SUPERCAPACITÉS ÉLECTROCHIMIQUES Daniel Bélanger Université du Québec à Montréal...

SUPERCAPACITÉS ÉLECTROCHIMIQUES

Daniel BélangerUniversité du Québec à Montréal

[email protected]

15 mars 2013

mailto:[email protected]

NUMBER OF PAPERS AND CITATIONS

Search on Web of Science with : Electrochemical capacitor

PLAN DU COURS• CONTEXTE ÉNERGÉTIQUE-STOCKAGE• ACCUMULATEURS & SUPERCAPACITÉ ÉLECTROCHIMIQUE

– CONCEPTS IMPORTANTS D’ÉLECTROCHIMIE

• STRUCTURE ET CAPACITÉ DE LA DOUBLE COUCHE• MÉTHODES DE CARACTÉRISATION

– Evaluation de la performance

• MATÉRIAUX– Carbon, Conducting polymers, metal oxides– Concept of pseudocapacitance

• FONCTIONNEMENT– Systèmes symétrique et asymétrique

http://www.hbcpnetbase.com//articles/14_15_91.pdf

Electricity and heating

Transportation

Manuf. ind and construction

CO2 emission by sectors

How can we reduce them ?How can we reduce them ?

ENERGY STORAGE SYSTEMS

Poizot, Dolhem, Energy Environ. Sci. 2011, 4, 2003.

PSA Peugeot Citroën Start-Stop System

Reduce fuel consumption by up to 15%

7

City Bus-Volvo-Simplified system for a city bus, 220kW

NiMH-battery + EC

Battery310 kgEC 280 kgDC/DC 90 kg

Total weight 680 kg

Battery 1150 kgDC/DC 45 kg

Total weight 1195 kg

NiMH-battery

Weight reduction:43 %

AVANTAGES DES CONDENSATEURS ÉLECTROCHIMIQUES

ENERGY STORAGE WITH ELECTRICAL DOUBLE LAYER CAPACITOR AND

BATTERY

Simon, Gogotsi, Nature Materials, 2008, 7, 845.


BATTERY


Chuck Norris

70 kJ of Energy

2 MT vehicle moving 19 mph2 MT mass lifted to 12 ft height1 tsp sugar 4 g1 D-cell alkali battery 140 g22 kF / 2.5 V capacitor 4.6 kg

JME

From John Miller, JME Capacitor


BATTERY


E = 0.5 C V2

E= EnergyC= CapacitanceV= Voltage

CAPACITOR• VACUUM

• DIELECTRIC

• OXIDE ELECTROLYTIC– Ta2O5, Al2O3

C =A / d

Accumulateur au plombAccumulateur au plomb

Accumulateur au plombAccumulateur au plomb

Pb + PbOPb + PbO22 + H + H22SOSO44

Pb + carbonePb + carbone+ expandeurs+ expandeurs

Importance du « curing » ou mûrissage plaques positives empilées dans une étuve 72h avec fort taux d’humidité

Importance de la « formation » charge (formation Pb et PbO2)

Chemistry of Lead Acid Batteries

When the battery is discharged:

• Lead (-) combines with the sulfuric acid to create lead sulfate (PbSO4),

Pb + SO42- PbSO4 + 2e-

• Lead oxide (+) combines with hydrogen and sulfuric acid to create lead sulfate and water (H2O).

PbO2 + SO42- + 4H+ + 2e- PbSO4 + 2H2O

• lead sulfate builds up on the electrodes, and the water builds up in the sulfuric acid solution.

• Global reaction:• Pb + PbO2 + 2 H2SO4 2 PbSO4 + 2 H2O

– Concentration of H2SO4 changes from 5.5 M to 2 M

Lead Acid Batteries Consist of:

Lead (Pb) electrode (-) Lead oxide (PbO2) electrode (+) Water and sulfuric acid (H2SO4) electrolyte.

Chemistry of Lead Acid Batteries

When the battery is charged:

• The process reverses; lead sulfate combining with water to build up lead and lead oxide on the electrodes.

Lead Acid Batteries Consist of:

Lead (Pb) electrode (-) Lead oxide (PbO2) electrode (+) Water and sulfuric acid (H2SO4) electrolyte.

