CN115818607B - Method for recycling lithium iron phosphate material - Google Patents

Method for recycling lithium iron phosphate material Download PDF

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Publication number
CN115818607B
CN115818607B CN202111181904.5A CN202111181904A CN115818607B CN 115818607 B CN115818607 B CN 115818607B CN 202111181904 A CN202111181904 A CN 202111181904A CN 115818607 B CN115818607 B CN 115818607B
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iron phosphate
lithium iron
heat treatment
temperature heat
current collector
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CN115818607A (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 recycling a lithium iron phosphate material, wherein a lithium iron phosphate pole piece consists of a lithium iron phosphate membrane 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) with water to peel off the lithium iron phosphate membrane from the current collector; recovering a current collector, and filtering the rest solid-liquid mixture to obtain a lithium iron phosphate membrane; (3) Drying the lithium iron phosphate membrane obtained in the step (2); (4) Carrying out low-temperature heat treatment at 380-600 ℃ on the lithium iron phosphate membrane obtained in the step (3), and then carrying out mechanical crushing, or carrying out mechanical crushing on the lithium iron phosphate membrane obtained in the step (3) and then carrying out low-temperature heat treatment at 380-600 ℃ to obtain lithium iron phosphate material powder; (5) And (3) carrying out high-temperature heat treatment on the lithium iron phosphate material powder obtained in the step (4) at 650-850 ℃ to obtain the 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 recycling a lithium iron phosphate material, a positive electrode plate obtained from the lithium iron phosphate material prepared by the method, and a secondary battery comprising the positive electrode plate.
Background
In recent years, along with the wider application range of lithium ion batteries, the lithium ion batteries are widely applied to energy storage power supply systems such as hydraulic power, firepower, wind power, solar power stations and the like, and a plurality of fields such as electric tools, electric bicycles, electric motorcycles, electric automobiles, military equipment, aerospace and the like. Among them, lithium iron phosphate batteries are one of the most important power batteries at present. The waste positive pole pieces are inevitably generated in a plurality of working procedures in the production process of the power battery, a large amount of positive pole materials are wasted due to the generation of the waste pole pieces, and the materials are effectively recycled under the conditions of rising material cost and environmental protection pressure.
Disclosure of Invention
The present application has been made in view of the above-mentioned practical problems, and an object thereof is to provide a simple, environmentally friendly, safe, high-yield method for recovering a lithium iron phosphate material, such that the obtained lithium iron phosphate material exhibits excellent electrochemical properties in a corresponding secondary battery, while the method can achieve efficient recovery of aluminum foil.
In order to achieve the above object, the present application provides a method of recovering a lithium iron phosphate material, a positive electrode sheet obtained from the lithium iron phosphate material prepared by the method, and a secondary battery including the positive electrode sheet.
In a first aspect the present application provides a method of recovering lithium iron phosphate material from a spent lithium iron phosphate pole piece, the lithium iron phosphate pole piece consisting of a lithium iron phosphate diaphragm and a current collector, the method comprising the steps of:
(1) Extruding a lithium iron phosphate pole piece;
(2) Soaking the lithium iron phosphate pole piece obtained in the step (1) with water to peel off the lithium iron phosphate membrane from the current collector; recovering a current collector, and filtering the rest solid-liquid mixture to obtain a lithium iron phosphate membrane;
(3) Drying the lithium iron phosphate membrane obtained in the step (2);
(4) Carrying out low-temperature heat treatment at 380-600 ℃ on the lithium iron phosphate membrane obtained in the step (3), and then carrying out mechanical crushing, or carrying out mechanical crushing on the lithium iron phosphate membrane obtained in the step (3) and then carrying out low-temperature heat treatment at 380-600 ℃ to obtain lithium iron phosphate material powder;
(5) And (3) carrying out high-temperature heat treatment on the lithium iron phosphate material powder obtained in the step (4) at 650-850 ℃ to obtain the lithium iron phosphate material.
