Primary Batteries 2020

Energy Storage
Lecture 9: Primary Cells and Batteries

Lecture 10: Secondary Cells and Batteries
Winter Term 2015/2016
Carsten Agert
NEXT ENERGY
Lectures
Date Lecture
12. Okt. 15 power grids and motivation for storage
19. Okt. 15 (no lecture)
26. Okt. 15 storage for buildings, including heat pump and CHP (Herena)
2. Nov. 15 storage for buildings, including heat pump and CHP (Herena)
9. Nov. 15 compensating RE fluctuations - the transmission grid level
16. Nov. 15 compensating RE fluctuations - the distribution grid level
23. Nov. 15 non-electrochemical electricity storage: overview
30. Nov. 15 fundamentals of electrochemical storage
7. Dez. 15 electrochemical electricity storage devices (except batteries)
14. Dez. 15 batteries: primary cells
4. Jan. 16 batteries: secondary cells
11. Jan. 16 course summary & exam preparation // electric cars (I)
18. Jan. 16 electric cars (II)
25. Jan. 16 exam
only for internal use (storage lecture) 2

Energy Storage
Carsten Agert
NEXT ENERGY
Categorization of batteries
Zn/MnO2 battery
Alkaline manganese battery
Primary Battery Zn/Ag2O battery
Zn/Air battery
(Non-rechargeable) Li primary batteries
electrical energy
Others
Chemical Batteries
chemical energy
Lead-Acid battery
Ni-Cd battery
Secondary Battery Ni-MH battery
(Rechargeable) Li-ion battery
High-temperature secondary battery
Others

Commercialized primary batteries: A brief introduction
Zinc-Carbon battery (Zn/MnO2)

Alkaline manganese battery (alkaline Zn/MnO2)
Zinc-Silver oxide battery (Zn/Ag2O)
electric energy
Zinc-Air battery (Zn/Air)

Aqueous system Magnesium-manganese battery (Mg/MnO2)
Nickel-Zinc battery (NiOOH/MnO2)
Chemical Batteries
Zinc-Mercury oxide battery (Zn/HgO)

Cadmium-Mercury oxide battery (Cd/HgO)
chemical energy
Lithium manganese battery (Li/MnO2)

Lithium carbon fluoride battery (Li/CFx)
Non-aqueous system Lithium Thionyl Chloride battery (Li/SOCl2)
Lithium iodine battery (Li/I2)
red = discussed in the lecture

Zinc carbon and alkaline manganese battery
Zn/carbon Alkaline manganese
OCV 1.5 V 1.5 V

Work voltage 1.4 -1.2 V 1.4-1.2 V
Specific energy 40-90 Wh/kg 80-150 Wh/kg
density (Wh/kg)
Discharge has a sloped has a sloped

Characteristics discharge curve discharge curve
Shelf life 1-2 years 2-5 years
Performance comparison of Zn/carbon and alkaline

manganese

Zinc carbon battery
The overall reaction in the cell is:

Zn + 2MnO2 +2 NH4Cl → Zn(NH3)2Cl2 + 2MnO(OH)
The exact mechanism for this is complicated, and
there is still controversy over the exact
mechanism, however the approximate half-cell
reactions are:
Anode:
Zn → Zn2+ + 2e-
Zn2+ + 2 NH4Cl → Zn(NH3)Cl2 + 2H+
Cathode:
2H+ + 2MnO2 + 2e- → 2MnO(OH)
Source of picture: Wikipedia

Alkaline manganese battery
The first modern alkaline manganese cell was developed in the 1960s.
Alkaline/manganese oxide batteries have broadly replaced the zinc/carbon cell today.
It is the most widely produced primary battery of the world.
Source: DoITPoMS TLP – Batteries, University of Cambridge
Reversed geometry: zinc anode in the centre,

MnO2 cathode “cup”, alkaline electrolyte
(KOH, potassium hydroxide)
Main advantage over zinc carbon battery:

higher energy density due to increased
density of the active cathode material
At the anode:
Zn + 2OH– → ZnO + H2O + 2e –
At the cathode => reduction of MnO2, e. g.:
2MnO2 + H2O + 2e – → Mn2O3 + 2OH–
Overall: Zn + 2MnO2 → ZnO + Mn2O3

