Advanced Batteries for Hybrid and Electric Vehicles

Advanced Secondary Batteries And
Their Applications for Hybrid and

Electric Vehicles
Su-Chee Simon Wang

IEEE (Dec. 5, 2011)
1
Outline
Introduction to batteries
• Equilibrium and kinetics
• Various secondary batteries
Lead acid batteries
Nickel metal hydride batteries
Lithium ion batteries
• Applications
Electric vehicles
Hybrid electric vehicles
2
Introduction to Batteries
• Battery terminology
– Primary and secondary batteries
– Cell voltage (open circuit)
– Positive and negative electrodes
– Cathode and anode
– Power energy and charge
– Battery cell module and pack
– Charge and discharge curves
– Cycle life
3
Primary and Secondary Batteries
• Primary Battery: not rechargeable (dry
cell)
• Secondary Battery: rechargeable (lithium
ion batteries) E = E+ - E-
oc
(Cell V) (Half cell V)
• Battery is composed of _
+
– Positive electrode Pos
E
– Negative electrode
– Electrolyte + _ electrolyte
– Separator P N separator
– Current collectors o e
current
s g
collector
4
How to Determine Positive and
Negative Electrodes
5
How to Calculate Cell Voltage
• Use half cell reduction potentials (25 °C)
Electrode reaction E°, V Electrode reaction E°, V
Li+ + e ↔ Li -3.01 Ni+2 + 2e ↔ Ni -0.23
Rb+ + e ↔ Rb Less stable -2.98 Sn+2 + 2e ↔ Sn -0.14
Cs+ + e ↔ Cs -2.92 Pb+2 + 2e ↔ Pb -0.13
K+ + e ↔ K -2.92 O2 + H2O + 2e ↔ HO2- + OH- -0.08
Ba+2 + 2e ↔ Ba -2.92 D+ + e ↔1/2D2 -0.003
Sr+2 + 2e ↔ Sr -2.89 H+ + e ↔ 1/2H2 0.00
Ca+2 + 2e ↔ Ca -2.84 HgO + H2O + 2e ↔ Hg + 2OH- 0.10
Na+ + e ↔ Na -2.71 CuCl + e ↔ Cu + Cl- 0.14
Mg(OH)2 +2e ↔ Mg + 2OH- -2.69 AgCl + e ↔ Ag + Cl- 0.22
Mg+2 + 2e ↔ Mg -2.38 Cu+2 + 2e ↔ Cu 0.34
Al(OH)3 + 3e ↔ Al + 3OH- -2.34 Ag2O + H2O + 2e ↔ 2Ag + 2OH- 0.35
Ti+2 + 2e ↔ Ti -1.75 1/2O2 + H2O + 2e ↔ 2OH- 0.40
Be+2 + 2e ↔ Be -1.70 NiOOH + H2O + e ↔ Ni(OH)2 + OH- 0.45
Al+3 + 3e ↔ Al -1.66 Cu+ + e ↔ Cu 0.52
Zn(OH)2 + 2e ↔ Zn + 2OH- -1.25 I2 + 2e ↔ 2I- 0.54
Mn+2 + 2e ↔ Mn -1.05 2AgO + H2O + 2e ↔ Ag2O + 2OH- 0.57
Fe(OH)2 + 2e ↔ Fe + 2OH- -0.88 Hg+2 + 2e ↔ Hg 0.80
2H2O + 2e ↔ H2 + 2OH- -0.83 Ag+ + e ↔ Ag 0.80
Cd(OH)2 + 2e ↔ Cd + 2OH- -0.81 Pd+2 + 2e ↔ Pd 0.83
Zn+2 + 2e ↔ Zn -0.76 Ir+3 + 3e ↔ Ir 1.00
Ni(OH)2 + 2e ↔ Ni + 2OH- -0.72 Br2 + 2e ↔ 2Br- 1.07
Ga+3 + 3e ↔ Ga -0.52 O2 + 4H+ + 4e ↔ 2H2O 1.23
S + 2e ↔ S-2 -0.48 MnO2 + 4H+ + 2e ↔ Mn+2 + 2H2O 1.23
Fe+2 + 2e ↔ Fe -0.44 Cl2 + 2e ↔ 2Cl- 1.36
Cd+2 + 2e ↔ Cd -0.40 PbO2 + 4H+ + 2e ↔ Pb+2 + 2H2O 1.46
PbSO4 + 2e ↔ Pb + SO4-2 -0.36 PbO2 + SO4-2 + 4H+ + 2e
In+3 + 3e ↔ In -0.34 ↔ PbSO4 + 2H2O 1.69
Tl+ + e ↔ Tl -0.34 F2 + 2e ↔ 2F- More stable 2.87
Co+2 +2e ↔ Co -0.27 6
How to Calculate Cell Voltage
• Half cell reduction potentials are measured
as follows:
– Cell voltage is measured between electrode A (Cu) and
hydrogen electrode (Eoc = EA – EH2)
– The potential of hydrogen electrode in “acid” is defined as
zero volt (Eoc = EA – 0)
– The measured cell voltage is the half cell reduction
potential of electrode A - +
E
7
Calculate Cell Voltage
(Open circuit)
E?
Chemical Chemical
reactions? reactions?
Cu Zn
CuSO4 ZnSO4
Cell open circuit voltage Eoc = E°+ - E°-

