Energy Science and Technology III

Lecture
Winter Term 2015/16

Introduction to Batteries
7 January 2016

Mario Wachtler
Zentrum für Sonnenenergie- und Wasserstoff-Forschung (ZSW)
Baden-Württemberg
 Outline

Basic Concepts

Electrode and Cell Designs

Battery Parameters

Comparison of Battery Systems

Battery Market

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 Electrochemistry

Please repeat the following concepts:

(→ EST III Lecture: Module “Fuel cell fundamentals”)

 Oxidation and reduction reactions

 Nernst equation
 Formal potential
 Relation between Gibbs free enthalpy ∆G and electrical potential difference ∆E
 Faraday's law and Faraday's constant
 Ohm's law
 Overvoltage / overpotential
 Current-voltage curve
 Butler-Volmer equation

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 Cell vs. Battery

Cell Battery

Basic electrochemical unit Assembly of one or more cells

Converts chemical to electrical energy connected in parallel or in series
(and vice versa for rechargeable cells)
Consists of: cell(s), monitors, controls,
Consists of: electrodes, electrolyte, fuses, diodes, case, terminals, etc.
separators, current collectors, cell
housings, terminals, etc.

Source: SAFT Source: Daimler (1st generation Li-ion battery for S-class HEV)

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 Non-Rechargeable vs. Rechargeable Batteries

Non-rechargeable batteries Rechargeable batteries

Primary batteries Secondary batteries

“Batteries” Accumulators
Storage batteries

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 Shortcut Notation of Cell Chemistry

negative electrode | electrolyte | positive electrode

• Negative electrode on the left
• Positive electrode on the right
• | denotes a phase boundary
• || denotes a liquid-liquid phase boundary (e.g. via salt bridge)
• During discharge electrons flow from left to right via external circuit and cations flow from left to right
via electrolyte
• Cell voltage is positive: ∆E = E(right) – E(left) = E(+) – E(–) > 0

Examples:

Li | electrolyte | LiFePO4 Zn0 | Zn2+ (aq.) || Cu2+ (aq) | Cu0

Li + FePO4 → LiFePO4 Zn0 + Cu2+ → Zn2+ + Cu0
∆E = 3.5 V ∆E = 1.1 V

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 Primary and Secondary Batteries
Selected Systems

Primary batteries Secondary Batteries

(Non-rechargeable batteries) (Rechargeable batteries, accumulators)

• Zn-carbon - Leclanché: Zn | NH4Cl | MnO2 • Lead acid: Pb | H2SO4 | PbO2

• Zn-carbon - Zn chloride: Zn | ZnCl2 | MnO2 • Valve regulated lead acid (VRLA):
• Alkaline MnO2: Zn | KOH | MnO2 Pb | immobilised H2SO4 | PbO2
• Ni-Cd: Cd | KOH | Ni oxide
• Magnesium: Mg | Mg(ClO4)2-Li2CrO4 | MnO2 • Ni-MH: metal hydride | KOH | Ni oxide
• Zinc-silver oxide Zn | KOH or NaOH | Ag2O • Li-Ion: LiC6 | aprotic organic | Li(1-x)CoO2
• Mercury-zinc: Zn | KOH or NaOH | HgO LiC6 | apro. org. | Li(1-x)Ni1/3Co1/3Mn1/3O2
• Mercad: Cd | KOH or NaOH | HgO LiC6 | aprotic organic | FePO4
• Zinc/air: Zn | KOH | O2 • Edison (NiFe): Fe | KOH-LiOH | Ni oxide
• Lithium: Li | LiAlCl4-SOCl2 | SOCl2 • Rechargeable alkaline manganese (RAM):
Li | aprotic organic | SO2 Zn | gelled KOH | MnO2
Li | aprotic organic | MnO2 • Sodium-sulfur:
Li | aprotic organic | FeS2 Na | β''-alumina (~ NaAl11O17) or NaSiCONs | S
Li | aprotic organic | (CF)n • Na-Nickel chloride (ZEBRA):
Li | LiI | I2•poly-2-vinylpyridine Na | β''-alumina + NiAlCl4 | NiCl2
• Zinc-bromine: Zn | ZnBr2 | Br2
• Vanadium redox flow: V2+ | Vx+, H2SO4 | V5+
anode | electrolyte | cathode
D. Linden, T.B. Reddy (eds.): Handbook of batteries, 3rd ed., McGraw-Hill, New York (USA), 2002.

