CN108767226B - Metal phthalocyanine compound coated ternary cathode material and preparation method thereof - Google Patents

Metal phthalocyanine compound coated ternary cathode material and preparation method thereof Download PDF

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CN108767226B
CN108767226B CN201810540787.9A CN201810540787A CN108767226B CN 108767226 B CN108767226 B CN 108767226B CN 201810540787 A CN201810540787 A CN 201810540787A CN 108767226 B CN108767226 B CN 108767226B
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cobalt
lithium
phthalocyanine compound
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王继锋
王夏阳
寇亮
张超
张�诚
田占元
邵乐
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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Abstract

The invention discloses a ternary positive electrode material coated by a metal phthalocyanine compound and a preparation method thereof. Uniformly mixing a lithium source with a nickel-cobalt-manganese hydroxide or nickel-cobalt-aluminum hydroxide precursor, and calcining in high-temperature equipment in an oxygen atmosphere to obtain a matrix of the high-nickel-cobalt lithium manganate or nickel-cobalt lithium aluminate material; and (3) uniformly mixing the metal phthalocyanine compound with the matrix material, and calcining in high-temperature equipment in an oxygen atmosphere to obtain the modified ternary cathode material. The metal phthalocyanine compound has higher electronic conductivity, heat resistance, acid resistance and high-efficiency catalytic action, and is very favorable for improving the charge-discharge capacity and the cycle stability of the high-nickel ternary cathode material.

Description

Metal phthalocyanine compound coated ternary cathode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and relates to a metal phthalocyanine compound coated ternary anode material and a preparation method thereof.
Background
The lithium ion battery is used as a new generation of green high-energy battery, is widely applied to various 3C products and new energy power automobiles, and has a wide market prospect. The current research focus is mainly on further improving the power density and energy density of the material and improving the safety performance. From the anode currently used by lithium ion batteries, the transition metal oxide anode is obviously superior to polyanion anodes such as lithium iron phosphate in the aspect of improving the specific energy of the batteries, and nickel cobalt manganese, nickel cobalt aluminum and the like are mainly used anode materials. As is known, the higher the nickel content of the ternary cathode material is, the higher the energy of the material is, but the preparation conditions of the high-nickel material are harsh, the thermal stability is poor, and the ternary cathode material is sensitive to moisture due to the higher nickel content, so that lithium hydroxide and lithium carbonate are easily generated on the surface of the cathode, and the alkalinity of the surface of the material is too high. On one hand, the loss of active lithium ions is caused, and the charge and discharge capacity of the material is reduced; on the other hand, alkaline substances on the surface are easy to generate side reaction with the electrolyte in the circulation process, so that the layered structure of the material is damaged, and the capacity is quickly attenuated. Therefore, much attention has been paid to the problem of poor thermal stability and electrochemical cycle stability. At present, the main modification method is to coat nano inorganic material particles such as nano aluminum oxide, zinc oxide and the like on the surface, and the nano inorganic materials have poor coating effect and large interfacial electrochemical resistance, so that the polarization of the battery in the cycle process is large, and the capacity exertion is reduced.
Disclosure of Invention
Aiming at the problems of unstable structure, poor electrochemical cycle performance and the like of a ternary material, the invention aims to provide a metal phthalocyanine compound-coated ternary cathode material and a preparation method thereof, so that the electrochemical cycle stability of the ternary cathode material is effectively improved under the condition of not reducing the first charge-discharge capacity of the material.
The invention is realized by the following technical scheme:
a ternary positive electrode material coated by a metal phthalocyanine compound takes nickel cobalt lithium manganate or nickel cobalt lithium aluminate as a matrix, and the matrix is coated with the metal phthalocyanine compound.
Preferably, the metal phthalocyanine compound is a mononuclear phthalocyanine metal complex, a binuclear phthalocyanine metal complex or a heteronuclear phthalocyanine metal complex.
Preferably, the metal in the metal phthalocyanine compound refers to one or two of nickel, manganese, cobalt, yttrium and neodymium.