Positive electrode: Cu Negative electrode: Zn
E°+ = 0.34 V E = 1.1 V
E°- = -0.76 V Cu Zn
Eoc = 0.34 – (- 0.76) = 1.1 V (intrinsic)*
*Current: extrinsic 8
Table
Half Cell Reduction Potentials (25 °C)
Electrode reaction E°, V Electrode reaction E°, V
Li+ + e ↔ Li -3.01 Ni+2 + 2e ↔ Ni -0.23
Rb+ + e ↔ Rb -2.98 Sn+2 + 2e ↔ Sn -0.14
Cs+ + e ↔ Cs -2.92 Pb+2 + 2e ↔ Pb -0.13
K+ + e ↔ K -2.92 O2 + H2O + 2e ↔ HO2- + OH- -0.08
Ba+2 + 2e ↔ Ba -2.92 D+ + e ↔1/2D2 -0.003
Sr+2 + 2e ↔ Sr -2.89 H+ + e ↔ 1/2H2 0.00
Ca+2 + 2e ↔ Ca -2.84 HgO + H2O + 2e ↔ Hg + 2OH- 0.10
Na+ + e ↔ Na -2.71 CuCl + e ↔ Cu + Cl- 0.14
Mg(OH)2 +2e ↔ Mg + 2OH- -2.69 AgCl + e ↔ Ag + Cl- 0.22
Mg+2 + 2e ↔ Mg -2.38 Cu+2 + 2e ↔ Cu 0.34
Al(OH)3 + 3e ↔ Al + 3OH- -2.34 Ag2O + H2O + 2e ↔ 2Ag + 2OH- 0.35
Ti+2 + 2e ↔ Ti -1.75 1/2O2 + H2O + 2e ↔ 2OH- 0.40
Be+2 + 2e ↔ Be -1.70 NiOOH + H2O + e ↔ Ni(OH)2 + OH- 0.45
Al+3 + 3e ↔ Al -1.66 Cu+ + e ↔ Cu 0.52
Zn(OH)2 + 2e ↔ Zn + 2OH- -1.25 I2 + 2e ↔ 2I- 0.54
Mn+2 + 2e ↔ Mn -1.05 2AgO + H2O + 2e ↔ Ag2O + 2OH- 0.57
Fe(OH)2 + 2e ↔ Fe + 2OH- -0.88 Hg+2 + 2e ↔ Hg 0.80
2H2O + 2e ↔ H2 + 2OH- -0.83 Ag+ + e ↔ Ag 0.80
Cd(OH)2 + 2e ↔ Cd + 2OH- -0.81 Pd+2 + 2e ↔ Pd 0.83
Zn+2 + 2e ↔ Zn -0.76 Ir+3 + 3e ↔ Ir 1.00
Ni(OH)2 + 2e ↔ Ni + 2OH- -0.72 Br2 + 2e ↔ 2Br- 1.07
Ga+3 + 3e ↔ Ga -0.52 O2 + 4H+ + 4e ↔ 2H2O 1.23
S + 2e ↔ S-2 -0.48 MnO2 + 4H+ + 2e ↔ Mn+2 + 2H2O 1.23
Fe+2 + 2e ↔ Fe -0.44 Cl2 + 2e ↔ 2Cl- 1.36
Cd+2 + 2e ↔ Cd -0.40 PbO2 + 4H+ + 2e ↔ Pb+2 + 2H2O 1.46
PbSO4 + 2e ↔ Pb + SO4-2 -0.36 PbO2 + SO4-2 + 4H+ + 2e
In+3 + 3e ↔ In -0.34 ↔ PbSO4 + 2H2O 1.69
Tl+ + e ↔ Tl -0.34 F2 + 2e ↔ 2F- 2.87
Co+2 +2e ↔ Co -0.27 9
Calculate Cell Voltage
(Open Circuit)
• Hydrogen Fuel Cells (with hydrogen and
oxygen electrodes)
O2 + 4H+ + 4e ↔ 2H2O 1.23 V
H+ + e ↔ 1/2H2 0.00 V
Eoc = 1.23 – 0 = 1.23 V
• Lithium Fluorine Battery

