PCAM
Lectures


Science
and
Engineering

of
Electrochemical
Energy
Storage


Yi
Cui

Department
of
Materials
Science
and
Engineering

Stanford
University



1

 Needs
For
Electrical
Energy
Storage

Portable
Electronics
 Hybrid,
Plug‐in,
Electrical
Vehicles

25‐30%
CO2
emission


Tesla
Roadster


Large
Scale
Energy
Storage


Building

Solar
 Wind

Grid


2

Comparison
of
Energy
Storage
Technologies

Ragone
Plot

Capacitors

Specific
power
(w/kg)

106

105

104


103
 Supercapacitors

102

BaAeries
 Fuel
cells

10

1

10‐2
 10‐1
 1
 10
 102
 103

Specific
energy
(wh/kg)


Important
parameters:

‐ 
Energy
density
(Energy
per
weight
or
volume)

‐ 
Power
density
(Power
per
weight
or
volume)

‐ 
Cycle
life,
calendar
life
and
safety

‐ 
Cost
 3

 Energy
Storage
Mechanisms

Capacitor
 Supercapacitor
(Electrochemical
capacitor)


+
 ‐
 ‐
 +
 ‐

+

+
 ‐
 ‐
 +
 ‐

+

‐

Metal
 +
 Metal
 +
 ‐
 +
 ‐

+
 ‐
 ‐
 +
 ‐

‐
 Metal
 +

+
 +
 ‐
 +
 ‐


Dielectrics,
thickness:
>1000nm.
 Electrolyte
soluYon

Double
layer
thickness,
<1nm

Ba[ery


+
+
+
 ‐
 ‐
 ‐
 Capacitors
and
supercapacitor:
surface
storage.


+
+
+
 ‐
 ‐
 ‐
 Ba[ery:
bulk
storage.

+
+
+
 ‐
 ‐
 ‐

+
+
+
 ‐
 ‐
 ‐

+
+
+
 ‐
 ‐
 ‐

Electrolyte
soluYon
 4

Three
Lectures:


Lecture
1
IntroducYon
to
ba[eries


Lecture
2
Next
generaYon
of
lithium
ion
ba[eries


Lecture
3
Supercapacitors


5

Lecture
1
IntroducYon
to
Ba[eries


‐
Thermodynamics
of
ba[eries


‐
Materials
issues
of
ba[eries


‐
Ba[ery
device
parameters


6

 Ba[eries
Have
High
Energy
Efficiency

BaAeries


Heat
Engine


For
lead
acid
baAery:

ΔG = −377kJ /mol,ΔH = −228kJ /mol,ΔS = 502J /Kmol
Th = 600K,Tc = 300K
w electrical
=3
w thermal

CombusYon
engines:
35%
energy
efficiency.

Ba[eries:
90%
energy
efficiency.

€
7

8

 Chemical
ReacYon
 Electrochemical
ReacYon
Path

ΔG
ΔG
A + B → AB A + B  → AB
→ A + + e−
1)A 
2)B + A + + e− 
→ AB
ΔG = −nFE
€

9

 A + B ΔG,E
→ AB

,E1 ,E 2
B + δA ΔG
1 → γ1, γ1 + δA ΔG
2  →γ 2
Single
phase
solid
soluTon,
composiTon
and
voltage
change
with
reacTon.

,E 3
γ + δA ΔG
3  →β
Two
phase
con‐existence,
fixed
composiTon
for
each
phase,
fixed
voltage.

€
4 ,E
β + δA ΔG 4 →α
€ α + δA ΔG ,E 5
5  →α1,α1 + δA 
→α 2
10


€
11

Phase
behaviors
of
baAery
electrode
materials
affect:

‐
Voltage
profile

‐ 
Possibility
to
be
rechargeable

‐ 
Cycle
life

‐ 
Safety


12

 Single
Phase
ReacYon:
Solid
SoluYon

A

B


LiAle
structure
change
or
volume
expansion,
reversible
reacTon.


