The present disclosure is directed to a composite yarn and a method of preparing carbon nanotube composite yarns.
Carbon nanotube-based yarns are promising candidates for use in various applications due to their unique properties, such as their ultra-high strength, high electrical conductivities, high thermal conductivities, and electric field emissions, among others.
However, it may be possible to dramatically expand the range of these yarns' unique applications by depositing or decorating the surface of the yarns or incorporating/embedding with secondary materials, such as metals and their oxides, ceramics, and/or thin films and various molecular species, depending on the required application. As such, there is a need in the art for an effective and efficient method of preparing carbon nanotube composite yarns.
The present disclosure is directed to a method of making carbon nanotube composite yarns, the method comprising the steps of growing floating carbon nanotubes in a reactor, removing webs of the carbon nanotubes from the reactor and, optionally in parallel, depositing secondary particles on at least a portion of the webs of carbon nanotubes to provide a carbon nanotube composite mat, and densifying the carbon nanotube composite mat to provide a carbon nanotube composite yarn. The disclosure is also directed to carbon nanotube composite yarns provided by the method described herein and devices comprising the carbon nanotube composite yarns provided by the method described herein, as well as methods of using the same. Optionally, the webs of carbon nanotubes are continuously removed from the reactor.
The present disclosure is directed to a method of making carbon nanotube composite yarns, the method comprising the steps of growing floating carbon nanotubes in a reactor, removing webs of the carbon nanotubes from the reactor and, optionally in parallel, depositing secondary particles on at least a portion of the webs of carbon nanotubes to provide a carbon nanotube composite mat, and densifying the carbon nanotube composite mat to provide a carbon nanotube composite yarn. The disclosure is also directed to carbon nanotube composite yarns provided by the method described herein and devices comprising the carbon nanotube composite yarns provided by the method described herein, as well as methods of using the same.
The method may comprise growing floating carbon nanotubes in a reactor. As used herein, the term “nanotube” refers to a tube having at least one dimension on the nanoscale, that is, at least on dimension between about 0.6 and 100 nm. For example, a nanotube may comprise a tube having a diameter on the nanoscale. According to some aspects, the nanotubes according to the present disclosure may be selected from the group consisting of single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), and multi-walled carbon nanotubes (MWNTs), and combinations thereof.
The floating carbon nanotubes may be grown in a reactor, such as a chemical vapor deposition (CVD) reactor. For example,
Examples of carbon sources include, but are not limited to, one or more carbon-containing gases, one or more hydrocarbon solvents, and mixtures thereof. Specific examples include, but are not limited to, gases and/or solvents containing and/or consisting of a hydrocarbon, an alcohol, an ester, a ketone, an aromatic, an aldehyde, and a combination thereof. For example, the carbon source may be selected from xylene, toluene, propane, butane, butene, ethylene, ethanol, carbon monoxide, butadiene, pentane, pentene, methane, ethane, acetylene, carbon dioxide, naphthalene, hexane, cyclohexane, benzene, methanol, propanol, propylene, commercial fuel gases (such as liquefied petroleum gas, natural gas, and the like), and combinations thereof.
The carbon source chamber 13 may also be configured to provide a catalyst and/or a catalyst precursor, such as a catalyst and/or a catalyst precursor vapor.
As used herein, the term “catalyst” refers to a component that provokes or speeds up a chemical reaction, for example, the synthesis of nanotubes. Examples of catalysts useful according to the present disclosure include, but are not limited to, transition metals, lanthanide metals, actinide metals, and combinations thereof. For example, the catalyst may comprise a transition metal such as chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), copper (Cu), silver (Ag), gold (Au), cadmium (Cd), scandium (Sc), yttrium (Y), lanthanum (La), platinum (Pt), and/or combinations thereof. The catalyst may be a supported catalyst or an unsupported catalyst. According to some aspects, a combination of two or more metals may be used, for example, an iron, nickel, and cobalt mixture. In one example, the mixture may comprise 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, other compounds containing one or more of the metals described herein, and/or a combination thereof.
