CN110581259A - Monocrystalline ternary cathode material with good dispersibility, mixed lithium and nickel and low residual alkali, and preparation method and application thereof - Google Patents

Monocrystalline ternary cathode material with good dispersibility, mixed lithium and nickel and low residual alkali, and preparation method and application thereof Download PDF

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CN110581259A
CN110581259A CN201810580850.1A CN201810580850A CN110581259A CN 110581259 A CN110581259 A CN 110581259A CN 201810580850 A CN201810580850 A CN 201810580850A CN 110581259 A CN110581259 A CN 110581259A
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combination
oxide
tellurium
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CN110581259B (en
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杨春香
严武渭
黄友军
温伟城
杨顺毅
黄友元
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Shenzhen Battery Nanotechnology 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

the invention discloses a single crystal ternary cathode material with good dispersibility, lithium-nickel mixed arrangement and low residual alkali, a preparation method and application thereof. The invention adds Ir3+、Y3+、Te4+、In3+、Ga3+The cationic additive can promote the surface energy reduction of the ternary materialLow, thereby reducing the sintering temperature of the material and reducing the effect of volatilization of the lithium salt; on the other hand, the method can also reduce the mixed discharge of lithium and nickel, control the directional growth of the crystal face of the material and inhibit the crystal face and CO in the air2And H2the adsorption effect and the reaction activity of O, thereby reducing the surface residual alkali of the ternary material, improving the processing performance of the material and improving the rate discharge capacity and the cycle performance of the single crystal ternary material.

Description

Monocrystalline ternary cathode material with good dispersibility, mixed lithium and nickel and low residual alkali, and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion battery anode materials, relates to a single crystal ternary anode material, a preparation method and application thereof, and particularly relates to a single crystal ternary anode material with good dispersibility, low lithium-nickel mixed row content and low residual alkali content, a preparation method thereof and application thereof in a lithium ion battery.
Background
The existing layered ternary cathode material has the advantages of high energy density, long cycle life, low production cost and the like, and is widely applied to the fields of electric vehicles, hybrid electric vehicles and the like. However, the bottleneck limiting the application of the ternary cathode material is the safety problem caused by gas generation due to residual Li on the surface of the ternary material2o is equal to CO in air2And H2O reaction to produce residual alkali Li2CO3And LiOH, which form CO during cell cycling2、H2and O gas causes the battery to expand, thereby causing potential safety hazards. In addition, most ternary cathode materials in the current market are secondary spherical particles formed by agglomeration of primary particles, and with the increase of cycle times, the secondary particles can generate interface pulverization of the primary particles, so that the internal resistance is increased, the capacity is quickly attenuated, and the cycle performance is reduced.
the material is made into a single crystal shape, so that the cycle performance and the safety performance of the material can be improved, however, compared with a non-single crystal material, the single crystal ternary material has higher calcination temperature, and is more prone to generating lithium volatilization and causing lithium loss, so that the lithium-nickel mixed emission is serious and the capacity is reduced.
patent No. CN 101847722A discloses a micron-sized single crystal ternary material, the synthesized single crystal material has serious agglomeration and non-uniform distribution of primary particles. Patent No. CN101707252A discloses a method for preparing a ternary cathode material of polycrystalline oxide from a mixture of multiple metal salts and lithium salts by wet ball milling, wherein the ternary cathode material has a large primary particle size and is a secondary spherical particle formed by agglomeration of primary particles, and the agglomerated secondary spherical particle affects the improvement of material compaction density and volume energy density, and has a complex preparation process, too high cost and poor processability.
Therefore, the preparation of the single crystal ternary material with regular shape, low residual alkali and excellent electrochemical performance is a difficult problem in the field of lithium ion batteries.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a single crystal ternary cathode material with good dispersibility, lithium-nickel mixed-row performance and low residual alkali, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a single crystal ternary cathode material, wherein a raw material for preparing the single crystal ternary cathode material comprises a cation additive, and the cation additive is any one or a combination of at least two of an iridium source, an yttrium source, a tellurium source, an indium source or a gallium source, preferably any one or a combination of two of the tellurium source or the gallium source.
By introducing the specific cation additive into the raw materials, the lithium-nickel mixed row and residual alkali of the single crystal ternary cathode material can be reduced, and the dispersibility and the single crystal development degree are improved. The preparation method reduces the surface energy of the material through the cation additive, achieves the effects of reducing the calcination temperature of the material and reducing the volatilization of the lithium salt, and simultaneously can control the directional growth of the crystal face of the material and inhibit the crystal face and CO in the air through the addition of the cation additive2And H2And the adsorption effect and the reaction activity of O are realized, so that the surface residual alkali of the ternary material is reduced.
In the cationic additive of the present invention, the cation Ir3+、Y3+、Te4+、In3+、Ga3+Ionic radius of (2) and Ni2 +the phase difference is not large, so that the nickel can occupy the 3b position of the nickel, nickel ions are prevented from occupying the position of the lithium ions, and the lithium-nickel mixed discharge can be reduced. When the type of the cationic additive is selected, the melting points of different types of cationic additives can be comprehensively considered, and the lower the melting point is, the more beneficial the formation of the single crystal morphology of the invention is, and the electrochemical performance is improved.
in the invention, the single crystal ternary cathode material can be an undoped single crystal ternary cathode material and can also be a doped single crystal ternary cathode material.
