Solid Al Electrolytics, MnO2, Conductive Polymer and TCNQ Salt

C 3.4 SOLID ALUMINUM ELECTROLYTICS (SAL) with MANGANESE DIOXIDE (obsolete capacitor technology)

The SAL are aluminum electrolytic capacitors with anodic oxidized aluminum oxide as dielectric and with the semiconducting solid manganese dioxide as electrolyte. They are made of etched and formed aluminum anodes, which are folded for the dipped pearl types or wound into a roll for the axial style. The solid manganese dioxide electrolyte is formed onto this roll in a pyrolytic process, similar to that for solid tantalum capacitors.

SAL-capacitors were developed and introduced in the market in the 1960s by Philips. Up until December 30, 2015, it was a single source product manufactured by Vishay.

As of December 31, 2015 the SAL are end-of-life and have ceased production. Nevertheless, we still list the technology features here for comparison and overview.

C 3.4.1 Introduction

The electrolyte is a solid one. Thus, life is independent of drying effects and leakage currents and theoretically unlimited. Storage has no impairing effect on the dielectric. The stability is much better than that of wet types. The capacitance tolerance is ±20%. The price is high.… Compared to solid tantalums the price for solid aluminum (Al) electrolytics of the same CV product is between two and three times higher. The solid electrolyte doesn’t penetrate the pores of the highly etched aluminum foil equally well as a wet one. Its conductivity, however, is between one and two orders of magnitude larger than that of the wet electrolyte and its temperature dependence smaller.

Principle cross section of a SAL capacitor with solid manganese oxide electrolyte, graphite/silver cathode connection, 1: Anode, 2: Al2O3, 8: MnO2, 9: graphite, 10: silver; source: Vishay

Thus, the solid Al electrolytic is relatively insensitive to the pore effect that in wet Al electrolytics creates a deep network of series and parallel resistances as was shown in Figure C3-13. The capacitor can’t stand any breakdowns. This requires large margins between the forming and rated voltages. The forming rate usually is 2 to 3 times and the rated voltage maximum 40 V DC. Unlike solid tantalums the capacitor is relatively insensitive to pulse loads which, among other things, depends on its higher ESR that reduces the need for an additional circuit impedance.

Nevertheless, just as in solid tantalums, very high pulse currents can initiate a fire. There were two construction styles on the market, the epoxy encapsulated radial types for maximum 175 °C and the axial aluminum can type designed for maximum 200 °C. The radial lead design has a stacked aluminum plate construction which renders a very low ESL (equivalent series inductance). It ranged from 9 to 20 nH. The cylindrical can has a winding of anode and cathode foils plus glass fiber spacers. The reliability of the cylindrical can types is high. Of these there are designs with epoxy fillings intended for extreme acceleration and shock stress.

C 3.4.2 Properties

Capacitance versus temperature

Both the radial and the axial lead types are represented in Figure C3-36.

Figure C3-36. Typical temperature dependence in a solid Al electrolytic

ESR versus temperature

In comparison with wet aluminum electrolytics (Figure C3-28) ESR of the solid ones have a less pronounced temperature dependence as shown in Figure C3-37.

Figure C3-37. Normalized ESR versus ambient temperature in solid Al electrolytics with different temperature ranges. Reference ESR at 25 °C

ESR versus frequency Typical normalized diagrams are shown in Figure C3-38 and 39. The former concerns the radial lead designs with their lower ESL and higher operating frequency range.

Figure C3-38. Normalized ESR versus frequency in solid Al electrolytics with radial leads. Reference ESR at 100 Hz

Note the lower frequency range of the following axial lead design. The steeper slope of the diagrams in the lower part of the frequency range depends on the oxide losses (Figure C3-39).

Figure C3-39. Normalized ESR versus frequency in solid Al electrolytics with axial leads. Reference ESR at 100 Hz

The ESR characteristics are poorer than those of solid tantalums, especially at cooler temperatures. In other word the impedance curve levels off and touches the ESR bottom at lower frequencies in solid Al electrolytics of comparable sizes.

Leakage current versus temperature

Figure C3-40. Normalized leakage current versus temperature in solid Al electrolytics. DCL reference at 25 °C

In Table C3-2 we referred to standards and depicted time to reading to 5 minutes. Figure C3-22 shows a comparison between the time dependence of solid and wet tantalums. In the solid type the curve levels out relatively quick. The same also applies to solid Al electrolytics. Thus, DCL often is measured already after 15 seconds or 1 minute.

C 3.4.3 Reverse voltage

The permissible reverse voltage is stated to be:

  • @ ≤ 85°C max 0.3 x VR
  • @ 85 → 125°C from max 0.3xVR → max 0.15xVR

C 3.4.4 Failure modes

Epoxy-dipped types with radial leads are sensitive to mechanical forces applied on the leads at mounting. Inappropriate handling results in an increase of the leakage current.



