The Future of Advanced Lead Batteries and the New ALABC Program

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1 Threats The Future of Advanced Lead Batteries and the New ALABC Program Boris Monahov* and Alistair Davidson** *Advanced Lead Acid Battery Consortium **International Lead Association

2 ILA and ALABC PRODUCT OF CHOICE Creating conditions in which the lead industry can prosper BENEFITS RECOGNISED BY SOCIETY LEGISLATION FOCUSED ON SUSTAINABILITY 2 / 18

3 MEMBER SIGN UP 72 members 20 battery manufacturers 32 lead producers 13 suppliers 7 research & testing 3 / 18

4 ALABC PROGRAM FOCUS 4 / 18

5 AUTOMOTIVE TECHNICAL PROGRAM TARGET AREAS FOR IMPROVEMENT Gassing and Water Loss Corrosion Resistance DCA High and Low Temp Performance Charge Efficiency PERFORMANCE OBJECTIVES Improved Performance (x% Increase in DCA by 20xx*) at High Rate PSoC Longer Lifetime- Increase of x% by 20xx* THE GOAL Advanced lead batteries in 12V and 48V applications continue to be capable of delivering equivalent fuel and CO 2 savings at lower cost than alternatives battery parameters all interrelated 5 / 18 *Still in draft phase. Proposal for performance objectives still under discussion, and will be circulated to membership for comment shortly.

6 AUTOMOTIVE- INFORMATION TRANSFER PROGRAM WORK AREA Collate and analyse car and battery data from previous demo projects Communicate results to OEMS Technical Publications Present/exhibit at major events OBJECTIVE By mid 2017, OEMs to be made aware of all data and messaging from demo projects and the full potential for cost effective CO2 saving OVERALL GOAL OEM vehicle development programs aimed at meeting future emission targets to include 12V and 48V lead batteries 6 / 18

7 INDUSTRIAL AND ENERGY STORAGE TECHNICAL PROGRAM TARGET AREAS FOR IMPROVEMENT PERFORMANCE OBJECTIVES THE GOAL High Rate Charge Acceptance Gassing and Water Loss Corrosion Resistance High Temp Performance Active Material Durability Energy and Charge Efficiency Longer Life at PsoC -x% increase by 20xx* Longer Deep Cycle Life-increase of x% by 2021* Advanced lead batteries continue to deliver required performance with lower lifetime cost than alternatives battery parameters all interrelated 7 / 18 *Still in draft phase. Proposal for performance objectives still under discussion, and will be circulated to membership for comment shortly.

8 ENERGY STORAGE INFORMATION TRANSFER PROGRAM WORK AREAS OBJECTIVE OVERALL GOAL Compile existing data showing superior performance of lead batteries Present/exhibit at major energy storage events By 2017, benefits of lead batteries recognised by end users and systems designers. Lead batteries specified as product of choice in utilities and domestic energy storage sector Technical publications 8 / 18

9 Battery Operation Conditions in mild HEV and ES Systems HRPSoC cycling in Stop-Start and Mild HEVs HRPSoC 1) 12V / 48V high energy battery 2) Narrow S.O.C. window 3) Steady & high DCA 4) No gassing, HI/LO temperature BMS 1) 12V / 48V charge / discharge control 2) State of charge control 3) State of health monitoring 4) Battery history Car (load and charger) 1) 12V car consumers 2) 48V power / energy system 3) Electric functionalities 4) Battery temperature PSoC and HRPSoC cycling in Advanced Energy Storage Systems Charger 1) Pulses, CC/CV or floating 2) New charge algorithms 3) State of charge control 4) State of health monitoring HRPSoC 1) 2V cells / blocks / modules, high voltage 2) Wide S.O.C. window, deep discharge 3) AM stability, corrosion, stratification 4) years service life Load 1) High / low frequency 2) Seconds to hours range 3) Various users 4) Various temperatures 9 / 18

10 Example Modern Automotive Batteries: Transition From SLI to 48V Mild HEVs Regular SLI (12V) Stop-Start or micro hybrid (12V) Mild hybrids: 48 V Cold cranking: 5C 10C A, State of Charge: about 100% Recharge: 1C 2C A or 14.4V Hotel loads: covered by the recharge + Frequent warm start: 0.5C 3C A + Hotel loads: powered by the battery when engine idle + Recharge pulses: up to 15C, 3s 30s, irregular DCA issues + HRPSoC cycling: narrow S.O.C window ++ Start boost: 1C 5C (power) ++ Acceleration support: 1C 5C, (energy), ++ Propulsion (sailing, downhill): 3C 10C, deep discharge (energy) ++ HRPSoC cycling: wide S.O.C. window Challenges for lead batteries: NAM sulfation, PAM stability, VRLAB stratification 10 / 18

