VRLA Batteries (Valve Regulated Pb-acid Batteries)

Pb–acid cells ( conventional flooded/wet cell) :

Consist of two plates of lead, which serve as electrodes, suspended in an electrolyte consisting
of diluted sulfuric acid.
Charging current must be adjusted to match the ability of the battery to absorb the energy.
If the charging current is too great, electrolysis will occur, decomposing water into hydrogen and
oxygen, in addition to the intended conversion of lead sulfate and water into lead dioxide, lead,
and sulfuric acid (reverse of the discharge process).
VRLA Batteries
Standard lead-acid batteries employ Lead-alloys as plates in the form of bars ( Calcium or
Magnesium are used to make the alloy). These are placed being dipped inside the liquid electrolyte
and electron exchange takes place by direct contact between the electrolyte and the plates.
The valve regulated lead–acid (VRLA) battery have the same chemistry, except the electrolyte is
immobilized.
A limited amount of electrolyte ("starved" electrolyte) absorbed in a plate separator or formed into a
gel; proportioning of the negative and positive plates so that oxygen recombination is facilitated
within the cell.
Under normal operating conditions the gases can recombine within the battery itself, sometimes with
the help of a catalyst, and no additional electrolyte is needed.
Each cell has a pressure relief valve which will activate when the battery starts building pressure of
hydrogen gas, generally a result of being recharged.
In contrast to the flooded Pb-acid batteries, VRLA batteries retain generated gases within the battery
as long as the pressure remains within safe levels.
If the pressure exceeds safety limits, safety valves open to allow the excess gases to escape, and in
doing so regulate the pressure back to safe levels (hence "valve regulated" battery).
Two types of VRLA batteries: Gel cell (gel battery) and absorbent glass mat (AGM) cell batteries.
Also called VRSLAB (Valve Regulated Sealed Lead-Acid Battery)
Gel cell (gel battery):
Contains a mixture of H2SO4 and finely divided silica. Mixture forms a thick paste or gel, which
makes the resulting mass gel like immobile ( so named - Gel Cell).
Chemically the same as wet (non sealed) batteries except that the antimony in the lead plates is
replaced by calcium, and gas recombination can take place.
Positive plates may be flat or tubular. Unlike a flooded wet cell lead–acid battery, these batteries do
not need to be kept upright.
Gel batteries reduce the electrolyte evaporation, spillage (and subsequent corrosion problems)
common to the wet cell battery, and boast greater resistance to shock and vibration.

Absorbent Glass Mat (AGM) battery:

Each cell of the battery has two pure thin lead plates- positive electrode and negative
electrode.
In between the lead plates, there is an AGM separator. It holds and absorbs the liquid
electrolyte.
AGM separator : thin ultra-fine fiberglass mat sandwiched between the plates that are saturated with
battery acid to about 95% of what they can hold the electrolyte (non-spillable) and separates the
plates.
Very thin glass fibers are woven into a mat to increase the surface area enough to hold a sufficient
amount of electrolyte on the cells for their lifetime. The fibers that compose the fine glass mat do not
absorb and are not affected by the acidic electrolyte.

The plates and mats are packed fairly tight, they are almost immune to vibration. All these are
highly compressed and closely packed to each other. It acts as a single cell with two
terminals. The outermost side of the plates has grids.
The plates in an AGM battery may be of any shape. Some are flat, whereas others are bent or rolled.
Both deep cycle and starting type of AGM batteries, are built into a rectangular case.

There are six cells that are interconnected to each other in a series connection.

Battery Internal Resistance Losses:

Internal resistance of a battery denotes its overall charge/discharge efficiency; batteries tend to get
warm or heated (hence, losses) while charged or discharged. Delivering deliver high currents
without significant drops in voltage, is a measure of the quality of the components and construction.

In standard flooded Lead-Acid batteries, internal resistance is usually around 10% to 15% for a new
battery, and can be as high as 25%+ for older batteries…. depending mainly on the age and quality of
the battery.

Gel batteries are better at approximately 12% to 16% internal resistance so would require around 115
amp-hours of charge for every 100 amp-hours used.

