CN114122379B - Positive electrode material, preparation method and application thereof - Google Patents

Positive electrode material, preparation method and application thereof Download PDF

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Publication number
CN114122379B
CN114122379B CN202111319925.9A CN202111319925A CN114122379B CN 114122379 B CN114122379 B CN 114122379B CN 202111319925 A CN202111319925 A CN 202111319925A CN 114122379 B CN114122379 B CN 114122379B
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positive electrode
electrode material
coating layer
sintering
cobalt
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CN114122379A (en
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莫方杰
朱呈岭
李岚
杨元婴
杨文龙
孙化雨
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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Abstract

The invention provides a positive electrode material, a preparation method and application thereof, wherein the positive electrode material comprises a positive electrode material inner core, a first coating layer coated on the surface of the positive electrode material inner core and a second coating layer coated on the surface of the first coating layer, the first coating layer comprises a first cobalt compound, and the second coating layer comprises a second cobalt compound. According to the invention, the first coating layer and the second coating layer are respectively coated on the surface of the inner core of the positive electrode material, and the cobalt compound is contained in each of the first coating layer and the second coating layer, so that the ion and electron conductivity of the surface of the material can be effectively improved, and the internal resistance of the battery is reduced; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, and the prepared battery has low direct current resistance and high capacity retention rate and also has good electrochemical performance at low temperature.

Description

Positive electrode material, preparation method and application thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a positive electrode material and a preparation method and application thereof.
Background
With the growth of energy demand and the exhaustion of fossil fuels, energy crisis is becoming a global issue. In order to solve the problem of exhaustion of the conventional energy, researchers have begun to develop green, sustainable energy sources, where lithium ion batteries exhibit great advantages in applications. Ternary layered material LiNi x Co y Mn 1-x-y O 2 The (y is less than 0.13) has large capacity and low cost, is a battery positive electrode material with excellent performance, and is widely applied to lithium ion batteries. However, the electrode material is contacted with electrolyte in the charge and discharge process of the low-cobalt ternary layered material, so that the dissolution of active substances can be caused, the surface structure of the material is collapsed, and the electrochemical performance of the battery is affected.
The current common way to improve the electrochemical performance of the positive electrode material is to coat the surface of the material. One prior art scheme uses Al 2 O 3 The coating is coated on the surface of the anode material, so that the contact between the electrode material and electrolyte is isolated, and the stability of the material in the electrochemical circulation process can be improved. In another prior art scheme, the carbon source and the precursor are subjected to operations such as freeze drying and sintering, so that the carbon is coated in the active material and on the surface of the active material, and the high-voltage stability of the electrode material is improved. In addition, a gas phase cladding mode is used in the technical scheme, a compact cladding layer is formed on the surface of the ternary positive electrode material, so that the contact between the ternary positive electrode material and electrolyte is reduced, and the cycle performance of the ternary positive electrode material is improved.
However, in the prior art, the coating layer has poor conductive effect, the interface structure is unstable when the coating layer is coated in multiple layers, and the material has lower ionic and electronic conductivity, is not beneficial to the diffusion of lithium ions, and limits the further development of the lithium ion battery.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a positive electrode material, and a preparation method and application thereof. According to the invention, the first coating layer and the second coating layer are respectively coated on the surface of the inner core of the positive electrode material, and the cobalt compound is contained in each of the first coating layer and the second coating layer, so that the ion and electron conductivity of the surface of the material can be effectively improved, and the internal resistance of the battery is reduced; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, and the prepared battery has low direct current resistance and high capacity retention rate and also has good electrochemical performance at low temperature.
As used herein, "low temperature" means a temperature below-20 ℃.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a positive electrode material, which comprises a positive electrode material core, a first coating layer coated on the surface of the positive electrode material core, and a second coating layer coated on the surface of the first coating layer, wherein the first coating layer comprises a first cobalt compound, and the second coating layer comprises a second cobalt compound.
According to the invention, the surface of the inner core of the positive electrode material is sequentially coated with the first coating layer and the second coating layer from inside to outside, the first coating layer and the second coating layer both comprise cobalt compounds, the cobalt compounds have strong conductivity and stable structure, the coating effect on the surface of the inner core of the positive electrode material is good, the direct current resistance of the material can be reduced, the stability of the material is improved, and the electrochemical performance of the material at low temperature is improved; meanwhile, compared with single-layer coating, the double-layer coating has higher stability, is more resistant to strain in long circulation, and because the first coating layer and the second coating layer both contain cobalt compounds, the first coating layer and the second coating layer have good combination effect, and the interface structure is stable, so that the ionic conductivity and the electronic conductivity of the surface of the material can be effectively improved, and the conductivity and the stability of the material are further improved.