As used herein, the term “catalyst precursor” refers to a component that can be converted into an active catalyst. Examples of catalyst precursors include, but are not limited to, transition metal salts, such as a nitrate, acetate, citrate, chloride, fluoride, bromide, iodide, and/or hydrates thereof, and combinations 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, a metal sulfate, a metal hydroxide, a metal carbonate, 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.
It should be understood that while
The carbon source and catalyst and/or catalyst precursor may be provided to the reactor via a carrier gas, such as an inert carrier gas. For example,
As shown in
The method may comprise growing floating carbon nanotubes in the reactor. For example, floating carbon nanotubes 17 may be grown in reactor 11, as shown in
The method may comprise providing a structure including, but not limited to, a mat of the carbon nanotubes, alternatively referred to herein as a “web.” As used herein, the term “mat” or “web” refers to a tangled or bundled mass, such as a tangled, non-densified mass formed downstream of the nanotube growth zone by the floating carbon nanotubes. The mat of carbon nanotubes may be provided, for example, in and/or on the reactor and/or by continuously pulling the floating carbon nanotubes from the reactor. For example,
The method may comprise depositing a secondary material on at least a portion of the carbon nanotubes to provide a carbon nanotube composite yarn. According to some aspects, the method may comprise depositing a secondary material on at least a portion of the mat of carbon nanotubes to provide a carbon nanotube composite mat followed by a densification step wherein the carbon nanotube composite mat is densified to provide a carbon nanotube composite yarn. Alternatively or additionally, the method may comprise a simultaneous deposition and densification step, wherein the secondary material is deposited on at least a portion of the mat of carbon nanotubes while the mat of carbon nanotubes is simultaneously densified to provide a carbon nanotube composite yarn. According to some aspects, the deposition and/or densification steps may be continuous steps performed in parallel with continuously pulling the mat of carbon nanotubes from the reactor, as described herein.
As used herein, the term “secondary material” refers to a material comprising at least one material that is different from the carbon nanotube mat. Examples of materials useful as secondary materials according to the present disclosure include, but are not limited to, metals, metal oxides, lithium metal oxides, lithium iron phosphate, ceramics, carbon-based materials, and combinations thereof. Examples of carbon-based materials include, but are not limited to, graphite particles, graphite and graphene flakes, hard carbon, and combinations thereof.
In an illustrative example, the carbon-based material is an electrode active material for use in an electrode, and in particular, in the anode of a battery. Examples of metal oxides include, but are not limited to, any metal oxide that may be used as an electrode active material in an electrode. In an illustrative example, the metal oxide is a material for use in the cathode of a battery. Non-limiting examples of metal oxides include those that comprise Ni, Mn, Co, Al, Mg, Ti, or any mixtures thereof. The metal oxide may be lithiated. In an illustrative example, the metal oxide is lithium nickel manganese cobalt oxide (LiNiMnCoO2). In another illustrative example, the metal oxide is Li-Me-O. 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.
“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.
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.
According to some aspects, the secondary material may be provided as secondary particles that are deposited on at least a portion of the mat of carbon nanotubes. According to some aspects, the particles may have a particle size from about 1 nanometer to about 100 microns, optionally from about 1 nanometer to about 10 nanometers.
It is to be understood that the secondary particle chamber 111 and delivery mechanism is not limited. In a non-limiting example, the secondary particle chamber 111 may include one or more of belt feeders, gravimetric feeders, pneumatic feeders, vacuum feeders, screw feeders, vibratory feeders, volumetric feeders, and valves.
