh et al. | Jan 2016 | A1 |
| 20160013458 | Suh et al. | Jan 2016 | A1 |
| 20160020437 | Sohn et al. | Jan 2016 | A1 |
| 20160023905 | Wei | Jan 2016 | A1 |
| 20160036059 | Tokune et al. | Feb 2016 | A1 |
| 20160040780 | Donahue | Feb 2016 | A1 |
| 20160049569 | Negrin | Feb 2016 | A1 |
| 20160079629 | Abe et al. | Mar 2016 | A1 |
| 20160082404 | Pigos | Mar 2016 | A1 |
| 20160094079 | Hiroki et al. | Mar 2016 | A1 |
| 20160126554 | Beneventi et al. | May 2016 | A1 |
| 20160149193 | Seong | May 2016 | A1 |
| 20160149253 | Yi et al. | May 2016 | A1 |
| 20160166837 | Strommer et al. | Jun 2016 | A1 |
| 20160329533 | Tajima | Nov 2016 | A1 |
| 20160365544 | Lee et al. | Dec 2016 | A1 |
| 20160372717 | Noda | Dec 2016 | A1 |
| 20170005504 | Rho et al. | Jan 2017 | A1 |
| 20170018799 | Jeong | Jan 2017 | A1 |
| 20170033326 | Goto et al. | Feb 2017 | A1 |
| 20170040582 | Kim | Feb 2017 | A1 |
| 20170155098 | Park et al. | Jun 2017 | A1 |
| 20170155099 | Song et al. | Jun 2017 | A1 |
| 20170214052 | Xu | Jul 2017 | A1 |
| 20170263972 | Rho et al. | Sep 2017 | A1 |
| 20170288255 | Kim et al. | Oct 2017 | A1 |
| 20170338439 | Yokoyama | Nov 2017 | A1 |
| 20170338449 | Rho et al. | Nov 2017 | A1 |
| 20170338489 | Miwa et al. | Nov 2017 | A1 |
| 20180026236 | Lee et al. | Jan 2018 | A1 |
| 20180062417 | Choi et al. | Mar 2018 | A1 |
| 20180115026 | Mairs | Apr 2018 | A1 |
| 20180240609 | Park et al. | Aug 2018 | A1 |
| 20180241081 | Deng et al. | Aug 2018 | A1 |
| 20180309117 | Zhu et al. | Oct 2018 | A1 |
| 20190027638 | Masuda et al. | Jan 2019 | A1 |
| 20190033602 | Lee et al. | Jan 2019 | A1 |
| 20190036103 | Pierce et al. | Jan 2019 | A1 |
| 20190088925 | Harutyunyan et al. | Mar 2019 | A1 |
| 20190099129 | Kopelman et al. | Apr 2019 | A1 |
| 20190115633 | Akihisa | Apr 2019 | A1 |
| 20190122464 | Delong et al. | Apr 2019 | A1 |
| 20190140270 | Wang et al. | May 2019 | A1 |
| 20190171315 | Park et al. | Jun 2019 | A1 |
| 20200264663 | Kumta et al. | Aug 2020 | A1 |
| Number | Date | Country |
|---|---|---|
| 102047488 | May 2011 | CN |
| 102482098 | May 2012 | CN |
| 102593436 | Jul 2012 | CN |
| 102674316 | Sep 2012 | CN |
| 102674316 | May 2014 | CN |
| 204072059 | Jan 2015 | CN |
| 104752651 | Jul 2015 | CN |
| 103219467 | Nov 2015 | CN |
| 103715394 | Jan 2016 | CN |
| 205375473 | Jul 2016 | CN |
| 103280846 | Aug 2016 | CN |
| 106024969 | Oct 2016 | CN |
| 205697720 | Nov 2016 | CN |
| 106299237 | Jan 2017 | CN |
| 104392845 | Mar 2017 | CN |
| 104362326 | Aug 2017 | CN |
| 107074534 | Aug 2017 | CN |
| 107086306 | Aug 2017 | CN |
| 107611340 | Jan 2018 | CN |
| 108878717 | Nov 2018 | CN |
| 109088071 | Dec 2018 | CN |
| 208690415 | Apr 2019 | CN |
| 106129536 | Jul 2019 | CN |
| 102017123752 | Mar 2019 | DE |
| 2 213 369 | Aug 2010 | EP |
| 2 476 648 | Jul 2012 | EP |
| 2 835 177 | Feb 2015 | EP |
| 6-267515 | Sep 1994 | JP |
| 11-31502 | Feb 1999 | JP |
| 11-87875 | Mar 1999 | JP |
| 2005-272277 | Oct 2005 | JP |
| 2007-49789 | Feb 2007 | JP |
| 2008-305608 | Dec 2008 | JP |
| 2010-277925 | Dec 2010 | JP |
| 2012-512956 | Jun 2012 | JP |
| 2015-105208 | Jun 2015 | JP |
| 2015-521347 | Jul 2015 | JP |
| 2015-220004 | Dec 2015 | JP |
| 2016-25077 | Feb 2016 | JP |
| 2016-31922 | Mar 2016 | JP |
| 2016-54113 | Apr 2016 | JP |
| 2016-73196 | May 2016 | JP |
| 2017-130274 | Jul 2017 | JP |
| 2017-147222 | Aug 2017 | JP |
| 2017-162637 | Sep 2017 | JP |
| 10-2007-0001220 | Jan 2007 | KR |
| 10-1548465 | Aug 2015 | KR |
| 10-2016-0047643 | May 2016 | KR |
| 10-1632109 | Jun 2016 | KR |
| 10-2016-0114389 | Oct 2016 | KR |
| 10-2016-0127641 | Nov 2016 | KR |
| 10-2016-0129440 | Nov 2016 | KR |
