Patent Application
20240254643
This application claims priority to Japanese Patent Application No. 2023-007609 filed on Jan. 20, 2023, incorporated herein by reference in its entirety.
The present disclosure relates to a metal recovery method and a metal recovery device.
In recent years, storage batteries, such as nickel-metal hydride storage batteries and so forth, have become popular as storage batteries for in-vehicle use and the like. One major usage of storage batteries is in hybrid electric vehicles and battery electric vehicles. Accordingly, as automobiles end their life cycles, great numbers of used storage batteries installed therein are left as waste. There is demand for reusing such used storage batteries as resources.
For example, a storage battery generally has a structure in which electrodes (cathode and anode), a separator, and an electrolytic solution are enclosed in an exterior casing. Materials containing metals such as cobalt (Co), nickel (Ni), and so forth (e.g., anode active materials such as nickel hydroxide, cobalt hydroxide, and so forth, which are used for anodes), are sometimes used in the electrodes. There is demand to recover and reuse metals contained in such electrodes, from the used storage batteries.
For example, Japanese Unexamined Patent Application Publication No. 2022-085446 (JP 2022-085446 A) discloses a method for recovering valuable metals (copper (Cu), Ni, Co, etc.), which includes a step of preparing a charge containing at least valuable metals as a raw material, a step of heating and melting the raw material to yield alloys and slag, and a step of separating out the slag to recover alloys containing valuable metal, in which metal aluminum is introduced into the raw material as a reductant at the time of heating and melting the raw material.
It should be noted that there is demand in various fields to recover metals contained in members, from the perspective of reusing metals, which is not limited to storage batteries.
In view of such conventional demands, the present disclosure provides a metal recovery method and a metal recovery device capable of easily recovering Co component as metal Co.
The present disclosure includes the following aspects.
1
A first aspect of the present disclosure provides a metal recovery method. This metal recovery method includes causing a metal recovery device including a power source, an electronic load, an electrolytic solution, a first tank that includes an anode, a first supply port for H2O and a first discharge port and that is immersed in the electrolytic solution, the anode being connected to the power source and the electronic load and containing at least Co, and a second tank that includes a cathode, a second supply port for H2O and a second discharge port and that is immersed in the electrolytic solution, the cathode being connected to the power source and the electronic load, to recover Co eluted from the anode by maintaining voltage by the power source and the electronic load such that a potential of the anode is higher than a potential of the cathode.
2
In the metal recovery method according to the above aspect, the anode may contain Ni. The metal recovery method may further include recovering residual Ni in the anode by maintaining the voltage by the power source and the electronic load such that the potential of the anode is higher than the potential of the cathode.
3
In the metal recovery method according to the above aspect, at least one of the first tank and the second tank may be a nickel-metal hydride storage battery.
4
In the metal recovery method according to the above aspect, the nickel-metal hydride storage battery may be a used storage battery.
5
The metal recovery method according to the above aspect may further include maintaining the voltage such that water electrolysis reaction occurs, extracting O2 gas from the first tank, and extracting H2 gas from the second tank.
6
Another aspect of the present disclosure provides a metal recovery device. The metal recovery device includes a power source, an electronic load, an electrolytic solution, a first tank that includes an anode, a first supply port for H2O and a first discharge port and that is immersed in the electrolytic solution, the anode being connected to the power source and the electronic load and containing at least Co, and a second tank that includes a cathode, a second supply port for H2O and a second discharge port, and that is immersed in the electrolytic solution, the cathode being connected to the power source and the electronic load. The metal recovery device is configured to recover Co eluted from the anode by maintaining voltage by the power source and the electronic load such that a potential of the anode is higher than a potential of the cathode.
7
In the metal recovery device according to the above aspect, the anode may contain Ni. The metal recovery device may be configured to recover residual Ni in the anode by maintaining the voltage by the power source and the electronic load such that the potential of the anode is higher than the potential of the cathode.
8
In the metal recovery device according to the above aspect, at least one of the first tank and the second tank may be a nickel-metal hydride storage battery.
9
In the metal recovery device according to the above aspect, the nickel-metal hydride storage battery may be a used storage battery.
10
The metal recovery device according to the above aspect may be configured to maintain the voltage such that water electrolysis reaction occurs, extract O2 gas from the first tank, and extract H2 gas from the second tank.
