With the rapid development of the lithium battery industry and the continuous expansion of market demand for lithium batteries, recycle lithium batteries are imperative. This article will briefly analyze the rigid demand of the recycle lithium batteries industry and introduce its recycling cost and industry optimization.
Table of Contents
Composition of lithium battery
Lithium ion batteries (LIBs) were successfully developed and commercialized by Sony Corporation of Japan in 1990, and have been widely used in various fields, mainly including portable electronic products, electric vehicles and large-scale energy storage.
Compared with nickel-cadmium and nickel-metal hydride batteries, lithium ion batteries have the advantages of high energy, good cycle performance, low self-discharge and no memory effect. The main composition of a lithium ion battery includes a battery case and a battery cell, where the battery cell includes a cathode, an anode, a separator, a current collector, and electrolyte.
Cathode 88-89wt.% cathode active material, 7-8wt.% acetylene black conductive agent and 3-4wt.% organic adhesive, uniformly mixed and coated on 10-20 micron aluminum foil fluid collector, that is, to form the cathode of lithium ion battery.
Common cathode active materials include lithium iron phosphate (LiFePO4, LFP), lithium cobalt oxide (LiCoO2, LCO), nickel-cobalt-manganese ternary material (LiNixMnyCo1-x-yO2, NCM), nickel-cobalt-aluminum ternary material (LiNixCoyAl1-x-yO2, NCA), etc.
Anode 88-90wt.% anode active material (graphite or carbon with similar graphite structure), 4-5wt.% acetylene black conductive agent and 6-7wt.% organic binder, uniformly mixed and coated on 7-15 micron copper foil collector fluid, that is, to form the anode of lithium ion battery.
Organic electrolyte It is mainly composed of electrolyte salts, organic solvents and additives. Electrolyte lithium salts include LiPF6, LiBF4, etc. Organic solvents include esters, ethers, sulfones, nitriles and nitro compounds. Additives can be divided into SEI film forming additives, cathode protection additives, lithium salt stabilizers, overcharge and overdischarge protective agents and flame retardant additives.
Separator A lithium battery separator has a specially shaped polymer film microporous structure, which allows lithium ions to pass freely, while electrons cannot. There are mainly polyolefin membranes (polyethylene, polypropylene and other polymers), non-woven membranes (natural fibers, microfibrillated cellulose and cellulose nanofibers) and ceramic composite membranes.
The rigid demand of recycle lithium batteries
China is the world’s largest producer and consumer of lithium ion batteries. There is a complete industrial chain and a number of leading battery companies with international competitiveness . In recent years, policies have continued to support the development of the new energy industry in China, and new energy and energy storage have shown a rapid growth trend, driving the simultaneous rapid expansion of the recycle lithium batteries industry.
According to GGII, China’s lithium ion battery shipments in 2022 was 655GWh, +100.3% year-on-year, among which power batteries are the largest sub-category of lithium ion batteries in China, accounting for 73% in 2022.
As a key component of electric vehicles, the installed capacity of power batteries has grown simultaneously with the sales of electric vehicles. Referring to the China Association of Automobile Manufacturers, the sales volume of electric vehicles in China in 2022 was 6.887 million, +95.6% year-on-year; referring to Frost & Sullivan, the installed capacity of power batteries is 294.6GWh, +90.7% year-on-year.
If calculate according to CAGR29% in 2022-2025 and CAGR22% in 2025-2030, it is estimated that China’s power battery installed capacity will reach 632GWh in 2025 and 1707GWh in 2030.
Currently, the battery life of the power battery is about 8-10 years, but for the electric vehicle power battery, when the battery capacity decays to 80% of the rated capacity, it no longer meets the requirements for use, so the actual effective life is about 5-7 years. After decommissioning, the power battery can be directly recycled or can be used in scenarios with low performance requirements.
Cascade utilization is suitable for power batteries whose capacity has decayed to below 70-80% of the rated capacity. Although such batteries do not meet the standards for the use of electric vehicles, the remaining battery capacity can still meet the energy needs of other equipment.
This type of battery can be disassembled, screened, reassembled, and then system-integrated into a small battery pack, which is used in some fields that do not require high energy density, such as low-speed electric vehicles (electric bicycles, express vehicles, etc.), solar street lights, communication base station, etc. For power batteries whose battery capacity has decayed by more than 40%, they will enter the dismantling and recycling process.
Since the average cycle life of lithium iron phosphate batteries is relatively longer (4000 times), the battery capacity decay mode is slow and uniform, so it is more suitable for cascade utilization. While the average cycle life of ternary batteries is relatively short (2000 times), and less stable. And it contains rare metals such as nickel, cobalt and manganese, so the recycling method is mainly dismantling and recycling.
