CN109755549B - Nickel-based positive electrode material, preparation method thereof, lithium ion battery positive electrode, lithium ion battery and application - Google Patents
Nickel-based positive electrode material, preparation method thereof, lithium ion battery positive electrode, lithium ion battery and application Download PDFInfo
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Abstract
The invention provides a nickel-based anode material, a preparation method thereof, a lithium ion battery anode, a lithium ion battery and application, and relates to the technical field of lithium ion batteries. The nickel-based anode material comprises a kernel and a mixed-arrangement phase protection layer formed on the surface of the kernel, and the kernel and the mixed-arrangement phase protection layer are limited in chemical composition and spatial structure, so that an oxygen atom dense-arrangement structure with consistent orientation is formed between the kernel and the mixed-arrangement phase protection layer, and lattice dislocation is avoided, thereby relieving internal stress caused by structural distortion of the kernel and the mixed-arrangement phase protection layer in the charging and discharging processes, and improving the structural stability of the nickel-based anode material; meanwhile, the mixed-phase protective layer has strong chemical stability, so that the mixed-phase protective layer can effectively prevent the core from generating side reaction with the electrolyte under high voltage in the charging and discharging reaction process, and the interface stability and the cycle stability of the nickel-based anode material are improved. The invention also provides a preparation method of the nickel-based anode material, which has simple process and low cost.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nickel-based positive electrode material, a preparation method thereof, a lithium ion battery positive electrode, a lithium ion battery and application.
Background
With the continuous development of consumer electronic products and power automobiles in recent years, the field of lithium ion batteries is rapidly developed, particularly in the aspect of anode materials. Traditional LiCoO2The lithium ion battery cathode material is the most commonly used cathode material of the current commercial lithium ion battery by virtue of higher working voltage and long cycle life. But cobalt resources are scarce and toxic, and people have to pay attention to and develop other anode materials, wherein nickel-based ternary materials are concerned. Compared with LiCoO2The nickel-based ternary material realizes the reduction of the production cost and has higher energy density. Among them, the nickel-based ternary material has the advantage of high specific capacity due to high nickel content, and becomes a hotspot of research on the anode material. However, the nickel-based ternary material still has several important problems to be solved: (1) continuous structural degradation, namely a layered-spinel-rock salt structure, easily occurs in a lithium removal state, and the subsequent formation of the rock salt structure seriously affects the lithium ion extraction, thereby causing capacity attenuation and voltage drop; (2) tetravalent nickel and oxygen with strong oxidability are generated in the charging and discharging processes, and the tetravalent nickel and the oxygen are easy to react with an organic solvent in the electrolyte to generate gas, so that the overall performance of the battery is reduced, and potential safety hazards are brought.
Therefore, improvement of the composition structure and cycle stability of such nickel-based positive electrode materials is urgently needed while maintaining the advantages of high energy density and low cost, and the use of surface modification technology is the most common and accepted method.
The coating materials commonly used at present mainly include metal oxides, phosphides or fluorides, etc. However, these mixed phase protective layers can generate stress and cracks during electrochemical cycling due to mismatch of volume changes, which ultimately leads to failure of the protective coating.
In view of the above, the present invention is particularly proposed to solve at least one of the above technical problems.
Disclosure of Invention
The first purpose of the invention is to provide a nickel-based anode material, which comprises a kernel and a mixed-arrangement phase protection layer formed on the surface of the kernel, wherein the mixed-arrangement phase protection layer can effectively prevent the kernel from carrying out side reaction with electrolyte under high voltage, so that the interface stability and the cycle stability of the material are improved, and no lattice dislocation exists between the mixed-arrangement phase protection layer and the kernel, so that the internal stress caused by structural distortion of the kernel and the mixed-arrangement phase protection layer in the charging and discharging processes can be effectively relieved, and the structural stability of the nickel-based anode material is improved.
The second purpose of the invention is to provide a preparation method of the nickel-based positive electrode material, which has the advantages of simple process flow, easy operation and low production cost and is suitable for industrial mass production.
The third purpose of the invention is to provide a lithium ion battery anode, which comprises the nickel-based anode material or the nickel-based anode material prepared by the preparation method of the nickel-based anode material.
A fourth object of the present invention is to provide a lithium ion battery comprising the above lithium ion battery positive electrode.
The fifth purpose of the invention is to provide an application of the lithium ion battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a nickel-based cathode material, which comprises an inner core and a mixed-phase protective layer formed on at least one part of the surface of the inner core;
the chemical composition general formula of the inner core is Li1+aNixMyO2+zWherein a, x, y, z satisfy the following relationships: -0.1 < a < 0.1, 0.5 < x < 0.9, x + y ═ 1, -0.1 < z < 0.1, M comprises any one or a combination of at least two of the elements Co, Al or Mn; the inner core has an R-3m space group layered structure;
the mixed-arranged phase protection layer comprises a solid solution formed by Li, Ni and M, and high-valence metal ions are doped in the solid solution and comprise any one or the combination of at least two of Zr, V, Mo, W or Sn ions; the mixed-arrangement phase protection layer has an Fm-3m space group mixed-arrangement structure.
As an alternative embodiment of the present invention, the high-valence metal ions are Zr ions;
and/or the mass of the high-valence metal ions accounts for 0.01-5% of the mass of the nickel-based anode material.
As an alternative embodiment of the present invention, the inner core and the mixed-phase protective layer have a close-packed structure of oxygen atoms with consistent orientation;
and/or the thickness of the mixed-phase protective layer is 2-30 nm;
and/or D50 of the nickel-based cathode material is 2-20 mu m.
The invention also provides a preparation method of the nickel-based anode material, which comprises the following steps:
providing a precursor A for forming the inner core;
forming a precursor B for forming the mixed-phase protective layer on at least one part of the surface of the precursor A to obtain a precursor C;
and mixing the precursor C with a Li source, and calcining to obtain the nickel-based positive electrode material.
