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addiBatt™ - tetra L2 A New Approach to Tetrabasic Cured Positive Plates The idea of
addiBatt™ - tetra L2 A New Approach to Tetrabasic Cured Positive Plates The idea of

addiBatt™ - tetra L2

A New Approach to Tetrabasic Cured Positive Plates

The idea of ‘seeding’ the tetra-basic lead sulphate crystals as a means to control the growth of these crystals is a well known technology. The principle is to add a powdered tetra-basic lead sulphate crystal to the paste in the paste mixer. In this way a number of crystal seed sites are created. This leads to a large number of relatively even sized tetra-basic lead sulphate crystals.

Addenda have worked with many battery companies world-wide in applying this powerful technology. The following information describes some of the lessons learned in applying seeding technology. This technology has proceeded from a research and development product into a standard additive for many battery producers.

Performance Advantages

Tetra basic cured active material seeded with addiBatt™ - tetra L2 additive delivers improvements for the battery performance in terms of:

Cold Cranking Amps (CCA) Battery life time Charge Acceptance Capacity

In the past it was not common to cure to tetrabasic lead sulphate crystals, because the crystal size could not be controlled at higher temperatures and lead to longer formation times and higher energy consumption during the formation process. Only the use of seeding crystals like addiBatt™ - tetra L2 gave the possibility to control the crystal size. Today addiBatt™ - tetra L2 is the most efficient additive available on the market that helps to control the size of tetrabasic lead sulphate crystals during the curing operation.

add iBatt™ - tetra L2 Application Recommendations Add addiBatt™ - tetra L2 to the leady
add iBatt™ - tetra L2 Application Recommendations Add addiBatt™ - tetra L2 to the leady

addiBatt™ - tetra L2

Application Recommendations

Add addiBatt™- tetra L2 to the leady oxide in the paste mixer before starting the acid addition

Suggested Manufacturing Methods

-0.5 to 3 % addiBatt™ - tetra L2 to the leady oxide

standard SLI applications 1 1.5 % are recommended

-High temperature (>70°C) paste mixing

-High temperature (>70°C) high humidity (>95%) curing ovens Alternative curing method -1 h steaming of plates in stacks at > 80°C / high humidity

The tetrabasic curing is the most beneficial way to cure and improves paste grid adherence for less corrosive grid alloys (eg. PbSnCa) Improves process performance and reduces rejection rates within the process With experience, small changes in the recipe (e.g. acid: oxide ratio) can be introduced to maximize the benefits

addiBatt™ - tetra L2 Past History of Tetrabasic Cured Positive Plates The formation of a
addiBatt™ - tetra L2 Past History of Tetrabasic Cured Positive Plates The formation of a

addiBatt™ - tetra L2

Past History of Tetrabasic Cured Positive Plates

The formation of a homogenous tetra-basic sulphate crystal structure in the positive plates of lead-acid batteries is well known to offer significant electrochemical improvements in battery performance in respect of improved cycling and battery life.

A number of methods for controlling the tetra-basic lead sulphate crystals are

also well known in the literature. Simply heating the pasted plates during curing

to more than 70 degC, for example will generate a significant tetra-basic crystal

structure although with a wide ranging crystal size distribution, sizes of more than 50 microns are common.

Another method uses the control of the temperature-time profile in the paste mixer to generate a tetra-basic lead sulphate structure. This method makes it difficult to control crystal structure and size.

One significant issue in creating the tetra-basic structure is to control the crystal size distribution. Tetra-basic crystals, in comparison to tri-basic crystals, are much harder to create. As the lead sulphate crystals develop there may be a limited number of developing crystal seed sites due to a higher activation energy compared to tri-basic and hence it is common to produce a relatively wide distribution across a plate with a number of very large crystals. These larger tetra-basic crystals lead to problems in the later formation / charging of the plates as evidenced by increased specific energy consumption and extended formation times when compared to tri-basic active materials.

addiBatt™ - tetra L2 Large Scale Trials and Establishment of addiBatt-tetra-L2 as a Standard Additive
addiBatt™ - tetra L2 Large Scale Trials and Establishment of addiBatt-tetra-L2 as a Standard Additive

addiBatt™ - tetra L2

Large Scale Trials and Establishment of addiBatt-tetra-L2 as a Standard Additive

Over the past 3 years more than 30 full-scale plant trials for starter and industrial batteries have been carried out across Europe, South America, United States and Asia. As a result of these many trials there have been a number of areas where improvements in the application of tetra-basic seeding have been made.

Paste Mixer

addiBatt-tetra-L is best added after the oxide and water but before the acid addition. Add the addiBatt-tetra-L directly to the oxide mixture. Allowing one or two minutes of mixing before the acid addition will produce a homogeneous distribution. Add acid to the paste mixer according to past practices.

One area to watch for is over-filling of the paste mixer and general poor paste mixing. It has been noted in some cases that efforts to improve the productivity have lead to increased batch sizes in the mixer leading to some mixing problems that finally can result in greater batch-to-batch variations of the paste plasticity and the paste density values.

Also it has been noticed that very often in the paste recipe the acid-oxide ratio has been reduced to minimize the possibility of temperature spikes in the paste mixer. These temperature spikes can lead to uncontrolled tetra-basic crystal formation. With addiBatt-tetra-L this is no longer such a problem and it is common to increase acid-oxide ratios from 6 or 7 liters per 100kg lead oxide up to 8 or 10 liters per 100kg lead oxide giving higher porosity values for the paste and obviously reduces the work in the formation section. But these changes have to fit into the electrical characteristics of the battery produced.

