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The Future of Battery Technologies – Part II
Focus on Lithium-Ion Batteries




Dr. Annika Ahlberg Tidblad
The Future of Battery Technologies – Part II



This paper is the second in our ongoing series about batteries. This installment provides an overview of
lithium-ion batteries– typical properties, principal applications, and trends. This white paper was authored
by Dr Annika Ahlberg Tidblad, Intertek’s resident expert in battery testing. Her background is in research
at KTH, the Swedish Royal Institute of Technology, with PhDs in applied electrochemistry and corrosion
science, along with ten years of experience in battery technology.



The Future of Battery Technologies – Part II – Focus on
Lithium Ion Batteries

The expression “lithium batteries” is a generic name for battery technologies in which
lithium ions play a part in the primary electrochemical discharge and charge reactions.
Lithium batteries are available both as primary batteries (disposable batteries) and
secondary batteries (rechargeable batteries). The choice of the best battery for a
specific purpose is determined by a number of parameters, such as the power and
energy requirements of the application, the operating environment, the electrical
preconditions and the cost aspects. The most important factors are:

    1. The type of battery – disposable or rechargeable battery
    2. Electrochemical system – matching the benefits and disadvantages of the battery
        type to the requirements of the application.
    3. The voltage requirements – rated and operating voltage respectively, the
        minimum and maximum levels, voltage regulation, discharge profile, etc.
    4. Load profile – type of load: resistive, current or power discharge, single vs.
        variable load, etc.
    5. Work cycle – continual or intermittent
    6. Temperature specifications
    7. Lifetime
    8. Physical requirements – size, shape, connections, etc.
    9. Storage requirements – shelf life, charge state when stored, environment, etc.
    10. Charge and discharge states (rechargeable batteries) – cycling batteries vs.
        energy storage batteries (flow charging), charge characteristics, efficiency and
        accessibility, discharge requirements
    11. Environmental conditions – climate (temperature, humidity), pressure conditions,
        physical environment (impact, vibration, dust, acceleration, etc)
    12. Safety and reliability – permitted variance, acceptable faults, sensitivity to gas
        leaks or leaks of electrolyte from the battery, etc.
    13. Unusual or demanding operating conditions – e.g. extreme temperature
        conditions, standby times, high reliability and rapid activation, etc.
    14. Maintenance and replacement of unserviceable batteries
    15. Costs – initial, and operating costs



www.intertek.com                                                                                   1
The Future of Battery Technologies – Part II



Lithium-based battery systems are characterised by high energy
density levels, relatively high voltages, and low weight-to-volume
ratio but, in general, tend to be more expensive than equivalent
battery technologies with aqueous electrolytes, such as alkali
disposable batteries and zinc/air batteries in the primary battery
sector, and nickel metal hydride, nickel cadmium and lead batteries
in the secondary battery sector.

Primary Lithium Batteries

Primary batteries have existed since the 1970s, are easy to use and provide convenient
sources of energy for portable applications. The batteries usually require no or very little
maintenance and they have a long shelf life; modern lithium batteries can usually be
stored for up to 10 years, and there are special batteries with solid state electrolyte that
can be stored for more than 20 years. The storage tolerance at elevated temperatures
is generally good, in some cases up to 70° C.

There are 3 classes of primary lithium batteries:

   1. Solid state batteries – Characterized by low power but superior shelf lives, and
      are used, for example, in pacemakers and computer memory backup. The
      expression ‘solid state’ is used because the electrolyte is solid and the ion
      transmission between the electrodes takes place in a solid, non-electrically
      conductive material, usually a polymer.

   2. Batteries with a solid cathode – Usually found in coin cells or small cylindrical
      batteries and used in a huge numbers of applications, such as clocks, memory
      circuits, photo and communication equipment, toys, flashlights, etc.

   3. Batteries with soluble cathodes – Industrial and military batteries that are
      manufactured in large cell sizes, up to 35-40 Ah, but are also available in smaller
      sizes, used, for example, in medical and civilian applications.

All of these batteries have lithium anodes (the battery’s negative terminal). The cathode
material determines the battery system.

