Filled carbon nanotubes and methods of synthesizing the same

Abstract

Filled carbon nanotubes (CNTs), methods of synthesizing the same, and lithium-ion batteries comprising the same are provided. In situ methods (e.g., chemical vapor deposition techniques) can be used to synthesize CNTs (e.g., multi-walled CNTs) filled with metal sulfide nanowires. The CNTs can be completely (or nearly completely) and continuously (or nearly continuously) filled with the metal sulfide fillers up to several micrometers in length. The filled CNTs can be synthesized on a carbon substrate. A lithium-ion battery can comprise a cathode, an anode comprising filled CNTs as described herein, and an electrolyte in contact with the cathode and/or the anode.

Claims

1. A compound comprising: a carbon-based substrate; a carbon nanotube (CNT) disposed on the carbon-based substrate; and a nanowire of a metal sulfide filled in the CNT, the CNT filled with the nanowire being straight from a first end thereof to a second end thereof, and each of the first end and the second end of the CNT filled with the nanowire being closed with respective carbon shells.

2. The compound according to claim 1, the carbon-based substrate being carbon cloth, graphene, graphite, graphene oxide, carbon block, carbon fiber threads, carbon nanotube films, a carbon-coated substrate, a graphite-coated substrate, or a carbon nanotube film-coated substrate.

3. The compound according to claim 1, the metal sulfide being nickel sulfide, cobalt sulfide, or iron sulfide.

4. The compound according to claim 1, the metal sulfide being Ni.sub.3S.sub.2.

5. The compound according to claim 1, the CNT having a filling ratio of the metal sulfide of at least 0.80.

6. The compound according to claim 1, the CNT having a filling ratio of the metal sulfide of at least 0.90.

7. The compound according to claim 1, the CNT having a filling ratio of the metal sulfide of at least 0.95.

8. The compound according to claim 1, the CNT having a filling ratio of the metal sulfide of at least 0.99.

9. The compound according to claim 1, the CNT having a filling ratio of the metal sulfide of at least 0.999.

10. The compound according to claim 1, comprising a plurality of CNTs disposed on the carbon-based substrate, each CNT being filled with the nanowire, each CNT of the plurality of CNTs when filled with the nanowire being straight from a first end thereof to a second end thereof, each CNT of the plurality of CNTs when filled with the nanowire having the first end and the second end of the CNT being closed with respective carbon shell.

11. The compound according to claim 10, the plurality of CNTs having a filling rate of the metal sulfide of at least 0.80.

12. The compound according to claim 10, the plurality of CNTs having a filling rate of the metal sulfide of at least 0.90.

13. The compound according to claim 10, the plurality of CNTs having a filling rate of the metal sulfide of at least 0.95.

14. The compound according to claim 10, the plurality of CNTs having a filling rate of the metal sulfide of at least 0.99.

15. The compound according to claim 10, the plurality of CNTs having a filling rate of the metal sulfide of at least 0.999.

16. A battery, comprising: a cathode comprising lithium or sodium; an anode; and an electrolyte in contact with at least one of the cathode and the anode, the battery being a lithium-ion battery or a sodium-ion battery, and the anode comprising the compound according to claim 1.

17. A compound comprising: a carbon-based substrate; a plurality of carbon nanotubes (CNTs) disposed on the carbon-based substrate, each CNT of the plurality of CNTs comprising a nanowire of a metal sulfide filled therein, each CNT of the plurality of CNTs when filled with the nanowire being straight from a first end thereof to a second end thereof, each CNT of the plurality of CNTs when filled with the nanowire having the first end and the second end of the CNT being closed with respective carbon shells, the carbon-based substrate being carbon cloth, graphene, graphite, graphene oxide, carbon block, carbon fiber threads, carbon nanotube films, a carbon-coated substrate, a graphite-coated substrate, or a carbon nanotube film-coated substrate, the metal sulfide being Ni.sub.3S.sub.2, the plurality of CNTs having an average filling ratio of the metal sulfide of at least 0.80, and the plurality of CNTs having a filling rate of the metal sulfide of at least 0.80.

18. A battery, comprising: a cathode comprising lithium or sodium; an anode; and an electrolyte in contact with at least one of the cathode and the anode, the battery being a lithium-ion battery or a sodium-ion battery, and the anode comprising the compound according to claim 17.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1a is a scanning electron microscope (SEM) image of pristine carbon cloth (CC). The scale bar is 10 micrometers (μm).

(2) FIG. 1b is an SEM image of CC after loading nickel (Ni) nanoparticle (NP) catalysts. The scale bar is 10 μm.

(3) FIG. 1c is a high magnification SEM image of as-dispersed Ni NPs. The scale bar is 100 nanometers (nm).

(4) FIG. 1d is an SEM image of nickel sulfide (Ni.sub.3S.sub.2)-filled carbon nanotubes (CNTs) on CC. The scale bar is 10 μm.

(5) FIG. 1e is a lower magnification SEM image of Ni.sub.3S.sub.2-filled CNTs on CC. The scale bar is 2 μm.

(6) FIG. 1f is an SEM image of Ni.sub.3S.sub.2-filled carbon nanotubes (CNTs) collected via ultrasonication and deposited on a silicon wafer by spin-coating. The scale bar is 2 μm.

(7) FIG. 2 is an X-ray diffraction (XRD) spectrum of Ni.sub.3S.sub.2-filled CNTs FIG. 3a is an SEM image of Ni.sub.3S.sub.2-filled CNTs in contact with four gold (Au) electrodes. The scale bar is 2 μm.

