Particles comprising stacked graphene layers

Abstract

According to the invention there is a particle including a plurality of stacked sub-structures, each sub-structure including a stack of graphene layers, in which the separation between successive stacked sub-structures is greater than the separation between successive graphene layers in each sub-structure.

Claims

1. A particle including a plurality of stacked sub-structures, each sub-structure including a stack of graphene layers, in which the separation between successive stacked sub-structures is greater than the separation between successive graphene layers in each sub-structure, wherein the sub-structures have a net negative charge.

2. A particle according to claim 1 in which the separation between successive stacked sub-structures is in the range 2 to 100 nm.

3. A particle according to claim 1 in which the sub-substructures each have a stack thickness which is in the range 0.7 to 15 nm.

4. A particle according to claim 1 in which each sub-structure includes a stack of between 2 and 12 graphene layers.

5. A particle according to claim 1 in which the sub-structures each have a stack thickness, and the stack thicknesses are less than the separation between successive stacked sub-structures.

6. A particle according to claim 1 having a thickness in the range 0.7 to 5 microns.

7. A particle according to claim 1 having a width in the range of 1 to 15 microns.

8. A particle according to claim 1 which has Stone-Wales defects.

9. A particle according to claim 1 which has a carbon content of greater than 80 wt. %.

10. A particle according to claim 1 in which at least some of the graphene layers in the sub-structures are doped and/or surface modified.

11. A particle according to claim 10 in which at least some of the graphene layers are surface modified by functionalisation.

12. A particle according to claim 10 in which at least some of the graphene layers are surface modified by decoration with a material.

13. A particle according to claim 12 in which the material is silicon, sulfur or selenium.

14. A particle according to claim 12 in which the material is a metal.

15. A particle according to claim 14 in which the metal is one or more of silver, gold, platinum, copper and iron.

16. A particle according to claim 1 further including an intercalated substance which is intercalated between successive stacked sub-structures.

17. A particle according to claim 16 in which the intercalated substance is sulfur or hydrogen.

18. Particulate material including a plurality of particles according to claim 1.

19. Particulate material according to claim 18 having a surface area in the range 15 to 70 m.sup.2g.sup.1.

20. Particulate material according to claim 18 which is crystalline.

21. Particular material according to claim 18 made by subjecting a starting material to a plasma treatment.

22. A particle according to claim 1 in which the separation between successive stacked sub-structures is in the range 5 to 50 nm.

23. A particle according to claim 1 in which the separation between successive stacked sub-structures is in the range 10 to 20 nm.

24. A particle according to claim 1 in which the sub-substructures each have a stack thickness which is in the range 0.7 to 4 nm.

25. A particle according to claim 1 having a thickness in the range 1 to 5 microns.

26. A particle according to claim 1 having a thickness in the range 1.5 to 3 microns.

27. A particle according to claim 1 having a width in the range of 2 to 5 microns.

28. A particle according to claim 1 which has a carbon content of greater than 90 wt. %.

29. A particle according to claim 12 in which the material is a transition metal.

30. A method of making particulate material according to claim 18 including subjecting a starting material to a plasma treatment.

31. A method according to claim 30 in which the plasma treatment includes generating plasma using a plurality of electrodes which are moved during the plasma treatment to agitate the starting material and/or the particulate material.

Description

(1) Embodiments of particles and methods of making same in accordance with the invention will now be described with reference to the accompanying drawings, in which:

(2) FIG. 1 is a SEM (scanning electron microscope) image of graphitic starting material;

(3) FIG. 2 is a SEM image of a particle;

(4) FIG. 3 is a SEM image of a particle at a higher resolution than FIG. 2;

(5) FIG. 4 is a SEM image of a particle decorated with silicon nano-pods;

(6) FIG. 5 is a SEM image of a particle decorated with a metal;

(7) FIG. 6 is a perspective view of apparatus of the invention;

(8) FIG. 7 is an exploded view of the interior of the rotating drum; and

(9) FIG. 8 shows (a) an exploded perspective view and (b) a side view of an end plate having a plurality of electrodes disposed therein.