As an alternative embodiment of the invention, the method comprises the following steps:
(a) mixing a mixed solution formed by a Ni source and an M source with a first precipitator and a first complexing agent to perform coprecipitation reaction to obtain a solution containing a precursor A;
(b) adding a high-valence metal ion source, a Ni source, an M source, a second precipitator and a second complexing agent into the solution containing the precursor A to perform coprecipitation reaction, so as to form a precursor B on at least one part of the surface of the precursor A and obtain a solution containing a precursor C;
(c) and separating the solution containing the precursor C, mixing the obtained precursor C with a Li source, and calcining to obtain the nickel-based positive electrode material.
As an alternative embodiment of the present invention, the M source includes any one of a Co source, an Al source, or an Mn source, or a combination of at least two thereof;
and/or the high-valence metal ion source comprises any one of a Zr source, a V source, a Mo source, a W source or a Sn source or a combination of at least two of the Zr source, the V source, the Mo source, the W source or the Sn source;
and/or the first precipitator and the second precipitator are respectively and independently any one of sodium carbonate, sodium bicarbonate or sodium hydroxide;
and/or the first complexing agent and the second complexing agent are respectively and independently ammonia water or ammonium salt.
As an alternative embodiment of the present invention, in the step (a), the temperature of the coprecipitation reaction is 40 to 80 ℃ and the pH is 7.5 to 11;
and/or, in the step (b), the temperature of the coprecipitation reaction is 40-80 ℃, and the pH value is 7.5-11;
and/or, in the step (c), the calcining temperature is 700-900 ℃, the calcining time is 5-25h, and the calcining atmosphere is oxygen atmosphere or air atmosphere.
The invention also provides a lithium ion battery anode which comprises the nickel-based anode material or the nickel-based anode material prepared by the preparation method of the nickel-based anode material.
The invention also provides a lithium ion battery which comprises the lithium ion battery anode.
The invention also provides application of the lithium ion battery in an electronic device, an electric tool, an electric vehicle or an electric power storage system.
Compared with the prior art, the nickel-based anode material and the preparation method thereof, the lithium ion battery anode and the lithium ion battery provided by the invention have the following advantages:
(1) the invention provides a nickel-based anode material, which comprises a kernel and a mixed-arrangement phase protection layer formed on the surface of the kernel, wherein the kernel and the mixed-arrangement phase protection layer are limited in chemical composition and spatial structure, so that an oxygen atom dense-arrangement structure with consistent orientation is formed between the kernel and the mixed-arrangement phase protection layer, and lattice dislocation is avoided, thereby relieving internal stress caused by structural distortion of the kernel and the mixed-arrangement phase protection layer in the charge-discharge process, effectively reducing a gap between the kernel and the mixed-arrangement phase protection layer, and improving the structural stability of the nickel-based anode material; meanwhile, the mixed-arranged phase protection layer has strong chemical stability, so that the mixed-arranged phase protection layer can effectively prevent the core from generating side reaction with the electrolyte under high voltage in the charge-discharge reaction process of the nickel-based anode material, and the interface stability and the cycle stability of the material are improved.
(2) The invention provides a preparation method of a nickel-based anode material, which has the advantages of simple process flow, easy operation and low production cost and is suitable for industrial mass production.
(3) The invention provides a lithium ion battery anode which comprises the nickel-based anode material and has the same advantages as the nickel-based anode material.
(4) The invention provides a lithium ion battery, which comprises the lithium ion battery anode. In view of the advantages of the positive electrode of the lithium ion battery, the lithium ion battery has good electrochemical performance and stability.
(5) The invention provides application of the lithium ion battery in the fields of electronic devices, electric tools, electric vehicles, electric power storage systems and the like. In view of the advantages of the lithium ion battery, the same effects can be obtained in an electronic device, an electric tool, an electric vehicle, and a power storage system including the lithium ion battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is XRD patterns of nickel-based positive electrode materials provided in example 1 of the present invention and comparative example 1;
FIG. 2 is an SEM electron micrograph of the precursor C (a) and the nickel-based positive electrode material (b) in comparative example 1 of the present invention;
FIG. 3 is an SEM electron micrograph of the precursor C (a) and the nickel-based positive electrode material (b) in example 1 of the present invention;
FIG. 4 is an electron microscope image of a surface microstructure of a nickel-based positive electrode material according to comparative example 1 of the present invention;
fig. 5 is an electron microscope image of a surface microstructure of the nickel-based positive electrode material provided in example 1 of the present invention;
fig. 6 is a graph showing electrochemical cycle performance of nickel-based positive electrode materials provided in example 1 of the present invention and comparative example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that: in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the percentage (%) or parts means the weight percentage or parts by weight with respect to the composition, if not otherwise specified.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6 to 22" means that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is simply a shorthand representation of the combination of these values.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In the present invention, unless otherwise specified, the individual reactions or operation steps may be performed sequentially or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
According to one aspect of the present invention, there is provided a nickel-based positive electrode material including an inner core and a mixed-alignment phase protective layer formed on at least a part of a surface of the inner core;
the chemical composition general formula of the inner core is Li1+aNixMyO2+zWherein a, x, y, z satisfy the following relationships: -0.1 ≦ a ≦ 0.1, 0.5 ≦ x ≦ 0.9, x + y ≦ 1, -0.1 ≦ z ≦ 0.1, and M includes any one or a combination of at least two of the elements Co, Al, or Mn; the inner core has an R-3m space group layered structure;
the mixed-arranged phase protection layer comprises a solid solution formed by Li, Ni and M, and high-valence metal ions are doped in the solid solution and comprise any one or the combination of at least two of Zr, V, Mo, W or Sn ions; the mixed arrangement phase protection layer has an Fm-3m space group mixed arrangement structure.
