IMERYS GRAPHITE & CARBON CARBONS FOR ADVANCED LEAD ACID
BATTERIES: PROPERTIES AND ROLE
imerys-graphite-and-carbon.com
Albena, 13th June 2017
1. ABOUT IMERYS GRAPHITE & CARBON
3. «ONE-STOP SHOP»: YOUR PARTNER FOR CARBONS FOR LAB
4. SPECIALTY CARBONS FOR LEAD ACID BATTERIES
OVERVIEW
June 2017 IGC – YOUR PARTNER FOR LAB
1. ABOUT IMERYS GRAPHITE & CARBON
3. «ONE-STOP SHOP»: YOUR PARTNER FOR CARBONS FOR LAB
4. SPECIALTY CARBONS FOR LEAD ACID BATTERIES
OVERVIEW
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THE WORLD
LEADER IN
MINERAL-BASED
SPECIALTY
SOLUTIONS
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IMERYS GROUP KEY FIGURES – 2016
IMERYS GRAPHITE & CARBON - A MEMBER OF IMERYS
IMERYS GRAPHITE & CARBON – OUR VISION
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INNOVATIONS TO POWER EVERYDAY LIFE
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IMERYS GRAPHITE & CARBON – YOUR RELIABLE PARTNER
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SMALL SHARE OF CLIENTS’ COSTS
PRODUCT, PROCESS & APPLICATION
KNOW-HOW
CARBON (SYNTHETIC & NATURAL)
UNIQUE & SUSTAINABLE TECHNOLOGY
INDUSTRIAL ASSET
5 PILLARS FOR A SUSTAINABLE COMPETITIVE ADVANTAGE
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Headquarters
Sales Offices
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IMERYS GRAPHITE & CARBON – WORLDWIDE PRESENCE
IMERYS GRAPHITE & CARBON – MARKETS
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CONSUMER ELECTRONICS
AUTOMOTIVE
ENERGY
MAIN
END-MARKETS
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1. ABOUT IMERYS GRAPHITE & CARBON
3. «ONE-STOP SHOP»: YOUR PARTNER FOR CARBONS FOR LAB
4. SPECIALTY CARBONS FOR LEAD ACID BATTERIES
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OVERVIEW
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Carbon Materials
Natural Flake
Graphite Synthetic
Graphite Carbon
Black
Exfoliation
Mixing
Sieving
Milling
Size modification
Surface modification
Shape modification
Purification Added Value Processes
R&D Laboratories Product Development
Application Development
Scientific Support to Customers Security of Supply
Customization
Sustainable
Solutions Specialty Carbon Additives
for Lead Acid Batteries
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Innovative
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HIGHLY DIVERSIFIED OFFER OF SPECIALTY CARBONS TO
FULFILL VARIED REQUIREMENTS
TIMREX® GRAPHITE: High-purity expanded graphite
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ENSACO® Carbon Black: High-purity and extra conductive carbons
with a very high structure and specific surface area, supplied in soft
granules
SUPER P® Carbon Black: High-purity and highly conductive carbons
with a moderate surface area
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NOVEL CARBON MATERIALS FOR ADVANCED LEAD ACID BATTERIES
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TEM picture of
CyPbridTM particle
TIMREX® CYPBRIDTM: Hybrid carbon which combines the relevant
properties of the graphite and the carbon black in a unique product
‘ONE-STOP SHOP’: YOUR PARTNER FOR CARBONS FOR LAB
1. ABOUT IMERYS GRAPHITE & CARBON
3. «ONE-STOP SHOP»: YOUR PARTNER FOR CARBONS FOR LAB
4. SPECIALTY CARBONS FOR LEAD ACID BATTERIES
June 2017 IGC – YOUR PARTNER FOR LAB
OVERVIEW
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Product Type of material BET SSA Pour density OAN Wettability (contact angle)
m2/g g/cm3 ml/100g °
Super P® Carbon Black 62 0.06 290 ~ 90 Mildly hydrophobic
Ensaco® 350G Carbon Black 780 0.13 320 130 Hydrophobic
TIMREX® BNB90 Expanded graphite 28 0.03 N.A. < 30 Highly hydrophilic
TIMREX® CyPbrid™ 1 Hybrid carbon 300 0.35 100 < 30 Highly hydrophilic
TIMREX® CyPbrid™ 2 Hybrid carbon 200 0.30 N.A. < 30 Highly hydrophilic
TIMREX® CyPbrid™ 3 Hybrid carbon 100 0.35 N.A. < 30 Highly hydrophilic
Highly diversified carbon portfolio
SPECIALTY CARBONS FOR LEAD ACID BATTERIES
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High pour density for easy handling and less effect on plate density
Product Type of material BET SSA Pour density OAN Wettability (contact angle)
m2/g g/cm3 ml/100g °
Super P® Carbon Black 62 0.06 290 ~ 90 Mildly hydrophobic
Ensaco® 350G Carbon Black 780 0.13 320 130 Hydrophobic
TIMREX® BNB90 Expanded graphite 28 0.03 N.A. < 30 Highly hydrophilic
TIMREX® CyPbrid™ 1 Hybrid carbon 300 0.35 100 < 30 Highly hydrophilic
TIMREX® CyPbrid™ 2 Hybrid carbon 200 0.30 N.A. < 30 Highly hydrophilic
TIMREX® CyPbrid™ 3 Hybrid carbon 100 0.35 N.A. < 30 Highly hydrophilic
SPECIALTY CARBONS FOR LEAD ACID BATTERIES
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Correlates with the conductivity of a carbon black
Correlates with the amount of water and H2SO4 needed in the pasting
Product Type of material BET SSA Pour density OAN Wettability (contact angle)
m2/g g/cm3 ml/100g °
