carbon additive solutions for stop-start batteries
TRANSCRIPT
CARBON ADDITIVE SOLUTIONS FOR START-STOP BATTERIES Presented by Paolina Atanassova, Aurelien DuPasquier, Miki Oljaca Cabot Corporation Billerica, Massachusetts, USA
BCI Convention + Power Mart Expo May 1-3rd 2016, San Antonio, Texas, USA
Outline
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Market adoption of carbon additives in advanced lead acid batteries
Performance needs for Start-Stop application and role of carbon
New optimized formulation for Enhanced Flooded Batteries (EFB)
New developments of PBX® products
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Market Adoption of Micro-Hybrids
3 BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Market Adoption of Carbon Additives More than 15 M micro-hybrid (ISS) new cars on the road in 2015,
expected to exceed 35M in 2020
New cycling applications in electricity storage also demand
improved battery solutions
Lead acid batteries are still the preferred choice for micro-hybrids
and storage due to low cost and existing broad manufacturing
infrastructure, but threat from lithium is real
Carbon additives are a critical part of the solution for improved
performance of lead acid batteries and gaining broad market
adoption
Often less than 1% additive to negative mass can bridge key
performance gaps like dynamic charge acceptance and cycle life
4 BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Carbon blacks
Activated carbons
Fibers
Nanotubes
Graphenes Graphites
Nanofibers
Carbide-derived carbons
Carbon Blacks Most Widely Used in Advanced Lead Acid Batteries
Aerogels
0.5µ
10µ 2µ
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BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
30-100% improvement in DCA, and 3-10 times improvement in cycle life have been demonstrated on a cell and battery level
Full spectrum of carbon’s effects not completely known yet, but some performance effects are clear: Increased NAM surface area
Depolarization of negative plate Capacitive contribution:
Supercapacitive effect for high surface area carbons Additional nucleation sites
Carbon facilitates the PbSO4 Pb reaction by providing a conductive surface area for Pb nucleation
Restriction of crystal growth: Carbon particles affect the Pb/PbSO4 crystallization
Carbon Additives Enable Significant Improvements in Dynamic Charge Acceptance (DCA) and Cycle Life
6 BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Effect of Carbon: Increasing Surface Area of Negative Electrodes
D. Pavlov et all, J. Power Sources, 191 (2009) 58 D. Pavlov et. all, 8th International Conference, LABAT 2011, Albena, Bulgaria
7 BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
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NAM Surface Area Depends on Carbon Type and Loading
Pb
Pb
0.25% PBX51
1% PBX09
1% PBX135
0.5% PBX135
Carbons vary in morphology, surface area and surface properties
Optimal loading level depends on carbon type and is also determined by the application
For high surface area carbons typically < 1% carbon loading is necessary to achieve positive impact on performance 1%
PBX09
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Surface Areas of Cabot’s PBX® Carbon Blacks vs their NAM BETs
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Without carbon additive With 0.5% carbon black
Carbon Black Additives Change the NAM Morphology
CB
Pb Pb
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
How Does Carbon Affect Lead Acid Battery Performance?
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Our PBX® additives are tailored for different applications by combining structure and surface properties
Cell performance
Which carbon characteristics influence battery performance
Mechanism of influence
Charge acceptance
Carbon type, loading and surface area of carbon and negative active mass morphology
Higher NAM surface area leads to depolarization of the negative plate and higher currents can be accepted at fixed voltage
Water loss Surface area and properties of carbon and negative active mass
When the battery is overcharged hydrogen evolution occurs on the negative active mass, both from the lead surface and from carbon surface
Cold crank
Cold crank depends mostly on lignosulfonate, less on carbon, but can be affected by the interaction between them
The ratio of lignosulfonate to lead surface area determines cold crank performance
0 % carbon 0.5 m2/g
1% PBX 135, 1.3 m2/g
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Different Applications Require Different Solutions
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Carbon Type Carbon Loading Paste Formulation
Tim
e at
Flo
at
Time Cycling/ Depth of Discharge
PAM Failure
Water Loss Grid Corrosion
PSoC: NAM Sulfation
m HEV
SLI
Reliable grid
Unreliable grid
Traction/ Forklifts
E-bikes
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Our PBX® Carbon Additive Products for Lead Acid Battery Applications
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AGM Batteries Enhanced Flooded Batteries
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
High and Controlled Purity of PBX® Carbon Additives PBX products produced at scale, impurities part of COA
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Focus on metals which have strong influence on hydrogen evolution
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Property Test Method
Unit Value
BET Nitrogen surface area
ASTM D6556 m2/g 1300 – 1550
OAN ASTM D2414 ml/100g 140 – 200
Iron Internal method
ppm <40
Total Co, Cr, Cu, Fe, Mn, Ni
Internal method
ppm <50
General Characteristics Formula: Carbon Aspect: Carbon black pellets CAS Number: 133-86-84 Standard Packaging 8 kg bags
PBX51 Typical Values*
*The data in the table above are typical test values intended as guidance only, and are not product specifications.