Therefore, the method can simply, environmentally-friendly, safely and high-yield recover the lithium iron phosphate material. Specifically, 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, so that the lithium iron phosphate material can be directly used for the preparation of subsequent battery cells; 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 less than or equal to 1.05 and less than or equal to 3.
After extrusion, the lithium iron phosphate film is extremely easy to peel from the current collector, so that the recovery efficiency is improved, meanwhile, the pole pieces can be loosely soaked in a whole piece, and the phenomenon that current collector scraps and post-treatment steps are introduced due to the fact that the pole pieces are broken into small pole pieces is avoided.
In any embodiment, the soaking in water in step (2) is performed at a temperature of no more than 40 ℃ for 0.05 to 1 hour; the water is raw water, distilled water, deionized water, 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 of the surface structure can be reduced, and the pole piece is safe and environment-friendly.
In any embodiment, the current collector is aluminum foil. Thereby making the lithium iron phosphate material more easily peeled off.
In any embodiment, in step (3), the drying is performed at 100-180 ℃ in an air atmosphere for 1-12 hours. The lithium iron phosphate material thus obtained is more susceptible to subsequent mechanical crushing.
In any embodiment, in step (4), the lithium iron phosphate film obtained in step (3) is first subjected to low temperature heat treatment at 380-600 ℃ and then mechanically crushed. Therefore, the lithium iron phosphate membrane can be mechanically crushed under the condition that the lithium iron phosphate membrane is dried more thoroughly, and the lithium iron phosphate membrane is easier to crush and has higher efficiency.
In any embodiment, the low temperature heat treatment and the high temperature heat treatment are both performed in an inert atmosphere, the inert atmosphere being 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 film is mechanically crushed to a volume average particle diameter D of the obtained material powder v50 0.5-3 μm. The material powder thus obtained is easier to carry out subsequent high-temperature heat treatments and facilitates the use of lithium iron phosphate materials.
In any embodiment, the duration of the high temperature heat treatment in step (5) is from 0.5 to 3 hours, preferably from 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 on one hand, the good electron conductivity of the lithium iron phosphate material is ensured, the electrochemical performance of the lithium iron phosphate material is fully exerted, and the gram capacity is high.
The second aspect of the application also provides a positive electrode sheet comprising a current collector and a lithium iron phosphate material obtained by the method of the first aspect of the application.
A third aspect of the application provides a secondary battery characterized by comprising a lithium iron phosphate material obtained by the method according to the first aspect of the application or the positive electrode sheet according to the second aspect of the application.
Drawings
Fig. 1 shows K values of full cells of each example and comparative example.
Fig. 2 is a schematic flow chart of a method according to a preferred embodiment of the application.
Detailed Description
Hereinafter, embodiments of a method for recovering a lithium iron phosphate material, and a positive electrode sheet and a secondary battery including the lithium iron phosphate material according to the present application are specifically disclosed with reference to the accompanying drawings. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can 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 the present application, unless otherwise indicated, 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, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed 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 of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
In the production process of lithium ion batteries, the waste electrode plates are inevitably generated, and under the conditions of rising material cost and environmental protection pressure, the waste electrode plates are urgently needed to be effectively recycled. At present, a chemical method is generally adopted to recycle the lithium iron phosphate, so that the cost is high and the pollution is serious. Secondly, in the physical recovery process, the generated aluminum scraps impurities easily cause the safety risk of the battery cell during recycling, and if the aluminum scraps are controlled by adopting winnowing, screening and the like, the recovery rate is reduced. If the aluminum scraps are removed by adopting alkali liquor for cleaning, the recovery process is complex, and meanwhile, the use of the alkali liquor brings the problem of subsequent waste liquid treatment. In some prior arts, the pole piece is soaked by alkali liquor or organic solvent to separate lithium iron phosphate material from aluminum foil, which can reduce the impurity content of aluminum scraps in the recovered material, but the method also has the problem of treating chemical reagent waste liquid such as alkali liquor or organic solvent, and a large amount of H can be generated when the pole piece is directly soaked by alkali liquor 2 There is a safety risk.
