Brief history of the battery

Battery University online:

 First battery

-0.76V vs SHE 0.34V vs SHE

Total voltage: 1.1 V

 Energy Storage: Lithium ion
battery
e- e-

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

Tarascon, J.M. & Armand, M., Nature, 414, (2001)

 Conducting current collectors
Lightweight, typically
metallic
Chemically resistant
Stable at cell voltages
Stainless steel anode current collector

Courtesy: Lt. Col. F. John Burpo

 Seperators: permeability and
stability
Must be an
electronic insulator
Must be ionic
conductor
Chemically
resistant
Stable in electrolyte

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

Xu, K., Chemical Reviews, 2004 4303-4417

 Safety concerns with current Li ion
batteries drive to higher potential anodes
Safety
improvements
Electrolyte
stabilization
Li dendrite
formation
 Lithium plating and dendrites

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

2.5 Measured by intentionally

shorting the battery using a
Potential (V)

2.0 defined resistor

1.5 Once the internal resistance is
DV=1.22 V known, the maximum cell
1.0 output can be calculated
0.5 Internal resistance is a function
of SEI, electrode conductivity,
0.0 and surface area
10 20 30 40 50
Time (sec)

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

The electrodes must allow ions to flow through them

This is helped by using layered structures
Making nanoscale materials
Coating or percolating the system with conducting material
How do we measure battery materials?
Specific Capacity
Energy
Power
Ragone plot
Galvanostatic measurement
 Chemistries of electrodes
Most common electrode
system is that of LiCoO2 and
graphite
0.1 V vs. Li

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

8e X 95484 A sec 1hour 1000mA 1mole

X X X
1mole 3600sec 1Amp 240.8 g
Capacity calculated for cobalt oxide to be 881 mAh/g
 Volume changes in battery
electrodes
Metallic anodes behave
entirely different from
typical oxide anodes
Typically a metal will form
an alloy with lithium by
formally reducing the
lithium
Failures in metallic
anodes are usually due
to volume changes
Volume changes literally
cause for the electrode to
be destroyed
Most alloying electrodes
are not stable for more
than a couple
charge/discharge cycles

Tirado, J.L., Materials Science and Engineering R 40, 2003, 103-136

 Gold or metallic anodes
Au anode can alloy with lithium (this is not the
same as graphite being plated with lithium
Phases of gold/lithium alloys
Ag and Au can have several alloy phases (AgLi9
or Au4Li15)
There are many systems that can form alloys
with lithium (tin or silicon) but the volumetric
expansion is so great that the electrode is
unstable
These electrodes are special in that they actually
catalyze the reduction of Li+ to Lio
This catalysis has various potentials vs. Li metal,
typically around 0.7 V
 Alloy forming anodes for Lithium ion batteries

Au or Ag : capable of alloying with Li

up to AgLi9 and Au4Li15 at very
negative potential
Advantages in minimizing cell voltage
reduction

High theoretical capacity

http://www.asminternational.org/ Taillades, 2002, Sold State Ionics

 Pure Au viral nanowires

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

Au0.5Ag0.5 Au0.67Ag0.33 Au0.9Ag0.1

Gradual changes in potential during Curve shape

discharge similar with Au
Capacity at 2nd cycle : 499 for Au0.5Ag0.5 Capacity at 2nd
459 for Au0.67Ag0.33 cycle : 439
 Calculating capacity for Gold Anode

Capacity is measured in mAh/g and is a measure of the amount of

current you can get out of your electrode with respect to mass

This will yield an overall capacity of 445.9 mAh/g

 Calculating capacity for Gold Anode

Use the theoretical capacity to determine the charge rate

First find the active mass, not everything in the electrode is active
Example: a 2 mg electrode with 20% inactive material (super P and PTFE
binder)

2 mg X 0.8 1.12 mg active material

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

Courtesy: Lt. Col. F. John Burpo

Testing battery on Solartron

16 channels for
testing batteries

8 coin cell
testers

Celltest program for

measurement and
analysis
 Preparing test schedule
Battery measurements are done on the Solartron using the program Celltest:
In order to test the battery, place in coin cell holder:
Celltest works in a simple order, first make a test schedule, then an experiment, then
run.

Each test schedule will

consist of:
Initial rest that lasts one
minute (this is just to
make sure that the coin
cell is being tested
correctly)
A discharge step
A charge step
Preparing test schedule
Do a 1C charge and discharge

Change to
current control

Constant
for 60
hours

Type in calculated
charge/discharge
current (negative for
discharge)
Preparing test schedule

Measure on change

On termination tab jump

to next step based on
voltage:
0.1V for discharge, 2.5V for
charge
Preparing a Celltest experiment

Save data file as

your group name

Select your test schedule to

run on the correct channel

You must set safety limits of 5 V and 4 A, in

case something got connected incorrectly
Calculating actual capacity for Gold Anode

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

Necessary for comparing different energy types

For comparison Gasoline has an energy density of 12 kWh/kg and nuclear fission
can yield 25 billion Wh/kg
The chart plots the total amount of energy stored vs how quickly the energy if made
available
 Rate Capability of a-FePO4 nanowire/SWCNTs
conjugate templated on different phages.

Ragone plot showing

improvement in high
power performance
with higher binding
affinity towards SWCNTs

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