Electrically conductive porous particle

Abstract

There is provided a method of forming a porous particle comprising an electrically conductive continuous shell encapsulating a core, said core comprising an elemental compound that reversibly reduces in the presence of a cation and oxidizes in the absence of said cation, said method comprising the steps of: a) encapsulating an elemental compound precursor with said electrically conductive shell; b) reacting said elemental compound precursor with an oxidation agent to oxidise said elemental compound precursor to form said elemental compound, thereby forming said electrically conductive shell encapsulating said core comprising said elemental compound.

Claims

1. A porous particle comprising an electrically conductive shell encapsulating a core, said core comprising an elemental compound precursor that oxidizes in the presence of an oxidation agent to form an elemental compound, wherein the elemental compound precursor is a metal chalcogenide comprising a metal selected from Group 7, 8, 9, 10, 11, 12, or 14 of the Periodic Table of Elements.

2. The porous particle according to claim 1, wherein said elemental compound reversibly reduces in the presence of a cation and oxidizes in the absence of said cation.

3. The porous particle according to claim 1, wherein a void is present between said shell and said elemental compound.

4. A cathode comprising a plurality of porous particles, each porous particle made according to a method of forming a porous particle comprising an electrically conductive shell encapsulating a core, said core comprising an elemental compound that reversibly reduces in the presence of a cation and oxidizes in the absence of said cation, said method comprising: a) encapsulating an elemental compound precursor with said electrically conductive shell, wherein the elemental compound precursor is a metal chalcogenide comprising a metal selected from Group 7, 8, 9, 10, 11, 12, or 14 of the Periodic Table of Elements; and b) reacting said elemental compound precursor with an oxidation agent to oxidize said elemental compound precursor to form said elemental compound, thereby forming said electrically conductive shell encapsulating said core comprising said elemental compound, wherein each porous particle comprises an electrically conductive shell encapsulating a core, said core comprising an elemental compound that reversibly reduces in the presence of a cation and oxidizes in the absence of said cation, and wherein a void is present between said shell and said elemental compound and the volume occupancy of the void between the shell and the core in the oxidized state is between about 10% to about 95%.

5. A battery comprising: a) an anode; b) the cathode of claim 4; and c) an electrolyte comprising said cation.

6. The battery of claim 5, wherein said cation is dissociated from said anode.

7. The battery of claim 5, wherein said cation is selected from the group consisting of lithium, sodium, potassium, rubidium, beryllium, magnesium, calcium, strontium and barium.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) The accompanying drawings illustrate a disclosed embodiment and serves to explain the principles of the disclosed embodiment. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.

(2) FIG. 1 is a schematic diagram representing the method of forming a porous particle in accordance to one embodiment.

(3) FIG. 2A is a scanning electron microscopy (SEM) image of ZnS spherical nanoparticles obtained via a hydrothermal method in accordance with Example 1. The scale bar in FIG. 2A is 1 micron.

(4) FIG. 2B is a transmission electron microscopy (TEM) image of ZnS spherical nanoparticles obtained via a hydrothermal method in accordance with Example 1. The scale bar in FIG. 2B is 50 nm.

(5) FIG. 3A is a TEM image of carbon coated ZnS hollow spheres. The scale bar in FIG. 3A is 50 nm.

(6) FIG. 3B is a TEM image of a carbon nanoparticle containing sulfur, in which the nanoparticle has a yolk-shell configuration. The scale bar in FIG. 3B is 50 nm.

(7) FIG. 4A is a SEM image of a carbon coated ZnS nanoparticle. The scale bar in FIG. 4A is 1 micron.

(8) FIG. 4B is a TEM image of the same carbon coated ZnS nanoparticle as FIG. 4A. The scale bar in FIG. 4B is 200 nm.

(9) FIG. 4C is a SEM image of a carbon containing sulfur nanoparticle denoted as CS1 made in accordance with Example 1. The scale bar in FIG. 4C is 1 micron.

(10) FIG. 4D is a TEM image of the same nanoparticle as FIG. 4C. The scale bar in FIG. 4D is 200 nm.

