IP Library › Granted Patent US 12,245,507
Granted Patent B2
US 12,245,507 · App. 17/609,159 · Granted Mar 4, 2025

Aerosol jet printing and sintering of thermoelectric devices

Inventors: Yanliang Zhang (South Bend, IN); Mortaza Saeidi-Javash (South Bend, IN)
Assignee: UNIVERSITY OF NOTRE DAME DU LAC
H10N10/852C09D7/61C09D7/66C09D11/322C09D11/36C09D11/38C09D11/52H10N10/01
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Quick Facts
Patent No.
US 12,245,507
App. No.
17/609,159
Granted
Mar 4, 2025
Kind
B2
Abstract

Methods, ink compositions, and 3D conformal printed flexible films. The method may include aerosol jet printing a thermoelectric ink composition, followed by photonic or other sintering of the ink to remove surfactant included therein, and to convert the thermoelectric nanoparticles of the ink composition into a dense structure capable of charge carrier transport. The ink compositions may be solution-processed semimetal-chalcogenides (e.g., Te containing materials) in a suitable carrier (e.g., polyol(s), alcohol(s), etc.). A surfactant (e.g., PVP) may be present in the ink. Within seconds of photonic sintering, the electrical conductivity of the printed film is dramatically increased from non-conductive to a value on the order of at least 1×10 4 S/m. The films may demonstrate a room-temperature power factor of at least 500 μWm −1 K −2 . The realized values of 730-2200 μWm −1 K −2 achieved are among the highest values reported for flexible thermoelectric films. The film is durable (e.g., 500 bending cycles with no significant performance drop).

Claims (46)

1. An aerosol jet printable ink composition comprising:

a carrier including two different polyols and a lower alcohol having 1-4 carbon atoms;

thermoelectric nanoparticles dispersed in the carrier; and

a surfactant for preventing or minimizing agglomeration of the nanoparticles, wherein the first polyol and second polyol being present at a weight ratio of from 2:1 to 10:1.

2. The ink composition as recited in claim 1 , wherein the thermoelectric nanoparticles comprise a chalcogenide.

3. The ink composition as recited in claim 2 , wherein the chalcogenide comprises Te.

4. The ink composition as recited in claim 1 , wherein the thermoelectric nanoparticles comprise a thermoelectric material comprising Bi, Te, and Se, or a thermoelectric material comprising Sb and Te.

5. The ink composition as recited in claim 1 , wherein the thermoelectric nanoparticles comprise at least one of Bi 2 Te 2.7 Se0 .3 or Sb 2 Te 3 .

6. The ink composition as recited in claim 1 , wherein the thermoelectric nanoparticles comprise an Sb 2 Te 3 -Te composite including Sb 2 Te 3 nanoplates and Te nanorods.

7. The ink composition as recited in claim 1 , wherein the carrier comprises ethylene glycol, glycerol, and ethanol.

8. The ink composition as recited in claim 1 , wherein the two different polyols comprises from 20-60% by weight of the carrier, and the alcohol comprises from 40-80% by weight of the carrier.

9. The ink composition as recited in claim 1 , wherein the thermoelectric nanoparticles comprise nanoplates.

10. The ink composition as recited in claim 1 , wherein the carrier comprises at least 60%, at least 65%, at least 70%, at least 80%, or from 80-90% by weight of the ink composition.

11. The ink composition as recited in claim 1 , wherein the nanoparticles comprise up to 40%, up to 35%, up to 30%, up to 25%, up to 20%, or from 10-20% by weight of the ink composition.

12. The ink composition as recited in claim 1 , wherein the surfactant comprises polyvinylpyrrolidone.

13. The ink composition as recited in claim 1 , wherein the ink composition is shelf-stable for at least 3 months, or at least 6 months.

14. An aerosol jet printable ink composition comprising:

a liquid carrier including at least one polyol and a lower alcohol having 1-4 carbon atoms;

thermoelectric nanoparticles dispersed in the carrier; and

a surfactant for preventing or minimizing agglomeration of the nanoparticles, wherein the at least one polyol comprises from 20-60% by weight of the carrier, and the alcohol comprises from 40-80% by weight of the carrier.

