NICKEL-METAL HYDRIDE (NiMH) BATTERY RECYCLING

Abstract

To provide recycling of nickel-metal hydride (NiMH) batteries.SOLUTION: Recycling of nickel-metal hydride (NiMH) batteries extracts substantially pure nickel based on adding a leachant to granular cathode material resulting from agitation of the NiMH batteries to form a leach solution. A pH of the leach solution is maintained for precipitating iron, aluminum and lanthanide rare earth elements (REE) for yielding a nickel solution for forming a cathode material precursor in a recycled battery, often with a high nickel content.SELECTED DRAWING: Figure 1

Description

[Background technology]

[0001] background Electrical energy storage is a technology field that is continually improving, driven by the increasing demand for portable electronics, electric vehicle (EV) and portable power (e.g., tools and equipment) applications. Lithium-ion batteries have evolved into the mainstream for short- to medium-term high discharge applications. Lithium-ion batteries use a variety of battery chemistries, typically metals combined with conductive powders and binders. Because the metals used in battery charge materials are often processed at significant cost, various battery chemistries have evolved based on technological advancements, usage demand and resource availability. Nickel metal hydride (NiMH) batteries represent an example of a transitional technology that was once popular for certain secondary (rechargeable) battery applications. More recent battery chemistries, such as nickel manganese cobalt (NMC) and similar battery chemistry applications, have surpassed NiMH batteries for most applications. Summary of the Invention [Means for solving the problem]

[0002] overview The configurations herein demonstrate advantageous improvements resulting from recycling nickel metal hydride (NiMH) batteries to extract substantially pure nickel, which includes adding a leachant to granular cathode and anode materials resulting from agitation of the NiMH batteries to form a leach solution, the pH of which is maintained to precipitate iron, aluminum, and lanthanide rare earth elements (REEs) to produce a nickel solution, forming a cathode material precursor for the recycled battery, often having a high nickel content.

[0003] The compositions herein are based in part on the observation that the increasing use of rechargeable batteries, especially in the EV market, introduces large volumes of batteries with typical life spans of approximately 10 years. Unfortunately, the traditional approach to battery use is manifesting itself as a trend for batteries with older, obsolete charge materials. These older batteries, such as NiMH batteries, contain a large amount of nickel mixed with other metals that are no longer desirable in modern batteries. Thus, the compositions herein substantially overcome the shortcomings of expiring battery chemistries by providing a recycling approach to produce nickel charge material precursors suitable for use with newer batteries while removing unwanted extra and / or contaminating metals, such as lanthanide REEs, such as La, Ce, Pr, and Nd. The result is a nickel-rich solution that can be directly introduced into the formulation of various battery chemistries (molar ratios) for NMC and other recycled batteries.

[0004] In further detail, a method for recycling nickel metal hydride (NiMH) batteries includes receiving or producing a recycle stream containing NiMH batteries and agitating (crushing, crushing, etc.) the batteries to produce granular cathode and anode materials in a mixed form. A leachant is added to the granular cathode and anode materials resulting from the agitation of the NiMH batteries to form a leach solution. Adjustment of the pH of the leach solution maintains the pH of the leach solution at various levels to precipitate iron, aluminum, and lanthanide rare earth elements, resulting in a nickel solution to form a cathode material precursor. The resulting recycled cathode material precursor takes the form of a nickel sulfate solution, which can have a Ni concentration of, for example, 1.1 M to 1.7 M.

[0005] BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and other features will become apparent from the following description of specific embodiments disclosed herein as illustrated in the accompanying drawing figures, in which like reference characters refer to the same parts throughout the different views, and in which the drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention. [Brief description of the drawings]

[0006] [Figure 1] 1 is a process flow for recycling NiMH batteries according to the present disclosure. [Diagram 2] 1 is an analytical chart of the resulting material including the intermediate solution (recycle) step. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Detailed Description Described below are exemplary methods and apparatus for recycling batteries, such as NiMH batteries, to separate the highly sought-after nickel from contaminants and disused charge material metals, such as lanthanide elements. Recycled batteries are obtained from a spent stream, sometimes referred to as exhausted or used batteries, that are no longer usable. In many cases, this means that the charge material in the battery has lost its ability to hold a sufficient charge, or it may be a battery with newer material that has become unusable due to an automobile accident, manufacturing error, or other inability to function.

