CN115810742B - Preparation method of positive electrode active material - Google Patents
Preparation method of positive electrode active material Download PDFInfo
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- CN115810742B CN115810742B CN202210010091.1A CN202210010091A CN115810742B CN 115810742 B CN115810742 B CN 115810742B CN 202210010091 A CN202210010091 A CN 202210010091A CN 115810742 B CN115810742 B CN 115810742B
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Abstract
本申请提供了一种正极活性材料的制备方法、正极活性材料、正极极片、二次电池和用电装置，正极活性材料的制备方法包括以下步骤：将废旧镍钴锰酸锂二次电池放电，烘干、拆解得到正极极片，焙烧除去杂质；得到的正极极片加酸溶解，过滤得到混合溶液，加入金属盐调配金属元素的摩尔比，在碱溶液中发生共沉淀反应，过滤得到镍钴锰铝酸锂前驱体；滤液重结晶得到氢氧化锂；镍钴锰铝酸锂前驱体与氢氧化锂混合后焙烧得到镍钴锰铝酸锂正极活性材料。本申请提供的正极活性材料的制备方法免去活性物质和铝箔分离步骤，简化了回收方法，提升了回收效率。
The present application provides a method for preparing a positive electrode active material, a positive electrode active material, a positive electrode plate, a secondary battery and an electric device. The method for preparing a positive electrode active material comprises the following steps: discharging a waste nickel cobalt manganese oxide lithium secondary battery, drying and disassembling to obtain a positive electrode plate, and roasting to remove impurities; dissolving the obtained positive electrode plate with acid, filtering to obtain a mixed solution, adding a metal salt to adjust the molar ratio of the metal elements, causing a coprecipitation reaction in an alkaline solution, and filtering to obtain a nickel cobalt manganese aluminum oxide lithium precursor; recrystallizing the filtrate to obtain lithium hydroxide; and roasting the nickel cobalt manganese aluminum oxide lithium positive electrode active material after mixing the nickel cobalt manganese aluminum oxide lithium precursor with lithium hydroxide. The method for preparing a positive electrode active material provided by the present application eliminates the step of separating the active substance and the aluminum foil, simplifies the recycling method, and improves the recycling efficiency.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to a preparation method of an anode active material, the anode active material, an anode plate, a secondary battery and an electric device.
Background
The secondary battery (such as lithium ion battery) has the characteristics of large specific energy, high working voltage, low self-discharge rate, small volume, light weight and the like, and is widely applied to products such as electric vehicles, electronic equipment and the like. Lamellar Li [ Ni xCoyMn1-x-y]O2 (0 < x <1,0< y <1,0<1-x-y < 1) has been widely studied as a positive electrode active material for secondary batteries. Because of its low cost and high capacity, it is considered to be one of the most promising positive electrode active materials that meet the requirements of Electric Vehicles (EV) and hybrid electric vehicles. The rapid increase of the secondary battery demand is a direct cause of the price of raw materials nickel, cobalt and manganese ores, so the recovery of waste nickel cobalt lithium manganate batteries is urgent.
The recovery process of lithium nickel cobalt manganate is usually a mechanical crushing separation method, but the active substance separation is incomplete in the process, and foil scraps are mixed into the active substance, so that a subsequent impurity removal step is added. Therefore, the existing recovery process of nickel cobalt lithium manganate still needs to be improved.
Disclosure of Invention
The present application has been made in view of the above problems, and an object of the present application is to simplify a recovery method of a lithium nickel cobalt manganese oxide battery and to improve recovery efficiency.
In order to achieve the above object, the present application provides a method for preparing a positive electrode active material, a positive electrode tab, a secondary battery, and an electric device.
The first aspect of the present application provides a method for preparing a positive electrode active material, comprising the steps of:
(1) Discharging a waste nickel cobalt lithium manganate (NCM) secondary battery in a saturated aqueous solution of sodium chloride for 1-3 days, and drying and disassembling to obtain a positive electrode plate;
(2) Roasting the positive electrode plate obtained in the step (1) in a flowing air atmosphere, and removing conductive carbon and a binder;
(3) Putting the positive electrode plate obtained in the step (2) into a soaking tank, adding an acid solution and a reducing substance into the soaking tank to react until the positive electrode current collector is completely dissolved, and filtering after the reaction is finished to obtain a mixed solution containing nickel, manganese, cobalt, aluminum and lithium elements;
(4) Adding nickel salt, cobalt salt and manganese salt into the mixed solution, preparing the molar ratio of nickel, cobalt, manganese and aluminum elements to obtain mixed salt solution, further performing coprecipitation reaction in sodium hydroxide and ammonia water, and filtering to obtain a nickel cobalt manganese lithium aluminate (NCMA) precursor, wherein the nickel cobalt manganese lithium aluminate precursor satisfies (Ni tCouMnvAlw)(OH)2, wherein t is more than or equal to 0.5 and less than or equal to 1, u is more than or equal to 0 and less than or equal to 0.5, v is more than or equal to 0 and less than or equal to 0.3, and t+u+v+w=1;
(5) Evaporating the filtrate obtained in the step (4) to dryness at 50-80 ℃ to obtain a solvent, recrystallizing and drying to obtain lithium hydroxide powder;
(6) And uniformly mixing the nickel cobalt manganese lithium aluminate precursor and the lithium hydroxide powder according to the molar ratio of 1:1.03-1:1.2, roasting in an oxygen atmosphere, crushing, sieving and demagnetizing to obtain the nickel cobalt manganese lithium aluminate anode active material.
