BIOMASS-BASED METHOD AND COMPOSITION

Abstract

Methods and compositions suitable for forming electrodes and other components of energy storage devices are disclosed.

Claims

1. A method of forming a composition suitable for use as an electrode material, the method comprising the steps of: providing biomass material; forming biochar material using a first process; mixing and grinding the biochar material with an activation compound comprising one or more of fungi material and silicaceous material to form a mixture; and exposing the mixture to a second process to form the composition.

2. The method of claim 1, wherein the biomass material comprises hemp material.

3. The method of claim 1, wherein the activation compound further comprises one or more of a metal salt, an acid, and a base.

4. The method of claim 3, wherein the activation compound comprises one or more of zinc chloride (ZnCl.sub.2), phosphoric acid (H.sub.3PO.sub.4), aluminum chloride (AlCl.sub.3), magnesium chloride (MgCl.sub.2), sodium hydroxide (NaOH), and potassium hydroxide (KOH).

5. The method of claim 1, wherein one or more of the first process and the second process comprise pyrolysis.

6. The method of claim 1, wherein the silicaceous material comprises polysilicate material.

7. The method of claim 1, wherein the silicaceous material comprises mica.

8. The method of claim 1, wherein the composition comprises about 0 or greater than 0 to about 14%, greater than 0 to about 14%, or about 4 to about 10% percent of the silicaceous material.

9. The method of claim 1, wherein the composition comprises 0 or greater than 0 to about 14%, greater than 0 to about 12%, or about 4 to about 10% of the fungi material.

10. A composition suitable for forming an electrode, the composition comprising: an activated material mixture formed from biochar material and an activation compound comprising one or more of fungi material and silicaceous material.

11. The composition of claim 10, wherein the biochar material comprises hemp biochar material.

12. The composition of claim 10, wherein the biochar material is pyrolyzed prior to forming the activated material mixture.

13. The composition according to claim 10, wherein the activation compound further comprises one or more of a metal salt, an acid, and/or a base.

14. The composition of claim 13, wherein the activation compound comprises one or more of zinc chloride (ZnCl.sub.2), phosphoric acid (H.sub.3PO.sub.4), aluminum chloride (AlCl.sub.3), magnesium chloride (MgCl.sub.2), sodium hydroxide (NaOH), and potassium hydroxide (KOH).

15. The composition of claim 10, wherein the activation compound comprises the fungi material and the silicaceous material.

16. The composition of claim 10, wherein the silicaceous material comprises polysilicate material.

17. The composition of claim 10, wherein the silicaceous material comprises mica.

18. The composition of claim 10, wherein the composition comprises about 0 or greater than 0 to about 14%, greater than 0 to about 14%, or about 4 to about 10% percent of the silicaceous material.

19. The composition claim 10, wherein the composition comprises 0 or greater than 0 to about 14%, greater than 0 to about 12%, or about 4 to about 10% of the fungi material.

20. The composition of any claim 10, wherein the composition does not include an additional binder.

21. An electrode comprising the composition of claim 10.

22. The electrode according to claim 21, wherein the electrode does not comprise an additional binder.

23. An electrostatic device or electrochemical cell comprising at least one electrode according to claim 21.

24. A capacitor comprising at least one electrode according to claim 21.

25. A supercapacitor comprising at least one electrode according to claim 21.

Description

BRIEF DESCRIPTION OF THE DRAWING FIGURES

[0017] A more complete understanding of the embodiments of the present disclosure may be derived by referring to the detailed description and claims when considered in connection with the following illustrative figures.

[0018] FIG. 1 illustrates performance characteristics of exemplary energy storage devices.

[0019] FIG. 2 illustrates a method in accordance with exemplary embodiments of the disclosure.

[0020] FIG. 3 illustrates another method in accordance with exemplary embodiments of the disclosure.

[0021] FIG. 4 illustrates a device in accordance with exemplary embodiments of the disclosure.

[0022] FIG. 5 illustrates a device in accordance with additional exemplary embodiments of the disclosure.

[0023] FIG. 6 illustrates an energy storage device life cycle in accordance with additional exemplary embodiments of the disclosure.

[0024] It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

[0025] The description of exemplary embodiments of methods, compositions, devices and portions thereof provided below is merely exemplary and is intended for purposes of illustration only; the following description is not intended to limit the scope of the disclosure or the claims. Moreover, recitation of multiple embodiments having stated features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the stated features. For example, various embodiments are set forth as exemplary embodiments and may be recited in the dependent claims. Unless otherwise noted, the exemplary embodiments or components thereof may be combined or may be applied separate from each other.

