Lecture # 11

Batteries & Energy Storage

Ahmed F. Ghoniem
March 9, 2020

• Storage technologies, for mobile and stationary applications ..

• Batteries, primary and secondary, their chemistry.
• Thermodynamics and electrochemistry
• Performance, ….

© Ahmed F. Ghoniem 1
THE RAGONE DIAGRAM is more applicable to
mobile applications.
Electric mobility is totally dependent on battery
storage.

an important definition:
Round trip efficiency:
ηround = ηch arg eηdisch arg e

For stationary applications, criteria for selection and

hence technologies can be very different.

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THE RAGONE DIAGRAM. Figure shows approximate estimates for peak

power density and specific energy for a number of storage technology
mostly for mobile applications.
2
Round-trip efficiency of electrical energy storage technologies. Markers show efficiencies of
plants which are currently in operation.

Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.

Xing Luo, et al. Applied energy, 137:511–536, 2015.

Niklas Hartmann, et al. Applied Energy, 93:541–548, 2012. 3
Behnam Zakeri and Sanna Syri. 42:569–596, 2015.
 Energy Storage: Overview and other options
Characteristic PHS CAES Batteries Flywheel
Energy Range (MJ) 1.8x106- 180,000- 1,800 – 1 – 18,000
The table shows technologies for stationary
36x106 18x106 180,000
and mobile applications including mechanical Power Range (MW) 100-1000 100-1000 0.1 – 10 1-10
and electrochemical. Capacitors are integral Overall Cycle Efficiency 64-80% 60-70% ~75% ~90%
parts of mobile storage! Charge/Discharge Time Hours Hours Hours Minutes
Cycle Life 10,000 10,000 2,000 10,000
Not inclusive and other options are available
Footprint/Unit Size Large if Moderate if Small Small
and under development.
above under ground
ground
Does not show thermal (storage) and Siting Ease Difficult Difficult- N/A N/A
chemical (hydrogen, fuels and Moderate
thermochemical) options which are very Maturity Mature Development Mature Development
important. except for
flow type
Estimated Capital Costs 600 – 500-1,000 100-200 200 - 500
Prices change constantly but comparison is - Power ($/kWe) 1,000 (LA)
still reasonable. Estimated Capital Costs 10 - 15 10 - 15 150-300 100 - 800
- Energy ($/kWh)

4
 Batteries

• Similar to fuel cells in that they convert

chemical to electrical energy directly, and the
secondary type can reverse the reactions
• But they store their chemicals internally in
their electrodes (except for flow batteries)
• Have seen a very wide range of applications,
at many scales for centuries!
• Still relatively expensive for large scales
storage deployment, although convenient.
• Also heavier than ideal in mobile application.
• Must be carefully managed thermally to avoid
thermal run away and fires.
Both images © Source unknown. All rights reserved. This content is excluded from our
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© Ahmed F. Ghoniem 5
 Primary Batteries: the alkaline dry cell

Zn (s) +2MnO(s) → ZnO(s) +Mn 2O 3(s) Non conducting tube Carbon (graphite)
electrode surrounded by
anode: Zn (s) + 2OH −aq → ZnO(s) + H 2O(l ) + 2e− carbon and manganese
oxide acting as the

cathode: 2MnO 2(s) + H 2O(l) + 2e− → Mn 2O 3(s) + 2OH −aq _ +

cathode

ΔG Ro = −277kJ / mol, ne = 2 Zinc metal sleeve

acts as the anode Electrolyte contains potassium
Δε o =
277000
= 1.44V hydroxide, zinc chloride and
96485 × 2 water

Zn: Zink A schematic drawing showing the internal detail of an alkaline battery

Mn: Manganese

6
© by Ahmed F. Ghoniem
 Secondary Batteries: The Lead Acid Battery
(look under the hood)

a lead electrode and a lead oxide electrode are immersed in sulfuric acid-water solution
During discharge:
Pb (s) + PbO 2(s) + 2H 2SO 4(aq) → PbSO 4(s) + 2H 2O(aq)
The Redox reactions:
Pb (s) + SO 2−
4(aq) → PbSO 4(s) + 2e -

PbO 2(s) + 4H + + SO 24− + 2e− → PbSO 4(s) + 2H 2O(l)

Δε = 2.04V

During charging, the above reactions are reversed by applying an external voltage.
Lead acid batteries charge below this value to prevent water electrolysis © Source unknown. All rights reserved. This content is
excluded from our Creative Commons license. For more
can be dangerous but used extensively in cars, etc. information, see https://ocw.mit.edu/fairuse.

