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Univ. of Illinois team develops high-power Li-ion microbatteries that can out-power supercapacitors while retaining comparable energy density

20 April 2013

King
Ragone plot showing the performance of the new microbattery cells (A-H) and conventional power technologies. The energy and power density of our microbattery cells (A–H) at low to high C rates, along with previous microbattery cells having 3D electrodes (MB1 through MB3). The plot also includes the performance range of conventional power technologies and commercial batteries from A123 (high power) and Sony (high energy). Source: Pikul et al. Click to enlarge.

Researchers at the University of Illinois at Urbana-Champaign have demonstrated a high-power and high-energy density microbattery constructed from interdigitated three-dimensional (3D) bicontinuous nanoporous electrodes. The new microbatteries out-power supercapacitors while retaining comparable energy density. The researchers published their results in Nature Communications.

The lithium-ion microbatteries show power densities up to 7.4 mW cm-2 µm-1, which equals or exceeds that of the best supercapacitors, and which is 2,000 times higher than that of other microbatteries, the researchers said. The microbatteries show energy densities of up to and energy densities up to 15 mW h cm-2 mm-1. The battery microarchitecture affords trade-offs between power and energy density that result in a high-performance power source, and which is scalable to larger areas.

The performance of power sources is typically measured by power and energy stored per unit mass or unit volume. For conventional lithium ion batteries, typical volumetric energy and power densities are around 10–60 mW h cm-2 mm-1 and 1–100 mW cm-2 mm-1. It is possible to achieve higher power density, up to 1,000 mW cm-2 mm-1, by using porous battery electrodes that reduce ion diffusion through the active anode and cathode materials, as well as designs that reduce ion diffusion time in the electrolyte and decrease electrical resistance in the electrodes. Most publications on high-power batteries focus on either anode or cathode half cells, and show improved power density at the expense of energy density. In principle, a battery architecture based on 3D integrated porous microelectrodes could achieve high-power density without sacrificing energy density by combining small ion diffusion distances, large percentage of active material and highly conductive electrodes. Such a microarchitecture could also enable miniature batteries suitable for microelectronics integration.

...It has proven difficult for batteries of any size to achieve the high power of a supercapacitor, which can be fabricated at nearly any size and have power density larger than 4.0 mW cm-2 mm-1. It is challenging to integrate 3D electrodes into a complete microbattery cell, owing to the difficulty of integrating 3D elements of anode and cathode materials, along with the need to control materials uniformity and feature sizes across a range of length scales of 10 nm–1 mm.

—Pikul et al.

Building on a novel fast-charging cathode design by materials science and engineering professor Paul Braun’s group, William King’s team developed a matching anode and then developed a new way to integrate the two components at the microscale.

King2
Microbattery design. The nanoporous microbattery electrodes consist of an electrolytically active layer (red and yellow) coated on an electrically conductive bicontinuous nickel scaffold (blue). The nickel scaffold acts as the current collector attached to an outside circuit. A nickel–tin alloy is used as the anode (red), and lithiated manganese oxide as the cathode (yellow). Pikul et al. Click to enlarge.

The electrodes are a thin layer of nickel–tin (anode) or lithiated manganese oxide (LMO) (cathode) conformally coated onto interdigitated highly porous metallic scaffolds. The microarchitecture provides short electron and ion transport lengths in the electrolytically active material and electrolyte (yielding high-power density) while maintaining a high volume of active material (yielding high-energy density). The active material thickness varies between 17 and 90 nm.

The architecture allows compact integration of the anode and cathode on a single substrate for microelectronics applications.

The batteries could be further improved by taller 3D electrodes, which would require improvements in the fabrication process. Additional research could explore the fundamentals of ion transport in this type of 3D battery, explore other battery chemistries and routes to microelectronics packaging, the authors suggested.

The National Science Foundation and the Air Force Office of Scientific Research supported this work. King also is affiliated with the Beckman Institute for Advanced Science and Technology; the Frederick Seitz Materials Research Laboratory; the Micro and Nanotechnology Laboratory; and the department of electrical and computer engineering at the University of Illinois.

Resources

  • James H. Pikul, Hui Gang Zhang, Jiung Cho, Paul V. Braun & William P. King (2013) High-power lithium ion microbatteries from interdigitated three-dimensional bicontinuous nanoporous electrodes. Nature Communications 4, Article number: 1732 doi: 10.1038/ncomms2747

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According BBC, this could be one of the leading technology for future scalable high energy density, high power batteries, for potential mass production applications, by the end of the current decade.

If it can be scaled up and mass produced at an affordable price, this could be 'one' of the most promising technology for future extended range BEVs.

Naysayers, ICEVs fan clubs, Big Oil and puppet politicians in most Moneycracies will do their best to stop or delay further development.