Typical discharge characteristics of alkaline manganese battery
Advantages
Similar to, and interchangeable with, zinc/carbon
battery but with more than twice the energy
density.
Constant capacity over a wide range of current
drains and suitable for high drain rate appli-
cations.
Longer shelf life (3-5 years) due to reduced self
discharge.
Better low temperature performance and less
leakage than zinc/carbon battery. Continues to
function in sub-zero temperatures.
Suitable for a wide range of consumer
applications.
Shortcomings
(Usually) not rechargeable
Source: DURACELL, USA

Zinc-Silver oxide battery (Zn/Ag2O)
Firstly developed in the 1930’s by André. Note the flat discharge characteristics:
Source: http://hittorf.nw.lo-net2.de/chemiegkabi2010/.ws_gen/?4
At the anode: Zn + 2OH– → Zn(OH)2 + 2e- Source: DURACELL, USA
At the cathode: Ag2O + H2O +2e- → 2Ag + 2OH–

Overall: Ag2O + H2O + Zn → 2Ag + Zn(OH)2

Advantages and limitations of Zn/Ag2O battery
Performance Characteristics Advantages

» High capacity per unit weight.
» Long operating life. A tiny button cell will keep
OCV ~1.65 V a watch running 24 hours per day for 3 to 5
years!!
Work voltage 1.5-1.2 V » Low self discharge and hence long shelf life
(better than zinc/air)
Specific energy 130 Wh/kg » Better low temperature performance than
density (Wh/kg) and above
zinc/air
» Flat discharge characteristics - flatter than the
Discharge has a flat alkaline manganese cell battery.
Characteristics discharge curve
Shortcomings
» Uses expensive materials.
» Lower energy density than zinc/air.
» Poor low temperature performance.

The Zinc/Air battery
Typical discharge curves of Zn/Air battery
Anode/Fluid: Zn + 2OH– → ZnO + H2O + 2e-

Cathode: ½O2 + H2O + 2e- → 2OH–
Overall: Zn + ½O2 → ZnO (E0 = 1.65 V)
Source: Energizer, USA

Characteristics of Zn/Air battery
Advantages
» High energy density. Zinc/Air batteries store more energy per
unit of weight (~350 Wh/kg; OCV ~ 1,4V) than almost any
other primary type (excluding lithium primary batteries)
» Low cost
» When sealed, has excellent shelf life, with a self-discharge rate
of only 2 percent per year.
» Standard battery for hearing aids
Shortcomings
» Low power density (oxygen diffusion limited)
» Sensitive to extreme temperature and humid conditions.
» Carbon dioxide from the air forms carbonate which reduces
conductivity
» High self-discharge after activation, chemicals tend to dry out
and the batteries have to be used quickly

The lithium primary battery (Li/MnO2 and Li/SOCl2)
Lithium gives a very high

electrode potential

Lithium gives a very high

electrode potential
AND
is a very lightweighed element.
=>
Highest energy density of all

battery systems

Li/MnO2 Li/SOCL2
OCV 3.2 V 3.67 V
Work voltage 3.0-2.5 V 3.5 V
Specific energy density ~ 370 Wh/kg ~ 500 Wh/kg
(Wh/kg)
Discharge Characteristics has a flat discharge curve has a flat discharge curve
Work temperature range -40 °C to 60 °C -45 °C to 85 °C
Shelf life More than 10 years 10-15 years

The lithium manganese primary battery (Li/MnO2)
Positive Electrode: Manganese Dioxide (MnO2) (same as in zinc carbon battery),

a solid active material
Negative Electrode: Lithium Metal
Electrolyte: organic solvent with e. g. Lithium Perchlorate - Salt
Separator: Polyethylene, Polypropylene
Overall: Li + MnO2 → LiMnO2 (Eo = 3.2 V)

Source: Battery Association of Japan

The Lithium Thionyl Chloride primary battery (Li/SOCl2)
Typical discharge curves of Li/SOCl2 battery at 25 °C
Liquid active material on the cathode (Thionylchloride, SOCl2)

available only for equipment manufacturers as a built-in part
Source: GMBpower, China
4Li (s) + 2SOCl2 (l) → 4LiCl (s) + SO2 (diss.) + S (s) E0 = 3.65 V
Characteristics of lithium primary batteries
Advantages
» High energy density, double that of alkaline manganese batteries
» High cell voltage (3-4 V)
» Flat discharge characteristic
» Low self-discharge
» Very long shelf life (at least 10 years)
» Very long operating life (15 to 20 years for lithium thionyl chloride)
» Wide operating temperature range ( -60 °C to 85 °C )
» Excellent durability
» Small cell size
Shortcomings
» High cost
» Safety (may explode)

Energy density comparison for primary batteries
Source: NSF Workshop: Emerging Opportunities of Nanoscience to Energy Conversion and Storage

