CN113903884B - Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery - Google Patents
Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
A preparation method of a cladding co-doping modified positive electrode active material comprises the following steps: providing nickel salt, cobalt salt, manganese salt, lithium salt, strong alkali liquor and a coating co-doping agent; mixing the nickel salt, the cobalt salt, the manganese salt and the strong alkali liquor to obtain a mixed liquor; heating the mixed solution in an inert atmosphere to obtain a nickel-cobalt-manganese precursor; mixing the nickel-cobalt-manganese precursor, lithium salt and coating codopant to obtain a mixture; and sintering the mixture in an oxygen atmosphere to obtain the anode active material, wherein the anode active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material. The application also provides a positive electrode active material prepared by the preparation method of the positive electrode active material, a positive electrode applying the positive electrode active material and a lithium ion battery applying the positive electrode. The preparation method of the positive active material has the advantages of simple process, energy conservation, high efficiency and low production cost.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a preparation method of a positive electrode active material, the positive electrode active material prepared by the preparation method of the positive electrode active material, a positive electrode applying the positive electrode active material and a lithium ion battery applying the positive electrode.
Background
With the rapid development of electric vehicles, the requirements of people on power batteries are continuously improved. Currently, lithium ion batteries are currently the most promising power batteries due to their good performance and lower cost.
The nickel-cobalt-manganese (NCM) ternary positive active material which can be applied to the lithium ion battery has the advantages of high specific capacity, good cycle performance, stable structure, low cost and the like. However, the existing NCM ternary cathode active material has the defects of low conductivity, coating of 'residual alkali' substances on the surface, easy reaction with electrolyte, easy Li/Ni ion mixed discharge, easy generation of layered-spinel phase transformation and the like, thereby limiting the application of the NCM ternary cathode active material.
At present, a high-temperature sintering method can be adopted to reduce the mixed arrangement degree of cations in the NCM ternary positive electrode active material so as to improve the stability of a crystal structure. And a low-temperature coating method can be adopted to reduce the interface reaction between the NCM ternary positive electrode active material and the electrolyte so as to improve the cycle performance of the lithium ion battery. However, the existing preparation method of the NCM ternary cathode active material has the defects of complex process, high energy consumption and high cost.
Disclosure of Invention
In view of this, it is necessary to provide a method for preparing an anode active material to solve the disadvantages of the existing NCM ternary anode active material, such as complex process, high energy consumption and high cost.
In addition, it is necessary to provide a positive electrode active material.
In addition, it is necessary to provide a positive electrode.
In addition, a lithium ion battery is also provided.
A method for preparing a positive electrode active material, comprising the steps of:
providing nickel salt, cobalt salt, manganese salt, lithium salt, strong alkali liquor and coating codopant;
mixing the nickel salt, the cobalt salt, the manganese salt and the strong alkali liquor to obtain a mixed liquor;
heating the mixed solution in an inert atmosphere to obtain a nickel-cobalt-manganese precursor,the structural formula of the nickel-cobalt-manganese precursor is NixCoyMnz(OH)2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33;
mixing the nickel-cobalt-manganese precursor, the lithium salt and the coating co-dopant to obtain a mixture;
sintering the mixture in an oxygen atmosphere to obtain a positive active material, wherein the positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
Further, the thickness of the coating layer is 1-20 nm; and/or
The particle size of the nickel-cobalt-manganese ternary material is 5-15 mu m.
Further, the nickel salt is at least one of nickel sulfate, nickel sulfate hexahydrate, nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel bromide and nickel sulfamate; and/or
The cobalt salt is at least one of cobalt sulfate, cobalt sulfate heptahydrate, cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt bromide and cobalt sulfamate; and/or
The manganese salt is at least one of manganese sulfate, manganese sulfate monohydrate, manganese nitrate tetrahydrate, manganese chloride tetrahydrate, manganese bromide and manganese sulfamate; and/or
The lithium salt is at least one of lithium nitrate, lithium carbonate, lithium hydroxide monohydrate, lithium acetate and lithium bromide; and/or
The coating codopant is at least one of phosphates such as alumina, zirconia, ferroferric oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, lithium phosphate, manganese phosphate, lithium iron phosphate, aluminum phosphate and the like, and sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate and lithium difluorophosphate; and/or
The solute of the strong alkali liquor is at least one of sodium hydroxide, potassium hydroxide and barium hydroxide.
