10+Battery+Technology (1) | Lithium Ion Battery | Battery (Electricity)

Battery Technology

MSE 6080 – Spring 12

Where our energy comes from

MRS Bull 33 (2008) 264

Renewable energy

Power Generation Devices Chem Soc Rev 38. 226 .

1800 • Today – 8 – 15 batteries for every human on Earth • World market in excess of $ 200 billion .Electrochemical Power Sources • Chemical energy transformed directly into electrical currents – Portable sources of electrical power (watches. portable electronics. supplementary power supply during peak requests) • First battery – Volta. start-up of cars) – Store electrical energy supplied by an external source (electric vehicles.

autonomous systems (MEMS) may require batteries with performances unavailable today • Electric car: capacity. cost .Mobile Power • Portable electronic devices → increasing power requirements • Microsized. weight.

Nomenclature • Primary battery – life has ended once the reactants have been consumed • Secondary battery – can be recharged when the reactants have been used up .

5 – 2 uA. 45 Wh/kg . 15-60 mWh/yr • Dry batteries – toys radios – 10 mAh – 15 Ah • SLI batteries – Pb acid – 12 V. 40-60 Ah.Survey • Battery energies: 10-6 Wh to 3 MWh • Miniature batteries – watches and other miniature apps – 0.

increase base load capacity to stockpile energy and meet peak energy needs . 25x the room of the equivalent IC engine – Longer time to recharge – Currently NiMH – Na or Li based batteries up to 100 Wh/kg • • Stationary batteries – standby power emergency (250 Wh – 5 MWh) Load leveling – public power supply.Future/current uses • A Pb acid battery capable to drive a vehicle is 50x heavier.

Theoretical • An electrochemical reaction provides current through chemical transformations at the electrodes and in the electrolyte Max energy obtainable: ΔG = -zFE Amount of transformation proportional to the charge passed through the cell Cathode: e flow from the external circuit (red) Anode: e flow to the external circuit (ox) • • • • Discharge Charge .

Fe2+⏐⏐Ce4+. Ce3+/Pt Fe2+ + Ce4+ → Fe3+ + Ce3+ • Zn/ZnO/KOH/HgO/Hg Zn + HgO → ZnO + Hg .Theoretical 2 • The EMF of a battery tends to decrease with operation • Design to provide for small changes in OCP • Pt/Fe3+.

Losses • Due to the passage of current – Ohmic drop in the electrolyte bulk – Electrode losses due to CT step • Processes of formation of a solid phase (crystallization overvoltage) • Porous electrodes – interface increase. resistivity decrease • Impregnation to immobilize liquid electrolyte .

Characteristics • Capacity. current – Electrode polarization – Cell resistance – Diffusion overvoltage (reactant depletion) • Discharge curve – OCP vs. Energy. Power • Polarization curve – cell voltage vs. fraction discharge – Cell voltage during deep discharge .

weight Discharge → 2NiO(OH) + Cd + 2H2O = 2Ni(OH)2 + Cd(OH)2 ← Charge • • • • • EMF in 30% KOH is 1.8 Energy density = 208 Wh/kg Practical values ~ 40 Wh/kg ~ 20% .4.7.29 V zFE = 2.Theoretical Energy p. MCd = 112.5×105 Ws ~ 6 Wh MNi = 58. Mtot = 331.u.

com/science_engineering/batteries.and Mg-based Leclanché Schematics of a Leclanche’ battery http://www.wisedude.htm .Primary Batteries • Leclanché (1866) • Zn chloride • Alkaline manganese oxide • Al.

NH4Cl/MnO2. electrolyte ZnCl2 + NH4Cl • Cathode: carbon rod in a mixture C/MnO2 • Anode: Zn rod in sat NH4Cl • Electrolyte immobilized with a paste Zn + 2H2O → Zn(OH)2 + 2H+ + 2e 2MnO2 + 2H+ + 2e → 2MnO(OH) Zn/ZnCl2.Leclanché Cell • Zn anode. MnO2 cathode.C E ~ 1.5 V Zn + 2MnO2 + 2H2O → Zn(OH)2 + 2MnO(OH) .

cont Zn + 2H2O → Zn(OH)2 + H2 • Self-discharge and gas build-up • Slow down by amalgamating Zn with Hg (recently eliminated) • Other drawbacks – Short shelf life (needs refrigeration) – Small energy density (75 Wh/kg) – Voltage decreases over time • Alternative: alk battery (KOH) .Leclanché Cell.

