Aluminum composite material and preparation method thereof

Abstract

Aluminum composites and methods of making the same are disclosed. The aluminum composite materials are useful intermediates in recycling of lithium ion batteries. For example, some materials may be readily leached to obtain one or more valuable metals.

Description

Technical Field

[0001] Disclosed are aluminum composite materials and methods for their preparation. These aluminum composite materials are useful intermediates in the recycling of lithium-ion batteries. For example, some materials can be readily leached to obtain one or more valuable metals. Background Art

[0002] Lithium-ion battery materials are complex mixtures of various elements and compounds. For example, many lithium-ion battery materials contain valuable metals such as lithium, aluminum, copper, nickel, cobalt, and / or manganese. It may be desirable to recover various elements and compounds from lithium-ion battery materials. For example, it may be advantageous to recover lithium, aluminum, copper, nickel, cobalt, and / or manganese. During some battery recycling processes, different process parameters can produce intermediate materials with different compositions and / or properties. Intermediate materials having, for example, favorable compositions, mechanical properties, surface hydrophilicity, and / or porosity can, for example, result in improved processability and / or recovery in subsequent downstream processing steps. Such downstream processing steps can be, for example, part of a lithium-ion battery recycling process and / or a more general metal recycling and / or recovery step.

[0003] Accordingly, there is a need for materials having improved processability and / or metal recovery in subsequent downstream recycling and / or recovery processes. For example, there is a need for intermediate lithium-ion battery recycling materials having, for example, favorable compositions, mechanical properties, surface hydrophilicity, and / or porosity. In addition, there is a need for improved battery recycling methods for producing such improved intermediate materials.

[0004] LOMBARDO, Gabriele et al.: "Chemical Transformations in Li-Ion Battery Electrode Materials by Carbothermic Reduction", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, Vol. 7, No. 16 (2019) pp. 13668 - 13679, relates to the effect of pyrolysis on the composition of battery cell materials as a function of treatment time and temperature. The waste of Li-ion batteries was pyrolyzed at 400 °C, 500 °C, 600 °C, and 700 °C in a nitrogen atmosphere for 30, 60, and 90 min. Treatment of a mixture of the cathode and anode of an NMC Li-ion battery at temperatures between 400 °C and 700 °C triggered carbothermal reduction of the cathode active material and obtained Co, Mn, and Ni in lower oxidation states.

[0005] WO 2021 / 201055 A1 discloses a heat treatment method for lithium-containing battery waste. The method includes: flowing an atmospheric gas containing oxygen and at least one selected from the group consisting of nitrogen, carbon dioxide, and water vapor in a heat treatment furnace in which the battery waste is placed; and heating the battery waste while adjusting the oxygen partial pressure in the furnace.

[0006] JP 2020 / 191184 A discloses a method for recovering foil and active material from the positive electrode of a non-aqueous electrolyte secondary battery, which enables prevention of foil embrittlement and thereby enables easy separation and recovery of the foil and the active material. The method includes adding an additive to the positive electrode and heating the positive electrode to which the additive has been added. When the positive electrode is heated, the non-aqueous electrolyte and the binder are thermally decomposed to generate HF and carbon oxides, and before the HF and carbon oxides react with Al contained in the foil, the HF and carbon oxides react with the additive added to the positive electrode, thereby preventing foil embrittlement. Summary of the Invention

[0007] Disclosed herein is an aluminum composite material comprising 1 wt% to 80 wt% of aluminum, 1 wt% to 20 wt% of manganese, 1 wt% to 20 wt% of cobalt, and 2 wt% to 50 wt% of nickel; wherein each wt% is based on the total weight of the aluminum composite material, and the wt% of aluminum plus the wt% of manganese plus the wt% of cobalt plus the wt% of nickel is less than or equal to 100%. The aluminum composite material has an average puncture force in the range of 0.1 N to 1.5 N; wherein the average puncture force is determined by measuring the puncture resistance according to European Standard EN 14477:2004.

[0008] Also provided is a method for preparing the composite material. The method includes providing an intermediate lithium-ion battery recycling material comprising an aluminum foil and a cathode active material (CAM) at a first temperature; heating the intermediate lithium-ion battery recycling material at a second temperature in the range of 400 °C to 630 °C; and contacting the material with a gas comprising less than 1% by volume of oxygen and comprising at least one selected from the group consisting of combustible gas, reducing gas, carbon dioxide (CO2), and inert gas to obtain the aluminum composite material; optionally, cooling the aluminum composite material to a third temperature in the range of 10 °C to 100 °C.

[0009] Furthermore, provided is the use of the composite material in recovering valuable materials from lithium-ion batteries.

[0010] Brief Description of the Drawings

[0011] Figure 1 Shows an exemplary process for preparing an exemplary aluminum composite material;

[0012] Figure 2 Shows an exemplary downstream process for recovering valuable metals from an exemplary aluminum composite material;

[0013] Figure 3 Illustrates the XRD pattern of an exemplary aluminum composite material;

[0014] Figure 4 Shows the SEM image of an exemplary intermediate lithium-ion battery material, which comprises an aluminum foil coated with a cathode active material on both sides;

[0015] Figure 5 Shows the SEM image of an exemplary aluminum composite material;

[0016] Figure 6 Shows the SEM image and EDX image of an exemplary aluminum composite material.

[0017] Definition

[0018] As used herein, the term "composite material" refers to a material comprising two or more different components.

[0019] As used herein, the term "intermediate lithium-ion battery recycling material" refers to a material that can be obtained by mechanically processing a lithium-ion battery or battery waste and comprises an aluminum foil and a cathode active material (CAM).

[0020] As used herein, a "reducing gas" is a gas capable of reducing metal oxides and / or metal hydroxides. For example, some reducing agents can reduce some metal oxides and / or some metal hydroxides, but not others.

[0021] As used herein, a "flammable gas" is a gas that can burn when exposed to oxygen and a flame.

[0022] As used herein, "hydrocarbon" is a compound composed of carbon and hydrogen. For example, "C1 to C 10 hydrocarbons" refers to one or more hydrocarbons having a total number of carbon atoms in the range of 1 to 10.

[0023] As used herein, "oxy-hydrocarbon" is a compound composed of oxygen, carbon, and optionally hydrogen. Exemplary oxy-hydrocarbons include carbon monoxide, carbon dioxide, ethanol, and acetone. And, "C1 to C 10 oxy-hydrocarbons" refers to one or more oxy-hydrocarbons having a total number of carbon atoms in the range of 1 to 10.