Preferably, the ratio of the mass of the positive electrode material core to the total mass of the first and second coating layers in the positive electrode material is (100-p) p, wherein p is 0.005 to 2, and may be, for example, 0.005, 0.006, 0.008, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 0.8, 1, 1.5, or 2, etc.
Preferably, the mass ratio of the first coating layer to the second coating layer is q (100-q), wherein q is 7 to 26, for example, 7, 8, 9, 10, 12, 15, 18, 20, 22, 24 or 26, etc., preferably 21 to 23.
Preferably, the first cladding layer and the second cladding layer each comprise cobalt oxide.
As a further preferable technical scheme of the positive electrode material of the present invention, the first coating layer is distributed on the surface of the positive electrode material core in a planar manner. The first coating layer is distributed in a planar manner, so that the surface of the positive electrode material is protected, and the continuous side reaction of the positive electrode material and the electrolyte is restrained.
Preferably, the crystal form of the first cobalt compound is an amorphous form.
Preferably, the second coating layer is distributed on the surface of the first coating layer in a dot shape. The second coating layers are distributed in a dot shape, so that the conductivity of the material surface is improved, and the dynamic performance is further improved.
Preferably, the crystal form of the second cobalt compound is in a crystalline state.
In the invention, the first coating layer is preferably distributed in a planar mode, the second coating layer is preferably distributed in a dot mode, the second coating layer can be uniformly dispersed on the first coating layer, and a three-dimensional coating structure is constructed by cooperation with the first coating layer, so that the interface bonding effect is good, the material structure is stable, the diffusion of lithium ions and the conduction efficiency of electrons are high, the direct current resistance of the material is reduced, and the capacity retention rate of the material is improved.
Preferably, the chemical composition of the positive electrode material core is LiNi x Co y Mn 1-x-y O 2 Wherein 0.5.ltoreq.x.ltoreq.0.9, 0.ltoreq.y.ltoreq.0.13, wherein x may be, for example, 0.5, 0.6, 0.7, 0.8, 0.9 or the like; y may be, for example, 0, 0.01, 0.03, 0.05, 0.08, 0.1, 0.12, 0.13, or the like.
Preferably, the positive electrode material core is a secondary sphere.
Preferably, the positive electrode material core is a single crystal material.
Preferably, the positive electrode material core is secondarily spherical, and the particle diameter D50 of the positive electrode material core is 9 μm to 25 μm, and may be, for example, 9 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 25 μm, or the like.
Preferably, the positive electrode material core is a single crystal material, and the particle diameter D50 of the positive electrode material core is 2 μm to 6 μm, and may be, for example, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 5 μm, or 6 μm, or the like.
In a second aspect, the present invention provides a method for preparing the positive electrode material according to the first aspect, the method comprising:
mixing the inner core of the anode material with a first cobalt source, and performing first sintering; and
and mixing the product after the first sintering with a second cobalt source, and performing second sintering to obtain the anode material.
According to the invention, through two-step sintering, the first coating layer and the second coating layer are respectively coated on the surface of the inner core of the positive electrode material, so that the combination property of the coating layer and the inner core of the positive electrode material can be improved, and the stability and the conductivity of the positive electrode material are enhanced.
Preferably, the ratio of the total mass of the first and second cobalt sources to the mass of the positive electrode material core is m (100-m), where m is 0.01 to 2, for example may be 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 0.8, 1, 1.1, 1.2, 1.5, 1.8 or 2, etc., preferably 1.4 to 1.6.
Preferably, the mass ratio of the first cobalt source to the second cobalt source is n (100-n), wherein n is 10 to 30, for example, 10, 11, 12, 15, 20, 22, 25, 28 or 30, etc., preferably 24 to 26.
As a further preferred embodiment of the preparation method according to the present invention, the first cobalt source comprises CoOOH, coCO 3 、Co(NO 3 ) 2 And Co (NO) 3 ) 4 Any one or a combination of at least two of these, for example CoOOH and CoCO 3 Co (NO) 3 ) 2 And Co (NO) 3 ) 4 Is a combination of (C) and (C) CoCO 3 And Co (NO) 3 ) 2 Or CoOOH, cooo 3 And Co (NO) 3 ) 2 And the like, coOOH is preferred.