I don't know, but according to the graph they might outperform capacitor but not batteries yet, for comparable power density, the power density is not better than for batteries, or maybe I don't read the graph correctly.

this doesn't seem like a battery technology for cars. They say the energy density can be scaled up. But how much? The chart seems to show the highest "scaled up" energy density is equivalent to Ni-Zn, which is only 100 Wh/kg, much smaller than Envia Systems or CalBattery batteries at 4-500 Wh/kg. The microbattery architecture seems expensive to manufacture. It might be fine for microelectronic applications.

up to 1,000 mW cm-2 mm-1

(superscripts munged in paste) Note, that is 1e5 watts per liter.  If you can even get within a factor of 3 of this, a battery the size of a couple large soft-drink bottles can supply the surge power to move a car very smartly down the road.

Sure, it can get the car moving. But for how long?

"The architecture allows compact integration of the anode and cathode on a single substrate for microelectronics applications.

The batteries could be further improved by taller 3D electrodes, which would require improvements in the fabrication process."

This kind of microchip-style fabrication is expensive.

"The electrodes are a thin layer of nickel–tin (anode) or lithiated manganese oxide (LMO) (cathode) conformally coated onto interdigitated highly porous metallic scaffolds. "

This implies something like a photolithographic process in a clean room environment. The conformal coating and interdigitated scaffolds requires additional expensive processing. A battery suitable for a car might require hundreds of layers of 3D substrates. It would be very expensive for a BEV battery, but practical on a miroelectronic chip as a power source.

If a battery of reasonable cost and bulk can absorb the energy of a stop at high power and return it the same way, who cares how long it can keep the car moving?  It has everything a hybrid needs to eliminate idling losses and slash the peak-power demands on the engine, allowing the engine to be designed and operated for thermal efficiency.

If it's a battery that works like a capacitor on steroids, it doesn't matter if it's inferior to a conventional battery in other respects.  Use its strengths.

Agreed: good for hybrids, not the best for PHEV, BEV. Fastcap claims (1.4, 3700) in the graph units - about the B-D cluster - so just as good. With both you would only need a few kilograms so their energy and power density is high enough. Other things like cycle life and cost will decide which wins out. That's where I think ZIP-cap will win out.

Are they good for billions of cycles like conventional capacitors? If not, then no market to replace supercaps, and much lower energy density than A123. Why wasn't the very important specification of cycle life given?

This is just' one of '101+' new e-storage technologies being developed in various places.

One thing is about certain, units with up to 10X current batteries energy density will be developed sooner or latter.

Cars and small trucks ICEs will be progressively replaced with silent, clean e-motors with 95+% efficiency.

Clean intermittent energy production, such as solar and wind, will also greatly benefit from mass produced, lower cost, e-storage units.

The high cost of many new e-storage technologies may delay their mass production and use but others will make the jump.

Many of the one+ billion smart phones-tablets-laptops owners would not mind paying another $100 or so to extend the time between charges by 10X.

E-storage evolution is in its early life and will not stop soon but will gain speed as more and more funds become available.

@Roy H,
"a capacitor usually can be cycled millions of times. We have a long way to go in this regard. Almost all Li-ion batteries exhibit capacity fade with cycling, including our system."
http://spectrum.ieee.org/energywise/green-tech/fuel-cells/miracle-microbattery-breakthrough-is-promising-but-cycling-and-safety-are-still-issues

So, half empty or half full? Just a thousand cycles would cover a lot of miles.

The idea of >lead-acid energy density capable of near instant recharge has infinite possibilities.

'[asked]..if costs would be prohibitive, but he said the process would actually be relatively simple.
"The key will be developing a manufacturing process which is compatible with both the battery and the device one wishes to power," he said.'

Notice that they give the power and energy densities in units of area and thickness - mW cm-2 µm-1 and mW h cm-2 mm-1, instead of W/kg or Wh/kg, like for BEV batteries. This is because the applications for microbatteries are intended for very small devices, specifically chips and tiny circuit boards, where "real estate" is at a premium. Applications for microbatteries like this to traction motors in BEVs is not likely, which should be obvious from this article and the one Kelly found. The 3D fabrication process may be simple compared to that of microcircuit chips, but it's not compared with one for a practical BEV battery. I'd put my money on Rice's Vanadium Graphene battery for BEVs.

As with so many breakthrough battery announcements, we likely won't touch much for years.

Even the May 1994 Ovonics US NiMH patent wasn't on US roads until the Toyota RAV4 EV in May 1997.

Another PR post and it off the fantasy land by the GCC crowd.

“designed and operated for thermal efficiency. ”

Nice theory but sort of violates the KISS principle. This might sound good to the control system engineer who makes a hobby of not understand heat engines and the second law of thermodynamics.

The lack of independent data for a theory that has now been around ten years is astounding. I suspect there is one major problem with the HEV theory. It does not match how people drive. I had this debate at work on Friday with a young supervisor. Engineers like to over design things without talking to the operators who use it.

