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

Electrochemical Power Sources

Chemical energy transformed directly into electrical currents
Portable sources of electrical power (watches, portable electronics, start-up of cars) Store electrical energy supplied by an external source (electric vehicles, supplementary power supply during peak requests)

First battery Volta, 1800 Today 8 15 batteries for every human on Earth World market in excess of $ 200 billion

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

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

Survey
Battery energies: 10-6 Wh to 3 MWh Miniature batteries watches and other miniature apps 0.5 2 uA, 15-60 mWh/yr Dry batteries toys radios 10 mAh 15 Ah SLI batteries Pb acid 12 V, 40-60 Ah, 45 Wh/kg

Future/current uses
A Pb acid battery capable to drive a vehicle is 50x heavier, 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. increase base load capacity to stockpile energy and meet peak energy needs

Theoretical
An electrochemical reaction provides current through chemical transformations at the electrodes and in the electrolyte Max energy obtainable: G = -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

Theoretical 2
The EMF of a battery tends to decrease with operation Design to provide for small changes in OCP
Pt/Fe3+,Fe2+Ce4+, Ce3+/Pt Fe2+ + Ce4+ Fe3+ + Ce3+

Zn/ZnO/KOH/HgO/Hg
Zn + HgO ZnO + Hg

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, Energy, Power Polarization curve cell voltage vs. current
Electrode polarization Cell resistance Diffusion overvoltage (reactant depletion)

Discharge curve
OCP vs. fraction discharge Cell voltage during deep discharge

Theoretical Energy p.u. weight

Discharge

2NiO(OH) + Cd + 2H2O = 2Ni(OH)2 + Cd(OH)2

Charge

EMF in 30% KOH is 1.29 V zFE = 2.5105 Ws ~ 6 Wh MNi = 58.7, MCd = 112.4, Mtot = 331.8 Energy density = 208 Wh/kg Practical values ~ 40 Wh/kg ~ 20%

Primary Batteries
Leclanch (1866) Zn chloride Alkaline manganese oxide Al- and Mg-based Leclanch

Schematics of a Leclanche battery

http://www.wisedude.com/science_engineering/batteries.htm

Leclanch Cell
Zn anode, MnO2 cathode, 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, NH4Cl/MnO2,C E ~ 1.5 V

Zn + 2MnO2 + 2H2O Zn(OH)2 + 2MnO(OH)

Leclanch Cell, 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)

Li-Thionyl Chloride
Li0M Li+ + e 2SOCl2 + 4e SO2 + S + 4Cl-

EMF 3.65 V (Li+/Li = -3.04 VSHE) Theoretical 1480 Wh/kg vs. 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- insulator) Stoichiometric Li deficiency

Li

LiCl

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

Pb acid
Pb + SO42- PbSO4 + 2e PbO2 + 2H2SO4 + 2e PbSO4 + SO42- + 2H2O PbO2 + Pb + 2H2SO4 2PbSO4 + 2H2O
discharge

Why water does not dissociate? Theor 171 Wh/kg, actual 40 Wh/kg ~ 23% Cyclability depends strongly on microstructure Heavy, low cost
Pb PbSO4 PbO2 PbSO4

25% H2SO4 EMF = 2.1 V

Microstructural evolution of Pb electrode

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, T affect capacity Longer cycle life than Pb (up to 3500, 5-10 yrs) High cost, but decreasing

J Power Sources 100, 125

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

Li-ion battery
Li ve electrode TM oxide +ve electrode (Li intercalation) EMF up to 4.5 V

LI anode

Cathode

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

Trends in R&D
Spec. 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. Power Density (W/kg) Courtesy Hyun-Soo Kim

Some designs
LiCoO2 Structure Layered LiNiO2 Layered LiMn2O4 Spinel Li[CoNi LiNiMn LiFePO4 Mn]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 4.4-3V:90 Capacity
3-2.0V:90

Operation Voltage

3.6V
High electric conductivity, easy preparation

3.5V

3.8V

3.6V
High capacity & thermal stability, low cost Low tap density

3.6V

3.45V
Low cost, thermal stability

3.4V

Merits

High capacity

Low cost, nontoxic

High capacity

Low cost, nontoxic

Demerits

Hard Mn High cost, preparation, dissolution toxicity Low thermal (@E.T.) stability

Hard Low electric Low electric preparation, conductivity conductivity Mn dissolution

Thermal management
Above T2, 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, avoid heat loss, use a cooling system to avoid overheating

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 = 0/d

Conventional

Electrochemical

Q=CV
Means of charge storage
From Halper and Hellenbogen

Energy Density
E = 0.5CV2 = 0.5QV Increase in V advantageous but limited
0.8-1.2 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