Enhancing the performance of

advanced lead batteries for

start-stop and energy storage applications
Boris Monahov,
ILA / ALABC,
Program manager

September 22, 2017, Kuala Lumpur, MALAYSIA

 In memoriam
Prof. DSc.
Dechko Pavlov Dechkov,
86
Academician, full member
of the Bulgarian Academy
of Sciecnes

Rest in piece, Teacher!

From his last paper

prepared for LABAT’2017
which he couldn’t present
because of health issues.
It was written to help us
understand lead batteries.

Three slides say it all

 In memoriam
Prof. DSc
Dechko Pavlov Dechkov,
86
Academician, full member
of the Bulgarian Academy
of Sciecnes

Rest in piece, Teacher!

From his last paper

prepared for LABAT’2017
which he couldn’t present
because of health issues.
It was written to help us
understand lead batteries.

Three slides say it all

 In memoriam
Prof. DSc
Dechko Pavlov Dechkov,
86
Academician, full member
of the Bulgarian Academy
of Sciecnes

Rest in piece, Teacher!

From his last paper

prepared for LABAT’2017
which he couldn’t present
because of health issues.
It was written to help us
understand lead batteries.

Three slides say it all

 ALABC TECHNICAL PROGRAM 2016-2018

OBJECTIVE

Fundamental R&D work on lead batteries to deliver in line with new ALABC strategy:
• Automotive - improved performance at PSoC (DCA), increased lifetime
• ESS - increased lifetime at PSoC, increased deep cycle life

CURRENT STATUS AND FUTURE WORK PLAN

– 11 fundamental R&D studies going on
– Equally split between Automotive and Energy Storage projects
– Possibility of further research projects funding (2018)
– Couple of new proposals already sent by members
 BATTERY MARKET BY STORED ENERGY (MWh) TILL 2016

 Battery market and energy stored in batteries rapidly growing due to various reasons
 Storage in lead-acid batteries dominating
 Li-ion and other chemistries: fast growth after 2000, massive investments and R&D

Based on data presented by Christophe Pillot, AABC, Mainz, January 30-th, 2017
 BATTERY MARKET TRENDS (in US $) , JANUARY 2017

 SLI market dominating till 2005, steady growth  30 years ago: lead-acid batteries dominated fully
 Other application markets dominating now  Faster growth of Li-ion after 2010
 EV and HEV batteries more expensive then SLI  Lead and alternatives markets to be equal in 2018

Based on data presented by Christophe Pillot, AABC, Mainz, January 30-th, 2017
 2016 BATTERY MARKETS (in US $) BY APPLICATION

55%
30%
15%

SLI: lead-acid batteries – about 32% Forklift, telecom, UPS – mainly lead-acid
Others + portable: various chemistries - 51% Energy storage systems – all chemistries
EV and E-buses: various chemistries - < 17.5% Electric bikes and rickshaws – lead & Li-ion
Variety of other others – all chemistries

Based on data presented by Christophe Pillot, AABC, Mainz, January 30-th, 2017
 AUTOMOTIVE BATTERY MARKET TRENDS, EUROPE

BEV Li OEMs looking how to rapidly reduce CO2 emissions:

PHEV (>60V) Li  More electric models (VW-80; BMW – 30 till 2025)
 An electric alternative to every ICE model (VW – 300 till 2030, Daimler – to all
FHEV (>60V) Ni models till 2022)
 Profit on electric vehicels is not sure: risk for producers, employees
$ 12V 48V Li ? Pb ?
Mild Hybrids Pb Li ?
Start-Stop Pb Li ?
Gasoline Diesel  Low oil price: reduced interest in electric (reached 2.5% only)
ICE vehicles Pb  Diesel scandal (D): shift towards gasoline (from 53% down to 45%), electric
 Downtown diesel ban: shift towards electric (diesel: -12%, electric: up to 4?)

