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Supercapacitors: key systems for
energy sustainability
Dipartimento di Chimica “Giacomo Ciamician”
http://www.ciam.unibo.it/leme
LEME - Laboratory of Electrochemistry of Materials for Energetics
Francesca Soavi
23/05/2017 OCEM
Laboratorio di Elettrochimica
dei Materiali per l’Energetica
ALMA MATER STUDIORUM
UNIVERSITA’ DI BOLOGNA 1088 - STUDIUM IN BOLOGNA
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1
69th ISE Annual Meeting
2-7 September 2018 Bologna, Italy
Abstract submission
Opening date
15 December 2017
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K.Kanamura, H. Uchida (Vice-Chairs) – 1532 Members
Topics: Batteries, Fuel cells, Supercapacitors: materials, processes and systems
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Symposium 8 Supercapacitors: from double-layer electrochemical capacitors to faradaic-based high power systems
Department of Chemistry
“Giacomo Ciamician”
The first chair in Chemistry in Italy was established
in Bologna in 1737
Research Areas
Analytical Sciences
Computational Chemistry
Electrochemistry
Molecular Spectroscopy
Organic Synthesis
Photochemistry and Supramolecular Chemistry
Physical Organic Chemistry
Polymers and Materials
Structural and Solid State Chemistry
http://www.chimica.unibo.it/it
Staff: 17 Full Professors, 36 Associate Professors,
25 Assistant Professors , 45 Post-doc (Assegnisti)
31 administrative assistants and technicians
Electrochemistry of Molecular and
Functional Materials (Prof. F. Paolucci)
Electrochemistry of Materials for
Energetics - LEME (Prof. C. Arbizzani)
10
LEME- Laboratory of Electrochemistry
of Materials for Energetics
https://site.unibo.it/leme/en
Systems
Lithium Batteries
Supercapacitors
Fuel cells
Materials
Nanostructured
electrodes
Novel electrolytes
Electrospun
membranes
Applications
Electric vehicles
Renewable energy
storage
Portable device
DAAD
Prof. Catia Arbizzani
Dr. Francesca Soavi
Electrochemical energy storage/conversion
High efficiency
renewable energy storage & electric grid quality
700
600
500
400
300
200
100
0
Mill
ion to
nn
es o
il equiv
ale
nt
1990 2000 2010 2020 2030
Global Renewable Energy
Consumption
BP Energy Outlook to 2030
Battery, Supercapacitors, Fuel cells
Italy 7 GW storage installed (mainly hydro) 75 MW Li-ion, Na-Ni, Flow batteries and
Supercaps (pilot plants -250 mln €)
World
170 GW storage installed
http://www.energystrategy.it
Electrochemical energy storage/conversion
High efficiency
electric/hybrid vehicles Hybrid electric vehicles sold per year
M units worldwide
Battery, Supercapacitors, Fuel cells
automotive accounts for > 20% of CO2
EU emissions
2016
518000
BEV &PHEV Battery cost
Vehicle
Models
http://www.energystrategy.it
90 kWh
350 kW
8
Battery, Supercapacitors, Fuel cells
Electrochemical energy storage/conversion
High efficiency
Maintenance-free implantable biosensors
Remote and mobile environmental sensors
Nanorobotics,
Portable and wearable personal electronics
ICT
Self-powered and autonomous systems
www.iea.org.
C. Pangy C. Lee, K.-Y. Suh, J. APPL. POLYM. SCI. 2013, DOI: 10.1002/APP.39461I
Global energy demand of network-enabled devices
140 TWh by 2025 (6% of current total global electricity consumption.)
≲ Wh
mW
DOUBLE-LAYER ELECTROCHEMICAL CAPACITOR
EDLC capacitance
CEDLC =(C1-1+ C2
-1)-1
capacitance
C = kA/d =Q/V
k dielectric permettivity.
A plate area
d plate distance
EDLC Supercapacitors
2
- + dielectric
d
plane capacitor
-
-
-
-
-
-
-
+
+
+
+
+
+
+
pF to µF
charged/discharged by electrostatic processes
plates
separator
High surface area carbon electrode/electrolyte interfaces
Electrolyte ions
• High Electrode area A 1000-2000 m2 g-1
• Small “Plate distance” d double layer thickness (10-10 m)
Supercapacitance up to 1 F and 100-200 F/g
B.E. Conway, Electrochemical Supercapacitors, KA/PP, New York 1999
EDLC Supercapacitors
3 M. Winter, R.J. Brodd, Chem. Rev., 2004, Vol. 104, No. 10 4247
Upon charge EDLC voltage linearly
increases up to a Vmax limit set by the
electrochemical stability of the
electrolyte.
