CN111326810B - Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece - Google Patents
Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece Download PDFInfo
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- CN111326810B CN111326810B CN201811526063.5A CN201811526063A CN111326810B CN 111326810 B CN111326810 B CN 111326810B CN 201811526063 A CN201811526063 A CN 201811526063A CN 111326810 B CN111326810 B CN 111326810B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a method for photocatalytic degradation of organic matters in a waste lithium ion battery pole piece and a method for recycling a current collector and active substances in the pole piece, and belongs to the technical field of waste lithium ion battery recycling. The method for degrading organic matters in the waste lithium ion battery pole pieces through photocatalysis comprises the following steps: providing a composite system comprising a photocatalyst, a waste pole piece and water; and (3) oxygenating the composite system and simultaneously illuminating the composite system. The method can degrade and mineralize organic matters in the pole pieces into carbon dioxide, water and corresponding lithium ions such as SO by oxygenating a composite system containing waste pole pieces, a photocatalyst and water and illuminating4 2‑、NO3 ‑、PO4 3‑And the recovery process is simple in process, low in production cost, free of toxic and harmful gas, free of adverse effect on the environment, free of oxidation of the current collector and convenient for recovery and utilization of the current collector.
Description
Technical Field
The invention relates to a method for photocatalytic degradation of organic matters in a waste lithium ion battery pole piece and a method for recycling a current collector and active substances in the pole piece, and belongs to the technical field of waste lithium ion battery recycling.
Background
With the wide application of lithium batteries, China becomes the world with the largest lithium battery production and consumption, particularly, in recent years, the country has a series of preferential policies such as purchase subsidy, tax deduction and exemption, so that the market of new energy automobiles is increasingly developed vigorously, the new energy automobiles are used as the heart of new energy automobiles, the industry of power lithium batteries is also developed rapidly, and accordingly a large number of scrapped power lithium batteries are obtained, and the accumulated waste power lithium batteries in China exceed 12GWH and the scrappage reaches 17 million tons by the end of 2018. A large amount of electrolyte in the waste lithium battery can release various organic pollutants, and meanwhile, heavy metal substances such as cobalt, copper, nickel and the like in the battery can also permeate into water and soil, so that serious potential safety hazards of the ecological environment are brought to people. In order to promote the benign development of the power lithium battery industry, waste lithium batteries must be recycled and treated, so that the environmental pollution is reduced, and the waste of mineral resources is reduced. Therefore, accelerating the recycling of power lithium batteries is an important issue affecting the development of new energy industries.
The lithium battery recovery technology can be divided into a wet method and a fire method, wherein the wet method is to leach metal components in the waste batteries by using an inorganic or organic acid solution to separate recovered materials from organic matters, and then to recover the metal materials by using a complex exchange method, an alkaline boiling-acid dissolving method, an acid dissolving-extracting-precipitating method and the like, so that the process is discontinuous, cannot be recycled, and has high cost and serious pollution. The pyrogenic process is mainly to remove organic matters such as a binder, a diaphragm, electrolyte and the like through high-temperature incineration and decomposition, so that the separation among the lithium battery component materials is realized, but through high-temperature combustion, high-purity metal copper foil and aluminum foil can be oxidized and combusted, so that a large amount of energy consumption loss is caused, and toxic gases containing fluorine, chlorine and the like can be decomposed and generated in the roasting process, so that the environment is damaged.
Disclosure of Invention
The invention aims to provide a method for degrading organic matters in waste lithium ion battery pole pieces by photocatalysis with low cost and environmental friendliness.
The invention also provides a method for recovering the current collector and the active substances in the waste lithium ion battery pole piece.
In order to achieve the purpose, the method for degrading organic matters in the waste lithium ion battery pole pieces through photocatalysis adopts the technical scheme that:
a method for photocatalytic degradation of organic matters in waste lithium ion battery pole pieces comprises the following steps:
providing a composite system comprising a photocatalyst, a waste pole piece and water;
and (3) oxygenating the composite system, and simultaneously illuminating the composite system to perform a photocatalytic degradation reaction.
The method for degrading organic matters in the waste lithium ion battery pole pieces through photocatalysis can degrade and mineralize the organic matters in the pole pieces into carbon dioxide, water and corresponding lithium ions such as SO by oxygenating a composite system containing the waste pole pieces, a photocatalyst and water and illuminating4 2-、NO3 -、PO4 3-、Cl-And the whole recovery process is simple in process, low in production cost, free of toxic and harmful gas and free of adverse effect on the environment, and the oxidation of the current collector in the pole piece is avoided, so that the current collector is convenient to recycle.
In order to increase the efficiency of the photocatalytic degradation reaction, the photocatalyst is selected from TiO2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4And/or TiO2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4At least one modified photocatalyst as described in (1).
In order to improve the photocatalytic efficiency and keep the cost low, the mass ratio of the photocatalyst to water in the composite system is preferably 0.1-1: 100.