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 Basic Concepts
Special Battery Types
“Dry Cells”: Reserve batteries
No electrolyte leakage:  During storage a key component is
 Liquid electrolyte is contained in separated from rest of battery.
absorbent or separator Battery is activated only before use.
 Solid electrolyte  Excellent storage characteristics
(chemical degradation and
discharge are eliminated)

Mechanically rechargeable batteries Thermal batteries

 Mechanical replacement of  Battery is activated by heating, e.g.
discharged or depleted electrode melting of solid electrolyte
 Usually metal anode in metal/air  Especially for military applications
batteries (e.g. Zn/air) (missiles, torpedos, weapon
systems)

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 Anode and Cathode
Charge Discharge
Electrolysis Galvanic element

e e
− + − +

Li+ Li+

Cathode Anode Electrochemical Anode Cathode

(is reduced) (is oxidised) definition (is oxidised) (is reduced)

„Anode“ „Cathode“ Battery Anode Cathode

convention
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 Electrodes: Anode and Cathode

Anode Cathode
Negative electrode Positive electrode

During discharge the anode gives electrons During discharge the cathode accepts
to external circuit and is oxidised. electrons from external circuit and is
reduced.
Red → Ox + n e-
Ox + n e- → Red

 Be aware:
• In electrochemistry the electrode which is oxidised (or at which oxidation takes place) is defined as
anode and the electrode which is reduced (or at which reduction takes place) is defined as cathode.
During discharge of a cell the negative electrode is oxidised and is thus the anode, and the positive
electrode is reduced and is thus the cathode. During charge the oxidation / reduction reactions are
reversed: hence, from a strict electrochemical point of view the negative electrode becomes the
cathode and the positive electrode becomes the anode.
• To avoid confusion in battery science the terms anode and cathode are always used in the discharge
sense, i.e. the negative electrode is called anode and the positive electrode is called cathode,
irrespectively of whether the electrode is discharged or charged.
• To be on the safe side, negative electrode and positive electrode should be used.

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 Basic Concepts
Active vs. Inactive Materials
“Active” materials “Inactive” materials

Take part in the charge storage reaction: Do not take part in the charge storage
reactions, but are needed to support the
E.g. electrode materials, electrolyte in lead active materials
acid batteries etc.
E.g. conductive additives, binders, current
collectors, electrolyte in Li-ion batteries, cell
housing, etc.

– + Electrolyte solution
Separator or polymer electrolyte
Current collector (-)
Current collector (+)
[optional] Current collector coating (-+)
Polymer binder (-+)
Conductive additive (-+)
Active material (-)
Active material (+)
[optional] Particle coating (-+)

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 Basic Concepts
Electrolyte
Function / requirements:
 Conducting for ions
 Insulating for electrons (to prevent self-discharge)

Can be with or without separator function:

 Separator function: prevent direct contact between anode and cathode (short circuit)
 Without separator function: liquid electrolytes, additional mechanical separator is
required
 With separator function: solid electrolytes (including polymer electrolytes)

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 Basic Concepts
Electrolyte
Can act as active or inactive material:

 Inactive material: electrolyte does not take part in net cell reactions, composition of
electrolyte remains constant during charge and discharge

E.g. Li-ion batteries:

Anode: C6 + Li+ + e− ↔ LiC6
Cathode: LiFePO4 ↔ FePO4 + Li+ + e−
Cell: C6 + LiFePO4 ↔ LiC6 + FePO4

 Active material: electrode takes part in electrode reactions, composition of electrolyte

changes during charge and discharge

E.g. lead acid batteries:

Anode: Pb + SO42– ↔ PbSO4 + 2e−
Cathode: PbO2 + SO42– + 4H+ + 2e− ↔ PbSO4 + 2H2O
Cell: Pb + PbO2 + 2SO42– + 4H+ ↔ 2PbSO4 + 2H2O

(red: electrolyte components)

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 Electrode Design

Active material (e.g. MH) in

a porous structure plus
electrolyte

The energy is stored inside

the active materials (volume
related)
Active material

Additive The energy conversion

(e.g. Co for NiOOH) (power) takes place on the
surface of the active
Electrolyte
materials (area related)