Preferably, the metal phthalocyanine compound is mononuclear cobalt phthalocyanine, binuclear nickel phthalocyanine, heteronuclear manganese cobalt phthalocyanine, mononuclear yttrium phthalocyanine or mononuclear neodymium phthalocyanine.
A preparation method of a ternary cathode material coated by a metal phthalocyanine compound comprises the steps of uniformly mixing the metal phthalocyanine compound with matrix nickel cobalt lithium manganate or nickel cobalt lithium aluminate, and calcining in an oxygen atmosphere to obtain the ternary cathode material coated by the metal phthalocyanine compound.
Preferably, the metal phthalocyanine compound is used in a molar percentage of 0.05-2% of the matrix.
Preferably, the calcination temperature is 400-600 ℃.
Preferably, the preparation method of the matrix lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate comprises the following steps: and uniformly mixing a lithium source with the nickel-cobalt-manganese hydroxide or the nickel-cobalt-aluminum hydroxide, and calcining in high-temperature equipment in an oxygen atmosphere to obtain matrix lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate.
Further, the lithium source is one or two of lithium hydroxide and lithium carbonate; in the nickel-cobalt-manganese hydroxide or nickel-cobalt-aluminum hydroxide, the molar content of nickel element is 80-96%, the molar content of cobalt element is 2-15%, and the molar content of manganese element or aluminum element is 2-15%; the molar ratio of the lithium element to the nickel cobalt manganese hydroxide or nickel cobalt aluminum hydroxide is (1-1.15): 1.
Further, the calcination is two-stage calcination, wherein the first-stage calcination temperature is 500-550 ℃, and the second-stage calcination temperature is 700-800 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the ternary cathode material coated by the metal phthalocyanine compound, on one hand, the surface base number of the surface-coated high-nickel ternary cathode is reduced, the generation of lithium hydroxide and lithium carbonate is avoided, and the loss of active lithium ions is reduced. On the other hand, the metal phthalocyanine compound is acid-resistant and heat-resistant and has higher electronic conductivity, can avoid the corrosion of the surface of the anode material by the electrolyte solution at normal temperature, even high temperature and high voltage, and improves the cycling stability of the material. In addition, the metal phthalocyanine compound has good catalysis, and can improve the discharge voltage of the battery, prolong the discharge time of the battery and further improve the energy of the battery.
The preparation method of the metal phthalocyanine compound-coated ternary cathode material has simple steps and is easy to operate.
Drawings
FIG. 1 is SEM of the finished product of example 1.
FIG. 2 is a cycle chart of the product obtained in example 1.
FIG. 3 is a cycle chart of the product obtained in example 2.
FIG. 4 is a cycle chart of the product obtained in example 3.
FIG. 5 is a cycle chart of the product obtained in example 4.
FIG. 6 is a cycle chart of the product obtained in example 5.
FIG. 7 is a cycle chart of a product in a comparative example.
In each cycle chart, the abscissa represents the number of cycles, and the ordinate represents the specific discharge capacity.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The ternary positive electrode material coated by the metal phthalocyanine compound takes high-nickel cobalt lithium manganate or nickel cobalt lithium aluminate as a matrix, and the matrix is coated with the metal phthalocyanine compound.
The metal phthalocyanine compound comprises a mononuclear phthalocyanine metal complex, a binuclear phthalocyanine metal complex or a heteronuclear phthalocyanine metal complex.
The metal in the metal phthalocyanine compound refers to one or two of nickel, manganese, cobalt, yttrium and neodymium, for example, the metal phthalocyanine compound is mononuclear cobalt phthalocyanine, binuclear nickel phthalocyanine, heteronuclear manganese cobalt phthalocyanine, mononuclear yttrium phthalocyanine or mononuclear neodymium phthalocyanine.
The preparation method comprises the following steps:
step one, preparing raw materials, namely uniformly mixing a lithium source and a nickel-cobalt-manganese hydroxide or nickel-cobalt-aluminum hydroxide precursor, and calcining the mixture in high-temperature equipment in an oxygen atmosphere to obtain a high-nickel-cobalt-lithium manganate or nickel-cobalt-lithium aluminate material as the substrate;
and step two, material modification, namely uniformly mixing the metal phthalocyanine compound with the matrix obtained in the step one, and calcining the mixture in high-temperature equipment in an oxygen atmosphere to obtain the ternary cathode material coated by the metal phthalocyanine compound.
