CN111411232B - Total recovery method of valuable metal elements in positive pole piece of waste power lithium battery - Google Patents

Total recovery method of valuable metal elements in positive pole piece of waste power lithium battery Download PDF

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CN111411232B
CN111411232B CN202010167038.3A CN202010167038A CN111411232B CN 111411232 B CN111411232 B CN 111411232B CN 202010167038 A CN202010167038 A CN 202010167038A CN 111411232 B CN111411232 B CN 111411232B
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positive pole
power lithium
metal elements
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valuable metal
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CN111411232A (en
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马亚赟
杨娟
周向阳
唐晶晶
王辉
周昊宸
刘晓剑
王鹏
周进辉
周向清
周昶猷
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Hunan Xifu Environmental Protection Technology Co ltd
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Hunan Chenyu Fuji New Energy Technology Co ltd
Hunan Xifu Environmental Protection Technology Co ltd
Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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

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Abstract

The invention discloses a full recovery method of valuable metal elements in a positive pole piece of a waste power lithium battery, which comprises the steps of carrying out hydrothermal reaction on biomass in a weak acid condition in advance, separating to obtain a biomass solution S1 and filter residues, reacting the filter residues in an alkali liquor, and separating to obtain a biomass solution S2; stripping the waste positive plate in the biomass solution S2, and separating to obtain aluminum metal and positive slurry; and reducing and leaching the positive electrode slurry and the biomass solution S1 in an acid solution to obtain leachate rich in Li, Ni, Co and Mn. The method can realize the metal separation of Al, can realize the high-efficiency leaching of Li, Ni, Co and Mn, and can realize the full recovery of the waste ternary material with low cost and high efficiency.

Description

Total recovery method of valuable metal elements in positive pole piece of waste power lithium battery
Technical Field
The invention belongs to the technical field of lithium battery recovery, and particularly relates to a total recovery method of valuable metal elements in a positive pole piece of a waste power lithium battery.
Background
In the important period of rapid development of new energy vehicles in China, a power battery is a core component of the new energy vehicles, and a lithium ion battery is considered to be the first choice of the power battery of the vehicles due to the advantages of high energy density, high power density, long cycle life, environmental friendliness and the like. With the rapid industrialization of new energy vehicles, the sales volume of the new energy vehicles will be leaped forward, and the reserve volume of the lithium ion power batteries will also increase in geometric progression. Meanwhile, the environmental pollution problem and the reasonable resource recycling problem of the waste lithium ion power battery become the problems which are generally concerned and urgently needed to be solved at present and even at home and abroad in future. The solution of the problem is not only beneficial to the environmental protection, but also more beneficial to the cyclic utilization of resources, and has great practical significance. At present, the main recovered substances in the waste lithium ion battery are copper, aluminum, positive electrode materials and negative electrode materials, wherein a positive plate of the lithium battery is an aluminum foil coated positive electrode material, and a negative plate of the lithium battery is a copper foil coated negative electrode material. In combination with the current situation of domestic and foreign research, the recovery usually comprises three main steps: firstly, performing early-stage discharge treatment and disassembly on the waste battery; second, separation of the electrode material from the current collector; thirdly, the valuable metals are recovered and utilized.
Because the preparation of the positive pole piece of the lithium ion battery usually adopts an oily binder, the conventional water immersion method is difficult to realize the separation of the aluminum current collector and the waste positive pole material. The prior art mainly comprises two methods: the first is the dissolution of the positive current collector by the leaching method of aluminum. For example, most of the acid leaching is adopted, but the currently known acid leaching technology is difficult to realize selectivity, so that the leaching solution contains valuable metals such as Li, Ni, Co, Mn and the like, and the current collector Al is inevitably dissolved into the solution, so that on one hand, the impurity removal process of the leaching solution is complicated, and on the other hand, the aluminum enters a slag phase and is not recycled at a high value; in addition to acid leaching, there are also literature reports of using alkaline solutions to dissolve the current collector of the positive plate. The first method cannot recover the positive electrode current collector in a metallic form. The second method is to peel off the positive current collector by a physical method, mainly to destroy the combination between the aluminum current collector and the positive active material by high-temperature treatment, or to recover the aluminum current collector by utilizing the similar compatibility characteristic of the organic solvent to the binder. High-temperature treatment inevitably causes high energy consumption and inevitably produces smoke pollution; in addition, the cost of the organic solvent is high, and there is a disadvantage in the environmental protection of the organic solvent.