(8) FIG. 3b is a plot of current (in milliamps (mA)) versus voltage (in Volts (V)), showing the current-voltage (I-V) characteristics of ten different Ni.sub.3S.sub.2-filled CNTs measured using a two-probe method. The inset shows an atomic force microscope (AFM) image of an individual Ni.sub.3S.sub.2-filled CNT in contact with two Au electrodes; the scale bar for the inset is 10 μm. The legend for the lines on the plot list “Ni.sub.3S.sub.2@CNT #1”, “Ni.sub.3S.sub.2@CNT #2”, and so on through “Ni.sub.3S.sub.2@CNT #10” (where “Ni.sub.3S.sub.2@CNT is a shorthand notation for Ni.sub.3S.sub.2-filled CNT).

(9) FIG. 3c is a plot of current (in mA) versus voltage (in V), showing the I-V characteristics of segment 2-3 (as labeled in FIG. 3a) of two samples (labeled A and B) using a four-point probe method.

(10) FIG. 3d is a plot of current (in mA) versus voltage (in V), showing the I-V characteristics of segment 2-3 (as labeled in FIG. 3a) of two samples (labeled A and B) using a two-point probe method.

(11) FIG. 4a is an SEM image showing electrical breakdown of a thin Ni.sub.3S.sub.2-filled CNT. The scale bar is 100 nm.

(12) FIG. 4b is an SEM image showing electrical extrusion of Ni.sub.3S.sub.2 from the open end of an Ni.sub.3S.sub.2-filled CNT. The scale bar is 500 nanometers (nm).

(13) FIG. 5a is a plot of voltage (in V, versus lithium*/lithium (Li.sup.+/Li)) versus specific capacity (in milliamp-hours per gram (mAh/g)), showing galvanostatic charge and discharge curves of an anode of Ni.sub.3S.sub.2-filled CNTs on CC at different cycles. The curve with highest value at 4150 mAh/g of the discharge grouping is for the first cycle; the other four curves, which are grouped closely together at 3410-3600 mAh/g in the discharge grouping, are for the second cycle, the fifth cycle, the tenth cycle, and the twentieth cycle, respectively. The closely grouped curves with the highest values at 3550-3600 mAh/g of the charge grouping are for the first cycle, the second cycle, the fifth cycle, and the tenth cycle; the other curve with highest value at 3420 mAh/g of the charge grouping is for the twentieth cycle

(14) FIG. 5b shows a plot of specific capacity (in mAh/g) versus cycle number, showing cyclic stability of an anode of Ni.sub.3S.sub.2-filled CNTs on CC for the first 20 cycles at a current density of 100 milliamps per gram (mA/g). The upside-down-triangular data points are for discharge; and the right-side-up-triangular data points are for charge.

(15) FIGS. 6a-6f show a series of transmission electron microscope (TEM) captured at 37.5 frames per second during dynamic in situ lithiation of a thin Ni.sub.3S.sub.2-filled CNT. The arrow in FIG. 6a shows the direction of propagation of lithium ions (Li.sup.+). FIG. 6a is at time=0 seconds; FIG. 6b is at time=20 seconds; FIG. 6c is at time=30 seconds; FIG. 6d is at time=40 seconds; FIG. 6e is at time=50 seconds; and FIG. 6f is at time=60 seconds. The scale bar for each is 200 nm.

(16) FIG. 6g is a TEM image of a large-diameter Ni.sub.3S.sub.2-filled CNT before lithiation. The scale bar is 200 nm.

(17) FIG. 6h is a TEM image of the large-diameter Ni.sub.3S.sub.2-filled CNT shown in FIG. 6g, after lithiation. The scale bar is 200 nm.

(18) FIG. 7 is a table of estimations of the resistivity of individual Ni.sub.3S.sub.2-filled CNTs.

(19) FIG. 8 is a schematic view of a setup for in situ synthesis of filled CNTs using a chemical vapor deposition technique, according to an embodiment of the subject invention.

DETAILED DESCRIPTION

(20) Embodiments of the subject invention provide novel and advantageous filled carbon nanotubes (CNTs) and methods of synthesizing the same. In situ methods (e.g., chemical vapor deposition techniques) can be used to synthesize CNTs (e.g., multi-walled CNTs) filled with metal sulfide (e.g., nickel sulfide, iron sulfide, cobalt sulfide) nanowires. The CNTs can be completely (or nearly completely) and continuously (or nearly continuously) filled with the metal sulfide fillers (e.g., metal sulfide nanowires, such as single crystalline nanowires) up to several micrometers (μm) in length. The filled CNTs can be synthesized on a carbon substrate (e.g., graphene, graphite, graphene oxide, carbon block, carbon fiber threads, carbon nanotube films, (flexible) carbon cloth, or carbon/graphite coated substrates (for example, carbon-coated stainless steel, carbon-coated copper, etc.))). The carbon substrate does not require any pre-treatment process (e.g., heat treatment, chemical activation, plasma treatment, etc.) and can be used in pristine form to load catalyst particles and subsequently synthesize filled CNTs in one step.

(21) The filled CNTs grown on the carbon substrate (e.g., graphene, graphite, graphene oxide, carbon block, carbon fiber threads, carbon cloth, carbon nanotube films, or carbon/graphite coated substrates (for example, carbon-coated stainless steel, carbon-coated copper, etc.)) have excellent electrical conductivity, as well as high lithium storage and excellent cyclability when used as anode materials for lithium-ion batteries (LIBs). In addition, the filled CNTs grown on the carbon substrate (e.g., carbon cloth) can also be used as an anode materials for sodium-ion batteries (SIBs) and have great potential to develop high-performance SIBs. The allowed maximum electrical current in the filled CNTs is size-dependent so the filled CNTs can advantageously be used as nano breakers for electronic devices.

