EDITOR: | September 4th, 2015 | 17 Comments

Lithium Titanate Battery Technology – Bigger and Better

| September 04, 2015 | 17 Comments
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For a long time talk has swirled about the potential for Lithium-based batteries, in things as elementary as laptops and cellphones, to self-combust. This talk reached frenzy in recent times when the disappearance of Malaysian Airlines Flight 370 was initially attributed to some sort of problem with its cargo of lithium batteries. As time has gone on this theory has been discarded to be replaced by pilot misdemeanor. However the concerns about lithium batteries spontaneously overheating, even when not in use have not gone away.

mh370

Indeed in recent months United Airlines has become the second major US airline to announce it will no longer carry bulk shipments of lithium-ion batteries. Delta Airlines stopped bulk shipments of the batteries in February of 2015. This was due to aviation officials believing that lithium-ion batteries contributed to fires that destroyed two Boeing 747 cargo planes, killing all four crew members.

Tests by the Federal Aviation Administration found overheating batteries could cause major fires. In its tests, the FAA filled a cargo container with 5,000 lithium-ion batteries and a cartridge heater, which was added to simulate a single battery overheating. The heat from the cartridge triggered a chain reaction in other batteries, with temperatures reaching about 600C. This was followed by an explosion, which blew open the container door and set the cargo box on fire.

These fears are starting to filter through to the general population and anyone who has felt a cellphone or a laptop get very hot needs little persuading that where there is heat, there is fire. Therefore I shall be reviewing a new technology in Lithium batteries which promises to bring safety benefits amongst its other attractions.

A Less Explosive Option

Lithium titanate (lithium titanium oxide or LTO) batteries have appeared on the scene in recent times but have only gained a lot of traction in usages for mass storage devices such as for operating electric buses, with Toshiba being a major developer of the technology.

LTO battery technology are significant incorporates a number of economical as well as ecological aspects important for expanding renewable green energy.

LTO-battery

The LTO technology is based on modified lithium-ion batteries and employs additional lithium-titanate nanocrystals on the surface of its anode and instead of the conventional carbon material that is used in normal lithium-ion batteries.

As a result the anode has a surface area of around 100 square meters per gram, which is a quantum more than the three square meters per gram achieved when using conventional carbon material, allowing electrons to enter and leave the anode far more quickly.

As a result of this larger surface area re-charging of the LTO battery is faster. The improvement in the surface area of the battery drastically increases the LTO cells general stability and further improves the LTO batteries safety aspects.

Uses – Going Lightweight

While in the past I have written about large scale Vanadium batteries (some the size of shipping containers) the Lithium titanate batteries fill a niche in between the very large and more micro formats in hand-held devices. They are able to store and deliver current peaks that are between 30 and 100 times that of ordinary lithium batteries.

LTO batteries have applications in electric vehicles and charging stations, tourist coaches, yachts, wind and solar energy storage power, traffic signals, solar hybrid street lighting, UPS power supply, home storage, disaster relief emergency, weather radar, electricity, smart grid, communication base stations, hospitals, finance, telecommunications as well as system critical backup power systems.

LTO technology offers the highest energy to weight ratio seen yet, with particular usage potential in transport modes that require a low weight battery, such as light vehicles, e-cars and fork lifts.

Clearly the tendency here is for locations that are off grid but where the device being powered is not a substantial consumer of energy.

The Main Advantages

It is surprising that more airtime has not been given to Lithium Titanate batteries considering that they have several crucial advantages over their more prolific competition, the Lithium Ion battery. The main points on which they do better are:

  • Long lifespan
  • Rapid charging
  • Less risk of auto-combustion
  • Operates better in low temperatures than Lithium Ion batteries

From the point of view of the manufacturers of the appliances into which the batteries are installed the main attraction is the long lifespan with user gripes mostly being about the short lifespan of laptops and particularly cellphones these days with apps installed chewing through the charged power in no time. LTO batteries have a lifecycle of up to 20,000 cycles as compared to only 2000 in standard lithium based batteries.

As for the other advantages:

Rapid Battery Charging – As mentioned the higher surface area per gram allows the electrons to enter and exit the anode faster, thus making it possible to recharge the battery very rapidly. These batteries can be safely charged between six and ten minutes in contrast to the 8 hours required for other rechargeable batteries. Additionally, the recharge efficiency exceeds an entire 98%, much higher than conventional energy storage mechanisms.

