Applications Header

Raman Spectroscopy for Lead Acid Battery Analysis

PDF Download (7.26 MB)

Lead Acid Battery Analysis Using the Raman Spectrometer

Lead-acid batteries remain a cornerstone of energy storage technology, valued for their reliability, low cost, and high recyclability, particularly in automotive and stationary applications. Despite their maturity, these batteries face performance limitations and degradation mechanisms such as negative plate sulfation, grid corrosion, and oxygen recombination issues that restrict their lifespan and efficiency.

 

To overcome these challenges and enhance performance in modern micro-hybrid systems, detailed, real-time understanding of electrochemical processes at the electrode-electrolyte interface is required. 

 

Raman spectroscopy has emerged as a powerful, non-destructive analytical technique capable of providing high-resolution structural and chemical information on lead-acid battery components, including lead oxides, lead sulfates, and various forms of carbon additives. Raman spectroscopy is a precise, "technique of choice" for studying the formation of lead sulfate (PbSO4) crystals, which is the primary cause of capacity loss in partial state of charge operation.

Lead Acid Battery Analysis.png

 

IndiRAM CTR Series.png

Material and Method: 

 

Raman spectra were acquired using Technos IndiRAM CTR 300 Raman Spectrometer, designed to provide high spectral resolution, wavelength stability, and excellent signal-to-noise performance for Battery analysis.

 

Three type of battery were analysis -

  • Scooter Battery : Old (Dead)
  • UPS Battery : Old (Dead)
  • Small Battery: NEW

 

These new and old battery is decided to see the effect of impurities (additive common material: BaSO4 (0.5-1%), Sb, As, Cr, Cu, and Sn)) in Raman spectrum. 

Result and Discussion:

Chemical reaction in Lead acid battery as follows:

(1) Discharging state: Product  at both electrode : PbSO4
Cathode reaction: PbO2 + 3H+ + HSO4- → PbSO4 + 2H2O
Anode reaction: Pb + HSO4- → PbSO4 + H+ + 2e-

 

(ii) Charging state:  Cathode: PbO2, Anode: Pb
Cathode reaction: PbSO4 + 2H2O → PbO2 + 3H+ + HSO4-
Anode reaction:  PbSO4 + H+ + 2e- → Pb + HSO4-

Discharging state.jpeg

 

Raman mode of lead sulphate (PbSO4), lead oxide (PbO2) and barium sulphate (BaSO4).

 

1. Raman mode of Anglesite (Pure PbSO4 : ref 1 & 2)

  • Tetrahedra symm. bend mode: [437 cm-1, 449 cm-1: ref 1], [436 cm-1, 439 cm-1, 451 cm-1: ref 2]  
  • Tetrahedra asymm. bend mode : [617 cm-1, 640 cm-1: ref 1], [605 cm-1, 613 cm-1, 635 cm-1: ref 2 ]  
  • Tetrahedra symm. Stretch. of (SO4)-2: 977 cm-1 [ref 1], [974 cm-1, 980 cm-1, 981 cm-1: ref 2]  

  • Tetrahedra asymm. stretching mode: [1051 cm-1, 1140 cm-1, 1157 cm-1: ref 1], [1057 cm-1, 1060 cm-1, 1065 cm-1 : ref 2], [1148 cm-1, 1154 cm-1, 1160 cm-1: ref 2]

 

2. Raman mode of lead oxides (ref 3)

  • PbO2:  eg : 424 cm-1, a1g: 515 cm-1 and  b2g :653 cm-1 [ref 3 ]
  • PbO: 117 cm-1, 139 cm-1, 270 cm-1, 314 cm-1, 500 cm-1, 533 cm-1
  • Pb3O4: 122 cm-1, 148 cm-1, 540-550 cm-1

 

3.  Raman mode of Barite (Pure BaSO4 : ref 4) 

  • Symmetry bend vibration at ~ 450 cm–1
  • Asymmetry bend vibration ν4(F2) at ~ 620 cm–1
  • Symmetric stretching of [SO4]-2 at ~ 988-1000 cm-1

Asymmetric stretching at ~1080 cm-1, 1150 cm-1, 1167 cm–1

Lead Acid Battery Analysis Using the Raman Spectrometer.jpeg

Fig.1

 

Peak Assignment:

 

Scooter old /dead battery:

  • (436 cm-1, 454 cm-1), (601 cm-1, 636 cm-1,), (970 cm-1), (1052 cm-1, 1153 cm-1):  PbSO4
  • 147 cm-1, 170 cm-1, 506 cm-1 : PbO, PbO2, Pb3O4
  • 388 cm-1, 400 cm-1, 536 cm-1, 557 cm-1,670 cm-1, 688 cm-1:  Cr2O3, Cr8O21, Fe2O3, Fe3O4
  • 454 cm-1, 987 cm-1 : BaSO4

Conclusion: Mainly PbSO4 with small amount of BaSO4, PbO, PbO2, Pb3O4, Cr2O3, Cr8O21, Fe2O3, Fe3O4.

 

UPS old/dead battery :

  • (437 cm-1, 455 cm-1), 635 cm-1, 970 cm-1, 1155 cm-1: PbSO4
  • 455 cm-1, 612 cm-1, 992 cm-1, (1072 cm-1, 1155 cm-1, 1194 cm-1):BaSO4

Conclusion: Mainly BaSO4 with PbSO4

 

Portable electronic new battery:

  • 436 cm-1, 445 cm-1, (603 cm-1, 639 cm-1), 974 cm-1, (1056 cm-1, 1152 cm-1): PbSO4
  • 134 cm-1, 150 cm-1, 488 cm-1 :  PbO, PbO2

Conclusion: Mainly PbSO4 with small amount of PbO, PbO2

Lead Acid Battery Analysis Using Raman Spectrometer.jpeg

Fig.2

 

High resolution: The grating of 1800/mm was used for separating out peak of BaSO4 and PbSO4 clearly in fig. 2.

 

Conclusion:  

Raman spectroscopy analysis revealed that the scooter battery sample was primarily composed of PbSO₄, along with minor amounts of  BaSO₄, various lead oxides (PbO, PbO₂, Pb₃O₄), chromium oxides (Cr₂O₃, Cr₈O₂₁)  and iron oxides (Fe₂O₃, and Fe₃O₄). The UPS battery sample mainly contained BaSO₄ and PbSO₄, whereas the small portable electronic battery sample was predominantly composed of PbSO₄ with trace amount of lead oxide (PbO and PbO₂). Raman spectroscopy provides a fast, non-destructive, and highly specific method for identifying Lead acid battey. The distinct spectral signatures of impurity of BaSO4 and other products demonstrate Raman’s effectiveness for Lead acid battery in exploration and energy application.

 

Using high-resolution IndiRAM CTR 300 Raman Spectrometer and with ongoing development of Portable Raman solutions, TechnoS Instruments enables accurate, Lead acid battery identification to support the growing demand for critical %  Barium sulphate. (Since BaSO4 is used ~ 0.8-1% by weight relative to the leady oxide).
 

References

1. Krista Sawchuk, Earl F. O’Bannon III, Cara Vennari,  Abby Kavner, Elise Knittle, Quentin Williams, Physics and Chemistry of Minerals (2019), 46, 623–637.
2. G.L.J. Trettenhahn, G.E. Nauer and A. Neckel, Vibrational Spectroscopy (1993), 5, 85-100.
3. Lucia Burgio, Robin J. H. Clark and Steven Firth, Analyst (2001), 126, 222–227.
4. V. E. Shukshina, P. P. Fedorova, and M. E. Generalov, Russian Journal of Inorganic Chemistry (2019), 64,1442–1445.