[0008] Nickel metal hydride (NiMH) batteries are becoming more prevalent, being used in applications such as phones, laptops, power tools, and electric vehicles. Used NiMH batteries can still serve as a source of raw metals for the preparation of cathode active materials for various chemistries of recycled batteries (i.e. batteries made from recycled materials). The main elements present in NiMH batteries are generally 17.9% by weight nickel, 4.4% by weight cobalt, and 17.3% by weight REEs such as lanthanum, cerium, praseodymium, and neodymium. The metals in NiMH batteries represent a potential environmental hazard if used batteries are simply discarded without special treatment, and nickel can be toxic to humans and is considered to be a carcinogenic metal. Thus, recycling used NiMH batteries is beneficial for both environmental protection and preservation of natural resources.

[0009] Recycle streams typically contain expensive raw materials that must first be disassembled by physical crushing, crushing, and / or shredding of the entire battery casing, current collectors, cathode and anode materials, as well as any other electrical connectors and circuitry that may interconnect the individual cells of the battery. Thus, the recycle stream has a somewhat unspecified composition of intermingled cathode material, anode material, and current collectors, as well as physical casings such as plastics and other containment. Various physical separations may be performed, often resulting in a granular mixture or "black mass" of electrode materials that includes both cathode and anode materials from the recycle stream. Cathode and anode materials that contain nickel and lanthanide elements (La, Ce, Pr, Nd, etc.) and various other metals are handled by the techniques disclosed below.

[0010] The specific configurations discussed further below provide an economically and environmentally advantageous recycling method for NiMH batteries. An illustrative description is as follows: In a specific example, black mass is leached in sulfuric acid solution (2-5 molar), hydrogen peroxide is added to the solution to promote further leaching of the desired metal ions, and impurities such as aluminum and iron dissolved in the solution are precipitated by raising the pH of the solution to 5-6. After solid-liquid separation by filtration, the lanthanide rare earth elements (La, Ce, Pr, and Nd) are removed by adding sulfuric acid and sodium hydroxide to form insoluble sodium REE sulfate double salts at pH=0-3. The goal is to obtain a solution pH for salt precipitation with Na / REE molar ratio of about 15-25 and SO4 / REE molar ratio of about 35-60. + After removing the REEs, the cleaned solution is further adjusted by concentrating and selectively crystallizing excess sodium sulfate. During the selective crystallization of sodium sulfate, the REEs are also further removed. The solution reaches the desired nickel concentration for synthesizing the cathode active material precursor or isolating the nickel sulfate product for many applications. The separated REEs can be fed into the REE recycle stream to recover the valuable rare earth elements.

[0011] Figure 1 is a process flow 100 for recycling NiMH batteries according to the configurations herein. A typical process uses a leachant in combination with granular cathode and anode materials obtained from agitation (physical crushing, crushing and / or shredding) of NiMH batteries to form a leach solution to recycle nickel metal hydride (NiMH) batteries. Sulfuric acid with or without hydrogen peroxide is the preferred leachant for removal of REEs, although other leachants can be used. The pH of the leach solution is adjusted and maintained to precipitate the iron, aluminum and lanthanide REEs resulting in a nickel solution to form the cathode material precursor.

[0012] More specifically, in step 102, a recycle stream containing NiMH batteries is received and discharged to eliminate the risk of arcing or burning from residual charges, as illustrated in step 104. It is recalled that Li-ion batteries are advantageous due to their high discharge capacity, so that even "dead" batteries can retain significant electrical energy. As disclosed in step 106, a disassembly or shredding process can be used to agitate the batteries to produce granular cathode and anode material, and separation and sizing of the granular particles. The result is a black mass from the recycle stream containing granular cathode and anode material resulting from the agitation of NiMH batteries.

[0013] In step 108, a leaching agent is added comprising sulfuric acid with or without hydrogen peroxide. For example, the sulfuric acid concentration for leaching is 1M-5M, preferably 2-3M, and hydrogen peroxide (at a concentration of about 30-34%) is in a volume ratio of 0.2-0.6, preferably 0.3-0.4, to the weight of the black mass. Preferably, the pH of the leaching solution is brought to about 5-6, while the hydrogen peroxide is in a relatively small amount. As illustrated in step 110, the leaching solution is stirred for about 5 hours or overnight while maintaining the pH of the leaching solution at 5-6, to allow impurities, including iron and aluminum, to precipitate from the leaching solution. If the pH is less than 5, the pH is adjusted to 5.5 to remove Al and Fe impurities and minimize Ni loss.