F2 + 2e ↔ 2F- 2.87 V
Li+ + e ↔ Li -3.01 V
Eoc = 2.87 – (–3.01) = 5.88 V
10
How to Make High Voltage Batteries
Strong
Strong reducing oxidants
agents
11
Cathode and Anode
• Cathode: the electrode where reduction reaction
takes place
• Anode: the electrode where oxidation reaction
takes place
Secondary battery
• During charge
– Negative electrode is the cathode
– Positive electrode is the anode
• During discharge
– Positive electrode is the cathode
– Negative electrode is the anode
12
Cathode and Anode
Charge
Secondary Battery V
e
• During charge
– Negative electrode is the cathode + cation -
Zn+2 + 2e- Zn Cu Zn
– Positive electrode is the anode anion
Cu Cu+2 + 2e- CuSO4 ZnSO4
• During discharge
Discharge
– Positive electrode is the cathode e
Load
Cu+2 + 2e- Cu
– Negative electrode is the anode
+ -
Zn Zn+2 + 2e-
Cu Zn
anion
CuSO4 ZnSO4
13
Power Energy and Charge
• Power = Voltage * Current
– 1 W (watt) = 1 V (volt) * 1 A (ampere)
– 1 kW = 1000 W
• Energy = Power * Time
– 1 Wh (watt-hour) = 1 W * 1 h (hour)
– 1 kWh = 1000 Wh
– 1 Wh = 3600 J (joules)
• Charge = Current * Time
– 1 Ah = 1 A * 1 h
– 1 kAh = 1000 Ah
– 1 Ah = 3600 C (coulombs)
14
• Specific power: power withdrawn per unit
battery weight
– W/kg
• Power density: power withdrawn per unit battery
volume
– W/L
• Specific energy: energy stored per unit battery
weight
– Wh/kg
• Energy density: energy stored per unit battery
volume
– Wh/L
15
• Examples
– AA primary alkaline battery 4.5 Wh
• 1.5 V (3 Ah)
– Lead acid SLI battery
600 Wh
• 12 V (50 Ah)
– Prius battery
• 202 V (6.5 Ah) 1300 Wh (1.3 kWh)
– Lithium ion battery (laptop)
• 10 V (5 Ah) 50 Wh
• Gasoline (tank)
– 600 kWh
16
Cell Module and Pack
NiMH Cell
1.2 V
NiMH Module
11 cells
11 x 1.2 = 13.2 V
NiMH Pack for EV1

26 Modules
26 x 13.2 = 343 V
17
Charge and Discharge Curves
Constant current charge (Ich) and discharge (Idis)
1.3
+ (ch)
Ech
1.1 +
overpotential:ηch Eoc
Voltage
overpotential:ηdis + (dis) Ech

0.9 Edis Edis
Eoc
(dis) -
0.7 charge
overcharge discharge -
0.5 (ch) -
0 5 10 15 20 25 30
Time
0 SOC (%) 100 0 DOD (%) 100
18
• Charge voltage Ech > Eoc
• Discharge voltage Edis < Eoc
• Energy efficiency = (voltaic efficiency * coulombic
efficiency) = (Edis / Ech) * (Idis* tdis / Ich* tch) < 1
• The voltage drop is caused by cell resistance
– ∆ Edis = Eoc – Edis = ηdis = Idis * R (R: broader resistance)
– ∆ Ech = Ech - Eoc = ηch = Ich * R (R: extrinsic)
1.3
charge Ech
1.1 Eoc
Voltage
0.9 discharge E
dis
0.7 tch tdis
0.5
0 5 10 15 20 25 30 19
Tim e
Battery Component Resistance
Distribution
• Nickel metal hydride electric vehicle
battery (~300 W/kg)
Component Resistance Percentage
terminals 0.1 mohm 0.8 %
tabs 0.6 mohm 4.7 %
KOH/separators 3 mohm 23.6 %
positive electrode 1.5 mohm 11.8 %
positive substrate 2.5 mohm 19.7 %
negative electrode 2 mohm 15.7 %
negative substrate 3 mohm 23.6 %
TOTAL 12.7 mohm 100 % 20

