Patent Application
20240413419
This patent application claims priority to Korean Patent Applications No. 10-2023-0072764 filed on Jun. 7, 2023, the entire disclosure of which is incorporated by reference herein.
Embodiments of the present disclosure relate to a method of recovering a transition metal from a lithium secondary battery. More particularly, the embodiments relate to a method of recovering a transition metal from a cathode active material of a lithium secondary battery.
Secondary batterie are widely employed as a power source for mobile electronic devices including camcorders, mobile phones, laptop computers, and also for electric and hybrid vehicles. Lithium secondary batteries are already widely applied and are also actively developed due to their high operational voltage and energy density per unit weight, high charging rate, and compact dimension characteristics.
A lithium metal oxide is typically used as the cathode active material for the lithium secondary battery. The lithium metal oxide may further contain a valuable metal such as iron, nickel, cobalt, manganese, etc.
As the above-mentioned high-cost valuable metals are used for the cathode active material, at least 20% of the production cost of the secondary battery is required for the manufacturing of the cathode active material. Additionally, as environment protection issues have recently been highlighted regarding the potential pollution caused by waste secondary batteries, various recycling methods of the secondary batteries and in particular of the cathode active material are being actively researched.
According to an embodiment of the present disclosure, there is provided a method of recovering a target material including a transition metal from a lithium secondary battery exhibiting generally an improved balance of efficiency and purity over existing methods.
According to another embodiment of the present disclosure, there is provided a method of recovering a transition metal from a lithium secondary battery exhibiting generally improved efficiency and purity.
According to an embodiment, a method of recovering a transition metal from a lithium secondary battery is provided, the method including adding an acidic solution to a recovery target material containing a transition metal to form a leachate. A basic compound may then be added to the leachate, for example, in an amount of 0.5 wt % to 1.9 wt % based on a total weight of the leachate to form a first transition metal solution. A fluorine compound may also be added to the first transition metal solution to form a second transition metal solution.
In some embodiments, in the formation of the second transition metal solution, calcium contained in the first transition metal solution may be precipitated by the fluorine compound.
In some embodiments, the transition metal may include at least one of nickel, cobalt, and manganese.
In some embodiments, cobalt and nickel may be sequentially extracted from the second transition metal solution.
In some embodiments, manganese may be extracted from the second transition metal solution.
In some embodiments, in the extraction of manganese, calcium remaining in the second transition metal solution may be removed.
In some embodiments, the recovery target material may include a precipitated product containing the reduced transition metal.
In some embodiments, the acidic solution may include sulfuric acid.
In some embodiments, a pH of the leachate may be in a range from 1 to 2.
In some embodiments, the basic compound may include at least one of sodium hydroxide, lithium hydroxide and potassium hydroxide.
In some embodiments, a pH of the first transition metal solution may be in a range from 3 to 4.5.
In some embodiments, the fluorine compound may include at least one of sodium fluoride, magnesium fluoride and potassium fluoride.
In some embodiments, the first transition metal solution may contain calcium and aluminum.
In some embodiments, the fluorine compound may be added to satisfy the following Formula 1.
Wherein in Formula 1, FL # is the number of moles of fluorine contained in the fluorine compound, CA # is the number of moles of calcium contained in the first transition metal solution, and AL # is the number of moles of aluminum contained in the first transition metal solution.
In some embodiments, a pH of the second transition metal solution may be greater than 5, and less than or equal to 7.
In some embodiments, the formation of the first transition metal solution and the formation of the second transition metal solution may be performed at a temperature ranging from 50° C. to 90° C.
According to the above-described embodiments, impurities (e.g., aluminum, iron, calcium, etc.) may be removed through a selective precipitation of metal ions due to a difference in solubility, and transition metals (e.g., nickel, cobalt, manganese, etc.) may be recovered with high purity.
For example, a basic compound may be added to form a pH section in which nickel, cobalt and manganese are not precipitated, so that aluminum and iron may be removed while reducing a loss of nickel, cobalt and manganese.
In some embodiments, calcium may be removed by adding a predetermined amount of a fluorine compound, and the loss of nickel, cobalt and manganese may be reduced even in a pH section in which nickel, cobalt and manganese are precipitated.