In summary, in order to realize efficient leaching of valuable elements in the positive electrode, performing reduction roasting on the positive electrode or adding a reducing agent in leaching is a conventional technology adopted by people at present, however, the reduction roasting needs energy consumption and the equipment investment is not small; most of the existing reduction leaching is to add a reducing agent such as sodium sulfite, so that the cost of the leaching process is high, and the traditional reduction leaching with the reducing agent is difficult to ensure that the total amount of valuable elements enters the leaching solution.
Disclosure of Invention
Aiming at the problems of high treatment cost, difficult metal state recovery of an aluminum current collector, difficult total leaching of valuable elements and the like in the conventional process for treating the positive pole piece of the waste power lithium battery, the invention aims to provide a total recovery method of the valuable metal elements in the positive pole piece of the waste power lithium battery, which is realized with the assistance of biomass waste materials, wherein Al in the positive pole piece is completely recovered in a metal state product, and Li, Ni, Co and Mn in an ionic state are completely introduced into a solution to be recovered.
A total recovery method of valuable metal elements in a positive pole piece of a waste power lithium battery comprises the following steps:
step (1): carrying out hydrothermal reaction on a mixed solution of the biomass waste and the dilute acid solution A, and then carrying out solid-liquid separation to obtain a biomass solution S1 and filter residue;
step (2): reacting the filter residue obtained in the step (1) in an alkali liquor, then carrying out solid-liquid separation, and regulating the pH of the solution obtained by separation to 3-5 to obtain a biomass solution S2;
and (3): placing the waste power lithium battery positive pole piece in a biomass solution S2, stirring and stripping, and separating to obtain an aluminum current collector and slurry dispersed with a positive pole material;
and (4): and (3) mixing the slurry obtained in the step (3), the biomass solution S1 obtained in the step (1) and an acid liquor B, carrying out reduction leaching, and then carrying out solid-liquid separation to obtain a leaching solution enriched with Li, Ni, Co and Mn.
According to the technical scheme, the total recovery of Al in the positive plate in the form of a metal simple substance, Li, Ni, Co and Mn in the form of ions in the solution is realized with the assistance of biomass waste materials through the process innovatively.
The invention changes the existing means for stripping Al current collectors such as roasting, organic solvents and the like, and provides a brand new idea and means for stripping Al current collectors in a simple substance form: namely, the biomass solution S2 from the biomass is innovatively obtained through the treatment of the step (1) and the step (2), and the high-efficiency stripping of the Al current collector and the positive electrode material is innovatively carried out in the biomass solution S2, so that the Al can be efficiently recovered in a metal form at low cost in an environment-friendly manner, and the metal leaching of the subsequent positive electrode material and the impurity removal difficulty are facilitated to be reduced. Moreover, the invention further researches and discovers that the positive electrode slurry obtained by stripping and the biomass solution S1 in the step (1) are subjected to reduction leaching of positive electrode components under the synergistic action of the acid liquor B, so that the leaching rate is improved, and the cost is reduced.
The biomass waste adopted by the invention is rich in components such as cellulose, hemicellulose or crude fiber, preferably at least one of straw, corn stalk or corncob, and the granularity of the biomass waste is 200-400 meshes.
Preferably, in the step (1), the dilute acid solution a and the biomass waste are mixed and soaked, then the mixture is placed in a closed reaction kettle for hydrothermal reaction, after the hydrothermal reaction, a discharge valve of the closed reaction kettle is opened, the slurry is sprayed and exploded from the inside of the reaction kettle to a spray explosion bin outside the reaction kettle to obtain slurry after hydrothermal treatment, and the biomass solution S1 and the filter residue are obtained through solid-liquid separation.
Preferably, the dilute acid solution A is a dilute acid solution, preferably dilute sulfuric acid with the volume percentage of 0.25-2%.
Preferably, the liquid-solid ratio of the dilute acid solution A to the biomass waste (on a dry basis) is 1:1 to 1.2: 1.
Preferably, the soaking time is 12-24 h.
Preferably, the temperature of the hydrothermal reaction is preferably 100-.
Preferably, the hydrothermal reaction time is preferably 30 to 60 min.