Current collector
(e.g. Ni foil (NiMH))

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 Electronic and Ionic Conductivity
Electrode Active material
e‒

Li+

For the charge / discharge reaction to occur electron and ion conduction is required:
• Electron conduction via current collector and active material
• Ion conduction via electrolyte and active material
Active material:
• Insertion and conversion electrodes require diffusion of active species (ions) otherwise metal deposition occurs at surface
Increase of electron conduction:
• Proper design of active materials, e.g. doping
• Conductive additives and carbon coating of active material: provide additional electron conduction pathways in electrode
Increase of ion conduction:
• In active material: Nanoparticles: shorter diffusion lengths, grain broundary diffusion
• In electrode: increased porosity to provide more and better electrolyte access

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 High Power vs. High Energy

Optimized for power Optimized for energy

 High conductivity of electrolyte  Very efficient electrode reaction

 Avoid long diffusion paths and material usage
(thin electrode layers, thin  Thick electrodes with high
separators) electrode mass
 Good grain to grain contact,  Save inactive / passive
electrically conducting agents components like additives or
 Short distance from active material current collector
to current collector
 Fast reaction kinetics (electrode
reaction)

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 Battery Components

Safety valve /
Electrodes and other safety features
and current collector

Housing
• mechanically stable
• gas/liquid-tight (H2,
electrolyte)
• chemically stable
• steel, Al, plastic or
composite material
Separator:
Electrolyte • Mechanical separation of electrodes
• Good ion conductivity
• Very thin

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 Outline

Basic Concepts

Electrode and Cell Designs

Battery Parameters

Comparison of Battery Systems

Battery Market

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 Electrode Types
Metal Electrodes
 Usually as negative electrode
 Dissolution during discharge
 Deposition during charge

 Ni-Cd, Li (metal), metal-air

Cd ↔ Cd2+ + 2e−
Li ↔ Li+ + e−

 High capacity
 Problems with rechargeability, as metal deposition often occurs dendritic
(safety problems)

Lithium dendrite formation

after repeated cycling

F. Orsini, L. Dupont, B. Beaudoin, S.

Grugeon, J.-M. Tarascon; Int. J. Inorg.
Mater. 2 (2000), 701.

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 Electrode Types
Non-Reacting (Inert) Electrodes
 Are not reduced / oxidised during charge / discharge but deliver / accept
electrons to reduce / oxidise active species dissolved in the electrolyte

 redox-flow battery, metal/air, fuel cells

(C) + V2+ ↔ (C) + V3+ + e−
(C) + VO2+ + 2H+ + e− ↔ (C) + VO2+ + H2O
(C/catalyst) + O2 + 2Li+ + 2e− ↔ (C/catalyst) + Li2O2

 electrical double-layer capacitor

(C) + Cation+ ↔ (C)−...Cation+
(C) + Anion+ ↔ (C)−...Anion−

 May age and lose activity

Vanadium redox flow battery

Source:
http://www.messib.eu/about_project/m
essib_innovative_elements/redox_flow
_batteries.php (2013)

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 Electrode Types
Insertion and Conversion Electrodes
 During discharge / charge a species from the electrolyte is inserted into / de-
inserted from the electrode

 Li-ion, Ni-MH, lead acid

LiC6 ↔ C6 + Li+ + e−
FePO4 + Li+ + e− ↔ FePO4
MH + OH− ↔ M + H2O + 2e−
NiOOH + H2O + 2e− ↔ Ni(OH)2 + OH−

 redox supercapacitors
RuO2 + xH+ + xe− ↔ RuO2-x(OH)x

 Good rechargeability
 Usually lower capacity than for metal electrodes

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 Electrode Types
Insertion and Conversion Electrodes
Insertion Reactions Conversion Reactions

Topotactic reactions without major changes New phases are formed during charge and
of host material discharge putting mechanical stress onto
→ Good cycling stability the system
→ More difficult to obtain cycling stability
Usually only small amounts of Li can be
inserted into / extracted from the interstitial Compounds can usually react with a larger
sites amount of Li
→ Low capacity → High capacity

Source: M. Armand, J.-M. Tarascon; Nature 451 (2008), 652.