Thus, the basic compound and the fluorine compound serving as precipitating agents may each be added for each pH section, and a transition metal recovery efficiency of a lithium secondary battery may be improved.
These and other features and advantages of the embodiments of the present disclosure may become better understood from the following detailed description in conjunction with the drawings.
According to embodiments of the present disclosure, a method for recovering a transition metal from a lithium secondary battery including sequential additions of a basic compound and a fluorine compound.
Hereinafter, embodiments of the present disclosure will be described in detail with reference to embodiments and examples, and the accompanying drawings. However, those skilled in the art will appreciate that such embodiments and drawings are provided to further understand the spirit of the present disclosure and do not limit subject matters to be protected as disclosed in the detailed description and appended claims.
Referring to
In some embodiments, the transition metal may include at least one selected from the group consisting of nickel, cobalt and manganese. For example, the transition metal may include nickel and cobalt.
In some embodiments, the recovery target material may include a precipitated product containing a reduced transition metal. For example, a cathode active material may be obtained by crushing a waste lithium secondary battery or a used lithium secondary battery, and the lithium may be removed from the cathode active material to obtain the precipitated product containing the reduced transition metal.
The lithium secondary battery may be of any suitable type, including, for example, a typical type comprising an electrode assembly including a cathode, an anode and a separator interposed between the cathode and the anode. The cathode and the anode may include cathode and active material layers coated on cathode and anode current collectors, respectively.
For example, the cathode active material included in the cathode active material layer may include an oxide containing lithium and a transition metal.
In some embodiments, the cathode active material may include a compound having a structure represented by Chemical Formula 1 below.
LixNi1−yMyO2+z Chemical Formula 1
In Chemical Formula 1, 0.9≤x≤1.1, 0≤y≤0.7, −0.1≤z≤0.1, and M may include at least one selected from Na, Mg, Ca, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Fe, Cu, Ag, Zn, B, Al, Ga, C, Si, Sn and Zr.
In some embodiments, the cathode active material may include an NCM-based lithium oxide containing nickel, cobalt and manganese.
For example, a waste cathode may be recovered by separating the cathode from the used lithium secondary battery. The waste cathode may include the cathode current collector (e.g., aluminum (Al)) and the cathode active material layer as described above, and the cathode active material layer may include a conductive material and a binder together with the cathode active material as described above.
The conductive material may include, e.g., a carbon-based material such as graphite, carbon black, graphene, carbon nanotube, etc. The binder may include a resin material, e.g., vinylidenefluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, etc.
For example, the waste cathode may be pulverized to collect the cathode active material. The cathode active material may include a powder of the lithium-transition metal oxide, e.g., a powder of the NCM-based lithium oxide (e.g., Li(NCM)O2.
In some embodiments, the retrieved cathode active material may include some components derived from the cathode current collector, the binder or the conductive material. In some embodiments, the retrieved cathode active material may substantially consist of cathode active material particles such as NCM-based lithium oxide.
In some embodiments, the cathode active material may be heat-treated to remove or reduce the conductive material and binder included in the cathode active material, thereby obtaining lithium transition metal oxide particles with high purity.
A temperature of the heat treatment temperature may be, e.g., in a range from about 100° C. to 500° C., or from about 350° C. to 450° C. Within the above range, the conductive material and the binder may be substantially removed, thereby preventing decomposition and damage to the lithium transition metal oxide particles.
In some embodiments, lithium may be removed from the cathode active material in the form of lithium hydroxide, and the precipitate product containing the reduced transition metal may be obtained.
For example, the cathode active material may be reduced using a hydrogen gas that is a reducing gas to generate a preliminary lithium precursor containing lithium hydroxide (LiOH), lithium oxide (e.g., Li2O), etc., and a transition metal or a transition metal oxide. For example, Ni, Co, Mn, NiO, CoO or MnO may be produced together with the preliminary lithium precursor through the reductive reaction.
