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Tsinghua, MIT, Argonne team discovers lithium titanate hydrates for superfast, stable cycling in Li-ion batteries

An international research team from Tsinghua University, MIT and Argonne National Laboratory has discovered a series of novel lithium titanate hydrates that show better electrochemical performances compared to all the Li2O–TiO2 materials reported so far—including those after nanostructuring, doping and/or coating.

Reported in an open access paper in the journal Nature Communications, the novel lithium titanate hydrates show a specific capacity of about 130 mA h g−1 at ~35 C (fully charged within ~100 s) and sustain more than 10,000 cycles with capacity fade of only 0.001% per cycle.

Compounds on the binary Li2-TiO2 composition line, such as Li4Ti5O12 (2Li2O•5TiO2, LTO) and various TiO2 polymorphs (TO), are generally considered the most promising anode materials for Li-ion batteries in terms of rate capability and cycling stability, as well as the improved safety over graphite anode. Producing nanostructured materials on the Li2O–TiO2 composition line often requires water-based synthesis such as hydrothermal or sol-gel approaches, and thus one often deals with reaction intermediates that contain water (lithium titanate hydrates, LTHs) in the Li2O–TiO2–H2O ternary composition space.

Because water is considered “harmful” in high-voltage window aprotic electrolytes (free water can be highly reactive to LiPF6, lithium metal anode and lithium alkyl carbonates), most researchers calcine the nanostructured LTHs to completely remove all water by raising temperature to above 500 °C. However, this can cause an unwanted side effect of coarsening and aggregation of the structure.

Herein, we demonstrate that the high-temperature calcining may not be necessary. One may only need to remove the more loosely bound water (such as adsorbed and crystallographic water) by heating to a much lower temperature of <260 °C, which does not induce significant coarsening of the nanostructure. The deeply trapped water inside LTHs, or pseudohydrates (i.e., hydroxide or hydroxonium ions or as –OH and –H groups), does not necessarily degrade stability or performance in aprotic electrolytes, even with H2O:TiO2 molar ratio as high as 0.41. Indeed, the trapped water can promote structural diversity and nanostructuring that could be highly beneficial for battery performance in aprotic electrolytes.

—Wang et al.

The team called its approach to the discovery of these materials optimized dehydration induced nanostructuring (ODIN).

41467_2017_574_Fig2_HTML
Schematic diagram in the dehydration process and the fast lithium insertion/extraction within the hydrated nanocomposite (HN) material in battery. The tiny clusters appeared on the nanosheet after 190 °C represent LTO and TO nanocrystallites, and the clusters grow gradually to bigger crystals with the increase of temperature. Wang et al. Click to enlarge.

When the scientists tested the materials in the laboratory, cycling stability improved and capacity degraded only slightly over 10,000 cycles. The material also charged very quickly—within less than two minutes—the team found. As noted by Jun Lu, Argonne battery scientist and co-author, “Most of the time, water is bad for non-aqueous lithium-ion batteries. But in this case, it can be downright good.

The research team tracked how material composition and structure changed when heated by using various advanced characterization techniques, including x-ray diffraction provided by the Advanced Photon Source, a DOE Office of Science User Facility located at Argonne. When analyzing the combined characterization data, the team reported that the trapped water in the anode material improved performance by promoting structural diversity and forming nanostructures.

The video shows the change in composition and structure as the starting material is heated and water is expelled to form a new layered structure (LS), then the desired hydrated nanostructure (HN), then beyond the desired structure all the way to a completely dehydrated nanostructure (DN).

Looking to the future, Jun Lu observed that, because water is everywhere in nature and common in chemical synthesis, the fabrication approach reported in this research could open the door to discovery of other high-performance electrode materials.

The research was funded by DOE’s Office of Energy Efficiency and Renewable Energy’s Vehicle Technologies Office, the National Science Foundation, the National Natural Science Foundation of China and the Ministry of Education of the People's Republic of China. The scientists used resources of the Advanced Photon Source, a DOE Office of Science User Facility.