Typical applications for primary batteries

Energy Storage
Carsten Agert
NEXT ENERGY
Secondary batteries: A general introduction
The five most widely-used secondary batteries

» Lead-acid (Pb-Acid) battery
» Nickel-Cadmium (Ni-Cd) battery
» Nickel-Metal hydride (Ni-MH) battery
» Lithium ion battery (LIB)
» High-temperature (Na-S and ZEBRA) battery
The (potential) future of the secondary battery

General requirements for a successful secondary battery system
Two reversible redox couples

Thermodynamic Voltage gap
Theoretical capacity (Q/W)
considerations
Electrolyte system
electric energy
Electronic conductivity
Electrode fabrication
Secondary Batteries
Carriers mobility Ion conductivity /
Battery design
Ion diffusion coefficient
Kinetic factors Microstructure stability

phase transition
volume change
chemical energy
electrode materials
Solubility intermediates
Raw materials
Economic aspects Manufacturing costs
Cost on the application level

State-of-the-art commercialized secondary batteries
Lead-Acid battery
Nickel Iron (Ni-Fe) battery
Nickel Cadmium (Ni-Cd) battery
Nickel Hydrogen (Ni-H2) battery
Aqueous electrolyte Nickel Metal Hydride (Ni-MH) battery
electric energy
Nickel Zinc (Ni-Zn) battery

Zinc Silver oxide (Zn-Ag2O) battery
Reusable Alkaline (Zn-MnO2) battery
Secondary Batteries
Lithium ion battery (LIB)

chemical energy
Non-aqueous electrolyte Polymer LIB

Metal Li secondary battery
Sodium Sulphur (Na-S) battery

High temperature ZEBRA (Na-NiCl2) battery

Comparison of power and energy density for some secondary batteries
Source: SAFT, France

The global secondary battery market (data from 2008)
Source: 2008, Machinery statistics released by the Ministry of Economy, Trade and Industry, Japan

Part II: The five most widely-used secondary batteries
Lead-acid (Pb-Acid) battery
Nickel-Cadmium (Ni-Cd) battery
Nickel-Metal hydride (Ni-MH) battery
Lithium ion battery (LIB)
High-temperature battery

Brief history and technical development of Pb-Acid battery
Invented by Planté in 1859

Further developed by Faure in 1881.
Technical milestones of lead-acid battery development:

The replacement of early glass containers by hard rubber and later by high impact
polypropylene
The development of through-the-wall cell interconnects, rather than external cell connectors
Heat-sealed plastic case-to-cover assemblies
Automatic central watering systems for traction batteries
The development of sealed cells with safety vents (VRLA – Valve Regulated Lead Acid Battery)

Fundamental electrochemical principle of Lead-Acid battery
Charging of the battery Discharging of the battery

NB: Both electrodes are based on the same material, i. e. lead (metallic/oxidised).
During discharge both electrodes produce lead sulfate:
Electrolyte: diluted sulfuric acid
Negative electrode: Pb + SO42- ＝> PbSO4 +2e- (E = - 0.356 V)
Positive electrode: PbO2 + SO42- +4H+ +2e- ＝> PbSO4 + 2H2O (E = 1.685 V)
Overall (dis)charge reaction: Pb + PbO2 + 2H2SO4 <＝> 2PbSO4 + 2H2O (E = 2.031 V)
Source: http://www.chemie.uni-regensburg.de

Typical Cell structure of the Lead-Acid battery
Source: DoITPoMS TLP – Batteries, University of Cambridge

Valve-regulated lead-acid (VRLA) batteries
Traditional Flooded Cell:

Gases are vented, thus
topping-up is essential .
In a VRLA battery, the separator is only partially saturated with acid, so that it stays
permeable to gas. Oxygen produced at the positive electrode can diffuse to the
negative electrode, where a number of chemical reactions finally lead to the
recombination of the hydrogen and oxygen into water. „Valve-regulated“ only refers to
an overpressure valve for safety reasons.
This concept minimizes leakage and maintenance.
Typical charge-discharge characteristics of lead-acid battery
Technical characteristics of Lead-Acid batteries

Advantages: Shortcomings:
1. Low cost, tolerant to abuse (over charge). 1. Very heavy and bulky.
3. Can be discharged at very high currents. 2. Typical coulombic charge efficiency is not high
4. Can be left on trickle or float charge for prolonged (about 70% ).
periods (=> UPS, Cars, etc.). 3. Not suitable for fast charging.
5. Wide range of sizes and capacities available. 4. Typical cycle life only 200 to 400 cycles.
6. The world's most recycled product. Source: www.sunturnbattery.com

Typical applications for Lead-Acid batteries

Nickel-Cadmium (Ni-Cd) battery
In 1899, Waldmar Jungner, a Swedish inventor, developed the Nickel

Cadmium pocket plate battery.
The Germans further developed a sintered plate, flooded electrolyte
nickel-cadmium battery in 1940’s, that is essentially identical to those still
used on today's military and commercial jet aircraft.
European experimenters designed the first recombinant nickel-cadmium
battery in the early 1950's that is the basis for today's nickel-cadmium
industry.