The reductive reaction may be performed at a temperature from about 400° C. to 700° C., or from about 450° C. to 550° C. Within the above reaction temperature range, the reductive reaction may be promoted without causing re-agglomeration or recombination of the preliminary lithium precursor and the transition metal/transition metal oxide.
For example, when the mixture of the preliminary lithium precursor, and the transition metal or the transition metal oxide is washed with water containing a calcium compound, the preliminary lithium precursor in the form of lithium hydroxide (LiOH) may be substantially dissolved in water. For example, the preliminary lithium precursor in the form of lithium oxide and lithium carbonate may be partially converted to lithium hydroxide and dissolved in water by the washing treatment.
In an embodiment, the calcium compound may include at least one of calcium hydroxide and calcium oxide. For example, the calcium compound may be added during the washing process, so that lithium carbonate and lithium fluoride may be converted into lithium hydroxide to be included in a lithium aqueous solution containing the preliminary lithium precursor, and calcium carbonate and calcium fluoride having low solubility may be precipitated.
In an embodiment, the lithium aqueous solution and a precipitated product containing the reduced transition metal may be separately obtained through a solid-liquid separation process after the washing treatment. For example, the precipitated product containing the reduced transition metal may include nickel, cobalt and manganese produced by the reductive reaction, and may include calcium carbonate and calcium fluoride.
An acidic solution may be added to the recovery target material containing the transition metal prepared according to the above-described embodiments to form a leachate. For example, the acidic solution may be added to the precipitated product containing the reduced transition metal and solid-liquid separated to obtain the leachate and a leach residue.
In some embodiments, the leachate may include nickel, cobalt, manganese, aluminum, iron and calcium. For example, a total concentration of nickel, cobalt and manganese in the leachate may be in a range from 100 g/L to 120 g/L.
In some embodiments, the acidic solution may include at least one of sulfuric acid, hydrochloric acid, nitric acid, oxalic acid and citric acid. In some embodiments, the acidic solution may include sulfuric acid. For example, when using the types of the acidic solution, the transition metal may be easily leached.
In some embodiments, a pH of the leachate may be in a range from 1 to 2. Within the above range, the transition metal may be sufficiently leached while an amount of a basic compound used in a formation of a first transition metal solution may be reduced.
In some embodiments, the leaching may be performed at a temperature of 50° C. to 90° C. and a rotation rate of 100 rpm to 500 rpm for 4 to 8 hours.
For example, the temperature may be in a range from 60° C. to 85° C., or from 70° C. to 80° C. The rotation rate may be in a range from 150 rpm to 400 rpm, or from 200 rpm to 300 rpm, and the leaching period may be in a range from 5 hours to 7 hours, or from 5.5 hours to 6.5 hours. Performing leaching within the above parameter ranges, the leaching of the transition metals may be further easily implemented.
For example, in an operation S20, the basic compound may be added to the leachate in an amount of 0.5 weight percent (wt %) to 1.9 wt % based on a total weight of the leachate to form the first transition metal solution.
In some embodiments, the basic compound may include at least one selected from sodium hydroxide, lithium hydroxide and potassium hydroxide. In some embodiments, the basic compound may include sodium hydroxide.
For example, the above-mentioned types of the basic compound may at least partially precipitate iron and aluminum contained in the leachate in the form of a hydroxide, e.g., Fe(OH)3 and Al(OH)3. Thereafter, the first transition metal solution from which iron and aluminum are removed may be obtained by a solid-liquid separation from the leachate.
In some embodiments, the added amount of the basic compound may be in a range from 0.5 wt % to 1.9 wt %, from 0.6 wt % to 1.8 wt %, from 0.6 wt % to 1.7 wt %, from 0.7 wt % to 1.5 wt %, from 0.5 wt % to 1.5 wt %, from 0.5 wt % to 1.4 wt %, from 0.6 wt % to 1.3 wt %, from 0.7 wt % to 1 wt %, or from 0.5 wt % to 1 wt % based on the total weight of the leachate.
For example, if the added amount of the basic compound is less than 0.5 wt % based on the total weight of the leachate, a small amount of iron and aluminum may be precipitated in the form of the hydroxide and may not be sufficiently removed. If the added amount of the basic compound exceeds 1.9 wt % based on the total weight of the leachate, the pH may be increased to cause a loss of nickel, cobalt and manganese.
