CN111924886A - Lithium cobaltate cathode material with core-shell structure and preparation method thereof - Google Patents
Lithium cobaltate cathode material with core-shell structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a lithium cobaltate cathode material with a core-shell structure and a preparation method thereof. The chemical formula of the lithium cobaltate cathode material with the core-shell structure is as follows: (1-x) LiaCo(1‑b)M1bO1·xLicCo(1‑d)M2dO2Wherein LiaCo(1‑b)M1bO1Is a core, LicCo(1‑d)M2dO2Is a shell, M1 is a shell having +2And +3, and M2 is an element having a valence of +4, +5, + 6. The invention provides four methods for preparing the lithium cobaltate positive electrode material, and an interface does not appear between core shells, but a transition region with gradient distribution and co-doping of M1 and M2 is generated. The lithium cobaltate with the core-shell structure has good structural stability and safety performance as the positive electrode material of the lithium ion battery, does not hinder the desorption/insertion and diffusion of Li ions while protecting the surface of the lithium cobaltate, and has good safety performance under high voltage.
Description
Technical Field
The invention belongs to the field of lithium ion battery electrode active materials, and relates to a lithium cobaltate positive electrode material with a core-shell structure and a preparation method thereof.
Background
The lithium cobaltate cathode material with a layered structure is the most fully researched and widely applied cathode material of consumer lithium ion batteries at present. In recent years, lithium cobaltate has been used in a higher operating voltage to meet the demand for higher energy density, and charging has been shown in the marketThe voltage is higher than 4.45V. With the increase of the working voltage, more Li ions are extracted from the crystal lattice of lithium cobaltate, and more Co3+To higher valence Co4+The electrolyte in contact with the positive electrode material is more easily oxidized, with more Co elution and oxygen release, resulting in degradation of battery performance and even expansion and explosion. Therefore, the market also puts higher demands on the safety performance of lithium cobaltate. One solution is to design and prepare lithium cobaltate with a core-shell structure.
For example, granted patent (CN102394295B) of new energy limited of eastern guan suggests preparing a two-phase core-shell structure cathode material, where the core layer is a layered structure cathode material and the shell layer is a spinel structure lithium nickel manganese oxide. However, the cation species, ion occupation and lattice constant in the layered structure are different from those in the spinel structure, and a lattice distorted transition layer appears at the interface of two phases, and the transition layer can reduce the diffusion speed of Li ions in the transition layer and increase the interface resistance. In addition, a patent (CN108232127A) applied by the Ganjin Guli new material science and technology company Limited proposes to prepare lithium cobaltate with a core-shell structure with different doping elements, wherein the core is doped with an element A, and the shell is doped with an element X. Although the type and doping amount of A, X are limited, these two elements are independently selected, and no synergy of A, X is considered in this scheme.
Disclosure of Invention
The invention aims to provide a lithium cobaltate cathode material with a core-shell structure and a preparation method thereof, which can protect the surface of lithium cobaltate and simultaneously can not hinder the desorption/insertion and diffusion of Li ions, so that the lithium cobaltate cathode material has good safety performance at a voltage of 4.45V or even higher.
The chemical formula of the lithium cobaltate cathode material with the core-shell structure is as follows:
(1-x)LiaCo(1-b)M1bO1·xLicCo(1-d)M2dO2。
wherein LiaCo(1-b)M1bO1Is a core, LicCo(1-d)M2dO2Is a housing, 0<x≤0.5，0.98<a≤1.00，0<b<0.1，1.00≤c≤1.01，0<d<0.1, 1.90 is less than or equal to 1 and less than or equal to 2.10, and 1.90 is less than or equal to 2 and less than or equal to 2.10. Wherein M1 is an element having a valence of +2, +3, including at least one of Mg, Ca, Ni, Al, Ga, Sc, V, Cr, Mn, Fe, Y, La, Sm, Ce, and M2 is an element having a valence of +4, +5, +6, including at least one of Ti, Mn, Zr, Ce, Si, Ge, Sn, V, Nb, P, Cr, Mo, W. The average valence of the element at the transition metal site of the inner core (Co + M1) is therefore less than the average valence of the element at the transition metal site of the outer shell (Co + M2). The core of lithium cobaltate is doped with the low-valence element M1, so that the bond energy of a transition metal-oxygen bond can be increased, and the structural stability is improved; the shell of lithium cobaltate is doped with high-valence element M2, so that the bond energy of a transition metal-oxygen bond is increased, the structural stability is improved, the average valence state of the transition metal can be reduced, and the surface Co is reduced4+The content of Co is reduced, the Co elution amount is reduced, and the safety performance is improved.
In order to prepare the lithium cobaltate cathode material with the core-shell structure, the invention adopts the following four technical schemes:
the first method is to prepare lithium cobaltate with a core-shell structure by preparing a precursor with a core-shell structure, and the method is as follows:
(1) preparation of core Co of precursor by coprecipitation method(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2Then using the crystal nucleus as the precursor shell Co prepared by coprecipitation method(1-d)M2d(CO3)kOr Co(1-d)M2d(OH)nOr Co(1-d)M2dO(OH)n-2. Adding a proper amount of reducing agent in the precipitation process, and introducing nitrogen for protection.