The electrochemical fundamentals for Ni-Cd battery
Both NiCd- and NiMH-batteries have alkaline electrolytes (KOH).

Due to the low freezing point of KOH solutions (between -40 and -60°C),
the batteries have an excellent low temperature behaviour.
The active material of the positive electrode is Nickel(oxy)hydroxide
(NiOOH), that changes between a Ni2+- and a Ni3+-state.
The following reactions take place at the electrodes:

Typical cell structure of Ni-Cd battery

The “memory effect” of Ni-Cd battery
NiCd- and NiMH-batteries once suffered from the so-called memory effect. The
“genuine” memory effect of NiCd batteries was caused by overcharging and resulted in a
kink in the discharge curve. In contrast, the “lazy effect” (nowadays often referred to as
the memory effect) means that a partial discharge leaves the battery at a reduced
voltage over most of the discharge curve.
The latter can be overcome by a full discharge that “refreshes” the cell.
Both effects are shown in the graph.
As both NiCd and NiMH cells show the lazy

battery effect, recent studies attribute it to
processes in the Ni electrode.
However, the effects have been greatly

reduced in modern batteries.
http://media.maxim-ic.com/images/appnotes/3999/3999Fig01.gif

Typical electrochemical characteristics of Ni-Cd battery
Source: JYH battery CO., LTD, China

Advantages and shortcomings of Ni-Cd batteries
Advantages
Fast and simple charging behaviour.
Long shelf life - five-year storage is possible.
Good low temperature performance, can be charged and discharged at low temperature.
Forgiving if abused - nickel-cadmium is one of the most rugged rechargeable batteries.
Economically priced - nickel-cadmium is lowest in terms of cost per cycle.
Limitations
Relatively low energy density.
Memory effect - nickel-cadmium periodically had to be reconditioned
(discharge/charge) to prevent memory.
Environmentally unfriendly - nickel-cadmium contains toxic metals. Some countries restrict its use.
Relatively high self-discharge - needs recharging after storage.
Typical application of Ni-Cd batteries

Nowadays, the Ni-Cd battery is limited to some special applications, due to environmental concerns.

Nickel-Metal hydride (Ni-MH) batteries
The Ni-MH battery was developed from the high

pressure Ni-H2 battery.
The high pressure Ni-H2 battery was first invented by
M. Klein and J.F. Stockel in 1970’s.
» Anode: Pt/H2 (gas diffusion electrode)
» Cathode: sintered nickel oxide electrode
» Electrolyte: KOH saturated asbestos film
» Working pressure:2-40 bar

Nickel-Metal hydride (Ni-MH) batteries
The hydrogen storage alloy (MH), LaNi5, was invented by Markin 1970’s.
The LaNi5 was further developed by Willems at Philips Research in 1984.
The first commercial Ni-MH battery was produced by SANYO in 1989.

Technology development for the AA-size Ni-MH battery
State of the Art 2016: Ansmann sells 2850 mAh in NiMH AA.
Source: ECD Ovonic, The 24th International Seminar & Exhibit on Primary and Secondary Batteries

Typical cell structure of Ni-MH battery
Cylindrical Cells Prismatic Cells

Commercial anode materials for Ni-MH batteries
Metal hydride (hydrogen storage alloy, MH)

Type of Typical Hydride Hydrogen Theoretical Normal
Alloy Storage mass Capacity (mAh/g) Capacity
(%) (mAh/g)
AB5 LaNi5H6 1.3 348 330
MmNi5H6
AB2 Ti1.2Mn1.6H3 1.8 482 420
ZrMn2H3
AB TiFeH2 2.0 536 350
TiCoH2
A2B Mg2NiH4 3.6 965 500

