AU2021102334A4 - Method for recovering cobalt, copper and iron from waste cobalt-containing lithium ion batteries - Google Patents
Method for recovering cobalt, copper and iron from waste cobalt-containing lithium ion batteries Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 65
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 36
- 239000010941 cobalt Substances 0.000 title claims abstract description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 23
- 239000002893 slag Substances 0.000 claims abstract description 93
- 238000003723 Smelting Methods 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 claims abstract description 11
- OBLMUVZPDITTKB-UHFFFAOYSA-N [Fe].[Co].[Cu] Chemical compound [Fe].[Co].[Cu] OBLMUVZPDITTKB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012530 fluid Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000011888 foil Substances 0.000 claims abstract description 6
- 230000005291 magnetic effect Effects 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 5
- 230000000171 quenching effect Effects 0.000 claims abstract description 5
- 230000003068 static effect Effects 0.000 claims abstract description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 230000007423 decrease Effects 0.000 claims abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 235000013980 iron oxide Nutrition 0.000 claims description 5
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 238000005496 tempering Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 208000028659 discharge Diseases 0.000 abstract description 6
- 238000000227 grinding Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000002791 soaking Methods 0.000 abstract description 6
- 229910020598 Co Fe Inorganic materials 0.000 abstract description 3
- 229910002519 Co-Fe Inorganic materials 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000004320 controlled atmosphere Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present disclosure discloses a method for recovering cobalt, copper and iron from waste
cobalt-containing lithium ion batteries, and belongs to the technical field of metallurgy. The
method of the present disclosure utilizes the sensible heat and existing slag system of a copper
converter, as well as the high-temperature reduction characteristics of the negative electrode
carbon and aluminum foil carrier fluid in the cobalt-containing lithium ion battery to achieve a
self-reduction smelting, which decreases the magnetic iron content in the slag, lowers the slag
viscosity, reduces copper in the oxidation state in the slag and cobalt oxide, a pyrolysis product
of the battery, and combines copper slag depletion and waste lithium ion battery recovery to
yield a copper-cobalt-iron alloy and produce low-copper-content depleted slag. The method of
the present disclosure is simple to operate, adaptable, and useful for the treatment of slag
systems similar to copper slag, and facilitates the comprehensive recovery of metal elements
such as Cu, Co, Fe, and the like.
1/1
DRAWINGS:
Molten Cu slag
N 2
Heating
Battery
material
Reduction
smelting
Static
settlement
Slag-metal
separation
Quenching and Depletion of tailings
tempenng
Cu-Co-Fe alloy
FIG.1
Filtrate treatment
Pretreatment Grinding
Discharge treatment Soaking
Disassembly Crushing
FIG. 2
Description
1/1
Molten Cu slag
N2
Heating Battery material
Reduction smelting
Static settlement
Slag-metal separation
Quenching and Depletion of tailings tempenng
Cu-Co-Fe alloy
FIG.1
Filtrate treatment
Pretreatment Grinding Discharge treatment Soaking
Disassembly Crushing
FIG. 2
[0001] The present disclosure relates to a method for recovering cobalt, copper and iron from waste cobalt-containing lithium ion batteries, and belongs to the technical field of metallurgy.
[0002] Since the commercialization of lithium ion batteries, they have been widely used in various fields, such as the fields of electric tools, electric vehicles/automobiles, military equipment, aerospace engineering, and the like, showing excellent comprehensive performance. According to their application scenarios, lithium ion batteries can be divided into three types for power, consumption and energy storage purposes. With the development of lithium ion batteries, they have a wider range of applications, and the main components such as cobalt and lithium in the batteries are more expensive, making their costs a major factor preventing their expansion into the field of renewable resource applications. The issue of making waste lithium ion batteries non-hazardous and the recycling of valuable components in the batteries need to gain more attention in the society.
[0003] At present, methods for recovering waste lithium ion batteries in industry mainly include three methods, which are physical sorting, hydrometallurgical recovery and pyrometallurgical recovery. In recent years, studies related to the recycling of waste lithium ion batteries have been made both at home and abroad, but they mainly focus on hydrometallurgical recovery to find cost-effective leaching agents and improve related processes. The disadvantage is that it is difficult to handle waste batteries of complex components and multi-sizes.