Preferably, the single-crystal ternary cathode material is a nickel-cobalt-manganese ternary cathode material or a doped nickel-cobalt-manganese ternary cathode material.
Preferably, the chemical formula of the nickel-cobalt-manganese ternary cathode material is LiaNixCoyMn1-x-yO2wherein a is more than or equal to 1.0 and less than or equal to 1.1, 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 0.05 and less than or equal to 0.25. For example, a is 1.0, 1.05, 1.1, etc., x is 0.5, 0.6, 0.65, 0.7, 0.8, 0.9, etc., and y is 0.05, 0.08, 0.10, 0.15, 0.20, 0.25, etc.
Preferably, the chemical formula of the doped nickel-cobalt-manganese ternary cathode material is LiaNixCoyMn1-x-y-zMzO2Wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.05, and M comprises any one or the combination of at least two of B, Ti, Zr, Mg, Sr, Ba, V, Zn or Bi. For example, a is 1.0, 1.05, 1.1, etc., x is 0.5, 0.6, 0.65, 0.7, 0.8, 0.9, etc., and y is 0.05, 0.08, 0.10, 0.15, 0.20, 0.25, etc. The M is preferably any one or a combination of at least two of B, Ti, Zr, Mg, Sr, Ba, V, Zn or Bi.
Preferably, the iridium source includes any one or a combination of at least two of iridium nitrate, iridium acetate, iridium oxalate and iridium oxide, but is not limited to the iridium sources listed above, and other iridium sources commonly used in the art to achieve the same effect may also be used in the present invention.
preferably, the yttrium source comprises any one or a combination of at least two of yttrium nitrate, yttrium acetate, yttrium oxalate or yttrium oxide, but is not limited to the above-listed yttrium sources, and other yttrium sources commonly used in the art to achieve the same effect can be used in the present invention.
Preferably, the tellurium source comprises any one of tellurium nitrate, tellurium acetate, tellurium oxalate or tellurium oxide or a combination of at least two of the above, preferably the tellurium source, but is not limited to the above-listed tellurium sources, and other tellurium sources commonly used in the art to achieve the same effect can also be used in the present invention.
Preferably, the indium source includes any one or a combination of at least two of indium nitrate, indium acetate, or indium oxide, but is not limited to the above-listed indium sources, and other indium sources commonly used in the art to achieve the same effects may be used in the present invention.
Preferably, the gallium source includes any one or a combination of at least two of gallium nitrate, gallium acetate or gallium oxide, preferably gallium oxide, but is not limited to the above-listed gallium sources, and other gallium sources commonly used in the art to achieve the same effect may also be used in the present invention.
As a preferred technical scheme of the method, the method comprises the following steps:
(1) Mixing:
In stoichiometric ratio LiaNixCoyMn1-x-yO2Or LiaNixCoyMn1-x-y-zMzO2Weighing raw materials, and mixing;
(2) And (3) heat treatment:
in an oxygen atmosphere, firstly heating to a first temperature, preserving heat, then continuously heating to a second temperature, and preserving heat to obtain a single crystal ternary cathode material;
Step (1) said LiaNixCoyMn1-x-yO2The corresponding raw materials are as follows: a nickel-cobalt-manganese hydroxide precursor, a lithium salt and a cationic additive;
Alternatively, the Li in the step (1)aNixCoyMn1-x-y-zMzO2The corresponding raw materials are as follows:The composite material comprises a nickel-cobalt-manganese hydroxide precursor, a compound of M, a lithium salt and a cationic additive, wherein the M comprises any one or a combination of at least two of B, Ti, Zr, Mg, Sr, Ba, V, Zn or Bi; the cation additive is any one or the combination of at least two of an iridium source, an yttrium source, a tellurium source, an indium source or a gallium source, and preferably any one or the combination of two of the tellurium source or the gallium source.
according to the preferred technical scheme, the single crystal ternary material is synthesized in one step by a solid phase method, the sintering temperature of the material can be reduced by adding the cationic additive (taking the single crystal 523 as an example, the 523 material with the single crystal morphology synthesized in the existing reported literature has the temperature higher than 900 ℃, and the 523 material with the single crystal morphology can be synthesized at a lower temperature by adding the cationic additive in the method), the volatilization of lithium salt is reduced, the heat treatment time is remarkably shortened, and the production cost is reduced. The proper content of the specific cationic additive can control the crystal face growth of the material, reduce the residual alkali of the material, improve the processing performance of the material, enable the cations to occupy the 3b position of nickel, prevent the nickel ions from occupying the position of lithium ions, and reduce the mixed discharge of lithium and nickel.
The single crystal ternary cathode material formed by the preferred technical scheme can obviously improve electrochemical behaviors such as rate discharge capacity, circulation and the like when applied to the lithium ion battery.
