CN115799694A - Crushing, disassembling and recycling method for lithium battery - Google Patents
Crushing, disassembling and recycling method for lithium battery Download PDFInfo
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- CN115799694A CN115799694A CN202211349870.0A CN202211349870A CN115799694A CN 115799694 A CN115799694 A CN 115799694A CN 202211349870 A CN202211349870 A CN 202211349870A CN 115799694 A CN115799694 A CN 115799694A
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Abstract
The invention discloses a crushing, disassembling and recycling method of lithium batteries, which comprises the following steps of S1, carrying out module disassembling treatment on waste lithium batteries to obtain single batteries and auxiliary circuit components. And S2, carrying out charge-discharge test on the single batteries, and screening out the single batteries with low capacity and large internal resistance. And S3, discharging the screened single batteries. And S4, disassembling the single battery after the discharge treatment to obtain a battery shell, a positive plate, a negative plate and a diaphragm. And S5, drying the negative plate, and separating a graphite reclaimed material and a current collector copper foil. And S5, treating the positive plate, and precipitating aluminum from the liquid. Lithium and iron were precipitated by filtration of the slag. S7, treating filter residues, wherein Fe is Fe (OH) 3 Precipitated in the form of lithium II 2 CO 3 Can obtain aluminum hydroxide with chemical purity level, iron hydroxide with the purity of 98.7 percent and lithium carbonate meeting the zero-grade requirement.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery, in particular to a crushing, disassembling and recovering method for a lithium battery.
Background
A large amount of waste batteries cause waste of resource and energy and environmental pollution, and the waste lithium ion batteries contain a large amount of available resources, such as valuable metals like aluminum and copper, graphite and carbon-based materials; if the waste lithium batteries are not properly disposed, great resource waste and environmental pollution can be caused.
However, in the prior art, the recycling of lithium batteries is just started, and the existing separation method generally has great limitations, the reusable resources of the waste batteries cannot be effectively separated at one time, and the purity of the recycled materials is not high, so that improvement on the recycling method needs to be made by those skilled in the art.
Disclosure of Invention
The invention aims to provide a crushing, disassembling and recycling method for a lithium battery.
The technical problem solved by the invention is as follows:
the existing separation method generally has great limitation, can not effectively separate the reusable resources of the waste batteries at one time, and has low purity of the recovered materials.
The purpose of the invention can be realized by the following technical scheme:
a crushing, disassembling and recycling method for lithium batteries comprises the following steps:
s1, performing module splitting treatment on the waste lithium battery to obtain a single battery and an auxiliary circuit component.
And S2, carrying out charge and discharge tests on the single batteries, and screening out the single batteries with low capacity and high internal resistance.
And S3, performing discharge treatment on the screened single batteries.
And S4, disassembling the single battery after the discharge treatment to obtain a battery core and a battery shell. And further disassembling the battery cell to obtain the positive and negative pole pieces and the diaphragm. And directly recycling the battery shell and the separator.
And S5, drying the negative plate, and separating a graphite recovery material and a current collector copper foil.
And S6, crushing the positive plate to obtain positive material residues. Dissolving the positive electrode material residue in NaOH alkaline liquor, filtering and separating the solution, and separating aluminum from the liquid. Lithium and iron were precipitated by filtration of the slag.
S7, using sulfuric acid solution and H 2 O 2 The solution dissolves the filter residue, phosphorus and iron are Fe 2 (SO4) 3 And Li 2 SO 4 The form of the iron-containing compound enters a solution, is separated from impurities, is filtered, and is adjusted in pH value by using sodium hydroxide and ammonia water, wherein Fe is Fe (OH) 3 Precipitated in the form of (1), and the remaining solution was saturated with Na 2 CO 3 Precipitation of Li from solution 2 CO 3 。
As a further scheme of the invention: in the step S1, the auxiliary circuit components comprise electric wires and cables, a PCB, screws, nuts and a box body.
As a further scheme of the invention: in step S2, during the charge and discharge test, the screened high-capacity and low-internal-resistance batteries are reserved as power battery echelon utilization resources.