The most common primary lithium batteries on the market are lithium disulphide
(LiFeS2) and lithium manganese dioxide (LiMnO2) batteries. Both of these are of the
solid cathode type and are sold as consumer batteries from electrical goods stores and
supermarkets. Other primary lithium batteries are mainly intended for the professional
market. Table 1 (at end) lists the most common primary lithium battery chemistries and
their properties.

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The Future of Battery Technologies – Part II



Over the last few years the market has seen the introduction of battery types in which
the cathode consists of a mixture of different electrode materials. The purpose of these
batteries is to provide a system that can accommodate both high and low loads. One
example is the battery that is used for implanted defibrillators that consist of silver-
vanadium oxide (SVO) cathodes to absorbs the peak load of a defibrillation, and carbon
monofluoride ((CF)x) for the baseline load between the defibrillation pulses.

Secondary Lithium Batteries

There are two main groups of rechargeable lithium batteries, one of which uses lithium
metal as the negative electrode. These are called lithium metal batteries. Lithium metal
batteries were launched on a limited scale for consumer electronic products in the
1980s, but were withdrawn quickly because of safety problems with the lithium
electrode. Lithium reacts with the electrolyte, forming dendrites on the surface of the
electrode. Under repeated charging, the surface of the anode increases, with a
corresponding increase in its reactivity and thermal sensitivity. More recently, however,
the lithium metal anodes have once again found practical application in research,
although they have not yet been marketed on a large scale. One way of reducing the
fire risk in lithium metal batteries is to replace the electrolyte with a solid state polymer
electrolyte, that does not react with lithium.

The second type of rechargeable lithium battery is called a lithium ion battery, which has
a negative terminal that consists of a carbon-based material, usually graphite, or
another type of alloy or material that permits intercalation, i.e. storage, of lithium in the
structure. This category includes lithium polymer batteries, which differ from traditional
lithium ion batteries in that they have an electrolyte that is bound within a non-
conducting polymer matrix. Lithium ion batteries were introduced by SONY in 1991, and
were first used in advanced consumer electronics products, mobile phones, digital still
and video cameras, as well as laptop computers. This type of battery is constantly
gaining new ground, and the areas of use are constantly expanding, and lithium ion
batteries are currently used in all sorts of portable applications within consumer
electronics, medical technology and military systems. The general properties that
contribute to this are the high energy density of the lithium ion battery and its specific
energy, i.e. a lot of energy from a small volume and weight, compared with other
rechargeable types of battery. Its other properties include low self-discharge, relatively
long recharge lifetimes (300-500 complete charges and even more if the battery is used
within a more restricted charge state range). High costs and the safety aspects are the
main barriers, as well as the fact that access to large cell types, battery cells with a
capacity exceeding 5 Ah, is limited. Existing lithium ion batteries also suffer from
functional limitations at low temperatures.

Carbon materials are used in lithium ion batteries because carbon has the ability to
reversibly absorb and release large quantities of lithium (Li:C=1:6) without altering the
www.intertek.com                                                                      3
The Future of Battery Technologies – Part II



mechanical and electrical properties of the material. Graphite and coke also have an
electrode potential that is close to that of lithium, 0.0-0.1 for graphite, and 0.0-0.3 for
coke. On the first charge of lithium in the carbon material an outer layer is formed (Solid
Electrolyte Interface, SEI). The SEI layer is important because it prevents the carbon
anode from reacting with the electrolyte. Dissolution of the SEI layer at elevated
temperature poses an important safety risk to lithium ion batteries.

There are a number of different chemistries within the lithium ion family that are based
on the choice of cathode material. Traditional lithium ion batteries use cathodes made
from cobalt dioxide (LiCoO2). By adding nickel (LiNi1-xCoxO2), a layered material is
obtained that is more stable and less expensive than pure CoO2. Manganese oxide
spinel (LiMn2O4) is another common cathode material for lithium ion batteries. The
manganese oxide has a lower energy density but is cheaper and more stable than
cobalt. Extensive research is being carried out into new cathode materials, and in the
last few years lithium ion batteries with cathodes made from lithium iron phosphate
(LiFePO4) have been marketed on a large scale, based on their high safety levels and
low cost compared with conventional lithium ion systems. The benefits of LiFePO4 have
been achieved at the expense of their energy density and voltage. New electrode
materials are being developed and tested constantly in order to produce lithium ion
batteries with properties that are suitable for different applications and areas of use.
Table 2 (at end) shows a comparison of the main types of lithium ion batteries that are
currently on the market. All of them have graphite as the most commonly occurring
anode, but there are also high power batteries using hard carbon. At present, research
into rechargeable lithium ion batteries is being driven mainly by the requirement in the
automotive industry for long calendar and charge lifetimes, high discharge currents and
the need for rapid charging, in addition to cost targets.