The inventors have found after a great deal of research that the method of the first aspect of the present application realizes simple, environment-friendly, safe and high-yield recovery of lithium iron phosphate materials by extruding the waste sheet, then soaking the waste sheet in water and combining with the subsequent specific heat treatment, so that the obtained lithium iron phosphate materials exhibit excellent electrochemical properties in the corresponding secondary batteries, and at the same time the method can realize effective recovery of aluminum foils.
The method for recycling the lithium iron phosphate material is suitable for treating the waste lithium iron phosphate pole pieces. The waste lithium iron phosphate pole piece refers to pole piece scraps which are not assembled in the battery, such as waste pole pieces and leftover material pole pieces generated in the process of manufacturing battery cells; the electrode sheet present in the secondary battery subjected to the 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 one embodiment of the application, the application provides a method for recovering lithium iron phosphate material from a waste lithium iron phosphate pole piece, wherein the lithium iron phosphate pole piece consists of a lithium iron phosphate membrane and a current collector, and the method comprises the following steps of:
(1) Extruding a lithium iron phosphate pole piece;
(2) Soaking the lithium iron phosphate pole piece obtained in the step (1) with water to peel off the lithium iron phosphate membrane from the current collector; recovering a current collector, and filtering the rest solid-liquid mixture to obtain a lithium iron phosphate membrane;
(3) Drying the lithium iron phosphate membrane obtained in the step (2);
(4) Carrying out low-temperature heat treatment at 380-600 ℃ on the lithium iron phosphate membrane obtained in the step (3), and then carrying out mechanical crushing, or carrying out mechanical crushing on the lithium iron phosphate membrane obtained in the step (3) and then carrying out low-temperature heat treatment at 380-600 ℃ to obtain lithium iron phosphate material powder;
(5) And (3) carrying out high-temperature heat treatment on the lithium iron phosphate material powder obtained in the step (4) at 650-850 ℃ to obtain the lithium iron phosphate material.
Although the mechanism is not yet clear, the inventors have unexpectedly found that: the method realizes simple, environment-friendly, safe and high-yield recovery of the lithium iron phosphate material by extruding the waste lithium iron phosphate pole piece, then soaking the waste lithium iron phosphate pole piece in water and combining with the subsequent specific heat treatment, so that the obtained lithium iron phosphate material shows excellent electrochemical performance in the corresponding secondary battery, and meanwhile, the method can realize effective recovery of the aluminum foil. And the interface of the lithium iron phosphate material can be better repaired by high-temperature heat treatment, so that the carbon content of the lithium iron phosphate material is moderate, the gram capacity is high, and the good electron conductivity of the lithium iron phosphate material is ensured.
The waste lithium iron phosphate pole piece is prepared by adopting an aqueous base coating process, and the base coating is composed of an aqueous binder and conductive carbon, wherein the aqueous binder is sodium carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylate (PAA), polyacrylamide (PAN) and the like, and the content of the aqueous 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 generally 125 mu m to 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 less than or equal to 1.05 and less than or equal to 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 usually 35% -45%, and the porosity of the lithium iron phosphate pole piece after extrusion is usually 15% -32%, preferably 19% -28%.
The manner of extrusion is any manner generally known to those skilled in the art, roll compaction being preferred.
After the porosity of the lithium iron phosphate pole piece reaches a specific degree through extrusion, the lithium iron phosphate membrane is extremely easy to peel off from the current collector, so that the recovery efficiency is improved, meanwhile, the pole piece can be loosely soaked in a whole piece, and the current collector scraps and the post-treatment steps are prevented from being introduced due to the fact that the pole piece is broken into small pole pieces.
In some embodiments, in step (2), the soaking with water is performed at a temperature of not more than 40 ℃, preferably room temperature, for 0.05 to 1 hour, preferably 0.15-0.35 hour. The temperature is not too high when the water is used for soaking, otherwise, the dissolution of ions is accelerated, and the element proportion of the recycled materials can be influenced. The soaking time is proper, so that the separation of the lithium iron phosphate membrane and the current collector can be ensured, and meanwhile, the dissolution of metal elements in the lithium iron phosphate material and the damage of the surface structure of the membrane can be reduced.
