Granted Patent
B2
US 12,646,769 · App. 18/166,655 · Granted Jun 2, 2026
Carbon aerogel-based cathodes for lithium-air batteries
Assignee:
Aspen Aerogels, Inc.
H01M12/06C01B32/15H01M4/382H01M4/42H01M4/583H01M4/663H01M4/8647H01M4/96H01M12/08H01M12/085H01M2004/8689
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Abstract
Nanoporous carbon-based scaffolds or structures, and specifically carbon aerogels and their manufacture and use thereof. Embodiments include a cathode material within a lithium-air battery, where the cathode is formed of a binder-free, monolithic, polyimide-derived carbon aerogel. The carbon aerogel includes pores that improve the oxygen transport properties of electrolyte solution and improve the formation of lithium peroxide along the surface and/or within the pores of the carbon aerogel. The cathode and underlying carbon aerogel provide optimal properties for use within the lithium-air battery.
Claims (18)
1 . A nanoporous carbon composition comprising a polyimide-derived carbon aerogel, the nanoporous carbon composition comprising a plurality of interconnected carbon structures defining a plurality of pores, wherein a width of carbon structures of the interconnected carbon structures is from 2 nm to 5 nm, wherein the plurality of pores comprise pores characterized by a pore size distribution with an average pore size of 150 nm or less and a full width at half maximum from 5 nm to 25 nm, the plurality of pores comprising pores surrounding particles of an electrochemically active species, and wherein the nanoporous carbon composition is characterized by:
a porosity of from 10% to 80%;
a surface area of at least 20 m 2 /g;
a Young's modulus of from 2 GPa to 8 GPa;
a density of from 0.1 grams per cubic centimeter (g/cm 3 ) to 1.5 g/cm 3 ; and
a pore volume in a range from about 1 to about 4 cubic centimeters/gram (cm 3 /g).
2 . The nanoporous carbon composition of claim 1 , wherein the electrochemically active species comprises silicon.
3 . The nanoporous carbon composition of claim 1 , wherein the electrochemically active species is lithium, lithium peroxide, or both.
4 . The nanoporous carbon composition of claim 1 , further comprising a catalyst species, a scavenger species, or both within the nanoporous carbon compositions, wherein the catalyst species and the scavenger species reduce side reactions producing H 2 O, CO 2 , or both.
5 . The nanoporous carbon composition of claim 1 , wherein the carbon aerogel further comprises MoS 2 nanoflakes.
6 . The nanoporous carbon composition of claim 1 , further comprising a surface modification layer on at least a portion of an interior surface of pores of the plurality of pores, wherein the surface modification layer favors formation and confinement of Li 2 O 2 .
7 . The nanoporous carbon composition of claim 6 , wherein the surface modification layer comprises a hydrophobic layer.
8 . The nanoporous carbon composition of claim 6 , wherein the surface modification layer comprises a hydrophobic silica aerogel.
9 . The nanoporous carbon composition of claim 1 , wherein the composition comprises material in the form of a monolithic structure.
10 . The nanoporous carbon composition of claim 1 , wherein the composition comprises material in the form of a powder.
11 . The nanoporous carbon composition of claim 1 , wherein the interconnected carbon structures have a fibrillar morphology.
12 . An energy storage system comprising an electrode formed from the nanoporous carbon composition of claim 1 .
13 . The energy storage system of claim 12 , wherein the electrode is collector-less and includes a tab in direct contact with the nanoporous carbon composition, a metal lead in direct contact with a surface of the nanoporous carbon composition, or both.
Assignments (2)
SECURITY INTEREST
Recorded Aug 28, 2024
From: ASPEN AEROGELS, INC.; ASPEN AEROGELS RHODE ISLAND, LLC
To: MIDCAP FUNDING IV TRUST
Reel/Frame 068792/0245 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Mar 29, 2023
From: ZAFIROPOULOS, NICHOLAS A.; GOULD, GEORGE
To: ASPEN AEROGELS, INC.
Reel/Frame 063156/0732 →
Continuity (3)
Provisional Application
62822710
· Mar 22, 2019
References Cited (172)
US 3612819A
· Gibson
· 1971
[cited by applicant]
US 4474662A
· Makino et al.
· 1984
[cited by applicant]
US 4606955A
· Eastman et al.