According to the present disclosure, a metal recovery method and a metal recovery device that can easily recover a Co component as metal Co can be provided.
Features, advantages, and technical and industrial significance of exemplary embodiments of the disclosure will be described below with reference to the accompanying drawings, in which like signs denote like elements, and wherein:
A metal recovery method and a metal recovery device according to the present disclosure will be described below in detail with reference to the drawings. Each drawing shown below is schematically illustrated, and the sizes and shapes of the parts are exaggerated as appropriate, to facilitate understanding. In the present specification, when the terms “above” or “below” alone are used to describe how one member is disposed with respect to another member, this includes both a case in which the one member is disposed directly above or directly below the other member in such a manner that the one member is in contact with the other member, and a case in which the one member is disposed above or below the other member with still another member interposed therebetween, unless stated otherwise.
The metal recovery device according to the present disclosure includes a power source, an electronic load, an electrolytic solution, a first tank that includes an anode connected to the power source and the electronic load and contains at least cobalt (Co), has a supply port and a discharge port for H2O, and is immersed in the electrolytic solution, and a second tank that includes a cathode connected to the power source and the electronic load, has a supply port and the discharge port for H2O, and is immersed in the electrolytic solution. Voltage is maintained by the power source and the electronic load so that the potential of the anode is higher than the potential of the cathode, thereby recovering Co eluted from the cathode.
An embodiment of the metal recovery device according to the present disclosure will be described with reference to
The recovery device 20A uses nickel-metal hydride storage batteries as each of the first tank 100A having the anode containing Co and Ni, and the second tank 200A having the cathode. This nickel-metal hydride storage battery may be a used nickel-metal hydride storage battery. Note that the term “used” means that the charge capacity of the battery is lower than that of the battery immediately after being manufactured.
In the recovery device 20A, the power source 3 and the electronic load 30 maintain the voltage such that the potential of the anode in the first tank 100A is higher than the potential of the cathode in the second tank 200A. Thus, water electrolysis reaction occurs in the water (H2O) supplied to the first tank 100A and the second tank 200A, and O2 gas is generated at the first tank 100A. The generated O2 gas is sent to the distillation device 5 through the discharge passage 101, so as to be reduced with HCoO2−, which will be described later, and extracted from the discharge port 8 as water vapor (H2O) at the distillation device 5. Also, water electrolysis reaction occurs in the second tank 200A, generating H2 gas, and this H2 gas is extracted from the discharge passage 201. From the perspective of efficiently causing the water electrolysis reaction to occur in the water (H2O) supplied to the first tank 100A and the second tank 200A, the potential difference between the anode and the cathode preferably is maintained at no less than 1.48 V. Reaction formulas for the anode and the cathode are shown below.
From the perspective of causing the water electrolysis reaction to proceed more readily, the potential difference obtained by subtracting the potential of the cathode in the second tank from the potential of the anode in the first tank is preferably in a range of no less than 1.48 V and no more than 2.00 V, and more preferably is in a range of no less than 1.55 V and no more than 1.80 V from the perspective of efficiency. Also, in this case, the temperature is preferably high, with the upper limit thereof being 80° C.
Also, in the recovery device 20A, the voltage is maintained by the power source 3 and the electronic load 30 such that the potential of the anode in the first tank 100A is higher than the potential of the cathode in the second tank 200A, whereby Co is eluted from the anode into the electrolytic solution 40 as HCoO2−. The eluted HCoO2− is sent to the distillation device 5 by driving the liquid feeding pump 7, is oxidized by O2 gas, thus enabling precipitation and recovery thereof as metal CoO2. Note that some Co is extruded as a solid from the anode without being eluted, and this can also be recovered. Also, after the voltage is continuously maintained by the power source 3 and the electronic load 30 such that the potential of the anode is higher than the potential of the cathode, and Co and the like are completely eluted from the anode, Ni2O3 and Ni(OH)2 remain at the anode, and accordingly can be recovered and separated from the anode as metal Ni. For example, Fe and Ni may remain at the anode, and metal Ni can be recovered by performing separation thereof in accordance with the difference in melting point. From the perspective of efficient elution of Co from the anode, the voltage at the anode is preferably maintained at no less than 0.60 V and no more than 1.00 V. Reaction formulas for elution of Co and residual Ni are shown below.