Commercial cathode materials for Ni-MH batteries
As the active material Ni(OH)2 itself is a bad

electrical conductor, a good current
collector is needed. Foamed films are
widely used for this:
A synthetic material is foamed, coated with
nickel, and the synthetic material is then
burned away. A highly conductive and
porous nickel foam remains, which is then
(chemically or electrochemically) filled with
Foamed metallic Ni film
the active material.
Source: ECD Ovonic, The 24th International Seminar & Exhibit
on Primary and Secondary Batteries

Typical charge-discharge characteristics of Ni-MH battery
Source: http://www.chinabatteryweb.com

The replacement of Ni-Cd batteries with Ni-MH batteries
Similar charge and discharge voltage
Same charger, similar application
Source: DURACELL, USA

The advantages and disadvantages of Ni-MH batteries
Advantages
» Relatively high energy density
» Typical cycle life is more than 500 cycles
» Flat discharge characteristic (but falls off rapidly at the end of the cycle)
» Wide operating temperature range
» Rapid charge possible in 1 hour
» Reconditioning is possible (to overcome a potential memory effect).
» Environmentally friendly (No cadmium, mercury or lead)
» Can be used robustly
Shortcomings
» Very high self-discharge rate, nearly ten times worse than lead acid or Lithium ion
batteries, especially at high working temperature
» High rate discharge not as good as Ni-Cd
» Less tolerant against overcharging (compared to Ni-Cd)
» Relatively high cost

Typical applications of Ni-MH battery

Future prospects of the Ni-MH battery
Small Ni-MH battery for consumer electronic devices

Compared with AA alkaline
battery, 3500-4500 mAh
» Improve the capacity of AA size battery even further
(discharge at 10Ω)
» Up to 2850 mAh is commercialized

Large Ni-MH battery for EV and HEV
» Continued advances in power:
2400 W/kg specific power demonstrated and 3000 W/kg projected
World’s best low temperature power at -30°C of 340 W/kg.
Improve the rate performance at very low (-30-0°C) and high temperature (50-70°C)
» Improving Shelf and Cycle Life, Voltage Stand
» Cost Reduction
lower cost raw materials
higher utilization
longer life for warranty

The Lithium ion battery (LIB)
The concept of the “rocking chair battery” was firstly reported by M. Armand in 1980.
Underlying concept:
Li-ions (not atoms!) are stored between the layers of graphite (so-called intercalation
mechanism) in the anode and within complex (often layered) metal oxide compounds that
allow for two valency stages (e. g. Mn4+/Mn3+ in LiMnO2) in the cathode.
Both electrode materials are structurally stable against charging/discharching with Li+.
Layered lithium transition compounds LiMO2（M=Co, Ni, Mn）were synthesized by J.B.
Goodenough in 1980’s.
In 1991, the first commercial LIB was commercialized by SONY.
The polymer LIB was firstly patented by Bellcore in 1994.
The high power LIB is being tested in HEV and EV since the year 2000.

Fundamental principle of LIB
The unique “intercalation

mechanism”
Two key properties for

intercalation electrodes:
» Open crystal structures which
allow the insertion or extraction
of lithium ions
» The ability to accept
compensating electrons at the
same time

The Solid Electrolyte Interphase (SEI) layer of LIB
In the first charging processes, the electrolyte reacts vigorously with the carbon anode. A thin
passivating SEI layer is built upon the surface of the carbon anode which is electrically
insulating yet sufficiently conductive to lithium ions. This SEI layer is essential for the stability of
the Lithium ion battery using carbon anodes, as it prevents further interaction between the
electrolyte and the carbon.
The composition of the SEI layer is complicated and Li3CO3, LiOH, Li2O, LiOR, LiOCO2R
(R=hydrocarbon) as well as lithium halide can be detected.
Typical cell structure for LIB
a: Cylindrical Cell; b: Coin Cell; c: Prismatic Cell; d: Pouch Cell

J.-M. Tarascon, M. Armand, Nature, 414 (2001),359-367

Commercial cathode materials for LIB
-> standard cathode material since

market introduction by Sony (1991)
Disadvantages:
• high cost
• environmental considerations
-> commercially available from
Samsung, Panasonic, …
• lower energy density
But: - enhanced safety, environmentally
friendly, lower cost
-> mixed oxide which combines advantages
of cobalt, nickel and manganese
Manufacturer e.g. Li-Tec Battery GmbH,
Kamenz (Germany) – joint venture of
Evonik (50,1%) and Daimler (49,9%)
-> excellent thermal stability and safety,
low cost and enhanced conductivity by
carbon coating and doping
• lower working potential
Manufacturer e.g. A123 (USA)
Commercial anode materials for LIB
meso carbon micro beads (MCMB)

based graphitic carbon
-> used as anode material by

Altairnano (USA)
• higher working potential
-> lower cell voltage
• excellent cycling stability and
negligible volume change during
lithiation
Commercial electrolyte materials for LIB
Electrolyte Salt: LiPF6,