Charge and Discharge
• State of charge (SOC, %)
• Depth of discharge (DOD, %)
• SOC + DOD = 100
• Self discharge 1.3
Ech
• Discharge 1.1
Voltage Eoc
0.9 Edis
– “C” rate
0.7 charge
1C, 2C, 1/2C discharge
0.5
0 5 10 15 20 25 30
Tim e
0 SOC (%) 100 0 DOD (%) 100
21
Cycle Life
• Cycle life is the number of charge-
discharge cycles a battery can deliver (has
to meet energy and power performance
targets)
• Cycle life depends on depth of discharge
and temperature
– Examples
• lead acid battery
• nickel cadmium battery
22
Outline
• Introduction to batteries
Equilibrium and kinetics, Eoc > Edis
Lead acid batteries
• Applications
Electric vehicles
23
Equilibrium: Thermodynamics
• ∆G: Free energy change from reactants to
products during discharge (J/mole)
negative value
• ∆G = - nFEoc (nFEoc: electric work) Max.
– n: Number of moles of electron transferred
– F: Faraday’s constant (96500 C/mole)
– Eoc: Open circuit cell voltage
• Theoretical Specific energy
nFEoc / total weight of reactants
24
Theoretical Specific Energy
(Lithium Ion Battery)
• Lithium ion battery half cell reactions
(+) CoO2 + Li+ + e ↔ LiCoO2 n = 1
Eº = 1 V Theoretical specific
energy = nFEoc/ total
(-) Li+ + C6+ e ↔ LiC6 weight of reactants
Eº ~ -3 V
• Overall reaction during discharge
CoO2 + LiC6 LiCoO2 + C6
Eoc = E+ - E- = 1 - (-3) = 4 V
Eoc = 4 V
25
(Lithium Ion Battery)
• Free energy change (∆G) during discharge
∆G = -nFEoc = -1 * 96500 * 4 = - 386000 J
= -386 kJ = -107.2 Wh/mole
• Total weight of reactants
CoO2 91 grams
LiC6 7 + 12 * 6 = 79 grams
Total weight 170 grams (0.17 kg)/mole
• Theoretical specific energy
107.2 Wh/ 0.17 kg = 630.6 Wh/kg
• Theoretical energy density
107.2 Wh/0.055 L = 1949 Wh/L
26
Practical Specific Energy
• Practical specific energy of a battery is
significantly lower than the theoretical
value (~30%) ~ 190 Wh/kg for lithium
battery (USABC target for EV > 150
Wh/kg)
– Lower discharge voltage (Edis < Eoc)
• Voltage losses (broader resistance)
– Extra material weight
• Current collectors Theoretical specific
• Terminals energy = nFEoc / total
• Battery case weight of reactants =
• Separators 630.6 Wh/kg
27
Extra Materials
• Battery current collectors and terminals
– Collect current from electrodes and interconnect to
next battery cells
– Use materials with high electric conductivity and good
heat transfer coefficient
• Battery case
– Contain all battery components
– Use materials inert with electrolyte and electrodes
– Need safety release valve with sealed cells
• Separator
– Separate positive and negative electrodes (prevent
short circuit)
– Made of insulating materials with high porosity
28
• Practical specific energy of a battery is
significantly lower than the theoretical
value (<30%)
– Lower discharge voltage (Edis < Eoc)
• Activation polarization losses
• Ohmic losses
• Concentration polarization losses
– Extra material weight
• Current collectors
• Terminals
• Battery case
• Separators
29
Kinetics in Batteries
• Source of voltage losses (broader
resistance)
– Electrode activation polarization losses (ηa)
• Butler-Volmer equation
– Depends on electrode reactions
– Ohmic losses (ηΩ )
• Ohm’s law (Ohmic resistance)
– Electronic resistance (electrode current collector, tabs. and
terminals)
– Ionic resistance (electrolyte and separator)
– Temperature effects
– Concentration polarization losses (ηc)
• Nernst equation
– Depends on diffusion in electrolyte and solid state
30
1.3
Ech
1.1 + η+
overpotential:ηch Eoc
Voltage
overpotential:ηdis + (dis)
0.9 ηdis = ηa + ηΩ + ηc Edis Edis
Eoc
(dis) -
0.7 charge η-
overcharge discharge -
0.5
0 5 10 15 20 25 30
Time
0 SOC (%) 100 0 DOD (%) 100
31
Kinetics in Batteries
• Sources of voltage losses (Eoc – Edis):
– Electrode activation polarization losses
• Butler-Volmer equation P
P < Po
– Ohmic losses Po
• Ohm’s law
– Electronic resistance (electrode current collector, tabs.
and terminals)
– Ionic resistance (electrolyte and separator)
– Concentration polarization losses
• Nernst equation
P’
Po’ P’ < P
32
Activation Polarization Losses
(Butler-Volmer Equation)
(1−α )η F / RT − αη F / RT
i = i0 [ e −e ]
• Current density i (electrochemical reaction at
electrode/electrolyte interface) is a function of:
– ηa : Activation polarization loss
– i0 : Exchange current density Discharge
– α : The symmetry factor e
– F : Faraday’s constant + -
– R : Molar gas constant Cu Zn
– T : Temperature anion
CuSO4 ZnSO4
+2 - +2 -
Cu + 2e Cu Zn Zn + 2e
33
Effect of Rate on Discharge
C/8 Rate
2-C Rate
(1−α )ηF / RT −αη F / RT
i = i0 [e −e ]
Higher current higher ηa
Concentration
polarization losses
34
Concentration Polarization
Losses (Nernst Equation)
• During discharge Discharge
– Reaction at the positive electrode: V
Cu+2 + 2e- Cu
– Reaction at the negative electrode:
+ -
Zn Zn+2 + 2e-
– Cell reaction: Cu Zn
Zn + Cu+2 Cu + Zn+2 ηc
• Nernst equation CuSO4 ZnSO4
RT ( A) a
Eoc ,real = Eoc ,table + Ln
nF ( B)b
– A: Concentration of Cu+2
– B: Concentration of Zn+2
– a and b (= 1): factor for Cu+2 and Zn+2
– R : Molar gas constant RT (Cu +2 )
– T : Temperature
Eoc , real = Eoc ,table + Ln
– F : Faraday’s constant
nF ( Zn + 2 )
(If Zn+2 = Cu+2 =1M)
35
Total Voltage Losses
• Eoc – Edis = Total voltage losses (ηdis, extrinsic) =
Activation losses (ηa) + Ohmic losses (ηΩ) +
Concentration losses (ηc)
Voltage Los s es in Fuel Cell
1.4
1.23 V
1.2
1
Cell voltage (V)
Activation polarization losses in electrodes
0.8
Ohmic losses
0.6 Polarization curve
Concentration polarization losses
0.4
0.2
ηdis = Eoc- Edis ~ Idis * R (broader resistance)
0
0 500 1000 1500
Current density (mA /cm2)
36
Model: Porous Electrode Theory
• Porous electrode theory For a battery cell
– Butler-Volmer equation Power = f (1/R)
– Ohm’s law R = f (1/surface area)
Current flow
Current
Current flow collector
Electrode decreasing
Pores
(electrolyte)
37
MATLAB Model
38
Experimental Results
V.S. MATLAB Model
Marine Lead Acid Battery (12V, 32 Ah)
13 C/2 Test
1C Test
2C Test
12 C/2 Model
1 C Model
2 C Model
Voltage (V)
11
10
9
0.00 0.25 0.50 0.75 1.00 1.25 1.50
Time (Hours)
39
Outline
Various secondary batteries
Lead acid batteries
• Applications
Electric vehicles
40
Lead Acid Batteries
• Invented by Planté in 1860
• Lead acid starter batteries are enabling
technology for gasoline powered IC engine
cars
• Almost all vehicles use lead acid batteries
for starter lighting and ignition (SLI)
systems
• It is 20 billion dollars industry (total battery
industry ~ 30 billion dollars)
41
Lead Acid Batteries
Expanded metal
• Positive electrodes
– PbO2
• Negative electrodes Cast
– Pb
– Lead (or alloy) grids
1. Positive
• Separators 2. Negative
– Porous or glass mat 3. Separator