Preferably, when the raw material of step (1) does not contain a compound of M, the stoichiometric ratio is LiaNixCoyMn1-x-yO2the chemical formula of the nickel-cobalt-manganese hydroxide precursor is NixCoyMn1-x-y(OH)2Wherein a is more than or equal to 1.0 and less than or equal to 1.1, 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 0.05 and less than or equal to 0.25. The nickel-cobalt-manganese ternary cathode material is prepared under the condition.
Preferably, when the raw material of step (1) contains a compound of M, the stoichiometric ratio is LiaNixCoyMn1-x-y-zMzO2The chemical formula of the nickel-cobalt-manganese hydroxide precursor is NixCoyMn1-x-y-z(OH)2wherein a is more than or equal to 1.0 and less than or equal to 1.1, and a is more than or equal to 0.5x is less than or equal to 0.9, y is less than or equal to 0.05 and less than or equal to 0.25, and z is less than or equal to 0.01 and less than or equal to 0.05. The doped nickel-cobalt-manganese ternary cathode material is prepared under the condition.
Preferably, in the cationic additive, an iridium source (Ir)3+) Including any one or a combination of at least two of iridium nitrate, iridium acetate, iridium oxalate or iridium oxide, but not limited to the iridium sources listed above, other iridium sources commonly used in the art to achieve the same effect may also be used in the present invention.
preferably, among the cationic additives, yttrium source (Y)3+) Including any one or a combination of at least two of yttrium nitrate, yttrium acetate, yttrium oxalate, or yttrium oxide, but not limited to the above listed sources of yttrium, other sources of yttrium commonly used in the art to achieve the same effect may also be used in the present invention.
preferably, among the cationic additives, a tellurium source (Te)4+) Including any one or a combination of at least two of tellurium nitrate, tellurium acetate, tellurium oxalate or tellurium oxide, preferably tellurium nitrate, but not limited to the above-listed tellurium sources, other tellurium sources commonly used in the art to achieve the same effect may also be used in the present invention.
Preferably, among the cationic additives, a source of indium (In)3+) Including any one or a combination of at least two of indium nitrate, acetate, or oxide, but not limited to the above-listed sources, other sources commonly used in the art to achieve the same effect may be used in the present invention.
Preferably, among the cationic additives, a gallium source (Ga)3+) Including any one or a combination of at least two of gallium nitrate, gallium acetate or gallium oxide, preferably gallium oxide, but not limited to the above-listed sources, other sources commonly used in the art to achieve the same effect may be used in the present invention.
Preferably, the lithium salt in step (1) includes any one or a combination of at least two of lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate, but is not limited to the above-mentioned lithium salts, and other lithium salts commonly used in the art to achieve the same effect can also be used in the present invention.
Preferably, in the step (1), the molar ratio of the cations in the cationic additive to the nickel-cobalt-manganese hydroxide precursor is (0.0001-0.001):1, and if the molar ratio is less than 0.0001:1, the single crystal particles are incompletely developed, the primary particle agglomeration phenomenon is serious, and the residual alkali is higher; if the molar ratio is greater than 0.001:1, the capacity of the material will be lower. Preferably (0.0002-0.0007): 1.
Preferably, the compound of M in step (1) is any one or a combination of at least two of zirconium oxide, magnesium oxide, titanium oxide, boron oxide, strontium oxide, barium oxide, vanadium pentoxide, zinc oxide, or bismuth oxide.
Preferably, the compound of M in step (1) has a particle size of 10nm to 50nm, such as 10nm, 20nm, 25nm, 30nm, 40nm, 45nm, 50nm, or the like.
Preferably, the mixing of step (1) is carried out in a three-dimensional mixer.
As a preferred technical scheme of the method of the invention, the first temperature in the step (2) is 400-500 ℃, such as 400 ℃, 425 ℃, 450 ℃, 470 ℃, 485 ℃, or 500 ℃ and the like.
Preferably, in step (2), the heating rate for heating to the first temperature is 3 ℃/min-5 ℃/min, such as 3 ℃/min, 4 ℃/min, 4.5 ℃/min, or 5 ℃/min, etc.
Preferably, in step (2), the incubation time at the first temperature is 2h to 3h, such as 2h, 2.2h, 2.5h, 2.8h or 3h, etc.
Preferably, the second temperature in step (2) is 750-900 ℃, such as 750 ℃, 775 ℃, 785 ℃, 800 ℃, 820 ℃, 850 ℃, 875 ℃ or 900 ℃, etc.
