CN111793824B - Surface-modified high-nickel cathode material and preparation method and application thereof - Google Patents

Surface-modified high-nickel cathode material and preparation method and application thereof Download PDF

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CN111793824B
CN111793824B CN202010706071.9A CN202010706071A CN111793824B CN 111793824 B CN111793824 B CN 111793824B CN 202010706071 A CN202010706071 A CN 202010706071A CN 111793824 B CN111793824 B CN 111793824B
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heat treatment
nickel
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anode material
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韩永康
郑洪河
曲群婷
朱国斌
王艳
沈鸣
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Suzhou Huaying New Energy Materials Technology Co ltd
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Abstract

The invention belongs to the technical field of lithium ion batteries. The invention provides a preparation method of a surface-modified high-nickel anode material, a modifier and surface residual lithium Li of the high-nickel anode material2And O reaction realizes in-situ generation of the LiBOB surface coating layer under the low-temperature condition, so that residual lithium on the surface of the high-nickel anode material is eliminated, and BOB salt coating on the surface of the high-nickel anode material is realized. According to the cathode material provided by the invention, the lithium bis (oxalato) borate protective layer is formed on the surface, so that the surface alkalinity of the modified material is obviously reduced, and the cycling stability of the material, including the cycling stability under high-temperature and high-pressure conditions, is obviously improved. The invention also provides application of the surface modified high-nickel cathode material in preparation of a lithium ion battery, and has important significance in development of the lithium ion battery with high performance, high safety and long service life.

Description

Surface-modified high-nickel cathode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a surface-modified high-nickel cathode material and a preparation method and application thereof.
Background
In recent years, with the rapid development of electric vehicles and hybrid vehicles, higher demands have been made on the energy density of lithium ion batteries for vehicles. The nickel-based positive electrode material, particularly the high-nickel ternary positive electrode material, has the advantages of high specific capacity and specific energy, low toxicity, low cost and the like, is widely concerned by battery workers, and is considered to be an ideal positive electrode material for high-end and hybrid power electric vehicles. The single crystal high nickel anode material has obvious advantages in the aspects of mechanical stress resistance, gas generation reduction and compaction improvement, and is an important development direction in recent years.
However, the problem of residual lithium on the surface of the high-nickel cathode material is serious because the high-nickel cathode material is mostly prepared by a high-temperature solid-phase synthesis method, and a solid lithium source such as LiOH and Li needs to be added in the preparation process2CO3Etc., since such solid lithium sources are volatile at high temperatures, an excessive amount of lithium source is generally added at the time of raw material mixing to compensate for the problem of lithium volatilization during high-temperature sintering. However, the amount of lithium volatilized during sintering of the material is not controllable, thereby causing residual Li on the surface of the material2Phenomenon of O, Li2O is unstable and easily reacts with H in the air2O and CO2Combined and further converted into LiOH and Li 2CO3The alkalinity of the surface of the material is higher, the phenomenon not only influences the pulping and size mixing of the anode, but also has important influence on the electrochemical performance of the electrode, and not only can bring about the serious gas generation problem in the battery cycle process, but also influences the cycle performance of the material. For this reason, elimination of residual lithium is one of the important concerns in the lithium ion battery industry. At present, water washing and secondary high-temperature calcination (700-800 ℃) are generally adopted in industry, although the method is simple, a large amount of metal ion wastewater and high energy consumption can be generated, small-molecular organic acids such as formic acid, acetic acid and the like are also used for directly washing the high-nickel anode material, and borate and phosphate are also directly added to 500 DEG CCalcination at temperatures above this temperature gives unsatisfactory properties. Moreover, the high-nickel anode material is a material very sensitive to moisture, and only expensive organic solvents can be used in the wet modification process, so that the cost in the treatment process is further increased.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a surface-modified high-nickel cathode material and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a preparation method of a surface-modified high-nickel cathode material, which comprises the following steps:
(1) reacting the modifier A, the modifier B and the high-nickel anode material to obtain a primary modified high-nickel anode material;
(2) pressing the primarily modified high-nickel anode material to obtain a sheet;
(3) and carrying out heat treatment on the sheet to obtain the surface-modified high-nickel cathode material.
