International Conference “Global/Local Innovations for Next Generation Automobiles”
Sendai International Center, Sendai, Miyagi (October 27, 2015)
A metal-free organic crystalline electrode
for high energy density batteries
Applications
● Large Scale electricity storage devices
Itaru HONMA
(Tohoku University)
“Green Energy/ Nanotechnology researches” @ HONMA lab., IMRAM
Advanced secondary batteries for EV/HEV, Robots and iPhones
● high power lithium ion battery
● all solid state LIB
● Mg (multi-valence ion) secondary battery
Super-capacitor for winds & solar renewable energy storage
● aqueous proton capacitor
● redox flow capacitor
Nanotechnology for advanced energy materials
● nanoparticles/ ionic liquids
● graphene & nanoporous carbons
● supercritical fluid processing for nanoelectrodes
Rare metal’s price and resources limitation are critical
Prices of Rare (Minor, Critical) Metals ($/kg)
1
10
Mn
Fe
Ni
Cu
Cheap
100
Co
Li
1,000
In
Ag
Expensive
10,000
100,000
Pt
Au
Super Expensive
Natural Abundance of Metals (Co = 1)
Rare metal news;
2008-2010
Barbalace, Kenneth;
“Periodic Table of Elements”
Organic Crystal as “Green Nanotechnology of Electrode”
TCNQ crystals
(Tetracyano- quinodimethane)
● Metal free electrodes
● Natural abundance
● Environmentally friendly
● Safety & recyclability
● Cost effective
● No high temperature process
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)
Exploration of rare-metal free, low cost & high energy density electrodes
High Capacity Cathode Candidates of Organic & Inorganic Materials
1e- redox cathode
LiCoPO4
5V
Potential (V vs. Li/Li+)
2e- redox cathode
Li2MnO3- LiMO2
●
LiMnPO4
LiMn2O4 ● ●
LiFePO4
4V
●
3V
Li2FePO4F
●
●
●
DDQ
TCHQ
●
TCNQ
● ●
LiNi1/3Mn1/3Co1/3O2
●
Li2CoSiO4
4e- redox
●
Li2MnSiO4
BQ
●
● DHBQ ●
Li2FeSiO4
● ●
NQ
AT
THBQ
2V
16e-
●
●
0
100
200
300
Capacity (mAh/g)
400
O
O
O
O
S8
January 16th, 2013, B787 flight emergency by LIB burst
http://news.goo.ne.jp/photo/kyodo
/nation/PN2013011901001640.html
Accident shows the weakness of B787 “Electric airplane”
http://www.asahi.com/business/reuters/RTR201301160063.html
More safe, low cost, high energy density battery ?
Aqueous electrolyte in spite of organic
H+ in stead of Li+
Absolutely metal-free battery
(employing only 5 elements of H, C, O, Cl, S )
Potential
4V
Lithium ion battery
Proton super-capacitor
1V
150
300
450
Capacity (mAh/g)
600
Large Redox Capacity of Organic Molecular Crystals
(Quinone)
257 mAh/g
AQ
Anthraquinone
383 mAh/g
DHBQ
Dihydroxybenzoquinone
295 mAh/g
TFBQ
Tetrafluorobenzoquinone
496mAh/g
BQ
Benzoquinone
262 mAh/g
TCNQ
Tetracyanoquinodimethane
237 mAh/g
DDQ
Dichlorodicyano
benzoquinone
310 mAh/g
THBQ
Tetrahydroxybenzoquinone
339mAh/g
NQ
Naphthoquinone
319mAh/g
DMBQ
Dimethoxybenzoquinone
243mAh/g
DtBu-BQ
Di-t-Butylbenzoquinone
Proton shuttle redox-capacitor
e-
●
anode
cathode
Proton/ H2O sol.
H+
Hydroquinone
(HQ)
●● ● ● ● ●
257 mAh/g
~ 0.6 V
Anthraquinone
(AQ)
●
487 mAh/g
Organic nanocrystals in Nanoporous carbon electrodes
AQ (27wt.%)/Maxsorb /PTFE
TCHQ (27wt.%)/Maxsorb /PTFE
Organic nanocrystals are supported within 1-10nm sized Nanopores of
carbon electrodes to suppress dissolution into the electrolyte solution
Rate capability of proton shuttle redox-capacitor
AQ(anode)
–
TCHQ(cathode)
H+
Charge at 5.6 A/g
Charge at 0.11 A/g
Discharge at 0.11 A/g
Discharge at 5.6 A/g
Energy density and power density is larger than that of EDLC capacitor
Device potential of proton super-capacitor
(Proton shuttle redox-capacitor)
Battery device
Energy density
price Cycle life
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)
safety