CONTINUOUS MANUFACTURE OF GRAPHENIC COMPOUNDS

Abstract

Provided herein are high throughput continuous or semi-continuous reactors and processes for manufacturing graphenic materials, such as graphene. Such processes are suitable for manufacturing graphenic materials at rates that are up to hundreds of times faster than conventional techniques, and have little batch-to-batch variation. Also provided herein are graphenic compositions of matter, including large, high quality and/or highly uniform graphene.

Claims

1. A process for manufacturing a graphenic compound (e.g., graphene), the process comprising: a. injecting a first stock into a first inlet of a continuous or semi-continuous reactor, the first stock comprising graphite (e.g., and an additive, such as a surfactant and/or thickening agent); and b. collecting the graphenic compound (e.g., graphene) from an outlet of the continuous reactor, the graphene oxide being collected downstream from the injection points of the first stock.

2. The process of claim 1, wherein the continuous reactor has a flow from the first inlet to the outlet, the flow being a non-vortex flow.

3. The process of claim 2, wherein the non-vortex flow is a helical non-vortex flow.

4. The process any one of the preceding claims, wherein the continuous reactor is configured to produce a helical laminar or cylindrical Couette flow.

5. The process of any one of the preceding claims, wherein the flow is a high shear flow with a shear rate of at least 1,000 1/s.

6. The process of any one of the preceding claims, wherein the continuous reactor is a continuous Taylor-Couette reactor.

7. The process of any one of the preceding claims, wherein the continuous reactor comprises a reactor chamber into which the first stock is injected; the reactor chamber being configured between an outer surface of a cylindrical body and the inner surface of a cylindrical bore, one or both of the cylindrical body and/or bore rotating around an axis thereof.

8. The process of claim 7, wherein the outer surface of the cylindrical body and the inner surface of the cylindrical bore are rotating in opposite directions.

9. The process of any one of the preceding claims, wherein the surface of the cylindrical body forms an elliptical (or oval) cylinder.

10. The process of claim 9, wherein the cylindrical body is rotating.

11. The process of claim 10, wherein the surface of the cylindrical bore is stationary.

12. The process of any one of the preceding claims, wherein the cylindrical body is circular cylinder and the cylindrical bore is a circular cylinder.

13. The process of any one of the preceding claims, wherein the cylindrical bore or surface thereof is rotating.

14. The process of claim 13, wherein the cylindrical body or surface thereof is stationary.

15. The process of any one of the preceding claims, wherein the stock further comprises a surfactant and/or stabilizer.

16. The process of any one of the preceding claims, wherein the graphene is not fully exfoliated.

17. The process of any one of the preceding claims, wherein the graphene comprises more than one graphene sheet, on average.

18. The process of any one of the preceding claims, wherein the graphene is in comprises about 2 to about 20 graphene sheets, on average.

19. The process of any one of the preceding claims, wherein the first stock comprises graphite in a concentration of about 0.1 wt. % to about 50 wt. % (e.g., about 2 to about 10 wt. %).

20. The process of any one of the preceding claims, wherein the stock is aqueous.

21. A process for manufacturing graphene, the process comprising: a. injecting a first stock into a toroidal vortex flow, a first stock comprising graphite (e.g., and a surfactant and/or thickening agent), and the continuous flow reactor configured to produce and/or producing a helical non-vortex (e.g., shear, laminar or cylindrical Couette) flow; and b. collecting the graphene.

22. The process of claim 21, wherein the continuous flow reactor is a modified Taylor-Couette reactor.

23. A continuous or semi-continuous reactor or reactor system comprising: a. a first body, the first body comprising an outer surface; b. a second body, the second body comprising an inner surface, the inner surface defining a bore, the first body being configured within the bore; c. a reaction chamber, the reaction chamber being configured between the outer surface of the first body and the inner surface of the second body; d. a first inlet, the first inlet being configured in fluid communication with the reaction chamber; and e. a first outlet, the first outlet being configured in fluid communication with the reaction chamber (e.g., the first body and/or the bore being configured around an axis, the first inlet and first outlet being configured at different axial positions along the axis).

24. The reactor or reactor system of claim 23, further comprising a motor configured to rotate the first and/or second body.

25. The reactor or reactor system of either of claim 23 or 24, further comprising a pump configured to inject a fluid into the first inlet.

26. The reactor or reactor system of any one of the preceding claims, wherein the outer surface of the first body defines a cylindrical body.

27. The reactor or reactor system of claim 26, wherein the cylindrical body is a circular cylindrical body.

28. The reactor or reactor system of claim 26, wherein the cylindrical body is an elliptical cylindrical body.

29. The reactor or reactor system of any one of the preceding claims, wherein the inner surface of the second body defines a cylindrical bore.

30. The reactor or reactor system of claim 29, wherein the cylindrical bore is a circular cylindrical bore.

31. The reactor or reactor system of any one of the preceding claims, further comprising a motor, the motor being configured to rotate the first body or surface thereof.

32. The reactor or reactor system of any one of the preceding claims, further comprising a motor, the motor being configured to rotate the second body or surface thereof.

33. The reactor or reactor system of any one of the preceding claims, wherein the first body and/or second body independently comprise a stainless-steel alloy (e.g., 304 stainless steel, 310M stainless steel), an austenitic stainless steel (e.g., Avesta 254 SMO), an austenitic chromium-nickel stainless steel (e.g., 316 stainless steel), a super duplex stainless steel alloy (e.g., ZERON® 100), polytetrafluoroethylene (e.g., TEFLON™), glass (e.g., borosilicate) coated metal, borosilicate glass, polytetrafluoroethylene (e.g., TEFLON™) coated metal, nickel-chromium-molybdenum-tungsten alloy (e.g., Alloy 22), stainless steel with silicon, a Ni—Fe—Cr—Mo alloy (e.g., Alloy 20, Alloy G-30, Alloy 33, Cronder 2803 Mo), a Ni—Cr—Mo alloy (e.g., Alloy C-22, Alloy-C-276, Hastelloy C-2000), an alloy (e.g., LEWMET, Hastelloy D-205, Sandvik HT 9076), lead, high silicon cast iron, cast iron (e.g., Meehanite, grey cast iron), ductile iron (e.g., MONDI), any combination thereof.

34. The reactor or reactor system of any one of the preceding claims, further comprising a stock reservoir, the stock reservoir in fluid contact with the first inlet.

35. The reactor or reactor system of any one of the preceding claims, further comprising one or more additional inlet(s), the one or more additional inlet(s) in fluid communication with the reaction chamber, and the one or more additional inlet(s) being configured in a longitudinal position between the first inlet and the first outlet.