Preferably, in step (2), the holding time at the second temperature is 10h to 15h, such as 10h, 11h, 11.5h, 12h, 13h, 13.5h, 14h or 15 h.
preferably, the method further comprises a step of cooling after the step (2) is completed, wherein the cooling rate is 5 ℃/min-10 ℃/min, such as 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min and the like.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) Mixing:
In stoichiometric ratio LiaNixCoyMn1-x-y-zMzO2Weighing Ni-Co-Mn hydroxide precursor NixCoyMn1-x-y-z(OH)2A is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.05, the M is any one or combination raw material of at least two of B, Ti, Zr, Mg, Sr, Ba, V, Zn or Bi, and the compound of the M is mixed in a three-dimensional mixer, and the particle size of the compound of the M is 10nm-50 nm;
The cation additive is any one or the combination of at least two of an iridium source, an yttrium source, a tellurium source, an indium source or a gallium source;
The molar ratio of cations in the cationic additive to nickel cobalt manganese hydroxide precursor is (0.0001-0.001) 1;
(2) And (3) heat treatment:
heating to 400-500 ℃ at the speed of 3-5 ℃/min in the oxygen atmosphere, preserving heat for 2-3 h, then continuously heating to 750-900 ℃, preserving heat for 10-15 h, and cooling to obtain the single crystal ternary cathode material LiaNixCoyMn1-x-y- zMzO2。
In a second aspect, the invention provides the single crystal ternary cathode material prepared by the method of the first aspect, which has regular morphology, good dispersibility, low agglomeration, low lithium-nickel mixed-row and low residual alkali (taking the single crystal 622 as an example, OH)-≤0.1wt％，CO3 2-less than or equal to 0.1 wt%) and complete development.
Preferably, the grain size of the single crystal ternary cathode material is 5-7 nm.
In a third aspect, the invention provides a lithium ion battery, and a positive electrode of the lithium ion battery comprises the single crystal ternary positive electrode material of the second aspect or the single crystal ternary positive electrode material prepared by the method of the first aspect.
compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention adopts a solid phase method to synthesize the single crystal ternary material by one step with the assistance of the cationic additive, and the addition of the cationic additive can promote the reduction of the surface energy of the single crystal ternary material, thereby reducing the sintering temperature of the material and the volatilization of lithium salt, obviously shortening the heat treatment time and reducing the production cost.
(2) although the prior art has a method for reducing the mixed lithium-nickel discharge through doping, the method for reducing the mixed lithium-nickel discharge and reducing the residual alkali of the material through a cation additive iridium source, an yttrium source, a tellurium source, an indium source or a gallium source is not reported, the growth of the crystal face of the material can be controlled by adjusting the amount of the cation additive, and the crystal face and the CO in the air are inhibited2And H2The adsorption and reaction activity of O reduce the residual alkali of the material, and are beneficial to improving the processing performance and electrochemical performance of the material.
(3) Cationic additives (Ir) of the present invention3+、Y3+、Te4+Etc.) of these kinds of cationic radii with Ni2+The phase difference is not large, so that the nickel can occupy the 3b position of the nickel, nickel ions are prevented from occupying the position of the lithium ions, and the lithium-nickel mixed discharge can be reduced.
(4) The lithium ion battery prepared from the single crystal ternary material has excellent electrochemical performance, especially excellent rate discharge capacity and cycle performance.
(5) The method has the advantages of simple process, convenient operation, no special requirements on experimental environment, no pollution and suitability for expanded reproduction.
Drawings
FIG. 1 is a schematic representation of example 1 with addition of Ir3+Additive and comparative example 1 without addition of Ir3+XRD contrast of the sample obtained by the additive;
FIG. 2(a) and FIG. 2(b) are each a diagram showing the addition of Ir in example 13+Additive and comparative example 1 without addition of Ir3+SEM images of the resulting samples of additives;
FIG. 3 addition of Ir as in example 23+And Te4+Comparative example 2 cycle performance of the samples without additives.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
example 1
this embodiment uses Ir2O3Assisted synthesis of Li1.04Ni0.5Co0.2Mn0.27Zn0.01Ba0.02O2the single crystal material specifically comprises the following steps:
(1) In stoichiometric ratio Li1.04Ni0.5Co0.2Mn0.27Zn0.01Ba0.02O238.42g of lithium carbonate and 89.92g of Ni were weighed0.5Co0.2Mn0.27(OH)2precursor, 0.814g ZnO, 3.067g BaO and 0.06g Ir2O3Additive (Ir)3+And Ni0.5Co0.2Mn0.27(OH)2Molar weight ratio 0.000275: 1) putting the mixture into a three-dimensional mixer, adding polyurethane balls, and uniformly mixing.
(2) And (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 450 ℃ at the speed of 4 ℃/min, preserving heat for 3h, heating to 900 ℃ and preserving heat for 15h, and cooling to room temperature at the speed of 5 ℃/min.
Example 2
In the embodiment, the synthesis of Li is assisted by iridium nitrate and tellurium oxide1.025Ni0.6Co0.2Mn0.15B0.04V0.01O2The single crystal material specifically comprises the following steps:
(1) In stoichiometric ratio Li1.025Ni0.6Co0.2Mn0.15B0.04V0.01O218.93g of lithium carbonate, 21.5g of lithium hydroxide and 89.24g of Ni were weighed0.6Co0.2Mn0.15(OH)2Precursor 2.785g B2O3、1.82g V2O50.2458g of iridium nitrate and 0.0319g of tellurium oxide additive (Ir)3+And Y3+And Ni0.6Co0.2Mn0.15(OH)2Molar weight ratios of 0.00065:1 and 0.0002:1, respectively), placed in a three-dimensional mixer,adding polyurethane balls and mixing uniformly.