In the step (2), the alkali in the alkali liquor is at least one of NaOH or KOH.
Further preferably, the concentration of alkali in the alkali liquor is 50-100 g/L.
Preferably, in the step (2), the liquid-solid ratio of the alkali liquor to the filter residue is controlled to be (1:1) - (3: 1).
Preferably, in the step (2), the reaction temperature is preferably 150 to 300 ℃.
Preferably, in the step (2), the reaction time is preferably 30 to 90 min.
According to the invention, the obtained biomass solution S2 is innovatively used as a stripping system of the positive plate, so that Al metal can be stripped, the subsequent leaching of the positive material is facilitated, and the impurity removal difficulty of the subsequent leachate is reduced.
In the step (3), the waste power lithium battery positive pole piece is coarsely crushed to be not less than 120 meshes (not less than 120um), and then placed in a biomass solution S2 to be stirred and peeled; then sieving, wherein oversize products are aluminum current collectors; the undersize is slurry in which the positive electrode material is dispersed.
The waste power lithium battery is a nickel-cobalt-manganese ternary battery. The positive electrode material on the positive plate is a nickel-cobalt-manganese ternary positive electrode material.
Preferably, the temperature of the stripping process is 50-70 ℃.
In step (3), the liquid-solid ratio of the positive electrode sheet to the biomass solution S2 is, for example, (1:1) to (3: 1).
The stirring and stripping time is for example 30-120min,
in the invention, the anode slurry obtained by stripping, the biomass solution S1 and the acid liquor are also innovatively subjected to reduction leaching, so that the efficient recovery of all elements is facilitated.
Preferably, the acid solution B is concentrated sulfuric acid.
Preferably, the concentration of the acid (acid solution B) in the initial solution of the reduction leaching is 1-3 mol/L.
Preferably, the temperature during the reduction leaching is 75-95 ℃.
The invention discloses a preferable total recovery method of valuable metal elements in a positive pole piece of a waste power lithium battery, which comprises the following steps:
step 1: respectively preparing biomass solutions S1 and S2 by using biomass waste as a raw material;
and a step 2: separating (stripping) the current collector aluminum from the waste positive active material to obtain a product of metal aluminum powder;
step 3: through reduction leaching, the total amount of Li, Ni, Co and Mn in the waste anode enters the leaching solution to be recovered.
The process 1 comprises the following steps: step 1: adding biomass waste into volume concentration (V)Sulfuric acid/VWater (W)) Preparing slurry with a liquid-solid ratio of 1: 1-1.2: 1 in 0.25-2% of dilute sulfuric acid, soaking for 12-24h at room temperature, placing the slurry in a closed reaction kettle, preserving heat for 30-60min at the temperature of 100-; step 2: placing the obtained filter residue in NaOH or KOH solution with the concentration of 50-100 g/L, and carrying out liquid-solid reactionControlling the ratio of (1:1) - (3:1), then heating the solution system to 150-300 ℃, preserving the heat for 30-90 min, cooling to obtain filtrate, and adjusting the pH value of the filtrate to 3-5 by using 5-10mol/L sulfuric acid to obtain the biomass solution S2.
The process 2 comprises the following steps: step 1: coarsely crushing the positive pole piece of the waste power lithium battery to be not less than 120 meshes (not less than 120 um); step 2: controlling the liquid-solid ratio to be (1:1) - (3:1), adding the coarsely crushed anode piece powder of the waste power lithium battery into a biomass solution S2 at 50-70 ℃, and continuously stirring for 30-120min so as to separate an aluminum current collector from an anode active substance, and simultaneously fully dispersing the anode active substance in the solution in a powder form. And 3, pouring the slurry in the previous step into a vibration separation sieve with a sieve with the aperture of 240-400 meshes, separating out the aluminum current collector, and allowing the slurry under the sieve to enter into subsequent reduction leaching.
And 3, the reduction leaching refers to combining the undersize slurry from which the aluminum current collector is separated with a biomass solution S1, adding concentrated sulfuric acid into the combined solution according to 1-3 mol/L, heating the solution to 75-95 ℃, and reacting for 4-10h, so that the total amount of Li, Ni, Co and Mn in the waste anode enters the leaching solution to be recovered.