Resources

  • Shitong Wang, Wei Quan, Zhi Zhu, Yong Yang, Qi Liu, Yang Ren, Xiaoyi Zhang, Rui Xu, Ye Hong, Zhongtai Zhang, Khalil Amine, Zilong Tang, Jun Lu & Ju Li (2017) “Lithium titanate hydrates with superfast and stable cycling in lithium ion batteries” Nature Communications 8, Article number: 627 doi: 10.1038/s41467-017-00574-9

Comments

HarveyD

If this process can be repeated and mass produced at an affordable cost, an ideal very quick charge battery may be around in about 10 years?

Engineer-Poet

Harvey, note well:

The material also charged very quickly—within less than two minutes

Hype-drogen is toast.  Hybrids will do very well with this battery.

HarveyD

Yes EP, this new battery could have the potential to store/supply enough e-energy (150 KW or so) for all weather (down to -40C) extended range BEVs, if and when mass produced at a lower affordable cost (well below $100/KW).

Let me know who will produce the first all weather affordable BEVs, using those batteries, so I can place my name on the reserve list. Our HEVs are good for another 5+ year. Enough public quick charge facilities will be installed in our area by 2025 or so to make extended range quick charge BEVs practical for users without home charging facilities.

Engineer-Poet

Harvey, you Just Don't Get It.

With a battery that charges in 2 minutes, you can shrink the battery in the BEV to cover perhaps 60 miles of range and have in-motion charging.  1.5 miles of live guardrail every 30 miles would do even for 70 MPH cruising.  That takes my 7.5% of highway mileage of charging rail down to 5%.  It becomes by far the cheaper, cleaner and more efficient solution.

mahonj

The high power capacity will be very good for Hybrids where you want to absorb braking energy at high power.
Also busbarr type applications where you want to charge up a bus at a stop - you can do it quicker.
What it will come down to is - is this real, and at what cost?
Assuming it is more expensive than conventional LiIon, it will start in specialised applications where ultra rapid charging is a benefit.
Phones - watches, hybrids, BusBarrs perhaps first, who knows what if it becomes cheap enough.
Also, the 10K charging cycles is excellent.
You could get 30 years at one discharge per day, 10x many battery types.
But can they make them, and at what cost ?

Calgarygary

the Toshiba SCiB has been professing to have said properties for a long time. Their latest press release in October claims their batteries could deliver 320 km range and be recharged in 6 minutes. I think the downside of these batteries is energy density and cost but I'm sure there are applications where they are the solution.

HarveyD

Good potential idea E-P but it is difficult to picture six lanes of 80+ mph vehicles picking up electrons on highway 95 and or other similar highways.

If and where high speed electrons pick-up is limited to 1.5 miles, saturation and tremendous jams would build up fast.

Many EV owners would prefer very quick charge stations to pick up electrons every 600/800 Km or so, much the same way as we pick up liquid fuel for current ICEVs.

Engineer-Poet

That's precisely why you DON'T do 6 lanes of charging at 80 MPH.  You do 1 lane.

Let's take a Tesla Model S as our representative vehicle.  Its LOA is 196 inches.  Adding 24 inches for inter-vehicle spacing in a computer-controlled platoon, each vehicle takes 220 inches.  This is 2880 vehicles per mile, 2880 veh/min at 60 MPH (more at higher speeds).

Accepted carrying capacity for an 8-lane divided freeway is about 11400 veh/hr/direction.  This is about 190 vehicles/minute, less than 7% of capacity of a single charging lane with vehicles under computer control.

tl;dr We can do it with current technology without even breathing hard.

gryf

Good idea E-P.
While any EV could benefit from your dynamic charging concept, long distance trucks and buses would benefit the most. Already the Siemens eHighway is demonstrating a test running in California near the two largest U.S. Ports of Los Angeles and Long Beach. Trucking firms also do not like spending off road time "charging batteries".
The Cummins AEOS Electric truck with a 100 mile range looks like a good candidate for this concept and with the acquisition of Brammo they should be including a fast charging battery pack to support the truck.

HarveyD

With near future BEVs with 5X batteries and/or FCEVs with very compact FCs for up to 500 miles all weather range, charging on-the-go or beamed microwave energy will not be required.