Further, the concentration sum of nickel ions, cobalt ions and manganese ions in the mixed solution is 1.5-3.5 mol/L; and/or
The concentration of the strong alkali liquor is 3.75-4.25 mol/L;
the molar ratio of the lithium salt to the nickel-cobalt-manganese precursor is 1.0-1.1: 1;
in the mixture, the coating codopant accounts for 0.05-2 wt%.
Further, the preparation method of the positive electrode active material further comprises the following steps:
providing a pH adjusting agent;
and mixing the nickel salt, the cobalt salt, the manganese salt, the strong alkali liquor and the pH regulator to obtain the mixed liquor, wherein the pH value of the mixed liquor is 11-11.4.
Further, the sintering treatment temperature is 500-1000 ℃, and the time is 4-20 h.
Further, the temperature of the heating treatment is 20-80 ℃, and the time is 10-48 h.
The positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, wherein the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
The coating layer is made of at least one of aluminum oxide, zirconium oxide, ferroferric oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, phosphates such as lithium phosphate, manganese phosphate, lithium iron phosphate and aluminum phosphate, sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate and lithium difluorophosphate; and/or
The thickness of the coating layer is 1-20 nm.
Furthermore, the particle size of the nickel-cobalt-manganese ternary material is 5-15 mu m.
A positive electrode contains the positive electrode active material.
A lithium ion battery comprising the positive electrode.
In the preparation method of the positive active material provided by the application, under an inert atmosphere, a mixed liquid containing nickel salt, cobalt salt, manganese salt and strong alkali liquor is heated to obtain a nickel-cobalt-manganese precursor, and then under an oxygen atmosphere, a mixture containing the nickel-cobalt-manganese precursor, lithium salt and a coating co-dopant is sintered to obtain the positive active material. The positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33. According to the preparation method of the positive active material, the mixture containing the nickel-cobalt-manganese precursor, the lithium salt and the coating codopant is sintered to obtain the coating codoped positive active material, so that the steps of pre-sintering, secondary sintering, grinding and the like are reduced, the process flow is simplified, the energy consumption is reduced, and the production cost of the positive active material is reduced. Furthermore, the coating layer coated outside the nickel-cobalt-manganese ternary material can isolate the nickel-cobalt-manganese ternary material from water and carbon dioxide in the air, so that residual alkali is prevented from being generated on the surface of the nickel-cobalt-manganese ternary material, electrolyte can be prevented from corroding the nickel-cobalt-manganese ternary material, and the positive active material has better circulation stability. The nickel-cobalt-manganese ternary material can reduce the degree of Li/Ni mixed discharge in the nickel-cobalt-manganese ternary material, inhibit transition metal migration and reduce oxygen loss, so that the structure of the nickel-cobalt-manganese ternary material is stabilized, the phase transition temperature of the nickel-cobalt-manganese ternary material is increased, and the electrochemical performance of the anode active material is improved.
Drawings
Fig. 1 is an XRD pattern of the cathode active material of the first embodiment of the present application;
fig. 2 is an SEM image of the positive active material according to the first embodiment of the present disclosure.
Fig. 3 is an XRD pattern of the cathode active material of example two of the present application.
Fig. 4 is an SEM image of the cathode active material according to example two of the present application.
Fig. 5 is an XRD pattern of the positive active material of comparative example one of the present application;
fig. 6 is an SEM image of a positive electrode active material of comparative example one of the present application;
fig. 7 is an XRD pattern of the cathode active material of comparative example no.
Fig. 8 is an SEM image of the positive electrode active material of comparative example No. 8.
The following detailed description will further illustrate the present application in conjunction with the above-described figures.
