Electric Grid Reliability: Increasing Energy Storage in Vanadium Redox Batteries by 70 Percent

In a paper published by the journalAdvanced Energy Materials,researchers at the Department of Energy's Pacific Northwest National Laboratory found that adding hydrochloric acid to the sulfuric acid typically used in vanadium batteries increased the batteries' energy storage capacity by 70 percent and expanded the temperature range in which they operate.

"Our small adjustments greatly improve the vanadium redox battery," said lead author and PNNL chemist Liyu Li."And with just a little more work, the battery could potentially increase the use of wind, solar and other renewable power sources across the electric grid."

Unlike traditional power, which is generated in a reliable, consistent stream of electricity by controlling how much coal is burned or water is sent through dam turbines, renewable power production depends on uncontrollable natural phenomena such as sunshine and wind. Storing electricity can help smooth out the intermittency of renewable power while also improving the reliability of the electric grid that transmits it. Vanadium batteries can hold on to renewable power until people turn on their lights and run their dishwashers. Other benefits of vanadium batteries include high efficiency and the ability to quickly generate power when it's needed as well as sit idle for long periods of time without losing storage capacity.

A vanadium battery is a type of flow battery, meaning it generates power by pumping liquid from external tanks to the battery's central stack, or a chamber where the liquids are mixed. The tanks contain electrolytes, which are liquids that conduct electricity. One tank has the positively-charged vanadium ion V5+ floating in its electrolyte. And the other tank holds an electrolyte full of a different vanadium ion, V2+. When energy is needed, pumps move the ion-saturated electrolyte from both tanks into the stack, where a chemical reaction causes the ions to change their charge, creating electricity.

To charge the battery, electricity is sent to the vanadium battery's stack. This causes another reaction that restores the original charge of vanadium ions. The electrical energy is converted into chemical energy stored in the vanadium ions. The electrolytes with their respective ions are pumped back into to their tanks, where they wait until electricity is needed and the cycle is started again.

A battery's capacity to generate electricity is limited by how many ions it can pack into the electrolyte. Vanadium batteries traditionally use pure sulfuric acid for their electrolyte. But sulfuric acid can only absorb so many vanadium ions.

Another drawback is that sulfuric acid-based vanadium batteries only work between about 50 and 104 degrees Fahrenheit (10 to 40 Celsius). Below that temperature range, the ion-infused sulfuric acid crystallizes. The larger concern, however, is the battery overheating, which causes an unwanted solid to form and renders the battery useless. To regulate the temperature, air conditioners or circulating cooling water are used, which causes up to 20 percent energy loss and significantly increasing the battery's operating cost, the researchers noted.

Wanting to improve the battery's performance, Li and his colleagues began searching for a new electrolyte. They tried a pure hydrochloric acid electrolyte, but found it caused one of the vanadium ions to form an unwanted solid. Next, they experimented with various mixtures of both hydrochloric and sulfuric acids. PNNL scientists found the ideal balance when they mixed 6 parts hydrochloric acid with 2.5 parts sulfuric acid. They verified the electrolyte and ion molecules present in the solution with a nuclear magnetic resonance instrument and the Chinook supercomputer at EMSL, DOE's Environmental Molecular Sciences Laboratory at PNNL.

Tests showed that the new electrolyte mixture could hold 70 percent more vanadium ions, making the battery's electricity capacity 70 percent higher. The discovery means that smaller tanks can be used to generate the same amount of power as larger tanks filled with the old electrolyte.

And the new mixture allowed the battery to work in both warmer and colder temperatures, between 23 and 122 degrees Fahrenheit (-5 to 50 Celsius), greatly reducing the need for costly cooling systems. At room temperature, a battery with the new electrolyte mixture maintained an 87 percent energy efficiency rate for 20 days, which is about the same efficiency of the old solution.

The results are promising, but more research is needed, the authors noted. The battery's stack and overall physical structure could be improved to increase power generation and decrease cost.

"Vanadium redox batteries have been around for more than 20 years, but their use has been limited by a relatively narrow temperature range," Li said."Something as simple as adjusting the batteries' electrolyte means they can be used in more places without having to divert power output to regulate heat."

This research was supported by DOE's Office of Electricity Delivery and Energy Reliability and internal PNNL funding.

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Testing Smart Energy Systems

In an innovative test laboratory, the SmartEnergyLab, they are investigating how to network various electrical household appliances and operate them remotely. In the residential housing sector in particular there is still a great deal of potential for smart energy-management systems that are capable of tailoring local power generation and consumption optimally to the power grid: What is the best time of day for utilizing solar power? How can we store the energy produced and possibly feed it back into the power grid at a lucrative price?

