News Column

"Functionalized Carbon Nanotube Composite" in Patent Application Approval Process

July 3, 2014



By a News Reporter-Staff News Editor at Politics & Government Week -- A patent application by the inventors Zimrin, Tomer (Kiryat Ono, IL); Shapira, Roni (Ramat Gan, IL); Auback, Doron (Bnei Brak, IL); Cahana, Beni (Nesher, IL), filed on July 19, 2012, was made available online on June 19, 2014, according to news reporting originating from Washington, D.C., by VerticalNews correspondents.

This patent application is assigned to Bar Ilan University.

The following quote was obtained by the news editors from the background information supplied by the inventors: "The lead-acid battery has been a successful secondary battery system for over a century [1]. The advantages of these batteries are their low cost, stable voltage profile, high reliability, and safety. The main disadvantages of such flooded type configuration are a low specific energy and, subsequently, the poor utilization of the positive active-material (PAM). Both the cycle life and the capacity of these batteries are limited due to the properties of the active material in the positive plate. Compared to the negative plate, the positive plate has low performance in deep discharge (high DOD), and therefore much research has been conducted to improve the performance of lead-acid batteries [2].

"The low utilization of PAM stems from the associated sulfation and crumbling of the active material. The crumbling of the active material originates from the significant difference between the densities of the PbO.sub.2 and PbSO.sub.4, leading to expansion of the active material that occurs during the discharge process [3]. During discharging, non-conductive crystals of PbSO.sub.4 are formed. When these electrically insulating crystals grow, as either plates or spatial crystals, they either prevent the lead ion oxidation back to the active PbO.sub.2 material or reach a stable crystal size (above 1-1.5 micron in diameter), which cannot be recharged via the common dissolution/precipitation mechanism.

"Carbonaceous additives were studied mainly for negative active materials of valve-regulated lead acid (VRLA) cells. Amongst others, their contribution may be associated to the enhancement of the overall conductivity of the active material, facilitation of the formation of small isolated PbSO.sub.4 particles which are easy to dissolve, and the ability of carbon to act as an electro-osmotic pump that facilitate acid diffusion within the inner volume of the active material, especially at high rates of charge and discharge. Pavlov et al. [4] suggested a mechanism for the role of the carbonaceous additives in the negative active material. According to the proposed mechanism, the lead sulfate dissolves and diffuses to conductive sites (i.e. pure lead, extremely thin lead sulfate layer or the carbonaceous additives surface), in which it may be reduced into metallic lead due to its sufficient electrical conductivity. At later stages, due to the mismatch in the crystal lattice parameters, the reduced lead diffuses from the carbon surface, releasing the electro-active sites on the carbonaceous surface to be available for further reduction.

"Among the various carbon allotropes, carbon nanotubes (CNTs) seem to be a prominent additive due to their outstanding features, including high mechanical properties, and excellent electric and thermal conductivities. Many of these properties are best exploited by incorporation of CNTs into composites [5]. The extremely high aspect ratio of the CNT (up to 10.sup.6) turns the formation of dispersion into a challenge, as there is a need to overcome all of the local Van der Waals interactions which tend to hold the CNTs macro-scale bundles intact [6].

"Chemical methods have been used to surface-functionalize CNTs to improve their chemical compatibility with a target medium (solvent or polymer solution/melt), to enhance wetting or adhesion characteristics and reduce their tendency to agglomerate [7]."

In addition to the background information obtained for this patent application, VerticalNews journalists also obtained the inventors' summary information for this patent application: "The inventors of the invention disclosed herein have developed composites (composition of matter) containing functionalized carbon nanotubes (CNTs), e.g., for use as electrode materials in electrochemical cells such as lead-acid batteries. The composites of the invention allow the construction of electrodes in electrochemical cells, e.g., as a lead acid cathode, which are capable of surviving the cathodic potential and the acidic conditions in the battery, e.g., lead acid cell.

"In one aspect, the present invention provides a composite comprising lead oxide particles (PbO.sub.2) and functionalized carbon nanotubes (CNTs), said functionalized CNTs being randomly distributed, in spaced-apart fashion in said composite, each functionalized CNT being coated with a plurality of said lead oxide particles, e.g., the particles having an average size in the micron scale, ranging between 0.2 and 2 microns in diameter.

"The 'CNTs' employed in the products and methods of the invention are carbon nanowires selected in a non-limited fashion from single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), double-walled carbon nanotubes (DWCNTs), few-walled carbon nanotubes (FWCNTs), each may or may not be further functionalized (substituted by one or more organic or inorganic non-carbon atom or group). In some embodiments, the CNTs are single-walled (SWCNTs) or multiwalled (MWCNTs) CNTs.