[0014] As shown in step 112, the precipitated Al and Fe can be filtered, resulting in a filter "cake" in step 114, which can go to waste stream or provide additional leaching in step 116. After filtering the leach solution to remove precipitated solids, a calculated amount of sulfuric acid is added using a concentration of 93%-98% to give a sulfate to REE ratio = 35-60, as illustrated in step 118, and then sodium hydroxide is added at a concentration of 25%-50% until the pH reaches 1-3 to precipitate the REEs remaining in the leach solution. Instead of using only H2SO4, sodium sulfate can be used to achieve a ratio of SO4 / REE = 35-60, as shown in steps 120 and 136, and the required amount of sulfuric acid and / or sodium hydroxide is added to maintain the pH and precipitate the sodium REE double sulfates. The lanthanide rare earth elements (such as La, Ce, Pr and Nd) are precipitated in step 122 and removed by filtration (step 124) in step 126 as lanthanide-alkali double sulfates at pH 0-3, preferably pH=2. Because rare earths are generally considered to be high value commodities, the REEs can enter an alternative recycle stream as illustrated in step 128.

[0015] As an example, the removal of REEs involves forming an alkali to REE molar ratio of 15-25 and a sulfate to REE ratio of 35-60 for the removal of REEs by lanthanide-alkali double sulfates. To remove REEs by forming insoluble sodium REE double sulfates (Na(REE)(SO4)2), sulfate is added in a molar ratio of 35-60 relative to the moles of REE in the leach solution. To match the ratio, a calculated amount of concentrated sulfuric acid is added to the leach solution from which Al and Fe are removed, and then the pH of the solution is brought to 1-2 to precipitate the lanthanide-alkali double sulfates. It should be further pointed out that the use of sulfuric acid promotes the formation of sulfates of lanthanides.

[0016] The resulting REE-removed leach solution is concentrated to ≧1.2M Ni as depicted in step 130. During concentration, excess alkali sulfate is removed by selective crystallization depending on Ni concentration as depicted in step 136. Sodium sulfate 138 is generated and the extracted water can be reused as depicted in step 132. Once the crystallized excess sodium sulfate 138 is filtered in step 134, in step 140, the nickel ion concentration should be 1.1M-1.7M suitable for synthesis in Li-ion batteries.

[0017] A specific example can be illustrative as follows: To leach 250 g of black mass from a NiMH battery in 1500 mL of 2 M sulfuric acid solution, the black mass is slowly added to the solution at room temperature, and then 98 mL of 34 wt. % H2O2 is added dropwise to the solution. The solution is then stirred overnight. The solution mixture is filtered to separate the undissolved and impurity precipitated solids from the leachate. A dark green leachate (pH = 5.7) is obtained. Since the pH of the solution is within the acceptable range for removing aluminum and iron impurities, no further pH adjustment was performed to remove Al and Fe. Then, to remove the REEs, 175 mL of 95-97% sulfuric acid is added to the solution, and the pH of the solution is raised to 2 by adding 200 mL of 50% NaOH solution. During the increase in the pH of the solution, sodium REE double sulfate precipitates as a white crystalline powder. This white precipitate is separated and removed by filtration. The purity of the solution is analyzed by ICP-OES (Inductively Coupled Plasma Optical Emission Spectroscopy) shown in the following Figure 2. The solution is concentrated to remove excess sodium sulfate in the solution by selective crystallization and filtration of Na2SO4, resulting in a nickel ion concentration in the range of 1.1M to 1.7M.

[0018] Figure 2 is an analytical chart of the resulting material including the intermediate solution (recycle) steps. Referring to Figures 1-2, chart 200 illustrates the leach solution at the stages of leaching 210 from step 110, removal of impurities 220 after steps 112 and 124, and the final nickel sulfate solution 230 of step 140.

[0019] Nickel sulfate solutions can be used to form the precursor of the recycled cathode material in new batteries. The cathode material contains metals such as lithium, nickel, manganese, cobalt, aluminum, iron and phosphorus in predetermined ratios that define the so-called "battery chemistry" of the Li-ion cell. The preferred battery chemistry varies between suppliers and applications, and the outcome of recycling Li-ion batteries typically follows a predefined molar ratio of battery chemicals in the recycled charge material product. Industry trends are moving towards more nickel-rich chemistries, with nickel, manganese and cobalt (NMC) in N:M:C molar ratios such as 5:3:2 (532), 6:2:2 (622) and 8:1:1 (811) being preferred in many cases.