Referring to
In some embodiments, the pH of the first transition metal solution may be in a range from 3.0 to 4.5. In some embodiments, the pH of the first transition metal solution may be in a range from 3.0 to 4.3, from 3.0 to 4.0, from 3.5 to 4.0, or from 3.8 to 4.0. Within the above range, the first transition metal solution in which iron and aluminum are sufficiently removed while suppressing the loss of nickel, cobalt and manganese may be obtained.
In an embodiment, the basic compound may be added in the form of an aqueous solution. For example, a sodium hydroxide aqueous solution may be added to the leachate.
In some embodiments, the first transition metal solution may include calcium and aluminum. For example, after iron and aluminum are removed from the leachate, the first transition metal solution may include nickel, cobalt, manganese, a residual calcium and a residual aluminum.
In some embodiments, a content of aluminum contained in the first transition metal solution may be in a range from 0.08 wt % to 0.21 wt %, from 0.1 wt % to 0.2 wt %, or from 0.15 wt % to 0.18 wt % based on a total weight of the first transition metal solution.
For example, when aluminum is excessively removed from the leachate, the pH of the first transition metal solution may be increased to 6.0 or more. Accordingly, an excessive amount of a colloidal precipitate (Al(OH)3) may be generated, and the solid-liquid separation may not be easily implemented.
Thus, within the above range, the first transition metal solution from which aluminum is sufficiently removed while suppressing the loss of nickel, cobalt, and manganese may be obtained.
In some embodiments, a temperature for forming the first transition metal solution may be in a range from 50° C. to 90° C., from 60° C. to 85° C., or from 70° C. to 80° C. A rate at which the precipitation reaction of iron and aluminum occurs may be decreased at room temperature (25° C.). Thus, an equilibrium state may be rapidly reached within the above temperature range.
In some embodiments, the formation of the first transition metal solution may proceed for 1 hour to 4 hours, for 1.5 hours to 3 hours, or for 2 hours to 3 hours. In the above range, the precipitation reaction for the formation of the iron and aluminum hydroxides (Fe(OH)3 and Al(OH)3) may sufficiently proceed.
For example, in an operation of S30, a fluorine compound may be added to the first transition metal solution to form a second transition metal solution.
In some embodiments, the fluorine compound may include at least one of sodium fluoride, magnesium fluoride and potassium fluoride. In some embodiments, the fluorine compound may include sodium fluoride.
In some embodiments, calcium contained in the first transition metal solution may be precipitated by the fluorine compound.
For example, the above-mentioned type of fluorine compound may at least partially precipitate calcium and the residual aluminum contained in the first transition metal solution in the form of fluorides (e.g., CaF2 and AlFx(OH)3−x). Thereafter, the second transition metal solution in which calcium and the residual aluminum are removed from the first transition metal solution may be obtained through a solid-liquid separation.
In some embodiments, the fluorine compound may be added to satisfy the following Formula 1.
For example, the fluorine compound may be added to satisfy Equation 2 or Equation 3 below.
Wherein in Formula 1 to Formula 3, FL # is the number of moles of fluorine contained in the fluorine compound, CA # is the number of moles of calcium contained in the first transition metal solution, and AL # is the number of moles of aluminum contained in the first transition metal solution.
The fluorine compound may be added to satisfy Formula 1, Formula 2 or Formula 3, and calcium and the residual aluminum may be sufficiently removed while suppressing the loss of nickel, cobalt and manganese. Accordingly, purity of recovered nickel and cobalt may be increased.
In some embodiments, a pH of the second transition metal solution may be greater than 5 and less than or equal to 7. In some embodiments, the pH of the second transition metal solution may be greater than 5 and less than 7, from 5.5 to 7, from 5.5 to 6.5, or from 6.0 to 6.5. In the above range, the second transition metal solution in which calcium and residual aluminum are sufficiently removed while suppressing the loss of nickel, cobalt and manganese may be effectively obtained.
