ELECTROCHEMICAL

SYSTEMS FOR ELECTRIC

POWER GENERATION

Dzmitry Malevich

Depatrment of Chemistry and Biochemistry

University of Guelph
Electric power conversion in electrochemistry

Electrolysis / Power consumption

Electric Chemical
Power Reactions

Electrochemical battery / Power generation

 Volta’s battery (1800)

Alessandro Volta
1745 - 1827

Paper moisturized with

NaCl solution

Cu

Zn
Principles of power generation in the electrochemical systems

Me2n+ - ne- = Me20 Me20 - ne- = Me2n+

CATHODE ANODE

Me2
Me1

Me1n+ SO42- Me2n+ SO42-

Salt Bridge
 IMPORTANT NOTICE !

Electrolysis Battery
System consumes energy System releases energy
∆G>0 ∆G<0

ANODE + ANODE -
(oxidation process) (oxidation process)

CATHODE - CATHODE +
(reduction process) (reduction process)
Principles of power generation in the electrochemical systems

Me2n+ - ne- = Me20 Me20 - ne- = Me2n+

CATHODE ANODE

Me2
Me1
Diaphragm
or
Membrane

Me1n+ SO42- Me2n+ SO42-

 Primary batteries

Leclanché’s
battery
(1866)

Georges Leclanché
(1839-1882)
Anode: Zn → Zn2+ + 2e-
Cathode: 2MnO2 + 2H2O +2e- → 2MnOOH + 2OH-
Seal Electrolyte: Zn2+ 2NH4Cl +2OH- → Zn(NH3)Cl2 + 2H2O
2MnO2 + Zn + 2NH4Cl → 2MnOOH + Zn(NH3)Cl2
Zn-container

MnO2 paste
(cathode)

Carbon rod

NH4OH
electrolyte
 Primary batteries
Zinc-Manganese alkaline battery

MnO2 paste (cathode) Porous Zn (anode) Anode: Zn + 2OH - 2e → Zn(OH)2

- -

Gel electrolyte
Cathode: MnO2 + H2O +1e- → MnOOH + OH-
aaaaaaaaa MnOOH + H2O +e- → Mn(OH)2 + OH-

Zinc-Air battery
Anode: Zn + 2OH- - 2e- → Zn(OH)2
Cathode: 1/2 O2 + H2O + 2e- → Zn(OH)2
 Secondary (rechargeable) batteries
E=2.06 V Lead-acid battery
Lead-acid battery

Pb PbO2 Safety valve

36% H2SO4
discharge discharge
Pb+(2H++SO42-)-2e- PbO2+(2H++SO42-)+2H++2e-
charge charge
PbSO4+ 2H+ PbSO4+H2O

Lead dioxide paste in

PbSO4 PbSO4 Pb-mesh (cathode)

Lead paste in Porous separator

Pb-mesh
PbO2 + Pb
PbO Pb4 + H2SOdischarge
+ 2H+2SO 2PbSO
4 = 2PbSO4 + 2H2O 4 + 2H2O (anode)
 Secondary (rechargeable) batteries
Lithium-ion battery
Cathode:
Discharge CHARGE
LiMeO2 - xe- Li1-xMeO2 + xLi+
DISCHARGE
Anode:
CHARGE
C + xLi+ + xe- CLix
Charge DISCHARGE

Anode (CLix)
Cathode (LiMexOy)
Negative terminal
LiCoO2 -utilized for commercial batteries
LiNiO2, LiMn2O4-prospective

Separator

Aluminum can

Positive terminal
 Secondary (rechargeable) batteries
Nickel-Metal Hydride battery
Cathode:
CHARGE
NiOOH + H2O - e- Ni(OH)2 + OH-
DISCHARGE

Anode:
CHARGE
Me + OH- + e- Me + H2O
DISCHARGE

Picture from: T. Takamura / Solid State

Ionics 152-153(2002)19
 Types of the electrochemical system for electric
power generation
Reductant Oxidant
(fuel)

Primary Secondary Fuel cells

batteries batteries

POWER POWER
POWER
Reaction
Recharge products
(exhaust)

POWER
 Grove’s fuel cell (1839)

O2 H2

Sir William Grove

1811–1896

4H+ + 4e- 2H2

2H2O - 4e- O2 + 4H+
 Fuel Cells performance improving
Raising the current: Raising the voltage:
Connection of cells
Cell stackin series
• Increasing the temperature
ANODE
• Increasing the area of
ELECTROLYTE
eelectrode electrolyte interface CATHODE
• The use of catalyst ANODE
ELECTROLYTE
ANODE
Anode catalyst Bipolar CATHODE
ELECTROLYTE
Cathode catalyst
electrode ANODE
CATHODE
ELECTROLYTE
H2 CATHODE
ANODE
ANODE
ELECTROLYTE
ELECTROLYTE
CATHODE
O2 CATHODE
ANODE
ELECTROLYTE
CATHODE
Electrolyte frame Bipolar plate
Phosphoric Acid Fuel Cell (PAFC)
Electrolyte in SiC porous matrix

O2
Pt-particles catalysts
(anode or cathode)

Gas (H2 or O2)

PACF parameters:
current density - 200- 400 mA cm-2
At atmospheric
pressure single cell voltage - 600-800 mV
temperature - 220 oC

H2
 Gas Diffusion Electrode

Dry zone (no reaction)

Electrode

Reaction zone
H2

Gas
e-
e-
Electrolyte

Reaction zone

Dip zone (reaction is

slow because diffusion
limitation)
Disadvantages of liquid electrolyte fuel cell
Low operation temperature !
(reaction is slow, expensive catalysts
are needed to produce valuable current)

Difficulties in three-phase interface

maintaining !