[0024] Unless otherwise specified, all temperatures refer to the temperature of the environment in which the material is located and may or may not be different from the temperature of the material itself.

[0025] Detailed Description of the Drawings

[0026] Figure 1 Illustrates an exemplary process for preparing an exemplary aluminum composite from lithium-ion battery materials. In steps 101 and 102, the lithium-ion battery is discharged and disassembled to obtain lithium-ion battery materials. In step 103, the lithium-ion battery materials are shredded. The shredded lithium-ion battery materials are dried in step 104 to remove solvents, screened in step 105, and then subjected to a pyrolysis process in step 106.

[0027] Figure 2 Illustrates an exemplary downstream process for recovering valuable metals from an exemplary composite material. After pyrolysis in step 201, the aluminum composite is leached in an acid solution in step 202, and various impurities are removed in step 203. Subsequently, nickel and / or cobalt are extracted in step 204, and lithium is recovered in step 205.

[0028] Figure 3 Illustrates the XRD pattern (upper curve) of an exemplary aluminum composite. The lines in the bottom region indicate the expected positions of the diffraction lines of LiAlO2.

[0029] Figure 4 Shows the SEM image of an exemplary intermediate lithium-ion battery material 500, which comprises an aluminum foil 510 coated with a cathode active material 520. The intermediate lithium-ion battery material 500 can be used in the method disclosed herein to produce an aluminum composite.

[0030] Figure 5 Shows the origin from Figure 4 the SEM image of the exemplary aluminum composite 600 of the intermediate lithium-ion battery material 500 disclosed herein. The porous weathered structure of the central layer 610 derived from the aluminum foil 510 is clearly visible. Adjacent to the central layer 610, there is a layer 620 derived from Figure 4 the cathode active material 520.

[0031] Figure 6 Shows Figure 5 the SEM image (upper) and the corresponding EDX image (lower) of the aluminum composite 600 at a higher resolution. Detailed Description of the Embodiments

[0032] Aluminum composite material

[0033] This disclosure provides an aluminum composite material comprising 1 wt% to 80 wt% aluminum, 1 wt% to 20 wt% manganese, 1 wt% to 20 wt% cobalt, and 0 wt% to 50 wt% nickel; where each wt% is based on the total weight of the aluminum composite material, and the wt% of aluminum plus the wt% of manganese plus the wt% of cobalt plus the wt% of nickel is less than or equal to 100%.

[0034] In some embodiments, the aluminum composite material comprises 1 wt% to 60 wt% aluminum based on the total weight of the aluminum composite material.

[0035] In some embodiments, the aluminum composite material comprises 0 to 45 wt%, such as 2 to 35 wt%, such as 11 to 26 wt% nickel based on the total weight of the aluminum composite material.

[0036] In some embodiments, the aluminum composite material further comprises lithium and oxygen.

[0037] The aluminum composite material has an average puncture force in the range of 0.1 N to 1.5 N; where the average puncture force is determined by measuring the puncture resistance according to European standard EN 14477:2004.

[0038] The aluminum composite material has beneficial properties for improving one or more downstream processes, such as leaching. For example, at least some of the aluminum in the aluminum composite material is present in the form of the formed oxide, thereby reducing the amount of hydrogen gas (H2) released during subsequent leaching steps.

[0039] Also, embrittlement of the aluminum composite material can, for example, produce smaller particles that have a more beneficial surface area to volume ratio, thereby facilitating dissolution during acid leaching. In addition, the smaller particle size can facilitate subsequent transport steps, such as conveying.

[0040] In some embodiments, the aluminum composite material has a hydrophilic surface; where surface hydrophilicity is determined by sessile drop static water contact angle. In some embodiments, the aluminum composite material has a sessile drop static water contact angle in the range of 1° to 30°.

[0041] In some embodiments, the aluminum composite material has by using Cu K αX-ray diffraction pattern determined by radiated powder X-ray diffraction (P-XRD), the X-ray diffraction pattern including a reflection with an intensity normalized to 100 at a 2θ diffraction angle in the range of 21.7 to 22.8; a reflection with an intensity in the range of 55 to 75 at a 2θ diffraction angle in the range of 32.8 to 33.9; a reflection with an intensity in the range of 65 to 85 at a 2θ diffraction angle in the range of 34.2 to 35.2; a reflection with an intensity in the range of 34 to 54 at a 2θ diffraction angle in the range of 60.8 to 61.9; and a reflection with an intensity in the range of 12 to 32 at a 2θ diffraction angle in the range of 27.7 to 28.8.

[0042] In some embodiments, the aluminum composite material has a porosity in the range of 5% to 80%; wherein the porosity is determined by scanning electron microscopy as described below. In some embodiments, the aluminum composite material has a porosity in the range of 10% to 60%; in some embodiments, the aluminum composite material has a porosity in the range of 15% to 40%.

[0043] In some embodiments, the aluminum composite material is prepared according to the method disclosed herein.

[0044] Method for preparing aluminum composite material

[0045] This disclosure also provides a method for preparing an aluminum composite material. The method includes:

[0046] a) Providing an intermediate lithium-ion battery recycling material at a first temperature, the material comprising aluminum foil and cathode active material (CAM) and having an average particle size (D 50 ) in the range of 1 μm to 500 μm measured by laser scattering as described below;

[0047] b) Heating the intermediate lithium-ion battery recycling material at a second temperature in the range of 400 °C to 630 °C;

[0048] c) Contacting the intermediate lithium-ion battery recycling material with a gas comprising less than 1% by volume of oxygen and comprising at least one selected from combustible gas, reducing gas, carbon dioxide (CO2), and inert gas to obtain the aluminum composite material;

[0049] d) Optionally, subsequently cooling the aluminum composite material to a third temperature in the range of 10 °C to 100 °C.

[0050] In some embodiments of the method, in the heating step, the intermediate lithium-ion battery recycling material further comprises at least one organic material selected from polymer binders, conductive carbon, organic carbonates, and combinations thereof, and the reducing gas is in-situ generated by thermal decomposition of the at least one organic material.

[0051] In some embodiments of the method, the organic material includes at least one selected from the following: polyvinylidene fluoride, polyethylene, polypropylene, ethylene methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, and combinations thereof.

[0052] In some embodiments of the method, the reducing gas comprises: 5 vol% to 70 vol% of C1 to C 10 hydrocarbons, 5 vol% to 45 vol% of carbon dioxide (CO2), 0.1 vol% to 10 vol% of carbon monoxide (CO), and 1 vol% to 15 vol% of H2; where each vol% is based on the total volume of the reducing gas, and the vol% of C1 to C 10 hydrocarbons plus the vol% of CO2 plus the vol% of carbon monoxide (CO) plus the vol% of H2 is less than or equal to 100%.