Trends in Lithium Ion Batteries
Trends that are noticeable within research & development of lithium ion batteries are:

   1. A transition to cheaper and less toxic electrode materials (cathodes), e.g.
      phosphates and silicates.
   2. The transition to materials that have higher reversible lithium reception. The more
      lithium atoms that the material can absorb in each unit cell, the higher will be the
      potential battery capacity.
   3. Materials that can withstand rapid charges (from 0 to 90% SOC in ten minutes)
   4. Power and energy batteries for the automotive industry and stationary
      installations.
   5. Increased cell size in the form of stored energy capacity.
   6. Battery systems with high voltage levels, including electrolytes that can withstand
      higher electrode potential without degrading or reacting with the environment.
   7. Battery systems with enhanced safety compared to current battery types.
www.intertek.com                                                                   4
The Future of Battery Technologies – Part II




Titanate, silicon and silicides, as well as tin and tin alloys, are the new anode materials
that have been discussed in the context of research and development. All of these
materials are regarded as offering improved safety as they do not form an SEI layer.
The main advantage of titanate is that its structure is highly stable and there is no
increase in volume during battery charging. Lithium’s mobility within the material is very
rapid, which permits the battery to be charged and discharged at high currents.
Charging times of less than 10 minutes have been postulated. The limitations include
low cell voltage, due to the high electrode potential of titanate compared to that of
lithium. The electrodes are also more expensive than carbon-based electrodes. Silicon
and tin are limited both by very large electrode expansion during charging, around 300
and 250% respectively. Both of these material groups have relatively low electrode
potential compared with lithium, which results in battery cells with acceptable cell
voltages of between 3.5-4 V, depending on the choice of cathode material. Silicon is
especially interesting as it permits storage of large quantities of lithium in the anode
structure, e.g. the reversible Li ion insertion capacity is >1. Moreover, the material is
neither expensive nor toxic.

Development on the cathode side is more multi-faceted. The list of substances and
variants of substances that are being studied is extremely long, and many of them will
never be marketed. Some of them will only be of interest for niche applications on cost
grounds. Among the materials being discussed are metal phosphates (in particular
vanadium, magnesium and manganese, as well as various compounds), layered metal
oxides (often with manganese oxide bases) and silicates (e.g. iron silicate). The metal
phosphates are being promoted thanks to their chemical stability, leading to increased
safety compared to traditional cobalt-based cathode materials. Magnesium and
manganese phosphates are also relatively cheap and non-toxic materials, which is also
one of the strengths of iron silicate. The layered metal oxide structures are expected to
offer rapid lithium mobility, thereby permitting high charge and discharge currents, but
the material is still relatively expensive and associated with safety problems.



       Intertek’s expertise in battery testing & energy storage services ensures products meet
  performance, reliability and safety criteria. Intertek has expanded global energy storage testing
 facilities and advisory services. Throughout design, manufacturing & system deployment cycles,
     Intertek provides evaluations for performance, electrical safety, interoperability, fit for use,
   component selection and more. Please visit our website at www.intertek.com/energy-storage,
                        contact icenter@intertek.com or call your regional lab:

                                  Europe: +46 8 750 00 00
                                  North America: +1 800 967-5352
                                  Asia Pacific: +86 21 6127-8200

www.intertek.com                                                                           5
The Future of Battery Technologies – Part II