· 1986
[cited by applicant]
US 4610863A
· Tewari et al.
· 1986
[cited by applicant]
US 4898753A
· Inoue et al.
· 1990
[cited by applicant]
US 4997804A
· Pekala
· 1991
[cited by applicant]
US 5231162A
· Nagata
· 1993
[cited by applicant]
US 5234966A
· Barringer et al.
· 1993
[cited by applicant]
US 5260855A
· Kaschmitter et al.
· 1993
[cited by applicant]
US 5275796A
· Tillotson et al.
· 1994
[cited by applicant]
US 5284519A
· Gadgil
· 1994
[cited by applicant]
US 5358802A
· Mayer et al.
· 1994
[cited by applicant]
US 5366828A
· Struthers
· 1994
[cited by applicant]
US 5376209A
· Stoakley et al.
· 1994
[cited by applicant]
US 5395805A
· Droege et al.
· 1995
[cited by applicant]
US 5420168A
· Mayer et al.
· 1995
[cited by applicant]
US 5476878A
· Pekala
· 1995
[cited by applicant]
US 5502156A
· St. Clair et al.
· 1996
[cited by applicant]
US 5520960A
· Rancourt et al.
· 1996
[cited by applicant]
US 5565142A
· Deshpande et al.
· 1996
[cited by applicant]
US 5575955A
· Caplan et al.
· 1996
[cited by applicant]
US 5601938A
· Mayer et al.
· 1997
[cited by applicant]
US 5626977A
· Mayer et al.
· 1997
[cited by applicant]
US 5677418A
· Thompson et al.
· 1997
[cited by applicant]
US 5859171A
· Sawasaki et al.
· 1999
[cited by applicant]
US 5908896A
· Mayer et al.
· 1999
[cited by applicant]
US 5962539A
· Perrut et al.
· 1999
[cited by applicant]
US 6194099B1
· Gernov et al.
· 2001
[cited by applicant]
US 6315971B1
· Wallace et al.
· 2001
[cited by applicant]
US 6332990B1
· Mayer et al.
· 2001
[cited by applicant]
US 6399669B1
· Suzuki et al.
· 2002
[cited by applicant]
US 6451965B1
· Kanada et al.
· 2002
[cited by applicant]
US 6544648B1
· Nesbitt et al.
· 2003
[cited by applicant]
US 6586081B1
· Nishinaka et al.
· 2003
[cited by applicant]
US 6670402B1
· Lee et al.
· 2003
[cited by applicant]
US 6726962B1
· Loszewski
· 2004
[cited by applicant]
US 7071287B2
· Rhine et al.
· 2006
[cited by applicant]
US 7811711B2
· Cooper et al.
· 2010
[cited by applicant]
US 8404278B2
· Albrecht et al.
· 2013
[cited by applicant]
US 8414805B2
· Wang
· 2013
[cited by applicant]
US 8999202B2
· Mulik et al.
· 2015
[cited by applicant]
US 9178208B2
· Park et al.
· 2015
[cited by applicant]
US 9745198B2
· Leventis et al.
· 2017
[cited by applicant]
US 9871248B2
· Rayner et al.
· 2018
[cited by applicant]
US RE46771E
· Worsley
· 2018
[cited by examiner]
US 20040132845A1
· Rhine et al.
· 2004
[cited by applicant]
US 20060029857A1
· Cherepy et al.
· 2006
[cited by applicant]
US 20060084707A1
· Ou et al.
· 2006
[cited by applicant]
US 20090053594A1
· Johnson et al.
· 2009
[cited by applicant]
US 20090136809A1
· Wang
· 2009
[cited by applicant]
US 20100310847A1
· Suh et al.
· 2010
[cited by applicant]
US 20110223494A1
· Feaver et al.
· 2011
[cited by applicant]
US 20120134909A1
· Leventis et al.
· 2012
[cited by applicant]
US 20120141889A1
· Lee et al.
· 2012
[cited by applicant]
US 20120152846A1
· Leventis et al.
· 2012
[cited by applicant]
US 20120202112A1
· Yushin et al.
· 2012
[cited by applicant]
US 20130040229A1
· Grigorian et al.
· 2013
[cited by applicant]
US 20130220974A1
· Yushin
· 2013
[cited by applicant]
US 20130224594A1
· Yushin et al.
