Method for harmless treatment of waste lithium battery involving heavy waste residues

Abstract

The application discloses a method for harmless treatment of heavy waste slag of waste lithium batteries, comprising the following steps: (1) drying and crushing the heavy waste slag, calcium carbonate slag and magnesium calcium slag generated in the treatment of waste lithium batteries; (2) grinding silicon sand, solvent minerals and regenerated micro powder; (3) mixing the materials prepared in steps (1) and (2) to obtain glass liquid; (4) water quenching, crushing and drying the glass liquid prepared in step (3) to obtain water-quenched slag, or performing a glass forming process on the glass liquid to obtain a glass finished product. The method can solidify heavy metals in the heavy waste slag generated in the treatment of waste lithium batteries, realizes harmless and resourceful treatment of the heavy waste slag generated in the treatment of waste lithium batteries, and the treated product can be used for preparing microcrystalline glass and building materials without secondary pollution, and has good social, environmental and economic benefits.

Description

Technical Field

[0001] This invention belongs to the field of waste lithium battery recycling technology, and specifically relates to a method for harmlessly treating heavy waste residue from waste lithium batteries. Background Technology

[0002] Currently, the industry's recycling of spent lithium batteries mainly focuses on recovering valuable metals from the cathode materials, with the main recycling methods including hydrometallurgy, dry metallurgy, and bioleaching. With continuous technological advancements, cathode material recycling has become quite mature and has formed an industrial chain. However, methods for recycling and processing anode materials are somewhat lacking. This is because the value of anode materials is far lower than that of cathode materials and they are more difficult to recycle. Nevertheless, the recycling and disposal of spent lithium battery anode materials remains a problem that cannot be ignored.

[0003] The relevant technologies mainly involve recycling lithium batteries by internal short-circuiting or immersing them in brine to fully discharge them. After the batteries are fully discharged, waste graphite powder is obtained through manual disassembly, machine crushing, and screening. Throughout this process, some metallic impurities such as Li, Al, Co, Ni, and Mn, as well as organic electrolytes and binders, inevitably become trapped in the graphite. Removing metallic impurities from graphite typically involves leaching with inorganic acids as solvents. The leaching process yields a leachate containing metal ions and graphite slag. After precipitation with hydrochloric acid, carbon black slag solid waste is obtained. This step can extract 99.9% of the metallic impurities from the waste graphite, but small amounts of heavy metals and radioactive metals remaining in the carbon black slag can still pose a significant environmental hazard. The purification process of cathode materials also generates various waste residues containing residual heavy metals and radioactivity, posing risks to human health and the environment.

[0004] Existing technologies for disposing of spent lithium batteries mainly focus on recycling positive electrode materials and purifying and reusing graphite from the negative electrode. However, regardless of the method used to recycle and dispose of spent lithium batteries, a certain amount of heavy waste residue is generated. With the popularization of electric vehicles, the production, usage, and scrap volume of lithium batteries are increasing rapidly. Finding a suitable, harmless, and valuable new way to dispose of the heavy waste residue from spent batteries is extremely urgent. Summary of the Invention

[0005] This invention aims to solve at least one of the technical problems existing in the prior art. To this end, this invention proposes a method for the harmless treatment of heavy metals in waste lithium battery residue. This method can solidify the heavy metals in the waste lithium battery residue, realizing the harmless and resource-based treatment of solid waste and hazardous waste generated from waste battery disposal. The treated products can be used to prepare microcrystalline glass and building materials, without secondary pollution, and have good social, environmental and economic benefits.

[0006] The above-mentioned technical objective of the present invention is achieved through the following technical solution:

[0007] A method for harmlessly treating heavy waste residue from spent lithium batteries includes the following steps:

[0008] (1) Dry and crush the heavy waste residue, calcium carbonate residue and magnesium calcium residue generated from the treatment of waste lithium batteries;

[0009] (2) Grind silica sand, solvent minerals and regenerated micro powder;

[0010] (3) The materials obtained in steps (1) and (2) are mixed and then melted to obtain glass liquid;

[0011] (4) The glass liquid obtained in step (3) is subjected to water quenching, crushing and drying to obtain water quenching slag, or the glass liquid is subjected to glass forming process to obtain finished glass products.