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0.25% PBX51
0.25% PBX51
PBX® Additive Properties and Typical Applications
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
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PBX® 09 and PBX 51 Additives Provide DCA/Cycle Life Benefit in AGM batteries
At loadings of 0.25-0.5% in negative paste, PBX additives can deliver:
State of the art DCA
2-3x cycle life improvements
Battery applications:
High DCA Start Stop
E-bikes
Telecom
Energy Storage
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Carbon Additives in EFB Automotive Start-Stop
Must improve cycle-life and dynamic charge acceptance (DCA); AND pass cold
crank and water loss testing
New benefit Test method
Dynamic charge acceptance
Current at 5-20sec Karden DCA test
Cycle-life HRPSoC (VRLA) 17.5% DOD cycling (EFB)
Conventional target Test method
Cold crank Cold start, -18°C
Water loss Water loss on overcharge, 60°C
16 BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
0 200 400 600 800 1000 1200 1400 1600 1800
1.8
1.9
2.0
2.1
1% PBX55_dry mix
1% PBX55_pre wet
1% PBX135_dry mix
1% PBX135 pre-wet
0.2% VXC72_control
En
d o
f d
isch
arg
e v
olta
ge
Cycle#
PBX® 135 Additive Best Cycle Life at 17.5%, DOD Cycling at 50% SOC (without equalization) in Flooded Cells
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PBX 135
PBX 55
control
Paste mixing recipe has strong impact of performance
Carbon and lignosulfonate loadings optimization study was conducted with PBX135 at loading of 0.5%, 0.75% and 1% and two types of lignosulfonate
Vanisperse - A
Vanisperse D-2314
control
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Flooded Cells Design
NAM Paste Mix
Test Conditions
Charge Acceptance
Water Loss
PBX® Additive Performance Testing
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Single 2V cells 2 negatives, 3 positives 4.4 Ah nominal capacity
Wrapped positives Compressed electrodes
1 kg, Barton PbO 0.75% PBX® 135 additive (pre-wet)
VS- A or D-2314 lignosulfonate at 0.2%, 0.4%, 0.6% loading
0.8% BaSO4
CCA Test - 18oC, I = 5x Cn A; down to 1V 17.5 DOD cycle test:
C/3 current, at 50% SOC, 17.5% DOD (40 min charge, 30 min discharge) 2.4V limit on charge voltage, cutoff at V<1.66V Without equalization step after each 85 cycles
Static CA – A, 10 min, 0oC DCA – W/g or A/Ah, 5 sec
Overcharge at 2.4V Water bath 60oC, 3 weeks
PBX® 135 Additive/LS Formulations Lead to Marked Increase of DCA
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Increased VS-A loading beyond 0.4% eliminates the PBX 135 carbon additive benefit on DCA New VS (D-2314) formulations maintain DCA benefit even at high loadings
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
0.2% VXC72,0.2% LS control
0.75% PBX135,0.2% LS
0.75% PBX135,0.4% LS
0.75% PBX135,0.6% LS
DC
A 5
se
c, 8
0%
SO
C [
A/A
h]
Dynamic Charge Acceptance VS-A VS-New
0
20
40
60
80
100
120
140
160
180
0.2% VXC72,0.2% LS control
0.75% PBX135,0.2% LS
0.75% PBX135,0.4% LS
0.75% PBX135,0.6% LS
Co
ld c
ran
kin
g ti
me
[s]
Cold Crank -18oC VS-A VS-New
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
0.2% VXC72,0.2% LS control
0.75% PBX135,0.2% LS
0.75% PBX135,0.4% LS
0.75% PBX135,0.6% LS
3 w
ee
ks w
ate
r lo
ss [
g/A
h]
Water Loss on Overcharge
VS-A VS-New
PBX® 135 Additive/LS Formulations Lead to 2-4x Increase in Cycle
Life and Minimal Water Loss at Optimized Loading
20 BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
0
500
1000
1500
2000
2500
0.2% VXC72,0.2% LS control
0.75% PBX135,0.2% LS
0.75% PBX135,0.4% LS
0.75% PBX135,0.6% LS
Nu
mb
er
of
cycl
es
[#]
17.5% DOD Continuous Cycling
VS-A VS-New
New EFB Formulation Summary
Optimized formulation of 0.75% PBX® 135 carbon additive (pre-wet) with 0.3 - 0.4% D-2314 lignosulfonate delivers significant improvement in DCA/cycle-life and meets water loss/cold crank performance requirements for EFB in Start/Stop application.