Detailed Description
In order that the above objects, features and advantages of the present application can be more clearly understood, a detailed description of the present application will be given below with reference to the accompanying drawings and detailed description. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present application, and the described embodiments are merely a subset of the embodiments of the present application, rather than all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.
The embodiment of the application provides a preparation method of a positive electrode active material, which comprises the following steps:
step S1: providing nickel salt, cobalt salt, manganese salt, lithium salt, strong alkali liquor and a coating co-doping agent;
step S2: mixing the nickel salt, the cobalt salt, the manganese salt and the strong alkali liquor to obtain a mixed liquor;
step S3: under an inert atmosphere, forHeating the mixed solution to obtain a nickel-cobalt-manganese precursor, wherein the structural formula of the nickel-cobalt-manganese precursor is NixCoyMnz(OH)2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33;
step S4: mixing the nickel-cobalt-manganese precursor, the lithium salt and the coating co-dopant to obtain a mixture;
step S5: sintering the mixture in an oxygen atmosphere to obtain a positive active material, wherein the positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
In at least one embodiment, the thickness of the coating layer is 1 to 20nm, such as 1nm, 5nm, 10nm, 15nm, 20 nm.
In at least one embodiment, the particle size of the nickel-cobalt-manganese ternary material is 5 to 15 μm, such as 5 μm, 10 μm, and 15 μm.
In at least one embodiment, the nickel salt is at least one of nickel sulfate, nickel sulfate hexahydrate, nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel bromide, and nickel sulfamate.
In at least one embodiment, the cobalt salt is at least one of cobalt sulfate, cobalt sulfate heptahydrate, cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt bromide, and cobalt sulfamate.
In at least one embodiment, the manganese salt is at least one of manganese sulfate, manganese sulfate monohydrate, manganese nitrate tetrahydrate, manganese chloride tetrahydrate, manganese bromide, manganese sulfamate.
In at least one embodiment, the lithium salt is at least one of lithium nitrate, lithium carbonate, lithium hydroxide monohydrate, lithium acetate, and lithium bromide.
In at least one embodiment, the coating co-dopant is at least one of phosphates such as alumina, zirconia, ferroferric oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, lithium phosphate, manganese phosphate, lithium iron phosphate, aluminum phosphate, and the like, and sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate, and lithium difluorophosphate.
In at least one embodiment, the solute of the strong alkali solution is at least one of sodium hydroxide, potassium hydroxide and barium hydroxide.
In at least one embodiment, the total concentration of nickel ions, cobalt ions, and manganese ions in the mixed solution is 1.5 to 3.5mol/L, for example, the total concentration of nickel ions, cobalt ions, and manganese ions is 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, and 3.5 mol/L.
In at least one embodiment, the concentration of the strong alkali solution is 3.75-4.25 mol/L.
In at least one embodiment, the molar ratio of the lithium salt to the nickel-cobalt-manganese precursor is 1.0-1.1: 1, for example 1: 1. 1.05: 1. 1.1: 1.
in at least one embodiment, the mass percentage of the cladding co-dopant in the mixture is 0.05-2 wt.%, for example, the mass percentage of the cladding co-dopant is 0.05 wt.%, 0.1 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%.
In at least one embodiment, the temperature of the heating treatment is 20-80 ℃ and the time is 10-48 h.
In at least one embodiment, the sintering temperature is 500-1000 ℃ and the time is 4-20 h. Specifically, the temperature is raised to 500 ℃ at a rate of 5 ℃/min, and then to 1000 ℃ at a rate of 2 ℃/min.
In at least one embodiment, the nickel-cobalt-manganese precursor precipitate obtained after the heating treatment of the mixed solution may be filtered, washed, and dried to obtain the nickel-cobalt-manganese precursor. The drying treatment temperature can be 60-150 ℃, and the drying treatment time can be 2-24 h.
In at least one embodiment, the inert atmosphere may be nitrogen, helium, neon, argon, krypton, or xenon.
In at least one embodiment, the oxygen atmosphere may be oxygen or air.
It can be understood that the mixed solution can be stirred at the speed of 300-1000 r/min.
