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CN111785957A - Monocrystal-like ternary cathode material and preparation method and application thereof - Google Patents

Monocrystal-like ternary cathode material and preparation method and application thereof Download PDF

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CN111785957A
CN111785957A CN202010523830.8A CN202010523830A CN111785957A CN 111785957 A CN111785957 A CN 111785957A CN 202010523830 A CN202010523830 A CN 202010523830A CN 111785957 A CN111785957 A CN 111785957A
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cathode material
ball milling
ternary cathode
monocrystal
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赵文誉
阮丁山
林波
刘伟健
李长东
陈喜
柳娜
杜锐
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • 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
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract

The invention discloses a monocrystal-like ternary cathode material and a preparation method and application thereof, wherein the chemical formula of the monocrystal-like ternary cathode material is LiNixCoyMn(1‑x‑y‑i‑j)WiNbjO2(ii) a Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0, i is more than or equal to 0.0001 and less than or equal to 0.01, and j is more than or equal to 0.0001 and less than or equal to 0.01. Preparation method of the inventionThe ternary cathode material has the performance advantages of low gas generation of large single crystal particles, high safety, long circulation and high capacity of polycrystalline aggregates, and is suitable for lithium ion power batteries.

Description

Monocrystal-like ternary cathode material and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a monocrystal-like ternary cathode material as well as a preparation method and application thereof.
Background
In the field of electric automobiles, people generally concern the endurance mileage of electric automobiles, and along with the occurrence of various spontaneous combustion events of electric automobiles, people also pay more and more attention to the safety performance of electric automobiles. The most critical part of the electric automobile is a lithium ion battery, which generally consists of a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the performance of a positive electrode material directly determines the energy density, the safety performance and the service life of the lithium ion battery. At present, lithium intercalation compounds such as LiMn are commonly adopted as the anode of the lithium ion battery2O4、LiFePO4、LiCoO2Ternary positive electrode material Li (Ni)xCoyMnz)O2. Among them, the ternary positive electrode material has a higher energy density advantage, and thus has been the focus of research in various large battery manufacturers. The theoretical ternary positive electrode material has an ultra-high capacity of 274mAh/g, but due to irreversible loss of the first effect and the material itselfThe structure defect of (2) is difficult to fully embody the capacity.
In addition, the traditional ternary cathode material has a spherical secondary particle distribution in the microscopic morphology, is easy to break due to overlarge pressure in the manufacturing process of a battery pole piece, and is easy to break due to volume shrinkage expansion in the long-term cyclic charge and discharge process, so that fresh active substances are directly exposed in electrolyte, and the deoxidation reaction is easy to occur, so that the battery expands and potential safety hazards are caused. In order to solve the problems of the traditional ternary cathode material, an effective method is to perform single crystallization on the ternary cathode material, namely the morphology of the ternary cathode material is in primary large particle distribution. The material has the advantages of high compaction, good circulation, higher safety, more stable use under high voltage and high compaction and high voltage, thereby attracting more and more attention of people. However, the size of primary particles of the ternary cathode material after single crystallization is increased, so that the lithium ion inlet and outlet paths are increased, and the lithium ion transmission resistance is increased in the charging and discharging processes, so that the material is faced with lower first coulombic efficiency and poorer rate performance.
Disclosure of Invention
The invention aims to provide a monocrystal-like ternary cathode material, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a monocrystal-like ternary cathode material with a chemical formula of LiNixCoyMn(1-x-y-i-j)WiNbjO2(ii) a Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0, i is more than or equal to 0.0001 and less than or equal to 0.01, j is more than or equal to 0.0001 and less than or equal to 0.01, and 1-x-y-i-j is more than or equal to 0.
Preferably, the compacted density of the monocrystal-like ternary cathode material is 3.35-3.65g/cm3。
A preparation method of a monocrystal-like ternary cathode material comprises the following steps:
(1) mixing a nickel-cobalt-manganese hydroxide precursor with a lithium source, adding ball milling beads, and carrying out primary ball milling to obtain a bead mixture A;
(2) adding a tungsten compound and a niobium compound into the bead mixture A, and performing secondary ball milling to obtain a bead mixture B;
(3) and (3) taking out the ball milling beads in the bead mixture B, sintering, cooling, carrying out jet milling, and sieving to obtain the monocrystal-like ternary cathode material.