11 Steady Enhancement of Dynamic Charge Acceptance DCA problem in regular lead-acid batteries Ford DCA Battery Test: Microhybrid Duty ambient air 23 o C I recu / C n (A / Ah) EFB plus AGM poor flooded T. Okoshi, Shin Kobe El. Machinery, Japan, 2013 Advanced Automotive Batteries Conference, Strasbourg, June 2013 EFB AGM Gen. 2 Gen. 1 time / days E. Karden, F. Jöris, H. Budde-Meiwes, D.U. Sauer, Test Methods for Dynamic Charge Acceptance (DCA) of Microhybrid Starter Batteries, 13ELBC European Lead Battery Conference, Paris, France, September 2012 DCA performance getting closer to target: steady up to 1.25 A/Ah Malta 11 / 18

12 New knowledge about microstructure and cell performance (ALABC) Active mass surface, microstructure, additives, theoretical models, test cell measurements HRPSoC cycles p2n 1.32 sp. gr. Cell17 Ref. Cell g/l Na 2 SO 4 Cell g/l MgSO Cycle-set 12 / 18

13 Advanced Lead Battery Demonstrations (ALABC and Member s Programs) BAE Ecoult, East Penn Sufficient cycle life in HEVs, RES, remote PS 13 / 18 East Penn Narada Exide, East Penn

14 Contribution of ALABC R&D and demonstration projects Advanced lead batteries perform as well as other chemistries in micro / mild HEVs and energy storage systems but are fully recycled and offer the lowest cost 14 / 18

15 Observed Best Performance, Future Battery Advancement Targets Observed (membership): 52 Wh/kg, 1300 W/kg, 1800 W/L 280,000 HRPSoC cycles 1,000 deep cycles (pasted) steady DCA at 1.2 A/Ah, production costs of 15 $/kw Grid / current collectros 1.New lead alloys 2.Lead-graphene composites** 3.Carbon materials to replace or support lead** 4.New plate design* 5.New grid material** ADVANCEMENTS OF LEAD BATTERIES Negative plate 1.Carbon addition* research needed! 2.Expanders pairing well with carbon* ** 3.Carbon modified for reduced gassing** 4.Silica additives** 5.Glass flock** 6.New plate design* 7.New grid design* Electrolyte 1.Adjust density* 2.Sulfate crystal growth reductors* 3.Metal ion additives* 4.Compression* 5.Organic additives** 6.AGM saturation and recombination** 7.AGM of membrane properties** 8.New cell design* Positive plate 1.Carbon nano particles added to the active mass** 2.Alloy composition* 3.New grid design* 4.New plate design* 15 / 18 * - subject of previous or current ALABC program studies ** - studies outside ALABC Programs

16 Beneficial Effects of Carbon on Cell Components Micro / nano sized solids Carbon & NAM 1. Enhanced macro and nano NAM structure 2. Lead sulfate crystallization 3. HRPSoC cycle life 4. Dynamic charge acceptance 2. Cold crank ability 3. Active mass utilization (Cn) 4. Oxygen recombination 5. Some weight benefit 6. Affordable extra costs 7. DANGER: hydrogen! Functional groups, liquids Carbon & Electrolyte 1. Sufficient amount of H 2 SO 4 and H 2 O 2.Gassing rates 3. Lead solubility and lead sulfate crystallization 4.Ionic transport 5.Wetting of solid surfaces 6. Specific adsorption Nano sized solids) Carbon & PAM 1.Reversible porous partially hydrated PAM structure a) micro porosity, surface b) gel reaction layer c) corrosion layers 2.Embedding of nano carbons in PAM micro structure 3.Carbon oxidation and organic compounds effect 4.Composite grid materials, interaction with PAM, O 2 and H 2 SO 4 16 / 18

17 Strategy Plan Target Areas, Battery Components to be optimized New projects for the ALABC Program Group A Group B Group C 17 / 18

18 Open Questions and Future Research Tasks 1. How to use the EDL capacitance for optimizing battery performance? 2. How does carbon interact with expanders and other organics? 3. How do non-reacting additives improve the negative active mass? 4. How to control active mass structure self-organization? 5. How to control lead sulfate crystals growth and re-crystallization? 1. Mechanisms of action of carbon, organics, metal ions: DCA and gassing 2. Pulse charge, end of charge, charge profiles: high energy efficiency 3. Optimized cell design but same cell materials / chemistry for high power 4. New cell materials and additives for high energy and long cycle life 5. Temperature dependence of charge/discharge processes 6. Beneficial effect of periodic processes on battery performance Surface chemistry & electrochemistry of C H- O= -O- H-O- C N 2- SO 4 OH - H 3 O + Pb 2+ Adsorption, active groups CH 2 CH 3 CH 2 OH COOH C=C Expander and organic molecules PbSO 4 Pb Pb skeleton lignosulfonate molecule carbon PbSO 4 C Pb Pb skeleton Expander adsorbed on carbon surface 18 / 18

19 Thank you very much for your attention!

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