Table 1 – Primary lithium batteries

                                        Cell voltage [V]        Specific
                                                                                  Energy
 System       Construction                    Operating          energy                         Power density       Discharge profile            Usages                    Properties
                                  Rated                                        density [Wh/l]
                                              voltage (20 °C)   [Wh/kg]
                                                                           Category 1 – Solid state system
                                                                                                                                                                   - High energy density.
                                                                                                                                                                   - Withstands low current
                                                                                                                                                                   and power loads
                                                                                                                                                                   - High reliability
                                                                                                                                                                   - Cells constructed with
                                                                                                                                                                   cathode limitation
                                                                                                                                             Coin cells and
                                                                                                                                                                   - Long shelf life, 15-20
   LiI2                              2.8          2.6-2.8       220-280          820-1030         Very low            Relatively flat      special batteries for
                                                                                                                                                                   years under normal
                                                                                                                                            e.g. pacemakers
                                                                                                                                                                   conditions, but can be
                                                                                                                                                                   stored for up to 1 year at
                                                                                                                                                                   100 °C
                                                                                                                                                                   - Normally used in
                                                                                                                                                                   pacemakers and digital
                                                                                                                                                                   watches
                                                                  Category 2 – Batteries with solid cathodes

                                                                                                                                                                   - Highest theoretical
                                                                                                                                                Coin cells         energy density
               Coin cell                                                                                                                   Cylindrical batteries    - Withstands medium to
 Li(CF)n    Spiral ”jelly-roll”      3.0          2.7-2.5       220-590          550-1050       Low-medium            Relatively flat       (commercial and        low loads
           Rectangular plates                                                                                                                    military)         - Wide temperature range
                                                                                                                                                                   -20-60 °C
                                                                                                                                                                   Flat discharge curve
                                                                                                                                                                   - Replacement batteries
                                                                                                                                                                   for type AA household
           ”Bobbin” and ”jelly-                                                                                                                                    batteries
                                                                                                                    High initial drop in
 LiFeS2      roll” cylindrical       1.5          1.5-1.4         260               500         Medium-high                                                        - Tolerates high power
                                                                                                                    voltage, then flat
                   cells                                                                                                                                           Good temperature
                                                                                                                                                                   properties
                                                                                                                                                                   Long charge retention
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The Future of Battery Technologies – Part II



                                                                                                                                                 - High specific energy and
                                                                                                                                                 energy density
                                                                                                                         Cylindrical up to 22    - Wide temperature range
 LiMnO2          Coin cell         3.0    3.0-2.7    230-270      535-620         Low-high             Low-high
                                                                                                                                  Ah             - Withstands relatively
                                                                                                                                                 high discharge currents
                                                                                                                                                 - Relatively cheap
                                                                                                                                                 - Used in implants and
                                                                                                                                                 other medical applications
                                                                                                     Rel. complex        Special batteries for
LiAgV4O11        Prismatic         3.2    3.2-1.5     270           780         Low-medium                                                       - High energy density.
                                                                                                    discharge curve       medical implants
                                                                                                                                                 - Multi-step discharge
                                                                                                                                                 -Good load properties
                                                     Category 3 – Batteries with soluble cathodes
                                                                                                                                                 - Manages high current
                                                                                                                                                 and power loads
                                                                                                                          Cylindrical cells up
  LiSO2      Spiral ”jelly-roll”   3.0    2.9+-2.7    260           415             High               Very flat                                 - Excellent low
                                                                                                                               to 35 Ah
                                                                                                                                                 temperature properties
                                                                                                                                                 - Long shelf life
                                                                                                                                                 - One of the highest OCV
                                                                                                                                                 voltages and energy
                  Bobbin
                                                                                                                                                 densities of all of the
                  Spiral                                                                                                  Cylindrical cells 2-
 LiSOCl2                           3.6    3.6-3.4    275-590      630-1100      Low-medium               Flat                                    commercial batteries
            Prismatic cells with                                                                                                30 Ah
                                                                                                                                                 - High specific energy
             electrode plates
                                                                                                                                                 - Withstands low
                                                                                                                                                 discharge loads
                                                                                                                                                 - High energy density.
                                                                                                                                                 - Manages high discharge
                                                                                                                                                 loads
                  Spiral                                                                                                  Cylindrical cells 7-
 LiSO2Cl2                          3.95   3.5-3.1     450           900         Medium-high              Flat                                    - Good high temperature
                                                                                                                                30 Ah
                                                                                                                                                 properties
                                                                                                                                                 Excellent storage
                                                                                                                                                 Properties




www.intertek.com                                                                              2
The Future of Battery Technologies – Part II