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 Cell and Battery Designs

Open batteries:
 Batteries with removable lid
 Batteries without case (e.g. power paper printable Zn|MnO2 thin-film battery)

Vented batteries (geschlossene Batterien)

 Batteries with plug, gasses are emitted during charge (e.g. SLI lead acid)

Valve-regulated batteries (verschlossene Batterien)

 Batterie with resealable valve and gas recombination cycle (e.g. VRLA)

Sealed batteries
 Batteries with complete gas recombination cycle (Ni-Cd, Ni-MH)
 Batteries which do not show gassing (Li-ion)

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 Cell Designs
Bobbin Constructions

Electrodes shaped in 2 concentrical cylinders

 Maximised amount of active materials

 Simple and cheap
 Small surface area for electrochemical
reaction
 High internal resistance
 Low rate / power

E.g. Zn-carbon primary cells

Alkaline MnO2 cells

Source: Varta

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 Cell Designs
Wound Designs

Spirally wound: cylindrical cells

Elliptically wound: prismatic cells

Electrodes and separators are wound

up to form a “jelly roll”

 Thin electrodes,
 Large surface areas for
electrochemical reaction
 Low internal resistance
 High rate / power
 More complex and expensive than
bobbin construction
Sony: Li-Ion battery rechargeable battery, catalogue, 2001.
E.g. Li-ion batteries

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 Cell Designs
Cylindrical vs. Prismatic
Cyclindrical Prismatic

Sony: Li-Ion battery rechargeable battery, catalogue, 2001.

• Minimum diameter (>10 mm) • Thin cells possible (>3mm)

• Simple and cheap manufacturing (winding) • More complex and costly manufacturing
• Defined pressure on electrodes • Easier cooling
• Defined path for gas release during opening of • Defined pressure on electrodes
• Problems with cooling especially for large cells (build-up • Defined path for gas release during opening of
of temperature gradients) • Good shape factor, high packing density in modules
• Mechanically very robust
• Limited maximum capacity: approx. 40 Ah
• Bad shape factor, low packing density in module

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 Cell Designs
More Prismatic Cell Designs

Elliptically wound

T. Knoche, Electrical Energy Storage Conference and Fair, Munich, 2012.

E.g. Li-ion batteries

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 Cell Designs
Stacked Designs: Plate Design

 Thicker electrodes are possible

(better ratio of active to inactive
materials)
 Still large surface areas for
electrochemical reaction
www.varta-automotive.de (last access: 01/2011)  Complex manufacturing and
current collector design

E.g. Lead-acid

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 Cell Designs
Bipolar Designs

• Bipolar electrodes: one side of the electrode acts as an

anode in one cell and the other side acts as a cathode in
the next cell
• Bipolar electrode must be ion-impermeable to avoid self-
discharge

 Efficient design: reduced number of plates, elimination of

D. Linden; in D. Linden, T.B. Reddy (eds.): Handbook of
Batteries, 3rd ed., McGraw Hill, New York, 2002; Ch. 3.
external connections, reduced weight of the battery,
increased energy density
 Shorter current pathway, lower internal resistance, higher
power
 Uniform current distribution over entire surface of
electrodes provides more efficient utilization of electrode
materials
 High voltage batteries can be realised in small space
 Strong requirements for stability of bipolar electrodes and
tightness of cell compartments
 Risk of higher self discharge due to shunt currents

E.g. Lead-acid, redox flow batteries, Ni-MH

Source: Altraverda

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 Cell Standardisation

Why standardisation:
 Ensure interchangeability of cells from different manufacturers

Standardisation of:
 Size, shape, voltage and terminals

Standards:
 International Standards:
IEC (International Electrotechnical Commission)
 National Standards:
E.g. ANSI (American National Standards Institute)
 Specific Nomenclatures from battery manufacturers

F. Ciliberti, S. Wicelinski; in D. Linden, T.B. Reddy (eds.): Handbook of Batteries, 3rd ed.; McGraw-Hill, New York, 2002; Chapter 4.

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 Cell Standardisation by Size
Cylindrical Cells
Special nomenclature:

AA (“double A”) d = 13.5 – 14.5 mm, h = 49.2 – 50.5 mm

AAA (“triple A”) d = 9.5 – 10.5 mm, h = 43.3 – 44.5 mm
C d = 24.9 – 26.2 mm, h = 48.5 – 50.0 mm
D d = 32.2 – 34.3 mm, h = 59.5 – 61.5 mm
etc.

