CN108899602A - The separator of different magnetic metals in a kind of waste and old lithium ion battery - Google Patents

Abstract

The invention discloses a kind of separators of magnetic metals different in waste and old lithium ion battery, including high-temperature vacuum furnace and sorting module；Wherein, high-temperature vacuum furnace is used to carry out vacuumize process to by the electrode powder sieved in waste and old lithium ion battery, obtains mixed-powder to be sorted；Sorting module is for sorting mixed-powder to be sorted for magnetic metallic powder and nonmagnetic powder.Technical solution of the present invention is by carbothermic method and magnetic force-wind-force effect come the magnetic metal in separating waste, worn lithium ion battery, it is avoided that generation secondary pollution, have the characteristics that environmentally friendly, and the present apparatus is able to achieve efficiently separating for variety classes magnetic metal mixed oxide, improves the separation quantity and separative efficiency of magnetic metal.

Description

A device for separating different magnetic metals in waste lithium-ion batteries

technical field

The invention relates to the technical field of battery recycling, in particular to a device for separating different magnetic metals in waste lithium ion batteries.

Background technique

As a representative of modern high-energy batteries, lithium-ion batteries have been widely used in consumer electronic devices since the 1990s, such as mobile phones, notebook computers, and power banks. In recent years, with the acceleration of the replacement of consumer electronics products, the generation of waste lithium-ion batteries is also faster and faster. In 2015, there were more than 5,000 mobile power manufacturers of different sizes in China. According to forecasts, by 2020, my country will produce 528,100 tons of waste lithium-ion batteries, and the number of produced batteries will reach 264.06 million. The metal content in such a huge amount of waste lithium-ion batteries is very large. According to statistics, the value of metal resources contained in each ton of lithium-ion batteries is about 7,708 US dollars. If the metal resources cannot be effectively recovered, it will be Cause huge waste of resources and environmental pollution. The electrode materials of lithium-ion batteries contain a large amount of metal nickel and cobalt, which are high-value magnetic metals and exist in the form of composite oxides. Since the properties of cobalt and nickel are very close, and both belong to magnetic metals, after unified reduction cannot be separated precisely. Therefore, the precise reduction, separation and recovery of oxidized nickel and cobalt in lithium-ion batteries is of great significance to the sustainable exploitation and utilization of resources.

At present, the traditional technologies for processing lithium-ion battery electrode materials mainly focus on chemical leaching, precipitation, electrochemical and solvent extraction to recover and enrich magnetic metals. They have disadvantages such as adding a large amount of chemical reagents and generating acid-base wastewater, such as Patent No. CN107293820A, CN107267759A, CN101921917A and other patents. However, the prior art not only uses a large amount of chemical reagents and solutions, resulting in a large amount of waste water, but also cannot effectively separate mixed oxides with different types of magnetic metals. Therefore, there is an urgent need for a green, pollution-free and efficient device and method for reducing, separating and recovering different kinds of magnetic metals in lithium-ion battery electrode materials.

Contents of the invention

The embodiment of the present invention proposes a separation device for different magnetic metals in waste lithium-ion batteries, which can effectively separate different types of magnetic metal mixed oxides, reduce the addition of chemical reagents and avoid the generation of waste water.

An embodiment of the present invention provides a device for separating different magnetic metals in waste lithium-ion batteries, including: a vacuum high-temperature furnace and a sorting module;

Wherein, the vacuum high-temperature furnace is used to vacuumize the electrode powder obtained by screening the waste lithium-ion battery to obtain the mixed powder to be sorted;

The sorting module is used for sorting the mixed powder to be sorted into magnetic metal powder and non-magnetic powder; the sorting module includes: feeding port (21), vibrating motor (22), vibrating feeding Plate (23), driving roller (24), electromagnetic plate (25), material baffle brush (26), driven magnetic roller (27), fan (28), belt (210), baffle plate (211), magnetic Metal powder receiving tank (214) and non-magnetic powder receiving tank (213);

Wherein, the below of feed opening (21) is vibrating feeding plate (23), and vibrating feeding plate (23) is connected with vibrating motor (22);