Compared with the prior art, the invention has the following advantages:
(1) the biomass waste is adopted, so that the full recovery of valuable metal elements in the positive pole pieces of the waste power lithium batteries is realized, and the treatment cost of the waste positive poles is reduced;
(2) a brand-new stripping idea and means of Al in a metal elementary substance form are provided, namely, a solution S2 obtained by performing combined treatment on biomass waste in the steps (1) and (2) is innovatively adopted as a stripping system to realize the separation of an aluminum current collector and an active substance, and finally, the aluminum in a metal product is recovered;
(3) the positive electrode slurry obtained by the stripping system and the biomass solution S1 are subjected to a reduction leaching process under an acid condition, so that on one hand, the full leaching of valuable components in the waste positive electrode can be promoted, and in addition, the loss of valuable elements in the leachate due to physical entrainment and the like is avoided due to the adoption of the reducing solution, and the characteristic of the invention is also realized;
(4) by adopting the method, the recovery rate of valuable elements such as lithium, nickel, cobalt, manganese and the like in the ternary anode waste can reach nearly 100%, and the aluminum current collector is recovered with low cost in the form of aluminum particles, which is another bright point of the invention.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention
FIG. 2 is a picture of the pole piece after the treatment of example 1 and comparative example 3, wherein FIG. 2(a) the picture of the pole piece after the treatment of example 1 shows that the active material on the pole piece can be completely removed in example 1;
fig. 2(b) shows that the pole piece is treated with a single organic acid, and obviously, the pole piece also has an active substance, that is, the active substance on the pole piece is difficult to completely fall off by the single organic acid treatment.
The following further describes the practice of the present invention with reference to the drawings, but the present invention is not limited thereto.
See fig. 1.
Detailed Description
The waste battery is a waste nickel-cobalt-manganese ternary battery.
Example 1, the total recovery of valuable metal elements in the positive electrode plate of waste power lithium batteries with the assistance of biomass waste corncobs.
The corncobs used in this example were crushed to 200 mesh before use. The specific implementation procedure of this embodiment is as follows:
step 1:
step 1: adding corn cob into volume concentration (V)Sulfuric acid/VWater (W)) Preparing slurry with a liquid-solid ratio of 1.2:1 in 2% dilute sulfuric acid, soaking for 12h at room temperature, placing the slurry in a closed reaction kettle, preserving heat at 105 ℃ for 30min, opening a discharge valve of the reaction kettle, enabling the slurry to be sprayed and exploded from the inside of the reaction kettle to a spraying and explosion bin outside the reaction kettle to obtain slurry after hydrothermal treatment, and filtering to obtain a biomass solution S1 and filter residues;
step 2: and (3) placing the obtained filter residue in a NaOH solution with the concentration of 70g/L, controlling the liquid-solid ratio to be 2.5:1, then heating the solution system to 280 ℃, preserving the heat for 60min, cooling to obtain a filtrate, and adjusting the pH value of the filtrate to 4 by using 10mol/L sulfuric acid to obtain a biomass solution S2.
And a step 2: and separating the current collector aluminum from the waste positive active material to obtain the product metal aluminum powder. The process comprises the following steps:
step 1: the method comprises the following steps of (1) roughly crushing a positive pole piece of a waste 523 type power lithium battery to be not less than 120 meshes (not less than 120 um);
step 2: controlling the liquid-solid ratio to be 3:1, adding the coarsely crushed waste power lithium battery positive pole piece powder into a biomass solution S2 at 60 ℃, and continuously stirring for 60min so as to separate an aluminum current collector from a positive active material, and simultaneously fully dispersing the positive active material in the solution in a powder form.
And 3, pouring the slurry in the previous step into a vibration separation sieve with a 300-mesh screen mesh, separating out the aluminum current collector, and carrying out subsequent reduction leaching on the slurry under the sieve.
Step 3: through reduction leaching, the total amount of Li, Ni, Co and Mn in the waste anode enters the leaching solution to be recovered. Firstly, combining undersize slurry from which an aluminum current collector is separated with a biomass solution S1, then adding concentrated sulfuric acid into the combined solution according to the proportion of 2mol/L, heating the solution to 90 ℃, and reacting for 6 hours, so that Li, Ni, Co and Mn in the waste anode enter a leaching solution to be recovered.
