CN115818607A - Method for recycling lithium iron phosphate material - Google Patents

Method for recycling lithium iron phosphate material Download PDF

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Publication number
CN115818607A
CN115818607A CN202111181904.5A CN202111181904A CN115818607A CN 115818607 A CN115818607 A CN 115818607A CN 202111181904 A CN202111181904 A CN 202111181904A CN 115818607 A CN115818607 A CN 115818607A
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iron phosphate
lithium iron
heat treatment
temperature heat
current collector
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CN202111181904.5A
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CN115818607B (en
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王嗣慧
柳娜
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to CN202111181904.5A priority Critical patent/CN115818607B/en
Priority to PCT/CN2022/117763 priority patent/WO2023061115A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The application provides a method for recovering a lithium iron phosphate material, wherein a lithium iron phosphate pole piece is composed of a lithium iron phosphate diaphragm and a current collector, and the method comprises the following steps: (1) extruding a lithium iron phosphate pole piece; (2) Soaking the lithium iron phosphate pole piece obtained in the step (1) in water to enable a lithium iron phosphate membrane to be stripped from a current collector; recovering the current collector, and then filtering the remaining solid-liquid mixture to obtain a lithium iron phosphate membrane; (3) Drying the lithium iron phosphate membrane obtained in the step (2); (4) Performing low-temperature heat treatment on the lithium iron phosphate membrane obtained in the step (3) at 380-600 ℃, and then performing mechanical crushing, or performing mechanical crushing on the lithium iron phosphate membrane obtained in the step (3) and then performing low-temperature heat treatment at 380-600 ℃, so as to obtain lithium iron phosphate material powder; (5) And (4) carrying out high-temperature heat treatment on the lithium iron phosphate material powder obtained in the step (4) at 650-850 ℃ to obtain a lithium iron phosphate material.

Description

Method for recycling lithium iron phosphate material
Technical Field
The application relates to the technical field of lithium batteries, in particular to a method for recovering a lithium iron phosphate material, a positive pole piece obtained from the lithium iron phosphate material prepared by the method, and a secondary battery comprising the positive pole piece.
Background
In recent years, with the application range of lithium ion batteries becoming wider, lithium ion batteries are widely used in energy storage power systems such as hydraulic power, thermal power, wind power and solar power stations, and in a plurality of fields such as electric tools, electric bicycles, electric motorcycles, electric automobiles, military equipment and aerospace. Among them, lithium iron phosphate batteries are one of the most important power batteries at present. The production of waste positive pole pieces inevitably occurs in a plurality of working procedures in the production process of the power battery, the waste of a large amount of positive pole materials is caused by the production of the waste positive pole pieces, and the materials are subject to effective recycling under the conditions of rising material cost and environmental protection pressure.
Disclosure of Invention
The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a simple, environmentally friendly, safe, and high-yield method for recovering a lithium iron phosphate material, so that the obtained lithium iron phosphate material exhibits excellent electrochemical performance in a corresponding secondary battery, and the method can achieve effective recovery of aluminum foil.
In order to achieve the purpose, the application provides a method for recovering a lithium iron phosphate material, a positive pole piece obtained from the lithium iron phosphate material prepared by the method, and a secondary battery comprising the positive pole piece.
The first aspect of the application provides a method for recovering a lithium iron phosphate material from a waste lithium iron phosphate pole piece, wherein the lithium iron phosphate pole piece is composed of a lithium iron phosphate diaphragm and a current collector, and the method comprises the following steps:
(1) Extruding the lithium iron phosphate pole piece;
(2) Soaking the lithium iron phosphate pole piece obtained in the step (1) in water to enable a lithium iron phosphate membrane to be stripped from a current collector; recovering the current collector, and then filtering the residual solid-liquid mixture to obtain a lithium iron phosphate membrane;
(3) Drying the lithium iron phosphate membrane obtained in the step (2);
(4) Performing low-temperature heat treatment on the lithium iron phosphate membrane obtained in the step (3) at 380-600 ℃, and then performing mechanical crushing, or performing mechanical crushing on the lithium iron phosphate membrane obtained in the step (3) and then performing low-temperature heat treatment at 380-600 ℃, so as to obtain lithium iron phosphate material powder;
(5) And (5) carrying out high-temperature heat treatment on the lithium iron phosphate material powder obtained in the step (4) at 650-850 ℃ to obtain a lithium iron phosphate material.
