High nickel cathode material for lithium-ion battery and intended use for the same

Abstract

To provide a high nickel cathode material for lithium-ion battery that has good cycle characteristics, high capacity, and relatively small impedance increase during battery cycling.SOLUTION: A high nickel cathode material for lithium-ion battery has an elemental composition represented by Li1+aNibMncAdO2, where 0.01≤a≤0.24, 0.79<b≤0.96, 0.01<c≤0.20, 0<d≤0.06. A is one or more elements selected from Mn, Co, Al, Zr, Y, Rb, Cs, W, Ce, Mo, Ba, Ti, Mg, Ta, Nb, Ca, V, Sc, Sr and B, has a single or multi-peak pore size distribution in the pore size range of 1.5 to 20 nm in a BJH pore size distribution curve, and has a total pore volume of 0.007 cm3 / g or less by one-point adsorption method in the pore size range of 1.5 to 20 nm, and the specific surface area of the cathode material is 0.33 to 1.5 m2 / g.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention belongs to the technical field of lithium-ion batteries, and relates to a high-nickel cathode material for lithium-ion batteries, a manufacturing method thereof, and uses thereof.

Background Art

[0002] In 2019, the new energy market underwent dramatic changes. With the continuous increase in electric vehicles, the needs for the energy density and cost-effectiveness of lithium-ion batteries have been on the rise. Among them, in the lithium-cobalt-nickel-manganese ternary cathode material, cobalt is a scarce resource and has a high price. Therefore, in order to improve the cost-effectiveness and ensure a high energy density, the content of nickel or manganese elements is appropriately increased to reduce the usage amount of cobalt. Increasing the nickel content can provide a high-capacity battery. However, when the nickel content increases, the structure of the material becomes unstable, it is easy to react with the electrolyte solution, and cracks occur in the cathode material due to repeated charge and discharge, resulting in a shortened cycle life of the lithium-ion battery, an increase in impedance, and a decrease in capacity. Therefore, it is urgent to develop new materials or find new materials to replace cobalt, which is a scarce resource, or to reduce the usage amount of cobalt in the material.

[0003] Chinese Patent CN102280636A discloses a cathode active material, a manufacturing method thereof, and a lithium secondary battery including the same. The cathode active material of the lithium secondary battery is obtained by preparing a precursor by a coprecipitation method and then mixing it with a lithium source and performing a firing process. The material includes pores having an average diameter of about 10 nm to about 60 nm, and the porosity of the material is about 0.5% to about 20%. Since the material has good particle strength, crushing after pressing is prevented or reduced. Since the material is difficult to react with the electrolyte and exhibits good thermal stability, it is possible to provide a high-capacity lithium secondary battery. However, the chemical formula of the material Li a Ni x Co y Mn z M kAs can be seen from O2 (where 0.45 ≦ x ≦ 0.65, 0.15 ≦ y ≦ 0.25, 0.15 < z ≦ 0.35), the cobalt content of the material is high and the capacity is insufficient, so the cost-effectiveness cannot meet the requirements.

[0004] Chinese Patent CN108123119A discloses a nickel-based active material for a lithium secondary battery, a method for manufacturing the same, and a lithium secondary battery including a positive electrode including the same. In this patent, a mixture of a lithium precursor and a metal hydroxide is heat-treated at a low temperature in an oxygen atmosphere and then heat-treated at a high temperature to obtain a nickel-based active material. The material includes secondary particles including aggregates of two or more plate-shaped primary particles, and at least a part of the secondary particles includes a structure in which the plate-shaped primary particles are radially arranged. The outside of the secondary particles is described as having a higher porosity (pore rate) than the inside of the secondary particles. However, this patent does not mention which field of problems is improved.