4. Tab
• Electrolyte 5. Bus bar

6. Terminal
– 5M H2SO4 aqueous solution
42
• Lead acid battery half cell reactions
PbO2 + SO42- + 4 H+ + 2 e ↔ PbSO4 + 2 H20
E°= 1.69 V
PbSO4 + 2 e ↔ Pb + SO42-
E°= -0.36 V
PbO2 + Pb + 2H2SO4 2 PbSO4 + 2 H20
Voc = V+ - V- = 1.69 – (-0.36) = 2.05 V
43
∆G = -nFE = -2 * 96500 * 2.05 = -395700 J
= -395.7 kJ = -109.9 Wh/mole
PbO2 + Pb + 2H2SO4 2 PbSO4 + 2 H20
PbO2 239 grams
Pb 207 grams
2H2SO4 98 *2 = 196 grams
109.9 Wh/ 0.642 kg = 171 Wh/kg
109.9 Wh/0.1 L = 1099 Wh/L
44
• Practical specific energy < 20 % theoretical
specific energy (171 Wh/kg) ~ 34 Wh/kg due
to:
– Voltage losses (up to 10%)
– Inactive weight (~75%)
• Tabs and terminals
• Solvent (water) in electrolyte
– Low utilization of active material
USABC target for EV applications: > 150 Wh/kg
45
Charge Lead Acid Batteries
• During charge:
– 2 PbSO4 + 2 H20 PbO2 + Pb + H2SO4 (2.05 V)
– Competing reaction: 2H2O O2 + 2H2 (1.23 V)
H2 Pb Lead acid PbO2 O2

evolution battery voltage evolution
2.05 V
Current
Water
decomposi-
tion voltage
1.23 V
-0.36 1.23 1.69

-1 0 1 2
Voltage (V)
46
Electrolyte (H2SO4)
Concentration
• Overall reaction during charge
2 PbSO4 + 2 H20 PbO2 + Pb + H2SO4
The concentration of sulfuric acid increases to 5 M
• Overall reaction during discharge Diffusion!
PbO2 + Pb + H2SO4 2 PbSO4 + 2 H20 Power?
The concentration of sulfuric acid decreases
discharge
e e
V
+ - Cation: H+
anion
Pb Pb Anion: SO4-2
O2 cation
H2SO4 H2SO4 47
Cell Capacity Under Different
Discharge Rates
4.59 5.10 5.6

Ah Ah Ah
6.00
Ah
48
Failure Mode
• Positive electrode
– Lead grid corrosion
PbO2 + Pb + H2SO4 2 PbSO4 + 2 H20
– Shedding
• 70% volume change from PbO2 to PbSO4 (discharge)
• Negative electrode
– Sulfation (the formation of PbSO4)
• Cycle life depends on DOD and temperature
Capacity available (%)
Active
material Grid
PbSO4
Number of cycles
49
Outline
Lead acid batteries
• Applications
Electric vehicles
50
Nickel Metal Hydride Batteries
• Became commercially available around
1992
• Metal hydride is actually a solid phase
hydrogen intercalation electrode
• Nickel metal hydride battery has high
power and good cycle life for HEV
applications
• It is > 1 billion dollars industry (total battery
industry ~ 30 billion dollars)
51
Nickel Metal Hydride Batteries
– Nickel hydroxide pasted onto
nickel foam or sheet substrate
• Negative electrodes
– Most common material is AB5
or MmNi3.55Co0.75Al0.2Mn0.5
where Mm is misch metal, an
alloy consisting of 50%
cerium, 25% lanthanum, 15%
neodymium, and 10% other
rare-earth metals and iron
• Separators
– Polymer with submicron pores
• Electrolyte
– 30% KOH aqueous solution
52
• Nickel metal hydride battery half cell
reactions
NiOOH + H2O + e ↔ Ni(OH)2 + OH-
Eº = 0.45 V
M + H2O + e ↔ MH + OH-
Eº = -0.83 V
NiOOH + MH Ni(OH)2 + M
Eoc = E+ - E- = 0.45 –(-0.83) = 1.28 V
53
∆G = -nFE = -1 * 96500 * 1.28 = - 123520 J
= -123.5 kJ = -34.3 Wh/mole
NiOOH + MH Ni(OH)2 + M
NiOOH 92 grams
MH 70 grams
34.3 Wh/ 0.162 kg = 212 Wh/kg
34.3 Wh/0.02 L = 1715 Wh/L
54
• Practical specific energy up to 45%
theoretical specific energy (212
Wh/kg)up to 90 Wh/kg due to:
– Less inactive weight (~50%)
• Solvent (water) in electrolyte
– High utilization of active material (~90%)
55
Effects of Discharge Rate on Capacity
• Capacity least affected by discharge rate
among commonly used batteries (best
abuse tolerance)
Flat discharge voltage curve

