Towards competitive European batteries GC.NMP.2013-1 Grant. 608936 Lecture I: Materials improvement and cells manufacturing Leclanché GmbH External Workshop Brussels, 23.05.2016 1
Plan About Leclanché Cell development & manufacturing Generation 1 Generation 2 Generation 3 Intellectual properties Conclusion 2
About Leclanché Headquartered in Yverdon-les-Bains, Switzerland, since 1909 2 entities: Leclanché SA (LSA), CH, & Leclanché GmbH (LEC), DE LEC: R&D labs and production Production capacity of 1 M units/year since end 2013 Water-based 3
About Leclanché 2 cell chemistries commercially available: Lithium Titanate/NCA: 76 Wh/kg Graphite/NMC: 160 Wh/kg Make good use of Leclanché unique technologies in the project: o Patented Water-based production: envir. friendly, cost effective o Patented Ceramic separator*: safer batteries o Bicell lamination + stacking * * specific design for stationary applications volume not critical R&D: continuous cell development 4
About Leclanché Within the project Status Entity Project activities Beneficiary Leclanché SA Decision making Scientific input (H. Buqa, P. Blanc) 3 rd Party Leclanché GmbH Prj. Management Tests and production H.-Y. Amanieu, S. Wussler, (Prev. G. Jutz, W. Scheifele) 5
Cell development & manufacturing material in-/output + Active material + Binders + Additives + water Project Umicore NMC (cathode) Aceton (Cathode) + Al electrode foil + Cu electrode foil - Solvent (water) emission Aceton (Cathode) Adapted from Roland Berger, 2011 6
Cell development & manufacturing material in-/output - Cutting scrap Al foil - Cutting scrap Cu foil + Separator - Carrier foil + Adhesive tapes + Al tabs (positive) + Ni/Cu tabs (negative) Adapted from Roland Berger, 2011 7
Cell development & manufacturing material in-/output Project - Solvent (water) emission + Electrolyte Adapted from Roland Berger, 2011 8
Cell development & manufacturing material in-/output Project - Cutting scrap from pouch foil Adapted from Roland Berger, 2011 9
Cell development & manufacturing Improve cell energy density and cycle life through: o New cathode material: Nickel Cobalt Manganese Oxide NMC 1:1:1 NMC 5:3:2 NMC 6:2:2 High Energy NMC (layered manganate and NMC) o Fine tuning of electrolyte/electrode system o Design and production of the full cell Economy of Scale (larger format) 10
Cell development & manufacturing Gen 1 NMC Cathode Lab Halfcells Pilot full cells Commercial cells Gen 2 NMC Cathode Lab Halfcells Pilot full cells Production Testing partners Gen 3 NMC Cathode Lab Halfcells Pilot full cells Production 11
Generation 1 Objective: deliver reference samples o Material development (2013) NMC Cathode Cathode type Chemistry Capacity Average Voltage (v. Gr) Standard NMC NMC 1:1:1 147 mah/g 3,7 V Gen 1 NMC NMC 5:3:2 160 mah/g 3,7 V o Two Umicore NMC 5:3:2 provided Lab Halfcells 12
voltage (V) Generation 1 Two NMC chemistries tried Cathode made in the lab (mixing and coating) One chemistry was selected Lab Halfcells 4,30 4,20 4,10 4,00 3,90 3,80 3,70 3,60 3,50 3,40 3,30 3,20 3,10 3,00 NMC 532 (WB), 1.40 mah/cm² NMC 532 (WB), 1.24 mah/cm² NMC 532 (SB), 1.07 mah/cm² NMC 532 (SB), 1.80 mah/cm² 0 20 40 60 80 100 120 140 160 capacity (Ah/kg) 13
capacity (% of initial capacity at C/10) Generation 1 Pilot production of cathode with 20 kg Water-based mixing showed bad results (yellow/red curves) Aceton-based mixing was used to go to full production (blue curve) 120 110 Lab Halfcells 100 90 80 70 60 50 40 30 20 10 0 NMC 532 (SB), 1.80 mah/cm², lab NMC 532 (SB), 1.80 mah/cm², pilot NMC 532 (SB), 1.91 mah/cm², pilot, cal NMC 532 (SB), 1.91 mah/cm², pilot, cal NMC 532 (SB), 1.20 mah/cm², lab, cal; acet. 0 50 100 150 200 250 300 cycles 14
Generation 1 Full cells were assembled: o Water-based production of graphite anode o Aceton-based production of NMC cathode o Standard electrolyte o Ceramic-based separator Pilot full cells 15
