Production of carbonaceous nano-fibrous materials with ultra-high specific surface area from alkali (Kraft) lignin

9,190,222

13/830043

March 14, 2013

The present application discloses carbonaceous nano-fibrous materials developed by electrospinning mixtures of alkali lignin with a polymer at varied mass ratios. The present application also discloses processing of the lignin/polymer fibers via progressive heat treatments for stabilization, pre-carbonization and carbonization. The resulting carbon nanofibers maintain a uniform shape and have high specific surface area.

North Carolina Agricultural and Technical State University (Greensboro, NC, US); South Dakota School of Mines and Technology (Rapid City, SD, US)

North Carolina Agricultural and Technical State University (Greensboro, NC, US), South Dakota School of Mines and Technology (Rapid City, SD, US)

1. A method for the manufacture of carbon nanofibers comprising: (a) providing intermediate nanofibers stabilized by heating in an oxygen-containing atmosphere; and (b) pre-carbonization heating comprising providing stabilized intermediate nanofibers in an inert atmosphere, wherein said pre-carbonization heating comprises heating said inert atmosphere from at least about 150° C. to between about 400° C. and about 600° C. at a heating rate of up to about 2° C. per minute and holding at a pre-carbonization temperature between about 400° C. and about 600° C. for a sufficient time to increase the crosslinking of the nanofibers and/or to begin to remove non-carbon elements from the nanofibers.

2. The method of claim 1 , further comprising carbonization heating between about 700° C. and about 2200° C., for a sufficient time to yield carbon nanofibers.

3. The method of claim 2 , wherein said sufficient time for carbonization heating is at least about 30 minutes.

4. The method of claim 1 , wherein said pre-carbonization temperature is between about 450° C. and about 550° C.

5. The method of claim 1 , wherein said heating rate is up to about 0.5° C./min.

6. The method of claim 5 , wherein said heating rate is up to about 0.1° C./min.

7. The method of claim 6 , wherein said heating rate is up to 0.05° C./min.

8. The method of claim 1 , wherein said sufficient time to increase the crosslinking of said nanofibers and/or to begin to remove non-carbon elements from said nanofibers is at least about 30 minutes.

9. The method of claim 1 , wherein said intermediate nanofibers are prepared by electrospinning a mixture comprising alkali lignin and a polymer.

10. The method of claim 9 , wherein said electrospinning is solution electrospinning.

11. The method claim 10 , wherein said mixture further comprises water and said polymer is soluble in said mixture.

12. The method of claim 11 , wherein said polymer is poly(vinyl alcohol).

13. A method for preparing carbon nanofibers comprising: (a) electrospinning a mixture comprising alkali lignin and a polymer to provide electrospun alkali lignin/polymer nanofibers; (b) providing said electrospun alkali lignin/polymer nanofibers in an oxygen-containing atmosphere and heating the oxygen-containing atmosphere to a first stabilization temperature of at least about 100° C. at a heating rate of no more than 2.0° C. per minute; (c) heating from said first stabilization temperature to a second stabilization temperature of at least about 160° C. at a heating rate of no more than about 1.0° C. per minute; (d) heating from said second stabilization temperature to a third stabilization temperature of at least about 180° C. at a heating rate of no more than about 1.0° C. per minute; and (e) heating from said third stabilization temperature to a fourth stabilization temperature of at least about 200° C. at a heating rate of no more than about 1.0° C. per minute; wherein said stabilization heating yields stabilized nanofibers.

14. The method of claim 13 , wherein said mixture further comprises water and said polymer is soluble in said mixture.

15. The method of claim 14 , wherein said polymer is poly(vinyl alcohol).

16. The method of claim 13 , further comprising providing said stabilized nanofibers in an inert atmosphere and heating the inert atmosphere to a pre-carbonization temperature of at least about 400° C. at a heating rate of no more than about 0.5° C. per minute to yield pre-carbonized nanofibers.

17. The method of claim 16 , wherein said nanofibers in (c) are held at said second stabilization temperature for at least about 8 hours; in (d) are held at said third stabilization temperature for at least about 12 hours; and in (e) are held at said fourth stabilization temperature for at least about 2 hours.

18. A method for preparing carbon nanofibers comprising (a) electrospinning a mixture of alkali lignin and a polymer; (b) heat treating said electrospun alkali lignin/polymer nanofibers wherein said heat treating comprises providing said nanofibers in an oxygen-containing atmosphere and progressive stabilization heating of said oxygen-containing atmosphere from a first stabilization temperature of at least about 100° C. to an final stabilization temperature of at least about 200° C. at a heating rate of no more than 1° C. per minute to yield stabilized nanofibers; (c) providing said stabilized nanofibers in an inert atmosphere and heating the inert atmosphere up to a pre-carbonization temperature of at least about 400° C. at a heating rate of no more than about 0.2° C. per minute and holding at said pre-carbonization temperature for a sufficient time to increase crosslinking in said nanofibers to yield pre-carbonized nanofibers; and (d) providing said pre-carbonized nanofibers in an inert atmosphere and heating the inert atmosphere up to a carbonization temperature of at least about 700° C. at a heating rate of no more than about 10° C. per minute and holding at said carbonization temperature for a sufficient time to remove most of the non-carbon impurities in said nanofibers.

19. The method of claim 18 , wherein said rate of heating in (b) is between about 0.05° C./min and about 1° C./min; said rate of heating in (c) is no more than about 0.1° C./min and said pre-carbonization temperature is held for at least about 30 minutes; and said carbonization temperature is held for at least about 30 minutes.

20. The method claim 19 , wherein said polymer is soluble in an aqueous solvent.

21. The method of claim 20 , wherein said mixture comprises water and said polymer is poly(vinyl alcohol).

22. The method of claim 21 , wherein said mixture of poly(vinyl alcohol) and alkali lignin contains at least about 50 wt % alkali lignin.

23. The method of claim 22 , wherein said mixture of poly(vinyl alcohol) and said alkali lignin contains at least about 70 wt % alkali lignin.

24. Carbon nanofibers having a surface area of from about 250 m 2 /g to about 750 m 2 /g and a peak pore volume greater than about 0.04 cm 3 /nm/g for pores having a diameter of less than about 5 nm and an average pore size of no more than about 4 nm.

25. A electric double layer capacitor comprising the carbon nanofiber of claim 24 .

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