· 2013
[cited by applicant]
US 20130344391A1
· Yushin et al.
· 2013
[cited by applicant]
US 20140170503A1
· Yushin et al.
· 2014
[cited by applicant]
US 20140272592A1
· Thompkins et al.
· 2014
[cited by applicant]
US 20140287641A1
· Steiner, III
· 2014
[cited by applicant]
US 20140315100A1
· Wang et al.
· 2014
[cited by applicant]
US 20150236372A1
· Yushin et al.
· 2015
[cited by applicant]
US 20150283534A1
· Costantino et al.
· 2015
[cited by applicant]
US 20150325882A1
· Yushin et al.
· 2015
[cited by applicant]
US 20160104882A1
· Yushin et al.
· 2016
[cited by applicant]
US 20160133394A1
· Sakshaug et al.
· 2016
[cited by applicant]
US 20160149278A1
· Woehrle et al.
· 2016
[cited by applicant]
US 20160240840A1
· He et al.
· 2016
[cited by applicant]
US 20160244332A1
· Zhao
· 2016
[cited by examiner]
US 20160344030A1
· Sakshaug et al.
· 2016
[cited by applicant]
US 20170015559A1
· Costantino et al.
· 2017
[cited by applicant]
US 20170062219A1
· Li et al.
· 2017
[cited by applicant]
US 20170098823A1
· Yushin et al.
· 2017
[cited by applicant]
US 20170121483A1
· Poe et al.
· 2017
[cited by applicant]
US 20170170477A1
· Sakshaug et al.
· 2017
[cited by applicant]
US 20170170515A1
· Yushin et al.
· 2017
[cited by applicant]
US 20170233579A1
· Yushin et al.
· 2017
[cited by applicant]
US 20170316888A1
· Geramita et al.
· 2017
[cited by applicant]
US 20170355829A1
· Sakaguchi et al.
· 2017
[cited by applicant]
US 20170373311A1
· Salehi-Khojin et al.
· 2017
[cited by applicant]
US 20180043656A1
· Song et al.
· 2018
[cited by applicant]
US 20180067262A1
· Larson et al.
· 2018
[cited by applicant]
US 20180145328A1
· Mullins et al.
· 2018
[cited by applicant]
US 20180151884A1
· Yushin et al.
· 2018
[cited by applicant]
US 20180331356A1
· Feaver et al.
· 2018
[cited by applicant]
US 20180346337A1
· Tour et al.
· 2018
[cited by applicant]
US 20190006672A1
· Yushin et al.
· 2019
[cited by applicant]
US 20190062517A1
· Steiner, III et al.
· 2019
[cited by applicant]
US 20190157682A1
· Ho et al.
· 2019
[cited by applicant]
US 20190198837A1
· Yushin et al.
· 2019
[cited by applicant]
US 20190259546A1
· Kron et al.
· 2019
[cited by applicant]
US 20190326589A1
· Ho et al.
· 2019
[cited by applicant]
US 20200083542A1
· Yushin et al.
· 2020
[cited by applicant]
CN 102277648A
· 2011
[cited by applicant]
CN 104241734A
· 2014
[cited by applicant]
CN 106207142A
· 2016
[cited by applicant]
CN 106450116A
· 2017
[cited by examiner]
CN 109301263A
· 2019
[cited by applicant]
DE 102015207552A1
· 2016
[cited by applicant]
EP 0987294A1
· 2000
[cited by applicant]
EP 1205512A1
· 2002
[cited by applicant]
WO 2002052086A2
· 2002
[cited by applicant]
WO 2004009673A1
· 2004
[cited by applicant]
WO 2016127084A1
· 2016
[cited by applicant]
WO 2018095283A1
· 2018
[cited by applicant]
WO 2018095285A1
· 2018
[cited by applicant]
WO 2018200827A1
· 2018
[cited by applicant]
Machine English translation of CN106450116A originally published to Chen Feb. 22, 2017 (Year: 2017).
[cited by examiner]
Swapnil et al, Decoration of Ultrathin MoS Nanoflakes over MWCNTs: Enhanced Supercapacitive Performance through Electrode to Symmetric All-Solid-State Device, Nov. 13, 2017, Chemistry Select, vol. 2 / Issue 32 (Year: 20…
[cited by examiner]
Kondrat et al, Effect of pore size and its dispersity on the energy storage in nanoporous supercapacitors, Jan. 17, 2012, Royal Society of Chemistry (Year: 2012).
