CN113451560B - Positive electrode active material, preparation method thereof, positive electrode and ternary lithium ion battery - Google Patents
Positive electrode active material, preparation method thereof, positive electrode and ternary lithium ion battery Download PDFInfo
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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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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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- H01M4/48—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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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
A positive electrode active material comprises secondary particles formed by stacking primary particles, and a coating layer coated on the surfaces of the primary particles and the secondary particles, wherein the primary particles have a structural formula of LiNi (1‑x‑y) Co x Mn y O 2 Wherein, 0<x<0.4，0<y<0.4, 1-x-y is more than or equal to 0.6. The invention also provides a preparation method of the positive active material, a positive electrode and a ternary lithium ion battery. The ternary lithium ion battery using the anode active material provided by the invention has longer service life and better safety performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a positive active material, a preparation method of the positive active material, a positive electrode applying the positive active material and a ternary lithium ion battery applying the positive electrode.
Background
Compared with a lithium iron phosphate battery, the ternary lithium ion battery has higher specific energy and specific power, and has great application value and development prospect in the field of lithium ion batteries. However, the nickel content of the cathode active material of the existing ternary lithium ion battery is high, so that the ternary lithium ion battery has the defects of short service life and poor safety performance.
Disclosure of Invention
In view of the above, it is necessary to provide a positive electrode active material to solve the problems of short service life and poor safety performance of the ternary lithium ion battery.
In addition, a preparation method of the positive electrode active material is also needed.
In addition, it is necessary to provide a positive electrode.
In addition, it is necessary to provide a ternary lithium ion battery.
A positive electrode active material comprises secondary particles formed by stacking primary particles, and a coating layer coated on the surfaces of the primary particles and the secondary particles, wherein the primary particles have a structural formula of LiNi (1-x-y) Co x Mn y O 2 Wherein, 0<x<0.4，0<y<0.4，1-x-y≥0.6。
Further, the coating layer is at least one of lithium cobaltate, lithium aluminate and lithium manganate.
Further, the coating layer is at least one of fluorine-doped lithium cobaltate, fluorine-doped lithium aluminate and fluorine-doped lithium manganate.
Further, the fluorine doping amount of the fluorine-doped lithium cobaltate is 0.3-0.8 wt%; and/or
The fluorine doping amount of the fluorine-doped lithium aluminate is 0.3-0.8 wt%; and/or
The fluorine doping amount of the fluorine-doped lithium manganate is 0.3-0.8 wt%.
Further, the thickness of the coating layer is 3-300 nm; and/or
The Ni (1-x-y) Co x Mn y (OH) 2 The mass ratio of the ternary precursor to the lithium salt is 1: 1 to 1.5.
A method for preparing a positive electrode active material, comprising the steps of:
providing Ni (1-x-y) Co x Mn y (OH) 2 Ternary precursor, lithium salt and coating agent, wherein 0<x<0.4，0<y<0.4, 1-x-y is more than or equal to 0.6, and the coating agent is metal oxide and/or metal hydroxide;
uniformly mixing the Ni (1-x-y) Co x Mn y (OH) 2 Ternary precursor and lithium salt to obtain a first mixture;
subjecting the first mixture to a first heat treatment to diffuse the lithium salt to the Ni (1-x-y) Co x Mn y (OH) 2 In the ternary precursor；
Subjecting the first mixture subjected to the first heat treatment to a second heat treatment, wherein the Ni is (1-x-y) Co x Mn y (OH) 2 The ternary precursor reacts with lithium salt to generate LiNi (1-x-y) Co x Mn y O 2 A ternary material of said LiNi (1-x-y) y Co x Mn y O 2 The ternary material comprises secondary particles formed by stacking primary particles, wherein 0<x<0.4，0<y<0.4，1-x-y≥0.6；
Subjecting the LiNi to a reaction (1-x-y) Co x Mn y O 2 The ternary material is placed in a constant temperature and humidity environment, and the LiNi (1-x-y) Co x Mn y O 2 Secondary particles of the ternary material are opened along the grain boundary of the primary particles, and the primary particles and the secondary particles react with water and carbon dioxide in the constant-temperature and constant-humidity environment to generate residual alkali layers on the surfaces of the primary particles and the secondary particles;
mixing the coating agent with the LiNi having a residual alkali layer formed on the surface (1-x-y) Co x Mn y O 2 Ternary material to obtain a second mixture;
performing third heating treatment on the second mixture to enable the coating agent to diffuse to the LiNi with the residual alkali layer formed on the surface (1-x-y) Co x Mn y O 2 Primary particles of ternary material; and
and carrying out fourth heating treatment on the second mixture, and carrying out in-situ lithium supply reaction on the coating agent and the residual alkali layer to generate a coating layer so as to prepare the anode active material.
Further, the coating layer is at least one of lithium cobaltate, lithium manganate, lithium aluminate, fluorine-doped lithium cobaltate, fluorine-doped lithium aluminate and fluorine-doped lithium manganate;
in the second mixture, the mass percentage range of the coating agent is 1-3%, and LiNi with a residual alkali layer formed on the surface is used (1-x-y) Co x Mn y O 2 The mass percentage range is 97-99%; and/or
The thickness of the coating layer is 3-300 nm.