(22) In many embodiments, in situ chemical vapor deposition (CVD) can be used to synthesize CNTs (e.g., multi-walled CNTs or single-walled CNTs) with metal sulfide (e.g., nickel sulfide (Ni.sub.3S.sub.2), iron sulfide (Fe.sub.xS.sub.y), cobalt sulfide (Co.sub.9S.sub.8)) nanowires. Pure metal (e.g., nickel, iron, cobalt, etc.) nanoparticles or their salts can be used as a catalyst and filling precursor of the CNTs. Examples of salts that can be used as a catalyst and filling precursor include but are not limited to metal nitrates (e.g., nickel nitrate, iron nitrate, cobalt nitrate, etc.), metal chlorides (nickel chloride, iron chloride, cobalt chloride, etc.), and metal sulfates (e.g., nickel sulfate, iron sulfate, cobalt sulfate, etc.). An organosulfur (can also be spelled as organosulphur) compound (also called organic sulfur compound) (e.g., thiophene, dimethyl sulfide, thiourea, etc.) can be used as both a carbon precursor and sulfur precursor for the synthesis of metal sulfide-filled CNTs. The CNT growth and filling of its core with metal sulfide can occur simultaneously, which can be referred to as an in situ filling process. The metal sulfide-filled CNTs can be synthesized on a carbon substrate (e.g., graphene, graphite, graphene oxide, carbon block, carbon fiber threads, carbon cloth, carbon nanotube films, or carbon/graphite coated substrates (for example, carbon-coated stainless steel, carbon-coated copper, etc.)). In some embodiments, ultrasonication can be used to collect the filled CNTs after synthesis (a magnet may optionally be used to purify the filled CNTs during/after collection; and/or the collected filled CNTs may optionally be deposited on a substrate (e.g., a wafer such as a silicon wafer), for example by spin-coating). The substrate can be flexible (i.e., not rigid), such as flexible carbon cloth.

(23) The synthesis of the filled CNTs is in situ in synthesis methods of embodiments of the subject invention, unlike related art ex situ filling methods, which are post-synthesis techniques that involve three steps (CNT synthesis, CNT opening, and CNT filling). The filled CNTs of embodiments of the subject invention are closed at both of their ends while the filled CNTs in related art ex situ methods are open at one or both of their ends. Synthesis methods for filling CNTs according to embodiments of the subject invention are reliable and efficient at producing metal sulfide-filled CNTs with closed ends, and the in situ methods can encapsulate very long metal-sulfide nanowires (e.g., up to 30 m or more in length) inside carbon nanotubes, which cannot be reliably achieved using state-of-the-art related art synthesis methods.

(24) Embodiments of the subject invention provide the first methods of synthesizing metal sulfide-filled CNTs on carbon-based materials (e.g., graphene, graphite, graphene oxide, carbon block, carbon fiber threads, carbon cloth, carbon nanotube films, or carbon/graphite coated substrates). The size-dependent maximum current flow through the metal sulfide-filled CNTs is also novel, as is the excellent lithium storage capability of the metal sulfide-filled CNTs grown on a carbon substrate (carbon cloth in particular).

(25) The metal sulfide-filled CNTs can be directly grown on the carbon-based substrate, which avoids the process of binding filled CNTs on the substrate using glue or any other adhesive or binder. The amount of metal sulfide-filled CNTs on carbon-based substrates can be controlled by tuning the growth parameters, which is not possible in state-of-the-art related art synthesis methods. By controlling the synthesis conditions, the filling rate (the proportion of CNTs that are filled as a fraction of all CNTs) and the filling ratio (the (average) proportion of an individual CNT that is filled as a fraction of the total CNT) of the CNTs by the metal sulfides can be controlled. The metal sulfide filling leads to the high crystallization of the carbon nanotubes. Embodiments of the subject invention enable large-scale production of metal sulfide-filled CNTs on carbon-based substrates, as well as easy synthesis of large-scale, high-quality, and high purity metal sulfide-filled CNTs on carbon-based materials to meet various application requirements.