15. An aerosol jet printable ink composition comprising:

a carrier including at least one polyol and a lower alcohol having 1-4 carbon atoms, wherein the carrier comprises at least 60% by weight of the ink composition;

thermoelectric nanoparticles dispersed in the carrier; and

a surfactant for preventing or minimizing agglomeration of the nanoparticles.

16. The ink composition as recited in claim 1 , wherein the composition, once sintered using photonic sintering with intense pulsed light, results in a film that exhibits an electrical conductivity value on the order of at least 1×10 4 S/m.

17. The ink composition as recited in claim 15 , wherein the carrier comprises at least 65% by weight of the ink composition.

18. The ink composition as recited in claim 15 , wherein the carrier comprises at least 70% by weight of the ink composition.

19. The ink composition as recited in claim 15 , wherein the carrier comprises at least 80% by weight of the ink composition.

20. The ink composition as recited in claim 15 , wherein the carrier comprises from 80-90% by weight of the ink composition.

21. The ink composition as recited in claim 16 , wherein the thermoelectric nanoparticles comprise a chalcogenide.

22. The ink composition as recited in claim 16 , wherein the thermoelectric nanoparticles comprise a thermoelectric material comprising Bi, Te, and Se, or a thermoelectric material comprising Sb and Te.

23. The ink composition as recited in claim 16 , wherein the thermoelectric nanoparticles comprise at least one of Bi 2 Te 2.7 Se0 .3 or Sb 2 Te 3 .

24. The ink composition as recited in claim 1 , wherein the thermoelectric nanoparticles comprise an Sb 2 Te 3 -Te composite including Sb 2 Te 3 nanoplates and Te nanorods.

25. The ink composition as recited in claim 15 , wherein the carrier comprises two different polyols, the first polyol and second polyol being present at a weight ratio of from 2:1 to 10:1.

26. The ink composition as recited in claim 15 , wherein the carrier comprises ethylene glycol, glycerol, and ethanol.

27. The ink composition as recited in claim 15 , wherein the at least one polyol comprises from 20-60% by weight of the carrier, and the alcohol comprises from 40-80% by weight of the carrier.

28. The ink composition as recited in claim 15 , wherein the nanoparticles comprise up to 40% by weight of the ink composition.

29. The ink composition as recited in claim 15 , wherein the nanoparticles comprise up to 35% by weight of the ink composition.

30. The ink composition as recited in claim 15 , wherein the nanoparticles comprise up to 30% by weight of the ink composition.

31. The ink composition as recited in claim 15 , wherein the nanoparticles comprise up to 25% by weight of the ink composition.

32. The ink composition as recited in claim 15 , wherein the nanoparticles comprise up to 20% by weight of the ink composition.

33. The ink composition as recited in claim 15 , wherein the nanoparticles comprise from 10-20% by weight of the ink composition.

34. The ink composition as recited in claim 15 , wherein the surfactant comprises polyvinylpyrrolidone.

35. The ink composition as recited in claim 1 , wherein the ink composition, once sintered using photonic sintering with intense pulsed light, results in a film that demonstrates a room temperature power factor of at least 500 mWm −1 K −2 .

36. The ink composition as recited in claim 1 , wherein the ink composition, once sintered using photonic sintering with intense pulsed light, results in a flexible film, such that the flexible film exhibits little or no change in electrical conductivity or resistivity or power factor after 500 bending cycles at a bending radius from 1 to 10 mm.

37. The ink composition as recited in claim 1 , wherein the ink composition, once sintered using photonic sintering with intense pulsed light, results in a film that can be 3D printed onto any 3D conformal surface.

