Академический Документы
Профессиональный Документы
Культура Документы
Date Lecture
12. Okt. 15 power grids and motivation for storage
19. Okt. 15 (no lecture)
26. Okt. 15 storage for buildings, including heat pump and CHP (Herena)
2. Nov. 15 storage for buildings, including heat pump and CHP (Herena)
9. Nov. 15 compensating RE fluctuations - the transmission grid level
16. Nov. 15 compensating RE fluctuations - the distribution grid level
23. Nov. 15 non-electrochemical electricity storage: overview
30. Nov. 15 fundamentals of electrochemical storage
7. Dez. 15 electrochemical electricity storage devices (except batteries)
14. Dez. 15 batteries: primary cells
4. Jan. 16 batteries: secondary cells
11. Jan. 16 course summary & exam preparation // electric cars (I)
18. Jan. 16 electric cars (II)
25. Jan. 16 exam
Zn/MnO2 battery
Alkaline manganese battery
Primary Battery Zn/Ag2O battery
Zn/Air battery
(Non-rechargeable) Li primary batteries
electrical energy
Others
Chemical Batteries
chemical energy
Lead-Acid battery
Ni-Cd battery
Secondary Battery Ni-MH battery
(Rechargeable) Li-ion battery
High-temperature secondary battery
Others
Anode:
Zn → Zn2+ + 2e-
Zn2+ + 2 NH4Cl → Zn(NH3)Cl2 + 2H+
Cathode:
2H+ + 2MnO2 + 2e- → 2MnO(OH)
The first modern alkaline manganese cell was developed in the 1960s.
Alkaline/manganese oxide batteries have broadly replaced the zinc/carbon cell today.
It is the most widely produced primary battery of the world.
At the anode:
Zn + 2OH– → ZnO + H2O + 2e –
At the cathode => reduction of MnO2, e. g.:
2MnO2 + H2O + 2e – → Mn2O3 + 2OH–
Advantages
Similar to, and interchangeable with, zinc/carbon
battery but with more than twice the energy
density.
Constant capacity over a wide range of current
drains and suitable for high drain rate appli-
cations.
Longer shelf life (3-5 years) due to reduced self
discharge.
Better low temperature performance and less
leakage than zinc/carbon battery. Continues to
function in sub-zero temperatures.
Suitable for a wide range of consumer
applications.
Shortcomings
(Usually) not rechargeable
Source: DURACELL, USA
Firstly developed in the 1930’s by André. Note the flat discharge characteristics:
Source: http://hittorf.nw.lo-net2.de/chemiegkabi2010/.ws_gen/?4
Advantages
» High energy density. Zinc/Air batteries store more energy per
unit of weight (~350 Wh/kg; OCV ~ 1,4V) than almost any
other primary type (excluding lithium primary batteries)
» Low cost
» When sealed, has excellent shelf life, with a self-discharge rate
of only 2 percent per year.
» Standard battery for hearing aids
Shortcomings
» Low power density (oxygen diffusion limited)
» Sensitive to extreme temperature and humid conditions.
» Carbon dioxide from the air forms carbonate which reduces
conductivity
» High self-discharge after activation, chemicals tend to dry out
and the batteries have to be used quickly
=>
Li/MnO2 Li/SOCL2
OCV 3.2 V 3.67 V
Work voltage 3.0-2.5 V 3.5 V
Specific energy density ~ 370 Wh/kg ~ 500 Wh/kg
(Wh/kg)
Discharge Characteristics has a flat discharge curve has a flat discharge curve
Advantages
» High energy density, double that of alkaline manganese batteries
» High cell voltage (3-4 V)
» Flat discharge characteristic
» Low self-discharge
» Very long shelf life (at least 10 years)
» Very long operating life (15 to 20 years for lithium thionyl chloride)
» Wide operating temperature range ( -60 °C to 85 °C )
» Excellent durability
» Small cell size
Shortcomings
» High cost
» Safety (may explode)
Source: NSF Workshop: Emerging Opportunities of Nanoscience to Energy Conversion and Storage
Electronic conductivity
Electrode fabrication
Secondary Batteries
Battery design
Ion diffusion coefficient
electrode materials
Solubility intermediates
Raw materials
Economic aspects Manufacturing costs
Cost on the application level
Lead-Acid battery
Nickel Iron (Ni-Fe) battery
Nickel Cadmium (Ni-Cd) battery
Nickel Hydrogen (Ni-H2) battery
Aqueous electrolyte Nickel Metal Hydride (Ni-MH) battery
electric energy
Source: 2008, Machinery statistics released by the Ministry of Economy, Trade and Industry, Japan
High-temperature battery
In a VRLA battery, the separator is only partially saturated with acid, so that it stays
permeable to gas. Oxygen produced at the positive electrode can diffuse to the
negative electrode, where a number of chemical reactions finally lead to the
recombination of the hydrogen and oxygen into water. „Valve-regulated“ only refers to
an overpressure valve for safety reasons.