Therefore, the method can be used for recovering the lithium iron phosphate material simply, environmentally, safely and with high yield. Particularly, the method can quickly and simply realize the separation of the lithium iron phosphate material and the current collector; the recovery rate of the obtained lithium iron phosphate material is high (more than or equal to 98 percent), subsequent impurity removal (such as aluminum scraps and the like) treatment is not needed, and the interface of the lithium iron phosphate material is repaired by carbon and can be directly used for the preparation of a subsequent battery cell; the safety performance and the cycle performance of the battery cell prepared from the lithium iron phosphate material are improved.
In any embodiment, the porosity of the lithium iron phosphate pole pieces before and after extrusion in step (1) satisfies the following formula:
the ratio of the porosity before extrusion to the porosity after extrusion is not less than 1.05 and not more than 3.
After extrusion, the lithium iron phosphate membrane is extremely easy to peel off from the current collector, the recovery efficiency is improved, and meanwhile, the pole pieces can be loosely soaked in whole pieces, so that the introduction of current collector chips due to the fact that the pole pieces are broken into small pole pieces and the subsequent processing steps are avoided.
In any embodiment, the soaking with water in step (2) is carried out at a temperature not exceeding 40 ℃ for 0.05 to 1 hour; the water is domestic water, distilled water, deionized water or industrial water, preferably deionized water. The pole piece is soaked in water for 0.05 to 1 hour at the temperature of not more than 40 ℃, so that the dissolution of metal elements in the lithium iron phosphate material and the damage to the surface structure can be reduced, and the method is safe and environment-friendly.
In any embodiment, the current collector is an aluminum foil. Thereby making the lithium iron phosphate material more easily stripped.
In any embodiment, in the step (3), the drying is performed at 100 to 180 ℃ for 1 to 12 hours in an air atmosphere. The lithium iron phosphate material thus obtained is easier to perform subsequent mechanical crushing.
In any embodiment, in the step (4), the lithium iron phosphate membrane obtained in the step (3) is subjected to low-temperature heat treatment at 380 to 600 ℃ and then to mechanical crushing. Therefore, the lithium iron phosphate membrane can be mechanically crushed under the condition of more thorough drying, and is easier to crush and higher in efficiency.
In any embodiment, the low temperature heat treatment and the high temperature heat treatment are both performed in an inert atmosphere, wherein the inert atmosphere is N 2 Ar, he, ne, kr, xe, preferably N 2 And Ar. The heat treatment is carried out in an inert atmosphere, so that the lithium iron phosphate material can be better protected from being damaged by oxygen in the air.
In any embodiment, in step (4), the lithium iron phosphate membrane is mechanically crushed to a volume average particle diameter D of the resulting material powder v50 Is 0.5-3 μm. The obtained material powder is easier to carry out subsequent high-temperature heat treatment, and is beneficial to the use of the lithium iron phosphate material.
In any embodiment, the duration of the high temperature heat treatment in step (5) is 0.5 to 3 hours, preferably 1 to 2 hours. Through high-temperature heat treatment, the interface of the lithium iron phosphate material is better repaired by carbon, and the carbon content is moderate, so that the good electronic conductivity of the lithium iron phosphate material is ensured, the electrochemical performance of the lithium iron phosphate material is fully exerted, and the gram volume is high.
The second aspect of the present application also provides a positive electrode plate, which comprises a current collector and the lithium iron phosphate material obtained by the method of the first aspect of the present application.
A third aspect of the present application provides a secondary battery characterized by comprising the lithium iron phosphate material obtained by the method of the first aspect of the present application or the positive electrode sheet of the second aspect of the present application.
Drawings
Fig. 1 is a K value of a full cell of each example and comparative example.
FIG. 2 is a schematic flow diagram of a method according to a preferred embodiment of the present application.
Detailed Description
Embodiments of the method for recovering a lithium iron phosphate material, and a positive electrode sheet and a secondary battery comprising the lithium iron phosphate material according to the present invention are specifically disclosed below in detail with reference to the accompanying drawings as appropriate. But a detailed description thereof will be omitted. For example, detailed descriptions of already known matters and repetitive descriptions of actually the same configurations may be omitted. This is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. The drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited in the claims.