capacity (Ah) Generation 1 Unable to charge over 4.1V Significant temperature increase 23 22 1C, U max 4.2 V 2C, U max 4.2 V 1C, U max 4.2 V 21 20 C/5, U max 4.1 V 1C, U max 4.1 V Pilot full cells 19 18 17 16 C/5, U max 4.1 V NCA dch NCA ch NCA dch NCA ch NMC dch NMC ch NMC dch NMC ch 0 20 40 60 80 100 120 140 cycles For comparison, same recipe using Nickel Cobalt Aluminum (NCA) 16
Generation 1 Alternative commercial cells were used as reference Commercial cells Gen Max Voltage Nominal Voltage Capacity Energy Energy Density 1 4,15 V 3,65 V 20 Ah 73 Wh 174 Wh/kg Parallely, research continued: o Problem arose from electrolyte compatibility o Later, a suitable electrolyte was found out Experience was constructive for Generation 2 and 3 manufacturing. 17
Generation 2 Materials development (End 2013) Cathode type Chemistry Capacity Average Voltage (v. Gr) Standard NMC NMC 1:1:1 147 mah/g 3,7 V Gen 1 NMC NMC 5:3:2 160 mah/g 3,7 V Generation 2 High Ni NMC NMC 6:2:2 180 mah/g 3,85 V NMC Cathode Higher capacity Low Co NMC NMC 5:4:1 160 mah/g 3,9 V Cheaper o 3 Umicore NMC 6:2:2 provided Lab Halfcells 18
discharge capacity (mah/cm²) C-rate The 3 materials were tested in half-cells Aceton-based production in lab 1,40 Generation 2 Lab Halfcells 2,5 1,20 2,0 1,00 0,80 1,5 0,60 0,40 0,20 0,00 1,0 NMC-523 (SB), 1.20 mah/cm², LP30 (A) NMC-622 A, 1.64 mah/cm², LP30 (A) NMC-622 A, 1.64 mah/cm², LP30 (A) NMC-622 B, 1.47 mah/cm², LP30 (A) 0,5 NMC-622 B, 1.47 mah/cm², LP30 (A) NMC-622 C, 1.50 mah/cm², LP30 (A) NMC-622 C, 1.50 mah/cm², LP30 (A) C-Rate Dischrg. 0,0 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 cycle 19
capacity (mah/cm²) C-rate (A/Ah) Generation 2 Lab production of full cells: o Water-based production of graphite anode o Aceton-based production of NMC cathode o Standard electrolyte o Ceramic separator Pilot full cells 2,50 7,00 2,00 6,00 5,00 1,50 1,00 C Discharge C-Rate Dischrg. 4,00 3,00 0,50 2,00 1,00 0,00 0,00 0 10 20 30 40 50 60 70 80 cycle Discharge capacity 20
Capacity (Ah) Generation 2 Pilot production of full cells: o Water-based production of graphite anode o Aceton-based production of NMC cathode o Standard electrolyte o Ceramic separator Pilot full cells 30,0 29,0 28,0 27,0 26,0 25,0 graphite/nmc-622; LP30; formation A graphite/nmc-622; LP30; formation B graphite/nmc-622; LP30; formation C graphite/nmc-622; LP30; formation D Energy density too low <160 Wh/kg 24,0 23,0 22,0 21,0 20,0 0 50 100 150 200 250 300 cycle Discharge capacity 21
Capacity (Ah) Generation 2 Pilot production of full cells 2: o Same electrolyte, Higher load o Different electrolytes tested Pilot full cells 30,0 29,0 Higher capacity Higher efficiency (not plotted) 28,0 27,0 26,0 25,0 graphite/nmc-622; LP30; formation C graphite/nmc-622; EL1; formation C graphite/nmc-622; EL2; formation C graphite/nmc-622; EL3; formation C graphite/nmc-622; LP30; formation C; high loading graphite/nmc-622; LP30; formation C; high loading 24,0 176 Wh/kg 23,0 22,0 21,0 20,0 0 20 40 60 80 100 120 140 160 180 200 cycle Discharge capacity 22
Generation 2 Selected recipe transferred to mass-production line Aceton-based production was selected due to better mechanical properties on the line (water-based worked well in lab production) 129 Production Testing partners Gen Max Voltage Nominal Voltage Capacity Energy Energy Density 1 4,15 V 3,65 V 20 Ah 73 Wh 174 Wh/kg 2 4,2 V 3,7 V 28 Ah 104 Wh 176 Wh/kg 23
Generation 3 Materials development (End 2013) Cathode type Chemistry Capacity Average Voltage (v. Gr) Standard NMC NMC 1:1:1 147 mah/g 3,7 V Gen 1 NMC NMC 5:3:2 160 mah/g 3,7 V Generation 2 High Ni NMC NMC 6:2:2 180 mah/g 3,85 V Low Co NMC NMC 5:4:1 160 mah/g 3,9 V High Energy NMC (layered) Li 2 MnO 3 // NMC Generation 3 257 mah/g 3,5 V NMC Cathode Unstable! 24
