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Advanced Rechargeable Batteries The Lithium-Ion Battery Service Life Parameters Geneva May, 2013 JP. Wiaux & C. Chanson RECHARGE aisbl 1 Li-ion battery ageing mechanisms The battery life duration is generally limited by the ageing of the Li-ion battery electrodes and chemistry. It can be measured through the evolution of two performances criteria: The evolution of the battery capacity The evolution of the battery internal resistance According usage conditions, other criteria may limit the performances of the battery such as the effect of temperature and the shelf life,…. 2 Li-ion battery ageing mechanisms The progressive reduction of the battery capacity over life The progressive increase of the internal resistance of the battery: it limits the battery power due to voltage reduction. The ageing is often attributed to 2 cumulative mechanisms Calendar life ageing: effect of time and temperature on performances. Cyle life ageing: effect of charge and discharge cycles on performances. 3 • 4 Li-ion chemistries The battery chemistry is characterized by the cathode material (LCO, NMC, LFP, etc…)* and the anode material ( Graphite, LTO, ..)** *Cathode materials: LCO= Lithiated Cobalt Oxyde, NMC= Lithiated Nickel Manganese Cobalt Oxyde, LFP= Lithium Iron Phosphate. **Anode material: LTO= Lithium Titanate. 4 5 Li-ion batteries key features • Multiple Chemistries: Li-Ion is a generic termc for rechargeable batteries It overs several types of battery chemistries and several formats for various applications (see next slides). • Improving technology: This technology is still in an development phase New chemistries and designs are progressively introduced on the market. 5 Choices in Li-ion Chemistry • The type of chemistry will impact performances and safety. LCO NCA NMC LMO LFP LiNiCoAlO2 LiNiMnCoO2 LiMn2O4 LiFePO4 LTO* Li4Ti5O12 Si-C* LiCoO2 4.2V/ 3.8V 4.0V/ 3.6V 4.2V/ 3.7V 4.2V/ 3.9V 3.6V/ 3.3V 2.8V/ 2.4V 4.2V/ 3.9V Energy ++ +++ +++ + ++ - +++ Power ++ +++ ++ +++ ++ + ++ Calendar Life + +++ + - ++ - - Cycle Life + ++ ++ ++ ++ +++ -- Safety + + + ++ +++ +++ + Cost - + ++ ++ + - ++ Cell Voltage, 100%/50% SOC * LTO and Si-C are anodes, which can be combined with any cathode. The selection of a chemistry for a given application is a trade off Between various parameters 7 Li-ion batteries / Formats 1. The battery is also characterized by its format. 1. Button cells 2. Hard cases: cylindrical or prismatic (aluminium welded can) 3. Soft case or « pouch » Reference: IEEE 1725 Standard 7 8 Li-ion packs technologies The industrial battery is independent of the cell format. EV Laptop Bicycle Battery Management System HEV 8 Li-ion ageing: power vs temperature and SOC The battery power is impacted by the storage temperature and by the state of charge during storage 350 20° C Puissance (W) 300 40° C 250 +20°C-100% SOC +40°C-100% SOC 60° C 200 +60°C-100% SOC +20°C-50% SOC 150 +40°C-50% SOC +60°C-50% SOC 100 0 1440 1080 720 Storage time, Days Ref: Saft Li-ion NCA/graphite, M. Broussely IMLB12 360 1800 9 Li-ion ageing: capacity & energy vs temperature Capacity and energy are impacted by the storage temperature 120% 120% 100% 100% 80% 80% 60°C 60% 60% capa +20°C capa +40°C 40% ENERGY, % CAPACITY, % 40-20°C 40% capa +60°C energy +20°C energy +40°C 20% 20% energy +60°C 0% 0% 0 180 360 540 720 900 1080 1260 Days of storage @ 100% SOC Ref: Saft Li-ion NCA/graphite, M. Broussely IMLB12 10 Li-ion ageing: capacity evolution with cycles The cycle life duration is often measured with cycling at 100% depth of discharge: in this case -15% capacity after 1000 cycles 6 Electrolyte "A" Capacity (Ah) 5,5 5 -15% 4,5 4 0 100 200 300 400 500 600 700 800 900 1000 1100 Cycle number But the large majority of applications do not use 100 % of the battery capacity at each cycle ( limited depth of discharge by the user or by the Battery Management System). Ref: Saft Li-ion LCO/graphite, M. Broussely IMLB12 11 Li-ion ageing: cycle life vs depth of discharge The depth of discharge has a large effect on the number of cycle: 1 million cycles can be achieved at low DOD. => the battery management system can protect the battery while limiting the DOD Typical cycle life of a Li-ion cell Ref: Saft Li-ion LCO/graphite, M. Broussely IMLB12 12 Li-ion life duration by application The battery life duration is determined by 3 key factors The battery design: type and quality of selected materials and components, design of the product. The application constraints: temperature of operation, type of usage ( from high power permanent cycling to permanent charge for back-up). The Battery Management System regulation mode: the more efficient is the battery protection, the longer the service life. Consequently, the service life expectation can be as short as 1 to 2 years, (e.g. in cordless power tool) or up to 20 years (e.g. in in stationnary back-up applications)! 13