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• Materials for Ceramics

Spodumene

Description: Lithium sourcing feldspar

Oxide Analysis Formula Li2O 8.01% 1.00 Al2O3 27.41% 1.00 SiO2 64.59% 4.00 Oxide Weight 372.07 Formula Weight 372.07

Notes

The name is from the Greek spodos, meaning burnt to ash. Spodumene is a silicate mineral often referred to as lithium feldspar. Its mineral form is characterized by hard needle-like grains of brilliant white color. It is used in ceramics as a source of lithia.

In ceramics, lithia is a very powerful flux, especially when used in conjunction with potash and soda feldspars. As one of only a few natural lithium source materials, spodumene is a valuable component in glass and ceramic/enamel glazes (Li2O reduces thermal expansion, melting temperature and viscosity of the glaze melt). It was also used in huge quantities to make Corning Ware.

Spodumene is only slightly soluble (in contrast to lithium carbonate). Because spodumene is a natural combination of silica, alumina and lithia it melts better than a chemically equivalent mixture of lithium carbonate, kaolin and silica. Since almost all raw glazes contain kaolin and silica it is normally fairly easy to juggle recipe ingredients, using glaze chemistry, to replace lithium carbonate with spodumene (provided, of course, that the lithium carbonate percentage is not too high). Spodumene can also be substituted for part of the feldspar complement in a recipe without disturbing overall chemistry too much (other than substituting Li2O for KNaO).

That being said, the price of spodumene is increasing rapidly as industry learns to extract the lithium from it. This is being done via calcination to convert the crystal structure from monoclinic alpha (a-form) to tetragonal beta (β-form). Calcination is then further employed in the acid roasting of spodumene, so that lithium can be extracted as water-soluble lithium sulfate.

Some types of spodumene do contribute to the formation of bubbles in the glaze slurry. You can wash spodumene before use to alleviate this issue (mix it well in plenty of hot water, allow to settle overnight, pour off the water the next day and dry it).

Spodumene is a little more readily fusible than petalite since it is higher in lithium. It is considered a better source of Li2O for frits. Some sources quote the percentage of Li2O in molar percent rather than weight percent (resulting in a much higher figure).

Spodumene powder, although heavy, dusts easily and is very unpleasant to smell or breathe. And it sticks to tools, scoops and containers. Good ventilation equipment is essential when working with it.

Related Information

Spodumene ore

Spodumene ore: Typically refiners want 6% or more LiO2 content.

Sourcing Li2O from spodumene instead of lithium carbonate comes at a cost

Lithium carbonate is now ultra-expensive. Yet the reactive glaze on the left needs it. Spodumene has a high enough Li2O concentration to be a possible source here. It also has a complex chemistry, but the other oxides it contains are those common to glazes anyway. Using my account at insight-live.com, I did the calculations and got a pretty good match in the formulas (lower section in the green boxes). Then I made 10-gram balls and did a GLFL test at F (notice the long crystals in the glass pools below the runways). Not surprisingly, this recipe is very runny, that's why the tiny yellow crystals grow during cooling. The new version fires very similar, perhaps better. Our calculated cost to mix this recipe in was $17.84/kg vs. $10.40/kg. But there is a practical cost: Poor slurry properties. The spodumene sources so much Al2O3 that 70% Alberta Slip had to be dropped to accommodate it! How does one use this type of glaze without ruining kiln shelves? Using a catcher glaze is one answer.

Example of a commercial spodumene

Our theoretical chemistry is fairly close to this (notice these numbers are not precise, they indicate a range or minimum).

Spodumene can bubble when mixed with water.

This is what happens when some spodumenes are mixed with water. They generate foam and bubbles. This is disruptive in glazes and can be alleviated by washing and drying the powder before use. Or calcining at 500-600F.

Spodumene glaze with natural ironstone concretion speckle

LA speckle test cone 10R (G spodumene) using ground ironstone concretions (50% 70-100 mesh, 35% 50-70 mesh, 15% 40-50 mesh) at 0.5%, 0.3%, 0.1% (left to right).

Adding spodumene to this floating blue tones down the white patches

GA6-C (left) and GA6-E (right) at cone 6 oxidation. The E version adds 4% spodumene onto the 4% rutile in the C (the base is 80% Alberta Slip and 20% frit ). The spodumene eliminate the overly whitish areas that can appear. This glaze requires the "Slow Cool (Reactive Glazes)" firing schedule. It looks the best on dark bodies.

A problem with spodumene fluxed glazes: bubbles, surface dimples

This is a closeup of GB, a recipe with 11% spodumene. Although the glaze is very glossy, its surface is marred by tiny dimples, the remnant of broken and partially healed bubbles escapes. These bubbles were in the laydown and dried in place (the spodumene generates these in the slurry itself, making it frothy). This can be reduced by drop-and-hold firing techniques, but a better answer is to find a frit to source the Li2O.

Here is why Spodumene powder glistens in the light

Spodumene ceramic grade, used in glazes, is a 200 mesh material. How could the particles be big enough to glisten in the light? This is a micrograph of some of the particles from the 0.6% plus 100 mesh material that I extracted in a particle size distribution test. And 8% is plus 200 mesh. And all that material is flakey like this, millions of tiny mirrors. This also explains why the material becomes airborne so easily and why it is really really not good to breathe this stuff in.