Preferably, the second cobalt source comprises CoF 2 、CoF 3 、CoO、CoO 2 、Co 3 O 4 、CoN、Co 2 N、CoH、Co 3 H and Co 3 (BO 3 ) 2 Any one or a combination of at least two of them, for example, may be CoF 2 And CoF 3 Co 3 H and Co 3 (BO 3 ) 2 Co 3 O 4 And CoF 3 And CoO, or CoF 2 、Co 3 H and Co 3 (BO 3 ) 2 Preferably CoN and/or Co 2 N is more preferably CoN.
The cobalt source selected in the invention has different activity and structure, and the prepared cobalt compound has different crystal forms. The first cobalt source is preferably a cobalt source with higher activity, which is favorable for generating a first cobalt compound with an amorphous state, and the second cobalt source is preferably a cobalt source with lower activity, which is favorable for generating a second cobalt compound with a crystalline state; meanwhile, the two cobalt sources have different melting points, the first cobalt source has a lower melting point, the second cobalt source has a higher melting point, and the cobalt sources can be distributed on the surface of the positive electrode material in different modes by matching with different sintering temperatures. The cobalt compounds with two different crystal forms and distribution modes are mutually matched to jointly construct a three-dimensional structure, so that the combination effect between the first cobalt compound and the second cobalt compound can be improved, the interface performance between the first coating layer and the second coating layer is further improved, and the conductivity and the capacity retention rate of the anode material are improved.
Preferably, the temperature of the first sintering is 700 ℃ to 900 ℃, for example, 700 ℃, 730 ℃, 750 ℃, 780 ℃, 800 ℃, 830 ℃, 850 ℃, 900 ℃, or the like, preferably 750 ℃ to 850 ℃.
Preferably, the time of the first sintering is 12h to 30h, for example, 12, 14h, 15h, 18h, 20h, 22h, 25, 28h or 30h, etc., preferably 15h to 25h.
Preferably, the temperature of the second sintering is 600 ℃ to 700 ℃, for example, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, or the like, preferably 650 ℃ to 690 ℃.
Preferably, the second sintering time is 6h to 12h, for example, 6, 7h, 8h, 9h, 10h, 11h or 12h, etc., preferably 8h to 10h.
In the invention, the preferred temperatures of the first sintering and the second sintering are different, and the first coating layer and the second coating layer with different forms are formed by matching different cobalt sources. The first sintering is preferably carried out at a relatively high temperature of 700-900 ℃, which is favorable for forming a first cobalt source on the surface of the inner core of the positive electrode material to form a first coating layer in a planar distribution; the second sintering is preferably carried out at a relatively low temperature of 600-700 ℃, which is favorable for forming second coating layers distributed in a punctiform manner on the surface of the first coating layer by the second cobalt source, so that the second coating layers can be uniformly dispersed on the first coating layer, a three-dimensional structure constructed by the punctiform coating layers and the planar coating layers is presented, the interface bonding effect is improved, the structural stability of the positive electrode material is improved, the direct current resistance of the positive electrode material is further reduced, and the capacity retention rate of the positive electrode material is improved.
As a further preferable technical scheme of the preparation method of the present invention, mixing the positive electrode material core and the first cobalt source to perform the first sintering includes: mixing the positive electrode material core and CoOOH, and sintering at 700-900 ℃ for 12-30 hours;
mixing the first sintered product with a second cobalt source for second sintering to obtain the positive electrode material comprises the following steps: mixing the sintered product with CoN, and sintering at 600-700 ℃ for 6-12 h to obtain the positive electrode material.
In a third aspect, the present invention provides a positive electrode sheet comprising the positive electrode material according to the first aspect.
Preferably, the positive electrode sheet further comprises conductive carbon black, carbon nanotubes and a binder, wherein the mass ratio of the positive electrode material, the conductive carbon black, the carbon nanotubes and the binder in the positive electrode sheet is (90 to 99) 1:0.5:1, for example, 90:1:0.5:1, 91:1:0.5:1, 92:1:0.5:1, 93:1:0.5:1, 94:1:0.5:1, 95:1:0.5:1, 96:1:0.5:1, 97:1:0.5:1, 98:1:0.5:1 or 99:1:0.5:1, etc.).