Strong fuel crossover!

Recombination (no electron transfer through
outer socket - energy loss)

H2 O2
Anode Liquid electrolyte Cathode
Proton Exchange Membrane Fuel Cell (PEMFC)

H2O +Air (O2)

H2
Nafion®
membrane
Catalyst support
Current collector /
(carbon cloth)
gas distributor
H+

H2 crossover
H2 Air (O2)

- +
 Proton Exchange Membrane (PEM)
Ethylene Polyethylene
H H H H H H
H H Polymerization
C C C C C C
C C
H H H H H H H H
F F F F F F
Fluorination
C C C C C C
F O F F F F
F F F F F F
F C F Grafting

F C F C C C C C C
O F F F F F F
F C F Polytetrafluoroethylene (PTFE, Teflon®)
F C F
O S O
- Nafion® (DuPont)
O H +
 Fuel reforming

CnHm + nH2O = nCO + (m/2 + n)H2

CH4 + H2O = CO + 3H2 T~ 500 oC, Ni-catalyst

CO + H2O = CO2 + H2
CH3OH + H2O = 3 H2 + CO2 T~ 250 oC, Ni-catalyst

no CO

CH4 + O2 CO2 + H2O

Catalyst

Stainless still HEAT

Catalyst
CH4 + H2O H2 + COx
 Direct Methanol Fuel Cell (DMFC)

CH3OH + H2O + CO2 H2O +Air (O2)

Nafion®
membrane
Catalyst support
Current collector /
(carbon cloth)
fuel distributor
H+
CH3OH
crossover
CH3OH + H2O Air (O2)

- +
 Direct Methanol Fuel Cell (DMFC)

Theoretical voltage = 1.182 V

Real voltage
Current

0.046 1.23
Potential vs. HRE, V

CH3OH + H2O = CO2 + 6H+ + 6e- 3/2O2 + 6H+ + 6e- = 3H2O

 Carbon monoxide tolerant anode

carbon
oxygen
hydrogen
Ru

Pt
 Methanol crossover through Nafion

From M.P. Hogharth and G.A. Hards, Platinum Metals Rev. 40 (1996) 150

Temperature oC Current density, A cm-2 Crossover rate, A cm-2

90 0.1 0 .32
90 0.2 0.30
90 0.3 0.27
S. R. Narayanan, DOE/ONR Fuel Cell Workshop, Baltimore, MD, Oct 6-8 1999
Number of methanol moles (Nm) transported by crossover can be calculated by
Faraday low:
Nm = jc·S·t/n·F, where j - current density(crossover rate) , S - membrane area, t -
time, n-number of electrons (n=6 for methanol oxidation), F - Faraday constant
 Catalysts for fuel cells with polymer electrolyte

PEMFC DMFC

Anode: Pt or PtRu (~50% Pt) black 1-10 nm Anode: usually PtRu (~50% Pt) black 1-10 nm
Cathode: Pt (~50% Pt) black 1-10 nm Cathode: Pt (~50% Pt) black 1-10 nm

Catalysts are supported on carbon nanoparticles Catalysts are usually unsupported

(50-200 nm, for example Vulcan XC72)

Precious metals load is 0.2 - 0.5 mg cm-2 Precious metals load is 1.0 - 10.0 mg cm-2
for both electrodes for both electrodes

Power density - 500 mW cm -2 at cell voltage 0.5 V Power density - 100 mW cm -2 at cell voltage 0.5 V
(t=80 oC, CO-free hydrogen) (t=90 oC, CH3OH concentration - 0.75 M)

Catalysts cost ~ 0.8 g per kW Catalysts cost ~ 10 g per kW

( ~140 CAN$ per kW) ( ~1750 CAN$ per kW)
 Molten Carbonate Fuel Cell (MCFC)
Anode Porous electrolyte support Cathode
NiCr alloy LiNiO2 or
Alkali metal carbonates LiCoO2
in LiAlO2 matrix
H2 +CO2 + H2O O2 +CO2
CO32-
H2 O2 +CO2

0.2 - 1.5 mm 0.5 - 1.0 mm 0.5 - 1.0 mm

T= 600-700 oC O2 + 2CO2 + 4e - = 2CO32-
2H2 + 2CO32- - 4e- = 2H2O + 2CO2
 Solid Oxide Fuel Cell (SOFC)
Anode Electrolyte Cathode Sr doped La-manganite

H2 + H2O
O2
O2-
H2 O2
YSZ
2H2 + 2O2- - 4e - = 2H2O O2 + 4e - = O2-
Ni+YSZ
T= 800-1100 oC
Electrolyte
Anode

Air Air

Fuel
Cathode
 Types of Fuel Cells
Mobile Operating Power
ion temperature range

Phosphoric Acid H+ ~220 oC 10 - 1000 kW

Fuel Cell (PAFC)

Proton Exchange
Membrane Fuel Cell H+ 50 - 100 oC 1 - 100 kW
(PEMFC)

Direct Methanol H+ 50 - 100 oC 1 - 100 kW

Fuel Cell (DMFC)

Molten Carbonate
CO32- ~650 oC 0.1 - 10 MW
Fuel Cell (MCFC)

Solid Oxide O2- 500 - 1000 oC 0.01 - 10 MW

Fuel Cell (SOFC)