[0053] In some embodiments, the reducing gas comprises at least one gas selected from argon (Ar), nitrogen (N2), carbon dioxide (CO2), helium (He), and mixtures thereof, and at least one gas selected from the group consisting of hydrocarbons, hydrogen (H2), carbon monoxide (CO), and mixtures thereof.

[0054] In some embodiments of the method, the provided intermediate lithium-ion battery recycling material comprising aluminum foil and cathode active material is obtained by a method including the following steps: shredding the battery material and drying the shredded battery material.

[0055] In some embodiments of the method, the range of the first temperature is -10°C to 50°C. In some embodiments of the method, the range of the first temperature is 0°C to 35°C. In some embodiments, the first temperature is the ambient temperature.

[0056] In some embodiments of the method, the heating step includes dwelling at one or more intermediate temperatures in the range from a first temperature to a second temperature. In some embodiments of the method, the heating step includes dwelling at two or more intermediate temperatures in the range from a first temperature to a second temperature. In some embodiments of the method, the heating step includes dwelling at one or more intermediate temperatures in the range from a first temperature to a second temperature; wherein each dwelling time ranges from 5 minutes to 3 hours. In some embodiments of the method, the heating step includes dwelling at one or more intermediate temperatures in the range from a first temperature to a second temperature; wherein each dwelling time ranges from 5 minutes to 2 hours. In some embodiments of the method, the heating step includes dwelling at one or more intermediate temperatures in the range from a first temperature to a second temperature; wherein each dwelling time ranges from 5 minutes to 1 hour. In some embodiments of the method, the heating step includes dwelling at one or more intermediate temperatures in the range from a first temperature to a second temperature; wherein each dwelling time ranges from 5 minutes to 30 minutes.

[0057] In some embodiments of the method, the heating step includes a temperature ramp from the first temperature to the second temperature over a period of 10 minutes to 2 hours. In some embodiments of the method, the heating step includes a temperature ramp from the first temperature to the second temperature over a period of 10 minutes to 1 hour. In some embodiments of the method, the heating step includes a temperature ramp from the first temperature to the second temperature over a period of 10 minutes to 30 minutes.

[0058] In some embodiments, the temperature ramp has an average rate of temperature increase of at least 1 K / minute. In some embodiments, the temperature ramp has an average rate of temperature increase of at least 5 K / minute. In some embodiments, the temperature ramp has an average rate of temperature increase of at least 10 K / minute. In some embodiments, the temperature ramp has an average rate of temperature increase of at least 15 K / minute. In some embodiments, the temperature ramp has an average rate of temperature increase of at least 20 K / minute. In some embodiments, the temperature ramp has an average rate of temperature increase of at least 25 K / minute. In some embodiments, the temperature ramp has an average rate of temperature increase in the range from 1 K / minute to 100 K / minute. In some embodiments, the temperature ramp has an average rate of temperature increase in the range from 10 K / minute to 50 K / minute.

[0059] In some embodiments of the method, the second temperature ranges from 400 °C to 630 °C. In some embodiments of the method, the second temperature ranges from 450 °C to 630 °C. In some embodiments of the method, the second temperature ranges from 500 °C to 630 °C.

[0060] In some embodiments, during any heating step, the material does not at least partially transform from a solid state to a liquid state. In some embodiments, during all heating steps, at least 95 wt% of the material remains solid (based on the total weight of the material). In some embodiments, during all heating steps, at least 90 wt% of the material remains solid (based on the total weight of the material). In some embodiments, during all heating steps, at least 80 wt% of the material remains solid (based on the total weight of the material). In some embodiments, during all heating steps, at least 50 wt% of the material remains solid (based on the total weight of the material). In some embodiments, during any heating step, the material does not completely transform from a solid state to a liquid state.

[0061] In some embodiments, the method further includes dwelling for a period of time ranging from 0 minutes to 2 hours at a second temperature. In some embodiments, the method further includes dwelling for a period of time ranging from 1 minute to 2 hours at a second temperature. In some embodiments, the method further includes dwelling for a period of time ranging from 10 minutes to 2 hours at a second temperature. In some embodiments, the method further includes dwelling for a period of time ranging from 10 minutes to 1 hour at a second temperature.

[0062] In some embodiments, a method for preparing an aluminum composite material includes: providing an intermediate lithium-ion battery recycling material comprising an aluminum foil and a cathode active material at a first temperature ranging from -10 °C to 50 °C; heating the intermediate lithium-ion battery recycling material at a second temperature ranging from 480 °C to 630 °C; wherein the heating step includes a temperature ramp from the ambient first temperature to the second temperature over a period of time ranging from 10 minutes to 1 hour; dwelling at the second temperature for a time ranging from 0 minutes to 1 hour; contacting the intermediate lithium-ion battery recycling material with a gas comprising less than 1 vol% oxygen and comprising at least one selected from combustible gases, reducing gases, CO2, inert gases, and combinations thereof to obtain the aluminum composite material; and optionally, cooling the aluminum composite material to a third temperature ranging from 50 °C to 70 °C.

[0063] In some embodiments, a method for preparing an aluminum composite material includes: providing an intermediate lithium-ion battery recycling material comprising an aluminum foil and a cathode active material at a first ambient temperature; heating the intermediate lithium-ion battery recycling material at a second temperature in the range of 480 °C to 580 °C; wherein the heating step includes a temperature ramp from the ambient first temperature to the second temperature over a period in the range of 10 minutes to 1 hour; holding at the second temperature for a time in the range of 0 minutes to 1 hour, contacting the intermediate lithium-ion battery recycling material with a gas comprising less than 1 vol.-% oxygen and comprising at least one selected from combustible gases, reducing gases, CO2, inert gases, and combinations thereof, to obtain the aluminum composite material; and, optionally, cooling the aluminum composite material to a third temperature in the range of 50 °C to 70 °C.

[0064] In some embodiments, the aluminum composite material is characterized by an X-ray diffraction pattern substantially as Figure 3 shown therein.

[0065] Intermediate lithium-ion battery recycling material

[0066] The intermediate lithium-ion battery recycling material of the present disclosure comprises an aluminum foil and a cathode active material (CAM) adhered to at least one of the surfaces of the aluminum foil. In some embodiments, the CAM is adhered to both surfaces of the aluminum foil.