Further, the residual alkali layer is lithium carbonate and/or lithium hydroxide; and/or
The thickness of the residual alkali layer is 5-500 nm.
Further, the lithium salt is at least one of lithium nitrate, lithium carbonate and lithium hydroxide; and/or
The metal oxide is at least one of cobalt oxide, cobaltosic oxide, manganese oxide and aluminum oxide; and/or
The metal hydroxide is at least one of cobalt hydroxide, aluminum hydroxide and manganese hydroxide.
Further, the LiNi (1-x-y) Co x Mn y O 2 The mass ratio of the ternary precursor to the lithium salt is 1: 1 to 1.5.
Further, the temperature of the first heating treatment is 300-600 ℃, and the time is 3-10 hours; and/or
The temperature of the second heating treatment is 700-900 ℃, and the time is 10-20 h; and/or
The temperature of the third heating treatment is 200-600 ℃, and the time is 3-10 h; and/or
The temperature of the fourth heating treatment is 700-900 ℃, and the time is 3-10 h.
A positive electrode contains a conductive agent, a binder, and the positive electrode active material.
Further, the conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fibers and carbon nanotubes; and/or
The binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate.
A ternary lithium ion battery includes the positive electrode.
The positive active material provided by the invention comprises a primary particleSecondary particles formed by stacking the particles, and a coating layer that coats the surfaces of the primary particles and the secondary particles. The structural formula of the primary particle is LiNi (1-x-y) Co x Mn y O 2 Wherein, 0<x<0.4，0<y<0.4, 1-x-y is more than or equal to 0.6. The nickel content of the anode active material is high, so that the ternary lithium ion battery using the anode active material has high specific energy and specific power. In the charging and discharging process of the ternary lithium ion battery, the coating layers coated on the surfaces of the primary particles and the secondary particles of the positive electrode active material can inhibit the volume enlargement of the primary particles and the secondary particles, so that the intragranular cracks and the intergranular cracks caused by the volume enlargement are avoided, and the service life of the ternary lithium ion battery is further prolonged. The coating layers coated on the surfaces of the primary particles and the secondary particles of the positive electrode active material can also prevent the primary particles and the secondary particles from contacting with electrolyte to generate side reaction, prevent the ternary lithium ion battery from expanding gas due to the side reaction, and further improve the safety performance of the ternary lithium ion battery.
Drawings
Fig. 1 is an XRD pattern of NCM811 according to a first embodiment of the present invention.
FIG. 2 is an XRD pattern of FC-NCM811 according to a first embodiment of the present invention.
Fig. 3 is a cyclic voltammogram of the ternary lithium ion battery of comparative example one of the present invention.
Fig. 4 is a cyclic voltammogram of a ternary lithium ion battery according to a first embodiment of the present invention.
Fig. 5 is a graph of the diffusion coefficient of lithium ions at different scan speeds for the ternary lithium ion battery of comparative example one of the present invention.
Fig. 6 is a lithium ion diffusion coefficient diagram of the ternary lithium ion battery according to the first embodiment of the present invention at different scanning speeds.
Fig. 7 is an electrochemical impedance spectrum of the ternary lithium ion battery of comparative example i and the ternary lithium ion battery of example i after 10 and 60 cycles of charge and discharge cycles according to the present invention.
Fig. 8 is a discharge capacity curve diagram of the ternary lithium ion battery of comparative example one and the ternary lithium ion battery of example one at different temperatures according to the present invention.
Fig. 9 is a graph of the cycling performance of the comparative example one lithium ion battery and the example one lithium ion battery of the present invention at a temperature of 25 ℃.
Fig. 10 is a graph of the cycle performance of the ternary lithium ion battery of comparative example one and the ternary lithium ion battery of example one of the present invention at a temperature of 60 ℃.
Fig. 11 is a graph of the cycling performance of the comparative example i lithium ion battery and the example i lithium ion battery of the present invention at a temperature of 25 ℃.
Fig. 12 is a graph of the cycling performance of the ternary lithium ion battery of comparative example one and the ternary lithium ion battery of example one of the present invention at a temperature of-20 ℃.
Fig. 13 is a graph of the cycle performance of the ternary lithium ion battery of comparative example one and the ternary lithium ion battery of example one of the present invention at a temperature of 60 ℃.
Fig. 14 is an XPS deep cross-sectional view of oxygen and fluorine in a solid electrolyte of a ternary lithium ion battery according to a first embodiment of the present invention after 100 cycles of charge and discharge.
Fig. 15 is an XPS deep cross-sectional view of oxygen and fluorine in the solid electrolyte after 100 cycles of charge and discharge for the ternary lithium ion battery of comparative example of the present invention.
Fig. 16 is a composition analysis chart of solid electrolytes of the ternary lithium ion battery according to the first embodiment of the present invention and the ternary lithium ion battery according to the first comparative example after 100 cycles of charge and discharge.
Fig. 17 is a graph showing young's modulus distribution of solid electrolyte interface films of the ternary lithium ion battery of example one and the ternary lithium ion battery of comparative example one after 100 cycles of charge and discharge.
Fig. 18 is a high resolution transmission electron image of the solid electrolyte interface film of the ternary lithium ion battery of comparative example one after charge-discharge cycling according to the present invention.