In a fourth aspect, the present invention provides a lithium ion battery, which includes the positive electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the first coating layer and the second coating layer are respectively coated on the surface of the inner core of the positive electrode material, and the cobalt compound is contained in the first coating layer and the second coating layer, so that the ion and electron conductivity of the surface of the material can be effectively improved, and the internal resistance of the battery is reduced; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, and the prepared battery has low direct current resistance and high capacity retention rate and also has good electrochemical performance at low temperature.
(2) The invention preferably adopts cobalt sources with different activities and different sintering temperatures to prepare the positive electrode material, can regulate and control the forms and crystal forms of the first coating layer and the second coating layer, improves the interface bonding effect, improves the structural stability of the positive electrode material, further reduces the direct current resistance of the positive electrode material, and improves the capacity retention rate of the positive electrode material.
Drawings
FIG. 1 is a DC resistance diagram at 25℃for example 1 and comparative example 1.
FIG. 2 is a graph showing the DC resistance at-20℃of example 1 and comparative example 1.
FIG. 3 is a graph showing the capacity retention at-20℃for example 1 and comparative example 1.
Detailed Description
In the prior art, the electrochemical performance of the anode material is improved through coating, but the conductive effect of the coating layer in the prior art is poor, the interface structure is unstable during multi-layer coating, the material has lower ionic and electronic conductivity, the diffusion of lithium ions is not facilitated, and the further development of the lithium ion battery is limited.
In order to at least solve the problems, the invention provides a positive electrode material, a preparation method and application thereof.
The embodiment part of the invention provides a positive electrode material, which comprises a positive electrode material inner core, a first coating layer coated on the surface of the positive electrode material inner core and a second coating layer coated on the surface of the first coating layer, wherein the first coating layer comprises a first cobalt compound, and the second coating layer comprises a second cobalt compound.
According to the invention, the first coating layer and the second coating layer are respectively coated on the surface of the inner core of the positive electrode material, and the cobalt compound is contained in the first coating layer and the second coating layer, so that the ion and electron conductivity of the surface of the material can be effectively improved, and the internal resistance of the battery is reduced; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, and the prepared battery has low direct current resistance and high capacity retention rate and also has good electrochemical performance at low temperature.
In some embodiments, the ratio of the mass of the positive electrode material core to the total mass of the first and second cladding layers in the positive electrode material is (100-p): p, wherein p is 0.005 to 2.
In some embodiments, the mass ratio of the first cladding layer to the second cladding layer is q (100-q), wherein q is 7 to 26, preferably 21 to 23.
In some embodiments, the first cladding layer and the second cladding layer each comprise cobalt oxide.
In some embodiments, the first coating layer is distributed in a planar shape on the surface of the positive electrode material core.
In some embodiments, the crystalline form of the first cobalt compound is an amorphous form.
In some embodiments, the second cladding layer is distributed in a dot pattern on the surface of the first cladding layer.
In some embodiments, the crystalline form of the second cobalt compound is crystalline.
In some embodiments, the chemical composition of the positive electrode material core is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13.
In some embodiments, the positive electrode material core is a secondary sphere.
In some embodiments, the positive electrode material core is a single crystal material.
In some embodiments, the positive electrode material core is secondarily spherical and the positive electrode material core has a particle size D50 of 9 μm to 25 μm.
In some embodiments, the positive electrode material core is a single crystal material, and the positive electrode material core has a particle size D50 of 2 μm to 6 μm.
Yet another embodiment provides a method for preparing the positive electrode material, the method comprising:
mixing the inner core of the anode material with a first cobalt source, and performing first sintering; and
and mixing the product after the first sintering with a second cobalt source, and performing second sintering to obtain the anode material.
In some embodiments, the ratio of the total mass of the first and second cobalt sources to the mass of the positive electrode material core is m (100-m), where m is 0.01 to 2, preferably 1.4 to 1.6.
In some embodiments, the mass ratio of the first cobalt source to the second cobalt source is n (100-n), where n is 10 to 30, preferably 24 to 26.
In some embodiments, the first cobalt source comprises CoOOH, cocoo 3 、Co(NO 3 ) 2 And Co (NO) 3 ) 4 Any one or a combination of at least two of these, preferably CoOOH.
In some embodiments, the second cobalt source comprises CoF 2 、CoF 3 、CoO、CoO 2 、Co 3 O 4 、CoN、Co 2 N、CoH、Co 3 H and Co 3 (BO 3 ) 2 Any one or a combination of at least two, preferably CoN and/or Co 2 N is more preferably CoN.