[cited by examiner]
Patel et al, Vertically oriented MoS2 nanoflakes coated on 3D carbon nanotubes for next generation Li-ion batteries, Nov. 9, 2016, IOPScience Nanotechnology 1-10 (Year: 2016).
[cited by examiner]
Mirzaeian et al, Preparation of controlled porosity carbon aerogels for energy storage in rechargeable lithium oxygen batteries, Aug. 5, 2009, Electrochimica Acta 54 (2009) 7444-7451 (Year: 2009).
[cited by examiner]
Lan et al. ‘Fabrication of nano-sized attapulgite-baased aerogels as anode material for lithium ion batteries.’ J. Mater. Sci. 53(2018): 2054-2064.
[cited by applicant]
Bekyarova et al. “Structure and Physical Properties of Tailor-Made Ce, Zr-Doped Carbon Aerogels”, Advanced Materials, 12, [21] (2000) 1625-1628.
[cited by applicant]
Biesmans, et al., “Polyurethane based organic aerogels and their transformation into carbon aerogels”, Journal of Non-Crystalline Solids, 225, (1998) 64.
[cited by applicant]
Bock, et al., “Influence of Monomer and Catalyst Concentration on RF and Carbon Aerogel Structure”, Journal of Non-Crystalline Solids, 225 (1998), 69.
[cited by applicant]
Chidambareswarapattar et al. “One-step room-temperature synthesis of fibrous polyimide aerogels from anhydrides and isocyanates and conversion to isomorphic carbons.” J. Mater. Chem. 20(2010): 9666-9678.
[cited by applicant]
Dai et al. “Metal organic framework-templated synthesis of sulfur-doped core-sheath nanoarrays and nanoporous carbon for flexible all-solid-state asymmetric supercapacitors.” Nanoscale. 10(2018): 15454-15461.
[cited by applicant]
Frackowiak et al. “Carbon materials for the electrochemical storage of energy in capacitors,” Carbon, 39(2001): 937.
[cited by applicant]
Gash et al. “New Sol-gel Synthetic Route to Transition and Main-group Metal Oxide Aerogels Using Inorganic Salt Precursors.” J. Non-Crystall. Solids. 285(2001): 22.
[cited by applicant]
Glora et al. “Integration of Carbon Aerogels in PEM Fuel Cells.” J. Non-Crystall. Solids. 285(2001): 283-287.
[cited by applicant]
Gorgolis et al. “Graphene aerogels: a review.” 2D Mater. 4.3(2017): 1-21.
[cited by applicant]
Guo et al., Polyimide Aerogels Cross-Linked through Amine Funclionalized Polyoligomeric Silsesquioxane, ACS Appl. Maler. Interfaces 2011, 3, 546-552.
[cited by applicant]
Hanzawa, et al., “Activated carbon aerogels”, Langmuir, 12, [26], (1996) 6167.
[cited by applicant]
Hutagalung et al. “Optical and Electrical Characlerislics of Silicon Nanowires Prepared by Electroless Etching”, Nanoscale Research Letters, vol. 12, 2017, pp. 425.
[cited by applicant]
International Search Report and Written Opinion of the International Searching Authority in PCT/US2020/020148, Sep. 3, 2020.
[cited by applicant]
International Search Report and Written Opinion of the International Searching Authority in PCT/US2020/024086, Oct. 1, 2020.
[cited by applicant]
International Search Report and Written Opinion of the International Searching Authority in PCT/US2020/024113, Oct. 1, 2020.
[cited by applicant]
Kistler, “Coherent Expanded Aerogels,” J. Phys Chem. 1932, 36(1), pp. 52-64.
[cited by applicant]
Eventis et al., Isocyanate-Derived Organic Aerogels: Polyureas, Polyimides, Polyamides, MRS Proceedings, 1306 (2011).
[cited by applicant]
Leventis et al., Polyimide Aerogels by Ring-Opening Metathesis Polymerization {ROMP), Chem. Mater. 2011, 23, 8, 250-2261.