In the preparation method of the positive active material provided by the application, under an inert atmosphere, a mixed liquid containing nickel salt, cobalt salt, manganese salt and strong alkali liquor is heated to obtain a nickel-cobalt-manganese precursor, and then under an oxygen atmosphere, a mixture containing the nickel-cobalt-manganese precursor, lithium salt and a coating co-dopant is sintered to obtain the positive active material. The positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33. According to the preparation method of the cathode active material, the mixture containing the nickel-cobalt-manganese precursor, the lithium salt and the coating codopant is sintered to obtain the coating codoped cathode active material, the steps of pre-sintering, secondary sintering, grinding and the like are reduced, the process flow is simplified, the energy consumption is reduced, and the production cost of the cathode active material is reduced. Furthermore, the coating layer coated outside the nickel-cobalt-manganese ternary material can isolate the nickel-cobalt-manganese ternary material from water and carbon dioxide in the air, avoid the formation of residual alkali on the surface of the nickel-cobalt-manganese ternary material, and can prevent electrolyte from corroding the nickel-cobalt-manganese ternary material, so that the anode active material has better circulation stability. The nickel-cobalt-manganese ternary material can reduce the degree of Li/Ni mixed discharge in the nickel-cobalt-manganese ternary material, inhibit transition metal migration and reduce oxygen loss, so that the structure of the nickel-cobalt-manganese ternary material is stabilized, the phase transition temperature of the nickel-cobalt-manganese ternary material is increased, and the electrochemical performance of the anode active material is improved.
The preparation method of the positive electrode active material further comprises the following steps:
providing a pH adjusting agent; and
and mixing the nickel salt, the cobalt salt, the manganese salt, the strong alkali liquor and the pH regulator to obtain the mixed liquor, wherein the pH value of the mixed liquor is 11-11.4.
In at least one embodiment, the pH regulator may be ammonia water with a concentration of 1-4 mol/L.
Among this application technical scheme, can with the pH regulator adds to mixed liquid in, in order to adjust the pH value of mixed liquid, so that it is right mixed liquid carries out heat treatment's in-process and obtains nickel cobalt manganese precursor deposit.
The preparation method of the positive active material further comprises the following steps:
grinding the mixture to obtain uniform powder; and
and screening the mixture after the grinding treatment to obtain the mixture with the particle size of less than 0.334 mm.
In the preparation method of the positive electrode active material, the mixture can be ground and screened to obtain a mixture with a particle size of less than 0.334 mm. Since the size of the mixture is small and uniform, the size of the positive active material is also small and uniform.
The embodiment of the application also provides a positive electrode active material.
The positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
In at least one embodiment, the material of the coating layer is at least one of aluminum oxide, zirconium oxide, ferroferric oxide, phosphates such as lithium fluoride, magnesium fluoride, aluminum fluoride, lithium phosphate, manganese phosphate, lithium iron phosphate, and aluminum phosphate, sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate, and lithium difluorophosphate.
In at least one embodiment, the thickness of the coating layer is 1 to 20nm, such as 1nm, 5nm, 10nm, 15nm, 20 nm.
In at least one embodiment, the particle size of the nickel-cobalt-manganese ternary material is 5 to 15 μm, such as 5 μm, 10 μm, and 15 μm.
The application discloses positive active material, the coating outside nickel cobalt manganese ternary material not only can with water and carbon dioxide in nickel cobalt manganese ternary material and the air keep apart, avoid in "residual alkali" is generated on the surface of nickel cobalt manganese ternary material, still can block electrolyte to corrode nickel cobalt manganese ternary material makes positive active material has the circulation stability of preferred. The nickel-cobalt-manganese ternary material can reduce the degree of Li/Ni mixed discharge in the nickel-cobalt-manganese ternary material, inhibit transition metal migration and reduce oxygen loss, thereby stabilizing the structure of the nickel-cobalt-manganese ternary material, increasing the phase transition temperature of the nickel-cobalt-manganese ternary material and improving the electrochemical performance of the anode active material.
The embodiment of the application also provides a positive electrode.
The positive electrode contains the positive electrode active material, a conductive agent, and a binder.