(2) The final precipitation product Co in (1)(1-b)M1b(CO3)j·Co(1-d)M2d(CO3)kOr Co(1-b)M1b(OH)m·Co(1-d)M2d(OH)nOr Co(1-b)M1bO(OH)m-2·Co(1-d)M2dO(OH)n-2The mixture is calcined and then is added with the catalyst,obtaining a precursor [ Co ] with a core-shell structure(1-b)M1b]3O4·[Co(1-d)M2d]3O4。
(3) Preparing the precursor [ Co ] with the core-shell structure in the step (2)(1-b)M1b]3O4·[Co(1-d)M1d]3O4Mixing with Li source solid phase in corresponding proportion.
(4) And (4) calcining the mixed powder in the step (3) in an air atmosphere.
(5) Crushing, grinding and sieving (such as 300 mesh sieve) the calcined material blocks in the step (4) to obtain lithium cobaltate (1-x) Li with a core-shell structureaCo(1-b)M1bO1·xLicCo(1-d)M2dO2。
Wherein the M1 source and the M2 source used in the coprecipitation method are at least one of sulfate, chloride, nitrate, normal acid salt, partial acid salt and organic salt of M1 and M2 respectively.
Wherein the Li source used for solid phase mixing is at least one of lithium carbonate, lithium hydroxide, lithium acetate and lithium fluoride.
Wherein the calcination in the step (4) adopts the following preferred sintering system: firstly, raising the temperature to 400-800 ℃, preserving heat for 1-5 hours, then raising the temperature to 850-1100 ℃, preserving heat for 5-15 hours, then lowering the temperature to 550-1000 ℃, preserving heat for 1-5 hours, and cooling along with the furnace.
The second method is to prepare lithium cobaltate with a core-shell structure by primary doping, and the method is as follows:
(1) preparation of core Co of precursor by coprecipitation method(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2. Adding a proper amount of reducing agent in the precipitation process, and introducing nitrogen for protection.
(2) The final precipitation product Co in (1)(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2Calcining to obtain the core [ Co ] of the precursor with the core-shell structure(1-b)M1b]3O4。
(3) The precursor core [ Co ] in the step (2)(1-b)M1b]3O4Mixing with Li source, Co source and M2 source in corresponding proportion.
(4) And (4) calcining the mixed powder in the step (3) in an air atmosphere.
(5) Crushing, grinding and sieving (such as 300 mesh sieve) the calcined material blocks in the step (4) to obtain lithium cobaltate (1-x) Li with a core-shell structureaCo(1-b)M1bO1·xLicCo(1-d)M2dO2。
Wherein the M1 source used in the coprecipitation method is at least one of sulfate, chloride, nitrate, normal acid salt, partial acid salt and organic salt of M1.
The Li source used for solid phase mixing is at least one of lithium carbonate, lithium hydroxide, lithium acetate and lithium fluoride, the Co source is at least one of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt oxyhydroxide and cobalt acetate, and the M2 source is at least one of M2 nano oxide, nano hydroxide, carbonate, basic carbonate, acetate, organic salt and lithiumoxide.
Wherein the calcination in the step (4) adopts the following preferred sintering system: firstly, raising the temperature to 400-800 ℃, preserving the heat for 1-5 hours, then raising the temperature to 850-1100 ℃, preserving the heat for 5-15 hours, then lowering the temperature to 550-1000 ℃, preserving the heat for 1-5 hours, and preparing lithium cobaltate with a core-shell structure by secondary doping in a third furnace cooling way, wherein the third method is as follows:
(1) preparation of core Co of precursor by coprecipitation method(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2. Adding a proper amount of reducing agent in the precipitation process, and introducing nitrogen for protection.
(2) The final precipitation product Co in (1)(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2Calcining to obtain the core shellCore of structural precursor [ Co ](1-b)M1b]3O4。
(3) The precursor core [ Co ] in the step (2)(1-b)M1b]3O4Mixing with Li source solid phase in corresponding proportion.
(4) And (4) calcining the mixed powder in the step (3) in an air atmosphere.
(5) Crushing and grinding the calcined material block in the step (4), and sieving the crushed material block with a 300-mesh sieve to obtain lithium cobaltate core LiaCo(1-b)M1bO1。
(6) Lithium cobaltate inner core Li in (5)aCo(1-b)M1bO1Mixing with Li source, Co source and M2 source in corresponding proportion.
(7) And (4) calcining the mixed powder in the step (6) in an air atmosphere.
(8) Crushing, grinding and sieving (such as 300 mesh sieve) the calcined material blocks in the step (7) to obtain lithium cobaltate (1-x) Li with a core-shell structureaCo(1-b)M1bO1·xLicCo(1-d)M2dO2。
Wherein the M1 source used in the coprecipitation method is at least one of sulfate, chloride, nitrate, normal acid salt, partial acid salt and organic salt of M1.