C/8 rate
2C rate
5.6 Ah 6 Ah
4.6 Ah 5.1 Ah
56
Outline
Lead acid batteries
• Applications
Electric vehicles
57
Lithium Ion Batteries
• Invented by Dr. Goodenough at U. Texas in
1982 and became commercially available in
1991 (Sony)
• Both lithium cobalt oxide and carbon electrodes
are intercalation electrodes
• Have safety issues for applications in HEV and
plug-in HEV
• It is 5 billion dollars industry for applications in
portable electronics (total battery industry ~ 30
billion dollars)
58
– Layered lithium metal oxide (LiMO2, M = cobalt,
nickel, manganese, aluminum, or combination of two
to three metals), spinel lithium manganese oxide
(LiMn2O4), and lithium iron phosphate (LiFePO4) on
aluminum current collector
• Negative electrodes
– Carbon or graphite on copper current collector
• Separators
– Celgard microporous, polyethylene, or ceramic
separators
• Electrolyte
– LiPF6 dissolved in ethylene carbonate (EC)
• Solvent with high dielectric constant (89.6 at 40°C)
• Lithium salt with high conductivity
• 0.005 S/cm as compared to 0.5 S/cm for aqueous electrolyte
59
59
Carbon Negative Electrode
• Prevent lithium metal deposition (or
formation of lithium dendrite)
– Lithium metal deposition could still happen
during rapid charge when Temp < 5°C
– Dendrite could cause short circuit and
thermal runaway
Negative Positive
Electrolyte
electrode electrode
Li
metal Dendrite
60
65
mm
18
mm
Lithium ion battery18650 Alkaline AA battery

3.6 V, 2 Ah 1.5 V, 1.5 Ah
7.2 Wh 2.25 Wh
61
• Lithium ion battery half cell reactions
CoO2 + Li+ + e ↔ LiCoO2
Eº = 1 V Li
metal Dendrite
Li+ + C6+ e ↔ LiC6

Eº ~ -3 V
Eoc = E+ - E- = 1 - (-3.01) = 4 V
62
∆G = -nFE = -1 * 96500 * 4 = - 386000 J
= -386 kJ = -107.2 Wh/mole
CoO2 91 grams
LiC6 79 grams
107.2 Wh/ 0.17 kg = 630.6 Wh/kg
107.2 Wh/0.055 L = 1949 Wh/L
63
• Practical specific energy up to 30%
theoretical specific energy (630.6
Wh/kg) ~190 Wh/kg due to:
– Less inactive weight (~35%)
• Electrolyte
• Carbon in negative electrode
– Utilization of active material (~50%)
• Intercalation electrodes
64
Charge and Discharge
• Lithium batteries cannot use aqueous
electrolyte
Lithium batteries with aqueous electrolyte
Lithium
ion
battery
Current
~4V
H2 Water O2
evolution decomposit evolution
ion voltage
1.23 V
-3.2 -2.7 -2.2 -1.7 -1.2 -0.7 -0.2 0.3 0.8 1.3 1.8
Voltage (V)
65
Charge
• Overall reaction during charge
LiCoO2 + C6 CoO2 + LiC6
Charge
Li+ + e Li
Carbon LiCoO2
Lithium
Lithium ion
66
Overcharge
• Positive electrode is oxidized and oxygen
released (exothermic reaction)
67
Discharge
Discharge
Li Li+ + e
Carbon LiCoO2
Lithium
Lithium ion
68
Thermal Runaway
• Overcharge
– Exothermic reaction of oxidized positive
electrode material with electrolyte
• High ambient temperature
– SEI (solid electrolyte interphase) decomposition
at temperature 90 to 120 °C
• Short circuit
– Internal
– External
• High charge or discharge current
69
Formation of SEI
• Lithium ion battery is assembled inside a dry
room (does not need a dry box w/inert
atmosphere) with lithium ions impregnated in the
positive electrode (the smaller electrode)
• During the first charge, lithium ions are
transferred from the positive to the negative
electrode and form lithium metal
Graphite
(or C) CoO2
Enlarged - particles particles
+ Enlarged
graphite CoO2
particle particle
Capacity determined by
the positive electrode
Formation of SEI
• The electrolyte, ethylene carbonate (EC), is not
thermodynamically stable with lithium metal
• SEI is formed on carbon or graphite particles
during the first charge (Li active material wasted)
• SEI properties
– SEI has porous structure (more porous if SEI
formation steps are not optimized)
– SEI is ionic conductor (electronic insulator)
ethylene
carbonate
Li+ (during
SEI charge)
Li-C
(Li + EC) Li+ + C6+ e ↔ LiC6
Li+ (during
pores discharge)
71
Thickening of SEI (Failure Mode)
• Charge discharge cycles
– Volume changes in the carbon or graphite
particles crack SEI and expose fresh Li to
electrolyte (EC)
• Storage (calendar life)
– Ethylene carbonate (EC) diffuse through SEI
(pores) and react with Li inside SEI
ethylene
carbonate
Li + EC thicker SEI
SEI (capacity loss & high
Li-C
impedance rate
capability loss)
pores
72
Advantages and Disadvantages
• Advantages
– Very high energy and power
– Excellent charge retention
• Disadvantages
– Safety concerns
– High cost (control systems)
– Lithium deposition during charge at low
temperature
– Short calendar life
73
New Development
(Positive Electrode)
Structure Material Eoc Capacity Safety Cost
Layered LiCoO2 3.6 to 151 Ah/kg Accept- high
oxides (2D) Li(Co-Ni)O2 3.7 able
LiCo1/3Ni1/3Mn1/3O
2
(L-333)
Spinel (3D) LiMn2O4 3.7 119 Ah/kg good Low
Olivine (1D) LiFePO4 3.4 161 Ah/kg best Low
– Spinel is more proven than olivine except a high