In some embodiments, the temperature of the first sintering is 700 ℃ to 900 ℃, preferably 750 ℃ to 850 ℃.
In some embodiments, the first sintering time is 12h to 30h, preferably 15h to 25h.
In some embodiments, the temperature of the second sintering is 600 ℃ to 700 ℃, preferably 650 ℃ to 690 ℃.
In some embodiments, the second sintering is for a time of 6h to 12h, preferably 8h to 10h.
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present embodiment provides a positive electrode material including single crystal LiNi 0.53 Co 0.11 Mn 0.36 O 2 The inner core is coated on the single crystal LiNi in a planar form 0.53 Co 0.11 Mn 0.36 O 2 The lithium ion battery comprises a first coating layer and a second coating layer, wherein the first coating layer is coated on the surface of the first coating layer in a punctiform form, the first coating layer comprises amorphous cobalt oxide, the second coating layer comprises crystalline cobalt oxide, the ratio of the mass of a positive electrode material core in the positive electrode material to the total mass of the first coating layer and the second coating layer is 98.54:1.46, and the mass ratio of the first coating layer to the second coating layer is 21:79.
The embodiment also provides a preparation method of the positive electrode material, which comprises the following steps:
(1) CoOOH and single crystal LiNi 0.53 Co 0.11 Mn 0.36 O 2 Mixing the inner cores, and sintering at 800 ℃ for 20 hours;
(2) And (3) mixing the sintered product in the step (1) with CoN, and sintering at 650 ℃ for 20 hours to obtain the positive electrode material.
Wherein the mass ratio of CoOOH in step (1) to CoN in step (2) is 25:75, and the total mass of CoOOH and CoN is compared with single crystal LiNi 0.53 Co 0.11 Mn 0.36 O 2 Ratio of mass of cores1.5:98.5.
Example 2
The present embodiment provides a positive electrode material including a secondary spherical LiNi 0.53 Co 0.11 Mn 0.36 O 2 The inner core is coated on the secondary spherical LiNi in a planar shape 0.53 Co 0.11 Mn 0.36 O 2 The lithium ion battery comprises a first coating layer and a second coating layer, wherein the first coating layer is coated on the surface of the first coating layer in a punctiform form, the first coating layer comprises amorphous cobalt oxide, the second coating layer comprises crystalline cobalt oxide, the mass ratio of a positive electrode material core in the positive electrode material to the total mass of the first coating layer and the second coating layer is 99.25:0.75, and the mass ratio of the first coating layer to the second coating layer is 12.6:87.4.
The embodiment also provides a preparation method of the positive electrode material, which comprises the following steps:
(1) CoCO is to 3 And a secondary spherical LiNi 0.53 Co 0.11 Mn 0.36 O 2 Mixing the inner cores, and sintering at 750 ℃ for 25 hours;
(2) Mixing the sintered product obtained in the step (1) with CoF 2 Mixing, and sintering at 700 ℃ for 7 hours to obtain the positive electrode material;
wherein in step (1) CoCO 3 And CoF in step (2) 2 Is 15:85, coCO 3 And CoF 2 Is the total mass of (2) and the secondary spherical LiNi 0.53 Co 0.11 Mn 0.36 O 2 The mass ratio of the cores was 1:99.
Example 3
The present embodiment provides a positive electrode material including single crystal LiNi 0.53 Co 0.11 Mn 0.36 O 2 The inner core is coated on the single crystal LiNi in a planar form 0.53 Co 0.11 Mn 0.36 O 2 A first coating layer on the surface of the inner core and a second coating layer coated on the surface of the first coating layer in a punctiform form, wherein the first coating layer comprises amorphous cobalt oxide, and the second coating layer comprises crystalline cobalt oxide, and the inner core of the positive electrode material in the positive electrode materialThe ratio of the mass to the total mass of the first coating layer and the second coating layer was 98.34:1.66, and the mass ratio of the first coating layer to the second coating layer was 15:85.
The embodiment also provides a preparation method of the positive electrode material, which comprises the following steps:
(1) Co (NO) 3 ) 2 And single crystal LiNi 0.53 Co 0.11 Mn 0.36 O 2 Mixing the inner cores, and sintering at 850 ℃ for 15 hours;
(2) And (3) mixing the sintered product in the step (1) with CoO, and sintering at 600 ℃ for 10 hours to obtain the positive electrode material.