AGM batteries are usually having the lowest internal resistance - only 2% in a new battery and low
self-discharge rates. This allows the batteries to be charged much faster if needed and the ability to
deliver higher currents when required.
Advantages and Disadvantages of both types of VRLA batteries:
The gel provides a better means of heat conduction from the plates to the cell walls than in AGM
batteries. Since the heat produced on overcharge is lost more efficiently, they are suitable for deep
cycle applications.
AGM batteries, on the other hand, offer fastest charging rate, offer long service life.
The term "maintenance free" is a misnomer as VRLA batteries still require cleaning and regular
functional testing. They are not permanently sealed, but are designated to be maintenance free.
AGM automobile batteries are typically about twice the price of flooded-cell batteries; gel batteries as
much as five times the price.
Because of calcium added to its plates to reduce water loss, a sealed AGM or gel battery recharges
more quickly than a flooded lead–acid battery of either VRLA or conventional design.
AGM battery should never be opened as this would damage the battery with additional O2 from the
air.

VRLA batteries vs. Wet cell/ flooded Pb-acid batteries:

1) Have shorter recharge time than flooded lead–acid batteries because of calcium added to
its plates to reduce water loss.
2) Cannot tolerate overcharging: overcharging leads to premature failure.
3) Discharge significantly less hydrogen gas.
4) AGM batteries are by nature, safer for the environment, and safer to use.
5) VRLA batteries can be used or positioned in any orientation and do not require constant
maintenance.
6) In contrast to the flooded Pb-acid batteries, VRLA batteries retain generated gases within
the battery as long as the pressure remains within safe levels.
7) VRLA batteries are more vulnerable to thermal runaway during abusive charging. The
electrolyte cannot be tested by hydrometer to diagnose improper charging that can reduce
battery life.
8) The VRLA battery can be mounted in any position.
9) To ensure maximum life, a flooded lead–acid battery should be fully recharged as soon
after a discharge cycle as possibcklle to prevent sulfation.
10) Because of calcium added to its plates to reduce water loss, a sealed AGM or gel battery
recharges more quiy than a flooded lead–acid battery of either VRLA or conventional
design.
11) Compared to flooded batteries, The electrolyte cannot be tested by hydrometer to
diagnose improper charging that can reduce battery life.
12) For VRLA batteries, Lead–calcium alloys harden extremely rapidly; 80% of the ultimate
strength is reached in one day and virtually full ageing in seven days. Such rapid hardening
enhances grid handling and battery production.
13) Alloying with Sn or Al in lead-calcium grids produces even better lead acid batteries since
Sn and Al improve castability, mechanical properties, and electrochemical interactions
during battery charging and discharging, and inhibit corrosion; effects of high tin on
positive-grid corrosion in VRLA batteries improves the cycle-life and capacity.
Applications of VRLA Batteries
Modern motorcycles and all-terrain vehicles (ATVs) use AGM batteries to reduce likelihood of acid
spilling during cornering, vibration, or after accidents, and for packaging reasons. Due to the higher
manufacturing costs, currently used on specific vehicles.
VRLA batteries are used extensively in power wheelchairs, as the extremely low gas and acid output
makes them much safer for indoor use.
As vehicles become heavier and equipped with more electronic devices such as navigation
and stability control, AGM batteries are being employed to lower vehicle weight and provide better
electrical reliability compared with flooded lead–acid batteries.
5 series BMWs from March 2007 incorporate AGM batteries in conjunction with devices for
recovering brake energy using regenerative braking and computer control to ensure the alternator
charges the battery when the car is decelerating. Vehicles used in auto racing may use AGM
batteries due to their vibration resistance.
Deep-cycle AGMs are also commonly used in off-grid solar power and wind power installations as
an energy storage bank and in large-scale amateur robotics. AGM batteries are routinely chosen for
remote sensors such as ice monitoring stations in the Arctic. AGM batteries, due to their lack of free
electrolyte, will not crack and leak in these cold environments.
VRLA batteries are used in the uninterruptible power supply (UPS) as a backup when the electrical
power goes off.
VRLA batteries are the standard power source in sailplanes, due to their ability to withstand a variety
of flight attitudes and a relatively large ambient temperature range with no adverse effects. However,
charging regimes must be adapted with varying temperature.
VRLA batteries are used in the US Nuclear Submarine fleet, due to their power density, elimination
of gassing, reduced maintenance, and enhanced safety.
AGM and gel-cell batteries are also used for recreational marine purposes, with AGM being more
commonly available.
Comparison
Flooded cell lower costs per kWh.
In a gel battery, the volume of free electrolyte that could be released on damage to the case or
venting is very small. There is no need (or ability) to check the level of electrolyte or to top up water
lost due to electrolysis, thus reducing inspection and maintenance requirements.
Wet-cell batteries can be maintained by a self-watering system or by topping up every three months.
The requirement to add distilled water is normally caused by overcharging.
All lead–acid batteries require a relatively long recharge cycle time arising from an inherent three-
stage charging process: bulk charge, absorption charge, and (maintenance) float charge stages. All
lead–acid batteries are quick to bulk charge to about 70% of capacity during which the battery will
accept a large current input, determined at a voltage setpoint, within a few hours (with a charge
source capable of supplying the design C-rate bulk stage current for a given Ah battery).
However, they then require a longer time spent in the current-tapering off intermediate absorption
charge stage after the initial bulk charge, when the LA battery charge acceptance rate gradually
reduces, and the battery will not accept a higher C-rate. When the absorption stage voltage setpoint
is reached (and charge current has tapered off), the charger switches to a float voltage setpoint at a
very low C-rate to maintain the battery's fully charged state indefinitely (the float stage offsets the
battery's normal self-discharge over time).
To ensure maximum life, a lead–acid battery should be fully recharged as soon after a discharge
cycle as possible to prevent sulfation, and kept at a full charge level by a float source when stored or
idle (or stored dry new from the factory, an uncommon practice today).
This valve regulated lead-acid battery range has a design life of 20 years at 27°C under ideal float
condition. The capacity of these batteries ranges from 200Ah to 6000 Ah at 27°C down to 1.75 VPC.
The operating temperature range is -5°C to 40°C. These batteries give 1800 cycles at 50% DOD.

