Energy storage: EDLC & Pseudo –

Doron Aurbach Department of chemistry, Bar Ilan University Ramat-Gan 52900 Israel Email: [email protected]

Energy is found everywhere we just need to harvest and store it

We lack good storage technologies can be used for load leveling applications

We want to move ASAP to sustainable energy overview Material design Aqueous SC High voltage SC PsC Summery cells (time constants inred) cells(time constants common Faradaic electrochemicalenergy storage plot,A typicalof Ragone overview Power gap between batteries and Suprecapacitors fill (EDLC) the Energy atre r vlae ntrso energy Batteries are evaluated in terms of

Material design Specific Power (Wkg-1) 10 10 10 10 10 10 10 10 10 10 1 1 4 4 3 3 5 5

2 2 10 10

- - 2 2

and

Specific energySpecific( 10 10 ECs (

Aqueous SC Aqueous

- - 1 1

power densities 2008 )

1 1

Ni/Cd Ni/Cd

Ni/MH Ni/MH

Whkg acid Lead acid Lead Comm. Li Comm. Comm. Li

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5 5 V. Li V. Li 1 1 10 10 s s

2 2 - - ion ion

1 1 Primary Primary min

min

Li Li

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capacitors PsC

Vs. Summery

What is Capacitor?

• A capacitor (originally known as condenser) is a passive two- terminal electrical component used to store energy in an electric field. • When there is a potential difference across the conductors, a static electric field develops across the dielectric, causing positive charge to collect on one plate and negative charge to accumulate on the other plate. Energy is formed in terms of electrostatic field.

overview Material design Aqueous SC High voltage SC PsC Summery What is ? Supercapacitor (SC) also known as electric double-layer capacitor (EDLC) or Ultracapacitor, is electrochemical capacitor. The capacitance value of an electrochemical capacitor is determined by two storage principles, which both contribute indivisibly to the total capacitance: • Double layer capacitor – Electrostatic storage achieved by separation of charge in a Helmholtz double layer at the interface between the surface of a conductive and an . The separation of charge is of the order of a few angstrom (0.3–0.8 nm), much smaller than in a conventional capacitor than in a conventional capacitor. • Pseudocapacitor - Faradaic electrochemical storage with charge transfer, achieved by interaction, intercalation or electrosorption.

overview Material design Aqueous SC High voltage SC PsC Summery Up to 109 V/m potential fall exist on charged interfaces Electrical Double Layer (EDL) - - - - + + - - + + - - - + - - + -

OHP Water molecule + Counter ion Outer Helmholtz plane - Co- overview Material design Aqueous SC High voltage SC PsC Summery The difference between

More power is required for short time Constant but less power required for interval in 200m race long time in 20km race

overview Material design Aqueous SC High voltage SC PsC Summery Charged species can be stored electrostaticly by the EDL   C  A  0  r d A = Surface area (very high in Activated carbon). d = Dielectric thickness, single solvent molecule. = limited by the solvent properties. εr

Possible :

1. Aqueous electrolyte, high rates small ions high ionic conductivity, limited voltage.

2. Organic electrolyte, moderate conductivity and capacity up to 3V.

3. Ionic liquids- Low conductivity, lower capacity, high voltage, safe. www.youtube.com/watch?v=FJZKm5khaAA overview Material design Aqueous SC High voltage SC PsC Summery From dead leaves till energy storage devices

M. Biswal, A. Banerjee, M. Deo, S. Ogale, Energy & Environmental Science 2013, 6, 1249-1259.

overview Material design Aqueous SC High voltage SC PsC Summery High capacitance graphene SC

P. A. Basnayaka, M. K. Ram, E. K. Stefanakos, A. Kumar, Electrochimica Acta 2013, 92, 376-382 overview Material design Aqueous SC High voltage SC PsC Summery Increasing the electrochemical window using neutral electrolyte solutions

Q. Gao, L. Demarconnay, E. Raymundo-Pinero, F. Beguin, Energy & Environmental Science 2012, 5, 9611-9617. overview Material design Aqueous SC High voltage SC PsC Summery Electrodeposition of Mn-Mo oxide film on CNT/ITO

M. Nakayama, K. Okamura, L. Athouël, O. Crosnier, T. Brousse, ECS Transactions 2012, 41, 53-64.

overview Material design Aqueous SC High voltage SC PsC Summery Activated carbons possess unique physicochemical properties:

Carbon Carbon Carbon Activated precursor precursor material carbon

M M M M Oxidizing M M M M Polymerization Carbonization M M M M under inert agent M M M M atmosphere

Activated carbon (AC)

General features: • Highly disordered • High surface area (up to ~3000m2/g) • Electrically conductive

overview Material design Aqueous SC High voltage SC PsC Summery 300 400

350 250

300 200

250

150 200 cc/g cc/g 150

100 volumeadsorbed (ml/gr)

volumeadsorbed (ml/gr) 100 50 50

0 Activation 0 0 0.2 0.4 0.6 0.8 1 1.2 0 0.2 0.4 0.6 0.8 1 1.2 RelativeRelative Pressure pressure (p/p0) RelativeRelative Pressurepressure (p/p 0) C C O C 150 100 CO2 CO+ CO+2 100

50 50 0

-50

0 (F/gr) C

C (F/gr) C -100

-50 -150 -200 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 -100 E (volts) vs S.C.E E (volts) Vs S.C.E M. Noked, E. Avraham, A. Soffer, D. Aurbach, The Journal of Physical Chemistry C 2009, 113, 21319-21327. overview Material design Aqueous SC High voltage SC PsC Summery Using CNTs as a conductive additive and as a reinforcing agent in novel

Rolling up a graphene sheet to form a tube. Properties: • Very strong and flexible molecular material due to the C-C covalent bonding and seamless hexagonal network architecture. •Thermal conductivity ~ 3000 W/m.K in the axial direction

•Electric conductivity six orders of a b magnitude higher than copper

CNTs grow methods: a) Arc-discharge b) Laser ablation c) Catalytic chemical vapor deposition (CCVD)

overview Material design Aqueous SC High voltage SC PsC Summery Carbon precursor

Carbon Activated material carbon

Stirring Carbonization Oxidizing under inert 5µm agent atmosphere CNT

5µm

CNT dispersion

overview Material design Aqueous SC High voltage SC PsC Summery