Wherein Co (NO) in step (1) 3 ) 2 And the mass ratio of CoO in the step (2) is 30:70, co (NO 3 ) 2 And the total mass of CoO and single crystal LiNi 0.53 Co 0.11 Mn 0.36 O 2 The mass ratio of the cores was 2:98.
Example 4
The procedure of example 1 was followed except that CoOOH was replaced with CoN in step (1) so that the first clad layer comprised crystalline cobalt oxide.
Example 5
The procedure of example 1 was repeated except that CoN in the step (2) was replaced with CoOOH so that the second coating layer comprised cobalt oxide in an amorphous state.
Example 6
Except that CoOOH was replaced with Co (NO) in step (1) 3 ) 2 Except for this, the procedure was the same as in example 1.
Example 7
The procedure of example 1 was repeated except that CoN in step (2) was replaced with CoO.
Example 8
Except that the sintering temperature in the step (1) is replaced by 280 ℃ so that the first coating layer is coated on the single crystal LiNi in a punctiform form 0.53 Co 0.11 Mn 0.36 O 2 The remainder of the core surface was the same as in example 1.
Example 9
The procedure of example 1 was repeated except that the sintering temperature in step (2) was changed to 750℃to coat the second coating layer on the surface of the first coating layer in a planar form.
Example 10
The procedure of example 1 was repeated except that the mass ratio of CoOOH in step (1) to CoN in step (2) was 35:65.
Example 11
The procedure of example 1 was followed except that the mass ratio of CoOOH in step (1) to CoN in step (2) was 8:92.
Comparative example 1
Removal of single crystal LiNi 0.53 Co 0.11 Mn 0.36 O 2 The inner core surface was free of coating layers, and the rest was the same as in example 1.
Comparative example 2
Except for the operation not in step (1), i.e. single crystal LiNi 0.53 Co 0.11 Mn 0.36 O 2 The inner core surface was free of the first cladding layer, and the rest was the same as in example 1.
Comparative example 3
Except for the operation not carried out in step (2), i.e. single crystal LiNi 0.53 Co 0.11 Mn 0.36 O 2 The core surface was the same as in example 1 except that the second cladding layer was not present.
Comparative example 4
Except that CoOOH in step (1) is replaced with Ni (NO) 3 ) 2 Except for this, the procedure was the same as in example 1.
The positive electrode materials prepared in examples 1 to 11 and comparative examples 1 to 4 were used to prepare 1Ah soft pack batteries, and the preparation method comprises the following steps:
conducting carbon black, carbon nano-tubes, NMP and polyvinylidene fluoride are dispersed and stirred for 2 hours at a mass ratio of 1:0.5:40:1 at high speed to prepare conducting slurry, then the anode materials prepared in examples 1-11 and comparative examples 1-4 are stirred and mixed with the conducting slurry at high speed to prepare anode slurry with certain viscosity, the mass ratio of the anode materials, the conducting carbon black, the carbon nano-tubes, the NMP and the polyvinylidene fluoride in the anode slurry is 97.5:1:0.5:40:1, the anode slurry is uniformly coated on aluminum foil by utilizing a scraper, and the aluminum foil is placed in a blast drying box, and the anode slurry is prepared in the following mannerDrying at 120 ℃ for 20min to obtain a positive plate; rolling and cutting the positive plate, taking graphite as a negative electrode, and LiPF 6 And (3) using the ester-based solution as electrolyte, and assembling the 1Ah soft package battery.
1. DC resistance test
After the formation and aging process of the 1Ah soft pack battery containing the positive electrode materials of examples 1 to 11 and comparative examples 1 to 4, the battery was charged to 4.3V at a rate of 0.33C and discharged to 2.8V at room temperature to obtain a capacity C 0 Then, after the state of charge (SOC) of the battery is adjusted to 70% SOC, the battery is discharged at 4C rate for 30s, and the voltage difference before and after the discharge divided by the current density is the dc resistance value of the battery at the SOC. The DC resistance values of 50% SOC and 20% SOC were measured by this method, and the test results are shown in Table 1.
Similarly, the 1Ah soft pack batteries containing the positive electrode sheets of examples 1 to 11 and comparative examples 1 to 4 were placed in a constant temperature oven at-20 ℃ to test the direct current resistance values of the batteries at-20 ℃ and the test results are shown in table 1.