Preferably, the modifier A in the step (1) is one or more of oxalic acid, ammonium oxalate, lithium oxalate, aluminum oxalate, titanium oxalate and zirconium oxalate;
the modifier B is one or more of boric acid, fluoboric acid, lithium borate, boron trioxide and metaboric acid;
the high-nickel anode material is LiNi1-x-yCoxMyO2The value range of x is more than or equal to 0 and less than or equal to 1, the value range of y is more than or equal to 0 and less than or equal to 1, the value range of x + y is less than or equal to 1, and M is Mn or Al.
Preferably, in the step (1), the molar ratio of the modifier B to the modifier A is (1-15): (1-10), wherein the sum of the mass of the modifier A and the modifier B is 0.5-5 wt% of the mass of the high-nickel cathode material.
Preferably, the reaction time in the step (1) is 1-3 h.
Preferably, the pressing pressure in the step (2) is 10-50 kg/cm 2When said pressing is performedThe time is 5-10 s.
Preferably, the heat treatment in the step (3) is performed in an inert atmosphere or dry air; the heat treatment is a first-step heat treatment and a second-step heat treatment which are sequentially performed.
Preferably, the temperature of the first heat treatment is 80-120 ℃, and the time of the first heat treatment is 1-3 h.
Preferably, the temperature of the second heat treatment is 200-300 ℃, and the time of the second heat treatment is 3-8 hours.
The invention also provides a surface-modified high-nickel cathode material obtained by the preparation method.
The invention also provides application of the surface modified high-nickel cathode material in preparation of a lithium ion battery.
The invention provides a preparation method of a surface-modified high-nickel anode material, a modifier and surface residual lithium Li of the high-nickel anode material2The O reaction realizes the in-situ generation of the LiBOB surface coating under the low-temperature condition, thereby not only eliminating residual lithium on the surface of the high-nickel anode material, but also realizing the BOB salt coating on the surface of the high-nickel anode material; and pressing the obtained product and then carrying out heat treatment to obtain the surface-modified high-nickel cathode material. The preparation method provided by the invention does not need organic solvent and high-temperature treatment, is environment-friendly, and has low energy consumption and simple process flow.
The invention also provides the surface-modified high-nickel cathode material obtained by the preparation method, and the lithium bis (oxalato) borate protective layer is formed on the surface of the cathode material provided by the invention, so that the surface alkalinity of the modified material is obviously reduced, and the cycling stability of the material, including the cycling stability under high-temperature and high-pressure conditions, is obviously improved.
The invention also provides application of the surface modified high-nickel cathode material in preparation of a lithium ion battery, and has important significance in development of high-performance, high-safety and long-service-life lithium ion batteries.
Drawings
FIG. 1 is a scanning electron micrograph of comparative example 1 and example 1;
FIG. 2 is an infrared spectrum of comparative example 1 and example 1;
FIG. 3 is a comparison of the charge and discharge cycle performance at 1C rate for example 1 of comparative example 1;
FIG. 4 is a comparison of 0.5C charge-discharge cycles under high voltage (2.8-4.5V) charging conditions for comparative example 1 and example 1;
FIG. 5 is a graph showing the charge and discharge cycle characteristics at high temperature of 60 ℃ of 0.5C in comparative example 1 and example 1;
fig. 6 is a graph of ac impedance after charge and discharge cycles of comparative example 1 and example 1.
Detailed Description
The invention provides a preparation method of a surface-modified high-nickel cathode material, which comprises the following steps:
(1) Reacting the modifier A, the modifier B and the high-nickel anode material to obtain a primary modified high-nickel anode material;
(2) pressing the primarily modified high-nickel anode material to obtain a sheet;
(3) and carrying out heat treatment on the sheet to obtain the surface-modified high-nickel cathode material.
In the invention, the modifier a in the step (1) is preferably one or more of oxalic acid, ammonium oxalate, lithium oxalate, aluminum oxalate, titanium oxalate and zirconium oxalate, more preferably one or more of ammonium oxalate, aluminum oxalate, zirconium oxalate and lithium oxalate, and more preferably aluminum oxalate and/or lithium oxalate.