(11) FIG. 4E is a SEM image of a carbon containing sulfur nanoparticle denoted as CS2 made in accordance with Example 1. The scale bar in FIG. 4E is 1 micron.

(12) FIG. 4F is a TEM image of the same nanoparticle as FIG. 4E. The scale bar in FIG. 4F is 200 nm.

(13) FIG. 4G is a SEM image of a carbon containing sulfur nanoparticle denoted as CS3 made in accordance with Example 1. The scale bar in FIG. 4G is 1 micron.

(14) FIG. 4H is a TEM image of the same nanoparticle as FIG. 4G. The scale bar in FIG. 4H is 200 nm.

(15) FIG. 4I is a SEM image of a carbon containing sulfur nanoparticle denoted as CS4 made in accordance with Example 1. The scale bar in FIG. 4I is 1 micron.

(16) FIG. 4J is a TEM image of the same nanoparticle as FIG. 4I. The scale bar in FIG. 4J is 200 nm.

(17) FIG. 5A is a graph comparing the various X-ray powder diffractions of a commercial sulfur, a carbon-containing sulfur nanoparticle and a carbon-containing ZnS nanoparticle. Graph from top to bottom: Commercial S, S@C and ZnS@C.

(18) FIG. 5B is a graph comparing the thermal gravimetric analysis of the various carbon containing sulfur nanoparticles (CS1, CS2, CS3 and CS4) made in accordance with Example 1. Graph: CS1 (—), CS2 (- - -), CS3 (⋅ ⋅ ⋅) and CS4 (- ⋅ -).

(19) FIG. 6 is a graph showing the Li—S battery performance test of the various carbon containing sulfur nanoparticles (CS1, CS2, CS3 and CS4) made in accordance with Example 1. Graph: CS1 (.Math.), CS2 (.box-tangle-solidup.), CS3 (.circle-solid.), CS4 (.square-solid.) and coulombic efficiency (solid line).

(20) FIG. 7 is a schematic diagram representing a method as depicted in Comparative Example 1 in which a porous carbon nanoparticle was impregnated with sulfur using a conventional melt-diffusion process.

(21) FIG. 8 is a SEM image at 20,000× magnification of the resultant product obtained from the method of FIG. 7, showing the presence of micron-sized sulfur particles.

(22) FIG. 9 is a graph comparing the Li—S battery performance between the carbon containing sulfur nanoparticle denoted as CS1 made in accordance with Example 1 and the carbon containing melt impregnated sulfur nanoparticle denoted as MCS made in accordance with Comparative Example 1.

(23) FIG. 10A is a elemental mapping of the carbon containing sulfur nanoparticle in which sulfur is present in the core of the particle which has a carbon shell.

(24) FIG. 10B is an elemental mapping of the carbon shell portion of the nanoparticle of FIG. 10A.

(25) FIG. 10C is an elemental mapping of the core (sulfur) portion of the nanoparticle of FIG. 10A.

DETAILED DESCRIPTION OF DRAWINGS

(26) Referring to FIG. 1, there is shown a schematic diagram of a method 100 of forming a porous particle 2. The porous particle 2 comprises an electrically conductive shell 20 encapsulating an elemental compound 22 in the core. In the method 100, a plurality of elemental compound precursor 4 particles are mixed with carbon precursor 6 to form a mixture of both precursors 8. The carbon precursor may be in a resin form so as to hold the elemental compound precursor 4 particles in a matrix configuration. The mixture 8 is then subjected to a forming step 10 (such as a carbonization step) to form the electrically conductive shell 20 from the carbon precursor 6. The particle 12 then comprises an electrically conductive shell 20 encapsulating the elemental compound precursor 4. The particle 12 is then subjected to oxidation in the presence of an oxidation agent 14 to oxidise the elemental compound precursor 4 to elemental compound 22. The resultant porous particle 2 is then formed. When the porous particle 2 is part of a cathode of a rechargeable battery, the elemental compound 22 within the porous particle polymerizes during discharge of the cathode to form a poly(elemental compound) 24 (that is still encapsulated by the electrically conductive shell 20). The poly(elemental compound) 24 dissociates during charging of the cathode to revert back to the elemental compound 22.

