- Conductance alone doesn’t uniquely determine capacity, but it sets hard limits. A point can only fall within a narrow feasible region defined by electrolyte and plate constraints.
- Below ~60% conductance ((G_d/G_n < 0.6)), capacity is guaranteed to be <100%, and in practice is very likely <80%.
- Undercharge / soft or hard sulfation can lower capacity while keeping conductance unchanged or slightly higher.
- Electrolyte dry-out tends to reduce conductance first; capacity may remain near-normal initially, then declines as dry-out progresses.
- Use trendlines: a steady decline in (G) at stable float voltage and temperature typically signals progressive dry-out.
- (G): battery conductance, (g): specific conductivity of the electrolyte.
- (Ah): deliverable capacity at a defined rate/cutoff.
- Subscripts: n = new reference; d = degraded in service.
- We compare batteries by ratios:
- Normalized conductance: (G_d/G_n)
- Normalized capacity: (Ah_d/Ah_n)
Open-circuit voltage (OCV) rises with sulfuric acid molality (m). A widely used fit (25 °C) is:
$$
OCV = 1.9228 + 0.147519\log(m) + 0.063552\log^2(m) + 0.073772\log^3(m) + 0.033612\log^4(m)\quad \mathrm{V/cell}
$$
Because float voltage clamps terminal voltage, it indirectly caps the maximum acid concentration achievable in service.
For a uniform electrolyte path of effective length (L), cross-section (A), resistivity (\rho), and specific conductivity (g = 1/\rho):
- Resistance: (R = \rho,L/A)
- Conductance: (G = 1/R = g,A/L)
In porous electrodes (VRLA), the effective area/geometry makes (G) scale with the amount and concentration of electrolyte. A convenient proportional form is:
$$
G \propto g \times \frac{V}{L^2}
$$
where (V) is electrolyte volume. When we normalize to the new state and track how concentration (affecting (g)) and quantity (affecting (V)) change, we obtain an electrolyte conductance ratio:
$$
\frac{G_d}{G_n} \approx \left(\frac{g_d}{g_n}\right)\left(\frac{B_d}{B_n}\right)\left(\frac{D_n}{D_d}\right)
$$
Here (B) is electrolyte mass and (D) is density; this form captures how losing water or acid shifts both (g) and the total electrolyte present.
- Electrolyte concentration drops (lower (m)), often because the battery is chronically under-floated, cycled shallowly without recovery, or sulfated.
- Capacity falls (active material is poorly utilized), while conductance may stay flat or even rise slightly in mild cases.
- Diagnostic signature: Low (Ah_d/Ah_n) with moderate (G_d/G_n).
- Water is lost (electrolysis, evaporation, seal leakage), acid becomes more concentrated until float-limited.
- Once the acid reaches a float-limited ceiling (about (m \approx 10.3 ,\mathrm{mol/kg}); density (\approx 1.394,\mathrm{kg/L}) at typical floats), further water loss forces acid removal from solution as PbSO(_4) on plates.
- Diagnostic signature: (G_d/G_n) trends downward over time; capacity may lag, then falls.
By conserving how much acid and how much water the cell can have relative to new, and by enforcing the float-limited maximum concentration, one obtains an upper envelope: the highest capacity possible for a given conductance ratio. Intuitively:
- Undercharge zone (left branch): capacity can be low even if conductance hasn’t dropped much.
- Dry-out zone (right branch): conductance must decrease as electrolyte is lost; capacity initially declines slowly.
Once the electrolyte sits at the float-limited concentration, mass-balance links additional water loss to acid precipitation as PbSO(_4) and to a nearly linear relation between the two ratios:
$$
\frac{Ah_d}{Ah_n} \approx k \cdot \frac{G_d}{G_n}\quad\text{(dry-out lower bound)}
$$
where (k) is a constant calculated from the new-state density, the float-limited density, and specific conductivities. In practical terms: as conductance drops further in dry-out, capacity must drop proportionally along (or above) this line—never below.