| 10-2016-0129500 | Nov 2016 | KR |
| 10-1676641 | Nov 2016 | KR |
| 10-1703516 | Feb 2017 | KR |
| 10-2017-0036478 | Apr 2017 | KR |
| 10-2017-0037510 | Apr 2017 | KR |
| 10-1729702 | Apr 2017 | KR |
| 10-1765459 | Aug 2017 | KR |
| 10-1795544 | Nov 2017 | KR |
| 10-2019-0040554 | Apr 2019 | KR |
| WO 2005052053 | Jun 2005 | WO |
| WO 2005096089 | Oct 2005 | WO |
| WO 2012156297 | Nov 2012 | WO |
| WO 2013052704 | Apr 2013 | WO |
| WO 2014102131 | Jul 2014 | WO |
| WO 2014153465 | Sep 2014 | WO |
| WO 2015100762 | Jul 2015 | WO |
| WO 2016031335 | Mar 2016 | WO |
| WO 2016178210 | Nov 2016 | WO |
| WO 2017052248 | Mar 2017 | WO |
| WO 2017083566 | May 2017 | WO |
| WO 2017120391 | Jul 2017 | WO |
| WO 2017131451 | Aug 2017 | WO |
| WO 2018110933 | Jun 2018 | WO |
| WO 2018194414 | Oct 2018 | WO |
| WO 2018194415 | Oct 2018 | WO |
| WO 2019027147 | Feb 2019 | WO |
| Entry |
|---|
| Communication dated Dec. 22, 2020, from the Japanese Patent Office in counterpart application No. 2020-002026. |
| David Schiller, “Development of a Stretchable Battery Pack for Wearable Applications”, submitted by David Schiller, BSc., Johannes Kepler University Linz, Nov. 2019, 28 Pages Total, https://epub.jku.at/obvulihs/content/titleinfo/4605900/full.pdf. |
| International Search Report and Written Opinion, issued by International Searching Authority in related International Application No. PCT/US2020/043017, dated Dec. 14, 2020. |
| A.J. Clancy et al., “A One-Step Route to Solubilised, Purified or Functionalised Single-Walled Carbon Nanotunes”, Journal of Materials Chemistry A, pp. 16708-16715, 2015. |
| Beate Krause et al., “Disperability and Particle Size Distribution of CNTs in an Aqeous Surfactant Dispersion as a Function of Ultrasonic Treatment Time” Carbon 48, pp. 2746-2754, 2010. |
| Communication dated Aug. 26, 2019, from the European Patent Office in related European Application No. 18186402.6. |
| Communication dated Feb. 4, 2020, from the European Patent Office in related European Application No. 18 173 644.8. |
| Extended European Search Report issued in related European Patent Application No. 18173644.8 dated Oct. 12, 2018. |
| Extended Search Report of related EP Application No. 18 19 4454 dated Jul. 23, 2019. |
| Howard Wang, “Dispersing Carbon Nanotubes Usuing Surfactants” Current Opinion in Colloid & Interface Science 14, pp. 364-371, 2009. |
| International Search Report and Written Opinion, issued by International Searching Authority in related International Application No. PCT/US2020/039821, dated Sep. 30, 2020. |
| Linqin Jiang et al., “Production of Aqueous Colloidal Dispersions of Carbon Nanotubes”, Journal of Colloid and Interface Science, pp. 89-94, 2003. |
| Office Action issued by the European Patent Office in related European Patent Application No. 18184002.6, dated May 13, 2020. |
| O.M. Marago, et al, “Optical trapping of carbon nanotubes”, Physica E, 40 (2008), pp. 2347-2351. |
| International Search Report and Written Opinion, issued by International Searching Authority in related International Application No. PCT/US2020/020993, dated Jul. 2, 2020. |
| Notice of Reasons for Rejection dated Aug. 17, 2021, from the Japanese Patent Office in related application No. 2020-002545. |
| Notification of the First Office Action dated Jul. 16, 2021, from the State Intellectual Property Office of People's Republic of China in related Application No. 201710151455.7. |
| Kim et al., “A Half Millimeter Thick Coplanar Flexible Battery with Wireless Recharging Capability”, Nano Letters, American Chemical Society, 2015, (8 Pages Total). |