Note that the voltage may be repeatedly changed from the perspective of efficiently causing the water electrolysis reaction to occur and efficiently causing elution of Co from the anode. For example, the voltage may be maintained such that the potential difference between the anode and the cathode is no less than 1.48 V, and thereafter the voltage is maintained such that the voltage at the anode is no less than 0.60 V and no more than 1.00 V, which is then repeatedly performed. Thus, the water electrolysis reaction occurs more efficiently when the potential difference between the anode and the cathode is maintained at no less than 1.48 V, and on the other hand, elution of Co from the anode can be performed more efficiently when the voltage at the anode is maintained at no less than 0.60 V and no more than 1.00 V. For example, a cycle may be repeatedly performed, in which maintaining the voltage for 50 minutes in a state in which the potential difference between the anode and the cathode is no less than 1.48 V, and thereafter maintaining the voltage that is adjusted for 10 minutes in a state in which the voltage at the anode is no less than 0.60 V and no more than 1.00 V, make up one cycle.
Next, another embodiment will be described.
Another embodiment of the metal recovery device according to the present disclosure will be described with reference to
In the recovery device 20B, the nickel-metal hydride storage batteries used in the first tank 100B and the second tank 200B may be used nickel-metal hydride storage batteries.
In the recovery device 20B, the power source 3 and the electronic load 30 maintain the voltage such that the potential of the anode in the first tank 100B is higher than the potential of the cathode in the second tank 200B. Thus, water electrolysis reaction occurs in the water (H2O) supplied to the first tank 100B and the second tank 200B, and O2 gas is generated at the first tank 100B. The generated O2 gas is sent to the distillation device 5 through the discharge passage 101, so as to be reduced with HCoO2−, which will be described later, and extracted from the discharge port 8 as water vapor (H2O) at the distillation device 5. Also, water electrolysis reaction occurs in the second tank 200B, generating H2 gas, and this H2 gas is extracted from the discharge passage 201. From the perspective of efficiently causing the water electrolysis reaction to occur in the water (H2O) supplied to the first tank 100B and the second tank 200B, the potential difference between the anode and the cathode preferably is maintained at no less than 1.48 V. The potential difference between the anode and the cathode is preferably in a range of no less than 1.48 V and no more than 2.00 V, and more preferably is in a range of no less than 1.55 V and no more than 1.80 V. Also, the temperature is preferably high, with the upper limit thereof being 80° C.
In the recovery device 20B, the voltage is maintained by the power source 3 and the electronic load 30 such that the potential of the anode in the first tank 100B is higher than the potential of the cathode in the second tank 200B, whereby Co is eluted from the anodes of the six nickel-metal hydride storage batteries into the electrolytic solution 40 as HCoO2−. The eluted HCoO2− is sent to the distillation device 5 by driving the liquid feeding pump 7, is oxidized by O2 gas, thus enabling precipitation and recovery thereof as metal CoO2. Note that some Co is extruded as a solid from the anode without being eluted, and this can also be recovered. Also, after the voltage is continuously maintained by the power source 3 and the electronic load 30, and Co and the like are completely eluted from the anodes of the six nickel-metal hydride storage batteries, Ni2O3 and Ni(OH)2 remain at the anodes, and accordingly can be recovered from the anode as metal Ni. From the perspective of efficient elution of Co from the anode, the voltage at the anode is preferably maintained at no less than 0.60 V and no more than 1.00 V.
Note that the voltage may be repeatedly changed from the perspective of efficiently causing the water electrolysis reaction to occur and efficiently causing elution of Co from the anode. For example, maintaining the voltage such that the potential difference between the anode and the cathode is no less than 1.48 V (e.g., maintained for 50 minutes), and thereafter maintaining the voltage such that the voltage at the anode is no less than 0.60 V and no more than 1.00 V (e.g., maintained for 10 minutes), may be repeated. Thus, the water electrolysis reaction occurs more efficiently when the potential difference between the anode and the cathode is maintained at no less than 1.48 V, and on the other hand, elution of Co from the anode can be performed more efficiently when the voltage at the anode is maintained at no less than 0.60 V and no more than 1.00 V.
