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 Power

Chemical Reactions

Electrochemical battery / Power generation

Voltas 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
Me1

ANODE
Me2

Me1n+

SO42-

Salt Bridge

Me2n+

SO42-

IMPORTANT NOTICE !
Electrolysis
System consumes energy G>0

Battery
System releases energy G<0

(oxidation process)

ANODE

(oxidation process)

ANODE

CATHODE

(reduction process)

(reduction process)

CATHODE

Principles of power generation in the electrochemical systems

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

CATHODE
Me1

ANODE Diaphragm or Membrane

Me2

Me1n+

SO42-

Me2n+

SO42-

Primary batteries
Leclanchs battery (1866)
Georges Leclanch (1839-1882)

Anode: Zn Zn2+ + 2eCathode: 2MnO2 + 2H2O +2e- 2MnOOH + 2OHElectrolyte: Zn2+ 2NH4Cl +2OH- Zn(NH3)Cl2 + 2H2O 2MnO2 + Zn + 2NH4Cl 2MnOOH + Zn(NH3)Cl2

Seal Zn-container MnO2 paste (cathode) Carbon rod NH4OH electrolyte

Primary batteries
Zinc-Manganese alkaline battery
Porous Zn (anode) Anode: Zn + 2OH - 2e Zn(OH)2

MnO2 paste (cathode) Gel electrolyte

Cathode: MnO2 + H2O +1e- MnOOH + OHaaaaaaaaa 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
Pb+(2H++SO42-)-2edischarge charge PbSO4+ 2H+ PbO2+(2H++SO42-)+2H++2ePbSO4+H2O discharge charge

PbSO4

PbSO4 Lead paste in Pb-mesh (anode)

Lead dioxide paste in Pb-mesh (cathode) Porous separator

discharge PbO2 + Pb + 2 +SO4 + H2SO4 = 2PbSO4 + 2H2O 4 + 2H2O 2PbSO PbOH2 Pb

Secondary (rechargeable) batteries

Lithium-ion battery
Discharge Cathode: LiMeO2 - xeAnode: Charge
Anode (CLix) Cathode (LiMexOy) LiCoO2 -utilized for commercial batteries LiNiO2, LiMn2O4-prospective Separator Negative terminal
CHARGE DISCHARGE

Li1-xMeO2 + xLi+ CLix

C + xLi+ + xe-

CHARGE DISCHARGE

Aluminum can Positive terminal

Secondary (rechargeable) batteries

Nickel-Metal Hydride battery
Cathode: NiOOH + H2O - eAnode: Me + OH+ eCHARGE DISCHARGE CHARGE DISCHARGE

Ni(OH)2 + OH-

Me + H2O

Picture from: T. Takamura / Solid State Ionics 152-153(2002)19

Types of the electrochemical system for electric power generation

Reductant (fuel) Oxidant

Primary batteries

Secondary batteries

Fuel cells

POWER

POWER

POWER

Recharge

Reaction products (exhaust)

POWER

Groves fuel cell (1839)

O2 H2

Sir William Grove 18111896

4H+ + 4e- 2H2 2H2O - 4e- O2 + 4H+

Fuel Cells performance improving

Raising the current: Increasing the temperature Increasing the area of eelectrode electrolyte interface The use of catalyst
Cathode catalyst Anode catalyst

Raising the voltage:

Connection of cells in series Cell stack ANODE ELECTROLYTE CATHODE ANODE ELECTROLYTE ANODE CATHODE ELECTROLYTE ANODE CATHODE ELECTROLYTE CATHODE ANODE ANODE ELECTROLYTE ELECTROLYTE CATHODE CATHODE ANODE ELECTROLYTE CATHODE

Bipolar electrode

H2

O2

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

H2

Gas Diffusion Electrode

Dry zone (no reaction)

Electrode

H2
Gas

Reaction zone

eeElectrolyte
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
Anode Liquid electrolyte Cathode

O2

Proton Exchange Membrane Fuel Cell (PEMFC)

H2O +Air (O2)