Generation 3 High Energy NMC is still highly unstable, requires more fundamental work Umicore developed further NMC 6:2:2 o New surface coating/particle morphology o Mass production o Supply compatible electrolyte OBJECTIVE: go to 4,3 V cut-off voltage (standard is 4,2 V) NMC 6:2:2 o 3 new Umicore NMC 6:2:2 provided o 1 electrolyte sample 25
Discharge capacity [mah/cm²] C-Rate Half-cells built with standard electrolyte The three NMC types showed acceptable results Full cells were built with the three types: Generation 3 Lab Halfcells G3 coin full cell cycling capacity Pilot full cells 2,0 1,9 1,8 1,7 1,6 1,5 1,4 1,3 1,2 1,1 1,0 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0,0 0 10 20 30 40 50 60 70 80 0 Grade A-1 10 20 Grade B-1 30 40 Grade C-1 50 60 Grade A-2 70 80 Grade B-2 Grade C-2 Zyklen C-Rate Dischrg. 7,0 6,0 5,0 4,0 3,0 2,0 1,0 0,0 26
Generation 3 Grade B was picked Cells were assembled in the mass-prod line without electrolyte: o Larger cell format: DIN-A5 (Gen2) > DIN-A4 (Gen3) o Capacity below 50Ah: loading 5% decrease versus Gen 2 o Aceton-based production of cathode o Test prototype electrolyte from Umicore in full cells 181 Umicore (prototype) Standard 3 3 27
Capacity [Ah] 50,0 G3 cells cycled in lab Charge C/2 discharge C/2 ; 4,2V -- 3,0V Generation 3 48,0 46,0 4.3V cut-off voltage 44,0 42,0 40,0 38,0 36,0 34,0 32,0 30,0 0 50 100 150 200 250 300 350 400 450 500 Zyklus Umicore, 4.3V from cycle 209 Umicore Standard, 4.3V from cyc 220 Standard 28
Generation 3 Umicore Electrolyte shows higher capacity However, cycle life is much shorter 4,3 V cut-off voltage limits cycle life as well Continue with standard electrolyte Production 48 Testing partners Gen Max Voltage Nominal Voltage Capacity Energy Energy Density 1 4,15 V 3,65 V 20 Ah 73 Wh 174 Wh/kg 2 4,2 V 3,7 V 28 Ah 104 Wh 176 Wh/kg 3 4,2 V 3,7 V 45 Ah 161 Wh 172 Wh/kg 3 4,3 V 3,7 V 48 Ah 174 Wh 178 Wh/kg With normal loading 177 Wh/kg 182 Wh/kg 29
IPR management IPR management within consortium: IPR identification IPR analysis IPR protection IPR utilization What are the potentially interesting innovations? How to protect? How to utilize? Economically justified protection Turning IP into business 30
IPR identification IPR analysis IPR protection IPR utilization What are the potentially interesting innovations? How to protect? How to utilize? Economically justified protection Turning IP into business Internal outlook (Umicore s): o Gen 2 and Gen 3 materials have been protected o Both went to mass production o Next step is commercialization Internal outlook (Leclanché s): o Gen 2 and Gen 3 cells show a higher energy density than our standard Graphite/NMC cells o Compatibility with water-based production of cathode (NMC-622) is critical to pursue in this direction o Overall design of the cell should be adapted to automotive application 32
Conclusions Project outlook: improving cell density to 250 Wh/kg o More development at the material level is necessary (before assembling): Stability of new cathode material Electrolyte/Material interaction o Joint work between: Cell assembler Electrolyte manufacturer Active material manufacturer Materials science research institutes 33
Conclusion Take-away message: o A battery is a complex chemical system o Changing the recipe of one component can have a huge effect on the other components. o In this project, finding the right electrolyte was critical: Instability of Leclanché s Gen 1 cells Capacity and projected cycle life of Gen 3 cells 34
Discussion Thanks for you attendance Questions? This project has received funding from European Union s Seventh Programme for research, technological development and demonstration under grant agreement No. 608936 35