In at least one embodiment, the conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber, polypyrrole, and carbon nanotube.
In at least one embodiment, the binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene, and polyethylene carbonate.
In at least one embodiment, the positive electrode active material is 60-90% by mass, the conductive agent is 5-30% by mass, and the binder is 5-10% by mass.
Since the positive electrode adopts various positive electrode active materials provided in the embodiments of the present application, at least all the beneficial effects brought by the positive electrode active materials of the embodiments are obtained, and are not described in detail herein.
The embodiment of the application also provides a lithium ion battery.
The lithium ion battery comprises the anode, the lithium cathode and electrolyte, wherein the anode and the lithium cathode are both arranged in the electrolyte.
It can be understood that the lithium ion battery also comprises necessary elements such as a negative electrode shell, a diaphragm, a gasket, a spring plate, a positive electrode shell and the like.
In at least one embodiment, the electrolyte contains lithium salt with a concentration of 1-2 mol/L and a solvent. The solvent contains a solvent with a volume ratio of 1: 1: 1 fluoroethylene carbonate, methylethyl carbonate, and diethyl carbonate, or said solvent contains a mixture of 1: 1: 1 ethylene carbonate, diethyl carbonate, dimethyl carbonate. The lithium salt is at least one selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium difluorooxalato borate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide.
In at least one embodiment, the lithium ion battery comprises the positive electrode, the lithium negative electrode and a solid electrolyte, wherein the positive electrode and the lithium negative electrode are respectively positioned on two sides of the solid electrolyte.
In at least one embodiment, the solid electrolyte contains a polymer and a lithium salt and a filler dispersed in the polymer. The lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium difluorooxalato borate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide.
The polymer is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate.
The filler is at least one of lanthanum zirconate and lanthanum lithium zirconate so as to further improve the transmission efficiency of lithium ions and the ionic conductivity of the solid electrolyte lithium ion battery. The mass ratio of lithium salt, polymer and filler in the solid electrolyte is 7-9: 1-3: 1 to 2, for example, 8: 1: 1.
since the lithium ion battery can adopt various anodes of all the above embodiments, at least all the beneficial effects brought by the technical solutions of the above embodiments are achieved, and details are not repeated herein.
The present application will be specifically described below with reference to specific examples.
Example one
Providing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·6H2O and water, wherein Ni: co: the molar ratio of Mn is 8: 1: 1;
mixing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·6H2Adding O into water to obtain a mixed solution, wherein the ion concentration sum of the mixed solution is 2 mol/L;
providing a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 4 mol/L;
simultaneously pouring the mixed solution, the sodium hydroxide solution and the ammonia water solution into a reactor at the speed of 30ml/min, 10ml/min and 8ml/min respectively to obtain a mixed solution with the pH value of 11.2;
heating the mixed solution to 50 ℃, introducing nitrogen into the reactor, continuously stirring the mixed solution at the rotating speed of 300r/min, and filtering to obtain a nickel-cobalt-manganese precursor precipitate;
washing the nickel-cobalt-manganese precursor precipitate, and drying in an oven at 80 ℃ for 24h to obtain the nickel-cobalt-manganese precursor, wherein the structural formula of the nickel-cobalt-manganese precursor is Ni0.8Co0.1Mn0.1(OH)2；
To provide LiOH. H2O and sodium monofluorophosphate, wherein the LiOH. H2The molar ratio of O to the nickel-cobalt-manganese precursor is 1.05: 1;
mixing the LiOH. H2O, sodium monofluorophosphate and a nickel-cobalt-manganese precursor to obtain a mixture, wherein the sodium monofluorophosphate is contained in the mixture in a mass percentage of 0.33 wt.%;