According to some aspects, the secondary particles may be provided via one or more carriers. Examples of carriers include any substance known in the art configured to supply secondary particles to a substrate (for example, a mat of carbon nanotubes) as described herein without damaging the carbon nanotubes and/or the secondary particles. Examples of suitable carriers include gas carriers, liquid carriers, and combinations thereof. Example gas carriers include, but are not limited to, Ar, He, N2, dry air, and combinations thereof. Example liquid carriers include, but are not limited to, water, acetone, ethanol, and combinations thereof. According to some aspects, the one or more carriers may be provided with the secondary particles 112 in the secondary particle chamber 111, as shown in
The method may comprise densifying the carbon nanotube composite mat to provide a carbon nanotube composite yarn as described herein. For example, the carbon nanotube composite mat may be subjected to a liquid bath and/or a rolling press and/or a spindle and/or a cylindrical pipe and/or a tube, such as by spinning, pulling, and/or passing the carbon nanotube composite mat through or around the liquid bath and/or the rolling press and/or the spindle and/or the cylindrical pipe and/or the tube. In this way, the carbon nanotube composite mat 114 may be compacted to provide a carbon nanotube composite yarn 115, for example, as shown in
As shown in
It should be understood that the method may comprise a simultaneous deposition and densification step as described herein, wherein the secondary material is deposited on at least a portion of the mat of carbon nanotubes while the mat of carbon nanotubes is simultaneously or about simultaneously densified to provide a carbon nanotube composite yarn. For example, the carrier as described herein may be configured to simultaneously deposit the secondary particles on the mat of carbon nanotubes and densify the mat of carbon nanotubes. One non-limiting example of such a step comprises the use of a solvent as described herein, wherein the solvent is used as a carrier to deposit the secondary particles on the mat of carbon nanotubes, as described herein. The solvent may simultaneously densify the mat of carbon nanotubes as described herein (e.g., as described in relation to liquid bath densification step 118 shown in
In an illustrative example, the entire process for making the carbon nanotube composite yarn may be a continuous process. For example, the carbon source may be fed continuously to the reactor 11 so that the carbon nanotube mat may be continuously fed to the secondary particle chamber 111 for continuous deposition of the secondary particles, and the resulting composite structure may be continuously processed to form the carbon nanotube composite yarn. It is to be understood, however, that one or more stages may be performed separately in a continuous, batch, or semi-batch operation. For example, individual segments of carbon nanotube mats may be fed to the secondary particle chamber 111 for deposition of the particles thereon. The resulting composite structure may go through additional processing to evenly distribute the particles throughout the carbon nanotube mat.
The present disclosure is also directed to carbon nanotube composite yarns prepared according to the method described herein. The carbon nanotube composite yarn may comprise carbon nanotubes as described herein having secondary particles as described herein deposited thereon.
The present disclosure is also directed to devices comprising the carbon nanotube composite yarns prepared according to the method described herein. For example, the device may comprise an electrode (such as an electrode for a battery), a supercapacitor, a solar cell, a thermoelectric material, a sensor, an actuator, an element of an electronic device, an interconnect, or an E-textile, among others.
According to some aspects, the device may comprise a coaxial cable having at least two electrodes, and separator layer between them in some cases (e.g., in the use of liquid electrolyte) wherein at least one of the electrodes comprises a carbon nanotube composite yarn as disclosed herein. According to some aspects, at least two of the electrodes each comprises a carbon nanotube composite yarn as disclosed herein. The coaxial cable may further comprise an electrolyte, an insulating layer, and a conducting layer.
According to some aspects, the coaxial cable may comprise the first electrode 51 and the second electrode 51 in a twisted configuration, for example, as shown in
The coaxial cable may further comprise an electrolyte (liquid, gel, or solid) 53 substantially surrounding the first electrode 51 and the second electrode 51, an insulating layer 54 substantially surrounding the electrolyte 53, and a conducting layer 55 substantially surrounding the insulating layer 54.
Materials useful for the electrolyte include, but are not limited to, mixtures of alkyl carbonates (e.g., ethylene carbonate (EC), dimethyl (DMC), diethyl (DEC), and ethyl-methyl carbonates (EMC)) and LiPF6 as the electrolyte solution as well as gel and solid electrolytes.
Materials useful for the insulating layer include, but are not limited to, non-conductive materials such as polymer-based materials. Example non-conductive polymer-based materials include plastics such as polyethylene.
Materials useful for the conducting layer include, but are not limited to, materials capable of conducting AC current such as copper, nickel, aluminum, and alloys thereof. In one example, the conducting layer 54 comprises copper. It should be understood that the thickness of the conducting layer 54 may be selected based on the frequency of exploited AC current. According to some aspects, the thickness of the conducting layer may be between about 1 μm to about 10 mm.