In some embodiments, the second transition metal solution may include nickel, cobalt and manganese. In some embodiments, the second transition metal solution may not include calcium and aluminum, or may include a trace amount of calcium and aluminum.
In some embodiments, a formation temperature of the second transition metal solution may be in a range from 50° C. to 90° C., from 60° C. to 85° C., or from 70° C. to 80° C. A rate of the precipitation reaction of calcium and aluminum which occurs may be reduced. Thus, an equilibrium state may be rapidly reached by increasing the reaction temperature.
In the above temperature range, a rate of the calcium removal may be accelerated while suppressing the loss of nickel, cobalt and manganese. Thus, nickel and cobalt may be efficiently obtained with high purity
In some embodiments, the formation of the second transition metal solution may proceed for 30 minutes to 3 hours, 30 minutes to 2 hours, or 30 minutes to 1 hour. In the above range, a precipitation reaction by which the fluorides of calcium and aluminum (CaF2 and AlFx(OH)3−x) are formed may sufficiently proceed.
In some embodiments, manganese may be extracted from the second transition metal solution.
In some embodiments, the manganese extraction may include removing calcium remaining in the second transition metal solution. For example, the residual calcium remaining in the second transition metal solution obtained through the precipitation reaction and the solid-liquid separation in the S30 operation may be removed.
In some embodiments, when extracting manganese, an extractant may be added to the second transition metal solution.
For example, the extractant may include a phosphoric acid-based extractant. For example, the phosphoric acid-based extractant may include di-2-ethylhexyl phosphoric acid (D2EHPA), 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, tributyl phosphate. For example, the extractant may be added together with sodium hydroxide and sulfuric acid.
Accordingly, a trace amount of the residual calcium contained in the second transition metal solution may be removed in the S40 operation, thereby increasing purity of recovered nickel and cobalt.
In some embodiments, cobalt and nickel may be sequentially extracted from the second transition metal solution (e.g., an operation of S50).
For example, the second transition metal solution may be input into a cobalt extraction process (e.g., an operation of S51), and then further subjected to a nickel extraction process (e.g., an operation of S52). The second transition metal solution may be added to the manganese extraction process (e.g., the operation of S40) as described above before being introduced to the cobalt extraction process.
Accordingly, high purity cobalt and nickel may be extracted from the second transition metal solution. For example, the cobalt extraction and nickel extraction described above may be performed sequentially or continuously.
In some embodiments, an extractant used in the cobalt extraction may include a hypophosphorous acid-based extractant, e.g., bis(2,4,4-trimethylpentyl)phosphinic acid.
In some embodiments, an extractant used in the nickel extraction may include a phosphoric acid-based extractant, a phosphorous acid-based extractant and/or a carboxylic acid-based extractant. For example, di-2-ethylhexyl phosphoric acid (D2EHPA), 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, tributyl phosphate, trioctyl phosphine oxide, alkyl monocarboxylic acid, etc., may be used.
In some embodiments, the extractant used in the cobalt extraction and the nickel extraction may be added together with sodium hydroxide and sulfuric acid. Accordingly, nickel and cobalt may be extracted in the form of nickel sulfate and cobalt sulfate, respectively.
Hereinafter, embodiments of the present disclosure are described in more detail with reference to experimental examples. However, the following examples are only given for illustrating the embodiments and those skilled in the related art will obviously understand that various alterations and modifications are possible within the scope and spirit of the present disclosure. Such alterations and modifications are duly included in the appended claims. Furthermore, the embodiments may be combined to form additional embodiments.
A Li—Ni—Co—Mn oxide cathode active material as a scrap metal was reduced with a hydrogen gas, washed with water while adding calcium hydroxide, and then solid-liquid separated to obtain a precipitated product (an NCM Paste) containing the reduced transition metal.
A 2M sulfuric acid solution was added to the precipitated product and leached for 6 hours at 80° C. and 250 rpm. Thereafter, a leached residue was separated by a centrifugation and two types of leachate (a leachate 1 and a leachate 2) were obtained (the operation of S10).
Sodium hydroxide (50%) aqueous solution was added to the obtained leachates 1 and 2, reacted at 80° C. for 2 hours, and then centrifuged to obtain a first transition metal solution from which precipitates were removed (the operation S20 process).