Fig. 19 is a high-resolution electron transmission image of a solid electrolyte interface film of a ternary lithium ion battery according to a first embodiment of the present invention after charge-discharge cycling.
Fig. 20 is an in-situ XRD pattern of the positive active material of the ternary lithium ion battery according to comparative example of the present invention during the first charge and discharge.
Fig. 21 is an in-situ XRD pattern of the positive electrode active material of the ternary lithium ion battery according to the first embodiment of the present invention during the first charging and discharging.
Fig. 22 is a cycle performance diagram of a ternary lithium ion battery according to a second embodiment of the present invention.
Fig. 23 is a cycle performance diagram of a ternary lithium ion battery according to a third embodiment of the present invention.
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
So that the manner in which the above recited objects, features and advantages of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. 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 in order to provide a thorough understanding of the present invention, and the embodiments described are merely some, but not all embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
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 invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.
In various embodiments of the present invention, for convenience in description and not in limitation, the term "coupled" as used in the specification and claims of the present application is not limited to physical or mechanical couplings, either direct or indirect. "upper", "lower", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships are changed accordingly.
The embodiment of the invention provides a positive electrode active material.
The positive electrode active material comprises secondary particles formed by stacking primary particles and a coating layer coated on the surfaces of the primary particles and the secondary particles, wherein the structural formula of the primary particles is LiNi (1-x-y) Co x Mn y O 2 Wherein, 0<x<0.4，0<y<0.4，1-x-y≥0.6。
In at least one embodiment, the coating layer is at least one of lithium cobaltate, lithium aluminate, and lithium manganate.
In at least one embodiment, the coating layer is at least one of fluorine-doped lithium cobaltate, fluorine-doped lithium aluminate and fluorine-doped lithium manganate. The fluorine doping can reduce the migration barrier of lithium ions and improve the diffusion kinetics of the lithium ions in crystal lattices.
In at least one embodiment, the fluorine doping amount of the fluorine-doped lithium cobaltate is 0.3 to 0.8 wt%, preferably 0.5 to 0.6 wt%.
In at least one embodiment, the fluorine doping amount of the fluorine-doped lithium aluminate is 0.3 to 0.8 wt%, preferably 0.5 to 0.6 wt%.
In at least one embodiment, the fluorine doping amount of the fluorine-doped lithium manganate is 0.3 to 0.8 wt%, preferably 0.5 to 0.6 wt%.
In at least one embodiment, the thickness of the coating layer is 3 to 300nm, preferably 10 to 200nm, and more preferably 50 to 100 nm.
In at least one embodiment, the primary particles have a particle size of 150 to 300nm, preferably 200 to 250 nm.
In at least one embodiment, the secondary particles have a particle size ranging from 5 to 15 μm, preferably 8 to 12 μm.
The positive electrode active material provided by the present invention comprises secondary particles formed by stacking primary particles, and a coating layer that coats the surfaces of the primary particles and the secondary particles. The primary particle agglomerateHas a structure formula of LiNi (1-x-y) Co x Mn y O 2 Wherein, 0<x<0.4，0<y<0.4, 1-x-y is more than or equal to 0.6. The nickel content of the anode active material is high, so that the ternary lithium ion battery using the anode active material has high specific energy and specific power. In the charge and discharge process of the ternary lithium ion battery, the coating layers coated on the surfaces of the primary particles and the secondary particles of the positive electrode active material can inhibit the volumes of the primary particles and the secondary particles from being increased, so that the intracrystalline cracks and intercrystalline cracks caused by the increased volumes are avoided, and the service life of the ternary lithium ion battery is further prolonged. The coating layers coated on the surfaces of the primary particles and the secondary particles of the positive electrode active material can also prevent the primary particles and the secondary particles from contacting with electrolyte to generate side reaction, prevent the ternary lithium ion battery from expanding gas due to the side reaction, and further improve the safety performance of the ternary lithium ion battery.
The embodiment of the invention also provides a preparation method of the positive active material, which comprises the following steps:
step S1: providing Ni (1-x-y) Co x Mn y (OH) 2 A ternary precursor, a lithium salt and a coating agent, wherein 0<x<0.4，0<y<0.4, 1-x-y is more than or equal to 0.6, and the coating agent is metal oxide and/or metal hydroxide;
step S2: uniformly mixing the Ni (1-x-y) Co x Mn y (OH) 2 Ternary precursor and lithium salt to obtain a first mixture;
step S3: subjecting the first mixture to a first heat treatment to diffuse the lithium salt to the Ni (1-x-y) Co x Mn y (OH) 2 In a ternary precursor;
step S4: subjecting the first mixture subjected to the first heat treatment to a second heat treatment, wherein the Ni is (1-x-y) Co x Mn y (OH) 2 The ternary precursor reacts with lithium salt to generate LiNi (1-x-y) Co x Mn y O 2 A ternary material of said LiNi (1-x-y)y Co x Mn y O 2 The ternary material comprises secondary particles formed by stacking primary particles, wherein 0<x<0.4，0<y<0.4，1-x-y≥0.6；
Step S5: subjecting the LiNi to (1-x-y) Co x Mn y O 2 The ternary material is placed in a constant temperature and humidity environment, and the LiNi (1-x-y) Co x Mn y O 2 Secondary particles of the ternary material are opened along the grain boundary of the primary particles, and the primary particles and the secondary particles react with water and carbon dioxide in the constant-temperature and constant-humidity environment to generate residual alkali layers on the surfaces of the primary particles and the secondary particles;
step S6: mixing the coating agent with the LiNi having a residual alkali layer formed on the surface (1-x-y) Co x Mn y O 2 Ternary material to obtain a second mixture;
step S7: and carrying out third heating treatment on the second mixture to enable the coating agent to diffuse to the LiNi with the residual alkali layer formed on the surface (1-x-y) Co x Mn y O 2 Primary particles of ternary material; and
step S8: and carrying out fourth heating treatment on the second mixture, and carrying out in-situ lithium supply reaction on the coating agent and the residual alkali layer to generate a coating layer so as to prepare the anode active material.