Therefore, after the positive electrode plate is baked, the baked positive electrode plate is placed into the soaking tank to be dissolved by adding acid, so that the active substance and aluminum foil separation step is omitted, the recovery method is simplified, the aluminum element in the aluminum foil is fully recovered, and the recovery efficiency is improved.
In any embodiment, the positive electrode active material of the waste nickel cobalt lithium manganate secondary battery accords with a general formula Li (Ni xCoyMnz)O2, wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and x+y+z=1, so that nickel, manganese, cobalt, aluminum and lithium elements can be provided, and the recovery efficiency is improved.
In any embodiment, the drying temperature is 50-80 ℃ and the drying time is 8-12 h, so that the sodium chloride solution can be prevented from being mixed into the reaction system, the loss of aluminum foil is reduced, and the recovery efficiency is improved.
In any embodiment, the roasting temperature in the flowing air atmosphere is 400-600 ℃, and the roasting time is 3-8 hours, so that impurities such as conductive carbon and binder can be fully carbonized, and further removed by the flowing air, thereby reducing the loss of aluminum foil.
In any embodiment, the acid solution includes one or more of sulfuric acid, hydrochloric acid, nitric acid, citric acid, acetic acid, maleic acid, oxalic acid, lactic acid, aspartic acid, and ascorbic acid, and the reducing substance includes one or more of sulfite, bisulfite, and thiosulfate, and by using the acid solution and the reducing substance in combination, the positive current collector can be dissolved, so that the leaching rate of metal ions, particularly the leaching rate of high-valence metal ions (such as positive trivalent metal ions or positive tetravalent metal ions), can be improved, and the recovery efficiency can be improved.
In any embodiment, the concentration of the acid solution in the step (3) is 0.2mol/L-2mol/L, the solid-to-liquid ratio of the positive electrode plate to the acid solution is 10g/L-100g/L, and the mass ratio of the positive electrode plate to the reducing substance is 1-10, so that the leaching rate of high-valence metal ions can be improved, and the recovery efficiency can be improved.
In any embodiment, the temperature of the reaction in the step (3) is 25-60 ℃ and the reaction time is 0.5-3 h, so that the positive electrode current collector, the positive electrode active material and the acid solution can be fully reacted, and the recovery efficiency is improved.
In any embodiment, the concentration of the metal salt in the mixed salt solution in the step (4) is 0.5mol/L-2mol/L, the concentration of the sodium hydroxide is 2mol/L-10mol/L, and the mass fraction of the ammonia water is 5% -25%, so that the metal salt and the alkali can be fully contacted, the rate of the coprecipitation reaction is improved, and the recovery efficiency is improved.
In any embodiment, the temperature of the coprecipitation reaction in the step (4) is 50-70 ℃ and the reaction time is 30-200 hours, so that the coprecipitation reaction rate can be improved, and the recovery efficiency is improved.
In any embodiment, the nickel salt in the step (4) includes one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate and nickel oxalate, the cobalt salt includes one or more of cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt acetate and cobalt oxalate, and the manganese salt includes one or more of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate and manganese oxalate, so that the metal salt can fully undergo coprecipitation reaction in an alkali solution, and the recovery efficiency is improved.
In any embodiment, the temperature of the roasting process in the step (6) is 700-850 ℃ and the roasting time is 8-16 h, so that NCMA precursors and lithium hydroxide can be fully reacted under oxygen, and the recovery efficiency is improved.
The second aspect of the application also provides a positive electrode active material prepared by the preparation method according to any one of the first aspect of the application.
In any embodiment, the particle size D50 of the positive electrode active material is 5-20 mu m, in an X-ray diffraction spectrum of the positive electrode active material, the peak intensities I (003) and I (104) of the (003) diffraction peaks meet 1.2< I (003)/I (104), and the positive electrode active material prepared by the method is applied to a secondary battery, so that the cycle performance of the secondary battery is improved.
A third aspect of the present application provides a positive electrode sheet comprising the positive electrode active material of the second aspect of the present application.
A fourth aspect of the application provides a secondary battery comprising the positive electrode tab of the third aspect of the application.
A fifth aspect of the application provides an electric device comprising the secondary battery of the fourth aspect of the application.
The application has the beneficial effects that:
The preparation method of the positive electrode active material comprises the following steps of adding acid to dissolve aluminum foil and the positive electrode active material together after roasting the positive electrode active material, adding nickel salt, cobalt salt and manganese salt to perform coprecipitation reaction in alkali liquor, filtering to obtain a nickel cobalt manganese lithium aluminate precursor, recrystallizing filtrate, drying to obtain lithium hydroxide, mixing and roasting the nickel cobalt manganese lithium aluminate precursor and the lithium hydroxide, and finally obtaining the nickel manganese cobalt lithium aluminate positive electrode active material.
