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Energy Storage in Graphene

Batteries… Supercapacitors

Pedro GOMEZ-ROMERO

NEO-Energy Group Leader, ICN2

Campus UAB, Bellaterra (Barcelona) Spain

pedro.gomez@icn2.cat

1605

Solar PV crop in Castilla La Mancha (Solaer).

Don Quijote

La Mancha

Spain

The new Energy Landscape

Wind power at Sisante

Pioneer thermosolar power plant. Sanlucar (Sevilla) Spain (Abengoa)

The new Energy Landscape

The new Energy Landscape

Renewable electricity in Spain (%)

6

Electricity generation in Spain

2014 (as of August 19)

1 h

1 min

1 s

1 MW 1GW 1 KW

Ni-MH Batt

Li ion Batt

Ni-Cd Batt

Pb-Acid Batt

Flywheels

High-Power DL Supercaps Supercond Mag

Thermal storage

Compressed air

Na-S Batt

Redox Flow Batteries

Pumped

hydro H2 – Fuel Cells

Bulk

Energy

Storage

Power Supply

Grid

Support

1 day

High-Energy

Hybrid Supercaps

M-Air Batt

Energy storage systems

Energy storage

in transition

A 32 MW fleet of batteries smooths the output from AES Corporation’s wind

farm in Laurel Mountain, W.Va. MRS Bulletin • Vol 37 • Nov 2012

Centralized… or distributed

Smart Grids

Centralized AND

Distributed Energy

Anyone betting on this new energy model? Elon Musk

• Tesla Motors EVs

• Photovoltaics

• Power Wall Home battery

Energy storage: Power vs. Energy densities

Prof. Pedro Gómez-Romero

Hybrid Energy Storage. The merging of battery and supercapacitor chemistries.

D. P. Dubal, O. Ayyad, V. Ruiz, and P. Gomez-Romero* Chem.Soc.Rev. 44(7):1777-90 2015

Supercapacitors applications

Supercapacitors

from niche to widespread applications

Lower costs (economy of scale)

R+D for wider performance (i.e. high E)

Widen industrial use of supercaps

Supercapacitor Market worth

$2.10 Billion by 2020

Supercapacitors Market to

Reach $4.2 Billion by 2020

Supercapacitors vs. batteries

carbon-based EDLC Co3O4 LiFePO4 (vs. Li)

supercapacitors pseudocapacitor battery

But NOT mixed mecanisms

Pseudocap. RuO2 Trasatti 1971, Conway 1975-1980

Graphite intercalation anode

LiC6

Single layer graphene. Double layer capacitance

And something in between?

Few-layer graphene.

An Advanced Lithium-Ion Battery Based on a Graphene Anode and a Lithium Iron Phosphate Cathode

Jusef Hassoun*, Francesco Bonaccorso* et al. Nano Lett., 2014, 14 (8), pp 4901–4906

Graphene as active electrode material in Lithium-Ion Batteries

Layer Number Dependence of Li+ Intercalation on Few-Layer Graphene and Electrochemical Imaging

of Its Solid−Electrolyte Interphase Evolution

Jingshu Hui, Mark Burgess, Jiarui Zhang and Joaquín Rodríguez-Lopez* ACS Nano 2016, 10, 4248

Graphene as active electrode material in Lithium-Ion Batteries

Stage Intercalation, SEI, as a function of the number of layers

Graphene in lithium ion battery cathode materials: A review

G. Kucinskis et al. J. Power Sources 2013, 240. 66-79

The application of graphene in lithium ion battery electrode materials. J. Zhu et al. SpringerPlus, 2014, 3:585

How a very trace amount of graphene additive works for constructing an efficient conductive network in

LiCoO2-based lithium-ion batteries. R, Tang et al. Carbon 2016, 103, 356–362

Graphene as additive in Lithium-Ion Batteries

Anodes Sn, Si

Cathodes LiCoO2, LiFePO4

Conducting component

Mechanical reinforcement

Prevents aglomeration

Reduced amount of additives

Energy storage: Power vs. Energy densities

Prof. Pedro Gómez-Romero

Hybrid Energy Storage. The merging of battery and supercapacitor chemistries.

D. P. Dubal, O. Ayyad, V. Ruiz, and P. Gomez-Romero* Chem.Soc.Rev. 44(7):1777-90 2015

Chenguang Liu, Zhenning Yu, David Neff, Aruna Zhamu, and Bor Z. Jang*

Nano Lett., 2010, 10 (12), pp 4863–4868

Graphene Supercap Development: Microstructure

Graphene Supercap Development:

Hybridization

J. Suárez-Guevara, V. Ruiz, P. Gomez-Romero*, Phys. Chem. Chem. Phys. 2014, 16 (38), 20411

0

0,2

0,4

0,6

0,8

1V

Energy

Power

Cyclab

price

safety

batteries

supercaps

Batteries and/or supercapacitors

Beyond the Ragone plot

0,00

0,20

0,40

0,60

0,80

1,00V

Energy

Power

Cyclab

price

safety

batteries

supercaps+

Batteries and/or supercapacitors

Beyond the Ragone plot

Hybrid devices

Hybrid electrodes

Hybrid materials

Hybrid approaches

possible hybridization approaches between

supercapacitor and battery electrodes and materials.

Hybrid Energy Storage. The merging of battery and supercapacitor chemistries.