Specifically, the chemical composition general formula of the core is Li1+aNixMyO2+z. Wherein a is typically, but not limited to, -0.1, 0, or 0.1; x is typically, but not limited to, 0.6, 0.7, or 0.8; y is typically, but not limited to, 0.4, 0.3, or 0.2; z is typically, but not limited to, -0.1, 0, or 0.1; the M element may be any one of Co, Al, and Mn elements, or a combination of any two of them, or a combination of three elements.
According to the difference of the values of a, x, y and z and the types of the M elements, the chemical composition of the inner core comprises but is not limited to Li0.9Ni0.8Co0.1Mn0.1O1.95、Li0.9Ni0.6Co0.2Mn0.2O1.95、Li0.9Ni0.5Co0.2Mn0.3O1.95、LiNi0.8Co0.1Mn0.1O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.5Co0.2Mn0.3O2、Li1.1Ni0.8Co0.1Mn0.1O2.05、Li1.1Ni0.6Co0.2Mn0.2O2.05、Li1.1Ni0.5Co0.2Mn0.3O2.05、Li0.9Ni0.8Co0.1Al0.1O1.95、Li0.9Ni0.6Co0.2Al0.2O1.95、Li0.9Ni0.5Co0.2Al0.3O1.95、LiNi0.8Co0.1Al0.1O2、LiNi0.6Co0.2Al0.2O2、LiNi0.5Co0.2Al0.3O2、Li1.1Ni0.8Co0.1Al0.1O2.05、Li1.1Ni0.6Co0.2Al0.2O2.05、Li1.1Ni0.5Co0.2Al0.3O2.05、Li0.9Ni0.8Co0.2O1.95、LiNi0.6Co0.4O2、Li1.1Ni0.5Co0.5O2.05、Li0.9Ni0.8Mn0.2O1.95、LiNi0.6Mn0.4O2、Li1.1Ni0.5Mn0.5O2.05、Li0.9Ni0.8Al0.2O1.95、LiNi0.6Al0.4O2Or Li1.1Ni0.5Al0.5O2.05And the like.
The mixed-arrangement phase protection layer formed on the surface of the inner core may be a mixed-arrangement phase protection layer completely coated on the surface of the inner core, or a mixed-arrangement phase protection layer partially coated on the surface of the inner core.
The element composition in the mixed-arrangement phase protection layer is required to be consistent with the element species in the kernel except for high-valence metal ions, so that the mixed-arrangement phase protection layer can form an epitaxial phase of the kernel.
In the present invention, a higher valent metal ion generally refers to a metal cation that is greater than or equal to trivalent. The high-valence metal ions are mainly used as surface modification elements, and can promote the mixed arrangement of the cations in the mixed arrangement phase protective layer and promote the formation of the mixed arrangement phase protective layer.
The mixed-arranged phase protection layer has strong chemical stability, so that the mixed-arranged phase protection layer can effectively prevent the core from generating side reaction with the electrolyte under high voltage in the charge-discharge reaction process of the nickel-based anode material, and the interface stability and the cycling stability of the material are improved; meanwhile, the inner core in the nickel-based anode material is of an R-3m space group layered structure, and the mixed-arrangement phase protection layer is of an Fm-3m space group mixed-arrangement structure, so that an oxygen atom dense-arrangement structure with consistent orientation is formed between the inner core and the mixed-arrangement phase protection layer, the internal stress caused by structural distortion of the inner core and the mixed-arrangement phase protection layer in the charging and discharging process can be relieved, the gap between the inner core and the mixed-arrangement phase protection layer is effectively reduced, and the structural stability of the nickel-based anode material is improved.
In an alternative embodiment of the present invention, the high-valence metal ions are Zr ions. Zr ion as surface modifying ion can make Ni3+Reduction to Ni2+To maintain charge balance and enhance the lithium-nickel mixed-arrangement so as to promote the in-situ generation of the mixed-arrangement phase protective layer on the surface.
As an optional embodiment of the invention, the mass of the high-valence metal ions accounts for 0.01-5% of the mass of the nickel-based positive electrode material.
In the present invention, the amount of the high-valence metal ions should not be too much, which may cause a serious capacity loss, and the amount of the high-valence metal ions should not be too little, which may cause a failure to form a uniform protective layer on the surface to aggravate the structural degradation, so the amount of the high-valence metal ions should be controlled within a specific range of values.
The mass fraction of the mass of the higher valent metal ions in the nickel-based positive electrode material is typically, but not limited to, 0.01%, 0.05%, 0.1%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%.
As an optional embodiment of the invention, the thickness of the mixed-arrangement phase protective layer is 2-30 nm; the thickness of the hybrid aligned phase protective layer coating on the inner core surface is typically, but not limited to, 2nm, 5nm, 8nm, 10nm, 12nm, 14nm, 15nm, 18nm, 20nm, 22nm, 24nm, 25nm, 28nm, or 30 nm.
The thickness of the mixed arrangement phase protective layer is too thin, which easily causes that a uniform protective layer cannot be formed on the surface, thereby aggravating the structure recession, and if the thickness of the mixed arrangement phase protective layer is too thick, the capacity loss is easily serious, so the thickness of the mixed arrangement phase protective layer should be controlled within a proper range.
As an alternative embodiment of the present invention, the nickel-based positive electrode material has D50 of 2-20 μm.
Typical, but non-limiting, D50 particle sizes for nickel-based positive electrode materials are 2 μm, 4 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, or 20 μm.
The particle size of the nickel-based cathode material D50 is limited, so that the nickel-based cathode material particles are in a more appropriate particle size distribution, and the nickel-based cathode material has good electrochemical performance and long service life.
As an optional embodiment of the invention, the inner core and the mixed-phase protective layer have a densely-arranged structure of oxygen atoms with consistent orientation;
the oxygen atom close-packed structure with consistent orientation is arranged between the kernel and the mixed-arrangement phase protection layer, so that lattice dislocation cannot exist between the kernel and the mixed-arrangement phase protection layer, the gap between the kernel and the mixed-arrangement phase protection layer is reduced, the volume change generated in the electrochemical cycle process of the kernel and the mixed-arrangement phase protection layer is weakened, the generation of phenomena such as stress and cracks caused by volume mismatch is greatly reduced, and the structural stability of the nickel-based anode material is effectively improved.
