IP Library › Granted Patent US 12,365,590
Granted Patent B2
US 12,365,590 · App. 17/613,421 · Granted Jul 22, 2025

Monolithic and fractal carbon foams and methods of preparing and using same

Inventors: Barbaros Oezyilmaz (Singapore, SG); Jonghak Lee (Singapore, SG); Clarissa Chui Ling Wong (Singapore, SG); Cagdas Cetin (Singapore, SG); Xiao Feng Lim (Singapore, SG); Yong Kang Ong (Singapore, SG)
Assignee: National University of Singapore
C01B32/05C01B32/18C04B35/528C04B35/64C04B38/009H01G11/28H01G11/36B22F3/105C01P2002/82C01P2006/40C04B2235/422C04B2235/428C04B2235/446C04B2235/6581C04B2235/666
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,365,590
App. No.
17/613,421
Granted
Jul 22, 2025
Kind
B2
Abstract

A monolithic carbon foam formed of fused onion-like carbon (OLC) nanoparticles, in which the monolithic carbon foam contains interconnected pores, has a volumetric micropore surface area of 200 m 2 /cc-600 m 2 /cc, and has an electrical conductivity of 20 cm-140 S/cm. Also disclosed are a fractal carbon foam prepared from the monolithic carbon foam, methods of preparing both foams, and supercapacitors constructed therefrom. Specifically, the methods of preparing the foams comprising, inter alia, spark plasma sintering the OLC nanoparticles at a pressure of 30 MPa-1000 MPa and a temperature of 300° C.-800° C. for 2 seconds-30 minutes.

Claims (21)

1. A method of preparing a monolithic carbon foam, the method comprising the steps of:

compacting onion-like carbon (OLC) nanoparticles,

placing the compacted OLC nanoparticles in a vacuum or in a space filled with an inert gas, and

spark plasma sintering the OLC nanoparticles at a pressure of 30 MPa to 1000 MPa and a temperature of 300° C. to 800° C. for 2 seconds to 30 minutes to obtain the monolithic carbon foam.

2. The method of claim 1 , wherein the spark plasma sintering step is performed at a pressure of 40 MPa to 300 MPa.

3. The method of claim 1 , wherein the spark plasma sintering step is performed at a temperature of 400° C. to 600° C.

4. The method of claim 2 , wherein the spark plasma sintering step is performed at a temperature of 400° C. to 600° C. for 2 seconds to 10 minutes.

5. The method of claim 1 , wherein the OLC nanoparticles is compacted with a material selected from the group consisting of a non-OLC-based material, an oxide material, a metal, and a semiconductor material.

6. The method of claim 5 , wherein the material is in the form of a fiber, a tube, a hollow sphere, a wire, a sheet, or a powder.

7. The method of claim 5 , wherein the material is silicon, molybdenum oxide, a non-OLC-based material containing activated carbon, or molybdenum disulfide in the form of a sheet.

8. A method of preparing a fractal carbon foam, the method comprising the step of:

crushing the monolithic carbon foam prepared by the method of claim 1 to form a monolithic carbon foam powder,

compacting the monolithic carbon foam powder,

placing the compacted monolithic carbon foam powder in a vacuum or in a space filled with an inert gas, and

spark plasma sintering the monolithic carbon foam powder at a pressure of 30 MPa to 1000 MPa and a temperature of 300° C. to 800° C. for 2 seconds to 30 minutes to form the fractal carbon foam.

9. The method of claim 8 , wherein the monolithic carbon foam powder is sintered at a pressure of 40 MPa to 200 MPa.

10. The method of claim 8 , wherein the monolithic carbon foam powder is sintered at a temperature of 600° C. to 800° C.

11. The method of claim 9 , wherein the monolithic carbon foam powder is sintered at a temperature of 600° C. to 800° C. for 2 seconds to 10 minutes.

12. The method of claim 8 , wherein the monolithic carbon foam contains a material selected from the group consisting of a non-OLC-based material, an oxide material, a metal, and a semiconductor material.

13. The method of claim 12 , wherein the material is in the form of a fiber, a tube, a hollow sphere, a wire, a sheet, or a powder.

