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MSE 156/256 - Solar Cells, Fuel Cells and

Batteries: Materials for the Energy Solution


Stanford University
Autumn 2012
Unit 11: Battery Types, Construction and
Performance
Specific charge for different technologies
Battery examples
Alkaline
Ni-metal hydride
Li ion
General battery construction
Rechargeable battery issues
Battery potential under use
Current-voltage characteristics
Battery lifetime issues

User:Alksub / Wikimedia Commons / CC-BY-SA-3.0

Anode Material Capacities


Material Atomic or Standard Valence Density Specific
molecular Potential at Change (g/cm3) Charge
weight 25C (V) (Ah/g)
(g/mol)
H2 2.01 0.00 2 26.59
Li 6.94 -3.01 1 0.54 3.86
Na 23.0 -2.71 1 0.97 1.16
Mg 24.3 -2.38 2 1.74 2.20
Al 26.9 -1.66 3 2.69 2.98
Ca 40.1 -2.84 2 1.54 1.34
Fe 55.8 -0.44 2 7.85 0.96
Zn 65.4 -0.76 2 7.14 0.82
Cd 112.4 -0.40 2 8.65 0.48
Pb 207.2 -0.13 2 11.34 0.26
(Li)C6 72.06 -2.8 1 2.25 0.37
MH 116.2 -0.83 2 0.45
Li-ion Alkaline MnO2
Ni-Cd Pb acid

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Cathode Material Capacities
Material Atomic or Standard Valence Density Specific
molecular Potential at Change (g/cm3) Charge
weight 25C (V) (Ah/g)
(g/mol)
O2 32.0 1.23 4 3.35
Cl2 71.0 1.36 2 0.756
SO2 64.0 1 0.419
MnO2 86.9 1.28 1 5.0 0.308
NiOOH 91.7 0.49 1 7.4 0.292
CuCl 99.0 0.14 1 3.5 0.270
FeS2 119.9 4 0.89
AgO 123.8 0.57 2 7.4 0.432
Br2 159.8 1.07 2 0.335
HgO 216.6 .010 2 11.1 0.247
Ag2O 231.7 0.35 2 7.1 .0231
PbO2 239.2 1.69 2 9.4 0.224
LixCoO2 98.0 2.7 0.5 0.137

Li-ion Ni-Cd Pb acid Alkaline MnO2

Alkaline Battery Example


Oxidizing Zn at
the anode
Reducing MnO2 at
the cathode

Standard Potential

Load
Theoretical specific charge: e-
Zn anode OH- MnO2 cathode

H 2O Aqueous
KOH
electrolyte

Actual specific charge = 2.8 Ah/25 g = 0.11 Ah/g

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Alkaline Battery Construction

Theoretical specific charge = 0.22 Ah/g


Where is our factor of two!!?
Actual capacity = 2.8 Ah/25 g = 0.11 Ah/g

Anode is Zn powder gel


Cathode made of MnO2
and carbon powder
pressed into tablets and
inserted into can
Separator soaked in
aqueous KOH electrolyte

Nickel Metal Hydride


Discharging (use) Cell Reactions
Anode Oxidizing metal hydride
Cathode Reducing nickel oxyhydroxide
Cell

Load
M = hydride forming metal e-
e.g. LaNi5 which forms LaNi5H6
M anode OH- NiOOH cathode
More generally AB5 where:
A = La, Ce, Nd, Pm, and H 2O Aqueous
B = Ni, Co, Mn KOH
electrolyte
Theoretical specific charge:

Actual specific charge = 2.3 Ah/28 g = 0.08 Ah/g

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Li Ion Batteries
Discharge
Graphitic CoO2 Layers
sheets Li+

Charge
LixC6 anode Li Ion Electrolyte LiCoO2 Cathode
Both anode and cathode reactions are intercalation reactions, meaning
that Li is shuttled in and out of existing, layered structure.
Discharging (use) Cell Reactions
x,y not fixed, but
Anode depend on charging
Cathode and operating
conditions
Cell
Specific Charge Capacity:
Anode has specific charge of 0.37 Ah/g Cell specific charge is 0.10 Ah/g
Cathode has specific charge of 0.137 Ah/g
Actual capacity = 0.94 Ah/19 g = 0.05 Ah/g
This is about half that of an alkaline battery. But the voltage is over twice as high (4.1 V
vs 1.5 V), so the specific energy is greater