Here is why Petalite and Spodumene will seldom substitute for Lithium Carbonate

Of course, if a recipe only calls for 1-5% lithium carbonate either of these might be candidates to supply the Li2O. However, Petalite is eight times less and Spodumene five times less concentrated than lithium carbonate so to make either worthwhile the prices would need to be eight and five times cheaper. But if a recipe calls for more there is another problem: Petalite is extremely high in silica, which means supplying the needed Li2O from it is almost certainly going to oversupply SiO2. Spodumene will likely do the same. Both are also high in Al2O3 and likely to oversupply that (or at minimum supply the bulk preventing the presence of kaolin in the recipe).

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But traders can have difficulty carrying stock and might face greater risks than other market participants, Fastmarkets learned.

Historically, lithium salts are mostly purchased by end users who sign long-term fixed contracts directly with producers. But more traders were attracted to the market when prices soared in and .

&#;For instance, spot spodumene prices climbed to $8,000 per tonne from $395 [per tonne] at the end of . When there was a real shortage, buyers were willing to take anything with lithium in it. On the way down, users can be much more selective, which can be an issue for traders looking to restock,&#; Will Adams, head of battery raw materials research at Fastmarkets, said.

But in many ways, lithium is still considered an emerging market, and one which is no stranger to volatility and price cycles.

Prices for lithium hydroxide and lithium carbonate on a CIF China, Japan, and South Korea (CJK) basis fell by more than 80% throughout and into after reaching record highs in .

Fastmarkets assessed lithium hydroxide monohydrate LiOH.H2O 56.5% LiOH min, battery grade, spot price cif China, Japan & Korea at $12.50-14.00 per kg on Friday February 9, down by 84.13% since January 3, .

And Fastmarkets assessed lithium carbonate 99.5% Li2CO3 min, battery grade, spot prices cif China, Japan & Korea at $14.00-14.50 per kg on Friday, down by 81.96% since January 3, . 

This significant decline in prices has affected participants across the supply chain. There have been production halts at spodumene producers in Australia, strategic reviews of operations and staff cuts and cost-cutting measures in many companies amid squeezed margins.

The recent market downturn also resulted in one trading house, Trafigura, parting ways with the head of their lithium book.

Traders exposed to risk

Traders can sometimes face even greater risks than other market participants, depending on their positioning.

Lithium is a difficult market to operate in, particularly when compared with other, more mature battery raw material markets. Lithium chemicals need to be stored under specific conditions and often have a relatively short shelf life &#; as low as six months.

Besides storage issues, users of battery-grade lithium hydroxide &#; and, to a lesser extent, lithium carbonate &#; are quite particular about the specifications of the material they are buying; therefore, they can become more selective of what they want to buy at time of surplus. That can be an issue for a &#;distressed&#; seller looking to destock, according to Adams.

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This means that carrying stock can be difficult.

&#;If you&#;re carrying stock, it&#;s a terrible time to be in the market,&#; one trader told Fastmarkets.

&#;I think the volatility of the last 12 months does illustrate the importance of exit liquidity,&#; a consumer told Fastmarkets.

&#;Traders who aim to be market makers by having readily available spot tonnes at warehouse must have suffered badly over the last year if they&#;ve had to write down more than 80% of the value of some of their stock,&#; the consumer said.

In other markets, such as nickel or cobalt, producers and traders can opt to withhold material from the market and stockpile during times of price weakness and oversupply. Due to the nature of lithium chemicals, this is not possible for many lithium traders, highlighting the need for hedging and risk management tools within the lithium market.

&#;The impact is mitigated if you hedged or if you are back-to-back on your physical sale,&#; a second trader said. &#;But if you have stock without hedge, some companies will take losses.&#;

Risk management tools

The role of risk management tools in the lithium industry are expected to increase significantly soon, while participants look to guard against further significant fluctuations in prices.

Multiple futures contracts have been launched for lithium products, including cash settled contracts on the Chicago Mercantile Exchange and Singapore Exchange, as well as physically delivered contracts on the Guangzhou Exchange.

Open interest has grown significantly on some of these contracts in recent months, while participants look for hedging opportunities to optimize price exposure.

Opportunities emerge

The significant price slump in lithium has undoubtedly created a difficult market situation for many traders to operate in, but opportunities are also emerging.

&#;Current market conditions actually represent an opportunity for those looking to enter or grow,&#; the first trader said. &#;Lower prices mean a lower barrier for entry into the market, and sellers are often more receptive to negotiations.&#;

Despite the decline in prices, traders reportedly continue to take fresh deliveries of materials.

One such instance was Glencore, which announced on February 5 that it received a 22,000 tonne cargo of spodumene from Brazilian producer Sigma Lithium.

Though this additional shipment is part of a broader agreement between the two companies, the payable associated with the agreement has declined from 9% of the Fastmarkets lithium hydroxide CIF CJK to 7.5%.

Spodumene offers several advantages for traders in the lithium market because it does not have the same shelf-life issues as other lithium chemical products.

Importance of traders

Though some in the market believe that traders have added a further layer of complexity to the lithium market dynamics, many also note the positive elements traders add.

One such advantage is improved liquidity.

&#;Having traders in the market over the long term will help liquidity, even if at times it increases volatility, but as liquidity increases in the exchange contracts, that price volatility will be easier to hedge,&#; William Adams, Fastmarkets head of battery raw material research, said.

Traders also increasingly play an important role in providing financing for the industry, particularly to newer lithium producers.

&#;I think it&#;s important to think about&#; the financing and capital that [traders] can bring to the market, [which] is important for long-term growth,&#; the first trader said.

Indeed, many participants said that falling lithium prices have the potential for disincentivizing investors from making additional investment in upstream projects.

&#;The long-term lithium story is still there; demand for the material will continue to increase, and traders will help contribute to meeting that demand,&#; the first trader added.