Drawings
FIG. 1 is a flow chart of the preparation of the present application;
FIG. 2 is a scanning electron microscope picture of NCMA precursor prepared in example 1 of the present application;
FIG. 3 is a scanning electron microscope image of NCMA positive electrode active materials prepared in example 1 of the present application;
FIG. 4 is a scanning electron microscope picture of NCMA positive electrode active materials prepared in comparative example 1 of the present application;
FIG. 5 is a scanning electron microscope picture of NCMA positive electrode active material prepared in comparative example 2 of the present application;
FIG. 6 is an X-ray diffraction chart of NCMA positive electrode active material prepared in example 1 of the present application;
FIG. 7 is an X-ray diffraction chart of NCMA positive electrode active material prepared in comparative example 2 of the present application;
fig. 8 is a graph showing cycle performance at 25 ℃ of the secondary batteries prepared in example 1, comparative example 1 and comparative example 2 according to the present application;
fig. 9 is a schematic view of a secondary battery according to an embodiment of the present application;
fig. 10 is an exploded view of the secondary battery according to an embodiment of the present application shown in fig. 9;
Fig. 11 is a schematic view of a battery module according to an embodiment of the present application;
fig. 12 is a schematic view of a battery pack according to an embodiment of the present application;
fig. 13 is an exploded view of the battery pack of the embodiment of the present application shown in fig. 12;
Fig. 14 is a schematic view of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Reference numerals illustrate:
1 battery pack, 2 upper case, 3 lower case, 4 battery module, 5 secondary battery, 51 case, 52 electrode assembly, 53 cover plate.
Detailed Description
Hereinafter, embodiments of a method for producing a positive electrode active material, a secondary battery, and an electric device according to the present application, and embodiments of a battery module and a battery pack including the secondary battery according to the present application are specifically disclosed with reference to the accompanying drawings as appropriate. 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 minimum range values 1 and 2 are listed, and if maximum range values 3,4, and 5 are listed, then the following ranges are all contemplated as 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 condition satisfies the condition "A or B" that A is true (or present) and B is false (or absent), that A is false (or absent) and B is true (or present), or that both A and B are true (or present).
The inventor finds that the recovery of the nickel cobalt lithium manganate in the waste secondary battery generally adopts a mechanical crushing separation method in the research process, but the active material separation is incomplete in the process, and foil scraps are mixed into the active material to cause the subsequent impurity removal step. In order to simplify the recovery method of the nickel cobalt lithium manganate battery, improve the recovery efficiency and reduce the nickel lithium mixed discharge degree of the positive electrode active material, the application provides a preparation method of the positive electrode active material, a positive electrode plate, a secondary battery and an electric device.
In one embodiment of the present application, the present application provides a method for preparing a positive electrode active material, referring to fig. 1, comprising the steps of:
(1) Discharging the waste nickel cobalt lithium manganate secondary battery in a saturated aqueous solution of sodium chloride for 1-3 days, and drying and disassembling to obtain a positive electrode plate;
(2) Roasting the positive electrode plate obtained in the step (1) in a flowing air atmosphere, and removing conductive carbon and a binder;
(3) Putting the positive electrode plate obtained in the step (2) into a soaking tank, adding an acid solution and a reducing substance into the soaking tank to react until the positive electrode current collector is completely dissolved, and filtering after the reaction is finished to obtain a mixed solution containing nickel, manganese, cobalt, aluminum and lithium elements;
(4) Adding nickel salt, cobalt salt and manganese salt into the mixed solution, preparing the molar ratio of nickel, cobalt, manganese and aluminum elements to obtain mixed salt solution, further performing coprecipitation reaction in sodium hydroxide and ammonia water, and filtering to obtain a nickel cobalt manganese lithium aluminate precursor, wherein the nickel cobalt manganese lithium aluminate precursor satisfies (Ni tCouMnvAlw)(OH)2, wherein t is more than or equal to 0.5 and less than or equal to 1, u is more than or equal to 0 and less than or equal to 0.5, v is more than or equal to 0 and less than or equal to 0.3, and t+u+v+w=1;
(5) Evaporating the filtrate obtained in the step (4) to dryness at 50-80 ℃ to obtain a solvent, recrystallizing and drying to obtain lithium hydroxide powder;
(6) And uniformly mixing the nickel cobalt manganese lithium aluminate precursor and lithium hydroxide powder according to the molar ratio of 1:1.03-1:1.2, roasting in an oxygen atmosphere, crushing, sieving and demagnetizing to obtain the nickel cobalt manganese lithium aluminate anode active material.