This concept minimizes leakage and maintenance.
only for internal use (storage lecture) 32
Typical charge-discharge characteristics of lead-acid battery
NiCd- and NiMH-batteries once suffered from the so-called memory effect. The
“genuine” memory effect of NiCd batteries was caused by overcharging and resulted in a
kink in the discharge curve. In contrast, the “lazy effect” (nowadays often referred to as
the memory effect) means that a partial discharge leaves the battery at a reduced
voltage over most of the discharge curve.
The latter can be overcome by a full discharge that “refreshes” the cell.
http://media.maxim-ic.com/images/appnotes/3999/3999Fig01.gif
Advantages
Fast and simple charging behaviour.
Long shelf life - five-year storage is possible.
Good low temperature performance, can be charged and discharged at low temperature.
Forgiving if abused - nickel-cadmium is one of the most rugged rechargeable batteries.
Economically priced - nickel-cadmium is lowest in terms of cost per cycle.
Limitations
Relatively low energy density.
Memory effect - nickel-cadmium periodically had to be reconditioned
(discharge/charge) to prevent memory.
Environmentally unfriendly - nickel-cadmium contains toxic metals. Some countries restrict its use.
Relatively high self-discharge - needs recharging after storage.
The hydrogen storage alloy (MH), LaNi5, was invented by Markin 1970’s.
The LaNi5 was further developed by Willems at Philips Research in 1984.
The first commercial Ni-MH battery was produced by SANYO in 1989.
State of the Art 2016: Ansmann sells 2850 mAh in NiMH AA.
Source: ECD Ovonic, The 24th International Seminar & Exhibit on Primary and Secondary Batteries
Source: http://www.chinabatteryweb.com
Advantages
» Relatively high energy density
» Typical cycle life is more than 500 cycles
» Flat discharge characteristic (but falls off rapidly at the end of the cycle)
» Wide operating temperature range
» Rapid charge possible in 1 hour
» Reconditioning is possible (to overcome a potential memory effect).
» Environmentally friendly (No cadmium, mercury or lead)
» Can be used robustly
Shortcomings
» Very high self-discharge rate, nearly ten times worse than lead acid or Lithium ion
batteries, especially at high working temperature
» High rate discharge not as good as Ni-Cd
» Less tolerant against overcharging (compared to Ni-Cd)
» Relatively high cost
The concept of the “rocking chair battery” was firstly reported by M. Armand in 1980.
Underlying concept:
Li-ions (not atoms!) are stored between the layers of graphite (so-called intercalation
mechanism) in the anode and within complex (often layered) metal oxide compounds that
allow for two valency stages (e. g. Mn4+/Mn3+ in LiMnO2) in the cathode.
Both electrode materials are structurally stable against charging/discharching with Li+.
Layered lithium transition compounds LiMO2(M=Co, Ni, Mn)were synthesized by J.B.
Goodenough in 1980’s.
In 1991, the first commercial LIB was commercialized by SONY.
The polymer LIB was firstly patented by Bellcore in 1994.
The high power LIB is being tested in HEV and EV since the year 2000.
In the first charging processes, the electrolyte reacts vigorously with the carbon anode. A thin
passivating SEI layer is built upon the surface of the carbon anode which is electrically
insulating yet sufficiently conductive to lithium ions. This SEI layer is essential for the stability of
the Lithium ion battery using carbon anodes, as it prevents further interaction between the
electrolyte and the carbon.
The composition of the SEI layer is complicated and Li3CO3, LiOH, Li2O, LiOR, LiOCO2R
(R=hydrocarbon) as well as lithium halide can be detected.
only for internal use (storage lecture) 54
Typical cell structure for LIB
Separator:
poly(tetrafluoroethylene)-PTFE
In a polymer LIB, a solid polymer electrolyte is used instead of the ordinary liquid electrolyte.