36. A continuous or semi-continuous reactor system comprising a first reactor and a second reactor, the first reactor comprising: a first body, the first body comprising a first outer wall; a second body, the second body comprising a first inner wall, the first inner wall defining a first bore, the first body being configured within the first bore; a first reaction chamber, the first reaction chamber being configured between the first outer wall of the first body and the first inner wall of the second body; a first inlet, the first inlet being configured in fluid communication with the first reaction chamber; and a first outlet, the first outlet being configured in fluid communication with the first reaction chamber; and the second reactor comprising: a third body, the third body comprising a second outer wall; a fourth body, the fourth body comprising a second inner wall, the second inner wall defining a second bore, the third body being configured within the second bore; a second reaction chamber, the second reaction chamber being configured between the second outer wall of the third body and the second inner wall of the fourth body; a second inlet, the second inlet being configured in fluid communication with the second reaction chamber; and a second outlet, the second outlet being configured in fluid communication with the second reaction chamber; and the first outlet being in fluid communication with the second inlet.

37. The system of claim 36, wherein the first and/or second reactor are as described in any ones of claims 23-36.

38. A graphenic compound (e.g., graphene) having a two dimensional structure, the two dimensional structure having an average lateral dimension of at least 10 micron.

39. The graphenic compound of any one of the preceding claims, wherein the two dimensional structure has an average lateral dimension of at least 25 micron.

40. The graphenic compound of any one of the preceding claims, wherein the two dimensional structure has an average lateral dimension of at least 30 micron.

41. The graphenic compound of any one of the preceding claims, wherein the two dimensional structure comprises at least two graphenic layers.

42. The graphenic compound of any one of the preceding claims, wherein the two dimensional structure comprises 3 to 15 graphenic layers.

43. The graphenic compound of any one of the preceding claims, wherein the two dimensional structure comprises at least two graphenic layers, and the average interlayer spacing of about 0.8 nm or more.

44. The graphenic compound of any one of the preceding claims, wherein the two dimensional structure comprises at least two graphenic layers, and the average interlayer spacing of about 0.8 nm to about 1.2 nm.

45. The graphenic compound of any one of the preceding claims, wherein the two dimensional structure comprises at least two graphenic layers, and the average interlayer spacing of about 0.8 nm to about 1 nm.

46. The process of any one of the preceding claims, wherein the graphenic compounds (graphene) produced thereby each have a two dimensional structure, the two dimensional structures having a lateral dimension of at least 10 micron on average.

47. The process of claim 46, wherein the two dimensional structures have a lateral dimension of at least 25 micron on average.

48. The process of claim 47, wherein the two dimensional structures have a lateral dimension of at least 30 micron on average.

49. The process of any one of the preceding claims, wherein the two dimensional structures comprise at least two graphenic layers on average.

50. The process of any one of the preceding claims, wherein the two dimensional structures comprise at least 3 to 15 graphenic layers on average.

51. The process of any one of the preceding claims, wherein each two dimensional structure comprises at least at least two graphenic layers, and the average interlayer spacing between the layers being about 0.8 nm or more.

52. The process of any one of the preceding claims, wherein each two dimensional structure comprises at least at least two graphenic layers, and the average interlayer spacing between the layers being about 0.8 nm to about 1.2 nm.

53. The process of any one of the preceding claims, wherein each two dimensional structure comprises at least at least two graphenic layers, and the average interlayer spacing between the layers being about 0.8 nm to about 1 nm.

54. A composition comprising a plurality of graphenic compounds (e.g., graphenes) each have a two dimensional structure, the two dimensional structures having a lateral dimension of at least 10 micron on average.

55. The composition of any one of the preceding claims, wherein the two dimensional structures have a lateral dimension of at least 25 micron on average.

56. The composition of any one of the preceding claims, wherein the two dimensional structures have a lateral dimension of at least 30 micron on average.

57. The composition of any one of the preceding claims, wherein the two dimensional structures comprise at least two graphenic layers on average.

58. The composition of any one of the preceding claims, wherein the two dimensional structures comprise at least 3 to 15 graphenic layers on average.

59. The composition of any one of the preceding claims, wherein each two dimensional structure comprises at least at least two graphenic layers, and the average interlayer spacing between the layers being about 0.8 nm or more.

60. The composition of any one of the preceding claims, wherein each two dimensional structure comprises at least at least two graphenic layers, and the average interlayer spacing between the layers being about 0.8 nm to about 1.2 nm.

61. The composition of any one of the preceding claims, wherein each two dimensional structure comprises at least at least two graphenic layers, and the average interlayer spacing between the layers being about 0.8 nm to about 1 nm.

62. The composition of any one of the preceding claims, wherein the composition comprises less than 10 wt. % graphite.

63. The composition of any one of the preceding claims, wherein the composition comprises less than 5 wt. % graphite.

64. The composition of any one of the preceding claims, wherein the composition comprises less than 1 wt. % graphite.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:

[0041] FIG. 1 illustrates XRD traces of exemplary graphite materials utilized in processes and compositions herein.

[0042] FIG. 2 illustrates a schematic of an exemplary semi-continuous toroidal flow reactor provided herein, with an inlet (additional inlets are optional) and an outlet.

[0043] FIG. 3 illustrates the cross section of an exemplary reactor comprising a rotating elliptical cylindrical inner body (or surface thereof).

[0044] FIG. 4 illustrates a schematic of an exemplary continuous toroidal flow reactor provided herein, with an inlet (additional inlets are optional) and an outlet.

[0045] FIG. 5 illustrates the cross section of a reactor comprising a circular cylindrical inner body and a rotating circular cylindrical outer body (or surface thereof).

[0046] FIG. 6 illustrates traces of FTIR patterns of an exemplary graphene oxide materials obtained from a batch reactor using identical reagents and reaction conditions.

[0047] FIG. 7 illustrates traces of FTIR patterns of an exemplary graphene oxide materials obtained from a toroidal reactor using identical reagents and reaction conditions.

[0048] FIG. 8 illustrates an exemplary system provided herein comprising a plurality of exemplary reactors provided herein.

[0049] FIG. 9 illustrates various exemplary flow types of a process or reactor provided herein

[0050] FIG. 10 illustrates XRD images of the resulting material prepared according to a process provided herein using various flow types.

[0051] FIG. 11 illustrates interlayer spacing and multi-layered characteristics of exemplary graphenic materials prepared according to exemplary processes provided herein.

[0052] FIG. 12 illustrates a schematic of an exemplary toroidal flow reactor provided herein, with a variety of inlets and an outlet.

[0053] FIG. 13 illustrates Raman spectra G Peak results of various exemplary graphenic structures provided herein.

[0054] FIG. 14 illustrates Raman spectra G, D, and 2D peak results of various exemplary graphenic structures provided herein.