[0067] A lithium-ion battery can be disassembled, stamped, milled (e.g., in a hammer mill, a rotary mill), and / or shredded (e.g., in an industrial shredder). The active materials of the battery electrodes can be obtained by such mechanical processing. Lightweight fractions (such as the housing parts made of organic plastics and aluminum foil or copper foil) can be removed, for example, by forced air flow, air separation, or classification or sieving.

[0068] Battery waste can originate from, for example, spent batteries or production waste such as defective materials. In some embodiments, the material is obtained from mechanically treated battery waste, for example, from battery waste treated in a hammer mill, a rotary mill, or an industrial shredder. Such a material can have an average particle size (D50) in the range of 1 μm to 1 cm, such as 1 μm to 500 μm, and further, for example, 3 μm to 250 μm, measured by sieve analysis according to DIN 66165. The material can have an average particle size (D50) in the range of 1 μm to 1 cm, such as 1 μm to 500 μm, and further, for example, 3 μm to 250 μm, measured by laser scattering as described hereinafter.

[0069] A relatively large portion of the battery waste (such as the casing, wiring, and electrode carrier film) can be mechanically separated so that the corresponding materials can be excluded from the battery materials used in the disclosed method. In some embodiments, the separation is accomplished by manual or automatic sorting. For example, magnetic parts can be separated via a vortex separator by magnetic separation of non-magnetic metals. Other techniques can include jigs and air tables.

[0070] The mechanically treated battery waste can be subjected to solvent treatment to dissolve and separate the polymer binder used to bond the transition metal oxide to the current collector film or, for example, to bond graphite to the current collector film. Examples of suitable solvents include, but are not limited to, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, and dimethyl sulfoxide, in pure form, as a mixture of at least two of the foregoing, or as a mixture with 1% to 99% by weight of water (based on the total weight of the mixture).

[0071] In some embodiments, the intermediate lithium-ion battery recycling material contains nickel, cobalt, manganese, copper, aluminum, iron, phosphorus, or a combination thereof.

[0072] In some embodiments, the intermediate lithium-ion battery recycling material has a weight ratio of lithium to the total weight of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 10. In some embodiments, the intermediate lithium-ion battery recycling material has a weight ratio of lithium to the total weight of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 5. In some embodiments, the intermediate lithium-ion battery recycling material has a weight ratio of lithium to the total weight of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 2. In some embodiments, the intermediate lithium-ion battery recycling material has a weight ratio of lithium to the total weight of nickel, cobalt, manganese, copper, aluminum, iron, and phosphorus in the range of 0.01 to 1.

[0073] In some embodiments, the intermediate lithium-ion battery recycling material exhibits a particle size distribution having a D(10) value in the range of 2 to 6 μm (e.g., 4 to 5 μm), a D(50) value in the range of 10 to 30 μm, and a D(90) value in the range of 150 to 250 μm as determined by laser scattering as described hereinafter. In some embodiments, the intermediate lithium-ion battery recycling material has a D(10) value in the range of 4 to 4.5 μm, a D(50) value in the range of 20 to 25 μm, and a D(90) value in the range of 200 to 210 μm. In certain embodiments, the intermediate lithium-ion battery recycling material has a D(10) value of 4.2 μm, a D(50) value of 22.4 μm, and a D(90) value of 203 μm. In other embodiments, the intermediate lithium-ion battery recycling material has a D(10) value in the range of 4 to 4.5 μm, a D(50) value in the range of 12 to 16 μm, and a D(90) value in the range of 140 to 170 μm. In certain embodiments, the intermediate lithium-ion battery recycling material has a D(10) value of 4.2 μm, a D(50) value of 14.1 μm, and a D(90) value of 158 μm.

[0074] For example, the particle size distribution can be measured by: dispersing a sample of the intermediate lithium-ion battery recycling material in water containing a non-ionic surfactant and measuring the dispersion in a laser diffraction particle size analyzer (e.g., 3000, Malvern Panalytical GmbH, Kassel 34123, Germany) coupled to an automatic dispersion unit (Hydro MV, Malvern Panalytical GmbH, Kassel 34123, Germany). In a specific example, the sample is dispersed in 120 ml of water containing 1 - 2 ml of polyethylene glycol ether (0.5 wt% XL 80 solution, BASF SE), stirred at 3500 rpm and sonicated using ultrasound for 2 min.

[0075] In some embodiments of the method, the provided intermediate lithium-ion battery recycling material comprises aluminum foil and cathode active material and is obtained by a method comprising the steps of: shredding the battery material and drying the shredded battery material.

[0076] In some embodiments, the method for recycling lithium-ion battery materials comprises mechanically pulverizing at least one selected from lithium-ion batteries, lithium-ion battery waste, lithium-ion battery production scrap, lithium-ion battery cell production scrap, lithium-ion cathode active materials, and combinations thereof.

[0077] In some embodiments, the intermediate lithium-ion battery recycling material comprises 1 wt% to 90 wt% of aluminum in the form of aluminum foil in a zero oxidation state and 1 wt% to 90 wt% of a cathode active material; where each wt% is based on the total weight of the intermediate lithium-ion battery recycling material. In some embodiments, the intermediate lithium-ion battery recycling material comprises 1 wt% to 75 wt% of aluminum in the form of aluminum foil in a zero oxidation state and 1 wt% to 75 wt% of a cathode active material; where each wt% is based on the total weight of the intermediate lithium-ion battery recycling material. In some embodiments, the intermediate lithium-ion battery recycling material comprises 10 wt% to 75 wt% of aluminum in the form of aluminum foil in a zero oxidation state and 10 wt% to 75 wt% of a cathode active material; where each wt% is based on the total weight of the intermediate lithium-ion battery recycling material. In some embodiments, the intermediate lithium-ion battery recycling material comprises 1 wt% to 5 wt% of aluminum in the form of aluminum foil in a zero oxidation state and 50 wt% to 95 wt% of a cathode active material; where each wt% is based on the total weight of the intermediate lithium-ion battery recycling material.

[0078] Cathode active material

[0079] The intermediate lithium-ion battery recycling material used in the methods of the present disclosure comprises a cathode active material (CAM). In some embodiments of the method, the cathode active material corresponds to the formula Li p M q M’ r O s . In some embodiments, M comprises one or more metals selected from nickel, manganese, and cobalt, M’ comprises one or more metals selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Fe, V, Mo, and W; p ranges from 1 to 1.4; q ranges from 0.6 to 2; r ranges from 0 to 1; s ranges from 2 to 4.