Preferably, the oxygenation is by passing an oxygen-containing gas through the composite system. In order to increase the efficiency of the photocatalytic degradation, the oxygen-containing gas is kept per m3The introduction amount of oxygen in water is 2-6.5 m3/min。
Oxygenation of the composite system is achieved by aerating the composite system. The aeration process is to provide oxygen to generate active free radicals, and the aeration can play a role in stirring, so that the photocatalytic degradation rate and the treatment efficiency can be improved in the aeration process, and the photocatalytic reaction can be more sufficient.
The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece adopts the technical scheme that:
a method for recovering a current collector and active substances in a waste lithium ion battery pole piece comprises the following steps:
providing a composite system comprising a photocatalyst, a waste pole piece and water;
introducing oxygen-containing gas into the composite system, and simultaneously illuminating the composite system to perform photocatalytic degradation reaction; and stripping the active substance on the irradiated pole piece from the current collector.
The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece has the advantages of simple process, low cost and easy continuous production, can effectively separate the electrode active substances, adopts photocatalysis to degrade the organic substances with low recovery value in the pole piece, has higher purity of the recovered materials due to no introduction of new impurities, can well prepare the electrode material precursor with high added value, and simultaneously recovers high-purity copper foil and/or aluminum foil.
Preferably, the stripping is to perform ultrasonic oscillation on the irradiated pole piece in an aqueous phase. Compared with the conventional technology, the method has the advantages that the active substances are stripped from the current collector through ultrasonic oscillation, so that the amount of the current collector metal entering the recovered active substances can be reduced, the purity of the recovered active substances is improved, and the loss amount of the current collector metal is reduced.
In order to improve the peeling effect, it is preferable that the ultrasonic frequency used for the ultrasonic oscillation is 30 to 130kHz, and the ultrasonic oscillation time is 10 to 60 min.
Preferably, the method for recovering the current collector and the active material in the waste lithium ion battery pole piece further comprises separating the current collector from a system obtained by ultrasonic oscillation, and then centrifuging. The catalyst and the active substance can be separated through centrifugation, the active substance and the water phase can be conveniently separated, and the separation efficiency is improved.
Drawings
FIG. 1 is an SEM photograph of an active material obtained by the recovery method of example 3 in Experimental example 1;
FIG. 2 is an XRD pattern of an active material obtained by the recovery method of example 3 in Experimental example 1;
FIG. 3 is an SEM photograph of an active material obtained by the recovering method of example 4 in example 1;
FIG. 4 is an XRD pattern of an active material obtained by the recovery method of example 4 in example 1;
FIG. 5 is a top view of a photocatalytic degradation device used in an embodiment;
FIG. 6 is a top view of a small tray in a photocatalytic degradation apparatus used in an embodiment;
FIG. 7 is a top view of an open basket container in a photocatalytic degradation apparatus used in an embodiment;
FIG. 8 is a top view of a mesh basket in a photocatalytic degradation apparatus used in an embodiment;
FIG. 9 is a schematic view of an assembly of a small tray, an open basket container, and an aeration apparatus of the photocatalytic degradation apparatus employed in the embodiment;
FIG. 10 is a front view of an open basket container in a photocatalytic degradation apparatus employed in an embodiment;
FIG. 11 is a front view of a mesh basket in a photocatalytic degradation apparatus employed in an embodiment;
FIG. 12 is a front view of an aeration apparatus in the photocatalytic degradation apparatus employed in the embodiment;
FIG. 13 is a schematic view showing the connection between an aeration apparatus and an air intake pipe in the photocatalytic degradation apparatus according to the embodiment;
FIG. 14 is a front view of an ultrasound device used in an embodiment;
the device comprises a large tray 1, a small tray 2, a net-type basket 3, a circular rib 301, a support rib 302, an open basket container 4, a first columnar ultraviolet light source 5, a second columnar ultraviolet light source 501, an aeration device 6, a first pipe section 601, a rotary joint 602, a second pipe section 603, a pull ring 7, a clamp 8, an ear plate 9, a bolt hole 10, a double-layer sleeve 11, a gas channel 12, a gas inlet 13, an aeration hole 14 and a holding container 15.
Detailed Description
The invention provides a method for photocatalytic degradation of organic matters in waste lithium ion battery pole pieces, which comprises the following steps:
providing a composite system comprising a photocatalyst, a waste pole piece and water;
and (3) oxygenating the composite system, and simultaneously illuminating the composite system to perform a photocatalytic degradation reaction.
The method for degrading organic matters in the waste lithium ion battery pole pieces through photocatalysis can degrade and mineralize the organic matters in the pole pieces into carbon dioxide, water and corresponding lithium ions such as SO by oxygenating a composite system containing the waste pole pieces, a photocatalyst and water and illuminating4 2-、NO3 -、PO4 3-、Cl-And the whole recovery process is simple in process, low in production cost, free of toxic and harmful gas and free of adverse effect on the environment, and the oxidation of the current collector in the pole piece is avoided, so that the current collector is convenient to recycle.