In the first step, the lithium source is one or two of lithium hydroxide and lithium carbonate.
In the first step, the content of nickel element in the nickel-cobalt-manganese hydroxide or nickel-cobalt-aluminum hydroxide precursor is 80-96% of the total mol amount, the content of cobalt element is 2-15% of the total mol amount, the content of manganese element or aluminum element is 2-15% of the total mol amount, and the molar ratio of lithium to nickel-cobalt-aluminum hydroxide is (1-1.15): 1.
In the first step, the calcination is performed in two stages, wherein the first stage calcination temperature is 500-550 ℃, and the second stage calcination temperature is 700-800 ℃.
In the second step, the dosage of the phthalocyanine compound is 0.05-2% of the dosage of the matrix according to molar percentage.
In the second step, the calcination temperature is 400-600 ℃.
Specific examples are as follows.
Example 1
Step one, uniformly mixing lithium hydroxide and a nickel-cobalt-manganese hydroxide precursor, wherein the molar ratio of three metal elements of nickel-cobalt-manganese in nickel-cobalt-manganese lithium manganate is 80:10:10, the molar ratio of lithium to nickel-cobalt-manganese hydroxide is 1:1, calcining the mixture in high-temperature equipment in an oxygen atmosphere, keeping the temperature for 6h at 550 ℃ for the first time, 2 ℃/min at the temperature rise speed, 700 ℃ for the second time, 16h at the temperature rise speed, and obtaining a nickel-cobalt-manganese lithium substrate material;
and step two, uniformly mixing the mononuclear cobalt phthalocyanine (CoPc) and the matrix material, placing the mononuclear cobalt phthalocyanine (CoPc) in high-temperature equipment to calcine in an oxygen atmosphere at the calcining temperature of 400 ℃ to obtain the modified material, wherein the dosage of the mononuclear cobalt phthalocyanine is 1% of that of the matrix.
And step three, crushing the modified material, mixing the crushed modified material with a conductive agent and a binder according to the mass ratio of 8:1:1, coating, preparing a pole piece, assembling a button type half cell, and evaluating the electrochemical performance of the cell.
As shown in fig. 2, the test results are: the first charging specific capacity of 0.1C is 220mAh/g, the first discharging specific capacity is 201mAh/g, and the capacity retention rate of 100 cycles of 1C is 90.4%.
The mononuclear cobalt phthalocyanine in this example can be replaced with mononuclear manganese phthalocyanine without changing other conditions.
Example 2
Uniformly mixing lithium carbonate and a nickel-cobalt-aluminum hydroxide precursor, wherein the molar ratio of three metal elements of nickel-cobalt-aluminum in the nickel-cobalt-aluminum aluminate is 83:15:2, the molar ratio of lithium to the nickel-cobalt-aluminum hydroxide is 1.15:1, calcining the mixture in high-temperature equipment in an oxygen atmosphere, keeping the temperature for 6h at 500 ℃ for the first time, and keeping the temperature for 16h at 2 ℃/min and 800 ℃ for the second time to obtain a nickel-cobalt-lithium manganate matrix material;
and step two, uniformly mixing the binuclear nickel phthalocyanine (Ni2Pc2) and the matrix material, wherein the dosage of the binuclear nickel phthalocyanine is 0.05 percent of the dosage of the matrix, placing the binuclear nickel phthalocyanine in high-temperature equipment, and calcining the binuclear nickel phthalocyanine in an oxygen atmosphere at the calcining temperature of 600 ℃ to obtain the modified material.
And step three, crushing the modified material, mixing the crushed modified material with a conductive agent and a binder according to the mass ratio of 8:1:1, coating, preparing a pole piece, assembling a button type half cell, and evaluating the electrochemical performance of the cell.