Table 2 – Rechargeable lithium ion batteries
                             Rated voltage   Charge limit   Max charge and discharge   Energy density
       Cathode material                                                                                      Common applications                    Comments
                                  [V]            [V]                currents              [Wh/kg]
                                                                                                            Mobile phones          Highest energy density
            LiCoO2                3.6            4.2                1C limit              110-190           Cameras                The most common battery type in portable
                                                                                                            Laptop PCs             appliances since the 1990s.
                                                                                                                                   Low internal impedance
                                                                10C continuous                              Hand tools             Withstands relatively rapid charging
            LiMn2O4             3.7-3.8          4.2                                      110-120
                                                                  40C pulse                                 Medical equipment      Withstands relatively high discharge currents
                                                                                                                                   Low energy density
        NCM (compound
                                                                                                                                   High energy density.
       oxide consisting of                                       5C continuous                              Hand tools
                                  3.7          4.1-4.31                                   95-130                                   Withstands rapid charge
       nickel, cobalt and                                          30C pulse                                Medical equipment
                                                                                                                                   Withstands high discharge currents
          manganese)
        NCA (compound
       oxide consisting of                                                                                                         High energy density.
                                  3.7          4.3-4.51                                                     Vehicles
       nickel, cobalt and                                                                                                          High cell voltage
           aluminium)
                                                                                                                                   Long charge lifetime
                                                                                                            Hand tools
            LiFePO4             3.2-3.3          3.61           35C continuous            95-140                                   Withstands rapid charge
                                                                                                            Medical equipment
                                                                                                                                   Withstands high discharge currents
1
    Charging at higher voltage leads to fewer charge cycles




www.intertek.com                                                                                        3