The "ranges" disclosed herein are defined in terms of lower limits and upper limits, with a given range being defined by a selection of one lower limit and one upper limit that define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not otherwise specified.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, any one of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
In the production process of the lithium ion battery, waste pole pieces can be inevitably generated, and the waste pole pieces are urgently needed to be effectively recycled under the conditions of material cost rising and environmental protection pressure. At present, the lithium iron phosphate is generally recovered by a chemical method, so that the cost is high and the pollution is serious. Secondly, in the physical method recovery process, the generated aluminum scrap impurities easily cause the safety risk of the battery cell during the recycling, and if air separation, screening and the like are adopted to control the content of the aluminum scrap, the recovery rate is reduced. If the aluminum scraps are cleaned by alkali liquor, the recovery process is complex, and the use of the alkali liquor brings about subsequent waste liquorThe problem of treatment. In some prior art, the pole piece is soaked in alkali liquor or organic solvent to realize the separation of the lithium iron phosphate material and the aluminum foil, which can reduce the content of aluminum scrap impurities in the recovered material, but the method also has the problem of treating the waste liquid of chemical reagents such as alkali liquor or organic solvent, and the pole piece is directly soaked in the alkali liquor to generate a large amount of H 2 There is a security risk.
After a great deal of research, the inventor finds that the method of the first aspect of the application realizes simple, environment-friendly, safe and high-yield recovery of the lithium iron phosphate material by extruding the waste pole pieces, soaking the waste pole pieces in water and combining with subsequent specific heat treatment, so that the obtained lithium iron phosphate material shows excellent electrochemical performance in a corresponding secondary battery, and meanwhile, the method can realize effective recovery of aluminum foil.
The method for recycling the lithium iron phosphate material is suitable for treating waste lithium iron phosphate pole pieces. The waste lithium iron phosphate pole pieces refer to pole piece waste materials which are not assembled in the battery, such as waste pole pieces and leftover material pole pieces generated in the battery cell manufacturing process; the electrode sheet present in a secondary battery that has undergone charge and discharge is not included.
The lithium iron phosphate material comprises lithium iron phosphate and carbon.
Method for recovering lithium iron phosphate material
In an embodiment of the present application, the present application provides a method for recovering a lithium iron phosphate material from a waste lithium iron phosphate pole piece, where the lithium iron phosphate pole piece is composed of a lithium iron phosphate membrane and a current collector, and the method includes the following steps:
(1) Extruding the lithium iron phosphate pole piece;
(2) Soaking the lithium iron phosphate pole piece obtained in the step (1) in water to enable a lithium iron phosphate membrane to be stripped from a current collector; recovering the current collector, and then filtering the remaining solid-liquid mixture to obtain a lithium iron phosphate membrane;
(3) Drying the lithium iron phosphate membrane obtained in the step (2);
(4) Performing low-temperature heat treatment on the lithium iron phosphate membrane obtained in the step (3) at 380-600 ℃, and then performing mechanical crushing, or performing mechanical crushing on the lithium iron phosphate membrane obtained in the step (3) and then performing low-temperature heat treatment at 380-600 ℃, so as to obtain lithium iron phosphate material powder;
(5) And (5) carrying out high-temperature heat treatment on the lithium iron phosphate material powder obtained in the step (4) at 650-850 ℃ to obtain a lithium iron phosphate material.
Although the mechanism is not clear, the applicant has surprisingly found that: the waste lithium iron phosphate pole pieces are extruded, then soaked in water and combined with subsequent specific heat treatment, so that the lithium iron phosphate material is recovered simply, environmentally friendly, safely and at high yield, the obtained lithium iron phosphate material shows excellent electrochemical performance in corresponding secondary batteries, and meanwhile, the method can realize effective recovery of aluminum foil. And the high-temperature heat treatment can better repair the interface of the lithium iron phosphate material, so that the carbon content of the lithium iron phosphate material is moderate, the gram volume of the lithium iron phosphate material is high, and the good electronic conductivity of the lithium iron phosphate material is ensured.
The waste lithium iron phosphate pole piece is prepared by a water-based primer coating process, wherein the primer coating comprises a water-based binder and conductive carbon, the water-based binder is sodium carboxymethylcellulose (CMC), polytetrafluoroethylene (PTFE), styrene Butadiene Rubber (SBR), polyacrylate (PAA), polyacrylamide (PAN) and the like, and the content of the water-based binder is 20% -80%. The thickness of the bottom coating is less than or equal to 5 mu m, and the thickness of the waste lithium iron phosphate pole piece is 125-145 mu m.
