The Comic Book World Of Capacitor Marketing

The Economist is an interesting publication, a British weekly newspaper that looks for all the world like a magazine, and contains pithy insights into world politics and economic movements. It’s one of those rare print news publications that manages to deliver fresh insights even to hardened web news junkies despite its weekly publication date.

It was typical then of their wide-ranging coverage of world industries to publish a piece recently on the world of supercapacitors, with particular focus on Estonia’s Skeleton Technologies. This is an exciting field in which the products are inching their way towards energy density parity with conventional batteries, and news of new manufacturing facilities coming online should be of interest to many Hackaday readers.

Exciting though it may be it was not the news of a new capacitor plant in Germany that provided the impetus for this piece. Instead it was the language used by the Economist writer delicately skirting the distinction between the words “Supercapacitor” and “Ultracapacitor”. Images of flying crimefighters in brightly coloured capes spring instantly to mind, as Captain Ultra and Superman battle an arch-villain who is no doubt idly bouncing a piece of burning Kryptonite against the wall in readiness for the final denouement.

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History Of The Capacitor – The Modern Era

The pioneering years in the history of capacitors was a time when capacitors were used primarily for gaining an early understanding of electricity, predating the discovery even of the electron. It was also a time for doing parlor demonstrations, such as having a line of people holding hands and discharging a capacitor through them. The modern era of capacitors begins in the late 1800s with the dawning of the age of the practical application of electricity, requiring reliable capacitors with specific properties.

Leyden Jars

Marconi with transmitting apparatus
Marconi with transmitting apparatus, Published on LIFE [Public domain], via Wikimedia Commons
One such practical use was in Marconi’s wireless spark-gap transmitters starting just before 1900 and into the first and second decade. The transmitters built up a high voltage for discharging across a spark gap and so used porcelain capacitors to withstand that voltage. High frequency was also required. These were basically Leyden jars and to get the required capacitances took a lot of space.

Mica

In 1909, William Dubilier invented smaller mica capacitors which were then used on the receiving side for the resonant circuits in wireless hardware.

Early mica capacitors were basically layers of mica and copper foils clamped together as what were called “clamped mica capacitors”. These capacitors weren’t very reliable though. Being just mica sheets pressed against metal foils, there were air gaps between the mica and foils. Those gap allowed for oxidation and corrosion, and meant that the distance between plates was subject to change, altering the capacitance.

In the 1920s silver mica capacitors were developed, ones where the mica is coated on both sides with the metal, eliminating the air gaps. With a thin metal coating instead of thicker foils, the capacitors could also be made smaller. These were very reliable. Of course we didn’t stop there. The modern era of capacitors has been marked by one breakthrough after another for a fascinating story. Let’s take a look.

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Lint And Dog Hair Supercapacitor

[Mechanicus] has made a supercapacitor with a claimed 55 Farads per gram of active material. And he’s made it using dryer lint and dog hair. And he’s done it in 24 hours. That’s the short story. The longer story is an epic journey of self-discovery and dog ownership, and involves a cabin in the Wyoming backwoods.

So how did he do it?

He started with a home-made crucible that you maybe wouldn’t want to carry around in public as it bears more than a passing resemblance to a pipe bomb. Into that he packed his dog hair and lint, along with a generous helping of ammonia. An hour or two in a woodstove glowing red, and he’d made a rod of mostly carbon with the required high surface area. He sawed off a carbon slice, bathed it in lithium sulphate and potassium iodide electrolyte, and with the addition of a couple of pieces of stainless steel he had a supercapacitor.

Full details of his build can be found on the hackaday.io pages linked above, but there is also a handy YouTube video below the break.

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Graphene Super Caps: Coming Soon?

If you read Hackaday regularly, you’ve probably heard that you can use a LASER to create graphene. There’s been a bit of research on how to make practical graphene supercapacitors using the technique (known as LIG or LASER-induced graphene). Researchers at Rice University have been working on this, and apparently they’ve had significant success inducing graphene capacitors on a Kapton substrate. The team has published a paper in Advanced Materials (which is behind a paywall) about their work.

In particular, Rice claims that they have easily produced supercapacitors with an energy density of 3.2 mW/cubic centimeter (that’s what the University’s website reports; they probably mean mW-hours/cubic centimeter) with capacitances near one millifarad per square centimeter. A key benefit of the construction method is that the capacitors continued to work after researchers bent them 10,000 times. A flexible capacitor is useful in wearable devices that would often flex, or in a device like a cell phone that could bend in your back pocket as you sit.

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Paper Thin Conductors

Swedish scientists have created something they call power paper by using nanocellulose and a conductive polymer. The paper is highly conductive and has applications in supercapacitor technology and printed electronics.

The paper, technically called NFC-PEDOT paper, combines high conductivity and compatibility with conventional paper handling machines that could lead to less expensive manufacturing. The team used the material to create supercapacitors (up to 2F) as well as FET-like transistors known as OECTs (Organic Electrochemical Transistors).