"Smart energy-systems technology for the consumer end of the distribution grid is the key to sustainable, secure energy supply," explains Christof Wittwer, group manager at Fraunhofer ISE. By mapping all the thermal and electrical energy flows, the lab constitutes a unique platform for analyzing, assessing and developing smart homes and smart grid solutions for the distribution grid."Basically, our lab is a simulator for potential energy systems for houses," says Wittwer.

The lab is equipped with renewable as well as electric and thermal producers and storage devices for tomorrow's single-family dwellings and apartment buildings. It boasts a stand-alone 5kW cogeneration plant, a two-cubic-meter buffer storage tank, a photovoltaic simulator, several PV inverters and various stand-alone inverters, a lithium-ion battery pack, a lead battery bank, a charging infrastructure for electric vehicles as well as other equipment. The combination of virtual and real components means researchers can simulate almost any energy system. For any given system they then assess and evaluate the potential energy savings for the customer associated with managing that system.

The service portfolio includes everything from"Integration assessment of thermal and electrical equipment in the system,""Function and communications testing for energy management systems" to the"Efficiency assessment of energy management and generation equipment." Energy suppliers and grid operators from across Germany are already leveraging the know-how of the Freiburg-based experts to determine the potential inherent in the decentralized management of this kind of equipment. Tariff models need to be assessed and their impact on the power grids investigated.

At the Hannover Messe from April 4 to 8, researchers on the joint Fraunhofer Energy Alliance will be showcasing a small yet very sophisticated device: The Smart Energy Gateway -- a component from the test lab -- organizes the way in which data is shared between energy supplier and consumer. The smart box networks the power meters for heat, water and electricity and ensures that the right control function is used to increase efficiency based on current consumption figures and tariff information. But the Gateway is not just a networked meter and energy management optimization device: It can also be used to control household appliances or heaters and to program on/off times. When should the heat pump, the washing machine or the dishwasher come on? In future, one worry you won't have when you're on vacation is whether you forgot to switch the stove off.

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Better Batteries for Electric Cars

Electric cars are the future -- a view shared by government and the automotive industry alike.  By 2020, a million passenger cars with an electric drive should be on the roads in Germany. The ADAC, the German motoring organization, found out in a survey, 74 percent of those surveyed would buy an electric car if they did not have to compromise in terms of cost, comfort and safety.

Consumers are not willing to compromise one iota when it comes to range. Around one third of drivers are looking for a range of at least 500 kilometers. And here is the crux: A lack of charging stations and limited battery life have so far prevented compact electric vehicles from going mainstream. The lithium-ion batteries used by most automakers are simply too heavy, too expensive and go flat too quickly. New materials should improve the performance, service life and safety of the energy storage device, yet the development of these kinds of materials is time-consuming and costly. In the Fraunhofer System Research for Electromobility (FSEM) project, researchers from the Fraunhofer Institute for Industrial Mathematics ITWM in Kaiserslautern are developing software to simulate lithium-ion batteries, which should in turn speed up this process and make it more efficient. The new software is dubbed BEST, short for Battery and Electrochemistry Simulation Tool.

A lithium-ion battery consists of two porous electrodes kept apart by a separator filled with electrolyte. Lithium ions flow between the electrodes when the battery is charged and discharged."Battery performance depends on the materials used in the components. These materials need to work in harmony with each other," explains Jochen Zausch, a scientist in the Complex Fluids group at Fraunhofer ITWM."Various material combinations can be simulated using our software, enabling us to come up with the ideal mix. The kind of trial-and-error testing done in the past is no longer necessary."

The Fraunhofer ITWM researchers have managed to simulate on macroscopic and microscopic level the entire battery cell as well as the transport and reaction processes of the lithium ions themselves."We can show the microscopic structure of the electrodes. Every individual pore measuring 10 micrometers can be seen -- something none of today's off-the-shelf programs can do. The position and shape of the electrodes can also be varied," says Zausch. By resolving the structure of the electrodes in three dimensions, parameters such as lithium ion concentrations and current density can be calculated. For these computations a specializes"Finite Volume" code is used that was developed and implemented at the ITWM. The distribution of the current flow provides an indication of heat production in the battery. Therefore, the software can pinpoint possible hotspots that may overheat and can lead to ignition of the battery. Aging effects can also be assessed using BEST. After all, temperature development within the battery affects its service life. The scientists intend to upgrade the program to include aging models which would make these kinds of studies even easier to conduct.