PbSO4 + 2e- Pb + SO42-

PbSO4 + 2H2O PbO2 + SO42- + 4 H+ + 2e-

Global reaction:2 PbSO4 + 2 H2O Pb + PbO2 + 2 H2SO4

Accumulateur au Pb acide

-

+

- 0.36 V

1.69 V

Pb/PbSO4

PbSO4/PbO2

Accumulateur au Pb acide

-

+

- 0.36 V

1.69 V

Pb/PbSO4

H2O /O2

PbSO4/PbO2

1.23 V

0 V H2 /H+

vs. ENH

Pt/H2SO4(aq)/Pt vs Pb/H2SO4(aq)/PbO2

Platinum

Platinum

H2SO4 solution H2SO4 solution

O2H2

Pt/H2SO4(aq)/Pt vs Pb/H2SO4(aq)/PbO2

Platinum

Platinum

H2SO4 solutionH2SO4 solution H2SO4

solutionH2SO4 solution

PbO2Pb

O2H2

ACCUMULATEUR

STRUCTURE D’UN SUPERCONDENSATEUR ÉLECTROCHIMIQUE

CAPACITÉ ÉLECTROCHIMIQUE

DOUBLE LAYER MODELS

Helmholtz Gouy-Chapman

Cdl = dq/d()

STRUCTURE OF THE DOUBLE LAYERModels of Grahame and Bockris

STRUCTURE DE LA DOUBLE COUCHE

• 1/C = 1/CI + 1/CO

• 1/C = 1/CI

• 1/C = dH2O/

• C= 5 x 8.85 x 10-12 F/m2.8 x 10-10 m= 16 F/cm2

CAPACITY FOR CARBON

CAPACITYCDL = 20 µF/cm2 with S = 1000 m2/g

C = 20 x 10-6 F/cm2 x 1000 m2/g x 104

cm2/m2

= 200 F/g

ACCUMULATEUR/CAPACITÉ ÉLECTROCHIMIQUE

ENERGY STORAGE DEVICESENERGY STORAGE DEVICES

• BATTERIES

• FaradaicFaradaic charge

• Chemical reaction

• SlowSlow charge/discharge process

• Shorter operational life

• High energy density

– 50-15050-150 Wh/kg

• SUPERCAPACITORS

• CapacitiveCapacitive or pseudocapacitive charge

• FastFast charge/discharge

• Long operational life

– > 1 000 0001 000 000 cycles• High power density

– > 11 kW/kg

MÉTHODES DE CARACTÉRISATION

• CELLULE ÉLECTROCHIMIQUE• VOLTAMÉTRIE CYCLIQUE• CHARGE/DÉCHARGE À COURANT CONSTANT• PERFORMANCES

– ÉNERGIE, PUISSANCE

CelluleCellule

VOLTAMETRIE CYCLIQUE

VOLTAMÉTRIE CYCLIQUE- Électrode capacitive

CALCUL DE LA CAPACITÉ

C = QCV/V

C= CapacitéQcv = ChargeV= Voltage

UNITÉSFarad = Coulombs/Volt

Imoyen = 45 mAV = 2.25 VVitesse de balayage = 225 mV/sMasse = 10 mgC = 20 F/g

CHARGE/DÉCHARGE À COURANT CONSTANT

COURBE CHARGE/DÉCHARGE

CAPACITÉ => Inverse de la pente

CHARGE ET CAPACITÉ

COULOMBIC EFFICIENCY, CE

CE (%) =

Qdischarge x 100

Qcharge

PERFORMANCEDensité d’énergie et de puissance

Densité d’énergie, Wh kg-1 Densité de puissance, W kg-1

ELECTROCHEMICAL CAPACITOR

Electrolyte

Current collector

ACTIVE ELECTRODE MATERIAL

Current collector

Equivalent Series Resistance (ESR)

CONTRIBUTION TO ESR-ELECTRONIC RESISTANCE OF THE ELECTRODE MATERIAL

-INTERFACIAL RESISTANCE – ELECTRODE/CURRENT COLLECTOR

-IONIC DIFFUSION RESISTANCE OF IONS MOVING IS SMALL PORES

-ELECTROLYTE RESISTANCE

-IONIC RESISTANCE OF IONS MOVING THROUGH THE SEPARATOR

COMPOSANTS D’UN SUPERCONDENSATEUR ÉLECTROCHIMIQUE

• MATÉRIAUX D’ÉLECTRODES– Carbones, Oxydes, Polymères conducteurs– Fabrication de l’électrode (additifs)