Preferably, the chemical formula of the nickel-cobalt-manganese hydroxide precursor in the step (1) is NixCoyMn(1-x-y)(OH)2Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0, and 1-x-y is more than or equal to 0.
Preferably, the lithium source in step (1) is Li2O、LiOH、LiOH·H2O or Li2CO3One kind of (1).
Preferably, the molar ratio of the sum of the molar amounts of the nickel element, the cobalt element and the manganese element in the Li and nickel cobalt manganese hydroxide precursor in the lithium source in step (1) is (1-1.3): 1.
preferably, the mass ratio (ball milling ratio) of the nickel-cobalt-manganese hydroxide precursor mixed with the lithium source to the ball milling beads in step (1) is 1: (0.5-2).
Preferably, the rotation speed of the ball milling in the step (1) is 100-400 r/min, and the time is 1-4 h.
Preferably, the tungsten compound in step (2) is nano-sized WO3、WS2Or WF6At least one of (1).
Preferably, the niobium compound in step (2) is nano-sized Nb2O5、NbS2Or C4H4NNbO9At least one of (1).
Preferably, the mass ratio of the tungsten compound, the niobium compound and the precursor in the step (1) in the step (2) is (0.01% -1%): (0.01% -1%): 1.
preferably, the rotation speed of the secondary ball milling in the step (2) is 50-300 r/min, and the time is 0.1-3 h.
Preferably, the sintering in the step (3) comprises two calcining sections, the temperature rise rate of the first calcining section is 1-6 ℃/min, the temperature of the first calcining section is 400-700 ℃, and the time is 2-8 h; the temperature rise rate of the second calcining section is 1-6 ℃/min, the temperature of the second calcining section is 700-1000 ℃, and the time is 8-16 h.
Preferably, the atmosphere for sintering in step (3) is one of air or oxygen.
A lithium battery comprises the monocrystal-like ternary cathode material.
Advantageous effects
1. The ternary cathode material prepared by the preparation method has the performance advantages of low gas production of large single crystal particles, high safety, long circulation and high capacity of polycrystalline aggregates, and is suitable for lithium ion power batteries; the preparation method overcomes the defects of complicated steps and high energy consumption of the traditional secondary sintering process, is simple and easy to control, has high efficiency and low cost, is safe in production process, and is easy for industrial production.
2. The grain growth of the tungsten-rich precursor after secondary ball milling in the primary sintering process is inhibited, so compact secondary particles are obtained, on the contrary, the precursor with partial tungsten deficiency grows normally to obtain loose large-particle aggregates, the primary particles are easy to break loose and bind in the crushing process to obtain large single crystal particles, and simultaneously, the addition of the niobium compound can form LiNbO in the primary sintering initial stage of the material3The coating layer can inhibit the growth rate of primary particles at the later stage of primary sintering by cooperating with tungsten doping so as to obtain the monocrystal-like morphology of large monocrystal particles and polycrystal aggregates in graded distribution.
Drawings
FIG. 1 is an XRD pattern of a quasi-single crystal ternary cathode material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a single crystal-like ternary cathode material prepared in example 1 of the present invention;
fig. 3 is a cycle stability curve and a coulombic efficiency curve of the single crystal-like ternary positive electrode materials prepared in examples 1 to 3 and comparative example 1 of the present invention at a discharge rate of 1C.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
The chemical formula of the single crystal-like ternary cathode material prepared in the embodiment is LiNi0.9Co0.05Mn0.04725W0.00129Nb0.00146O2The compacted density is 3.42g/cm3。
The preparation method of the single crystal-like ternary cathode material of the embodiment specifically comprises the following steps:
(1) 100g of Ni were weighed0.9Co0.05Mn0.05(OH)248.86g of LiOH. H2Placing the O and 148.86g of ball milling beads in a ball milling tank with the rotating speed of 300r/min, and carrying out ball milling for 1h to obtain a bead mixture A;
(2) 129mg of WO are weighed out3And 146mg of Nb2O5Adding the mixture into the bead mixture A obtained in the step (1), adjusting the ball milling rotation speed to 100r/min, and performing ball milling for 0.5h to obtain a bead mixture B;
(3) removing the ball milling beads of the bead mixture B, placing the ball milling beads in a clean sagger, transferring the sagger into a box furnace, heating at the heating rate of 3 ℃/min, sintering at 500 ℃ for 4h, sintering at 760 ℃ for 12h, naturally cooling to room temperature, jet milling, and sieving to obtain the monocrystal-like ternary cathode material named WNB 1-NCM.
