new developments for electrochemical energy storage · new developments for electrochemical energy...
TRANSCRIPT
0STYRIAN ACADEMY for Sustainable EnergiesSTYRIAN ACADEMY for Sustainable Energies
NEW DEVELOPMENTS FOR NEW DEVELOPMENTS FOR NEW DEVELOPMENTS FOR ELECTROCHEMICAL ENERGY ELECTROCHEMICAL ENERGY ELECTROCHEMICAL ENERGY
STORAGESTORAGESTORAGEKAIKAIKAI---CHRISTIAN MCHRISTIAN MCHRISTIAN MÖÖÖLLERLLERLLER
1STYRIAN ACADEMY for Sustainable Energies
History and Primary Batteries
Lead Acid Accumulator
Nickel Cadmium Accumulator
Nickel Metal Hydride Accumulator
Sodium Sulfur Accumulator
Sodium Nickel Chloride Accumulator
Redox-Flow Batteries
Electrochemical Double Layer Capacitors
Lithium-Ion Batteries
Outlook
2STYRIAN ACADEMY for Sustainable Energies
History and Primary Batteries
3STYRIAN ACADEMY for Sustainable Energies
Volta Pile (1799)
• medical investigations• discovery of elektrolysis• preparation of Na, K, Ba, Sr,
Ca, Mg, …
Electrolyte
Zinc
Silver
4STYRIAN ACADEMY for Sustainable Energies
Leclanché Element (1866)
supply of railway telegraphs and electric bells
5STYRIAN ACADEMY for Sustainable Energies
Different Types of Primary Batteries
Zinc Silveroxide
Zinc Carbon
Zinc Manganese(Alkaline)
Lithium Metal
Zinc Air
6STYRIAN ACADEMY for Sustainable Energies
Lead Acid Accumulator
7STYRIAN ACADEMY for Sustainable Energies
History
The first Electric Vehicle (1881)
Truck Starter Battery (1960)
Battery after Planté (1859)
8STYRIAN ACADEMY for Sustainable Energies
Reactions
Pb + SO42- PbSO4 + 2 e-, E°= - 0.356 V
PbO2 + SO42- + 2 e- + 4 H+ PbSO4 + 2 H2O, E°= +1.685 V
Overall Reaction
Pb + PbO2 + 2 SO42- + 4 H+ 2 PbSO4 + 2 H2O, ∆E°= 2.04 V
-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
E / V vs. H2/H+
2.04 V
9STYRIAN ACADEMY for Sustainable Energies
Valve regulated lead acid batteries (VRLA)
• closed cells • fixed electrolyte
effectiver internal charge/discharge cycle oxygen diffuses through the electrolyte as gas
10STYRIAN ACADEMY for Sustainable Energies
Absorbent Glass Mat Technology(AGM)
11STYRIAN ACADEMY for Sustainable Energies
Nickel Cadmium Accumulator
12STYRIAN ACADEMY for Sustainable Energies
History
Waldemar Jungner(1869-1924)
1899 developed in Sweden by Waldemar Jungner
13STYRIAN ACADEMY for Sustainable Energies
Design
negative electrode: Cd
positive electrode: NiO(OH)
electrolyty: 20-%ige KOH
14STYRIAN ACADEMY for Sustainable Energies
Applications
Société des Accumulateurs Fixes et de Tractionvalue, 2008
15STYRIAN ACADEMY for Sustainable Energies
Market Data 2008
NiCd: 0.8 Mrd US $(-16 % to prior year)
NiMH: 1.2 Mrd US $(± 0 % to prior year)
16STYRIAN ACADEMY for Sustainable Energies
Nickel Metal Hydride Accumulator
17STYRIAN ACADEMY for Sustainable Energies
History
since 1967: first developments at the Battelle Geneva Research Center withTiNi anodes and the Philips Laboratories / CNRS with rare earth metals
1990: market introduction of Ni-metalhydride cells by SANYO
energy density: 30 - 80 Wh/kgvoltage: 1.3 V
18STYRIAN ACADEMY for Sustainable Energies
Design
AB5 (LaNi5)
(appr. 30 % „Mischmetal“ from rare
earth elements (La, Ce, Nd, Pr, …),
appr. 50 % Ni, + Al, Mn, Co)
take-up of 1.37 m% H
AB2 (TiMn2), Zr(Ni, V, Mn)2
NiO(OH)
20-% KOH
19STYRIAN ACADEMY for Sustainable Energies
Development of SANYO NiMH Batteries (1997 - 2004)
20STYRIAN ACADEMY for Sustainable Energies
SANYO Superlattive Alloy (2003)
• Mm0.83Mg0.17Ni3.1Al0.2 gives 25 % more capacity
21STYRIAN ACADEMY for Sustainable Energies
dissolution of Co and Mn and stripping on the separator
„shuttle effekt“ with nitrogen compounds
Mechanisms of Self Discharge
decomposition with O2 generation
22STYRIAN ACADEMY for Sustainable Energies
further improvements
• increase of the decomposition of the positive with additives
• anode material without Mn, Co, Zn, …
• new electrolyte ( + NaOH)
• hydrophilic separator
Decrease of the self discharge
• more crystalline anode materialwith optimized composition
• additiv coating on the ande material
