Aerogel metallic compositions

• US 7,071,287 B2
• Filed: 01/28/2005
• Issued: 07/04/2006
• Est. Priority Date: 07/22/2002
• Status: Active Grant

• Current Assignee: Aspen Aerogels, Incorporated
• Original Assignee: Aspen Aerogels, Incorporated
• Inventors: Wang, Jing, Begag, Redouane, Rhine, Wendell
• Primary Examiner(s): HAMPTON HIGHTOWER, PATRICIA
• Application Number:
  US11/047,200
• Publication Number:
  US 20050131163A1
• Time in Patent Office: 522 Days
• Field of Search: 528/170, 528/353, 525/420, 423/439, 423/445.R
• US Class Current: 528/353
• CPC Class Codes: B01J 13/0091 Preparation of aerogels, e.g. xerogels
• CPC Class Codes: C08G 73/10 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08G 73/1028 characterised by the process itself, e.g. steps, continuous
• CPC Class Codes: C08G 73/106 containing silicon
• CPC Class Codes: C08J 2201/0502 the liquid phase being organic
• CPC Class Codes: C08J 2203/08 Supercritical fluid
• CPC Class Codes: C08J 2205/026 Aerogel, i.e. a supercritically dried gel
• CPC Class Codes: C08J 2379/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08J 9/28 by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
• CPC Class Codes: Y10T 428/31721 Of polyimide

Abstract

A preparation process of polyimide aerogels that composed of aromatic dianhydrides and aromatic diamines or a combined aromatic and aliphatic diamines is described. Also descried is a process to produce carbon aerogels derived from polyimide aerogel composed of a rigid aromatic diamine and an aromatic dianhydride. Finally, the processes to produce carbon aerogels or xerogel-aerogel hybrid, both of which impregnated with highly dispersed transition metal clusters, and metal carbide aerogels, deriving from the polyimide aerogels composed of a rigid aromatic diamine and an aromatic dianhydride, are described. The polyimide aerogels and the polyimide aerogel derivatives consist of interconnecting mesopores with average pore size at 10 to 30 nm and a mono-dispersed pore size distribution. The gel density could be as low as 0.008 g/cc and accessible surface area as high as 1300 m²/g.

Claims

1. A process for producing carbon aerogels impregnated with dispersed metal particles comprising:

contacting a diamine monomer and an aromatic dianhydride monomer in a solvent under conditions conducive to formation of a poly(amic acid);

dissolving a soluble metal ion salt and the poly(amic acid) in a solvent;

contacting the solution of poly(amic acid) and soluble metal ion salt with a dehydrating agent to form a polyimide gel by imidization of the poly(amic acid);

drying the polyimide gel in the presence of supercritical CO₂ to afford an polyimide aerogel; and

pyrolyzing the derived aerogel under protection of an inert atmosphere to form the carbon aerogel having highly dispersed transition metal particles.

4. The process of any one of claims 1 through 3 in which the first solvent is not miscible with supercritical CO₂, the method further comprises the step of exchanging the first solvent with a second solvent which is miscible with supercritical CO₂ prior to drying the polyimide gel.

5. The process of any one of claims 1 through 3, wherein the metal is selected from the group consisting of Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Si, Sn, Pb, Sb, Nb, Bi, Hf, Ba, Al, B, P, As and combinations thereof.

11. The process of claim 4, wherein the process further comprises addition of a gelation controlling agent to the poly(amic acid) solution such that a molar ratio of gelation controlling agent to metal ion is between about 1 and about 8.

12. The process of claim 11, wherein the molar ratio of gelation controlling agent to metal ion is between about 1 and about 4.

13. The process of claim 11, wherein the gelation controlling agent is an optionally substituted acetoacetonate or an optionally substituted alkyl acetoacetate.

14. The process of claim 11, wherein the gelation controlling agent is selected from the group of 2,4-pentanedione and ethyl acetoacetate.

15. The process of any one of claims 1–

3, wherein a reinforcing agent is added to the polyimide wet gel before drying with supercritical CO₂.

16. The process of claim 15, wherein the reinforcing agent is selected from a reinforcement pad, organic or inorganic fibers carbon nanotubes, metallic fillers or particles or inorganic fillers or particles.

17. The process of claim 15, wherein the fiber reinforcement pad is selected from a non-woven or woven fiber reinforcement composed of a polymeric organic fiber, a glass fiber, a ceramic fiber, a carbon precursor fiber, or a biopolymer fiber.