Example:


ω − LixV2O5

C.
Delmas
et.
al.
Solid
State
Ionics
69,
257
(1994)

 13

 Two
Phase
ReacYon:
Type
I


LiAle
structure
change/volume
expansion,
reversible.

Example:


FePO4 + Li + + e− 
→ LiFePO4

14

 Two
Phase
ReacYon:
Type
II


The
new
phase
has

a
completely
different
structure
and

significantly
larger
volume.


Example:
NegaTve
electrodes
of
lead
acid
baAeries



Pb(s) + SO42− (aq) ↔ PbSO4 (s) + 2e−

€ 15

 Three
Phase
ReacYon


‐
There
are
three
phases
coexistent.

‐
Significant
structure
and
volume
change.

‐
Very
complex
reacTon.


Example:
conversion
reacTon
electrode
materials.


2Li + + SnO2 (s) + 2e− ↔ Li2O(s) + SnO(s)

€
16

The
Whole
BaAery
Device


17

 Li
Ion
Ba[ery
101


(Courtesy
of
Venkat
Srinivasan)

Chemistry
and
physics
issues
in
baAeries:

‐ 
Ionic
diffusion

‐ 
Electron
transport

‐ 
Interfaces

‐ 
NucleaTon
and
growth
of
new
phases:
strain

18

Ba[ery
components:

 Separator

‐ 
Metal
foil:

current
collector

‐ 
Anode
and
cathode
parTcles

‐ 
Binder:
polymer

‐ 
ConducTng
carbon
parTcles

‐ 
Separator:
polymer

‐ 
Electrolyte:
organic
and
salt

‐ 
AddiTves
 19

Charge/discharge
method:

Constant
current
charge/discharge


and
monitor
voltage
over
Tme.


C
rate:



1C
is
one
hour
charge/discharge.


C/2
is
two
hour
charge/discharge


2C
is
half
an
hour
charge/discharge.

20

 Anode
(‐)
 Cathode
(+)

Cu
current
collector


Al
current
collector

Separator

Li+


Ba[ery
parameter
set
#I:
by
Fundamental
Materials
ProperYes

1)
Specific
charge
capacity:
charge
per
weight





Charge
density:
charge
per
volume

2)
Voltage:
potenTal
different
between
electrodes


3)
Specific
energy:
charge
x
voltage/weight


Energy
density:
charge
x
voltage/volume


21

 Anode
(‐)
 Cathode
(+)

Cu
current
collector


Al
current
collector

Separator

Li+


Ba[ery
parameter
set
#II:
by
half‐fundamental
and
half‐engineering

1)  Specific
power:
power/weight





Power
density:
power/volume

2)
Cycle
life:
300
cycles
for
electronics,
3000
cycles
for
electric
cars.

3)
Coulombic
efficiency:
charge
out/charge
in.


for
example:
need
99.99%
for
3000
cycles
with
74%
capacity
retenTon.

4)
Safety:
oxygen
release,
thermal
runaway.

5)
Cost

6)
Calendar
life:
3yr
for
electronics,
10
yr
for
electric
cars.

22

Chemical
Processes
in
Ba[ery
Charging


(Courtesy
of
Venkat
Srinivasan)

23

 Electrode
Materials
in
ExisYng
Li
Ion
Ba[eries

Electrode
materials
determine
the
energy
density.

Anode
materials
 Cathode
Materials

Graphite:
370
mAh/g
 LiCoO2 
140
mAh/g,
3.7V

LiMn2O4 
140
mAh/g,
3.9V

LiFePO4 
170
mAh/g,
3.4V


24

Important
ba[ery
parameters:

‐ 
Energy
density,
the
most
fundamental
parameter.

‐ 
Power
density

‐ 
Cycle
life,
calendar
life
and
safety

‐ 
Cost

‐ 
Temperature
performance

Voltage
×
#
of
movable
Li
ions
in
electrodes


Energy
density
=

Electrode
weight
(or
volume)


Need
new
high
capacity
or
high
voltage
materials

25