(2) And (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 500 ℃ at the speed of 3 ℃/min, preserving heat for 2h, heating to 880 ℃ and preserving heat for 12.5h, and then cooling to room temperature at the speed of 7 ℃/min.
example 3
In the embodiment, iridium oxalate is adopted to assist in synthesizing Li1.0Ni0.55Co0.25Mn0.17Ti0.02Bi0.01O2The single crystal material specifically comprises the following steps:
(1) In stoichiometric ratio Li1.0Ni0.55Co0.25Mn0.17Ti0.02Bi0.01O236.95g of lithium carbonate and 87.42g of Ni were weighed0.5Co0.25Mn0.17(OH)2Precursor, 1.6g TiO2、4.66g Bi2O3And 0.0648g of iridium oxalate additive (Ir)3+And Ni0.5Co0.25Mn0.17(OH)2the molar weight ratio is 0.0001: 1) putting the mixture into a three-dimensional mixer, adding polyurethane balls, and uniformly mixing.
(2) And (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 450 ℃ at the speed of 3 ℃/min, preserving heat for 2.5h, heating to 890 ℃, preserving heat for 13h, and cooling to room temperature at the speed of 8 ℃/min.
Example 4
This example uses yttrium oxalate to assist in the synthesis of Li1.05Ni0.7Co0.15Mn0.125Mg0.025O2The single crystal material specifically comprises the following steps:
(1) In stoichiometric ratio Li1.05Ni0.7Co0.15Mn0.125Mg0.025O226.43g of lithium hydroxide, 28.96g of lithium nitrate and 56.79g of Ni were weighed0.7Co0.15Mn0.125(OH)2Precursor, 1.0g MgO and 0.622g yttrium oxalate additive (Y)3+And Ni0.7Co0.15Mn0.125(OH)2Molar weight ratioIs 0.001: 1) putting the mixture into a three-dimensional mixer, adding polyurethane balls, and uniformly mixing.
(2) And (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 400 ℃ at the speed of 4 ℃/min, preserving heat for 3h, heating to 825 ℃ and preserving heat for 12h, and cooling to room temperature at the speed of 8 ℃/min.
Example 5
in this example, TeO was used2Assisted synthesis of Li1.1Ni0.88Co0.09Mn0.014Zr0.016O2The single crystal material specifically comprises the following steps:
(1) In stoichiometric ratio Li1.1Ni0.88Co0.09Mn0.014Zr0.016O272.58g of lithium acetate and 91.72g of Ni were weighed0.88Co0.09Mn0.014(OH)2Precursor, 1.97g ZrO2And 0.0878g TeO2Additive (Te)4+And Ni0.88Co0.09Mn0.014(OH)2molar weight ratio 0.00055: 1) putting the mixture into a three-dimensional mixer, adding polyurethane balls, and uniformly mixing.
(2) And (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 450 ℃ at the speed of 5 ℃/min, preserving heat for 2.5h, heating to 800 ℃ and preserving heat for 10h, and then cooling to room temperature at the speed of 10 ℃/min.
Example 6
This example uses Y2O3And TeO2Assisted synthesis of Li1.07Ni0.9Co0.05Mn0.04Sr0.01O2The single crystal material specifically comprises the following steps:
(1) In stoichiometric ratio Li1.07Ni0.9Co0.05Mn0.04Sr0.01O244.9g of lithium hydroxide and 91.42g of Ni were weighed0.9Co0.05Mn0.04(OH)2Precursor, 1.04g SrO, 0.1694g Y2O3And 0.0399g TeO2Additive (Y)3+and Te4+And Ni0.9Co0.05Mn0.04(OH)2The molar weight ratio of the polyurethane to the polyurethane is 0.00075:1 and 0.00025:1 respectively), placing the mixture into a three-dimensional mixer, adding polyurethane balls, and uniformly mixing.
(2) and (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 500 ℃ at the speed of 3 ℃/min, preserving heat for 2h, heating to 750 ℃ and preserving heat for 12h, and cooling to room temperature at the speed of 6 ℃/min.
Example 7
This example uses Ga (NO)3)3Assisted synthesis of Li1.03Ni0.6Co0.2Mn0.2O2The single crystal material specifically comprises the following steps:
(1) in stoichiometric ratio Li1.03Ni0.6Co0.2Mn0.2O276.11g of lithium carbonate and 89.24gNi g of lithium carbonate are weighed0.6Co0.2Mn0.2(OH)2Precursor and 0.1511g gallium nitrate additive (Ga)3+And Ni0.6Co0.2Mn0.2(OH)2The molar weight ratio is 0.00045:1), placing the mixture into a three-dimensional mixer, adding polyurethane balls, and uniformly mixing.
(2) And (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 450 ℃ at the speed of 3.5 ℃/min, preserving heat for 2h, heating to 880 ℃ and preserving heat for 13h, and then cooling to room temperature at the speed of 8 ℃/min.
