Producers of TEXEX® brand Negative Expanders

New expanders for new battery applications.

Start/Stop and HEV
(melchor7749@gmail.com)
4ª FENIBAT Londrina Sao Paulo 2019

Definition

 The term “Expanders” define a series of substances that added to the negative active material during
the mixing process, strongly modify their structural characteristics and their electrical performance in
the lead acid battery.

 The word Expander is derived from the fact that the inner structure of the negative AM is modified in the
sense of becoming more open and as a consequence more accessible to the acid and to the
development of electrochemical reactions of charge and discharge.

 Also they modify the process of crystallization of the lead sulphate generated during the discharge by
providing nucleation sites. In this way lead sulphate crystallize as numerous and small crystals more
prone to experiment electrochemical reaction
4ª FENIBAT Londrina Sao Paulo 2019

Expanders. Components

 The Expanders are composed of three main components

- Organic expander, a derivative from wood
- Inorganic expander, Barium sulphate
- Carbon black or graphite
 Their function in the battery is.
 Organic Expander. Modifies the deposition process of lead on Charge generating a more open structure.

 Barium sulphate. Due to its isomorphic crystal structure with the one of lead sulphate, it provides
nucleation sites for lead sulphate generating numerous and small crystals.

 Carbon black. It provides some extra conductivity to the negative plate when concentration of lead
sulphate becomes too high (High depth of discharge, high sulphation). An additional task is to provide a
dark grey color to the negative plate that helps to visually distinguish it form the positive
 4ª FENIBAT Londrina Sao Paulo 2019

Mechanism of action
Organic expander.
 The way in which organic expander actuates, is depicted in the following slide. Organic expander is
adsorbed in the surface of the lead, and the sites in which it adsorb, becomes unavailable for the lead
deposition during charge. Lead is only deposited on the sites not occupied by expander, which
generates a more open structure.

 On discharge solubilisation and oxidation of lead, takes place on the sites not covered by expander, but
the reduction of electrochemical area is compensated by the increase of SSA brought about by the use
of the expander.
4ª FENIBAT Londrina Sao Paulo 2019

Mechanism of action. Organic expander

I. Ban & co. YUASA

4ª FENIBAT Londrina Sao Paulo 2019

Orgánic expandes. Effects on battery performance

 1.- Organic expanders have a critical influence on battery performance especially on High Rate Low
Temperature discharges and on water loss
 2.- -Organic expanders, strongly increase negative plate polarization. The increase are in the range 0.15 – 0.25V
 3.-There is a correlation between dosage and SSA of negative active material
 4.- A strong positive influence on High Rate Low Temperature discharges. The maximum positive influence
occur at dosages in the range 0.15 – 0.30 %. Above this limit normally there is a decrease
 5.- Charge acceptance is strongly negatively affected, being the effect more marked as the dosage increase.
This fact can be overcome by the use of carbon and graphite
 6.- Decrease of Charge Acceptance, is a consequence of the coverage of part of the negative AM by the
expander. This reduce the electrochemical reaction area and as a consequence the plate polarization
increases.
 7.- Organic expanders markedly reduce water consumption, because they reduce hydrogen evolution on the
negative plate. This fact is again a consequence of the increase of negative plate polarization
 8.- The effects of organic expander and carbon on Charge Acceptance and water consumption are opposite.
Organic expanders tend to reduce it, whereas carbon tend to increase. This fact open the possibility of
controlling them by using the right ratio of organic expander/Carbon
4ª FENIBAT Londrina Sao Paulo 2019

Organic expanders. Effect on High Rate Low

Temperature Discharges
4ª FENIBAT Londrina Sao Paulo 2019

Organic expanders. Effect on Charge acceptance

4ª FENIBAT Londrina Sao Paulo 2019

Barium sulphate

 The main effect of Barium sulphate as already mentioned, is to act as nucleation site for the
crystallization of lead sulphate, due to the isomorphism between the crystals of both compounds.

 This fact decrease the concentration of divalent lead ions generated during the discharge and
consequently the polarization developed by the increase of concentration of oxidized Pb+2 . This fact
increase the efficiency of the discharge reaction.