H2

Nafion membrane
Catalyst support (carbon cloth)

Current collector / gas distributor

H+
H2 crossover

H2

Air (O2)

Proton Exchange Membrane (PEM)

Ethylene

H H C C

H H

Polymerization

H H H H H H C C C C C C H H H H H H
Fluorination

Polyethylene

F F F F F F C C C C C C

F O F F F F F F F F F F F C F Grafting C C C C C C F C F F F F F F F O F C F Polytetrafluoroethylene (PTFE, Teflon) F C F O S O - H+ Nafion (DuPont) O

Fuel reforming
CnHm + nH2O = nCO + (m/2 + n)H2 CH4 + H2O = CO + 3H2 CO + H2O = CO2 + H2 CH3OH + H2O = 3 H2 + CO2 no CO CH4 + O2
Catalyst Stainless still Catalyst HEAT T~ 250 oC, Ni-catalyst T~ 500 oC, Ni-catalyst

CO2 + H2O

CH4 + H2O

H2 + COx

Direct Methanol Fuel Cell (DMFC)

CH3OH + H2O + CO2 H2O +Air (O2)

Nafion membrane
Current collector / fuel distributor Catalyst support (carbon cloth)

H+
CH3OH crossover

CH3OH + H2O

Air (O2)

Direct Methanol Fuel Cell (DMFC)

Theoretical voltage = 1.182 V Real voltage Current

0.046

Potential vs. HRE, V

1.23

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 90 90 90

Current density, A cm-2 0.1 0.2 0.3

Crossover rate, A cm-2 0 .32 0.30 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 = jcSt/nF, 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
Anode: Pt or PtRu (~50% Pt) black 1-10 nm Cathode: Pt (~50% Pt) black 1-10 nm Catalysts are supported on carbon nanoparticles (50-200 nm, for example Vulcan XC72) Precious metals load is 0.2 - 0.5 mg cm-2 for both electrodes

DMFC
Anode: usually PtRu (~50% Pt) black 1-10 nm Cathode: Pt (~50% Pt) black 1-10 nm Catalysts are usually unsupported

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

Power density - 500 mW cm -2 at cell voltage 0.5 V (t=80 oC, CO-free hydrogen) Catalysts cost ~ 0.8 g per kW ( ~140 CAN$ per kW)

Power density - 100 mW cm -2 at cell voltage 0.5 V (t=90 oC, CH3OH concentration - 0.75 M) Catalysts cost ~ 10 g per kW ( ~1750 CAN$ per kW)

Molten Carbonate Fuel Cell (MCFC)

NiCr alloy
H2 +CO2 + H2O

Anode

Porous electrolyte support Alkali metal carbonates in LiAlO2 matrix CO32-

Cathode

LiNiO2 or LiCoO2

O2 +CO2 O2 +CO2

H2
0.2 - 1.5 mm 0.5 - 1.0 mm 0.5 - 1.0 mm

2H2 +

2CO32-

4e-

T= 600-700 oC

= 2H2O + 2CO2

O2 + 2CO2 + 4e - = 2CO32-

Solid Oxide Fuel Cell (SOFC)

Anode H2 + H2O O2H2
YSZ 2H2 + 2O2- - 4e - = 2H2O Ni+YSZ

Electrolyte

Cathode

Sr doped La-manganite

O2 O2
O2 + 4e - = O2-

T= 800-1100 oC

Electrolyte Anode Air Air

Cathode

Fuel

Types of Fuel Cells

Mobile ion Operating temperature ~220 oC Power range 10 - 1000 kW

Phosphoric Acid Fuel Cell (PAFC) Proton Exchange Membrane Fuel Cell (PEMFC) Direct Methanol Fuel Cell (DMFC) Molten Carbonate Fuel Cell (MCFC) Solid Oxide Fuel Cell (SOFC)

H+

H+

50 - 100 oC

1 - 100 kW

H+

50 - 100 oC

1 - 100 kW

CO32O2-

~650 oC

0.1 - 10 MW

500 - 1000 oC

0.01 - 10 MW