Li-ion Battery Industry Is Shaping The Lithium Industry

| Jerry Huang

Li-ion Battery Industry Is Shaping The Lithium Industry

Lithium ion battery and EV industry occupy 32% of world’s lithium consumption in 2015, with ceramics and glass, lubricating grease, medicine, metallurgy and polymers being 68% at the same time; while it is estimated that Lithium ion battery will consume 67% of world’s lithium supply right after six years by the end of 2021.

Source: Benchmark Mineral Intelligence, Lithium Forecast Database.

In China market, the lithium ion battery industry consumes approximately 80% of lithium hydroxide in 2018 already, according to data from Lithium Research Institute. As a result, the lithium industry has been shaped by lithium ion battery and EV industry since 2015/2016; and lithium refinery has experienced a big shift of thinking for a dominant application in lithium ion battery and electric vehicles out of various end use.

With increasing investment in lithium ion battery, such as NCM, NCA and LFP, especially the resurgence of LFP battery in China market, the demand of battery grade lithium carbonate, being 80% of all grades lithium carbonate's output in 2020, is estimated to continue its growth in the future.

Applications of Lithium Carbonate

| Jerry Huang

Lithium carbonate, an inorganic compound with its chemical formula Li2CO3, is a colorless monoclinic crystal or white powder. Its density is 2.11g/cm3, melting point 618°C (1.013*10^5Pa), soluble in dilute acid. Lithium carbonate is slightly soluble in water, greater in cold water than in hot water, but it is insoluble in alcohol and acetone. It’s often used in ceramic and pharmaceutical, metallurgical industries etc. It is a key ingredient in alkaline storage battery, NMC111, NMC442, NMC532, NMC622 and LFP lithium-ion batteries.

Applications of lithium carbonate:

----Production of lithium batteries: In the field of high-energy lithium-ion battery (automotive, energy storage) production, it is used to produce materials such as LCO(Lithium Cobalt Oxide), LMO(Lithium ion Manganese Oxide), LTO(Lithium Titanate Oxide), LFP, NMC111, NMC442, NMC532, NMC622 for Li-ion battery and those for other alkaline batteries.

----Used in the metallurgical industry: Lithium is a light metal, which can strongly combine with oxygen atoms. It is used as a deoxidizer in the process of industrial copper and nickel smelting; lithium can be used as a sulfur cleaner. It is also used in alloys with a variety of metals. Magnesium-lithium aluminum alloy is the lightest metal structure material among the magnesium alloys so far, which have wide applications in aerospace and telecommunications.

----Application in medicine: Lithium carbonate, as an ingredient in certain medicine, has a significant inhibitory effect on mania and can improve the affective disorder of schizophrenia. Patient with severe acute mania can be first cured with chlorpromazine or haloperidol, and then maintained by lithium carbonate ingrediented medicine alone, after the acute symptoms are controlled.

----Application in lubricating grease: Lithium carbonate is also used in production of industrial lithium-based grease, which has good water resistance, good lubrication performance both at low and high temperature.

----Application in ceramics & glass: In the glass industry, it is used in preparation of special and optical glass, and it is used as a flux in preparation of ductile ceramics, ceramic coatings for metal maintenance and heat-resistant ceramic coatings.

Higher Growth of Li-ion Battery Pack for E-bike Expected

| Jerry Huang

Higher Growth of Li-ion Battery Pack for E-bike Expected

Despite the eye-catching global trend of four-wheel #EV market, there has already been an enormous and existing market for E-Bikes and three-wheelers in Asia Pacific region, with a 94.39% of the global market share in 2019, according to a report from Statista.

By the end of the year 2020, there have been massive E-Bike users, running more than 300 million E-Bikes & three wheelers in China alone, together with an annual output of more than 30 million new ones to world market (most for domestic sale in the country). While till the same year, lead-acid batteries are still the major energy solution for them. The high cost of lithium battery has long been a key barrier that slows the growth of lithium-ion battery packed E-bike market. However things are changing in recent couple of years, benefited from a remarkable cost decline of lithium-ion battery.

The market share of lithium-ion battery packed E-Bike & Three-Wheelers is now expected to grow in comparatively higher rate in coming 5 to 8 years in China. SPIR and ZOL have different estimates.