[0005] Chinese Patent CN1856890 discloses lithium composite oxide particles for a lithium secondary battery positive electrode, a lithium secondary battery positive electrode using the particles, and a lithium secondary battery. This patent discloses lithium composite oxide particles for a lithium secondary battery electrode material and explains that it can improve the low-temperature load characteristics of the battery and the coating property during the manufacture of the positive electrode. The material must satisfy the following condition (A) in the measurement using the mercury intrusion method and at the same time satisfy at least one of the following conditions (B) and (C). Condition (A): In the mercury intrusion curve, when the pressure increases from 50 MPa to 150 MPa, the mercury intrusion volume is 0.02 cm 3 / g or less. Condition (B): In the mercury intrusion curve, when the pressure increases from 50 MPa to 150 MPa, the mercury intrusion volume is 0.01 cm 3 / g or more. Condition (C): The average pore radius is 10 to 100 nm, and the pore size distribution curve has a main peak with the upper end located at a pore radius of 0.5 to 50 μm and a sub-peak with the upper end located at a pore radius of 80 to 300 nm. This patent mainly focuses on low-temperature characteristics and does not consider high-temperature characteristics.

[0006] Chinese Patent CN104272520A discloses a non-aqueous electrolyte secondary battery and a method for manufacturing the same. In this patent, the positive electrode composite layer constituting the positive electrode of the non-aqueous electrolyte secondary battery has, in the pore size distribution curve measured by a mercury porosimeter, a peak A of the differential pore volume in the range of pore diameters from 0.05 μm to 2 μm and a peak B located on the side of smaller pore diameters than the peak A. The pore size distribution curve has a minimum point C where the differential pore volume is at a minimum value between the peak A and the peak B. The differential pore volume X of the peak A A and the differential pore volume X of the peak B B Among them, the larger differential pore volume X of the differential pore volumes L The differential pore volume X of the minimum point C C The ratio to (X C / X L ) is described as being 0.6 or more. This patent mainly reduces problems such as gas generation in the battery by adding an overcharge additive in the process of manufacturing the battery.

[0007] Chinese Patent CN112993239A discloses a high-voltage-resistant and low-cobalt ternary cathode material and a method for manufacturing the same. The cathode material is made from a precursor containing nickel, cobalt, and manganese, a lithium source, and an additive containing a metal element, and is mainly obtained at low temperature, medium-high temperature, and high temperature with (Ni 0.5 Co 0.1 Mn 0.4 )(OH)2 as the precursor. The cathode material has high morphological regularity, uniform particle size, and the lithium-ion battery manufactured with this material still has a low internal resistance and excellent high-temperature cycle characteristics even under high voltage. However, the capacity of this material is low and cannot meet the requirements in use.

[0008] Chinese Patent CN108963218A discloses a method for manufacturing and using a low-cobalt and high-nickel ternary lithium system. The cathode material is obtained by mixing nickel nitrate, titanium nitrate, and manganese nitrate in a molar ratio of 8.75:0.25:1 to obtain an aqueous solution, spray-drying to obtain a precursor, then using an inducer to cause the exchange of titanium and cobalt, preparing a suspension from the precursor, the inducer, and lithium hydroxide in a predetermined molar ratio, and after spray-drying, firing. While reducing the cobalt content, this material greatly improves thermal stability, cycle life, and safety. However, this material is mainly obtained by only one firing. Due to the limited firing time, it cannot provide sufficient time and kinetic energy, the structure of the material cannot be synthesized well, and it is not always possible to obtain cycle characteristics and thermal stability characteristics.

[0009] Chinese Patent CN112811475A discloses a single-crystalline cathode material, a method for manufacturing the same, and a lithium-ion battery. In this patent, it is described that large particles of a polycrystalline precursor are jet-milled to obtain a single-crystalline precursor, and the cathode material is obtained by blending lithium and firing. This method has a simple process and reduces manufacturing costs compared to the wet method. This material is produced by only one firing. Due to the limited firing time, it cannot provide sufficient time and kinetic energy, the structure of the material cannot be synthesized well, and it is not always possible to obtain cycle characteristics and thermal stability characteristics.