In the invention, the modifier B is preferably one or more of boric acid, fluoboric acid, lithium borate, diboron trioxide and metaboric acid, and is more preferably boric acid and/or diboron trioxide.
In the present invention, the high nickel positive electrode material is preferably LiNi1-x-yCoxMyO2More preferably LiNi0.8CO0.1Mn0.1O2、LiNi1.5Mn0.5O4Or LiNi0.8CO0.15Al0.05O2(ii) a The value range of x is preferably 0-1, more preferably 0.1-0.9, and even more preferably 0.15-0.85; the value range of y is preferably 0-1, more preferably 0.05y is less than or equal to 0.95, and more preferably is less than or equal to 0.1 and less than or equal to 0.9; the value range of x + y is preferably that x + y is less than 1, more preferably that x + y is less than 0.95, and even more preferably that x + y is less than 0.9; the stoichiometric coefficient of Ni is preferably greater than 0.5, more preferably greater than 0.55, and even more preferably greater than 0.6; the M is preferably Mn or Al;
The high-nickel positive electrode material is preferably powdery, and the particle size of the high-nickel positive electrode material is preferably 1-8 μm, and more preferably 2-6 μm; the high-nickel cathode material preferably has a layered or spinel crystal structure, and a single crystal or polycrystalline morphology.
In the present invention, it is preferable to carry out mixing of the modifier A and the modifier B before carrying out the reaction of step (1), and the temperature of the mixing is preferably room temperature; the mixing is preferably carried out in a grinding state, and the rotation speed of the grinding is preferably 300-500 rpm, more preferably 320-480 rpm, and more preferably 380-420 rpm; the grinding time is preferably 1-3 h, more preferably 1.5-2.5 h, and even more preferably 1.8-2.2 h.
In the invention, the grinding before the reaction in the step (1) can crush and uniformly mix the two modifiers, so that the two modifiers can be conveniently reacted with the high-nickel anode material at the same time.
In the present invention, the molar ratio of the modifying agent B to the modifying agent a in the step (1) is preferably (1 to 15): (1-10), more preferably (3-12): (3-7), more preferably (6-9): (4-6); the mass sum of the modifier A and the modifier B is preferably 0.5-5 wt%, more preferably 1-4 wt%, and even more preferably 2-3 wt% of the mass of the high-nickel cathode material.
In the invention, the reaction time in the step (1) is preferably 1-3 h, more preferably 1.5-2.5 h, and even more preferably 1.8-2.2 h; the reaction temperature is preferably room temperature, the reaction is preferably carried out in a grinding state, and the rotation speed of the grinding is preferably 300-500 rpm, more preferably 320-480 rpm, and even more preferably 380-420 rpm.
In the invention, the lithium-remaining Li on the surface of the high-nickel cathode material is compounded by the boric acid compound and the oxalic acid compound2The joint reaction of O realizes the surface coating of the LiBOB generated in situ under the low temperature conditionOn one hand, residual lithium on the surface of the high-nickel anode material is effectively eliminated, and on the other hand, the BOB salt coating on the surface of the high-nickel anode material is realized. The lithium bis (oxalato) borate and oxygen on the surface of the high-nickel anode form a strong B-O bond to participate in forming a boron-rich and oxygen-rich anode surface passivation film (CEI film), so that electrolytic corrosion and transition metal dissolution are inhibited.
In the invention, the LiBOB protective layer can effectively inhibit the oxidation of the electrolyte on the surface of the anode, and can further generate a synergistic effect with aluminum ions after being doped with Al, so that the surface of the material is stabilized, and the macroscopic electrochemical performance of the material is improved.
In the invention, the pressing pressure in the step (2) is preferably 10-50 kg/cm 2More preferably 20 to 40kg/cm2More preferably 25 to 35kg/cm2(ii) a The pressing time is preferably 5-10 s, more preferably 6-9 s, and even more preferably 7-8 s.
In the invention, the gaps among the raw materials are reduced by pressing, and various materials are better mixed on the basis of not damaging the materials.