| Pu et al., “A Self-Charging Power Unit by Integration of a Textile Triboelectric Nanogenerator and a Flexible Lithium-Ion Battery for Wearable Electronics”, Advanced Materials. 2015, (2015), (7 Pages Total). |
| A. Weidenkaff et al. “Metal Nanoparticles for the Production of Carbon Nanotube Composite Materials by Decomposition of Different Carbon Sources” Materials Science and Engineering C, vol. 19, pp. 119-123, 2002. |
| Chee Howe See et al., “CaCO3 Supported Co—Fe Catalysts for Carbon Nanotube Synthesis in Fluidized Bed Reactors” Particle Technology and Fluidization, vol. 54, No. 3, pp. 657-664, Mar. 2008. |
| Communication dated Jul. 31, 2019, from the European Patent Office in counterpart European Application No. 18194454.7. |
| Communication issued by the International Searching Authority in corresponding International Application No. PCT/US19/49923, dated Nov. 13, 2019 (PCT/ISA/206). |
| Danafar, F. et al., “Fluidized bed catalytic chemical vapor deposition synthesis of carbon nanotubes—A review,” The Chemical Engineering Journal, vol. 155, pp. 37-48, 2009. |
| Dunens, O., et al., “Synthesis of Multiwalled Carbon Nanotubes on Fly Ash Derived Catalysts,” Environ. Sci. Technol., vol. 43, pp. 7889-7894, 2009. |
| Extended European Search Report issued in corresponding European Application No. 18184002.6 dated Nov. 30, 2018. |
| Extended European Search Report issued in corresponding European Patent Application No. 18194469.5 dated Dec. 4, 2018. |
| Hasegawa Kei et al., “Lithium Ion Batteries Made of Electrodes with 99 wt% active materials and 1wt% carbon nanotubes without binder or metal foils”, Journal of Power Sources, vol. 321, pp. 155-162, 2016. |
| Hu, Liangbing et al., Thin, Flexible Secondary Li-Ion Paper Batteries, ACS Nano, vol. 4, No. 10, pp. 5843-5848, 2010. |
| International Search Report and Written Opinion, issued by International Searching Authority in corresponding International Application No. PCT/US19/49923, dated Jan. 23, 2020. |
| Jenax Inc., Flexible Lithium Polymer Battery J . FLEX, Copyright 2014, (6 Pages Total). |
| Joo-Seong Kim et al., Supporting Information, A Half Millimeter Thick Coplanar Flexible Battery with Wireless Recharging Capability, Nano Letters 2015 15 (4), 9 Pages Total, (2015). |
| Kun Kelvin Fu et al., “Flexible Batteries: From Mechanics to Devices”, 2016 American Chemical Society, ACS Publications, ACS Energy Letters 1, pp. 1065-1079, (2016). |
| Luo Shu et al., “Binder-Free LiCoO2/Carbon Nanotube Cathodes for High-Performance Lithium Ion Batteries” Advanced Materials, vol. 24, pp. 2294-2298, 2012. |
| Nanalyze., A Flexible Battery from Blue Spark Technologies, Apr. 8, 2014, (4 Pages Total). |
| Panasonic Corp., Panasonic Develops Bendable, Twistable, Flexible Lithium-ion Battery, Sep. 29, 2016, (8 Pages Total). |
| ProLogium Technology Co., Ltd., FLCB Flexible Type LCB, Copyright 2015, (6 Pages Total). |
| Sarah Maghsoodi et al., “A Novel Continuous Process for Synthesis of Carbon Nanotubes Using Iron Floating Catalyst and MgO Particles for CVD of methane in a fluidized bed reactor” Applied Surface Science, vol. 256, pp. 2769-2774, 2010. |
| Sau Yen Chew et al., “Flexible free-standing carbon nanotube films for model lithium-ion batteries”, Carbon 47, pp. 2976-2983, (2009). |
| Sebastian Anthony., LG produces the first flexible cable-type lithium-ion battery, ExtremeTech, Aug. 30, 2012, (9 Pages Total). |
| Sheng Xu et al., “Stretchable batteries with self-similar serpentine interconnects and integrated wireless recharging systems,” Nature communications 4:1543, DOI: 10.1038/ncomms2553, 8 Pages Total, (2013). |
| Shu Luo et al., “Binder-Free LiCoO2/ Carbon Nanotube Cathodes for High-Performance Lithium Ion Batteries”, Advanced Materials 24, pp. 2294-2298, (2012). |