Separator
The building blocks of a battery are the cathode and anode, and these two electrodes
are isolated by a separator. Separators are microporous diaphragms placed between the negative
and positive plates of lead-acid batteries to prevent any contact between them to avoid internal short
circuit but at the same time allow free circulation of the electrolyte.

The separator is moistened with electrolyte and forms a catalyst that promotes the
movement of ions freely from cathode to anode on charge and in reverse on discharge.

Although ions pass freely between the electrodes, the separator is an isolator with no
electrical conductivity. The small amount of current that may pass through the separator
is self-discharge and this is present in all batteries to varying degrees.

In the maintenance-free lead acid, the electrolyte is absorbed into a porous separator
that is compressed against the electrodes to achieve chemical reaction.

Early separators were made of rubber, glass fiber mat, cellulose and polyethylene
plastic. Nickel-based batteries use separators of porous polyolefin films, nylon or
cellophane.

Commercially available Li-ion cells use polyolefin as a separator

The absorbed glass mat (AGM) in the sealed lead acid version uses a fiberglass mat or
an ultra thin glass mat as a separator that is soaked in sulfuric acid.

The earlier gel lead acid converts the liquid electrolyte into a semi-stiff paste by mixing
the sulfuric acid with a silica-gelling agent. Synthetic wood-pulp (SWP) separators used
widely.

Separator for VRLA: Non-woven glass fiber fabric with high oxidation and heat
resistance offers superior electrolyte absorption and satisfactory ion retention and
conductivity.
Additives in the Negative Plates
Additives: to reduce lead sulfate build-up on plates and improve battery condition when
added to the electrolyte of a vented lead–acid battery.

VRLA batteries in HEV applications are often charged and discharged with high
currents for a short period. As VRLA batteries could be charged only while the HEV are
braking, they are usually operated at an intermediate state of charge (SoC) of 50%-
53%.