EXAMPLES

(27) Non-limiting examples of the invention and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.

Experimental

(28) General Synthetic Procedure of Sulfur Containing Carbon Yolk-Shell Nanostructures:

(29) The method 100 depicted in FIG. 1 is used here to synthesize zinc sulfide nanoparticles (ZnS NP) by hydrothermal process. In the process, equal mol of zinc acetate dehydrate (with 2 mol H.sub.2O), Zn(CH.sub.3COO).sub.2.Math.2H.sub.2O, and thiourea, H.sub.2NC(═S)NH.sub.2, were added into deionized water to form the precursor solution. Gum arabic was then added as a surfactant for the formation of the nanospheres. The mixture was stirred and sonicated to ensure complete dissolution of the reagents, before it was transferred into an autoclave which was then sealed and placed into an oven for a reaction at 120° C. over 12 hours. The resultant white precipitate of zinc sulfide was retrieved via centrifugation, washed with deionized water for 3 times and dried at 70° C. for 3 hours. A small volume of acetone solution of phenol formaldehyde (PF) resin was thoroughly mixed with the zinc sulfide nanoparticles through stirring and sonication for about 10 minutes before the mixture was dried in a vacuum over 5 hours. The samples were then subjected to high temperature treatment in a tube furnace at 900° C. under argon gas for 1 hour. The treated samples were ground into fine powder using a mortar and pestle, and ferric nitrate aqueous solution was added to the sample and left with stirring overnight in an ice water bath to convert the zinc sulfide to sulfur. The sulfur-in-carbon samples were recovered via centrifugation, and concentrated HCl was added to each sample as a precaution to remove any possible zinc sulfide residue. After the removal of HCl via centrifugation, the obtained sample was further washed 3 times with deionized water, subsequently dried at 70° C. for 3 hours, prior to use for further characterization and battery testing. All chemicals used were obtained from Sigma-Aldrich (of Missouri of the United States of America) or from Alfa Aesar (of Massachusetts of the United States of America).

(30) Characterization:

(31) Scanning Electron Microscope (SEM) images were taken on a JEOL JSM-6700F FESEM with an accelerating voltage of 5 kV. Transmission Electron Microscope (TEM) images were taken on a Philips CM300 FEGTEM with an accelerating voltage of 200 kV. X-ray diffraction was recorded on Bruker D8 General Area Detector Diffraction System using Cu Kα radiation. Thermogravimetric analysis was conducted on a TA instruments TGA Q500 at a heating rate of 10° C. min.sup.−1 under nitrogen gas. Elemental analysis was carried out using the Flash EA1112 Elemental Analyzer from Thermo Scientific.

(32) Battery Testing:

(33) To fabricate the working cathodes for battery testing, the samples were each mixed with carbon black (Denka) and polyvinylidene binder dissolved in N-methyl-2-pyrolidinone in a weight ratio of (8:4:3) to form a black colored slurry. This slurry was then coated evenly onto an aluminum foil using doctor blade. The foil was dried in an oven at 70° C. for 3 hours and the working cathodes were cut out from the foil using a hole puncher with a diameter of 15 mm. CR2032 type coin cells were assembled in a glove box with argon environment using lithium foil as counter anodes. The electrolyte used was lithium bis(tri-fluoromethanesulfonyl)imide dissolved in 1:1 (v/v) mixture of 1,2-dimethoxyethane and 1,3-dioxolane, with lithium nitrate and dilithium hexasulfide (Li.sub.2S.sub.6) as additives. The concentrations of the 3 lithium salts were 1M, 0.5M and 0.2M, respectively. Lithium-sulfur battery cycling tests were performed on Neware battery tester with the electric potential set as 1.5 to 3.2 V. Capacity values was calculated based on the weight of composite material. The mass loading of composite (carbon and sulfur) is around 2.2 mg per electrode.