[0004] Copper converter slag is characterized by "three highs", high in heat, high in copper containing slag, and high in magnetic iron content, which often requires the addition of a reducing agent for depletion or slow cooling to recover copper in the slag. The former has a simple process and the hot slag can be used directly. However, the copper content in the tailings is often as high as 0.5%-1.0%, and the copper recovery rate is low. The latter requires large infrastructure investment and has a complex process; the slag needs to be subjected to slow cooling, and the heat is difficult to utilize; moreover, it is impossible to recover metal elements such as Ni and Co in the slag. Therefore, it is necessary to develop a comprehensive and efficient copper slag recovery method.
[0005] In order to solve the above problems, it is an object of the present disclosure to provide a method for recovering cobalt, copper and iron from waste cobalt-containing lithium ion batteries, which realizes the comprehensive recovery of heat, reducing agents, and valuable metals in solid waste and hazardous waste resources, obtains a multi-purpose copper-cobalt-iron alloy, and facilitates separation of slag and metal. The tailings meet relevant standards for disposal of waste slag in China, and the overall depletion effect is better than current electric furnace reduction depletion and pyrometallurgical recovery of waste lithium ion batteries. The specific process is as follows: The sensible heat and existing slag system of the copper converter, as well as the high-temperature reduction characteristics of the negative electrode carbon and aluminum foil carrier fluid in the cobalt-containing lithium ion battery are utilized, so that the magnetic iron content in the slag is decreased, the slag viscosity is lowered, and copper in the oxidation state in the slag and cobalt oxide, a pyrolysis product of the battery, are reduced to achieve a self-reduction smelting which combines copper slag depletion and waste lithium ion battery recovery, yields a copper-cobalt-iron alloy, and produces low-copper-content depleted slag.
[0006] It specifically includes the following steps:
[0007] (1) Hot molten copper slag produced from a converter is fed into a depletion furnace, and the depletion furnace, into which an inert gas is introduced, is heated to decompose part of Fe304 in the slag into FeO and Fe203;
[0008] (2) Pretreated waste lithium cobaltate battery material is sprayed onto the upper layer of the slag through a powder spraying device for reduction smelting, so that copper oxides in the slag, cobalt oxides obtained from the pyrolysis of the battery and part of iron oxides in the slag are reduced to the metallic state; after static settlement, the metal phase is separated from the slag phase, and the upper slag is discharged, in which the copper content is below 0.5%;
[0009] (3) The obtained molten alloy is subjected to a quenching and tempering treatment, if desired.
[0010] Preferably, in step (1) of the present disclosure, the mass percentage content of Cu in the molten copper slag is 2%-5%, and the temperature thereof is 1200-1250°C.
[0011] Preferably, in step (1) of the present disclosure, the heating rate in the depletion furnace is 5-10°C/min, and the temperature is increased to 1400-1500°C.
[0012] Preferably, the amount of the positive and negative electrode materials of the waste lithium cobaltate battery of the present disclosure is 10%-30% of the total mass of the copper slag, and the reduction smelting is carried out for 30-60 minutes.
[0013] Preferably, in step (2) of the present disclosure, the pretreatment of the waste lithium cobaltate battery material successively includes: physical discharge, soaking inactivation, disassembly after drying, crushing, preheating at 200°C, and grinding to 160 meshes.
[0014] Preferably, in step (2) of the present disclosure, the waste lithium cobaltate battery material includes positive electrode lithium cobaltate + aluminum foil carrier fluid, and negative electrode carbon + copper foil carrier fluid, wherein the Li content is 2%-4%, the Co content is %-30%, the content of Ni is 0.01%-5%, the content of C is 20%-30%, the content of Cu is %-20%, and the content of Al is 5%-15%.
[0015] Preferably, the Cu content is 15%-60%, the Co content is 10%-30%, and the Fe content is 10%-55% in the copper-cobalt-iron alloy phase obtained in step (2) of the present disclosure, and the copper content in the depleted slag is 0.2%-0.5%.