In at least one embodiment, the lithium salt is at least one of lithium nitrate, lithium carbonate, and lithium hydroxide.
In at least one embodiment, the residual alkali layer is lithium carbonate and/or lithium hydroxide.
In at least one embodiment, the thickness of the residual alkali layer is 5 to 500nm, preferably 10 to 300nm, and more preferably 100 to 200 nm.
In at least one embodiment, the coating layer is at least one of lithium cobaltate, lithium aluminate, lithium manganate, fluorine-doped lithium cobaltate, fluorine-doped lithium aluminate, and fluorine-doped lithium manganate. The fluorine doping can change the interaction force between the oxygen layer and the transition metal layer, reduce the migration potential barrier of lithium ions and improve the diffusion kinetics of the lithium ions in crystal lattices.
It can be understood that the coating agent reacts with the residual alkali layer, not only can eliminate the residual alkali on the surfaces of the primary particles and the secondary particles, but also can generate a coating layer on the surfaces of the primary particles and the secondary particles to increase the mechanical properties and the compaction density of the positive electrode active material, thereby improving the specific capacity and the cycling stability of the positive electrode active material. Moreover, since the LiNi (1-x-y) Co x Mn y O 2 And the composite structure of the coating layer can change the energy band structure of the transition metal and oxygen, and improve the electronic conductivity of the anode active material.
In at least one embodiment, the fluorine doping amount of the fluorine-doped lithium cobaltate is 0.3 to 0.8 wt%, preferably 0.5 to 0.6 wt%.
In at least one embodiment, the fluorine doping amount of the fluorine-doped lithium aluminate is 0.3 to 0.8 wt%, preferably 0.5 to 0.6 wt%.
In at least one embodiment, the fluorine doping amount of the fluorine-doped lithium manganate is 0.3 to 0.8 wt%, preferably 0.5 to 0.6 wt%.
In at least one embodiment, the thickness of the coating layer is 3 to 300nm, preferably 10 to 200nm, and more preferably 50 to 100 nm.
In at least one embodiment, the Ni (1-x-y) Co x Mn y (OH) 2 The mass ratio of the ternary precursor to the lithium salt is 1: 1-1.5, preferably 1: 1.
in at least one embodiment, the mass percentage of the coating agent in the second mixture is 1-3%, and the LiNi with the residual alkali layer formed on the surface thereof (1-x-y) Co x Mn y O 2 The mass percentage range is 97-99%.
In at least one embodiment, the metal oxide is at least one of cobalt oxide, tricobalt tetraoxide, manganese oxide, and aluminum oxide.
In at least one embodiment, the metal hydroxide is at least one of cobalt hydroxide, aluminum hydroxide, and manganese hydroxide.
In at least one embodiment, the primary particles have a particle size of 150 to 300nm, preferably 200 to 250 nm.
In at least one embodiment, the secondary particles have a particle size ranging from 5 to 15 μm, preferably 8 to 12 μm.
In at least one embodiment, the temperature of the first heat treatment is 300 to 600 ℃, preferably 400 to 500 ℃. The time of the first heating treatment is 3-10 hours, preferably 5-8 hours. The temperature rise rate of the first heating treatment is 1-3 ℃/min.
In at least one embodiment, the temperature of the second heating treatment is 700 to 900 ℃, preferably 750 to 800 ℃. The time of the second heating treatment is 10-20 hours, preferably 15-17 hours. The temperature rise rate of the second heating treatment is 2-4 ℃/min.
In at least one embodiment, the temperature of the third heat treatment is 200 to 600 ℃, preferably 400 to 500 ℃. The time of the third heating treatment is 3-10 hours, preferably 5-8 hours.
In at least one embodiment, the temperature of the fourth heat treatment is 700 to 900 ℃, preferably 750 to 800 ℃. The time of the fourth heating treatment is 3-10 hours, preferably 5-8 hours.
In at least one embodiment, the first to fourth heat treatments may be performed in a tube furnace under an oxygen or artificial air atmosphere.
In at least one embodiment, the first mixture can be stored in a constant temperature and humidity chamber, wherein the storage temperature of the constant temperature and humidity environment is 25-200 ℃, the storage humidity is 1-100% rh, and the storage time is 1-30 days.