B.E. Conway, Electrochemical Supercapacitors, KA/PP, New York 1999
Electrolyte Electrode
capacitance F/g
Vmax
V
Emax
Wh/kg
Pmax
kW/kg
Aqueous
H2SO4, KOH
150-200 1.0-1.5 1-2 1
Organic
Et4NBF4 -PC/ACN
80-100 2.5-2.7 5-6 6
…Ionic liquids for Vmax 3,0-3.5 V
Energy E= ⎰V dQ
Emax = 1/2 CEDLCVmax2
Power Pmax = Vmax2 / 4ESR
Capacitance CEDLC = Q/V
Energy storage by FAST and highly REVERSIBLE electrostatic
surface processes
Higher Energy than Capacitors but
lower Power
Higher Power than batteries but lower
Energy
Longer Cycle life than batteries
Higher safety than batteries
EDLC Supercapacitors
3 M. Winter, R.J. Brodd, Chem. Rev., 2004, Vol. 104, No. 10 4247 C. Arbizzani, F. Soavi, Enciclopedia Treccani, IX Appendice (2015)
Specific
Pow
er
(W/k
g)
Specific Energy (Wh/kg)
Ragone Plot
Other Types of Supercapacitors (SCs)
• Pseudo-supercapacitors with battery-like electrodes (electronically
conducting polymers and metal oxides) that are charged/discharged by fast
and reversible redox processes.
• Hybrid supercapacitors with positive and negative electrode materials of
different nature that are charged/discharged via different electrostatic and
faradic modes.
Increasing C and V increases specific energy of supercacitors
Emax = 1/2 CV2
4
SC Applications
6 J.R. Miller and A. F. Burke The Electrochemical Society Interface, Spring 2008, 53
H. Chen et al. / Progress in Natural Science 19 (2009) 291
Regenerative Braking, short-term energy storage or burst-mode power delivery
High power – Rapid charge/discharge cycles
power tools
memory backup
Electric grid quality
High frequency
Peak shaving
Load levelling
SC Applications and novel frontiers
LIB EDLC
$/Wh 1-2 10-20
$/kW 75-150 25-50
6 J.R. Miller and A. F. Burke The Electrochemical Society Interface, Spring 2008, 53
X. Luo et al. Applied Energy 137 (2015) 511
• High power lithium-ion batteries (LIBs) may compete with
organic EDLCs
• While EDLCs materials are cheaper than LIB’s, the EDLC
cost is higher when normalized to energy
• EDLC are safer and more stable than batteries
Cell prototype 3.7V - 340 F
…towards novel SC frontiers
7
Self-powered and autonomous systems
energy-generating
cloth and shoes IMC wearable wireless
electroencephalograpy
system with hybrid power
supply
(PV+thermoelectric)
from ambient: PV, thermoelectrics, mechanical
vibration, piezoelectric, enzimatic and microbial
fuel cells … but low power and voltage output
batteries or supercapacitors for power quality,
regulation and to boost power output
….towards sustanibility, integration and
miniaturization
sensors, transceivers
…but high power and voltage operation
Z. L. Wang, Adv. Mater., 2012, 24, 280–285., M. Beidaghi, Y. Gogotsi, Energy Environ. Sci., 2014, 867–884 9
Self-powered and autonomous systems Maintenance-free remote and mobile environmental sensors, nanorobotics,
and portable and wearable personal electronics need autonomy.
ENERGY
HARVESTER
ENERGY
STORAGE
FUNCTION
DEVICE
...towards low-power integrated devices
Why supercapacitors (SC) ?
SCs outperform batteries in applications having high peak-to-average power
demand
SCs feature superior cycling stability, which is of paramount importance for
applications, like sensors, where repeated power peaks are required.
Electrode components (carbons, polymers) of SCs
are easily processable for in-plane, flexible
architectures.
10
Supercapacitors are key components of low-power and autonomous
systems
They can store the energy harvested from the environment and provide
power pulses
M. F. El-Kady and R. B. Kaner, Nat. Commun., 2013, 4, 1475.
Why supercapacitors (SC)?
High “electric response flexibility” of SCs:
• EDLC charge takes place at any voltage > 0 V. The voltage linearly
increases up to a limit set by the electrochemical stability of the
electrolyte.
