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Itaru HONMA
(Tohoku University)
A metal-free organic crystalline electrodefor high energy density batteries
International Conference “Global/Local Innovations for Next Generation Automobiles” Sendai International Center, Sendai, Miyagi (October 27, 2015)
Applications
● Large Scale electricity storage devices
“Green Energy/ Nanotechnology researches” @ HONMA lab., IMRAM
● high power lithium ion battery
● all solid state LIB
● Mg (multi-valence ion) secondary battery
Nanotechnology for advanced energy materials
Advanced secondary batteries for EV/HEV, Robots and iPhones
Super-capacitor for winds & solar renewable energy storage
● aqueous proton capacitor
● redox flow capacitor
● nanoparticles/ ionic liquids
● graphene & nanoporous carbons
● supercritical fluid processing for nanoelectrodes
Prices of Rare (Minor, Critical) Metals ($/kg)
1 10 1,000100 10,000 100,000
Co
Li
NiMn
Cu Ag
In Pt
Au
Barbalace, Kenneth; “Periodic Table of Elements”
Fe
Expensive Super ExpensiveCheap
Natural Abundance of Metals (Co = 1)
Rare metal news;2008-2010
Rare metal’s price and resources limitation are critical
Organic Crystal as “Green Nanotechnology of Electrode”
● Metal free electrodes
● Natural abundance
● Environmentally friendly
● Safety & recyclability
● Cost effective
● No high temperature process
Exploration of rare-metal free, low cost & high energy density electrodes
TCNQ crystals(Tetracyano- quinodimethane)
TTF-TCNQ (organic metals)L.B.Coleman et al., Solid State Commun. 12, 1125 (1973)J. Ferraris et al., J.Am.Chem.Soc., 95, 948 (1973)
(TMTSF)2PF6 (organic superconductor)D.Jerome et al., J.Physique Lett. 41, L95 (1980)
5 V
4 V
3 V
2 V
0 100 200 300 400
LiCoPO4
LiMnPO4
LiFePO4
Li2CoSiO4
Li2MnSiO4
Li2FeSiO4
Capacity (mAh/g)
Po
ten
tial
(V
vs.
Li/
Li+ )
High Capacity Cathode Candidates of Organic & Inorganic Materials
LiNi1/3Mn1/3Co1/3O2
2e- redox cathode1e- redox cathode
Li2FePO4F
Li2MnO3- LiMO2
LiMn2O4 ●●
●●
●
●
S8
●
DHBQ
TCNQ
DDQ
THBQ
●
●
● ●
●
●
● ●
●NQ
BQ● ●
TCHQ
●
AT
4e- redox
O
O
O
O
16e-
http://www.asahi.com/business/reuters/RTR201301160063.html
http://news.goo.ne.jp/photo/kyodo/nation/PN2013011901001640.html
January 16th, 2013, B787 flight emergency by LIB burst
Accident shows the weakness of B787 “Electric airplane”
H+ in stead of Li+
Aqueous electrolyte in spite of organic
Capacity (mAh/g)
Po
ten
tial
150 600450300
1 V
4 VLithium ion battery
Proton super-capacitor
More safe, low cost, high energy density battery ?
Absolutely metal-free battery(employing only 5 elements of H, C, O, Cl, S )
257 mAh/gAQ
Anthraquinone
295 mAh/gTFBQ
Tetrafluoro-benzoquinone
262 mAh/gTCNQ
Tetracyano-quinodimethane
237 mAh/gDDQ
Dichlorodicyanobenzoquinone
310 mAh/gTHBQ
Tetrahydroxy-benzoquinone
383 mAh/gDHBQ
Dihydroxy-benzoquinone
496mAh/gBQ
Benzoquinone
339mAh/gNQ
Naphthoquinone
319mAh/gDMBQ
Dimethoxy-benzoquinone
243mAh/gDtBu-BQ
Di-t-Butyl-benzoquinone
Large Redox Capacity of Organic Molecular Crystals(Quinone)
H+
Proton shuttle redox-capacitor
e-
Proton/ H2O sol.anode cathode
~ 0.6 V
Hydroquinone
(HQ)257 mAh/g
487 mAh/g
Anthraquinone
(AQ)
● ● ● ● ●●
●
●
Organic nanocrystals in Nanoporous carbon electrodes
Organic nanocrystals are supported within 1-10nm sized Nanopores of carbon electrodes to suppress dissolution into the electrolyte solution
AQ (27wt.%)/Maxsorb /PTFE TCHQ (27wt.%)/Maxsorb /PTFE
Energy density and power density is larger than that of EDLC capacitor
Charge at 0.11 A/g
Discharge at 0.11 A/g
Charge at 5.6 A/g
Discharge at 5.6 A/g
Rate capability of proton shuttle redox-capacitor
AQ(anode) – TCHQ(cathode)
H+
Battery device Energy density price Cycle life safety
EDLC < 5 Wh kg-1 ◎ > 10000 ◎
proton super-capacitor 10-20 Wh kg-1 ◎ > 1000 ◎
Pb-acid 20-30 Wh kg-1 ○ < 1000 ◎
Lithium ion capacitor 10-30 Wh kg-1 △ > 10000 △
Lithium ion battery (LIB) 100-150 Wh kg-1 △ ~ 1000 △
The proton super-capacitor device in this work (only 5 elements of H, C, O, Cl, S are employed) is low cost, long cycle life and safety, however, has as same energy density as that of Pb-acid
Applications to stationary electricity storage for the smart grid, renewable energy (solar & wind power)
Device potential of proton super-capacitor (Proton shuttle redox-capacitor)