Although the mechanism is not clear, the inventor surprisingly discovers that the method reduces transition metal into bivalent by adding acid into a soaking tank to dissolve the positive electrode plate after roasting the positive electrode plate and using the combination of inorganic acid and reducing agent, improves the leaching rate of nickel, cobalt, manganese and aluminum metal, simplifies the recovery method by omitting the separation steps of active substances and aluminum foil, fully recovers aluminum element in the aluminum foil, improves the recovery efficiency, and simultaneously has low nickel-lithium mixed discharge degree of nickel-cobalt-manganese lithium aluminate precursor obtained by coprecipitation and positive active material obtained by roasting lithium hydroxide powder, thereby being beneficial to improving the cycle performance of the secondary battery. In the present application, the apparatus used for the above-mentioned soaking tank in the step (3) and the coprecipitation reaction in the step (4) is not particularly limited, and a soaking tank and a coprecipitation reaction apparatus known in the art may be used.
In some embodiments, the positive electrode active material of the waste nickel cobalt lithium manganate secondary battery accords with a general formula Li (Ni xCoyMnz)O2, wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and x+y+z=1.
In some embodiments, the drying temperature in the step (1) is 50-80 ℃ and the drying time is 8-12 h, so that the sodium chloride solution can be prevented from being mixed into the reaction system, the loss of high-valence metal is reduced, and the recovery efficiency is improved.
In some embodiments, the roasting temperature in the flowing air atmosphere in the step (2) is 400-600 ℃ and the roasting time is 3-8 h, by roasting the positive electrode plate under the above conditions, impurities such as conductive carbon and binder can be fully carbonized, and further carbonized impurities are taken away and removed by flowing air, so that compared with the method of directly adopting roasting and mechanical crushing separation in the prior art, the loss of aluminum foil can be reduced, and the recovery efficiency is improved. Among them, the impurities may include, but are not limited to, residues of the electrolyte and lithium salt after firing, and the like.
In some embodiments, the acid solution in the step (3) includes one or more of sulfuric acid, hydrochloric acid, nitric acid, citric acid, acetic acid, maleic acid, oxalic acid, lactic acid, aspartic acid, and ascorbic acid, the reducing substance includes one or more of sulfite, bisulfite, and thiosulfate, and by using the above acid solution and the reducing substance in combination, the positive electrode current collector can be completely dissolved, and the transition metal can be reduced to be divalent, so that the solubility of the metal salt in the acid solution can be improved, and the recovery efficiency can be improved. The sulfite in the application can comprise one or more of sodium sulfite and potassium sulfite, the bisulfite can comprise one or more of sodium bisulfite and potassium bisulfite, and the thiosulfate can comprise one or more of sodium thiosulfate and potassium thiosulfate.
In some embodiments, the concentration of the acid solution in the step (3) is 0.2mol/L-2mol/L, the solid-to-liquid ratio of the positive electrode plate to the acid solution is 10g/L-100g/L, and the mass ratio of the positive electrode plate to the reducing substance is 1-10, and the leaching rate of high-valence metal ions in the positive electrode plate can be further improved by cooperatively controlling the contents of the acid solution, the reducing substance and the positive electrode plate to meet the above conditions, so that the recovery efficiency is improved.
In some embodiments, the reaction temperature in the step (3) is 25 ℃ to 60 ℃ and the reaction time is 0.5h to 3h, and the positive electrode current collector can be fully dissolved, the positive electrode active material and the acid solution can be fully reacted by adjusting the reaction temperature and the reaction time of the positive electrode plate, the acid solution and the reducing material, so that the recovery efficiency is improved.
In some embodiments, the concentration of the metal salt of the mixed salt solution in the step (4) is 0.5mol/L-2mol/L, the concentration of the sodium hydroxide is 2mol/L-10mol/L, the mass fraction of the ammonia water is 5% -25%, and the concentration of the metal salt and the concentration of the sodium hydroxide are controlled within the scope of the application by selecting the ammonia water with the mass fraction within the scope of the application, so that the metal salt can fully react in an alkaline environment, the rate of the coprecipitation reaction is improved, and the recovery efficiency is improved.
In some embodiments, the temperature of the coprecipitation reaction in step (4) is 50-70 ℃ and the reaction time is 30-200 h, and the rate of the coprecipitation reaction can be improved by controlling the temperature and time of the coprecipitation reaction, thereby improving the recovery efficiency.
In some embodiments, in the step (4), the nickel salt includes one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate and nickel oxalate, the cobalt salt includes one or more of cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt acetate and cobalt oxalate, and the manganese salt includes one or more of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate and manganese oxalate, and by selecting the divalent metal salt, the solubility of the metal salt in the alkaline solution can be improved, the coprecipitation reaction rate can be improved, and the recovery efficiency can be improved.
In some embodiments, the temperature of the roasting process in the step (6) is 700 ℃ to 850 ℃ and the roasting time is 8h to 16h, and by controlling the temperature and the time of the roasting process within the above ranges, the NCMA precursor and lithium hydroxide can be fully reacted under oxygen, so that the recovery efficiency is improved.
In one embodiment of the present application, there is provided a positive electrode active material prepared by any one of the embodiments described above. The positive electrode active material prepared by the preparation method of the application improves the thermal stability and the cycle stability of the positive electrode active material due to the doping of aluminum element.