(10) FIG. 1 is a SEM image of graphite which may be used as the starting material to produce particles of the invention. FIGS. 2 and 3 are SEMs of particles of the invention. Significant exfoliation has taken place, and the material has been cleaned. The particles are in the form of a stacking of a plurality of sub-structures. FIG. 2 shows measurements of the gap between successive sub-structures. It can be seen that gaps of 12.5 nm, 14.3 nm and 15.9 nm are measured. FIG. 3 shows the gaps between successive sub-structures in greater detail. It can be seen that in some instances the edges of successive sub-structures are more or less in alignment. Quite commonly, there are observed a first plurality of successive sub-structures having edges which are substantially in alignment, followed by a second group of successive sub-structures having edges which are substantially in alignment but which are not aligned with the first plurality of sub-structures, and so on. It has been shown that each sub-structure comprises a number of layers of graphene. Typically there are up to about ten layers of graphene in each sub-structure. Often, sub-structures are observed to have about three graphene layers with a sub-structure thickness of about 2.1 nm. The gaps between successive layers of graphene in each sub-structure are considerably smaller than the gaps between successive sub-structures. Typical gaps between successive graphene layers in the sub-structures are 0.5-0.8 nm. It will be appreciated that individual graphene layers are not resolved in FIGS. 2 and 3, and instead the sub-structures appear as apparently discrete features.

(11) XRD analysis has revealed that particles of the invention such as those shown in FIGS. 2 and 3 exhibit a high degree of crystallinity, with both the alpha graphitic form (hexagonal) and the beta graphitic form (rhombohedral) being observed.

(12) Without wishing to be bound by any particular theory or conjecture, it is believed that the sub-structures have a nett negative charge which acts to keep them apart. This gives rise to the relatively large separations between sub-structures. It is believed that the relatively large gaps between sub-structures give rise to a number of highly advantageous properties. Firstly, it is believed that these relatively large gaps improve friability, and permit easy dispersion via, for example, shear type forces or sonication. This gives rise to improved packaging, handling, and incorporation into liquid media or matrix material, for example to produce composite materials. In contrast, prior art nanoparticles such as CNTs, GNPs and single flakes of graphene are notoriously difficult to handle, and commonly exhibit a high degree of entanglement and poor friability.

(13) A further advantage associated with the relatively large gaps between successive sub-structures is that a range of materials can be intercalated into particles of the invention. Examples of materials which may be intercalated in this way include sulfur and molecular hydrogen. The particles may be modified in other ways. This may be instead of, or in addition to, intercalation. For example, the particles may be functionalised in a desired way. Particles of the invention can be readily decorated with a range of materials. Decoration with silicon can be performed. The particles can be essentially coated with silicon. However, the invention also provides a form of silicon decorated particle where the silicon decoration is present as a plurality of discrete structures or islands. FIG. 4 is an SEM of particles of the invention decorated with silicon in this way. It can be seen that the silicon is present as a plurality of discrete nano-pods having dimensions less than 500 nm and often less than 100 nm. This gives rise to useful properties, such as an ability for the silicon nano-pods to expand and contract independently of each other. This provides the potential for the material to cope with multiple electrical charge-discharge cycles.

(14) The particles may be decorated with a metal. FIG. 5 is an SEM showing particles of the invention decorated with silver. Table 1 shows an elemental analysis of particles of the invention decorated with silver.

(15) TABLE-US-00001 TABLE 1 Elemental analysis of silver decorated with particles. Element Weight % Atomic % Compound % Formula C K 70.90 93.77 0.00 O K 1.97 1.95 28.46 OAg.sub.2 Al K 0.63 0.37 0.00 Ag 26.50 3.90 Total 100.00

(16) Apparatus suitable for producing particles of the invention will now be described. FIG. 6 shows a suitable treatment chamber 10 positioned on a bed 12 through coupling portions 14, 16. The coupling portion 16 is in operative connection with a suitable motor or actuator disposed in a housing 18. The motor or actuator is coupled to the treatment chamber 10 so that, in operation, the treatment chamber 10 may be rotated at a desired rotational speed.

(17) The treatment chamber 10 is a three-part modular arrangement comprising a central drum 20 and first and second frusto-conical sections 22, 24. The first frusto-conical section 22 is in contact with the receiving portion 16, and second frusto-conical section 24 is in contact with the receiving portion 14 so as to allow the treatment chamber 10 to be rotated. The drum 20 and first and second frusto-conical sections 22, 24 can be formed from any suitable material, such as stainless steel.

(18) FIG. 7 shows the internal arrangement of the drum 20 in more detail. In particular, the drum 20 comprises a cylindrical portion 26 and a first circular end plate 28. The first end plate 28 is in communication with the first frusto-conical section 22. A second circular end plate (not shown) is positioned at the end of the cylindrical portion 26 opposite the first end plate 28 and is in communication with the second frusto-conical section 24. A plurality of electrodes 32 project out of the first end plate 28 into the interior of the drum 20. The electrodes 28 are radially disposed around the longitudinal axis of the drum 20 in a circular pattern. As shown in FIG. 7, the electrodes are equally spaced, although it is not critical that this is so. The electrodes 28 are arranged towards the circumferential edge of the first end plate 28. As explained in more detail below, this arrangement is preferred in order to provide agitation of particles which are disposed in the treatment chamber in order to undergo plasma treatment. In the embodiment shown in the figures, an arrangement of twelve electrodes project into the treatment chamber. However, a greater or a lesser number of electrodes might be used. In the embodiment shown in the figures, the electrodes 32 are formed from an electrically conductive material such as stainless steel. Isolator sleeves 34 formed from an electrically insulating material such as ceramic are disposed at both ends of each electrode 32. The sleeves may be coatings on the electrodes. The electrodes should generally be arranged to project a significant way into the chamber. The active plasma producing areas of the electrodes may be coated with a conductive ceramic coating such as boron silicate glass. This can act to reduce unwanted sputtering.