[0010] Chinese Patent CN112750999A discloses a cathode material, a method for manufacturing the same, and a lithium-ion battery. The cathode material includes a high-nickel and cobalt-free multi-component cathode material intermediate and a cobalt-containing compound coating the outer surface of the high-nickel and cobalt-free multi-component cathode material intermediate, and the content of cobalt element in the cobalt compound is 0.5 - 5 mol% of the total molar number of nickel and manganese. The material manufactured by this method has a stable structure, a high energy density, excellent rate characteristics, and a high capacity retention rate. However, the free lithium in this material is high, and gel may occur in the pulp manufacturing process, which may affect the processing of the battery.

Summary of the Invention

Problems to be Solved by the Invention

[0011] Due to the reduction of cobalt content, especially in cobalt-free materials and ternary materials, the structural stability decreases, and the capacity, rate performance, and cycle performance of the materials cannot be normally exhibited. Therefore, various methods have been proposed according to different specification requirements. When high cycle performance and safety are required, high-temperature firing is adopted to obtain large single-crystal materials. When high rate performance is required, low-temperature firing is adopted to obtain secondary particles with very small primary particles. However, there are defects in the actual use of batteries by such methods.

[0012] The technical problem to be solved by the present invention is that the cobalt-free cathode materials according to the prior art cannot simultaneously achieve high rate performance, high capacity, long cycle life, and low DC internal resistance. The present invention provides a high-nickel cathode material for lithium-ion batteries and a method for manufacturing the same, and obtains a high-nickel cathode material for lithium-ion batteries by adding a modifying element and performing at least two firings and one coating treatment. The cathode material has a porous structure, provides many paths for the movement of lithium ions and the paths are short, so the lithium-ion battery not only has a higher capacity but also has good rate performance. The lithium-ion battery also has excellent structural stability. During the charge and discharge of the lithium-ion battery, the decrease in capacity is small, the cycle performance is excellent, and the increase in DC internal resistance is small. The present invention further provides a cathode including the cathode material for lithium-ion batteries and a lithium-ion battery, and further provides the use of the high-nickel cathode material for lithium-ion batteries, the lithium-ion battery cathode, or the lithium-ion battery in the fields of digital batteries, power batteries, or storage batteries.

Means for Solving the Problems

[0013] The technical solution of the present invention is as follows. The present invention provides a high-nickel cathode material for lithium-ion batteries, and the high-nickel cathode material has a porous structure. The chemical formula 1 has an elemental composition represented by Li 1+a Ni b Mn c A d O2, provided that 0.01 ≦ a ≦ 0.24, 0.79 < b ≦ 0.96, 0.01 < c ≦ 0.20, 0 < d ≦ 0.06, and A is selected from any one or more elements of Mn, Co, Al, Zr, Y, Rb, Cs, W, Ce, Mo, Ba, Ti, Mg, Ta, Nb, Ca, V, Sc, Sr, and B, or is selected from a phosphorus-containing compound containing at least one element of Ti, Al, Mg, Zr, La, and Li.

[0014] Preferably, when measured by the nitrogen adsorption method, in the BJH pore size distribution curve, it has a single-peak or multi-peak pore size distribution within the pore size range of 1.5 to 20 nm, and the high-nickel cathode material has a one-point adsorption total pore volume of 0.01 cm 3 / g or less within the range of 1.5 to 20 nm in pore size, preferably 0.007 cm 3 / g or less.

[0015] Preferably, in the powder X-ray diffraction pattern of the cathode material, the full width at half maximum FWHM(101) of the (101) diffraction peak at a diffraction angle 2θ of around 36.6° in the powder X-ray diffraction pattern of the cathode material is 0.080 to 0.180.

[0016] Preferably, the Dv50 particle size of the cathode material is 3 to 20 μm.

[0017] Preferably, the specific surface area of the cathode material is 0.33 to 1.5 m 2 / g, and / or the tap density of the cathode material is 1.9 g / cm 3 or more, and / or the total free lithium amount of the cathode material is less than 1800 ppm.

[0018] Preferably, in the chemical formula 1, 0.001 ≦ d ≦ 0.04.

