Chương 7

Nguồn điện hóa học

7.1 Mở đầu
Nguồn điện hóa học: thiết bị điện hóa chuyển năng lượng
hóa học thành năng lượng điện thông qua mạch điện hóa.

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1. Primary (single-discharge) batteries. A primary battery contains
a finite quantity of the reactants participating in the reaction; once this
quantity is consumed (on completion of discharge), a primary battery
cannot be used again (“throwaway batteries”).

2. Storage (multiple-cycle) batteries (also called secondary or

rechargeable batteries). On the completion of discharge, a storage
battery can be recharged by forcing an electric current through it in the
opposite direction; this will regenerate the original reactants from the
reaction (or discharge) products. Good rechargeable batteries or cells will
sustain a large number of such charge–discharge cycles (hundreds or
even thousands).

3. Fuel cells. In the fuel-cell mode of operation, reactants are fed into
the cell (or battery) continuously while reaction products are removed
continuously. Hence, fuel cells can deliver current continuously for a
considerable length of time that depends primarily on external reactant
storage.
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7.2 Nguồn điện sơ cấp
Pin Leclanche muối

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Pin Leclanche kiềm

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7.3 Nguồn điện thứ cấp
Ắc quy chì

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7.4 Pin lithium

Lithium Cells are Primary cells in which lithium acts as anode

and cathode may differ. Lithium metal is used as anode
because of its light weight, high standard oxidation
potential(>3v) and good conductivity.
As the reactivity of lithium in aqueous solution is more,
Lithium cells use non aqueous solvents as electrolyte.

Lithium cells are classified into two categories:

a) Lithium cells with solid cathodes
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b) Lithium cells with liquid cathodes
 (a) Lithium cells with solid cathode: The
electrolyte in these systems is a solid electrolyte most
widely used cell is Lithium-Manganese dioxide cell(3V)
MnO2 should be heated to over 3000C to remove water
before keeping it in the cathode, thereby the efficiency
of the cell is increased.
Anode: Lithium metal
Cathode: MnO2 as an active material
Electrolyte:LiBF4 salt in a solution of propylene
carbonate and dimethoxy ethane.
Reactions:
At Anode: Li  Li+ +e-
At Cathode: e-+ MnO2  MnO2-
Net reaction: Li + MnO2  Li MnO2
Applications: 1) The coin type cells are used in watches and
calculators 21

2) Cylindrical cells are used in fully

automatic cameras.
(b) Lithium cells with Liquid cathode:
Lithium- Sulphur dioxide cell is an example of liquid cathode. The co-
solvents used are acrylonitrile or propylene carbonate (or) mixture of the
two with SO2 in 50% by volume.
Cell reaction: 2Li + 2SO2 → LiS2O4
Lithium thionyl chloride cell is another example of liquid cathode. It
consists of high surface area carbon cathode, a non-woven glass separator.
Thionyl chloride acts as electrolyte and as cathode.
Cell Reaction:
At Cathode: 4Li → Li + 4e-
At Anode: 4 Li + 4e- + 2 SOCl2 → 4 LiCl + SO2 +S
4 Li + 2 SOCl2 → 4 LiCl + SO2 +S
In this cell no co- solvent is required as SOCl2 is a liquid with moderate
vapour pressure.
The discharging voltage is 3.3- 3.5 V.
Uses: 1) They are used for military and space application.
2) In medicinal devices like neuro-stimulators, drug delivery systems,
lithium batteries are widely used.
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3) They are also used in electric circuit boards for supplying fixed voltage
for memory protection and standby functions.
7.5 Pin nhiên liệu
POLYMER ELECTROLYTE MEMBRANE
FUEL CELL
 Chemical structure of Nafion

 Hydration of membrane dissociates proton of acid

group
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 Solvated protons are mobile in polymer and provide
conductivity
 POLYMER ELECTROLYTE MEMBRANE
FUEL CELL

Anode: C/Pt Cathode: C/Pt

H2 O2
H+

H2O
NAFION

H2  2H+ + 2e- O2 + 2H+ + 2e-  H2O2

H2O2 + 2H+ + 2e-  H2O 24
 Advantages:
 Nonvolatile membrane
 CO2 rejecting electrolyte
 few material problems
 Problems:
 Slow O2 kinetics
 Hydration of membrane is difficult (30-60%)
 Formed at cathode, but difficult to keep in membrane
 Too little = dehydration and loss of ion transport

 Solutions

- Humidify gases
- Impregnate Nafion with SiO2 or TiO2

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DIRECT METHANOL FUEL CELL

Anode: Pt/Ru/C Cathode: Pt/C

N
A
F
I
O
N

O2 + 2H+ + 2e-  H2O2 26

CH3OH + H2O CO2 + 6H+ + 6e- H2O2 + 2H+ + 2e-  H2O
 DIRECT METHANOL FUEL CELL
 Pt catalyst have highest activity for MeOH oxidation
thus far
 Ru enhances MeOH catalytic activity
OH- forms at lower voltage
 CO blocks sites on Pt surface, Ru helps oxidize to CO2

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 Advantages:
 Direct fuel conversion – no reformer needed, all positive aspects
of PEMFC
 CH3OH – natural gas or biomass
 Existing infastructure for transporting petrol can be converted to
MeOH

 Problems:
 High catalyst loading (1-3mg/cm2 v. 0.1-0.3 mg/cm2)
 CH3OH hazardous
 Low efficiency (MeOH crossover – lowers potential)

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 Solving the Crossover Dilemma
 Alter thickness of polymer membrane
 Thinner = decreases ion flow resistance
 Thicker = decreases MeOH crossover

 Cs+ doped membranes

 Tricolli, University of Pisa, 1998
 Lower affinity for H2O

 MeOH tolerant cathodes

 Mo2Ru5S5 – N. Alonso-Vante, O. Solorza-Feria
 Higher oxygen reduction activity in presence of MeOH
 (Fe-TMPP)2O – S. Gupta, Case Western, 1997
 High oxygen reduction, insensitive to MeOH

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 SOLID OXIDE FUEL CELL
 1899 Nernst observed conduction in various
types of stabilized zirconia at T > 600oC
 1937 Baur and Preis demonstrated a fuel cell
based on zirconium oxide

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 SOLID OXIDE FUEL CELL
Anode = NiO-YSZ (Yttria
stabilized zirconia) 800-1000oC Cathode = La1-xSrxMnO3
cermet

H2, CxH2x+2 O2
O2- Interconnector
material = Mg
or Sr doped
Y doped lanthanum
ZrO2 (ZrO2 chromate
doped with
Y2O3)

H2 + O2-  H2O + 2e- OR O2 + 2e-  2O2-

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CH4 + 4O2-  2H2O + CO2 + 8e-
 Advantages:
 Solid electrolyte eliminates leaks
 H2O management, catalyst flooding, slow O2
kinetic are not problematic
 CO and CO2 are not problematic
 Internal reforming - almost any hydrocarbon or
hydrogen fuel
 Problems:

 Severe material constraints due to high T

 Stainless steel at lower temperatures

 Alloyed metal or Lanthanum Chromite

material
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