As a further scheme of the invention: when the discharging treatment is performed in step S3, the stacked batteries should be placed into a discharging tank filled with brine one by one to be soaked, and the batteries after discharging should be dried.
As a further scheme of the invention: in step S4, when the discharged unit batteries are disassembled, any one of a clamping-type cell separation method, a case-core peeling-type separation method, and a cell ejecting-type separation method should be used.
As a further scheme of the invention: and S5, when the negative plate is dried, putting the negative plate into a watch glass, drying the negative plate in an oven at 100 ℃ for 1h, and shaking the negative plate after drying to separate graphite from a current collector copper foil.
As a further scheme of the invention: in step S5, when the positive plate is crushed, the positive plate is mechanically crushed into fragments with the diameter of 1-5 mm.
As a further scheme of the invention: when aluminum is precipitated, the pH of the solution is adjusted to 9.0 by using a sulfuric acid solution, so that the aluminum is precipitated in the form of aluminum hydroxide.
The invention has the beneficial effects that:
the current collector is recovered in the form of Al (OH) 3, and Al (OH) 3 is obtained by mechanically crushing, alkaline leaching and adding acid to neutralize the positive pole piece; for the separation of lithium and iron, the sulfuric acid leaching recovery cost is low and the efficiency is high. By the process, aluminum hydroxide with a chemical purity level, iron hydroxide with a purity of 98.7% and lithium carbonate meeting zero-grade requirements can be obtained, and the precipitation rate of primary lithium exceeds 80%.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic flow chart of a crushing, disassembling and recycling method of a lithium battery according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the invention relates to a method for crushing, disassembling and recycling lithium batteries, in particular to a waste lithium iron phosphate battery, which comprises the following steps S1 to S7.
S1, performing module splitting treatment on the waste lithium battery to obtain a single battery and an auxiliary circuit component. Specifically, the auxiliary circuit components include wires and cables, a PCB, screws, nuts, a box body, etc., and these auxiliary circuit components can be recycled.
And S2, carrying out charge-discharge test on the single batteries, and screening out the single batteries with low capacity and large internal resistance. Specifically, charge and discharge tests are performed on the separated single batteries, and good batteries which can be used continuously are sorted out according to test results. Reserving a battery with high capacity and low internal resistance as a gradient utilization resource of the power battery; and the single battery with low capacity and large internal resistance is scrapped and recycled as resources.
And S3, performing discharge treatment on the screened single batteries. Specifically, the battery to be recycled should be completely discharged in the discharge tank to ensure the safety of the battery in the disassembling process. Firstly, the stacked batteries are put into a discharge tank with inner saline water for soaking for 0.5 to 1 hour by a traveling crane or other hoisting equipment one by one, the discharged batteries can be dried naturally or dried by hot air, but the temperature of the hot air is controlled below 80 ℃ to ensure the safety. The battery is generally discharged to 1.5V, and lithium ions are inserted into the positive electrode as much as possible to reduce the lithium content in the graphite layer of the negative electrode, thereby facilitating efficient recovery of lithium.
And S4, disassembling the single battery after the discharge treatment to obtain a battery core and a battery shell. And further disassembling the battery cell to obtain the positive and negative pole pieces and the diaphragm. The battery case and the separator are directly recycled.
Specifically, when disassembling, any one of a clamping-type cell separation method, a shell-core peeling-type separation method, and a cell ejection-type separation method should be adopted. After the battery core is disassembled, the battery core is disassembled and collected to obtain the positive and negative pole pieces and the diaphragm, and the diaphragm material which can be directly recycled and made of PP materials is sent to a manufacturer special for recycling plastics. And the positive plate and the negative plate are dried at low temperature to remove a small amount of electrolyte (mainly DC, DMC and the like), then immersed in 10% NaOH solution for about 10min, and LiPF6 precipitated on the plates is removed through reaction, so that the positive plate and the negative plate are obtained. LiPF 6 Easily thermally decomposed into PF 5 And LiF (30 ℃), which is easily decomposed, can also be recovered by thermal treatment techniques, but care should be taken to exhaust emissions.
And S5, drying the negative plate, and separating a graphite reclaimed material and a current collector copper foil.