“The idea of >lead-acid energy density capable of near instant recharge has infinite possibilities. ”

Wow! Did you all see that? Kelly posted a useful link. Kelly who has an irrational fear of radiation.

“Prof King acknowledged that safety was an issue due to the fact the current electrolyte was a combustible liquid. ”

Got to love college professors. Do you think that electrical circuits and a combustible liquid could be more than just an issue.

Periodically some college professors suggest that steam plants could be more efficient if propane was used. Safety is more than an issue, unless something is safer than the current process you can not do it just to save a few pennies.

@Kit P, you can't even understand that any financial project, like a nuke plant, hundreds(100s) of percent over construction budget(75 plants @208% average cost overrun, is UNECONOMICAL BY DEFINITION.

3 strikes and your out, so the real question is how did America get stuck with EACH of the next hundred nuke plant overruns?

You love nuclear radiation - normal people don't, 1000s of victims certainty don't.

[Demonstrated] '2,000 times higher than that of other microbatteries' is important.

'This battery can charge at speeds resembling capacitors..' is important.

The electrolyte is in a sealed battery - at least more sealed than a screw-on gas tank cap.

To paraphrase, "Another PR post and it off the fantasy land with Kit."

Nice theory but sort of violates the KISS principle.

Do tell me how this is any more non-KISS than Atkinson-cycle engines in Prii, CCGT's, etc.

This might sound good to the control system engineer who makes a hobby of not understand heat engines and the second law of thermodynamics.

I would just love to see you post a 2nd Law analysis of some news item here you care to dispute.  I'm sure it would be chock-full of hilarious errors, unless it forced you to make admissions against interest.

Wow! Did you all see that? Kelly posted a useful link. Kelly who has an irrational fear of radiation.

I admit, I love to see you two beat up on each other.  You're both nuts in different ways.

"You're both nuts in different ways"

You paid what for your last car. A fool and his money and soon parted. Of course it has lots of gadgets to impress a control system engineer.

this will make possible nano sized individual computers/sensors, smart dust in popular fiction..

My choice of powertrain for my last car saved me about 1800 gallons of fuel, which more than paid for the extra cost.

I expect to do as well or better with the new car, especially after the dollar tanks.

@Engineer-Poet, I back my comments with more facts and references than the nuts make an effort to read or counter.

Your references for matters nuclear are long-debunked ideologue nutcases.

I'll accept historic statistics and the Union of Concerned Scientists over the nuts:

claiming 200% cost overruns are fine and economical

wasting 12.2 $billion cleaning NOTHING of Hanford's
nuclear waste sinkhole is great.

and believing a few more $billion and decades will endear Chernobyl and nuclear radiation to humanity psychosis.

Proof, the 50 year nuclear power history has now ended new nuke construction permits and non-gov-guaranteed finance in most democracies, including the US.

“My choice of powertrain for my last car saved me about 1800 gallons of fuel, which more than paid for the extra cost. ”

Notice how E-P failed to answer the question about how much is new car cost?

A VW Jetta TDI @ $23K gets 42 mpg compared to a 2.5L SE @ $19k and 29 mpg.

So how much do you save for the $4000 extra for a diesel?

Assuming 20,000 highway miles a year:

200000/42 = 476 gal, 200000/29 = 689 gal or 213 gallons per year.

$3.50/gal = about $750/yr (if diesel and gas were the same price). A five year payback is not too bad

Of course everyone and his brother knows that if you are going to put a lot of miles on a car that a diesel is worth the extra cost.

So making a better choice on a power train rather than on the car itself does not make any sense at all. A Civic or Corolla get 35-40 mpg on the highway for $6l less.

So matching how you drive with the car you buy will save energy. Hauling batteries around the highway instead of a diesel, not so much.

@Kelly

"or counter"

Not true. Many times I have explained why you are wrong but you keep repeating the same comment. Other reader may learn something new have long since learned it. For example.

"wasting 12.2 $billion cleaning NOTHING of Hanford's
nuclear waste sinkhole is great."

The facility being built is to immobilize in glass waste from making weapons. It has nothing to do with commercial nuclear power.

@kp, check http://en.wikipedia.org/wiki/Hanford_Site

Look at the thousands of MILLIONS of watts of energy generated from the nine nuclear reactors, besides plutonium, and proof that even dozens of $billions can't render nuclear waste safe.

Are you saying ALL that power listed was thrown away?

None of the operations experience and R&D since 1944 advanced commercial nuclear power or even powered a light bulb?

In other words, my Harbor Freight solar system makes more electricity than the 9 Hanford nuclear reactors ever had made.

New note on your dream retirement home:

"US residents near the Hanford Nuclear Reservation may be in grave danger: a nuclear safety board found that the underground tanks holding toxic, radioactive waste could explode at any minute, due to a dangerous buildup of hydrogen gas."
http://rt.com/usa/hanford-nuclear-waste-tanks-288/

bon voyage..

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