In some embodiments, in step (1), the porosity of the lithium iron phosphate pole pieces before and after extrusion satisfies the following formula:
the ratio of the porosity before extrusion to the porosity after extrusion is not more than 1.05 and not more than 3;
preferably, the ratio of the porosity before extrusion to the porosity after extrusion is 1.1. Ltoreq.2.
The porosity of the lithium iron phosphate pole piece before extrusion is generally 35% -45%, and the porosity of the lithium iron phosphate pole piece after extrusion is generally 15% -32%, preferably 19% -28%.
The manner of said extrusion is any manner generally known to the person skilled in the art, preferably rolling.
After the porosity of the lithium iron phosphate pole piece reaches a specific degree through extrusion, the lithium iron phosphate diaphragm is very easy to peel off from the current collector, the recovery efficiency is improved, meanwhile, the pole piece can be loosely soaked in a whole piece, and the current collector debris and the post-treatment step caused by the fact that the pole piece is broken into small pole pieces are avoided.
In some embodiments, in step (2), the soaking with water is carried out at a temperature of not more than 40 ℃, preferably room temperature, for 0.05 to 1 hour, preferably 0.15 to 0.35 hour. The temperature should not be too high when soaking in water, otherwise the ion dissolution is accelerated, and the element proportion of the recovered material may be influenced. The soaking time is proper, so that the separation of the lithium iron phosphate membrane and a current collector can be ensured, and simultaneously, the dissolution of metal elements in the lithium iron phosphate material and the damage to the surface structure of the membrane can be reduced.
The water is domestic water, distilled water, deionized water or industrial water, preferably deionized water. The mass of the water is 5-8 times of that of the lithium iron phosphate pole piece. Therefore, the pole piece can be fully soaked by water, and the lithium iron phosphate membrane can be conveniently separated from the current collector.
In some embodiments, the current collector is aluminum foil. The lithium iron phosphate pole piece is generally used as a positive pole piece, and a metal foil or a composite current collector can be adopted as a current collector used for the positive pole, preferably the metal foil. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, in step (3), the drying is performed at 100 to 180 ℃ for 1 to 12 hours in an air atmosphere.
In some embodiments, in the step (4), the lithium iron phosphate membrane obtained in the step (3) is subjected to mechanical crushing and then low-temperature heat treatment at 380-600 ℃. In this case, the drying of step (3) is carried out for 1 to 12 hours, preferably 1 to 6 hours. In this embodiment, the obtained lithium iron phosphate material powder is subjected to the high-temperature heat treatment in step (5) directly after the low-temperature heat treatment, which is more favorable for repairing the interface of the lithium iron phosphate material, i.e., repairing damage to the carbon coating layer of the lithium iron phosphate material more effectively.
In some preferred embodiments, in the step (4), the lithium iron phosphate membrane obtained in the step (3) is subjected to low-temperature heat treatment at 380 to 600 ℃ and then to mechanical crushing, as shown in fig. 2. In this case, the drying of step (3) is carried out for 1 to 12 hours, preferably 1 to 3 hours. In the embodiment, the drying time in the step (3) can be shortened, and the crushing efficiency can be improved.
In some embodiments, the low temperature heat treatment and the high temperature heat treatment are both performed in an inert atmosphere. The inert atmosphere is N 2 Ar, he, ne, kr, xe, preferably N 2 And Ar.
The low-temperature heat treatment is carried out at the temperature of 380-600 ℃, preferably 450-550 ℃ for 0.5-5h, preferably 1-2h; the high temperature heat treatment is carried out at a temperature of 650 to 850 deg.C, preferably 680 to 780 deg.C, for 0.5 to 3 hours, preferably 1 to 2 hours.
The low-temperature heat treatment and the high-temperature heat treatment of the lithium iron phosphate material are both performed in an inert atmosphere, so that the lithium iron phosphate material is prevented from being damaged by oxygen in the air.