Admittedly, the supercapacitor prototype didn’t look very practical (as they dunked it in a beaker full of potassium chloride). The black-colored paper is relatively conductive (42,000 S/m at 20 degrees C), at least for a paper. As a point of reference, silicon is about 1,000 S/m and iron conducts at about 10,000,000 S/m.

What can we do with NFC-PEDOT? Time will tell. We couldn’t help but wonder, however, if paper-based 3D printing couldn’t be adapted to use paper as an insulator or dielectric, foil as a conductor, and something like this material to build resistive elements. After all, we’ve seen something similar using foil and paper before.

Better Capacitors Through Nanotechnology

Traditionally, capacitors are like really bad rechargeable batteries. Supercapacitors changed that, making it practical to use a fast-charging capacitor in place of rechargeable batteries. However, supercapacitors work in a different way than conventional (dielectric) capacitors. They use either an electrostatic scheme to achieve very close separation of charge (as little as 0.3 nanometers) or electrochemical pseudocapacitance (or sometime a combination of those methods).

In a conventional capacitor the two electrodes are as close together as practical and as large as practical because the capacitance goes up with surface area and down with distance between the plates. Unfortunately, for high-performance energy storage, capacitors (of the conventional kind) have a problem: you can get high capacitance or high breakdown voltage, but not both. That’s intuitive since getting the plates closer makes for higher capacitance but also makes the dielectric more likely to break down as the electric field inside the capacitor becomes higher with both voltage and closer plate spacing (the electric field, E, is equal to the voltage divided by the plate spacing).

[Guowen Meng] and others from several Chinese and US universities recently published a paper in the journal Science Advances that offers a way around this problem. By using a 3D carbon nanotube electrode, they can improve a dielectric capacitor to perform nearly as well as a supercapacitor (they are claiming 2Wh/kg energy density in their device).

cap1The capacitor forms in a nanoporous membrane of anodic aluminum oxide. The pores do not go all the way through, but stop short, forming a barrier layer at the bottom of each pore. Some of the pores go through the material in one direction, and the rest go through in the other direction. The researchers deposited nanotubes in the pores and these tubes form the plates of the capacitor (see picture, right). The result is a capacitor with a high-capacity (due to the large surface area) but with an enhanced breakdown voltage thanks to the uniform pore walls.

cap2To improve performance, the pores in the aluminum oxide are formed so that one large pore pointing in one direction is surrounded by six smaller pores going in the other direction (see picture to left). In this configuration, the capacitance in a 1 micron thick membrane could be as high as 9.8 microfarads per square centimeter.

For comparison, most high-value conventional capacitors are electrolytic and use two different plates: a plate of metallic foil and a semi-liquid electrolyte.  You can even make one of these at home, if you are so inclined (see video below).

We’ve talked about supercapacitors before (even homebrew ones), and this technology could make high capacitance devices even better. We’ve also talked about graphene supercaps you can build yourself with a DVD burner.

It is amazing to think how a new technology like carbon nanotubes can make something as old and simple as a capacitor better. You have to wonder what other improvements will come as we understand these new materials even better.

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Mostly Non-Volatile Memory With Supercapacitors

Back in the days of old, computers used EPROMs to store their most vital data – usually character maps and a BASIC interpreter. The nature of these EPROMs meant you could write to them easily enough, but erasing them meant putting them under an ultraviolet light. Times have changed and now we have EEPROMs, which can be erased electronically, and Flash, the latest and greatest technology that would by any other name be called an EEPROM. [Nicholas] wanted an alternative to these 27xx-series EPROMs, and found his answer in supercapacitors.

[Nick]’s creation is a mostly non-volatile memory built around an old 62256 32k SRAM. SRAM is completely unlike EPROMs or Flash, in that it requires power to keep all its bits in memory. Capacitor technology has improved dramatically since the 1980s, and by using a supercap and one of these RAM chips, [Nick] has created a substitute for a 27-series EPROM that keeps all its memory alive for days at a time.

The circuit requires a small bit of electronics tucked between the EPROM socket and the SRAM chip; just enough to turn the 12 Volts coming from the EPROM programming pin to the 5 Volts expected from the SRAM’s Write Enable pin. This is accomplished by a few LEDs in series, and a 0.1F 5.5V supercap which keeps the SRAM alive when the power is off.

As for why anyone would want to do this when modern technologies like Flash can be found, we can think of two reasons. For strange EPROM sizes, old SRAMs abound, but a suitable Flash chip in the right package (and the right voltage) might be very hard to find. Also, EEPROMs have a write lifetime; SRAMs can be written to an infinite number of times. It’s not the best solution in every case, but it is certainly interesting, and could be useful for more than a few vintage computing enthusiasts.

This project makes us think of another where an LED may have been supplying keep-alive power to some volatile memory.