For the gradually growing scrap recycle lithium batteries market, the necessity of recycling is mainly reflected in two aspects: environmental protection and economy.
From the perspective of environmental protection, recycle lithium batteries contain a variety of heavy metals, organic and inorganic compounds and other toxic and harmful substances, once leaked into the soil, water and atmosphere, it will cause serious pollution; Cobalt, nickel, copper, aluminum, manganese and other metals also have a cumulative effect, enriched in the human body through the food chain with great harm.
Therefore, it is necessary to carry out centralized harmless treatment of recycle lithium batteries and recycle the metal materials in them to ensure the sustainable development of human health and the environment. In addition, recycling the raw materials of used power batteries can effectively reduce the carbon emissions of ore raw materials by more than 40%.
From an economic point of view, the cathode materials of recycle lithium batteries usually contain valuable metal elements such as Li, Co, Ni and Mn, and their metal content is even higher than that of some natural ores. Extracting valuable metals from ores requires high cost and energy consumption, and recycling these metals from recycle lithium batteries can not only obtain high-purity products, but also effectively reduce costs and generate considerable economic benefits.
Recyclable metal in used batteries
At present, the main raw materials in the industry come from waste battery packs and scraps in the production process of battery packs or cathode. From the perspective of recycling objects, the recycling of waste batteries/scraps is mainly metal materials. It is mainly distributed in the shell, fluid collector and cathode material.
The metals in the shell and the fluid collector basically exist in the form of simple substances, including copper, aluminum, iron, etc. The recovery of metal elements is relatively simple, and can be completed by dismantling and stripping in the early stage. The metals in the cathode include cobalt, nickel, lithium, manganese, aluminum, iron, etc. The scarce metals have a high value, however, because these metals exist in the form of compounds, recycling is more difficult, so it is also the core of the current recycling process.
For the recovery of cathode material production scrap: 88-89wt.% of the total mass is cathode active material, 7-8wt.% is acetylene black conductive agent, and 3-4wt.% is organic adhesive.
For the recycling of waste battery pack/battery pack production scraps: for lithium iron phosphate battery pack, the monomer accounts for 60% and the shell accounts for 24%. Among them, the cathode active material lithium iron phosphate accounts for 32.1%, so for the lithium iron phosphate battery pack as a whole, lithium iron phosphate accounts for about 20%.
For ternary polymer recycle lithium batteries packs, the monomer accounts for 68.2%, and the shell accounts for 21%. Among them, the cathode material accounts for 39% of the mass of the ternary recycle lithium batteries. 88-89 wt.% of the reference cathode material is the cathode active material, so for the ternary recycle lithium batteries packs as a whole, the ternary material accounts for about 24%.
Battery recycling process
There are four mainstream processes for recycle lithium batteries are hydrometallurgy, pyrometallurgy, combined process, and repair and regeneration process. Traditional recycling processes are mainly hydrometallurgy and pyrometallurgy recycling.
The recycling process that most widely used around the world is mainly based on pyrometallurgy. The pretreated active materials are placed in an incinerator at high temperature to remove organic matter, smelted to obtain metal alloys, and then metal compounds are obtained through leaching/extraction processes.
In terms of specific operations, the recycling and treatment of waste batteries are mainly divided into three processes: pretreatment, secondary treatment and advanced treatment. Pretreatment mainly includes deep discharge, crushing and physical sorting.
The secondary treatment is to separate the cathode and anode active materials from the substrate, and mainly includes heat treatment, organic solvent dissolution, and lye dissolution. Advanced treatment includes leaching and separation and purification, and the extraction of valuable metal materials is the key to the recycle lithium batteries recycling process.
Recycle lithium batteries undergo pretreatment steps such as discharging, dismantling, crushing, and sorting to separate the cathode, anode, and separator from the current collector, and then undergo operations such as crushing, sieving, and magnetic separation to obtain high-value invalid cathode powder.
The cathode material is treated by pyrometallurgy or hydrometallurgy to regain the precursor of the cathode material, mixed with a certain amount of lithium salt, and sintered to generate a new cathode material. The two recycling processes completely destroy the original composition and structure of the materials in the battery, and extract the elements in them as precursors for the synthesis of new raw materials.