Systematic nomenclature:

dd(d)hh(h)
d = diameter in mm
h = height in 1/10 mm h

(Small) Li-ion cells: 18650 (d = ~18 mm, h = ~65.0 mm)

26650 (d = ~26 mm, h = ~65.0 mm)
etc. h
Coin cells: 2032 (d = ~20 mm, h = 3.2 mm) d
etc.
d
Picture source:
http://www.varta-microbattery.com (2013)

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 Cell Standardisation by Size
Prismatic Cells
Special nomenclature:

Many …
l

Systematic nomenclature: t

ttwwll
w
t = thickness in 1/10 mm
w = width in mm
Picture source:
l = length in mm http://www.varta-microbattery.com (2013)

(Small) Li-ion cells: e.g. 553450 (t = ~5.5 mm, w = ~34 mm, l = ~50 mm)
many more (customised sizes)

Other systems for large cells (e.g. lead acid)

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 Examples for Prismatic Cells
Development of Prismatic Cells at Panasonic

O. Sonnemann (Panasonic), Electrical Energy Storage Conference and Fair, Munich 2012.

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 Standardisation by Battery Chemistry

F. Ciliberti, S. Wicelinski; in D. Linden, T.B. Reddy (eds.): Handbook of Batteries, 3rd ed.; McGraw-Hill, New York, 2002; Chapter 4.

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 Standardisation by Shape

F. Ciliberti, S. Wicelinski; in D. Linden, T.B. Reddy (eds.): Handbook of Batteries, 3rd ed.; McGraw-Hill, New York, 2002; Chapter 4.

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 Outline

Basic Concepts

Electrode and Cell Designs

Battery Parameters

Comparison of Battery Systems

Battery Market

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 Typical Cell / Battery Parameters

Nominal voltage Generally accepted typical operation voltage

(e.g. Ni-MH and Ni-Cd: 1.2 V, Li-ion (graphite-LCO/NCA/NMC): 3.6 – 3.7 V,
Lead-acid: 2.0 V)

Open circuit voltage Voltage under a no-load condition

(is usually a close approximation of the theoretical voltage)

Rated capacity Charge which is obtained at defined conditions

Specific capacity / energy / power Capacity / energy / power per mass of active material or cell
(usually given in Ah/kg, Wh/kg, W/kg)

Charge / energy / power density Capacity / energy / power per volume of active materials or cell
(usually given in Ah/L, Wh/L, W/L)

Cycle life Number of cycles until capacity falls below a threshold value
(usually 80% of initial capacity)

Calendar life Time until capacity falls below a threshold value

(usually 80% of initial capacity)

Self-discharge Loss of charge per time starting from a fully charged state
(usually given in %/month)

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 General Requirements for Cells / Batteries

Performance High specific energy and energy density

High specific power and power density
Supported energy and power range
High charge efficiency
High energy efficiency
Low self-discharge
Low energy consumption of required auxilary units (heating, pumping, battery
management, …)

Battery life Long cycle life / high cycling stability

Long calendar life

Safety High safety during regular operation

High tolerance towards abuse
Low damage potential

Environmental impact Manufacture

Operation
Disposal / recycling

Cost effectiveness Low acquisition costs

Low operation costs
Low maintenance costs

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 Theoretical (Specific) Capacity of Electrode Materials

Capacity Charge
Specific capacity Capacity per mass, usually given in Ah/kg or mAh/g
Volumetric capacity Capacity per volume, usually given in Ah/L

Qspec,th = z • F / Mw (derived from Faraday‘s law)

Qspec,th = theoretical specific capacity, usually given in Ah/kg or mAh/g
z = number of transfered electrons
F = Faraday constant, 96485 As/mol
Mw = molecular weight, usually given in g/mol

Note:
 The specific capacity (as well as the volumetric capacity) are usually refered to the
mass of discharged materials!