In the present invention, the heat treatment in the step (3) is preferably performed in an inert atmosphere or dry air; the inert atmosphere is preferably helium, neon or argon, and more preferably argon; due to Li on the surface of the high-nickel cathode material2O is prone to H in air2The O reaction is preferably carried out in dry air because LiOH is produced; the heat treatment is preferably a first-step heat treatment and a second-step heat treatment which are performed sequentially.
In the invention, the temperature of the first heat treatment is preferably 80-120 ℃, more preferably 90-110 ℃, and more preferably 95-105 ℃; the time of the first heat treatment is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and even more preferably 1.8 to 2.3 hours.
In the invention, after the first-step heat treatment is finished, the temperature is preferably raised, wherein the rate of temperature rise is preferably 1-10 ℃/min, more preferably 2-8 ℃/min, and more preferably 4-6 ℃/min; the second heat treatment is preferably performed after the temperature is raised to the target temperature.
In the invention, the temperature of the second heat treatment is preferably 200-300 ℃, more preferably 230-270 ℃, and more preferably 240-260 ℃; the time of the second heat treatment is preferably 3-8 h, more preferably 2-7 h, and even more preferably 3-6 h.
In the present invention, it is preferable that the heat-treated sheet is naturally cooled; in dry air, the cooled flakes are preferably ground to obtain particles; the grinding is not particularly required, and the particle size of the particles is preferably 3-8 μm, more preferably 4-7 μm, and even more preferably 5-6 μm.
The invention also provides a surface-modified high-nickel cathode material obtained by the preparation method.
The invention also provides application of the surface modified high-nickel cathode material in preparation of a lithium ion battery.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
0.0093g H3BO3And 0.0237g of Al2(C2O4)3·H2O was ground at 400rpm for 1 hour at room temperature.
1.2g of single-crystal LiNi was taken0.8Co0.1Mn0.1O2And adding the positive electrode material into the ground material, and grinding for 2h at the rotating speed of 400rpm to obtain the primary modified high-nickel positive electrode material.
Flatly placing the obtained primarily modified high-nickel anode material in a die of a tablet press, and using 10kg/cm2Pressing for 8s to obtain the thin sheet.
And (3) carrying out heat treatment on the obtained slice in a tubular furnace at 100 ℃ for 2h, then heating to 220 ℃ at the speed of 5 ℃/min, and continuing to carry out heat treatment for 6h to obtain the surface modified cathode material.
And after natural cooling, grinding the surface modified anode material subjected to heat treatment into powder under a dry condition, assembling the powder into a C2032 button cell in an argon filled glove box, and carrying out electrochemical performance test at room temperature. After being converted into 5 circles by 0.1C current, the charge-discharge cycle test is carried out under the conditions of different temperatures and 0.5C in different voltage intervals. The test results are reported in table 1.
Example 2
0.00465g H will be mixed3BO3And 0.01185g Al2(C2O4)3·H2O was milled at 300rpm for 1.5 hours at room temperature.
1.2g of single-crystal LiNi was taken0.8Co0.1Mn0.1O2And adding the positive electrode material into the ground material, and grinding for 2h at the rotating speed of 300rpm to obtain the primary modified high-nickel positive electrode material.
Flatly placing the obtained primarily modified high-nickel anode material in a tablet press die, and using 20kg/cm2Pressing for 6s to obtain the thin sheet.
And (3) carrying out heat treatment on the obtained slice in a tube furnace at the temperature of 90 ℃ for 2.5h, and then heating to 230 ℃ at the speed of 5 ℃/min to continue heat treatment for 5h to obtain the surface modified cathode material.
And after natural cooling, grinding the surface modified anode material subjected to heat treatment into powder under a dry condition, assembling the powder into a C2032 button cell in an argon filled glove box, and carrying out electrochemical performance test at room temperature. After being converted into 5 circles by 0.1C current, the charge-discharge cycle test is carried out under the conditions of different temperatures and 0.5C in different voltage intervals. The test results are reported in table 1.
Example 3
0.01g B2O3And 0.068g Li2C2O4Milling was carried out at room temperature for 2 hours at 320 rpm.