[0016] The battery pyrolysis process in step (2) of the present disclosure mainly include the following equations:
[0017] 6Lio. 5Co02= 3LiCoO2+ C0304+ 02(g)
[0018] 12LiCoO2= 6Li 2 O + 4Co304+ 02(g)
[0019] Li 2 0 + C= CO(g) + 2Li(g)
[0020] 2Co304= 6CoO + 02(g)
[0021] C + 02(g)= C02(g)
[0022] C + 02(g)= CO(g)
[0023] C + C02(g )= 2CO(g)
[0024] 3CoO + 2Al= 3Co + A1 2 0 3
[0025] CoO + C = Co + CO(g)
[0026]2CoO+C=2Co+C02(g)
[0027] In the S2, the metal oxide reduction stage mainly includes the following equations:
[0028] 2Cu20 + C = 4Cu + C02(g)
[0029] Cu20 + CO(g)= 2Cu + C02(g)
[0030] 3Cu20 + 2Al= 6Cu + A1 2 0 3
[0031] Fe304= Fe203+ FeO
[0032] Fe304 + 4C = 3Fe + 4CO(g)
[0033] Fe304 + C = 3FeO + CO(g)
[0034] 2Fe34 + C = 6FeO + C02(g)
[0035] Fe304 + CO(g)= 3FeO + C02(g)
[0036] FeO + C = Fe + CO(g)
[0037] 2Fe23 + 3C = 3CO2(g)+ 2Fe
[0038] In the reduction smelting process of the present disclosure, lithium obtained by reduction from the waste cobalt-containing lithium ion battery and metals such as zinc and the like in the melt are transferred to the gas phase by a strengthening method, and the exhaust gas is enriched and recovered with a bag dust collection device, wherein the valuable metals are recovered. The discharged molten slag, after cooling, can be used for other purposes, thereby realizing the comprehensive utilization of solid waste copper slag and hazardous waste lithium ion batteries.
[0039] The beneficial effects of the present disclosure include the following:
[0040] (1) The present disclosure proposes a new idea of using hot copper slag to co-process waste cobalt-containing lithium ion batteries to recover valuable metals of Co, Cu, Fe, which sufficiently utilizes the sensible heat and existing slag system of copper converter slag, significantly promotes decomposition of Fe304 in the slag and subsequent reduction effect by providing a small amount of heat to increase the temperature, and reduces the viscosity of the slag, as well as subsequent quenching and tempering treatment.
[0041] (2) The method of the present disclosure makes full use of the high-temperature reduction characteristics of the negative electrode carbon and aluminum foil carrier fluid material in the waste lithium ion battery to realize self-reduction in the smelting process. The obtained Cu-Co-Fe ternary alloy has excellent magnetic and physiochemical properties, and has good application prospects in the fields of magnetic materials and electronic materials, which can be widely used in alloy substrates for diamond tools, ferromagnetic materials, wire and cable materials, electrical contact materials, and integrated circuit lead materials.
[0042] (3) The method of the present disclosure is simple, and can directly use existing equipment to realize a comprehensive and efficient recovery of solid waste copper slag and hazardous waste lithium ion batteries, which needs less investment, is energy-saving and environmentally friendly, and has low cost and a higher economic value. The obtained depleted copper slag meets relevant standards for disposal of waste slag in China, and can be used as the main material of cement, building stone, and the like, achieving waste-free recycling.
[0043] (4) Carbon and aluminum in waste lithium ion batteries used in the present disclosure are "natural" reducing agents in the entire reaction process, so that metallization reduction of oxides such as copper and cobalt and selective reduction of magnetic iron in slag can be carried out without the addition of further reducing agents, realizing self-reduction in the smelting process. The reaction is rapid and sufficient, and the process flow is short.
[0044] FIG. 1 is a process flow diagram of the present disclosure;
[0045] FIG. 2 is a flow diagram of pretreatment of waste lithium ion batteries of the present disclosure.
[0046] The present disclosure is further described in detail hereinbelow in conjunction with specific examples, but the protection scope of the present disclosure is not limited thereto.
[0047] The equipment used in the present disclosure is a depletion electric furnace used for industrially depleting converter slag. Converter slag in the copper smelting process and waste lithium ion batteries obtained by recovery are used as raw materials. With N 2 as the carrier gas, treated battery material is sprayed onto the upper layer of the molten slag through a powder spraying device.
[0048] The composition of the molten copper slag used in the examples of the present disclosure is shown in Table 1.
[0049] Table 1 Composition of converter slag used in the experiment, mass percentage, %
Composition Cu S A1 20 3 MgO Si0 2 CaO Fe304 TFe
Content /% 4.49 0.53 2.57 0.61 21.04 0.86 34.10 44.91
[0050] The waste lithium cobaltate battery material used in the examples of the present disclosure includes positive electrode lithium cobaltate + aluminum foil carrier fluid, and negative electrode carbon + copper foil carrier fluid. The composition of the waste lithium cobaltate battery material is shown in Table 2.