Estimated Share of Li-ion Battery packed E-Bike in China, replacing lead-acid battery: Share of Li-ion battery packed E-bike in China market

A Comparison of NMC/NCA Lithium ion Battery and LFP Battery

| Jerry Huang

A Comparison of NMC/NCA Lithium ion Battery and LFP Battery

Currently, there are two mainstream battery technologies in the market for all-electric vehicles, lithium iron phosphate (LFP) battery and NMC/NCA lithium batteries. These two types of battery compete in many application fields/scenarios, and the toughest competition field is in electric vehicle industry, which consumes the biggest amount of lithium batteries in China.

There has long been comparison between these two types of lithium-ion batteries. The comparison of cost-effectiveness can be easily made by comparing the prices and market feedbacks of the EV using above batteries. But for battery performance, let’s take a look at some details of NMC/NCA battery and LFP battery by setting conditions, observing experimental data of them for a better understanding.

According to the experiments from battery laboratories, electric vehicle manufacturers, and lithium-ion battery manufacturers, although each test may have subtle different data, the conclusion of their advantages and disadvantages tends to be clear. More important, the market has made its own choice and it is still going on.

Energy density----Upon current technology, the energy density of commercial single cell NMC lithium battery is around 200Wh/kg, and NCA battery may get more than 300Wh/kg soon; while energy density of LFP lithium battery is basically hovering around 100~110Wh/kg, some may get 130~190Wh/kg, but it is very difficult for it to exceed 200Wh/kg. NCA/NMC battery is applied mostly in cars which consume less power and in favor of fast speed and long range. Theoretically, cars using NCA lithium batteries can run farther than those using same number of LFP batteries; and LFP vehicles are preferably chosen to be city buses at present, because the range of them is not long, and they can be charged within a short distance in cities, where a lot of charging piles can be easily built.

Space occupation----Choose BYD for buses and Tesla for cars. Benefited from higher energy density, a single NMC/NCA battery cell can provide twice as much space as an LFP battery, which is very important for cars with limited space. So we can see it in the commercial market, Tesla focus on NMC/NCA battery, and BYD produces LFP battery. So there is a saying in China's EV market, "Choose BYD for buses and Tesla for cars". While this year in March 2020, BYD announced their new LFP battery pack saving 50% space of their previous pack, and got positive sales with their Han EV sedan installed with the Blade Battery. At the same time, Tesla unveiled their new model powered by LFP battery from CATL as well.

Safety----Most important of all, the reason for choosing LFP battery for city buses is the essential concern of safety. There have been many fire accidents with Tesla cars from consumers since Tesla Model S was brought to market, although direct reason of fire may differ. One reason is that Tesla's battery pack is composed of more than 7,000 units of Panasonic / Tesla NCA lithium battery. If these units or the entire battery pack has an internal short circuit, they may generate open flames even big fire, especially in car crash; thankfully it is improving. While LFP material will much less likely burn encountering a short circuit, and its high temperature resistance is much better than that of NCA/NMC lithium battery.

Low-temperature & high-temperature resistance----The lithium iron phosphate (LFP) battery has better performance for its high temperature resistance, while NCA/NMC is better for its low temperature resistance. Let me introduce one example. At a temperature of -20℃, the NMC lithium battery can release 70.14% of its capacity; while the lithium iron phosphate (LFP) battery can only release 54.94%. The discharge voltage plateau of NMC lithium battery is far higher, and it starts earlier than that of the LFP battery at low temperature. Therefore, NMC battery is a better choice for applications at low temperature.

Charging efficiency----The charging efficiency of NMC/NCA lithium battery is higher than that of LFP battery. Lithium battery charging adopts current-control and voltage-control method. That is, constant current charging is applied first, when the current and charging efficiency are comparatively high. After the lithium battery reaches certain voltage, the recharger switches to the second stage of constant voltage charging, at this period the current and charging efficiency are low. To measure the charging efficiency of a lithium battery, we use a ratio between the constant-current charging capacity and the total battery capacity, called “the constant-current ratio”. The experimental data on the constant-current ratio shows that there is little difference between NMC/NCA and LFP batteries charging them at a temperature lower than 10℃, but it's quite different at a temperature higher than that. Here is an example, when we charge them at 20℃, the constant-current ratio of NMC lithium battery is 52.75%, which is five times that of the lithium iron phosphate (LFP) battery (10.08 %).

