Insight into the role of the problematic element cobalt in lithium ion batteries.

[NNadir]

I'm not going to spend a lot of time with this paper, but will simply remark on it: Insight into the Role of Co and Mn Elements in Ni-Rich LiNi0.9CoxMn0.08–xAl0.02O2 Cathode Materials Zeng Zeng, Fuqiren Guo, Yang Song, Ting Chen, Zhen-guo Wu, Yang Hu, Pan Zhang, Huan Yang, Changyan Hu, Yuting Deng, and Xiaodong Guo Industrial & Engineering Chemistry Research 2023 62 (43), 17776-17786

In the Ennui and Excuses around here for doing nothing about climate change we hear a lot of nonsense talk about the thermodynamic nightmare of energy storage, as if wasting energy is "green." I find myself needing to point out repeatedly, not that it does any good, that the laws of physics do not go away as a result of wishful thinking. Storing energy makes energy more dirty than it was without energy storage.

There are some minor caveats to this, for example, if one stores energy that would be otherwise be wasted - the technical term for this is "exergy recovery" - then an energy storage device can be of moderate environmental value. For example, a hybrid car which recovers energy of braking, or going down hill while maintaining the speed limit, recovers exergy, but there is a material cost, which in the case of the element cobalt, an essential element in the lithium batteries so popular around the world, translates into a moral cost: Much of the world supply of cobalt is mined by de facto modern day slaves, many of whom are children.

We are not going, however, to make the useless solar and wind industry "green" by wasting the already trivial amounts of energy these already land and mass intensive forms of energy produce, we will only make them even worse.

As I pointed out in response to the rhetoric of one of those "I'm not an antinuke" antinukes who run around here, saying how the antisemite DeSantis loving Elon Musk's corporate interest will save the world with Powerwalls® I pointed out last November, during an episode of Dunkeflaute in that antinuke coal burning hellhole Germany, there isn't enough cobalt on the planet to carry even Germany through a November with Powerwalls®.

The Number of Tesla Powerwalls Required That Would Address the Current German Dunkleflaute Event.

Here are the specifications of Tesla Powerwalls®: Specifications of Powerwalls®.

It is claimed they have a useable capacity of 13.5 kWh after being charged with 14 kWh of electricity, presumably at 25°C, with a putative thermodynamic efficiency - should you choose to believe it - of 96%. The maximum continuous power output is said to be 5 kW. The power requirements to match the combined coal and gas average continuous power of combined German coal and gas over the last 30 days, 44.4 GW would require 8,880,000 million Powerwalls®, to cover each day of Dunkelflaute; for 30 days, given that the wind wasn't blowing that much over that period, 266,400,000 Powerwalls®.

The specifications say that each Powerwall® weighs 114 kg, meaning that 30,369,600,000 kg of Powerwalls® would be required just for Germany.

According to Forbes, 15% of the weight of a Tesla Powerwall is cobalt, mined by Elon's happy Congolese slaves, meaning that the happy Congolese cobalt slaves would be required to mine and isolate 4,555,400 metric tons of cobalt to make Powerwalls® to cover this instance of Dunkleflaute with batteries.

This is 31.63 times as large as the world production of cobalt in 2021 according to the US Geological Survey

I'm sorry!!! I forgot to use "percent talk!" The demand for cobalt to cover month long Dunkleflaute in Germany observed in Nov-Dec 2022 would be 3163% the demand for all the world cobalt supply in 2021.

Now of course, the wishful thinking crowd, who has bet the world on the antinuke fantasy that the world "could" live on solar and wind energy, even though it hasn't; it isn't; and, as should be increasingly clear after half a century of bullshit, it won't, would like to tell us that "with research" we'll make batteries as efficient and as high capacity as modern LIBs without cobalt, except we haven't, we aren't and it seems likely we won't.