Field rule of thumb: Below ~60% conductance ((G_d/G_n < 0.6)), the combined electrolyte + plate constraints force (Ah_d/Ah_n < 1.0) (i.e., capacity <100%), and in service datasets it is very often <80%.
Theoretical active material per 1 Ah (before utilization factors):
- ( \mathrm{PbO_2} ): (4.462\ \mathrm{g/Ah}) (effective ~11.155 g/Ah at ~40% utilization)
- ( \mathrm{Pb} ): (3.865\ \mathrm{g/Ah}) (effective ~8.589 g/Ah at ~45% utilization)
Because sulfation consumes active surfaces and blocks pores, plate-limited capacity gives additional upper/lower bounds that can dominate when plate loss or hard sulfate is severe—even if electrolyte looks “acceptable.”
- Test rate: 4 h at 10.1 A, cutoff 1.8 V/cell (10.8 V/block).
- New references used for normalization: (Ah_n \approx 40.4\ \mathrm{Ah}) at test conditions; (G_n \approx 800\ \mathrm{S}).
- 41 blocks had (G_d/G_n < 0.6) and all delivered <100% capacity; 40/41 were <80%, one was 83% ⇒ 97.5% chance that (G_d/G_n<0.6) implies (Ah<80%) for this population.
- Scatter points fell within the theoretical envelopes, especially close to the linear dry-out lower bound at low conductance—consistent with dry-out being a dominant degradation path.
- Normalize conductance: measure after adequate rest or float stabilization; compute (G_d/G_n) against a new-battery baseline (from vendor spec or your own acceptance data at the same temperature).
- If (G_d/G_n < 0.6): capacity is certainly reduced; plan a capacity test and prepare for replacements (very likely <80% in similar fleets).
- If capacity is low but (G_d/G_n) is moderate/high: suspect undercharge/sulfation. Check float voltage set-point, charger health, OCV, and (if accessible) specific gravity.
- If (G_d/G_n) trends down slowly with time at stable temperature and float: suspect dry-out; review ambient heat, ventilation, charge voltage, and seal/valve health.
- Always pair conductance with at least one more indicator (OCV trend, temperature history, or periodic capacity sampling) to avoid misclassification.
- Focused on flat-plate VRLA geometries; very large tubular or front-access blocks may add metallic path resistance effects that slightly alter conductance readings.
- Float at ~2.25 V/cell sets the practical concentration ceiling.
- Electrolyte-only conductance modeled (metallic paths treated as small).
- Equations and envelopes describe feasible regions, not exact points—manufacturing tolerances and service histories matter.
- OCV–molality (25 °C):
$$
OCV = 1.9228 + 0.147519\log(m) + 0.063552\log^2(m) + 0.073772\log^3(m) + 0.033612\log^4(m)
$$
- Conductance–geometry:
$$
R = \rho \frac{L}{A},\quad G=\frac{1}{R}=g\frac{A}{L}
$$
- Electrolyte conductance ratio (simplified mass–density form):
$$
\frac{G_d}{G_n} \approx \left(\frac{g_d}{g_n}\right)\left(\frac{B_d}{B_n}\right)\left(\frac{D_n}{D_d}\right)
$$
- Dry-out lower bound (float-limited concentration):
$$
\frac{Ah_d}{Ah_n} \approx k \cdot \frac{G_d}{G_n}\quad\text{with }k\text{ computed from }(g,D,m)\text{ at new and float-limited states.}
$$
By separating electrolyte and plate effects and enforcing mass/voltage constraints, we get hard boundaries between normalized conductance and capacity in VRLA batteries. Practically:
- Treat (G_d/G_n < 0.6) as a red flag—capacity is not only below nameplate; in fleet data it’s very likely <80%.
- Distinguish mechanisms: undercharge can devastate capacity with small conductance change; dry-out steadily drags conductance down before capacity collapses.
- Use trends and a second indicator to make confident maintenance decisions.