7
© by Ahmed F. Ghoniem
 Lithium-ion batteries
• During operation, reversible Li+ intercalation
(insertion) into the layered electrodes’ materials
(leaving graphite anode during discharge).
• The overall reaction, where x is the fraction of the
anode Li leaving and joining the cathode lithium
cobalt oxide:

!"# $% + !"'(# $)*+ ↔ $% + !"$)*+

• Forward reaction: discharge (∆. < 0), Li+ move

towards cathode, as shown in figure
Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).
• Reverse reaction: charge (∆. > 0)
© American Chemical Society. All rights reserved. This content is excluded from our
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• Anode (-ve electrode, electrons leaving): Li metal and graphite

• Cathode (+ve electrode, electrons returning): Metal oxides (MnO2, CoO2, LiFePO4)
• Electrolyte: Organic solvents, carbonates and lithium salts (LiPF6)
• Current collectors, Cu on the anode side and Al on the cathode side.
Goodenough and Park, JACS 135 (2013): 1167 8
 Lithium-ion batteries

During discharge (cobalt cathode):

Anode: xLi(s) (C) → xLi(sol)
+
+xe- + (C)
Cathode: xLi+ +xe- + Li1-xCoO 2(s) → LiCoO 2(s)
Overall: Li(s) + CoO 2(s) → LiCoO 2(s)
The backward reactions occur during charging.

Material Theoretical Theoretical specific

Voltage V energy Wh/kg

Li/CoO2 3.6 570 Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.
Li/Mn2O4 4 593

Li-Mn battery during discharge:

Lithium is single valent, giving up a single electron Li ions move from –ve electrode (anode)
during discharging (more advanced batteries to +ve electrode (cathode)
would use multi valent metal such as magnesium). through solid or liquid electrolyte
9
“Batteries, Overview” by E Cairns, Encyclopedia of Energy, V 1, 2004, Elsevier.
 Specific Energy
The theoretical specific energy is −ΔGR / ∑ M i
where the sum is taken over all the reactants (and
products) in the redox reaction.

This expression ignores the mass of the battery

housing, inert electrode material and electrolytes.

Actual specific energy is 20-35% of this value

because of the weight of these components and
the energy losses

(Elton j Cairns, “Batteries, Overview, Encyclopedia of Energy, Vol 1, 2004 ,

Elsevier Inc) Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.

© Ahmed F. Ghoniem 10
 Battery Materials

Electrode materials are selected to maximize the theoretical specific energy of the battery, using
reactants/reactions with a large (-ve) DG and light weight (small SM).

• Negative electrode (anode) reactants that can give up electrons easily have large (-ve) DG.
These elements are located on the LHS of the periodic table.
• Elements with a low MW are located toward the top of the periodic table.
• Positive electrode (cathode) reactants (oxides) should readily accept electrons. These elements
are located on the RHS of the periodic table.

(Elton j Cairns, “Batteries, Overview, Encyclopedia of Energy, Vol 1, 2004 , Elsevier Inc)

© Ahmed F. Ghoniem 11
 1
Periodic Table of the Elements 18
1 2
H
Hydrogen
He
Helium
2 14 15 16
1.01 © Todd Helmenstine. All rights reserved. This content is 13 17 4.00
3 4 excluded from our Creative Commons license. For more 5 6 7 8 9 10
Li
Lithium
Be
Beryllium
information, see https://ocw.mit.edu/fairuse. B
Boron
C
Carbon
N
Nitrogen
0
Oxygen
F
Fluorine
Ne
Neon
6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18

s
11 12 13 14 15 16 17 18
Na Mg Al Si p Cl Ar
10
Sodium Magnesium Aluminum Silicon Phosphorus Sulfur Chlorine Argon
22.99 24.31 3 4 5 6 7 8 9 11 12 26.98 28.09 30.97 32.06 35.45 39.95
121 n22 2
n3o
- --
l 1 9 l
19 20 28 31 32 33 34 35 36
K
Potassium
Ca
Calcium
Sc
Scandium
Ti
Titanium Manganese Iron Cobalt
Ni
kel
Cu Zn Ga Ge As
Copper lnc Gallium Germanium Arsenic
Se
Selenium
Br
Bromine
Kr
Krypton
39.10 40.08 44.96 47.88 54.94 55.85 58.93 .69 63.S� L_
65.� 69.72 72.63 74.92 78.97 79.90 84.80

u Zr Ag
37 38 39 40 43 44 45 49 50 51 52 53 54
Rb Sr Tc Ru Rh d n Cd In Sn Sb Te I Xe
4 4

y
Rubidium Strontium Yttrium Zirconium Niobium Ruthenium Rhodium Palladium � Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
""'=
85.47 87.62 88.91 91.22 92.91 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.6 126.90 131.29
p2
J]79
w
55 56 57-71 73 74 75 76 77 78 80 81 82 83 84 85 86
Cs Ba
Barium
Lanthanides Hf Ta Re Os Ir pt Au Hg Tl Pb Bi Po At Rn
Cesium [ Hafnium Tantalum Tungsten Rhenium Osmium num � Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
132.91 137.33 178.49 180.95 183.85 186.21 190.23 .08 196.97 200.5.2..... 204.38 207.20 208.98 [208.98) 209.98 222.02
po4
_........;;.a;