The water is raw water, distilled water, deionized water, 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 is convenient to separate from the current collector.
In some embodiments, the current collector is aluminum foil. The lithium iron phosphate electrode sheet is usually used as a positive electrode sheet, and a current collector used for the positive electrode can be a metal foil or a composite current collector, preferably a metal foil. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric 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 polymer material substrate (such as a substrate 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 100-180 ℃ in an air atmosphere for 1-12 hours.
In some embodiments, in step (4), the lithium iron phosphate film obtained in step (3) is mechanically crushed and then subjected to a low temperature heat treatment at 380-600 ℃. In this case, the drying in step (3) is carried out for 1 to 12 hours, preferably 1 to 6 hours. Under the embodiment, the obtained lithium iron phosphate material powder is directly subjected to the step (5) low-temperature heat treatment, so that the interface repair of the lithium iron phosphate material is facilitated, and the damage of the carbon coating layer of the lithium iron phosphate material is more effectively repaired.
In some preferred embodiments, in step (4), the lithium iron phosphate film obtained in step (3) is first subjected to a low temperature heat treatment at 380-600 ℃ and then to mechanical disruption, as shown in fig. 2. In this case, the drying in step (3) is carried out for 1 to 12 hours, preferably 1 to 3 hours. In this embodiment, the drying time in 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 a temperature of 380-600 ℃, preferably 450-550 ℃ for 0.5-5 hours, preferably 1-2 hours; the high temperature heat treatment is carried out at a temperature of 650-850 ℃, preferably 680-780 ℃ for 0.5-3 hours, preferably 1-2 hours.
The low-temperature heat treatment and the high-temperature heat treatment of the lithium iron phosphate material are both in an inert atmosphere so as to prevent the lithium iron phosphate material from being damaged by oxygen in the air.
In some embodiments, in step (4), lithium iron phosphate film is mechanically crushed to a volume average particle diameter D of the resulting material powder v50 0.5-3 μm. The mechanical disruption is carried out in any suitable commercially available equipment such as ball mills and the like by means known to those skilled in the art such as ball milling and the like. The volume average particle diameter of the obtained material powder is 0.5 to 3. Mu.m, preferably 0.8 to 2.0. Mu.m. The material powder thus obtained is easier to carry out subsequent high-temperature heat treatments and facilitates the use of lithium iron phosphate materials.
In some embodiments, the duration of the high temperature heat treatment in step (5) is from 0.5 to 3 hours, preferably from 1 to 2 hours. And 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 interfacial 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, there is provided a positive electrode sheet comprising 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 comprising 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. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
[ Positive electrode sheet ]
The positive electrode sheet comprises a positive electrode current collector and a positive electrode membrane arranged on at least one surface of the positive electrode current collector, wherein the positive electrode membrane comprises a positive electrode active material, and the positive electrode active material comprises the lithium iron phosphate material obtained by the method of the first aspect of the application.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode membrane is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive 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 polymeric material base layer and a metal layer formed on at least one surface of the polymeric 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 polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.). In a preferred embodiment, the current collector is 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 application.
In some embodiments, the positive electrode membrane further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode membrane 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 (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
[ negative electrode sheet ]
The negative electrode sheet comprises a negative electrode current collector and a negative electrode membrane arranged on at least one surface of the negative electrode current collector, wherein the negative electrode membrane comprises a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode membrane is provided on either one or both of the two surfaces opposing the anode 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 may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode active material for a battery, which is well 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 may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may 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 includes 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 includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode membrane may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining a negative electrode plate after the procedures of drying, cold pressing and the like.
[ electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The application is not particularly limited in the kind of electrolyte, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. 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-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl 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, dimethyl sulfone, methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
[ isolation Membrane ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used.
In some embodiments, the material of the isolating 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 outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
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 exterior package of the secondary battery may also be a pouch type pouch, for example. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square, or any other shape.