In the method for preparing the positive electrode active material provided by the invention, the Ni is added (1-x-y) Co x Mn y (OH) 2 Carrying out first heating treatment on the ternary precursor and lithium salt to diffuse the lithium salt to the Ni (1-x-y) Co x Mn y (OH) 2 In the ternary precursor, the first mixture after the first heating treatment is subjected to second heating treatment, and the Ni (1-x-y) Co x Mn y (OH) 2 Ternary precursor and lithiumSalt reaction to produce LiNi (1-x-y) Co x Mn y O 2 A ternary material. Subjecting the LiNi to a reaction (1-x-y) Co x Mn y O 2 The ternary material is placed in a constant temperature and humidity environment, and the LiNi (1-x-y) Co x Mn y O 2 The secondary particles of the ternary material are opened along the grain boundary of the primary particles, and a residual alkali layer is generated on the surfaces of the primary particles and the secondary particles. Mixing the coating agent with the LiNi having a residual alkali layer formed on the surface (1-x-y) Co x Mn y O 2 Ternary material to obtain a second mixture. And carrying out third heating treatment on the second mixture to enable the coating agent to diffuse to the LiNi with the residual alkali layer formed on the surface (1-x-y) Co x Mn y O 2 Between primary particles of the ternary material. And carrying out fourth heating treatment on the second mixture, and carrying out in-situ lithium supply reaction on the coating agent and the residual alkali layer to generate a coating layer so as to prepare the anode active material. The preparation method of the cathode active material has the advantages of simple steps, convenient operation, environmental friendliness and strong repeatability. The positive electrode active material includes secondary particles formed by stacking primary particles, and a coating layer that coats surfaces of the primary particles and the secondary particles. The structural formula of the primary particle is LiNi (1-x-y) Co x Mn y O 2 Wherein 0 is<x<0.4，0<y<0.4, 1-x-y is more than or equal to 0.6. The nickel content of the anode active material is high, so that the ternary lithium ion battery using the anode active material has high specific energy and specific power. In the charge and discharge process of the ternary lithium ion battery, the coating layers coated on the surfaces of the primary particles and the secondary particles of the positive electrode active material can inhibit the volumes of the primary particles and the secondary particles from being increased, so that the intracrystalline cracks and intercrystalline cracks caused by the increased volumes are avoided, and the service life of the ternary lithium ion battery is further prolonged. The coating layer coated on the surfaces of the primary particles and the secondary particles of the positive electrode active material can also prevent the primary particles and the secondary particles from contacting with electrolyte to generate side reaction, and prevent the ternary lithium ion battery caused by the side reactionAnd (4) expanding the gas, so that the safety performance of the ternary lithium ion battery is improved.
The step S2 includes the steps of:
step S21: adding the Ni (1-x-y) Co x Mn y (OH) 2 Placing the ternary precursor and the lithium salt in a mortar for dry mixing for 5-20 min to mix the Ni (1-x-y) Co x Mn y (OH) 2 A ternary precursor and a lithium salt;
step S22: adding an organic solvent to the mortar to react with the Ni (1-x-y) Co x Mn y (OH) 2 Wet mixing the ternary precursor and lithium salt for 5-20 min to remove Ni (1-x-y) Co x Mn y (OH) 2 Impurities on the surface of the ternary precursor, and reacting the Ni (1-x-y) Co x Mn y (OH) 2 The ternary precursor and the lithium salt can be uniformly mixed;
step S23: after the organic solvent is volatilized, the Ni is continuously dry-mixed in a mortar (1-x-y) Co x Mn y (OH) 2 Ternary precursor and lithium salt for 5-20 min to ensure the Ni (1-x-y) Co x Mn y (OH) 2 And uniformly mixing the ternary precursor and the lithium salt to obtain a first mixture.
In at least one embodiment, the organic solvent is at least one of an organic solvent, ethanol, acetone, and hexane.
In the technical scheme of the invention, the Ni is sequentially reacted (1-x-y) Co x Mn y (OH) 2 Sequentially dry-mixing, wet-mixing and dry-mixing the ternary precursor and the lithium salt to remove the Ni (1-x-y) Co x Mn y (OH) 2 Uniformly mixing the Ni with impurities on the surface of the ternary precursor (1-x-y) Co x Mn y (OH) 2 Ternary precursor and lithium salt.
The step S6 includes the steps of:
step S61: subjecting the LiNi to a reaction (1-x-y) Co x Mn y O 2 The ternary material and the coating agent are placed in a mortar for dry mixing for 5-20 minTo mix said LiNi (1-x-y) Co x Mn y O 2 Ternary materials and capping agents;
step S62: adding an organic solvent into the mortar, and reacting the LiNi (1-x-y) Co x Mn y O 2 Wet mixing the ternary material and a coating agent for 5-20 min to remove the LiNi (1-x-y) Co x Mn y O 2 Impurities on the surface of the ternary material, and reacting the LiNi (1-x-y) Co x Mn y O 2 The ternary material and the coating agent can be uniformly mixed;
step S63: after the organic solvent is volatilized, continuously dry-mixing the LiNi in a mortar (1-x-y) Co x Mn y O 2 Ternary material and coating agent for 5-20 min to ensure that the LiNi is adopted (1-x-y) Co x Mn y O 2 The ternary material and the coating agent are uniformly mixed to obtain a second mixture.
In at least one embodiment, the organic solvent is at least one of an organic solvent, ethanol, acetone, and hexane.