In some embodiments, in step (4), the lithium iron phosphate membrane is mechanically crushed to volume average particle diameter D of the obtained material powder v50 Is 0.5-3 μm. The mechanical disruption is carried out by means known to those skilled in the art, such as ball milling and the like, in any suitable commercially available apparatus, such as ball mills and the like. The volume-average particle diameter of the resulting material powder is 0.5 to 3 μm, preferably 0.8 to 2.0. Mu.m. The obtained material powder is easier to carry out subsequent high-temperature heat treatment, and is beneficial to the use of the lithium iron phosphate material.
In some embodiments, the duration of the high temperature heat treatment in step (5) is 0.5 to 3 hours, preferably 1 to 2 hours. Through the high-temperature heat treatment, the carbon content of the obtained lithium iron phosphate material is 1.8-2.6%. Meanwhile, the high-temperature heat treatment can repair the interface carbon damage of the lithium iron phosphate material, so that the electrochemical performance of the obtained material is improved.
In one embodiment of the present application, a positive electrode sheet is provided, which includes a current collector and a lithium iron phosphate material obtained by the above method.
In one embodiment of the present application, there is provided a secondary battery including the lithium iron phosphate material obtained by the above method or the above positive electrode sheet.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. In the process of charging and discharging the battery, active ions are embedded and separated back and forth between the positive pole piece and the negative pole piece. The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The isolating membrane is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the short circuit of the positive pole and the negative pole, and can enable ions to pass through.
[ Positive electrode sheet ]
The positive pole piece includes the anodal mass flow body and sets up the anodal diaphragm on the anodal mass flow body at least one surface, anodal diaphragm includes anodal active material, wherein anodal active material contains the lithium iron phosphate material that obtains through the method of the first aspect of this application.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode membrane is disposed on either or both of the two surfaces opposite to the positive electrode current collector.
In some embodiments, the positive electrode current collector employs a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.). In a preferred embodiment, the current collector is an aluminum foil.
In some embodiments, the positive electrode active material is a lithium iron phosphate material obtained by the method of the first aspect of the present application.
In some embodiments, the positive electrode membrane sheet further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroacrylate resin.
In some embodiments, the positive electrode tab further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and the like to obtain the positive electrode piece.
[ negative electrode sheet ]
The negative pole piece comprises a negative pole current collector and a negative pole diaphragm arranged on at least one surface of the negative pole current collector, wherein the negative pole diaphragm comprises a negative pole active material.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode membrane is disposed on either or both of the two surfaces opposite to the negative electrode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base layer. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the negative active material may employ a negative active material for a battery known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate and the like. The silicon-based material can be at least one selected from the group consisting of elemental silicon, a silicon oxy compound, a silicon carbon compound, a silicon nitrogen compound and a silicon alloy. The tin-based material may be selected from at least one of elemental tin, tin-oxygen compounds, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery negative active material may also be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode membrane further optionally comprises a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode membrane further optionally comprises a conductive agent. The conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode membrane optionally further comprises other adjuvants, such as thickeners (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet can be prepared by: dispersing the components for preparing the negative electrode plate, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (such as deionized water) to form negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and drying, cold pressing and the like to obtain the negative electrode pole piece.
[ electrolyte ]
The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The kind of the electrolyte is not particularly limited and may be selected as desired. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte solution. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium dioxaoxalato borate, lithium difluorodioxaoxalato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethylsulfone, methylethylsulfone, and diethylsulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include a negative electrode film-forming additive, a positive electrode film-forming additive, and may further include additives capable of improving certain properties of the battery, such as an additive for improving overcharge properties of the battery, an additive for improving high-temperature or low-temperature properties of the battery, and the like.
[ isolation film ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known separator having a porous structure and good chemical and mechanical stability may be used.
In some embodiments, the material of the isolation film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an exterior package. The exterior package may be used to enclose the electrode assembly and electrolyte.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The outer package of the secondary battery may also be a pouch, such as a pouch-type pouch. The material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
The shape of the secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, or any other shape.
In some embodiments, the overpack may include a shell and a cover plate. Wherein, the casing can include the bottom plate and connect the curb plate on the bottom plate, and bottom plate and curb plate enclose to close and form and hold the chamber. The shell is provided with an opening communicated with the accommodating cavity, and the cover plate can be covered on the opening to seal the accommodating cavity. The positive electrode tab, the negative electrode tab, and the separator may be formed into an electrode assembly through a winding process or a lamination process. An electrode assembly is encapsulated in the accommodating cavity. The electrolyte is impregnated into the electrode assembly. The number of electrode assemblies included in the secondary battery may be one or more, and those skilled in the art can select them according to specific practical needs.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
In some embodiments, the battery modules may be assembled into a battery pack, and the number of the battery modules contained in the battery pack may be one or more, and the specific number may be selected by one skilled in the art according to the application and the capacity of the battery pack.