[0080] In some embodiments, the cathode active material comprises a lithium nickel cobalt manganese oxide having the formula Li (1+x) (Ni a Co b Mn c M’ d ) (1-x) O2, where: M’ is selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Mo, V, and Fe; 0 ≤ x ≤ 0.2; 0.1 ≤ a ≤ 0.95, 0 ≤ b ≤ 0.9, or 0.05 < b ≤ 0.5; 0 ≤ c ≤ 0.6; 0 ≤ d ≤ 0.1; and a + b + c + d = 1.

[0081] In some embodiments, the cathode active material comprises a lithium [Ni h Coi Al j O 2+t Lithiated nickel-cobalt-aluminum oxide, wherein: h ranges from 0.8 to 0.95; i ranges from 0.1 to 0.3; j ranges from 0.01 to 0.10; and t ranges from 0 to 0.4.

[0082] In some embodiments, the cathode active material comprises a lithiated manganese oxide having the formula Li (1+x) Mn 2-x-y-z M y M’ z O4, wherein: x ranges from 0 to 0.2; y + z ranges from 0 to 0.1; and M’ is selected from Al, Mg, Fe, Ti, V, Zr, and Zn.

[0083] In some embodiments, the cathode active material comprises a compound of the formula xLi (1+1 / 3) M (2 / 3) O 2· yLiMO2·zLiM’O2, wherein M comprises at least one metal of Mn, Ni, Co in an oxidation state of +4, M’ is at least one transition metal, and 0 < x < 1, 0 < y < 1, 0 < z < 1 and x + y + z = 1.

[0084] In some embodiments, the cathode active material comprises at least one cathode active material selected from: lithiated nickel cobalt manganese oxide, lithiated nickel cobalt aluminum oxide, lithiated manganese oxide, lithium ion battery waste containing cathode active material (such as production waste from the production of cathode active material), and combinations thereof.

[0085] In some embodiments, the cathode active material comprises a lithiated nickel cobalt manganese oxide having the formula Li 1+x (Ni a Co b Mn c M 1 d ) 1-x O2, wherein M 1 is selected from Mg, Ca, Ba, Al, Ti, Zr, Zn, Mo, V, and Fe, 0 ≤ x ≤ 0.2, 0.1 ≤ a ≤ 0.95, 0 ≤ b ≤ 0.9 (such as 0.05 < b ≤ 0.5), 0 ≤ c ≤ 0.6, 0 ≤ d ≤ 0.1, and a + b + c + d = 1. Exemplary lithiated nickel cobalt manganese oxides include Li (1+x) [Ni 0.33 Co 0.33 Mn 0.33 (1-x) O2, Li (1+x) [Ni 0.5 Co 0.2 Mn​0.3 (1-x) O2, Li (1+x) [Ni 0.6 Co 0.2 Mn 0.2 (1-x) O2, Li (1+x) [Ni 0.7 Co 0.2 Mn 0.3 (1-x) O2, Li (1+x) [Ni 0.8 Co 0.1 Mn 0.1 (1-x) O2 (each having x as defined above), and Li[Ni 0.85 Co 0.13 Al 0.02 O2.

[0086] In some embodiments, the cathode active material comprises a lithiated nickel-cobalt-aluminum oxide having the formula Li[Ni h Co i Al j O 2+t where h ranges from 0.8 to 0.95, i ranges from 0.1 to 0.3, j ranges from 0.01 to 0.10, and t ranges from 0 to 0.4.

[0087] In some embodiments, the cathode active material comprises Li x MO2; where x is an integer greater than or equal to 1, and M is selected from metals, transition metals, rare earth metals, and combinations thereof.

[0088] In some embodiments, the cathode active material comprises a lithiated manganese oxide having the formula Li (1+x) Mn 2-x-y-z M y M’ z O4, where: x ranges from 0 to 0.2; y + z ranges from 0 to 0.1; and M’ is selected from Al, Mg, Fe, Ti, V, Zr, and Zn.

[0089] In some embodiments, the cathode active material comprises a compound of the formula xLi (1+1 / 3) M (2 / 3) O2·yLiMO2·zLiM’O2, where M comprises at least one metal of Mn, Ni, Co in an oxidation state of +4, M’ is at least one transition metal, and 0 < x < 1, 0 < y < 1, 0 < z < 1 and x + y + z = 1.

[0090] ​​​​In some embodiments, the cathode active material includes LiCoO2. In some embodiments, the cathode active material includes LiFePO4.

[0091] In some embodiments, the cathode active material is prepared according to the method disclosed in WO 2019 / 011 786A1.

[0092] In some embodiments, the cathode active material is prepared by a method for preparing an electrode active material according to the general formula Li 1+x TM 1-x O2, where TM is a combination of metals including Mn, Co, and Ni and at least one metal M selected from Al, Ti, and W, where at least 60 mol-% of TM is Ni, this percentage being relative to the sum of Ni, Co, and Mn, and x ranges from 0 to 0.2, and the method includes: (a) mixing (A) a mixed oxide or mixed oxyhydroxide of Mn, Co, and Ni, and (B) at least one lithium compound selected from lithium hydroxide, lithium oxide, and lithium carbonate, and (C) an oxide, hydroxide, or oxyhydroxide of Al, Ti, or W, (b) subjecting the mixture to a heat treatment at a temperature in the range of 700 °C to 1000 °C.

[0093] In some embodiments, the cathode active material is prepared by a method in which TM in the electrode active material is a metal combination according to the general formula (I) (Ni a Co b Mn c ) 1-d M d (I), where a ranges from 0.6 to 0.85, b ranges from 0.05 to 0.2, c ranges from 0.05 to 0.2, and d ranges from 0.005 to 0.1, and M is Al, and a + b + c = 1.

[0094] In some embodiments, the cathode active material is prepared by a method in which the mixing in step (a) is carried out in a dry state.

[0095] In some embodiments, the cathode active material is prepared by a method in which step (b) is carried out in a rotary kiln or a roller hearth kiln.

[0096] In some embodiments, the cathode active material is prepared by a method in which (C) is Al2O3.

[0097] In some embodiments, the cathode active material is prepared by a method in which (A) is an oxide of Mn, Co, and Ni.

[0098] In some embodiments, the cathode active material is prepared by a method in which a precursor (A) is obtained by co-precipitating a mixed hydroxide of nickel, cobalt, and manganese, followed by drying and dehydrating in air.

[0099] In some embodiments, the cathode active material has a surface area (BET) in the range of 0.1 m 2 / g to 0.8 m 2 / g as determined according to DIN-ISO 9277:2003-05.