The Li source used for solid phase mixing is at least one of lithium carbonate, lithium hydroxide, lithium acetate and lithium fluoride, the Co source is at least one of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt oxyhydroxide and cobalt acetate, and the M2 source is at least one of M2 nano oxide, nano hydroxide, carbonate, basic carbonate, acetate, organic salt and lithiumoxide.
Wherein, the calcination of the steps (4) and (7) adopts the following preferred sintering system: firstly, raising the temperature to 400-800 ℃, preserving heat for 1-5 hours, then raising the temperature to 850-1100 ℃, preserving heat for 5-15 hours, then lowering the temperature to 550-1000 ℃, preserving heat for 1-5 hours, and cooling along with the furnace.
The fourth method is to prepare lithium cobaltate with a core-shell structure by step doping, and the method is as follows:
(1) by usingPreparation of inner core CoCO of precursor by coprecipitation method3Or Co (OH)2Or CoOOH. Adding a proper amount of reducing agent in the precipitation process, and introducing nitrogen for protection.
(2) The final precipitation product CRCO in (1)3Or Co (OH)2Or calcining CoOOH to obtain kernel Co of precursor with core-shell structure3O4。
(3) The precursor core Co in (2)3O4Mixing with Li source and M1 source in corresponding proportion.
(4) And (4) calcining the mixed powder in the step (3) in an air atmosphere.
(5) Crushing, grinding and sieving (such as 300-mesh sieve) the calcined material blocks in the step (4) to obtain lithium cobaltate inner core LiaCo(1-b)M1bO1。
(6) Lithium cobaltate inner core Li in (5)aCo(1-b)M1bO1Mixing with Li source, Co source and M2 source in corresponding proportion.
(7) And (4) calcining the mixed powder in the step (6) in an air atmosphere.
(8) Crushing, grinding and sieving (such as 300 mesh sieve) the calcined material blocks in the step (7) to obtain lithium cobaltate (1-x) Li with a core-shell structureaCo(1-b)M1bO1·xLicCo(1-d)M2dO2。
The Li source used for solid phase mixing is at least one of lithium carbonate, lithium hydroxide, lithium acetate and lithium fluoride, the M1 source is at least one of M1 nano oxide, nano hydroxide, carbonate, basic carbonate, acetate, organic salt and lithium oxide, the Co source is at least one of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt oxyhydroxide and cobalt acetate, and the M2 source is at least one of M2 nano oxide, nano hydroxide, carbonate, basic carbonate, acetate, organic salt and lithium oxide.
Wherein, the calcination of the steps (4) and (7) adopts the following preferred sintering system: firstly, raising the temperature to 400-800 ℃, preserving heat for 1-5 hours, then raising the temperature to 850-1100 ℃, preserving heat for 5-15 hours, then lowering the temperature to 550-1000 ℃, preserving heat for 1-5 hours, and cooling along with the furnace.
According to the invention, the lithium cobaltate cathode material with the core-shell structure is designed and prepared according to the valence state of the doped elements and the synergistic effect between the elements, and has better high-temperature cycle and safety performance under high voltage (more than or equal to 4.45V).
According to the lithium cobaltate with the core-shell structure, the inner core is doped with the low-valence element M1, the outer shell is doped with the high-valence element M2, so that the average valence of Co in the outer shell is lower than that of Co in the inner core, and the average valence of Co in the outer shell and the average valence of Co in the inner shell can be distinguished by an ion reduction XPS detection method. In the high-temperature sintering process of lithium cobaltate, the interface between the core and the shell can be eliminated by a solid phase diffusion mechanism, because the products of the core and the shell are the lithium cobaltate with a layered structure, the cation species, the ion occupation and the lattice constant are approximate, and the two phases have high solid solubility. Meanwhile, the core-doped low-valence element M1 can generate gradient distribution in the outer shell part, and the shell-doped high-valence element M2 can also generate gradient distribution in the inner core part, and the depths of the two gradient distributions are determined by the diffusion rates of M1 and M2. The two gradient distributions overlap in the lithium cobaltate to form a transition region codoped with M1 and M2, and the valence difference between the low-valence element M1 and the high-valence element M2 is favorable for the overall valence of the transition region to reach equilibrium. The lithium cobaltate with the core-shell structure as the lithium ion battery anode material has good structural stability and safety performance, and the two indexes can be characterized by high-temperature circulation and floating Co dissolution test of the button type half battery.
Drawings
Fig. 1 is a first-cycle charge-discharge curve of the lithium cobaltate positive electrode materials in comparative example 1 and example 1.
Fig. 2 is a high-temperature cycle-capacity retention rate curve of the lithium cobaltate positive electrode materials in comparative example 1 and example 1.
Fig. 3 is a first-cycle charge-discharge curve of the lithium cobaltate positive electrode materials in comparative example 2 and example 2.
Fig. 4 is a high-temperature cycle-capacity retention rate curve of the lithium cobaltate positive electrode materials in comparative example 2 and example 2.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, the present invention shall be described in further detail with reference to the following detailed description and accompanying drawings.