The bottom of the vibrating feed plate (23) is the upper surface of the transmission module; the transmission module is made up of a transmission roller (24), an electromagnetic plate (25), a driven magnetic roller (27) and a belt (210); the electromagnetic plate ( 25) set on the inner side of the transmission module, and close to the inner surface of the belt (210);

The end of the transmission module is the air outlet of the fan (28), wherein the wind direction and the transmission direction are perpendicular to each other; the lower surface of the transmission module is provided with a material baffle brush (26);

A baffle (211) is arranged above the air outlet of the blower fan (28), and one end of the baffle (211) is provided with a non-magnetic powder receiving tank (213);

The end of the material baffle brush (26) is provided with a magnetic metal powder receiving tank (214).

Further, the vacuum high-temperature furnace includes: air release valve (1), backing pump valve (2), oil diffusion pump valve (3), corundum tube (4), material holding tank (5), heating and heating Control system (6), gas pipeline (7), composite vacuum gauge (8), gas outlet (9), backing pump (10), return condensate inlet (11) and oil diffusion pump (12);

Wherein, one end of the corundum tube (4) is the deflation valve (1), and the other end is the air inlet of the gas pipeline (7); 5) and the outside of the corundum tube (4) is provided with a heating and temperature rise control system (6);

The gas pipeline (7) is provided with two gas outlets, and the two gas outlets are respectively connected with the backing pump valve (2) and the oil diffusion pump valve (3); the backing pump valve (2) is connected with the backing pump ( 10) connection; the oil diffusion pump valve (3) is connected to the oil diffusion pump (12); the oil diffusion pump (12) is respectively connected to the backflow condensate inlet (11) and the backing pump (10);

The composite vacuum gauge (8) is used to measure the air pressure in the gas pipeline (7).

Further, the storage tank (5) includes three sub-storage tanks; the heating and temperature rise control system (6) includes three control modules and three heating devices;

The three sub-storage tanks respectively correspond to a control module and a heating device;

The control module is used to set the heating temperature of the heating device.

Further, the transmission roller (24), vibration motor (22), blower fan (28) and electromagnetic board (25) are devices with adjustable power.

Further, the transmission module forms an included angle with the horizontal direction, and the included angle ranges from 20° to 45°.

Further, the sorting module is a sealed system, and cover plates are respectively provided at the feed inlet (21), the magnetic metal powder receiving tank (214) and the non-magnetic powder receiving tank (213).

Implementing the embodiment of the present invention has the following beneficial effects:

The embodiment of the present invention provides a separation device for different magnetic metals in waste lithium-ion batteries, including a vacuum high-temperature furnace and a sorting module; Vacuumize to get the mixed powder to be sorted; the sorting module is used to sort the mixed powder to be sorted into magnetic metal powder and non-magnetic powder. Compared with the prior art that uses a large amount of chemical reagents and produces waste water, the technical solution of the present invention separates magnetic metals in waste lithium-ion batteries through carbothermal reduction and magnetic force-wind force, which can avoid secondary pollution and is environmentally friendly. Type characteristics, and this device can realize the effective separation of different kinds of magnetic metal mixed oxides, and improve the separation quantity and separation efficiency of magnetic metals.

Description of drawings

Fig. 1 is a schematic structural view of an embodiment of a vacuum high-temperature furnace provided by the present invention;

Fig. 2 is a schematic structural diagram of an embodiment of a sorting module provided by the present invention.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

The invention provides a device for separating different magnetic metals in waste lithium ion batteries, which includes: a vacuum high-temperature furnace and a sorting module. Referring to Fig. 1 and Fig. 2, Fig. 1 is a schematic structural diagram of an embodiment of a vacuum high-temperature furnace provided by the present invention. Fig. 2 is a schematic structural diagram of an embodiment of a sorting module provided by the present invention.

In this embodiment, the vacuum high-temperature furnace is used to vacuumize the electrode powder obtained by screening the waste lithium-ion battery to obtain the mixed powder to be sorted; the sorting module is used to separate the mixed powder to be sorted Selected as magnetic metal powder and non-magnetic powder.