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Battery white-paper-part-ii

  • 1. The Future of Battery Technologies – Part II Focus on Lithium-Ion Batteries Dr. Annika Ahlberg Tidblad
  • 2. The Future of Battery Technologies – Part II This paper is the second in our ongoing series about batteries. This installment provides an overview of lithium-ion batteries– typical properties, principal applications, and trends. This white paper was authored by Dr Annika Ahlberg Tidblad, Intertek’s resident expert in battery testing. Her background is in research at KTH, the Swedish Royal Institute of Technology, with PhDs in applied electrochemistry and corrosion science, along with ten years of experience in battery technology. The Future of Battery Technologies – Part II – Focus on Lithium Ion Batteries The expression “lithium batteries” is a generic name for battery technologies in which lithium ions play a part in the primary electrochemical discharge and charge reactions. Lithium batteries are available both as primary batteries (disposable batteries) and secondary batteries (rechargeable batteries). The choice of the best battery for a specific purpose is determined by a number of parameters, such as the power and energy requirements of the application, the operating environment, the electrical preconditions and the cost aspects. The most important factors are: 1. The type of battery – disposable or rechargeable battery 2. Electrochemical system – matching the benefits and disadvantages of the battery type to the requirements of the application. 3. The voltage requirements – rated and operating voltage respectively, the minimum and maximum levels, voltage regulation, discharge profile, etc. 4. Load profile – type of load: resistive, current or power discharge, single vs. variable load, etc. 5. Work cycle – continual or intermittent 6. Temperature specifications 7. Lifetime 8. Physical requirements – size, shape, connections, etc. 9. Storage requirements – shelf life, charge state when stored, environment, etc. 10. Charge and discharge states (rechargeable batteries) – cycling batteries vs. energy storage batteries (flow charging), charge characteristics, efficiency and accessibility, discharge requirements 11. Environmental conditions – climate (temperature, humidity), pressure conditions, physical environment (impact, vibration, dust, acceleration, etc) 12. Safety and reliability – permitted variance, acceptable faults, sensitivity to gas leaks or leaks of electrolyte from the battery, etc. 13. Unusual or demanding operating conditions – e.g. extreme temperature conditions, standby times, high reliability and rapid activation, etc. 14. Maintenance and replacement of unserviceable batteries 15. Costs – initial, and operating costs www.intertek.com 1
  • 3. The Future of Battery Technologies – Part II Lithium-based battery systems are characterised by high energy density levels, relatively high voltages, and low weight-to-volume ratio but, in general, tend to be more expensive than equivalent battery technologies with aqueous electrolytes, such as alkali disposable batteries and zinc/air batteries in the primary battery sector, and nickel metal hydride, nickel cadmium and lead batteries in the secondary battery sector. Primary Lithium Batteries Primary batteries have existed since the 1970s, are easy to use and provide convenient sources of energy for portable applications. The batteries usually require no or very little maintenance and they have a long shelf life; modern lithium batteries can usually be stored for up to 10 years, and there are special batteries with solid state electrolyte that can be stored for more than 20 years. The storage tolerance at elevated temperatures is generally good, in some cases up to 70° C. There are 3 classes of primary lithium batteries: 1. Solid state batteries – Characterized by low power but superior shelf lives, and are used, for example, in pacemakers and computer memory backup. The expression ‘solid state’ is used because the electrolyte is solid and the ion transmission between the electrodes takes place in a solid, non-electrically conductive material, usually a polymer. 2. Batteries with a solid cathode – Usually found in coin cells or small cylindrical batteries and used in a huge numbers of applications, such as clocks, memory circuits, photo and communication equipment, toys, flashlights, etc. 3. Batteries with soluble cathodes – Industrial and military batteries that are manufactured in large cell sizes, up to 35-40 Ah, but are also available in smaller sizes, used, for example, in medical and civilian applications. All of these batteries have lithium anodes (the battery’s negative terminal). The cathode material determines the battery system. The most common primary lithium batteries on the market are lithium disulphide (LiFeS2) and lithium manganese dioxide (LiMnO2) batteries. Both of these are of the solid cathode type and are sold as consumer batteries from electrical goods stores and supermarkets. Other primary lithium batteries are mainly intended for the professional market. Table 1 (at end) lists the most common primary lithium battery chemistries and their properties. www.intertek.com 2