In the photocatalytic degradation process, the oxidative decomposition process of organic matters can be represented by the following reaction formula:
TiO2+hv→e-+h+
h++e-→ heat quantity
h++H2O→·OH+H+
h++OH-→·OH
e-+O2→·O2 -
H2O+·O2 -→HO2·+OH-
2HO2·→O2+H2O2
HO2·+H2O+e-→H2O2+OH-
H2O2+e-→·OH+OH-
The oxidative decomposition process generates many active free radicals, such as OH, O2 -OOH, etc., which have a strong oxidizing action, are free of transition products and can be converted into small inorganic molecules, such as carbon dioxide, H2O, and the like. OH is very active in catalytic systems, it can oxidize a variety of organic species at any time and any place, until a full degree of mineralization is reached.
The method for degrading the organic matters in the waste lithium ion battery pole pieces through photocatalysis further comprises the steps of discharging and disassembling the waste lithium ion battery, removing the diaphragm and recycling to obtain the pole pieces. In order to facilitate the recovery and utilization of the current collector in the pole piece, the positive pole piece and the negative pole piece are separately recovered when the pole piece is recovered.
The water in the composite system completely submerges the pole piece. The pole piece is completely submerged by water, so that organic matters in the pole piece can be removed as much as possible.
Semiconductors having photocatalytic activity are generally metal oxides, sulfides, noble metal semiconductors, and non-metal semiconductors. The photocatalyst is selected from TiO2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4And/or TiO2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4At least one modified photocatalyst, such as may be modified by doping. Due to TiO2The (titanium dioxide) has excellent catalytic performance, no toxic and side effects, low price and no secondary pollution, so the photocatalyst is preferably titanium dioxide and/or doped modified titanium dioxide photocatalyst. When titanium dioxide is used as the catalyst, titanium dioxide nanoparticles, titanium dioxide nanotubes, and a load supporting titanium dioxide can be usedAt least one of type (II) catalysts.
In order to improve the photocatalytic efficiency and keep the cost low, the mass ratio of the photocatalyst to water in the composite system is preferably 0.1-1: 100.
Preferably, the oxygenation is by passing an oxygen-containing gas through the composite system. In order to increase the efficiency of the photocatalytic degradation, the oxygen-containing gas is kept per m3The introduction amount of oxygen in water is 2-6.5 m3/min。
The illumination time is 10-30 h.
The light for illuminating the composite system is at least one of ultraviolet light and sunlight. The light for illuminating the composite system is selected according to the selected photocatalyst, and the selected light can enable the photocatalyst to play a photocatalytic role.
Generally, the energy E of a photon has an inverse relationship E of h c/λ with the wavelength λ (Lambda). For titanium dioxide, the anatase titanium dioxide can be excited by light with the wavelength less than 380nm, most of the light with the wavelength less than 380nm is ultraviolet light, the sunlight contains ultraviolet light and visible light, and the wavelength range of the visible light is larger. The titanium dioxide modified by doping, which is now being studied, can increase the wavelength range and allow it to undergo catalytic reactions under visible light. However, in the experimental process, the effect of using modified or unmodified titanium dioxide as a photocatalyst and adopting ultraviolet light for illumination or using the ultraviolet light and sunlight for illumination is much better than that of using the sunlight alone. But for g-C3N4The photocatalyst does not need to be irradiated by ultraviolet light, has photocatalysis effect under the irradiation of visible light, and can realize the photocatalytic degradation of organic matters in the pole piece.
The oxygen-containing gas is introduced into the composite system to aerate the composite system. Preferably, the aeration process is controlled every m3The aeration rate in water is 10-30 m3And/min. The aeration can be performed by arranging an aeration pipeline at the bottom of a container for containing the composite system and then oxygenating the composite system by using the aeration pipeline. Continuous exposure in the process of adopting illumination on the composite systemAnd (4) qi. The aeration process can provide oxygen to generate active free radicals, and the aeration can play a role in stirring, so that the photocatalytic degradation rate can be increased, the treatment efficiency can be improved, and the photocatalytic reaction can be more sufficient.
Preferably, the complex system is stirred during the oxygenation of the complex system. The stirring of the composite system is beneficial to the uniform dispersion of active free radicals in liquid, so that the photocatalytic reaction is more sufficient.
The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece adopts the technical scheme that:
a method for recovering a current collector and active substances in a waste lithium ion battery pole piece comprises the following steps:
providing a composite system comprising a photocatalyst, a waste pole piece and water;
introducing oxygen-containing gas into the composite system, and simultaneously illuminating the composite system to perform photocatalytic degradation reaction; and stripping the active substance on the irradiated pole piece from the current collector.
The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece has the advantages of simple process, low cost and easy continuous production, can effectively separate the electrode active substances, adopts photocatalysis to degrade the organic substances with low recovery value in the pole piece, has higher purity of the recovered materials due to no introduction of new impurities, can well prepare the electrode material precursor with high added value, and simultaneously recovers high-purity copper foil and/or aluminum foil.