[0020] Solution forms of cathode materials such as nickel, manganese, cobalt and aluminum sulfates can be combined to produce recycled cathode precursors corresponding to the 811, 622 or 532 battery chemistries or other molar ratio combinations discussed above, by adjusting the ratio. The recycled nickel sulfate disclosed herein can be combined with other sulfate forms of cathode materials to form cathode precursors of predetermined battery chemistries. The precursors are typically in powder form that are sintered with lithium to produce the cathode active material and attached to a current collector to form the electrodes of new recycled batteries. When combined with sulfate forms from older low nickel content recycle streams, the disclosed nickel sulfate complements the higher nickel ratios such as 622 and 811 of new recycled batteries.

[0021] While the apparatus and method defined herein have been particularly shown and described with reference to embodiments thereof, it will be understood by those skilled in the art that various changes in form and detail may be made thereto without departing from the scope of the invention as encompassed by the appended claims. [Explanation of symbols]

[0022] 100 Process Flow 102 processes 104 Process 106 Process 108 process 110 processes 112 Process 114 Process 116 Process 118 Process 120 processes 122 process 124 processes 126 Process 128 process 130 processes 132 process 134 Process 136 Process 138 Sodium Sulfate 140 processes 200 Charts 210 Leaching 220 Removal 230 Final Nickel Sulfate Solution

Claims

1. 1. A method for recycling nickel metal hydride (NiMH) batteries, comprising: combining a leaching agent with the particulate cathode material obtained from the agitation of the NiMH battery to form a leaching solution; adjusting or maintaining the pH of the leach solution to precipitate impurities including iron, aluminum, and lanthanide rare earth elements (REEs) to produce a nickel solution; A method comprising:

2. 10. The method of claim 1, wherein the pH of the leach solution is adjusted to 5-6 to remove Fe and Al.

3. 10. The method of claim 1, wherein the pH of the leaching solution is adjusted to 0-3 to remove the REEs.

4. agitating the leach solution for at least 5 hours to dissolve nickel and cobalt in the leach solution; adjusting or maintaining the pH of the leach solution at 5-6 after dissolution of the nickel and cobalt to precipitate Fe and Al; filtering the precipitated impurities, including Fe and Al, to recover the dissolved nickel and cobalt in the leach solution; The method of claim 1 further comprising:

5. After filtering the precipitated impurities, lowering the pH to 0-3 to precipitate the lanthanide element; filtering said lanthanide rare earth element as sodium double sulfate; The method of claim 4 further comprising:

6. After filtering the precipitated impurities, At least one of sulfuric acid and sodium hydroxide is added to provide sodium ions in a molar ratio of 15 to 25 relative to the lanthanide rare earth element, and SO ４ to a molar ratio of 35 to 60 with respect to the lanthanide rare earth element; Removing excess sodium sulfate The method of claim 4 further comprising:

7. 10. The method of claim 1, wherein the lanthanide rare earth elements include La, Ce, Pr, and Nd.

8. receiving a recycle stream containing the NiMH batteries; agitating the battery to form the particulate cathode material; The method of claim 1 further comprising:

9. The method of claim 1 further comprising forming a cathode material precursor from the nickel solution.

10. 1. A method for recycling nickel metal hydride (NiMH) batteries, comprising: receiving black mass in a recycle stream comprising granular cathode material obtained from agitation of said NiMH batteries; adding 2-5M sulfuric acid to the black mass to form a leach solution; adding hydrogen peroxide to the leaching solution in an amount of 0.2 to 0.6 volume ratio relative to the weight of black mass; agitating the leach solution for at least 5 hours while maintaining the pH of the leach solution at 5-6 to precipitate impurities, including iron and aluminum, from the leach solution; filtering the leach solution to remove the impurity precipitated solids; adjusting the pH of the leach solution to 1-3 by adding 93%-98% sulfuric acid and 25%-50% sodium hydroxide to precipitate any REEs remaining in the leach solution; precipitating said double sulfate salt of REE as a crystalline powder; filtering the REE from the leaching solution; crystallizing excess sodium sulfate to achieve a nickel ion concentration of 1.1M to 1.7M in the leach solution; A method comprising:

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