[0055] FIG. 15 illustrates Raman spectra of various exemplary graphenic structures provided herein.

[0056] FIG. 16 illustrates Raman spectra G, D, and 2D peak results of various exemplary graphenic structures provided herein.

[0057] FIG. 17 illustrates an SEM image of an exemplary graphenic structure provided herein.

[0058] FIG. 18 illustrates a cross-sectional SEM image of a layer of exemplary graphenic structures provided herein.

[0059] FIG. 19 illustrates Raman spectra of various exemplary graphenic structures provided herein.

[0060] FIG. 20 illustrates Raman spectra G, D, and 2D peak results of various exemplary graphenic structures provided herein.

[0061] FIG. 21 illustrates an SEM image of an exemplary graphenic structure provided herein.

[0062] FIG. 22 illustrates a cross-sectional SEM image of a layer of exemplary graphenic structures provided herein.

DETAILED DESCRIPTION OF THE INVENTION

[0063] Provided in certain embodiments herein are processes and systems for manufacturing graphenic components, such as graphene oxide, including single layer graphene oxide and/or multi-layered graphene oxide. Also provided herein are compositions used to make graphenic products described herein and/or the graphenic products produced or produce-able by processes or from compositions described herein. In specific instances, the processes provided herein are continuous or semi-continuous (flow) processes. In certain instances, processes provided herein facilitate greatly improved (reduced) manufacturing times for graphenic products. Moreover, in some instances, processes provided herein facilitate greater control of the interaction between reagents of the processes thereof, providing greater control of and greater quality control of resulting graphenic products. For example, in certain embodiments, provided herein are processes that are utilized to control the degree of oxidation, the type of oxidation, the number of layers, the lateral dimension, other characteristics, or combinations thereof of graphenic products produced thereby. In addition, with the ability to precisely control flow, rotation/vortex parameters, and inputs characteristics, timing and location, greater quality control of the resultant products is achieved, whether the graphenic product is first out, last out, somewhere in-between, or even during a different run or using a separate system.

[0064] In specific embodiments, provided herein is a process for manufacturing a graphenic compound (e.g., graphene), the process comprising: [0065] a. injecting a first stock into a first inlet of a continuous or semi-continuous reactor, the first stock comprising graphite; [0066] b. collecting the graphenic compound (e.g., graphene) from an outlet of the continuous reactor, the graphenic compound being collected downstream from the injection points of the first stock.

[0067] In specific embodiments, the reactor having a fluid flowing therein, the flow having a flow type as described herein (e.g., laminar flow, toroid flow, or the like). In some instances, the fluid within the reactor comprises the first (graphite) stock, such as alone or in combination with one or more other fluid provided to the reactor.

[0068] FIG. 12 illustrates an exemplary embodiment of a process and a reactor 200 provided herein. As illustrated, the reactor 200 comprises a reaction chamber 201 into which the stock(s) are injected, the reactor chamber 201 being configured between an outer wall of a first body 202 and an inner wall of a second body 203. In specific embodiments, the outer wall of the first body 202 defines a cylindrical body and the inner wall of the second body 203 defines a cylindrical bore. In some instances, the first body 202 and/or the second body 203 is configured to rotate about or around an axis 204 thereof. In certain embodiments, the wall(s) of the cylindrical body and/or bore rotate(s) around an axis of the respective cylinder body and/or bore. The cylindrical body and/or bore form any suitable shape, such as a circular cylinder, an elliptical cylinder, a right cylinder, an oblique cylinder, or the like. In certain embodiments, the cylindrical bore and/or body is optionally substituted with conical frustum bore and/or body, respectively. In various embodiments, the first body and the second body (e.g., inner and outer walls or surfaces thereof, respectively) comprise any suitable material.

[0069] FIG. 3 illustrates the cross section of a reactor comprising a reaction chamber configured between the inner wall of a circular cylindrical outer (second body) and the outer wall of an elliptical cylindrical inner (first) body. As illustrated in FIG. 3, in some preferred embodiments, the inner cylindrical body of such a reactor rotates. In some instances, use of an elliptical inner body facilitates good (non-vortex) toroidal shear flow within the reactor, even at higher rotation speeds. By contrast, in some instances, use of a circular cylindrical inner body results in a non-vortex, toroidal shear flow only at low rotation speeds, with the shear flow quickly destabilizing to form a toroidal vortex flow. FIG. 5 illustrates the cross section of a reactor comprising a reaction chamber configured between the inner wall of a circular cylindrical outer (second) body and the outer wall of an cylindrical inner (first) body, as well as the lateral, toroidal flow of a fluid between the inner and outer walls. As illustrated in FIG. 5, in some preferred embodiments, the outer cylindrical body of such a reactor rotates. In some instances, rotation of the outer body facilitates good (non-vortex) toroidal shear flow within the reactor chamber, even at higher rotation speeds. By contrast, in some instances, rotation of the circular cylindrical inner body results in a non-vortex, toroidal shear flow only at low rotation speeds, with the shear flow quickly destabilizing to form a toroidal vortex flow.

[0070] In some embodiments, the first body and the second body (e.g., inner and outer wall or surfaces thereof, respectively) independently is or comprises a stainless-steel alloy (e.g., 304 stainless steel, 310M stainless steel), an austenitic stainless steel (e.g., Avesta 254 SMO), an austenitic chromium-nickel stainless steel (e.g., 316 stainless steel), a super duplex stainless steel alloy (e.g., ZERON® 100), polytetrafluoroethylene (e.g., TEFLON™), glass (e.g., borosilicate) coated metal, borosilicate glass, polytetrafluoroethylene (e.g., TEFLON™) coated metal, nickel-chromium-molybdenum-tungsten alloy (e.g., Alloy 22), stainless steel with silicon, a Ni—Fe—Cr—Mo alloy (e.g., Alloy 20, Alloy G-30, Alloy 33, Cronder 2803 Mo), a Ni—Cr—Mo alloy (e.g., Alloy C-22, Alloy-C-276, Hastelloy C-2000), an alloy (e.g., LEWMET, Hastelloy D-205, Sandvik HT 9076), lead, high silicon cast iron, cast iron (e.g., Meehanite, grey cast iron), ductile iron (e.g., MONDI), any combination thereof, or the like.