E.g.: LIB cathode materials LiFePO4

LiFePO4 ↔ FePO4 + Li+ + e–
(discharged) (charged)
z=1
Mw(LiFePO4) = 157.8 g/mol
Qspec,th = 169.9 Ah/kg

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 Theoretical and Practical Specific Capacities of
Electrode Materials
Example 1: Example 2:
Theoretical capacity of graphite (C6) Practical capacity of LiCoO2

Maximum intercalation state: At real conditions only 0.5 to 0.6 mol Li

1 mol Li (1 mol e–) per mol C6: can be deinserted:
1mole / molC6  96485 A  s / mole 0,6mole / molLiCoO2  96485 A  s / mole
 372mA  h / g  164mA  h / g
72,1g / molC6  3,6 A  s / mA  h  97,9 g / molLiCoO2  3,6 A  s / mA  h 

1C rate: 372 mA/g 1C rate: 164 mA/g

C/10 rate: 37.2 mA/g C/10 rate: 16.4 mA/g
10C rate: 3.72 A/g 10C rate: 1.64 A/g
etc. etc.

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 Theoretical (Specific) Capacity of Cells

Capacity refered to amount (mass) of anode and cathode active materials

For a general reaction a A + b B ↔ c C + d D with z e– transfered:

(discharged) (charged)

Qspec,th,cell = z • F / (a Mw,A + b Mw,B)

E.g.: Li-ion cell: C6 | 1M LiPF6 / EC:DMC (1:1 by wt.) | LiCoO2

Anode reaction: 0.6 C6 + 0.6 Li+ + 0.6 e– ↔ 0.6 LiC6

Cathode reaction: LiCoO2 ↔ 0.6 Li+ + 0.6 e– + Li0.4CoO2

Cell reaction: 0.6 C6 + 1 LiCoO2 ↔ 0.6 LiC6 + 1 Li0.4CoO2

aA bB

z = 0.6
a = 0.6
b=1
Mw(C6) = 72.1 g/mol
Mw(LiCoO2) = 97.9 g/mol
Qspec,th,cell = 94.6 mAh/g → Practical specific capacity will be lower, since
inactive components increase the cell weight

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 Electrode Balance and Cell Capacity

For a cell to deliver a given capacity, both the anode and the cathode have to deliver this
capacity.

For safety reasons and / or to improve the ageing behaviour usually on electrode is limiting
(smaller capacity) and the over one is over-dimensioned (higher capacity). (E.g. in Li-ion
batteries with graphite anode, the anode is usually over-dimensioned).
→ In this case the cell capacity corresponds to the capacity of the limiting electrode!

E.g.: Given is a cell with an anode which delivers 1.2 Ah and a cathode which delivers 1.0 Ah.
Limiting electrode = cathode
Cell capacity = capacity of cathode = 1 Ah

Practical specific capacity of cell = cell capacity per cell mass

Theoretical specific capacity of cell = often calculated as cell capacity per sum of
masses of active materials in anode and cathode
(Note: other definitions are in use, check conventions before comparing values!)

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 C-Rates
(Cells and Batteries)
Conventional definition for cells / batteries:
● A 1C rate corresponds to the current which allows a full charge or discharge of a cell in
1 h (for moderate rates*)

I[A] = M • Cn[Ah] / 1[h]

I Current
Cn Rated capacity (at a n h discharge*§)
M multiple or fraction of C

* Capacity decreases at high currents, therefore a capacity

value determined at low currents should be used
§ n is often omitted D. Linden, T.B. Reddy: Handbook of Batteries,
3rd ed., McGraw-Hill, New York, 2002, p.3.21.

E.g.: Battery with a rated capacity of 8 Ah (for a 5h discharge)

C5 = 8 Ah
1C-rate: M=1 I=8A
C/10-rate: M = 0.1 I = 0.8 A
10C-rate: M = 10 I = 80 A

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 C-Rates
(Electrode Materials)
Conventions for electrode materials:
(in analogy to cells and batteries)
● Based on practical capacity (of electrode or cell)
E.g. LFP: practical capacity 160 mAh/g
1C = 160 mA/g

● Based on theoretical capacity (of electrode or cell)

E.g. LFP: practical capacity 169.9 mAh/g
1C = 169.9 mA/g

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Influence of Current Rate on Capacity

With increasing current …

• the electrode / cell capacity decreases
- since the materials / cell cannot be fully discharged
- since the end-of-discharge (EOD) voltage is reached before the cell is fully
discharged
• the discharge voltage decreases
- due to increasing overvoltages and IR drop
→ i.e. discharge energy decreases

E.g.: LIB (Graphite/NCA), 7.5 Ah, GAIA

EOD voltage

Picture source: P. Kurzweil, K. Brandt, in J. Garche (ed.):

“Encyclopedia of Power Sources”, Vol. 5, Elsevier, Amsterdam
(The Netherlands), 2009, pp. 1ff.