It should be understood that the coaxial cable according to the present disclosure, for example, as shown in
According to some aspects, the device comprises an electronic incorporating the coaxial cable as described herein, including, for example, an electrical vehicle motor. It should be understood that conventional electrical vehicle motors, such as the electrical motor 61 shown in
The present disclosure is also directed to methods of using the carbon nanotube composite yarns prepared according to the method described herein. For example, the method may comprise preparing a device as described herein comprising the carbon nanotube composite yarns. For example, the method may comprise weaving the carbon nanotube composite yarns to provide an E-textile.
In another example, the method may comprise preparing a coaxial cable as described herein. For example, the method may comprise providing a first electrode (e.g., an anode) and a second electrode (e.g., a cathode) in a twisted configuration and separated by separator, wherein each of the first and second electrodes individually comprises a carbon nanotube composite yarn as disclosed herein. The method may further comprise providing an electrolyte surrounding the first and second electrodes, providing an insulating layer surrounding the electrolyte, and providing a conducting layer surrounding the insulating layer.
This detailed description uses examples to present the disclosure, including the preferred aspects and variations, and also to enable any person skilled in the art to practice the disclosed aspects, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims. Aspects from the various embodiments described, as well as other known equivalents for each such aspect, can be mixed and matched by one of ordinary skill in the art to construct additional embodiments and techniques in accordance with principles of this application.
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.
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. Moreover, nothing disclosed herein is intended to be dedicated to the public.
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.
As used herein, the term “about” and “approximately” are defined to being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the term “about” and “approximately” are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
This application claims priority to U.S. Provisional Patent Application No. 62/813,516, filed Mar. 4, 2019, the entirety of which is incorporated herein by reference.
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 |
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 |
10658651 | Pierce et al. | May 2020 | 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 |
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 |
20080280136 | Zachariah | Nov 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 et al. | May 2010 | A1 |
20100140560 | Wang et al. | Jun 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 |
20110020210 | Liu | Jan 2011 | 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 |
20110173198 | Malleshaiah et al. | Jul 2011 | A1 |
20110177393 | Park et al. | Jul 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 | Hooke et al. | Jun 2012 | A1 |
20120177934 | Vogel et al. | Jul 2012 | A1 |
20120193602 | Lieber et al. | Aug 2012 | A1 |
20120219490 | Noda et al. | Aug 2012 | A1 |
20120241666 | Hong et al. | Sep 2012 | A1 |
20120282522 | Axelbaum 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 |
20130065125 | Sawaki et al. | Mar 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 |
20130171496 | Wang et al. | Jul 2013 | A1 |
20130189565 | Lashmore et al. | Jul 2013 | A1 |
20130224651 | Hiralal et al. | Aug 2013 | A1 |
20131323583 | Phares | Dec 2013 | |
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. | Aug 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 |
20150059571 | Denton et al. | Mar 2015 | A1 |
20150064521 | Watanabe et al. | Mar 2015 | A1 |
20150087858 | Ci et al. | Mar 2015 | A1 |
20150133569 | Gong et al. | May 2015 | A1 |
20150149193 | Jester 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 | Gruner 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 | Nov 2015 | A1 |
20150340741 | Dong et al. | Nov 2015 | A1 |