The technical scheme of the invention is to sequentially react the LiNi (1-x-y) Co x Mn y O 2 Dry mixing, wet mixing and dry mixing are sequentially carried out on the ternary material and the coating agent so as to remove the LiNi (1-x-y) Co x Mn y O 2 Uniformly mixing the LiNi on the basis of impurities on the surface of the ternary material (1-x-y) Co x Mn y O 2 Ternary materials and coating agents.
The embodiment of the invention also provides the anode. The positive electrode contains a conductive agent, a binder, and the positive electrode active material.
In at least one embodiment, the conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber, and carbon nanotube; and/or
In at least one embodiment, the binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinyl pyrrolidone, polypropylene carbonate, chlorinated polyethylene, and polyethylene carbonate.
Since the positive electrode adopts all technical solutions of all the embodiments, at least all the beneficial effects brought by the technical solutions of the embodiments are achieved, and no further description is given here.
The embodiment of the invention also provides a ternary lithium ion battery.
In at least one embodiment, the ternary lithium ion battery comprises the positive electrode, a lithium negative electrode and an electrolyte, wherein the positive electrode and the potassium positive electrode are both arranged in the electrolyte.
In at least one embodiment, the electrolyte contains lithium hexafluorophosphate at a concentration of 1mol/L and a solvent. The solvent contains the following components in a volume ratio of 1: 1: 1 fluoroethylene carbonate, methylethyl carbonate, and diethyl carbonate.
In at least one embodiment, the ternary lithium ion battery includes the positive electrode, a lithium negative electrode, and a solid state electrolyte, with the positive electrode and potassium positive electrode being located on either side of the solid state electrolyte.
In at least one embodiment, the solid electrolyte is a solid electrolyte comprising 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 ternary lithium ion battery.
In one embodiment, the mass ratio of the lithium salt, the polymer and the filler in the solid electrolyte is 7-9: 4-6: 1 to 2, for example, 8: 5: 1.
since the ternary lithium ion battery adopts all technical solutions of all the embodiments, at least all the beneficial effects brought by the technical solutions of the embodiments are achieved, and no further description is given here.
The present invention will be specifically described below with reference to specific examples.
Example one
Providing Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Ternary precursor and LiOH, fluorine doped beta-Co (OH) 2 Acetylene black, vinylidene fluoride, and a solid electrolyte, wherein the Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 The mass ratio of the ternary precursor to LiOH is 2: 1, the solid electrolyte contains the following components in a mass ratio of 8: 5: 1 lithium hexafluorophosphate, polyethylene oxide, and lanthanum lithium zirconate;
adding the Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Placing the ternary precursor and LiOH in a mortar for dry mixing for 10min, adding ethanol into the mortar, and adding the Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Wet mixing the ternary precursor and LiOH for 10min, and continuing to mix the Ni after the ethanol is volatilized 0.8 Co 0.1 Mn 0.1 (OH) 2 Dry mixing the ternary precursor and LiOH for 10min to obtain a first mixture;
placing the first mixture in a tube furnace, and carrying out first heating treatment on the first mixture under an oxygen atmosphere, wherein the temperature of the first heating treatment is 500 ℃ and the time is 5 h;
and carrying out secondary heating treatment on the first mixture subjected to the primary heating treatment in the tube furnace in an oxygen atmosphere to obtain LiNi 0.8 Co 0.1 Mn 0.1 O 2 The layered ternary material (named NCM811) is characterized in that the temperature of the first heating treatment is 780 ℃ and the time is 11 h;
placing the NCM811 in a constant temperature and humidity box, and storing for 1 day at the temperature of 60 ℃ and the humidity of 60% rh, so that the secondary particles of the NCM811 are opened along the grain boundary of the primary particles, and simultaneously, residual alkali layers are generated on the surfaces of the first particles and the secondary particles, wherein the residual alkali layers are lithium carbonate and lithium hydroxide;
NCM811 with a residual alkali layer formed on the surface thereof and fluorine-doped beta-Co (OH) 2 Placing in a mortar, dry-mixing for 10min, adding ethanol into the mortar, and forming NCM811 with residual alkali layer on the surface and fluorine-doped beta-Co (OH) 2 Wet mixing for 10min, evaporating ethanol, and continuing to generate NCM811 with a residual alkali layer on the surface and fluorine-doped beta-Co (OH) 2 Dry mixing for 10min to obtain a second mixture, wherein the fluorine-doped beta-Co (OH) 2 The mass percentage of the second mixture is 1-2%;
subjecting the second mixture to a third heat treatment in the tube furnace under an oxygen atmosphere to obtain the fluorine-doped beta-Co (OH) 2 The particles can be fully diffused into the secondary particles along the grain boundary of the primary particles, wherein the temperature of the third heating treatment is 300 ℃, the time is 4h, and the heating rate is 1 ℃/min;
subjecting the third-heat-treated second mixture to a fourth heat treatment in the tube furnace under an oxygen atmosphere, the NCM811 optionally being doped with fluorine-doped beta-Co (OH) 2 Generating fluorine-doped lithium cobaltate-coated LiNi through in-situ lithium supply reaction 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode active material (named FC-NCM811) is prepared by the following steps of (1) heating, wherein the temperature of the fourth heating treatment is 780 ℃, the time is 4h, and the heating rate is 2 ℃/min;
mixing the FC-NCM811, the acetylene black and the vinylidene fluoride to prepare the positive electrode of the first embodiment, wherein the mass ratio of the FC-NCM811 to the acetylene black to the vinylidene fluoride is 8: 1: 1;
the ternary lithium ion battery of the first embodiment is assembled by the positive electrode, the lithium negative electrode and the solid state electrolyte of the first embodiment.