Comparative example 1
Preparation of homogeneously doped lithium cobaltate LiCo0.98Ni0.01Mn0.01O. Co precipitate with uniform doping is prepared by adopting coprecipitation method0.98Ni0.01Mn0.01(OH)2Wherein the Ni source is nickel sulfate heptahydrate, the Mn source is manganese sulfate heptahydrate, and a uniformly doped precursor [ Co ] is obtained after calcination0.98Ni0.01Mn0.01]3O4. The precursor and lithium hydroxide with corresponding proportion are mixed evenly in a solid phase, and are calcined in the air atmosphere, and the sintering system is as follows: the temperature is raised to 400 ℃ firstly, the temperature is kept for 1 hour, then the temperature is raised to 850 ℃, the temperature is kept for 5 hours, then the temperature is lowered to 550 ℃, the temperature is kept for 1 hour, and the furnace is cooled. And crushing the calcined material block, grinding and sieving by a 300-mesh sieve to obtain the uniformly doped lithium cobaltate.
Example 1
Preparation of lithium cobaltate 0.50LiCo of core-shell structure0.98Ni0.02O1·0.50LiCo0.98Mn0.02O2. Coprecipitation method is adopted to prepare precipitate 0.50Co with core-shell structure0.98Ni0.02(OH)2·0.50Co0.98Mn0.02(OH)2Wherein the Ni source is nickel sulfate heptahydrate and the Mn source is manganese sulfate heptahydrate. Calcining to obtain a precursor 0.50 (Co) with a core-shell structure0.98Ni0.02)3O4·0.50(Co0.98Mn0.02)3O4. The precursor and lithium hydroxide with corresponding proportion are mixed evenly in a solid phase, and are calcined in the air atmosphere, and the sintering system is as follows: the temperature is raised to 400 ℃ firstly, the temperature is kept for 1 hour, then the temperature is raised to 850 ℃, the temperature is kept for 5 hours, then the temperature is lowered to 550 ℃, the temperature is kept for 1 hour, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate with the core-shell structure.
Comparative example 2
Preparation of homogeneously doped cobaltLithium acid Li1.001Co0.970Al0.020Mn0.010O. Co precipitate with uniform doping is prepared by adopting coprecipitation method0.970Al0.020Mn0.010CO3Wherein the Al source is aluminum sulfate octadecahydrate, the Mn source is manganese dichloride tetrahydrate, and a uniformly doped precursor (Co) is obtained after calcination0.970Al0.020Mn0.010)3O4. Uniformly mixing the precursor with lithium carbonate solid phase in a corresponding proportion, and calcining in an air atmosphere, wherein the sintering system is as follows: the temperature is raised to 500 ℃ firstly, the temperature is kept for 2 hours, then the temperature is raised to 1100 ℃, the temperature is kept for 15 hours, then the temperature is lowered to 1000 ℃, the temperature is kept for 2 hours, and the furnace is cooled. And crushing the calcined material block, grinding and sieving by a 300-mesh sieve to obtain the uniformly doped lithium cobaltate.
Example 2
Preparation of lithium cobaltate 0.80LiCo of core-shell structure0.975Al0.025O1·0.20Li1.005Co0.950Mn0.050O2. Coprecipitation method is adopted to prepare precipitate 0.80 (Co) with core-shell structure0.975Al0.025)CO3·0.20(Co0.950Mn0.050)CO3Wherein the Al source is aluminum sulfate octadecahydrate, the Mn source is manganese dichloride tetrahydrate, and 0.80 (Co) precursor with a core-shell structure is obtained after calcination0.975Al0.025)3O4·0.20(Co0.950Mn0.050)3O4. Uniformly mixing the precursor with lithium carbonate solid phase in a corresponding proportion, and calcining in an air atmosphere, wherein the sintering system is as follows: the temperature is raised to 500 ℃ firstly, the temperature is kept for 2 hours, then the temperature is raised to 1100 ℃, the temperature is kept for 15 hours, then the temperature is lowered to 1000 ℃, the temperature is kept for 2 hours, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate with the core-shell structure.
Example 3
Preparation of lithium cobaltate 0.90LiCo of core-shell structure0.970Al0.030O1·0.10Li1.005Co0.995Ti0.005O2. Preparation of precipitate Co of inner core by coprecipitation method0.970Al0.030(OH)mWhereinThe Al source is sodium metaaluminate, and the precursor (Co) of the kernel is obtained after calcination0.970Al0.030)3O4. Uniformly mixing a precursor of the core with lithium hydroxide, cobalt acetate and nano titanium dioxide in a corresponding proportion in a solid phase manner, and calcining in an air atmosphere, wherein the sintering system is as follows: the temperature is raised to 700 ℃ firstly, the temperature is kept for 3 hours, then the temperature is raised to 1000 ℃, the temperature is kept for 10 hours, then the temperature is lowered to 800 ℃, the temperature is kept for 3 hours, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate with the core-shell structure.