As shown in fig. 3, the test results are: the first charge specific capacity of 0.1C is 227mAh/g, the first discharge specific capacity is 206mAh/g, and the capacity retention rate of 100 cycles of 1C is 89.2%.
Example 3
Step one, uniformly mixing lithium hydroxide and a nickel-cobalt-manganese hydroxide precursor, wherein the molar ratio of three metal elements of nickel-cobalt-manganese in nickel-cobalt-manganese lithium manganate is 96:2:2, the molar ratio of lithium to nickel-cobalt-manganese hydroxide is 1.05:1, calcining the mixture in high-temperature equipment in an oxygen atmosphere, keeping the temperature for 6h at 525 ℃ for the first time, raising the temperature at 2 ℃/min at 750 ℃ for the second time, and raising the temperature at 2 ℃/min for 16h to obtain a nickel-cobalt-manganese acid lithium matrix material;
and step two, uniformly mixing heteronuclear manganese cobalt phthalocyanine (MnCoPc2) and a matrix material, placing the heteronuclear manganese cobalt phthalocyanine accounting for 2% of the matrix material in high-temperature equipment, and calcining at 500 ℃ in an oxygen atmosphere to obtain the modified material.
And step three, crushing the modified material, mixing the crushed modified material with a conductive agent and a binder according to the mass ratio of 8:1:1, coating, preparing a pole piece, assembling a button type half cell, and evaluating the electrochemical performance of the cell.
As shown in fig. 4, the test results are: the first charging specific capacity of 0.1C is 235mAh/g, the first discharging specific capacity is 210mAh/g, and the capacity retention rate of 100 cycles of 1C is 87.9%.
Under other conditions, the heteronuclear manganese cobalt phthalocyanine in the embodiment can be replaced by heteronuclear nickel cobalt phthalocyanine, heteronuclear manganese yttrium phthalocyanine or heteronuclear nickel neodymium phthalocyanine
Example 4
Step one, uniformly mixing lithium carbonate and a nickel-cobalt-aluminum hydroxide precursor, wherein the molar ratio of three metal elements of nickel-cobalt-aluminum in the nickel-cobalt-lithium aluminate is 80:5:15, the molar ratio of lithium to the nickel-cobalt-aluminum hydroxide is 1:1, calcining the mixture in high-temperature equipment in an oxygen atmosphere, keeping the temperature for 6h at 550 ℃ for the first time, 2 ℃/min at the temperature rise speed, 700 ℃ for the second time, 16h at the temperature rise speed, and 2 ℃/min to obtain a nickel-cobalt-lithium aluminate matrix material;
and step two, uniformly mixing the mononuclear yttrium phthalocyanine with the matrix material, placing the mononuclear yttrium phthalocyanine in a high-temperature device to calcine in an oxygen atmosphere at the calcining temperature of 550 ℃, and thus obtaining the modified material, wherein the dosage of the mononuclear yttrium phthalocyanine is 0.05% of that of the matrix material.
As shown in fig. 5, the test results are: the first charging specific capacity of 0.1C is 217mAh/g, the first discharging specific capacity is 196mAh/g, and the capacity retention rate of 100 cycles of 1C is 75.7%.
Example 5
Uniformly mixing lithium carbonate and a nickel-cobalt-manganese hydroxide precursor, wherein the molar ratio of three metal elements of nickel-cobalt-manganese in nickel-cobalt-manganese lithium manganate is 80:5:15, the molar ratio of lithium to nickel-cobalt-manganese hydroxide is 1:1, calcining the mixture in high-temperature equipment in an oxygen atmosphere, keeping the temperature for 6h at 520 ℃ for the first time, and keeping the temperature for 10h at 780 ℃ for the second time at 2 ℃/min to obtain a nickel-cobalt-manganese acid lithium matrix material;
and step two, uniformly mixing the mononuclear neodymium phthalocyanine (NdPc) and the matrix material, placing the mononuclear neodymium phthalocyanine (NdPc) and the matrix material in high-temperature equipment, and calcining the mixture in an oxygen atmosphere at the calcining temperature of 500 ℃ to obtain the modified material.