2.4g of single crystal LiNi was taken0.8Co0.1Mn0.1O2And adding the positive electrode material into the ground object, and grinding for 2.5 hours at the rotating speed of 350rpm to obtain the primary modified high-nickel positive electrode material.
Flatly placing the obtained primarily modified high-nickel anode material in a die of a tablet press, and using 25kg/cm2And pressing for 5s to obtain the thin sheet.
And (3) carrying out heat treatment on the obtained slice in a 95 ℃ tube furnace for 2.5h, and then heating to 240 ℃ at the speed of 4 ℃/min to continue heat treatment for 5h to obtain the surface modified cathode material.
And after natural cooling, grinding the surface modified anode material subjected to heat treatment into powder under a dry condition, assembling the powder into a C2032 button cell in an argon filled glove box, and carrying out electrochemical performance test at room temperature. After being converted into 5 circles by 0.1C current, the charge-discharge cycle test is carried out under the conditions of different temperatures and 0.5C in different voltage intervals. The test results are reported in table 1.
Example 4
0.0047g H3BO3And 0.020gZrC2O4Milling was carried out at 500rpm for 2 hours at room temperature.
1.2g of single-crystal LiNi was taken0.8Co0.1Mn0.1O2And adding the positive electrode material into the ground object, and grinding for 3h at the rotating speed of 400rpm to obtain the primary modified high-nickel positive electrode material.
Flatly placing the obtained primarily modified high-nickel anode material in a tablet press die, and using 30kg/cm2The sheet was obtained by press pressing for 10 s.
And (3) carrying out heat treatment on the obtained slice in a tube furnace at 110 ℃ for 2.5h, and then heating to 260 ℃ at the speed of 8 ℃/min to continue heat treatment for 5h to obtain the surface modified cathode material.
And after natural cooling, grinding the surface modified anode material subjected to heat treatment into powder under a dry condition, assembling the powder into a C2032 button cell in an argon filled glove box, and carrying out electrochemical performance test at room temperature. After being converted into 5 circles by 0.1C current, the charge-discharge cycle test is carried out under the conditions of different temperatures and 0.5C in different voltage intervals. The test results are reported in table 1.
Example 5
0.0093g H3BO3And 0.0280g (NH)4)2C2O4Milling was carried out at 300rpm for 3 hours at room temperature.
1.2g of single-crystal LiNi was taken0.8Co0.1Mn0.1O2Adding the positive electrode material into the ground material, and grinding for 2.5h at the rotating speed of 450rpm to obtain the primarily modified high-nickel positive electrode material 。
Flatly placing the obtained primarily modified high-nickel anode material in a tablet press die, and using 35kg/cm2Pressing for 6s to obtain the thin sheet.
And (3) carrying out heat treatment on the obtained slice in a tube furnace at 110 ℃ for 2h, then heating to 260 ℃ at the speed of 6 ℃/min, and continuing to carry out heat treatment for 4h to obtain the surface modified cathode material.
And after natural cooling, grinding the surface modified anode material subjected to heat treatment into powder under a dry condition, assembling the powder into a C2032 button cell in an argon filled glove box, and carrying out electrochemical performance test at room temperature. After being converted into 5 circles by 0.1C current, the charge-discharge cycle test is carried out under the conditions of different temperatures and 0.5C in different voltage intervals. The test results are reported in table 1.
Example 6
0.078g H3BO30.009g of Li was used as oxalate2C2O4And 0.010g of Al2(C2O4)3·H2O was ground at room temperature at 420rpm for 1.8 hours.
Taking 3g of single crystal LiNi0.8Co0.1Mn0.1O2And adding the positive electrode material into the ground material, and grinding for 2h at the rotating speed of 400rpm to obtain the primary modified high-nickel positive electrode material.
Flatly placing the obtained primarily modified high-nickel anode material in a die of a tablet press, and using 45kg/cm2Pressing for 7s to obtain the thin sheet.
And (3) carrying out heat treatment on the obtained slice in a tube furnace at 110 ℃ for 2h, then heating to 260 ℃ at the speed of 8 ℃/min, and continuing to carry out heat treatment for 7h to obtain the surface modified cathode material.