Organic Solvent:
Additives: other organic carbonates, gaseous electrolyte additives like

CO2, N2O, SO2, inorganic additives to enhance cycling
stability -> crucial know-how of battery manufactures
Separator:
Source: EXXON, USA

Conventional binder systems for Li-Ion Batteries
Courtel et.al. JPS,196 (2011)2128

poly(vinylidene fluoride)-PVdF
poly(tetrafluoroethylene)-PTFE
poly(ethylene oxide) –PEO
Carboxy Methylcellulose -CMC

59
Influence of the binder on the electrode properties
Electrode architecture with respect to the

transport of the charge carriers (electrons
and lithium ions) toward the active matter
– electrode performance
Mechanical Stability of the electrode -

cohesion and adherence to the current
collector

60
Commercialization
Company Factory Location Type Cathode Anode
Sanyo Japan winded NMC/LMO Graphite
A123 USA,Korea,China winded LFP Graphite

AESC/Nissan Japan, USA, UK, Spain stacked LMO/NMC Hard Carbon
& NEC
JCS& Saft USA winded NCA Graphite
Li-Tec Germany stacked NMC Graphite
Hitachi Japan winded LMO/NMC Hard Carbon
Toshiba Japan winded LMO LTO
LG Chem S-Korea, USA stacked LMO Am. Carbon

Samsung S-Korea winded NMC/LMO Graphite
OMT Germany winded LFP Graphite

Leclanché Switzerland, Germany stacked LFP/LMO Graphite/LTO
Source: M. Wohlfahrt-Mehrens,FVEE Workshop Ulm,2010 (Just for illustration; the sector is developing rapidly.)

Polymer LIB: A brief introduction
In a polymer LIB, a solid polymer electrolyte is used instead of the ordinary liquid electrolyte.
The main difference here is that the lithium-salt electrolyte is stored in the matrix of a solid polymer
(gel type electrolyte), allowing for simpler, thinner and larger-area cell designs.
Another realization uses a truly solid state approach:

Here, the polymer acts not only as the matrix of the
liquid electrolyte but carries the ion transport itself.
However, in this case low ion mobilities make higher
temperatures necessary (=> no consumer applications).
This approach might also allow metallic lithium electrodes.
Source: Battery Association of Japan

Polymer LIB: A brief introduction
Advantages:
Very thin profile
Flexible geometry
Lightweight
Improved safety
High energy density and
good cycle performance
Limitations:
Lower energy density and decreased
cycle count compared to lithium-ion.
Expensive to manufacture.

Safety concerns regarding LIB
The safety problems for LIB are more serious than for
any other secondary battery.
Reasons: At abuse conditions (over-charging)
LiCoO2 may decompose and release active O2 and heat
Metallic Li electrodeposition is possible at anode
Li and O2 react with organic solvent to release gas and heat
Strategies:
Protection circuits and safety valves
Use alternative electrode materials (e.g. LiFePO4, Li4Ti5O12)
Additives in the electrolyte
Polymer LIB

Safety concerns regarding LIB

Typical charge-discharge characteristics of LIB
Source: NEC/TOKIN, Japan

Characteristics of LIB
Advantages
High cell voltage of 3.6 V
Very high energy density and very high power density
Flexible cell design (Cylindrical Cell, Coin Cell, Prismatic Cell, Pouch Cell and thin film cell)
Very low self discharge rate (< 5 %/month) and very high columbic efficiency (almost 100%)
Long cycle life (at least 500 cycles 100% DOD; today usually much more)
Does not need reconditioning as do nickel based batteries
Variants of the basic cell chemistry allow the performance to be tuned for specific
applications
Shortcomings
Performance degradation at very low or high temperature
Charge and discharge at high C-rate are restricted
Can only be charged with a highly controlled method to avoid over-charging
Safety concerns (protection circuit and valve are necessary)
Relative high materials and manufacture cost

Typical applications of LIB

Focal areas of LIB-R&D
High energy density LIB for consumer electronic market

» high capacity (e. g. novel anode concepts, e.g. Si/C)
Wh/kg= V*Ah/kg
» high potential (e. g. novel cathode materials)
High power density LIB for EV and HEV application

» Improve rate performance
manufacture technology
» Improve safety
Electrode materials
» Improve cycle life
Cell design
» Lower costs

Secondary batteries: A general introduction
The five most widely-used secondary batteries

» Lead-acid (Pb-Acid) battery
» Nickel-Cadmium (Ni-Cd) battery
» Nickel-Metal hydride (Ni-MH) battery
» Lithium ion battery (LIB)
» High-temperature (Na-S and ZEBRA) battery
The (potential) future of the secondary battery

Brief introduction of the Sodium-Sulphur (Na-S) battery and
the ZEBRA (Na-NiCl2) battery
In 1970’s, the Na-S battery was invented by J. T. Kummer.