In some embodiments, the outer package may include a housing and a cover. Wherein, the casing can include the bottom plate and connect the curb plate on the bottom plate, and bottom plate and curb plate enclose and close and form the chamber that holds. 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 sheet, the negative electrode sheet and the separator may be formed into an electrode assembly through a winding process or a lamination process. The electrode assembly is encapsulated in the accommodating cavity. The electrolyte is impregnated in the electrode assembly. The number of electrode assemblies included in the secondary battery may be one or more, and one skilled in the art may select according to specific practical requirements.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of secondary batteries included in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
In some embodiments, the above battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
The secondary battery, the battery module, or the battery pack may be used as a power source of the electric device, and may also be used as an energy storage unit of the electric device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
The device may also be a cell phone, tablet computer, notebook computer, etc. as examples. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
1. Recovery of lithium iron phosphate materials
Example 1
(1) 5kg of waste lithium iron phosphate pole pieces (mass of theoretical recoverable lithium iron phosphate material=mass of lithium iron phosphate pole pieces-mass of conductive agent-mass of binder-mass of current collector= 4.245 kg) with a porosity of 39% and the primer 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 deionized water, and soaking for 0.5 hour at room temperature to fully separate the lithium iron phosphate membrane from the aluminum foil of the current collector. And then taking out the aluminum foil with clean surface after the membrane is peeled off. Filtering the rest 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 of a conductive agent and a binder PVDF, and the filtrate contains a small amount of conductive agent.
(3) The resulting lithium iron phosphate film was transferred to a forced air drying oven and dried at 150 ℃ for 4 hours.
(4i) Drying the membrane, loading into an alumina sagger, and placing into a sintering furnace in N 2 The mixture was subjected to low-temperature heat treatment at 550℃for 1 hour in the atmosphere.
(4 ii) then placing the sintered lithium iron phosphate film into a wall breaking machine to be broken into powder D of lithium iron phosphate material v50 Reaching 1.5 μm.
(5) The iron phosphate material powder obtained was then collected in an alumina sagger in a sintering furnace under N 2 High temperature heat treatment is carried out for 1h at 750 ℃ in the atmosphere, thus obtaining 4.17kg of lithium iron phosphate material.
Examples 2 to 4
In the same manner as in example 1, except that in step (1), the spent lithium iron phosphate pole pieces were rolled to a porosity of 35.2%, 30.9% and 19.6%, respectively. 4.16kg, 4.16kg and 4.18kg of lithium iron phosphate material were obtained, respectively.
Example 5
The same procedure as in example 1 was carried out except that the pole piece was immersed in deionized water for 1 hour in step (2). 4.18kg of lithium iron phosphate material was obtained.
Example 6
In the same manner as in example 1, except that the drying time was changed to 12 hours while the steps (4 ii) and (4 i) were sequentially interchanged, i.e., the step (4 ii) was performed first, and then the step (4 i) was performed. 4.17kg of lithium iron phosphate material was obtained.
Examples 7 to 8
The procedure was carried out in the same manner as in example 1 except that the time of the high-temperature heat treatment in step (5) was changed to 1.5h and 2h, respectively. 4.17kg of lithium iron phosphate material, 4.17kg, respectively, were obtained.
Comparative example 1
The same procedure as in example 1 was conducted except that the waste lithium iron phosphate sheet was not rolled. 3.82kg of lithium iron phosphate material was obtained.
Comparative example 2
In the same manner as in example 1, except that step (5) was not performed. 4.18kg of lithium iron phosphate material was obtained.
Comparative example 3
The 5kg spent lithium iron phosphate pole pieces were broken into pieces of about 2 x 2cm in size. Treating according to (4 i) in the embodiment 1, transferring the pole piece after heat treatment into an abrasive machine for grinding, separating the material from the aluminum foil, and vibrating and screening to remove the aluminum foil (40 mesh screen); step (4 ii) of example 1 was then performed. 3.33kg of lithium iron phosphate material was obtained.