In one embodiment of the application, the particle size D50 of the positive electrode active material is 5-20 mu m, in an X-ray diffraction spectrum of the positive electrode active material, the peak intensities I (003) and I (104) of the (003) diffraction peaks meet 1.2< I (003)/I (104), the positive electrode active material prepared by the preparation method provided by the first aspect of the application has lower nickel-lithium mixed discharge degree, and the positive electrode active material prepared by the preparation method is further applied to a secondary battery, so that the cycle performance of the secondary battery is improved.
In one embodiment of the application, a positive electrode sheet is provided, which comprises a positive electrode current collector and a positive electrode film layer, wherein the positive electrode film layer comprises the positive electrode active material prepared in any one of the embodiments.
The secondary battery and the electric device according to the present application, and the battery module and the battery pack including the secondary battery according to the present application will be described below with reference to the drawings.
In one embodiment of the present application, there is provided a secondary battery including the positive electrode active material according to any one of the above embodiments. The secondary battery provided by the application comprises the positive electrode active material prepared by recycling the waste nickel cobalt lithium manganate secondary battery, and the obtained secondary battery has good cycle performance and basically accords with the cycle performance of the secondary battery comprising the newly prepared same positive electrode active material, so that the preparation method of the positive electrode active material provided by the application can effectively recycle metals such as nickel, cobalt, manganese, aluminum, lithium and the like in the waste nickel cobalt lithium manganate secondary battery, and has good practical value.
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 pole piece comprises a positive current collector and a positive film layer arranged on at least one surface of the positive current collector.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ 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 some embodiments, the positive electrode active material is prepared using the preparation method provided by the present application.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include one or more 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 film layer further optionally includes a conductive agent. As an example, the conductive agent may include one or more 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-described components for preparing a positive electrode sheet, such as a positive electrode active material, a conductive agent, a binder, and any other components, in a solvent (e.g., N-methylpyrrolidone) to form a positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and performing processes such as drying, cold pressing, and the like to obtain the positive electrode sheet.
[ Negative electrode sheet ]
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer 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 film layer 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 one or more of artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and the like. The silicon-based material may be selected from one or more of elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be selected from one or more of 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 film layer further optionally includes a binder. The binder may be selected from one or more of 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 film layer further optionally includes a conductive agent. The conductive agent can be one or more selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer 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 tab may be prepared by dispersing the above components for preparing the negative electrode tab, such as the negative electrode active material, the conductive agent, the binder, and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and performing processes such as drying, cold pressing, and the like to obtain the negative electrode tab.
[ Electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The electrolyte used in the present application may be a liquid electrolyte.
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 one or more 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 dioxaato borate, lithium difluorodioxaato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from one or more 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 one or more 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. For example, fig. 9 is a secondary battery 5 of a square structure as one example.
In some embodiments, referring to fig. 10, the outer package may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 included in the secondary battery 5 may be one or more, and those 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.
Fig. 11 is a battery module 4 as an example. Referring to fig. 11, in the battery module 4, a plurality of secondary batteries 5 may be sequentially arranged in the longitudinal direction of the battery module 4. Of course, the arrangement may be performed in any other way. The plurality of secondary batteries 5 may be further fixed by fasteners.
Alternatively, the battery module 4 may further include a case having an accommodating space in which the plurality of secondary batteries 5 are accommodated.
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.
Fig. 12 and 13 are battery packs 1 as an example. Referring to fig. 12 and 13, a battery case and a plurality of battery modules 4 disposed in the battery case may be included in the battery pack 1. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
In addition, the application also provides an electric device which comprises one or more of the secondary battery, the battery module or the battery pack. The secondary battery, the battery module, or the battery pack may be used as a power source of the power consumption device, and may also be used as an energy storage unit of the power consumption 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.
As the electricity consumption device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 14 is an electric device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the secondary battery by the power consumption device, a battery pack or a battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. 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.
Example 1
< Preparation of cathode active Material >
(1) And discharging the waste NCM811 (Li (Ni 0.8Co0.1Mn0.1)O2) secondary battery in a sodium chloride solution for 1 day, baking for 8 hours at 80 ℃, and disassembling to obtain the positive electrode plate.
(2) Roasting the positive pole piece prepared in the first step for 5 hours at 500 ℃ in a flowing air atmosphere, and removing impurities such as conductive carbon, binder and the like on the surface.
(3) And (3) putting the positive electrode plate obtained in the second step into a soaking tank, adding sulfuric acid solution and sodium thiosulfate solid into the soaking tank, wherein the concentration of sulfuric acid is 0.5mol/L, the solid-liquid ratio of the positive electrode plate to the sulfuric acid solution is 20g/L, the mass ratio of the positive electrode plate to the sodium thiosulfate is 2, the reaction temperature is 45 ℃, the reaction time is 1h, and filtering after the reaction is finished to obtain a mixed solution containing nickel, cobalt, manganese, aluminum and lithium elements.