Safety advantages – For us this is one of the biggest marketing angles for the future will be enhanced safety. Householders in particular are getting edgy about the stories they hear about Lithium Ion batteries and their combustibility which makes for a whole new niche in “low-risk” alternatives.

The higher level of safety with LTO batteries is due to the lower operating voltage of this technology. The argument goes that as the batteries are entirely free of carbon, they avoid thermal runaway or overheating which is a main cause of fires in traditional energy storage systems.

Low-Temperature Performance – due to the nanotechnology employed, LTO batteries have a much better low-temperature performance in comparison to other battery technologies as a result these batteries are able to obtain up to 80% of its full capacity at -30°C.

It should be noted though that there is a disadvantage to LTO batteries in that they have a lower inherent voltage (2.4 V/cell), which leads to a lower energy density than conventional lithium-ion battery technologies. However, the energy density of LTO batteries is still higher than lead acid and NiCd batteries.

Just in Passing

We might note that Neometals (NMT.ax), with its Mt Marion lithium deposit and its Barrambie Titanium deposit is the only company we know that has both parts of the chemical equation for Lithium Titanate batteries.

Conclusion

The first thought that struck us when noting the low to no carbon nature of these batteries was the potential implications for those in the graphite mining community who are hitching their stars to the carbon component of the Lithium Ion battery. We wonder if that might not be akin to investing in future development of the penny-farthing bicycle!

When we raised the subject of this new battery with Jack Lifton he responded that he had indeed heard of the new technology and in fact had been talking recently to a company in his bailiwick of Troy, Michigan, that was changing over to Lithium Titanate electrodes to improve power density. They told him that while it is more expensive and complicated, there is a big improvement in cycle life.

So it is obvious that LTO technology has managed to trump that of Lithium Ion batteries on four key fronts, but as yet has not captured the attention or imagination of the public. It is definitely a technology to be watched because it not only may oust Lithium Ion batteries from some of their applications but it also might provide a significant new demand source for Titanium miners.


Christopher Ecclestone

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Comments

  • Tracy Weslosky

    Another outstanding and powerful commentary with some unsettling ideas as you redirect my understanding on battery storage that I look forward to learning more about…

    I have been reading your emails with Jack Lifton on this topic, and we are lucky at InvestorIntel to have so many experienced professionals in the industry that write for InvestorIntel. Thanks.

    September 4, 2015 - 9:18 AM

  • Mike Booth

    Professionals? Well, perhaps, ill-informed professionals.

    The fires are not due to graphite. Look at youtube film of fires in damaged lithium-ion cells. The fires are due to flammable liquid electrolyte. After the fire, the graphite anode can be seen to be intact.

    Further your information on bans on lithium ion batteries is incorrect. IATA regs refer to lithium metal batteries only.

    Lithium metal anodes are used in all primary lithium cells and in some secondary lithium batteries. They have much higher capacity than lithium ion ones. The switch from lithium metal to lithium ion anode technology was made for safety issues. Lithium metal reacts violently with water , oxygen, and nitrogen. Look at explosions with lithium metal on youtube.

    Ballore in France makes secondary batteries with lithium metal anodes. These are used in the Blue cars which are used by the Autolib car sharing service in Paris. So far 25 cars of these cars have exploded and burned to the ground.

    LMP lithium metal anode technology was developed by HQ. A spin off to make these went bankrupt after their stationary power units used in US suburbs started to explode.

    September 4, 2015 - 4:48 PM

  • Christopher Ecclestone

    I didn’t say it was the carbon that caused the fire.. Here is a study testing various Lithium batteries for combustibility…

    http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4293605/

    I am talking of Lithium Titanate batteries and you are referring to Lithium Metal batteries which as you will see from my link come in a variety of different metals, including Mn in the mix…

    September 4, 2015 - 6:37 PM

  • Mike Booth

    Let’s try this again……..