[0026] As set forth in more detail below, various embodiments of the disclosure provide methods for forming compositions suitable for a variety of applications, including use in electrodes of, for example, energy storage devices. Exemplary methods can be relatively inexpensive, relatively environmentally friendly, and/or relatively easy to perform, compared to traditional methods. As a result, the compositions and devices formed with or using the methods can also be relatively inexpensive, environmentally friendly, or the like.

[0027] In this disclosure, “electrode” can include material that is conductive. An electrode can include a composition as set forth herein and, in some cases, may include additional material. An electrode can form part of various types of devices, such as electrochemical cells, capacitors, supercapacitors, ultracapacitors, pseudocapacitors, electrostatic devices, other energy storage devices, and the like.

[0028] As used herein, the term “biomass material” can refer to material that is derived from an animal or plant. In some cases, the biomass material is plant derived. In these cases, the biomass material includes lignocellulosic material. The lignocellulosic material can be derived from, for example, hardwoods (e.g., yellow poplar, white oak), coconut shells, fruit stones (e.g., almond shells, cherry pit shells), synthetic crystals (e.g., microcrystalline cellulose, which is derived from wood pulp), hemp, fungi, or the like. Biomass material can include, for example, bast fibers and/or hurd material. In some cases, the biomass may be innoculated with fungi.

[0029] As used herein, the term “pyrolyze,” “pyrolysis” or similar a term can refer to any reaction that includes use of applied heat.

[0030] Further, in this disclosure, any two numbers of a variable can constitute a workable range of the variable, and any ranges indicated may include or exclude the endpoints. Additionally, any values of variables indicated (regardless of whether they are indicated with “about” or not) may refer to precise values or approximate values and include equivalents, and may refer to average, median, representative, majority, or the like. Further, in this disclosure, the terms “including,” “constituted by” and “having” can refer independently to “typically or broadly comprising,” “comprising,” “consisting essentially of,” or “consisting of” in some embodiments. In this disclosure, any defined meanings do not necessarily exclude ordinary and customary meanings in some embodiments.

[0031] Turning again to the figures, FIG. 2 illustrates a method 200 in accordance with exemplary embodiments of the disclosure. Method 200 can be used to, for example, form a composition—e.g., suitable for use as or in the formation of an electrode—e.g., of an energy storage device.

[0032] Method 200 includes the steps of providing biomass material (step 202), forming biochar material using a first process (step 204), mixing and grinding the biochar material with an activation compound comprising one or more of fungi material and silicaceous material to form a mixture (step 206), and exposing the mixture to a second process to form the composition (step 208).

[0033] During step 202, biomass material is provided. As noted above, the biomass material can be or include a variety of materials, including, for example, lignocellulosic material. The lignocellulosic material can be derived from, for example, one or more of hardwoods, coconut shells, fruit stones, synthetic crystals (e.g., microcrystalline cellulose, which is derived from wood pulp), hemp, fungi, and the like. By way of particular examples, the biomass material can be or include hemp material, such as hemp bast material and/or hemp hurd material.

[0034] During step 204, biochar material is formed from the biomass material using a first process. The first process can include, for example, pyrolysis. The pyrolysis can be performed using a hydrothermal reactor. In some embodiments of the disclosure, step 204 includes heating the biomass material to a temperature of less than 1200° C. and/or more than 50° C. For example, in some embodiments of the disclosure, step 204 includes heating the biomass material to a temperature between about 150° C. and about 200° C., about 500° C. and about 800° C., or about 1000° C. and about 1200° C. A pressure within a reactor during step 204 may also be regulated. For example, in some embodiments of the disclosure, the pressure within the reactor may be less than 50,000 Torr or between 760 Torr and 1000 Torr, about 10,000 Torr and 15,000 Torr, or about 45,000 Torr and 50,000 Torr. A duration of step 204 can be about 0.1 to about 1 hours, about 10 to about 24 hours, or about 24 to about 96 hours.

[0035] During step 206, biochar material from step 204 is mixed and ground with an activation compound comprising one or more of fungi material and silicaceous material to form a mixture. The mixing and grinding can be performed using, for example, an agate mortar and pestle.

[0036] The mixture (or composition) can include about 0 or greater than 0 to about 14%, greater than 0 to about 12%, or about 4 to about 10% fungi material. All percentages set forth herein are weight percentages—unless noted otherwise. Additionally or alternatively, the activation compound can include about 0 or greater than 0 to about 14%, greater than 0 to about 14%, or about 4 to about 10% percent silicaceous material. Additionally or alternatively, the mixture (or composition) can include about 40-80%, about 45-75%, or about 40-60% biomass material and/or about 5-60%, about 10-70%, or about 40-60% activation compound.