And after natural cooling, grinding the surface modified anode material subjected to heat treatment into powder under a dry condition, assembling the powder into a C2032 button cell in an argon filled glove box, and carrying out electrochemical performance test at room temperature. After being converted into 5 circles by 0.1C current, the charge-discharge cycle test is carried out under the conditions of different temperatures and 0.5C in different voltage intervals. The test results are reported in table 1.
Example 7
0.0093g H3BO3And 0.0237g of Al2(C2O4)3·H2O was ground at 400rpm for 1 hour at room temperature.
Taking a single crystal LiNi with a particle size of 6 μm and a weight of 1.2g0.8Co0.1Mn0.1O2And adding the positive electrode material into the ground material, and grinding for 2h at the rotating speed of 400rpm to obtain the primary modified high-nickel positive electrode material.
Flatly placing the obtained primarily modified high-nickel anode material in a die of a tablet press, and using 10kg/cm2Pressing for 8s to obtain the thin sheet.
And (3) carrying out heat treatment on the obtained slices in a tubular furnace at 100 ℃ for 2h, and then heating to 220 ℃ at the speed of 5 ℃/min to continue heat treatment for 6h to obtain the surface modified cathode material.
And after natural cooling, grinding the surface modified anode material subjected to heat treatment into powder under a dry condition, assembling the powder into a C2032 button cell in an argon filled glove box, and carrying out electrochemical performance test at room temperature. After being converted into 5 circles by 0.1C current, the charge-discharge cycle test is carried out under the conditions of different temperatures and 0.5C in different voltage intervals. The test results are reported in table 1.
Example 8
0.0093g H3BO3And 0.0237g of Al2(C2O4)3·H2O was ground at 400rpm for 1 hour at room temperature.
Taking single crystal LiNi with the particle diameter of 8 mu m and the weight of 1.2g0.8Co0.1Mn0.1O2And adding the positive electrode material into the ground material, and grinding for 2 hours at the rotating speed of 400rpm to obtain the primarily modified high-nickel positive electrode material.
Flatly placing the obtained primarily modified high-nickel anode material in a die of a tablet press, and using 10kg/cm2Pressing for 8s to obtain the thin sheet.
And (3) carrying out heat treatment on the obtained slice in a tubular furnace at 100 ℃ for 2h, then heating to 220 ℃ at the speed of 5 ℃/min, and continuing to carry out heat treatment for 6h to obtain the surface modified cathode material.
And after natural cooling, grinding the surface modified anode material subjected to heat treatment into powder under a dry condition, assembling the powder into a C2032 button cell in an argon filled glove box, and carrying out electrochemical performance test at room temperature. After being converted into 5 circles by 0.1C current, the charge-discharge cycle test is carried out under the conditions of different temperatures and 0.5C in different voltage intervals. The test results are reported in table 1.
Example 9
0.0093g H3BO3And 0.0237g of Al2(C2O4)3·H2O was ground at 400rpm for 1 hour at room temperature.
Taking a single crystal LiNi with a particle size of 6 μm and a weight of 1.2g0.8Co0.1Mn0.1O2And adding the positive electrode material into the ground material, and grinding for 2h at the rotating speed of 400rpm to obtain the primary modified high-nickel positive electrode material.
Flatly placing the obtained primarily modified high-nickel anode material in a die of a tablet press, and using 10kg/cm2Pressing for 8s to obtain the thin sheet.
And (3) carrying out heat treatment on the obtained slices in a tubular furnace at 100 ℃ for 2h, and then heating to 220 ℃ at the speed of 5 ℃/min to continue heat treatment for 6h to obtain the surface modified cathode material.
And after natural cooling, grinding the surface modified anode material subjected to heat treatment into powder under a dry condition, assembling the powder into a C2032 button cell in an argon filled glove box, and carrying out electrochemical performance test at room temperature. After being converted into 5 circles by 0.1C current, the charge-discharge cycle test is carried out under the conditions of different temperatures and 0.5C in different voltage intervals. The test results are reported in table 1.
Comparative example 1
Single crystal LiNi0.8Co0.1Mn0.1O2The raw materials are not subjected to residual lithium elimination and surface coating.
