a lead monoxide precursor of high surface-area for lead-acid battery paste r vasant kumar department...
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![Page 1: A Lead Monoxide Precursor of High Surface-Area for Lead-Acid Battery Paste R Vasant Kumar Department of Materials Science University of Cambridge, UK](https://reader036.vdocuments.us/reader036/viewer/2022062417/551b3f08550346d31b8b4692/html5/thumbnails/1.jpg)
A Lead Monoxide Precursor of High Surface-Area for Lead-Acid Battery Paste
R Vasant Kumar
Department of Materials Science
University of Cambridge, UK
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Acknowledgements
Seref Sonmez, Vega Kotzeva, Jiakuan Yang, Lilia Sanchez, Richard Darby, Yingjun Liu, David Zou, of Department of Materials Science
Lei Wang, Nigel Williams of the Business School
Maggie Wilkinson & Zlatka Stoeva of Cambridge Enterprise
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A Schematic Cut-Away of Lead Battery
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Table 1 Range of Compositions from a dry lead battery paste
Material Wt %
Lead sulphate 55-65
Lead dioxide 15-40
Lead monoxide 5-25
Metallic lead 1-5
Carbon black, plastics, fibres, other sulphates
1-4
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Current Method - Pyrometallurgy
*For 10,000 tpy plantCapital: $4-5MEnergy: 14,000MWH*Independent Consultants
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Battery Manufacture
Lead is then chemically oxidised to PbO for the battery industry
PbO is electrochemically reduced to Pb and oxidised to PbO2 to make anode and cathode
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Lead containing Organic
Crystalline Compounds
PbO Precursor
New
A new process for recycling lead battery waste
→
↓↑
→
Special Leaching/Crystallization Process
Lead Battery
Combustion/Calcination Process
Manufacturing Lead Battery
Waste Battery
Paste
New Paste
Patent: PCT/GB2007/004222; WO2008/056125RV Kumar, S Sonmez and V Kotzeva
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A new process for recycling lead battery waste
→
Paste
Pb GridHeat Energy from pasterecycling
New Grid
New Paste directly from paste recycling
Kettle
Waste Battery
New lead Battery
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Green PB Recycling Process
Patent: PCT/GB2007/004222; WO2008/056125RV Kumar, S Sonmez, V Kotzeva
Leaching
Combustion-Calcination
SpentLead grid
MetallicLead
Energy
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0
1
2
3
4
5
6
0 10 20 30 40 50 60
Time / mins
Tem
pera
ture
Ris
e / °
C
1.5 : 1 1.25 : 1 1 : 1
Leaching of battery paste PbO and PbO2
Ratio ofPaste/reagent
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10
20
30
40
50
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Reaction time(min)
Tem
pera
ture
(℃
) Lead (II) oxide
Lead (IV) dioxide
Lead sulfate
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1
1.5
2
2.5
3
3.5
4
4.5
0 10 20 30 40 50 60
Time / mins
pH
1.5 : 1 1.25 : 1 1 : 1
pH vs time for varying paste/reagent ratio
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5 15 25 35 45 55 65
2 θ(degree)
Inte
nsi
ty(a
.u.) A
B
C
D
XRD Pattern of A: Standard Lead citrate; B: from PbO; C: fromPbO2 and D: from PbSO4
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Lead organic crystallites of Lead citrate (A) from PbO and PbO2
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SEM images of Lead Citrate (B) from PbSO4
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Precursors Ideal weight loss
Fromdehydrating
weight loss
(TGA)
Ideal weight loss
For decomposition to PbO
weight loss
after exothermic peak of TGA
weight loss
calcined at 350 for ℃1h
Precursor I[Pb(C6H6O7)]·H2O 4.3% 4.20% 46.3% 49.8% 48.2%
Precursor II[Pb(C6H6O7)]·H2O 4.3% 4.20% 46.3% 49.8% 49.0%
Precursor III[Pb3(C6H6O7)2]·3H2O
5.1% 5.50% 36.6% 38.3% 37.5%
Combustion-Calcination of Lead citrates in Air
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334.01°C
2000J/g
167.76°C
151.79°C238.7J/g
285.09°C
-5
0
5
10
15
20
25
He
at
Flo
w (W
/g)
0
20
40
60
80
100
120
We
igh
t (%)
40 80 120 160 200 240 280 320 360 400
Temperature (°C)
Sample: 20070423PbO-airSize: 7.8140 mgMethod: Ramp
DSC-TGAFile: C:...\yj231\20070423\20070423PbO-air.002Operator: yj231Run Date: 23-Apr-2007 14:50Instrument: SDT Q600 V8.2 Build 100
Exo Up Universal V4.3A TA Instruments
Wt loss and heat produced on decomposing Pb citrate (A)
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357.91°C2427J/g
117.77°C
284.16°C
9.869%
-5
0
5
10
15
20
25
He
at
Flo
w (W
/g)
0
20
40
60
80
100
120
We
igh
t (%)
40 80 120 160 200 240 280 320 360 400
Temperature (°C)
Sample: 20070411PbSO4airSize: 15.9840 mgMethod: Ramp
DSC-TGAFile: C:...\DSC\20070411-PbSO4air-analysis.001Operator: rs489Run Date: 11-Apr-2007 14:27Instrument: SDT Q600 V8.2 Build 100
Exo Up Universal V4.3A TA Instruments
Wt loss and heat produced from lead citrate (B)
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10 20 30 40 50 60 70 80 90
2 θ(degree)
Inte
nsity
(a.u
.)
300℃
350℃
400℃
450℃
Pb
PbO
Mixture of α and β PbO and metallic Pb – can be controlledto varying ratios
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Heat Produced
Combustion-calcination of lead citrates can generate thermal energy of 2 kJ/ g of lead battery paste
The Raceway Adiabatic Flame Temperature is over 1500K!
This energy is equivalent to 550 kWh/kg of paste!
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PbO morphology after combustion-calcination
SEM
TEM
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Spongy PbO Agglomerated PbO
Skeletal PbO
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Additives during leaching to control PbO morphology
Lead citrate PbO
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Addition of C-fibre to PbO precursor
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FEGSEM – Each fibre is coated FEGSEM – Each fibre is coated with PbOwith PbO
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Physical Properties of PbO
Free Pb: 0 to 20 % Crystal structure: α/β ratio: 0.05 to 1 Crystal size: 20 – 100 nm Particle average size: 1 – 5 μm Specific surface area (BET) m2/g: 2.4 to 5.5 Acid absorption (mg H2SO4/ g oxide): 270 –
530
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Preliminary Electrochemical Testing
First discharge capacity in the 130 – 160 mAh/g of PbO
Increase in discharge capacity with no of cycles up to 8-10 cycles and then remained constant to 50 cycles
Further work is ongoing
-5.0 -2.5 0 2.5-0.10
-0.05
0
0.05
0.10
E (Volts)
I (A
mps/
cm2 )
A
BC
DE
A: PbO /PbSO4 reduction to PbB: Pb oxidation to PbSO4
C: PbSO4 oxidation to PbO2
D: PbO2 reduction to PbSO4
E: PbSO4 reduction to Pb
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The Green PB Process
For 10,000 tpy plantCapital: $1-1.5 MEnergy: 1750 MWH
5000 MWhEnergy available
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Conclusions
New method for directly recovering PbO from spent battery paste
Many control variables available to vary physical properties of PbO product
Promising preliminary results Thank You