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Cell Energy

Specific energy energy per mass

usually given in Wh/kg
also often called “energy density”

Energy density energy per volume

4
usually given in Wh/L
Uav

Cell Voltage / V
W =  U(Q) • dQ = ~ Uav • Q 3

W = (specific) energy
U = cell voltage 2
Q = (specific) capacity

1
Practical specific energy refers to mass of
complete cell
0
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8
Theoretical specific energy is usually refered
to sum of masses of active materials in anode and Capacity / Ah
cathode

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Charge Efficiency and Energy Efficiency

Charge efficiency Energy efficiency

Charge/discharge efficiency WDCh
Coulombic efficiency Wh 
WCh
QDCh
 Ah  Energy efficiency considers charge losses
QCh (e.g. due to side reactions) and voltage
Charge efficiency consideres charge losses losses (e.g. due to overvoltage)
(e.g. due to side reactions or due to self-
discharge) Typical values
Li-ion: ~95%
Typical values: Lead acid: ~80%
Li-ion: ~100% (no side reactions) Ni-MH: ~75%
Lead acid: approx. ~90% Ni-Cd: ~65%
Ni-Cd, Ni: approx. ~70%

Charge Factor QCh 1

CF  
QDCh  Ah

→ Both charge efficiency and energy efficiency depend on the charging method used.

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Outline

Basic Concepts

Electrode and Cell Designs

Battery Parameters

Comparison of Battery Systems

Battery Market

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Electrochemical Series

Electrochemical Series Theoretical Specific Energy

(Standard reduction potentials)
System Ah/kg V Wh/kg

Li//F2 1035 5.88 6086

Li//O2 1787 4.24 7577
Mg//O2 1330 3.61 4801
Zn//O2 659 1.99 1317
3663
H2//O2 2978 1.23 (33,000 H2
only)
Li//Sx 1165 2.56 2.982
Na//NiCl2 304 2.58 784
Li//MO2 285 3.5 ca. 1000

C6//Li1-xCoO2 rated: 3.7

114 ca. 420
with xmax=0,6 max. 4.2
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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Nominal Voltage and Theoretical Energy Density

Theor.
Nominal Cell reaction
energy
System voltage (left: charged state / right: discharged state)
/V
density * (blue: anode / red: cathode)
/ Wh/kg

Pb/PbO2 1.93 161 Pb + PbO2 + 4 H+ + 2 SO42– ↔ 2 PbSO4 + 2 H2O

Ni/Cd 1.29 209 Cd + 2 NiOOH + 2 H2O ↔ 2 Ni(OH)2 + Cd(OH)2

Ni/MH 1.31 213 1/6 MmNi5H6 + NiOOH ↔ Ni(OH)2 + 1/6 MmNi5 **

Ni/Fe 1.37 267 Fe + 2 NiOOH + 2 H2O ↔ 2 Ni(OH)2 + Fe(OH)2

Ni/Zn 1.74 326 Zn + 2 NiOOH + 2 H2O ↔ 2 Ni(OH)2 + Zn(OH)2

Zn-Air 1.65 1087 2 Zn + O2 ↔ 2 ZnO

Na/NiCl2 2.58 783 2 Na + NiCl2 ↔ 2 NaCl + Ni

Li/MnO2 3.5 ~ 1000 x Li + MnO2 ↔ LixMnO2 (theor. xmax = 1)

Li-Ion C6/LiMO2 3.7 ~ 420 x LiC6 + Li1–xCoO2 ↔ x C6 + LiCoO2 (xmax = ~0.6)

* Energy density referred to sum of masses of anode and cathode active materials
** Mm = misch metal (= mixture of rare earth metals)

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Theoretical vs. Practical Energy Density

O2/Zn
1200

Li/MnO2
1000

Na/NiCl2
800
Wh/kg

C/LiMO2
600

O2/Zn
Ni/Zn

400
Ni/Fe
Pb/PbO2

Ni/MH

C/LiMO2
Ni/Cd

Li/MnO2
Na/NiCl2
Pb/PbO2

Ni/MH

Ni/Zn
Ni/Cd
200

Ni/Fe
0
theor.
Pb/PbO2 spez.
Ni/MH Energie
Theoretical specific
Ni/Zn
energy
Na/NiCl2 O2/Zn prakt.
Ni/Cd Spez.
Practical Energie
specific
Ni/Fe
energy
C/LiMO2 Li/MnO2

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Voltage Ranges
4,5

4,0
Li-Ion

3,5
Cell voltage / V

3,0
Na/NiCl2
2,5
Lead acid
2,0
DLC (org.)