The main difference here is that the lithium-salt electrolyte is stored in the matrix of a solid polymer
(gel type electrolyte), allowing for simpler, thinner and larger-area cell designs.
Advantages:
Very thin profile
Flexible geometry
Lightweight
Improved safety
High energy density and
good cycle performance
Limitations:
Lower energy density and decreased
cycle count compared to lithium-ion.
Expensive to manufacture.
The safety problems for LIB are more serious than for
any other secondary battery.
Reasons: At abuse conditions (over-charging)
LiCoO2 may decompose and release active O2 and heat
Metallic Li electrodeposition is possible at anode
Li and O2 react with organic solvent to release gas and heat
Strategies:
Protection circuits and safety valves
Use alternative electrode materials (e.g. LiFePO4, Li4Ti5O12)
Additives in the electrolyte
Polymer LIB
Advantages
High cell voltage of 3.6 V
Very high energy density and very high power density
Flexible cell design (Cylindrical Cell, Coin Cell, Prismatic Cell, Pouch Cell and thin film cell)
Very low self discharge rate (< 5 %/month) and very high columbic efficiency (almost 100%)
Long cycle life (at least 500 cycles 100% DOD; today usually much more)
Does not need reconditioning as do nickel based batteries
Variants of the basic cell chemistry allow the performance to be tuned for specific
applications
Shortcomings
Performance degradation at very low or high temperature
Charge and discharge at high C-rate are restricted
Can only be charged with a highly controlled method to avoid over-charging
Safety concerns (protection circuit and valve are necessary)
Relative high materials and manufacture cost
Advantages:
High ionic conductivity at 300 °C
High fracture toughness
Stable to moisture
Good wetting by sodium
Long life at high current densities
Resistant to electrical breakdown
Relative low cost production
Major problem:
High mechanical stress caused by
temperature cycles
ZEBRA and lead-acid battery comparison: sprint and low speed endurance
(identical battery compartment dimensions)
Source: Rolls-Royce, UK
Advantages
High energy density (3 times higher than Lead-acid)
Large cells (up to 500Ah) possible
Cycle life better than 2000 cycles
Tolerant of short circuits
Safer than Na-S battery, typical cell failure is short circuit which does not cause
complete failure of the battery.
Shortcomings
Suitable for large capacity batteries only (> 20KWh)
High internal resistance
High operating temperature. Uses 14% of its own capacity per day to maintain
temperature when not in use.
Relative high manufacture cost
Are there chances for a new rechargeable battery system with higher
energy density than LIB?
Battery recycling
Ni-Cd has been in the focus of the recycling efforts, but Li-Ion is expected
to catch up.
Decisive factors:
Energy and power density
Energy efficiency
Cost
Date Lecture
12. Okt. 15 power grids and motivation for storage
19. Okt. 15 (no lecture)
26. Okt. 15 storage for buildings, including heat pump and CHP (Herena)
2. Nov. 15 storage for buildings, including heat pump and CHP (Herena)
9. Nov. 15 compensating RE fluctuations - the transmission grid level
16. Nov. 15 compensating RE fluctuations - the distribution grid level
23. Nov. 15 non-electrochemical electricity storage: overview
30. Nov. 15 fundamentals of electrochemical storage
7. Dez. 15 electrochemical electricity storage devices (except batteries)
14. Dez. 15 batteries: primary cells
4. Jan. 16 batteries: secondary cells
11. Jan. 16 course summary & exam preparation // electric cars (I)
18. Jan. 16 electric cars (II)
25. Jan. 16 exam
Date Lecture
12. Okt. 15 power grids and motivation for storage
19. Okt. 15 (no lecture)
26. Okt. 15 storage for buildings, including heat pump and CHP (Herena)
2. Nov. 15 storage for buildings, including heat pump and CHP (Herena)
9. Nov. 15 compensating RE fluctuations - the transmission grid level
16. Nov. 15 compensating RE fluctuations - the distribution grid level
23. Nov. 15 non-electrochemical electricity storage: overview
30. Nov. 15 fundamentals of electrochemical storage
7. Dez. 15 electrochemical electricity storage devices (except batteries)
14. Dez. 15 batteries: primary cells
4. Jan. 16 batteries: secondary cells
11. Jan. 16 course summary & exam preparation // electric cars (I)
18. Jan. 16 Exam: W03 1-161, 25.electric
Januarycars (II) 2016, 08:30 – 9:30 am
25. Jan. 16 exam