2. Capacity retention side measure
Placing the 1Ah soft package battery subjected to direct current resistance test in a constant temperature oven at-20 ℃, charging and discharging twice in a voltage window of 2.8V to 4.3V at a rate of 0.33C, and recording the discharge capacity C of the second time 1 ，C 1 /C 0 Namely, the capacity retention rate of the battery at a low temperature of-20 ℃ is shown in table 1.
TABLE 1
As can be seen from the above embodiments 1 to 11, according to the present invention, the first coating layer and the second coating layer are respectively coated on the inner core surface of the positive electrode material, and the first coating layer and the second coating layer each include a cobalt compound, so that the ionic conductivity and the electronic conductivity of the material surface can be effectively improved, thereby reducing the internal resistance of the battery; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, and the prepared battery has low direct current resistance and high capacity retention rate and also has good electrochemical performance at low temperature.
As is clear from comparison of example 1 with examples 4 to 5, the crystal forms of the cobalt compounds in the first and second coating layers in the positive electrode material affect the performance of the prepared battery. In the embodiment 4 and the embodiment 5, the same cobalt source is used for sintering, and the surface of the inner core of the positive electrode material is coated with the coating layer with the same crystal form, so that cobalt oxide in the second coating layer cannot be uniformly dispersed on cobalt oxide of the first coating layer, a stable three-dimensional structure between the first coating layer and the second coating layer is influenced, the interface effect is poor, and further the conductivity and the stability of the positive electrode material are influenced, so that the conductivity and the capacity retention rate of the embodiment 4 and the embodiment 5 at 25 ℃ and-20 ℃ are slightly lower than those of the embodiment 1; meanwhile, both the first cobalt source and the second cobalt source are preferable, and as can be seen from comparison of examples 1 and examples 6 to 7, the first cobalt source uses CoOOH, and the second cobalt source uses CoN, the effect is the best.
As can be seen from a comparison of example 1 with examples 8 to 9, the morphology of the coating layer affects the performance of the prepared cathode material. The temperatures of the sintering in step (1) and the sintering in step (2) were changed in examples 8 and 9, respectively, so that the first clad layer and the second clad layer had the same clad morphology; when the first coating layer and the second coating layer are both planar or both dot-shaped, the three-dimensional structure is difficult to form, which affects the interface bonding effect and thus the direct current resistance and capacity retention rate of the positive electrode material, so that the direct current resistances of examples 8 to 9 at different temperatures are slightly higher than example 1 and the capacity retention rate is slightly lower than example 1.
As is evident from the comparison between the examples 1 and 10 to 11, the second cobalt source of the first cobalt source had the most suitable feed ratio, and the improvement effect of the low-temperature direct current resistance and the capacity retention was not obvious when the content of the first cobalt source was too large or too small.
As is apparent from comparison of examples 1 and comparative examples 1 to 3, when only one coating layer is included in the positive electrode material and even no coating layer is included, the ionic and electronic conductivities of the surfaces of the materials cannot be effectively improved, fig. 1 is a direct current resistance diagram at 25 c of the soft-packed batteries including the positive electrode materials of example 1 and comparative example 1, fig. 2 is a direct current resistance diagram at-20 c of the soft-packed batteries including the positive electrode materials of example 1 and comparative example 1, and fig. 3 is a capacity retention diagram at-20 c of the soft-packed batteries including the positive electrode materials of example 1 and comparative example 1, and it is apparent from fig. 1 to 3 that the direct current resistances at different temperatures of the batteries manufactured without the coating layer are high, the capacity retention is poor, and the conductivities and the capacity retention are poor even though the coating layer distribution states and crystal forms are different in the soft-packed batteries of comparative example 2 and comparative example 3.
As can be seen from a comparison of example 1 and comparative example 4, the choice of the coating layer affects the performance of the positive electrode material. The coating layer in comparative example 4 contains cobalt oxide and nickel oxide, wherein the nickel oxide has poor conductivity, and unlike the melting point of cobalt oxide, has poor interface bonding effect during sintering, is susceptible to chemical distortion during charge and discharge cycles, and affects interface structural stability, so that both conductivity and capacity retention rate of comparative example 4 are inferior to those of example 1.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (29)

1. The positive electrode material is characterized by comprising a positive electrode material inner core, a first coating layer coated on the surface of the positive electrode material inner core and a second coating layer coated on the surface of the first coating layer, wherein the first coating layer comprises a first cobalt compound, and the second coating layer comprises a second cobalt compound;
the first coating layers are distributed on the surface of the positive electrode material inner core in a planar manner, and the second coating layers are distributed on the surface of the first coating layers in a dot manner;
the first cladding layer and the second cladding layer each comprise cobalt oxide.