[0019] The present invention further provides a method for manufacturing a high-nickel cathode material for a lithium-ion battery, which includes performing at least two firings and one coating treatment after mixing raw materials.

[0020] Preferably, the temperature of the first firing is 700-900 °C, preferably 790-890 °C, and more preferably, the isothermal time is 8-40 hours. And / or, the temperature of the second firing is 400-800 °C, preferably 680-800 °C, and more preferably, the isothermal time is 5-20 hours. More preferably, the firing atmosphere is oxygen.

[0021] Preferably, the coating treatment is performed before the final firing.

[0022] Preferably, in the manufacturing method, the Li source is a lithium-containing oxide, a lithium-containing fluoride, or a lithium-containing salt, and preferably, the Li source is selected from one or more of anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium acetate, and lithium fluoride.

[0023] Preferably, the Dv50 particle size of the precursor in the raw materials is 2.0-20 μm.

[0024] The present invention further provides a high-nickel cathode material for a lithium-ion battery manufactured by the manufacturing method.

[0025] The present invention further provides a high-nickel cathode material for a lithium-ion battery including two or more of the cathode materials.

[0026] The present invention further provides a lithium-ion battery cathode including a current collector and a cathode material supported on the current collector, and the cathode material is the high-nickel cathode material for a lithium-ion battery.

[0027] The present invention further provides a lithium-ion battery including a positive electrode, a negative electrode, and a lithium salt-containing electrolyte, wherein the positive electrode is the positive electrode of the lithium-ion battery.

[0028] The present invention further provides the use of the high-nickel positive electrode material for the lithium-ion battery, or the positive electrode of the lithium-ion battery, or the lithium-ion battery in the fields of digital batteries, power batteries or storage batteries.

Advantages of the Invention

[0029] The beneficial effects of the present invention are as follows. Compared with the conventional positive electrode material for lithium-ion batteries, the present invention obtains a cobalt-free modified high-nickel positive electrode material for lithium-ion batteries by adding a modifying element and performing at least two firings and one coating treatment. It has a unique porous structure and crystal structure. Since the porous structure of the positive electrode material provides more paths for the movement of lithium ions and the paths are short, the lithium-ion battery not only has a higher capacity and good rate performance, but also the material has excellent structural stability due to the crystal structure. During the charge and discharge of the lithium-ion battery, the decrease in capacity is small, the cycle performance is excellent, the increase in DC internal resistance is small, and the capacity, rate performance and cycle performance of the cobalt-free positive electrode material are effectively balanced.

Brief Description of the Drawings

[0030]

Figure 1

Figure 2

Embodiments for Carrying out the Invention

[0031] To clearly and completely describe the technical solution according to the embodiments of the present invention so that the objectives, technical solutions, and technical effects of the embodiments of the present invention become clearer, the following described embodiments are not all embodiments of the present invention but are part of the embodiments of the present invention. If those skilled in the art obtain other embodiments from the embodiments of the present invention without performing creative work, all of them belong to the protection scope of the present invention.

[0032] In the description of the present invention, the term "multi-peak" refers to a pore size distribution in which the BJH pore size distribution curve includes two or more maximum values of pore volume. Generally, the maximum value of pore volume is 0.0008 cm 3 / g or more.

[0033] In the description of the present invention, the term "single-peak" refers to a pore size distribution in which the BJH pore size distribution curve includes one maximum value of pore volume. Generally, the maximum value of pore volume is 0.0008 cm 3 / g or more.

[0034] Hereinafter, to better understand the above technical solution, the present invention will be described in more detail.

[0035] The present invention provides a high-nickel cathode material for lithium-ion batteries. The high-nickel cathode material has a porous structure, and its chemical formula 1 is Li 1+a Ni b Mn c A d O2, where 0.01 ≤ a ≤ 0.24, 0.79 < b ≤ 0.96, 0.01 < c ≤ 0.20, 0 < d ≤ 0.06, and A is selected from any one or more elements of Mn, Co, Al, Zr, Y, Rb, Cs, W, Ce, Mo, Ba, Ti, Mg, Ta, Nb, Ca, V, Sc, Sr, and B, or is selected from phosphorus-containing compounds containing at least one element of Ti, Al, Mg, Zr, La, and Li. Note that as the phosphorus-containing compound, Li3PO4, lithium aluminum titanium phosphate (LATP), or [LiAl X Ti (2ーX)One or more of (PO4)3 are included, but not limited thereto.