Assignments (3)
CONFIRMATORY LICENSE Recorded May 23, 2025
From: UNIVERSITY OF NOTRE DAME
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 071342/0872 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 27, 2025
From: ZHANG, YANLIANG; SAEIDI-JAVASH, MORTAZA
To: UNIVERSITY OF NOTRE DAME DU LAC
Reel/Frame 070012/0328 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 24, 2025
From: SAEIDI-JAVASH, MORTAZA; ZHANG, YANLIANG
To: UNIVERSITY OF NOTRE DAME DU LAC
Reel/Frame 070001/0767 →
Continuity (4)
Provisional Application 62887845 · Aug 16, 2019
Provisional Application 62862515 · Jun 17, 2019
Provisional Application 62858848 · Jun 7, 2019
Related Publication 20220209091A1 · Jun 30, 2022
References Cited (44)
US 6274802B1 · Fukuda et al. · 2001 [cited by applicant]
US 7816006B2 · Yadav et al. · 2010 [cited by applicant]
US 8519505B2 · Hiroshige et al. · 2013 [cited by applicant]
US 8803141B2 · Mitzi et al. · 2014 [cited by applicant]
US 9299905B2 · Kim et al. · 2016 [cited by applicant]
US 10217922B2 · Petkie · 2019 [cited by applicant]
US 10283357B2 · Dolzhnikov et al. · 2019 [cited by applicant]
US 20070034838A1 · Imaoka et al. · 2007 [cited by applicant]
US 20140035995A1 · Chou et al. · 2014 [cited by applicant]
US 20160104829A1 · Hayashi · 2016 [cited by examiner]
US 20160172572A1 · Span et al. · 2016 [cited by applicant]
US 20190035996A1 · Chen · 2019 [cited by examiner]
EP 0369340A1 · 1990 [cited by applicant]
JP 2013175660A · 2013 [cited by applicant]
KR 101420022 · 2014 [cited by examiner]
WO 2010071749 · 2010 [cited by applicant]
WO 2017065306 · 2017 [cited by applicant]
WO 2017156296 · 2017 [cited by applicant]
Jo et al. (“Ink Processing for Thermoelectric Materials and Power Generating Devices”), Adv. Mater. 2019, 31, 1804930. First available Dec. 28, 2018. [cited by examiner]
Shah et al. (“Solution-Based Synthesis and Processing of Metal Chalcogenides for Thermoelectric Applications”), Appl. Sci. 2019, 9, 1511. Published Apr. 11, 2019. [cited by examiner]
Shi et al. (“Hydrothermal synthesis and thermoelectric transport properties of Sb2Te3—Te heterogeneous nanostructures”), CrystEngComm, 2013, 15, 2978. [cited by examiner]
English machine translation of Yoo et al. (KR 10 1420022), published Jul. 9, 2014. [cited by examiner]
Park et al. (“High-performance shape-engineerable thermoelectric painting”); Nature Communications, 7, Article No. 13403 ( 2016). [cited by examiner]
Ou et al. (“Fully Printed Organic-Inorganic Nanocomposites for Flexible Thermoelectric Applications”); ACS Appl. Mater. Interfaces 2018, 10, 23, 19580-19587. [cited by examiner]
International Search Report and Written Opinion issued in PCT/US2020/036609 mailed Oct. 16, 2020. [cited by applicant]
Varghese, “Additive Manufacturing of High Performance Flexible Thermoelectric Generators Using Nanoparticle Inks” May 2019, p. 66, para. 2, p. 66, para. 1, p. 54, para 1, p. 53, para 2. [cited by applicant]
Dun, Chaochao et al, “Flexible thermoelectric fabrics based on self-assembled tellurium nanorods with a large power factor,” Physical Chemistry Chemical Physics, Jan. 6, 2015, pp. 8591-8595. [cited by applicant]
Dun, Chaochao et al, “Layered Bi2Se3 nanoplate/polyvinylidene fluoride composite based n-type thermoelectric fabrics.” ACS Applied Materials & Interfaces, Mar. 23, 2015, pp. 7054-7059. [cited by applicant]