| The Extended European Search Report issued in corresponding European Patent Application No. 18186402.6 dated Oct. 11, 2018. |
| The Swatch Group Ltd., A revolutionary battery by Belenos: The Watchmaker Swatch Group Has Signed an Agreement With the Chinese Geely Group for Use of Its Innovative New Battery., as accessed on May 29, 2019, (3 Pages Total), https://www.swatchgroup.com/en/ swatch-group/innovation-powerhouse/industry-40/revolutionary-battery-belenos. |
| Vishwam Sankaran., Samsung is reportedly developing a curved battery for its foldable phone, Jul. 4, 2018, (4 Pages Total). |
| Wang Ke et al., “Super-Aligned Carbon Nanotube Films as Current Collectors for Lightweight and Flexible Lithium Ion Batteries” Advanced Functional Materials, vol. 23, pp. 846-853, 2013. |
| Xian-Ming Liu et al., “Carbon nanotube (CNT)-based composites as electrode material for rechargeable Li-ion batteries: A review”, Composite Science and Technology, vol. 72, pp. 121-144, (2012). |
| Xiong Pu et al., “A Self-Charging Power Unit by Integration of a Textile Triboelectric Nanogenerator and a Flexible Lithium-Ion Battery for Wearable Electronics”, Advanced Materials 27, pp. 2472-2478, (2015). |
| Zhao, M.Q. et al., “Towards high purity graphene/single-walled carbon nanotube hybrids with improved electrochemical capacitive performance,” Carbon, vol. 54, pp. 403-411, 2013. |
| Zhiqian Wang et al., “Fabrication of High-Performance Flexible Alkaline Batteries by Implementing Multiwalled Carbon Nanotubes and Copolymer Separator” Advanced Materials 26, pp. 970-976, (2014). |
| Zhiqiang Niu et al., “A “skeleton/skin” strategy for preparing ultrathin free-standing single-walled carbon nanotube/polyaniline films for high performance supercapacitor electrodes”, The Royal Society of Chemistry 2012, Energy & Environmental Science 5, pp. 8726-8733, (2012). |
| Aminy E. Ostfeld et al., “High-performance flexible energy storage and harvesting system for wearable electronics”, www.nature.com/scientificreports, Scientific Reports, 6:26122,DOI:10.1038/srep26122, (2016), (10 Pages Total). |
| Communication dated Jul. 27, 2021, issued by the Korean Intellectual Property Office in related Korean Application No. 10-2020-0005929. |
| Sungmook Jung et al., “Wearable Fall Detector using Integrated Sensors and Energy Devices”, www.nature.com/scientificreports, Scientific Reports, 5:17081, DOI: 10.1038/srep17081, (2015), (9 Pages Total). |
| Communication dated Jan. 6, 2021, from the Japanese Patent Office in related application No. 2020-002545. |
| Fenghua Su et al., “High-Performance Two-Ply Yarn Supercapacitors Based on Carbon Nanotube Yarns Dotted with CO3O4 and NiO Nanoparticles”, Small 2015, 11, No. 7, pp. 854-861 with Supporting lnformation(12 Pages Total), www.small-journal.com, (Year: 2015). |
| Communication dated Nov. 9, 2021, from the Japanese Patent Office in related application No. 2018-172178. |
| Communication dated Sep. 26, 2021, issued by the Korean Intellectual Property Office in related Korean Application No. 10-2018-0058433. |
| Communication dated Mar. 22, 2022, from the Japanese Patent Office in application No. 2018-142355. |
| Communication dated Mar. 22, 2022, from the State Intellectual Property Office of People's Republic of China in Application No. 201811076414.7. |
| Communication dated Feb. 23, 2022, from the State Intellectual Property Office of People's Republic of China in Application No. 202010079226.0. |
| Number | Date | Country | |
|---|---|---|---|
| 20200259160 A1 | Aug 2020 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15665171 | Jul 2017 | US |
| Child | 16845524 | US |