2. The positive electrode material according to claim 1, wherein a ratio of a mass of the positive electrode material core to a total mass of the first coating layer and the second coating layer in the positive electrode material is (100-p): p, wherein p is 0.005 to 2.
3. The positive electrode material according to claim 1, wherein a mass ratio of the first coating layer to the second coating layer is q (100-q), wherein q is 7 to 26.
4. The positive electrode material according to claim 3, wherein q is 21 to 23.
5. The positive electrode material according to claim 1, wherein the crystal form of the first cobalt compound is an amorphous form.
6. The positive electrode material according to claim 1, wherein the crystal form of the second cobalt compound is a crystalline state.
7. The positive electrode material according to claim 1, wherein the positive electrode material core has a chemical composition of LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13.
8. The positive electrode material of claim 1, wherein the positive electrode material core is secondarily spherical.
9. The positive electrode material of claim 1, wherein the positive electrode material core is a single crystal material.
10. The positive electrode material according to claim 1, wherein the positive electrode material core is a secondary sphere, and the positive electrode material core has a particle diameter D50 of 9 μm to 25 μm.
11. The positive electrode material according to claim 1, wherein the positive electrode material core is a single crystal material, and the positive electrode material core has a particle diameter D50 of 2 μm to 6 μm.
12. A method for producing the positive electrode material according to any one of claims 1 to 11, characterized in that the method comprises:
mixing the inner core of the anode material with a first cobalt source, and performing first sintering; and
mixing the product after the first sintering with a second cobalt source, and performing second sintering to obtain the anode material;
wherein the first cobalt source comprises CoOOH and cooo 3 And Co (NO) 3 ) 2 Any one or a combination of at least two of the following;
the second cobalt source comprises CoF 2 、CoF 3 、CoO、CoO 2 、Co 3 O 4 、CoN、Co 2 N, coH and Co 3 (BO 3 ) 2 Any one or a combination of at least two of the following;
the temperature of the first sintering is 700 ℃ to 900 ℃;
the second sintering temperature is 600 ℃ to 700 ℃.
13. The method of claim 12, wherein the ratio of the total mass of the first and second cobalt sources to the mass of the core of positive electrode material is m (100-m), wherein m is 0.01 to 2.
14. The method of claim 13, wherein m is 1.4 to 1.6.
15. The method of claim 12, wherein the mass ratio of the first cobalt source to the second cobalt source is n (100-n), wherein n is 10 to 30.
16. The method of claim 15, wherein the mass ratio of the first cobalt source to the second cobalt source is 24 to 26.
17. The method of claim 16, wherein the first cobalt source is CoOOH.
18. The method of claim 17, wherein the second cobalt source is CoN and/or Co 2 N。
19. The method of claim 18, wherein the second cobalt source is CoN.
20. The method of claim 12, wherein the first sintering temperature is 750 ℃ to 850 ℃.
21. The method of claim 12, wherein the first sintering is for a period of time from 12h to 30h.
22. The method of claim 21, wherein the first sintering is for a time period of 15h to 25h.
23. The method of claim 12, wherein the second sintering temperature is 650 ℃ to 690 ℃.
24. The method of claim 12, wherein the second sintering is for a period of time ranging from 6h to 12h.
25. The method of claim 24, wherein the second sintering is performed for a period of 8h to 10h.
26. The method of preparing as recited in claim 12, wherein mixing the core of the positive electrode material with the first cobalt source for the first sintering comprises: mixing the positive electrode material core and CoOOH, and sintering at 700-900 ℃ for 12-30 hours;
mixing the first sintered product with a second cobalt source for second sintering to obtain the positive electrode material comprises the following steps: mixing the sintered product with CoN, and sintering at 600-700 ℃ for 6-12 h to obtain the positive electrode material.
27. A positive electrode sheet, characterized in that the positive electrode sheet includes therein the positive electrode material according to any one of claims 1 to 11.
28. The positive electrode sheet according to claim 27, further comprising conductive carbon black, carbon nanotubes and a binder, wherein the mass ratio of the positive electrode material, conductive carbon black, carbon nanotubes and binder in the positive electrode sheet is (90 to 99): 1:0.5:1.
29. A lithium ion battery comprising the positive electrode sheet according to claim 28.
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