The secondary battery, the battery module, or the battery pack may be used as a power source of an electric device, and may also be used as an energy storage unit of the electric device. The powered device may include a mobile device (e.g., a mobile phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship, a satellite, an energy storage system, etc., but is not limited thereto.
The device may also be a cell phone, tablet, laptop, etc. as examples. The device is generally required to be thin and light, and a secondary battery may be used as a power source.
Examples
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
1. Recovery of lithium iron phosphate material
Example 1
(1) Waste lithium iron phosphate pole pieces (the mass of a theoretically recoverable lithium iron phosphate material = the mass of the lithium iron phosphate pole piece-the mass of the conductive agent-the mass of the adhesive-the mass of the current collector =4.245 kg) with a porosity of 39% and with an undercoat layer of PAA recovered in the pole piece coating process were rolled to a porosity of 26.8%.
(2) And then placing the rolled lithium iron phosphate pole piece in 25kg of deionized water for soaking for 0.5 hour at room temperature, so that the lithium iron phosphate membrane is fully separated from the current collector aluminum foil. Then the aluminum foil with clean surface is taken out after the membrane is stripped. And filtering the residual solid-liquid mixture by a 40-mesh filter screen, wherein the filtrate is a positive lithium iron phosphate membrane containing lithium iron phosphate, conductive carbon black serving as a conductive agent and PVDF serving as a binder, and the filtrate contains a small amount of the conductive agent.
(3) And transferring the obtained positive lithium iron phosphate membrane to a forced air drying oven to be dried for 4 hours at the temperature of 150 ℃.
(4i) Drying the membrane, putting the membrane into an alumina sagger, putting the alumina sagger into a sintering furnace, and putting the alumina sagger into a furnace 2 Heat treating at 550 deg.c for 1 hr.
(4 ii) then placing the sintered lithium iron phosphate membrane into a wall breaking machine to be broken into D of lithium iron phosphate material powder v50 Reaching 1.5 μm.
(5) The iron phosphate material powder obtained was then collected in an alumina sagger in a sintering furnace in N 2 And carrying out high-temperature heat treatment for 1h at 750 ℃ in the atmosphere to obtain 4.17kg of lithium iron phosphate material.
Examples 2 to 4
The same procedure as in example 1 was carried out except that in step (1), the waste lithium iron phosphate pole pieces were rolled to porosities of 35.2%, 30.9% and 19.6%, respectively. 4.16kg, 4.16kg and 4.18kg of lithium iron phosphate materials were obtained, respectively.
Example 5
The procedure was carried out in the same manner as in example 1 except that the electrode sheet was immersed in deionized water for 1 hour in step (2). 4.18kg of lithium iron phosphate material was obtained.
Example 6
This was carried out in the same manner as in example 1 except that the drying time was changed to 12 hours while interchanging the order of steps (4 ii) and (4 i), that is, step (4 ii) was carried out first and then step (4 i) was carried out. 4.17kg of lithium iron phosphate material was obtained.
Examples 7 to 8
The same procedure as in example 1 was conducted except that the high-temperature heat treatment time in step (5) was changed to 1.5h and 2h, respectively. 4.17kg of lithium iron phosphate material and 4.17kg of lithium iron phosphate material were obtained, respectively.
Comparative example 1
The process was carried out in the same manner as in example 1 except that the waste lithium iron phosphate pole pieces were not rolled. 3.82kg of lithium iron phosphate material was obtained.
Comparative example 2
The procedure was carried out in the same manner as in example 1 except that step (5) was not carried out. 4.18kg of lithium iron phosphate material was obtained.
Comparative example 3
5kg of spent lithium iron phosphate pole pieces were broken into pieces of about 2 x 2cm size. Treating according to (4 i) in example 1, then transferring the pole piece after heat treatment to an abrasive machine for grinding, separating materials from aluminum foil, and vibrating and screening to remove the aluminum foil (40-mesh screen); then, step (4 ii) in example 1 was carried out. 3.33kg of lithium iron phosphate material was obtained.