(4) Adding nickel sulfate, cobalt sulfate and manganese sulfate into the mixed solution to obtain a mixed salt solution, wherein the proportion of nickel, cobalt, manganese and aluminum elements in the obtained mixed salt solution is Ni to Co to Mn to Al=80 to 5 to 10 to 5, placing the mixed salt solution into a continuous reaction kettle, performing coprecipitation reaction in sodium hydroxide and ammonia water, and filtering to obtain NCMA precursor ((Ni 0.8Co0.05Mn0.1Al0.05)(OH)2), wherein the concentration of the mixed salt is 1.5mol/L, the concentration of sodium hydroxide is 8mol/L, the mass fraction of the ammonia water is 25%, the reaction temperature is 55 ℃, and the reaction time is 48 hours.
(5) The filtrate is evaporated with solvent at 70 ℃, wet lithium hydroxide is obtained by recrystallization, and lithium hydroxide powder is obtained by drying.
(6) And uniformly mixing NCMA precursors and lithium hydroxide powder according to a molar ratio of 1:1.05, roasting for 10 hours at 750 ℃ under an oxygen atmosphere, crushing, sieving, and demagnetizing to obtain NCMA positive electrode active material (Li (Ni 0.8Co0.05Mn0.1Al0.05)O2)), wherein a scanning electron microscope image of the NCMA positive electrode active material prepared in the example 1 is shown in fig. 3.
< Preparation of Positive electrode sheet >
Mixing NCMA positive electrode active material, conductive agent carbon black and binder polyvinylidene chloride (PVDF) according to the weight ratio of 67.34:30:28.86, adding N-methyl pyrrolidone (NMP) as a solvent, preparing into slurry with the solid content of 75wt%, and stirring the slurry into uniform positive electrode slurry under the action of a vacuum stirrer. And uniformly coating the positive electrode slurry on one surface of a positive electrode current collector aluminum foil with the thickness of 10 mu m, and drying at 90 ℃ to obtain a positive electrode plate with a positive electrode film layer thickness of 110 mu m and coated with a positive electrode active material on one side. And repeating the steps on the other surface of the positive electrode plate to obtain the positive electrode plate with the double-sided coating of the positive electrode active material. After the coating is finished, the positive pole piece is cut into the specification of 74mm multiplied by 867mm for standby after cold pressing.
< Preparation of negative electrode sheet >
Mixing negative electrode active material graphite, conductive agent carbon black, binder Styrene Butadiene Rubber (SBR) and thickener sodium carboxymethyl cellulose according to the weight ratio of 96.2:0.8:0.8:1.2, adding deionized water as a solvent, preparing into negative electrode slurry with the solid content of 70wt%, and stirring the negative electrode slurry into uniform negative electrode slurry under the action of a vacuum stirrer. And uniformly coating the negative electrode slurry on one surface of a negative electrode current collector copper foil with the thickness of 8 mu m, and drying at 90 ℃ to obtain the negative electrode plate with the negative electrode film layer with the thickness of 130 mu m and the single-sided coating of the negative electrode active material. And repeating the steps on the other surface of the negative electrode plate to obtain the negative electrode plate with the double-sided coating negative electrode active material. After the coating is finished, the negative pole piece is cut into the specification of 76mm multiplied by 851mm for standby after cold pressing.
< Preparation of electrolyte >
In an argon atmosphere glove box with the water content of less than 10ppm and the O 2 content of less than 0.1ppm, uniformly mixing the organic solvents of Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) according to the volume ratio of 3:7 to form a base solvent, adding LiPF 6, dissolving and uniformly stirring to form an electrolyte, wherein the mass percent of LiPF 6 is 12.5%, and the balance is the base solvent.
< Separation Membrane >
A porous polymer film of Polyethylene (PE) was used as a separator.
< Preparation of Secondary Battery >
And sequentially stacking the positive electrode plate, the isolating film and the negative electrode plate, enabling the isolating film to be positioned between the positive electrode plate and the negative electrode plate to play a role of isolation, then winding, ending and rubberizing the tail part, placing the isolating film in an aluminum shell, packaging the edge of the aluminum shell, then placing the aluminum shell in a vacuum oven at 85 ℃ for drying for 12 hours, removing the moisture in a dry battery core, finally injecting the prepared electrolyte into a vacuum-dried battery, and performing procedures such as vacuum packaging, standing, formation, forming and the like to finish the preparation of the secondary battery.
Example 2
The procedure of example 1 was repeated except that the reaction temperature in step (3) of < preparation of positive electrode active material > was 25 ℃.
Example 3
The procedure of example 1 was repeated except that the reaction time in step (3) of < preparation of positive electrode active material > was 0.5 h.
Example 4
The procedure of example 1 was repeated except that the mass ratio of the positive electrode sheet to sodium thiosulfate in step (3) of < preparation of positive electrode active material > was 5.
Example 5
The procedure of example 1 was repeated except that acetic acid was used as the acid solution in step (3) of < preparation of positive electrode active material >.