Emerging direct recycling technologies generally start with the composition and structure of the failed materials, without destroying the inherent structure of the battery materials and achieving structural regeneration, restoring the electrochemical activity of the materials. The mainstream technologies for direct recovery of cathode materials include solid-phase method, molten salt method, hydrothermal lithiation, low eutectic solvent method and atmospheric pressure lithiation, etc.
Solid-phase method: Simple and widely used, but it has high energy consumption.
Molten salt method: The reaction temperature is low, but the amount of lithium salt and heat treatment time are strictly required.
Hydrothermal lithiation: Has lower temperature, shorter time and more uniform reaction, but there are certain safety risks in high pressure environment.
Low eutectic solvent method: Can realize the regeneration of failed cathode at normal pressure, and DESs is green and recyclable, which can greatly reduce the recycling cost, and is expected to be used for large-scale recovery. However, there are few relevant studies at present, and DESs systems suitable for different cathode materials need to be developed.
At present, the direct regeneration process of recycle lithium batteries is still in the experimental stage of research and development, and has not yet been used on a large scale.
The battery recycling in China is mainly based on traditional process dismantling + hydrometallurgy. Recycling companies first manually/mechanically disassemble and break decommissioned batteries into different materials, and companies with disassembly as the main business will sell different materials such as shell plastic, aluminum powder, copper powder, and cathode powder to downstream related companies, and smelt the materials downstream.
Companies with a high degree of integration directly smelt the waste powder accordingly, which can be made into sulfates such as cobalt sulfate and nickel sulfate, and can also be made into precursors such as nickel hydroxide and cobalt hydroxide.
Cost and product value of recycle lithium batteries
From a cost point of view, the cost structure of battery recycling is mainly divided into two parts: the cost of the waste battery itself and the processing fee. The cost of the waste battery itself usually exceeds 50% of the total, and other processing costs include the cost of auxiliary materials, fuel and power costs, environmental governance costs, equipment costs, labor costs, and other expenses (site fees, public fees, taxes).
For recycle lithium batteries, assuming that the battery pack recovery price is 18,000 RMB/ton, the pyrometallurgy and hydrometallurgy recycling cost per ton (other than the purchase of battery packs) is 5900 RMB/ton and 11300 RMB/ton, respectively, the total recycling cost is 23900 RMB/ton and 29300 RMB/ton.
For ternary recycle lithium batteries, assume that the battery pack recovery price is 38,000 RMB/ton, pyrometallurgy and hydrometallurgy recycling cost per ton (outside the purchase of battery packs) are 6,000 RMB/ton and 14,400 RMB/ton, respectively, and the total recycling cost is 44,000 RMB/ton and 52,400 RMB/ton, respectively.
Although the dry process is relatively simple and the recycling cost is low, there are more impurities in the product, more pollution in the treatment process, and the recovery rate of the target recycle lithium batteries is lower than that of the hydrometallurgy process, so there are some process defects.
Therefore, the current battery recycling production line in China is mainly hydrometallurgy. For lithium iron phosphate batteries, the current main recycled products are scrap copper, lithium carbonate and iron phosphate.
Taking the lithium iron phosphate power battery pack as an example, the weight of the monomer is about 60%, the weight of the cathode material in the monomer is about 32.1% (the active material accounts for 88-89% of the cathode material), and the weight of the copper foil is about 10.8%.
Based on the assumption that the recovery rate of copper foil is 98%, lithium carbonate is 90%, and iron phosphate is 95%, a single ton of lithium iron phosphate battery pack can extract waste copper of 63.5kg, lithium carbonate of 35.9kg, and iron phosphate of 154.8kg, corresponding to the value of the main recovered product of 17,000 RMB/ton of lithium iron phosphate battery pack.
Through the cost and income accounting, the current recycle lithium batteries industry is still in a state of small profit or even loss; Mainly because of the high premium of waste battery packs at the raw material end since 2022. Previously, due to the low price of lithium, the recycling of ternary batteries is mainly nickel and cobalt, so the pricing discount factor only reflects the value of nickel and cobalt.
In 22 years, the price of lithium has risen sharply, and in order to reflect the value of lithium, the discount coefficient of nickel and cobalt can only be adjusted higher. Superposition industry participants fiercely compete for used battery pack resources, the discount factor of battery pack soared from the normal 70-80%, up to more than 200%, and there is a large deviation from the actual value level.
Battery recycling industry optimization
For participants in the battery recycling industry chain, the development trend after the normalization of the market should be more focused on the stable acquisition of raw materials, the cost simplification of the recycling process, and the improvement of product yield.