ALABC studies show advanced lead batteries are good for start-stop and mild hybrid vehicles(12V and 48V)
The OEM companies will make their choice
The market will show which is the battery of the future low emission cars before all they become electric
 NEW TECHNICAL CHALLENGES FOR LEAD BATTERIES
 Start-Stop: DCA, water loss, total energy throughput
(JCI data: required – 0.15 MWh/10y; EFB - 0.015 MWh/10y; AGM: 0.6 MWh/10y)
 Mild hybrids: power, energy, total energy throughput, OEM’s strategy and planning
 Forklifts, golf carts: start-stop and fast charge (PSoC, ChA/DCA), total energy throughput
 Grid support systems: seconds-minutes pulses (PSoC, ChA/DCA), total energy throughput
 Energy storage systems: cycle life, calendar life, energy throughput (5,000 – 6,000 cycels)

Very fast processes, parasitic reactions, reversibility not guaranteed – new solutions needed
Lead Battery Advancement and Research - overview
Lead Battery Advancement and Research - overview
Lead Battery Advancement and Research - overview
Lead Battery Advancement and Research - overview
 Lead Battery Advancement and Research

1. Basic science studies in the new ALABC program:

increase the performance of carbon-enhanced lead batteries in order to make sure they
will continue being the choice in automotive and storage applications.
2. Memebrs of ALABC (and not only) performing own R&D resulting in new carbons,
expanders, additves, materials and cell designs which, along with ALABC studies,
accelerate the promotion of more advanced batteries.
3. Each innovation offers certain improvements – 5%, 10%, some by times.
Synergy: bringing all (or at least some) of them together has the potential of making lead
batteries as good as the competitive chemistries.
 Factors with strong impact on lead-acid battery performance

1. Adding CARBON
2. Other additives
3. Pb, PbSO4, PbO2 crystals dissolution, nucleation and growth, reversibility
4. Interaction between carbon and Pb, PbSO4, PbO2 crystals
5. Interaction between other additives and Carbon, Pb, PbSO4, PbO2 crystals
6. Interaction between carbon and negative expander
7. Microstructure of negative and positive active mass and its self-organization
8. Alloys and current collector design
9. New cell designs
Some of these will be mentioned further in my presentation.
 Adding carbon and its effect – still subject of research
1. Solid carbon 3-D structures replacing / supporting the negative grid (RVC, foam, etc.)
2. High surface area and capacitance ancillary negative carbon plate (Ultrabattery®)
3. High surface area soft carbon active material 3-D (ArcActive)
4. Carbon powders (GR, CB, AC) added to the negative active mass – widely used
5. CNT added to both active masses (BD Structures, Vulcan)
6. Graphene added to both active masses (Chilwee / XG Sciences)
7. Carbon fibers
8. Pb-C composite grids

Activated carbon
 Adding carbon and its effect - mechanisms
A model of electrochemically active carbon additives to NAM Polarization of Carbon-enhanced NAM
(D. Pavlov, 2007-2009) (D. Pavlov, 2011)

Conductive carbon particles connected to the Pb substrate act as electrodes

Electrochemically active carbon involved in growth/dissolution of surrounding crystals
Carbon particles in NAM offer new active surface and change the polarization mechanism

17 Asian Battery Conference, Kuala Lumpur, Malaysia, September 19-22, 2017

 A “CARBON PARTICLE” ADDED TO NAM - FEATURES
Functional groups Wetting angle

Macro, meso, micro pores Ordered structure

Structure (carbon blacks)

Ultra micro pores < 7 Å
(molecular sieving) ???