(26) Embodiments of the subject invention provide methods to synthesize metal sulfide (e.g., Ni.sub.3S.sub.2) nanowire-filled CNTs on a carbon substrate (e.g., carbon cloth). A metal sulfide-filled CNT can be denoted using a shorthand notation as Ni.sub.3S.sub.2@CNTs (meaning Ni.sub.3S.sub.2-filled CNTs). Also, Ni.sub.3S.sub.2@CNTs/CC is a shorthand notation for Ni.sub.3S.sub.2-filled CNTs on carbon cloth (CC). The filling rate can be determined by the synthesis conditions and can be anywhere from 0 (i.e., 0%) to 1.0 (i.e., 100%), depending on the desired application. For example, the filling rate can be at least 0.80 (i.e., 80%), at least 0.85 (i.e., 85%), at least 0.90 (i.e., 90%), at least 0.95 (i.e., 95%), at least 0.99 (i.e., 99%), or at least 0.999 (i.e., 99.9%). The filling ratio can be determined by the synthesis conditions and can be anywhere from 0 (i.e., 0%) to 1.0 (i.e., 100%), depending on the desired application. For example, the filling ratio can be at least 0.80 (i.e., 80%), at least 0.85 (i.e., 85%), at least 0.90 (i.e., 90%), at least 0.95 (i.e., 95%), at least 0.99 (i.e., 99%), or at least 0.999 (i.e., 99.9%). The dimensions (length and average diameters) of the filled-CNTs can be controlled by changing the synthesis conditions. Any carbon-based material (substrate) of any size and shape (e.g., circular, square, rectangular, etc.) can be used, as long as it fits in the synthesis chamber. An organosulfur compound (e.g., thiophene (C.sub.4H.sub.4S), dimethyl sulfide, thiourea, etc.) can be used as both a carbon source and a sulfur source. Metal nanoparticles (e.g., nickel nanoparticles, iron nanoparticles, cobalt nanoparticles, etc.) can be used as catalysts to synthesize the metal sulfide nanowire-filled CNTs on carbon-based substrates. The size and loading amount of the metal nanoparticles can affect the filling rate and the filling ratio, as well as the yield of the metal sulfide nanowire-filled CNTs. Metal salts (e.g., metal nitrates, metal sulfates, or metal chlorides) can be used as the catalyst material to synthesize the metal sulfide nanowire-filled CNTs on carbon-based substrates. The concentration and the loading amount of the metal salt solution can affect the filling rate and the filling ratio, as well as the yield of the metal sulfide nanowire-filled CNTs. The filled CNTs have metallic properties (e.g., Ni.sub.3S.sub.2@CNTs have shown metallic properties with an average resistivity of 6.1×10.sup.−5 Ohm-meters (Ωm). The electrical breakdown of the filled CNTs is size-dependent, which makes them good candidates as nano circuit breakers. The filled CNTs (e.g., Ni.sub.3S.sub.2@CNTs/CC) can be used as an anode for an LIB or an SIB. For example, as an LIB anode, Ni.sub.3S.sub.2@CNTs/CC have been shown to have a lithium-ion storage capacity of about 3420 milliamp-hours per gram (mAhg.sup.−1) even after 20 cycles at a current density of 100 milliamps per gram (mAg.sup.−1), and they have also been shown to have high stability with a Coulombic efficiency of around 100% within 20 charge-discharge cycles. Thus, the filled CNTs of embodiments of the subject invention (e.g., Ni.sub.3S.sub.2@CNTs/CC) can help develop high-performance LIBs.

(27) Related art CNT synthesis methods can only generate a mixture of metallic and semiconducting CNTs, but when it comes to real applications, it is extremely important to separate the metallic CNTs and semiconducting CNTs. In view of the problems in the related art, there exists a need in the art for a reliable synthesis method that can yield 100% metallic or 100% semiconducting filled carbon nanotubes (CNTs) for different applications. The in situ fillings of CNT cores with metal sulfide (e.g., Ni.sub.3S.sub.2) nanowires, according to embodiments of the subject invention, can yield all metallic CNTs (100%) and solve the problem of separating metallic CNTs for any desired application. There are two major advantages of filling metal sulfide (e.g., Ni.sub.3S.sub.2) nanowires inside CNTs. First, metal sulfides possess intrinsic metallic behavior (e.g., Ni.sub.3S.sub.2 itself possesses a measured resistivity of 1.2×10.sup.−6 Ωm), which can dramatically change the electrical properties of CNTs facilitating the charge transportation along the filled CNTs, The other benefit of encapsulating metal sulfide (e.g., Ni.sub.3S.sub.2) nanowires inside the CNTs is that the robust walls of the CNTs can inhibit or prevent the metal sulfide filler from any damage or degradation during several applications, such as the application in lithium-ion batteries (LIBs) as an anode material.

(28) In situ (simultaneous synthesis and filling) synthesis methods of embodiments of the subject invention serve as reliable methods to fill CNT cores with long and continuous nanowires extending from the roots to the tip of the CNT. Also, being a one-step filling technique, the in situ filling allows easy control over the growth and filling parameters making the process efficient, quick, and economic. CNTs have been filled with a wide variety of materials using ex situ related art methods, but the in situ filling of embodiments of the subject invention is more challenging as it requires the presence of both the metal catalyst and the precursor of the filling material at the CNT growth sites causing a simultaneous graphitization of CNT walls and filling of its interior. Transition metal sulfide (e.g., Ni.sub.3S.sub.2) can be filled inside the CNTs using metal as the catalyst for CNT growth and the precursor for the filling material. When a proper amount of sulfur is released into the reaction chamber, both phenomena—the graphitization of CNT walls and formation of the metal sulfide (e.g., Ni.sub.3S.sub.2), can occur simultaneously at the active sites causing the in situ fillings of CNTs with long and continuous, single-crystalline metal sulfide (e.g., Ni.sub.3S.sub.2) nanowires.

