Friday, April 14, 2017

Supercapacitors: A Summary

A supercapacitor (SC) (also electric double-layer capacitor (EDLC), also called supercap, ultracapacitor or Goldcap) is a high-capacity capacitor with capacitance values much higher than other capacitors (but lower voltage limits) that bridge the gap between electrolytic capacitors and rechargeable batteries. They typically store 10 to 100 times more energy per unit volume or mass than electrolytic capacitors, can accept and deliver charge much faster than batteries, and tolerate many more charge and discharge cycles than rechargeable batteries.
Supercapacitors are used in applications requiring many rapid charge/discharge cycles rather than long term compact energy storage: within cars, buses, trains, cranes and elevators, where they are used for regenerative braking, short-term energy storage or burst-mode power delivery. Smaller units are used as memory backup for static random-access memory (SRAM).
Supercapacitors do not use the conventional solid dielectric of ordinary capacitors. They use electrostatic double-layer capacitance and electrochemical pseudocapacitance, both of which contribute to the total capacitance of the capacitor, however, with different amounts:
  • Electrostatic double-layer capacitors use carbon electrodes or derivatives with much higher electrostatic double-layer capacitance than electrochemical pseudocapacitance, achieving separation of charge in a Helmholtz double layer at the interface between the surface of a conductive electrode and an electrolyte. The separation of charge is of the order of a few ångströms (0.3–0.8 nm), much smaller than in a conventional capacitor.
  • Electrochemical pseudocapacitors use metal oxide or conducting polymer electrodes with a high amount of electrochemical pseudocapacitance additional to the double-layer capacitance. Pseudocapacitance is achieved by Faradaic electron charge-transfer with redox reactions, intercalation or electrosorption.
  • Hybrid capacitors, such as the lithium-ion capacitor, use electrodes with differing characteristics: one exhibiting mostly electrostatic capacitance and the other mostly electrochemical capacitance.
The electrolyte forms an ionic conductive connection between the two electrodes which distinguishes them from conventional electrolytic capacitors where a dielectric layer always exists, and the so-called electrolyte (e.g. MnO2 or conducting polymer) is in fact part of the second electrode (the cathode, or more correctly the positive electrode). Supercapacitors are polarized by design with asymmetric electrodes, or, for symmetric electrodes, by a potential applied during manufacture.
Lifetime of Supercapacitors
Since supercapacitors do not rely on chemical changes in the electrodes (except for those with polymer electrodes) lifetimes depend mostly on the rate of evaporation of the liquid electrolyte. This evaporation in general is a function of temperature, of current load, current cycle frequency and voltage. Current load and cycle frequency generate internal heat, so that the evaporation-determining temperature is the sum of ambient and internal heat. This temperature is measurable as core temperature in the center of a capacitor body. The higher the core temperature the faster the evaporation and the shorter the lifetime.
Evaporation generally results in decreasing capacitance and increasing internal resistance. According to IEC/EN 62391-2 capacitance reductions of over 30% or internal resistance exceeding four times its data sheet specifications are considered "wear-out failures", implying that the component has reached end-of-life. The capacitors are operable, but with reduced capabilities. Whether the aberration of the parameters have any influence on the proper functionality or not depends on the application of the capacitors.
Such large changes of electrical parameters specified in IEC/EN 62391-2 are usually unacceptable for high current load applications. Components that support high current loads use much smaller limits, e.g., 20% loss of capacitance or double the internal resistance.[83] The narrower definition is important for such applications, since heat increases linearly with increasing internal resistance and the maximum temperature should not be exceeded. Temperatures higher than specified can destroy the capacitor.
The real application lifetime of supercapacitors, also called "service life", "life expectancy" or "load life", can reach 10 to 15 years or more at room temperature. Such long periods cannot be tested by manufacturers. Hence, they specify the expected capacitor lifetime at the maximum temperature and voltage conditions. The results are specified in datasheets using the notation "tested time (hours)/max. temperature (°C)", such as "5000 h/65 °C". With this value and expressions derived from historical data, lifetimes can be estimated for lower temperature conditions.
Datasheet lifetime specification is tested by the manufactures using an accelerated aging test called "endurance test" with maximum temperature and voltage over a specified time. For a "zero defect" product policy during this test no wear out or total failure may occur.
The lifetime specification from datasheets can be used to estimate the expected lifetime for a given design. The "10-degrees-rule" used for electrolytic capacitors with non-solid electrolyte is used in those estimations and can be used for supercapacitors. This rule employs the Arrhenius equation, a simple formula for the temperature dependence of reaction rates. For every 10 °C reduction in operating temperature, the estimated life doubles.
Market for Supercapacitors
As of 2016 worldwide sales of supercapacitors is about US$400 million.
The market for batteries (estimated by Frost & Sullivan) grew from US$47.5 billion, (76.4% or US$36.3 billion of which was rechargeable batteries) to US$95 billion. The market for supercapacitors is still a small niche market that is not keeping pace with its larger rival.
In 2016, IDTechEx forecast sales to grow from $240 million to $2 billion by 2026, an annual increase of about 24%.
Supercapacitor costs in 2006 were US$0.01 per farad or US$2.85 per kilojoule, moving in 2008 below US$0.01 per farad, and were expected to drop further in the medium term.

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