According to a second aspect of the present invention, there is also provided a method for preparing the above nickel-based positive electrode material, comprising the steps of:
providing a precursor A for forming an inner core;
forming a precursor B for forming a mixed-phase protection layer on at least one part of the surface of the precursor A to obtain a precursor C;
and mixing the precursor C with a Li source, and calcining to obtain the nickel-based positive electrode material.
The precursors a, B and C may be formed by a method conventionally used in the art, such as a sol-gel method or a coprecipitation method, and are not particularly limited herein.
Because the lithium salt concentration product corresponding to the lithium source is large, and the lithium salt is generally difficult to form coprecipitation with the Ni source and the M source, the precursor C is prepared firstly, and then the precursor C and the Li source are mixed and calcined, so that the nickel-based positive electrode material mainly comprising the kernel and the mixed-phase protective layer coated on the surface of the kernel is formed.
The preparation method of the nickel-based cathode material provided by the invention has the advantages of simple and stable process, low cost and easy realization of commercial large-scale production.
As an alternative embodiment of the invention, the method comprises the following steps:
(a) mixing a mixed solution formed by a Ni source and an M source with a first precipitator and a first complexing agent to perform coprecipitation reaction to obtain a solution containing a precursor A;
(b) adding a high-valence metal ion source, a Ni source, an M source, a second precipitator and a second complexing agent into the solution containing the precursor A to perform coprecipitation reaction, so as to form a precursor B on at least one part of the surface of the precursor A and obtain a solution containing a precursor C;
(c) and separating the solution containing the precursor C, mixing the obtained precursor C with a Li source, and calcining to obtain the nickel-based positive electrode material.
In one embodiment of the invention, the precursor A and the precursor B are both prepared by coprecipitation reaction. The coprecipitation reaction can ensure that the raw materials are metered and mixed at an atomic or molecular level, and is beneficial to the accurate control of the particle size and the appearance of the final product.
In the above embodiment of the present invention, the precursor B is formed by directly precipitating the high-valence metal ion source, the Ni source and the M source on the surface of the precursor a under the action of the second precipitator and the second complexing agent, and the high-valence metal ion is used to perform the in-situ modification. Based on the chemical valence state equilibrium principle, under the induction action of high-valence metal ions, divalent nickel ions on the surface of the inner core are increased compared with trivalent nickel ions in the high-temperature calcination process, and are easy to migrate to the position of the structure where the lithium ions are located, and finally, a mixed-phase protective layer is formed.
And directly growing the precursor B on the surface of the precursor A in situ to obtain a precursor C, and then mixing the precursor C with a Li source and calcining.
The kind of the nickel salt corresponding to the Ni source used in the step (a) and the step (b) may be the same or different; the kind of the M source in step (a) and step (b) needs to be the same, for example, the M source in step (a) is a Co source and a Mn source, and the M source in step (b) is a Co source and a Mn source; however, the cobalt salts corresponding to the Co source used in the step (a) and the step (b) may be the same or different, and the manganese salts corresponding to the Mn source used may be the same or different.
The first precipitator, the first complexing agent, the second precipitator and the second complexing agent are all determined according to actual reaction. The specific substances adopted by the first precipitator and the second precipitator can be the same or different; the specific substances used for the first complexing agent and the second complexing agent can be the same or different.
As an alternative embodiment of the present invention, the first precipitant and the second precipitant are each independently any one of sodium carbonate, sodium bicarbonate, or sodium hydroxide;
as an alternative embodiment of the present invention, the first complexing agent and the second complexing agent are each independently ammonia or an ammonium salt.
The coprecipitation reaction in the step (a) and the step (b) is more sufficient through the definition of specific types of the first precipitator, the first complexing agent, the second precipitator and the second complexing agent.
As an alternative embodiment of the present invention, the nickel source includes any one of nickel sulfate, nickel chloride or nickel acetate or a combination of at least two thereof;
as an alternative embodiment of the present invention, the M source includes any one of a Co source, an Al source, or an Mn source, or a combination of at least two thereof;
the Co source, the Al source or the Mn source are all for providing Co, Al or Mn elements to the core. The Co source, the Al source and the Mn source can adopt common cobalt salt, aluminum salt and manganese salt.
Wherein, the Co source comprises any one or the combination of at least two of cobalt sulfate, cobalt acetate or cobalt chloride; the Al source comprises aluminum sulfate and/or aluminum chloride; the Mn source comprises any one of manganese sulfate, manganese acetate or manganese chloride or a combination of at least two of the manganese sulfate, the manganese acetate or the manganese chloride.
The lithium source may provide Li element to the core and the mixed-ordered phase protective layer. As an alternative embodiment of the present invention, the lithium source comprises one or a combination of at least two of lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate or lithium acetate.
As an alternative embodiment of the present invention, the high-valence metal ion source includes any one of a Zr source, a V source, a Mo source, a W source, or a Sn source, or a combination of at least two thereof;
the Zr source comprises any one of zirconium sulfate, zirconium acetate or zirconium chloride or a combination of at least two of the zirconium sulfate, the zirconium acetate and the zirconium chloride; the V source comprises vanadium chloride and/or ammonium metavanadate; the Mo source comprises molybdenum pentachloride; the W source comprises tungsten chloride; the Sn source includes tin chloride.
The compatibility among the raw materials is better through the limitation of specific types of the nickel source, the M source, the lithium source and the high-valence metal ion source.
As an alternative embodiment of the invention, in the step (a), the temperature of the coprecipitation reaction is 40-80 ℃, and the pH value is 7.5-11; typical but non-limiting co-precipitation reaction temperatures are 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, and typical but non-limiting co-precipitation reaction pH values are 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5 or 11.