Comparative example 1
This comparative example synthesizes Li without the aid of additives1.04Ni0.5Co0.2Mn0.27Zn0.01Ba0.02O2the material specifically comprises the following steps:
(1) In stoichiometric ratio Li1.04Ni0.5Co0.2Mn0.27Zn0.01Ba0.02O238.42g of lithium carbonate and 89.92g of Ni were weighed0.5Co0.2Mn0.27(OH)2The precursor, 0.814g ZnO and 3.067g BaO are placed in a three-dimensional mixer, polyurethane balls are added, and the mixture is uniformly mixed.
(2) And (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 450 ℃ at the speed of 4 ℃/min, preserving heat for 3h, heating to 900 ℃ and preserving heat for 15h, and cooling to room temperature at the speed of 5 ℃/min.
comparative example 2
This comparative example synthesizes Li without the aid of additives1.025Ni0.6Co0.2Mn0.15B0.04V0.01O2The material specifically comprises the following steps:
(1) In stoichiometric ratio Li1.025Ni0.6Co0.2Mn0.15B0.04V0.01O218.93g of lithium carbonate, 21.5g of lithium hydroxide and 89.24g of Ni were weighed0.6Co0.2Mn0.15(OH)2Precursor sum 2.785g B2O3、1.82gV2O5Putting the mixture into a three-dimensional mixer, adding polyurethane balls, and uniformly mixing.
(2) And (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 500 ℃ at the speed of 3 ℃/min, preserving heat for 2h, heating to 880 ℃ and preserving heat for 12.5h, and then cooling to room temperature at the speed of 7 ℃/min.
Comparative example 3
This example synthesizes Li without additives1.03Ni0.6Co0.2Mn0.2O2The single crystal material specifically comprises the following steps:
(1) In stoichiometric ratio Li1.03Ni0.6Co0.2Mn0.2O276.11g of lithium carbonate and 89.24gNi g of lithium carbonate were weighed out0.6Co0.2Mn0.2(OH)2And placing the precursor into a three-dimensional mixer, adding polyurethane balls, and uniformly mixing.
(2) And (3) putting the uniformly mixed materials into a sagger for heat treatment, calcining in an oxygen atmosphere, heating to 450 ℃ at the speed of 3.5 ℃/min, preserving heat for 2h, heating to 880 ℃ and preserving heat for 13h, and then cooling to room temperature at the speed of 8 ℃/min.
The positive electrode materials of examples 1 to 7 and comparative examples 1 to 3 were tested by the following methods:
The molecular structure and the material composition of the material are tested by adopting a Pasnake X-ray diffractometer.
The surface appearance and the particle size of the sample are observed by a scanning electron microscope of Hitachi S4800.
And testing the particle size of the material by using a Malvern laser particle size tester MS 2000.
The content of elements in the material was tested using an inductively coupled plasma emission spectrometer model OPTIMA 8000.
the material was tested for residual alkali using an automatic potentiometric titrator model METTLER TOLEDO G20.
Electrochemical performance tests were performed on the materials synthesized in each example and comparative example, specifically:
Respectively taking the products prepared in each example and each comparative example as active materials, stirring and mixing the active materials, acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1, preparing a working electrode, and preparing the working electrode by using LiPF containing 1mol/L6The EC-EMC (volume ratio is 3:7) of the battery is electrolyte, the polypropylene porous membrane is a diaphragm, the metal lithium sheet is a counter electrode, and the CR2025 type battery is assembled in an argon glove box. The charge and discharge test is carried out on a LAND battery test system of Wuhanjinnuo electronic Limited company, the voltage range is 3.0-4.35V, and the current magnitude is 1C.
FIG. 1 is a schematic representation of example 1 with addition of Ir3+Additive and comparative example 1 without addition of Ir3+XRD (X-ray diffraction) comparison of samples obtained by adding the additive shows that Ir is added3+I of (A)003/I104The ratio is 1.29, and no cationic additive Ir is added3+i of (A)003/I104The ratio is 1.01, which shows that the lithium-nickel mixed row is reduced after the cationic additive is added.
FIG. 2(a) and FIG. 2(b) are each a diagram showing the addition of Ir in example 13+Additive and comparative example 1 without addition of Ir3+SEM image of sample obtained with additive, from which it can be seen that Ir was added3+The agglomeration phenomenon of the post-material is reduced, the primary particles are completely developed, and the primary particles of the samples which are not added are smaller and are not dispersed.
TABLE 1 addition of Ir for example 13+cationic additive and comparative example 1 without addition of Ir3+The residual alkali of the sample obtained by the cationic additive is compared, and the result shows that the residual alkali is obviously reduced after the cationic additive is added, which indicates that Ir3+The cation additive can influence the growth of crystal faces of the single crystal material and reduce residual alkali on the surface of the single crystal material.