Anyway the paper is about the role of cobalt in batteries. The introduction:

The development of electric vehicles is inevitable in response to the energy security and environmental crises. (1,2) Lithium-ion batteries play a crucial role in the development of electric vehicles as the primary power source. (3?5) Lithium-ion cathode materials function as a decisive factor in the electrochemical properties of lithium-ion batteries, playing a leading role in the energy density and safety properties of the batteries, and the cost of cathode materials is relatively high. (6,7) Ni-rich layered oxide materials are considered as one of the most promising cathode materials for electric vehicle batteries due to their high energy density, low cost, and environmental friendliness. (8?10) Ni-rich ternary cathode materials are mainly LiNi_1–x–yCo_xAl_yO₂ (NCA) and LiNi_1–x–yCo_xMn_yO₂ (NCM) (1 – x – y )greater than or equal) 0.9). (11?13) It is well-known that elements are closely related to the structures and properties of materials. Therefore, the role of elements in Ni-rich ternary layered oxides has been intensively investigated by previous authors. (14?16) Liu et al. found that Co plays an essential role in fast capacity and structural degradation and found that Co is more destructive than Ni at high potentials. (17?19) Moreover, Mn substitution can effectively reduce the destructive effect of Co and make it have high-potential functional groups. In addition, Liu et al. found that the chemical and structural stability of deeply delithiated NCM cathodes is mainly determined by Co. (20) The reduction of Co4+ occurs prior to the reduction of Ni4+ and can thereby extend the migration of Ni by occupying the tetrahedral sites, thus delaying oxygen release and thermal failure. (21)

Recently, a LiNi_{1–x–y–z}Co_xMn_yAl_zO2 (NCMA) quaternary cathode material has been widely concerned because it combines the advantages of NCA and NCM cathode materials. (22?24) It remains to investigate the mechanism of the synergy between Co and Mn elements in the NCMA quaternary system. (25,26)

In this work, the Ni-rich quaternary cathode material LiNi_0.9Co_xMn_0.08–xAl_0.02O2 (x = 0.07, 0.05, 0.03) was synthesized by a hydroxide precipitate method and high-temperature solid-phase method. (27) The LiNi_0.9Co_0.07Mn_0.01Al_0.02O₂ (NCMA9712) sample exhibits an initial discharge specific capacity of 187 mAh g^–1 at 1 C and a 100-turn cycle retention rate of 70.6%. The NCMA9712 sample with the highest Co fraction has the best electrochemical performance between voltages of 2.7 and 4.3 V. The NCMA9352 has a discharge specific capacity of 191 mAh g–1 at 1 C and a cycle retention rate of 69.1% after 100 cycles. The roles of Co and Mn in NCMA are investigated in detail.

There's a lot of cool stuff discussed in the paper, lots of SEM, crystal/particle size analysis.

The conclusion. The authors like cobalt:

To investigate the role of Co and Mn in NCMA, NCMA9712, NCMA9532, and NCMA9352 with uniform particle sizes are prepared by hydroxide coprecipitation and high-temperature solid-phase methods. The results show that Co can enlarge the c-axis lattice parameter, reducing the Ni²⁺ content of the NCMA surface and suppressing the lattice expansion along the c-axis during charging, thus improving the cyclic structure and rate of the material. Therefore, NCMA9712 exhibited greatly better rate performance (144 mAh g–1 at 5 C) and cycle stability (187 mAh g[sup–1 at 1 C), with a Coulombic efficiency of almost 71% after 100 cycles. In addition, the Mn element can reduce the primary particle size and prevent the sharp collapse of the lattice along the c-axis in the deeply delithiated state, thereby enhancing the high-voltage (4.5 V) performance of the material. As a result, NCMA9352 had an impressive initial reversible capacity (191 mAh g–1 at 1 C), and a 69% cycle retention rate remained after 100 cycles. The role of Co and Mn elements in NCMAs is revealed, which provides guidance for further studies of Ni-rich quaternary layered oxides.

If you're looking to thank somebody for something over Thanksgiving, it might be in order to thank the cobalt slaves for digging stuff for our wonderful batteries.

I hope you will find the coming holidays pleasant.