Batteries are charged at high rates/intensity by regenerative braking and discharged at

high rates when the vehicle accelerates. Because the batteries are charged. Therefore,
VRLA batteries are operated in high-rate partial-state-of-charge (HRPSoC)
conditions, which is relevant to HEV.

The SoC of the battery cannot be below 30%,as it will not have enough power to start
the engine; on the other hand, too high SoC lowers the charge acceptance during
braking. Additionally, charging with the high current favors hydrogen generation, which
further lowers the charge acceptance.

In the operating conditions, the charge acceptance of the negative plates is limited;
PbSO4 particles are formed during the discharge process, and cannot be converted to
Pb completely in the subsequent charge process, which leaves a portion of PbSO4 in
the negative active materials and results in the accumulation of PbSO4 in the negative
plates.

An electrochemically passive film of lead sulfate is formed on the surface of the

Negative plates. This film cannot be reduced to lead by conventional recovery cycling,
and it becomes thicker with further cycling and causes a progressive reduction of
capacity leading to premature failure. This is accompanied by higher internal resistance
and cell dry out. The battery life is limited by the negative electrode, and cyclic life of
VRLA batteries is shortened .

This phenomenon does not occur in the positive plate.

Addition of additives to the negative activated materials (Additives to negative

active mass (NAM), the so-called Expanders) of VRLA batteries such as graphite,
carbon black, barium sulfate, activated carbon, poly-aspartic acid, etc. are
employed as inhibitors of PbSO4 recrystallization to extend the cycle life of VRLA
batteries in high-rate, partial state-of-charge cycling applications, such as hybrid electric
vehicles.

The positive active mass(PAM) additions are generally less beneficial than the negative
ones, and are less researched, not in wide Spread use. They had not shown positive
influence as in the case of the negative mass.
Active Mass:
Most plates are currently composed of the lead alloy current collector and active mass
(negative or positive) pasted into it. The amount of high-surface-area carbons in the
negative paste mix reduces sulfation, and the electrochemical processes of lead
oxidation or reduction occur in this paste during the battery operation.

Contemporary active masses contain not only lead paste but also additives, which
improve their properties during the battery operation.

One of the most widely used additives to negative mass is carbon (in different
forms), such as graphite or carbon black. It can also be used in positive pastes,
but with lesser beneficial effects.

Carbon also increases the conductivity of the negative plate and may add capacitance,
and it reduces cell heating on overcharge. These effects all contribute to increased
cycle life for VRLA batteries. The carbon additive represents less than a quarter of the
mass of the expander, and leads to insignificant cost escalation of the batteries.

The use of graphene as a negative additive for VRLA batteries in the negative active
materials also decreases the charge cut-off voltage and increases the discharge cut-off
voltage in HRPSoC cycling, and the cycle life was greatly improved as compared to the
electrodes without adding graphene.

[ Graphene is a single layer (monolayer) of carbon atoms, tightly bound in a hexagonal

honeycomb lattice. Layers of graphene stacked on top of each other form graphite. ]

The cut-off charging voltages of batteries are different and vary from 2.2 V to 2.9 V( 2.4v
for VRLA, 2.25V for float) , and the cut-off discharging voltages vary from 1.6 V to 2.0 V
(1.75V for VRLA).

Today, three main mechanisms are assumed to be responsible for the beneficial effects
of carbon addition. Firstly, carbon additives can increase the electroactive surface of an
electrode and increase the rate of the electrochemical processes. Secondly, the
additives can physically restrict the growth of the sulfate crystals and facilitate the
formation of small, isolated crystals. Finally, carbon can increase the amount of the
energy that can be stored in the electrical double layer.

EXPANDER Material:

It is common practice to add expander material to the negative plates of lead acid
storage batteries to prevent contraction on solidication on the spongy lead and the
consequent loss of capacity and life of the finished battery.

These expanders are normally added to the negative paste material in very small
amounts, usually less than about 3% of the total weight of the paste. These expanders
have traditionally incuded to the carbons such as lampblack or carbon black, barium
sulfate and sawdust, or organic extracts of wood.
The greater the surface area of lead particles, the greater the discharge capacity of the
battery. Organic expanders adsorb onto the surface of the lead particles and prevent
small lead particles from becoming larger crystals.