The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece further comprises the steps of discharging and disassembling the waste lithium ion battery, removing the diaphragm and recovering to obtain the pole piece. In order to facilitate the recovery and utilization of the current collector in the pole piece, the positive pole piece and the negative pole piece are separately recovered when the pole piece is recovered.
Preferably, the pole piece is completely submerged by water in the composite system.
The semiconductor having photocatalytic activity is usually a metal oxide, sulfide, noble metal semiconductorAnd a non-metal semiconductor. Preferably, the photocatalyst is selected from TiO2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4And/or TiO2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4At least one modified photocatalyst as described in (1). When titanium dioxide is used as the catalyst, at least one of titanium dioxide nanoparticles, titanium dioxide nanotubes, and a supported catalyst supporting titanium dioxide may be used.
Preferably, the mass ratio of the catalyst to the water in the composite system is 0.1-1: 100.
Preferably, the oxygenation is by passing an oxygen-containing gas through the composite system. It is further preferred that the flow of the oxygen-containing gas is maintained per m3The introduction amount of oxygen in water is 2-6.5 m3/min。
The illumination time is 10-30 h.
The light for illuminating the composite system is at least one of ultraviolet light and sunlight. The light for illuminating the composite system is selected according to the selected photocatalyst, and the selected light can enable the photocatalyst to play a photocatalytic role.
The oxygen-containing gas is introduced into the composite system to aerate the composite system. Preferably, the aeration process is controlled every m3The aeration rate in water is 10-30 m3/min。
Preferably, the complex system is stirred during the oxygenation of the complex system.
The active substance and the current collector on the pole piece after being irradiated can be stripped by adopting an ultrasonic or mechanical friction method. Preferably, the stripping is to perform ultrasonic oscillation on the irradiated pole piece in an aqueous phase. Compared with the conventional technology, the method has the advantages that the active substances are stripped from the current collector through ultrasonic oscillation, so that the amount of the current collector metal entering the recovered active substances can be reduced, the purity of the recovered active substances is improved, and the loss amount of the current collector metal is reduced.
The pole piece is subjected to ultrasonic oscillation in the water phase, the ultrasonic oscillation can be directly carried out on the illuminated composite system, and the pole piece can also be taken out after illumination and placed in water for ultrasonic oscillation. In order to facilitate the separation of the stripped active substance from the catalyst, the irradiated pole piece is preferably taken out and placed in water for ultrasonic oscillation.
In order to improve the peeling effect, it is preferable that the ultrasonic frequency used for the ultrasonic oscillation is 30 to 130kHz, and the ultrasonic oscillation time is 10 to 60 min.
No matter the composite system after being irradiated with light is directly subjected to ultrasonic oscillation or the pole piece is taken out and placed in water for oscillation, a catalyst inevitably exists in the system after oscillation, and in order to improve the purity of an active substance, the catalyst in the system needs to be removed and reused. Preferably, the method for recovering the current collector and the active material in the waste lithium ion battery pole piece further comprises separating the current collector from a system obtained by ultrasonic oscillation, and then centrifuging. The catalyst and the active substance can be separated through centrifugation, the active substance and the water phase can be conveniently separated, and the separation efficiency is improved.
The technical solution of the present invention will be further described with reference to the following embodiments.
The recovery system adopted in each embodiment of the recovery method of the current collector and the active material in the waste lithium ion battery pole piece comprises a photocatalytic degradation device and an ultrasonic device as shown in fig. 5-14; the photocatalytic degradation device comprises a circular large tray 1, 3 circular rotatable small trays 2 which are uniformly arranged on the large tray 1 at intervals along the circumferential direction of the large tray 1, a net type basket 3, a cylindrical open basket container 4 for placing the single net type basket 3, a first cylindrical ultraviolet light source 5, an aeration device 6 and a second cylindrical ultraviolet light source 501. The open basket vessel 4 is a silica glass lined PFA vessel. The mesh basket 3 is detachable from the open basket receptacle 4.
All be provided with an uncovered basket container 4 in every little tray 2, the fixed 3 otic placodes 9 that are provided with on the outer periphery of uncovered basket container 4 lower extreme, 3 otic placodes 9 are along the even interval distribution of uncovered basket container 4 circumference, each otic placode 9 all outwards extends along perpendicular uncovered basket container 4 axis direction, be provided with first bolt hole 10 on the otic placode 9, the corresponding second bolt hole (not shown in the figure) that is used for passing through bolt fixed connection with each otic placode 9 that is provided with of the diapire internal surface edge of little tray 2, uncovered basket container 4 passes through otic placode 9 and is fixed in little tray 2 through bolted connection.
The net type basket 3 comprises a cylindrical basket body and a pull ring 7 for pulling the basket body out of the open basket container 4, and the basket body comprises 4 circular ribs 301 and a plurality of support ribs 302 which are sequentially arranged and used for supporting the circular ribs 301. The pull ring 7 is arranged on a circular rib 301 at one end of the basket body. The circular ribs 301 and the supporting ribs 302 are both made of metal, and the circular ribs 301 and the supporting ribs 302 are connected in a welding mode. Each support rib 302 is provided with two clamps 8 which are arranged in sequence and used for clamping the same pole piece.