Example 2
The chemical formula of the single crystal-like ternary cathode material prepared in the embodiment is LiNi0.9Co0.05Mn0.0445W0.00258Nb0.00292O2The compacted density is 3.61g/cm3。
The preparation method of the single crystal-like ternary cathode material of the embodiment specifically comprises the following steps:
(1) 100g of Ni were weighed0.9Co0.05Mn0.05(OH)248.86g of LiOH. H2Placing the O and 148.86g of ball milling beads in a ball milling tank with the rotating speed of 300r/min, and carrying out ball milling for 1h to obtain a bead mixture A;
(2) weigh 258mg of WO3And 292mg of Nb2O5Adding the mixture into the bead mixture A obtained in the step (1), adjusting the ball milling rotation speed to 100r/min, and performing ball milling for 0.5h to obtain a bead mixture B;
(3) removing the ball milling beads of the bead mixture B, placing the ball milling beads in a clean sagger, transferring the sagger into a box furnace, heating at the heating rate of 3 ℃/min, sintering at 500 ℃ for 4h, sintering at 760 ℃ for 12h, naturally cooling to room temperature, jet milling, and sieving to obtain the monocrystal-like ternary cathode material named WNB 2-NCM.
Example 3
The chemical formula of the single crystal-like ternary cathode material prepared in the embodiment is LiNi0.9Co0.05Mn0.0445W0.00258Nb0.00292O2The compacted density is 3.49g/cm3。
The preparation method of the single crystal-like ternary cathode material of the embodiment specifically comprises the following steps:
(1) 100g of Ni were weighed0.9Co0.05Mn0.05(OH)248.86g of LiOH. H2Placing the O and 148.86g of ball milling beads in a ball milling tank with the rotating speed of 300r/min, and carrying out ball milling for 1h to obtain a bead mixture A;
(2) weigh 258mg of WO3And 292mg of Nb2O5Adding the mixture into the bead mixture A obtained in the step (1), adjusting the ball milling rotation speed to 100r/min, and performing ball milling for 2 hours to obtain a bead mixture B;
(3) removing the ball milling beads of the bead mixture B, placing the ball milling beads in a clean sagger, transferring the sagger into a box furnace, heating at the heating rate of 3 ℃/min, sintering at 500 ℃ for 4h, sintering at 760 ℃ for 12h, naturally cooling to room temperature, jet milling, and sieving to obtain the monocrystal-like ternary cathode material named WNB 3-NCM.
Example 4
The chemical formula of the single crystal-like ternary cathode material prepared in the embodiment is LiNi0.9Co0.05Mn0.04725W0.00129Nb0.00146O2The compacted density is 3.49g/cm3。
The preparation method of the single crystal-like ternary cathode material of the embodiment specifically comprises the following steps:
(1) 100g of Ni were weighed0.9Co0.05Mn0.05(OH)248.86g of LiOH. H2Placing the O and 148.86g of ball milling beads in a ball milling tank with the rotating speed of 300r/min, and carrying out ball milling for 1h to obtain a bead mixture A;
(2) 129mg of WO are weighed out3And 146mg of Nb2O5Adding the mixture into the bead mixture A obtained in the step (1), adjusting the ball milling rotation speed to 200r/min, and performing ball milling for 0.5h to obtain a bead mixture B;
(3) removing the ball milling beads of the bead mixture B, placing the ball milling beads in a clean sagger, transferring the sagger into a box furnace, heating at the heating rate of 3 ℃/min, sintering at 500 ℃ for 4h, sintering at 760 ℃ for 12h, naturally cooling to room temperature, jet milling, and sieving to obtain the monocrystal-like ternary cathode material named WNB 4-NCM.
Comparative example 1
The chemical formula of the monocrystal-like ternary cathode material prepared by the comparative example is LiNi0.9Co0.05Mn0.05O2The compacted density is 3.37g/cm3。
A preparation method of a shape-controllable single-crystal-like ternary cathode material comprises the following specific steps:
(1) 100g of Ni were weighed0.9Co0.05Mn0.05(OH)248.86g of LiOH. H2Placing the O and 148.86g of ball milling beads in a ball milling tank with the rotating speed of 300r/min, and carrying out ball milling for 1h to obtain a bead mixture A;
(2) removing the ball milling beads of the bead mixture A, placing the ball milling beads in a clean sagger, transferring the sagger into a box type furnace, and keeping the temperature at 500 ℃ for 4h and 760 ℃ for 12h at a heating rate of 3 ℃/min;
(3) and (4) after the calcined material in the step (3) is naturally cooled to room temperature, taking out the calcined material, and performing airflow crushing and sieving to obtain the monocrystal-like ternary positive electrode material named Pristine NCM.