• Battery charge takes place at the voltage set by the electrode processes
Only the EDLC stores the energy.
charge discharge
Voltage
time
battery
Energy
harvester
voltage
output
The energy havested is stored by
both EDLC and the battery
charge discharge
Voltage
time
battery Energy
harvester
voltage
output
EDLCs can be directly combined with a wide range of energy harvesters
including those operating at low voltage
11
Why supercapacitors (SC) ?
Many capacitive/pseudocapacitive electrode materials used in SCs exhibit
strategic additional properties that can be exploited for specific applications,
along with their capability of reversibly storing charge and, thus, energy
• High surface area carbons : catalysts or catalyst supports for various types
of fuel cells
• Pseudocapacitive polymers : mechanical, optical and electronic properties
that are exploited in actuators, electrochromic devices,
and sensors (PPY, PEDOT, PANI, etc..)
• Metal oxides : mediators for electrocatalytic processes (MnO2 and RuO2) and
may feature electrochromic and semiconductive properties
(e.g.WO3 and TiO2)
This enables integration of the energy storage capability and of
the target function at materials level
12
Supercapacitors at LEME
1
• High Specific Energy Supercapacitors
- Electronically conducting polymers
- Mesoporous carbons
- Ionic Liquids
• Supercapacitor Integration
- Solar Capacitor
- Supercapacitive Microbial Fuel Cells
• Supercapacitor Miniaturization
- Melanine flexible SC
- Supersonic Cluster Beam Deposition
- TransCap: and integrated SC-Transistor
Supercapacitors of high specific energy
Emax= 1/2CSCVmax2 Pmax= Vmax
2 /4 ESR
increase maximum cell voltage Vmax
-advanced electrolytes of wide ESW
good conductivity, safety and wide
operative T range
increase supercapacitor specific capacitance Csc
- capacitive carbons (optimized porosity and surface chemistry)
- pseudocapacitive materials charged/discharged by fast redox processes
(noble metal oxides, conducting polymers, lithium intercalation materials)
IONIC LIQUIDS
University of
Bologna
33
2005-2009
M. Lazzari, F. Soavi, M. Mastragostino, J. Electrochem. Soc. 156 (2009) A661-A666.
galvanostatic cycles at 20 mA cm-2 60°C
High-voltage EDLC (ionic liquid electrolytes)
9.9 31 20 22 3.7 1.49 15-20
Pmax
kW kgc.m.-1
Emax
Wh kgc.m.-1
ESR
Wcm2
Csc
F gc.m.-1
Vmax
V w+/w-
wc.m.
mgc.m.cm-2
fade of capacitance <5% on 20,000 deep cycles with Vmax of 3.5/3.8V
cut-off voltage: Vmax = 3.7 V; Vmin = 55% Vmax
Electrodes prepared at pre-industrial scale: mesoporous commercial carbon treated at 1050°C in Ar
for 2 h (ACT), 100 F g-1; electrode composition: 5% pTFE and 95% C
wc.m.= total composite electrode loading
Cell prototype 3.7V - 340 F
Solar capacitor
Perovskyte solar cell – ionic liquid based
electrochemical double layer capacitor
900 950 1000 1050 1100 1150 12000.0
0.2
0.4
0.6
0.8
1.0
1.2
Light Dark Light
Volta
ge
(V
)
time (s)
pDSSC-EDLC
DSSC OCV
(scheme 2a)
b)
0 2 4 6 8 10-35
-30
-25
-20
-15
-10
-5
0
Ligth
Dark
time (s)
I (m
A)
f)
pDSSC-EDLC
DSSC @ 0V
+
Electrochemical Double Layer
Capacitor (EDLC)
---
-----
C
A
T
H
O
D
E
A
N
O
D
E
+
+
+
+
+ + + +
+ + + +
+
+
+
+
+
+
+
+- - - -
- - - -
---
--
-
-
+
+
+
+
-
+
--
-
+
+
+ +
-
-
- +
Canode
Ranode
RbulkCcathode
Rcathode
LOAD
C a
t
h
o
d e
Anode
O2
H2O
Reduction
Organic
compounds
CO2
H+
e-
Anodophillic
bacteria
Oxidation
Rext
OH-
Microbial Fuel Cell (MFC)
Microbial Fuel Cell Integrated with Self-Powered SC
Supercapacitive
Microbial Fuel Cell
(SC-MFC)
17
biotechnology for
simultaneous
wastewater
treatment and
energy production
but low power
output 0
2
4
6
8
10
12
14
16
18
20
0 5 10 15 20 25 30 35 40 45 50
Pm
ax (
mW
)
Current (mA)
AC-AdE BOx-AdE Fe-AAPyr-AdE
Sustainable materials
Melanin-based SC
15 P. Kumar et al, J. Mater,. Chem. C, 2016, DOI:10.1039/C6TC03739A
18
Figure 5. Melanin-based flexible micro-supercapacitors with ~200 µg/cm2 melanin loading on each
electrode. (a) Optical image of the micro-supercapacitor (total three micro-supercapacitors) on a
flexible PET substrate. (b) Specific capacitance and specific capacity vs. scan rate of CV taking into
account the total melanin loading of the two electrodes (32 µg). (c) Galvanostatic charge/discharge
cycles with three different values of the current density (0.625, 1.25, and 12.5 mA/cm2). (d) Ragone
plot extracted from the galvanostatic discharge cycles at different values of the current density
(0.625, 1.25, 6.25, 12.5 a nd 25 mA/cm2). The area of each electrode is 0.08 cm
2.