    The DISADVANTAGES of LTO compared to GRAPHITE (Li-ion):

    a. 56-65% of voltage with graphite anodes (1.0 – 2.6 versus 3.5 – 4.0 for graphite)

    b. 44- 48% of specific capacity compared to graphite electrodes (theoretical 175 mAh/g vs 372 for graphite)

    c. Swells due to reaction with electrolyte to give off gases – carbon dioxide, and flammable/explosive hydrogen and carbon monoxide.
    Can be overcome by 5 nm carbon coating but specific capacity is only 151.3 mAh/g. Graphite does not produce gases on reacting with electrolyte

    d. 60% heavier than Graphite

    e. lower loading in anode paste due to high surface area (100 sq.m/g versus 3 for commercial graphite and 0.48-1.14 for Focus coated anode graphite)

    g. Low electronic conductivity – titanium dioxide is an insulator, graphite is a conductor. NTO will require more conductive carbon black additive

    f. High cost $30/kg versus $10/kg for spherical coated graphite.

    September 5, 2015 - 2:51 PM

    • Manaf Abdul

      Microvast has resolved the “off gassing” problem in a proprietary way. LTO cells can create internal gas when fast charging. Other companies solve this by mechanically compressing the cells – a second best solution.
      Microvast also has completely vertical integrated core battery chemistry, including cathode, anode, electrolyte, membrane separator, to application technologies including battery management systems (BMS) and other power control electronics.
      Microvast’s LTO is ‘ultra-fast charging’, ‘long life’, and ‘non-flammable’ technologies for automobile applications. Non-flammable battery technology takes both active and passive protection.
      Moreover, it has a higher melting point compared to commercial ones, which ensures that it does not shrink even at temperatures of up to 300 °C.
      LTO has High & Low Temperature tolerance that operates to – 40 °C. Most other Lithium batteries start to become useless at about -10C. This can be a huge advantage in cold climates.
      Even though LTO is more expensive per kWh than most common chemistries, the cycle life is very low. This is the contrary of the amount of electricity that can be stored and discharged by the battery during its lifetime.

      July 23, 2017 - 6:17 AM

      • Christopher Ecclestone

        Thanks Manaf. You make an interesting side point on temperature tolerance that is oft swept under the rug. With half of North America, half of Europe, most of Russia and half of China and Japan having brutal winters the auto industry has blithely charged ahead with EV technology which frankly involves batteries that will not last the distance in very cold start-up situations. There is a good reason why HEVs get more traction (pardon the pun) in North America than pure electric vehicles. Is it no surprise that Elon Musk hangs out in California and not northern Minnesota? The technology that addresses battery discharge (and usability) in cold climates will be the long term winner.

        July 23, 2017 - 6:49 AM

        • Manaf Abdul

          Li-ion batteries have made progress. However, durability with the Pure EV duty cycle and the technology’s ultimate life cycle cost and safety remain challenges. For decades now we have been pushing the limits of Li-ion batteries in terms of energy density.

          “The lithium-ion battery has certain risk of random short-circuiting during its production and use, which can cause accidents. Even with a high quality control standard in place (i.e., 2ppm for 18650 cylindrical batteries), in every 100,000 packs sold, 1,600 of them would have batteries at risk of bursting into flame.”

          According to media reports, Panasonic’s President Kazuhiro Tsuga said “We think the existing technology can still extend the energy density of LIBs by 20% to 30%. But there is a trade-off between energy density and safety. So, if you look for even more density, you have to think about additional safety technology as well.” These safety concerns about LIBs are also pushing Panasonic to look at alternative battery power sources.

          But, with safety issues surrounding LIBs and the limitations of their charge capacity, all conventional LiB vendors have to invest in R&D toward a new battery system with advanced high-capacity cathode materials and stabilized high-capacity anode is needed to significantly increase the energy density of lithium batteries through developing high-energy cathode material coupled with high-voltage electrolyte.

          Nissan Leaf is close to selling its stake in AESC (Automotive Energy Supply Corp). Nissan currently owns 51% of the AESC that supplied cells and modules for LEAF, e-NV200 and some of the Renault models). Remaining 49% belongs to NEC Corp. What prompted the change of heart for Nissan (and several other OEMs build, or with plans to build batteries themselves)?

          Nissan, with the largest automotive lithium battery manufacturing base in the world, operating out of 3 continents is saying NEC technology couldn’t meet their expectations? Nissan apparently is also in talks with GSR to sell its U.S. and U.K. facilities that make automotive batteries. The car maker intends to exit operations employing existing lithium-ion battery technologies, while continuing R&D of next-generation batteries made with new materials.