Standardization of recycle lithium batteries source channels
From the perspective of raw material acquisition, the lack of norms and standards in the early stage of the industry caused the disorder of the front-end waste battery recycling system, and a large number of informal manufacturers competed for acquisition at high prices, squeezing the space of formal companies.
Although formal companies have perfect systems and operational capabilities in terms of recycling qualifications, channels, technology and scale, for waste battery resource channels, choosing formal channels for recycling means paying higher costs. For example, regular companies need invoices for recycle lithium batteries to offset VAT in later sales, resulting in additional costs for small-scale recyclers. Therefore, raw material suppliers tend to prefer small workshops and second-hand car markets.
Different from professional third-party recycling companies, although the OEM has the right to dispose of the dismantled lithium batteries, it is more familiar with the echelon utilization of the post-process of battery manufacturing. The scrap recycling process is mainly involved in dismantling and metallurgy, the lack of technical advantages of the vehicle factory, high equipment investment, labor costs and technical costs, recycle lithium batteries have become a burden.
Therefore, the OEMs usually choose to cooperate with third-party recycling companies, material companies, metallurgical companies, etc. The OEM provides waste batteries and technical guidance as the main body and resource side, and the follow-up process and production are completed by the partner.
Process optimization
From the perspective of process flow, the process mode, smelting technology and capacity scale of Chinese companies are basically the same, and the difference in recovery rate and profit level among companies is mainly reflected in the degree of automation of dismantling at the front end of pretreatment, as well as the yield of crushing and screening at the front end and hydrometallurgy at the back end, and the optimization process from two aspects of cost reduction and efficiency.
Intelligent disassembly There are many problems in front-end manual dismantling, and intelligence is the future focus of the industry. In the front-end pretreatment process, the crushing and screening of the existing production line has been basically automated, which can realize one end of the feed (disassembled module) and one end of the product.
However, due to the wide variety of power battery packs, diverse brand models, complex structure and uncertain retirement status, the shell of the battery pack and the outer packaging of the single battery are still mainly manually disassembled.
In the mass battery disassembly, manual disassembly has many problems: the battery pack voltage is high, yet the internal wiring harness arrangement is complicated, resulting in electric shock and short circuit risks. There is a large amount of glue inside the battery pack, which needs to be disassembled by brute force. Meanwhile, attention should be paid to improving the dismantling efficiency and reducing labor costs. Therefore, intelligent dismantling is a big topic that the industry needs to focus on.
For the intelligent and flexible disassembly of power recycle lithium batteries with machines instead of manual ones, the main steps include: the establishment of 3D camera data acquisition system, multi-robot collaborative disassembly of top cover screws, top cover handling, battery module handling, intelligent sorting of disassembled products, module & core milling and other steps.
The main breakthrough points involved in intelligent dismantling come from the diversification of the appearance of different models of batteries, the intelligent recognition and grasp of components, and the deformation generated after many years of operation, requiring the dismantling system to dynamically adjust according to the specific situation.
Hydrometallurgy The recovery rate of lithium metal in recycle lithium batteries is only 85-90%, and there is still room for improvement. The limitation of recycle lithium batteries mainly comes from the adsorption of 10% of lithium ions in the waste residue during the extraction and impurity removal process of nickel-cobalt-manganese solution.
In the solution after acid leaching of ternary battery black powder, lithium is the smallest and most active metal; Although 80% of lithium carbonate can be extracted in the front calcination reduction process, in the second phase of nickel, cobalt and manganese extraction process, the formed slag will adsorb 10% of lithium ions, resulting in a reduction in the crystallization recovery of the third phase of lithium carbonate, so the recovery rate of lithium in the current process is difficult to exceed 90%.
In addition to the optimization of the front-end lithium extraction process to improve the yield, the end recycle lithium batteries also has room for cost reduction. At present, for the recovery of lithium in nickel-cobalt raffinate at the end, MVR evaporation process is mainly used to concentrate, and the concentration of lithium is increased by evaporating the water in the solution, and then the precipitation of lithium at the back end is completed.
The advantage of MVR evaporation process is that the technology is mature and widely used, but it needs to consume a lot of electricity in the operation process (the production of 1 ton of lithium carbonate MVR equipment needs to consume 9000 KWH of electricity), and the cost is high.
On this basis, some companies in the industry also try to achieve lithium concentration with more economical solutions such as adsorption + membrane and extraction, and reduce the use of MVR equipment. The concentration of adsorption + membrane is increased mainly through the process of adsorption and desorption, and extraction is achieved through extraction and reverse extraction.
Compared with MVR process, the electricity consumption of these two processes is greatly reduced, and the consumption of adsorbents, membranes, extractants and other reagents is only increased. The upfront investment is also smaller than the MVR process, which helps companies reduce costs.