 In summary, both Charge and discharge reactions are more effective

Carbon for EFB batteries.
Start/Stop applications
4ª FENIBAT Londrina Sao Paulo 2019

Carbon and Graphite

Mechanisms of action
 Several mechanisms of action of carbon in the negative AM have been proposed. Among them are:
- Increase electrical conductivity
- Modification of lead sulphate crystallization
- Modification of TAFEL characteristics
- Development of supercapacitor effect
- Electrochemical activity of carbon
- Electroosmotic pumping
- Nucleation sites for lead sulphate crystallization
 Taking into account the information from the huge amount of work done with carbon and graphite, the
most probable mechanisms are:
- Increase electrical conductivity.
- Increase of negative AM reaction area
- Modification of lead sulphate crystallization
- Development of supercapacitor effect.
- Modification of lead sulphate distribution
4ª FENIBAT Londrina Sao Paulo 2019

Electrical Conductivity of Negative AM

4ª FENIBAT Londrina Sao Paulo 2019

Electrical Conductivity of Negative AM

 The previous slide, shows the modification of the electrical resistivity of the negative active material
when different carbon and graphites are added.

 There is a Sharp decrease of the resistivity when carbon and graphite are added in percentages ranging
from 1 to 2%. Percolation values are in this range for most part of carbons

 The decrease is dependent on the electrical conductivity of the added carbon. Expanded graphites and
conductive carbon blacks are more effective for increasing the conductivity of negative AM
Increase of SSA of Negative AM
4ª FENIBAT Londrina Sao Paulo 2019

Water consumption
TAFEL Lines

10.000

Current Density/mA/cm2

1.000
-0.4000 -0.3500 -0.3000 -0.2500 -0.2000 -0.1500 -0.1000 -0.0500 0.0000 0.0500 0.1000 0.1500 0.2000 0.2500 0.3000

0.100

0.010
Overpotential/V

2% PBX 42 Standard 2% PBX 09 Sulphonated 2% PBX 33

2%PBX 51 Average Positive Potential 2% BP2000 2% PBX70
2% PBX09 2% ENSACO 2% BP2000 Dispersed 1% PBX51
 4ª FENIBAT Londrina Sao Paulo 2019

EPMA analysis of Batch 1 (control)

Inside Middle Outside

Dense
Top PbSO4

Trace
PbSO4
Bottom

EXIDE Technologies
 4ª FENIBAT Londrina Sao Paulo 2019

EPMA analysis of Batch 6 (with Graphite)

Inside Middle Outside

Top Dense
PbSO4

Trace
PbSO4
Bottom

EXIDE Technologies
4ª FENIBAT Londrina Sao Paulo 2019

Modification of Lead Sulphate distribution

 The previous two slides, shows how the lead sulphate distribution is affected by the addition of carbon
and graphite.

 On batch 1 (Control) the lead sulphate generated on discharge, is located in the outer side of the plate in
which it form a very dense layer that clog the pores and inhibit the acid diffusion to the interior of the
plate and consequently stop the electrochemical reactions.

 On batch 6 with graphite addition lead sulphate still exist, but it is evenly distributed over all the
thickness of the plate. There is not clogging of the pores of active material and consequently Charge and
discharge reactions proceed in more extent
4ª FENIBAT Londrina Sao Paulo 2019

Supercapacitor effect

350

300

40% SOC

250
Charge current (A)

20%SO
60%
SOC
200

150

80% SOC

100

Standard batch
50
2%CB250m2/g+1%EG-1
2%CB770m2/g+1%EG-1
Standard+supercap
0
1 3 5 7 9 11 13 15 17 19

Time (s)
4ª FENIBAT Londrina Sao Paulo 2019

Supercapacitor effect

 One of the most desirable effect of the carbon and graphite on negative AM, would be to provide the
supercapacitor effect.

 If carbon bring supercapacitor effect, the high initial peaks of power of the regenerative braking energy,
could be taken by the supercapacitor and the rest of lower power, by the active material.