Curing and Drying First plant trials with addiBatt-tetra-L are usually without any changes to the
Curing and Drying First plant trials with addiBatt-tetra-L are usually without any changes to the

Curing and Drying

First plant trials with addiBatt-tetra-L are usually without any changes to the existing process. This establishes a base case or reference for further developments. A number of issues have been identified with many current curing processes. With large curing chambers, the pallets holding the plates can take a full day to load. During this period a general loading temperature-humidity profile, in most cases the same as for the curing operation is used. However, due to the opening and closing of the doors and the movements of the pallets the actual conditions inside the chamber can vary significantly. The actual temperature-humidity profile experienced by the first pallets is very different to the last pallet loaded. Likewise it can be observed that the free lead in the paste can start an exothermic reaction and can sometimes dry out the plates especially if the more reactive mill oxides are used. During trials, small data-loggers were used to check the actual temperature- humidity at several points across the chamber and usually within a stack of plates. In many cases it is noticed that the conditions in the chambers are very variable. This is often due to poor air circulation within the chamber. Care must be taken to correct deficiencies in the curing ovens

Current Curing Deficiencies

-Use of big sized chambers without steam -Temperature and humidity are hard to control -Long loading times lead to dryout effects and gave bad lead reduction

-Bad grid/paste adhesion for “anticorrosive“ grids (Pb/Ca/Sb,,

-Long curing and drying processes (24 36 h for curing; 24 48 h for

)

drying)

addiBatt-tetra-L treated plates in general are better able to cope with the above mentioned problems in the curing chamber. However, it has been found that curing at temperatures of more than 70 degC on the plates leads to a very well developed tetra-basic crystal structure and helps to improve the adherence of the paste on the grid, especially if the more corrosion resistant lead alloys are in use. Thereafter, the plates are less sensitive to the secondary curing that was implemented to speed up the free lead reduction. It has also found to be important to have a good air circulation during the final drying to ensure the reaction of the small parts of residual free lead.

Advantages of Steam or High Temperature Curing -Use of smaller sized chambers -Easy control of
Advantages of Steam or High Temperature Curing -Use of smaller sized chambers -Easy control of

Advantages of Steam or High Temperature Curing

-Use of smaller sized chambers -Easy control of temperature and humidity -Shorter loading times -Shorter curing times give an increase of curing capacity -Improved paste/grid adhesion for all types of grids -Important for neg. plates to improve porosity by use of addiBatt™ - tetra

L2

Formation

addiBatt-tetra-L has been used in a number of different formation processes like air cooled; water bath; acid recirculation. In general addiBatt-tetra-L has shown very positive effects due to the very much improved porosity of the plates. In general, addiBatt-tetra-L provides much deeper pores allowing a much better contact between the acid and the active material. Thanks to the smaller sized tetra basic crystals the active material does not need so many resting periods during the formation to allow the active material to relax. This was more important for the large sized tetra basic crystals to prevent a reduction in the paste-grid adhesion.

Plate Mass Reductions

Once a good level of confidence has been established in the application of addiBatt-tetra-L the next step is to look at reducing the quantity of the active mass on the positive plate. The significantly improved porosity of the plates means that much more of the active mass is taking part in the electrochemical process. The active mass is reduced by small changes in the paste recipe to reduce the paste density for example from 4.2 kg/liter to 4.0 kg/liter by changing the acid/oxide ratio as previously mentioned.

The combined effect of a homogenous crystal structure with a uniform and high porosity with good penetration of the acid into the active material provides an excellent positive plate for the lead-acid battery.

Customer Trials and Production Process Development Customer trials with addiBatt-tetra-L very quickly showed benefits in
Customer Trials and Production Process Development Customer trials with addiBatt-tetra-L very quickly showed benefits in

Customer Trials and Production Process Development

Customer trials with addiBatt-tetra-L very quickly showed benefits in the curing and formation in positive plate production related to process time reductions and energy savings.

These trials showed for example that using a high temperature high humidity curing for gravity casted grids produced a very homogeneous tetra-basic crystal structure. The excellent tetra basic crystal structure had no crystals bigger than 15 microns and achieved good paste porosity

This lead to significant reductions in curing and formation times when compared to plates with larger uncontrolled tetra-basic crystals

The addiBatt-tetra-L2 was added to displace varying amounts of the lead oxide in the batch. The final crystal size of the plates can be controlled easily by the amount of addiBatt-tetra-L added to the paste batch as shown in the following images:

no addiBatt™ - tetra L2

as shown in the following images: no addiBatt™ - tetra L2 +1 % addiBatt™ - tetra

+1 % addiBatt™ - tetra L2

no addiBatt™ - tetra L2 +1 % addiBatt™ - tetra L2 +0.5% addiBatt™ - tetra L2

+0.5% addiBatt™ - tetra L2

no addiBatt™ - tetra L2 +1 % addiBatt™ - tetra L2 +0.5% addiBatt™ - tetra L2

+3 % addiBatt™ -tetra L2

no addiBatt™ - tetra L2 +1 % addiBatt™ - tetra L2 +0.5% addiBatt™ - tetra L2
addiBatt™ - tetra L2 Benefits of using addiBatt™ - tetra L2 in Positive Plates Process
addiBatt™ - tetra L2 Benefits of using addiBatt™ - tetra L2 in Positive Plates Process

addiBatt™ - tetra L2

Benefits of using addiBatt™ - tetra L2 in Positive Plates

Process improvements and cost savings

-40-60% reduction in curing times

-Less Time and Energy used for Formation of Tetra Basic cured Plates

-No Limitation for Batch Mixing Temperatures

-Plate Mass Reductions

Performance improvements

-Improved porosity-------------------------Cold Cranking Amps -Small uniform particles-------------------Capacity -Less internal resistance------------------Charge Acceptance -Greater grid adhesion---------------------Longer Lifetime