As shown in Figure 1, the vacuum high-temperature furnace includes: air release valve 1, front pump valve 2, oil diffusion pump valve 3, corundum tube 4, material storage tank 5, heating and temperature rise control system 6, gas pipeline 7, compound Vacuum gauge 8, gas outlet 9, backing pump 10, return condensate inlet 11 and oil diffusion pump 12. Wherein, one end of the corundum tube 4 is the deflation valve 1, and the other end is the air inlet of the gas pipeline 7; Heating temperature rise control system 6; the gas pipeline 7 is provided with two gas outlets, and the two gas outlets are respectively connected to the backing pump valve 2 and the oil diffusion pump valve 3; the backing pump valve 2 is connected to the backing pump 10; The oil diffusion pump valve 3 is connected with the oil diffusion pump 12; the oil diffusion pump 12 is respectively connected with the return condensed water inlet 11 and the backing pump 10; the composite vacuum gauge 8 is used to measure the air pressure in the gas pipeline 7.

As shown in Figure 2, the sorting module includes: feeding port 21, vibrating motor 22, vibrating feeding plate 23, driving roller 24, electromagnetic plate 25, material baffle brush 26, driven magnetic roller 27, fan 28, belt 210 , baffle plate 211 , magnetic metal powder receiving tank 214 and non-magnetic powder receiving tank 213 . Wherein, the below of feeding port 21 is vibrating feeding plate 23, and vibrating feeding plate 23 is connected with vibrating motor 22; The below of vibrating feeding plate 23 is the upper surface of transmission module; , the driven magnetic roller 27 and the belt 210; The end of the transmission module is the air outlet of the fan 28 , wherein the direction of the wind force and the transmission direction are perpendicular to each other; the lower surface of the transmission module is provided with a material baffle brush 26 . A baffle 211 is arranged above the air outlet of the fan 28 , and a non-magnetic powder receiving tank 213 is arranged at one end of the baffle 211 . The end of the material baffle brush 26 is provided with a magnetic metal powder receiving tank (214). In this embodiment, the upper surface of the vibrating feed plate 23 may be provided with, but not limited to, wavy folds, regular folds or irregular folds.

In this embodiment, the storage tank 5 includes three sub-storage tanks; the heating and temperature rise control system 6 includes three control modules and three heating devices; the three sub-storage tanks correspond to a control module and a heating device respectively; the control module Used to set the heating temperature of the heating device. The three heating temperatures can be set independently, which can not only improve the processing efficiency, but also avoid the mutual infection of three different magnetic metals.

In this embodiment, the transmission roller 24, the vibrating motor 22, the fan 28 and the electromagnetic plate 25 are devices with adjustable power, so as to adjust the optimal sorting parameters and achieve the best sorting effect.

In this embodiment, the transmission module forms an included angle with the horizontal direction, and the range of the included angle is 20° to 45°, so that the fan 28 can be used to concentrate the non-magnetic powder to one side of the non-magnetic material collection tank 213, or it can be Reduce cross-contamination of materials.

In this embodiment, the sorting module is a sealed system, and cover plates are respectively provided at the feeding port 21, the magnetic metal powder receiving tank 214 and the non-magnetic powder receiving tank 213 to prevent dust pollution.

In order to better illustrate the operating principle of the separation device of the present invention, the lithium ion battery mixed with nickel, cobalt, and iron is taken as an example below, and the specific operation steps are as follows:

(1) Add the electrode powder of the lithium-ion battery to the storage tank 5 and place it in the heating zone of the corundum tube 4 of the vacuum high-temperature furnace, close the air release valve 1, and turn on the backing pump 10, the return condensate inlet 11 and the oil diffusion pump 12. Open the valve 2 of the backing pump to vacuumize the furnace cavity. When the composite vacuum gauge 8 shows that the vacuum pressure is less than 10Pa, close the valve 2 of the backing pump and open the valve 3 of the oil diffusion pump. Under the combined action of the pump 12 and the backing pump 10, vacuumize the furnace cavity;