The development of small Na-S batteries has now ceased, partly on safety grounds, but also
because the lack of a good market. However, large Na-S battery systems are promising for
energy storage purposes in the grid and are still under development in Japan.
The ZEBRA (Na-NiCl2) battery was developed directly from Na-S battery system in 1985, by
the Zeolite Battery Research Africa Project (ZEBRA) group led by Dr. Johan Coetzer, hence the
name ZEBRA battery.
In 2009, the ZEBRA battery had been under development for more than 20 years and
commercialized by MES-DEA in Switzerland.
Source: MES-DEA S.A. Switzerland Source: NGK Insulators Ltd.

Principles and cell structure of Na-S battery
Anode: Na (liquid during operation)

Cathode: S (liquid during operation)
Electrolyte and separator: beta-
alumina sodium ion exchange
membrane (solid)
Cell case: coated steel
Battery case: thermal insulator
Working temperature: 290°C-390°C
Overall electrochemical reactions:

Anode: 2 Na <=> 2 Na+ + 2e-
Cathode: S + 2 e- <=> S2-
overall: 2 Na + S <=> Na2S
Source: NGK Insulators Ltd.

The characteristics of the electrolyte-β-Al2O3
Advantages:
High ionic conductivity at 300 °C
High fracture toughness
Stable to moisture
Good wetting by sodium
Long life at high current densities
Resistant to electrical breakdown
Relative low cost production
Major problem:
High mechanical stress caused by
temperature cycles

Applications of large Na-S battery system
34 MW Na-S alongside 51 MW Wind Farm

Large Na-S battery system for “load
leveling” in Tokyo
Performance characteristics
» 2 MW
» 1165 V DC
» 40 modules (12,800 cells)
» Weight ＞136 tons
1.5 MW Na-S alongside 5 MW Solar PV Array

The electrochemical principles of the ZEBRA battery
Anode: Na (liquid during operation)

Electrolyte: beta-alumina sodium ion
exchange membrane (solid separator) plus molten
Sodium- aluminiumchloride
Cathode: NiCl2
Electrochemical reactions:
Anode: 2 Na <=> 2 Na+ + 2e-
Cathode: NiCl2 + 2 e- <=> Ni +2 Cl-
overall: 2 Na + NiCl2 <=> 2NaCl + Ni
While the Na-S-battery can only be cooled

down a few times (and therefore has to be
operated continuously), the ZEBRA-battery
can be cooled down as often as desired.
Source: MES-DEA S.A. Switzerland (E0 = 2.58 V)
Typical discharge behaviors of ZEBRA battery
ZEBRA and lead-acid battery comparison: sprint and low speed endurance
(identical battery compartment dimensions)
Source: Rolls-Royce, UK

The advantages and shortcomings of ZEBRA battery
Advantages
High energy density (3 times higher than Lead-acid)
Large cells (up to 500Ah) possible
Cycle life better than 2000 cycles
Tolerant of short circuits
Safer than Na-S battery, typical cell failure is short circuit which does not cause
complete failure of the battery.
Shortcomings
Suitable for large capacity batteries only (> 20KWh)
High internal resistance
High operating temperature. Uses 14% of its own capacity per day to maintain
temperature when not in use.
Relative high manufacture cost

Applications of the ZEBRA battery
Source: EVS-20, Nov. 15 -19, 2003 Long Beach, CA

Part III: The future of the secondary battery
Are there chances for a new rechargeable battery system with higher
energy density than LIB?
Battery recycling
Will the secondary battery replace the primaries?
Competition between the secondary battery and fuel cells

Is a new rechargeable battery system with higher energy density
than the state of the art LIB possible?
Lithium-Air...the ‘Ultimate’ Battery?

Is a commercial rechargeable Li-Air battery possible?
Comparison of the specific energy for different kinds of
batteries
Li-air primary pouch cell
Source: SAFT, France Source: Lithion, Inc. USA

Battery recycling
Why should we recycle rechargeable batteries?