Dun, Chaochao et al, “Flexible n-type thermoelectric films based on Cu-doped Bi2Se3 nanoplate and Polyvinylidene Fluoride composite with decoupled Seebeck coefficient and electrical conductivity.” Nano Energy, Oct. 22, … [cited by applicant]
Dun, Chaochao et al, “2D chalcogenide nanoplate assemblies for thermoelectric applications.” Advanced Materials, Jan. 4, 2017, pp. 1-8. [cited by applicant]
Zhou, Chongjian et al, “Environmentally benign synthesis of high-quality, band gap-tunable, homogeneous Te/Se alloyed nanowires.” RSC Advances 5.85, Jul. 31, 2015. [cited by applicant]
Dun, Chaochao et al, “Bi2Te3 Plates with Single Nanopore: The Formation of Surface Defects and Self-Repair Growth.” Chemistry of Materials, Jan. 30, 2018, pp. 1965-1970, vol. 30. [cited by applicant]
Dun, Chaochao et al, “Topological doping effects in 2D chalcogenide thermoelectrics,” 2D Materials, Feb. 7, 2018, pp. 1-8, vol. 5, Issue 4. [cited by applicant]
Dun, Chaochao et al, “Flexible Thermoelectric Fabrics Based on Layered Topological Insulator Bi2Se3 Nanoplates/Polyvinylidene Fluoride Composite,” Bulletin of the American Physical Society, Nov. 14, 2014, pp. 1-19. [cited by applicant]
Dun, Chaochao, “Low-dimensional chalcogenide based thermoelectric composites,” Wake Forest University, Doctoral Thesis, May 2017, pp. 1-175. [cited by applicant]
Sumithra, S. et al, “Enhancement in thermoelectric figure of merit in nanostructured Bi2Te3 with semimetal nanoinclusions,” Advanced Energy Materials, Sep. 9, 2011, pp. 1141-1147, vol. 1. [cited by applicant]
Min, Yuho et al, “Surfactant-Free Scalable Synthesis of Bi2Te3 and Bi2Se3 Nanoflakes and Enhanced Thermoelectric Properties of Their Nanocomposites,” Advanced Materials, Nov. 15, 2012, pp. 1425-1429, vol. 25. [cited by applicant]
Liu, Yu, “Bottom-up Engineering of Chalcogenide Thermoelectric Nanomaterials,” Dissertation at Universitat de Barcelona, Apr. 2018, pp. 1-240. [cited by applicant]
Schumacher, Christian et al, “Optimizations of Pulsed Plated p and n-type Bi2Te3-Based Ternary Compounds by Annealing in Different Ambient Atmospheres,” Advanced Energy Materials, Jun. 7, 2012, pp. 95-104. [cited by applicant]
Varghese, Tony et al, “High-performance and flexible thermoelectric films by screen printing solution-processed nanoplate crystals,” Scientific Reports, Sep. 12, 2016, pp. 1-6, vol. 6: 33135. [cited by applicant]
Gaul, Andrew, “A Theoretical Study of Enhancing Thermoelectric Efficiency in Pnictogen-Chalcogen Alloys via Doping, Strain, and Nanostructuring,” Dissertation at Rensselaer Polytechnic Institute, Mar. 2018, pp. 1-24. [cited by applicant]
Zhang, Yanliang, “Thermal and thermoelectric transport in nanostructured materials from pnictogen chalcogenide nanoplate crystals,” Dissertation at Rensselaer Polytechnic Institute, Nov. 2011, pp. 1-24. [cited by applicant]
Tangirala, Ravisubhash et al, “Modular inorganic nanocomposites by conversion of nanocrystal superlattices,” Angewandte Chemie International Edition, Mar. 18, 2010, pp. 2878-288, vol. 49. [cited by applicant]
Mehta, Rutvik J. et al, “A new class of doped nanobulk high-figure-of-merit thermoelectrics by scalable bottom-up assembly.” Nature materials, as early as Jan. 1, 2012, pp. 1-12. [cited by applicant]