(2) Set the temperature and time parameters of the heating and temperature rise control system 6, and start to carry out vacuum heating and reduction to the lithium ion battery electrode material in the corundum tube 4;

(3) After the heating is finished, close the diffusion pump valve 3 and the oil diffusion pump, keep the 11 condensed water backflow and run the foreline pump 10 to the oil in the oil diffusion pump 12 and then close the foreline pump 10, and wait for the materials in the furnace to cool down After that, the mixed powder to be sorted is obtained;

(4) Open the vibrating motor 22, drive roller 24, electromagnetic plate 25 and blower fan 28 in the sorting module, the mixed powder to be sorted is added in the sorting module by the feed port 21, and the powder is on the vibrating feed plate 23 Spread evenly on the belt 210 under the action of the electromagnetic plate 25, and be transported to the driven magnetic roller 27 by the belt 210. On the driven magnetic roller 27, the mixed powder is subjected to the wind force from the fan 28 , the non-magnetic powder leaves the driven magnetic roller 27 under the combined effect of the wind force in the direction 212 and the gravity, and finally falls into the non-magnetic material receiving trough 213, while the magnetic powder continues to remain under the magnetic force of the driven magnetic roller 27. On the belt, turn to leave the driven magnetic roller 27 to lose the magnetic force and drop into the magnetic material receiving trough 214. The effect of the material baffle brush 26 is mainly to scrape the magnetic powder that is attracted by the electromagnetic plate 25 and stays on the belt. Down, thereby falling in the magnetic material receiving groove 214.

Since the lithium-ion battery in this example contains three kinds of magnetic metals, the temperature required for the reduction reaction of the magnetic metals can be obtained through the calculation of the Gibbs free energy of the carbothermal reduction reaction, which are:

The first temperature zone: 500℃≤T≤550℃, used to reduce Ni ²⁺ in the mixed powder;

The second temperature zone: 600℃≤T≤1000℃, used to reduce Co ²⁺ in the mixed powder;

The third temperature zone: 1000℃≤T, used to reduce Fe ³⁺ in the mixed powder.

This separation device can place the non-magnetic powder after the first sorting into the vacuum high-temperature furnace, set the second temperature zone, and repeat the above operations to obtain the second magnetic metal, and then repeat the same operation to obtain the third magnetic metal. Metal, but in order to save energy as much as possible and make the reduction reaction more thorough, the temperature settings of the three temperature zones in the vacuum furnace are set in turn: the first temperature zone is 550 ° C for nickel reduction, and the second temperature zone is 700 ° C for cobalt reduction. , The third temperature zone 1200 ℃ iron reduction. At the same time, three different sorting modules can be used to run simultaneously to form an assembly line and increase processing efficiency. In addition, for a more complete carbothermal reduction reaction, the set temperature may be slightly higher than the first temperature, such as 5 to 50° C. and so on.

The magnetic metal to be recovered in this embodiment starts from the oxidized state, and the magnetic metal in the oxidized state does not possess magnetism. The graphite carbon in the lithium-ion battery is used as a reducing agent to reduce the oxidized magnetic metal in the electrode powder. It can be formed into a single metal substance, so that it is magnetic, and then screened by a composite sorting method of wind and magnetism. In this embodiment, the separation device of the present invention can, but is not limited to, separate magnetic metal particles with a particle size of 2-20 um.

It can be seen from the above that the embodiment of the present invention provides a separation device for different magnetic metals in waste lithium-ion batteries, including a vacuum high-temperature furnace and a sorting module; wherein, the vacuum high-temperature furnace is used to sieve waste lithium-ion batteries The electrode powder is vacuumized to obtain the mixed powder to be sorted; the sorting module is used to separate the mixed powder to be sorted into magnetic metal powder and non-magnetic powder. Compared with the prior art that uses a large amount of chemical reagents and produces waste water, the technical solution of the present invention separates magnetic metals in waste lithium-ion batteries through carbothermal reduction and magnetic force-wind force, which can avoid secondary pollution and is environmentally friendly. Type characteristics, and this device can realize the effective separation of different kinds of magnetic metal mixed oxides, and improve the separation quantity and separation efficiency of magnetic metals.