18. The process of any one of claims 1–

3, in which the process further comprises a post-curing step, at an elevated temperature, to induce substantially complete imidization, wherein the post curing step is conducted;

(a) prior to the solvent removal step wherein the post-curing step is conducted under a pressure of about 20 psi to about 4000 psi;

or

(b) after the solvent removal step, wherein the post-curing step is conducted under an inert atmosphere or in a vacuum at a temperature of between about 50°

C. to about 450°

C.

19. The process of any one of claims 1–

3, wherein the diamine monomer is represented by the formula H₂N—

X—

NH₂, wherein X represents a difunctional aliphatic hydrocarbon group, an amino-terminated polysiloxane, a difunctional aromatic hydrocarbon group, or difunctional heteroaromatic group which may be optionally substituted.

20. The process of claim 19, wherein the aromatic diamine is represented by either formula (I) and (II)

21. The process of claim 20, wherein the aromatic diamine is 1,4-phenylenediamine or 4,4′

-diamino-biphenyl.

22. The process of claim 19, wherein the diamine monomer is an aliphatic diamine containing a linear alkyl chain unit of formula

NH₂CH_2nNH₂

wherein n is a integer number from 1 to 12.

23. The process of claim 19, wherein the diamine monomer is an amino terminated polysiloxane of the formula

24. The process of claim 25, wherein the amino terminated polysiloxane is a thermally stable polysiloxane of the formula

25. The process of any one of claims 1–

2, wherein the aromatic dianhydride is monomer represented by either formula III or IV

26. The process of claim 25, wherein the aromatic dianhydride is selected from the group consisting of optionally substituted pyromellitic dianhydride, optionally substituted 3,3′

,4,4′

-biphenyltetracarboxylic dianhydride, optionally substituted 3,3′

,4,4′

-benzophenone tetracarboxylic dianhydride, and optionally substituted 2,3,6,7-naphthylene tetracarboxylic acid dianhydride.

27. The process of any one of claims 1–

3, wherein the dehydrating agent comprises at least one compound selected from the group consisting of acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, and phosphous trichloride.

28. The process of claim 19, wherein the organic base is selected from optionally substituted mono-, di- and trialkylamines, optionally substituted pyridines, optionally substituted isoquinoline, optionally substituted morpholine, optionally substituted piperadine, and optionally substituted piperazine.

29. A composite carbon aerogel comprising carbon and at least one metal where the composite aerogel is prepared by the process of any one of claims 1 through 3.

39. A composite metal-carbon aerogel of claim 29, in which the composite aerogel is electrically conductive.

2. A process for producing carbon xerogel-aerogel hybrid impregnated with highly dispersed metal particles, the process comprising the steps of:

contacting a diamine monomer and an aromatic dianhydride monomer in a solvent under conditions conducive to formation of a poly(amic acid);

dissolving a soluble metal salt and the poly(amic acid) in a solvent;

contacting the solution of poly(amic acid) and soluble metal ion salt with a dehydrating agent to form a polyimide gel by imidization of the poly(amic acid);

precipitating at least a portion of the soluble metal salt onto the polyimide gel;

drying the polyimide gel in the presence of supercritical CO₂ to afford an polyimide aerogel; and

pyrolyzing the derived aerogel under protection of an inert atmosphere to form the carbon xerogel-aerogel having highly dispersed transition metal particles.

52. A xerogel/aerogel hybrid prepared by the process of claim 2.

3. A process for producing a metal carbide aerogel, a metal carbide-carbon aerogel or carbon aerogel impregnated with highly dispersed metal particles, the process comprising the steps of:

contacting a diamine monomer and an aromatic dianhydride monomer in a solvent under conditions conducive to formation of a poly(amic acid);

preparing a solution of a soluble metal ion salt, an epoxide compound and the poly(amic acid) in a solvent such that a molar ratio of epoxide compound to the metal ion is between about 1 to about 8;

contacting the solution of poly(amic acid), an epoxide compound and soluble metal ion salt with a dehydrating agent to form a polyimide gel by imidization of the poly(amic acid);

drying the polyimide gel in the presence of supercritical CO₂ to afford an polyimide aerogel; and

pyrolyzing the derived aerogel under protection of an inert atmosphere to form the aerogel having highly dispersed transition metal particles.

6. The process of claim 3, wherein the epoxide is a 1,2-epoxyalkane having from 2 to about 12 carbon atoms.

7. The process of claim 3, wherein the epoxide is selected from the group of 1,2-epoxybutane and 1,2-epoxypropane.

8. The process of claim 3, wherein the epoxide compound is added to the reaction as an admixture with deionized water and wherein the epoxide compound is added to the reaction after gelation of the polyimide.