D. P. Dubal, O. Ayyad, V. Ruiz, and P. Gomez-Romero* Chem.Soc.Rev. 44(7):1777-90 2015

Inorganics

COPs Carbons

MnO2 H3PMo12O40

LiFePO4

G -

GO

AC

PPy PAni

PVK PEDOT

Our window to the

hybrid material landscape

Inorganics

COPs Carbons

G - GO

oxides

Prof. Pedro Gómez-Romero

hybrid materials

with extended phases

Hybrid reduced graphene oxide and transition metal hydroxides

on sponge support for hybrid energy storage devices

Prof. Pedro Gómez-Romero

D.P. Dubal*, R. Holze, P. Gomez-Romero*. Scientific Reports 2014, 4 : 7349

SP@rGO@Ni

SP@rGO@Co

Hybrid reduced graphene oxide and transition metal hydroxides

on sponge support for hybrid energy storage devices

Prof. Pedro Gómez-Romero

D.P. Dubal*, R. Holze, P. Gomez-Romero*. Scientific Reports 2014, 4 : 7349

D.P. Dubal*, R. Holze, P. Gomez-Romero*. Scientific Reports 2014, 4 : 7349

Hybrid reduced graphene oxide and transition metal hydroxides

on sponge support for hybrid energy storage devices

Prof. Pedro Gómez-Romero

Inorganics

COPs Carbons

H3PMo12O40

G - GO

AC

PPy PAni

PVK

PEDOT

hybrid materials

with molecular species

Prof. Pedro Gómez-Romero

RedOx Chemistry of Polyoxometalates (POMs) Cyclic Voltammogram (CV) of H4 [SiW12O40] (SiW12)

H4 [SiW12O40] (aq.HCl), pH=0.8

Photoredox Chemistry in Oxide Clusters. Photochromic and Redox Properties of

Polyoxometalates in Connection with Analog Solid State Colloidal Systems.

Pedro Gómez-Romero* et al J.Phys.Chem. 1996, 100(30), 12448-54.

SEM images of (a) rGO and (b) rGO-PMo12 hybrid materials, respectively, (c) EDS mapping of rGO-PMo12 hybrid sample,

(d) HR-TEM image of rGO-PMo12 sample, (e, f) STEM images of rGO and rGO-PMo12 hybrid samples, respectively.

Hybrid rGO-H3PMo12O40

D.P. Dubal J. Suarez-Guevara, D. Tonti, E. Enciso, P. Gomez-Romero Journal of Materials Chemistry A, 2015, 3(46), 23483

D.P. Dubal J. Suarez-Guevara, D. Tonti, E. Enciso, P. Gomez-Romero Journal of Materials Chemistry A, 2015, 3(46), 23483

(a) CV and (b) Carge-discharge curves of rGO and rGO-PMo12 symmetric cells

(c) Variation of volumetric capacitance of rGO and rGO-PMo12 based symmetric cells as a function of scan rates,

(d) volumetric power and energy density values of rGO and rGO-PMo12 symmetric cells.

Hybrid rGO-H3PMo12O40

31 LED indicators with word “NEO” powered rGO-PMo12

symmetric cell with 0.2 M HQ doped polymer gel electrolyte.

30 s charge 2 min lit

Hybrid rGO-H3PMo12O40

D.P. Dubal J. Suarez-Guevara, D. Tonti, E. Enciso, P. Gomez-Romero Journal of Materials Chemistry A, 2015, 3(46), 23483

RGO-POM hybrid Supercapacitor electrode

Hybrids C-POMs CNTs ACs RGO

rGO Ni(OH)2

Scientific Reports 2014, 4 : 7349

NB: our devices are SYMMETRICAL Supercapacitors and thus

benchmark comparison should be with area “D”

Nanofluids: size matters dispersions of nanoparticles in base fluids

THERMAL Nanofluids Applied as Heat Transfer Fluids (HTFs)

(SO colaboration with Clivia Sotomayor)

ELECTROACTIVE Nanofluids for energy storage in Novel Flow Cells.

Graphene Nanofluids

Electroactive Graphene Nanofluids

for New Flow Cell Concepts.

D. P. Dubal, D. Gomez, P. Gómez-Romero, Patent ES1641.1064. “Electroactive nanofluids on graphene-based materials for energy storage in flow cells.” 20-05-2015

Electroactive Graphene Nanofluids for Fast Energy Storage.

D.P. Dubal and P. Gomez-Romero 2D-Materials 2016, 3, 031004

58

Electroactive Graphene Nanofluids

for New Flow Cell Concepts.

Electroactive Graphene Nanofluids for Fast Energy Storage.

D.P. Dubal and P. Gomez-Romero 2D-Materials 2016, 3, 031004

ultrafast electrochemical

response

59

Hybrid Electroactive Graphene

Nanofluids for New Flow Cell Concepts.

H3PMo12O40 H3PW12O40

Conclusions

Graphene for Energy Storage Graphene itself has been proposed and tested for a wide variety of energy

and environmental applications, particularly in supercapacitors but also in

batteries

In batteries most frequently used as electrode additive. As active material

several hurdles must be overcome (SEI, reversible cap, cyclability)

For supercap apps, microstructure and hybrid developments can be key

The hybrid approach widens enormously the potential of G, GO and rGO by

combining them with a plethora of inorganic phases polymers or molecules

which add functionality and allow for synergy and enhanced energy density.

Dispersion of graphene in nanofluids provides a new format for G, GO or

rGO electrodes suitable for novel Flow Cells

NEO-Energy Group: The people (Feb 2016)

Vanesa Ruiz

Jullieth Suárez

… for your attention!

Gracias

neoenergy.cat