As described above, according to the metal recovery method and the metal recovery device of the present disclosure, Co contained in the anode can be easily recovered as metal Co (i.e., pure Co). Further, when Ni is contained in the anode, this Ni can be easily recovered as metal Ni (i.e., pure Ni).
In the present disclosure, nickel-metal hydride storage batteries can be applied to one or both of the first tank and the second tank. This nickel-metal hydride storage battery may be a used nickel-metal hydride storage battery. That is to say, according to the present disclosure, Co and Ni contained in the anodes of used nickel-metal hydride storage batteries can be easily recovered as metal Co and metal Ni.
According to the present disclosure, the voltage applied to water (H2O) supplied to the first tank and the second tank by the power source and the electronic load is maintained such that the potential of the anode is higher than the potential of the cathode (e.g., the potential difference between the anode and the cathode is maintained at no less than 1.48 V), thereby causing water electrolysis reaction to occur, and O2 gas generated at the first tank and H2 gas generated at the second tank can be extracted. Also, maintaining the voltage such that the potential of the anode is higher than the potential of the cathode by the power source and the electronic load (e.g., maintaining the voltage of the anode at no less than 0.60 V and no more than 1.00 V) enables Co and Ni contained in the anode to be recovered as metal Co and metal Ni. Thus, in the metal recovery method and the metal recovery device according to the present disclosure, the Co and Ni contained in the anode can be recovered as metal Co and metal Ni, while causing water electrolysis reaction to occur and extracting O2 gas and H2 gas. Accordingly, from the perspective of electrical energy maintained by the power source and the electronic load, the electrical energy required for extracting O2 gas and H2 gas by the water electrolysis reaction can also be used to recover metals contained in the anode, and accordingly energy consumption can be reduced.
From the perspective of increasing the efficiency of recovering metal Co and metal Ni, the electrolytic solution in which the first tank and the second tank are immersed preferably has a pH value of 14 or higher, more preferably 15 or higher, and even more preferably 16 or higher. The pH value is a value measured using a PH meter at 25° C.
The electrolytic solution preferably is an aqueous electrolytic solution, although not limited thereto in particular. An alkaline aqueous solution or the like, for example, can be suitably used as the aqueous electrolytic solution. Alkaline aqueous solutions contain, for example, water and an alkali metal hydroxide dissolved in water. The concentration of the alkali metal hydroxide may be, for example, 1 mol/L to 45 mol/L. Examples of alkali metal hydroxides include potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH) and the like.
From the perspective of efficiently causing the water electrolysis reaction, the voltage is preferably maintained such that the potential difference between the anode and the cathode is no less than 1.48 V. On the other hand, from the perspective of efficient elution of Co from the anode, the voltage at the anode is preferably maintained at no less than 0.60 V and no more than 1.00 V. Accordingly, maintaining the potential difference between the anode and the cathode at no less than 1.48 V (e.g., maintained for 50 minutes), and thereafter maintaining the voltage that is adjusted such that the voltage at the anode is no less than 0.60 V and no more than 1.00 V (e.g., maintained for 10 minutes), may be repeated.
Water (H2O) is preferably supplied to both of the first tank and the second tank from below (from the direction of gravity toward the direction against gravity), from the perspective of ease of extracting the generated O2 gas and H2 gas. For example, supplying from bottom faces of the tanks toward top faces thereof by capillary action is preferable.
The distance between the first tank and the second tank is preferably no less than 0 cm and no more than 5 cm, more preferably no less than 0 cm and no more than 1 cm, from the perspective of facilitating water electrolysis reaction. Note that the phrase “distance between the first tank and the second tank” refers to the shortest distance between the first tank and the second tank.
In the recovery devices 20A and 20B illustrated in
Now, nickel-metal hydride storage batteries that can be used for the first tank and the second tank will be described. Note that the nickel-metal hydride storage batteries (hereinafter may be abbreviated to “batteries”) may be, for example, used nickel-metal hydride storage batteries, which have been used as batteries for mobile equipment, batteries for in-vehicle use, storage batteries for renewable energy generation, and so forth.