As an alternative embodiment of the invention, in the step (b), the temperature of the coprecipitation reaction is 40-80 ℃, and the pH value is 7.5-11; typical but non-limiting co-precipitation reaction temperatures are 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, and typical but non-limiting co-precipitation reaction pH values are 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5 or 11.
The temperature and pH of the coprecipitation reaction in step (a) may be the same as or different from those in step (b). The reaction is carried out more fully by limiting the temperature and pH parameters in the coprecipitation reaction process.
As an alternative embodiment of the invention, the calcination temperature is 700-900 ℃, the calcination time is 5-25h, and the calcination atmosphere is an oxygen atmosphere or an air atmosphere.
Typical but not limiting calcination temperatures are 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, typical but not limiting calcination times are 5h, 8h, 10h, 15h, 18h, 20h, 22h, 24h or 25 h.
And mixing and calcining the precursor C and a Li source, so that Li ions enter the inner core and the mixed-discharge phase protective layer respectively.
According to the third aspect of the invention, the invention also provides a lithium ion battery anode which comprises the nickel-based anode material or is prepared by adopting the preparation method of the nickel-based anode material.
In view of the advantages of the nickel-based positive electrode material, the positive electrode of the lithium ion battery comprising the nickel-based positive electrode material also has the same advantages.
According to a fourth aspect of the present invention, there is also provided a lithium ion battery comprising the above lithium ion battery positive electrode.
In view of the advantages of the nickel-based positive electrode material, the lithium ion battery has good electrochemical performance.
According to a fifth aspect of the present invention, there is also provided an electronic device, an electric tool, an electric vehicle, or an electric power storage system including the lithium ion battery described above. In view of the advantages of the lithium ion battery described above, the same effects can be obtained also in an electronic device, an electric tool, an electric vehicle, and a power storage system using the lithium ion battery according to the embodiment of the present invention.
An electronic device is an electronic device that performs various functions (e.g., playing music) using a lithium ion battery as a power source for operation. The electric power tool is an electric power tool that moves a component (e.g., a drill) using a lithium ion battery as a driving power source. The electric vehicle is an electric vehicle that runs on a lithium ion battery as a drive power source, and may be an automobile (including a hybrid vehicle) equipped with other drive sources in addition to the lithium ion battery. The power storage system is a power storage system that uses a lithium ion battery as a power storage source. For example, in a home power storage system, power is stored in a lithium ion battery serving as a power storage source, and the power stored in the lithium ion battery is consumed as needed to enable use of various devices such as home electronics.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
The embodiment provides a nickel-based cathode material, which comprises an inner core and a mixed-phase protective layer formed on the surface of the inner core;
the chemical composition general formula of the inner core is LiNi0.8Co0.1Mn0.1O2The inner core has an R-3m space group layered structure;
the mixed-arrangement phase protection layer is a solid solution of lithium, nickel, cobalt and manganese doped with Zr (high-valence metal ions), the mass of the high-valence metal ions Zr ions accounts for 0.05% of the mass of the nickel-based positive electrode material, the thickness of the formed mixed-arrangement phase protection layer is 5nm, and the mixed-arrangement phase protection layer has an Fm-3m space group mixed-arrangement structure.
The preparation method of the nickel-based positive electrode material provided by the embodiment comprises the following steps:
(a) providing a mixed solution of a Ni source and an M source (a Co source and a Mn source): preparing a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with a concentration of 2M with deionized water (the molar ratio of nickel to cobalt to manganese is 0.8: 0.1: 0.1, referred to as solution a 1);
providing a first precipitant: at a concentration of 2M Na2CO3A solution;
providing a first complexing agent: an aqueous ammonia solution with a concentration of 0.24M;
adding a certain amount of deionized water (1L) into a reaction kettle (5L) under stirring, heating to 55 ℃, firstly dropwise adding a proper amount of first complexing agent into the reaction kettle until the pH value is stabilized at about 7.8, then dropwise adding a solution A1, a first precipitator and the first complexing agent simultaneously to perform coprecipitation reaction, adjusting the dropwise adding speed of the solution A1, the first precipitator and the first complexing agent to maintain the pH value of the solution in the reaction kettle between 7.7 and 7.9, and completely dropwise adding the solution A1 after 11 hours of feeding to form a solution containing a precursor A;
(b) lifting deviceHigh valence metal ion source: zr (SO) concentration of 0.03M4)2A solution;
providing a second precipitant: at a concentration of 2M Na2CO3A solution;
providing a second complexing agent: an aqueous ammonia solution with a concentration of 0.24M;
continuously dropwise adding a high-valence metal ion source, a second precipitator and a second complexing agent into the solution of the precursor A at the same time to perform coprecipitation reaction, adjusting the dropwise adding speed of the high-valence metal ion source, the second precipitator and the second complexing agent to maintain the pH value of the solution in the reaction kettle between 7.7 and 7.9 until the ratio of the molar number of Zr ions in the high-valence metal ion source to the total molar number of nickel, cobalt and manganese is 0.015, forming a precursor B on at least one part of the surface of the precursor A, and obtaining a solution containing a precursor C;
(c) aging the solution containing the precursor C for 60min, filtering, washing with deionized water until the pH value is less than 10, and drying in a drying oven at 110 ℃ to obtain a dried precursor C; analyzing the content of Transition Metal (TM) nickel, cobalt and manganese in the dried precursor C by adopting an induced plasma atomic emission spectrum (ICP), weighing a certain amount of lithium hydroxide according to a molar ratio (Li: TM is 1.03), uniformly mixing the lithium hydroxide with the dried precursor C, putting the mixture in a box-type furnace, heating to 750 ℃ at a speed of 3 ℃/min, keeping the temperature for 15h, and cooling to room temperature along with the furnace to obtain the nickel-based positive electrode material.
Example 2
This example provides a nickel-based positive electrode material, which is the same as example 1 except that the mixed-phase protective layer is formed to a thickness of 25 nm.