[0071] As illustrated in FIG. 12, exemplary embodiments of the reactor have at least one inlet 205 configured to receive a stock, particularly a graphite stock (e.g., a stock comprising a graphite 206, such as in a suspension). In some instances, the graphite stock further comprises a surfactant and/or thickening agent (stabilizer) 207. The reactor further comprises at least one outlet 208, from which product is extracted from the reactor. In the case of a continuous flow reactor, the extracted product comprises the graphenic component (e.g., single or multi-layered graphene) 209. In the case of a semi-continuous or semi-batch reactor, the extracted product is injected back into the reactor one or more times until a graphenic component is ultimately collected from the reactor. In general, the reactor facilitates the (axial) flow 210 of the stock(s) and/or reagents from one or more inlet 205 of the reactor to one or more outlet 208 of the reactor 200. Moreover, with one or more of the inner cylinder or the inner surface of the bore cylinder rotating relative to the other, the flow has a toroidal and/or lateral aspect 211. Moreover, as illustrated in the expanded view 212 of the cut-out 213, the flow of the fluid within the reactor comprises, in some instances, a plurality of vortices (a vortex flow herein) 214. In some preferred embodiments, the rotation speed of the first and/or second bodies are maintained at a rate (e.g., that is slow enough) to prevent the destabilization of a non-vortex or shear flow, such as forming the vortices 214 in the expanded view of 213. In some instances, a batch reactor configured such as described herein can be configured to provide a plurality of stirred domains (e.g., the series of domains or vorticies can be considered a series of continuous stirred tank reactors) or vortices such as illustrated in the expanded view of 212, wherein each of the plurality of vortices have a toroidal shape. In certain instances, with the flow 210 of a continuous or semi-continuous reactor 200 herein, the toroidal shapes of the vortices 214 are distorted (e.g., forming distorted toroidal vortices), such as forming vortices with a helical shape (e.g., forming helical vortices).

[0072] In certain embodiments, a toroid provided herein is helical or a distorted toroid (e.g., having an axial and lateral dimension (e.g., around and along a cylinder axis, respectively), rather than simply around the axis) and/or a toroidal flow provided herein is a helical or distorted toroidal flow (e.g., having an axial and a lateral flow direction (both around and along a cylinder axis, respectively), rather than simply around the axis). In some embodiments herein, a toroidal vortex provided herein is a distorted toroidal vortex and/or a toroidal vortex flow is a helical or distorted toroidal vortex flow.

[0073] As illustrated in FIG. 12, additional inlets are optionally included in a reactor provided herein. In certain instances, a continuous or semi-continuous reactor provided herein comprises at least one additional inlet for injecting one or more reagent into the reactor. As illustrated in the reactor 200, in certain embodiments, the reactor 200 comprises, in some embodiments, a second inlet 215 facilitating the injection of a desired agent 216 into the reactor chamber 201. As exemplarily illustrated, the second inlet 215 is downstream from the first inlet 205. In some instances, a reactor 200 provided herein comprises a (optional) third inlet 217, such as for injecting a desired agent 218 into the reactor chamber 201. Additional inlets can also be provided, as desired. For example, the reactor 200 of FIG. 12 illustrates in additional inlet 219 that is near the first inlet 205, the additional inlet 219 being configured for injecting any suitable or desired agent 220 into the reactor chamber 201.

[0074] In certain embodiments, a reactor provided herein has a (e.g., fluid) flow (e.g., within the chamber thereof) from an input to an output (e.g., at different axial positions of the reactor). In other words, one or more fluid stock (e.g., solutions, suspensions, or combinations thereof) is input into the reactor via one or more inlet, such one or more fluid stocks shearing, mixing and flowing toward and out of one or more outlet, at least one outlet being down-flow (“downstream”) from the one or more inlet. In various embodiments, any suitable flow is provided within the reactor (e.g., chamber thereof), such as a toroidal flow, a vortex flow (e.g., a Taylor vortex flow), a non-vortex flow, a shearing flow, a laminar flow (e.g., a Couette flow), a turbulent flow, and/or the like. In some embodiments, the fluid has a toroidal flow. In certain embodiments, the fluid has a non-vortex flow, such as a toroidal non-vortex flow. In some embodiments, a reactor provided herein is configured to provide a non-vortex flow, e.g., non-toroidal vortex flow, within a reactor chamber thereof. In certain embodiments, the flow is a modified Couette flow (e.g., a (non-vortex) Taylor-Couette with axial flow) and/or the reactor is a continuous Taylor-Couette reactor. In specific embodiments, the flow dynamics are configured by adjustment of flow rate, drum size, bore size, gap between the inner wall and the outer wall, rotation speed, or any combination thereof. FIG. 12 illustrates a Taylor vortex flow, however, depending on the rotation speed, rotating body, rotation direction, etc., other flow types can be observed in the reactor.

[0075] FIG. 9 illustrates the Couette (laminar) flow observed at slow (inner) rotational speeds (e.g., wherein Ta<Ta.sub.c). Further, as illustrated in FIG. 9, when Ta exceeds Tac, vortexes form, but when Ta is close to Tac, instabilities (vortexes) form near the reactor inlet, but as the flow continues toward the reactor exit, laminar flow resumes. This type of flow is illustrated as primary instabilities (PI). As Ta increases, instabilities form throughout the reactor, forming a Taylor vortex flow (TVF). Increasing the Ta/Ta.sub.c further, however, creates a secondary instability (SI), where a wavy flow is observed near the inlet of the reactor. Further increase of Ta/Ta.sub.c leads to a full wavy vortex flow (WVF). In some embodiments, the flow is a stable laminar (e.g., Couette) flow and/or a flow having a Ta/Ta.sub.c of less than 1, such as less than 0.9, such as less than 0.8 (e.g., 0.5 to 0.9 or 0.6 to 0.8). In certain embodiments, the flow is a stable vortex (e.g., Taylor) flow and/or a flow having a Ta/Ta.sub.c of about 1.05 to about 1.4, such as about 1.05 to about 1.3, such as about 1.1 to about 1.2.

[0076] In certain embodiments, a process or reactor provides a high shear (e.g., to graphite, such as injected or utilized therein). Shear rate is determined by any suitable process, such as γ=v/h, wherein γ is shear rate measured in reciprocal seconds, v is velocity of a moving plate (e.g., relative to a stationary plate, such as described herein), and h is the distance between parallel plates. In some instances variations are contemplated to account for the cylindrical shapes contemplated herein. In some embodiments, high shear rates are provided by the flows described herein, such as at least 10.sup.3 s.sup.−1, at least 5×10.sup.3 s.sup.−1, at least 10.sup.3 s.sup.−1, or the like. As such, a small gap corresponds, in some instances, with high shear. Moreover, at larger diameters, higher cylinder/bore surface velocities are achieved at lower rotation rates. In certain embodiments, a reactor provided herein has a gap between the inner surface of the outer body and the outer surface of the inner body (“gap”) that is relative to the inner surface of the bore (“r.sub.o”). In some embodiments, gap/r.sub.o is about 0.01 to about 0.2, such as about 0.03 to about 0.1.