1,5
NiMH
Stability window of H2O
1,0

DLC (aqu.)
0,5
DLC = electrical double layer
capacitor (= supercapacitor)
0,0
0 20 40 60 80 100 % 120

(discharged) 100  C/Cn (charged)

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Energy and Power
Ragone* Diagramme

+HDLC

Redox-flow

* David. V. Ragone

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Energy Efficiency

Efficiency

120

100

80
efficiency in %

60

40

20

0
Lead acid Li-Ion DLC HDLC Redox Flow NiMH Metal Air Fuel Cell

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Costs

Costs/kWh

10000

1000
Costs in €/kWh

100 Costs/kWh

10

1
Lead acid Li-Ion DLC HDLC Redox NiMH Metal Air Fuel Cell
Flow

Li-ion: Small consumer cells: <300 €/kWh

Large cells: 300-800 €/kWh, costs rapidly decreasing

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Cycle Life

1000000

100000
Cycle Lifetime (100% DOD

10000

1000

100

10

1
Lead acid Li-Ion DLC HDLC Redox NiMH Metal Air Fuel Cell
Flow

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Safety

12

10

8
Safety Level (1-10)

0
Lead acid Li-Ion DLC HDLC Redox Flow NiMH Metal Air Fuel Cell

For Li-ion, redox flow and metal air safety depends strongly on specific technology

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Comparison of Technologies

specific Energy (1=200 Wh/kg)

1 LAB
0,9 NiMH
0,8 Me-Air
DLC
0,7
Li-Ion
0,6
Costs (1=100 €/kg) 0,5 specific Power (1=5000W/kg)
0,4
0,3
0,2
0,1
0

Energy Efficiency in % Lifetime (cycles) (1=3500 Cycles)

Low temp. Performance (1 = -40°C)

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Outline

Basic Concepts

Electrode and Cell Designs

Battery Parameters

Comparison of Battery Systems

Battery Market

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Battery Market Volume

Global revenues: Revenue contributions of different

battery chemistries (2009)
2009: 47.5 billion USD
2015: 74 billion USD

Source: Frost and Sullivan

2009:
Primary batteries: 23.6% of global battery market, share is decreasing
Secondary batteries: 76.4% of global battery market, share is increasing

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Battery Market Development
Rechargeable Batteries (without Lead-Acid)
Cost base!

H. Takeshita, H. Mukainakano, Institute of Information Technology; 28th Int. Battery Seminar & Echibit, Orlando (FL, USA), 2011.

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Recommended Literature

D. Linden, T.B. Reddy (eds.): Handbook of batteries, 3rd ed., McGraw-Hill, New York (USA),
2002.

J. Garche (ed.-in-chief): Encyclopedia of electrochemical power sources, Vols. 1 – 5,

Elsevier, Amsterdam (The Netherlands), 2009.

A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen; Leipheim and Munich

(Germany), 2006. (Book in German language).

J.O. Besenhard (ed.): Handbook of battery materials; Wiley-VCh, Weinheim (Germany),

1999.

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Acknowledgements

Parts of this lecture are based on lectures by

Prof. Andreas Jossen

(TU Munich, formerly ZSW)

and

Prof. Werner Tillmetz

(ZSW and University of Ulm)

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160107 | University of Ulm | EST-III | Batteries Introduction | MW
 Thank you for your attention!

mario.wachtler@zsw-bw.de
www.zsw-bw.de

Zentrum für Sonnenenergie- und Wasserstoff-Forschung

Baden-Württemberg
Helmholtzstraße 8, 89081 Ulm

Stuttgart Widderstall Ulm Ulm

Photovoltaics & Solab Solar test-field Electrochemical Energy eLab (Battery research centre)
- 64 -
Energy Policy & Energy160107
Carriers
| University of Ulm | EST-III | Batteries Introduction | MW Technologies FPL (Battery production research)