TABLE 2 addition of Ir for example 13+Cationic additive and comparative example 1 without addition of Ir3+Cationic additive the ICP results for the samples obtained are compared and the lithium/metal ratio of the ICP indicates that the volatilization of lithium is reduced after the cationic additive is added.
TABLE 1 addition of Ir3+And without addition of Ir3+Residual alkali of the obtained sample
TABLE 2 addition of Ir3+And without addition of Ir3+ICP of the obtained sample
Table 3 shows electrochemical performance data of each example and comparative example, and it can be found by comparison that the performance of the single crystal ternary material is obviously improved by adding the cationic additive.
FIG. 3 addition of Ir as in example 23+And Te4+Cationic additive and comparative example 2 without addition of Ir3+and Te4+comparison of the cycle performance of the cationic additive, it is evident that Ir was added3+And Te4+After the cationic additive is added, the degree of the lithium-nickel mixed arrangement of the single crystal is reduced, so that the capacity and the cycle performance of the single crystal ternary cathode material are obviously improved.
TABLE 3 electrochemical Performance data
Sample (I) First discharge capacity (mAh/g) Capacity retention (%) after 50 cycles
Example 1 161.8 96.1
Example 2 166.0 96.0
Example 3 163.2 95.8
example 4 170.3 95.4
Example 5 195.1 94.8
Example 6 200.5 94.2
Example 7 167.4 95.9
Comparative example 1 156.5 91.3
comparative example 2 161.0 91.0
Comparative example 3 162.1 90.8
The invention can synthesize the single-crystal ternary material by a solid phase method under the condition of the assistance of the cation additive, and the addition of the cation additive can obviously reduce the residual alkali of the material, reduce the mixed discharge of lithium and nickel, and greatly improve the capacity and the cycle performance of the single-crystal ternary cathode material.
TeO in example 52Being a cationic additive, Te4+And Ni0.88Co0.09Mn0.014(OH)2When the molar weight ratio is 0.00055:1, the capacity retention rate of 50 cycles of the cycle is 94.8 percent through electrochemical tests, the electrochemical performance is excellent, and Ga (NO) is used in example 73)3Cationic additive, Ga3+And Ni0.6Co0.2Mn0.2(OH)2When the molar weight ratio is 0.00045:1, the capacity retention rate of the cycle 50 cycles is 95.9%, because when the amount of the cationic additive is too large, the capacity of the material is reduced, when the amount of the cationic additive is too small, the primary particles of the material are incompletely developed, the ratio of cations in the cationic additive to precursors is optimal when the ratio is (0.0002-0.0007):1, and at the same time, the formation of the morphology of the single crystal is more facilitated and the performance is more excellent because the melting points of tellurium oxide and gallium nitrate are lower.
the applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The preparation method of the single crystal ternary cathode material is characterized in that a raw material for preparing the single crystal ternary cathode material contains a cation additive, and the cation additive is any one or a combination of at least two of an iridium source, an yttrium source, a tellurium source, an indium source or a gallium source.
2. The method of claim 1, wherein the single-crystal ternary positive electrode material is a nickel-cobalt-manganese ternary positive electrode material or a doped nickel-cobalt-manganese ternary positive electrode material;
Preferably, the chemical formula of the nickel-cobalt-manganese ternary cathode material is LiaNixCoyMn1-x-yO2Wherein a is more than or equal to 1.0 and less than or equal to 1.1, 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 0.05 and less than or equal to 0.25;
Preferably, the chemical formula of the doped nickel-cobalt-manganese ternary cathode material is LiaNixCoyMn1-x-y-zMzO2wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.05, and M comprises any one or the combination of at least two of B, Ti, Zr, Mg, Sr, Ba, V, Zn or Bi.
3. the method according to claim 1 or 2, wherein the cationic additive is preferably any one or a combination of two of a dysprosium source or a gallium source;
preferably, the iridium source comprises any one of iridium nitrate, iridium acetate, iridium oxalate or iridium oxide or a combination of at least two thereof;
preferably, the yttrium source comprises any one of yttrium nitrate, yttrium acetate, yttrium oxalate or yttrium oxide or a combination of at least two of the foregoing;
Preferably, the tellurium source comprises any one of tellurium nitrate, tellurium acetate, tellurium oxalate or tellurium oxide or a combination of at least two of the above, preferably tellurium nitrate;
Preferably, the indium source comprises any one of indium nitrate, indium acetate or indium oxide, or a combination of at least two thereof;
preferably, the gallium source comprises any one of gallium nitrate, gallium acetate or gallium oxide or a combination of at least two of them, preferably gallium oxide.