grinding the mixture;
placing the mixture after grinding treatment in a tube furnace, heating to 500 ℃ at the temperature rise rate of 5 ℃/min under the pure oxygen atmosphere, preserving heat for 5h, and then taking the temperature of 2 ℃Heating to 780 ℃ at the temperature rise rate of min, preserving heat for 11h, and cooling to low temperature along with the furnace to obtain the positive active material (see figures 1 and 2) of the comparative example I, wherein the structural formula of the positive active material of the example I is LiNi0.8Co0.1Mn0.1O2；
Providing acetylene black, polyvinylidene fluoride, N-methyl pyrrolidone and an aluminum foil, wherein the mass ratio of the positive electrode active material, the acetylene black and the polyvinylidene fluoride in the first embodiment is 8: 1: 1, the mass sum of the positive electrode active material, the acetylene black and the polyvinylidene fluoride of the first embodiment is 500 mg;
mixing the positive electrode active material of the first embodiment, acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone to obtain a slurry;
coating the slurry on an aluminum foil, and drying to obtain the anode of the first embodiment;
providing a negative electrode shell, a lithium negative electrode, 40 mu L of electrolyte, a diaphragm, a gasket, a spring plate and a positive electrode shell, wherein the electrolyte contains LiPF with the concentration of 1mol/L6And a solvent comprising, by volume, 1: 1: 1 ethylene carbonate, diethyl carbonate, dimethyl carbonate;
and in a glove box filled with argon, assembling the cathode shell, the lithium cathode, the electrolyte, the diaphragm, the electrolyte, the anode of the first embodiment, the gasket, the spring plate and the anode shell into the button cell of the first embodiment as required.
Referring to fig. 1, the XRD diffraction peak of the positive electrode active material of the first example is sharp, which indicates that the positive electrode active material of the first example has higher crystallinity and no impurity phase.
Referring to fig. 2, the positive active material of the first embodiment has a coating layer.
Example two
The difference from the first embodiment comprises: in the mixture, the mass percent content of the sodium monofluorophosphate is 1 wt.%.
Other steps are the same as the first embodiment and are not repeated.
Referring to fig. 3, the XRD diffraction peak of the cathode active material of the second example is sharp, which indicates that the cathode active material of the second example has higher crystallinity and no impurity phase.
Referring to fig. 4, the cathode active material of the second embodiment has a coating layer.
EXAMPLE III
The differences from the first embodiment comprise: replacing sodium monofluorophosphate in the mixture with sodium hexafluorophosphate.
Other steps are the same as the first embodiment and are not repeated.
It can be understood that the XRD patterns and SEM patterns of the cathode active material of example three are substantially the same as those of the cathode active material of example one.
Example four
Differences from the third embodiment include: in the mixture, the mass percent content of the sodium hexafluorophosphate is 1 wt.%.
Other steps are the same as those in the embodiment and are not repeated.
It can be understood that the XRD patterns and SEM images of the cathode active material of example four are substantially the same as those of the cathode active material of example two.
EXAMPLE five
The difference from the first embodiment comprises: replacing sodium monofluorophosphate in the mixture with lithium hexafluorophosphate.
Other steps are the same as the first embodiment and are not repeated.
It can be understood that the XRD and SEM images of the cathode active material of example v are substantially the same as those of the cathode active material of example i.
EXAMPLE six
Differences from the fifth embodiment include: in the mixture, the mass percent content of the lithium hexafluorophosphate is 1 wt.%.
Other steps are the same as those in the fifth embodiment and are not repeated.
It can be understood that the XRD patterns and SEM images of the cathode active material of example six are substantially the same as those of the cathode active material of example two.