Example 1—Synthesis of Sulfur Containing Carbon Yolk-Shell Nanostructures

(34) ZnS nanoparticles were prepared using 65.85 g (0.3 mol) of zinc acetate dihydrate (FW: 219.50 g/mol) and 22.84 g (0.3 mol) of thiourea (FW: 76.12 g/mol) following the method described above. The amount of gum arabic used was 3 g. For the carbon coating formation, 0.5 g of ZnS nanoparticle was taken, and the PF resin acetone solution had a concentration of 0.5 g mL.sup.−1. Four samples of the ZnS nanoparticles were prepared in this example based on varying amounts of the PF resin acetone solution used (0.5 mL, 0.4 mL, 0.2 mL and 0.1 mL). For the sulfur formation process, the ferric nitrate applied had a concentration of 0.1 g mL.sup.−1, and the volume used was 20 mL. The resultant samples were denoted as CS1, CS2, CS3 and CS4, respectively

(35) The weight ratio of sulfur and carbon obtained in the nanoparticles as assessed by thermogravimetry is disclosed in the following Table 2:

(36) TABLE-US-00002 TABLE 2 TGA Analysis Sample Sulfur (wt. %) Carbon (wt. %) CS1 33.8 66.2 CS2 42.9 56.9 CS3 54.0 46.0 CS4 74.8 25.2

(37) The ZnS nanoparticles synthesized were typically about 250 nm in diameter (FIG. 2A and FIG. 2B). From the TEM image (FIG. 2B), one can see that these uniform particles were essentially secondary particles, arising from the assembly of ZnS nanoparticles (primary particles) with a diameter of 4 to 5 nm. Such structure showed the following advantages: 1) it possessed large population of micropores that allowed the oxidative ferric ions to easily impregnate into the nanoparticles; 2) the much smaller primary particles were more reactive; 3) some voids were reserved in the materials. Advantages (1) and (2) enabled easier and faster conversion of sulfide to sulfur, while advantage (3) facilitated the formation of the S@C yolk-shell structure (see FIG. 3B where the sulphur yolk is circled) with a void having a large volume percentage (as will be discussed later).

(38) When the ZnS nanoparticles containing phenol formaldehyde (PF) acetone dispersion was slowly dried at room temperature, the nanoparticles self-assembled into layered structure with PF resin filling the inter-particle voids which essentially coated over all these particles. As the dried composite (ZnS@resin) was carbonized in a tube furnace at high temperature in an inert atmosphere, interconnected carbon-coated ZnS nanoparticles were obtained. Representative SEM and TEM images of such composite material post-carbonization (ZnS@C) are shown in FIG. 3A, FIG. 4A and FIG. 4B, where carbon-coated ZnS hollow spheres are clearly visible.

(39) As the ground ZnS@C composite was soaked in ferric nitrate aqueous solution, the chemical reaction shown in equation (2) took place where zinc sulfide was converted to element sulfur and free zinc ions which can be washed away using deionized water.
[Math. 2]
2Fe.sup.3+.sub.(aq)+ZnS.sub.(s).fwdarw.2Fe.sup.2+.sub.(aq)+Zn.sup.2+.sub.(aq)+S.sub.(s)  (2)

(40) Loss of the zinc ions which contributed to ⅔ of the weight of zinc sulfide resulted in the generation of voids of large percentage volume within the carbon shells. Though the produced sulfur may exhibit a volume that is larger than its partial volume in the original ZnS, it by no means compensated for the loss in volume caused by the removal of zinc ions. In an ideal conversion where all sulfides are converted to sulfur that is retained in the shell, a volume reduction of 34.7% (smaller than the weight portion of ⅔) can be anticipated. The voids will present a larger volume percentage for incomplete conversion of ZnS (removed by washing with concentrated HCl). Hence, the void volume can be tuned by controlling the extent of sulfide conversion which is achievable by varying reaction conditions, such as the concentration of ferric nitrate, the soaking time, etc. In this way, carbon encapsulated sulfur nanoparticles (S@C) in yolk-shell nanostructure can be harvested with controlled void volume percentage.