Sodium fluoride was added to each of the first transition metal solutions obtained from the leachates 1 and 2, reacted at 80° C. for 30 minutes, and then centrifuged to obtain a second transition metal solution from which precipitates were removed (the operation of S30).
Concentrations of metals contained in the leachates 1 and 2 before adding the sodium hydroxide (50%) aqueous solution were measured.
Additionally, pHs of the leachates 1 and 2 were measured using a pH meter.
The measurement results are listed in Table 1 below.
As shown in Table 2 below, an amount of a sodium hydroxide (50%) aqueous solution was changed based on a total weight (150 g) of the leachate 1 to form first transition metal solutions of Examples and Comparative Examples by the method described in the above Preparation Example.
Concentrations of metals contained in the first transition metal solutions of Examples and Comparative Examples and pHs of the first transition metal solution were measured. The measured results are shown in Table 2 below.
Referring to Table 2, the loss of nickel, cobalt and manganese was suppressed without an excessive formation of colloidal precipitates in the first transition metal solutions according to Examples.
However, the first transition metal solution according to Comparative Example 1 had high contents of aluminum and calcium. In the first transition metal solution according to Comparative Example 2, the loss of nickel, cobalt and manganese was increased compared to those in the first transition metal solutions according to Examples.
In the first transition metal solution according to Comparative Example 2, an excessive amount of colloidal precipitates (Al(OH)3) was generated. Accordingly, the solid-liquid separation was not easily implemented.
A first transition metal solution of Reference Example 1 was prepared by adding 1.5 g (1 wt %) of a sodium hydroxide (50%) aqueous solution based on a total weight (150 g) of the leachate 2.
Concentration of metals contained in the first transition metal solution of Reference Example 1 and a pH of the first transition metal solution were measured. The measured results are shown in Table 3 below.
Thereafter, as shown in Table 4 below, an added amount of sodium fluoride to the first transition metal solution of Reference Example 1 obtained from the leachate 2 was changed to form second transition metal solutions of Examples 4 and 5, and Comparative Example 3 by the method described in the above Preparation Example.
Concentration of metals contained in the second transition metal solutions of Examples 4 and 5, and Comparative Example 3 and pHs of the second transition metal solution were measured. The measured results are shown in Table 4 below.
1) (FL#) ÷ [((CA#) × 2) + ((AL#) × 3)]
Wherein FL # is the number of moles of fluorine contained in the fluorine compound, CA # is the number of moles of calcium contained in the first transition metal solution, and AL # is the number of moles of aluminum contained in the first transition metal solution.
Referring to Table 4, the pHs in the second transition metal solutions according to Examples 4 and 5 were greater than 5, and the loss of nickel, cobalt and manganese was suppressed while lowering the concentrations of calcium and aluminum.
However, the second transition metal solution according to Comparative Example 3 had a higher concentration of calcium and aluminum than those in the second transition metal solution according to Examples 4 and 5.
A second transition metal solution was formed by the same method as that in Preparation Example, except that the S20 process was performed at room temperature (25° C.) for 2 hours and the S30 process was performed at room temperature (25° C.) for 22 hours.
1.5 g (1 wt %) of the sodium hydroxide (50%) aqueous solution was added based on the total weight (150 g) of the leachate 1 in the S20 process, and 1.5 eq (calculated by the same formula as indicated 1) in Table 4 above) of sodium fluoride was added to the first transition metal solution obtained from the leachate 1 in the S30 process.
Concentrations of metals contained in the formed second transition metal solution were measured based on a formation hour, and the measured results are shown in Table 5 below.
Referring to Table 5, when compared to the second transition metal solution of Example 5 of Table 4 in which added amounts of the basic compound and the fluorine compound were the same, a rate at which the precipitation reaction of calcium and aluminum occurred was slow in the second transition metal solution formed by performing the S20 process and the S30 process at room temperature. Accordingly, it may be predicted that high purity nickel and cobalt may be efficiently obtained when the reaction temperature is high.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0072764 | Jun 2023 | KR | national |