[0012] Preferably, in step (1), the heavy metal waste residue is the waste residue containing heavy metals generated during the treatment of waste lithium batteries.

[0013] Preferably, in step (1), the heavy waste residue is at least one of carbon black slag, activated carbon slag, and iron-aluminum slag.

[0014] Preferably, in step (1), the calcium carbonate slag and the magnesium calcium slag are waste residues generated during the treatment of waste lithium batteries.

[0015] Preferably, in step (1), the weight ratio of the dried heavy waste residue, the calcium carbonate slag and the magnesium calcium slag is (12-38): (18-36): (14-25).

[0016] Preferably, in step (1), the drying temperature is 120-300℃, and the moisture content of the material after drying is ≤1%.

[0017] Preferably, in step (1), the crushing refers to crushing the material to a particle size of <0.15mm.

[0018] Preferably, in step (2), the solvent mineral includes at least one of borax, dolomite, sodium silicate, sodium carbonate, and potassium carbonate.

[0019] Preferably, in step (2), the recycled micro powder is micro powder with a particle size of <0.15mm generated during the crushing of construction waste.

[0020] Preferably, in step (2), the weight ratio of the silica sand, the solvent mineral and the regenerated micro powder is (21-42):(14-27):(10-21).

[0021] Preferably, in step (2), the grinding refers to grinding the material to a residue of ≤10% on a 100-mesh sieve using a ball mill.

[0022] Preferably, in step (3), the melting parameters are as follows: first, the temperature is raised at a constant rate to 700-900℃ for 2-3 hours; then, the temperature is raised at a constant rate to 1000-1150℃ for 3-6 hours; then, the temperature is raised at a constant rate to 1200-1300℃ for 0.5-1 hours; then, the temperature is maintained for 0.3-1 hours; then, the temperature is lowered at a constant rate to 1000-1150℃ for 2-8 hours; and then the product is removed from the kiln.

[0023] Preferably, in step (3), the melting atmosphere is set as follows: when the temperature is uniformly increased to 700-900℃ and 1000-1150℃, it is an oxidizing atmosphere with an air excess coefficient of 1.1-1.2; when the temperature is uniformly increased to 1200-1300℃, it is a weak reducing atmosphere with an air excess coefficient of 0.8-0.9; when the temperature is uniformly decreased to 1000-1150℃, it is a weak oxidizing atmosphere with an air excess coefficient of 1.1±0.05.

[0024] Preferably, in the water-quenched slag or glass product, the content of SiO2 is 45%-55%, Al2O3 is 1%-8%, Fe2O3 is 1%-5%, CaO is 20%-30%, MgO is 4%-8%, and the sum of Na2O and K2O is 5%-15% by mass percentage.

[0025] The beneficial effects of this invention are:

[0026] (1) This invention provides a method for harmlessly, resourcefully, and collaboratively treating waste residue generated from waste lithium batteries, especially heavy metal-containing waste residue. After treatment by the method of this invention, the heavy metals inside the waste residue are solidified. After testing, the resulting product meets the standards of "Identification Standard for Hazardous Waste: Leaching Toxicity Identification" (GB / 5085.3-2007) and "Technical Requirements for Vitrification Products of Solid Waste" (GB / T41015-2021). It is completely non-toxic and harmless, and the product can be used in building materials. This method can achieve 100% full utilization of waste lithium battery heavy metal-containing waste residue, realizing value-added utilization. There is no secondary pollution throughout the process, which has good social, environmental and economic benefits.