[0077] FIG. 10 illustrates the results of injecting graphite into a reactor herein, with the various flow types illustrated in FIG. 9. As illustrated in FIG. 10, after just one minute, in a reactor having a (stable) laminar or Couette (shearing) flow is observed to have excellent conversion of graphite to graphenic compound (graphene oxide). By contrast the primary instability flow is observed to have good conversion to the graphenic compound, but some graphite remains. The stable vortex flow (Taylor vortex flow) is observed to provide excellent conversion of graphite to the graphenic compound, with no graphite component observed. By contrast, both flows having wavy morphologies and that use the most amount of energy produced good conversion of graphite to graphenic compound (graphene oxide), but had significant amounts of graphite also observed.

[0078] In various embodiments, a process provided herein utilizes or a system herein comprises any suitable reactor, such as a toroidal reactor. In some embodiments, the toroidal reactor is a toroidal flow reactor, a toroidal batch reactor, or the like. In various embodiments, the toroidal flow reactor is a toroidal continuous flow reactor, or a toroidal semi-continuous (semi-batch) reactor. FIG. 2 illustrates an exemplary toroidal semi-continuous (semi-batch) reactor provided herein. As illustrated, the reactor 1200 has at least one inlet 1201 and at least one outlet. In some instances, the reactor is charged via an opening or via the inlet 1201, such as with graphite and other reaction or suspending agents (e.g., surfactant and/or thickening agents and/or stabilizer), such as described herein. After being subjected to the reactor, a reaction mixture is expelled from the outlet 1202 and recycled back into the inlet 1202 (or a different inlet (not shown)). The outlet 1202 optionally feeds directly back into the inlet 1201, or proceeds through a collection container 1203. After a desired time or number of passes through the reactor 1200, the (e.g., final) graphenic product is expelled via an outlet 1202 and collected, such as in a collection receptacle 1203. The reactants are optionally subjected to the reactor any suitable number of times (passes through the reactor), such as one or more times, two or more times, 5 or more times, 10 or more times, or the like. FIG. 14 illustrates an exemplary toroidal continuous flow reactor, wherein a stock 1403 is provided to an inlet 1401 of a reactor provided herein, and the reaction product 1404 is collected via an outlet 1402 of the reactor 1400 after a single pass through the reactor.

[0079] In some embodiments, a system herein comprises (or a process provided herein comprises using) a series of reactors, such as illustrated in FIG. 8. FIG. 8 illustrates an exemplary system comprising a plurality of reactors (e.g., a first reactor 1801 and a second reactor 1802) provided herein, such as wherein a stock is provided to an inlet of a first reactor 1801, a first product is provided via an outlet of the first reactor 1801, the first product is provided to an inlet of a second reactor 1802 and a second product is provided via an outlet of a second reactor 1802. In some instances, the first product is optionally treated prior to providing to the second reactor. For example, in some instances, graphenic product (e.g., graphene) is separated or extracted from the first product before subjecting the remainder of the first product to the second reactor. FIG. 18 illustrates an exemplary continuous flow reactor, but semi-batch or semi-continuous reactors of such configurations are also provided herein.

[0080] In certain embodiments, the reactor comprises one or more temperature controlled domains. In certain embodiments, a jacket or coil is positioned in at least partial surrounding relation to the outer wall of the reactor. In some instances, the temperature control domain is a cooling domain (e.g., wherein the jacket or coil comprises a coolant). In certain embodiments, a system provided herein has a first temperature controlled domain comprising a cooling domain and a second temperature controlled domain comprising a heating domain. In some instances, a first and a second reactor are provided in a system herein, such as illustrated in FIG. 8, wherein the first reactor is cooled and the second reactor is heated.

[0081] In certain embodiments, graphite utilized herein is any suitable graphite, such as natural graphite, natural graphite flake, synthetic graphite, any combination thereof, or the like. In certain embodiments, the graphite is a multi-layered structure comprising any suitable number of layers and/or having any suitable (e.g., particle) dimension or size. In certain instances, a graphite provided herein comprises at least 25 layers (e.g., graphitic carbon layers stacked on top of one another), at least 50 layers, at least 75 layers, or the like. FIG. 1 illustrates XRD patterns of exemplary graphite materials utilized in processes and compositions herein. Various graphitic particle sizes are optionally utilized, such as having an average size of at least 1 micron (micrometer or μm), at least 5 micron, at least 10 micron, at least 25 micron, at least 100 micron, or the like. In specific instances, the average particle size is less than 1 mm, less than 500 micron, less than 250 micron, less than 100 micron, or the like. Any suitable concentration of graphite is utilized in a stock and/or reactor herein. In specific embodiments, the concentration of graphite in a stock described herein is about 0.1 wt. % to about 50 wt. %, e.g., 0.5 wt. % to 50 wt. %.

[0082] In some embodiments, any suitable strong acid, oxidizing agent and/or intercalating agent provided is utilized herein. In some embodiments, the strong acid, oxidizing agent and/or intercalating agent functions to swell and/or intercalate into and/or oxidize the graphite layers. In some embodiments, the strong acid, oxidizing agent and/or intercalating agent comprises one or more of the following: sulfuric acid, bisulfate, sulfate, nitric acid, nitrate, perchloric acid, perchlorate, permanganate, phosphoric acid, phosphate, biphosphate, or the like. In the case of bisulfate, sulfate, nitrate, perchlorate, permanganate, phosphate, biphosphate, or other anion utilized, any suitable cation is optionally utilized, such as sodium, potassium, or the like. It is to be understood that in a stock, however, reference to an ion or salt herein includes reference to the compound in ionic (e.g., solvated or disassociated) or salt form. Concentrations of strong acids or intercalating agents utilized herein are present in any suitable amount.

[0083] In certain embodiments, a process herein includes subjecting a reaction mixture to a quenching agent or an additional oxidizing agent. Any suitable quenching or oxidizing agent is utilized in any method or system or composition described herein. In specific embodiments, the quenching or oxidizing agent is a peroxide, such as hydrogen peroxide (e.g., 1-50 wt. %, such as 3 wt. %, 30 wt. %, or the like hydrogen peroxide). In certain embodiments, the oxidization of the graphite (e.g., to form graphite oxide) is achieved using the strong acid and/or intercalating agent, without the need for exposure to an additional oxidizing agent or stock. In some instances, the additional agent is a quenching agent, such as to quench residual oxidizing and/or intercalating agents, strong acids, and/or the like.