As can be seen from the picture of the pole piece after being processed in fig. 2(a), the surface of the pole piece after being processed in this embodiment is very clean, and there is almost no residual active material, which also indicates that the present invention can make all the active material on the pole piece fall off.
Tests show that 99.5% of Al in the waste positive pole piece is recovered in a metal state, and 100%, 99.5% and 98.5% of Li, Ni, Co and Mn in the positive pole piece enter the leaching solution respectively.
Comparative example 1:
compared with the embodiment 1, the difference of the comparative example is that the corncob and the positive pole piece are directly put into a 3mol/L sulfuric acid solution and react for 6 hours at 90 ℃; other parameters of this example are: the mass ratio of the corncobs to the positive pole piece is equivalent to that of example 1 and is about 1: 0.8; the liquid-solid ratio of the volume of 2mol/L sulfuric acid to the mass sum of the corncob and the positive pole piece is equivalent to that of example 1 and is about 2:1, and the test shows that:
firstly, Al in the positive pole piece is not recovered in a product form, but 100% enters a leaching solution in an impurity form, so that the difficulty of subsequent impurity removal is increased, and loss of valuable elements is possibly caused, because aluminum ions are usually removed in an aluminum hydroxide form, and the aluminum hydroxide is colloid, so that the difficulty in filtration and the difficulty in loss caused by overhigh attached liquid containing the valuable elements in slag are avoided;
② the leaching efficiencies of Li, Ni, Co and Mn are respectively 96%, 91%, 88% and 86%, which are obviously lower than that of the embodiment 1. Example 1 high leaching efficiencies of Li, Ni, Co and Mn were obtained because the cobs of example 1 underwent the acid-base combination treatment in step 1, and there was a synergistic effect of the components being released sufficiently.
Comparative example 2:
compared with the embodiment 1, the difference of the comparative example is that glucose and the anode piece are directly placed in 3mol/L sulfuric acid solution and react for 6 hours at 90 ℃; other parameters of this example are: the mass ratio of glucose to the positive electrode piece was equivalent to example 1, about 1: 0.8; the liquid-solid ratio of the volume of 2mol/L sulfuric acid to the sum of the mass of the glucose plus the mass of the positive electrode plate is also equivalent to that of example 1 and is about 2:1. the test shows that:
firstly, Al in the positive pole piece is not recovered in a product form, but 100% enters a leaching solution in an impurity form, so that the difficulty of subsequent impurity removal is increased, and loss of valuable elements is possibly caused, because aluminum ions are usually removed in an aluminum hydroxide form, and the aluminum hydroxide is colloid, so that the difficulty in filtration and the difficulty in loss caused by overhigh attached liquid containing the valuable elements in slag are avoided;
② the leaching efficiencies of Li, Ni, Co and Mn were 97%, 95%, 92% and 90%, respectively, although the list was significantly lower than example 1 above comparative example 1.
Comparative example 3:
the purpose of this comparative example was to examine whether a single organic acid could completely shed the positive active material on the current collector, and therefore a 5mm size positive plate was selected and placed in step 2 of example 1 for treatment. Organic acids examined are formic acid, acetic acid or malonic acid. After the treatment, it was found that a large amount of the positive electrode material remained on the aluminum current collector. Fig. 2(b) is a photograph of the electrode plate treated with a single formic acid, which shows that the positive active material on the electrode plate is difficult to completely separate due to the single organic acid treatment.
Comparative example 4:
the purpose of this comparative example was to investigate whether a single organic acid could ensure that the aluminium was not leached. This comparative example was conducted in the same manner as example 1 except that the solution S2 in the step 2 was replaced with formic acid. The test result shows that:
firstly, 8% of aluminum in the aluminum current collector is dissolved into leachate, and a plurality of positive active substances are found to be remained on the separated aluminum current collector;
② the leaching efficiencies of Li, Ni, Co and Mn are respectively 95%, 90%, 87% and 86%, which are obviously lower than that of the embodiment 1, the reason is related to the residual active substance on the aluminum current collector.
As can be seen from the above examples and the corresponding examples, with the assistance of the biomass waste, the present invention has the advantages of almost complete recovery of the aluminum current collector in a metallic state and efficient leaching of valuable elements in the positive electrode plate.