Comparative example 4
The procedure was carried out in the same manner as in comparative example 4 except that step (5) in example 1 was continued. 3.32kg of lithium iron phosphate material was obtained.
Comparative example 5
In order to reduce the safety problem caused by hydrogen production, 200g of waste lithium iron phosphate pole piece (the mass of the recoverable lithium iron phosphate material is 170g theoretically) is placed in a 2L 0.5M NaOH solution, the aluminum foil is taken out after the positive pole membrane is separated from the aluminum foil, and the lithium iron phosphate membrane is obtained by filtering. The membrane was washed with copious amounts of deionized water until the filtrate pH was neutral. Then, steps (3), (4) and (5) of example 1 were performed to obtain 164g of a lithium iron phosphate material.
Reference example
The reference example employed a secondary battery prepared from fresh lithium iron phosphate material.
The lithium iron phosphate materials obtained in the above examples 1 to 8, comparative examples 1 to 5 and reference example were prepared into button cells, and the examples 1 to 8, comparative examples 1 to 4 and reference example were prepared into full cells, respectively, the k values of the full cells were compared, and a high-temperature cycle performance test was performed. The test results are shown in fig. 1 and table 1.
(1) Preparation of button cell
The lithium iron phosphate materials obtained in the above examples 1 to 8, comparative examples 1 to 5 and reference example, the conductive agent SP and the binder PVDF were mixed in a ratio of 90:5:5, grinding the mixture evenly into slurry by taking N-methylpyrrolidone (NMP) as a dispersing agent, and coating the slurry on an aluminum foil to prepare the positive plate. And assembling the button cell by adopting a lithium metal sheet as a negative electrode.
(2) Capacitance-on-hold test
The button cells were run on a blue tester, charged to 3.75V at 0.1C, then to 0.01C at 3.75V with a constant voltage, and discharged to 2.0V at 0.1C after 5 minutes of standing, where 1c =170ma/g.
(3) Preparation of full cell
The lithium iron phosphate materials obtained in the above examples 1 to 8, comparative examples 1 to 6 and reference example, the conductive agent SP and the binder PVDF were mixed in a ratio of 95:2:3, and fully dispersing by taking NMP as a solvent; coating the prepared slurry on the aluminum foil on two sides, and drying, cold pressing, slitting, cutting and the like to obtain the positive plate. Graphite, conductive carbon black, and CMC were mixed at a ratio of 97. And coating the double surfaces of the negative electrode slurry on copper foil, and drying, cold pressing, slitting and cutting into pieces to obtain the negative electrode piece. And a diaphragm is added between the positive plate and the negative plate for winding, and the wound positive plate and the wound negative plate are packaged into an aluminum-plastic bag after hot-cold pressing and tab welding. And (4) completely drying the battery core, injecting electrolyte, and carrying out vacuum packaging to obtain the full battery.
(4) K value test of full cell
And (3) charging the battery cell which is subjected to the first formation-capacity step to 3V at 0.05C, standing for 24 hours at room temperature to test the voltage V1 of the battery cell, and continuously standing for 48 hours to test the voltage V2 of the battery cell, wherein the k value of the battery cell is = (V1-V2) × 1000/48, and the unit mV/h. The cell was judged to be free of abnormality if the k value was 0.1mV/h or less. Theoretically, the closer the k value is to 0, the higher the battery safety is represented.
(5) Cycle performance test of full cell at 45 DEG C
And testing the cycle performance of the battery cell in a high-low temperature box at 45 ℃, and starting testing after keeping the temperature for 2 hours. Charging to 3.65V at 0.5C, then charging to 0.05C at constant voltage at 3.65V, standing for 5 minutes, discharging to 2.5V at 1C, repeating the charging and discharging system to obtain cycle performance data.
Figure BDA0003297614000000171
As is clear from Table 1 and FIG. 1, the yield of the material of examples 1 to 8 exceeded 98%, the chargeback discharge capacity was 152.8 to 154.2mAh/g, no abnormality was observed in the k value in the production of the full cell, and the capacity retention rate was maintained at 93.5% or more after 500 cycles at 45 ℃.