[0084] As illustrated by the FTIR patterns in FIG. 6, even using the same oxidizing agents/intercalating agents can produce significant batch-to-batch variations in the graphenic products produced converting graphite to graphenic products. By contrast, in various instances herein, reactors (batch and flow) produce very consistent graphenic materials batch-to-batch (including, in the case of flow reactors, on a run-to-run basis or a first out, last out basis). As illustrated in the FTIR patterns of FIG. 7, processes and reactors provided herein are suitable for producing highly consistent materials on a batch-to-batch basis. Moreover, by controlling, where, when and what reagents are added to the reaction, with a high degree of precision, reactors provided herein prove a highly tunable platform for produce graphenic materials.

[0085] FIG. 16 further illustrates the uniformity of the graphenic compounds produced according to the processes herein, particularly when using stable toroidal flows. As illustrated, the TV and SI flows produce graphenic materials with the greatest oxidation levels, whereas the wavy vortex flow produces the least oxidation, despite using the most energy. Moreover, the peak variation of the TV flow is extremely small (small error bars) compared that that of the other flows, including the SI flow, which also had high oxidation. FIG. 17 illustrates ID/IG and I2D/IG ratios, with the TVF demonstrating the smallest error bars, indicating the greatest uniformity of the graphenic compounds produced thereby.

[0086] In some instances, increasing wavenumber of G band (about 1587 cm-1) corresponds with number of graphenic layers or sheets in a graphenic compound (e.g., with increasing intensity corresponding with increasing layers). In certain instances, increasing intensity of D band (about 1350 cm-1) corresponds with increasing graphitic/graphenic defect. In some instances, the 2D band (about 2700 cm-1) corresponds with stacking and decreases with increasing exfoliation. In certain instances, with decreasing intensity (area) of the D band relative to the G band (I.sub.D/I.sub.G) the number of layers are reduced (e.g., with single layered graphene having an I.sub.D/I.sub.G of about 0) and with increasing I.sub.2D/I.sub.G ratios the number of layers are reduced (e.g., with single layered graphene having an I.sub.2D/I.sub.G ratio of about 2). As illustrated in FIG. 16 and FIG. 20, various graphenes are produced by various exemplary iterations provided herein. In some embodiments, provided herein is a graphene compound (e.g., graphene) or composition having (e.g., average) ID/IG of less than 0.2, such as less than 1.5, less than 1, less than 0.05, or the like. In certain embodiments, provided herein is a graphene compound (e.g., graphene) or composition having (e.g., average) I2D/IG of at least 1.1, such as at least 1.5, at least 1.7, at least 1.8, at least 1.9, or about 2. In exemplary embodiments, ID/IG is less than 0.1 and I2D/IG is at least 1.9. In other exemplary embodiments, the ID/IG and/or I2D/IG ratios are about those illustrated in FIG. 16 or FIG. 20.

[0087] FIG. 11 illustrates the different interlayer spacing of the graphenic compounds prepared using the various types of flows described herein. As illustrated, Graphite has very low interlayer spacing, whereas all of the graphenic materials prepared according to a process described herein, using the various flow types described herein, produce graphenic compounds having an interlayer spacing of about 0.8 nm (nanometer) to about 1.1 nm (compared to less than 0.4 nm for graphite). Moreover, the graphenic compounds are observed to have fewer than 10 layers (e.g., 5 to about 10, such as about 8), as compared to about 84 (on average) for the graphite.

[0088] In certain embodiments, graphenic compounds described herein and/or produced according to a process herein have 1 to about 15 layers (e.g., on average), such as 1 to about 10 (e.g., on average), such as about 2 to about 10 layers (e.g., on average) or about 5 to about 10 layers (e.g., on average). In some embodiments, (multilayered) graphenic compounds described herein and/or produced according to a process described herein have an average interlayer spacing of about 0.8 nm to about 1.2 nm, such as about 0.8 nm to about 1 nm.

[0089] In certain embodiments, provided herein are graphenic compounds having large sizes. In some embodiments, graphenic compounds have a lateral dimension that is comparable to the size of a graphite (e.g., at least 50% the lateral dimension of the graphite, at least 60% the size of the graphite, at least 70% the size of the graphite, at least 80% the size of the graphite, or the like) from which it was produced. In certain embodiments, a graphenic compound provided herein and/or produced according to a process provided herein has a lateral dimension (e.g., longest or average lateral dimension) of at least 20 micron, such as 20 micron to about 200 micron. In some embodiments, the lateral dimension (e.g., longest or average lateral dimension) is at least 25 micron, such as 25 micron to about 200 micron. In certain embodiments, the later dimension (e.g., longest or average lateral dimension) is at least 30 micron, such as 30 micron to about 200 micron. In specific embodiments, the later dimension (e.g., longest or average lateral dimension) is at least 40 micron, such as 40 micron to about 200 micron.

EXAMPLES

Example 1—Graphene Oxide: Semi-Continuous Toroidal (Helical) Reactor

[0090] Graphite is obtained from a variety of sources, including a graphite labelled as 25 micron and a graphite labelled as 150 micron. FIG. 4 illustrates a powder X-ray diffraction (XRD) pattern for the two graphite materials. As illustrated in FIG. 4, 2-theta (2θ) values for the two materials are similar, with a value of about 26.5°. Interlayer spacing is calculated to be about 3.36 Å, with the materials having about 80-85 total layers.

[0091] Graphite (1 g, 25 micron) is dispersed in a mixture of 98% sulfuric acid (110 mL) and 85% phosphoric acid (25 mL) at room temperature using a mechanical stirrer. After 10 min of stirring, 4 wt equiv of KMnO.sub.4 (4 g) is added to a semi-continuous/semi-batch toroidal reactor (e.g., wherein components are added to the reactor chamber and sealed, without the use of the inlets and outlets described herein), such as illustrated in FIG. 2, is utilized to manufacture graphene oxide from graphite. The internal drum is rotated at a rate of about 600 revolutions per minute (rpm). The flow is controlled by a pump, which is operated at a rate of 50 rpm.

[0092] After cycling for 30 minutes, the product is quenched with a 30% hydrogen peroxide solution. The resultant graphene oxide product is evaluated with two materials being observed, with the first material (identified by a first XRD peak) has a powder XRD two-theta (2θ) value of about 8.49° and has a calculated interlayer spacing of about 10.40 Å. The graphene oxide thus provided is determined to comprise about 4 layers, on average. The second material (identified by a second XRD peak) has a powder XRD two-theta (2θ) value of about 26.3° and has a calculated interlayer spacing of about 3.38 Å. This peak corresponds with graphene oxide having about 17 layers, on average.