a
FlexibleMelanin mSC
Flexible melanin based micro-supercapacitors may serve in biocompatible and biodegradable
power sources for applications such as implantable medical devices and wearable electronics.
Eumelanin
Heterogeneous macromolecule
+ redox forms +
Natural pigment in animals, plants, human body (skin, eyes, inner ear, brain, hair)
melanin as active material in energy storage systems
Sustainable Miniaturization Processes
Supersonic Cluster Beam deposition (SCBD)
Supersonic Cluster Beam Deposition (SCBD) of nanostructured cabon (ns-C) electrodes
16
• thickness control (<< m)
•Low density (0.5 cm3/g)
• High porosity (700 m2/g)
• No binder, no carbon activation
• RT procedure for T sensitive substrates
L.G. Bettini et al, Electrochim. Acta, 170 (2015) 57
F. Soavi et al, J. Power Source, 326 (2016) 717
500 nm-thick
P-type Channel Electrolyte Gate Stacking
MEH-PPV N1113TFSI Activated Carbon sandwich
PEDOT:PSS polystyrenesulfonate (NaPSS) gel ns-C by SCBD planar, flexible
Z.Yi et al., J. Polymer Science, Part B: Polymer Physics.,
(2016) DOI: 10.1002/polb.24244
ns-C
SCBD
J. Sayago et al. J. Mater. Chem. C, 2014, 2,10273
J. Sayago et al., J. Mater. Chem. C, 2014, 2, 5690
J. Sayago et al., Appl. Phys., 117 (2015) 112809 21
TransCap: an integrated
electrolyte gated transistor (EGT) – hybrid SC
TransCap:
the proof-of-concept
potential steps at 0.8 V – 4s
J. Sayago, U. Shafique, F. Soavi, F. Cicoira, C. Santato, J. Mater. Chem. C, 2014, 2,10273
MEH-PPV/ionic liquid N1113TFSI/activated carbon
TransCap can operate with the channel
open (doped) without being connected
to an electric grid for relatively short times
To switch ON:
ETransCap= Igs dt = 53 J
ETransCap is then delivered upon switch OFF
with an efficiency of 99.5%,
.
22
8 10 12 14 16 18200
0
-200
-400
-600
Time (s)
I ds (
A
)
80
40
0
-40
-80
Po
we
r gs (
W
)
channel doping and
Sc charge at
|Vgs
|=0.8V
channel undoping and
Sc discharge at
|Vgs
|=0V
ON OFF
Channel current modulation
ON/OFF ratio 2 103 (Vgs +-0.8 V, Vds = -0.3V)
Acknowledgements
… and the funding:
Alma Mater Studiorum –Università di Bologna
RFO, Ricerca Fondamentale Orientata
Canada-Italy Innovation Award
ENEA and Italian Ministry of the Economic Development
Program Agreement “Electric System Research”
Special Thanks
To Carlo Santoro Plamen Atanassov
Alexey Serov
30 ….Thank you!!
Prof. P. Milani
Prof. P. Piseri
Special Thanks to
Luca Giacomo Bettini
Clara Santato
Fabio Cicoira
P. Kumar
Z. Yi
X.Meng
E. Di Mauro
F. Quenneville
J. Sayago
Prof. Catia Arbizzani
F. De Giorgio
I. Ruggeri
A. La Monaca
S. Intermite
Prof. Michael Grätzel
Prof. Anders Hagfeldt
Special Thanks to
Nick Vlachopoulos