• thinner casing (such as NiMH 2700 mAh)
23STYRIAN ACADEMY for Sustainable Energies
Applications
value, 2008
Toyota Prius Battery
Toyota Prius Battery
24STYRIAN ACADEMY for Sustainable Energies
Sodium Sulfur Accumulator
25STYRIAN ACADEMY for Sustainable Energies
History
• 1972 - 1987: Research of the BBC (Brown, Boveri & Cie, now ABB, Asea Brown Boveri) in Mannheim
• since 1984: NGK Insulators Ltd. (japanese industrial ceramic producer)
26STYRIAN ACADEMY for Sustainable Energies
Design
liquid Nainner metal cartidge with holes controls access
of Na to the electrolyte interface(0.1 mm gap for
safety)
liquid Sin graphite felt as current collector to the Cr/Mo-
steel outer container
β‘‘-Al2O3-ceramic (Na2O · Al2O3)solid electrolyte for Na-ions, at 300°C as good
conductivity as aqueous electrolytes, also
separator for the liquid electrodes
27STYRIAN ACADEMY for Sustainable Energies
Properties
• Energy density 200 Wh/kg
• Voltage (dep. on SOC) 1,78 - 2,08 V
• Temperature: 300 - 350 °C
• Thermal managment required, suitable for stationary applications
28STYRIAN ACADEMY for Sustainable Energies
Reactions
x S + 2e- Sx2- , E°= - 0.77 – -1.07 V
2 Na + x S Na2Sx, ∆E°= 2.08 – 1.78 V, x = 5 … 3
Na Na+ + e- , E°= - 2.85 V
29STYRIAN ACADEMY for Sustainable Energies
Applications
• Energy Storage for the grid, wind, solar energy
• Space: demonstrator for Space Shuttle flight november 1997 (STS-87 mission)
• EV such as Ford "Ecostar" (Prototype)
30STYRIAN ACADEMY for Sustainable Energies
wind park in USA
34 MW NAS for 51 MW wind park
Applications
31STYRIAN ACADEMY for Sustainable Energies
Europes biggest NaS battery (1 MW) will supply 1000 households for six hours on the Azoren island Graciosa (test in Berlin since 1.7. 2009)
Applications
32STYRIAN ACADEMY for Sustainable Energies
Applications
Ford Ecostar EV (1992-1994)
• ABB NaS Battery
• 37 kWh, 360 kg
• const. power 30 kW, max. 58 kW
• max speed: 115 km/h
• acceleration (0-88 km/h): < 14 s
• range: >160 km
• paxload: 410 kg (incl. driver and passenger)
• test fleet with105 cars (e.g., Deutsche Telekom)
33STYRIAN ACADEMY for Sustainable Energies
Sodium Nickel Chloride AccumulatorZEBRA Battery
34STYRIAN ACADEMY for Sustainable Energies
History
1985 Start of development within the Zeolite Battery Research Africa Project (ZEBRA) at the Council for Scientific and Industrial Research (CSIR) in Pretoria, south africa, for applications in cars and military applications
2010 FIAMM (ital. automotive supplier) and
MES-DEA lounch FZ Sonick SA
since 2006 Renault Twingo, range 120 km, 25 000 €; similar Smart, Panda
35STYRIAN ACADEMY for Sustainable Energies
Design
liquid Na outside: no expensive Ni container, square cells possible (better packaging), no mechanical stress with teperature cycles
porous Ni matrix (current collector) with NiCl2, impegnated with NaAlCl4 (molten salt as second electrolyte, mp. 157 °C)
β‘‘-Al2O3-ceramic (Na2O · Al2O3)
36STYRIAN ACADEMY for Sustainable Energies
Reactions
Ni2+ (Fe2+) + 2e- Ni (Fe) , E°= - 0.27 V (-0.5 V)
2 Na + Ni(Fe)Cl2 2 NaCl + Ni(Fe), ∆E°= 2.58 V (2.35 V)
Na Na+ + e- , E°= - 2.85 V
37STYRIAN ACADEMY for Sustainable Energies
Applications
Smart ForTwo electric drive
• power: 30 kW / 41 PS• acc. 0-60 km/h: 5,7s• max. speed: 112 km/h• range: 115 km• charge time ca. 8 h • battery life: 80 000 km
38STYRIAN ACADEMY for Sustainable Energies
Applications
Mercedes-Benz A class
39STYRIAN ACADEMY for Sustainable Energies
Applications: IVECO Daily
range (with 3 Batteries): 120 km
82 PS, max. 70 km/h
charge time: 8 hours (with 380 V)
battery life: 1000 cycles (130 000 km)
Price with 3 batteries 102 914 € (standard car ca. 27 000 €)
40STYRIAN ACADEMY for Sustainable Energies
Redox-Flow Batteries
41STYRIAN ACADEMY for Sustainable Energies
History
• beginning of 1970ies: NASA investigates different redox couples on their suitability for redox-flow batteries (Fe/Cr and Fe/Ti systems)
• 1986: Vanadium redox-flow battery patented by Maria Skyllas-Kazacos at the University of New South Wales in Australia