          Microvast’s LTO technology is a breakthrough for the industry, resolving battery safety issues through a multi-level approach from materials to the system level. The new technology takes both active and passive protection measures in order to enhance product safety, including improvements to the battery’s electrolyte, separator and protection system.

          Microvat’s LTO battery system solution paves the way for mass adoption of electric vehicles. With more than 15,000 Microvast powered buses operating in public transit networks around the world in 2016 and passing the 1.3 billion mark kilometers traveled without battery fire. The non-combustion electrolyte and the temperature tolerance separator are two active protection methods. Combined with STL intelligent thermal control fluid technology, Microvast has achieved its goals of non-combustion, advanced safety and high performance in a battery system.

          July 23, 2017 - 9:58 PM

  • Tom Shimmingham

    As a commercial pilot I can say any claim that batteries caused the explosion on MH370 are unfounded. I find it hard to believe that an explosion of batteries would cause an aircraft to travel such a long distance in the wrong direction, as it was seen doing before it dropped off radar. There is probably more L-ion batteries in the world than there are people, and I can’t remember ever hearing of an explosion, although with thousands of companies making billions of batteries I am there are some inferior designs.

    September 5, 2015 - 3:47 PM

  • John

    This article is wrong. Lithium-metal batteries caused fires and are banned on aircraft by IATA, but not Lithium-ion batteries which use graphite and were made as the safer solution and have proven themselves as that. To tell me that the batteries that I, and everyone I know use every day are not safe when I have never heard of any problems is ridiculose.

    It is important to note that graphite is inert, it is the electrolyte burning in any video you watch. There are many different types of batteries in development, most of which use graphite, including Lithium-Manganese, but it will take decades for any of them to catch up to Lithium-ion batteries in widespread use. Other uses for the supermineral graphite are growing by the day, the macbook I am writing this on has a graphite heat sink instead of a fan…….

    http://www.iata.org/whatwedo/cargo/dgr/Documents/lithium-battery-update.pdf

    September 5, 2015 - 5:30 PM

  • Christopher Ecclestone

    As for Tom’s comments I never said the batteries caused MH370.. I said that initially it was speculated that they had… its quite clear that if the plane had exploded it wouldn’t have kept flying for hours.. !!!

    September 6, 2015 - 4:10 AM

  • Christopher Ecclestone

    As for John’s comments I have quite clearly stepped on sensitive toes in the graphite boosterism clique… here are the US govt safety guidelines before there is any more ad libbing on this subject…

    http://phmsa.dot.gov/safetravel/batteries

    and here is a major shipping associations report on United Airways..

    http://www.bifa.org/news/articles/2015/mar/airlines-begin-ban-on-shipments-of-lithium-ion-batteries

    Do we need to have this chipped into Mt Rushmore before people will see the reality? United are not turning down paying business because of a whim…

    September 6, 2015 - 4:13 AM

  • Christopher Ecclestone

    Feast your eyes on this…

    Electrical and Thermal Modeling of a Large-Format Lithium Titanate Oxide Battery System
    April 2015
    MNTRC Report 12-32
    Timothy Cleary, M.S., Harshad Kunte, M.S., and Jim Kreibick

    The abstract reads: “The future of mass transportation is clearly moving towards the increased efficiency of hybrid and electric vehicles. Electrical energy storage is a key component in most of these advanced vehicles, with the system complexity and vehicle cost shifting from combustion engines to battery and electric drive systems.
    To assist engineers and technicians in this transfer, the Battery Application Technology Testing and Energy Research Laboratory (BATTERY) of the Thomas D. Larson Pennsylvania Transportation Institute in the College of Engineering at The Pennsylvania State University partnered with an advanced bus manufacturer to study lithium titanate oxide battery chemistry for use in transit buses. The research team found, other than proprietary data/models, scant technical information or research on electrical and thermal modeling of this advanced chemistry.
    The research team developed lithium titanate oxide modules to study their characteristic behaviors and produce state-of-charge estimators capable of running on the limited embedded processing power and memory of a typical battery management system. The team also investigated the thermal performance of this chemistry in the large format, producing a physics-based empirical thermal model for use in system-level simulations. This model predicts pack-level thermal behavior by reporting the minimum, maximum, and average temperatures within a system typically used for large automotive applications, as testing was concentrated on transit bus usage profiles.
    This work supports battery system integration and management. The tools produced are intended to assist automotive engineers to achieve optimal system performance and ultimately a more efficient vehicle”.