[0100] The method of the present disclosure includes contacting an intermediate lithium-ion battery recycling material with an inert gas and with a reducing gas in-situ generated by thermal decomposition of the intermediate lithium-ion battery recycling material to obtain the composite material.

[0101] In some embodiments, the flow rate of the inert gas is in the range of 100 to 300 Sm 3 / h, for example 150 to 250 Sm 3 / h, for example 200 Sm 3 / h (standard cubic meters per hour).

[0102] In some embodiments, the inert gas includes at least one gas selected from the group consisting of argon (Ar), nitrogen (N2), helium (He), and mixtures thereof.

[0103] In some embodiments, the reducing gas includes at least one gas selected from the group consisting of hydrocarbons, hydrogen (H2), carbon monoxide (CO), and mixtures thereof.

[0104] In some embodiments of the method, the reducing gas comprises: 5 vol% to 70 vol% of C1 to C 10 hydrocarbons, 5 vol% to 95 vol% of carbon dioxide (CO2), 0.1 vol% to 10 vol% of carbon monoxide (CO), and 0.1 vol% to 15 vol% of H2; where each vol% is based on the total volume of the reducing gas, and the vol% of C1 to C 10 hydrocarbons plus the vol% of CO2 plus the vol% of H2 is less than or equal to 100%.

[0105] In some embodiments of the method, the reducing gas comprises: 5 vol% to 70 vol% of C1 to C 10 hydrocarbons, 5 vol% to 45 vol% of C1 to C 10 oxygenated hydrocarbons, and 0.1 vol% to 15 vol% of H2; where each vol% is based on the total volume of the reducing gas, and the vol% of C1 to C 10 hydrocarbons plus the vol% of C1 to C 10The volume % of the oxygenated hydrocarbon plus the volume % of H2 is less than or equal to 100%.

[0106] In some embodiments of the method, the heating step is carried out in a rotary kiln. The rotary kiln is a cylindrical container that is slightly inclined to the horizontal plane and slowly rotates about its longitudinal axis. Process raw materials are fed into the upper end of the cylinder. As the kiln rotates, the material gradually moves downward towards the lower end and may undergo a certain amount of agitation and mixing.

[0107] In some embodiments of the method, the kiln has a length in the range of 12 to 18 m. In some embodiments of the method, the kiln has a length in the range of 15 to 17 m. The kiln length refers to the length of the heating zone of the kiln. Additional elements will make the entire kiln slightly longer. In some embodiments of the method, the inner diameter of the cylindrical tube is in the range of 1.5 m to 2.2 m, such as 1.7 m to 1.9 m.

[0108] In some embodiments of the method, the kiln is filled with intermediate lithium-ion battery recycling materials in an amount equal to 5% to 20% of the total volume of the kiln, such as 7% to 16%, such as 9% to 12%.

[0109] In some embodiments of the method, at least one screw conveyor is used to feed the intermediate lithium-ion battery recycling materials into the kiln.

[0110] In some embodiments of the method, the kiln rotates at 0.5 to 3 rpm. In some embodiments of the method, the kiln rotates at 1.4 to 2.6 rpm. In some embodiments of the method, the kiln rotates at 1.8 to 2.2 rpm.

[0111] In some embodiments of the method, an overpressure is maintained in the kiln during operation to prevent air from entering the kiln.

[0112] In some embodiments of the method, hot gas passes through the kiln in the same direction as the process material (cocurrent). In some embodiments of the method, the intermediate lithium-ion battery recycling materials and an inert gas are fed into the rotary kiln in cocurrent flow. Cocurrent flow ensures that no dust escapes from the upper end of the kiln. Cocurrent flow also ensures that the gases generated during pyrolysis do not reach the inlet section of the rotary kiln and form condensates on the kiln wall.

[0113] In some embodiments of the method, the rotary kiln is heated by external heating elements using electricity. In some embodiments of the method, the kiln comprises a number of heating zones. In some embodiments of the method, each heating zone operates at a temperature in the range of 520 °C to 630 °C. In some embodiments, thermoelectric elements are provided in each heating zone for measuring the temperature in the respective zone. In one embodiment, each heating zone has a length of from 0.5 m to 6 m, such as from 1 m to 4 m, such as from 1.5 m to 3 m.

[0114] In some embodiments of the method, the kiln is connected at its lower end to a material discharge hood and a duct for the exhaust gases. This requires an airtight seal at either end of the kiln. The exhaust contains hydrocarbons. Equipment is installed to remove these hydrocarbons from the gas stream before venting to the atmosphere.

[0115] In some embodiments, the method of the present disclosure involves cooling the obtained composite material to a third temperature in the range of 10 °C to 100 °C, such as 20 °C to 50 °C. In some embodiments, the cooling is carried out in a rotary cooler located at the lower end of the rotary kiln. In some embodiments, the rotary cooler has the same diameter as the rotary kiln and is cooled by a water jacket. In some embodiments of the method, the interior of the rotary cooler is purged with an inert gas (e.g., nitrogen).

[0116] In some embodiments of the method, the composite material leaving the rotary kiln falls into the rotary cooler, while the exhaust gas leaving the rotary kiln is withdrawn without being cooled. This prevents the hydrocarbons present in the exhaust gas from condensing on the composite material.

[0117] As provided herein, different process parameters can produce intermediate materials having different compositions and / or properties. Intermediate materials having, for example, advantageous compositions, mechanical properties, surface hydrophilicity and / or porosity can, for example, result in improved processability and / or recyclability in subsequent downstream processing steps.

[0118] The present disclosure also provides the use of the aluminum composite materials of the present disclosure for recovering valuable materials from lithium-ion batteries (e.g., for recycling materials from intermediate lithium-ion batteries). In some embodiments, the composite material is used as an intermediate for a downstream leaching process.

[0119] For example, the black mass fraction containing the composite material can be leached with an acidic aqueous solution containing, for example, sulfuric acid (H2SO4) to obtain a solution containing one or more valuable metal ions. The solution containing one or more valuable metal ions can be further purified via, for example, solvent exchange, ion exchange, precipitation, extraction and / or electrolysis.

[0120] Without wishing to be bound by theory, it is believed that the composite material has beneficial properties for improving one or more downstream processes, such as leaching. For example, it is believed that at least some of the aluminum in the aluminum composite material exists in the form of the formed oxide, and the amount of hydrogen gas (H2) released during a subsequent leaching step is reduced. This will, for example, improve the safety of the subsequent leaching step.

[0121] Also, it is believed that embrittlement of the aluminum composite material can, for example, produce smaller particles that have a more beneficial surface area to volume ratio, thus facilitating dissolution during acid leaching. In addition, the smaller particle size can facilitate subsequent transport steps, such as conveying.