(41) In this Example, the average volume shrinkage is typically 80%, if the outer diameter of the sulfur nanospheres and the internal diameter of the “hollow carbon” are measured in the TEM images. Since volumetric expansion of sulfur during discharge process in lithium sulfur batteries is calculated to be about 78.7%, this incidental match between volume-available and volume-in-need suggests a straightforward production of useful S@C materials based on the method defined herein.

(42) The sulfur content in S@C can be balanced by changing the amount of PF resin used, and TEM images of a series of the yolk-shell S@C with different sulfur content are shown in FIG. 4C to FIG. 4J. Low sulfur content (FIG. 4C to FIG. 4F) generally facilitated the formation of an interconnected 3D carbon matrix that is beneficial to electron conductivity, yielding better battery performance at high charge-discharge rates. With the increase of sulfur content, the thickness of carbon shell will be reduced. Once the sulfur content reached 50 wt % and above (FIG. 4G to FIG. 4J), the carbon matrix was broken and individual S@C particles formed. In this case the electron conductivity was compromised, which worsens the rate performance in battery test. Nevertheless, high sulfur content is essential for high specific capacity in batteries. Therefore, it is crucial to balance the carbon/sulfur ratio so that a continuous carbon matrix with maximized sulfur content can be achieved. From the TEM images, an optimized thickness of the carbon coatings is about 5 nm and the diameter of the sulfur nanospheres contained within these carbon shells is about 140 nm.

(43) The structure of ZnS@C and S@C composites were verified by powder XRD patterns, as shown in FIG. 5A. It can be seen that the ZnS obtained via hydrothermal method possessed a cubic phase (zinc blende or sphalerite), and the three strong peaks at 28.5°, 47.5° and 56.4° corresponded to the crystal planes of (111), (220) and (311), respectively. For S@C, all the diffraction peaks from the samples matched well with that of the orthorhombic phase of crystalline sulfur (XRD pattern of commercial S is shown as reference), proving the existence of such crystalline sulfur in the composite material.

(44) The thermogravimetric analysis was used to determine the actual sulfur content in the S@C composite obtained, and the profiles are presented in FIG. 5B. The weight loss from 150 to 500° C. was attributed to the evaporation of sulfur (melting point: 115.2° C.; boiling point: 444.6° C.). Details of the TGA profiles were analyzed and the calculated sulfur content for all S@C composites was summarized in Table 2 above. It is obvious that by controlling the amount of PF resin used, the sulfur content was tunable between 33.8 wt % to 74.8 wt %. The composition of the S@C composites was also further confirmed by the data obtained in elemental analysis.

Example 2—Battery Performance

(45) The cycling performance of the developed S@C yolk-shell materials was tested in Li—S batteries and the results are shown in FIG. 6. The initial discharge capacity of samples CS1, CS2, CS3 and CS4 were 443, 548, 796 and 878 mAh gram per electrode (including composite, carbon black and binder), respectively. The rate of capacity fading was very similar for CS1 to CS3 with thicker carbon shell; however, a much faster capacity fading was observed for CS4 that possessed the thinnest carbon shell and the highest capacity. After 20 cycles of discharge-charge processes, the discharge capacity of CS4 dropped to a value which is lower than that of CS3. The poorer cyclability of CS4 can be attributed to the thin carbon shell that was inadequate to prevent the polysulfides from leaking out of the carbon spheres. Therefore, it is crucial to have a balanced C and S content for high capacity and good cyclability of Li—S batteries, and the optimal ratio is around 1:1.