[0027] (2) This invention provides a method for the harmless treatment of heavy waste residue from waste lithium batteries. This method significantly reduces the glass transition temperature of the heavy waste residue while simultaneously achieving the synergistic treatment of various solid wastes. In a formulation system composed of heavy waste residue, calcium carbonate slag, silica sand, recycled micro-powder, magnesium-calcium slag, and solvent minerals, SiO2 is introduced through recycled micro-powder and silica sand. SiO2, as a glass network former, can enhance the network structure and thus slow down the tendency for high-temperature crystallization when its content is high, ensuring glass formation. CaO is introduced through calcium carbonate slag and magnesium-calcium slag, but when the CaO content in the system is high, the glass transition temperature may be affected. Glass has low viscosity at high temperatures and is easy to crystallize during heat treatment, but its material properties are short. However, if the CaO content is too low, it will not be conducive to the precipitation of β-wollastonite. At this time, Na2O+K2O in the formula can play a role as a network intermediate, which can significantly improve the melting regime of glass. Since the crystal content in building glass should not be too high, this invention controls the melting parameters and melting atmosphere to control the number of crystals inside the material and improve the physical properties of the material. At the same time, the small amount of Fe2O3 and TiO2 contained in heavy waste residue and calcium carbonate slag can be used as nucleating agents for the preparation of microcrystalline glass, promoting the synthesis of microcrystalline glass.

[0028] (3) The processing method of the present invention can solidify trace amounts of heavy metals such as Cu, Zn, Ni, Co, Cr, and Mn, as well as elements such as Zr, Fe, Ti, F, and P, present in the heavy metal ions generated from waste lithium batteries. 2+ Zn mainly exists in the glass matrix as a lead-oxygen tetrahedral structure; 2+ Due to Fe 2+ With similar ionic radii, Cd can enter the crystal structure of ferrophosphate through substitution; while Cd... 2+ It can also be achieved by replacing Ca. 2+ Some ions enter the diopside crystals; when the Cu content is high, it remains in the CuAlO2 crystals in the glass-ceramic, but when the content is low, most of it remains in the diopside crystals of the glass-ceramic as a solid solution; Mn ions are solidified by substituting Al or Si ions to form manganese-oxygen tetrahedra, or by combining with Al ions to form Mn-Al bonds; Cr exists in the glass as a high-field-strength interstitial cation, which can induce the separation of two immiscible or partially fusible phases in the glass, thereby promoting crystal precipitation. 3+ and Cr 6+ It exists in the form of Cr, and by extending the heat preservation time, Cr 6+ It will gradually transform into Cr 3+ This reduces toxicity. Throughout the process, most Cr in the glass-ceramic promotes the precipitation of the diopside phase by forming magnesium chromium spinel; a small amount of Cr enters the diopside phase and solidifies; when P2O5 content is low, it forms phosphorus-oxygen tetrahedra, inducing nucleation of the base glass; when its content is high, it depolymerizes the silicon-oxygen network structure, promoting crystallization; F2- It will depolymerize the silicon-oxygen network structure in the system, thereby increasing the density and crystallinity of the glass and enhancing the strength of the glass-ceramic; Ni 2+ Ions can induce ZnSiO precipitation, altering the crystallization behavior of this glass system, and thus doping into the ZnSiO3 microcrystalline phase to achieve solidification; Co 2+ Ions can be doped with KZnF3 microcrystalline phase, forming [CoF6]. 4- It is solidified by octahedral coordination geometry. Attached Figure Description

[0029] Figure 1 This is a flowchart illustrating Embodiment 1 of the present invention;

[0030] Figure 2 This is a picture of the finished product of the water-quenched slag prepared in Example 2. Detailed Implementation

[0031] The present invention will be further described below with reference to specific embodiments.

[0032] Example 1:

[0033] A method for harmlessly treating heavy waste residue from spent lithium batteries, such as... Figure 1 As shown, it includes the following steps:

[0034] (1) The heavy waste residue, calcium carbonate residue and magnesium calcium residue generated from the treatment of waste lithium batteries are sent to a drying kiln for drying at a temperature of 300°C until the moisture content is 0.1%.

