A New Cathode Material for Potassium-Ion Batteries
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1 A New Cathode Material for Potassium-Ion Batteries Monday, 29 May :40-14:00 Abstract #: A Haegyeom Kim, Jae Chul Kim, Shou-Hang Bo, Tan Shi, Deok-Hwang Kwon, and Gerbrand Ceder* Post-doc Fellow in Ceder group Materials Sciences Division Lawrence Berkeley National Laboratory H. Kim et al. Adv. Energy Mater (2017) 1 Download these slides at
2 Toward Large Scale Applications Low cost High energy High power High stability L. Gaines et al. Report#ANL/ESD-42. Argonne National Laboratory May (2000) 2
3 3 Global market for Li-ion batteries increases 22%/year. 35% of all lithium are already used by Li-ion industry. Li resources are geographically localized: rapid variations in price with demand. "An Increasingly Precious Metal." The Economist. The Economist Newspaper, 14 Jan ü Li-ion battery technology cannot meet the increasing demands on large scale energy storage systems, including electric vehicles and grids.
4 Concentration in seawater (mg/l) Cl - 18,980 Na + 10,556 SO 4 2-2,649 Mg 2+ 1,262 Ca K Li Accessed May Li 2 CO 3 Na 2 CO 3 K 2 CO 3 $7,000/ton $240/ton $450/ton Cu Al Al $5,000/ton $1,500/ton $1,500/ton accessed March
5 Standard potentials (vs. SHE) Li/Li + Na/Na + K/K + Aqueous PC solvent EC/DEC solvent (relative value) Redox potential of electrode ü Lower standard redox potential of alkali ions Working voltage è Potentially higher working voltage of battery system Standard redox potential of A/A + Standard redox potential of A/A + Komaba et al. Electrochem. Commun. 2015, 60, 172, 5
6 ü Graphite can store and release K ions, but not Na. ü It indicates we already have a good anode material!!! Komaba et al. Electrochem. Commun. 2015, 60, 172, 6
7 30 Number of papers Search at March 1 st, Year ü Recently, K-ion batteries attract much attention. H. Kim et al.in preparation. 7
8 ü Transition metal component èhigh redox activity ü 2-dimensional K migration pathways ègood rate capability ü Rigid oxide framework è Good cycle stability Layered transition metal oxides (K x TMO 2, TM= Transition Metal) can be promising cathode candidates for K-ion batteries. Xiang et al. J. Electrochem. Soc. 2015, 162, A1662 8
9 ü P2-type K 0.6 CoO 2 was synthesized by a conventional solid-state method. ü The smaller K content (compared to Na) likely results from the larger ionic size of K. H. Kim et al. Adv. Energy Mater (2017) 9
10 ü Reversible K storage in K 0.6 CoO 2 is observed in the electrochemical cells. H. Kim et al. Adv. Energy Mater (2017) 10
11 Time (Hours) Voltage (V vs. K) Two theta (Deg. Mo) ü Reversible K release/storage in K 0.6 CoO 2 is observed in the electrochemical cells. H. Kim et al. Adv. Energy Mater (2017) 11
12 ü Upon charge, (008) peak moves to lower angle, indicating the increase of CoO 2 slab distance. ü (008) peak moves back to the original position, indicating reversible reactions. H. Kim et al. Adv. Energy Mater (2017) 12
13 13 O3-LiCoO 2 P2-Na 0.74 CoO 2 P2-K 0.6 CoO 2 J. Electrochem. Soc. 1994, 141, 2972 Nat. Mater. 2011, 10, 74 1 V per 0.6 Li transfer 1.8 V per 0.52 Na transfer 2.3 V per 0.35 K transfer (1.66 V/Li + ) (3.46 V/Na + ) (6.57 V/K + ) Slope of voltage curves increases
14 14 O3-LiCoO 2 P2-Na 0.74 CoO 2 P2-K 0.6 CoO 2 J. Electrochem. Soc. 1994, 141, 2972 Nat. Mater. 2011, 10, 74 Ionic size of alkali ions ü Li Less + (0.76 screening Å) of electrostatics Na + (1.02 between Å) K ions by K oxygen + (1.38 Å) results in much larger effective interaction, forming remarkable amount of phase Slab distance for alkali ions in transitions. LiCoO 2 (2.64 Å) Na 0.74 CoO 2 (3.43 Å) K 0.6 CoO 2 (4.25 Å)
15 O-type structure P-type structure 100 Voltage (V vs. K) , 120, 100, 70, 10, 2 ma g Capacity (mah g -1 ) Capacity (mah g -1 ) ma g ma g ma g ma g ma g ma g Number of cycles ü P2-K 0.6 CoO 2 can provide a reversible capacity of ~43 mah/g at 150 ma/g ü Good rate capability would be attributable to P2 structure. H. Kim et al. Adv. Energy Mater (2017); Clement et al. J. Electrochem. Soc. 2015, 162, A2589, Mo et al. Chem. Mater. 2014, 26,
16 ü P2-K 0.6 CoO 2 cathode can maintain ~60% of the initial capacity after 120 cycles ü After refreshing the cells, the capacity was recovered. H. Kim et al. Adv. Energy Mater (2017) 16
17 ü Even after cycling, the crystal structure is not noticeably changed. H. Kim et al. Adv. Energy Mater (2017) 17
18 Before cycling After cycling ü The morphology of K 0.6 CoO 2 is not noticeably changed after cycling. H. Kim et al. Adv. Energy Mater (2017) 18
19 Before cycling After cycling ü The surface of K 0.6 CoO 2 becomes amorphous-like and nano-sized particles, which will be responsible for some capacity decays. H. Kim et al. Adv. Energy Mater (2017) 19
20 ü A full cell consisting of K 0.6 CoO 2 successfully. H. Kim et al. Adv. Energy Mater (2017) cathode and graphite anode works 20
21 21 ü New P2-type K 0.6 CoO 2 cathode is proposed for KIBs. ü P2-type K 0.6 CoO 2 shows reversible K storage properties. ü Multitude phase transitions occurs in K x CoO 2 during K de/intercalation, while it maintains P2-type structure. ü Surface degradation affects capacity decay of K 0.6 CoO 2. ü Practical feasibility of KIB is demonstrated while further optimization is required.
22 Gerbrand Ceder, Chancellor s Professor Department of Materials Science and Engineering Dr. Jae Chul Kim Prof. Shou-Hang Bo Mr. Tan Shi Dr. Deok-Hwang Kwon The Laboratory Directed Research and Development Program of Lawrence Berkeley National Laboratory under U. S. Department of Energy (DE-AC02-05CH11231) 22
23 Thank you Download these slides at H. Kim et al. Adv. Energy Mater (2017) 23
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