Specifically, when the negative plate is dried, the negative plate is placed into a watch glass and dried in an oven at 100 ℃ for 1h, and the negative plate is shaken after drying, so that the graphite is separated from the current collector copper foil. The negative plate is processed by the artificial shaking method, and the original appearance structure of the recovered copper foil of the negative current collector is not changed. After washing, the gloss is bright and can be recovered intact.
And S6, crushing the positive plate to obtain positive material residues. Dissolving the residue of the positive electrode material in NaOH alkaline liquor, filtering and separating the solution, and precipitating aluminum from the solution. Lithium and iron were precipitated by filtration of the slag.
In particular, the effective separation of the current collector from the active material is the basis for the concentrated recovery of the electrode active material and can provide the recovery rate and efficiency of the current collector, which occupies an important position in the whole recovery process, in the present invention the current collector is made of Al (OH) 3 Form recovery is carried out by mechanically crushing the positive plate into pieces with diameter of 1-5mm, dissolving the aluminum foil of current collector into 250mLNaOH alkali liquor, using NaAlO as aluminum 2 Into solution. The aluminum is completely dissolved in the alkali liquor, and the positive active material which is not dissolved in the alkali liquor comprises a conductive agent and a binder to form alkaline leaching residue. And (3) filtering and separating the solution, adding a sulfuric acid solution to adjust the pH of the alkali liquor to 9.0, and separating out aluminum in the form of aluminum hydroxide, wherein the purity of the separated product reaches the standard of a chemical pure reagent, and the recovery rate of metal aluminum is up to more than 92%. Al (OH) formed in the process 3 Has good filtering performance, and the obtained alkaline filtrate can be recycled after adding alkali without discharging sewage. The positive electrode active material is recovered by filtration because it is insoluble in alkali.
S7, using sulfuric acid solution and H 2 O 2 The solution dissolves the filter residue, phosphorus and iron are Fe 2 (SO4) 3 And Li 2 SO 4 The form of the iron-containing compound enters a solution, is separated from impurities, is filtered, and is adjusted in pH value by using sodium hydroxide and ammonia water, wherein Fe is Fe (OH) 3 Precipitated in the form of (1), and the remaining solution was saturated with Na 2 CO 3 Precipitation of Li from solution 2 CO 3 。
Specifically, after the current collector is recovered, lithium and iron in the cathode material need to be recovered. The positive electrode active material separated from the current collector aluminum by the wet method exists in the filter residue obtained after filtration because it is insoluble in alkali, and lithium and iron are recovered. Wherein the recovered Li 2 CO 3 Can be used as the raw material of lithium iron phosphate to reproduce LiFePO 4 To Li 2 CO3 or LiFePO 4 Packaging and directly selling to realize recycling. For better dissolving effect, the filter residue can be dissolved in sulfuric acid solution and H 2 O 2 The solution is dissolved. Lithium iron phosphate quilt H 2 SO4-H 2 O 2 After oxidation of the solution, with Fe 2 (SO4) 3 And Li 2 SO 4 Into solution, separated from impurities. After filtration, the pH of the filtrate was adjusted with sodium hydroxide and ammonia water. First, fe is Fe (OH) 3 Is precipitated, and the remaining solution is heated to 90 deg.C and saturated Na is added 2 CO 3 Precipitation of Li from solution 2 CO 3 . Through condition optimization, the optimal condition is 2mol/L H 2 SO 2 、30％H 2 O 2 The solid-liquid ratio is 1g/10mL. After the mixture was heated to 60 ℃ and stirred for 2 hours, 8% of non-fusible slag (carbon black in the positive electrode material, etc.) was precipitated after the acid leaching, and the mixture was black gel. After filtering the solution, in order to make Fe 3 + with Fe (OH) 3 Precipitating off with NH 3 H2 O And NaOH (5%) solution (v: v = 1) to adjust the pH of the filtrate. When ferric hydroxide is precipitated, precipitation occurs when the pH is 3.5, the pH rises with the continuous addition of alkali, and the precipitation amount is increased. A portion of the lithium was precipitated as lithium hydroxide, fe as the pH increased to 8.0 3 + almost completely precipitated, and Fe (OH) 3 Does not change. Lithium precipitation was 2.4% in the form of lithium hydroxide. Experiments show that the optimal condition for precipitating the ferric hydroxide is pH =8, and the precipitate is filtered and burned to obtain high-purity Fe 2 O 3 。
In the invention, the current collector is recovered in the form of Al (OH) 3, and the Al (OH) 3 is obtained by mechanically crushing, alkaline leaching and adding acid to neutralize the positive pole piece; for the separation of lithium and iron, the sulfuric acid leaching recovery cost is low and the efficiency is high. By the process, aluminum hydroxide with a chemical purity level, iron hydroxide with the purity of 98.7 percent and lithium carbonate meeting zero-grade requirements can be obtained, and the precipitation rate of primary lithium exceeds 80 percent.