Example 4
Preparation of lithium cobaltate 0.90LiCo of core-shell structure0.970Al0.030O1·0.10Li1.005Co0.995Nb0.005O2. Preparation of precipitate Co of inner core by coprecipitation method0.970Al0.030(OH)mWherein the Al source is sodium metaaluminate, and the precursor (Co) of the kernel is obtained after calcination0.970Al0.030)3O4. Uniformly mixing the precursor of the core with lithium hydroxide, cobalt acetate and nano niobium dioxide solid phases in corresponding proportion, calcining in air atmosphere, and sintering according to the following system: the temperature is raised to 700 ℃ firstly, the temperature is kept for 3 hours, then the temperature is raised to 1000 ℃, the temperature is kept for 10 hours, then the temperature is lowered to 800 ℃, the temperature is kept for 3 hours, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate with the core-shell structure.
Example 5
Preparation of core-shell structured lithium cobaltate 0.95Li0.990Co0.970Mg0.005Al0.025O1·0.05Li1.010Co0.990Ti0.005P0.005O2. Preparation of precipitate Co of inner core by coprecipitation method0.970Mg0.005Al0.025(CO3)jWherein the Mg source is magnesium sulfate heptahydrate, the Al source is aluminum trichloride hexahydrate, and a precursor (Co) of the kernel is obtained after calcination0.970Mg0.005Al0.025)3O4. Mixing the precursor of the inner core with lithium hydroxide and lithium carbonate (molar ratio of two Li sources is 1:1) in corresponding proportion in solid phase, and filling the mixture in a containerCalcining in a gas atmosphere, wherein the sintering system is as follows: the temperature is raised to 600 ℃ firstly, the temperature is kept for 5 hours, then the temperature is raised to 950 ℃, the temperature is kept for 8 hours, then the temperature is lowered to 800 ℃, the temperature is kept for 5 hours, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate core. Uniformly mixing a lithium cobaltate core with lithium acetate, cobalt hydroxide, nano titanium dioxide and lithium phosphate in a solid phase manner, calcining in an air atmosphere, wherein a sintering system is as follows: the temperature is raised to 600 ℃ firstly, the temperature is kept for 4 hours, then the temperature is raised to 900 ℃, the temperature is kept for 6 hours, then the temperature is lowered to 700 ℃, the temperature is kept for 3 hours, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate with the core-shell structure.
Example 6
Preparation of core-shell structured lithium cobaltate 0.95Li0.990Co0.970Mg0.005Al0.025O1·0.05Li1.010Co0.990Zr0.005P0.005O2. Preparation of precipitate Co of inner core by coprecipitation method0.970Mg0.005Al0.025(CO3)jWherein the Mg source is magnesium sulfate heptahydrate, the Al source is aluminum trichloride hexahydrate, and a precursor (Co) of the kernel is obtained after calcination0.970Mg0.005Al0.025)3O4. Uniformly mixing a precursor of the inner core with lithium hydroxide and lithium carbonate (the molar ratio of two Li sources is 1:1) in a corresponding proportion in a solid phase manner, calcining in an air atmosphere, and sintering according to the following steps: the temperature is raised to 600 ℃ firstly, the temperature is kept for 5 hours, then the temperature is raised to 950 ℃, the temperature is kept for 8 hours, then the temperature is lowered to 800 ℃, the temperature is kept for 5 hours, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate core. The lithium cobaltate kernel is evenly mixed with lithium acetate, cobalt hydroxide, nano zirconium dioxide and lithium phosphate in a solid phase mode, and is calcined in an air atmosphere, wherein the sintering system is as follows: the temperature is raised to 600 ℃ firstly, the temperature is kept for 4 hours, then the temperature is raised to 900 ℃, the temperature is kept for 6 hours, then the temperature is lowered to 700 ℃, the temperature is kept for 3 hours, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate with the core-shell structure.
Example 7
Preparing lithium cobaltate with a core-shell structure:
0.70Li0.995Co0.970Ni0.005Y0.005Al0.020O1·0.30Li1.005Co0.990Mn0.008Zr0.002O2。
preparing a precipitate CoOOH of the kernel by adopting a coprecipitation method, and calcining to obtain a precursor Co of the kernel3O4. Uniformly mixing the precursor of the core with lithium carbonate, nano nickel monoxide, nano yttrium oxide and nano aluminum hydroxide in corresponding proportion, calcining in air atmosphere, and sintering according to the following system: the temperature is increased to 450 ℃ firstly, the temperature is kept for 5 hours, then the temperature is increased to 1070 ℃, the temperature is kept for 15 hours, then the temperature is decreased to 1000 ℃, the temperature is kept for 1 hour, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate core. Uniformly mixing a lithium cobaltate core with lithium hydroxide, cobalt hydroxide, nano manganous hydroxide and nano zirconium dioxide in a solid phase, and calcining in an air atmosphere, wherein the sintering system is as follows: the temperature is increased to 450 ℃ firstly, the temperature is kept for 3 hours, then the temperature is increased to 950 ℃, the temperature is kept for 10 hours, then the temperature is decreased to 550 ℃, the temperature is kept for 3 hours, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate with the core-shell structure.