[0037] Fungi material suitable for use with examples of the disclosure include one or more of cordyceps, shiitake, lion's mane, cremini, portobello, turkey tail, and reishi, or other fungi in any combination. In some cases, the activation compound can include fungal fruiting body, mycelium, lichen, or mineral in addition to, or in place of, the fungi.

[0038] The silicaceous material can include, for example, polysilicate material. In some cases, the silicaceous material can include mica.

[0039] The activation compound can additionally include, for example, one or more of a metal salt and an acid, and/or a base (e.g., inorganic compounds). By way of particular examples, the activation compound can additionally include one or more of zinc chloride (ZnCl.sub.2), phosphoric acid (H.sub.3PO.sub.4), aluminum chloride (AICl.sub.3), magnesium chloride (MgCl.sub.2), sodium hydroxide (NaOH), and potassium hydroxide (KOH).

[0040] During step 208, the mixture from step 206 is exposed to a second process to form the composition. The second process can be, for example, a pyrolysis process. As above, the pyrolysis can be performed using a hydrothermal reactor. A temperature during step 208 can be less than 1200° C. and/or more than 50° C. For example, in some embodiments of the disclosure, step 208 includes heating the mixture to a temperature between about 150° C. and about 200° C., about 500° C. and about 800° C., or about 1000° C. and about 1200° C. A pressure within a reactor during step 208 may also be regulated. For example, in some embodiments of the disclosure, the pressure within the reactor may be less than 50,000 Torr or between 760 Torr and 1000 Torr, about 10,000 Torr and 15,000 Torr, or about 45,000 Torr and 50,000 Torr. A duration of step 208 can be about 0.1 to about 1 hours, about 10 to about 24 hours, or about 24 to about 96 hours.

[0041] In accordance with examples of the disclosure, a composition formed using method 200 does not undergo chemical washing and/or mixing with binder material or binder solvent.

[0042] The composition formed using method 200 can include an activated material mixture formed from biochar material and an activation compound comprising one or more of fungi material and silicaceous material. The biochar material, activation compound, fungi material, and/or silicaceous material can be as described above.

[0043] In accordance with various examples of the disclosure, the composition includes highly conductive (e.g., conductivity of about 10-1000 S/m) and high surface area carbon (e.g., surface area of about 100-10,000 m2/g). Two generally desirable characteristics of electrode material for use in energy storage devices include high surface area and high cation exchange capacity (cation exchange capacity is generally related to electrical conductivity). Exemplary compositions described herein exhibit one or both of these desired characteristics.

[0044] In accordance with further examples, the composition includes minerals (e.g., from the activation compound) that are beneficial to soil health. Therefore, as illustrated in more detail below in connection with FIG. 6, in at least some cases, the electrode material can be composted after use in an energy storage device, and provide beneficial nutrients to soil. In such cases, the composition may not include any additional or any petroleum-based binders.

[0045] FIG. 3 illustrates another method 300 in accordance with examples of the disclosure. FIG. 3 includes additional steps used to form a device. Method 300 includes the steps of forming biochar material (step 302), mixing and grinding (step 304), forming a composition (step 306), coating a current collector (step 308), forming cell architecture (step 310), applying an electrolyte (step 312), and sealing a device (step 314).

[0046] Steps 302-306 can be the same or similar to steps 204-208 described above in connection with FIG. 2. During step 308, the composition formed using steps 302-306 is applied to a surface of a current collector. The current collector can be or include any suitable conducting material, such as, for example, graphite foil, copper, stainless steel, aluminum, titanium, or the like. Any suitable technique can be used to apply the composition to the current collector. By way of example, the composition can be applied to the current collector using roll-to-roll techniques, chemical vapor deposition techniques, or otherwise. In accordance with examples of the disclosure, the composition can be coated onto a surface of the current collector without the use of an additional (e.g., a petroleum-based) binder.

[0047] During step 310, a device cell architecture is formed. For example, in the case of electrochemical cells, an anode, a cathode, and a separator and/or electrolyte can be assembled. The anode and/or cathode can include the composition. In some cases, the separator can include the composition. The electrochemical cells can be cyclical, wound or stacked to form a battery.