Comparative example 1
Providing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·6H2O and water, wherein Ni: co: the molar ratio of Mn is 8: 1: 1;
mixing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·6H2Adding O into water to obtain a mixed solution, wherein the ion concentration sum of the mixed solution is 2 mol/L;
providing a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 4 mol/L;
simultaneously pouring the mixed solution, the sodium hydroxide solution and the ammonia water solution into a reactor at the speed of 30ml/min, 10ml/min and 8ml/min respectively to obtain a mixed solution with the pH value of 11.2;
heating the mixed solution to 50 ℃, introducing nitrogen into the reactor, continuously stirring the mixed solution at the rotating speed of 300r/min, and filtering to obtain a nickel-cobalt-manganese precursor precipitate;
washing the nickel-cobalt-manganese precursor precipitate, and drying in an oven at 80 ℃ for 24h to obtain the nickel-cobalt-manganese precursor, wherein the structural formula of the nickel-cobalt-manganese precursor is Ni0.8Co0.1Mn0.1(OH)2；
To provide LiOH. H2O, wherein the LiOH. H2The molar ratio of O to the nickel-cobalt-manganese precursor is 1.05: 1;
mixing the LiOH. H2O and a nickel-cobalt-manganese precursor to obtain a mixture;
grinding the mixture;
placing the mixture after grinding treatment in a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in a pure oxygen atmosphere, preserving heat for 5h, heating to 780 ℃ at a heating rate of 2 ℃/min, preserving heat for 11h, and cooling to a low temperature along with the furnace to obtain a positive electrode active material (shown in figures 5 and 6) of a comparative example I, wherein the structural formula of the positive electrode active material of the comparative example I is LiNi0.8Co0.1Mn0.1O2；
Providing acetylene black, polyvinylidene fluoride, N-methyl pyrrolidone and an aluminum foil, wherein the mass ratio of the positive electrode active material of the first comparative example, the acetylene black and the polyvinylidene fluoride is 8: 1: 1, the sum of the mass of the positive electrode active material, acetylene black and polyvinylidene fluoride of the comparative example one is 500 mg;
mixing the positive electrode active material of the first comparative example, acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone to obtain slurry;
coating the slurry on an aluminum foil, and drying to obtain the anode of the comparative example I;
providing a negative electrode shell, a lithium negative electrode, 40 mu L of electrolyte, a diaphragm, a gasket, a spring plate and a positive electrode shell, wherein the electrolyte contains LiPF with the concentration of 1mol/L6And a solvent comprising, by volume, 1: 1: 1 ethylene carbonate, diethyl carbonate, dimethyl carbonate;
and in a glove box filled with argon, assembling the cathode shell, the lithium cathode, the electrolyte, the diaphragm, the electrolyte, the anode of the first comparative example, the gasket, the elastic sheet and the anode shell into the button cell of the first comparative example as required.
Referring to fig. 5, the positive active material of comparative example i has a sharp XRD diffraction peak, indicating that the positive active material of comparative example i has a higher crystallinity without a heterogeneous phase.
Referring to fig. 6, the positive active material of the comparative example has no coating layer.
Comparative example No. two
The difference from the first embodiment comprises: in the mixture, the mass percent content of the sodium monofluorophosphate is 3 wt.%.
Other steps are the same as the first embodiment and are not repeated.
Referring to fig. 7, the XRD diffraction peak of the positive active material of comparative example ii is sharp, indicating that the positive active material of comparative example i has higher crystallinity and no hetero-phase.
Referring to fig. 8, the positive active material of the comparative example has a coating layer.
Comparative example No. three
Differences from the third embodiment include: in the mixture, the sodium hexafluorophosphate content is 3 wt.%.
Other steps are the same as those in the embodiment and are not repeated.
It can be understood that the XRD patterns and SEM patterns of the cathode active material of comparative example three are substantially the same as those of the cathode active material of comparative example two.
Comparative example No. four
Differences from the fifth embodiment include: in the mixture, the lithium hexafluorophosphate was contained in an amount of 3 wt.%.
The other steps are the same as the fifth embodiment and are not repeated.
It can be understood that the XRD patterns and SEM images of the positive electrode active material of comparative example four are substantially the same as those of the positive electrode active material of comparative example two.
Table 1 comparison of electrochemical performances of the button cells of examples one to six and of the buttons of comparative examples one to four
Under the working voltage of 2.8-4.7V and the multiplying power of 0.1C, the first charging specific capacity, the first discharging specific capacity, the first-circle coulombic efficiency, the capacity retention rate after 200-circle circulation under the multiplying power of 1C and the coulombic efficiency after 200-circle circulation under the multiplying power of 1C of the button batteries of the first to sixth embodiments and the button batteries of the first to fourth comparative examples are measured.