"In some other embodiments, the composite further comprises carbon black. The lead oxide (LO) particles of the invention may be of any shape and of random or preselected particle size. The term 'particle size' typically refers to the average diameter of the particles. When the particles are of non-spheroid shape, the term refers to the average equivalent diameter of the particle, namely the diameter of an equivalent spherical particle based on the longest dimension of the particle.

"In the composite of the invention, the functionalized CNTs are substantially not in a preordered contact with each other, namely, they are 'randomly distributed in a spaced-apart fashion', each being separable from the other by a plurality of lead oxide particles coating and protecting each functionalized CNT. In other words, the functionalized CNTs form a discontinuous net or a fragmented grid, wherein each functionalized CNT is distanced from the other by at most about 1 or 2 microns.

"The composite of the present invention exhibits superior characteristics in comparison to composites in which pristine CNTs are dispersed in the lead oxide, these superior characteristics being at least in composite morphology, and as reflected in battery operation, in at least enhanced electrical cycle ability and delayed cathode failure. Contrary to the highly hydrophobic nature of pristine CNT, which does not wet the lead oxide due to significant mismatch of their surface energies (resulting in a clear and fast phase separation), the functionalized CNTs employed in composites of the invention wet the lead oxide particles, resulting in a composition of high stability and homogeneity.

"Further, in contrast to known composites, such as those disclosed in WO 2011/029130 [11], in the composite of the invention the CNTs are distributed in a space-apart fashion, whereby substantially no continuous carbon-carbon structures are formed. As the CNTs are in a concentration slightly above the percolation concentration, electrical conductivity is maintained, without the need to form a continuous carbonaceous grid.

"As will be demonstrated hereinbelow, the electric conductivity of the functionalized CNTs and its homogeneous dispersion in the lead oxide, as well as the functionalized CNTs wetting of the lead oxide, ensures that in a functioning cell most of the PbSO.sub.4 crystals remain in the submicron size, which minimizes eventual sulfur concentration (i.e. 'sulfation'). This clearly indicates that the functionalized CNTs manage to form conductive spatial non-continuous arrangement, which enables the functionalized CNTs to act as 'electron sinks', i.e., enabling the creation of oxidation sites which significantly delays failure due to sulfation, resulting in enhanced cycle life of the cell.

"The CNTs used in a composite of the invention are 'functionalized' , namely the CNTs bare one or more functional groups which is associated with the CNT external carbon surface. In some embodiments, the CNTs are oxidized to afford oxygen-containing groups such as carboxyl and hydroxyl groups. The oxidation of CNTs may be achieved by wet chemical methods, photo-oxidation, oxygen plasma or gas phase treatment, as known in the art. Thus, in some embodiments, the functionalized CNT is oxidized CNT.

"In other embodiments, the oxidized CNTs are further functionalized for bonding with at least one polymer. In some embodiments, functionalization is achieved via ester bonds where the acid moiety is carried by the oxidized CNT or by the functionalizing moiety.

"In some embodiments, the CNTs are functionalized with polymers, e.g., conductive polymers, which assist in preventing physical and/or conductive disconnection of portions of an electrode. According to the present invention, the CNTs may also be functionalized by polymers, which may be conductive and/or which can undergo electrochemical doping, e.g., p-doping or n-doping, thereby functioning as an electrolytic capacitor.

"The oxidized CNTs, e.g., single walled or multiwalled, (being, in some embodiments, functionalized CNTs in accordance with the invention) may thus be functionalized through one or more of the oxygen-containing groups, and may be further functionalized with at least one suitably functionalization polymer to afford, in other embodiments, other and different functionalized CNTs in accordance with the invention. In some embodiments, the polymer is selected to have on average between about 10 and about 200 repeating monomeric units. In other embodiments, the polymer is selected to have a molecular weight between about 1,500 and 30,000 Da (Dalton).

"In some embodiments, the CNTs are functionalized with at least one semiconductive polymer. In some embodiments, the polymer is selected from polythiophene, polyaniline polypyrrol and poly(3,4-ethylenedioxythiophene) (PEDOT).

"According to some embodiments, said polymer is polythiophene.

"In some embodiments, the functionalized CNT is polythiophene-functionalized CNT. In such embodiments, the CNT may be multiwalled CNT (MWCNT).

"In some other embodiments, the CNT is oxidized (to bear a plurality of oxygen-containing groups) and subsequently reacted with a suitably functionalized polymer moiety. The polymer moiety, selected as above, bears in some embodiments, a plurality of carboxylic acid groups (as is the case with the exemplary polythiophene acetic acid (PTAA)), which are capable of interacting with the oxygen-containing groups on the surface of the CNT.

"In some embodiments, the functionalized CNTs are MWCNT, having a diameter of between about 8 and 15 nm, and a length of between about 10 and 50 .mu.m; the functionalized MWCNTs being covalently bonded to a plurality of polythiophene moieties.