temperature
– Spinel has relatively lower capacity (119 vs.150 or 160
Ah/kg for other materials) and solubility problems
– Olivine has very low conductivity
74
New Lithium Iron Phosphate Cells
(CALB, Thunder Sky, GBS)
75
New Development
(Negative Electrode)
• Spinel negative electrode (Altair)
– Lithium titanate (Li4Ti5O12)
• Advantages
– At lower voltage (~ 2.5 V) lithium is
thermodynamically stable in electrolyte no SEI
– Rapid charge and discharge
– Extremely long cycle life (> 20,000)
• Disadvantages
– Lower voltage (2.5 V)
– Low electronic coductivity (additives)
A supercapacitor!
76
Battery V.S. Supercapacitor
Gasoline
77
Battery V.S. Supercapacitor
Supercapacitors VS. Lithium Batteries
30
Commercial supercaps
Specific power (kW/kg)
Apower Cap Nickel-Carbon supercap

25
Graphene-Based supercap
20 CALB iron phosphate battery
Altair (国轩) titanate battery
15
10 Fuji Hybrid
5
Power Sys
0
0 20 40 60 80 100 120
Spesific energy (Wh/kg)
78
Summary (Three Batteries)
• Lead acid battery
– Low energy, < 40 Wh/kg
– Moderate power, > 200 W/kg
– Short life (deep discharge cycle), ~ 400 EV cycles
– Low cost, ~ $150/kWh
• Nickel metal hydride battery
– Moderate energy, < 100 Wh/kg
– High power, > 1000W/kg
– Long life, ~ 2000 EV cycles
– High cost, ~ $1000/kWh (cell)
• Lithium ion battery
– High energy, < 200Wh/kg
– High power, > 1000W/kg
– Long life, ~ 2000 EV cycles
– High cost, ~ $ 400/kWh (control system)
79
Outline
• Lead acid batteries
• Nickel metal hydride batteries
• Lithium ion batteries
Applications
Electric vehicles
80
Electric Vehicles
• History of electric vehicles
– Electric motor demonstrated in 1832
– Planté invented lead acid batteries in 1860
– Electric vehicles were more popular than
vehicles with internal combustion engines
early 20th century (from 1900 to 1912)
• 30,000 electric vehicles in US
• 200,000 electric vehicle worldwide
– The invention of battery powered starter
(1911) wiped out electric vehicles after 1920
81
Early Electric Vehicle
• Ayrton & Perry EV
(1882)
– Ten lead acid
battery cells (200
pounds)
– Peak power output
400 Watts
– Range 10 ~ 25
miles
– Speed 10 mph
82
Electric Vehicle Speed Record
Jenatzy electric race car sets world speed record at 61 mph