[0035] (2) The heavy waste residue, calcium carbonate slag and magnesium calcium slag dried in step (1) are dispersed to a particle size of <0.125mm according to a weight ratio of 32:25:14.

[0036] (3) Silica sand, solvent minerals and recycled micro powder are fed into a ball mill for grinding in a weight ratio of 21:20:10 until 8% residue remains on a 100-mesh sieve. The solvent mineral is borax and the recycled micro powder is micro powder with a particle size of <0.15mm generated during the crushing of construction waste.

[0037] (4) Mix the raw materials prepared in steps (2) and (3), stir evenly, and then send them into a glass furnace to melt glass. The melting parameters are as follows: first, heat the glass at a constant rate to 800℃ for 3 hours; then heat the glass at a constant rate to 1050℃ for 5 hours; then heat the glass at a constant rate to 1230℃ for 0.5 hours, then hold the glass at that temperature for 0.5 hours, and then cool the glass at a constant rate to 1100℃ for 8 hours. Then the glass is discharged from the furnace. The melting atmosphere is set as follows: when the glass is heated at a constant rate to 800℃ and to 1050℃, it is an oxidizing atmosphere with an excess air coefficient of 1.1; when the glass is heated at a constant rate to 1230℃, it is a weak reducing atmosphere with an excess air coefficient of 0.8; when the glass is cooled at a constant rate to 1100℃, it is a weak oxidizing atmosphere with an excess air coefficient of 1.15.

[0038] (5) The obtained glass liquid is subjected to the glass product forming process to obtain the finished glass product. The glass product contains 47.5% SiO2, 4.9% Al2O3, 5.0% Fe2O3, 21.4% CaO, 3.1% MgO, and 7.8% Na2O and K2O.

[0039] Example 2:

[0040] A method for harmlessly treating heavy waste residue from spent lithium batteries includes the following steps:

[0041] (1) The heavy waste residue, calcium carbonate residue and magnesium calcium residue generated from the treatment of waste lithium batteries are sent to the drying kiln for drying at a temperature of 120°C until the moisture content is 0.9%.

[0042] (2) The heavy waste residue, calcium carbonate slag and magnesium calcium slag dried in step (1) are dispersed to a particle size of <0.15mm according to a weight ratio of 26:32:20.

[0043] (3) Silica sand, solvent minerals and recycled micro powder are fed into a ball mill for grinding in a weight ratio of 40:14:17. Grind until 7.5% residue is left on a 100-mesh sieve. The solvent minerals are dolomite and sodium carbonate mixed in a weight ratio of 2:1. The recycled micro powder is micro powder with a particle size of <0.15mm generated during the crushing of construction waste.

[0044] (4) Mix the raw materials prepared in steps (2) and (3), stir evenly, and then send them into a glass furnace to melt glass. The melting parameters are as follows: first, heat the glass at a constant rate to 800℃ for 2.5 hours; then heat the glass at a constant rate to 1050℃ for 3 hours; then heat the glass at a constant rate to 1230℃ for 1 hour, then hold the glass at that temperature for 0.5 hours, and then cool the glass at a constant rate to 1100℃ for 8 hours. Then the glass is discharged from the furnace. The melting atmosphere is set as follows: when the glass is heated at a constant rate to 800℃ and to 1050℃, it is an oxidizing atmosphere with an excess air coefficient of 1.18; when the glass is heated at a constant rate to 1230℃, it is a weak reducing atmosphere with an excess air coefficient of 0.9; when the glass is cooled at a constant rate to 1100℃, it is a weak oxidizing atmosphere with an excess air coefficient of 1.10.

