Lithium Nickel Cobalt Aluminum Oxide (NCA) in Lithium-Ion Battery Applications

Lithium Nickel Cobalt Aluminum Oxide (NCA) in Lithium-Ion Battery Applications

Lithium-ion batteries are rechargeable batteries where the lithium-ions move from the negative to the positive electrode via the processes of charging and discharging. These batteries are highly efficient in performing their tasks and authenticating the industries and markets, in which they are working. Their characteristics are excellent which helps them perform best to their abilities.

Lithium nickel cobalt aluminum oxide is an excellent material that enhances the quality of lithium-ion batteries and enables them to function more effectively and efficiently. They add up to their productivity and enhance their work mechanism so that they get a better environment to work in and perform in excellent ways.

Introduction

A kind of rechargeable battery, Li-ion battery, or lithium-ion battery is a battery in which lithium ions move through an electrolyte during discharge from the negative electrode to the positive electrode and from the positive to negative electrode during charging. An intercalated lithium compound is used as the material at the positive electrode by the Lithium-ion batteries and the material that is commonly at the negative electrode is graphite.

Lithium-ion Batteries

High energy density

Low self-discharge, no memory effect (other than LFP cells), and high energy density are possessed by the Li-ion batteries. Cells are made for prioritizing either power density or energy. Although they can be dangerous because they have flammable electrolytes and they can result in fires and explosions if they are charged incorrectly or damaged.

Lithium-ion battery’s development

In 1985, Akira Yoshino made a prototype Lithium-ion battery as suggested in earlier research that was done during the 1970s-1989s by Koichi Mizushima, Rachid Yazami, M. Stanley Whittingham, and John Goodenough. Then in 1991, a team led by Yoshio Nishi, of Asahi Kasei and Sony, developed a commercial Li-ion battery. The common usage of lithium-ion batteries is in electric vehicles and portable electronics and their popularity is growing for applications in aerospace and military.

Properties of Lithium-Ion Batteries

Different Lithium-ion batteries have different safety properties, cost, performance, and chemistry. Mostly, a graphite anode, a lithium cobalt oxide (LiCoO2) cathode material, and lithium polymer batteries (with electrolyte-like polymer gel) are used by handheld electronics, and they provide high energy density together. Better rate capability and longer lives are offered by the lithium nickel manganese cobalt oxide (NMC or LiNiMnCoO2), lithium manganese oxide (Li2MnO3-based lithium-rich layered materials, or LiMn2O4 spinel), and lithium iron phosphate (LiFePO4). Such batteries are used broadly for medical equipment, electric tools, and other roles. There is a broad usage of NMC and its derivatives in electric vehicles.

More areas of research for lithium-ion batteries

Among many others, increasing the speed of charging, lessening cost, enhancing safety, increasing energy density, and increased lifetime are some of the research areas for Li-ion batteries. There has been going on research in non-flammable electrolytes area as a pathway for improved safety based on the organic solvent’s volatility and flammability which is utilized in the typical electrolyte. Heavy fluorinated systems, ionic liquids, polymer electrolytes, ceramic solid electrolytes, and aqueous lithium-ion batteries are included in the strategies.

Present Day Li-ion Batteries

As compared to the real small electronic devices for the 3C market that's told above, lithium-ion batteries' current market is way more difficult. There has been an opening of various additional markets for small devices like medical devices, vaporizers, e-cigarettes, lighting (fluorescent lights and LCD), toys, and various others. Using 26650, 26700, and 18650 sizes, lithium-ion battery packs a discovery that can be manufactured to function at way higher power as compared to originally suspected and that has paved the way toward markets for electronic bikes, garden tools, portable electric tools, and various other products.

Lithium Carbonate in Lithium-Ion Battery Applications

If you want to obtain more information about Lithium-ion Batteries,

you can read our other blog post.

High energy cells

ome of the capacity has been sacrificed by the high power cells for achieving 20A or more continuous discharge capability in the cell size of 18650, whereas 3.4 Ah is now possessed by high energy 18650 cells. Sustaining such high capacity during cycling is difficult whereas some cells possess 2.5 Ah or high capacity. The significant effect of tab placement and multiple tabs are shown by Spotnitz, Reimers, and coworkers in the modeling studies. Carbon type that is utilized in the negative electrode, electrodes porosities, positive electrode's content of carbon, and thickness of the electrode, are among the other major design variables.