Referring to table 1, the button cells of examples one to six had better capacity, cycle performance, and rate performance than the button cells of comparative examples one to four. If the coating layer is not formed or the content of the coating layer is too high, the electrochemical performance of the corresponding button cell is poor. This indicates that, when the coating is present in an appropriate amount, the electrochemical performance of the corresponding button cell is better.
Specifically, the first charge specific capacity and the first discharge ratio of the button cell batteries of the first to sixth embodimentsThe capacity and the first-turn coulombic efficiency are improved to a certain degree, and the capacity retention rate is greatly improved after 200 turns at the multiplying power of 1C. The coating layer can isolate the nickel-cobalt-manganese ternary material from water and carbon dioxide in the air, so that residual alkali is prevented from being generated on the surface of the nickel-cobalt-manganese ternary material, the corrosion of electrolyte to the nickel-cobalt-manganese ternary material can be resisted, and the Li is not reduced+The cycle stability of the positive electrodes of examples one to six was maintained on the basis of the diffusion rate. When the content of the coating codopant is too high, a large amount of lithium phosphate is newly added in the phase structure of the positive active materials of the first to fourth comparative examples, and the large amount of lithium phosphate covers the surface of the nickel-cobalt-manganese ternary material, so that Li is prevented+The first charge specific capacity, the first discharge specific capacity, the first coulomb efficiency and the capacity retention rate of the positive electrodes of the comparative examples I to IV are further reduced.
Although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the present application.
Claims (5)
1. A method for preparing a positive electrode active material, comprising the steps of:
providing a nickel salt, a cobalt salt, a manganese salt, a lithium salt, a strong alkali liquor, a pH regulator and a coating codopant, wherein the coating codopant is at least one of aluminum oxide, zirconium oxide, ferroferric oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, lithium phosphate, manganese phosphate, lithium iron phosphate, aluminum phosphate, sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate and lithium difluorophosphate;
mixing the nickel salt, the cobalt salt, the manganese salt, the strong alkali liquor and the pH regulator to obtain a mixed liquor;
heating the mixed solution in inert atmosphereThe temperature is 20-80 ℃, the heating time is 10-48 h, and a nickel-cobalt-manganese precursor is obtained, wherein the structural formula of the nickel-cobalt-manganese precursor is NixCoyMnz(OH)2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33;
mixing the nickel-cobalt-manganese precursor, the lithium salt and the coating co-dopant to obtain a mixture; and
performing step-type heating sintering treatment on the mixture in an oxygen atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 hours, then heating to 780 ℃ at a heating rate of 2 ℃/min, preserving heat for 11 hours to obtain a positive active material, wherein the positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
2. The method for preparing the positive electrode active material according to claim 1, wherein the coating layer has a thickness of 1 to 20 nm;
the particle size of the nickel-cobalt-manganese ternary material is 5-15 mu m.
3. The method for producing a positive electrode active material according to claim 1, wherein the nickel salt is at least one of nickel sulfate, nickel sulfate hexahydrate, nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel bromide, and nickel sulfamate;
the cobalt salt is at least one of cobalt sulfate, cobalt sulfate heptahydrate, cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt bromide and cobalt sulfamate;
the manganese salt is at least one of manganese sulfate, manganese sulfate monohydrate, manganese nitrate tetrahydrate, manganese chloride tetrahydrate, manganese bromide and manganese sulfamate;
the lithium salt is at least one of lithium nitrate, lithium carbonate, lithium hydroxide monohydrate, lithium acetate and lithium bromide;
the solute of the strong alkali liquor is at least one of sodium hydroxide, potassium hydroxide and barium hydroxide.
4. The method for producing a positive electrode active material according to claim 1, wherein the total concentration of nickel ions, cobalt ions, and manganese ions in the mixed solution is 1.5 to 3.5 mol/L;
the concentration of the strong alkali liquor is 3.75-4.25 mol/L;
the molar ratio of the lithium salt to the nickel-cobalt-manganese precursor is 1.0-1.1: 1;
in the mixture, the mass percent content of the coating co-dopant is 0.05-2 wt.%.
5. The method for producing a positive electrode active material according to claim 1, wherein the pH of the mixed solution is 11 to 11.4.
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