[0122] In some embodiments, the leaching process involves leaching the composite material to obtain at least one valuable metal selected from nickel, cobalt, manganese, and combinations thereof; wherein the at least one valuable metal obtained has a purity of at least 80% by weight.

[0123] In some embodiments, the leaching process includes contacting the composite material with an acidic aqueous solution having a pH less than 6. In embodiments of the leaching process, the acidic aqueous solution comprises at least one acid selected from hydrochloric acid (HCl), sulfuric acid (H2SO4), methanesulfonic acid, and nitric acid.

[0124] Examples 1 - 37

[0125] The following examples are intended to be illustrative and are not meant to limit the scope of the present disclosure in any way.

[0126] Samples were prepared as follows. First, an intermediate lithium-ion battery recycling material comprising an aluminum foil and a cathode active material was provided at a first temperature. The intermediate lithium-ion battery recycling material had a D(10) of 4.2 μm, a D(50) of 14.1 μm, and a D(90) of 158 μm, and contained 23.7 wt% carbon, 5.9 wt% aluminum, 13.1 wt% copper, 5.9 wt% cobalt, 5.1 wt% manganese, 15.5 wt% nickel, and 3.2 wt% lithium. Second, while an argon gas stream was directed through a rotary kiln, the intermediate lithium-ion battery recycling material was heated in the rotary kiln from the first temperature T 斜升 during a time interval t 开始 by ramping the temperature to a second temperature T 目标 . Third, while an argon gas stream was directed through the rotary kiln, the intermediate lithium-ion battery recycling material was held at the second temperature for a duration t 停留 . Details of each example are provided in Table 1.

[0127] Table 1

[0128]

[0129]

[0130] Elemental analysis

[0131] This section describes the analytical methods for quantitatively determining the composition of the composite materials disclosed herein.

[0132] Metal content

[0133] Elemental analysis is carried out using a combination of acid digestion and alkaline borate fusion digestion and analysis by inductively coupled plasma optical emission spectrometry (ICP-OES) on an inductively coupled plasma optical emission spectrometer (e.g., Agilent 5110 ICP-OES, Agilent Technologies Germany GmbH & Co. KG, Waldbronn 76337, Germany).

[0134] An aliquot (e.g., about 0.2 g) of the sample material is weighed into a volumetric flask and dissolved in 30 ml of HCl with slight heating. After cooling, the insoluble residue is filtered out and incinerated in a Pt crucible above an open flame together with the filter paper. Subsequently, the residue is calcined in a muffle furnace at about 600 °C and then mixed with 1.0 g of a K2CO3-Na2CO3 / Na2B4O7 flux mixture (4:1) and melted above an open flame until a clear melt is obtained. After cooling, the melt cake is dissolved in deionized (DI) water with slight heating and 12 ml of HCl is added. Finally, the solution is added to the initial filtered solution in the volumetric flask and made up to its final volume with DI water. Each sample is prepared in triplicate. Blank samples are prepared in a similar manner.

[0135] The digestion solution is analyzed by using externally calibrated inductively coupled plasma - optical emission spectrometry (ICP-OES). For some samples, the digestion solution can be diluted before analysis, for example, diluted to suit the concentration and calibration range of the corresponding analyte.

[0136] Table 2 shows the results of the elemental analysis of the aluminum composite material obtained in Example 7.

[0137] Table 2

[0138] Element Weight percentage Al 6.0 Co 11.6 Mn 10.7 Ni 34

[0139] Powder X-ray diffraction

[0140] Grind the sample into a fine powder in a mortar. Powder X-ray diffraction was carried out at room temperature using a D8 Series 2 diffractometer with a multi-sample holder from Bruker. Use the K α line of Cu as the X-ray source. The detector is a Lynx-Eye from Bruker. The sample was measured in the reflection mode in the 2θ range between 10° and 80°.

[0141] Figure 3 The XRD pattern of the aluminum composite obtained in Example 7 is shown (above), where the bottom region indicates the expected peak positions of LiAlO2.

[0142] General procedure for fabricating cathode sheets

[0143] Dissolve the PVDF binder ( 5130) in NMP (Merck) to produce a 10 wt% solution. For cathode preparation, the binder solution (3.5 wt%), carbon black (Super C65, 4 wt%) were slurried in NMP. After mixing using a planetary centrifugal mixer (ARE-250, Thinky Corp.; Japan), LiNi which is used as CAM was added 0.6 Co 0.2 Mn 0.2 O2 (92.5 wt%), and the suspension was mixed again to obtain a lump-free slurry. The slurry was coated onto both sides of an aluminum foil with a thickness of 15 μm using an Erichsen automatic coater, and then dried at 120 °C for 15 minutes under ambient pressure, and then dried at 120 °C for 4 hours in vacuo to obtain a coating with a thickness in the range of 60 μm to 90 μm. The loading amount was 8 to 10 mg / cm 2 . All cathodes were dried at 120 °C for 12 hours. Before further use, all electrodes were calendered.

[0144] Scanning electron microscopy

[0145] To elucidate the layered structure, samples of the intermediate lithium-ion battery material used as the starting material and the material obtained in Example 7 were cross-sectioned using an ion beam cutter (ArBlade 5000, Hitachi) and imaged using backscattered electrons (BSE) in a Zeiss Gemini 500 scanning electron microscope (15 kV). In the BSE image, regions of higher density appear brighter (higher concentration / higher atomic number of the element / lower porosity).

[0146] Figure 4 Shows a SEM image of the intermediate lithium-ion battery material 500 used in the example. The intermediate lithium-ion battery material 500 includes an aluminum foil 510 coated with a cathode active material 520 on both surfaces.

[0147] Figure 5 Shows a SEM image of the aluminum composite material 600 obtained in Example 7. The porous weathered structure of the central layer 610 derived from the aluminum foil 510 is clearly visible. Adjacent to the central layer 610, there is a layer 620 of the cathode active material 520 derived from the intermediate lithium-ion battery material 500.

[0148] The porosity of the aluminum composite material is estimated from the SEM image as follows. Assuming that the initial Al foil has a porosity of 0%, ignoring any lateral volume expansion, assuming that Al is completely retained within the layer during heat treatment, and assuming that the bulk Al is quantitatively converted to LiAlO2, the porosity of the specimen after heat treatment can be calculated by the following formula by subtracting the thickness ratio of the layer before and after heat treatment corrected for the different densities of Al in Al and LiAlO2:

[0149]

[0150] By this calculation, the porosity of the aluminum composite material obtained in Example 7 is estimated to be 19.7%.