The housing 2 accommodates a power storage element 10 and an electrolytic solution. The power storage element 10 includes an anode 11, a cathode 12, and a separator 13. The power storage element 10 that is illustrated is a spiral-wound type. The power storage element 10 is formed by spirally winding strip-shaped electrodes. The power storage element 10 may be of a laminated type, for example. The power storage element 10 may be formed by stacking sheet-like electrodes, for example.
The cathode 12 is sheet-like. The cathode 12 may have a thickness of, for example, 10 μm to 1 mm. The cathode 12 has a lower potential than the anode 11.
The cathode includes, for example, a cathode current collector and a cathode active material. Examples of the cathode current collector include a nickel mesh and so forth. Examples of the cathode active material include hydrogen absorbing alloys. The composition of the hydrogen absorbing alloy is not limited, as long as storing and releasing hydrogen can be performed. Examples of hydrogen absorbing alloys include Mm-Ni—Mn—Al—Co alloys. “Mm” indicates a mixture of rare earth elements called mischmetal.
The anode 11 is sheet-like. The anode 11 may have a thickness of, for example, 10 μm to 1 mm. The anode 11 has a higher potential than the cathode 12. The anode 11 contains an anode active material. The anode active material can contain any component. Examples of the anode active material include nickel hydroxide (Ni(OH)2), cobalt hydroxide (Co(OH)2), manganese dioxide, silver oxide, and so forth. The anode active material is preferably nickel hydroxide.
The anode 11 may essentially be made of the anode active material alone. The anode 11 may further include a current collector, an electroconductive material, a binder, and so forth, in addition to the anode active material. The current collector may include, for example, a porous metal sheet or the like. The current collector is made of Ni, for example.
For example, the anode 11 can be formed by coating a current collector with the anode active material, the electroconductive material, and the binder. The electroconductive material has electronic conductivity. The electroconductive material can contain any component. The electroconductive material may contain, for example, carbon black, Co, cobalt oxide, or the like. The content of the electroconductive material may be 0.1 parts by mass to 10 parts by mass, for example, as to 100 parts by mass of the anode active material. The binder binds the current collector and the anode active material. The binder can contain any component. The binder may include, for example, ethylene-vinyl acetate (EVA) or the like. The content of the binder may be 0.1 parts by mass to 10 parts by mass, for example, as to 100 parts by mass of the anode active material.
The separator 13 is sheet-like. The separator 13 is disposed between the anode 11 and the cathode 12. The separator 13 physically separates the anode 11 and the cathode 12. The separator 13 may have a thickness of, for example, 50 μm to 500 μm. The separator 13 is porous. The separator 13 may contain, for example, a stretched porous membrane, a non-woven fabric, or the like. The separator 13 is electrically insulating. The separator may be made of, for example, polyolefin, polyamide, or the like.
The electrolytic solution is preferably an aqueous electrolytic solution, although not limited thereto in particular. An alkaline aqueous solution or the like, for example, can be suitably used as the aqueous electrolytic solution. Alkaline aqueous solutions contain, for example, water and an alkali metal hydroxide dissolved in water. The concentration of the alkali metal hydroxide may be, for example, 1 mol/L to 20 mol/L. Examples of alkali metal hydroxides include potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH) and the like.
Now, whether any metal Co was recovered by the metal recovery device according to the embodiments of the present disclosure was confirmed by experimentation.
A recovery device was prepared having the same configuration as the recovery device 20A illustrated in
In this recovery device, water (H2O) was supplied from a water supply pump to the first tank and the second tank, and the potential of the anode in the first tank was maintained so as to be higher than the potential of the cathode in the second tank, by the power source and the electronic load. Specifically, as shown in the graph in
Elution of Co into Electrolytic Solution
After continuing to maintain the voltage for the above amount of time, confirmation was made regarding whether Co was eluted in the electrolytic solution circulating through the distillation device and the housing by the liquid feeding pump. As a result, it was confirmed that 3.1% by mass (1.2 atomic %) of Co was eluted into the electrolytic solution. Thus, in Experimental Example 1, it was confirmed that Co was eluted into the electrolytic solution, i.e., it was confirmed that metal Co could be recovered.
Also, in Experimental Example 1, Ni and Fe were detected when the elements remaining in the anode of the first tank were analyzed after the voltage was maintained for the above amount of time. That is to say, it was confirmed that metal Ni can be separated and recovered.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2023-007609 | Jan 2023 | JP | national |