A first columnar ultraviolet light source 5 which is vertical to the bottom surface of the large tray and is equivalent to the height of the basket body is arranged at the circle center of the large tray 1.
The aeration device 6 comprises a transparent annular double-layer sleeve 11 with two closed ends, which can penetrate ultraviolet light and sunlight, a gas channel 12 is formed between an inner pipe and an outer pipe of the double-layer sleeve 11, a gas inlet 13 communicated with the gas channel 12 is arranged on the outer side wall of one end of the outer pipe of the double-layer sleeve 11, the other end of the double-layer sleeve 11 is fixedly connected to the center of the bottom of the open basket container 4, and a plurality of aeration holes 14 communicated with the gas channel 12 are arranged on the outer side wall of the outer pipe at the end; the double-layer sleeve 11 is vertical to the bottom surface of the open basket container 4, and a second columnar ultraviolet light source 501 is fixedly arranged in an inner pipe of the double-layer sleeve 11; before aeration, the air inlet 13 is communicated with an air inlet pipeline; the air inlet pipeline comprises a first pipe section 601 connected with the air inlet 13 and a second pipe section 603 used for connecting an air source, the first pipe section 601 and the second pipe section 603 are connected through a rotary joint 602, and the first pipe section 601 can rotate along with the aeration device 6 after being communicated with the aeration device 6. The second cylindrical ultraviolet light source 501 may be an ultraviolet light source with a built-in power supply or an ultraviolet light source with an external power supply.
The ultrasonic device comprises a 304 stainless steel container 15 for holding the mesh basket 3 and an ultrasonic generator (not shown), and a drain port (not shown) is provided at the bottom of the container 15.
The device adopted in each embodiment of the method for photocatalytic degradation of organic matters in the waste lithium ion battery pole pieces is the photocatalytic degradation device.
Example 1 of method for photocatalytic degradation of organic matters in waste lithium ion battery pole pieces
The method for degrading organic matters in the waste lithium ion battery pole pieces through photocatalysis comprises the following steps:
1) collecting waste lithium ion batteries, discharging, disassembling, and separating the positive electrode plate and the negative electrode plate after removing the diaphragm;
2) putting the recovered waste positive plate into a net type basket, fixing the positive plate by using a clamp, putting the net type basket into an open basket container, and adding deionized water, wherein the adding amount of water is controlled to completely submerge the positive plate; then adding titanium dioxide nano particles, and controlling the mass ratio of the added titanium dioxide nano particles to the added water to be 0.5:100 to obtain a composite system;
3) then opening an oil pump to aerate the composite system with air every m3The aeration amount of water was controlled to 20m3Min, wherein the aeration time is 10 h; during aeration, an ultraviolet light source is turned on, the composite system is irradiated by sunlight, the small tray is driven to rotate, and the rotating speed of the small rotating disc is controlled to be 50 rpm;
4) and after the aeration is finished, the ultraviolet light source is turned off, the small tray is stopped from rotating, and the net type lifting basket is taken out.
Example 2 of method for photocatalytic degradation of organic matters in waste lithium ion battery pole pieces
The method for degrading organic matters in the waste lithium ion battery pole pieces through photocatalysis comprises the following steps:
1) collecting waste lithium ion batteries, discharging, disassembling, and separating the positive electrode plate and the negative electrode plate after removing the diaphragm;
2) putting the recovered waste positive plate into a net type basket, fixing the positive plate by using a clamp, putting the net type basket into an open basket container, and adding deionized water, wherein the adding amount of water is controlled to completely submerge the positive plate; then adding a titanium dioxide nanotube, and controlling the mass ratio of the added titanium dioxide nanotube to the added water to be 0.1:100 to obtain a composite system;
3) then opening an oil pump to aerate the composite system with air every m3The aeration amount of water was controlled to 30m3Min, wherein the aeration time is 20 h; during aeration, an ultraviolet light source is turned on, the composite system is irradiated by sunlight, the small tray is driven to rotate, and the rotating speed of the small rotating disc is controlled to be 50 rpm;
4) and after the aeration is finished, the ultraviolet light source is turned off, the small tray is stopped from rotating, and the net type lifting basket is taken out.
Example 3 of method for photocatalytic degradation of organic matters in waste lithium ion battery pole pieces
The method for degrading organic matters in the waste lithium ion battery pole pieces through photocatalysis comprises the following steps:
1) collecting waste lithium ion batteries, discharging, disassembling, and separating the positive electrode plate and the negative electrode plate after removing the diaphragm;
2) putting the recovered waste positive plate into a net type basket, fixing the positive plate by using a clamp, putting the net type basket into an open basket container, and adding deionized water, wherein the adding amount of water is controlled to completely submerge the positive plate; then adding a supported catalyst loaded with titanium dioxide, and controlling the mass ratio of the added titanium dioxide to the added water to be 1:100 to obtain a composite system;
3) then opening an oil pump to aerate the composite system with air every m3The aeration amount of water was controlled to 10m3Min, aeration time is 30 h; during aeration, an ultraviolet light source is turned on, the composite system is irradiated by sunlight, the small tray is driven to rotate, and the rotating speed of the small rotating disc is controlled to be 50 rpm;
4) and after the aeration is finished, the ultraviolet light source is turned off, the small tray is stopped from rotating, and the net type lifting basket is taken out.