[0051] Elemental composition of waste lithium ion batteries used in the experiment, mass percentage, %
Main elemental composition, mass%
Co Li Cu Al C 0 Others
22.78 3.20 11.40 7.95 28.15 14.55 11.95
[0052] Example 1
[0053] (1) 60 g of molten copper slag with a temperature of 1200-1250°C produced by a converter was fed into a depletion furnace; a N2-controlled atmosphere was introduced to prevent 02 in the air from interfering with the reduction smelting atmosphere; the gas flow rate was 200 ml/min; the molten copper slag was further heated to 1400°C with a heating rate of 8°C/min to decompose part of Fe304 in the slag into FeO and Fe203.
[0054] (2) Electrode materials of waste lithium cobaltate batteries were pretreated, including: physical discharge-soaking inactivation-disassembly after drying-crushing-preheating at 200°C grinding to 160 meshes.
[0055] (3) 10 g of pretreated positive and negative electrode materials of waste lithium cobaltate batteries were ground to 160 meshes, which were sprayed onto the upper layer of the molten slag through a powder spraying device with N 2 as the carrier gas for reduction smelting, and the spray flow rate was 100 ml/min; copper oxides in the slag, cobalt oxides obtained from the pyrolysis of the battery and part of iron oxides in the slag were reduced to the metallic state, and the reduction time was 50 minutes; after the completion of the reduction, the materials were settled for 35 minutes; a copper-cobalt-iron alloy melt was observed in the molten pool; the copper-cobalt-iron alloy melt was separated from the slag phase; and the upper slag was discharged.
[0056] In this example, the slag-alloy melt separation effect is good. The obtained alloy melt is 6.44 g, which contains 38.8% copper, 43.47% cobalt, and 13.75% iron; the slag contains 0.41% copper, 0.18% cobalt, and 40.43% iron; the copper recovery rate is 93.10%, and the cobalt recovery rate is 92.58%.
[0057] Example 2
[0058] (1) 160 g of molten copper slag with a temperature of 1200-1250°C produced by a converter was fed into a depletion furnace; a N2-controlled atmosphere was introduced to prevent 02 in the air from interfering with the reduction smelting atmosphere; the gas flow rate was 200 ml/min; the molten copper slag was further heated to 1450°C with a heating rate of °C/min to decompose part of Fe304 in the slag into FeO and Fe203.
[0059] (2) Electrode materials of waste lithium cobaltate batteries were pretreated, including: physical discharge-soaking inactivation-disassembly after drying-crushing-preheating at 200°C grinding to 160 meshes.
[0060] (3) 10 g of pretreated positive and negative electrode materials of waste lithium cobaltate batteries were ground to 160 meshes, which were sprayed onto the upper layer of the molten slag through a powder spraying device with N 2 as the carrier gas for reduction smelting, and the spray flow rate was 200 ml/min; copper oxides in the slag, cobalt oxides obtained from the pyrolysis of the battery and part of iron oxides in the slag were reduced to the metallic state, and the reduction time was 60 minutes; after the completion of the reduction, the materials were settled for 35 minutes; a copper-cobalt-iron alloy melt was observed in the molten pool; the copper-cobalt-iron alloy melt was separated from the slag phase; and the upper slag was discharged.
[0061] In this example, the slag-alloy melt separation effect is good. The obtained alloy melt is 13.72 g, which contains 51.5% copper, 13.16% cobalt, and 29.3% iron; the slag contains 0.35% copper, 0.52% cobalt, and 34.13% iron; the copper recovery rate is 84.88%, and the cobalt recovery rate is 79.26%.
[0062] Example 3
[0063] (1) 60 g of molten copper slag with a temperature of 1200-1250°C produced by a converter was fed into a depletion furnace; a N2-controlled atmosphere was introduced to prevent 02 in the air from interfering with the reduction smelting atmosphere; the gas flow rate was 200 ml/min; the molten copper slag was further heated to 1500°C with a heating rate of °C/min to decompose part of Fe304 in the slag into FeO and Fe203.
[0064] (2) Electrode materials of waste lithium cobaltate batteries were pretreated, including: physical discharge-soaking inactivation-disassembly after drying-crushing-preheating at 200°C grinding to 160 meshes.
[0065] (3) 8.6 g of pretreated positive and negative electrode materials of waste lithium cobaltate batteries were ground to 160 meshes, which were sprayed onto the upper layer of the molten slag through a powder spraying device with N 2 as the carrier gas for reduction smelting, and the spray flow rate was 150 ml/min; copper oxides in the slag, cobalt oxides obtained from the pyrolysis of the battery and part of iron oxides in the slag were reduced to the metallic state, and the reduction time was 60 minutes; after the completion of the reduction, the materials were settled for 35 minutes; a copper-cobalt-iron alloy melt was observed in the molten pool; the copper-cobalt-iron alloy melt was separated from the slag phase; and the upper slag was discharged.