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Recycle lithium batteries industry report
Composition of lithium battery
Lithium ion batteries (LIBs) were successfully developed and commercialized by Sony Corporation of Japan in 1990, and have been widely used in various fields, mainly including portable electronic products, electric vehicles and large-scale energy storage. Compared with nickel-cadmium and nickel-metal hydride batteries, lithium ion batteries have the advantages of high energy, good cycle performance, low self-discharge and no memory effect. The main composition of a lithium ion battery includes a battery case and a battery cell, where the battery cell includes a cathode, an anode, a separator, a current collector, and electrolyte.Cathode
88-89wt.% cathode active material, 7-8wt.% acetylene black conductive agent and 3-4wt.% organic adhesive, uniformly mixed and coated on 10-20 micron aluminum foil fluid collector, that is, to form the cathode of lithium ion battery.
Common cathode active materials include lithium iron phosphate (LiFePO4, LFP), lithium cobalt oxide (LiCoO2, LCO), nickel-cobalt-manganese ternary material (LiNixMnyCo1-x-yO2, NCM), nickel-cobalt-aluminum ternary material (LiNixCoyAl1-x-yO2, NCA), etc.
Anode
88-90wt.% anode active material (graphite or carbon with similar graphite structure), 4-5wt.% acetylene black conductive agent and 6-7wt.% organic binder, uniformly mixed and coated on 7-15 micron copper foil collector fluid, that is, to form the anode of lithium ion battery.
Organic electrolyte
It is mainly composed of electrolyte salts, organic solvents and additives. Electrolyte lithium salts include LiPF6, LiBF4, etc. Organic solvents include esters, ethers, sulfones, nitriles and nitro compounds. Additives can be divided into SEI film forming additives, cathode protection additives, lithium salt stabilizers, overcharge and overdischarge protective agents and flame retardant additives.
Separator
A lithium battery separator has a specially shaped polymer film microporous structure, which allows lithium ions to pass freely, while electrons cannot. There are mainly polyolefin membranes (polyethylene, polypropylene and other polymers), non-woven membranes (natural fibers, microfibrillated cellulose and cellulose nanofibers) and ceramic composite membranes.
The rigid demand of recycle lithium batteries
China is the world’s largest producer and consumer of lithium ion batteries. There is a complete industrial chain and a number of leading battery companies with international competitiveness . In recent years, policies have continued to support the development of the new energy industry in China, and new energy and energy storage have shown a rapid growth trend, driving the simultaneous rapid expansion of the recycle lithium batteries industry.
According to GGII, China’s lithium ion battery shipments in 2022 was 655GWh, +100.3% year-on-year, among which power batteries are the largest sub-category of lithium ion batteries in China, accounting for 73% in 2022.
As a key component of electric vehicles, the installed capacity of power batteries has grown simultaneously with the sales of electric vehicles. Referring to the China Association of Automobile Manufacturers, the sales volume of electric vehicles in China in 2022 was 6.887 million, +95.6% year-on-year; referring to Frost & Sullivan, the installed capacity of power batteries is 294.6GWh, +90.7% year-on-year.
If calculate according to CAGR29% in 2022-2025 and CAGR22% in 2025-2030, it is estimated that China’s power battery installed capacity will reach 632GWh in 2025 and 1707GWh in 2030.
Currently, the battery life of the power battery is about 8-10 years, but for the electric vehicle power battery, when the battery capacity decays to 80% of the rated capacity, it no longer meets the requirements for use, so the actual effective life is about 5-7 years. After decommissioning, the power battery can be directly recycled or can be used in scenarios with low performance requirements.
Cascade utilization is suitable for power batteries whose capacity has decayed to below 70-80% of the rated capacity. Although such batteries do not meet the standards for the use of electric vehicles, the remaining battery capacity can still meet the energy needs of other equipment.
This type of battery can be disassembled, screened, reassembled, and then system-integrated into a small battery pack, which is used in some fields that do not require high energy density, such as low-speed electric vehicles (electric bicycles, express vehicles, etc.), solar street lights, communication base station, etc. For power batteries whose battery capacity has decayed by more than 40%, they will enter the dismantling and recycling process.
Since the average cycle life of lithium iron phosphate batteries is relatively longer (4000 times), the battery capacity decay mode is slow and uniform, so it is more suitable for cascade utilization. While the average cycle life of ternary batteries is relatively short (2000 times), and less stable. And it contains rare metals such as nickel, cobalt and manganese, so the recycling method is mainly dismantling and recycling.