Example 4 of method for photocatalytic degradation of organic matters in waste lithium ion battery pole pieces
The method for degrading organic matters in the waste lithium ion battery pole pieces through photocatalysis comprises the following steps:
1) collecting waste lithium ion batteries, discharging, disassembling, and separating the positive electrode plate and the negative electrode plate after removing the diaphragm;
2) putting the recycled waste and old negative pole pieces into a net type basket, fixing the negative pole pieces by using a clamp, putting the net type basket into an open basket container, and adding deionized water, wherein the adding amount of the water is controlled to completely submerge the negative pole pieces; then adding titanium dioxide nanoparticles, and controlling the mass ratio of the added titanium dioxide to the added water to be 1:100 to obtain a composite system;
3) then opening an oil pump to aerate the composite system with air every m3The aeration amount of water was controlled to 15m3Min, wherein the aeration time is 15 h; during aeration, an ultraviolet light source is turned on, the composite system is irradiated by sunlight, the small tray is driven to rotate, and the rotating speed of the small rotating disc is controlled to be 50 rpm;
4) and after the aeration is finished, the ultraviolet light source is turned off, the small tray is stopped from rotating, and the net type lifting basket is taken out.
Example 1 of method for recovering current collector and active material from waste lithium ion battery pole piece
The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece comprises the following steps:
step 1) to step 4): completely similar to steps 1) to 4) of embodiment 1 of the method for photocatalytic degradation of organic matters in waste lithium ion battery pole pieces, no further description is given;
step 5): placing the taken net type basket in a containing container of an ultrasonic device, controlling an ultrasonic generator to generate ultrasonic waves with the vibration frequency of 130MHz, oscillating the ultrasonic waves for 10min to strip off active substances and a current collector, taking out the net type basket, separating out a clean and complete positive current collector, pouring out residual substances from the containing container, standing, removing most of clear liquid on the upper layer to enable the residual liquid to account for about one fourth of the total mass of active substance particles and titanium dioxide nanoparticles, carrying out high-speed centrifugal separation on the residual mixture, scraping titanium dioxide nanoparticles on the solid surface layer obtained by centrifugal separation (the titanium dioxide nanoparticles are concentrated on the solid surface layer after centrifugation because the amount of the titanium dioxide nanoparticles is very small and nano-scale), and drying the residual solid substances to obtain the active substances capable of being used for preparing the battery material.
Example 2 of method for recovering current collector and active material from waste lithium ion battery pole piece
The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece comprises the following steps:
step 1) to step 4): completely similar to the steps 1) to 4) of the method for photocatalytic degradation of organic matters in the waste lithium ion battery pole pieces in embodiment 2), no further description is given;
5) placing the taken net type basket in a containing container of an ultrasonic device, controlling an ultrasonic generator to generate ultrasonic waves with the vibration frequency of 30MHz, carrying out ultrasonic oscillation for 30min to strip off active substances and a current collector, taking out the net type basket, separating out a clean and complete positive current collector, pouring out residual substances from the containing container, standing, removing most of clear liquid on the upper layer to enable the residual liquid to account for about one fourth of the total mass of active substance particles and titanium dioxide nanotubes, carrying out high-speed centrifugal separation on the residual mixture, scraping the titanium dioxide nanotubes on the solid surface layer obtained by centrifugal separation, and drying the residual solid substances to obtain the active substances for preparing the battery material.
Example 3 of method for recovering current collector and active material from waste lithium ion battery pole piece
The recycling method of the embodiment comprises the following steps:
step 1) to step 4): step 1) to step 4) of embodiment 3 of the method for photocatalytic degradation of organic matters in the waste lithium ion battery pole pieces are completely the same, and are not described again;
step 5): placing the taken out net type basket in a containing container of an ultrasonic device, controlling an ultrasonic generator to generate ultrasonic waves with the vibration frequency of 80MHz, carrying out ultrasonic oscillation for 60min to strip off active substances and a current collector, taking out the net type basket, separating out a clean and complete positive current collector, discharging residual substances from a water outlet of the containing container, standing, removing most of clear liquid on the upper layer to enable the residual liquid to account for about one fourth of the total mass of active substance particles and a supported catalyst, carrying out high-speed centrifugal separation on the residual mixture, scraping the supported catalyst on the solid surface layer obtained by the centrifugal separation, and drying the residual solid substances to obtain the active substances for preparing the battery material.