As shown in fig. 6, the test results are: the first charging specific capacity of 0.1C is 221mAh/g, the first discharging specific capacity is 193mAh/g, and the capacity retention rate of 100 cycles of 1C is 73.9%.
Under the condition that other conditions are not changed, the lithium carbonate in the embodiment can be replaced by a mixture of lithium carbonate and lithium hydroxide in any proportion.
Comparative example
Step one, uniformly mixing lithium hydroxide and a nickel-cobalt-manganese hydroxide precursor, wherein the molar ratio of three metal elements of nickel-cobalt-manganese in nickel-cobalt-manganese lithium manganate is 80:10:10, the molar ratio of lithium to nickel-cobalt-manganese hydroxide is 1:1, calcining the mixture in high-temperature equipment in an oxygen atmosphere, keeping the temperature for 6h at 550 ℃ for the first time, 2 ℃/min at the temperature rise speed, 700 ℃ for the second time, 16h at the temperature rise speed, and 2 ℃/min to obtain a nickel-cobalt-manganese acid lithium anode material;
and secondly, crushing the positive electrode material, mixing the crushed positive electrode material with a conductive agent and a binder according to the mass ratio of 8:1:1, coating, preparing a pole piece, assembling a button type half cell, and evaluating the electrochemical performance of the cell.
As shown in fig. 7, the test results are: the first charging specific capacity of 0.1C is 200mAh/g, the first discharging specific capacity is 192mAh/g, and the capacity retention rate of 100 cycles of 1C is 59.8%.
FIG. 1 is an SEM photograph of the product obtained in example 1, and it can be seen that the particle size is uniform. From fig. 7, when the nickel cobalt lithium manganate cathode material without being coated and modified circulates for 100 circles, the capacity is reduced seriously, and is reduced from the original 192mAh/g to about 115mAh/g, that is, the capacity retention rate is only 59.8% after 1C circulation for 100 circles. After the metal phthalocyanine compound is used for coating, as can be seen from fig. 2-6, the capacity of the positive electrode material is slowly reduced, and the capacity retention rate is over 70% and optimally can reach about 90% when the positive electrode material is subjected to 1C cycle 100 cycles, so that the electrochemical performance of the positive electrode material can be greatly improved by coating the positive electrode material with the metal phthalocyanine compound.

Claims (3)

1. A ternary positive electrode material coated by a metal phthalocyanine compound is characterized in that nickel cobalt lithium manganate or nickel cobalt lithium aluminate is taken as a matrix, and the matrix is coated with the metal phthalocyanine compound; the metal phthalocyanine compound is mononuclear cobalt phthalocyanine, binuclear nickel phthalocyanine or heteronuclear manganese cobalt phthalocyanine;
the preparation method of the matrix lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate comprises the following steps: uniformly mixing a lithium source and nickel cobalt manganese hydroxide or nickel cobalt aluminum hydroxide, and calcining in high-temperature equipment in an oxygen atmosphere to obtain matrix lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate;
in the nickel-cobalt-manganese hydroxide or nickel-cobalt-aluminum hydroxide, the molar content of nickel element is 80-96%, the molar content of cobalt element is 2-15%, and the molar content of manganese element or aluminum element is 2-15%; the molar ratio of the lithium element to the nickel cobalt manganese hydroxide or nickel cobalt aluminum hydroxide is (1-1.15): 1.
2. The preparation method of the ternary cathode material coated with the metal phthalocyanine compound, according to claim 1, is characterized in that the metal phthalocyanine compound and the matrix lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate are uniformly mixed and calcined in an oxygen atmosphere to obtain the ternary cathode material coated with the metal phthalocyanine compound;
according to the mol percentage, the dosage of the metal phthalocyanine compound is 0.05-2% of the dosage of the matrix;
the calcination temperature is 400-600 ℃.
3. The method for preparing the metal phthalocyanine compound-coated ternary cathode material as claimed in claim 2, wherein the calcination is performed in two stages, wherein the first stage calcination temperature is 500-550 ℃, and the second stage calcination temperature is 700-800 ℃.
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