"In some embodiments, the concentration of the functionalized CNT in a composite of the invention is between about 0.05% and 5% (wt %) of the total lead oxide weight. In further embodiments, the concentration is between about 0.1% and 5% (wt %). In still further embodiments, the concentration is between about 1% and 5% (wt %).

"In some embodiments, the concentration is between about 0.05% and 1% (wt %). In other embodiments, the concentration is between about 0.05% and 2% (wt %). In additional embodiments, the concentration is between about 0.1% and 1% (wt %). In still other embodiments, the concentration is between about 0.1% and 2% (wt %).

"In another aspect, the invention provides a composite comprising functionalized MWCNTs, and lead oxide particles (PbO.sub.2), the functionalized MWCNTs being covalently bonded to a plurality of polythiophene moieties.

"In another aspect, a composite comprising functionalized MWCNTs, and lead oxide particles (PbO.sub.2), the MWCNTs being functionalized with oxygen-containing groups.

"In some embodiments, the functionalized MWCNTs have a diameter of between about 8 and 15 nm, and a length of between about 10 and 50 .mu.m. In other embodiments, the concentration of functionalized MWCNTs is between about 0.1% and 5% (wt %). In still other embodiments, the composite further comprises carbon black.

"In a further aspect, there is provided a composition comprising the composite of the invention as herein described and an acidic medium. In other embodiments, the invention provides a composition comprising the composite of the invention as herein described and a medium at an acidic pH (between 1 and 7). The medium may be made acidic by inclusion of an acid selected from sulfuric acid and nitric acid.

"In some embodiments, the acidic medium is sulfuric acid, which may be in a concentration of between about 1M and 20M (M being mole/liter).

"The composite of the present invention may be processed into components of lead acid batteries, e.g., electrodes (cathode and/or anode). Thus, the invention also provides a processing method for application of a composite of the invention as an electrode in order to prevent or minimize creep deformation, inter-granular corrosion and cracking in lead acid batteries. For such applications and others, the composite may be provided in the form of a paste.

"A composite of the invention, as an electrode active material, may be provided as a paste and applied on an electrode substrate. In some embodiments, the paste is applied or otherwise provided onto at least a portion of an electrode substrate and allowed to dry or cure to form an electrode plate. The lead acid battery may then be constructed.

"The surface of the electrode may be the entire surface or a portion thereof. The 'portion' (region) of the substrate's surface to be coated may be of any size and structure, the portion may be continuous or comprise of several non-continuous sub-regions on the surface. The electrode 'substrate' may be a flexible or rigid structure, which may be substantially two-dimensional (a thin flat substrate) or a three-dimensional, e.g., curved (non-flat) surface. The substrate can be of any smoothness. In most general terms, the substrate may be of a solid material.

"As known in the art, a lead acid battery comprises an electrode assembly (typically at least one anode and at least one cathode), a bus-bar, an electrolyte solution and housing. The electrode assembly and bus-bar may be made of either a cast or wrought lead alloy. While traditional lead acid batteries have proven to be dependable, they have a limited life span and energy density. The life span is typically limited by creep (growth), corrosion and cracking of the electrodes, as well as the formation of an insulating lead-sulfide layer, resulting from successive charge-discharge cycles, each of which disadvantages being minimized or resolved in a lead acid battery according to the present invention.

"The invention thus provides an energy storage device (e.g., lead acid battery) comprising an electrode assembly, a bus-bar, an electrolyte solution and housing. In an energy storage device (e.g., battery) according to the invention, at least one of the electrodes constituting the electrode assembly is composed of a composite according to the invention. In some embodiments, the positive electrode is composed of a composite according to the invention.

"According to some embodiments, the energy storage device is a lead-acid battery. In such embodiments, the electrolyte solution is typically a dilute aqueous sulfuric acid solution, comprising 3 to 5M sulfuric acid; the solution provides the sulfate ions necessary for the discharge reactions.

"In some other embodiments, the lead-acid battery is operational for at least 150 cycles of operation between charging at 14V and discharging at 10.5V, at 25%.+-.0.3% Depth of Discharge (DOD) of the initial capacity of the battery.

"The invention further provides an electrode, e.g., a cathode, comprising, or having at least on a portion of its surface, a composite according to the invention.

"In comparison to cathodes made of pure lead oxide and Dynel.RTM. fibers that demonstrated recharging over 180-253 cycles, measurements performed on a cathode of the invention demonstrated recharging over 387 cycles, with the Depth of Discharge (DOD) for the aforementioned cycles being 33.+-.0.3% of the initial capacity.

"Additionally, and as will be further detailed hereinbelow, high resolution SEM (HRSEM) supplemented by EDAX demonstrated that cathodes (without CNTs) containing a combination of large PbSO.sub.4 crystals and a small amount of submicron crystals failed due to the combined sulfation-crumbling mechanisms. In contrast, functionalized CNT-impregnated cathodes exhibited only sub-micron crystals and an improvement in the failure mechanism.