Referring to FIG. 1, NCM811 is a hexagonal system with a space group of (R-3m), Li + and transition metal ions alternately occupy the 3a (000) and 3b (001/2) positions, and O2-is located at the 6c (00 z) position. Wherein, the oxygen at the 6c position belongs to cubic close packing, the metal ions at the 3b position and the Li + at the 3a position respectively occupy the octahedral gaps alternately, the octahedral gaps are arranged on the (111) crystal face in a layered structure, and the percentage of the lithium-nickel mixed rows is 3.04%.
Referring to FIG. 2, the percentage of lithium-nickel shuffling in FC-NCM811 was reduced to 1.98%.
Comparative example 1
The difference from the first embodiment comprises: and mixing the NCM811, the acetylene black and the vinylidene fluoride to prepare the positive electrode of the comparative example I, wherein the mass ratio of the NCM811 to the acetylene black to the vinylidene fluoride is 8: 1: 1; and the ternary lithium ion battery of comparative example I is assembled by the positive electrode, the lithium negative electrode and the solid electrolyte of comparative example I.
Other steps are the same as the first embodiment and are not repeated.
Referring to fig. 3 and 4, the ternary lithium ion battery of example one has a lower reaction overpotential and a higher peak current than the ternary lithium ion battery of comparative example one. This indicates that the ternary lithium ion battery of example one has higher reaction kinetics.
Referring to fig. 5 and 6, according to the lithium ion diffusion coefficients of the ternary lithium ion battery of the first comparative example and the ternary lithium ion battery of the first example at different scanning speeds, it can be calculated: the lithium ion diffusion coefficient of the ternary lithium ion battery of example one is 2 times that of the ternary lithium ion battery of comparative example one.
Referring to fig. 7, after 60 cycles of charge and discharge cycles, the resistance of the positive electrode of the ternary lithium ion battery of comparative example a gradually increased, while the resistance of the positive electrode of the ternary lithium ion battery of example a remained substantially unchanged.
Referring to fig. 8, the discharge capacity of the ternary lithium ion battery of example one was higher than that of the ternary lithium ion battery of comparative example one at different test temperatures. And the lower the temperature, the larger the discharge capacity of the ternary lithium ion battery of example one.
Referring to fig. 9, the discharge capacity of the ternary lithium ion battery of example one was comparable to that of the ternary lithium ion battery of comparative example one at 25 ℃ at magnifications of 0.2C and 1C. However, at 25 ℃, rates of 2C, 3C, 5C, and 10C, the discharge capacity of the ternary lithium ion battery of example one was significantly higher than that of the ternary lithium ion battery of comparative example one.
Referring to fig. 10, the discharge capacity of the ternary lithium ion battery of example one was comparable to that of the ternary lithium ion battery of comparative example one at 60 ℃ at rates of 0.2C and 1C. However, at 25 ℃, the discharge capacity of the ternary lithium ion battery of example one was significantly higher than that of the ternary lithium ion battery of comparative example one at the rates of 2C, 3C, 5C and 10C.
Referring to fig. 11 to 13, the capacity retention rate of the ternary lithium ion battery of example one was significantly higher than that of the ternary lithium ion battery of comparative example one at 25 ℃, -20 ℃, and 60 ℃.
Referring to fig. 14 to 16, after 100 cycles of charge and discharge, the Solid Electrolyte of the ternary lithium ion battery according to the first embodiment has a higher LiF content and a thinner Solid Electrolyte Interface (CEI) film than the Solid Electrolyte of the ternary lithium ion battery according to the first embodiment.
Referring to fig. 17, after 100 cycles of charge and discharge, the young's modulus of the solid electrolyte interface film of the ternary lithium ion battery of example one was greater than that of the ternary lithium ion battery of comparative example one, indicating that the mechanical properties of the ternary lithium ion battery of example one were better.
Referring to fig. 18 and 19, after charge and discharge cycles, the solid electrolyte interface film of the ternary lithium ion battery of the first example is significantly thinner than that of the ternary lithium ion battery of the first comparative example, so as to facilitate diffusion and migration of lithium ions.
Referring to fig. 20 and 21, the volume expansion effect of the cathode active material of the ternary lithium ion battery of example one is smaller than that of the cathode active material of the ternary lithium ion battery of comparative example one. This indicates that the phase change reversibility of the positive electrode active material of the ternary lithium ion battery of the first embodiment is better, so that the ternary lithium ion battery of the first embodiment has better cycle performance and safety performance.
Example two
The difference from the first embodiment comprises: the coating agent is Co 2 O。
Other steps are the same as the first embodiment and are not repeated.
Referring to fig. 22, the capacity retention rate of the ternary lithium ion battery of example two is significantly higher than that of the ternary lithium ion battery of comparative example one.
EXAMPLE III
The difference from the first embodiment comprises: the coating agent is MnO 2 。
Other steps are the same as the first embodiment and are not repeated.