Example 6
The procedure of example 1 was repeated except that sodium sulfite was used as the reducing substance in the step (3) of < preparation of positive electrode active material >.
Example 7
The procedure of example 1 was repeated except that the firing temperature in step (6) of < preparation of positive electrode active material > was 800 ℃.
Example 8
The procedure of example 1 was repeated except that the baking time in step (6) of < preparation of positive electrode active material > was 12 hours.
Example 9
The procedure of example 1 was repeated except that nickel sulfate, cobalt sulfate, and manganese sulfate were added in step (4) of < preparation of positive electrode active material > to obtain a mixed salt solution, and the molar ratio of nickel, cobalt, manganese, and aluminum elements was Ni: co: mn: al=87:5:5:3.
Comparative example 1
The procedure of example 1 was repeated except that the positive electrode active material was prepared according to the following preparation method:
(1) Mixing nickel sulfate, cobalt sulfate, manganese sulfate and aluminum sulfate according to a molar ratio of Ni to Co to Mn to Al=80:5:10:5, putting the mixture into a continuous reaction kettle, performing coprecipitation reaction in sodium hydroxide and ammonia water, and filtering to obtain NCMA precursor ((Ni 0.8Co0.05Mn0.1Al0.05)(OH)2), wherein the mixed salt concentration is 1.5mol/L, the sodium hydroxide concentration is 8mol/L, the ammonia water mass fraction is 25%, the reaction temperature is 55 ℃, and the reaction time is 48h.
(2) The filtrate is evaporated with solvent at 70 ℃, wet lithium hydroxide is obtained by recrystallization, and lithium hydroxide powder is obtained by drying.
(3) And uniformly mixing NCMA precursors and lithium hydroxide according to a molar ratio of 1:1.05, roasting for 10 hours at 750 ℃ in an oxygen atmosphere, crushing, sieving and demagnetizing to obtain the NCMA anode active material (Li (Ni 0.8Co0.05Mn0.1Al0.05)O2).
A scanning electron microscope image of NCMA positive electrode active materials prepared in comparative example 1 is shown in FIG. 4.
Comparative example 2
The procedure of example 1 was repeated except that the positive electrode active material was prepared according to the following preparation method:
(1) Discharging a waste NCM811 (Li (Ni 0.8Co0.1Mn0.1)O2) secondary battery in a sodium chloride solution for 1 day, baking for 8 hours at 80 ℃, disassembling to obtain a positive electrode plate, soaking the positive electrode plate in sodium hydroxide for 7 hours to obtain black powder, and drying and sieving the black powder to obtain the positive electrode powder.
(2) Roasting the anode powder prepared in the first step for 5 hours at 500 ℃ in a flowing air atmosphere, and removing impurities such as conductive carbon and binder on the surface.
(3) And (3) putting the anode powder obtained in the second step into a soaking tank, adding an acetic acid solution into the soaking tank, wherein the concentration of the acetic acid is 1mol/L, the solid-liquid ratio of the anode powder to the acetic acid solution is 20g/L, the reaction temperature is 45 ℃, the reaction time is 1h, and filtering after the reaction is finished to obtain a mixed solution containing nickel, cobalt, manganese and lithium elements.
(4) Adding nickel acetate, cobalt acetate, manganese acetate and aluminum into the mixed solution prepared in the third step to prepare nickel, cobalt, manganese and aluminum, wherein the molar ratio of Ni to Co to Mn to Al=80:5:10:5, and adding lithium acetate to prepare the molar ratio of the metal elements to the lithium elements is 1:1.05.
(5) And (3) maintaining the mixture obtained in the fourth step at 120 ℃ for 20 hours, evaporating to obtain a precursor material, roasting at 750 ℃ for 10 hours in an oxygen atmosphere, crushing, sieving, and demagnetizing to obtain a regenerated NCMA positive electrode active material (Li (Ni 0.8Co0.05Mn0.1Al0.05)O2)) the scanning electron microscope image of the NCMA positive electrode active material prepared in the comparative example 2 is shown in fig. 5.
Comparative example 3
The procedure of example 1 was repeated except that sodium thiosulfate was not added to the dipping tank in step (3) of < preparation of positive electrode active material >.
Performance parameter testing:
positive electrode active material average particle size test (D50):
0.02g of the material to be measured is added into a 50ml clean beaker, 20ml of deionized water is added, a few drops of 1% surfactant are added dropwise, the positive electrode active material powder is dispersed into an aqueous solution at normal temperature, ultrasonic treatment is carried out for 5min in a 120W ultrasonic cleaner, and the particle size distribution is tested from the small particle size side by using a MasterSizer 2000. D50 is the cumulative 50% diameter of the volume basis distribution of particles as measured by a laser scattering particle sizer.
Particle morphology testing:
Preparing a positive electrode active material into a pole piece sample, testing by using a ZEISS sigma 300 scanning electron microscope, measuring the working distance from 5mm to 30mm, enabling the aperture of an objective lens to be 100 mu m to 200 mu m, accelerating the voltage to be 2kV to 20kV, exciting the surface of the sample by using a focused electron beam of an instrument to generate secondary information such as secondary electrons, back scattering electrons and characteristic X rays, and collecting and detecting the secondary information for microscopic morphology analysis of the surface of the sample.