    September 7, 2015 - 4:12 AM

  • John

    Please do not worry about stepping on my toes, I enjoy a healthy debate. Your article was very biased and failed to mention the massive weight, space, and dollars saved by using L-ion rather than LTO. If LTO cannot come even close to competing by either cost or weight they will not be accepted by most consumers.

    How can you put these two contradictory statements in your article?

    “LTO technology offers the highest energy to weight ratio seen yet”

    and

    “LTO batteries in that they have a lower inherent voltage (2.4 V/cell), which leads to a lower energy density than conventional lithium-ion battery technologies. ”

    You got it right the second time. Lithium ion anodes have 175-455 watt hr/kg compared to 1302-1488 watt hr/kg. The result is LTO batteries end up being heavier, bigger and more expensive than if they had used a graphite anode.

    The NCIB case study you posted about flammability of batteries is for an LTO anode, not a graphite one…..isn’t that the opposite of what you are claiming? Either way I think you were right by accident because LTO’s swell due to a reaction where the electrolyte gives off gases carbon dioxide, and highly flammable carbon monoxide and hydrogen. Graphite does not produce gasses from reacting with electrolyte. Not that safety concerns matters much for demand of L-ion batteries, they are time tested and proven safe, even if these airlines overreact to mere suspicions and ban transportation of batteries would that even be a bad thing? That just brings more battery factories and mines close to home.

    The other link you posted shows that L-ion batteries are the most accepted on aircraft out of any types of battery, again I thought you were saying the opposite?: http://phmsa.dot.gov/safetravel/batteries

    Did you read the end of the BIFA article you posted? The quote is below, they are not turning down business at all, just making sure they are packaged properly and restricting in shipments from Asia where there is quality control problems.

    “…thousands of the batteries may be packed onto pallets and loaded into the cargo holds of passenger planes. At this point it is important to emphasise that no cargo fires aboard passenger airlines have been attributed to batteries.

    United Airlines and Delta will continue to accept shipments when the batteries are packed inside or with equipment such as laptops or power tools.”

    September 8, 2015 - 11:59 AM

    • Manaf Abdul

      Microvast introduced LpCO technology, which uses modified amorphous carbon material that has higher energy density than LpTO, allowing us to produce fast-charge batteries at a reduced cost than LTO.. LpCO cells can be fully charged within 15 minutes, and retain 80% of their capacity after more than 10,000 full charging cycles.

      LTO is a promising anode material for certain niche applications that require high rate capability and long cycle life. LTO offers advantages in terms of power and chemical stability, but LTO‐based batteries have lower voltage than LFP. Nevertheless, the lower operating voltage brings significant advantages in terms of safety. Further, these batteries can be charged fast in less than 10 minutes.

      The LTO‐based batteries also have a wider operating temperature range and a recharge efficiency exceeding 98%. Although the energy density of LTO‐based batteries is low compared to other lithium ion batteries, it is still higher than NiCad batteries. The volumetric change during charge and discharge is very small compared to carbon and results provide much longer cycle life.
      The large cycle life and high rate capability of LTO‐based batteries also brings unique advantages in several applications. The batteries can be charged quickly and discharged slowly. For electric vehicles, the fast recharge capability makes a huge difference in recharge time compared to other chemistries: 10 minutes for LTO‐based batteries compared to 5-6 hours for certain Li-Ion chemistry. Pls contact on manaf@altaenergy.in for more information

      July 23, 2017 - 7:30 AM

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    September 11, 2015 - 1:48 AM

  • Jeff

    Hi to everyone, I enjoyed reading your debates. I have been researching and fabricating both carbon and lto anode Li-ion batteries. Each battery has its pros and cons as you all pointed out and I don’t believe they are mutually exclusive. But they are rather focusing on different applications. LTO Li-ion gassing issue can be solved by coating and certainty will lose some material capacity, and carbon anode needs to form a good “SEI” (solid electrolyte interphases) during its first charging and lose ~10% its original capacity. I see two types of batteries are complementary and wish them all to do well in different applications.

    September 29, 2015 - 5:21 PM

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