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)