The preparation method of the nickel-based cathode material provided in this example is the same as that of example 1.
Example 3
This example provides a nickel-based positive electrode material, which is the same as example 1 except that the mixed-phase protective layer is formed to a thickness of 35 nm.
The preparation method of the nickel-based cathode material provided in this example is the same as that of example 1.
Example 4
This example provides a nickel-based positive electrode material, which is the same as example 1 except that the mass of the high-valence metal ions Zr ions accounts for 5% of the mass of the nickel-based positive electrode material.
The preparation method of the nickel-based cathode material provided in this example is the same as that of example 1.
Example 5
This example provides a nickel-based positive electrode material, which is the same as example 1 except that the mass of the high-valence metal ions Zr ions accounts for 0.01% of the mass of the nickel-based positive electrode material.
The preparation method of the nickel-based cathode material provided in this example is the same as that of example 1.
Example 6
This example provides a nickel-based positive electrode material, which is the same as example 1 except that the high-valence metal ions doped in the mixed-phase protective layer are V ions.
In the preparation method of the nickel-based cathode material provided in this embodiment, except that the high-valence metal ion source Zr (SO) is used4)2Replacement of solution by NH4VO3The rest of the steps and parameters were the same as in example 1.
Example 7
This example provides a nickel-based positive electrode material, which is the same as example 1 except that the high-valence metal ions doped in the mixed-phase protective layer are Mo ions.
In the preparation method of the nickel-based cathode material provided in this embodiment, except that the high-valence metal ion source Zr (SO) is used4)2Replacement of the solution with MoCl5The rest of the steps and parameters were the same as in example 1.
Example 8
This example provides a nickel-based positive electrode material, which is the same as example 1 except that the high-valence metal ions doped in the mixed-phase protective layer are W ions.
In the preparation method of the nickel-based cathode material provided in this embodiment, except that the high-valence metal ion source Zr (SO) is used4)2Replacement of solution by WCl6The rest of the steps and parameters were the same as in example 1.
Example 9
The embodiment provides a nickel-based cathode material, which comprises an inner core and a mixed-phase protective layer formed on the surface of the inner core;
the chemical composition general formula of the core is Li0.9Ni0.5Co0.2Mn0.3O1.95The inner core has an R-3m space group layered structure;
the mixed-arrangement phase protection layer is a solid solution of lithium, nickel, cobalt and manganese doped with Zr (high-valence metal ions), the mass of the high-valence metal ions Zr ions accounts for 0.15% of the mass of the nickel-based positive electrode material, the forming thickness of the mixed-arrangement phase protection layer is 30nm, and the mixed-arrangement phase protection layer has an Fm-3m space group mixed-arrangement structure.
The preparation method of the nickel-based positive electrode material provided by the embodiment comprises the following steps:
(a) providing a mixed solution of a Ni source and an M source (a Co source and a Mn source): preparing a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with a concentration of 2M with deionized water (the molar ratio of nickel to cobalt to manganese is 0.5: 0.2: 0.3, referred to as solution a 1);
providing a first precipitant: at a concentration of 2M Na2CO3A solution;
providing a first complexing agent: an aqueous ammonia solution with a concentration of 0.24M;
adding a certain amount of deionized water (1L) into a reaction kettle (5L) under stirring, heating to 55 ℃, firstly dropwise adding a proper amount of first complexing agent into the reaction kettle until the pH value is stabilized at about 7.8, then dropwise adding a solution A1, a first precipitator and the first complexing agent simultaneously to perform coprecipitation reaction, adjusting the dropwise adding speed of the solution A1, the first precipitator and the first complexing agent to maintain the pH value of the solution in the reaction kettle between 7.7 and 7.9, and completely dropping the solution A1 after feeding for 11 hours to form a solution containing a precursor A;
(b) providing a high valence metal ion source: zr (SO) concentration of 0.03M4)2A solution;
providing a second precipitant: at a concentration of 2M Na2CO3A solution;
providing a second complexing agent: an aqueous ammonia solution with a concentration of 0.24M;
continuously dropwise adding a high-valence metal ion source, a second precipitator and a second complexing agent into the solution of the precursor A at the same time to perform coprecipitation reaction, adjusting the dropwise adding speed of the high-valence metal ion source, the second precipitator and the second complexing agent to maintain the pH value of the solution in the reaction kettle between 7.7 and 7.9 until the ratio of the molar number of Zr ions in the high-valence metal ion source to the total molar number of nickel, cobalt and manganese is 0.015, forming a precursor B on at least one part of the surface of the precursor A, and obtaining a solution containing a precursor C;
(c) aging the solution containing the precursor C for 60min, filtering, washing with deionized water until the pH value is less than 10, and drying in a drying oven at 110 ℃ to obtain a dried precursor C; analyzing the content of Transition Metal (TM) nickel, cobalt and manganese in the dried precursor C by adopting an induced plasma atomic emission spectrum (ICP), weighing a certain amount of lithium hydroxide according to a molar ratio (Li: TM is 0.93:1) and uniformly mixing the lithium hydroxide with the dried precursor C, putting the mixture into a box-type furnace, heating to 750 ℃ at a speed of 3 ℃/min, keeping the temperature for 15h, and cooling to room temperature along with the furnace to obtain the nickel-based positive electrode material.
Example 10
The embodiment provides a nickel-based cathode material, which comprises an inner core and a mixed-phase protective layer formed on the surface of the inner core;
the chemical composition general formula of the core is Li1.1Ni0.5Co0.2Mn0.2Al0.1O2.05The inner core has an R-3m space group layered structure;
the mixed-arranged phase protection layer is a solid solution of lithium, nickel, cobalt, manganese and aluminum doped with Zr (high-valence metal ions), the mass of the high-valence metal ions Zr ions accounts for 1.5% of the mass of the nickel-based positive electrode material, the forming thickness of the mixed-arranged phase protection layer is 30nm, and the mixed-arranged phase protection layer has an Fm-3m space group mixed-arranged structure.