Cycle life----The cycle life of lithium iron phosphate (LFP) battery is better than NMC/NCA lithium battery. The theoretical life of NMC lithium battery is 2000 cycles, but its capacity fades to 60% when it runs 1000 cycles; even the best-known Tesla NCA battery can only maintain 70% of its capacity after 3000 cycles, while the lithium iron phosphate (LFP) battery will remain 80% after 3000 cycles.

The above comparison gives a rough picture about the advantages and disadvantages of NMC/NCA battery and LFP battery. The LFP lithium battery is safe, with long cycle life and good resistance to high temperature; and NMC/NCA lithium battery is high in energy density, light in weight, efficient in charging, with good resistance to low temperature. These differences make them two major choices in the market for varied applications.

Nowadays NMC(Ni-rich types) and NCA battery manufacturers choose lithium hydroxide monohydrate battery grade as lithium source for cathode material. Production of LFP battery by hydrothermal method also uses lithium hydroxide, though most LFP battery manufacturers choose lithium carbonate. Here is a picture of lithium hydroxide consumption in China market in 2018, for your reference. 2018 Lithium Hydroxide Consumption

Which one is better for NMC, NCA and LFP battery, lithium carbonate or lithium hydroxide?

| Jerry Huang

As global EV, HEV, PHEV markets & energy storage markets continue to grow, the lithium ion battery industry is driven to boom as well, which consume big volume of lithium carbonate and lithium hydroxide today. But which one is better for NMC/NCA and LFP battery, lithium carbonate or lithium hydroxide? Let's take a look at some comparisons between these two lithium salts and their performance in battery production process.

Comparison on Stability- The Nickel Manganese Cobalt (NMC) cathode material prepared with lithium carbonate has a specific discharge capacity of 165mAh/g, with a capacity retention rate of 86% at 400th cycle, while battery materials prepared with lithium hydroxide has a specific discharge capacity of 171mAh/g, with a capacity retention rate of 91% high at 400th cycle. As the cycle life increases, the full life-circle curve is smoother, and the charge and discharge performance is stabler with the material processed from lithium hydroxide than those processed from lithium carbonate. In addition, the latter one has a rapid capacity fade after about 350 cycles. Producers of Lithium Nickel Cobalt Aluminium oxides (NCA) battery, such as Panasonic, Tesla and LG Chem, have long been using lithium hydroxide as their lithium source.

Comparison on Sintering temperature- Sintering is a very important step in the preparation of NMC/NCA cathode materials. The sintering temperature has a significant impact on capacity, efficiency and cycle performance of the material, and it also has certain impact on lithium salt residue and the pH level of the material. Research has shown that when lithium hydroxide is used as the lithium source, a low sintering temperature is enough to obtain materials with excellent electrochemical performance; while if lithium carbonate is used, the sintering temperature has to be 900+℃ to obtain materials with stable electrochemical performance.

It looks like that lithium hydroxide is better than lithium carbonate as the lithium source. While actually, lithium carbonate is also often used in the production of NMC cathode materials and LFP battery. Why? The lithium content of lithium hydroxide fluctuates more than lithium carbonate, and lithium hydroxide is more corrosive than lithium carbonate. Therefore a lot of manufacturers tend to use lithium carbonate for production of NMC cathode materials and LFP battery.

So lithium carbonate is the winner? Not yet.

Ordinary NMC cathode materials and LFP battery tend to use lithium carbonate, while Ni-rich NMC/NCA cathode materials are in favor of lithium hydroxide. The reasons rest exactly on the following:

The Ni-rich NMC/NCA material requires a low sintering temperature, otherwise it will cause low tap density and low rate of charge & discharge performance on battery. For example, NCM811 needs it to be controlled lower than 800℃, and NCM90505 needs it to be at about 740℃.

When we check the melting point of these two lithium salts, we will find lithium carbonate being 720℃, while lithium hydroxide monohydrate being only 471℃. Another factor is that, during the synthesis process, the molten lithium hydroxide can be evenly and fully mixed with the NMC/NCA precursor, thereby reducing lithium residue on surfaces, avoiding generation of carbon monoxide and improving the specific discharge capacity of the material. Using lithium hydroxide also reduces cation mixing and improve cycle stability. Thus lithium hydroxide is a must-choice for production of NCA cathode materials. The well-known Panasonic 18650 Lithium ion battery uses lithium hydroxide, as an example. However, the sintering temperature of lithium carbonate often has to be 900+℃ as previously discussed.