 Comparing the shape and absolute values of the curves of the formulations with carbon with the
standard, we can see that the initial peak markedly increases. This initial peak is related with the
supercapacitor effect, and hence some degree of supercapacitance is provided by carbon
4ª FENIBAT Londrina Sao Paulo 2019

Increase of Charge acceptance

4ª FENIBAT Londrina Sao Paulo 2019

Increase of Charge acceptance

4ª FENIBAT Londrina Sao Paulo 2019

Modules 6V/12Ah.
Charge acceptance W/Kg. 8V, 25ºC,
1000
927.0
GEN 0 (2% CB L6+1% EG-1)
900 GEN 1 (1.5% EG-1) 871.0
852.0
GEN 2 (1.5% EG-1)
800
GEN 2.1 (2% CB L6+1% EG-1) 750.3
727.8
GEN 2.1 1,5% High Conductive Carbon
Charge acceptance (W/Kg)

700 657.7

600
534.0
491.7 499.0
500 470.0

400 380.0
361.0
329.0
300 260.0 271.0
233.0
199.0
200
152.0
136 % 130.0
100 75.0

0
80 60 40 20

SoC (%)
4ª FENIBAT Londrina Sao Paulo 2019

Increase of Charge acceptance

 The previous graphs shows the strong effect of carbon and graphite on the battery charged acceptance.

 The most important characteristic of carbon with respect to charge acceptance is the Specific Surface
Area. The higher the SSA, the higher the charge acceptance will be. This fact has been confirmed
unambiguously in a lot of tests.

 The SSA of the added carbon determine the degree of the negative AM modification. The higher the SSA
of carbon, the higher the SSA of negative AM.

 SSA increase result in a decrease of the polarization on negative plate on charge and consequently an
increase of charge acceptance.

 The increases are spectacular. Increases of the order of 200 – 300% are achieved, which allow to obtain
values close to 1000W/Kg battery similar to the ones of Ni/Mh batteriesm.
4ª FENIBAT Londrina Sao Paulo 2019

Cycle life tests

Power Assist Test at 60% SOC (2.5% DOD)
7

6
End of Discharge Voltage / V

4
EG-1

3 EG-2
EG-3

2 EG-1+CCB
SG

1
0 50000 100000 150000 200000
Cycle Nº
4ª FENIBAT Londrina Sao Paulo 2019

Cycle life tests

4ª FENIBAT Londrina Sao Paulo 2019

Cycle life tests

 The addition of special carbons and graphites, have bring spectacular increases of the cycle life of the
lead acid battery.

 The cycle life of the standard negative formulation is around 80.000 cycles according to the Power
Assist Cycling of the EUCAR specification.

 When conductive graphite is added like ABG 1010, the life increase to 200.000 cycles a more that twofold
increase.

 For special high conductive carbon addition, there is a further increase to 300.000 as shown in last
slide. This figure according to the specification, is equivalent to the same number of Km on real use, and
close to the one of Ni/Mh batteries. This fact open the possibility of trying to use the lead acid battery for
Mild and full hybrid vehicles
4ª FENIBAT Londrina Sao Paulo 2019

Preblended mix

 Expender mix, can be prepared in different ways.

• - By battery Company. The individual components added as solid.
• - By battery Company and added as a slurry
• - By specialized Companies.
•
 The later case correspond to Preblended mix, and this way of preparation has
the following characteristics
• - The three components are milled and completely mixed for 1hour
• - They are packaged on individual bags with the required quantity for one
paste mix according to costumer request
•
4ª FENIBAT Londrina Sao Paulo 2019

Preblended mix. Advantages

Preblended mix, have the following characteristics.

 Complete uniformity. The three components are milled and totally mixed for 1 hour.

 They are delivered on individual bags with the weight corresponding to one paste mix.

 Weight of individual bags is according to costumer requirements.

 Possible errors related with the weighting of individual components and the harmful
consequences on the battery, are eliminated.

 Cost saving, due to high productivity of specialized Companies as well as their purchasing scale.

 Previous advantages should move battery Companies to consider ordering expander mix as
preblended through specialized Companies
4ª FENIBAT Londrina Sao Paulo 2019

Preblended mix. APG Products

•
• Expanders for SLI Batteries
• - TEXEX SLI – B
• - TEXEX SLI – SA
• - TEXEX SLI - A
• Expanders for Motive Power
• - TEXEX IND – A
• - TEXEX IND – 9090
• Expanders for Standby Power
• - TEXEX IND – SE
• - TEXEX IND – SBP
• Expanders for advanced batteries
• - CXEFB-A
• - CXEFB-B
• - CXEFB-C
• - CXAGM-A
• - CXAGM-B
• - CXAGM-C
4ª FENIBAT Londrina Sao Paulo 2019

Producers of TEXEX® brand Negative Expanders

Thanks for your attention

(melchor.Fernandez@atomizedproductsgroup.com)

Visit us at booth 93