Example 8
Preparing lithium cobaltate with a core-shell structure:
0.70Li0.995Co0.970Ni0.005La0.005Al0.020O1·0.30Li1.005Co0.990Mn0.008Zr0.002O2。
preparing a precipitate CoOOH of the kernel by adopting a coprecipitation method, and calcining to obtain a precursor Co of the kernel3O4. Uniformly mixing the precursor of the core with lithium carbonate, nano nickel monoxide, nano lanthanum oxide and nano aluminum hydroxide in corresponding proportion, calcining in air atmosphere, and sintering according to the following system: the temperature is increased to 450 ℃ firstly, the temperature is kept for 5 hours, then the temperature is increased to 1070 ℃, the temperature is kept for 15 hours, then the temperature is decreased to 1000 ℃, the temperature is kept for 1 hour, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate core. Mixing lithium cobaltate core withLithium hydroxide, cobalt hydroxide, nano manganous hydroxide and nano zirconium dioxide are evenly mixed in a solid phase and calcined in the air atmosphere, and the sintering system is as follows: the temperature is increased to 450 ℃ firstly, the temperature is kept for 3 hours, then the temperature is increased to 950 ℃, the temperature is kept for 10 hours, then the temperature is decreased to 550 ℃, the temperature is kept for 3 hours, and the furnace is cooled. And crushing the calcined material block, grinding, and sieving by using a 300-mesh sieve to obtain the lithium cobaltate with the core-shell structure.
The evaluation method of the lithium cobaltate cathode material with the core-shell structure, which is used by the invention, comprises the following steps:
and mixing the lithium cobaltate with the core-shell structure, the conductive carbon material and the polyvinylidene chloride binder according to the mass ratio of 90:5:5, dropwise adding N-methyl pyrrolidone, grinding into paste, coating the paste on the surface of an aluminum foil, and drying at 120 ℃ to obtain the positive electrode test electrode. The loading amount of the active substance on the positive plate is controlled to be 10-11 mg. The button cell is CR2032, the counter electrode (reference electrode) is made of metal lithium sheet, and the electrolyte is made of new Zea product. The button cells were assembled in a moisture and oxygen controlled glove box. The button cell is arranged in the thermostat and is connected with a blue light tester for carrying out charge and discharge tests. And (3) charging and discharging the assembled button cell at constant temperature of 45 ℃ and within the range of 3.0-4.60V at the rate of 0.7C, keeping the constant-voltage cutoff current at 0.02C, and observing the capacity retention rate of the anode material after circulating for 50 weeks. Charging the assembled button cell to 4.60V at a constant temperature of 55 ℃ at a rate of 0.1C, charging at a constant voltage for 72 hours, taking down the button cell, disassembling the button cell in a glove box, taking out the positive plate, the negative plate and the diaphragm, putting the positive plate, the negative plate and the diaphragm into 10mL of fresh electrolyte, standing the button cell for 24 hours, and detecting the content of Co dissolved in the electrolyte by using ICP-OES.
As shown in fig. 1, the lithium cobaltate with the core-shell structure in example 1 has a slightly higher discharge specific capacity and a slightly lower discharge plateau at the first cycle of 4.60V, compared to the uniformly doped lithium cobaltate in comparative example 1. Fig. 2 shows that the capacity retention rate of the lithium cobaltate of the core-shell structure in example 1 after high-temperature cycling is higher. Due to the high valence of Mn4+The effect of stabilizing the structure is more pronounced at the outer shell than at the inner core.
As shown in fig. 3, the capacity and plateau of the lithium cobaltate of the core-shell structure in example 2 were exerted at the same level at 4.60V, as compared with the uniformly doped lithium cobaltate in comparative example 2, with almost no difference. Fig. 4 shows that the high-temperature cycle performance of the lithium cobaltate with the core-shell structure in example 2 is better, the cycle curve tends to be gentle at the later stage, and no water jump phenomenon occurs, and the principle is the same as above.
Table 1 shows the amount of Co elution after high-temperature float-charging of the lithium cobaltate positive electrode materials in example 3, example 4, example 7, and example 8. The results in table 1 show that the amount of Co eluted from the lithium cobaltate with the core-shell structure in example 4 after the high-temperature high-voltage float charging is less than that in example 3, because Nb doped in the shell has a valence of +5 higher than Ti, which is more beneficial to reducing the average valence of Co in the shell and reducing the surface Co4+The content of (a). In examples 7 and 8, the amounts of Co elution in lithium cobaltate having a core-shell structure were substantially the same, the amounts of doping of high-valence elements Mn and Zr in the shell were completely the same, the amounts of doping of low-valence elements Ni, Al, and rare earth elements in the core were also completely the same, and only the kinds of doping of rare earth elements were different, and the difference in doping of Y and La was not reflected in the amount of Co elution.
TABLE 1 Co elution after high-temperature float-charging
The foregoing disclosure of the specific embodiments of the present invention and the accompanying drawings is directed to an understanding of the present invention and its implementation, and it will be appreciated by those skilled in the art that various alternatives, modifications, and variations may be made without departing from the spirit and scope of the invention. The present invention should not be limited to the disclosure of the embodiments and drawings in the specification, and the scope of the present invention is defined by the scope of the claims.