[0093] Relative to the graphene oxide prepared by a similarly run batch process, the graphene oxide materials in this semi-continuous example are much more highly processed after identical periods of time (30 minutes). In the batch process, the larger (graphene oxide) peak after 30 minutes has an interlayer spacing layer of 9.01 Å, versus the interlayer spacing of about 10.40 Å observed for the semi-continuous process. Moreover, the batch toroidal reactor process primarily produces graphene oxide having about 7 layers after 30 minutes, whereas the semi-continuous process primarily produces graphene oxide having about 4 layers after 30 minutes.

[0094] In addition, while the batch toroidal reactor process produces a mix of graphene oxide and graphite after 30 minutes, the semi-continuous process produces only graphene oxide. Where the secondary product of the batch process after 30 minutes is graphite, the secondary product of the semi-continuous process after 30 minutes is multi-layered graphene oxide. However, rather than the 4 layered graphene oxide of the primary product of the semi-continuous process, the secondary product of the semi-continuous process has 17 layers, on average.

[0095] Therefore, use of the semi-continuous process produces graphene oxide with increased exfoliation and increased interlayer spacing relative to an otherwise similar batch process. Moreover, both processes produce graphene oxide at a much faster rate than a non-toroidal batch process, which takes several hours to convert graphite to graphene oxide in a suitable amount.

Example 2—Graphene Oxide: Continuous Toroidal (Helical) Reactor

[0096] Using a process similar to described in Example 1, a continuous toroidal reactor (e.g., wherein components are added to the reactor chamber and sealed, with inlets providing raw materials and a graphene oxide product), such as illustrated in FIG. 4 is utilized to manufacture graphene oxide from graphite. The internal drum is rotated at a rate of about 600 revolutions per minute (rpm) and the flow is controlled by a pump, which is operated at a rate of 50 rpm.

[0097] The graphite raw material is injected into the reactor and passed through the reactor in 10 minutes, whereupon the product is collected and quenched with a 30% hydrogen peroxide solution. The resultant graphene oxide product (identified by a first XRD peak) has a powder XRD two-theta (2θ) value of about 7.39° and has a calculated interlayer spacing of about 11.95 Å. The graphene oxide thus provided is determined to comprise about 6 layers, on average.

[0098] Relative to the graphene oxide prepared by the batch process of Example 1 after 30 minutes, the graphene oxide materials in this continuous example are much more highly processed after just ⅓ of the time (10 minutes). In the batch process, a mixture of graphene oxide and a graphite is produced after 30 minutes, whereas the continuous process produces just graphene oxide after just 10 minutes. Moreover, the graphene oxide process of the batch process of Example 1 produces graphene oxide having an interlayer spacing layer of 9.01 Å after 30 minutes, versus the interlayer spacing of about 11.95 Å observed for the continuous process after just 10 minutes. Moreover, the batch toroidal reactor process primarily produces graphene oxide having about 7 layers after 30 minutes, whereas the continuous process primarily produces graphene oxide having about 6 layers after 10 minutes.

[0099] In addition, while the batch reactor process of Example 1 produces a mix of graphene oxide and graphite after 30 minutes, the continuous process of Example 2 produces only graphene oxide, even after a much shorter time period (10 minutes). Where the secondary product of the batch process of Example 1 after 30 minutes is graphite.

[0100] Relative to the mixed graphene oxide prepared by the semi-continuous process of Example 1 after 30 minutes, the graphene oxide materials in this continuous example are much more highly processed after just ⅓ of the time (10 minutes). In the semi-continuous process, a (e.g., bimodal) mixture of graphene oxides is produced after 30 minutes, whereas the continuous process produces a largely uniform graphene oxide after just 10 minutes. Moreover, the graphene oxide process of the semi-continuous process of Example 1 produces graphene oxide having an interlayer spacing layer of 10.40 Å after 30 minutes, versus the interlayer spacing of about 11.95 Å observed for the continuous process after just 10 minutes. However, the semi-continuous toroidal reactor process primarily produces graphene oxide having about 4 layers (with a secondary product having about 17 layers) after 30 minutes, whereas the continuous process primarily produces graphene oxide having about 6 layers after 10 minutes.

[0101] Therefore, use of the continuous process of Example 4 produces graphene oxide with increased exfoliation and increased interlayer spacing relative to the batch process of Example 2. Moreover, both processes produce graphene oxide at a much faster rate than the general batch process of Example 1, which takes several hours to convert graphite to graphene oxide in a suitable amount.

Example 3—Graphene Oxide: Continuous Toroidal (Helical) Reactor (1 Minute)

[0102] Using a process similar to described in Example 2, a continuous toroidal reactor (e.g., wherein components are added to the reactor chamber and sealed, with inlets providing raw materials and a graphene oxide product), such as illustrated in FIG. 4 is utilized to manufacture graphene oxide from graphite. The graphite raw material is injected into the reactor and passed through the reactor in just 1 minute, whereupon the product is collected and quenched with a 30% hydrogen peroxide solution. Similar to that observed in Example 4, the resultant graphene oxide product has a calculated interlayer spacing of about 12 Å and 6 layers, on average. Moreover, very large graphenic structures are obtained, generally over 20 micron (such as about 50 micron).

[0103] Various products prepared according to processes similar to those in Examples 1-5 are illustrated in Table 1.

TABLE-US-00001 TABLE 1 Reaction Average No. of GO Reaction scheme Time layers and layer spacing Batch reactor 8 hrs 5-11 layers, 11 Å (stirred tank) T-C reactor (batch) 30 min. 9 layers, 9 Å Semi-batch T-C reactor 30 min. 4 layers, 10 Å Continuous T-C reactor  1 min. 6 layers, 12 Å

Example 4—Graphene Oxide Variation

[0104] A single graphite sample from a single source is divided into three portions and subjected to identical batch processing conditions. FTIR analysis of the resultant products are evaluated and illustrated in FIG. 6. As illustrated, significant variations in oxidation are observed, batch-to-batch.

[0105] Similarly, a single graphite sample from a single source is divided into three portions and subjected to an identical process using a toroidal reactor, such as described in Example 1. FTIR analysis of the resultant products are evaluated and illustrated in FIG. 7. As illustrated, very little variations in oxidation is observed, batch-to-batch, with very good overlap of FTIR traces being observed between samples.

Example 5—Flow Variation

[0106] Graphitic stock is provided to a reactor as described in the examples above is utilized. The flow type used in the reactor is varied by varying the rotational rates of the reactor walls. FIG. 9 illustrates the Couette (laminar) flow observed at slow rotational speeds (e.g., wherein Ta<Ta.sub.c). Further, as illustrated in FIG. 9, when Ta exceeds Tac, vortexes form, but when Ta is close to Tac, instabilities (vortexes) form near the reactor inlet, but as the flow continues toward the reactor exit, laminar flow resumes. This type of flow is illustrated as primary instabilities (PI). As Ta increases, instabilities form throughout the reactor, forming a Taylor vortex flow (TVF). Increasing the Ta/Ta.sub.c further, however, creates a secondary instability (SI), where a wavy flow is observed near the inlet of the reactor. Further increase of Ta/Ta.sub.c leads to a full wavy vortex flow (WVF).