"Ultimately, BEST should help both automakers and manufacturers of electric storage devices to build robust, safe batteries with greater range and, at the same time, improved acceleration," says Zausch in conclusion. The software can be seen at the Hannover Messe from April 4 to 8.

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Solar Power Systems Could Lighten the Load for British Soldiers

With the aim of being up to fifty per cent lighter than conventional chemical battery packs used by British infantry, the solar and thermoelectric-powered system could make an important contribution to future military operations.

The project is being developed by the University of Glasgow with Loughborough, Strathclyde, Leeds, Reading and Brunel Universities, with funding from the Engineering and Physical Sciences Research Council (EPSRC). It is also supported by the Defence Science and Technology Laboratory (Dstl).

The system's innovative combination of solar photovoltaic (PV) cells, thermoelectric devices and leading-edge energy storage technology will provide a reliable power supply round-the-clock, just like a normal battery pack. The team is also investigating ways of managing, storing and utilising heat produced by the system.

Because it is much lighter, the system will improve soldiers' mobility. Moreover, by eliminating the need to return to base regularly to recharge batteries, it will increase the potential range and duration of infantry operations. It will also absorb energy across the electromagnetic spectrum, making infantry less liable to detection by night vision equipment that uses infra-red technology, for instance.

Minister for Universities and Science David Willetts said:"The armed forces often need to carry around a huge amount of kit and the means to power it. It's great that specialists from a range of science disciplines are coming together to develop lighter, more reliable technology that will help to make life easier for them in the field."

Although substantial research into solar power for soldiers has already been conducted worldwide, this new UK project differs in its use of thermoelectric devices to complement solar cells, delivering genuine 24/7 power generation capability. The project team is also investigating how both types of device could actually be woven into soldiers' battle dress, which has never been done before.

During the day, the solar cells will produce electricity to power equipment. During the night, the thermoelectric devices will take over and perform the same function. The system will also incorporate advanced energy storage devices to ensure electricity is always available on a continuous basis.

"Infantry need electricity for weapons, radios, global positioning systems and many other vital pieces of equipment," says Professor Duncan Gregory of the University of Glasgow."Batteries can account for over ten per cent of the 45-70kg of equipment that infantry currently carry. By aiding efficiency and comfort, the new system could play a valuable role in ensuring the effectiveness of army operations."

PV cells, thermoelectric devices and advanced energy storage devices are already widely used in a range of applications. A key aim of the project team, however, is to produce robust, hard-wearing designs specifically for military use in tough, hostile conditions.

Because it will harness clean, free energy sources, the new power system will also offer significant environmental advantages compared with the conventional battery packs currently used by the British army.

To tackle the many challenges that the project presents, the team includes specialists from a wide range of disciplines including chemistry, materials science, process engineering, electrical engineering and design. Feedback from serving soldiers will also play a crucial role in optimising the power system for front-line use.

"We aim to produce a prototype system within two years," says Professor Gregory."We also anticipate that the technology that we develop could be adapted for other and very varied uses. One possibility is in niche space applications for powering satellites, another could be to provide means to transport medicines or supplies at cool temperatures in disaster areas or to supply fresh food in difficult economic or climatic conditions."

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New High-Performance Lithium-Ion Battery 'Top Candidate' for Electric Cars

A report on this innovation appears in ACS'Journal of the American Chemical Society.

Bruno Scrosati, Yang-Kook Sun, and colleagues point out that consumers have a great desire for electric vehicles, given the shortage and expense of petroleum. But a typical hybrid car can only go short distances on electricity alone, and they hold less charge in very hot or very cold temperatures. With the government push to have one million electric cars on U.S. roads by 2015, the pressure to solve these problems is high. To make electric vehicles a more realistic alternative to gas-powered automobiles, the researchers realized that an improved battery was needed.

The scientists developed a high-capacity, nanostructured, tin-carbon anode, or positive electrode, and a high-voltage, lithium-ion cathode, the negative electrode. When the two parts are put together, the result is a high-performance battery with a high energy density and rate capacity."On the basis of the performance demonstrated here, this battery is a top candidate for powering sustainable vehicles," the researchers say.

The authors acknowledge funding from WCU (World Class University) program through the Korea Science and Engineering Foundation.