Particle crystallinity test:
And placing the anode active material powder into the cleaned glass slide circular groove, so that the surface of the sample to be measured is spread smoothly, and no sample is scattered around. The sample was scanned after excitation with an excitation source (cukα (λ=1.5406)) by means of an XD-3 type X-ray diffraction analyzer (XRD) (produced by beijing general instruments corporation), and XRD test data of the sample was collected. Wherein, the tube voltage is 40kV, the tube current is 40mA, the scanning speed is 1 degree/min, the step width is 0.02 degree, and the scanning range is 10 degrees to 80 degrees.
Metal leaching rate test:
And disassembling the waste secondary battery to obtain a positive electrode plate, adding aqua regia (the volume ratio of concentrated hydrochloric acid to concentrated nitric acid is 3:1) into 2g of the disassembled positive electrode plate, heating and digesting, filtering to obtain filtrate, and measuring the mass fraction of transition metal nickel, cobalt, manganese and aluminum to be A by using an inductively coupled plasma spectrometer (AGILENT ICP-S5800). Adding an acid solution and a reducing substance into a disassembled positive electrode plate with the mass of M0 for dissolution, filtering (wherein the addition amount of the acid solution and the reducing substance is the content of each embodiment and comparative example) to obtain filter residues with the mass of M1, digesting a small amount of filter residues with aqua regia, and measuring the mass fraction of transition metal nickel, cobalt, manganese and aluminum to be B by an inductively coupled plasma spectrometer, wherein the metal leaching rate mu is:
μ=[1-(M1×B/M0×A)]×100%。
Secondary battery capacity retention rate test:
the secondary battery was charged to 4.3V at a constant current of 0.3C, then charged to 0.05C at a constant voltage of 4.3V, left standing for 5min, then discharged to 2.8V at 0.3C, and the test capacity was recorded as an initial capacity C 0. Repeating the steps for the same battery, and simultaneously recording the discharge capacity C n of the battery after the 400 th cycle, wherein the capacity retention rate Pn after the cycle is as follows:
Pn=Cn/C0×100%。
The preparation parameters related to the above examples 1 to 9 and comparative examples 1 to 3 are shown in the following table 1;
The performance parameters of examples 1-9 and comparative examples 1-3 described above are shown in Table 2 below.
TABLE 1
Note that in table 1, "/" indicates that the corresponding preparation parameters are not present.
TABLE 2
Note that in table 2, "/" indicates that no corresponding performance parameter exists.
As can be seen from examples 1 to 9 and comparative example 3, the positive electrode sheet was immersed in the immersion tank containing both the acid solution and the reducing substance, the metal leaching rate was higher, the recovery efficiency was better, and the production cost of the positive electrode active material prepared by the preparation method provided by the application was lower.
The type of the acid solution, the type of the reducing substance, the mass ratio of the positive electrode sheet to the reducing substance, the reaction temperature in the soaking tank, the reaction time in the soaking tank, the roasting temperature in the step (6) and the roasting time in the step (6) also generally influence the performance of the prepared positive electrode active material, and further influence the performance of the secondary battery.
In addition, as can be seen from the comparison of the NCMA positive electrode active material scanning electron microscope image (shown in fig. 3) prepared in example 1, the NCMA positive electrode active material scanning electron microscope image (shown in fig. 4) prepared in comparative example 1 and the NCMA positive electrode active material scanning electron microscope image (shown in fig. 5) prepared in comparative example 2, the surface of the positive electrode active material prepared in the application has no obvious defect, the NCMA positive electrode active material prepared in example 1, the NCMA positive electrode active material prepared in comparative example 1 and the NCMA positive electrode active material prepared in comparative example 2 are applied to the secondary battery, and the cycle performance of the secondary battery prepared in example 1 is tested to obtain a cycle performance comparison image (shown in fig. 8), and the cycle performance of the secondary battery prepared in comparative example 1 is basically consistent with that of the secondary battery prepared in comparative example 1, so that the preparation method of the positive electrode active material provided in the application can effectively recover metals such as nickel, cobalt, manganese, aluminum, lithium and the like in the waste nickel cobalt lithium secondary battery, and has good practical values. As can be further seen from fig. 8 and table 2, the secondary battery prepared in example 1 has better cycle performance than the secondary battery prepared in comparative example 2, and the inventors speculate that the secondary battery prepared in the example 1 has better cycle performance because the positive electrode active material prepared in example 1 has higher I (003)/I (104) values (as shown in fig. 6 and 7) than the positive electrode active material prepared in comparative example 2, i.e., the nickel lithium is less miscible. As can be seen from examples 1 to 9 of table 2, the positive electrode active material prepared by the preparation method of the present application was applied to secondary batteries, which had I (003)/I (104) values within the scope of the present application, and the nickel lithium mixed discharge degree was low, and the obtained secondary batteries had good 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 (14)
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