Comparative example 4
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
To reduce the safety problem introduced by hydrogen production, 200g of waste lithium iron phosphate pole piece (the mass of the theoretical recoverable lithium iron phosphate material is 170 g) is placed in 2L of 0.5M NaOH solution, the positive pole membrane is separated from the aluminum foil, the aluminum foil is taken out, and the lithium iron phosphate membrane is obtained by filtering. The membrane was washed with a large amount of deionized water until the filtrate pH was neutral. Then, the steps (3), (4) and (5) of example 1 were performed to obtain 164g of a lithium iron phosphate material.
Reference example
Reference examples secondary batteries were prepared using fresh lithium iron phosphate materials.
The lithium iron phosphate materials obtained in the above examples 1 to 8, comparative examples 1 to 5 and reference examples were prepared as button cells as shown below, respectively, and examples 1 to 8, comparative examples 1 to 4 and reference examples were prepared as full cells, and 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 examples 1 to 8, comparative examples 1 to 5 and reference examples, the conductive agent SP and the binder PVDF were mixed in an amount of 90:5: and 5, mixing the materials according to the mass ratio, taking N-methyl pyrrolidone (NMP) as a dispersing agent, grinding the mixture uniformly into slurry, and coating the slurry on an aluminum foil to prepare the positive plate. The negative electrode adopts lithium metal sheet, and the button cell is assembled.
(2) Buckling capacity test
The button cell was run on a blue tester with 0.1C charged to 3.75V, then 3.75V constant voltage charged to 0.01C and after 5 minutes of rest 0.1C discharged to 2.0V, where 1c=170 mA/g.
(3) Preparation of full cell
The lithium iron phosphate materials obtained in examples 1 to 8, comparative examples 1 to 6 and reference examples, the conductive agent SP and the binder PVDF were prepared in a ratio of 95:2:3, mixing according to the mass ratio, and fully dispersing by taking NMP as a solvent; and (3) 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 are mixed in a ratio of 97:2:1, and water is used as a solvent for dispersion, so that negative electrode slurry is obtained. And (3) coating the two sides of the negative electrode slurry on a copper foil, and drying, cold pressing, slitting and cutting to obtain a negative electrode plate. And adding a diaphragm between the positive plate and the negative plate for winding, and packaging into an aluminum plastic bag after hot and cold pressing and tab welding. And (5) thoroughly drying the battery cell, and then injecting electrolyte into the battery cell for vacuum packaging to obtain the full battery.
(4) K-value test of full cell
And (3) charging the battery cell with the first formation-capacity step to 3V at 0.05C, standing for 24 hours at room temperature to test the battery cell voltage V1, and continuing standing for 48 hours to test the battery cell voltage V2, wherein the battery cell k value= (V1-V2) is 1000/48, and the unit is mV/h. And the k value is less than or equal to 0.1mV/h, and the battery is regarded as no abnormality. Theoretically, the closer the k value is to 0, the higher the battery safety is represented.
(5) Full cell cycle performance test at 45 DEG C
The cell is tested for cycle performance in a high-low temperature box at 45 ℃ and is started to be tested after being kept at a constant temperature for 2 hours. Charging the battery to 3.65V at 0.5C, then charging the battery to 0.05C at 3.65V at constant voltage, standing for 5 minutes, discharging the battery to 2.5V at 1C, and repeating the charging and discharging system to obtain cycle performance data.
As can be seen from Table 1 and FIG. 1, the yield of the materials of examples 1 to 8 exceeds 98%, the discharge capacity of the snap-in gram is 152.8 to 154.2mAh/g, the k value is not abnormal in the whole battery production, and the capacity retention rate is maintained above 93.5% after 500 cycles at 45 ℃, and compared with the reference group, the discharge capacity of the materials is slightly reduced, so that a good effect is obtained.