Super P® Carbon Black 62 0.06 290 ~ 90 Mildly hydrophobic
Ensaco® 350G Carbon Black 780 0.13 320 130 Hydrophobic
TIMREX® BNB90 Expanded graphite 28 0.03 N.A. < 30 Highly hydrophilic
TIMREX® CyPbrid™ 1 Hybrid carbon 300 0.35 100 < 30 Highly hydrophilic
TIMREX® CyPbrid™ 2 Hybrid carbon 200 0.30 N.A. < 30 Highly hydrophilic
TIMREX® CyPbrid™ 3 Hybrid carbon 100 0.35 N.A. < 30 Highly hydrophilic
SPECIALTY CARBONS FOR LEAD ACID BATTERIES
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This is a key property for an easy incorporation into the paste
Product Type of material BET SSA Pour density OAN Wettability (contact angle)
m2/g g/cm3 ml/100g °
Super P® Carbon Black 62 0.06 290 ~ 90 Mildly hydrophobic
Ensaco® 350G Carbon Black 780 0.13 320 130 Hydrophobic
TIMREX® BNB90 Expanded graphite 28 0.03 N.A. < 30 Highly hydrophilic
TIMREX® CyPbrid™ 1 Hybrid carbon 300 0.35 100 < 30 Highly hydrophilic
TIMREX® CyPbrid™ 2 Hybrid carbon 200 0.30 N.A. < 30 Highly hydrophilic
TIMREX® CyPbrid™ 3 Hybrid carbon 100 0.35 N.A. < 30 Highly hydrophilic
SPECIALTY CARBONS FOR LEAD ACID BATTERIES
Topic still under discussion not yet a clear answer neither from the scientific community nor from industry
Conductivity: increased plate conductivity improves high rate performance
Porosity: optimized pore structure kept during cycling
Affinity for lead: affinity of the carbon for lead improves the lead deposition
...
Likely the beneficial effect of carbon in the negative plate is a combination of several aspects.
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ACTION MECHANISM OF CARBON IN THE NEGATIVE ELECTRODE
Proposed mechanism for the role carbon in improving the charge acceptance and cycle life of the battery:
1. The carbon is exposed to a lead containing environment. Lead ions are present in solution.
2. Due to the surface properties of the carbon (either morphological or chemical properties) some lead is immobilized on the surface. This lead can be there either as immobilized ion or reduced lead.
3. The immobilized lead acts as nucleation seed for the deposition of lead during battery cycling.
J. Power Sources 324 (2016) 41
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1
Pb2+
Pb2+
Pb2+
Pb2+
Pb2+
Pb2+
2
Pb
3
Pb
Current
Pb
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ACTION MECHANISM OF CARBON IN THE NEGATIVE ELECTRODE
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1
Pb2+
Pb2+
Pb2+
Pb2+
Pb2+
Pb2+
2 Pb
3
Pb
Current
Pb
Spontaneous lead uptake experiments
1) Carbon is exposed to a lead rich environment
2) The amount of lead remaining immobilized on the surface is measured
3) TEM investigation clearly proved the presence of lead nanoparticles on the carbon substrate
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ACTION MECHANISM – EXPERIMENTAL EVIDENCE
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1
Pb2+
Pb2+
Pb2+
Pb2+
Pb2+
Pb2+
2 Pb
3
Pb
Current
Pb
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Product Lead uptake BET SSA
ppm m2/g
Super P® 700 62
Ensaco® 350G 8700 780
TIMREX® BNB90 1300 28
TIMREX® CyPbrid™ 1 7700 300
TIMREX® CyPbrid™ 2 5800 200
TIMREX® Synthetic graphite 300 9
Reference Carbon Black 320 29
ACTION MECHANISM – EXPERIMENTAL EVIDENCE
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1
Pb2+
Pb2+
Pb2+
Pb2+
Pb2+
Pb2+
2 Pb
3
Pb
Current
Pb
Lead plating (Battery simulation)
Model carbon electrodes undergo electrochemical deposition of lead
CyPbrid 1
Before After
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ACTION MECHANISM – EXPERIMENTAL EVIDENCE
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BNB90
Before After
E 350G
Before After
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ACTION MECHANISM – EXPERIMENTAL EVIDENCE
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Ref. Black
Before After
Synt. Graphite
Before After
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ACTION MECHANISM – EXPERIMENTAL EVIDENCE
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Peukert lines measured in flooded 2V cells PNP ca. 2Ah per cell. Excess of acid d1.28gcm-3.
«LOW STRUCTURE»
CARBON BLACK
«HIG
H S
TR
UC
TU
RE
»
CA
RB
ON
BL
AC
K
Due to the high conductivity of Super P
a better utilization of the active mass is achieved
leading to a better performance
PERFOMANCE IN 2 V CELLS - PEUKERT
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Charge acceptance
measured in flooded 2V
cells PNP ca. 2Ah per cell.
Excess of acid d1.28gcm-3.
Charge acceptance increase of ca. 40% with CyPbrid
compared to typical reference low structure carbon black
in this cell configuration
PERFOMANCE IN 2 V CELLS – CHARGE ACCEPTANCE
HIGHLY DIVERSIFIED PORTOFOLIO
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EASY PROCESSABLE CARBONS
PROVEN PERFORMANCE IMPROVEMENT
TECHNICAL EXPERTISE AND SUPPORT
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