(29) Metal sulfide-filled CNTs (on carbon substrates) of embodiments of the subject invention can be used as an anode material in an LIB (or SIB). With the rapidly growing use of battery powered electronic devices and electric vehicles, there exists a dire need for high-capacity LIBs to solve the global problem pertaining to the escalating crisis in renewable energy. Related art LIBs implement graphite as an anode material that has high stability but a very low lithium-ion storage capacity (about 372 mAhg.sup.−1). While attempts have been made in the related art to develop novel high-capacity nanomaterials and nanocomposites to use as LIB anodes, they have encountered several challenges such as the structural failure of the active material after several cycles of lithiation and de-lithiation, oxidation and corrosion of the metallic electrode (substrate), and poor binding between the active material and the electrode (substrate) surface due to the presence of a buffer layer or an extraneous binding agent. A major reason for the failure of such materials can be the low filling ratio obtained from the ex situ filling techniques. Also, semiconducting nanoparticles that are sometimes used in related art materials may not offer a quick transport of electrons and ions during the charge-discharge cycles. In addition, the extrusion of the lithiated filler, as the CNTs synthesized on anodic aluminum oxide (AAO) templates are open at both ends, can cause problems. Moreover, such related art devices suffer from instability and small diameter-CNTs (e.g., about 50 nm) along with a relatively low graphitization that can eventually breakdown over several cycles of expansion and contraction. All these problems can be solved by embodiments of the subject invention, by synthesizing a high-capacity material directly on a stable and conductive substrate such as carbon cloth (CC) encapsulating the active material inside a highly graphitized multi-walled CNT system closed at both ends. A CNT with closed ends can undergo a high radial expansion and contraction without falling apart during lithiation and de-lithiation of the filler and can inhibit (or prevent) extrusion of the active filler. Metal sulfide-filled CNTs on CC can address all these challenges and serve as an anode in improved LIBs. CC as a substrate has high tensile strength, high stiffness, thermal stability, low weight, and high chemical resistance against oxidation and corrosion. On the other hand, bulk Ni.sub.3S.sub.2 possesses a theoretical capacity of 445 mAhg.sup.−1, which is relatively high compared to that of graphite. The synergistic effects arising from the CNTs, the metal sulfide (e.g., Ni.sub.3S.sub.2) nanowire filler, the physiochemical stability of the CC, the absence of any buffer or binder between the filled CNTs and the CC surface, and the closed tip structure of the filled CNTs can produce excellent results and improved the capacity of LIBs. Meanwhile, the high metallicity of the individual filled CNTs can also support the ultra-fast charging of the LIBs.

(30) The metal sulfide-filled CNTs on carbon substrates (e.g., carbon cloth) of embodiments of the subject invention provide researchers with the opportunity to investigate the physical and chemical properties of this type of material. The filled CNTs can be used in electronic devices (e.g., microwave absorbers, sensing probes for magnetic force microscopy, magnetic recording, and data storage devices, nanothermometers, nano circuits, nano circuit breakers, etc.), biological or biomedical applications, (e.g., bio/chemical sensors, drug delivery/carrier systems, biomarkers, bioimaging, etc.), environmental protection (e.g., removing heavy metal ions and contaminants from water and/or purifying the air), energy storage (e.g., LIBs, SIBs, supercapacitors, solar cells, etc.), energy production (e.g., water splitting to generate oxygen and hydrogen, clean energy sources), and/or field emission devices (e.g., field emission electron microscopes, field emission spectrometers, etc.).

(31) The transitional term “comprising,” “comprises,” or “comprise” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. By contrast, the transitional phrase “consisting of” excludes any element, step, or ingredient not specified in the claim. The phrases “consisting” or “consists essentially of” indicate that the claim encompasses embodiments containing the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claim. Use of the term “comprising” contemplates other embodiments that “consist” or “consisting essentially of” the recited component(s).

(32) A greater understanding of the embodiments of the subject invention and of their many advantages may be had from the following examples, given by way of illustration. The following examples are illustrative of some of the methods, applications, embodiments, and variants of the present invention. They are, of course, not to be considered as limiting the invention. Numerous changes and modifications can be made with respect to the invention.

(33) Materials and Methods

(34) Nickel (Ni) nanoparticles (NPs) (99.9%, 40 nm, metal basis) were purchased from US Research Nanomaterials, Inc., and carbon cloth (CeTech carbon cloth without microporous layer) having a thickness of 330 μm was purchased from the Fuel Cell Store. Isopropyl alcohol (IPA) was purchased from Fisher Scientific and was used as received. Thiophene (C.sub.4H.sub.4S) of extra pure grade (99+%) was purchased from Acros Organics and was used as the precursor for both the carbon and sulfur. Gold (Au) electrodes (both two and four probes) were pre-patterned on a silicon oxide/silicon (SiO.sub.2/Si) wafer using photolithography to conduct the electrical measurements. For the electrochemical characterization, a coin cell was assembled in an argon-filled glovebox and used for half-cell test, which included Ni.sub.3S.sub.2@CNTs/CC as a working electrode, and lithium metal as both counter and reference electrodes. A 100 microliter (μl) volume of 1 molar (M) LiPF.sub.6 in ethylene carbonate-diethyl carbonate (1:1, volume ratio) was used as an electrolyte whereas Celgard 2400 polypropylene was used as a separator. In order to construct a nanobattery for in situ lithiation, Ni.sub.3S.sub.2@CNTs were scraped from the substrate using a razor blade and affixed to an aluminum (Al) wire using conductive epoxy. The sample was then loaded in a nanofactory STM-TEM vs. Li metal on a tungsten probe.

(35) The scanning electron microscope (SEM) images were obtained using JSM-F100 Schottky Field Emission Scanning Electron Microscope at an accelerating voltage of 15 kilovolts (kV). X-ray spectroscopy was performed on powder samples using Siemens Diffraktometer D5000 with Cu Kα radiation (λ=1.54 Å). The electrical characterizations were performed using Keithley 2400 Source meter, and the Galvanostatic charge/discharge (GCD) tests were conducted using a NEWARE BTS-610 battery tester. The dynamic in situ lithiation test was performed inside a Thermo Fisher Scientific Titan G2 ETEM with a Gatan K3-IS camera.