14. The method of claim 12 , wherein the material is silicon, molybdenum oxide, a non-OLC-based material containing activated carbon, or molybdenum disulfide in the form of a sheet.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 10, 2022
From: OEZYILMAZ, BARBAROS; LEE, JONGHAK; WONG, CLARISSA CHUI LING; CETIN, CAGDAS; LIM, XIAO FENG; ONG, YONG KANG
To: NATIONAL UNIVERSITY OF SINGAPORE
Reel/Frame 058974/0095 →
Continuity (2)
Provisional Application 62851793 · May 23, 2019
Related Publication 20220219987A1 · Jul 14, 2022
References Cited (48)
US 10984830B2 · Ozyilmaz et al. · 2021 [cited by applicant]
US 11114674B2 · Ozyilmaz et al. · 2021 [cited by applicant]
US 11192788B2 · Ozyilmaz et al. · 2021 [cited by applicant]
US 20130183511A1 · Dai et al. · 2013 [cited by applicant]
US 20170297923A1 · Ghosh · 2017 [cited by examiner]
US 20210017026A1 · Ozyilmaz et al. · 2021 [cited by applicant]
CN 107021761A · 2017 [cited by examiner]
CN 108530098A · 2018 [cited by applicant]
CN 110357074A · 2019 [cited by applicant]
WO WO2018156082A1 · 2018 [cited by applicant]
Rode, Andrei V., et al. “Structural analysis of a carbon foam formed by high pulse-rate laser ablation.” Applied Physics A 69 (1999): S755-S758. [cited by examiner]
Ukhina, Arina V., et al. “Porous electrically conductive materials produced by Spark Plasma Sintering and hot pressing of nanodiamonds.” Ceramics International 41.9 (2015): 12459-12463. [cited by examiner]
Su, Shi, et al. “Spark plasma sintering compaction of hybrid nanodiamond/carbon nanotubes/metal electrode and its application.” Diamond and Related Materials 104 (2020): 107746. [cited by examiner]
Wang, Ye et al. “Pre-lithiation of onion-like carbon/MoS [cited by applicant]
Mao, Shun et al. “Hierarchical nanohybrids with porous CNT-networks decorated crumpled graphene balls for supercapacitors.” ACS Applied Materials & Interfaces; 2014. [cited by applicant]
Office Action issued in Chinese Patent Application No. 202080037333.5 on Aug. 31, 2022. [cited by applicant]
Abdali et al “Preparation of Electrospun Nanocomposite Nanofibers of Polyaniline/Poly(Methyl Methacrylate) with Amino-Functionalized Graphene” Polymers vol. 9, pp. 1-12, 2017. [cited by applicant]
Barborini et al “Negatively Curved Spongy Carbon” Applied Physics Letters vol. 81, pp. 3359-3361, 2002. [cited by applicant]
Bourgeois et al “High-Resolution Transmission Electron Microscopic Study of Nanoporous Carbon Consisting of Curved Single Graphitic Sheets” Philosophical Magazine A vol. 76, pp. 753-768, 1997. [cited by applicant]
Braun et al “Generating Carbon Schwarzites via Zeolite-Templating” PNAS vol. 115, pp. E8116-E8124, 2018. [cited by applicant]
Brown “The Hardness of Irradiated Graphite” Carbon vol. 6, pp. 27-30, 1968. [cited by applicant]
Chen et al “Three-Dimensional Flexible and Conductive Interconnected Graphene Networks Grown by Chemical Vapour Deposition” Nature Materials vol. 10, pp. 424-428, 2011. [cited by applicant]
Ewing et al “Scale Dependence of Intragranular Porosity, Tortuosity, and Diffusivity” Water Resources Research vol. 46, pp. 1-12, 2010. [cited by applicant]
German “Sintering Trajectories: Description on How Density, Surface Area, and Grain Size Change” JOM vol. 68, pp. 878-884, 2016. [cited by applicant]
Guillon et al “Field-Assisted Sintering Technology/Spark Plasma Sintering: Mechanisms, Materials, and Technology Developments” Advanced Engineering Materials vol. 16, pp. 830-849, 2014. [cited by applicant]
Ishimoto et al “Degradation Responses of Activated-Carbon-Based EDLCs for Higher Voltage Operation and Their Factors” Journal of the Electrochemical Society vol. 156, pp. A563-A571, 2009. [cited by applicant]