[0066] In this example, the slag-alloy melt separation effect is good. The obtained alloy melt is 12.89 g, which contains 25.87% copper, 14.03% cobalt, and 51.7% iron; the slag contains 0.41% copper, 0.21% cobalt, and 30.81% iron; the copper recovery rate is 90.75%, and the cobalt recovery rate is 92.31%.
Claims (5)
1. A method for recovering cobalt, copper and iron from a waste cobalt-containing lithium ion battery, wherein the sensible heat and existing slag system of a copper converter, as well as the high-temperature reduction characteristics of the negative electrode carbon and aluminum foil carrier fluid in the cobalt-containing lithium ion battery are utilized to achieve a self-reduction smelting, which decreases the magnetic iron content in the slag, lowers the slag viscosity, reduces copper in the oxidation state in the slag and cobalt oxide, a pyrolysis product of the battery, and combines copper slag depletion and waste lithium ion battery recovery to yield a copper-cobalt iron alloy and produce low-copper-content depleted slag.
2. The method for recovering cobalt, copper and iron from a waste cobalt-containing lithium ion battery according to claim 1, wherein the method specifically includes the following steps: (1) Hot molten copper slag produced from a converter is fed into a depletion furnace, and the depletion furnace, into which an inert gas is introduced, is heated to decompose part of Fe304 in the slag into FeO and Fe203; (2) Pretreated waste lithium cobaltate battery material is sprayed onto the upper layer of the slag through a powder spraying device for reduction smelting, so that copper oxides in the slag, cobalt oxides obtained from the pyrolysis of the battery and part of iron oxides in the slag are reduced to the metallic state; after static settlement, the metal phase is separated from the slag phase, and the upper slag is discharged, in which the copper content is below 0.5%; (3) The obtained molten alloy is subjected to a quenching and tempering treatment, if desired.
3. The method for recovering cobalt, copper and iron from a waste cobalt-containing lithium ion battery according to claim 2, wherein the mass percentage content of Cu in the molten copper slag in step (1) is 2%-5%, and the temperature thereof is 1200-1250°C.
4. The method for recovering cobalt, copper and iron from a waste cobalt-containing lithium ion battery according to claim 2, wherein the heating rate in the depletion furnace in step (1) is 5 °C/min, and the temperature is increased to 1400-1500°C.
5. The method for recovering cobalt, copper and iron from a waste cobalt-containing lithium ion battery according to claim 2, wherein the amount of the positive and negative electrode materials of the waste lithium cobaltate battery is 10%-30% of the total mass of the copper slag, and the reduction smelting is carried out for 30-60 minutes.
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| CN202010981331.3A CN112176190A (en) | 2020-09-17 | 2020-09-17 | Method for recovering cobalt, copper and iron from waste cobalt-containing lithium ion battery |
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| CN112877545A (en) * | 2021-01-12 | 2021-06-01 | 昆明理工大学 | Method for recycling nickel, cobalt and iron by cooperatively treating waste nickel-hydrogen batteries through nickel smelting slag |
| CN113061725A (en) * | 2021-03-10 | 2021-07-02 | 昆明理工大学 | Method for recovering lithium from waste lithium ion battery by pyrogenic process |
| RU2768719C1 (en) * | 2021-09-22 | 2022-03-24 | Общество с ограниченной ответственностью "Русский Кобальт" (ООО "РК") | Method of recycling spent lithium-ion batteries |
| CN114350957A (en) * | 2022-01-07 | 2022-04-15 | 江西理工大学 | Method for comprehensively recovering valuable elements from waste lithium batteries |
| CN115959829A (en) * | 2022-12-27 | 2023-04-14 | 重庆科技学院 | Method for recovering pig iron-aluminum slag and waste carbon slag produced in recovery process of retired lithium battery |
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| CN102002598B (en) * | 2010-12-22 | 2012-08-29 | 东北大学 | Method for recovering copper and cobalt from cobalt-containing copper converter slag |
| CN103526035B (en) * | 2013-10-31 | 2015-08-05 | 长沙矿冶研究院有限责任公司 | The method of valuable metal is reclaimed from waste and old lithium ion battery and/or its material |
| PL3087208T3 (en) * | 2013-12-23 | 2018-03-30 | Umicore | Process for recycling li-ion batteries |
| JP6735192B2 (en) * | 2016-09-07 | 2020-08-05 | Ｊｘ金属株式会社 | Lithium-ion battery scrap processing method |
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