Claims (10)
1. The lithium cobaltate cathode material with the core-shell structure is characterized in that the chemical formula of the lithium cobaltate cathode material with the core-shell structure is as follows: (1-x) LiaCo(1-b)M1bO1·xLicCo(1-d)M2dO2；
Wherein LiaCo(1-b)M1bO1Is a core, LicCo(1-d)M2dO2Is a housing, 0<x≤0.5，0.98<a≤1.00，0<b<0.1，1.00≤c≤1.01，0<d<0.1，1.90≤1≤2.10，1.90≤2≤2.10；
Wherein M1 is an element having a valence of +2, +3, including at least one of Mg, Ca, Ni, Al, Ga, Sc, V, Cr, Mn, Fe, Y, La, Sm, Ce, and M2 is an element having a valence of +4, +5, +6, including at least one of Ti, Mn, Zr, Ce, Si, Ge, Sn, V, Nb, P, Cr, Mo, W.
2. The lithium cobaltate cathode material with the core-shell structure according to claim 1, wherein during the high-temperature sintering process for synthesizing lithium cobaltate, the interface between the core-shell structures is eliminated, the core-doped lower-valence element M1 forms a gradient distribution in the outer shell portion, the shell-doped higher-valence element M2 forms a gradient distribution in the inner core portion, and the two gradient distributions overlap to form a M1 and M2 co-doped transition region.
3. The method for preparing the lithium cobaltate cathode material with the core-shell structure according to claim 1, wherein the lithium cobaltate with the core-shell structure is prepared by preparing a precursor with the core-shell structure, and the method comprises the following steps:
(1) preparation of core Co of precursor by coprecipitation method(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2Then using the crystal nucleus as the precursor shell Co prepared by coprecipitation method(1-d)M2d(CO3)kOr Co(1-d)M2d(OH)nOr Co(1-d)M2dO(OH)n-2Adding a proper amount of reducing agent in the precipitation process, and introducing nitrogen for protection;
(2) the final precipitation product Co in (1)(1-b)M1b(CO3)j·Co(1-d)M2d(CO3)kOr Co(1-b)M1b(OH)m·Co(1-d)M2d(OH)nOr Co(1-b)M1bO(OH)m-2·Co(1-d)M2dO(OH)n-2Calcining to obtain a precursor [ Co ] with a core-shell structure(1-b)M1b]3O4·[Co(1-d)M2d]3O4；
(3) Preparing the precursor [ Co ] with the core-shell structure in the step (2)(1-b)M1b]3O4·[Co(1-d)M1d]3O4Evenly mixing with Li source solid phase in corresponding proportion;
(4) calcining the mixed powder in the step (3) in an air atmosphere;
(5) crushing, grinding and sieving the material blocks calcined in the step (4) to obtain lithium cobaltate (1-x) Li with a core-shell structureaCo(1-b)M1bO1·xLicCo(1-d)M2dO2。
4. The method of claim 3, wherein the M1 source and the M2 source used in the co-precipitation method are at least one of sulfate, chloride, nitrate, normal acid salt, partial acid salt and organic salt of M1 and M2, respectively; the Li source used for solid phase mixing is at least one of lithium carbonate, lithium hydroxide, lithium acetate and lithium fluoride; the sintering system adopted in the calcination in the step (4) is as follows: firstly, raising the temperature to 400-800 ℃, preserving heat for 1-5 hours, then raising the temperature to 850-1100 ℃, preserving heat for 5-15 hours, then lowering the temperature to 550-1000 ℃, preserving heat for 1-5 hours, and cooling along with the furnace.
5. The method for preparing the lithium cobaltate cathode material with the core-shell structure according to claim 1, wherein the lithium cobaltate with the core-shell structure is prepared by one-time doping, and the method comprises the following steps:
(1) preparation of core Co of precursor by coprecipitation method(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2Adding proper amount of the components during the precipitation processReducing agent and introducing nitrogen for protection;
(2) the final precipitation product Co in (1)(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2Calcining to obtain the core [ Co ] of the precursor with the core-shell structure(1-b)M1b]3O4；
(3) The precursor core [ Co ] in the step (2)(1-b)M1b]3O4Mixing with Li source, Co source and M2 source in corresponding proportion;
(4) calcining the mixed powder in the step (3) in an air atmosphere;
(5) crushing, grinding and sieving the material blocks calcined in the step (4) to obtain lithium cobaltate (1-x) Li with a core-shell structureaCo(1-b)M1bO1·xLicCo(1-d)M2dO2。
6. The method of claim 5, wherein the M1 source used in the co-precipitation method is at least one of sulfate, chloride, nitrate, normal acid salt, partial acid salt and organic salt of M1; the Li source used for solid phase mixing is at least one of lithium carbonate, lithium hydroxide, lithium acetate and lithium fluoride; the Co source is at least one of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt oxyhydroxide and cobalt acetate; the M2 source is at least one of M2 nano oxide, nano hydroxide, carbonate, basic carbonate, acetate, organic salt and lithiated compound; the sintering system adopted in the calcination in the step (4) is as follows: firstly, raising the temperature to 400-800 ℃, preserving heat for 1-5 hours, then raising the temperature to 850-1100 ℃, preserving heat for 5-15 hours, then lowering the temperature to 550-1000 ℃, preserving heat for 1-5 hours, and cooling along with the furnace.