Many current gasoline/diesel stations will be progressively changed/upgraded to ultra quick electron and H2 distribution stations.

Of course, current gasoline/diesel distributors will gladly switch to electrons and H2 distribution as soon as demand grows.

HarveyD

Note:

Long lasting, ultra quick charge, affordable 5X (+) batteries have been promised for the last 10+ years but have not materialized (yet).

Will these be the first to meet those promises?

If they do, all weather extended range BEVs (with up to 150+ KW packs) would get a major boast.

On-the-go charging would definitely not be required. Most travelers could charge overnight while resting at hotels/motels. The same would apply to e-trucks/buses with much larger battery packs.

CheeseEater88

I am curious where all these batteries and technologies go to die, or if they are bought up by some patent trolls, waiting quietly for a battery chemistry to be successful, so they can later sue it into oblivion. Surely, there has been some successes outside of the lab after all these years...maybe big battery is suppressing them.


I'm a little more accepting of your charging while moving plan EP, but it's still an infrastructure plan. States across the US have been using road and fuel taxes on nearly everything but transportation.

Some questions i would have, at what rates would your one mile charge a vehicle with a 2880 car queue? 100kw? 200kw? 500kw?

I think your idea would work great on an area with a two lane road, or more if autonomous vehicles were standard issue. If people were in control... People would be problematic to your vision.

I just have hard time a envisioning any national roll out of an electrified highway. Sure California or some other dense areas might see more than the current trial... But fly over states, the ones people will need the range for, might be out of luck.

I also don't think the demonstration e highway that California has now should not be implemented anywhere, overhead lines with large windsails to connect to them just speaks of inefficiencies. I rather see conductors in the ground.


Engineer-Poet

BTW, don't expect me to pick up on new traffic in discussions that have been idle for several days.  I don't use an RSS reader so these things disappear off my radar and almost never get back on it.

I am curious where all these batteries and technologies go to die, or if they are bought up by some patent trolls, waiting quietly for a battery chemistry to be successful, so they can later sue it into oblivion.

You can't really do that anymore.  There used to be the tactic of the "submarine patent" which would be sent in with flaws which prevented granting, but the process of correction allowed it to be kept secret for a long time while changes were negotiated with the PTO; this revision process could go on for years.  Only once the patent was granted did it become public and the 17-year clock begin.  But today, applications are published upon receipt and the 20-year clock starts running when the application is received.

Surely, there has been some successes outside of the lab after all these years...

Note that we are STILL using Planté cells almost 160 years after their invention.  Some things simply are too good to let go, and keep finding new applications.

maybe big battery is suppressing them.

I would have pooh-poohed that idea, except I know about Cobasys and its suppression of prismatic NiMH.

I'm a little more accepting of your charging while moving plan EP, but it's still an infrastructure plan. States across the US have been using road and fuel taxes on nearly everything but transportation.

Then they're going to have to get with the program, aren't they?

Some questions i would have, at what rates would your one mile charge a vehicle with a 2880 car queue? 100kw? 200kw? 500kw?

It's pretty simple, it's going to have to charge at roughly a rate of its power expenditure times 1 over the fraction of time spent charging.  For a reasonable passenger car charging over 7.5% of travel distance, this comes to per-vehicle power roughly equivalent to a Tesla Supercharger.  Something on the order of 150-200 kW.  The more length you cover with charging lanes the lower the power number gets, but the infrastructure cost increases.

This lends itself to grid-side storage pretty nicely, because a somewhat spotty charging load averaged out over spurts of power as vehicles hit charging opportunities at 50-mile intervals requires much less than an hour of storage to average out.

As for people being in control... definitely not, but if I understand correctly the steering control problems are well within the capabilties of mechanical-hydraulic systems, no electronics required.  We could have handled that part in the 1970's.

I just have hard time a envisioning any national roll out of an electrified highway.

We don't even have national rollout of hydrogen, and electricity is already everywhere.  Electric is a much smaller leap.

I rather see conductors in the ground.

Those have their uses, but are problematic when flooded, snowed or iced over.  A sort-of "3rd rail" beneath cover (to keep rain and snow off it) doesn't have the drawbacks of something at ground level.

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