Comparative Example 1—Synthesis of Reference Sample (Porous Carbon Nanostructures with Melt-Impregnated Sulfur)

(46) Fresh prepared carbon-sulfur composite (for example CS2) was soaked in toluene for 1 hour to remove the sulfur within the pores. The resulting porous material was recovered by centrifugation, washed repeatedly with toluene and then dried in oven at 70° C. for 12 hours. The obtained porous carbon was mixed with elemental sulfur in a 1:1 weight ratio and sulfur was impregnated into empty pores via the conventional melt-diffusion process in the autoclave at 150° C. for 12 hours. The final product was ground into fine powder using a mortar and pestle, and denoted as MCS. The method is summarised in FIG. 7.

(47) The sample MCS exhibited poor morphology control. A representative SEM image (FIG. 8) of MCS showed ill-defined morphology with numerous micron-sized sulfur particles on the surface of carbon matrix. As the electrical conductivity of sulfur is very low, these micron-sized sulfur particles gave poor electrical contact in the battery electrode and prevented the complete utilization of available sulfur, leading to much lower capacities. This is clearly shown in FIG. 9, where MCS with 50 wt % of sulfur displayed a capacity lower than that of CS1 (33.8 wt % of sulfur). The higher capacity fading rate for MCS in FIG. 9 was also caused by the unprotected sulfur on the surface of the carbon shells that readily contributed to the redox shuttle and gradually precipitated on the anode, leading to faster capacity fading.

(48) This comparative example shows the problems with using a melt-diffusion process to impregnate a porous carbon with the sulfur. Together with another convention process of using vapour-phase infusion, these methods result in poor control over the sulfur filling content in individual pores. Either overfill (>>50% (v/v) of the pore) or underfill (<<50% (v/v) of the pore) will have significant negative impact on the battery performance. Apart from poor control over the sulfur filling content, some sulfur will unavoidably be deposited on the surface of the host material. Such unprotected sulfur will contribute readily to the redox shuttle, resulting in large capacity losses during the initial cycles.

(49) Hence, it is clear that the S@C nanoparticles made according to the method as defined herein, that is, carbon-encapsulated sulfur in yolk-shell nanostructure from a ZnS precursor approach, is superior to the MCS sample that was made according to a conventional melt-diffusion process in term of the battery performance.

(50) In summary, a new method to prepare S@C nanoparticles with well-defined yolk-shell nanostructure has been developed. The well-defined yolk-shell nanostructure of the S@C nanoparticles can be seen in FIG. 10A (the presence of the sulfur yolk within the carbon shell), FIG. 10B (showing the carbon shell) and FIG. 10C (showing the sulfur present as the core).

(51) Such composite nanoparticles offer sufficient free volume to accommodate the expansion of sulfur during discharge process, and the effective carbon coating (which, as discussed above, cannot be too thin) can prevent excessive polysulfide leakage. Cathodes of such S@C materials exhibited high initial capacities and excellent cycling performance. The superiority of this method over traditional melt-diffusion methods was that (1) an even dispersion of sulfur nanoparticles can be achieved inside the pores, and (2) formation of bulk sulfur particles on the surfaces of the carbon matrix is absent or minimized. Both are crucial to a good cyclability of the lithium sulfur batteries.

INDUSTRIAL APPLICABILITY

(52) The method as defined herein can enable the synthesis of different novel nanostructures for future high performance lithium-sulfur batteries with high specific capacity and good cyclablility. Advantageously, due to the use of the disclosed method, as compared to traditional melt-diffusion methods, (1) an even dispersion of sulfur nanoparticles can be achieved inside the pores, and (2) formation of bulk sulfur particles on the surfaces of the carbon matrix is absent or at least substantially reduced.

(53) The porous particle made according to the method as defined herein may display superior performance when used as cathode material in a rechargeable Li—S battery, such as high initial capacities, good electric conductivity, high specific capacities and/or excellent cycling performance. In addition, the leakage of sulfur and polysulfides during battery discharge can be substantially reduced due to the presence of the shell that confines the sulfur within the nanoparticle. Moreover, due to the presence of the void in the nanoparticle, the sulfur can volumetrically expand during the discharge process while not damaging the shell. Further, due to the interconnected 3D carbon matrix between the various carbon containing sulfur nanoparticles, this results in good electrical contact.

(54) It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.