Electrical properties were tested on the same pole piece preparation and charge-discharge schedule as in example 1. The test results are recorded in table 1.
The cathode materials prepared in example 1 and comparative example 1 were subjected to electron microscope scanning and infrared spectrum scanning, and the results are shown in fig. 1 and 2: example 1 a functional li (al) BOB protective layer was grown on the surface of the cathode material, and the presence of this protective layer was further confirmed by ir spectroscopy.
The charge and discharge cycle performance of the positive electrode materials prepared in example 1 and comparative example 1 was compared at a rate of 1C, and the results are shown in fig. 3: the high nickel material subjected to surface treatment and Li (Al) BOB protection has the advantages that the cycling stability under the condition of 1C is obviously improved, the reversible capacity ratio of the material is higher than the ratio by 30mAh/g after 150 cycles, and the excellent interface protection effect of the Li (Al) BOB layer on the high nickel material is shown.
The positive electrode materials prepared in example 1 and comparative example 1 were compared in 0.5C charge-discharge cycle under high-voltage (2.8-4.5V) charging conditions and in 0.5C charge-discharge cycle performance under high-temperature 60℃ conditions, and the results are shown in fig. 4 and 5: the high nickel material subjected to surface treatment and Li (Al) BOB protection shows excellent cycle performance under the condition of high voltage, the charging voltage is increased to 4.5V, and the electrode material does not show obvious capacity decline. Similarly, high temperature cycling also exhibits excellent cycling performance.
The positive electrode materials prepared in example 1 and comparative example 1 were subjected to an ac impedance performance test, and the test results are shown in fig. 6: the impedance of example 1 is small compared to the comparative example, with excellent rate capability.
TABLE 1 comparison of electrochemical Properties of comparative and example
Figure BDA0002594777780000101
Figure BDA0002594777780000111
As can be seen from the above examples, the present invention provides a surface-modified high-nickel positive electrode material, and a surface-coated single crystal LiNi obtained by using the present technology 0.8Co0.1Mn0.1O2The first coulombic efficiency, reversible capacity and especially the cycle life are obviously improved, and the technology can greatly prolong the highThe service life of the nickel anode material solves the service life limit of the high-capacity anode material, and the nickel anode material has important industrial application value. The technology does not need to use an organic solvent, does not need high-temperature treatment, has low energy consumption, simple process flow and environmental protection, and is easy to realize large-scale production.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (2)

1. A preparation method of a surface-modified high-nickel cathode material is characterized by comprising the following steps:
(1) reacting the modifier A, the modifier B and the high-nickel anode material to obtain a primary modified high-nickel anode material;
(2) pressing the primarily modified high-nickel anode material to obtain a sheet;
(3) carrying out heat treatment on the sheet to obtain a surface-modified high-nickel cathode material;
the molar ratio of the modifier B to the modifier A in the step (1) is (1-15): (1-10), wherein the sum of the mass of the modifier A and the modifier B is 1-4 wt% of the mass of the high-nickel cathode material;
The reaction time in the step (1) is 1-3 h;
the heat treatment in the step (3) is carried out in an inert atmosphere or dry air; the heat treatment is a first heat treatment and a second heat treatment which are sequentially carried out;
the temperature of the first-step heat treatment is 80-120 ℃, and the time of the first-step heat treatment is 1-3 h;
the temperature of the second heat treatment is 230-270 ℃, and the time of the second heat treatment is 3-8 hours;
the modifier A in the step (1) is one or more of oxalic acid, ammonium oxalate, aluminum oxalate, titanium oxalate and zirconium oxalate;
the modifier B is one or more of boric acid, diboron trioxide and metaboric acid;
the high-nickel anode material is LiNi1-x-yCoxMyO2The value range of x is more than or equal to 0 and less than or equal to 1, the value range of y is more than or equal to 0 and less than or equal to 1, the value range of x + y is less than or equal to 1, and M is Mn or Al.
2. The method according to claim 1, wherein the pressing pressure in the step (2) is 10 to 50kg/cm2And the pressing time is 5-10 s.
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