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Discharged
Discharging state
Charged state
Cathode
Anode
C (graphite
LiC anode)
6 (graphite anode) FePO4 cathode
LiFePO4 cathode
= Li+
= LiPF6 Co
Li 3O4 (cobalt
2O/Co
oxide
o (cobalt anode)
oxide anode) CoO2 cathode
LiCoO2 cathode
Common to all Li ion batteries
Conducting
current
collectors
Anode
Cathode
Electrolyte
Seperator
Read: Arora, P., and Ahengming, Z., Chemical Reviews, 2004, 4419-4462
Electrolyte
The electrolyte must be a
good ionic conductor, and
an electronic insulator
Must be stable at
necessary potentials and
temperatures
Performs minimal side
reactions with electrodes
Much of battery failure
and degradation is caused
by electrolyte side
reactions
Tarascon, J.M. & Armand, M., Nature, 414, (2001) Xu, K., Chemical Reviews, 2004 4303-4417
Cathode SEI and internal
resistance
Cathodes can be fouled
by degradation of
electrolyte on the
surface of the material
For instance Ethyl
carbonate can form
polymeric olefins on the
surface of the electrode
Typically the SEI is a
poor ion conductor and
will increase the internal
resistance of the battery
Internal resistance
The internal resistance
increases in the battery
over time
The actual voltage output
is never exactly the same
when current is being
drawn from the battery as
when there is no current
being drawn
The higher the internal
resistance is, the lower
the observed voltage will
be when
Internal resistance measurement
3.0
U
I
Ri R
U
I
DU I sc
Ri Ri
2.978V
Chemical energy storage
Cell potential is determined by the difference in Gibbs
free energy of the Lithium in the anode and cathode
3.8-3.9 V vs. Li
3.7 V total
Characterization
The cell voltage is
the average voltage
of the discharge
cycle
LiCoO2 has an
average discharge
voltage of 3.7 V
From Nokia
Other Cathode Materials
LiFePO4
Li2MnSiO4
1. Ohzuku, T.; Brodd, R. J., J.Power Sources 2007, 174, (2), 449-456; 2. Amatucci, G. G.; Pereira, N., J. Fluorine
Chemistry 2007, 128, (4), 243-262; 3. Howard, W. F.; Spotnitz, R. M., J. Power Sources 2007, 165, (2), 887-891.
Capacity calculation on a typical
anode
8Li Co3O4 8e
4
Li2 O
Disch arg e
3Co 0
Ch arg e
Plateaus:
0.2 and 0.1 V/discharge
0.2 and 0.45V/charge
Capacity from 2nd cycle
Diameter: ~40 nm, free surface 501 mAh/g [AuLi3.69]
Discharge/charge curves from the
first two cycles
Au0.9Ag0.1
In order to discharge this electrode over one hour, apply a -0.499 mA current
Coin cell assembly
Used Mortar and
Pestle to prepare
electrodes
Added binder to roll
out electrode
Assemble into coin
Stainless steel anode current collector
cell
16 channels for
testing batteries
8 coin cell
testers
Change to
current control
Constant
for 60
hours
Type in calculated
charge/discharge
current (negative for
discharge)
Preparing test schedule
Measure on change
After running the electrode the data that will be available will be: the
negative applied current, the time of the measurement and the
mass of active material
Use the current (in milliAmps), time (in hours) and the mass (in
grams) to determine the actual capacity for your anode
The Ragone chart
Well-dispersed SWCNTs even with smaller amount alone make better electric wiring to
active materials due to better percolation networks than super p carbon powders.
Y. J. Lee et al., Science 324, 1051 (May, 2009). Tested 2 V and 4.3 V
Amount of material to provide electricity for
one hour, one day, one week and one month
with no external energy production
Daily short term:
For short term daily energy
storage, ~50 kg of Li-ion
batteries, will provide all
electrical needs of the average
household
Long term:
Insolation never drops below
50% of the average throughout
the year (even on the cloudiest
day!), so with >50% energy
production by solar, two 2000
gallon tanks will provide all
electricity required for the three
months of winter if they can be
adequately charged during the
summer months
Helpful websites
http://www.sandia.gov/ess/About/projects.ht
ml
http://www.eia.doe.gov/fuelelectric.html
(Nearly all information on energy production
and consumption in the US)
http://rredc.nrel.gov/solar/old_data/nsrdb/re
dbook/atlas/ (information on solar energy)
http://www.electricitystorage.org