[0045] (5) The obtained glass melt is quenched with water. The quenched slag is then crushed, dried, and sieved to obtain the finished quenched slag product. The finished quenched slag product is as follows: Figure 2 As shown, the water-quenched slag product contains 51.3% SiO2, 2.0% Al2O3, 1.7% Fe2O3, 27.7% CaO, 4.0% MgO, and a total of 5.7% Na2O and K2O.

[0046] Example 3:

[0047] A method for harmlessly treating heavy waste residue from spent lithium batteries includes the following steps:

[0048] (1) The heavy waste residue, calcium carbonate residue and magnesium calcium residue generated from the treatment of waste lithium batteries are sent to the drying kiln for drying at a temperature of 180°C until the moisture content is 0.7%.

[0049] (2) The heavy waste residue, calcium carbonate slag and magnesium calcium slag dried in step (1) are dispersed to a particle size of <0.115mm according to a weight ratio of 14:36:25.

[0050] (3) Silica sand, solvent minerals and recycled micro powder are fed into a ball mill for grinding in a weight ratio of 21:15:20 until 9.9% residue remains on a 100-mesh sieve. The solvent minerals are composed of borax, dolomite and potassium carbonate in a weight ratio of 1:1:0.5. The recycled micro powder is micro powder with a particle size of <0.15mm generated during the crushing of construction waste.

[0051] (4) Mix the raw materials prepared in steps (2) and (3), stir evenly, and then send them into a glass furnace to melt and obtain glass liquid. The melting parameters are as follows: first, heat up to 800℃ at a constant rate for 2 hours; then heat up to 1050℃ at a constant rate for 4 hours; then heat up to 1230℃ at a constant rate for 0.8 hours, then hold for 0.5 hours, then cool down to 1100℃ at a constant rate for 6 hours; then remove from the furnace. The melting atmosphere is set as follows: when heating up to 800℃ and 1050℃ at a constant rate, it is an oxidizing atmosphere with an air excess coefficient of 1.2; when heating up to 1230℃ at a constant rate, it is a weak reducing atmosphere with an air excess coefficient of 0.81; when cooling down to 1100℃ at a constant rate, it is a weak oxidizing atmosphere with an air excess coefficient of 1.05.

[0052] (5) The obtained glass melt is quenched with water. The water-quenched slag is crushed, dried and screened to obtain the finished water-quenched slag. The finished water-quenched slag contains 45.6% SiO2, 2.1% Al2O3, 2.3% Fe2O3, 30.8% CaO, 4.5% MgO and 6.2% Na2O and K2O.

[0053] Example 4:

[0054] A method for harmlessly treating heavy waste residue from spent lithium batteries includes the following steps:

[0055] (1) The heavy waste residue, calcium carbonate residue and magnesium calcium residue generated from the treatment of waste lithium batteries are sent to a drying kiln for drying at a temperature of 251°C until the moisture content is 0.5%.

[0056] (2) The heavy waste residue, calcium carbonate slag and magnesium calcium slag dried in step (1) are dispersed to a particle size of <0.109mm according to a weight ratio of 38:18:15.

[0057] (3) Silica sand, solvent minerals and recycled micro powder are fed into a ball mill for grinding in a weight ratio of 30:27:20 until 7.8% residue remains on a 100-mesh sieve. The solvent minerals are sodium silicate and sodium carbonate in a weight ratio of 1:1. The recycled micro powder is micro powder with a particle size of <0.15mm generated during the crushing of construction waste.

[0058] (4) Mix the raw materials prepared in steps (2) and (3), stir evenly, and then send them into a glass furnace to melt glass. The melting parameters are as follows: first, heat the glass at a constant rate to 800℃ for 3 hours; then heat the glass at a constant rate to 1050℃ for 6 hours; then heat the glass at a constant rate to 1230℃ for 1 hour, then hold the glass at that temperature for 0.5 hours, and then cool the glass at a constant rate to 1100℃ for 5 hours. Then the glass is discharged from the furnace. The melting atmosphere is set as follows: when the glass is heated at a constant rate to 800℃ and to 1050℃, it is an oxidizing atmosphere with an excess air coefficient of 1.15; when the glass is heated at a constant rate to 1230℃, it is a weak reducing atmosphere with an excess air coefficient of 0.88; when the glass is cooled at a constant rate to 1100℃, it is a weak oxidizing atmosphere with an excess air coefficient of 1.14.