Example 4 of method for recovering current collector and active material from waste lithium ion battery pole piece
The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece comprises the following steps:
step 1) to step 4): step 1) to step 4) of embodiment 4 of the method for photocatalytic degradation of organic matters in the waste lithium ion battery pole pieces are completely the same, and are not described again;
step 5): placing the taken net type basket in a containing container of an ultrasonic device, controlling an ultrasonic generator to generate ultrasonic waves with the vibration frequency of 50MHz, carrying out ultrasonic oscillation for 40min to strip off active substances and a current collector, taking out the net type basket, separating out a clean and complete negative current collector, pouring out residual substances from the containing container, standing, removing most of clear liquid on the upper layer to enable the residual liquid to account for about one fourth of the total mass of active substance particles and titanium dioxide nanoparticles, carrying out high-speed centrifugal separation on the residual mixture, scraping off titanium dioxide nanoparticles on the solid surface layer obtained by centrifugal separation, and drying the residual solid substances to obtain the active substances for preparing the battery material.
The active materials recovered in the embodiments 1 to 4 of the recovery method for photocatalytically degrading the current collector and the active materials in the waste lithium ion battery pole piece are mixed with the conductive agent, but the amount of the conductive agent is small, so that the recovered active materials can be directly used for preparing the active materials of the positive electrode or the negative electrode.
Comparative example 1
Organic matters such as a binder, a diaphragm, electrolyte and the like are removed by high-temperature incineration decomposition by adopting a pyrogenic process, so that the separation between the lithium battery component materials is realized, and the foil and the electrode material are recovered.
Comparative example 2
The wet method is adopted to leach metal components in the waste batteries through sulfuric acid solution, and then the foil and the electrode material are extracted and recovered.
Experimental example 1
Using ternary positive electrode active material LiNi0.5Co0.2Mn0.3O2Adding the positive active material, the conductive agent and the binder into an N-methyl pyrrolidone (NMP) solvent according to the mass ratio of 90:5:5, and uniformly mixing to obtain positive active material slurry, wherein the positive active material slurry is prepared by taking conductive carbon black as a conductive agent and polyvinylidene fluoride (PVDF) as a binder; the positive active material slurry was coated on an aluminum current collector, and then dried and pressed in a conventional method to prepare a positive electrode sheet.
Adding graphite powder as a negative active material, conductive carbon black as a conductive agent and PVDF as a binder into an NMP solvent according to a mass ratio of 90:5:5, and uniformly mixing to prepare a negative active material slurry; the negative active material slurry was coated on a copper current collector, and then dried and pressed in a conventional method to prepare a negative electrode sheet.
The positive plate and the negative plate prepared in the experimental example are respectively used as a waste positive plate and a waste negative plate obtained by recovery, the current collectors and the active substances in the plate are recovered by adopting the methods of examples 1 to 4 and comparative examples 1 to 2 of the recovery method of the current collectors and the active substances in the waste lithium ion battery plate, the recovery rates are respectively calculated, and the recovery rates are shown in table 1. The recovery rate calculation method comprises the following steps: mass of recycled material/mass of added material x 100%.
Table 1 examples of methods for recovering current collectors and active materials from used lithium ion battery electrode sheets
And the recovery rate of the active material and the current collector in the recovery method of comparative example
SEM test and XRD test were performed on the active materials recovered by the recovery methods of examples 3 and 4 of the recovery method of the current collector and the active material in the waste lithium ion battery electrode sheet, respectively, and the SEM image and the XRD image of the active material obtained by the recovery method of example 3 of the recovery method of the current collector and the active material in the waste lithium ion battery electrode sheet are shown in fig. 1 and fig. 2, respectively, and the SEM image and the XRD image of the active material obtained by the recovery method of example 4 of the recovery method of the current collector and the active material in the waste lithium ion battery electrode sheet are shown in fig. 3 and fig. 4, respectively.
As can be seen from fig. 1, the active particles of the lithium nickel cobalt manganese oxide positive electrode obtained by the recovery method of example 3, which is a recovery method of the current collector and the active material in the waste lithium ion battery pole piece, are approximately spherical, uniform in size, and good in structure retention; as can be seen from figure 2, the XRD spectrogram diffraction peak of the nickel cobalt lithium manganate positive active substance is relatively sharp, and the obtained product has a perfect crystal form, no impurity phase peak and good crystallinity.
As can be seen from fig. 3, the graphite negative active material particles obtained by the recovery method of example 4, which adopts the recovery method of the current collector and the active material in the waste lithium ion battery pole piece, have a lamellar structure, the size of the graphite negative active material particles is tens of microns to twenty microns, and the structure is well maintained; as can be seen from FIG. 4, the XRD spectrum diffraction peak of the graphite cathode active material corresponds to the standard spectrum, and the peak shape is relatively sharp, which shows that the graphite product has a perfect crystal form and no impurity phase peak.