Example 1—Synthesis of Ni.SUB.3.S.SUB.2.@CNTs/CC

(36) Ni nanoparticles (NPs) were dispersed in IPA (5-100 grams per liter (g/l)) and kept in an ultrasonication bath for 5 minutes to achieve a uniform suspension of NPs, and then the suspension was transferred in a clean beaker ready for use. CC was cut into small pieces in desired shapes (square, rectangular, or circular) and cleaned by deionized (DI) water and IPA successively by a rinsing and drying method. The CC substrates were individually immersed in the beaker containing the IPA-Ni NPs suspension and left for dip coating for 5 minutes. During that time, the contents of the beaker were continuously stirred using a magnetic stirrer at 500-1000 revolutions per minute (rpm) to inhibit or prevent the agglomeration of Ni NPs at the bottom of the beaker as well as to achieve a uniform coating of Ni NPs on the threads of CC. Immediately after dip-coating, the CC was transferred to a hot plate maintained at 150° C. and heated for 5 minutes to evaporate the IPA from its surface. Afterwards, three to four CC substrates loaded with Ni catalyst NPs were placed in a quartz boat and aligned to the center of a quartz tube which was then heated in a furnace at 600° C. for 10 minutes (mins) in the presence of argon (Ar) flowing at a rate of 100-200 standard cubic centimeters per minute (sccm) to stabilize an inert environment. Afterwards, hydrogen gas (H.sub.2) was passed into the reaction chamber at a flow rate of 100-200 sccm for 15 mins to reduce the catalyst Ni NPs in pure metallic form. After reduction, the flow of H.sub.2 was stopped while Ar continued to flow until the temperature of the furnace reached to 1000° C. -1200° C. The flow rate of Ar was then increased to 1650-1850 sccm and H.sub.2 was resumed to flow at 100-200 sccm along a new path bubbling through thiophene (C.sub.4H.sub.4S), which was used as a precursor for both carbon and sulfur. In a synthesis duration of 5-30 mins, the in situ growth of Ni.sub.3S.sub.2@CNTs could be achieved. When the synthesis was complete, the flow of H.sub.2 was stopped and the reaction chamber was cooled down gradually under an inert atmosphere maintaining the Ar flow at 100-200 sccm. It is very important to note that CC substrates do not require any pre-treatment process such as heat treatment, chemical activation, plasma treatment, etc., and can be used in pristine form to load the catalyst particles and subsequently synthesize Ni.sub.3S.sub.2@CNTs in one step. This method also applies to other types of carbon-based substrates such as graphene, graphite, graphene oxide, carbon block, and carbon fiber threads. The setup shown in FIG. 8 was used for the synthesis of Ni.sub.3S.sub.2@CNTs/CC.

(37) FIG. 1a shows a section of a pristine CC substrate containing a stack of several carbon threads, which can be loaded with Ni NPs catalysts by a dip-coating method. Such loading of catalyst particles can be clearly seen in FIG. 1b, where Ni NPs appear to attach to each individual carbon thread. This loading density, however, can be controlled by changing the concentration of Ni NPs-IPA suspension. For example, one shown in FIG. 1b was achieved using a 20 g/l concentration of the catalyst particles; however, successful growth was observed using any catalyst concentration in the range of 5-100 g/l. It was found that the catalyst concentration is directly related to the quantification of Ni.sub.3S.sub.2@CNTs meaning that the mass and growth density of Ni.sub.3S.sub.2@CNTs on the CC substrate can be controlled by changing the concentration of Ni NPs suspension. FIG. 1c shows a high magnification SEM image of a cluster of Ni NPs with an average diameter of 40 nm dispersed in the CC substrate. It is important to understand that these smaller catalyst particles can melt and fuse together at higher temperature to form bigger Ni NPs (200 nm-1 μm), which are the actual catalysts for the nucleation and growth of Ni.sub.3S.sub.2@CNTs. FIGS. 1d and 1e show the uniform growth of Ni.sub.3S.sub.2@CNTs on the CC substrate. It was observed that Ni.sub.3S.sub.2@CNTs possess a unique morphology characterized by their spherical roots and a tapering structure from the root towards the tip along with a high degree of linearity. Ni.sub.3S.sub.2@CNTs/CC can easily be collected in powder/cluster form through the ultrasonication of the substrate for 5-10 minutes and can be used to deposit as a thin film on another substrate as shown in Figure if.

(38) XRD measurement was employed to confirm the crystal structure and phase composition of the Ni.sub.3S.sub.2. The diffraction patterns marked with diamond symbols in FIG. 2 can be indexed as (101), (110), (003), (113), (104), (122), (214), and (401) planes of rhombohedral Ni.sub.3S.sub.2 (ICDD reference card No: 00-044-1418) which correspond to the 2θ values of 21.75°, 31.10°, 37.77°, 49.73°, 54.61°, 55.16°, 73.04°, and 77.89°, respectively. The (002) peak for the carbon nanotube can be clearly observed at 26.36°, whereas the three peaks (111), (200), and (220) designated with star symbols represent the diffraction patterns of Ni corresponding to the 2θ values of 44.50°, 51.84°, and 76.36° respectively. The presence of Ni in the XRD profile of Ni.sub.3S.sub.2@CNTs is due to unreacted Ni catalyst spheres present at the root of each Ni.sub.3S.sub.2@CNT.

(39) The electrical properties of individual Ni.sub.3S.sub.2@CNTs were measured using both four-point probe and two probe methods. First, Au electrodes (both four and two electrodes) were deposited on a SiO.sub.2/Si wafer using photolithography as shown in FIGS. 3a and 3b (AFM image in the inset of FIG. 3b). A very dilute suspension of Ni.sub.3S.sub.2@CNT-IPA was then made and a 5 μl volume of it was dropped and spin-coated on the pre-patterned wafer containing the electrodes. The electrode system was immediately investigated in an optical microscope at an operating magnification of 100× to confirm if any single Ni.sub.3S.sub.2@CNT has passed across the electrodes. The process was repeated several times until a single Ni.sub.3S.sub.2@CNT was observed to pass through the Au electrodes. The wafer containing Au electrodes was cleaned in an ultrasonication bath after each trial to remove any cluster of Ni.sub.3S.sub.2@CNTs in the intermediate steps. Once a nanotube was found to make contact with the electrodes, it was focused under a scanning electron microscope at higher magnifications (X5000 and above) and continuously welded using an SEM electron beam by scanning the nanotube-electrode contact regions 5-10 times. This process can make a better contact between the Ni.sub.3S.sub.2@CNT and the Au electrodes prior to their I-V measurements.