Claims (18)

1. A total recovery method of valuable metal elements in a positive pole piece of a waste power lithium battery is characterized by comprising the following steps: the method comprises the following steps:
step (1): carrying out hydrothermal reaction on a mixed solution of the biomass waste and the dilute acid solution A, and then carrying out solid-liquid separation to obtain a biomass solution S1 and filter residue;
step (2): reacting the filter residue obtained in the step (1) in an alkali liquor, then carrying out solid-liquid separation, and regulating the pH of the solution obtained by separation to 3-5 to obtain a biomass solution S2;
and (3): placing the waste power lithium battery positive pole piece in a biomass solution S2, stirring and stripping, and separating to obtain an aluminum current collector and slurry dispersed with a positive pole material;
and (4): and (3) mixing the slurry obtained in the step (3), the biomass solution S1 obtained in the step (1) and an acid liquor B, carrying out reduction leaching, and then carrying out solid-liquid separation to obtain a leaching solution enriched with Li, Ni, Co and Mn.
2. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery in the full scale as claimed in claim 1, wherein the biomass waste is biomass waste rich in cellulose, hemicellulose or crude fiber.
3. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery in the full scale as claimed in claim 1, wherein the biomass waste is at least one of straw, corn stalks or corncobs.
4. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery in the full scale as recited in claim 1, wherein the granularity of the biomass waste is 200-400 meshes.
5. The total recovery method of valuable metal elements in the waste power lithium battery positive pole piece, as recited in claim 1, is characterized in that, in the step (1), the dilute acid solution A and the biomass waste are mixed and soaked, then the mixture is placed in a closed reaction kettle for hydrothermal reaction, after the hydrothermal reaction, a discharge valve of the closed reaction kettle is opened, slurry is sprayed and exploded from the inside of the reaction kettle to a spray explosion cabin outside the reaction kettle, slurry after hydrothermal treatment is obtained, and the biomass solution S1 and filter residue are obtained through solid-liquid separation.
6. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery in the whole quantity as claimed in claim 5, wherein the dilute acid solution A is dilute sulfuric acid with the volume percentage of 0.25-2%;
the liquid-solid ratio of the dilute acid solution A to the biomass waste is 1: 1-1.2: 1.
7. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery in the full scale as claimed in claim 5 is characterized in that the soaking time is 12-24 h.
8. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery as claimed in any one of claims 1 and 5 to 6, wherein the temperature of the hydrothermal reaction is 100-120 ℃.
9. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery as claimed in claim 8, wherein the time of the hydrothermal reaction is 30-60 min.
10. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery in the full quantity according to claim 1, wherein the alkali in the alkali liquor is at least one of NaOH or KOH.
11. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery in the full quantity according to claim 1, is characterized in that the concentration of alkali in the alkali liquor is 50-100 g/L.
12. The method for recycling the valuable metal elements from the positive pole pieces of the waste power lithium batteries as claimed in claim 1, wherein in the step (2), the liquid-solid ratio of the alkali liquor to the filter residue is controlled to be (1:1) - (3: 1).
13. The method for recycling the valuable metal elements in the positive pole pieces of the waste power lithium batteries as claimed in claim 1, wherein the reaction temperature in the step (2) is 150-300 ℃.
14. The method for recycling the valuable metal elements from the positive pole pieces of the waste power lithium batteries as claimed in claim 13, wherein in the step (2), the reaction time is 30-90 min.
15. The method for recycling the valuable metal elements in the positive pole pieces of the waste power lithium batteries in the claim 1 is characterized in that in the step (3), the positive pole pieces of the waste power lithium batteries are coarsely crushed to be not less than 120 meshes and then placed in a biomass solution S2 to be stirred and peeled; then sieving, wherein oversize products are aluminum current collectors; the undersize is slurry in which the positive electrode material is dispersed.
16. The method for recycling the valuable metal elements in the positive pole pieces of the waste power lithium batteries as claimed in claim 1 or 15, wherein the temperature in the stripping process is 50-70 ℃.
17. The method for recycling the valuable metal elements in the positive pole pieces of the waste power lithium batteries in the claim 1 is characterized in that the acid solution B is concentrated sulfuric acid;
the concentration of acid in the initial solution of the reduction leaching is 1-3 mol/L.
18. The method for recycling the valuable metal elements in the positive pole piece of the waste power lithium battery as claimed in claim 1, wherein the temperature in the reduction leaching process is 75-95 ℃.
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