Experimental example 2
Taking the active material obtained by the recovery method of the embodiment 3, which adopts the recovery method of the current collector and the active material in the waste lithium ion battery pole piece in the experimental example 1, as the positive active material, taking the conductive carbon black Super-P as the conductive agent, taking the PVDF as the binder, adding the positive active material, the conductive agent and the binder into the NMP solution according to the mass ratio of 90:5:5, and uniformly mixing to prepare positive slurry; coating the obtained anode slurry on the surface of an aluminum current collector, coating, rolling, baking and cutting into pieces by a conventional method to prepare the anode piece. The used negative plate is a metal lithium plate with the diameter of 15.8mm and electrolyte solutionUsing 1mol/L LiPF6The solvent is a mixed solvent of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1:1:1, the isolating membrane is a polypropylene (PP) membrane, and the CR2032 button cell is obtained by assembling the membrane in an argon-filled glove box.
The battery assembly is completed, and the charging and discharging performance test is carried out on a blue test cabinet, wherein the specific test conditions are as follows: the half-cell was subjected to constant current charging to a cutoff voltage of 4.3V at a current density of 0.1C, constant current discharging to 3.0V at a current density of 0.1C, constant current charging to a cutoff voltage of 4.3V at a current density of 1C, constant current discharging to 3.0V at a current density of 1C, and thereafter cycling at a charge-discharge current density of 1C. According to the process, the charge and discharge performance of the half-cell is tested, and the test data result is shown in table 2:
TABLE 2 measurement results of the charge and discharge performance of button cell
From the test results in table 2, it can be seen that the lithium nickel cobalt manganese oxide positive active material recovered by the method of the present invention maintains good charge-discharge cycle performance, and although the gram capacity performance is reduced after a plurality of cycles, it is enough to show that the positive active material recovered by the method can still be applied to the battery.
Experimental example 3
The active material obtained by the recovery method of example 4, which is the recovery method of the current collector and the active material in the waste lithium ion battery pole piece in the experimental example 1, is used as a negative active material, conductive carbon black Super-P is used as a conductive agent, an acrylonitrile multipolymer aqueous dispersion LA-132 is used as a binder, the negative active material, the conductive agent and the binder are added into deionized water according to the mass ratio of 90:5:5 and mixed uniformly to obtain negative slurry, the negative slurry is coated on the surface of a copper current collector, and the negative plate is prepared by coating, rolling, baking and cutting the pieces by a conventional method. The used metal lithium sheet with the diameter of 15.8mm is a metal lithium sheet, and the electrolyte solution adopts 1mol/LLIPF6Ethylene carbonate, dimethyl carbonate and dicarbonate with a solvent volume ratio of 1:1:1And (3) mixing the ethyl ester with a solvent, and assembling the isolation film by adopting a polypropylene (PP) film in a glove box filled with argon to obtain the CR2032 button cell.
The battery assembly is completed, and the charging and discharging performance test is carried out on a blue test cabinet, wherein the specific test conditions are as follows: the half-cell was subjected to constant current charging to a cutoff voltage of 4.3V at a current density of 0.1C, constant current discharging to 3.0V at a current density of 0.2C, constant current charging to a cutoff voltage of 4.3V at a current density of 0.2C, constant current discharging to 3.0V at a current density of 1C, and thereafter, cycling was performed at a charge-discharge current density of 1C. According to the process, the charge and discharge performance of the half-cell is tested, and the test results are shown in table 3:
TABLE 3 measurement results of the charge and discharge performance of button cell
As can be seen from the test results in table 3, the graphite negative active material recovered according to the present invention maintained good charge and discharge cycle performance, and although gram capacity exertion was reduced after many cycles, it was sufficient to demonstrate that the negative active material recovered by the present method can be applied to batteries.
Claims (6)
1. A method for recovering a current collector and active substances in a waste lithium ion battery pole piece is characterized by comprising the following steps: the method comprises the following steps:
providing a composite system comprising a photocatalyst, a waste pole piece and water;
introducing oxygen-containing gas into the composite system, and simultaneously illuminating the composite system to perform photocatalytic degradation reaction; stripping the active substance on the irradiated pole piece from the current collector;
the photocatalyst is selected from TiO2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4And/or TiO2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4At least one ofSeeding the modified photocatalyst;
maintaining per m during the introduction of the oxygen-containing gas3The introduction amount of oxygen in water is 2-6.5 m3/min；
The introduction of the oxygen-containing gas into the composite system is achieved by aerating the composite system.
2. The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece according to claim 1, is characterized in that: the mass ratio of the photocatalyst to water in the composite system is 0.1-1: 100.
3. The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece according to claim 1, is characterized in that: the illumination time is 10-30 h.
4. The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece according to claim 1, is characterized in that: and the stripping is to perform ultrasonic oscillation on the irradiated pole piece in a water phase.
5. The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece according to claim 4, is characterized in that: the frequency of ultrasonic waves adopted by the ultrasonic wave oscillation is 30-130 kHz, and the time of the ultrasonic wave oscillation is 10-60 min.
6. The method for recovering the current collector and the active substances in the waste lithium ion battery pole piece according to claim 4, is characterized in that: further comprises separating the current collector from the system obtained by ultrasonic oscillation and then centrifuging.
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