7. The method for preparing the lithium cobaltate cathode material with the core-shell structure according to claim 1, wherein the lithium cobaltate with the core-shell structure is prepared by secondary doping, and the method comprises the following steps:
(1) preparing the core of the precursor by adopting a coprecipitation methodCo(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2Adding a proper amount of reducing agent in the precipitation process, and introducing nitrogen for protection;
(2) the final precipitation product Co in (1)(1-b)M1b(CO3)jOr Co(1-b)M1b(OH)mOr Co(1-b)M1bO(OH)m-2Calcining to obtain the core [ Co ] of the precursor with the core-shell structure(1-b)M1b]3O4；
(3) The precursor core [ Co ] in the step (2)(1-b)M1b]3O4Evenly mixing with Li source solid phase in corresponding proportion;
(4) calcining the mixed powder in the step (3) in an air atmosphere;
(5) crushing and grinding the calcined material block in the step (4), and sieving the crushed material block with a 300-mesh sieve to obtain lithium cobaltate core LiaCo(1-b)M1bO1；
(6) Lithium cobaltate inner core Li in (5)aCo(1-b)M1bO1Mixing with Li source, Co source and M2 source in corresponding proportion;
(7) calcining the mixed powder in the step (6) in an air atmosphere;
(8) crushing and grinding the calcined material block in the step (7), and sieving the crushed material block with a 300-mesh sieve to obtain lithium cobaltate (1-x) Li with a core-shell structureaCo(1-b)M1bO1·xLicCo(1-d)M2dO2。
8. The method of claim 7, wherein the M1 source used in the co-precipitation method is at least one of sulfate, chloride, nitrate, normal acid salt, partial acid salt and organic salt of M1; the Li source used for solid phase mixing is at least one of lithium carbonate, lithium hydroxide, lithium acetate and lithium fluoride; the Co source is at least one of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt oxyhydroxide and cobalt acetate; the M2 source is at least one of M2 nano oxide, nano hydroxide, carbonate, basic carbonate, acetate, organic salt and lithiated compound; the sintering system adopted by the calcination in the steps (4) and (7) is as follows: firstly, raising the temperature to 400-800 ℃, preserving heat for 1-5 hours, then raising the temperature to 850-1100 ℃, preserving heat for 5-15 hours, then lowering the temperature to 550-1000 ℃, preserving heat for 1-5 hours, and cooling along with the furnace.
9. The method for preparing the lithium cobaltate cathode material with the core-shell structure according to claim 1, wherein the lithium cobaltate with the core-shell structure is prepared by step-by-step doping, and the method comprises the following steps:
(1) preparation of inner core CoCO of precursor by coprecipitation method3Or Co (OH)2Or CoOOH, adding a proper amount of reducing agent in the precipitation process, and introducing nitrogen for protection;
(2) the final precipitation product CoCO in (1)3Or Co (OH)2Or calcining CoOOH to obtain kernel Co of precursor with core-shell structure3O4；
(3) The precursor core Co in (2)3O4Mixing with Li source and M1 source in corresponding proportion;
(4) calcining the mixed powder in the step (3) in an air atmosphere;
(5) crushing, grinding and sieving the material blocks calcined in the step (4) to obtain lithium cobaltate inner core LiaCo(1-b)M1bO1；
(6) Lithium cobaltate inner core Li in (5)aCo(1-b)M1bO1Mixing with Li source, Co source and M2 source in corresponding proportion;
(7) calcining the mixed powder in the step (6) in an air atmosphere;
(8) crushing, grinding and sieving the material blocks calcined in the step (7) to obtain lithium cobaltate (1-x) Li with a core-shell structureaCo(1-b)M1bO1·xLicCo(1-d)M2dO2。
10. The method of claim 9, wherein the Li source for solid phase mixing is at least one of lithium carbonate, lithium hydroxide, lithium acetate, and lithium fluoride; the M1 source is at least one of M1 nano oxide, nano hydroxide, carbonate, basic carbonate, acetate, organic salt and lithiated compound; the Co source is at least one of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt oxyhydroxide and cobalt acetate; the M2 source is at least one of M2 nano oxide, nano hydroxide, carbonate, basic carbonate, acetate, organic salt and lithiated compound; the sintering system adopted by the calcination in the steps (4) and (7) is as follows: firstly, raising the temperature to 400-800 ℃, preserving heat for 1-5 hours, then raising the temperature to 850-1100 ℃, preserving heat for 5-15 hours, then lowering the temperature to 550-1000 ℃, preserving heat for 1-5 hours, and cooling along with the furnace.
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