(19) The supply and removal of gases to and from the treatment chamber 10 will now be described with particular reference to FIG. 8 which shows a gas inlet module 38 (also shown in FIG. 7) which is in gas conducting connection with a plurality of gas inlet lines 40. Each gas inlet line 40 is connected to an electrode 32. Each electrode 32 is hollow, having an internal gas conducting conduit (not shown) leading to a gas outlet aperture at the distal end of each electrode 32 (not shown). The gas inlet module 38 is housed in the first frusto-conical section 22, and is supplied with the gases to be used during plasma processing from one or more external gas supply sources (not shown). The supply of gas can be controlled using known means such as mass flow controllers.

(20) The first end plate 28 has an exhaust port 42 formed therein. As shown in FIG. 8(b), a filter 44 is disposed in the exhaust port 42. The exhaust port 42 is in connection with a pumping arrangement (not shown) which is used to create a vacuum in the treatment chamber and to pump away process gases in a manner which is well-known to the skilled reader.

(21) Rotatable drum chambers are available commercially and may be adapted in order to produce apparatus of the invention. For example, a rotating drum plasma reactor is produced commercially by Diener Electronic GmbH & Co. KG, D-72224 Ebhausen, Germany having the product name Tetra 500. This apparatus may be adapted in accordance with the invention, for example by providing the plurality of electrodes described above.

(22) In use, a charge of the starting material is disposed on the floor of the drum 20. The chamber is evacuated to a desired baseline pressure, and the process gas or gases are introduced into the treatment chamber 20 through the electrodes 32. The treatment chamber 10 is rotated at a desired rotational speed. A plasma is generated at each electrode 32 in order to initiate processing of the particles. During the processing of the particles, the electrodes 32 are rotating, and this acts to continuously agitate the charge of particles in the treatment chamber. The particles may be physically transported through this agitation, for example through sideways displacement of the particles, or by way of the particles being thrown upwards the interior of the chamber. Scoops 36 can significantly assist in the process.

(23) In the embodiment shown in FIGS. 6 to 8, glow discharge plasmas are formed at each electrode 32. RF power is applied to electrode 32. A convenient RF frequency such as 13.56 MHz may be used. The electrodes 32 thereby act as working electrodes in a glow discharge system. A counter-electrode is provided, and conveniently this can be the inner surface of the drum 20 which might be coated with a conductive ceramic such as boron silicate glass. The RF power establishes a negative DC bias voltage on the electrodes 32 which thereby act as cathodes in the flow discharge system. It is also possible to use other methods to obtain glow discharge plasmas, such as through the application of a DC voltage through electrodes 32. Other forms of plasma might be utilised instead.

(24) Localised plasmas are generated around each electrode 32, but the process conditions are selected so that these plasmas are discrete and separated from one another. In this way, each electrode is surrounded with a plasma halo which contains clouds of energetic electrons, UV photons, ions and, typically, reactive neutral species. This rich plasma is used to produce the particles. The use of multiple electrodes increases the number of electron clouds and other useful species associated with the plasmas, and this has beneficial effect on processing efficiency. Additionally, the use of the electrodes to agitate the particles to be treated can also have a beneficial effect on processing efficiency as well as improving the results achieved.

(25) The apparatus may be used to exfoliate a graphitic starting material. Typically a high plasma power is utilised, at least in the initial stages of the process, to facilitate ion bombardment and ion intercalcation of the target material. For example, powers of up to 2000 W can be used. Effective bombardment and intercalcation causes layers of the starting material such as graphite to exfoliate. Without wishing to be limited by a particular theory or conjecture, it is believed that a result of this is that a nett negative charge is imparted onto the exfoliated layers so that they can push off from each other. This charge overcomes attractive van der Waals' forces, thereby retarding the usual inclination of the particles produced by the exfoliation to reagglomerate. A plasma formed in argon or oxygen is effective in producing exfoliation.