20150349325 | Chen et al. | Dec 2015 | A1 |
20150364750 | Maheshwari et al. | Dec 2015 | A1 |
20150372344 | Iwasaki et al. | Dec 2015 | A1 |
20150380738 | Zhou et al. | Dec 2015 | A1 |
20160009557 | Harutyunyan et al. | Jan 2016 | 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 |
20160126554 | Beneventi et al. | 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 |
20190237748 | Shin et al. | Aug 2019 | A1 |
20200264663 | Kumta et al. | Aug 2020 | A1 |
20210399289 | Eshraghi et al. | Dec 2021 | A1 |
Number | Date | Country |
---|---|---|
102482098 | May 2012 | CN |
102593436 | Jul 2012 | CN |
102674316 | Sep 2012 | CN |
204072059 | Jan 2015 | CN |
104752651 | Jul 2015 | CN |
103715394 | Jan 2016 | CN |
205375473 | Jul 2016 | CN |
103280846 | Aug 2016 | CN |
106024969 | Oct 2016 | CN |
205697720 | Nov 2016 | CN |
104392845 | Mar 2017 | CN |
104362326 | 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 |
2476648 | Jul 2012 | EP |
2 835 177 | Feb 2015 | EP |
6-267515 | Sep 1994 | JP |
11-31502 | Feb 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 |
2015-521347 | 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 |
10-2016-0127648 | 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 2011030821 | Mar 2011 | WO |
WO 2012156297 | Nov 2012 | WO |
WO 2014102131 | Jul 2014 | WO |
WO 2014153465 | Sep 2014 | WO |
WO 2015100762 | Jul 2015 | WO |
WO 2016031335 | Mar 2016 | WO |
WWO 2016178210 | Nov 2016 | WO |
WO 2017052248 | Mar 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 2019027847 | Feb 2019 | WO |
Entry |
---|
Zhang, et al., Porous, Platinum Nanoparticle-Absorbed Carbon Nanotube Yarns for Efficient Fiber Solar Cells, ACS Nano 2012; 6(8): 7191-7198 with Supporting Information (Year: 2012). |
Li, et al., Large area, highly transparent carbon nanotube spiderwebs for energy harvesting, J. Mater. Chem. 2010; 20: 7236-7240 (Year: 2010). |
Su, et al., High-Performance Two-Ply Yarn Supercapacitors Based on Carbon Nanotube Yarns Dotted with Co3O4 and NiO Nanoparticles, Small 2015; 11(7): 854-861 with Supporting Information (Year: 2015). |
Liu et al.; “Carbon nanotube (CNT)-based composites as electrode material for rechargeable Li-ion batteries: A review”; Composite Science and Technology, vol. 72, Issue 2 (Jan. 18, 2012); pp. 121-144. (Year:2012). |
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, 2015. |
Xiong Pu et al., “A Self-Charging Power Unit by Integration of a Textile Triboelectric Nanogenerator and a Flexible Lithium-Ion Battery for Wearable Elecronics”, Advanced Materials 27, pp. 2472-2478, (2015). |
Extended European Search Report dated Aug. 26, 2018. |
Extended Search Report of related EP Application No. 18 19 4454 dated Jul. 23, 2019. |
Jenax Inc., Flexible Lithium Polymer Battery J . Flex, Copyright 2014, 6 Pages. |
Nanalyze., A Flexible Battery from Blue Spark Technologies, Apr. 8, 2014, 4 Pages. |
Panasonic Corp., Panasonic Develops Bendable, Twistable, Flexible Lithium-ion Battery, Sep. 29, 2016, 8 Pages. |
ProLogium Technology Co., Ltd., FLCB Flexible Type LCB, Copyright 2015, 6 Pages. |
Sebastian Anthony., LG produces the first flexible cable-type lithium-ion battery, ExtremeTech, Aug. 30, 2012, 9 Pages. |
The Swatch Group Ltd., A revolutionary battery by Belenos: The Watchmaker Swatch Group Has SignedAn Agreement With The Chinese Geely Group For Use Of Its Innovative New Battery., as accessed on May 29, 2019, 3 Pages, 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. |
International Search Report issued by the International Searching Authority in corresponding International Patent Application No. PCT/US2020/020993, dated Jul. 2, 2020. |
Written Opinion issued by the International Searching Authority in corresponding International Patent Application No. PCT/US2020/020993, dated Jul. 2, 2020. |
Communication issued by the International Searching Authority in corresponding International Application No. PCT/US19/49923 dated Nov. 13, 2019. |
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). |
Sau Yen Chew et al., “Flexible free-standing carbon nanbtube films for model lithium-ion batteries”, Carbon 47, pp. 2976-2983, (2009). |
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). |
Zhiqian Wang et al., “Fabrication of High-Performance Flexible Alkaline Batteries by Implementing Multiwailed 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). |