  • 4. The Future of Battery Technologies – Part II Over the last few years the market has seen the introduction of battery types in which the cathode consists of a mixture of different electrode materials. The purpose of these batteries is to provide a system that can accommodate both high and low loads. One example is the battery that is used for implanted defibrillators that consist of silver- vanadium oxide (SVO) cathodes to absorbs the peak load of a defibrillation, and carbon monofluoride ((CF)x) for the baseline load between the defibrillation pulses. Secondary Lithium Batteries There are two main groups of rechargeable lithium batteries, one of which uses lithium metal as the negative electrode. These are called lithium metal batteries. Lithium metal batteries were launched on a limited scale for consumer electronic products in the 1980s, but were withdrawn quickly because of safety problems with the lithium electrode. Lithium reacts with the electrolyte, forming dendrites on the surface of the electrode. Under repeated charging, the surface of the anode increases, with a corresponding increase in its reactivity and thermal sensitivity. More recently, however, the lithium metal anodes have once again found practical application in research, although they have not yet been marketed on a large scale. One way of reducing the fire risk in lithium metal batteries is to replace the electrolyte with a solid state polymer electrolyte, that does not react with lithium. The second type of rechargeable lithium battery is called a lithium ion battery, which has a negative terminal that consists of a carbon-based material, usually graphite, or another type of alloy or material that permits intercalation, i.e. storage, of lithium in the structure. This category includes lithium polymer batteries, which differ from traditional lithium ion batteries in that they have an electrolyte that is bound within a non- conducting polymer matrix. Lithium ion batteries were introduced by SONY in 1991, and were first used in advanced consumer electronics products, mobile phones, digital still and video cameras, as well as laptop computers. This type of battery is constantly gaining new ground, and the areas of use are constantly expanding, and lithium ion batteries are currently used in all sorts of portable applications within consumer electronics, medical technology and military systems. The general properties that contribute to this are the high energy density of the lithium ion battery and its specific energy, i.e. a lot of energy from a small volume and weight, compared with other rechargeable types of battery. Its other properties include low self-discharge, relatively long recharge lifetimes (300-500 complete charges and even more if the battery is used within a more restricted charge state range). High costs and the safety aspects are the main barriers, as well as the fact that access to large cell types, battery cells with a capacity exceeding 5 Ah, is limited. Existing lithium ion batteries also suffer from functional limitations at low temperatures. Carbon materials are used in lithium ion batteries because carbon has the ability to reversibly absorb and release large quantities of lithium (Li:C=1:6) without altering the www.intertek.com 3
  • 5. The Future of Battery Technologies – Part II mechanical and electrical properties of the material. Graphite and coke also have an electrode potential that is close to that of lithium, 0.0-0.1 for graphite, and 0.0-0.3 for coke. On the first charge of lithium in the carbon material an outer layer is formed (Solid Electrolyte Interface, SEI). The SEI layer is important because it prevents the carbon anode from reacting with the electrolyte. Dissolution of the SEI layer at elevated temperature poses an important safety risk to lithium ion batteries. There are a number of different chemistries within the lithium ion family that are based on the choice of cathode material. Traditional lithium ion batteries use cathodes made from cobalt dioxide (LiCoO2). By adding nickel (LiNi1-xCoxO2), a layered material is obtained that is more stable and less expensive than pure CoO2. Manganese oxide spinel (LiMn2O4) is another common cathode material for lithium ion batteries. The manganese oxide has a lower energy density but is cheaper and more stable than cobalt. Extensive research is being carried out into new cathode materials, and in the last few years lithium ion batteries with cathodes made from lithium iron phosphate (LiFePO4) have been marketed on a large scale, based on their high safety levels and low cost compared with conventional lithium ion systems. The benefits of LiFePO4 have been achieved at the expense of their energy density and voltage. New electrode materials are being developed and tested constantly in order to produce lithium ion batteries with properties that are suitable for different applications and areas of use. Table 2 (at end) shows a comparison of the main types of lithium ion batteries that are currently on the market. All of them have graphite as the most commonly occurring anode, but there are also high power batteries using hard carbon. At present, research into rechargeable lithium ion batteries is being driven mainly by the requirement in the automotive industry for long calendar and charge lifetimes, high discharge currents and the need for rapid charging, in addition to cost targets. Trends in Lithium Ion Batteries Trends that are noticeable within research & development of lithium ion batteries are: 1. A transition to cheaper and less toxic electrode materials (cathodes), e.g. phosphates and silicates. 2. The transition to materials that have higher reversible lithium reception. The more lithium atoms that the material can absorb in each unit cell, the higher will be the potential battery capacity. 3. Materials that can withstand rapid charges (from 0 to 90% SOC in ten minutes) 4. Power and energy batteries for the automotive industry and stationary installations. 5. Increased cell size in the form of stored energy capacity. 6. Battery systems with high voltage levels, including electrolytes that can withstand higher electrode potential without degrading or reacting with the environment. 7. Battery systems with enhanced safety compared to current battery types. www.intertek.com 4