The above description is a preferred embodiment of the present invention, and it should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications are also considered Be the protection scope of the present invention.

Claims (6)

1. A separation device for different magnetic metals in waste lithium ion batteries, characterized in that it comprises: a vacuum high temperature furnace and a sorting module; Wherein, the vacuum high-temperature furnace is used to vacuumize and heat the electrode powder obtained by screening the waste lithium-ion battery to obtain the mixed powder to be sorted; The sorting module is used for sorting the mixed powder to be sorted into magnetic metal powder and non-magnetic powder; the sorting module includes: feeding port (21), vibrating motor (22), vibrating feeding Plate (23), driving roller (24), electromagnetic plate (25), material baffle brush (26), driven magnetic roller (27), fan (28), belt (210), baffle plate (211), magnetic Metal powder receiving tank (214) and non-magnetic powder receiving tank (213); Wherein, the below of feed opening (21) is vibrating feeding plate (23), and vibrating feeding plate (23) is connected with vibrating motor (22); The bottom of the vibrating feed plate (23) is the upper surface of the transmission module; the transmission module is made up of a transmission roller (24), an electromagnetic plate (25), a driven magnetic roller (27) and a belt (210); the electromagnetic plate ( 25) set on the inner side of the transmission module, and close to the inner surface of the belt (210); The end of the transmission module is the air outlet of the fan (28), wherein the wind direction and the transmission direction are perpendicular to each other; the lower surface of the transmission module is provided with a material baffle brush (26); A baffle (211) is arranged above the air outlet of the blower fan (28), and one end of the baffle (211) is provided with a non-magnetic powder receiving tank (213); The end of the material baffle brush (26) is provided with a magnetic metal powder receiving tank (214). 2. The separation device of different magnetic metals in the waste lithium-ion battery according to claim 1, characterized in that, the vacuum high-temperature furnace comprises: an air release valve (1), a backing pump valve (2), an oil diffusion Pump valve (3), corundum tube (4), material storage tank (5), heating temperature rise control system (6), gas pipeline (7), composite vacuum gauge (8), gas outlet (9), backing pump (10), return condensed water inlet (11) and oil diffusion pump (12); Wherein, one end of the corundum tube (4) is the deflation valve (1), and the other end is the air inlet of the gas pipeline (7); 5) and the outside of the corundum tube (4) is provided with a heating and temperature rise control system (6); The gas pipeline (7) is provided with two gas outlets, and the two gas outlets are respectively connected with the backing pump valve (2) and the oil diffusion pump valve (3); the backing pump valve (2) is connected with the backing pump ( 10) connection; the oil diffusion pump valve (3) is connected to the oil diffusion pump (12); the oil diffusion pump (12) is respectively connected to the backflow condensate inlet (11) and the backing pump (10); The composite vacuum gauge (8) is used to measure the air pressure in the gas pipeline (7). 3. The separation device of different magnetic metals in the waste lithium-ion battery according to claim 2, characterized in that, the storage tank (5) comprises three sub-storage tanks; the heating and temperature rise control system (6) comprises Three control modules and three heating units; The three sub-storage tanks respectively correspond to a control module and a heating device; The control module is used to set the heating temperature of the heating device. 4. the separation device of different magnetic metals in the waste lithium ion battery according to claim 1, is characterized in that, described transmission roller (24), vibrating motor (22), blower fan (28) and electromagnetic plate (25) are Adjustable power equipment. 5 . The device for separating different magnetic metals in waste lithium-ion batteries according to claim 1 , wherein the transmission module forms an included angle with the horizontal direction, and the included angle ranges from 15° to 30°. 6. The separation device of different magnetic metals in the waste lithium-ion battery according to claim 1, characterized in that, the sorting module is a sealed system, in the feed port (21), the magnetic metal powder receiving tank (214 ) and the non-magnetic powder receiving tank (213) are respectively provided with cover plates.