Ceramic coatings development

A beneficial effect has been possessed by the ceramic coating's development to the positive electrode or separator, on stopping internal short-circuiting from happening during cycling because of metal particles' adventitious presence on the electrode's surface. These are airborne and small particles in general and they result commonly from the electrode's mechanical slitting. The thickness of the separator is 12-25 micrometers so the penetration of the separator by the extremely small particles can be made possible and cause a short that has been recognized as a significant failure mechanism of the lithium-ion batteries. Such separator coatings may be as thin as the thickness of 2 micrometers. They can be on one or both of the sides of the polyolefin separator.

Additional benefits

Coating of the separator comes with some extra benefits e.g, separator's much-lessened shrinkage at the shutdown temperatures (shutdown of current due to separator's melting might not be successful if the separator's shrinking is taken that far that the direct contact between cathode and anode is permitted), better cycling that capacity is degraded by the weak short circuit without leading to a safety accident, and enhanced electrolyte wetting due to the readily wet inorganic oxide ceramic phase. Currently, many complex coatings are becoming common for instance, Tesla Motors and Panasonic uses the Sumitomo separator that involves a coating that contains ceramic particles and an aromatic polyamide (aramid polymer) for increasing the coating's penetration strength.

Present cathode materials

Original LiMn2O4 (abbreviated as LMO) and LiCoO2 (abbreviated as LCO) are included in the present cathode materials that are in common usage. LiNixMnyCo1-x-yO2 is an under development and excellent material. It is known as NMC in general and has a similar R3-m structure in the original Goodenough patent other than some ordering in the transition metal layer). 811, 442, or 532 are the atomic ratios of the subscripts that are used to call the subscripts (other than x=y=3 which was investigated initially and is known as 111 or 333). 532 and 111 are the most usually utilized materials.

Competitive materials

LiNi0.80Co0.15Al0.05 (NCA) is a layered R3-m structure too and it is an extremelycompetitive material. Recently, several groups competitively made a material, known as LiFePO4 (LFP) and it possesses a 1D tunnel structure. Each material possesses particular disadvantages and advantages and they have been implemented in various applications.

Lithium Nickel Cobalt Aluminum Oxide (NCA)

It is a group of mixed metal oxides. They are significant because of their applications in lithium-ion batteries. On the positive pole, NCAs are utilized as an active material. When the battery is discharged, the cathode is the positive pole. Cation of the chemical elements like aluminum, cobalt, nickel, and lithium make up NCAs. LiNixCoyAlzO2 is the general formula of the most significant representatives to date with x + y + z = 1. The voltage of the currently available NCA comprising batteries is between 3.6 V-4.0 V, at 3.6 V-3.7V of nominal voltage. They are also utilized in electric appliances and electric cars, x≈ 0,8. In 2019, LiNi0,84Co0,12Al0,04O2 is the version of the oxides that were in usage.

Buy PTFE

NCA’s Manufacturer

In 2015, Sumitomo Metal Mining was the 58% major manufacturer of NCA and their market shares, whereas Ecopro was with 5%, Nihon Kagaku Sangyo was with 13%, and Toda Kogyo (BASF) was with 16%. Panasonic and Tesla are supplied by Sumitomo and in 2014, Sumitomo was capable of making NCA of 850 tons per month. Sumitomo increased its monthly production capacity in 2016 to 2550 tons, and 4550 tons in 2018. Since 2019, a plant has been under construction in Qinghai province, Tongren County, and China. Initially, it will make 1500 tons NCA per month.

NCA’s characteristics

180-200 mAh/g is NCA’s usable charge storage capacity and it is far less than the theoretical values. 279 mAh/g is for LiNi0,8Co0,15Al0,05O2. Although, NCA’s capacity is way more as compared to the capacity of the alternative materials like NMC 333 LiNi0,33Mn0,33Co0,33O2 with 170 mAh/g, lithium iron phosphate LiFePO4 with 165 mAh/g, and lithium cobalt oxide LiCoO2 with 148 mAh/g. NCA belongs to the cathode materials with layer structures like NMC and LiCoO2. NCA enables batteries with high energy density because of the high voltage. Its remarkably fast-charging capability is NCA's other advantage. Nickel and cobalt's limited resources and high costs are the disadvantages.

Related structures

NMC and NCA are the two materials with related structures, similar performance, similar electrochemical behavior, comparatively high performance, and high energy densities. According to findings, Model 3's NCA battery possesses 11.6 kg of lithium and 4.5-9.5 kg of cobalt.