An abundance of smaller lead particles leads to better discharge capacity due to

greater surface area and, therefore, greater interaction with the electrolyte. This enables
higher ion transfer between the negative and positive, both for discharge and re-charge.

Organic expanders are combined with barium sulfate (blanc fixe) and carbon black.
The carbon black serves in the clearing of the negative plate on formation. It may give
the active material the necessary electric conductivity during the early part of formation
in which its permeability to acid is at a minimum. Towards the end of formation, the
carbon black appears to help remove the grey surface film occasionally encountered.

Ethylenediaminetetraacetic Acid (EDTA)

Two compounds used for such purposes are Epsom salts and EDTA. Epsom salts
reduce the internal resistance in a weak or damaged battery and may allow a small
amount of extended life. EDTA can be used to dissolve the sulfate deposits of heavily
discharged plates. However, the dissolved material is then no longer available to
participate in the normal charge-discharge cycle, so a battery temporarily revived with
EDTA will have a reduced life expectancy. A chemical that binds certain metal ions,
such as calcium, magnesium, lead, and iron

Acid Stratification
The acid concentration is light on top and heavy on the bottom. This raises the open
circuit voltage and the battery appears fully charged. Excessive acid concentration
induces sulfation on the lower half of the plates. AGM does not suffer from acid
stratification and is less sensitive to sulfation if undercharged than the flooded version.

Figure 1 illustrates a normal battery in which the acid is equally distributed from top to
bottom, providing good overall performance.

Figure 1: Normal battery Figure 2: Stratified battery

Figure 2 shows a stratified battery in which the acid concentration is light on top and
heavy on the bottom. The light acid on top limits plate activation, promotes corrosion
and reduces the performance, while the high acid concentration on the bottom makes
the battery appear more charged than it is and artificially raises the open circuit voltage.
The unequal charge across the plates reduces cold cranking amps, and starting the
engine is sluggish.

Failure Modes for Lead Acid Batteries

The lead acid battery failure modes comprise the following, with electrolyte
stratification and dry-out limited to VRLA

• Positive grid corrosion

• Positive active material softening and shedding
• Electrolyte stratification (VRLA)
• Electrolyte dry-out (VRLA)
• Negative active material sulfation

In flooded batteries positive grid corrosion is mitigated by using lead-antimony alloy

grids, Antimony also facilitates conversion of the highly resistive PbO corrosion product
to the conductive PbO2,

However, antimony dissolves in the electrolyte, migrates to the negative electrode, and
promotes hydrogen evolution during standby, charge and overcharge.

Hence for maintenance-free batteries, low antimony positive grid alloys are used.

Electrolyte dry-out is prevented by periodic addition of deionized water as part of

standard maintenance. For flooded batteries, grid corrosion mitigation by use of lead-
antimony alloy is expected to reduce positive active material shedding due to better
grid-active material bond,

For VRLA, antimony free alloys of Pb-Ca-Sn are used, with calcium providing
mechanical strength and tin mitigating grid corrosion, while Pb-Ca alloy is used for the
negative gird. Electrolyte stratification is mitigated by overcharging to promote gas
evolution with associated electrolyte mixing.

Related to VRLA, mitigation of electrolyte stratification and starting with a lower negative
to positive active material are expected to reduce negative electrode irreversible
sulfation.
Vanadium Redox (VRB) Flow Batteries
The Vanadium Redox Battery (VRB®)¹ is a true redox flow battery (RFB), which
stores energy by employing vanadium redox couples (V2+/V3+ in the negative and
V4+/V5+ in the positive half-cells). These active chemical species are fully
dissolved at all times in sulfuric acid electrolyte solutions. Like other true RFBs,
the power and energy ratings of Vanadium Redox Batteries are independent of
each other and each may be optimized separately for a specific application. All the
other benefits and distinctions of true RFBs compared to other energy storage
systems are realized by VRBs. The first operational vanadium redox battery was
successfully demonstrated at the University of New South Wales in the late 1980s
and commercial versions have been operating on scale for over 8 years.