Despite the above reasons, by raising the nickel content in lithium ion batteries, the energy density of these batteries increases accordingly, with less cobalt involved and it brings an important result of cost control at the same time.

It is quite clear today, from lithium-ion battery researchers and manufacturers, that lithium carbonate is a good choice for ordinary NMC cathode material and LFP battery; while lithium hydroxide monohydrate battery quality is preferable for Ni-rich NMC/NCA cathode materials.

Generally, every 1GWH Ni-rich NMC/NCA batteries consume about 780 tons of lithium hydroxide. With increasing demand of these NMC/NCA batteries, the demand for lithium hydroxide is expected to rise substantially in the coming five years.

Applications of Lithium Sulfate

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Lithium sulfate is a white inorganic salt with the formula Li2SO4. It is the lithium salt of sulfuric acid. It is soluble in water, though it does not follow the usual trend of solubility versus temperature — its solubility in water decreases with increasing temperature, as its dissolution is an exothermic process. Since it has hygroscopic properties, the most common form of lithium sulfate is lithium sulfate monohydrate. Anhydrous lithium sulfate has a density of 2.22 g/cm3, but weighing lithium sulfate anhydrous can become cumbersome as it must be done in a water lacking atmosphere.

Lithium sulfate is researched as a potential component of ion conducting glasses. Transparent conducting film is a highly investigated topic as they are used in applications such as solar panels and the potential for a new class of battery. In these applications, it is important to have a high lithium content; the more commonly known binary lithium borate (Li₂O · B₂O₃) is difficult to obtain with high lithium concentrations and difficult to keep as it is hygroscopic. With the addition of lithium sulfate into the system, an easily produced, stable, high lithium concentration glass is able to be formed. Most of the current transparent ionic conducting films are made of organic plastics, and it would be ideal if an inexpensive stable inorganic glass could be developed.

Lithium sulfate has been tested as an additive for Portland cement to accelerate curing with positive results. Lithium sulfate serves to speed up the hydration reaction which decreases the curing time. A concern with decreased curing time is the strength of the final product, but when tested, lithium sulfate doped Portland cement had no observable decrease in strength.

Lithium sulfate is used to treat bipolar disorder. Lithium (Li) is used in psychiatry for the treatment of mania, endogenous depression, and psychosis; and also for treatment of schizophrenia. Usually lithium carbonate (Li₂CO₃) is applied, but sometimes lithium citrate (Li₃C6H5O7), lithium sulfate or lithium oxybutyrate are used as alternatives.

Lithium sulfate has been used in organic chemistry synthesis. Lithium sulfate is being used as a catalyst for the elimination reaction in changing n-butyl bromide to 1-butene at close to 100% yields at a range of 320℃ to 370℃. The yields of this reaction change dramatically if heated beyond this range as higher yields of 2-butene is formed.

An Introduction to Lithium Perchlorate

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Lithium perchlorate is an inorganic compound with the formula LiClO4. This white or colourless crystalline salt is noteworthy for its high solubility in many solvents. It exists both in anhydrous form and as a trihydrate.

Application in Inorganic Chemistry- Lithium perchlorate is used as a source of oxygen in some chemical oxygen generators. It decomposes at about 400 °C, yielding lithium chloride and oxygen: LiClO4 → LiCl + 2 O2

Over 60% of the mass of the lithium perchlorate is released as oxygen. It has both the highest oxygen to weight and oxygen to volume ratio of all practical perchlorate salts.

Application in Organic Chemistry- LiClO4 is highly soluble in organic solvents, even diethyl ether. Such solutions are employed in Diels-Alder reactions, where it is proposed that the Lewis acidic Li+ binds to Lewis basic sites on the dienophile, thereby accelerating the reaction. Lithium perchlorate is also used as a co-catalyst in the coupling of α,β-unsaturated carbonyls with aldehydes, also known as the Baylis-Hillman reaction.

Solid lithium perchlorate is found to be a mild and efficient Lewis acid for promoting cyanosilylation of carbonyl compounds under neutral conditions.

Application in Li-ion Batteries- Lithium perchlorate is also used as an electrolyte salt in lithium-ion batteries. Lithium perchlorate is chosen over alternative salts such as lithium hexafluorophosphate or lithium tetrafluoroborate when its superior electrical impedance, conductivity, hygroscopicity, and anodic stability properties are of importance to the specific application. However, these beneficial properties are often overshadowed by the electrolyte's strong oxidizing properties, making the electrolyte reactive toward its solvent at high temperatures and/or high current loads. Due to these hazards the battery is often considered unfit for industrial applications.