Limitations and benefits of Nickel-rich NCA

Nickel rich are the NCAs LiNixCoyAlzO2 with x ≥ 0.8. They are the most significant ones in the substance class. They are low in cobalt and as cobalt is extremely expensive, it gives them a cost advantage. As there is an increase in the content of nickel, the voltage also increases, therefore increasing the amount of energy that can be stored in the battery. Although, the battery's premature aging and the thermal breakdown risk also increase with the increase in the content of nickel. An NCA battery will typically run away when it's heated to 180 °C. This can occur at 65 °C too if the battery was overcharged previously. In NCA, the aluminum ions increase safety and stability, but they lessen capacity too as they don't involve in reduction and oxidation.

The material’s modifications

The NCA active material is coated for making the NCA more resistant for those batteries which function at temperatures of more than 50 °C. In research, the demonstrated coatings may be comprised of phosphates like FePO4, fluorides like glassy oxides (silicon dioxide SiO2), crystalline oxides (NMC, TiO2, CoO2), or aluminum fluoride AlF3.

NCA batteries: Usage and Manufacturer

Panasonic or Cooperation partner of Panasonic, Tesla were the only important ones to reportedly manufacture the NCA batteries in 2018. NCA is utilized by Tesla as active material in the traction batteries of its car models. LiNi0,84Co0,12Al0,04O2 is utilized in Tesla Model X, and Tesla Model 3. Either alternatively, lithium nickel manganese cobalt oxides (NMC) or NCA are used by the current electric cars in 2019 with some exceptions. NCA is utilized mainly by Samsung, Sony, and Panasonic, in batteries for electronic devices and electric cars too. NCA batteries are used to equip some cordless vacuum cleaners.

Most Applications of the Lithium-ion Batteries

For most Li-ion battery (LIBs) applications like electric vehicles (EVs), the definition of the end of life (EoL) criterion is the decrease of the battery's dischargeable capacity by 20-30 % of its initial value. How fast will this threshold be reached depends significantly on extrinsic factors like the presence of efficient battery (thermal) management systems, rest periods, exposition to particular current/voltage windows, and temperature of operation, and On intrinsic factors like quality of manufacturing and chemistry.

Quantifying the effect of working conditions of the environment on the battery state-of-health (SoH) is thus important for improving the learning curve that will give more specific life-estimation models and more efficient strategies for prolonging the service life. Such data doesn't only tell the design of the battery but also risks the calculations for the battery-related warranty products and insurance, with an indirect effect on the costs of second and first life.

Nickel-based layered oxides

Over the last decade, Nickel-based layered oxides, for instance, Li[Ni1-x-yCoxAly]O2 (NCA) and Li[NiaCobMnc]O2 (a+b+c=1; NCM-abc), consolidated their position as the choice of cathode material for the passenger EV batteries, whereas phasing out the olivine LiFePO4 (LFP) and cubic spinel LiMn2O4 (LMO) based systems gradually. For instance, LMC-based LiBs power up Volkswagen ID3 and GM bolt cars, and Panasonic NCA-based LiBs are utilized in Tesla Models X and S. Panasonic (NCA, 21700 cylindrical formats) and Contemporary Amperex Technology (CATL, NCM-811, pouch format) have recently reached 300 Wh kg–1 of a milestone at cell-level, boosting even more interest in the Nickel-based cathodes, the chemistry of NCA specifically. Panasonic group disclosed a study earlier in which lithium-cobalt-oxide (LCO|Gr) and NCA/Gr cells were compared at 45 °C and 4.1 V upon calendar aging.

Uncommercialized NCA cells

According to the reports, even after 2 years, the uncommercialized NCA cells remained at 90% SoH in 2006. The major different capacity fade for cobalt-only and nickel-rich oxide cells was discussed regarding rates of distinct cathode degradation. SoC’s and temperature on the side reactions causing the capacity to fade has a strong impact on the NCA/Gr cells degradation according to further insights. According to consensus, low temperatures and low SoC values should be advantageous for graphite-based cells. Until now, there are no reports on the high-energy chemistry best operation which joins the NCA with silicon suboxide improved graphite (Gr-SiOx) comparing temperatures and various SoCs.

Physical Characterization

Anode material of 15 milligrams was scraped off mechanically from the copper current collector foil and for thermal gravitational analysis, it was brought to a tared and cleaned Al2O3 at 5 C/min in N2/O2 form from 0-1100. A Rigaku Smartlab X-ray diffractometer with a 9 Kw Cu source generator (λ Kα1=1.54051 Å) equipped with a D/teX-ULTRA 250 high-speed position sensitive detector system and a high-resolution Vertical θ/θ 4-Circle Goniometer was used to collect the powder X-ray diffraction (PXRD) data at ambient temperature. FESEM (Field emission scanning electron microscopy) was used to analyze the sample’s microstructure. In FESEM, a JEOL JSM-7800F was used to acquire the images by operating at 10.0 kV.