[0059] (5) The obtained glass liquid is subjected to the glass product forming process to obtain the finished glass product. The glass product contains 43.8% SiO2, 5.0% Al2O3, 4.3% Fe2O3, 21.5% CaO, 3.3% MgO, and a total of 10.4% Na2O and K2O.

[0060] Example 5:

[0061] A method for harmlessly treating heavy waste residue from spent lithium batteries includes the following steps:

[0062] (1) The heavy waste residue, calcium carbonate residue and magnesium calcium residue generated from the treatment of waste lithium batteries are sent to the drying kiln for drying at a temperature of 200°C until the moisture content is 0.3%.

[0063] (2) The heavy waste residue, calcium carbonate slag and magnesium calcium slag dried in step (1) are dispersed to a particle size of <0.20mm according to a weight ratio of 28:27:14.

[0064] (3) Silica sand, solvent minerals and recycled micro powder are fed into a ball mill for grinding in a weight ratio of 32:23:10 until 6% residue remains on a 100-mesh sieve. The solvent minerals are sodium silicate, potassium carbonate, dolomite and borax in a weight ratio of 1:1:0.3:0.2. The recycled micro powder is micro powder with a particle size of <0.15mm generated during the crushing of construction waste.

[0065] (4) Mix the raw materials prepared in steps (2) and (3), stir evenly, and then send them into a glass furnace to melt glass. The melting parameters are as follows: first, heat the glass at a constant rate to 800℃ for 2 hours; then heat the glass at a constant rate to 1050℃ for 3 hours; then heat the glass at a constant rate to 1230℃ for 0.5 hours, then hold the glass at that temperature for 0.5 hours, and then cool the glass at a constant rate to 1100℃ for 2 hours. Then the glass is discharged from the furnace. The melting atmosphere is set as follows: when the glass is heated at a constant rate to 800℃ and to 1050℃, it is an oxidizing atmosphere with an excess air coefficient of 1.12; when the glass is heated at a constant rate to 1230℃, it is a weak reducing atmosphere with an excess air coefficient of 0.87; when the glass is cooled at a constant rate to 1100℃, it is a weak oxidizing atmosphere with an excess air coefficient of 1.08.

[0066] (5) The obtained glass melt is quenched with water. The water-quenched slag is crushed, dried and screened to obtain the finished water-quenched slag. The finished water-quenched slag contains 40.7% SiO2, 3.0% Al2O3, 7.8% Fe2O3, 25.8% CaO, 2.9% MgO, and a total of 8.4% Na2O and K2O.

[0067] Experimental example:

[0068] The glass products or water-quenched slag products prepared in Examples 1-5 were subjected to leaching toxicity tests according to the standards of "Identification Standard for Hazardous Waste - Leaching Toxicity Identification" (GB / 5085.3-2007) and "Technical Requirements for Vitrification Products of Solid Waste" (GB / T 41015-2021). The heavy waste residue used in Examples 1-5 was used as a comparison for leaching toxicity tests. The glass products prepared in Examples 1-5 were subjected to performance tests, with ordinary microcrystalline glass used as a comparison for performance tests. The results of the leaching toxicity tests are shown in Table 1, and the results of the performance tests are shown in Table 2.

[0069] Table 1: Results of Toxin Immersion Test

[0070]

[0071]

[0072] Table 2: Performance Test Results

[0073]

[0074] As shown in Table 1, after treatment by the method of the present invention, the heavy metal content in the obtained glass products or water-quenched slag products meets the requirements of the standards "Identification Standard for Hazardous Waste: Leaching Toxicity Identification" (GB / 5085.3-2007) and "Technical Requirements for Vitrification Products of Solid Waste" (GB / T41015-2021) in the toxicity leaching test.