04 VSHE) • Theoretical 1480 Wh/kg vs.insulator) • Stoichiometric Li deficiency Li LiCl . actual 700 Wh/kg • Solvent works as active cathode • Very slow self-discharge • Voltage stable upon discharge • With MnO2 cathode use PC • Importance of solid/electrolyte interface (ion conductor/e.Li-Thionyl Chloride Li0M → Li+ + e 2SOCl2 + 4e → SO2 + S + 4Cl- • EMF 3.65 V (Li+/Li = -3.

Rechargeable batteries • Charge factor: charge used during charge vs. charge passed during discharge • CF > 1 if side rxns occur during charging • Cycle life: # of charge/discharge cycles before battery performance degrades ~ 103 • Full charging can often be achieved only by overcharging. Careful not to evolve gases! • Self-discharge less important .

→ PbSO4 + 2e PbO2 + 2H2SO4 + 2e → PbSO4 + SO42. low cost Pb PbSO4 PbO2 PbSO4 25% H2SO4 EMF = 2.Pb acid Pb + SO42.1 V . actual 40 Wh/kg – η ~ 23% • Cyclability depends strongly on microstructure • Heavy.+ 2H2O PbO2 + Pb + 2H2SO4 → 2PbSO4 + 2H2O discharge • Why water does not dissociate? • Theor 171 Wh/kg.

Microstructural evolution of Pb electrode .

125 .Ni-Cd NiO(OH) + H2O + e → Ni(OH)2 + OHCd + 2OH.→ Cd(OH)2 + 2e Discharge → 2NiO(OH) + Cd + 2H2O = 2Ni(OH)2 + Cd(OH)2 ← Charge • EMF 1.29 V • En density 208 Wh/kg • Rate of discharge. but decreasing J Power Sources 100. T affect capacity • Longer cycle life than Pb (up to 3500. 5-10 yrs) • High cost.

Ni-Metal hydride • Anode LaNi5 based (high H2 storage) • Electrolyte 30% KOH • En density 40-110 Wh/kg • 109 sales/yr .

5 V LI anode Cathode .Li-ion battery • “Li” –ve electrode • TM oxide +ve electrode (Li intercalation) • EMF up to 4.

Electrodes • Anode – graphite LiC6 → Li+ + 6C + e • Cathode Li+ + Mn2O4 + e → LiMn2O4 Li+ + Mn2IVO4 + e → LiMnIIIMnIVO4 Li+ + FeIIIPO4 + e → LiFeIIPO4 • Technological trends – Better graphite – Enhance +ve electrode – Improve solvent stability .

Power Density (W/kg) Courtesy Hyun-Soo Kim . Energy Density (Wh/kg) High Energy LIB 200 Mobile IT Next Generation Battery ? 150 Lithium-Ion Battery 100 Ni/MH 50 Lead Acid 100 200 400 Ni/Cd High Power LIB HEV 800 1.400 Spec.Trends in R&D Spec.

0V:90 Operation Voltage 3. nontoxic Demerits Hard Mn High cost.T.6V High capacity & thermal stability. thermal stability 3. nontoxic High capacity Low cost.8V 3.Some designs LiCoO2 Structure Layered LiNiO2 Layered LiMn2O4 Spinel Li[Co⅓Ni⅓ LiNi½Mn½ LiFePO4 Mn⅓]O2 O2 Layered Layered Olivine LiMnO2 Layered Theoretica 274mAh/g 275mAh/g 148mAh/g 285mAh/g 285mAh/g 170mAh/g 344mAh/g l Capacity 180mAh/g Practical 140mAh/g 180mAh/g 120mAh/g 170mAh/g 170mAh/g 150mAh/g 4. low cost Low tap density 3.6V High electric conductivity.4V Merits High capacity Low cost.4-3V:90 Capacity 3-2.45V Low cost. easy preparation 3. dissolution toxicity Low thermal (@E. preparation.6V 3.) stability Hard Low electric Low electric preparation.5V 3. conductivity conductivity Mn dissolution .

avoid heat loss. corrosion and degradation processes become very fast • Below T1 the electrolyte has too high a resistance and charge transfer is too slow • Heat must be dissipated during high charge/discharge rates • High T batteries: need to heat. use a cooling system to avoid overheating .Thermal management • Above T2.

Summary • Seek high energy density. high power. low cost • EMF is approaching its limits • Room to improve on rates. lifetime • 3D geometries for high rates • Low cost .

Supercapacitors C = ε0ε/d Conventional Electrochemical Q=CV Means of charge storage From Halper and Hellenbogen .

Energy Density • E = 0.2 V in aq electrolytes – 3-4 V in non aq (lower Cdl) • • • • Increase in spec area ↑ energy/weight 7-10% capacity of a battery Better cycle life Fast charge/discharge .5CV2 = 0.5QV • Increase in V advantageous but limited – 0.8-1.

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