87 88 89-103 105 108 J]111 112 113 114 115 116 117 118
Fr
Francium
Ra
Radium
Actinides Rf
t-- Rutherfordiumj
Db Hs s Rg Cn j Nh
adtiuml RoentgeniumJ Copernicium Nihonium
Fl
Flerovium
Mc Lv
Moscovium Livermorium
Ts Og
Tennessine Oganesson
223.02 226.03 [261] lL _j280L _£SSL [286) [289) [289] [293] [294] [2941

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La
Lanthanum
Ce
Cerium
Pr Nd Pm Sm Eu Gd Tb Dy Ho
Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium
Er Tm Yb
Erbium Thulium Ytterbium
Lu
Lutetium
138.91 140.12 140.91 144.24 144.91 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.06 174.97

u
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Ac Th
Actinium Thorium
Pa
Protactinium Uranium
Np Pu Am Cm Bk
Neptunium Plutonium Americium Curium Berkelium
Cf
Californium
Es Fm Md No
Einsteinium Fermium Mendelevium Nobelium
Lr
Lawrencium
227.03 232.04 231.04 238.03 237.05 244.06 243.06 247.07 247.07 251.08 [254) 257.10 258.10 j 259.10 [262]

Alkali Metal Alkaline Earth Transition Metal Basic Metal Metalloid Nonmetal Halogen Noble Gas I Lanthanide I Actinide )
L017 c � ,ensti
12
 Lead-acid, nickel-metal (Cd/Fe/Mn) hydrite and Zinc batteries.

• Th round-trip efficiency of Some rechargeable aqueous batteries

batteries ranges between 70% for
nickel/metal hydride and more System Cell Theoretical Actual Specific Cycle life
voltage specific specific power
than 90% for lithium-ion batteries.
[V] energy energy [W/kg]
• This is the ratio between electric [Wh/kg]) [Wh/kg]
energy out during discharging to
Pb/PbO2 2.1 175 30-45 50-100 >700
the electric energy in during Cd/NiOOH 1.2 209 35-55 400 2000
charging. Fe/NiOOH 1.3 267 40-62 70-150 500-2000
• The battery efficiency can change H2/NiOOH 1.3 380 60 160 1000-2000
Zn/NiOOH 1.74 326 55-80 200-300 500
on the charging and discharging Zn/Air 1.6 1200 65-120 <100 300
rates because of the dependency
of losses on the current. Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.

Elton j Cairns, “Batteries, Overview, Encyclopedia of Energy, Vol 1, 2004 , Elsevier Inc

The power density is ~ O(20 kW/100kg), need ~ 500 kg to power a 100 kW motor.
13
 Lithium Ion batteries
The open circuit potential of a LiCoO2 battery is ~ 4.2 V. Specific energy is ~3-5X, specific power is
2X higher than lead-acid. Table shows the characteristics of lithium ion batteries with different
positive electrode (cathode) materials: Co (cobalt), Mn (manganese), Fe (iron), Ti (titanium), or S
(sulfur), etc., for improved stability, specific energy and power.

Nonaqueous Rechargeable Battery Chemistries

Material Voltage Theoretical Actual Specific

[V] specific Specific power
energy energy [W/kg]
[Wh/kg]) [Wh/kg]

Li/CoO2 3.6 570 125 >200

Li/Mn2 O4 4 593 150 200
Li/FePO4 3.5 621 120 100
Li/V6 O13 2.4 890 150 200
Li/TiS 2 2.15 480 125 65
Li/S 2.1 2600 300 200

Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.

“Batteries, Overview” by E Cairns, Encyclopedia of Energy, V 1, 2004, Elsevier. Lopez, Jeffrey, et al. "Designing polymers for advanced battery chemistries." Nature Reviews Materials 4.5 (2019): 312-330.

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Creative Commons license. For more information, see https://ocw.mit.edu/fairuse.
 finite current performance

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• Since all the reactants are stored internally, performance

can change with degree of discharge.
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• As more current is drawn from a battery, the reactants
The i-V curve of a battery resembles that of a concentrations drop (and products concentrations
fuel cell, with similar loss mechanisms increase) leading to significant increase in concentration
affecting the performance at higher currents. overpotential and performance degradation under deep
discharge conditions.
Cho et al., PECS 48 (2013) 84 15
Redox Flow Batteries, the All-Vanadium design

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Cho et al., PECS 48 (2013) 84

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2.60J Fundamentals of Advanced Energy Conversion

Spring 2020

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