The single crystal-like ternary positive electrode materials prepared in examples 1-5 and comparative example 1 were uniformly mixed with acetylene black as a conductive agent and PVDF as a binder, then a proper amount of N-methylpyrrolidone (NMP) solvent was added dropwise to prepare a slurry, which was uniformly coated on a treated aluminum foil substrate, dried and punched into a circular positive electrode sheet, and the circular positive electrode sheet was assembled into a button cell for a button performance test. The test results are shown in table 1:
TABLE 1 test Properties of different materials
Figure BDA0002533021490000051
As can be seen from FIG. 1 and Table 1, the values of the buckling capacity, the compacted density and the particle size distribution coefficient of examples 1 to 3 are higher than those of comparative example 1, and it is proved that the performance of the single crystal-like ternary positive electrode material prepared by the method of the present invention is good, i.e., WNB2-NCM (example 2)(003)/I(104)Highest strength, evidence of Li+/Ni2+The mixed row is minimum, and the laminated structure is complete. As can be seen from FIG. 2 and Table 1, WNB2-NCM (example 2) is in the form of a polycrystalline spherical aggregate and is uniformly distributed with single crystal large particles, and the distribution coefficient of particle size shows that the morphology has a wide distribution of particle size and the highest holding capacity.
The foregoing has outlined, in detail, the positive electrode additive and the method of making and using thereof provided by the present invention so that the present principles and embodiments may be better understood, and so that the present invention may be better understood and appreciated by those skilled in the art. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. The monocrystal-like ternary cathode material is characterized in that the chemical formula of the monocrystal-like ternary cathode material is LiNixCoyMn(1-x-y-i-j)WiNbjO2(ii) a Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0, i is more than or equal to 0.0001 and less than or equal to 0.01, and j is more than or equal to 0.0001 and less than or equal to 0.01.
2. The preparation method of the mono-like ternary cathode material of claim 1, characterized by comprising the following steps:
(1) mixing a nickel-cobalt-manganese hydroxide precursor with a lithium source, adding ball milling beads, and carrying out primary ball milling to obtain a bead mixture A;
(2) adding a tungsten compound and a niobium compound into the bead mixture A, and performing secondary ball milling to obtain a bead mixture B;
(3) and (3) taking out the ball milling beads in the bead mixture B, sintering, cooling, carrying out jet milling, and sieving to obtain the monocrystal-like ternary cathode material.
3. The method according to claim 2, wherein the chemical formula of the nickel cobalt manganese hydroxide precursor in step (1) is NixCoyMn(1-x-y)(OH)2Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0, and 1-x-y is more than or equal to 0.
4. The production method according to claim 2, wherein the lithium source in the step (1) is Li2O、LiOH、LiOH·H2O or Li2CO3One kind of (1).
5. The production method according to claim 2, characterized in that the molar ratio of the sum of the molar amounts of the nickel element, the cobalt element, and the manganese element in the Li in the lithium source and the nickel-cobalt-manganese hydroxide precursor in step (1) is (1-1.3): 1.
6. the production method according to claim 2, wherein the tungsten compound in the step (2) is WO of nanometer scale3、WS2Or WF6At least one of (1).
7. The method according to claim 2, wherein the niobium compound in the step (2) is nano-sized Nb2O5、NbS2Or C4H4NNbO9At least one of (1).
8. The production method according to claim 2, wherein the mass ratio of the tungsten compound, the niobium compound, and the precursor in step (1) in step (2) is (0.01% to 1%): (0.01% -1%): 1.
9. the preparation method according to claim 2, wherein the sintering in the step (3) comprises two calcining sections, the temperature rise rate of the first calcining section is 1-6 ℃/min, the temperature of the first calcining section is 400-700 ℃, and the time is 2-8 h; the temperature rise rate of the second calcining section is 1-6 ℃/min, the temperature of the second calcining section is 700-1000 ℃, and the time is 8-16 h.
10. A lithium battery comprising the single crystal-like ternary positive electrode material of claim 1.
CN202010523830.8A 2020-06-10 2020-06-10 Monocrystal-like ternary cathode material and preparation method and application thereof Pending CN111785957A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
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