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In the previous article, we have mentioned the huge space for power battery recycling. This article mainly talks about the purpose and technical route of battery recycling.

The reason for the recovery of power batteries is mainly driven by two parts: environmental protection and economy.

The battery contains a variety of harmful substances, and random disposal will have a huge impact on the ecology.

A large number of retired batteries will pose a potential threat to the environment, especially the heavy metals, electrolytes, solvents and various organic auxiliary materials in power batteries. If discarded without proper disposal, it will cause great harm to soil and water, and the repair process will take a long time and cost is high, so the need for recovery is urgent.

The substances usually contained in lithium batteries are shown in the table below. According to the 2011 edition of the list of hazardous substances in the United States, Ni, Co and phosphide are considered as high-risk substances with a score of more than 1000. If the waste lithium-ion batteries are treated by ordinary garbage disposal methods (including landfill, incineration, composting, etc.), the metals such as cobalt, nickel, lithium, manganese and inorganic and organic compounds in them will cause serious pollution to the atmosphere, water and soil, with great harm.

If the substances in waste lithium ion batteries enter the ecosystem, they can cause heavy metal nickel and cobalt pollution (including arsenic), fluorine pollution, organic pollution, dust and acid and alkali pollution. Electrolytes and their conversion products of waste lithium-ion batteries, such as LiPF6, LiAsF6, LiCF3SO3, HF, P2O5, solvents and their decomposition and hydrolysis products, such as DME, methanol, formic acid, are toxic and harmful substances, which can cause personal injury or even death.

The economic value of battery material recovery mainly lies in the value of material regeneration and the value of energy.

This includes three aspects: 1. After the lithium battery is retired from high-end electrical appliances, it can still meet the needs of some low-end electrical appliances, usually electric toys, energy storage facilities, etc. The recycled cascade utilization can give more value to the lithium battery, especially the retired power lithium battery; 2. Even if the electrical properties can not meet the deeper use, the relatively rare metals such as Li, Co, Cu contained in it still have regeneration value; 3. Due to the huge difference between energy consumption of partial metal reduction and metal regeneration energy, such as Al, Ni and Fe, metal recovery has economic value in energy consumption.

Different types of lithium batteries contain different kinds of metals and their proportions. One ton of traditional consumer lithium cobalt battery corresponds to about 170 kg of cobalt metal, while the contents of copper, aluminum and lithium are mostly similar. Therefore, in general, the recovery value of lithium cobalt battery will be greater than that of other categories, such as lithium iron phosphate battery and lithium ternary battery.

The proportion of cell in the cost of power battery is up to 36%. If gross profit is deducted, the proportion of cell is up to 49%; In the consumer battery, the cost of battery cells accounts for a higher proportion. In the core, the cost of cathode materials rich in nickel, cobalt, manganese and other metal elements accounts for 45%.

At present, the recycling process includes two stages: pretreatment and subsequent treatment.

Pretreatment is to discharge the waste lithium battery in salt water, remove the outer packaging of the battery, and remove the metal steel shell to obtain the inner battery core.

The cell is composed of negative electrode, positive electrode, diaphragm and electrolyte. The negative pole is attached to the surface of copper foil, the positive pole is attached to the surface of aluminum foil, and the membrane is organic polymer; The electrolyte is attached to the surface of the positive and negative electrodes and is an organic carbonate solution of LiPF6.

The follow-up treatment is to recycle the high-value components in the disassembled wastes and carry out the reconstruction or repair of battery materials. The technical methods can be divided into three categories: dry recovery technology, wet recovery technology and biological recovery technology.

Dry recovery technology refers to the technical method of directly realizing the recovery of various battery materials or valuable metals without solution and other media, mainly including mechanical separation method and high-temperature thermal decomposition method.

The dry thermal repair technology can perform high-temperature thermal repair on the crude products recovered by the dry method, but the positive and negative materials produced contain certain impurities, and the performance can not meet the requirements of the power battery of new energy vehicles. It is mostly used for energy storage or small power batteries, and is suitable for lithium iron phosphate batteries.

Fire-metallurgy, also known as incineration or dry-metallurgy, is to remove the organic binder in the electrode material through high-temperature incineration, and at the same time make the metal and its compounds in it undergo oxidation-reduction reaction, recover the low-boiling metal and its compounds in the form of condensation, and recover the metal in the slag by screening, pyrolysis, magnetic separation or chemical methods. Pyro-metallurgy has low requirements for the composition of raw materials, which is suitable for large-scale treatment of more complex batteries. However, combustion will inevitably produce some waste gas to pollute the environment, and high temperature treatment also requires high equipment. At the same time, purification and recovery equipment need to be added, and the treatment cost is high.