Referring to fig. 23, the capacity retention rate of the ternary lithium ion battery of example three is significantly higher than that of the ternary lithium ion battery of comparative example one.
Although the present invention has been described in detail with reference to the preferred embodiments, it will 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 invention.
Claims (10)
1. A method for preparing a positive electrode active material, comprising the steps of:
providing Ni (1-x-y) Co x Mn y (OH) 2 Ternary precursor, lithium salt and coating agent, wherein 0<x<0.4，0<y<0.4, 1-x-y is more than or equal to 0.6, and the coating agent is metal oxide and/or metal hydroxide;
uniformly mixing the Ni (1-x-y) Co x Mn y (OH) 2 Ternary precursor and lithium salt to obtain a first mixture;
subjecting the first mixture to a first heat treatment to diffuse the lithium salt to the Ni (1-x-y) Co x Mn y (OH) 2 In a ternary precursor; wherein the temperature of the first heating treatment is 300-600 ℃, and the time is 3-10 h;
subjecting the first mixture subjected to the first heat treatment to a second heat treatment, wherein the Ni is (1-x-y) Co x Mn y (OH) 2 The ternary precursor reacts with lithium salt to generate LiNi (1-x-y) Co x Mn y O 2 A ternary material of said LiNi (1-x-y) Co x Mn y O 2 The ternary material comprises secondary particles formed by stacking primary particles, wherein 0<x<0.4，0<y<0.4, 1-x-y is more than or equal to 0.6; wherein the temperature of the second heating treatment is 700-900 ℃, and the time is 10-20 h;
subjecting the LiNi to a reaction (1-x-y) Co x Mn y O 2 The ternary material is placed in a constant temperature and humidity environment, and the LiNi (1-x-y) Co x Mn y O 2 Opening secondary particles of the ternary material along the grain boundary of the primary particles, and reacting the primary particles and the secondary particles with water and carbon dioxide in the constant-temperature and constant-humidity environment to generate alkali residue layers on the surfaces of the primary particles and the secondary particles; wherein the thickness of the residual alkali layer is 5-500 nm;
mixing the coating agent with the LiNi having a residual alkali layer formed on the surface (1-x-y) Co x Mn y O 2 Ternary material to obtain a second mixture;
and carrying out third heating treatment on the second mixture to enable the coating agent to diffuse to the LiNi with the residual alkali layer formed on the surface (1-x-y) Co x Mn y O 2 Primary particles of ternary material; wherein the temperature of the third heating treatment is 200-600 ℃, and the time is 3-10 h; and
carrying out fourth heating treatment on the second mixture, and carrying out in-situ lithium supply reaction on the coating agent and the residual alkali layer to generate a coating layer to prepare the positive electrode active material; wherein the temperature of the fourth heating treatment is 700-900 ℃, and the time is 3-10 h; the thickness of the coating layer is 3-300 nm.
2. The method for preparing a positive electrode active material according to claim 1, wherein the coating layer is at least one of lithium cobaltate, lithium manganate, lithium aluminate, fluorine-doped lithium cobaltate, fluorine-doped lithium aluminate, and fluorine-doped lithium manganate; and/or
In the second mixture, the mass percentage range of the coating agent is 1-3%, and LiNi with a residual alkali layer formed on the surface is used (1-x-y) Co x Mn y O 2 The mass percentage range is 97-99%.
3. The method for preparing a positive electrode active material according to claim 2, wherein the fluorine doping amount of the fluorine-doped lithium cobaltate is 0.3 to 0.8 wt%; and/or
The fluorine doping amount of the fluorine-doped lithium aluminate is 0.3-0.8 wt%; and/or
The fluorine doping amount of the fluorine-doped lithium manganate is 0.3-0.8 wt%.
4. The method for producing a positive electrode active material according to claim 1, wherein the residual alkali layer is lithium carbonate and/or lithium hydroxide.
5. The method for producing a positive electrode active material according to claim 1, wherein the lithium salt is at least one of lithium nitrate, lithium carbonate, and lithium hydroxide; and/or
The metal oxide is at least one of cobalt oxide, cobaltosic oxide, manganese oxide and aluminum oxide; and/or
The metal hydroxide is at least one of cobalt hydroxide, aluminum hydroxide and manganese hydroxide.
6. The method for producing a positive electrode active material according to claim 1, wherein the Ni is (1-x-y) Co x Mn y (OH) 2 The mass ratio of the ternary precursor to the lithium salt is 1: 1 to 1.5.
7. A positive electrode active material, characterized by being produced by the production method according to any one of claims 1 to 6;
the positive electrode active material includes a secondary particle formed by stacking primary particlesParticles and a coating layer coated on the surfaces of the primary particles and the secondary particles, wherein the structural formula of the primary particles is LiNi (1-x-y) Co x Mn y O 2 Wherein, 0<x<0.4，0<y<0.4，1-x-y≥0.6。
8. A positive electrode comprising a conductive agent, a binder, and the positive electrode active material according to claim 7.
9. The positive electrode according to claim 8, wherein the conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber, and carbon nanotubes; and/or
The binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate.
10. A ternary lithium ion battery, characterized in that it comprises a positive electrode according to claim 8 or 9.
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