9. The process of claim 3, wherein the ratio of epoxide to metal ion is at range of about 1 to about 8.

10. The process of claim 3, wherein the ratio of deionized water to epoxide is about 1 to about 4.

43. A metal carbide aerogel prepared by the process of claim 3.

44. The metal carbide aerogel of claim 43, wherein the composite aerogel further comprises 0.1 to about 15% nitrogen.

45. The metal carbide aerogel of claim 43 in which the metal carbide aerogel is electrically conductive.

46. A metal carbide aerogel of claim 43 having a yield strength of at least 1 MPa.

47. A metal carbide aerogel of claim 43, wherein the aerogel has an average pore size of between about 5 nm and about 50 nm.

48. A metal carbide aerogel of claim 43, wherein the aerogel has a surface area of about 200 m²/g or more.

49. A metal carbide aerogel of claim 48, wherein the aerogel has a surface area of between about 200 m²/g and about 1000 m²/g.

50. The metal carbide aerogel of claim 43, wherein the aerogel has nanoparticles of a second metal dispersed throughout pores of the aerogel where the second metal may be the same or dfferent from the metal of the metal carbide component of the composite aerogel.

51. A metal carbide aerogel of claim 50, wherein the second metal is selected from Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Si, Sn, Pb, Sb, Nb, Bi, Hf, Ba, Al, B, P, As and combinations thereof.

30. A composite metal-carbon aerogel comprising carbon aerogel domains, comprising carbon and nitrogen, metal carbide domains, or a combination thereof.

31. The composite metal-carbon aerogel of claim 30, wherein the composite aerogel comprises interpenetrating networks of a carbon aerogel and a metal carbide aerogel.

32. The composite metal-carbon aerogel of claim 30, wherein the composite aerogel further comprises 0.1 to about 15% nitrogen.

33. A composite metal-carbon aerogel of claim 30, having a yield strength of at least 1 MPa.

34. A composite metal-carbon aerogel of claim 30, wherein the aerogel has an average pore size of between about 5 nm and about 50 nm.

35. A composite metal-carbon aerogel of claim 30, wherein the aerogel has a surface area of about 100 m²/g to about 1000 m²/g.

36. A composite metal-carbon aerogel of claim 30, wherein the aerogel has a surface area of about 200 m²/g to about 600 m²/g.

37. The composite metal-carbon aerogel of claim 30, wherein the aerogel has nanoparticles of a second metal dispersed throughout pores of the aerogel where the second metal may be the same or different from the metal of the metal carbide component of the composite aerogel.

38. A composite metal-carbon aerogel of claim 37, wherein the second metal is selected from Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Si, Sn, Pb, Sb, Nb, Bi, Hf, Ba, Al, B, P, As and combinations thereof.

40. A composite metal-carbon aerogel of claim 30, in which the composite aerogel is electrically conductive.

41. A composite metal-carbon aerogel of claim 31, in which the composite aerogel is electrically conductive.

42. A composite metal-carbon aerogel of claim 37, in which the composite aerogel is electrically conductive.

54. The article of manufacture of claim 53, wherein the aerogel is selected from aerogels provided by any one of claims 37, 30, 43 or 50.

56. The electrode of claim 55, wherein the aerogel is selected from aerogels provided by any one of claims 37, 30, 43 or 50.

58. The electrochemical cell of claim 57, wherein the aerogel is selected from aerogels provided by any one of claims 37, 30, 43 or 50.

53. An article of manufacture comprising at least one aerogel selected from metal carbide aerogels, hybrid carbon-metal carbide aerogels, each of which may have metal particles dispersed in the pores of the aerogel.

55. An electrode composed of at least one aerogel selected from metal carbide aerogels, hybrid carbon-metal carbide aerogels, each of which may have metal particles dispersed in the pores of the aerogel.

57. An electrochemical cell comprising one or more electrodes composed of at least one aerogel selected from metal carbide aerogels, hybrid carbon-metal carbide aerogels, each of which may have metal particles dispersed in the pores of the aerogel.

59. An electrochemical cell of claim 57, wherein the electrochemical cell is selected from a battery, a capacitor, a supercapacitor, fuel cell, or capacitive deionization cell.

60. A supported metal catalyst comprising a metal carbide, or a composite carbon-metal carbide aerogel having metal particles dispersed therein or a metal carbide aerogel.