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Energy Storage in Graphene
Batteries… Supercapacitors
Pedro GOMEZ-ROMERO
NEO-Energy Group Leader, ICN2
Campus UAB, Bellaterra (Barcelona) Spain
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