Kang et al “Graphene Papers with Tailored Pore Structures Fabricated from Crumpled Graphene Spheres” Nanomaterials vol. 9, pp. 1-11, 2019. [cited by applicant]
Khelifa et al “Nanoindentation of Flexible Graphite: Experimental Versus Simulation Studies” Advanced Materials Science vol. 3, pp. 1-11, 2018. [cited by applicant]
Kotz et al “Aging and Failure Mode of Electrochemical Double Layer Capacitors During Accelerated Constant Load Tests” Journal of Power Sources vol. 195, pp. 923-928, 2010. [cited by applicant]
Luo et al “Diamond Synthesis From Carbon Nanofibers at Low Temperature and Low Pressure” Scientific Reports vol. 5, pp. 1-6, 2015. [cited by applicant]
MacKay et al “Diamond from Graphite” Nature vol. 352, p. 762, 1991. [cited by applicant]
Mason et al “The Young's Modulus of Carbon and Graphite Artefacts” Carbon vol. 5, pp. 493-506, 1967. [cited by applicant]
Neighbour “Modelling of Dimensional Changes in Irradiated Nuclear Graphites” Journal of Physics D: Applied Physics vol. 33, pp. 2966-2972, 2000. [cited by applicant]
Nelson et al “Electronic Excitations in Graphene in the 1-50 eV Range: The π and π+δ Peaks are Not Plasmons” Nano Letters vol. 14, pp. 3827-3831, 2014. [cited by applicant]
Nomura et al “4.4 V Supercapacitors Based on Super-Stable Mesoporous Carbon Sheet Made of Edge-Free Graphene Walls” Energy and Environmental Science vol. 12, pp. 1542-1549, 2019. [cited by applicant]
Ruoff “Personal Perspectives on Graphene: New Graphene-Related Materials on the Horizon” Materials Research Society Bulletin vol. 37, pp. 1314-1318, 2012. [cited by applicant]
Ryoo et al “Ordered Mesoporous Carbons” Advanced Materials vol. 13, pp. 677-681, 2001. [cited by applicant]
Shen et al “Spark Plasma Sintering Assisted Diamond Formation From Carbon Nanotubes at Very Low Pressure” Nanotechnology vol. 17, pp. 2187-2191, 2006. [cited by applicant]
Tevet et al “Friction Mechanism of Individual Multilayered Nanoparticles” PNAS vol. 108, pp. 19901-19906, 2011. [cited by applicant]
Valencia et al “Theoretical Characterization of Several Models of Nanoporous Carbon” New Journal of Physics vol. 5, pp. 1-16, 2003. [cited by applicant]
Weingarth et al “Cycle Versus Voltage Hold—Which is the Better Stability Test for Electrochemical Double Layer Capacitors?” Journal of Power Sources vol. 225, pp. 84-88, 2013. [cited by applicant]
Xu et al “Holey Graphene Frameworks for Highly Efficient Capacitive Energy Storage” Nature Communications vol. 5, pp. 1-9, 2014. [cited by applicant]
Yang et al “Liquid-Mediated Dense Integration of Graphene Materials for Compact Capacitive Energy Storage” Science vol. 341, pp. 534-537, 2013. [cited by applicant]
Zhang et al “Thermal Stability of Carbon Nanotubes, Fullerene and Graphite Under Spark Plasma Sintering” Chemical Physics Letters vol. 510, pp. 109-114, 2011. [cited by applicant]
Zhu et al “Carbon-Based Supercapacitors Produced by Activation of Graphene” Science vol. 332, pp. 1537-1541, 2011. [cited by applicant]
Ukhina et al “Porous Electrically Conductive Materials Produced by Spark Plasma Sintering and Hot Pressing of Nanodiamonds” Ceramics International vol. 41, pp. 12459-12463, 2015. [cited by applicant]
“Office Action” for German Patent Application No. 11 2020 002 480.6, Mar. 10, 2025, 12 pages, German Patent Office, Munich, Germany. [cited by applicant]
Zhang, et al., Fabrication and Properties of Three-Dimensional Nanoporous Graphene Foams with Magnesium Binder, Scripta Materialia, 2016, pp. 89-93, vol. 111, Elsevier. [cited by applicant]