[0151] Lying-drop static water contact angle

[0152] The lying-drop static water contact angle measurement was carried out using an OCA 50 / DataPhysics instrument with an optical contact angle measurement and profile analysis system. It was observed that the aluminum composite material obtained in Example 7 has a hydrophilic surface with a lying-drop static water contact angle of 14°. In contrast, it was observed that the untreated Al current collector foil coated with a cathode coating on both sides has a hydrophobic surface with a lying-drop static water contact angle of 110°.

[0153] Determination of puncture resistance

[0154] The puncture test resistance was determined using the European standard EN 14477:2004. The data reported here are the average values of 5 measurements. It was observed that the puncture test resistance of the aluminum composite material obtained in Example 7 is 0.8 N. In contrast, the puncture test resistance of the untreated Al current collector foil coated with a cathode coating on both sides is 2.27 N.

[0155] EDXS analysis

[0156] The distributions of C, O, F, P, Al, Ni, Co, and Mn in the cross-sectional sample were analyzed using energy-dispersive X-ray spectroscopy (EDXS) at 15 kV. Based on the element distributions, different phases present in the sample were identified.

[0157] Figure 6 Shows the SEM image (top) and the corresponding EDX image (bottom) of the aluminum composite 600 obtained in Example 7. The cross-section shows that the heat treatment caused significant structural changes in both the aluminum foil 510 and the cathode material 520. The central layer 610 originating from the aluminum foil 510 has a thickness of approximately 50 μm and shows a high porosity. Phase analysis yielded six different phases in the sample. The composition of each phase is shown in Table 3.

[0158] Table 3

[0159]

[0160] The results are given in weight percentages, normalized to a total weight of 100 weight percentages. For elements with Z > 5, the information depth is approximately 2 μm. For elements with Z > 10, the detection limit is approximately 0.1 weight percentage, and for elements with Z ≤ 10, the detection limit is in the range of several percentages. In cases where values are not listed in the table, the concentration is below the detection limit.

Claims

1. An aluminum composite material, which comprises 1 wt.-% to 80 wt.-% of aluminum, 1 wt.-% to 20 wt.-% of manganese, 1 wt.-% to 20 wt.-% of cobalt, and 0 wt.-% to 50 wt.-% of nickel; wherein each wt.-% is based on the total weight of the aluminum composite material, and the sum of the wt.-% of aluminum plus the wt.-% of manganese plus the wt.-% of cobalt plus the wt.-% of nickel is less than or equal to 100%, and the aluminum composite material has an average puncture force in the range of 0.1 N to 1.5 N as determined according to European standard EN 14477:2004.

2. The aluminum composite material according to claim 1, which comprises 11 to 26 wt.-% of nickel based on the total weight of the aluminum composite material.

3. The aluminum composite material according to claim 1 or 2, which further comprises lithium and oxygen.

4. The aluminum composite material according to any one of claims 1 to 3, which has an X-ray diffraction pattern measured by powder X-ray diffraction (P-XRD) using Cu Kα radiation, the X-ray diffraction pattern comprising a reflection with an intensity normalized to 100 at a 2θ diffraction angle in the range of 21.7 to 22.8; a reflection with an intensity in the range of 55 to 75 at a 2θ diffraction angle in the range of 32.8 to 33.9; a reflection with an intensity in the range of 65 to 85 at a 2θ diffraction angle in the range of 34.2 to 35.2; a reflection with an intensity in the range of 34 to 54 at a 2θ diffraction angle in the range of 60.8 to 61.9; and a reflection with an intensity in the range of 12 to 32 at a 2θ diffraction angle in the range of 27.7 to 28.

8.

5. The aluminum composite material according to any one of claims 1 to 4, which has a porosity in the range of 15% to 80% as determined as described in the specification.

6. A method for preparing an aluminum composite material, the method comprising a) providing an intermediate lithium-ion battery recycling material at a first temperature in the range of -10 °C to 50 °C, the material comprising an aluminum foil and a cathode active material (CAM) and having an average particle size (D50) in the range of 1 μm to 500 μm as determined by laser scattering as described in the specification; b) heating the intermediate lithium-ion battery recycling material at a second temperature in the range of 400 °C to 630 °C; c) contacting the intermediate lithium-ion battery recycling material with a gas comprising less than 1% by volume of oxygen and comprising at least one selected from combustible gases, reducing gases, carbon dioxide (CO2) and inert gases to obtain the aluminum composite material; d) optionally, subsequently cooling the aluminum composite material to a third temperature in the range of 10 °C to 100 °C.

7. The method according to claim 6, wherein The heating step b) comprises ramping the temperature from the first temperature to the second temperature over a period of from 10 minutes to 2 hours.

8. The method according to claim 7, wherein The temperature ramp has an average rate of temperature increase of at least 1 K / minute.

9. The method according to any one of claims 6 to 8, further comprising staying at the second temperature for a period ranging from 0 minutes to 2 hours.

10. The method according to any one of claims 6 to 9, wherein The intermediate lithium-ion battery recycling material comprises nickel, cobalt, manganese, copper, aluminum, iron, phosphorus, or a combination thereof.

11. The method according to any one of claims 6 to 10, wherein The intermediate lithium-ion battery recycling material further comprises at least one organic material selected from polymer binders, conductive carbon, organic carbonates, and combinations thereof, and the reducing gas is generated in situ by thermal decomposition of the at least one organic material.

12. The method according to any one of claims 6 to 11, wherein The intermediate lithium-ion battery recycling material exhibits a particle size distribution having a D(10) value in the range of 2 to 6 μm, a D(50) value in the range of 10 to 30 μm, and a D(90) value in the range of 150 to 250 μm as determined by laser scattering as described in the specification.

13. The method according to any one of claims 6 to 12, wherein The intermediate lithium-ion battery recycling material has been obtained by mechanically pulverizing at least one material selected from lithium-ion batteries, lithium-ion battery waste, lithium-ion battery production scrap, lithium-ion cell production scrap, lithium-ion cathode active materials, and combinations thereof and then drying the pulverized material.

14. The method according to any one of claims 6 to 13, wherein The intermediate lithium-ion battery recycling material comprises 1 wt% to 5 wt% of aluminum in the form of aluminum foil in the zero oxidation state and 50 wt% to 95 wt% of cathode active material; where each wt% is based on the total weight of the intermediate lithium-ion battery recycling material.

15. Use of the aluminum composite material according to any one of claims 1 to 5 for recovering valuable materials from a lithium-ion battery.

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