How Vanadium Flow Redox Batteries Work

Vanadium is a non-toxic, widely-available metal. The technology relies on the
ability of vanadium to exist in four different oxidation states (V2+, V3+, V4+ and
V5+), each of which holds a different electrical charge.
In contrast to lithium-ion batteries which store electrochemical energy in solid
forms of lithium, flow batteries use a liquid electrolyte instead, stored in large
tanks. In VFBs, this electrolyte is composed of vanadium dissolved in a stable,
non-flammable, water-based solution.
Unlike technologies that rely on different elements to make up the positive and
negative sides of the battery, vanadium’s ability to exist in different oxidation
states allows VFBs to use that metal as both the positive and negative “couple”
inside the battery cell. This eliminates many of the common modes by which
traditional battery chemistries become contaminated and degrade over time.

In July 2019, an Invinity (Co.) 300 kWh vanadium flow battery, situated at an
industrial site in Dorset, UK became the first flow battery.
VFBs can perform a wide range of fast response and Invinity’s vanadium flow
batteries have proven response times of 110ms (1/10th of a second),
VFBs do not degrade with use like lithium-ion batteries; Primarily this is due to the
liquid electrolyte not changing phase during the charge/discharge process.

During the discharge cycle, V2+ is oxidized to V3+ in the negative half-cell and an
electron is released to do work in the external circuit (either DC or, for AC
systems, through an AC/DC converter).

In the positive half-cell, V5+ in the form of VO2+ accepts an electron from the
external circuit and is reduced to V4+ in the form of VO2+. Hydrogen (H+) ions
are exchanged between the two half-cells to maintain charge neutrality. The
hydrogen ions diffuse through the anion or cation-ion permeable polymer
membrane that separates the half cells. Charged vanadium species and water can
also diffuse across the membrane. The cross-diffusion results in direct energy loss
for that cycle. However, when vanadium is the only element present on both sides
of the cell, this cross diffusion mechanism does not result in permanent capacity
loss, as long as the total vanadium in the system remains constant (i.e., there is no
loss due to precipitation).
In a V-only system there is no need to maintain balance between positive and
negative sides of the system. In the positive half-cell, the vanadium is present in
solution as oxy-cations. These oxy-cations are vulnerable to irreversible
precipitation as V2O5 if the electrolyte temperature exceeds ~50-60oC. However,
when precipitation occurs, it does so typically in the form of benign compounds,
not V2O5.
The normal operating temperature of a VRB is approximately between 10-40oC.
Active cooling sub-systems are employed if ambient temperatures exceed 40-
45oC. Being able to cool the system actively is an advantage since the system can
remain operating without risking any damage to it. By contrast, if integrated cell
architectures overheat, the best option is to stop using them until they cool down.
The cell voltage is 1.4-1.6 volts and cell power densities are hundreds mW/cm2
(although Prudent Energy reports their power densities are higher). The DC-DC
efficiency of this battery has been reported in the range of 60-80%. According to
EPRI, the vanadium redox battery is suitable for power systems in the range of 100
kW to 10 MW, with storage durations in the 2-8 hour range.
The vanadium redox battery offers a relatively high cell voltage, which is favorable
for higher power and energy density compared with other true RFBs, like the iron-
chromium system. However, the higher voltage and highly oxidative V5+
electrolyte puts more chemical stress on the materials used in the cell electrodes,
membranes, and fluid handling components. Cross-transport of vanadium ions
across the membrane is also reported as a challenge, and fairly expensive ion-
exchange membranes must be used to minimize losses due to cross-membrane
transport. These membranes can be vulnerable to fouling, wherein vanadium ions
become irreversibly trapped in the membrane and increase resistive losses in the
cell. On the other hand, lower cost membranes are under development.
Vanadium is a readily available material, used in steel manufacturing and as a
chemical catalyst, which is found naturally and can also be recovered from various
waste streams. The market price of vanadium as V2O5 has, however, been fairly
volatile since 2017 after enjoying several years of low prices.