(26) A cleaning step may be provided before, during or after the exfoliation step. An oxygen plasma is an advantageous means of cleaning. Representative but non-limiting process conditions are a temperature of less than 100 C. with a plasma power of 120 W for around thirty minutes at a pressure of 1.5 Torr. Higher powers can be used.

(27) A further possibility is to remove particles from the multi-electrode treatment chamber to a final stage treatment chamber using vacuum transfer or other appropriate means. The final treatment chamber may be used to facilitate high temperature processing which will provide additional treatment options, for example for decorating the particles with a desired material. The final stage treatment may be a microwave induced plasma treatment. In these embodiments, the final treatment chamber may have glass windows and an inner surface coated with a ceramic or glass. Appropriate wave guides are used to couple microwave energy into the chamber through the windows. The final treatment chamber can be configured to rotate in order to agitate the particles. A modified version of the Tetra 500 product described above can be used for this purpose. In another alternative, a final treatment step such as this can be performed in the original treatment chamber. In these embodiments, the original treatment chamber is provided with microwave means to generate the microwave induced plasma. The multi-electrode array can be used for this purpose if the electrodes are made from suitable materials such as a conductive glass, for example boron silicates.

(28) A potential problem during processing is electrical shorting of the electrodes. This can be at least ameliorated by reducing the plasma power as the processing continues. The likelihood of shorting occurring increases if the material volume increases during processing which is likely to occur if deagglomeration and/or disaggregation occurs. One approach which may be adopted is to reduce the plasma power as the volume of the particles increases. For example, an inverse relationship between the volume of the particles and the applied plasma power, or another relationship determined by routine investigation may be followed.

EXAMPLES

Example 1

(29) Production of Particles.

(30) The apparatus described in relation to FIGS. 6-8 was used. The reactor was charged with milled graphite. Other graphitic material such as graphene stacks, CNTs, fullerenes (such as bucky balls) or a mixture thereof may be used. Processing was performed with an oxygen plasma for a minimum of 10 minutes and a maximum of 60 minutes with the reactor barrel rotating at more than 30 rpm. This was followed by an argon exfoliation treatment under similar process conditions. Powers of up to 2000 W were employed. A reactor pressure in the range 0.4 to 1.5 m Bar and gas flow rates of up to 1500 sccm were employed. This resulted in the formation of particles as shown in FIGS. 2 and 3. During the oxygen cycle UV photons and/or ions bombard the surface creating mono, di and tri vacancies which provide sites for oxygen groups. The argon exfoliation cycle also has the effect of cleaning off oxygen groups, leaving sites for bonding desired moieties to the surface during a further process stage.

Example 2

(31) Silicon Decoration.

(32) Particles were produced in accordance with Example 1. After the argon exfoliation step, hexamethyldisiloxane in an argon carrier gas was introduced into the chamber via a bubbler system. A plasma was generated during a treatment which lasted for 10-60 minutes. It was found to be advantageous to rotate the reactor at 1 rpm to evenly expose the particles to the plasma but to avoid over exposure to UV photons.

(33) The resulting material comprises particles which are substantially coated with silicon.

Example 3

(34) Silicon Nano-Pod Decorated Particles.

(35) The silicon coated particles of Example 2 were subjected to a further treatment step using a microwave treatment. Most specifically, the material was subjected to a microwave induced plasma. This resulted in the formation of silicon nano-pods on the surface of the particles as shown in FIG. 4.

Example 4

(36) Metal Decoration.

(37) Particles produced in Example 1 were subjected to a further process step. The apparatus described in relation to FIGS. 6-8 was utilised. The electrode array consisted of electrodes coated with the metal or metals of choice. Examples of suitable metals are Au, Pt, Ag, Cu, and Fe. Process times of 10-180 minutes can be used. The barrel can be rotated at 1 rpm. The plasma was sustained in an argon atmosphere. This resulted in the formation of metal coated particles as shown in FIG. 5.

Example 5

(38) Metal Decoration and Functionalisation.

(39) Metal decoration was performed in addition to functionalisation with nitrogen or oxygen functional groups. The method described in Example 4 was performed, with the exception that instead of sustaining the plasma in argon, the plasma was sustained using nitrogen or oxygen gas.

Example 6

(40) Sulfur Intercalation

(41) The method described in Example 1 was performed, except that the starting material included dry sulfur powder as well as the graphitic starting material. A mixture of 20 wt % sulfur/80 wt % graphitic starting material produced good results, although ratios down to around 50 wt % sulfur/50 wt % graphitic starting material may be used.

(42) The skilled reader will appreciate that the particles of the invention will have utility in a very wide range of industrial applications. Examples include catalysis, sensors, medical devices, energy storage devices, advanced materials and optical devices.