[0075] As shown in Table 2, the bulk density of the glass product or water-quenched slag product obtained after treatment by the method of the present invention reaches 2.62 g / cm³. 3 The compressive strength can reach over 120MPa, the acid resistance mass loss is no more than 0.024%, the alkali resistance mass loss is no more than 0.003%, the Mohs hardness can reach level 6, and the water absorption rate is no more than 0.03%, which is superior to ordinary microcrystalline glass.

[0076] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for harmlessly treating heavy waste residue from spent lithium batteries, characterized in that: Includes the following steps: (1) Dry and crush the heavy waste residue, calcium carbonate residue and magnesium calcium residue generated from the treatment of waste lithium batteries; (2) Grind the silica sand, solvent minerals and recycled micro powder; (3) The materials obtained in steps (1) and (2) are mixed and then melted to obtain glass melt; (4) The glass melt obtained in step (3) is subjected to water quenching, crushing, and drying to obtain water-quenched slag, or the glass melt is subjected to a glass forming process to obtain a finished glass product; In step (3), the melting parameters are: first, the temperature is uniformly raised to 700-900℃ for 2-3 hours; then the temperature is uniformly raised to 1000-1150℃ for 3-6 hours; then the temperature is uniformly raised to 1200-1300℃ for 0.5-1 hour, then the temperature is maintained for 0.3-1 hour, and then the temperature is uniformly maintained for 1 hour. The temperature is rapidly reduced to 1000-1150℃ over a period of 2-8 hours. The solution is then removed from the kiln. The melting atmosphere is set as follows: an oxidizing atmosphere is used when the temperature is uniformly increased to 700-900℃ and 1000-1150℃, with an excess air coefficient of 1.1-1.2; a weak reducing atmosphere is used when the temperature is uniformly increased to 1200-1300℃, with an excess air coefficient of 0.8-0.9; and a weak oxidizing atmosphere is used when the temperature is uniformly reduced to 1000-1150℃, with an excess air coefficient of 1.1±0.

05.

2. The method for harmlessly treating heavy waste residue from waste lithium batteries according to claim 1, characterized in that: In step (1), the weight ratio of the dried heavy waste residue, the calcium carbonate slag and the magnesium calcium slag is (12-38): (18-36): (14-25).

3. The method for harmlessly treating heavy waste residue from waste lithium batteries according to claim 1, characterized in that: In step (1), the drying temperature is 120-300℃, and the moisture content of the material after drying is ≤1%.

4. The method for harmlessly treating heavy waste residue from waste lithium batteries according to claim 1, characterized in that: In step (1), the crushing refers to crushing the material to a particle size of <0.15mm.

5. The method for harmlessly treating heavy waste residue from waste lithium batteries according to claim 1, characterized in that: In step (2), the solvent mineral includes at least one of borax, dolomite, sodium silicate, sodium carbonate and potassium carbonate.

6. The method for harmlessly treating heavy waste residue from waste lithium batteries according to claim 1, characterized in that: In step (2), the recycled micro powder is micro powder with a particle size of <0.15mm generated during the crushing of construction waste.

7. The method for harmlessly treating heavy waste residue from waste lithium batteries according to claim 1, characterized in that: In step (2), the weight ratio of the silica sand, the solvent mineral and the regenerated micro powder is (21-42): (14-27): (10-21).

8. The method for harmlessly treating heavy waste residue from waste lithium batteries according to claim 1, characterized in that: In the water-quenched slag or glass product, by mass percentage, the SiO2 content is 45%-55%, the Al2O3 content is 1%-8%, the Fe2O3 content is 1%-5%, the CaO content is 20%-30%, the MgO content is 4%-8%, and the sum of the Na2O and K2O contents is 5%-15%.

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