Formulation can be applied starting from individual components, or as part of fully formulated expander provided by expander manufacturers.
EFB performance is driven by battery design as well:
Positive vs. negative active mass ratio and # plates
Plates compression and acid density
Lead oxide type and purity
Battery lid configuration to control evaporation during water loss test
21 BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Next Gen of PBX® Additives Aims to Eliminate Trade Offs
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New PBX Grades
Increase DCA and cycle-life and maintain low water loss
Hydrogen evolution reaction occurs on both carbon and lead surfaces
Surface properties of carbon can be controlled to minimize hydrogen evolution and water loss
Initial validation completed
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Cycling Voltammetry Test for Hydrogen Evolution Rates on Carbon Enables Selection of New Concepts
Ex-situ measurement in liquid 3 electrode cell
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Reference electrode RE = SCE Counter electrode CE = graphite rod Working electrode WE = CB coated on graphite rod
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
High DCA and Low Water Loss Validated on Cell Level
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0.00
1.00
2.00
3.00
4.00
5.00
6.00
0.5% PBX51,0.2% LS -Control 1
0.5% PBX51,0.4% LS -Control 2
0.5%PBX51modA,
0.2% LS
0.5%PBX51modB,
0.2% LS
0% carbon,control
g/A
h, A
/Ah
DCA, 80% SOC [A/Ah]3 week water loss, g/Ah
Modified PBX® 51
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Effect of Rest Time on DCA
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS 25
0.00
0.50
1.00
1.50
2.00
2.50
0.2% VXC72Control
0.5% PBX51Control 1
0.5% PBX51Control 2
0.5% PBX51Mod A
0.5% PBX51Mod A "Dry"
DC
A @
5s,
90
% S
OC
[A
/Ah
10 min rest
24h rest
Good Balance of Performance for Modified PBX® 51 Along with Formulation Optimization
Flooded 4.6 Ah single cells
All normalized to
PBX 51, 0.4% VS-A =100
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0.00
0.50
1.00
1.50
2.00
2.50
PBX51_modA(0.2%VSA)
PBX51_modA(0.4%VSA)
PBX51_modB(0.2%VSA)
PBX51_modB(0.3%VSA)
PBX51(0.2% VSA)
PBX51(0.4% VSA)
0% carbon(0.2% VSA)
CCA (s)
DCA
17.5% DOD Cycles
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
Over 130 years in operation
Founded in 1882
NYSE: CBT since 1968
Global specialty chemicals and performance materials company
44 manufacturing sites in 21 countries
Core technical competencies in fine particles and surface modification
FY2015 sales: $2.9B
About Cabot Corporation A rich and unique history
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Global Leaders
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carbon black #1 cesium formate #1
fumed metal oxides #2 activated carbon #2
inkjet colorants #1
Global Asset Base to Serve Customers
44 manufacturing sites in 21 countries, all with local management teams 30 sales locations in 20 countries
manufacturing sites sales locations affiliates regional headquarters
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Acknowledgements
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Cabot Corporation, USA
Institute of Electrochemistry and Energy Systems - BAS, Bulgaria
Lignotech, USA
Thank you for your attention!
BCI CONVENTION + POWER MART EXPO, MAY 1-3RD 2016, SAN ANTONIO, TEXAS
The data and conclusions contained herein are based on work believed to be reliable, however, Cabot cannot and does not guarantee that similar results and/or conclusions will be obtained by others. This information is provided as a convenience and for informational purposes only. No guarantee or warranty as to this information, or any product to which it relates, is given or implied. This information may contain inaccuracies, errors or omissions and CABOT DISCLAIMS ALL WARRANTIES EXPRESS OR IMPLIED, INCLUDING MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE AS TO (i) SUCH INFORMATION, (ii) ANY PRODUCT OR (iii) INTELLECTUAL PROPERTY INFRINGEMENT. In no event is Cabot responsible for, and Cabot does not accept and hereby disclaims liability for, any damages whatsoever in connection with the use of or reliance on this information or any product to which it relates. © 2016 Cabot Corporation.