C 3.5.1 Polymer electrolyte

Other variant of a solid electrolyte is conductive polymer electrolyte. The aluminum oxide on an etched and formed foil is covered with an electrically very conductive and doped polymer as previously shown in Figure C3-7. The polymer can withstand temperatures up to +105 °C. The ESR of the capacitor is several ten powers better than that of the wet electrolytic types. Its temperature dependence is negligible, but the frequency dependence is more pronounced (Figure C3-41).

Figure C3-41. Typical ESR versus frequency in polymer electrolytes.

The polymer electrolytic capacitor is manufactured in a can or a chip construction with ESR range from 4.5mΩ to 70mΩ, voltage range 2 V to 16 V and capacitance from μF to hundreds of μF. Recommended derating is to use ≤ 80% of VR. The capacitor must not be subjected to any reverse voltage. In case of a short-circuit the local heat generation from the current in the failure spot will be so high that the polymer either will oxidize or will be de-doped and thus creates an insulating “patch” over the failure area. Thus, the capacitor self-heals.

An advantageous chip design is the flat stacked type shown in Figure C3-42. It consists of stacked aluminum plates that have been etched and supplied with an anodic oxidation. The tunnel like structure is covered with a polymerized thin conductive film. Between this film and the following silver paint is added a graphite layer serving as a buffer between the polymer and the silver coating.

Figure C3-42. Schematic of a polymeric aluminum electrolytic capacitor.

The aluminum plates are dipped in a silver epoxy that covers the polymer and graphite surface and fills up the spongy structure of the aluminum plates. The device is then molded in the same plastic epoxy as the one used in solid tantalum SMDs. This construction has an excellent volumetric efficiency. There is a significant difference between this construction and that of a solid sintered tantalum capacitor.

In the latter case the current has to pass “horizontally” through the MnO2 cover to charge the inner capacitive elements in the porous tantalum pellet. In the stacked aluminum construction the current passes “vertically” through the silver, carbon and polymer layers to the inner capacitive elements in the etched tunnels as shown in Figure C3-43.

Figure C3-43. Schematic of an etched aluminum plate with additional cathode layers.

The vertical current paths means a considerably reduced ESR. Such capacitors are capable of a single-digit ESR in the 100 kHz region.
The polymer capacitor is well established and has its greatest advantages in smoothing and noise reduction applications. For high reliability applications, however, its capability in high-shock mechanical environments must be evaluated.

Hybrid Aluminum Electrolytic Capacitors

There also exists a hybrid version of the polymeric style. It has a construction of principle as shown in Figure C3-44. The combination of a liquid electrolyte and a polymer reduces the ESR at the same time as the self-healing properties are retained due to the ion movability.

This type is growing presence on the market as Al can construction (SMD variant is also available) due to its improved robustness to IR reflow mounting conditions compare to Al pure polymer electrolyte solution.

Figure C3-44. Schematic of a hybrid Al electrolytic capacitor with aluminum can and cathode foil.

C 3.5.2 TCNQ salt

Like the polymer electrolyte the semiconducting organic salt TCNQ has also been available on the market for a number of years. The winding is impregnated at a relatively high temperature with melted salt that at cooling is transformed into a solid state. Its ESR is better than that of wet electrolyte but somewhat poorer than that of the polymer electrolyte. The temperature dependence of the ESR is negligible but its frequency dependence more pronounced (Figure C3-45). Note its similarity with the polymer electrolytic.

Figure C3-45. Typical ESR versus frequency in TCNQ electrolytes.

This capacitor is sensitive both to mechanical shocks and ESD. It can endure certain vibration environments. Immediately after soldering it should not be subjected to handling due to the heat influence on the structural strength of the electrolyte/ dielectric system. The highest rated voltage should be derated linearly from 25 V at 85 °C to 20 V at 105 °C.

  • Capacitance range 0.1⋅⋅⋅680 µF
  • Temperature range -55/+105°C
  • Maximum rated voltage 30 V DC
  • ESR, frequency and temperature dependence ≈ that of the polymer capacitor.

Self-healing may occur at short-circuiting. In the failure spot the short-circuit current generates so much heat that the salt decomposes or disappears and thus creates a local insulation area. The capacitor must not be subjected to surge currents or to any overvoltage. Prolonged load at high temperatures will lead to capacitance decrease or in the worst case to open mode. TCNQ salt may also present some risk to environment and ROHS regulation due to presence of cyanide salts. Thus polymer/hybrid types are the main growing aluminum electrolytic capacitor technologies at present stage.


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