"In an aspect, the invention provides a process of manufacture of a dispersion of functionalized CNTs in lead oxide, the process comprising reacting CNTs being functionalized with oxygen-containing groups, under conditions permitting random distribution in spaced-apart fashion of said functionalized CNTs, each being coated with a plurality of said lead oxide particles.

"In some embodiments, prior to distribution of said functionalized CNTs in said lead oxide, the process comprises reacting the functionalized CNTs with at least one polymer under conditions permitting covalent association of said at least one polymer onto said functionalized CNTs.

"In another aspect of the invention, there is provided a process of manufacture of a dispersion of functionalized CNT in lead-oxide, the process comprising reacting oxidized CNTs (e.g., MWCNT, 8-15 nm diameter, 10-50 .mu.m length) with at least one polymer (e.g., polythiophene acetic acid (PTAA)) under conditions permitting covalent functionalization of said at least one polymer onto said oxidized CNTs.

"In some embodiments, said conditions involve mixing in a solvent permitting conjugation between the oxidized CNTs and the at least one polymer.

"In other embodiments, said conditions involve mixing by planetary centrifugal mixing, e.g., at 2,000 rpm for 2 minutes.

"In a further aspect, the invention provides a process for manufacturing electrode material, the process comprising: mixing a CNT/lead oxide dispersion (as above) with water and H.sub.2SO.sub.4 to obtain a paste; pasting said paste on a lead grid for electrode production; curing said electrode followed by formation of a conductive skeleton.

"The curing is typically carried out at an oven in at elevated temperatures, suitable for evaporation of substantially all of the water from the paste.

"In another aspect of the invention, contemplated is a lead acid battery system comprising one or more (or a plurality of alternating) positive and negative electrodes, at least one of said electrodes being an electrode according to the present invention; separator means disposed between said electrodes; an electrolyte solution being substantially in contact with said electrodes and separators, and a housing.

"As mentioned herein, the formation of PbSO.sub.4 is minimized when using an electrode or battery according to the invention. Therefore, in another aspect, the invention provides a process for operating a battery according to the present invention, the process comprising: constructing the energy storage device of the invention; and contacting and de-contacting said one or more negative electrode and one or more positive electrode in at least one cycle of operation.

"In another aspect, there is provided a process for generating energy, comprising: providing an energy storage device according to the invention; and contacting and de-contacting said one or more negative electrode and one or more positive electrode in at least one cycle of operation.

"The term 'cathode' refers to the positively charged electrode, while the term 'anode' refers to the negatively charged electrode of the cell.

"The energy storage device (e.g. battery) according to the present invention may be utilized in a variety of applications.

BRIEF DESCRIPTION OF THE DRAWINGS

"In order to understand the disclosure and to see how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

"FIGS. 1A-B provide SEM images of a homogeneous mixture of lead oxide and CNTs.

"FIGS. 2A-D depict: voltage vs. time and number of cycles of improved lead acid cell with a cathode modified by CNT according to the invention (FIG. 2A); a section of the voltage profiles vs. time of FIG. 2A (FIG. 2B); voltage vs. time and number of cycles of a regular reference battery (FIG. 2C); and a section of the voltage profiles vs. time to FIG. 2C (FIG. 2D).

"FIGS. 3A-B provide SEM images demonstrating combined sulfation-crumbling mechanisms of CNT free electrode (FIG. 3A) and exclusively crumbled (disintegrated) electrode after introduction of CNTs (FIG. 3B).

"FIG. 4 shows a SEM image of homogenously-mixed CNTs and leady oxide.

"FIGS. 5A-B depict: voltage vs. time and number of cycles of improved lead acid cell with a cathode modified by CNT according to the invention (FIG. 5A); and a section of the voltage profiles vs. time of FIG. 5A (FIG. 5B)."

URL and more information on this patent application, see: Zimrin, Tomer; Shapira, Roni; Auback, Doron; Cahana, Beni. Functionalized Carbon Nanotube Composite. Filed July 19, 2012 and posted June 19, 2014. Patent URL: http://appft.uspto.gov/netacgi/nph-Parser?Sect1=PTO2&Sect2=HITOFF&u=%2Fnetahtml%2FPTO%2Fsearch-adv.html&r=3140&p=63&f=G&l=50&d=PG01&S1=20140612.PD.&OS=PD/20140612&RS=PD/20140612

Keywords for this news article include: Chemistry, Chalcogens, Fullerenes, Electrolytes, Sulfur Acids, Nanotechnology, Sulfuric Acids, Electrochemical, Carbon Nanotubes, Bar Ilan University, Inorganic Chemicals, Emerging Technologies.

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