(40) FIG. 3a shows the SEM image of a Ni.sub.3S.sub.2@CNT in contact with four Au electrodes. Two samples (arbitrarily labeled A and B) were used to determine the contact resistance between the Ni.sub.3S.sub.2@CNT and the Au electrodes by measuring the resistance of the same segment 2-3 (as labeled in FIG. 3a) using both four-probe and two-probe measurements. It was found that the segment 2-3 of sample A measured a resistance of 5.499 kilo-ohms (kΩ) under the four-probe measurement and a resistance of 5.538 kΩ under the two-probe measurement, with both measurements showing a metallic behavior of Ni.sub.3S.sub.2@CNTs. Similarly, sample B had measured resistance values of 6.667 kΩ and 6.709 kΩ under the four-probe and two-probe measurements, respectively. Both these measurements revealed a very low contact resistance (about 40 Ohms) as compared to the intrinsic resistance of the segment of Ni.sub.3S.sub.2@CNT under investigation (5-7 kΩ). Thus, the two-probe measurements were performed to estimate the resistivity of Ni.sub.3S.sub.2@CNT using ten different samples given the simplicity and accuracy of the two-probe method in this case. The I-V characteristics of ten different Ni.sub.3S.sub.2@CNTs are shown in FIG. 3b while the I-V characteristics of samples A and B using four-probe and two-probe measurements are shown in FIGS. 3c and 3d, respectively. All these measurements show a perfect linear I-V relationship in individual Ni.sub.3S.sub.2@CNTs. The measured electrical parameters and resistivities of each Ni.sub.3S.sub.2@CNT are listed in FIG. 7. Interestingly, all Ni.sub.3S.sub.2@CNTs showed a purely metallic behavior with a mean resistivity of 6.1×10.sup.−5 Ωm. This metallic property of Ni.sub.3S.sub.2@CNTs can be due to the presence of the metallic Ni.sub.3S.sub.2 at the core of the CNTs and the highly graphitized multi-walled CNT system with a big diameter as the current can flow simultaneously from both the Ni.sub.3S.sub.2 core and the CNT walls.

(41) FIG. 4 shows the size-dependent electrical breakdown of individual Ni.sub.3S.sub.2@CNTs at higher currents. It was observed that Ni.sub.3S.sub.2@CNTs with smaller diameters (less than 150 nm) can undergo an electrical breakdown when an excessive current passes through them. As an example, FIG. 4a shows a thin CNT with a diameter of about 150 nm that eventually broke down as the current exceeded 0.8 milliamp (mA). However, in the case of empty metallic multi-walled CNTs (MWCNTs), the electrical breakdown can occur at relatively smaller currents. The reason Ni.sub.3S.sub.2@CNTs can pass a very high current is that a high proportion of current can pass through Ni.sub.3S.sub.2 core, which has a low resistivity of 1.2×10.sup.−6 Ωm, thereby inhibiting (or preventing) the rapid oxidation of CNT walls induced by the flow of current. If the diameter of the Ni.sub.3S.sub.2@CNT is smaller than 150 nm, there are relatively fewer CNT walls that will suffer defects and damages due to the current and can subsequently breakdown in fewer steps earlier than the melting of the Ni.sub.3S.sub.2 core that can be caused by Joule heating. After the breakdown of Ni.sub.3S.sub.2@CNT, the Ni.sub.3S.sub.2 nanowire is ejected out of the breakdown region, which can be seen in FIG. 4a. Thus, given their metallicity, thin Ni.sub.3S.sub.2@CNTs can be used as a nano circuit breaker to limit the flow of higher currents in electronic devices. On the other hand, if the diameter of Ni.sub.3S.sub.2@CNT is significantly higher, it doesn't breakdown even if a high amount of current (1 mA) passes through it. However, the Ni.sub.3S.sub.2 nanowire can melt and extrude out from the open end of the Ni.sub.3S.sub.2@CNT in the direction of the current flow. In this case, the melting temperature of Ni.sub.3S.sub.2 is reached before the breakdown of CNT. FIG. 4b illustrates an example of the electrical melting and extrusion of the Ni.sub.3S.sub.2 nanowire from a Ni.sub.3S.sub.2@CNT having a diameter of about 500 nm (and an open end), which was observed as the current exceeded 1 mA.