4. A method according to any one of claims 1-3, the method comprising the steps of:
(1) mixing:
In stoichiometric ratio LiaNixCoyMn1-x-yO2Or LiaNixCoyMn1-x-y-zMzO2Weighing raw materials, and mixing;
(2) And (3) heat treatment:
In an oxygen atmosphere, firstly heating to a first temperature, preserving heat, then continuously heating to a second temperature, and preserving heat to obtain a single crystal ternary cathode material;
Step (1) said LiaNixCoyMn1-x-yO2The corresponding raw materials are as follows: a nickel-cobalt-manganese hydroxide precursor, a lithium salt and a cationic additive;
Alternatively, the Li in the step (1)aNixCoyMn1-x-y-zMzO2The corresponding raw materials are as follows: the composite material comprises a nickel-cobalt-manganese hydroxide precursor, a compound of M, a lithium salt and a cationic additive, wherein the M comprises any one or a combination of at least two of B, Ti, Zr, Mg, Sr, Ba, V, Zn or Bi; the cation additive is any one or the combination of at least two of an iridium source, an yttrium source, a tellurium source, an indium source or a gallium source, and preferably any one or the combination of two of the tellurium source or the gallium source.
5. The method according to claim 4, wherein the stoichiometric ratio is Li when the raw material of step (1) does not contain M compoundsaNixCoyMn1-x-yO2The chemical formula of the nickel-cobalt-manganese hydroxide precursor is NixCoyMn1-x-y(OH)2Wherein a is more than or equal to 1.0 and less than or equal to 1.1, 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 0.05 and less than or equal to 0.25;
preferably, when the raw material of step (1) contains a compound of M, the stoichiometric ratio is LiaNixCoyMn1-x-y- zMzO2The chemical formula of the nickel-cobalt-manganese hydroxide precursor is NixCoyMn1-x-y-z(OH)2Wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.25, and z is more than or equal to 0.01 and less than or equal to 0.05.
6. The method of claim 4 or 5, wherein in the cationic additive, the iridium source comprises any one of iridium nitrate, iridium acetate, iridium oxalate or iridium oxide or a combination of at least two thereof;
Preferably, in the cationic additive, the yttrium source comprises any one of yttrium nitrate, yttrium acetate, yttrium oxalate or yttrium oxide or a combination of at least two of the above;
preferably, in the cationic additive, the tellurium source comprises any one of tellurium nitrate, tellurium acetate, tellurium oxalate or tellurium oxide or a combination of at least two of the tellurium oxide;
Preferably, in the cationic additive, the indium source comprises any one of indium nitrate, indium acetate or indium oxide or a combination of at least two of them;
Preferably, in the cationic additive, the gallium source comprises any one or a combination of at least two of gallium nitrate, gallium acetate or gallium oxide, preferably gallium nitrate;
preferably, the lithium salt in step (1) comprises any one of lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate or a combination of at least two thereof;
Preferably, in the step (1), the molar ratio of the cations in the cationic additive to the nickel-cobalt-manganese hydroxide precursor is (0.0001-0.001):1, preferably (0.0002-0.0007): 1;
Preferably, the compound of M in step (1) comprises any one or a combination of at least two of zirconium oxide, magnesium oxide, titanium oxide, boron oxide, strontium oxide, barium oxide, vanadium pentoxide, zinc oxide or bismuth oxide;
Preferably, the compound of M in the step (1) has a particle size of 10nm-50 nm;
Preferably, the mixing of step (1) is carried out in a three-dimensional mixer.
7. The method according to any one of claims 4 to 6, wherein the first temperature of step (2) is 400 ℃ to 500 ℃;
Preferably, in the step (2), the heating rate of heating to the first temperature is 3 ℃/min-5 ℃/min;
Preferably, in the step (2), the heat preservation time at the first temperature is 2h-3 h;
preferably, the second temperature of step (2) is 750 ℃ to 900 ℃;
Preferably, in the step (2), the heat preservation time at the second temperature is 10h-15 h;
Preferably, the method further comprises the step of cooling after the step (2) is completed, wherein the cooling rate is 5-10 ℃/min.
8. The method according to any one of claims 1-7, characterized in that the method comprises the steps of:
(1) Mixing:
In stoichiometric ratio LiaNixCoyMn1-x-y-zMzO2Weighing Ni-Co-Mn hydroxide precursor NixCoyMn1-x-y-z(OH)2A is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.05, the M is any one or combination raw material of at least two of B, Ti, Zr, Mg, Sr, Ba, V, Zn or Bi, and the compound of the M is mixed in a three-dimensional mixer, and the particle size of the compound of the M is 10nm-50 nm;
The cation additive is any one or the combination of at least two of an iridium source, an yttrium source, a tellurium source, an indium source or a gallium source;
The molar ratio of cations in the cationic additive to nickel cobalt manganese hydroxide precursor is (0.0001-0.001) 1;
(2) And (3) heat treatment:
Heating to 400-500 ℃ at the speed of 3-5 ℃/min in the oxygen atmosphere, preserving heat for 2-3 h, then continuously heating to 750-900 ℃, preserving heat for 10-15 h, and cooling to obtain the single crystal ternary cathode material LiaNixCoyMn1-x-y-zMzO2。
9. A single crystal ternary positive electrode material produced according to any of claims 1 to 8, wherein the particle size of the single crystal ternary positive electrode material is between 4 μm and 6 μm.
10. A lithium ion battery is characterized in that the anode of the lithium ion battery comprises the single crystal ternary anode material of claim 9 or the single crystal ternary anode material prepared by the method of any one of claims 1 to 8.
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