Dzmitry Malevich
Electric Chemical
Power Reactions
Alessandro Volta
1745 - 1827
Cu
Zn
Principles of power generation in the electrochemical systems
CATHODE ANODE
Me2
Me1
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
CATHODE ANODE
Me2
Me1
Diaphragm
or
Membrane
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
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
36% H2SO4
discharge discharge
Pb+(2H++SO42-)-2e- PbO2+(2H++SO42-)+2H++2e-
charge charge
PbSO4+ 2H+ PbSO4+H2O
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
POWER POWER
POWER
Reaction
Recharge products
(exhaust)
POWER
Grove’s fuel cell (1839)
O2 H2
O2
Pt-particles catalysts
(anode or cathode)
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
Reaction zone
H2
Gas
e-
e-
Electrolyte
Reaction zone
H2 O2
Anode Liquid electrolyte Cathode
Proton Exchange Membrane Fuel Cell (PEMFC)
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
CO + H2O = CO2 + H2
CH3OH + H2O = 3 H2 + CO2 T~ 250 oC, Ni-catalyst
no CO
Catalyst
CH4 + H2O H2 + COx
Direct Methanol Fuel Cell (DMFC)
- +
Direct Methanol Fuel Cell (DMFC)
Real voltage
Current
0.046 1.23
Potential vs. HRE, V
carbon
oxygen
hydrogen
Ru
Pt
Methanol crossover through Nafion
From M.P. Hogharth and G.A. Hards, Platinum Metals Rev. 40 (1996) 150
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
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)
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
Proton Exchange
Membrane Fuel Cell H+ 50 - 100 oC 1 - 100 kW
(PEMFC)
Molten Carbonate
CO32- ~650 oC 0.1 - 10 MW
Fuel Cell (MCFC)