Application in Biochemistry- Concentrated solutions of lithium perchlorate (4.5 mol/L) are used as a chaotropic agent to denature proteins.

Production- Lithium perchlorate can be manufactured by reaction of sodium perchlorate with lithium chloride. It can be also prepared by electrolysis of lithium chlorate at 200 mA/cm2 at temperatures above 20 °C.

Safety- Perchlorates often give explosive mixtures with organic compounds.

Application of Lithium Acetate

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Lithium acetate is a chemical compound with its chemical formula CH3COOLi. It is a salt that contains lithium and acetic acid.

Lithium acetate is used in the laboratory as buffer for gel electrophoresis of DNA and RNA. It has a lower electrical conductivity and can be run at higher speeds than can gels made from TAE buffer (5-30V/cm as compared to 5-10V/cm). At a given voltage, the heat generation and thus the gel temperature is much lower than with TAE buffers, therefore the voltage can be increased to speed up electrophoresis so that a gel run takes only a fraction of the usual time. Downstream applications, such as isolation of DNA from a gel slice or Southern blot analysis, work is expected when using lithium acetate gels.

Lithium boric acid or sodium boric acid are usually preferable to lithium acetate or TAE when analyzing smaller fragments of DNA (less than 500 bp) due to the higher resolution of borate-based buffers in this size range as compared to acetate buffers.

Lithium acetate is also used to permeabilize the cell wall of yeast for use in DNA transformation. It is believed that the beneficial effect of LiOAc is caused by its chaotropic effect. Lithium acetate is also used in denaturing DNA, RNA and proteins.

Introduction and Application of Lithium Acetate Dihydrate

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Lithium Acetate Dihydrate

CAS No.: 6108-17-4 EINECS(EC#): 208-914-3 Molecular Weight: 102.02 Molecular Formula: LiOOCCH3·2H2O MDL Number: MFCD00066949

Lithium Acetate Dihydrate (6108-17-4) is white moderately water-soluble crystalline powder with stench-acetic odor. It is also called for Acetic acid lithium salt dihydrate. It is incompatible with strong oxidizing agents. It decompounds to yield carbon monoxide, carbon dioxide, oxides of Lithium. All metallic acetates are inorganic salts containing a metal cation and the acetate anion, a univalent (-1 charge) polyatomic ion composed of two carbon atoms ionically bound to three hydrogen and two oxygen atoms (Symbol: CH3COO) for a total formula weight of 59.05. Acetates are excellent precursors for production of ultra-high purity compounds, catalysts, and nanoscale materials. Lithium acetate dihydrate (6108-17-4) can be used to separate saturated fatty acids from unsaturated fatty acids. In pharmaceutical industry, it is used for the preparation of diuretics. In addition, it is used as Lithium-ion battery material.

How to make electrolyte with LiPF6 and what else it can make?

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Lithium hexafluorophosphate is an inorganic compound with the formula LiPF6. It is a white crystalline powder. It is used in commercial secondary batteries, an application that exploits its high solubility in non-aqueous, polar solvents. Specifically, solutions of lithium hexafluorophosphate in carbonate blends of ethylene carbonate, dimethyl carbonate, diethyl carbonate and/or ethyl methyl carbonate, with a small amount of one or many additives such as fluoroethylene carbonate and vinylene carbonate, serve as state-of-the-art electrolytes in lithium-ion batteries. This application also exploits the inertness of the hexafluorophosphate anion toward strong reducing agents, such as lithium metal.

The salt is relatively stable thermally, but loses 50% weight at 200 °C (392 °F). It hydrolyzes near 70 °C (158 °F) according to the following equation forming highly toxic HF gas: LiPF6 + H2O → HF + PF5 + LiOH

Owing to the Lewis acidity of the Li-ions, LiPF6 also catalyses the tetrahydropyranylation of tertiary alcohols.

In lithium-ion batteries, LiPF6 reacts with Li2CO3, which may be catalysed by small amounts of HF: LiPF6 + Li2CO3 → POF3 + CO2 + 3 LiF

Furthermore, lithium hexafluorophosphate is also used in ceramic industries and for welding electrode manufacturing. It is also used in prism spectrometer and x-ray monochromator.