Macro pores: > 50 nm Source: http://www.sigmaaldrich.com

Hydrogen

Closed pores

Meso pores: 2-50 nm

Micro pores: < 2 nm

17 Asian Battery Conference, Kuala Lumpur, Malaysia, September 19-22, 2017

 Interaction between carbon and Pb, PbSO4 crystals
Effect of carbon foam Effect of added carbon particles

P.Atanassova, Cabot, Kl. Eberbach Battery Workshop proceedings, January 2017

The effect of C foam and C powder particles on NAM structure and SSA is similar. Why?
 Adding carbon and its effect – functional groups
Some carbons interact with expanders and change their effect – what is the mechanism?
Carbon foam polarized as a negative plate CNT exapmles

?
V. Gupta and T. Sale, "Carbon Nanotubes - From Research to
Applications“ in Nanotechnology and Nanomaterials, ISBN 978-953-307
1) D. Pavlov, B.O. Myrvold, T. Rogachev, M. Matrakova, Journal of Power Sources 85, 2000, 79: 500-6, July, 2011

Variety of funct. groups: Ar–COOH; R–COOH; –CHO; <C=O; Ar–OH; Ar–(OH)2 Ar–OH,–OMe; –OMe; –SO3H
Functional groups can be bound to carbon surface (sp3, sp2, sp bonds) – mechanism?
Same 17
functional groups exist
Asian Battery Conference, in expanders.
Kuala Lumpur, Selective
Malaysia, September interaction with Pb, PbSO4 and PbO2?
19-22, 2017
 Interaction of carbon additives with expanders
 Expanders (with functional groups) change crystal growth rate in NAM
Functional groups and NAM Expander mechanism Similar effect of carbon additives

1. Adsorbed oxygen, hydrogen and functional groups

1) D. Pavlov, B.O. Myrvold, T. Rogachev, M.
Matrakova, Journal of Power Sources 85 2000.
79–91
2) B.O. Myrvold, D. Pavlov, Journal of Power Sources
92 2000. 92–101
change the carbon surface and its affinity to Pb / PbSO4
2. Carbon (with functional groups) changes crystal growth
rates in NAM
3. Carbon particles can influence crystal growth locally
(strong enough as to cause local el-lyte alkalization!),
and interact with expander molecules
D. Pavlov in Lead-Acid Batteries Science and Technology,
Elsevier, 2011, p.318. Like in the presence of expand
presence of carbon the rate of

growth in the NAM change

Carbon-accelerated water loss at high temperature: a post-DCA issue?
Two mechanisms of water loss:
1. Physico-chemical – evaporation (surface sensitive)
2. Electrochemical (hydrogen and oxygen evolution – surface sensitive)

How to measure hydrogen evolution and water loss? Equipment? Procedure? Standards?

P. Atanassova, Cabot Corp., Kloster Eberbach, Proceedings, January 2017

Carbon-accelerated water loss at high temperature: Why? When? How?
issue?
Testing, alerting, no standards
1) Lab test results of polarization, gas flow, gas composition 2)

Hydrogen
evolution
increasing
with DCA? 3)

Carbon producers have ways to suppress

Hydrogen evolution hydrogen evolution but keep DCA high 6)
depends on additives
and cell design 5)

Hydrogen evolution rate

can be controlled by carbon
production technology 4)
1) E. Karden, Ford, Kloster Eberbach, Proceedings, January 2017
2) D. Hosaka, Hitachi Chem., Kloster Eberbach, Proceedings, January 2017
 Studies still in initial stage.
3) J. Settelein, ISC-Fraunhofer, Kloster Eberbach, Proceedings, January 2017  No standards.
4) S. Frederic, EnerG2, Kloster Eberbach, Proceedings, January 2017
5) R. Aliberti, FIAMM, Kloster Eberbach, Proceedings, January 2017
 ALABC actively supporting this
6) P. Atanassova, Cabot Corp., Proceedings, January 2017 research program
 TEST RESULTS FROM A RECENT ALABC PROJECT (SOFIA)
 Hydrogen evolved on Pb surface (increased),
0.6

and on C surface (very high, can be modified)

SA by POR

25oC
| Negative plate overvoltage | / V

0.5

0.4
w/o Exp  Some carbons accelerate the reaction (HER)
 Graphite doesn’t accelerate the HER
0.3 w/o Carbon
0.5% CB M
2.0% CB M

