New Territories of Sustainable Batteries by Carbon-Based Materials

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1 New Territories of Sustainable Batteries by Carbon-Based Materials Xingfeng Wang, Dr. Clement Bommier, Zhifei Li, Dr. Zhenyu Xing, Dr. Zelang Jian, Dr. Xianyong Wu, and Prof. Xiulei Ji Department of Chemistry Oregon State University

2 v Hydronium ion storage v Energetics of ion insertion in carbons: anions and cations 2

3 Earth-Abundancy of Elements Gordon B. Haxel, Sara Boore, and Susan Mayfield from USGS 3

4 Production Scale of Purified Minerals Vesborg and Jaramillo RSC. Adv. 2012, 2,

5 Molecular Solids: Hosts for H 3 O + Xingfeng Wang, Ji et al. Angew. Chem. Int. Ed. 2017, 56, Xing, Ji et al. Energy Storage Materials, 2016, 2, Luo, Ji, et al. Adv. Energy Mater., 2014, 4,

6 Structural and Computational Studies Confirm Reversible Hydronium Storage Wang, Bommier, Greaney, Ji et al., Angew. Chem. Int. Ed. 2017, 56,

7 Hydronium is a meaningful charge carrier for batteries Grotthuss mechanism may be applicable 7

8 v Hydronium ion batteries v Energetics of ion insertion in carbons 8

9 Dual-Ion Batteries/Dual-Graphite Batteries McCullough et al. U.S. Patent 4,830,938, 1989 Hofmann and Rüdorff Trans. Faraday Soc. 1938,1017 Armand, M.; Touzain, P. Mater. Sci. Eng. 1977, 31,

10 The Challenge of DIBs: Cathode Operation Potential Is Simply Too High! Winter and Placke, et al. Energy Environ. Sci., 2014, 7,

11 Thermodynamics of Inserting One Anion to Graphite in a Graphite/Metal Cell If we do not consider the entropy change of desolvation and ohmic IR drop G = -ev H = (E (C+A-) + E (n+1)m + H desolv. of M+ + H desolv. of A- ) (E C + E nm ) G = -ev H = E (C+A-) E C + E M + H desolv. of M+ + H desolv. of A- Ji et al. ACS Energy Letters an invited perspective accepted 11

12 Less Dense Hydrocarbons As Anion-Insertion Cathode Density: 1.47 g cm -3 vs 2.23 g cm -3 (graphite) Ismael Rodríguez-Pérez, Lerner, Carter, Ji et al. ACS Energy Letters 2016, 1,

13 Graphite is not uniquely redox amphoteric Oxidative insertion can be generic The operation potentials correlate more to the solid structures than to the molecules themselves 13

14 Na Does Not Intercalate Graphite LiC 6 GIC: 372 mah/g NaC 64 GIC: 35 mah/g Wang, C. Nat. Commun. 2014, 5, Jache, B.; Adelhelm, P. Angew. Chem., Int. Ed. 2014, 53,

15 Ion Size: The Decisive Factor? Li + Na + K + Stage III Stage II Stage I Schleede, A.; Wellmann, M. Kristallogr.-Cryst Mater. 1932, 83,

16 Reversible Electrochemical Insertion of K in Graphite Zelang Jian, Ji et al. J. Am. Chem. Soc., 2015, 137,11566 Komaba et al. Electrochem. Commun. 2015, 60, Luo, Hu et al. Nano Lett. 2015, 15,

17 Reversible Electrochemical Staging of K-GICs Jian, Ji et al. J. Am. Chem. Soc., 2015, 137,11566,

18 Hard-Soft Composite Carbon: Optimal for Cycling and Rate Jian, Su, Ji et al. Advanced Functional Materials (2017) DOI: /adfm

19 Non-Aqueous KIBs: An Emerging Field of Energy Storage Until June 25, 2017 Goodenough et al. J. Am. Chem. Soc., 2017, 139, Komaba et al. J. Mater. Chem. A, 2017,5, 4325 Ji et al. Electrochem. Commun. 77, 2017, 54 Nazar ACS Energy Lett. 2017, 2, Ji, Chem. Mater In press An invited Perspective Mai et al. Nano Lett., 2017, 17,

20 Why Non-Aqueous K-Ion Batteries? v Favorable potentials Redox Potentials In Water vs. SHE (V) In PC vs. SHE (V) Li + /Li Na + /Na K + /K Rb + /Rb v Compatible with the LIB carbon anode infrastructure Similar specific energy as NIBs Eftekhari, Jian, Ji ACS Appl. Mater. Interfaces, 2017, 9 (5), pp Komaba et al. Electrochem. Commun. 2015, 60,

21 Debated Mechanisms of Na-Ion Storage in Hard Carbon 21 Clem Slope capacity: Na intercalates turbostratic nanodomains Plateau Capacity: Na-sorption (nanoplating) in nanopores Slope capacity: Na-defects binding Plateau Capacity: Na intercalates turbostratic nanodomains Stevens and Dahn, J. Electrochem. Soc. 147, 1271, (2000) Bommier, Ji et al. Nano Lett., 2015, 15, 5888 Grey et al. Chem. Commun., 2016,52, 12430

22 Hard Carbon and Soft Carbon Hard Carbon Soft Carbon Franklin, R. E. Acta Cryst Jian, Bommier, Ji et al. Chem. Mater., 2017, 29 (5), pp

23 Thermodynamics of Inserting One Cation to Carbon in a Carbon/Metal Half Cell If we do not consider the entropy change of desolvation and ohmic IR drop G = -ev H = (E (C-M+) + E (n-1)m + H desolv. of M+ + H solv. of M+ ) (E C + E nm ) G = -ev H = (E (C-M+) - E M ) E C 23

24 Vacancy Defects Lead to High Sloping Potentials Monovacancy Divacancy Large-vacancy ev -1.1 ev ev ev Li, Bommier, Dolgos, Greaney, Ji et al. Advanced Energy Materials, DOI: /aenm

25 Decrease Vacancy Defects è Less Sloping Capacity G(r) = 2 π Q(S(Q) 1)sin(Qr) dq = 4πρ 0 r(g(r) 1) Bommier, Ji Nano Lett., 2015, 15,

26 Increase Vacancy or Heteroatom Defects è More Sloping Capacity HC S B P Electrodes HC P-HC B-HC S-HC Sodiation Desodiation Correlation: sloping capacity and defects Li, Dolgos, Greaney, Ji et al. Advanced Energy Materials, DOI: /aenm

27 A Design Principle More defective Expanded Structure Li, Ji et al. under preparation Li, Dolgos, Greaney, Ji et al. Advanced Energy Materials, DOI: /aenm

28 Conclusions v Hydronium ion storage: a promising new area v Anion insertion into carbon: energetics v Non-aqueous KIBs competitive to NIBs v An alternative mechanism for Na-ion storage in hard carbon

29 Collaborators Jun Lu, Tianpin Wu, Khalil Amine (Argonne National Laboratory) P. Alex Greaney (University of California Riverside) Chongmin Wang (Pacific Northwest National Laboratory) Dong Su (Brookhaven National Laboratory) Joerg Neuefeind (Oak Ridge National Laboratory) 29

30 Energy Materials Chemistry Group 30

31 Acknowledgements 2016 NSF CAREER Award OSU Venture Capital Fund 31

32 Thank you for your attention! Questions? 32