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Toward Computers That Fit on a Pen Tip: New Technologies Usher in the Millimeter-Scale Computing Era

And a compact radio that needs no tuning to find the right frequency could be a key enabler to organizing millimeter-scale systems into wireless sensor networks. These networks could one day track pollution, monitor structural integrity, perform surveillance, or make virtually any object smart and trackable.

Both developments at the University of Michigan are significant milestones in the march toward millimeter-scale computing, believed to be the next electronics frontier.

Researchers are presenting papers on each at the International Solid-State Circuits Conference (ISSCC) in San Francisco. The work is being led by three faculty members in the U-M Department of Electrical Engineering and Computer Science: professors Dennis Sylvester and David Blaauw, and assistant professor David Wentzloff.

Bell's Law and the promise of pervasive computing

Nearly invisible millimeter-scale systems could enable ubiquitous computing, and the researchers say that's the future of the industry. They point to Bell's Law, a corollary to Moore's Law. (Moore's says that the number of transistors on an integrated circuit doubles every two years, roughly doubling processing power.)

Bell's Law says there's a new class of smaller, cheaper computers about every decade. With each new class, the volume shrinks by two orders of magnitude and the number of systems per person increases. The law has held from 1960s' mainframes through the '80s' personal computers, the '90s' notebooks and the new millennium's smart phones.

"When you get smaller than hand-held devices, you turn to these monitoring devices," Blaauw said."The next big challenge is to achieve millimeter-scale systems, which have a host of new applications for monitoring our bodies, our environment and our buildings. Because they're so small, you could manufacture hundreds of thousands on one wafer. There could be 10s to 100s of them per person and it's this per capita increase that fuels the semiconductor industry's growth."

The first complete millimeter-scale system

Blaauw and Sylvester's new system is targeted toward medical applications. The work they present at ISSCC focuses on a pressure monitor designed to be implanted in the eye to conveniently and continuously track the progress of glaucoma, a potentially blinding disease. (The device is expected to be commercially available several years from now.)

In a package that's just over 1 cubic millimeter, the system fits an ultra low-power microprocessor, a pressure sensor, memory, a thin-film battery, a solar cell and a wireless radio with an antenna that can transmit data to an external reader device that would be held near the eye.

"This is the first true millimeter-scale complete computing system," Sylvester said.

"Our work is unique in the sense that we're thinking about complete systems in which all the components are low-power and fit on the chip. We can collect data, store it and transmit it. The applications for systems of this size are endless."

The processor in the eye pressure monitor is the third generation of the researchers' Phoenix chip, which uses a unique power gating architecture and an extreme sleep mode to achieve ultra-low power consumption. The newest system wakes every 15 minutes to take measurements and consumes an average of 5.3 nanowatts. To keep the battery charged, it requires exposure to 10 hours of indoor light each day or 1.5 hours of sunlight. It can store up to a week's worth of information.

While this system is miniscule and complete, its radio doesn't equip it to talk to other devices like it. That's an important feature for any system targeted toward wireless sensor networks.

A unique compact radio to enable wireless sensor networks

Wentzloff and doctoral student Kuo-Ken Huang have taken a step toward enabling such node-to-node communication. They've developed a consolidated radio with an on-chip antenna that doesn't need the bulky external crystal that engineers rely on today when two isolated devices need to talk to each other. The crystal reference keeps time and selects a radio frequency band. Integrating the antenna and eliminating this crystal significantly shrinks the radio system. Wentzloff's is less than 1 cubic millimeter in size.

He and Huang's key innovation is to engineer the new antenna to keep time on its own and serve as its own reference. By integrating the antenna through an advanced CMOS process, they can precisely control its shape and size and therefore how it oscillates in response to electrical signals.

"Antennas have a natural resonant frequency for electrical signals that is defined by their geometry, much like a pure audio tone on a tuning fork," Wentzloff said."By designing a circuit to monitor the signal on the antenna and measure how close it is to the antenna's natural resonance, we can lock the transmitted signal to the antenna's resonant frequency."

"This is the first integrated antenna that also serves as its own reference. The radio on our chip doesn't need external tuning. Once you deploy a network of these, they'll automatically align at the same frequency."

The researchers are now working on lowering the radio's power consumption so that it's compatible with millimeter-scale batteries.