In contrast, comparative examples 1, 3 and 4 were low in material recovery, and particularly comparative examples 3 and 4 had a material yield of only 78%. The gram capacities of the materials in comparative examples 2, 3 and 5 are lower, the gram capacities of the comparative examples 2 and 3 are lower because the surface structures of the materials cannot be repaired without high-temperature treatment, and the gram capacity of the comparative example 5 is lower because metal elements are dissolved and the surfaces of the materials are damaged due to alkali liquor treatment. Meanwhile, in comparative examples 3 and 4, metal aluminum scraps cannot be completely removed by adopting a vibration screening mode after the pole pieces are crushed, the electric core is subjected to electric leakage caused by local internal short circuit after the material is processed into the electric core, and the k value is abnormally large.
In conclusion, the method for recovering the lithium iron phosphate material realizes simple, environment-friendly, safe and high-yield recovery of the lithium iron phosphate material, so that the secondary battery containing the obtained lithium iron phosphate material has excellent safety and cycle performance.
The present application is not limited to the above embodiments. The above embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exhibiting the same operation and effect within the technical scope of the present application are all included in the technical scope of the present application. In addition, various modifications that can be conceived by those skilled in the art are applied to the embodiments and other embodiments are also included in the scope of the present application, in which some of the constituent elements in the embodiments are combined and constructed, without departing from the scope of the present application.

Claims (11)

1. A method for recovering lithium iron phosphate material from waste lithium iron phosphate pole pieces, wherein the lithium iron phosphate pole pieces are composed of lithium iron phosphate diaphragms and collectors, and the method comprises the following steps:
(1) Extruding the lithium iron phosphate pole piece;
(2) Soaking the lithium iron phosphate pole piece obtained in the step (1) in water to enable a lithium iron phosphate membrane and a current collector to be stripped; recovering the current collector, and then filtering the residual solid-liquid mixture to obtain a lithium iron phosphate membrane;
(3) Drying the lithium iron phosphate membrane obtained in the step (2);
(4) Performing low-temperature heat treatment on the lithium iron phosphate membrane obtained in the step (3) at 380-600 ℃, and then performing mechanical crushing, or performing mechanical crushing on the lithium iron phosphate membrane obtained in the step (3) and then performing low-temperature heat treatment at 380-600 ℃, so as to obtain lithium iron phosphate material powder;
(5) And (4) carrying out high-temperature heat treatment on the lithium iron phosphate material powder obtained in the step (4) at 650-850 ℃ to obtain a lithium iron phosphate material.
2. The method according to claim 1, wherein in the step (1), the porosity of the lithium iron phosphate pole pieces before and after extrusion satisfies the following formula:
the ratio of the porosity before extrusion to the porosity after extrusion is not less than 1.05 and not more than 3.
3. The method according to claim 1 or 2, wherein in step (2), the soaking with water is performed at a temperature of not more than 40 ℃ for 0.05 to 1 hour; the water is domestic water, distilled water, deionized water or industrial water, preferably deionized water.
4. The method of any one of claims 1-3, wherein the current collector is an aluminum foil.
5. The method according to any one of claims 1 to 4, wherein, in the step (3), the drying is performed at 100 to 180 ℃ for 1 to 12 hours in an air atmosphere.
6. The method according to any one of claims 1 to 5, wherein in the step (4), the lithium iron phosphate membrane obtained in the step (3) is subjected to low-temperature heat treatment at 380 to 600 ℃ and then to mechanical crushing.
7. The method according to any one of claims 1 to 6, wherein the low temperature heat treatment and the high temperature heat treatment are both carried out in an inert atmosphere, the inert atmosphere being N 2 Ar, he, ne, kr, xe, preferably N 2 And Ar.
8. The method according to any one of claims 1 to 7, wherein in step (4), the lithium iron phosphate membrane is mechanically crushed to a volume average particle diameter D of the resulting material powder v50 Is 0.5-3 μm.
9. The process according to any one of claims 1 to 8, wherein the duration of the high temperature heat treatment in step (5) is 0.5 to 3 hours, preferably 1 to 2 hours.
10. A positive electrode sheet comprising a current collector and a lithium iron phosphate material obtained by the method of any one of claims 1 to 9.
11. A secondary battery comprising the lithium iron phosphate material obtained by the method according to any one of claims 1 to 9 or the positive electrode sheet according to claim 10.
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