  • 6. The Future of Battery Technologies – Part II Titanate, silicon and silicides, as well as tin and tin alloys, are the new anode materials that have been discussed in the context of research and development. All of these materials are regarded as offering improved safety as they do not form an SEI layer. The main advantage of titanate is that its structure is highly stable and there is no increase in volume during battery charging. Lithium’s mobility within the material is very rapid, which permits the battery to be charged and discharged at high currents. Charging times of less than 10 minutes have been postulated. The limitations include low cell voltage, due to the high electrode potential of titanate compared to that of lithium. The electrodes are also more expensive than carbon-based electrodes. Silicon and tin are limited both by very large electrode expansion during charging, around 300 and 250% respectively. Both of these material groups have relatively low electrode potential compared with lithium, which results in battery cells with acceptable cell voltages of between 3.5-4 V, depending on the choice of cathode material. Silicon is especially interesting as it permits storage of large quantities of lithium in the anode structure, e.g. the reversible Li ion insertion capacity is >1. Moreover, the material is neither expensive nor toxic. Development on the cathode side is more multi-faceted. The list of substances and variants of substances that are being studied is extremely long, and many of them will never be marketed. Some of them will only be of interest for niche applications on cost grounds. Among the materials being discussed are metal phosphates (in particular vanadium, magnesium and manganese, as well as various compounds), layered metal oxides (often with manganese oxide bases) and silicates (e.g. iron silicate). The metal phosphates are being promoted thanks to their chemical stability, leading to increased safety compared to traditional cobalt-based cathode materials. Magnesium and manganese phosphates are also relatively cheap and non-toxic materials, which is also one of the strengths of iron silicate. The layered metal oxide structures are expected to offer rapid lithium mobility, thereby permitting high charge and discharge currents, but the material is still relatively expensive and associated with safety problems. Intertek’s expertise in battery testing & energy storage services ensures products meet performance, reliability and safety criteria. Intertek has expanded global energy storage testing facilities and advisory services. Throughout design, manufacturing & system deployment cycles, Intertek provides evaluations for performance, electrical safety, interoperability, fit for use, component selection and more. Please visit our website at www.intertek.com/energy-storage, contact icenter@intertek.com or call your regional lab: Europe: +46 8 750 00 00 North America: +1 800 967-5352 Asia Pacific: +86 21 6127-8200 www.intertek.com 5
  • 7. The Future of Battery Technologies – Part II Table 1 – Primary lithium batteries Cell voltage [V] Specific Energy System Construction Operating energy Power density Discharge profile Usages Properties Rated density [Wh/l] voltage (20 °C) [Wh/kg] Category 1 – Solid state system - High energy density. - Withstands low current and power loads - High reliability - Cells constructed with cathode limitation Coin cells and - Long shelf life, 15-20 LiI2 2.8 2.6-2.8 220-280 820-1030 Very low Relatively flat special batteries for years under normal e.g. pacemakers conditions, but can be stored for up to 1 year at 100 °C - Normally used in pacemakers and digital watches Category 2 – Batteries with solid cathodes - Highest theoretical Coin cells energy density Coin cell Cylindrical batteries - Withstands medium to Li(CF)n Spiral ”jelly-roll” 3.0 2.7-2.5 220-590 550-1050 Low-medium Relatively flat (commercial and low loads Rectangular plates military) - Wide temperature range -20-60 °C Flat discharge curve - Replacement batteries for type AA household ”Bobbin” and ”jelly- batteries High initial drop in LiFeS2 roll” cylindrical 1.5 1.5-1.4 260 500 Medium-high - Tolerates high power voltage, then flat cells Good temperature properties Long charge retention www.intertek.com 1
  • 8. The Future of Battery Technologies – Part II - High specific energy and energy density Cylindrical up to 22 - Wide temperature range LiMnO2 Coin cell 3.0 3.0-2.7 230-270 535-620 Low-high Low-high Ah - Withstands relatively high discharge currents - Relatively cheap - Used in implants and other medical applications Rel. complex Special batteries for LiAgV4O11 Prismatic 3.2 3.2-1.5 270 780 Low-medium - High energy density. discharge curve medical implants - Multi-step discharge -Good load properties Category 3 – Batteries with soluble cathodes - Manages high current and power loads Cylindrical cells up LiSO2 Spiral ”jelly-roll” 3.0 2.9+-2.7 260 415 High Very flat - Excellent low to 35 Ah temperature properties - Long shelf life - One of the highest OCV voltages and energy Bobbin densities of all of the Spiral Cylindrical cells 2- LiSOCl2 3.6 3.6-3.4 275-590 630-1100 Low-medium Flat commercial batteries Prismatic cells with 30 Ah - High specific energy electrode plates - Withstands low discharge loads - High energy density. - Manages high discharge loads Spiral Cylindrical cells 7- LiSO2Cl2 3.95 3.5-3.1 450 900 Medium-high Flat - Good high temperature 30 Ah properties Excellent storage Properties www.intertek.com 2
  • 9. The Future of Battery Technologies – Part II Table 2 – Rechargeable lithium ion batteries Rated voltage Charge limit Max charge and discharge Energy density Cathode material Common applications Comments [V] [V] currents [Wh/kg] Mobile phones Highest energy density LiCoO2 3.6 4.2 1C limit 110-190 Cameras The most common battery type in portable Laptop PCs appliances since the 1990s. Low internal impedance 10C continuous Hand tools Withstands relatively rapid charging LiMn2O4 3.7-3.8 4.2 110-120 40C pulse Medical equipment Withstands relatively high discharge currents Low energy density NCM (compound High energy density. oxide consisting of 5C continuous Hand tools 3.7 4.1-4.31 95-130 Withstands rapid charge nickel, cobalt and 30C pulse Medical equipment Withstands high discharge currents manganese) NCA (compound oxide consisting of High energy density. 3.7 4.3-4.51 Vehicles nickel, cobalt and High cell voltage aluminium) Long charge lifetime Hand tools LiFePO4 3.2-3.3 3.61 35C continuous 95-140 Withstands rapid charge Medical equipment Withstands high discharge currents 1 Charging at higher voltage leads to fewer charge cycles www.intertek.com 3