[0048] In the case of liquid electrolyte batteries, during step 312, an electrolyte can be added (e.g., by injection, sputtering, or other means) to the structures formed during step 310. Alternatively, a solid electrolyte can be included in the architecture formed during step 310. Exemplary liquid electrolytes include sulfuric acid and optionally one or more KOH, KCI, Na2SO4, K2504 or non-aqueous electrolytes including, for example, lithium hexafluorophosphate. Exemplary solid electrolytes include sodium electrolytes, polytetrafluoroethylene, polyvinyl acetate, polyvinylidene fluoride, and cellulose acetate.

[0049] During step 314, a device can be sealed—e.g., using a pouch, a button cell, a cylinder, or the like. In some cases, a vacuum can be applied to the cell(s) prior to sealing the device.

[0050] FIG. 4 illustrates a device 400 in accordance with exemplary embodiments of the disclosure. Device 400 can be an energy storage device, such as an electrochemical cell that forms part of a battery, a supercapacitor, an ultracapacitor, a capacitor, an electrical double layer capacitor (e.g., supercapacitor, pseudocapacitor, etc.), or the like. Device 400 includes current collectors 402, 404; electrodes 406, 408; and separator 410.

[0051] Current collectors 402, 404 can be formed of any suitable conductive material. By way of examples, current collectors can be formed of sheets—for example, conducting material, such as, for example, graphite foil, copper, stainless steel, aluminum, titanium, or the like.

[0052] Electrodes 406, 408 can be or include a composition as described herein. One of electrodes 406, 408 can function as an anode during discharge of device 400 and the other of electrodes 406, 408 can function as a cathode during discharge of device 400. During operation of device 400, cations can be reduced at the cathode and ions or metals can be oxidized at the anode. In secondary electrochemical cells, anodes and cathodes can be reversed upon application of sufficient voltage to charge the cell.

[0053] As illustrated in FIG. 4, electrodes 406, 408 can include graphene or graphene-like material. That is, a composition as described herein can include graphene or graphene-like material. Graphene or graphene-like material is thought to be advantageous, relative to non-graphene, activated carbon, because graphene has a higher surface area per weight or volume. Thus, cells formed with graphene material can exhibit higher energy and power densities.

[0054] Separator 410 can include any suitable non-conducting material. In accordance with some examples of the disclosure, separator 410 includes a composition as described herein. In accordance with further examples, separator 410 can be or include hemp-based material (e.g., hemp paper), polypropylene, woven polyester, polypropylene (PP), polyethylene (PE), Teflon, PVdF, PVC, fiberglass, cellulose (from various sources), cellophane, or the like.

[0055] Device 400 can also include an electrolyte. In some cases, the electrolyte and the separator can be the same or form part of the same layer (e.g., layer/separator 410). In other cases, device 400 can include a liquid electrolyte. Exemplary solid electrolytes suitable for use with device 400 include the exemplary solid electrolytes noted above. Exemplary liquid electrolytes suitable for use with device 400 include those noted above.

[0056] FIG. 5 illustrates operation of a device 500, which can be the same or similar to device 400. Device 500 includes current collectors 502, 504; electrodes 506, 508; and separator 510.

[0057] In the illustrated example, current collector 502 and electrode 506 are positively charged and current collector 504 and electrode 508 are negatively charged. When current collectors 502, 504 are applied to an external circuit and electrons are allowed to flow, negative ions are attracted to positively charged current collector 502 and electrode 506 and/or positive ions are attracted to negatively charged current collector 504 and electrode 508. The electrodes including a composition as described herein can provide hierarchical porous carbon structures with high surface area interstitial lattice sites allowing ionic intercalation on the electrodes.

[0058] FIG. 6 illustrates exemplary steps 602-616 for energy storage devices in accordance with examples of the disclosure. As illustrated, biomass material can be prepared during step 602. For example, the biomass material can be decorticated. Biochar material can then be formed, and a composition can be formed during steps 604 and 606—e.g., as described above in connection with FIGS. 2 and 3. A device can be assembled during step 608—e.g., as described in connection with FIG. 3. The device can then be used during step 610—e.g., until the device no longer provides the desired performance. During step 612, portions of the device—e.g., one or more electrodes and/or a separator—can be composted. During step 614, biomass can be grown—e.g., using the composted material from step 612. Finally, during step 616, the biomass can be harvested and used in step 602 to repeat a cycle.

[0059] Energy storage devices in accordance with the present disclosure when applied in supercapacitor chemistry exhibit energy densities in the range of about 0-400 Wh/kg or 100-400 Wh/kg and/or power densities in the range of about 500 W/kg-5 kW/kg.

[0060] The example embodiments of the disclosure described above do not limit the scope of the invention, since these embodiments are merely examples of the embodiments of the invention, which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combinations of the elements described, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.