 Smal effect at room temperature

0.2 0.5% CB H
2.0% CB H

 The effect increases at 40oC

0.1 0.5% CR E
25 C 2.0% CR E
o

 At 60oC probablhy the mechanism changes

0.0
1E-4 1E-3 0.01 0.1 1
| Current density | / A m
-2

60oC
0.6 0.6
SA by POR w/o Exp SA by POR

40oC
w/o Carbon

| Negative plate overvoltage | / V

0.5 0.5
| Negative plate overvoltage | / V

0.5% CB M
2.0% CB M
0.4 0.4 0.5% CB H
w/o Exp 2.0% CB H
0.3 w/o Carbon 0.3 0.5% CR E
0.5% CB M 2.0% CR E
2.0% CB M
0.2 0.5% CB H 0.2
2.0% CB H
0.1 0.5% CR E 0.1
2.0% CR E 60 C
o
40 C
o

0.0 0.0
1E-4 1E-3 0.01 0.1 1 1E-4 1E-3 0.01 0.1 1
| Current density | / A m | Current density | / A m
-2 -2
ENCOURAGING RESULTS FROM RECENT ALABC STUDIES (SOFIA)
0.55
Linear sweep voltammetry; 0.1 mV sec
-1

0.50
| Pb electrode overvoltage | / V
0.45

0.40

0.35 Blank
+ CB H
0.30 + CB M
Pb 99.99%; 1.28 g cm H2SO4 (Merck) + GR E
-3

0.25
1E-6 1E-5 1E-4 1E-3 0.01
| Current density | / mA cm
-2

Organic additives to the electrolyte suppress hydrogen

evolution, change the reaction mechanism
 Carbon Nano Tubes: One more promising carbon option (pos. & neg. plates)
Pre-dispersed CNT & charge polarization
Carbons Molecular Rebar
CNT

Formation, Ch. Acceptance 30%,

en. efficiency, c. life up to 30% 3)
4) xGnP graphene in the negative plate improve good for discharge power,
charge acceptance, CCA, no water loss (graphs to come)
5) Lead-Graphene alloys: current colelctors. light, low corrosion, confductive
Before a full model of the effect of macro/micro sized carbon to the NAM was developed, a new strong carbon option came on
stage – nano sized carbons. They promis – solely (or maybe in combination with other additives) – basic improvement of all
pereformance parameters: power, charge acceptance, CCA, HRPSoC and deep cycling life, now water loss
1) ALABC project data
2) A. Banerjee, B. Ziv, Y. Shilina, E. Levi, Sh. Luski, and D. Aurbach, Single-Wall Carbon Nanotube Doping in Lead-Acid Batteries: A New Horizon, ACS Applied Materials &
Interfaces, ACS Appl. Mater. Interfaces 2017, 9, 3634−3643
17 AsianSt.Battery
3) 3) Swogger,Conference,
P. Everill, D.P.Dubey,
Kuala N. Sugumaran, Discrete carbon
Lumpur, Malaysia, nanotubes19-22,
September increase2017
lead acid battery charge acceptance and performance, Journal of Power
4) 4) and 5) – XG Science and Chilwee presentation at ABC in San Francisco, June 2017, and Chilwee and L. Yolshina presentation at LABAT’ 2017 conference in Varna, Bulgaria
Carbon Nano Tubes: One more promising carbon option (pos. & neg. plates)

Adding Multi-Walled Carbon Nano Tubes (CNT) dispersions.

TEM showing 12 walls with average diameter of 12 nm and

variable length.