Greg Chen, a doctoral student in the Department of Electrical Engineering and Computer Science, presents"A Cubic-Millimeter Energy-Autonomous Wireless Intraocular Pressure Monitor." The researchers are collaborating with Ken Wise, the William Gould Dow Distinguished University Professor of Electrical Engineering and Computer Science on the packaging of the sensor, and with Paul Lichter, chair of the Department of Ophthalmology and Visual Sciences at the U-M Medical School, for the implantation studies. Huang presents"A 60GHz Antenna-Referenced Frequency-Locked Loop in 0.13μm CMOS for Wireless Sensor Networks." This research is funded by the National Science Foundation. The university is pursuing patent protection for the intellectual property, and is seeking commercialization partners to help bring the technology to market.

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'Nanoscoops' Could Spark New Generation of Electric Automobile Batteries

The new material, dubbed a"nanoscoop" because its shape resembles a cone with a scoop of ice cream on top, can withstand extremely high rates of charge and discharge that would cause conventional electrodes used in today's Li-ion batteries to rapidly deteriorate and fail. The nanoscoop's success lies in its unique material composition, structure, and size.

The Rensselaer research team, led by Professor Nikhil Koratkar, demonstrated how a nanoscoop electrode could be charged and discharged at a rate 40 to 60 times faster than conventional battery anodes, while maintaining a comparable energy density. This stellar performance, which was achieved over 100 continuous charge/discharge cycles, has the team confident that their new technology holds significant potential for the design and realization of high-power, high-capacity Li-ion rechargeable batteries.

"Charging my laptop or cell phone in a few minutes, rather than an hour, sounds pretty good to me," said Koratkar, a professor in the Department of Mechanical, Aerospace, and Nuclear Engineering at Rensselaer."By using our nanoscoops as the anode architecture for Li-ion rechargeable batteries, this is a very real prospect. Moreover, this technology could potentially be ramped up to suit the demanding needs of batteries for electric automobiles."

Batteries for all-electric vehicles must deliver high power densities in addition to high energy densities, Koatkar said. These vehicles today use supercapacitors to perform power-intensive functions, such as starting the vehicle and rapid acceleration, in conjunction with conventional batteries that deliver high energy density for normal cruise driving and other operations. Koratkar said the invention of nanoscoops may enable these two separate systems to be combined into a single, more efficient battery unit.

Results of the study were detailed in the paper"Functionally Strain-Graded Nanoscoops for High Power Li-Ion Battery Anodes," published Thursday by the journalNano Letters.

The anode structure of a Li-ion battery physically grows and shrinks as the battery charges or discharges. When charging, the addition of Li ions increases the volume of the anode, while discharging has the opposite effect. These volume changes result in a buildup of stress in the anode. Too great a stress that builds up too quickly, as in the case of a battery charging or discharging at high speeds, can cause the battery to fail prematurely. This is why most batteries in today's portable electronic devices like cell phones and laptops charge very slowly -- the slow charge rate is intentional and designed to protect the battery from stress-induced damage.

The Rensselaer team's nanoscoop, however, was engineered to withstand this buildup of stress. Made from a carbon (C) nanorod base topped with a thin layer of nanoscale aluminum (Al) and a"scoop" of nanoscale silicon (Si), the structures are flexible and able to quickly accept and discharge Li ions at extremely fast rates without sustaining significant damage. The segmented structure of the nanoscoop allows the strain to be gradually transferred from the C base to the Al layer, and finally to the Si scoop. This natural strain gradation provides for a less abrupt transition in stress across the material interfaces, leading to improved structural integrity of the electrode.

The nanoscale size of the scoop is also vital since nanostructures are less prone to cracking than bulk materials, according to Koratkar.

"Due to their nanoscale size, our nanoscoops can soak and release Li at high rates far more effectively than the macroscale anodes used in today's Li-ion batteries," he said."This means our nanoscoop may be the solution to a critical problem facing auto companies and other battery manufacturers -- how can you increase the power density of a battery while still keeping the energy density high?"

A limitation of the nanoscoop architecture is the relatively low total mass of the electrode, Koratkar said. To solve this, the team's next steps are to try growing longer scoops with greater mass, or develop a method for stacking layers of nanoscoops on top of each other. Another possibility the team is exploring includes growing the nanoscoops on large flexible substrates that can be rolled or shaped to fit along the contours or chassis of the automobile.

Along with Koratkar, authors on the paper are Toh-Ming Lu, the R.P. Baker Distinguished Professor of Physics and associate director of the Center for Integrated Electronics at Rensselaer; and Rahul Krishnan, a graduate student in the Department of Materials Science and Engineering at Rensselaer.

This study was supported by the National Science Foundation (NSF) and the New York State Energy Research and Development Authority (NYSERDA).

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