(1899-1902)
83
Electric Vehicles
• Renewed interests on electric vehicles
– Uncertainties on the supply of petroleum
based fuels
– High price of petroleum based fuels
– Improved technologies on batteries
• Global opportunities
– More opportunities in countries such as China
and India
• Less or no crude oil reserves compared to the US
• More city driving
• Shorter range requirements
84
Renewal of Electric Vehicles
Tesla
85
Chinese Electric Vehicles
Build Your Dreams (BYD)
86
GM Chevy Volt
Years in
development:
4
Battery range:
40 miles
Supplemented
by onboard
gas generator
Passengers: 4
Price: $40000
87
Nissan Leaf
Years in
development: 4
Battery range:
100 miles (100%
electric, 0
emissions)
Passengers: 4
Price: $32780
88
Chinese Concept Electric
Vehicles
89
Indian Electric Vehicles
90
USABC Goals for EV Batteries
91
Specific Energy VS Power for
Different Batteries
HEV
Chevy
Volt
Prius
EV
92
Specific Energy VS Power
(with the same capacity)
High Specific Power High Specific Energy
Cell Cell
terminal
terminal terminal
1 tab 2 tabs
+ - - + + - - + + -
+ -
2 tabs 1 tab
terminal
93
Specific Energy VS Power
High Specific Power High Specific Energy (Range)
•Bias power at the cost of energy •Bias energy at the cost of power
•Smaller particles, lower density •Larger particles, higher density
•Thinner electrodes •Thicker electrodes
•Thicker current collectors (minimize •Thinner current collectors (more
IR) active material)
94
Battery Design for EV (Example)
• Method I: Estimate force required to move the
vehicle
F = mg*Cr + ½ρCDAv2 + ma + mg*sin(θ)
Cr: coefficient of rolling resistance
CD: Coefficient of air drag
ρ: Density of air
A: Cross section of the vehicle
θ: Slope of the road
• Calculate power and energy required to drive
the vehicle for 200 km
Power P = F * v (velocity)
Energy = ∫P dt
(integration from time t = 0 to T for driving 200 km)
Total energy (Wh) required for the battery pack to drive
200 km
95
• Use the empirical equation
Range (km) = (Є/e) * Fb
Є: Usable battery specific energy (Wh/kg)
e: Specific weight consumption (Wh/(kg*km))
(e = 0.11 for a normal car driving on flat terrain)
Fb: Battery fraction
• For the battery pack
Є = 150 Wh/kg (lithium ion battery)
Fb = 250 / 1500 = 0.167
Range = (150 / 0.11) * 0.167 = ~ 220 km
(150 Wh/kg * 250 kg = 37.5 kWh)
96
• Specific weighted consumption
“e” CONDITIONS
0.06 Well designed, low acceleration rail vehicles, and level conditions
0.07 GM prototype impact with superior aerodynamics but impractical

features
0.09 Stop, start, low acceleration, slow speed bus on level roads,
good weather, stops every 300 m
0.11 For a normal car with all-season tires, generally flat terrain
0.15 Smooth freeway driving, good weather, level terrain
0.20 Hilly terrain
97
Battery Design for EV (summary)
• Energy: ~ 40 kWh for 200 km range
• Power (acceleration): ~ 100 kW , 250kg (400 W/kg)
• Power (regenerative braking): ~ 40 kW (160 W/kg)
• The efficiency of city driving is higher than that of
highway driving
• Weight: battery fraction Fb = 0.167 (less than 1/3
vehicle weight)
• Life: 10 years and 100,000 miles
• Cost: competitive with internal combustion drive
train
98
Outline
• Lead acid batteries
• Nickel metal hydride batteries
• Lithium ion batteries
• Applications
Electric vehicles
99
Introduction
• Hybrid electric vehicle types
Types Main Attributes Battery
Micro-1 Stop, power for idle loads, crank ICE VRLA
Micro-2 Micro-1 plus regenerative braking VRLA
Mild-1 Micro-2 plus lunch assist VRLA
Mild-2 Mild-1 plus limited power assist VRLA, NiMH
Moderate Mild-2 plus full power assist NiMH
Strong Moderate plus extended power assist (limited NiMH

electric drive)
Plug-in Strong plus extended electric drive NiMH, Li-ion
HEV
VRLA: Valve regulated lead acid battery NIMH: Nickel metal hydride battery
100
Battery Design with Higher
Power Output
• Thinner electrodes
and separators
• More electrodes in
parallel
• Shorter aspect ratio
• Thicker and heavier
current collectors
• Conductive additives
mixed with active
materials in
electrodes
101

Advanced Batteries for Hybrid and Electric Vehicles

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Advanced Batteries for Hybrid and Electric Vehicles

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Advanced Secondary Batteries And

Their Applications for Hybrid and

Su-Chee Simon Wang

Cell open circuit voltage Eoc = E°+ - E°-

• Lithium Fluorine Battery

NiMH Pack for EV1

overpotential:ηdis + (dis) Ech

terminals 0.1 mohm 0.8 %

tabs 0.6 mohm 4.7 %

KOH/separators 3 mohm 23.6 %

positive electrode 1.5 mohm 11.8 %

positive substrate 2.5 mohm 19.7 %

negative electrode 2 mohm 15.7 %

negative substrate 3 mohm 23.6 %

TOTAL 12.7 mohm 100 % 20

Activation polarization losses in electrodes

• Negative electrodes Cast

– Porous or glass mat 3. Separator

• Electrolyte 5. Bus bar

USABC target for EV applications: > 150 Wh/kg

H2 Pb Lead acid PbO2 O2

-0.36 1.23 1.69

4.59 5.10 5.6

Flat discharge voltage curve

Lithium ion battery18650 Alkaline AA battery

Li+ + C6+ e ↔ LiC6

Olivine (1D) LiFePO4 3.4 161 Ah/kg best Low

– Spinel is more proven than olivine except a high

Apower Cap Nickel-Carbon supercap

Jenatzy electric race car sets world speed record at 61 mph

Build Your Dreams (BYD)

0.07 GM prototype impact with superior aerodynamics but impractical

0.15 Smooth freeway driving, good weather, level terrain

0.20 Hilly terrain

Micro-1 Stop, power for idle loads, crank ICE VRLA

Micro-2 Micro-1 plus regenerative braking VRLA

Mild-1 Micro-2 plus lunch assist VRLA

Mild-2 Mild-1 plus limited power assist VRLA, NiMH

Moderate Mild-2 plus full power assist NiMH

Strong Moderate plus extended power assist (limited NiMH

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