Example 2—Electrochemical Properties of Ni.SUB.3.S.SUB.2.@CNTs/CC

(42) The electrochemical properties of the Ni.sub.3S.sub.2@CNTs/CC synthesized in Example 1 were evaluated as an anode material for LIBs using a coin cell assembly and constructing a nanobattery inside a transmission electron microscope (TEM). The initial lithiation results from the coin cell assembly are shown in FIGS. 5a and 5b. The half-cell including the Ni.sub.3S.sub.2@CNTs/CC anode delivered an initial discharge capacity of 4150 mAhg.sup.−1 and a capacity of 3600 mAhg.sup.−1 was retained during the first charge, which is about 86% of the initial discharge capacity as shown in FIG. 5a. In the subsequent cycles (2-10), the Ni.sub.3S.sub.2@CNTs/CC anode delivered a discharge capacity of 3600 mAhg.sup.−1 and a charge capacity of 3550 mAhg.sup.−1, showing very high reversibility of the lithiation and de-lithiation reactions. Even after 20 cycles, the Ni.sub.3S.sub.2@CNTs/CC anode exhibited a Coulombic efficiency of 99.7%, delivering the charge and discharge capacities of 3420 mAhg.sup.−1 and 3410 mAg.sup.−1, respectively, at a current density of 100 mAg.sup.−1. This capacity is more than 9 times that of graphite (372 mAhg.sup.−1) and 7 times greater than that of the theoretical capacity of bulk Ni.sub.3S.sub.2 (445 mAhg.sup.−1). This tremendous lithium-ion storage capacity offered by the Ni.sub.3S.sub.2@CNTs/CC anode surpasses the capacities obtained experimentally for all metal oxides, phosphides, sulfides, nitrides, and alloys and reaches very close to the theoretical capacities of Li metal (3860 mAhg.sup.−1) and Si (4200 mAhg.sup.−1). Although pure Li metal and Si possess a high theoretical capacity, their real-life application is inhibited or prevented due to the uncontrollable dendritic Li growth and structure pulverization caused by a high-volume expansion, respectively. This necessitates the development of novel anode material such as Ni.sub.3S.sub.2@CNTs/CC, which can offer a high capacity along with high efficiency and stability. FIG. 5b shows the cyclic stability of Ni.sub.3S.sub.2@CNTs/CC electrode for 20 cycles observed at a current density of 100 mAg.sup.−1. Interestingly, the charge-discharge stabilities after the first cycle can be clearly visualized by the perfect overlap between the right-side-up triangles (charge capacities) and the upside-down triangles (discharge capacities), forming a star shape in each cycle.

(43) The electrochemical properties of individual Ni.sub.3S.sub.2@CNT were further investigated using dynamic in situ lithiation inside TEM and the dynamic lithiation behavior was observed in a Titan ETEM as shown in FIGS. 6a-6h. FIG. 6a shows the initial Ni.sub.3S.sub.2@CNT with a thin diameter of 160 nm before the lithiation reaction. As the bias was increased (−2 to −3V vs. Li), lithium ions can propagate in the direction shown by an arrow in FIG. 6a. As the lithium propagates through the nanowire, the CNT swells in the transverse direction as seen in FIGS. 6b-6f. For example, the diameter of Ni.sub.3S.sub.2@CNT increased to 175 nm after 40 seconds, as seen in FIG. 6d, revealing that the volume expansion of Ni.sub.3S.sub.2 during the lithiation can be easily accommodated by the radial expansion of highly graphitized, multi-walled CNT system. FIGS. 6g and 6h show the TEM images of another Ni.sub.3S.sub.2@CNT having a relatively larger diameter of 485 nm. In FIG. 6g, a single crystalline Ni.sub.3S.sub.2 nanowire located at the CNT core before the bias was applied can be observed. After lithiation, a significant change of the phase in the CNT core can be spotted along with a preserved integrity of the CNT walls, as seen in FIG. 6h. During the first lithiation reaction, Ni.sub.3S.sub.2 can react with Li.sup.+ ions and reduce into Ni and Li.sub.2S according to the reaction Ni.sub.3S.sub.2+4Li.sup.++4e.sup.−.fwdarw.3Ni+2Li.sub.2S. However, the exact phases of the lithiation reaction products could not be identified due to the limitation of the data. These in situ studies clearly demonstrate the propagation of Li+ ions across the Ni.sub.3S.sub.2 nanowire and the role of CNT walls in accommodating the volume expansion, which can cause the Ni.sub.3S.sub.2@CNTs/CC anodes to deliver an extremely high capacity along with a high stability.

(44) In Examples 1 and 2, Ni.sub.3S.sub.2@CNTs were successfully synthesized on flexible CC substrates via a simple and reliable in situ method. Ni.sub.3S.sub.2@CNTs/CC material was characterized using techniques such as SEM and XRD to understand the morphology, microstructure, chemical composition, and functionalization. The intrinsic electrical properties of an individual Ni.sub.3S.sub.2@CNT were examined using both two-probe and four-point probe methods. The I-V measurements show the metallic properties of Ni.sub.3S.sub.2@CNTs along with an estimated resistivity of 6.1×10.sup.−5 Ωm. It was also observed that this synthesis method can yield 100% metallic nanotubes eliminating the requirement of a technique to separate metallic nanotubes from a mixture of metallic and semiconducting nanotubes for various purposes. Ni.sub.3S.sub.2@CNTs with thin diameters (below 150 nm), being a purely metallic conductor, can be used as nano circuit breakers to limit the flow of higher electric currents in electronic devices. The electrochemical properties of Ni.sub.3S.sub.2@CNT/CC electrodes were examined as an anode material for LIBs, revealing tremendous charge-discharge capacities along with high stability. It was observed that a Ni.sub.3S.sub.2@CNT/CC anode can deliver a capacity of 3420 mAhg.sup.−1 even after 20 cycles at a current density of 100 mAg.sup.−1, which is significantly greater than the capacities obtained by related art nanomaterials and composites. The dynamic lithiation and structural changes of an individual Ni.sub.3S.sub.2@CNT were examined using in situ TEM lithiation, which demonstrated the key role of the multi-layered carbon shells towards the accommodation of the volume expansion and inhibition or prevention of the structural failure of the Ni.sub.3S.sub.2@CNT anode during the lithiation reaction. Given the high conductivity of Ni.sub.3S.sub.2@CNTs and the remarkable lithium-ion storage capacity obtained, Ni.sub.3S.sub.2@CNTs/CC can be used as advantageous anodes in LIBs (and/or SIBs).

(45) It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.

(46) All patents, patent applications, provisional applications, and publications referred to or cited herein are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification.