Battery Basics and Beyond

First in a Series
Jim McDowall Saft America
Rick Tressler Liebert Corporation

Subjects
Electrochemistry
Cell Construction
Maintenance issues
Failure Mechanisms

Electrochemistry

Electrochemistry
Positive & negative electrodes
Electrically isolated
Common conducting medium
Separate but linked chemical reactions at
positive and negative
Reversible reaction in secondary cells

Electrochemical Reactions
Lead-acid

PbO 2 + Pb + 2H2SO 4
2PbSO 4 + 2H2O

Nickel-Cadmium

2NiO.OH + Cd + 2H2O 2Ni(OH)2 + Cd(OH)2

Lead-Acid Charging Reactions

Electrolysis
!Water

breaks down to produce oxygen at positive

!Hydrogen produced at negative

Grid Corrosion
!Oxygen

from water reacts with lead in positive grid

!Hydrogen produced at negative

Cell Construction

Construction
Lead-Acid
Pasted plate cells
Tubular cells
Plant cells
Round cells

Lead-Acid Charging Reactions

Recombination
!Only

significant for valve-regulated (VRLA)

!Electrolysis occurs at positive
!Oxygen passes through separator to negative
!Recombination at negative to release water
!No net chemical change, but heat produced
!Grid corrosion and associated water loss cannot be
prevented

Pasted Plate
Lead alloy grid
! Antimony
! Calcium
! Selenium

Active material paste

Pasted Plate
Advantages
!Low

cost
!High performance
!Good energy density

Disadvantages
!Limited

life
!Limited cycling capability

Tubular
Lead alloy spines
Non-woven polyester
tubes
Active material between
spines and tubes

Tubular
Advantages
!Excellent

energy density
!Superior cycling capability

Disadvantages
!Poor

high-rate performance
!Inability to see positive plate edges

Grid Alloys
Lead antimony
!First

lead alloy in pasted plates - 1880s

!Antimonial poisoning

Lead calcium
!1935

- Haring & Thomas

!1950s - Bell Labs

Lead Selenium
!Used

extensively in Europe since mid-70s

Lead Antimony
Advantages
!Predictable

aging
!Excellent cycling

Disadvantages
!Antimonial

poisoning

Antimonial Poisoning
Antimony migration to
negative
Increased self-discharge
and watering
Essentially eliminated
below 2% antimony

Lead Calcium
Advantages
!Stable

float current
!Low water consumption

Disadvantages
!Unpredictable
!Poor

cycling capability

Lead Selenium
Less than 2% antimony
!Eliminates

antimonial poisoning
!Maintains beneficial aspects of antimony
!predictability

& cycling capability

Low, stable float current

Other hardeners possible, e.g.
!Cadmium
!Silver

Recombination
Immobilized electrolyte
!Absorbed

(AGM)

!Gelled
!Gas

path from positive to negative

Positive internal pressure

Plate group compression
Recombination process is highly efficient
!But

charging energy is converted to heat

!Thermal management extremely important

Grid corrosion results in hydrogen evolution

VRLA Batteries
Advantages
!No

water additions
!High energy density

Disadvantages
!Unique

failure modes

!Dryout
!Thermal

runaway
!Negative strap corrosion

VRLA Reliability Issues

Shorter life expectancy
Additional failure modes
Higher operating temperature
!Double

whammy

Faster loss of high-rate capability

!Even

shorter life in UPS applications

Nickel-Cadmium
Construction
! Pocket

plate
! Sintered plate
! Plastic-bonded electrode
! Fiber construction
! Hybrid types

Pocket plate more rugged

mechanically
Others give better life
under harsh conditions

Nickel-Cadmium
Advantages
! Tolerant

of temperature extremes
! Good cycle life
! Fast recharge
! Impervious to ripple
! Ultra-low maintenance types available
! Lower cost of ownership under extreme conditions

Disadvantages
! High

initial cost compared with lead-acid

Maintenance Issues

Battery Maintenance Standards

IEEE 450 - vented lead acid
IEEE 1106 - nickel cadmium
IEEE 1188 - valve regulated lead acid
The IEEE mandate - cost implications are not to
be considered
!Recommended

maintenance and testing levels are

what is required to ensure a high level of reliability
!Less reliable batteries will require more maintenance

Maintenance
IEEE Recommendations
Every
Every
3 months 6 months
Float
voltage

VLA

Specific
gravity

VLA (10%)

Ohmic
meas.
Capacity
test

Every
year

Every
5 years

Ni-Cd
VRLA
VLA

VRLA
VRLA

VLA
Ni-Cd

Internal Ohmic Measurements

Ac impedance, ac conductance, dc resistance
Extremely useful for VRLA
!Dryout

has a major impact

!Not a direct readout of capacity!

Somewhat useful for vented lead-acid

!No

dryout
!More subtle differences in resistance of grid and other
hardware
!Can find gross irregularities not found by voltage or Sp.Gr.

Internal Ohmic Measurements

Of little use with Ni-Cd
!Problems

found with ohmic measurements can also

be seen with float voltage readings

Failure Mechanisms

Lead-Acid Failure Mechanisms

Charge-related
!Corrosion
!Grid

growth
!Post seal problems
!Ripple effects
!Sulfation

Lead-Acid Failure Mechanisms

Discharge-related
!Sulfation
!Reversal
!Passivation
!Short

circuits

Corrosion & Grid Growth

Most frequent cause of failure in vented cells
Cannot be eliminated
User actions
!Avoid

undercharging
!Eliminate frequent equalizing
!Specify the most appropriate battery type for the
application

Post Seal Problems

Two types of problems
Creep corrosion
!Blackening

of post above seal

!Maintenance issue - can increase connection
resistance

Crevice corrosion
!Local

action within seal area

!Large volume of corrosion product can crack cover

Post Seal Problems

User actions
!Avoid

overfilling
!Avoid frequent water additions

Ripple Effects
Can be a problem if there is a large connected load,
e.g. UPS
!High-frequency
!Ac

shallow cycling

corrosion

Also results in overcharging

!Accelerated

grid corrosion
!Heating effects in VRLA

User actions
!Limit

ripple current to <5%

!For 3-phase chargers, make sure phases are balanced

Sulfation
Buildup of large, hard sulfate crystals
!Persistent

undercharging
!Prolonged storage without refreshing charges
!Standing in discharged condition >24 hours

Leads to permanent capacity loss

User actions
!Avoid

undercharging
!Follow recommended storage procedures
!Recharge promptly after discharge

VRLA Failure Mechanisms

Other lead-acid failure modes, plus:
Dryout
Thermal runaway

Dryout
Often unrecognized, but probably the most prevalent
VRLA failure mode
Probably the major cause of premature capacity loss
Contributing factors
!Grid

corrosion
!Vapor diffusion through plastic container
(if relative humidity <40%)
!Loss of plate group compression
(lowered recombination efficiency)

User actions - None

Thermal Runaway
Much less prevalent than dryout, but much more
spectacular!
!Battery

fires
!Explosions

In extreme cases, batteries in thermal runaway

can emit hydrogen sulfide, which will destroy
surrounding electrical equipment

Thermal Runaway
User actions
!Specify

flame-retardant battery cases

!Use a temperature-compensated charger
!Monitor battery temperature, taking action if
temperature rises too high

Ni-Cd Failure Mechanisms

Normal aging is a slow decline in capacity
Gradual changes in active material
Plate structure unaffected
No sudden death
Other potential problems
!Partial

short circuits - can often be eliminated

!Operation with low electrolyte

Summary
Different application conditions demand different
battery types for optimum performance
Batteries supplied as original equipment are
often the cheapest available
Only end-user specifications can ensure that the
right battery is chosen
Correct operation and maintenance are
important in safeguarding battery investments