• ÉLECTROLYTE– Aqueux, Non-aqueux, Liquide ionique

• COLLECTEUR DE COURANT• SÉPARATEUR

EC-Areas of research

Electrolyte-Aqueous-Non-aqueous-Ionic liquid

Current collector: Surface treatment

Electrode materials:CarbonConducting polymersMetal oxides

PERFORMANCE

COST STABILITY/SAFETY

TECHNOLOGY

MATÉRIAUX D’ÉLECTRODES

MATERIALS-CAPACITANCE

K. Naoi, P. Simon, Interface, 2008, 17, 34

E = 0.5 CV2

CARBONE

• SURFACE SPÉCIFIQUE

• ACTIVATION– Température élevée

• COÛT

ELECTROCHEMICAL CAPACITOR

Symmetrical cell with 2 identical electrodes

PROPERTIES OF ACTIVATED CARBONS

Pore of activated carbon

Larger than 500Å

Smaller than 20Å

20Å ~ 500Å

Most surface area is composed of micropores ( more than 90%)

Carbon ElectrolyteDouble-layerCapacitance (F/g)

Specificcapacitance?F/cm2

Remarks

Activatedcarbon

10% NaCl 228 19 1200 m2/g

Activatedcarbon

1MEt4NBF4/PC

112 5.4 2000 m2/g

Carbon fibercloth

0.5MEt4NBF4 /PC

130 6.9 1630 m2/g

Graphite :basal: edge

0.9 N NaF 3 50-70

Highly orientedpyrolyticgraphite

Carbonaerogel

4M KOH 23 650 m2/g

Et4NBF4: tetraethylammonium tetrafluoroboratePC : propylene carbonate

Double-layer capacitance of some carbons

Micropores are likely to contribute the most to the energy storage

CAPACITANCE – SURFACE AREA

EFFECT OF PORE SIZE OF THE CARBON ELECTRODE

(CH3CH2)4N+

DiameterDesolvated: 0.68 nmSolvated; 1.33 nm

BF4-

Desolvated: 0.48 nm Solvated: 1.16 nm

FARADAIC PROCESS => Electron transfer

[Fe(CN)6]3- + e- <==> [Fe(CN)6]4-

PbSO4 + 2 H2O <==> PbO2 + 4 H+ + SO42- + 2 e-

CAPACITÉ ET PSEUDOCAPACITÉ

Cpseudo = 10 to 100 Cdl

Transfert d’électron à l’interface électrode/électrolyte

PSEUDOCAPACITÉ

MANGANESE DIOXIDE, MnO2

0.1 M Na2SO4/H2O @ 5 mV/s

Thin film

Composite

CHARGE STORAGE MECHANSIM FOR MANGANESE DIOXIDE

•Mn4+/3+

– MnO2 + H+ + e- <=====> MnOOH

– MnO2 + C+ + e- <=====> MnOOC

•Mn = no change

– (MnO2)surface + C+ + e- <=====> (MnO2-C+) surface

CHARGE STORAGE-CRISTALINITY

THIN ‘’FILM’’ ELECTRODE XPS-Mn 3s

Toupin, Brousse and Bélanger, Chem. Mat. 2004, 16, 3184.

0,0 0,2 0,4 0,6 0,8 1,0-0,00015

-0,00010

-0,00005

0,00000

0,00005

0,00010

0,00015

I(A

)

E(V) vs Ag/AgCl

Na2SO4 0.1 M

Mn(IV)

Mn(III)

Pt/MnO2

STRUCTURE-CAPACITANCE RELATIONSHIP

Brousse et al. J. Electrochem. Soc. 2006, 153, A2171.

CAPACITANCE vs. SURFACE AREA for Manganese Dioxide

•MnOMnO22/PTFE/AB/graphite (forte polarisation en absence de carbone)/PTFE/AB/graphite (forte polarisation en absence de carbone)

•Fenêtre électrochimique Fenêtre électrochimique 0,9-1V 0,9-1V

• Capacité ~ 150 F/gCapacité ~ 150 F/g

• qqchargecharge/q/qdéchargedécharge100 % (bonne réversibilité des processus électrochimiques)100 % (bonne réversibilité des processus électrochimiques)