The preparation method of the nickel-based positive electrode material provided by the embodiment comprises the following steps:
(a) providing a mixed solution of a Ni source and an M source (a Co source, a Mn source and an Al source): preparing a mixed solution of nickel sulfate, cobalt sulfate, manganese sulfate and aluminum sulfate with a concentration of 2M with deionized water (the molar ratio of nickel to cobalt to manganese to aluminum is 0.5: 0.2: 0.2: 0.1, referred to as solution a 1);
providing a first precipitant: at a concentration of 2M Na2CO3A solution;
providing a first complexing agent: an aqueous ammonia solution with a concentration of 0.24M;
adding a certain amount of deionized water (1L) into a reaction kettle (5L) under stirring, heating to 55 ℃, firstly dropwise adding a proper amount of first complexing agent into the reaction kettle until the pH value is stabilized at about 7.8, then dropwise adding a solution A1, a first precipitator and the first complexing agent simultaneously to perform coprecipitation reaction, adjusting the dropwise adding speed of the solution A1, the first precipitator and the first complexing agent to maintain the pH value of the solution in the reaction kettle between 7.7 and 7.9, and completely dropping the solution A1 after feeding for 11 hours to form a solution containing a precursor A;
(b) providing a high valence metal ion source: zr (SO) concentration of 0.03M4)2A solution;
providing a second precipitant: at a concentration of 2M Na2CO3A solution;
providing a second complexing agent: an aqueous ammonia solution with a concentration of 0.24M;
continuously dropwise adding a high-valence metal ion source, a second precipitator and a second complexing agent into the solution of the precursor A at the same time to perform coprecipitation reaction, adjusting the dropwise adding speed of the high-valence metal ion source, the second precipitator and the second complexing agent to maintain the pH value of the solution in the reaction kettle between 7.7 and 7.9 until the ratio of the molar number of Zr ions in the high-valence metal ion source to the sum of the molar numbers of nickel, cobalt and manganese is 0.015, forming a precursor B on at least one part of the surface of the precursor A, and obtaining a solution containing a precursor C;
(c) aging the solution containing the precursor C for 60min, filtering, washing with deionized water until the pH value is less than 10, and drying in a drying oven at 110 ℃ to obtain a dried precursor C; analyzing the content of Transition Metal (TM) nickel, cobalt and manganese in the dried precursor C by adopting an induced plasma atomic emission spectrum (ICP), weighing a certain amount of lithium hydroxide according to a molar ratio (Li: TM is 1.13:1) and uniformly mixing the lithium hydroxide with the dried precursor C, putting the mixture into a box-type furnace, heating to 750 ℃ at a speed of 3 ℃/min, keeping the temperature for 15h, and cooling to room temperature along with the furnace to obtain the nickel-based positive electrode material.
Comparative example 1
This comparative example provides a nickel-based positive electrode material, which was the same as example 1 except that no mixed-ordered phase protective layer was formed on the surface of the core.
The preparation method of the nickel-based positive electrode material provided in the comparative example is the same as that of example 1 except that step (b) is not performed, and after the solution containing the precursor a is filtered and dried in step (c), a certain amount of lithium hydroxide is weighed according to a molar ratio (Li: TM ═ 1.03) and uniformly mixed with the dried precursor a.
Comparative example 2
This comparative example provides a nickel-based positive electrode material, which was the same as example 9 except that no mixed-aligned phase protective layer was formed on the surface of the core.
The preparation method of the nickel-based cathode material according to the comparative example is the same as that of example 9 except that step (b) is not performed, and after the solution containing the precursor a is filtered and dried in step (c), a certain amount of lithium hydroxide is weighed according to a molar ratio (Li: TM ═ 0.93:1) and uniformly mixed with the dried precursor a.
Comparative example 3
This comparative example provides a nickel-based positive electrode material in which the mixed-alignment phase protective layer is a solid solution of lithium, nickel, cobalt, and manganese doped with Pb (high valent metal ion), and the rest is the same as in example 1.
The method for producing a nickel-based positive electrode material according to the present comparative example, except for the high-valence metal ion source provided in step (b): the same procedure was followed as in example 1 except that the lead acetate solution was used in a concentration of 0.03M.
Experimental example 1
In order to verify the influence of the doped high-valence metal ions on the nickel-based positive electrode material, taking example 1 and comparative example 1 as an example, XRD test, SEM electron microscope scanning and electrochemical performance test are performed on the nickel-based positive electrode materials provided in example 1 and comparative example 1, as shown in fig. 1 to 6.
As can be seen from FIG. 1, the doped high valence metal ion Zr ion does not generate obvious impurities to the nickel-based positive electrode material, and the Zr ion enters the inside of the crystal lattice. As can be seen from FIGS. 2 and 3, the doped high valence metal ion Zr ion does not affect the morphology of the nickel-based positive electrode material.
Fig. 4 and 5 are electron microscope images of the surface microstructure diagrams of the nickel-based positive electrode materials provided in comparative example 1 and example 1, respectively, and it can be seen from fig. 4 that a mixed-arrangement phase of 1-2nm exists on the surface of the nickel-based positive electrode material provided in comparative example 1, and the inside is a layered structure, and it can be seen from fig. 5 that the structure of the protective layer of the epitaxial mixed-arrangement phase on the surface of the nickel-based positive electrode material provided in example 1, the inside is a layered structure, and the thickness of the mixed-arrangement phase is about 5 nm.
Fig. 6 is a graph showing electrochemical cycle performance of nickel-based positive electrode materials provided in example 1 of the present invention and comparative example 1. As can be seen from the figure, the nickel-based positive electrode material provided in example 1 of the present invention exhibits more excellent cycle stability. Specifically, the retention rate of the nickel-based positive electrode material provided by the comparative example 1 after 100 cycles of 2.8-4.5V and 2C cycles is 85.84%, and the cycle retention rate of the nickel-based positive electrode material provided by the example 1 under the same conditions is as high as 93.22%.