For the gradually growing scrap recycle lithium batteries market, the necessity of recycling is mainly reflected in two aspects: environmental protection and economy.
From the perspective of environmental protection, recycle lithium batteries contain a variety of heavy metals, organic and inorganic compounds and other toxic and harmful substances, once leaked into the soil, water and atmosphere, it will cause serious pollution; Cobalt, nickel, copper, aluminum, manganese and other metals also have a cumulative effect, enriched in the human body through the food chain with great harm.
Therefore, it is necessary to carry out centralized harmless treatment of recycle lithium batteries and recycle the metal materials in them to ensure the sustainable development of human health and the environment. In addition, recycling the raw materials of used power batteries can effectively reduce the carbon emissions of ore raw materials by more than 40%.
From an economic point of view, the cathode materials of recycle lithium batteries usually contain valuable metal elements such as Li, Co, Ni and Mn, and their metal content is even higher than that of some natural ores. Extracting valuable metals from ores requires high cost and energy consumption, and recycling these metals from recycle lithium batteries can not only obtain high-purity products, but also effectively reduce costs and generate considerable economic benefits.
Recyclable metal in used batteries
At present, the main raw materials in the industry come from waste battery packs and scraps in the production process of battery packs or cathode. From the perspective of recycling objects, the recycling of waste batteries/scraps is mainly metal materials. It is mainly distributed in the shell, fluid collector and cathode material.
The metals in the shell and the fluid collector basically exist in the form of simple substances, including copper, aluminum, iron, etc. The recovery of metal elements is relatively simple, and can be completed by dismantling and stripping in the early stage. The metals in the cathode include cobalt, nickel, lithium, manganese, aluminum, iron, etc. The scarce metals have a high value, however, because these metals exist in the form of compounds, recycling is more difficult, so it is also the core of the current recycling process.
For the recovery of cathode material production scrap: 88-89wt.% of the total mass is cathode active material, 7-8wt.% is acetylene black conductive agent, and 3-4wt.% is organic adhesive.
For the recycling of waste battery pack/battery pack production scraps: for lithium iron phosphate battery pack, the monomer accounts for 60% and the shell accounts for 24%. Among them, the cathode active material lithium iron phosphate accounts for 32.1%, so for the lithium iron phosphate battery pack as a whole, lithium iron phosphate accounts for about 20%.
For ternary polymer recycle lithium batteries packs, the monomer accounts for 68.2%, and the shell accounts for 21%. Among them, the cathode material accounts for 39% of the mass of the ternary recycle lithium batteries. 88-89 wt.% of the reference cathode material is the cathode active material, so for the ternary recycle lithium batteries packs as a whole, the ternary material accounts for about 24%.
Battery recycling process
There are four mainstream processes for recycle lithium batteries are hydrometallurgy, pyrometallurgy, combined process, and repair and regeneration process. Traditional recycling processes are mainly hydrometallurgy and pyrometallurgy recycling.
The recycling process that most widely used around the world is mainly based on pyrometallurgy. The pretreated active materials are placed in an incinerator at high temperature to remove organic matter, smelted to obtain metal alloys, and then metal compounds are obtained through leaching/extraction processes.
In terms of specific operations, the recycling and treatment of waste batteries are mainly divided into three processes: pretreatment, secondary treatment and advanced treatment. Pretreatment mainly includes deep discharge, crushing and physical sorting.
The secondary treatment is to separate the cathode and anode active materials from the substrate, and mainly includes heat treatment, organic solvent dissolution, and lye dissolution. Advanced treatment includes leaching and separation and purification, and the extraction of valuable metal materials is the key to the recycle lithium batteries recycling process.
Recycle lithium batteries undergo pretreatment steps such as discharging, dismantling, crushing, and sorting to separate the cathode, anode, and separator from the current collector, and then undergo operations such as crushing, sieving, and magnetic separation to obtain high-value invalid cathode powder.
The cathode material is treated by pyrometallurgy or hydrometallurgy to regain the precursor of the cathode material, mixed with a certain amount of lithium salt, and sintered to generate a new cathode material. The two recycling processes completely destroy the original composition and structure of the materials in the battery, and extract the elements in them as precursors for the synthesis of new raw materials.
Emerging direct recycling technologies generally start with the composition and structure of the failed materials, without destroying the inherent structure of the battery materials and achieving structural regeneration, restoring the electrochemical activity of the materials. The mainstream technologies for direct recovery of cathode materials include solid-phase method, molten salt method, hydrothermal lithiation, low eutectic solvent method and atmospheric pressure lithiation, etc.