0.1M Na2SO4 - 2 mV/s

Capacitive behaviour of MnO2

MAXIMIZE UTILIZATION

Mn4+

Mn3+

MnO2

CBinder

Mn4+

Mn3+

MnO2

CBinder

Low electronic conductivity

Low ionic conductivity

e-C+= Li+, Na+, K+, H+

Carbon

MnO2Binder

Increase electronic conductivity

Increase ionic conductivity

Mass of MnO2

(mg/cm2)

Electrode thickness

(µm)Qcv/Qtheo

3 281 12.9

15-16 290 13.0

30-34 555 12.2

45 596 12.5

ELECTROCHEMICAL UTILIZATION OF MnO2

POLYMÈRES CONDUCTEURS

Electrochemistry of conducting polymersElectrochemistry of conducting polymers

Solution

Polymer

p-doping

p-dedoping

- +

+ ++

++-e-

-

+

-

+

-

+

-

+

-

+

-

+

+

++

++

- -

--

--

-

- - -

-

-

+

- +

-

+

-

+

-

+

-

+

-

+

-

+

+

+

p-dedoping

n-doping

- --

--

- - - --

+e-

+ ++

+ + +

+

+

+++

+

+++

- +

-

+

-

+

-

+

-

+

+

-

+

+

+

- +

-

+

-

+

-

+

-

+

-

+

-

+

+

+

POLYTHIOPHENE DERIVATIVEPOLYTHIOPHENE DERIVATIVE

P-n-doping

n-undoping+Et4N+ P Et4N+

p-doping

p-undopingBF4

- P+ P+BF4

-

V

-0.008

-0.006

-0.004

-0.002

0

0.002

0.004

0.006

0.008

-2.5 -2 -1.5 -1 -0.5 0 0.5 1

Cur

rent

(A

)

Potential (V/(Ag/Ag+))

GALVANOSTATIC GALVANOSTATIC CHARGE/DISCHARGE CYCLINGCHARGE/DISCHARGE CYCLING

PFPT/PFPTCut-off voltages: 1.6 to 2.8 ; 3.0 and 3.2 V

ICh = IDch = 2 mA/cm2 in 1 M Et4NBF4/ACN

E’

E

Cou

rant

(A

)

Potentiel (V vs. Ag/Ag+)Temps (s)

Pote

nti e

l de

cell

ule

(V)

MODE DE FONCTIONNEMENT

Cellule symétriqueCellule asymétrique

SYSTÈME SYMÉTRIQUE

NÉGATIVE POSITIVE

CARBON-BASED ELECTROCHEMICAL CAPACITORS

Potential

Current

Charge


Potential

Current

Discharge

VoltammetricCharge = QCV


Potential

Current

Voltammetric charge = QCV

QCV (ox)

QCV (red)

50% of the carbon is unemployed!

50% of the carbon is unemployed!

Qdischarge (-) = 0.5 QCV (ox)

Qdischarge (+) = 0.5 QCV (red)

CAPACITANCE OF A CELL

Single electrode capacitanceC+ = C- = 100 F/g

Capacitance of a cell(weight of both electrodes)

25 F/g

CARBON/CARBON

• NON-AQUEOUS ELECTROLYTE– CELL VOLTAGE = 3 V

• AQUEOUS ELECTROLYTE-CELL VOLTAGE = 1 V

Can an electrochemical capacitor have a cell potential > 1 V?

SYSTÈME HYBRIDE

CARBON/MnO2

J. Long, D. Bélanger, T. Brousse, W. Sugimoto, M.B. Sassin, O. CrosnierAsymmetric electrochemical capacitors—Stretching the limits of aqueous electrolytesMRS Bulletin, 2011, 36, 523

SYSTÈME HYBRIDE

MnO2/MnO2

Carbone/MnO2

CARBON/MnO2

CHARGE/DISCHARGE CURVES

MnO2/MnO2

Carbon/MnO2

0 50 100 150 200 2500,0

0,5

1,0

1,5

2,0

2,5

(a)0.53 A/g

(c)0.55 A/g

(b)0.45 A/g

E c

ell (

V)

time (s)

Symétrique vs Asymétrique- Effet du potentiel de Symétrique vs Asymétrique- Effet du potentiel de cellule cellule

SYSTÈME CARBONE/OXYDE DE PLOMBÉLECTROLYTE: ACIDE SULFURIQUE

C/H2SO4/PbO2

SUPERCAPACITÉS ÉLECTROCHIMIQUES Daniel Bélanger Université du Québec à Montréal...

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