Li Ion Batteries
Electrolyte:
Non aqueous electrolyte needed
Cell voltage is high enough to decompose water
Li reacts strongly with water
Electrolytes are:
Li salts such as LiPF6, LiBF4, or LiClO4
In organic solvent such as ethylene carbonate, dimethyl carbonate
Electrolyte reacts with anode
Controlled reaction produces reaction product called solid electrolyte
interphase (SEI) that prevents further reaction

Organic/Li-Salt
Electrolyte
Cu Contact Al Contact

Anode SEI Cathode


LixC6 Separator LiMO
RudolfSimon / Wikimedia Commons / CC-BY-SA-3.0

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Battery Construction
Battery design is a trade-off between high rate and high capacity
High rate batteries will have large surface areas between electrodes
High capacity batteries will have maximum amount of material

Bobbin construction Spirally wound construction


High capacity High rate
Alkaline-MnO2 Li-ion, NiMH, NiCd
Zn-C High-rate primary batteries

1. outer metal casing (also negative terminal)


2. separator (between electrodes)
3. positive electrode
4. negative electrode with current collector (metal
grid, connected to metal casing).

Rechargeable Battery Materials


Chemical oxidation and reduction
reactions must be reversible with
recharging, resulting in electrodes
recovering their original chemical
and physical state.
Repeated oxidization and
reduction (dissolution and re-
deposition) of electrode materials
can result in rough or filamentary
structures. These can eventually Marco Polo GNU Free Documentation License 1.2
result in shorts across the
electrolyte.

Reactions should be reversible safely


Example: Alkaline battery reaction is reversible
Capacity diminishes with each cycle
Recharging can evolve hydrogen!

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Polarization Losses in Batteries

Normalized Cell Power (P/(E0 Imax))


Normalized Cell Voltage (V/E0)
1.0 0.5

0.8 0.4

0.6 0.3
0.4 0.2

0.2 0.1

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0
Normalized Cell Current (I/Imax)

Energy losses Energy losses


associated with the Energy losses from electronic
impedances (electrodes, associated with mass
electrode reactions transport limitations
(Surface reaction contacts, and current
collectors) and ionic (reactants and/or
kinetics) products
impedances (from electrolyte)

Real Battery Potential and Lifetime

I Cell current
Load resistance
Ri
Rload
Internal resistance
Concentration polarization potential
Internal Resistance Activation potential
Electrolyte resistance
Internal contacts
Electrode bulk resistance
Electrode surface resistance
Can increase with time and cycling as surfaces are contaminated and reactions occur
e.g. Increase of SEI thickness
Other Degradation Mechanisms
Battery Capacity

Parasitic reactions consuming electrolyte,


electrodes
Other losses of battery materials
e.g. Evaporation of electrolyte during
charging
Battery lifetime depends on:
Temperature, depth of discharge, etc.
Battery technology Cycle Number

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Real Battery Discharge Behavior
Theoretical voltage is the cell potential we discussed earlier
Open circuit voltage is usually close to the theoretical voltage
Nominal voltage is one that is generally accepted as typical of the operating
voltage of the battery as, for example, 1.5 V for a zinc-manganese dioxide
battery.
Working voltage is more representative of the actual operating voltage of the
battery under load and will be lower than the open-circuit voltage.
End or cut-off voltage is designated as the end of the discharge. Usually it is the
voltage above which most of the capacity of the cell or battery has been
delivered. The end voltage may also be dependent on the application
requirements.

Typical discharge behavior


Pb-Acid Example 1.0
Voc = 2.1 V
0.8
Vnominal = 2.0 V

Voltage
Vworking = 1.8 - 2.0 V 0.6
Vend = 1.75 V (moderate discharge)
= 1.5 V (engine cranking loads) 0.4 Higher discharge
Vcharge = 2.3 - 2.8 V rate or internal
0.2 resistance
0.0
0.0 0.2 0.4 0.6 0.8 1.0
Time

MSE 156/256 - Solar Cells, Fuel Cells and


Batteries: Materials for the Energy Solution
Stanford University
Autumn 2012
Unit 11: Battery Types, Construction and
Performance
Specific charge for different technologies
Battery examples
Alkaline
Ni-metal hydride
Li ion
General battery construction
Rechargeable battery issues
Battery potential under use
Current-voltage characteristics
Battery lifetime issues

Coming up:

Unit 12: Fuel Cells

User:Alksub / Wikimedia Commons / CC-BY-SA-3.0