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (8)
1. A crushing, disassembling and recycling method for a lithium battery is characterized by comprising the following steps:
s1, performing module splitting treatment on a waste lithium battery to obtain a single battery and an auxiliary circuit component;
s2, carrying out charge-discharge test on the single batteries, and screening out the single batteries with low capacity and large internal resistance;
s3, performing discharge treatment on the screened single batteries;
s4, disassembling the single battery after the discharge treatment to obtain a battery core and a battery shell; then, further disassembling the battery cell to obtain a positive plate, a negative plate and a diaphragm; directly recycling the battery shell and the diaphragm;
s5, drying the negative plate to separate a graphite reclaimed material and a current collector copper foil;
s6, crushing the positive plate to obtain positive material residues; dissolving the positive electrode material residue in NaOH alkaline liquor, filtering and separating the solution, and separating out aluminum from the liquid; separating out lithium and iron through filtering slag;
s7, using sulfuric acid solution and H 2 O 2 The solution dissolves the filter residue, phosphorus and iron and Fe 2 (SO4) 3 And Li 2 SO 4 The form of the iron-containing compound enters a solution, is separated from impurities, is filtered, and is adjusted in pH value by using sodium hydroxide and ammonia water, wherein Fe is Fe (OH) 3 Precipitated in the form of (1), and the remaining solution was saturated with Na 2 CO 3 Precipitation of Li from solution 2 CO 3 。
2. The crushing, disassembling and recycling method for lithium batteries according to claim 1, wherein in step S1, the auxiliary circuit components comprise wires and cables, PCB boards, screws, nuts and boxes.
3. The crushing, disassembling and recycling method of the lithium battery as claimed in claim 1, wherein in the step S2, the screened high-capacity and low-internal-resistance batteries are reserved as power batteries for gradient utilization resources during the charge and discharge test.
4. The crushing, disassembling and recycling method of the lithium battery as claimed in claim 1, wherein when the discharging process is performed in the step S3, the stacked batteries are put into a discharging tank with an inner saline water injection for soaking one by one, and the discharged batteries are dried.
5. The crushing, disassembling and recycling method of the lithium battery as claimed in claim 1, wherein in the step S4, when the discharged single battery is disassembled, any one of a clamping-type cell separation method, a shell-core stripping-type separation method and a cell ejection-type separation method is adopted.
6. The crushing, disassembling and recycling method for the lithium battery as claimed in claim 1, wherein in the step S5, when the negative electrode sheet is dried, the negative electrode sheet is placed into a watch glass, dried in an oven at 100 ℃ for 1 hour, and shaken after drying, so that graphite is separated from a current collector copper foil.
7. The crushing, disassembling and recycling method for the lithium battery as claimed in claim 1, wherein in the step S5, the positive electrode sheet is mechanically crushed into pieces with a diameter of 1-5mm when being subjected to crushing treatment.
8. The crushing, disassembling and recycling method for lithium batteries according to claim 1, wherein when aluminum is precipitated, a sulfuric acid solution is used to adjust the pH of the solution to 9.0, so that the aluminum is precipitated in the form of aluminum hydroxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116885327A (en) * | 2023-08-17 | 2023-10-13 | 欧赛新能源科技股份有限公司 | Recycling process of lithium ion battery anode material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116885327A (en) * | 2023-08-17 | 2023-10-13 | 欧赛新能源科技股份有限公司 | Recycling process of lithium ion battery anode material |
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