Solid-phase method: Simple and widely used, but it has high energy consumption.
Molten salt method: The reaction temperature is low, but the amount of lithium salt and heat treatment time are strictly required.
Hydrothermal lithiation: Has lower temperature, shorter time and more uniform reaction, but there are certain safety risks in high pressure environment.
Low eutectic solvent method: Can realize the regeneration of failed cathode at normal pressure, and DESs is green and recyclable, which can greatly reduce the recycling cost, and is expected to be used for large-scale recovery. However, there are few relevant studies at present, and DESs systems suitable for different cathode materials need to be developed.
At present, the direct regeneration process of recycle lithium batteries is still in the experimental stage of research and development, and has not yet been used on a large scale.
The battery recycling in China is mainly based on traditional process dismantling + hydrometallurgy. Recycling companies first manually/mechanically disassemble and break decommissioned batteries into different materials, and companies with disassembly as the main business will sell different materials such as shell plastic, aluminum powder, copper powder, and cathode powder to downstream related companies, and smelt the materials downstream.
Companies with a high degree of integration directly smelt the waste powder accordingly, which can be made into sulfates such as cobalt sulfate and nickel sulfate, and can also be made into precursors such as nickel hydroxide and cobalt hydroxide.
Cost and product value of recycle lithium batteries
From a cost point of view, the cost structure of battery recycling is mainly divided into two parts: the cost of the waste battery itself and the processing fee. The cost of the waste battery itself usually exceeds 50% of the total, and other processing costs include the cost of auxiliary materials, fuel and power costs, environmental governance costs, equipment costs, labor costs, and other expenses (site fees, public fees, taxes).
For recycle lithium batteries, assuming that the battery pack recovery price is 18,000 RMB/ton, the pyrometallurgy and hydrometallurgy recycling cost per ton (other than the purchase of battery packs) is 5900 RMB/ton and 11300 RMB/ton, respectively, the total recycling cost is 23900 RMB/ton and 29300 RMB/ton.
For ternary recycle lithium batteries, assume that the battery pack recovery price is 38,000 RMB/ton, pyrometallurgy and hydrometallurgy recycling cost per ton (outside the purchase of battery packs) are 6,000 RMB/ton and 14,400 RMB/ton, respectively, and the total recycling cost is 44,000 RMB/ton and 52,400 RMB/ton, respectively.
Although the dry process is relatively simple and the recycling cost is low, there are more impurities in the product, more pollution in the treatment process, and the recovery rate of the target recycle lithium batteries is lower than that of the hydrometallurgy process, so there are some process defects.
Therefore, the current battery recycling production line in China is mainly hydrometallurgy. For lithium iron phosphate batteries, the current main recycled products are scrap copper, lithium carbonate and iron phosphate.
Taking the lithium iron phosphate power battery pack as an example, the weight of the monomer is about 60%, the weight of the cathode material in the monomer is about 32.1% (the active material accounts for 88-89% of the cathode material), and the weight of the copper foil is about 10.8%.
Based on the assumption that the recovery rate of copper foil is 98%, lithium carbonate is 90%, and iron phosphate is 95%, a single ton of lithium iron phosphate battery pack can extract waste copper of 63.5kg, lithium carbonate of 35.9kg, and iron phosphate of 154.8kg, corresponding to the value of the main recovered product of 17,000 RMB/ton of lithium iron phosphate battery pack.
Through the cost and income accounting, the current recycle lithium batteries industry is still in a state of small profit or even loss; Mainly because of the high premium of waste battery packs at the raw material end since 2022. Previously, due to the low price of lithium, the recycling of ternary batteries is mainly nickel and cobalt, so the pricing discount factor only reflects the value of nickel and cobalt.
In 22 years, the price of lithium has risen sharply, and in order to reflect the value of lithium, the discount coefficient of nickel and cobalt can only be adjusted higher. Superposition industry participants fiercely compete for used battery pack resources, the discount factor of battery pack soared from the normal 70-80%, up to more than 200%, and there is a large deviation from the actual value level.
Battery recycling industry optimization
For participants in the battery recycling industry chain, the development trend after the normalization of the market should be more focused on the stable acquisition of raw materials, the cost simplification of the recycling process, and the improvement of product yield.
Standardization of recycle lithium batteries source channels
From the perspective of raw material acquisition, the lack of norms and standards in the early stage of the industry caused the disorder of the front-end waste battery recycling system, and a large number of informal manufacturers competed for acquisition at high prices, squeezing the space of formal companies.