» Some metals are scarce materials.
» Some of the employed materials are toxic (cadmium, lead, …).
Ni-Cd has been in the focus of the recycling efforts, but Li-Ion is expected
to catch up.
From a recycling point of view, lead batteries are the environmental

success story of our time:
More than 99% of all battery lead is recycled and lead-acid batteries top
the list of the most highly recycled consumer product.

Will the secondary battery replace the primaries?
Primary batteries usually have higher energy densities

than secondary batteries (left on top).
The negative on the primary batteries is its relative high

internal resistance, which inhibits current flow
(left below).
Energy comparison of rechargeable and primary batteries

The most important single reason, however, is cost:
» Initial Cost of 4 AA Primary Alkaline = ~$2.74
» Initial Cost of 4 AA Ni-MH + Charger = ~$15 - 30
» Lifetime Cost of Primary batteries is approx.
a factor of 30 higher than that of rechargeables.
In fact, the global market for primary has

already begun to shrink in the past years.
Energy comparison under load. The alkaline works well
for a kitchen clock but fails on a digital camera Source: http://www.batteryuniversity.com/parttwo-50.htm

Competition between secondary battery and fuel cells
Decisive factors:
Energy and power density
Energy efficiency
Cost

Lectures
Date Lecture
18. Jan. 16 electric cars (II)
25. Jan. 16 exam

Lectures
Date Lecture
18. Jan. 16 Exam: W03 1-161, 25.electric
Januarycars (II) 2016, 08:30 – 9:30 am
25. Jan. 16 exam

Primary Batteries 2020

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Energy Storage

Lecture 9: Primary Cells and Batteries

only for internal use (storage lecture) 2

only for internal use (storage lecture) 4

Zinc-Carbon battery (Zn/MnO2)

Zinc-Air battery (Zn/Air)

Zinc-Mercury oxide battery (Zn/HgO)

Lithium manganese battery (Li/MnO2)

red = discussed in the lecture

Zn/carbon Alkaline manganese

OCV 1.5 V 1.5 V

Discharge has a sloped has a sloped

Shelf life 1-2 years 2-5 years

Performance comparison of Zn/carbon and alkaline

only for internal use (storage lecture) 6

The overall reaction in the cell is:

Source of picture: Wikipedia

only for internal use (storage lecture) 7

Source: DoITPoMS TLP – Batteries, University of Cambridge

Reversed geometry: zinc anode in the centre,

Main advantage over zinc carbon battery:

Overall: Zn + 2MnO2 → ZnO + Mn2O3

only for internal use (storage lecture) 9

At the anode: Zn + 2OH– → Zn(OH)2 + 2e- Source: DURACELL, USA

At the cathode: Ag2O + H2O +2e- → 2Ag + 2OH–

only for internal use (storage lecture) 10

Performance Characteristics Advantages

only for internal use (storage lecture) 11

Typical discharge curves of Zn/Air battery

Anode/Fluid: Zn + 2OH– → ZnO + H2O + 2e-

only for internal use (storage lecture) 12

only for internal use (storage lecture) 13

Lithium gives a very high

only for internal use (storage lecture) 14

Lithium gives a very high

Highest energy density of all

only for internal use (storage lecture) 15

Work temperature range -40 °C to 60 °C -45 °C to 85 °C

Shelf life More than 10 years 10-15 years

only for internal use (storage lecture) 16

Positive Electrode: Manganese Dioxide (MnO2) (same as in zinc carbon battery),

Overall: Li + MnO2 → LiMnO2 (Eo = 3.2 V)

only for internal use (storage lecture) 17

Typical discharge curves of Li/SOCl2 battery at 25 °C

Liquid active material on the cathode (Thionylchloride, SOCl2)

only for internal use (storage lecture) 19

only for internal use (storage lecture) 20

only for internal use (storage lecture) 21

The five most widely-used secondary batteries

The (potential) future of the secondary battery

only for internal use (storage lecture) 23

Two reversible redox couples

Carriers mobility Ion conductivity /

Kinetic factors Microstructure stability

only for internal use (storage lecture) 24

Nickel Zinc (Ni-Zn) battery

Lithium ion battery (LIB)

Non-aqueous electrolyte Polymer LIB

Sodium Sulphur (Na-S) battery

only for internal use (storage lecture) 25

Source: SAFT, France

only for internal use (storage lecture) 26

only for internal use (storage lecture) 27

Lead-acid (Pb-Acid) battery