[0107] FIG. 10 illustrates the results of injecting graphite into a reactor herein, with the various flow types illustrated in FIG. 9. As illustrated in FIG. 10, after just one minute, in a reactor having a (stable) laminar or Couette (shearing) flow is observed to have excellent conversion of graphite to graphenic compound (graphene oxide). By contrast the primary instability flow is observed to have good conversion to the graphenic compound, but some graphite remains. The stable vortex flow (Taylor vortex flow) is observed to provide excellent conversion of graphite to the graphenic compound, with no graphite component observed. By contrast, both flows having wavy morphologies and that use the most amount of energy produced good conversion of graphite to graphenic compound (graphene oxide), but had significant amounts of graphite also observed.

[0108] FIG. 11 illustrates the different interlayer spacing of the graphenic compounds prepared using the various types of flows described herein. As illustrated, Graphite has very low interlayer spacing, whereas all of the graphenic materials prepared according to a process described herein, using the various flow types described herein, produce graphenic compounds having an interlayer spacing of about 0.8 nm to about 1.1 nm (compared to less than 0.4 nm for graphite). Moreover, the graphenic compounds are observed to have fewer than 10 layers (e.g., 5 to about 10, such as about 8), as compared to about 84 (on average) for the graphite.

[0109] FIG. 13 illustrates the uniformity of the graphenic compounds produced according to the processes herein, particularly when using stable or Taylor vortex flows. As illustrated, the TV and SI flows produce graphenic materials with the greatest oxidation levels, whereas the wavy vortex flow produces the least oxidation, despite using the most energy. Moreover, the peak variation of the TV flow is extremely small (small error bars) compared that that of the other flows, including the SI flow, which also had high oxidation. FIG. 14 illustrates ID/IG and I2D/IG ratios, with the TVF demonstrating the smallest error bars, indicating the greatest uniformity of the graphenic compounds produced thereby.

Example 6—Graphene: Toroidal Reactor

[0110] A reactor similar to that described in Example 1 is provided (inner and outer bodies being circular cylinders). A graphitic stock is prepared by dispersing graphite in an aqueous medium comprising Pluronic F127 (polyethyleneoxide-b-polypropyleneoxide-b-polyethylene oxide or PEOx-b-PPOy-b-PPOz, wherein x and z˜100 and y˜65) and xanthan gum. The stock is provided to an inlet of the reactor and subjected to the toroidal flow conditions. The inner reactor body is rotated at a speed of about 600 rpm, forming toroidal vortices in the reactor. Little to no graphene is observed upon collection.

[0111] The processes are repeated, except in this experiment, the rate of rotation of the inner body is reduced until a non-vortex, laminar (Couette) flow is observed. After one hour, a product is collected and allowed to rest for 1-2 days; after resting, a top and bottom phase form, with the top phase comprising graphene and the bottom phase comprising a mixture of graphite and graphene. Low conversion (less than 5-10%) of graphite to graphene is observed.

Example 7—Graphene: Toroidal Reactor—Outer Rotation

[0112] A reactor similar to that described in Example 6 is provided (inner and outer bodies being circular cylinders), with the outer body, rather than the inner body, configured to rotate. A graphitic stock is prepared by dispersing graphite in an aqueous medium comprising Pluronic F127 (polyethyleneoxide-b-polypropyleneoxide-b-polyethylene oxide or PEOx-b-PPOy-b-PPOz, wherein x and z˜100 and y˜65) and xanthan gum. The stock is provided to an inlet of the reactor and subjected to the toroidal flow conditions. The inner reactor body is rotated at a speed of about 1500 rpm, forming non-vortex, toroidal flow conditions in the reactor. After exfoliation, the product is collected and allowed to rest for 1-2 days; after resting, a top and bottom phase form, with the top phase comprising graphene and the bottom phase comprising a mixture of graphite and graphene. Good conversion (up to 50% or more) of graphite to graphene is observed.

[0113] FIG. 15 illustrates Rama spectrometry traces of the top phase (CFR Gr), the bottom phase (CFR Gt/Gr), and unreacted graphite. As can be observed the top phase has good conversion to low layered graphene (e.g., by the absence of the D band indicated by the box). FIG. 16 illustrates a plot of the I.sub.D/I.sub.G and I.sub.2D/I.sub.G ratios relative the top phase, the bottom phase and unreacted graphite. With decreasing I.sub.D/I.sub.G ratios the number of layers are reduced (e.g., with single layered graphene having an I.sub.D/I.sub.G of about 0) and with increasing I.sub.2D/I.sub.G ratios the number of layers are reduced (e.g., with single layered graphene having an I.sub.2D/I.sub.G ratio of about 2). As is illustrated, the top phase comprises mono- to few-layered graphene, whereas the bottom phase comprises a mixture of graphenes and graphite. The graphene of the top phase are electrosprayed and observed by scanning electron microscopy (SEM), as illustrated in FIG. 17. As is observed, very large low-defect/pristine graphene (>20 micron lateral dimension) is obtained. Moreover, as illustrated in FIG. 18, SEM cross-sections of the graphene demonstrates that mono- and few-layered graphene is obtained and stacked during deposition.

Example 8—Graphene: Toroidal Reactor—Oval Cylinder

[0114] A reactor similar to that described in Example 6 is, with the inner body being an elliptical cylinder, rather than a circular cylinder. A graphitic stock is prepared similar to the process of Example 6. The stock is provided to an inlet of the reactor and subjected to the toroidal flow conditions. The inner reactor body is rotated, forming non-vortex, toroidal flow conditions in the reactor. After exfoliation, the product is collected and allowed to rest for 1-2 days; after resting, a top and bottom phase form, with the top phase comprising graphene and the bottom phase comprising a mixture of graphite and graphene.

[0115] FIG. 19 illustrates Rama spectrometry traces of the top phase (oTCR Gr), the bottom phase (oTCR Gt/Gr), and unreacted graphite. As can be observed the top phase has a substantial D band, indicating multi-layered graphene production. FIG. 20 illustrates a plot of the I.sub.D/I.sub.G and I.sub.2D/I.sub.G ratios relative the top phase, the bottom phase and unreacted graphite. The graphene of the top phase are electrosprayed and observed by scanning electron microscopy (SEM), as illustrated in FIG. 21. As illustrated in FIG. 22, SEM cross-sections of the graphene demonstrates that multi-layered graphene is obtained and stacked during deposition.