Although formal companies have perfect systems and operational capabilities in terms of recycling qualifications, channels, technology and scale, for waste battery resource channels, choosing formal channels for recycling means paying higher costs. For example, regular companies need invoices for recycle lithium batteries to offset VAT in later sales, resulting in additional costs for small-scale recyclers. Therefore, raw material suppliers tend to prefer small workshops and second-hand car markets.
Different from professional third-party recycling companies, although the OEM has the right to dispose of the dismantled lithium batteries, it is more familiar with the echelon utilization of the post-process of battery manufacturing. The scrap recycling process is mainly involved in dismantling and metallurgy, the lack of technical advantages of the vehicle factory, high equipment investment, labor costs and technical costs, recycle lithium batteries have become a burden.
Therefore, the OEMs usually choose to cooperate with third-party recycling companies, material companies, metallurgical companies, etc. The OEM provides waste batteries and technical guidance as the main body and resource side, and the follow-up process and production are completed by the partner.
Process optimization
From the perspective of process flow, the process mode, smelting technology and capacity scale of Chinese companies are basically the same, and the difference in recovery rate and profit level among companies is mainly reflected in the degree of automation of dismantling at the front end of pretreatment, as well as the yield of crushing and screening at the front end and hydrometallurgy at the back end, and the optimization process from two aspects of cost reduction and efficiency.
Intelligent disassembly
There are many problems in front-end manual dismantling, and intelligence is the future focus of the industry. In the front-end pretreatment process, the crushing and screening of the existing production line has been basically automated, which can realize one end of the feed (disassembled module) and one end of the product.
However, due to the wide variety of power battery packs, diverse brand models, complex structure and uncertain retirement status, the shell of the battery pack and the outer packaging of the single battery are still mainly manually disassembled.
In the mass battery disassembly, manual disassembly has many problems: the battery pack voltage is high, yet the internal wiring harness arrangement is complicated, resulting in electric shock and short circuit risks. There is a large amount of glue inside the battery pack, which needs to be disassembled by brute force. Meanwhile, attention should be paid to improving the dismantling efficiency and reducing labor costs. Therefore, intelligent dismantling is a big topic that the industry needs to focus on.
For the intelligent and flexible disassembly of power recycle lithium batteries with machines instead of manual ones, the main steps include: the establishment of 3D camera data acquisition system, multi-robot collaborative disassembly of top cover screws, top cover handling, battery module handling, intelligent sorting of disassembled products, module & core milling and other steps.
The main breakthrough points involved in intelligent dismantling come from the diversification of the appearance of different models of batteries, the intelligent recognition and grasp of components, and the deformation generated after many years of operation, requiring the dismantling system to dynamically adjust according to the specific situation.
Hydrometallurgy
The recovery rate of lithium metal in recycle lithium batteries is only 85-90%, and there is still room for improvement. The limitation of recycle lithium batteries mainly comes from the adsorption of 10% of lithium ions in the waste residue during the extraction and impurity removal process of nickel-cobalt-manganese solution.
In the solution after acid leaching of ternary battery black powder, lithium is the smallest and most active metal; Although 80% of lithium carbonate can be extracted in the front calcination reduction process, in the second phase of nickel, cobalt and manganese extraction process, the formed slag will adsorb 10% of lithium ions, resulting in a reduction in the crystallization recovery of the third phase of lithium carbonate, so the recovery rate of lithium in the current process is difficult to exceed 90%.
In addition to the optimization of the front-end lithium extraction process to improve the yield, the end recycle lithium batteries also has room for cost reduction. At present, for the recovery of lithium in nickel-cobalt raffinate at the end, MVR evaporation process is mainly used to concentrate, and the concentration of lithium is increased by evaporating the water in the solution, and then the precipitation of lithium at the back end is completed.
The advantage of MVR evaporation process is that the technology is mature and widely used, but it needs to consume a lot of electricity in the operation process (the production of 1 ton of lithium carbonate MVR equipment needs to consume 9000 KWH of electricity), and the cost is high.
On this basis, some companies in the industry also try to achieve lithium concentration with more economical solutions such as adsorption + membrane and extraction, and reduce the use of MVR equipment. The concentration of adsorption + membrane is increased mainly through the process of adsorption and desorption, and extraction is achieved through extraction and reverse extraction.
Compared with MVR process, the electricity consumption of these two processes is greatly reduced, and the consumption of adsorbents, membranes, extractants and other reagents is only increased. The upfront investment is also smaller than the MVR process, which helps companies reduce costs.