Office Action issued by the European Patent Office in corresponding European Patent Application No. 18184002.6, dated May 13, 2020. |
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. |
A.J. Clancy et al., “A One-Step Route to Solubilised, Purified or Functionalised Single-Walled Carbon Nanotunes”, Journal of Materials Chemistry A, p. 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. |
Chee Howe See et al., “CaCO3 Suppoerted 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 Aug. 26, 2019, from the European Patent Office in related European Application No. 18186402.6. |
Communication dated Jul. 31, 2019, from the European Patent Office in related European Application No. 18194454.7. |
Danafar 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 Patent Application No. 18186402.6 dated Oct. 11, 2018. |
Extended European Search Report issued in corresponding European Patent Application No. 18194469.5 dated Dec. 4, 2018. |
Extended European Search Report of related European Patent Application No. 18184002.6, dated Nov. 30, 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. |
Howard Wang, “Dispersing Carbon Nanotubes Usuing Surfactants” Current Opinion in Colloid & Interface Science 14, pp. 364-371, 2009. |
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 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. |
Luo Shu et al., “Binder-Free LiCoO2/Carbon Nanotube Cathodes for High-Performance Lithium Ion Batteries” Advanced Materials, vol. 24, pp. 2294-2298, 2012. |
O.M. Marago, et al., “Optical trapping of carbon nanotubes”, Physica E, 40 (2008), pp. 2347-2351. |
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. 2269-2274, 2010. |
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. |
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. |
Extended European Search Report issued in corresponding European Patent Application No. 18173644.8 dated Oct. 12, 2018. |
International Search Report and the Written Opinion issued by the International Searching Authority corresponding to PCT/US20/43017, dated Dec. 14, 2020. |
Notice of Reasons for Rejection issued by the Japanese Patent Office corresponding to Japanese Application No. 2017-048275, dated Dec. 1, 2020. |
Notice of Reasons for Rejection issued by the Japanese Patent Office corresponding to Japanese Patent Application No. 2017-048276, dated Dec. 1, 2020. |
Notice of Reasons for Rejection issued by the Japanese Patent Office corresponding to Japanese Patent Applivation No. 2020-002026, dated Dec. 22, 2020. |
Schiller, David. “Development of a Stretchable Battery Pack for Wearable Applications.” submittedby David Schiller, BSc. Diss. Universit't Linz, Nov. 2019, p. 19-37 [online] <https://epub.jku.at/obvulihs/content/titleinfo/4605900/full.pdf>. |
International Search Report and Written Opinion issued by the International Search Authority in corresponding International Application No. PCT/US19/49923, dated Jan. 23, 2020. |
Communication dated Sep. 26, 2021, issued by the Korean Intellectual Property Office in related Korean Application No. 10-2018-0058433. |
Office Action issued by Chinese Patent Office in related Chinese Patent Application No. 201710151455.7, dated Jul. 16, 2021. |
Notice of Reasons for rejection issued by the Japanese Patent Office related to Japanese Patent Application No. 2020-002545, dated Aug. 17, 2021. |
Jung, Sungmook, et al., “Wearable Fall Detector using Integrated Sansors and Energy Devices”, Scientific Reports, pp. 1-9, Nov. 24, 2015. |
Office Action issued by the Korean Patent Office in related Korean Patent Application No. 10-2020-0005929; dated Jul. 27, 2021. |
Ostfeld, Aminy E., et al., “High-performance flexible energy storage and harvesting systen for wearable electronics”, Scientific Reports, pp. 1-10, May 17, 2016. |
Communication dated Mar. 14, 2022, issued by the Japanese Patent Office in related Japanese Application No. 2618-142355. |
Shi, Yang, et al., “Graphene-based integrated electrodes for flexible lithium ion batteries”, 2D Materials 2.2 (2015) 0204004 (2015). |
Number | Date | Country | |
---|---|---|---|
20200399129 A1 | Dec 2020 | US | |
20210316991 A9 | Oct 2021 | US |
Number | Date | Country | |
---|---|---|---|
62813516 | Mar 2019 | US |