Wet recovery technology is to transfer metal ions from electrode materials to leaching solution using various acid-base solutions as transfer media, and then extract metal ions from solution in the form of salt and oxide by means of ion exchange, precipitation and adsorption, mainly including wet metallurgy, chemical extraction and ion exchange.

The process of wet recovery technology is relatively complex, but the recovery rate of lithium, cobalt, nickel and other valuable metals is high; The obtained metal salts, oxides and other products with high purity can meet the quality requirements of power battery materials, and are suitable for ternary batteries. They are also the main recovery methods adopted by domestic and foreign technology leading recovery enterprises.

The biological recovery technology mainly uses microbial leaching to convert the useful components of the system into soluble compounds and selectively dissolve them, so as to achieve the separation of target components and impurity components, and finally recover valuable metals such as lithium, cobalt, nickel, etc. At present, the biological recovery technology is not yet mature, such as the cultivation of efficient strains, the long cultivation period, the control of leaching conditions and other key issues still need to be solved.

At present, the wet recovery process, which is more efficient and relatively mature, is becoming the mainstream technology route in the specialized treatment stage; Most of the leading domestic enterprises such as Greenway and Bangpu Group, as well as the international leading enterprises such as AEA and IME, have adopted the wet technology route as the main technology for the recovery of valuable metal resources such as lithium, cobalt and nickel.

The specific capacity of the cathode material regenerated from the recovery of valuable metals by wet process is better than the cathode material recovered by dry process.

For the ternary battery, compared with lithium iron phosphate, its battery life is shorter. The 80% cycle life of the ternary battery is only 800-2000 times, and there is a certain risk of safety. It is not suitable for use in energy storage power stations, communication base station backup power supply and other application fields with complex application environment.

However, the ternary power battery contains rare metals such as nickel, cobalt and manganese. By disassembling and extracting lithium, cobalt, nickel, manganese, copper, aluminum, graphite, diaphragm and other materials, it can theoretically achieve an economic income of about 42900 yuan per ton, which is economically feasible.

Taking the ternary 523 battery as an example, the content of nickel, cobalt, manganese and lithium in each ton of ternary battery is about 96, 48, 32 and 19 kg. At present, the average recovery rate of nickel, cobalt and manganese in the market can reach more than 95%, and the recovery rate of lithium is about 70%. The market prices of metal lithium, cobalt, electrolytic nickel and electrolytic manganese are 900000 yuan/ton, 480000 yuan/ton, 100000 yuan/ton and 17000 yuan/ton respectively.

The nickel sulfate, cobalt sulfate, manganese sulfate and other metal salts recovered from the power battery can continue to be processed to produce ternary precursors, with obvious value-added space.

Taking the production of nickel sulfate as an example, the cost of recovering and treating nickel per ton through waste power batteries is less than 40000 yuan, while the cost of directly producing nickel ore is more than 60000 yuan. The cost of obtaining metal raw materials through resource recovery is lower than that of directly developing minerals. The resource recovery of ternary batteries has the significance of reducing costs.

Considering that the recycling enterprises of ternary batteries will resell the precious metals to downstream enterprises in the form of sulfates after disassembling them, the sales price should be lower than the market price of pure metal, so assuming that the sales price is 70% of the market price, the revenue from the disassembly of ternary batteries is 34000 yuan/ton, so the market scale of the disassembly of only ternary batteries is expected to reach 5.41 billion yuan by 2023.

In terms of cost, the recovery cost of ternary battery mainly consists of production cost, various expenses and taxes.

Among them, the composition of production (rough cost estimation) mainly includes:

Material cost (waste battery, liquid nitrogen, water, acid-base reagent, extractant, precipitator, etc.) 20000 yuan/ton;

Fuel and power costs (electricity, natural gas, gasoline consumption, etc.) 650 yuan/ton;

The cost of environmental treatment (waste gas, waste water purification and waste residue and ash treatment) is 550 yuan/ton;

Equipment cost (equipment maintenance and depreciation): 500 yuan/ton;

The labor cost (wages of operators, technicians, transportation personnel, etc.) is 400 yuan/ton.

The shared administrative expenses such as salaries of management personnel and sales expenses such as sales personnel and packaging are about 400 yuan/ton; VAT and income tax are 4000 yuan/ton. The total cost of dismantling the three-element battery is 26500 yuan/ton. Based on the above income of 34000 yuan/ton, the dismantling profit is 7500 yuan/ton. It can also be seen from the above table that the corresponding net profit margin is expected to exceed 1 billion yuan in 2023.

Through raw material recovery, nickel, cobalt, manganese and other metal elements can achieve a recovery rate of more than 95%, with significant economic benefits. Through recycling, nickel, cobalt, manganese and lithium salts can be produced, and even ternary cathode materials and precursors can be further produced, which can be directly used in the manufacturing of lithium battery cells. It is of great significance to build a closed-loop industrial chain.

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