[cited by applicant]
Li et al. “Novel approach toward a binder-free and current collector-free anode configuration: highly flexible hanoporous carbon nanotube electrodes with strong mechanical strength harvesting improved lithium storage.” …
[cited by applicant]
Maldonado-Hadar, et al., “Synthesis and textural characteristics of organic aerogels, transition-metal-containing organic aerogels and their carbonized derivatives,” Carbon, 37 (1999) 1199.
[cited by applicant]
Meador et al., Mechanically Strong, Flexible Polyimide Aerogels Cross-Linked with Aromatic Triamine, ACS Appl. Mater. Interfaces, 2012, 4 (2), pp. 536-544.
[cited by applicant]
Meador et al., Polyimide Aerogels with Amide Cross-Links: A Low Cost Alternative for Mechanically Strong Polymer Aerogels, ACS Appl. Mater. Interfaces 2015, 7, 1240-1249.
[cited by applicant]
Miller et al. “Morphology and electrochemistry of ruthenium/carbon aerogel nanostructures”, Langmuir, 15 (1999) 799.
[cited by applicant]
Nguyen et al., Development of High Temperature, Flexible Polyimide Aerogels, American Chemical Society, proceedings published 2011.
[cited by applicant]
Nitze et al. “A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithum sulfur batteries.” Sci. Rep. 6(2016).
[cited by applicant]
Pei et al., Preparation and Characterization of Highly Cross-Linked Polyimide Aerogels Based on Polyimide Containing Trimelhoxysilane Side Groups, Langmuir 2014, 30, 13375-13383 2014.
[cited by applicant]
Pekala, et al., “Carbon Aerogels for Electrochemical Applications”, Journal of Non-Crystalline Solids, 225 (1998): 74.
[cited by applicant]
Pelricevic, et al., “Planar fiber reinforced carbon aerogels for applications in PEM fuel cells”, Carbon, 39 (2001) g51-867.
[cited by applicant]
Saliger, et al., “High surface area carbon aerogels for supercapacitors”, Journal of Non-Crystalline Solids, 225(1998): 81.
[cited by applicant]
Singh et al. “Sulfur-Doped Laser-Induced Porous Graphene Derived from Polysulfone-Class Polymers and Membranes” ACS Nano. Dec. 14, 2017 vol 12, p. 289-297.
[cited by applicant]
Via et al. “Tensile modulus modeling of carbon black/polycarbonate, carbon nanotube/polycarbonate, and exfoliated graphite nanoplatelet/polycarbonate composites.” J. Appl. Poly. Sci. (2011).
[cited by applicant]
Wang et al. “Nanostructured Si—C composite anodes for lithium-ion batteries”, Electrochemistry Communications, Elsevier, Amsterdam, NL, vol. 6, No. 7, Jun. 2, 2004 (Jun. 2, 2004), pp. 689-692.
[cited by applicant]
Wang et al. “Preparation and performances of carbon aerogel microspheres for the application of supercapacitor.” J. Solid State Electrochem. 15(2011): 643-648.
[cited by applicant]
Wang et al.: “A dual pore carbon aerogel based air cathode for a highly rechargeable lithium-air battery”, J. Power Sources, vol. 272, Sep. 11, 2014 (Sep. 11, 2014), pp. 1061-1071.
[cited by applicant]
Wang, et al., “Carbon cloth reinforced carbon aerogel films derived from resorcinol formaldehyde”, J. Porous Materials, 8 (2001) 159.
[cited by applicant]
Wang, et al., “Electrical Transport Properties of Carbon Aerogels”, J. of Porous Materials, 8 (2001) 167.
[cited by applicant]
Worsley et al. “Mechanically Robuse and Electrically Conductive Carbon Nanotube Foams.” Appl. Phys. Lett. 94 (2009): 073115.
[cited by applicant]
Ye et al., “A New Electrocatalyst Consisting of a Molecularly Homogeneous Platinum-Aerogel Nanocomposite.” Can. J. Chem., 75 (1997) 1666.
[cited by applicant]
Yet et al. “A new fuel cell electrocatalyst based on carbonized polyacrylonitrile foam”, J. Electrochem. Soc., 144.1 (1997) 90.
[cited by applicant]
Zhang et al. Graphene/carbon aerogels derived from graphene crosslinked polyimide as electrode materials for supercapacitors, RSC Adv., 2015, 5, 1301.
[cited by applicant]