Experimental example 2
The nickel-based positive electrode materials prepared in the examples and the comparative examples and the acetylene black were made into slurry with a PVDF solution in NMP, and then coated on an aluminum foil and dried to obtain a positive electrode sheet. Using lithium metal as the negative electrode and 1M LiPF6(EC/DEC/DMC, volume ratio 1: 1: 1) as electrolyte, and using commercial polyolefin diaphragm to make button cell, and making electrochemical performance test under 2.8V-4.5V voltage window.
TABLE 1 electrochemical Properties of lithium ion batteries corresponding to the examples and comparative examples
As can be seen from the data in table 1, the electrochemical performance of the lithium ion battery according to the embodiment of the present invention is better than that of the lithium ion battery according to the comparative example as a whole.
Specifically, examples 2 and 3 are the control experiments of example 1, and the difference therebetween is that the thickness of the hybrid alignment phase protection layer is different. It can be seen from the data in the table that the 2C discharge capacity is gradually decreased with the increase of the thickness of the mixed-alignment phase protection layer, and when the thickness of the mixed-alignment phase protection layer exceeds a certain value, the capacity loss is relatively severe, and it can be seen that the thickness of the mixed-alignment phase protection layer should be controlled within a proper range.
Examples 4 and 5 are comparative experiments to example 1, and are different in that the mass fraction of the high-valence metal ions Zr ions in the nickel-based positive electrode material is different. As can be seen from the data in table 1, the amount of the high-valence metal ions directly affects the 2C cycle retention rate and the discharge capacity.
It is noted that the content of nickel in the nickel-based positive electrode material core affects the level of discharge capacity, and the discharge capacity is relatively lower as the content of nickel is lower, as can be seen from example 9 and example 1.
Comparative examples 1 and 2 are comparative experiments to examples 1 and 9. The misclassified phase protective layer was not formed on the surface of the core of comparative example 1 and comparative example 2. As can be seen from the data in table 1, the introduction of the hybrid-aligned phase protective layer mainly improves the cycle retention rate, the discharge capacity in this process generally decreases slightly, which is difficult to avoid, and the degree of the hybrid-aligned phase protective layer to the cycle retention rate (cycle stability) is significantly higher than the reduction of the discharge capacity, so that it is of certain industrial value to replace the reduction of the discharge capacity by a small reduction of the discharge capacity.
Comparative example 3 is a comparative experiment of example 1, which is different in the kind of the high-valence metal ions doped in the mixed phase protective layer. As can be seen from the data in the table, the selection of the high valence metal ion species is not arbitrary, and the selection should be performed in the specific metal ion species to achieve good technical effect.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. The preparation method of the nickel-based cathode material is characterized in that the nickel-based cathode material comprises an inner core and a mixed-phase protective layer formed on at least one part of the surface of the inner core;
the chemical composition general formula of the inner core is Li1+aNixMyO2+zWherein a, x, y, z satisfy the following relationships: -0.1 < a < 0.1, 0.5 < x < 0.9, x + y =1, -0.1 < z < 0.1, M comprising Al and/or Mn elements; the inner core has an R-3m space group layered structure;
the mixed-arranged phase protection layer comprises a solid solution formed by Li, Ni and M, and high-valence metal ions are doped in the solid solution and comprise any one or the combination of at least two of Zr, V, Mo, W or Sn ions; the mixed-arrangement phase protection layer has an Fm-3m space group mixed-arrangement structure;
an oxygen atom close-packed structure with consistent orientation is arranged between the inner core and the mixed-phase protective layer; the thickness of the mixed-phase protective layer is 2-30 nm; d50 of the nickel-based positive electrode material is 2-20 mu m;
the preparation method of the nickel-based cathode material comprises the following steps:
(a) mixing a mixed solution formed by a Ni source and an M source with a first precipitator and a first complexing agent to carry out coprecipitation reaction, wherein the temperature of the coprecipitation reaction is 40-80 ℃, and the pH value is 7.5-11 to obtain a solution containing a precursor A; the M source comprises an Al source and/or an Mn source;
(b) adding a high-valence metal ion source, a Ni source, an M source, a second precipitator and a second complexing agent into the solution containing the precursor A to perform a coprecipitation reaction, wherein the temperature of the coprecipitation reaction is 40-80 ℃, and the pH value of the coprecipitation reaction is 7.5-11, so that a precursor B is formed on at least one part of the surface of the precursor A, and the solution containing the precursor C is obtained; the high-valence metal ion source comprises any one of a Zr source, a V source, a Mo source, a W source or a Sn source or a combination of at least two of the Zr source, the V source, the Mo source, the W source and the Sn source; the mass of the high-valence metal ions accounts for 0.01-5% of the mass of the nickel-based positive electrode material;
(c) separating the solution containing the precursor C, mixing the obtained precursor C with a Li source, and calcining to obtain the nickel-based positive electrode material; the calcination temperature is 700-900 ℃, the calcination time is 5-25h, and the calcination atmosphere is oxygen atmosphere or air atmosphere.
2. The method for producing a nickel-based positive electrode material according to claim 1, wherein the high-valence metal ions are Zr ions.
3. The method for preparing a nickel-based positive electrode material according to claim 1, wherein the first and second precipitants are each independently any one of sodium carbonate, sodium bicarbonate, or sodium hydroxide;
and/or the first complexing agent and the second complexing agent are respectively and independently ammonia water or ammonium salt.
4. A positive electrode for a lithium ion battery, comprising the nickel-based positive electrode material obtained by the method for producing a nickel-based positive electrode material according to any one of claims 1 to 3.
5. A lithium ion battery comprising the positive electrode for a lithium ion battery according to claim 4.
6. Use of the lithium ion battery of claim 5 in an electronic device, a power tool, an electric vehicle, or a power storage system.
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