Elemental analysis

X-ray Energy Dispersive Spectrometer (EDS, large area 50 mm2 Silicon Drift Detector from Oxford instruments, X–Max50) was used to perform elemental analysis at 12.0 kV. A Quorum Q150RES sputter coater (Quorum Technologies Ltd) was used to place the samples over carbon tabs (Agar Scientific, G3348N), attach to the metal holder, and a thin gold layer was used to coat them for increasing their conductivity.

Temperature Dependences for Different SoC Regimes

Quantifying the impact of temperature on the capacity fading rate for elucidating degradation mechanism and the underlying reaction kinetics is common through apparent activation energies Eapp, which enables the changes to be visualized in time and the temperature-dependent behavior over different storage SoCs. High/low effects of the increased temperatures are reflected by Eapp’s high or low values.

Arrhenius plots of capacity losses

The apparent activation energies (Eapp) for calendar aging were computed based on Arrhenius plots of capacity losses at 3 different points in time: by end of 12, 6, and 3 storage months. Of all the conditions that were tested, the weakest temperature dependence was shown by the cells that were stored at 0 % SoC. Moreover, it was confirmed from Eapp’s time evolution that the storage temperature is significant in the storage's initial 3 months, as the higher Eapp suggested for this period as compared to the computed values of after 12 or 6 months, for SoCs≤60 % particularly.

Eapp steadily increases but with a decrease in the slope up to 60% SoC. Eapp drops majorly above 60% SoC and then for 100% SoC, it increases again. As the capacity fade data already suggested, Eapp’s analysis corroborates with a way more complex degradation scenario for cells stored at SoC>60 %. Eapp’s local minimum suggests that the temperature should be detrimental to the cell's degradation that was stored at 70-90 % SoC, and interestingly, that is the regime of the fastest fade in capacity.

Internal Short Circuits and OCV Drift

One can do calendar aging studies at both float mode or open circuit potential conditions, in which cells are forced continuously for maintaining a fixed voltage if enough load is provided. The former approach was used for minimizing the interference on the achieved results. Thus in the tests, there can be a difference between the open-circuit voltages before and after the month-long storage periods.

Tracking Self-Discharge: Float Mode

A particular subset of cells was tested in float mode for quantifying cell discharge to get a good understanding of the observed OCV drift of the 3 cells that were stored at 100 % SoC. In float mode, cell voltages are kept constant and the currents are measured to obtain this, which are equivalent to the internal self-discharge (SD) currents. After the cells were brought to a completely charged state, SD currents were measured for an eight-hour period at 40, 25, and 10 °C. The self-discharge currents were seen to average over the last 30 minutes out of the period of 8 hours. An experiment was done two times for all 3 cells. Much higher self-discharge (SD) currents were seen for the cells that at 50 and 40 C, were stored at 100 % SoC, in comparison with the cells that were stored at 25 °C, which guarantees the trends in OCV drift.

Lithium-ion Batteries

To get more information about how to make a lithium-ion coin cell battery,

you can read our other blog post.

Anode versus Cathode Contributions

Joined contributions from irreversible and self-discharge anode side reactions are reflected. Although, for the SoC>60%, the CEP slippage rate only grows more with SoC whereas the slippage rate of DEP becomes virtually SoC independent, which is possible if irreversible Li loss’s decreasing rate at the anode discontinues the increasing DEP slippage which however would have been the result from the self-discharge rate being increased. It is believed that cross-dependencies of two processes are reflected in this as this behavior is seen for 3 independent observations at the 3 tested temperatures.

Conclusion

Lithium nickel cobalt aluminum oxide is an excellent feature that works in lithium-ion batteries to speed up their working. They play a key role in enhancing the production of these batteries as their characteristics are highly efficient and even research has proved it in so many ways. Therefore, it is considered one of the most popular and authentic materials that are used by lithium-ion batteries. 

To get more information, you can visit our Blografi.

References:

https://www.smm.co.jp/en/business/material/products/nickel_lite/#:~:text=Cathode%20active%20material%20for%20lithium,mainly%20used%20in%20electric%20automobiles.

https://www.americanelements.com/lithium-nickel-cobalt-aluminum-oxide-193214-24-3

https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/batt.202100046

https://www.sciencedirect.com/science/article/pii/S0378775320304717

https://www.mdpi.com/1996-1073/9/4/281

29th Mar 2022 Hannah Rose

Recent Posts