INITIAL RESULTS
• Unformed paste: reduced pore size & increased surface area (linear effect)
• No influence on the phase composition of the active material.
• CNT increase positive potential and delay the onset of gassing on formation.
• Increased initial capacity (lowering after cycling) but reduced charge acceptance
• No CNT observed in formed PAM by SEM, surface SSAnot affected by CNT
(CNT detected (Raman) before formation, not after)

Francisco Trinidad, Microstructure and electrochemical studies on carbon nano material additives for
positive active mass of industrial cells, LABAT, June 13 , 2017 Varna, Bulgaria
17 Asian Battery Conference, Kuala Lumpur, Malaysia, September 19-22, 2017
Other additives – glass micro fibers, TiO2
RESULTS OF RECENT ALABC STUDIES (BRNO)

with glass fiber with Titanium dioxide

 EFFECT OF IONIC ADDITIVES TO THE ELECTROLYTE

Beneficial effect of Mg ions

Ionic additives don’t have any They have a strong effect for MgSO4 over 0.5 wt. %
effect on discharge capacity on gassing and HRPSoC

Questions, theory needed, control possibilites

1. How do metal (and other) ions influence crystal growth and dissoplution in H2SO4 solution?
2. Which ions are good for the cell crystals, and which are bad?
 RECENT ALABC STUDIES (Sofia
Electrolyte concentration and P-to-N ratio are crucial for HRPSoC cycle life:

1.28 g/cm3
LOW ELECTROLYTE CONCENTRATION =
LONGER CYCLE LIFE

2P / 3N (POSITIVE LIMITED) CELLS =

LONGER CYCLE LIFE
1.32 g/cm3

2P / 3N 3P / 2N
Questions, theory needed, control possibilites
1. How does electrolyte concentration (pH) control cystal growth and dissolution?
2. Wht is the mechanism of the effect of P:N:(E) ratio on AM morphology and performance?
 Crystal nucleation, growth, dissolution: crystal lattice of PBSO4
Negative / positive plate performance determined by the microstructure of the active masses
The microstructure of NAM and PAM depends on electrolyte concentration and Me+ additives.
XRD: metal ions change the shape of PbSO4 crystals and their crystal lattice – why?

NAM, bulk,
Left: electrolyte without Me ions, right: with MgSO4
2P / 3N cells, 1.28 g/cm3

Questions, theory needed, control possibilities as final goal

1. PbSO4 can be in form of fine crystals, large oness or shapeless/amorphous mass. Oswald
ripening. Self supporting 3D structure in discharged NAM? In discharged PAM?
2. PbO2 particles have an amorphous PbO(OH)2 shell and crystalline a-PbO2 / b-PbO2 areas.
Equilibrium gel - crystal. PAM degradataion. Self supporting 3D structure? Capacitance?
3. Pb crystals can have different morphology, too. Self supporting 3D structure? Capacitance?
New materials promising fast and affordable optimization

1. New carbon and graphite technologies

2. New expansser materials
3. ZnO additives
4. LEIT external treatment
5. Surfactants
6. Glass fibers
7. Aluminum ions
8. Nano Structured RGO coated TiO2
9. Lead-Carbon composites
 New cell designs

1. The UltraBattery®: carbon high surface area negative plate,

2. ABC: bipolar, regular materials. 50Wh/kg, 900 W/kg, lower weight, longer cycle life.
3. ArcActive: carbon fibers negative grid, regular paste materials. DCA >1A/Ah, stable
during Ford tests.
4. Gridtential: Semiconductor technology, Si based current collectors, thin AM layers. 2
– 5 times longer cycle life, 50% less weight. 64 Wh/kg, 1400 W/kg, no thermal
runaway, $150/kWh
5. GO battery: low profile, regular materials. 1000 W/kg.
6. CEA: thin layer bipolar: 66 Wh/kg, 202Wh/L, 0.2 mm Ti foil current collector
Recharge

Problem
– Fast charge and partial recharge of high efficiency become vitally important
– Charge often designed by end users or by electric engineers
– Cycling profiles not optimized versus the processes in the battery and vs. cell design

Research and development

– ALABC studies showed the benefits of pulse charge
– Theoretical studies and models published recently
– The ALABC PSoC (portal cranes) study with Narada revealed huge potential for
cycle life improvement by re-charge philosophy optimization
 THANK YOU VERY MUCH

FOR YOUR KIND ATTENTION!

Boris Monahov
monahov@ila-lead.org