• 2009: Prudent Energy Inc. takes over VRB Power Systems
• 2008: Cellstrom (Austria) produces in series the energy storage system FB10/100
42STYRIAN ACADEMY for Sustainable Energies
Design
43STYRIAN ACADEMY for Sustainable Energies
Design
Vanadium in different oxidation states (VII+, VIII+, VIV+, VV+)counter ion: sulfate
current collector: carbon felt
water / H2SO4
Ru for higher current densities H3PO4 and ammonium phosphate for stabilisation
Separator: Nafion, Polystyrenesulfonic acid
44STYRIAN ACADEMY for Sustainable Energies
Reactions
VO2+ + 2H+ + e- VO2+ + H2O , E°= 0.991 V
V2+ + VO2+ + 2H+ V3+ + VO2+ + H2O , ∆E°= 1.246 V
V2+ V3+ + e- , E°= - 0.255 V
45STYRIAN ACADEMY for Sustainable Energies
Applications
VRB Kanada – 2 MW
VRB Energy Storage System (VRB-ESS™) – 5kW
46STYRIAN ACADEMY for Sustainable Energies
Applications
47STYRIAN ACADEMY for Sustainable Energies
Applications
cellcube FB 10-100 (100kWh, 4.5 × 2.2 × 2.4 m, 10.3 t)
power modules
application as solar charging station
48STYRIAN ACADEMY for Sustainable Energies
Electrochemical Double Layer Capacitors
49STYRIAN ACADEMY for Sustainable Energies
Names
• Electrochemical (Double Layer) Capacitor (EC, EDLC)
• Supercapacitor, Ultracapacitor
50STYRIAN ACADEMY for Sustainable Energies
Different Types of Capacitors
elektrostatic capacitor
elektrolyte capacitor
Electrochemical (Double Layer) Capacitor, „Supercap“
51STYRIAN ACADEMY for Sustainable Energies
Design
Quelle: WIMA
active carbon with > 1000 m2/g
aq. H2SO4 or organic solvents with supporting electrolyte (e.g., acetonitrile with tetrabutylammonium tetrafluoroborate, AN / Bu4NBF4)
52STYRIAN ACADEMY for Sustainable Energies
History
• 1957: H. I. Becker of General Electric discovers the charge storage effect of porous carbon electrodes
• 1978: after licensing to NEC commercialisation as “supercapacitor” for memory backup for computer: bipolar construction with six to eight cells in series (to achieve the commonly voltage of 5.5 V)
53STYRIAN ACADEMY for Sustainable Energies
History
• 1998: TheDaewoo Group lounches in Korea NessCap (prismatical wound cells with organic electrolyte).
• 2002: Maxwell buys the SC producer Montena Components (Rossens, Schweiz): cylindrical wound cells with carcon coated alumina foils, trade name „Boostcap“
• 2005: Nippon Chemi-Con (NCC, Japan) puts DLCAP product line on the US market: Electrolyte contains propylene carbonate instead of acetonitrile
54STYRIAN ACADEMY for Sustainable Energies
Electrolytes
E / V vs. H2/H+
-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
aqueous electrolyte
organic electrolyte
1.2 V
2.7 V
55STYRIAN ACADEMY for Sustainable Energies
BMW Concept X3 EfficientDynamics
► overall capacity of 190 kW
► efficiency 98 %, (NiMH 84 %)
56STYRIAN ACADEMY for Sustainable Energies
► up to 30 % energy saving► cable free driving of ca. 1 km with two modules► 20-25 s charge time► 12/2009 six trains in field (19 in 2010, Rhein-Neckar)
Mitrac Energy Saver
57STYRIAN ACADEMY for Sustainable Energies
Lithium-Ion Batteries
58STYRIAN ACADEMY for Sustainable Energies
Host Compounds
LixCn xLi+ + xe- + Cn
Negative - "Anode" Positive - "Kathode"
Li1-xCoO2 + xe- + xLi+ LiCoO2
59STYRIAN ACADEMY for Sustainable Energies
Applications with High Energy Density
60STYRIAN ACADEMY for Sustainable Energies
Applications with High Power Density
61STYRIAN ACADEMY for Sustainable Energies
Tesla
• 6831 Lithium-IoCells (18650)
• 450 kg
• 55 kWh (≈≈≈≈ 120 Wh/kg)
• 0-100 km/h: 4 s
• range: 350 km
• guarantee for 80 % of initial capacity up to 160.000 km
62STYRIAN ACADEMY for Sustainable Energies
Tesla
Battery Box / Energy Storage System "PEM" Power Electronics Module
63STYRIAN ACADEMY for Sustainable Energies
Stationary Applications
64STYRIAN ACADEMY for Sustainable Energies
Stationary Applications
65STYRIAN ACADEMY for Sustainable Energies
Kai-Christian Möller
Fraunhofer Institute for Silicate Research ISCNeunerplatz 2D-97082 Würzburg, Germany