In contrast, comparative examples 1, 3 and 4 were low in material recovery, and in particular, comparative examples 3 and 4 were low in material recovery of only 78%. The low gram capacity of the materials in the comparative examples 2, 3 and 5 is because the surface structure of the materials cannot be repaired without high-temperature treatment, and the low gram capacity of the materials in the comparative examples 2 and 3 is because the metal elements are dissolved and the surface of the materials is 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 pole pieces are broken, and after materials are processed into battery cells, partial internal short circuits are caused to lead the battery cells to leak electricity, so that the k value is abnormally larger.
In summary, the method for recovering lithium iron phosphate material of the present application achieves simple, environment-friendly, safe, high-yield recovery of lithium iron phosphate material, so that the secondary battery including the obtained lithium iron phosphate material exhibits excellent safety and cycle performance.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.

Claims (16)

1. A method of recovering lithium iron phosphate material from a spent lithium iron phosphate pole piece, the lithium iron phosphate pole piece consisting of a lithium iron phosphate membrane and a current collector, the method comprising the steps of:
(1) Extruding a lithium iron phosphate pole piece;
(2) Soaking the lithium iron phosphate pole piece obtained in the step (1) with water to peel off the lithium iron phosphate membrane from the current collector; recovering a current collector, and filtering the rest solid-liquid mixture to obtain a lithium iron phosphate membrane;
(3) Drying the lithium iron phosphate membrane obtained in the step (2);
(4) Carrying out low-temperature heat treatment at 380-600 ℃ on the lithium iron phosphate membrane obtained in the step (3), and then carrying out mechanical crushing, or carrying out mechanical crushing on the lithium iron phosphate membrane obtained in the step (3) and then carrying out low-temperature heat treatment at 380-600 ℃ to obtain lithium iron phosphate material powder;
(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;
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 less than or equal to 1.05 and less than or equal to 3;
in step (2), the soaking in water is performed at a temperature of not more than 40 ℃ for 0.05 to 1 hour.
2. The method of claim 1, wherein the water is distilled water, deionized water.
3. The method of claim 2, wherein the water is deionized water.
4. A method according to any one of claims 1-3, characterized in that the current collector is an aluminium foil.
5. A method according to any one of claims 1-3, characterized in that in step (3) the drying is carried out in an air atmosphere at 100-180 ℃ for 1-12 hours.
6. The method according to claim 4, wherein in the step (3), the drying is performed at 100 to 180 ℃ in an air atmosphere for 1 to 12 hours.
7. The method according to any one of claims 1, 2, 3, 6, wherein in step (4), the lithium iron phosphate film sheet obtained in step (3) is subjected to low-temperature heat treatment at 380 to 600 ℃ and then subjected to mechanical crushing.
8. The method according to claim 4, wherein in the step (4), the lithium iron phosphate film obtained in the step (3) is subjected to low-temperature heat treatment at 380 to 600 ℃ and then subjected to mechanical crushing.
9. The method according to claim 5, wherein in the step (4), the lithium iron phosphate film obtained in the step (3) is subjected to a low-temperature heat treatment at 380 to 600 ℃ and then subjected to mechanical crushing.
10. The method according to any one of claims 1, 2, 3, 6, 8, 9, wherein the low-temperature heat treatment and the high-temperature heat treatment are both performed in an inert atmosphere, the inert atmosphere being N 2 、Ar、He、Ne、Kr、Xe。
11. The method of claim 10, wherein the inert atmosphere is N 2 And Ar.
12. The method according to any one of claims 1, 2, 3, 6, 8, 9, 11, characterized in that in step (4), lithium iron phosphate film is mechanically crushed to a volume average particle diameter D of the obtained material powder v50 0.5-3 μm.
13. The method according to any one of claims 1, 2, 3, 6, 8, 9, 11, wherein the duration of the high temperature heat treatment in step (5) is 0.5 to 3 hours.
14. The method according to claim 13, wherein the duration of the heat treatment in step (5) is 1-2 hours.
15. A positive electrode sheet comprising a current collector and a lithium iron phosphate material obtained by the method of any one of claims 1-14.
16. A secondary battery comprising the lithium iron phosphate material obtained by the method according to any one of claims 1 to 14 or the positive electrode sheet according to claim 15.
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