[0036] In a preferred embodiment of the present invention, when measured by the nitrogen adsorption method, in the BJH pore size distribution curve, it has a single-peak or multi-peak pore size distribution within the range of pore sizes from 1.5 to 20 nm, and the high-nickel cathode material has a one-point adsorption total pore volume of 0.01 cm 3 / g or less within the range of pore sizes from 1.5 to 20 nm, preferably 0.007 cm 3 / g or less.

[0037] In another preferred embodiment of the present invention, in the powder X-ray diffraction pattern of the high-nickel cathode material, the full width at half maximum FWHM(101) of the diffraction peak at a diffraction angle 2θ near 36.6° is from 0.080 to 0.180.

[0038] In another preferred embodiment of the present invention, the Dv50 particle size of the high-nickel cathode material is from 3 to 20 μm.

[0039] In another preferred embodiment of the present invention, the specific surface area of the high-nickel cathode material is from 0.33 to 1.5 m 2 / g, and / or the tap density of the high-nickel cathode material is 1.9 g / cm 3 or more, and / or the total amount of free lithium of the high-nickel cathode material is less than 1800 ppm.

[0040] In another preferred embodiment of the present invention, in Chemical Formula 1, 0.001 ≤ d ≤ 0.04.

[0041] The present invention further provides a method for manufacturing the cathode material for a lithium-ion battery, which includes performing at least two firings and one coating treatment after mixing the raw materials.

[0042] However, the raw materials include a Li source, a metal A source, and a nickel-manganese hydroxide precursor.

[0043] In a preferred embodiment of the present invention, the temperature of the first firing is 700 to 900 °C, preferably 790 to 890 °C, and more preferably, the isothermal time is 8 to 40 hours. And / or, the temperature of the second firing is 400 to 800 °C, preferably 680 to 800 °C, and more preferably, the isothermal time is 5 to 20 hours. More preferably, the firing atmosphere is oxygen.

[0044] In a preferred embodiment of the present invention, in the method for manufacturing the high-nickel cathode material for a lithium-ion battery, the coating treatment is performed before the final firing.

[0045] In another preferred embodiment of the present invention, in the manufacturing method, the Li source is a lithium-containing oxide, a lithium-containing fluoride, or a lithium-containing salt, and preferably, the Li source is selected from one or more of anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium acetate, and lithium fluoride.

[0046] In another preferred embodiment of the present invention, the Dv50 particle size of the precursor in the raw material is 2.0 to 20 μm.

[0047] The present invention further provides a high-nickel cathode material for a lithium-ion battery manufactured from the manufacturing method.

[0048] The present invention further provides a high-nickel cathode material for a lithium-ion battery including two or more of the cathode materials.

[0049] The present invention further provides a lithium-ion battery cathode including a current collector and a cathode material supported on the current collector, and the cathode material is the high-nickel cathode material for a lithium-ion battery.

[0050] The present invention further provides a lithium-ion battery including a positive electrode, a negative electrode, and a lithium salt-containing electrolyte, wherein the positive electrode is the positive electrode of the lithium-ion battery.

[0051] The lithium-ion battery of the present invention further includes a separator and an aluminum laminate film. Specifically, the electrode includes a positive electrode and a negative electrode. The positive electrode is made of materials such as a positive electrode current collector, a positive electrode active material coated on the positive electrode current collector, an adhesive, and a conductive assistant. The positive electrode active material is the positive electrode material for the lithium-ion battery. The negative electrode is made of materials such as a current collector, a negative electrode active material coated on the current collector, an adhesive, and a conductive assistant. The separator is a PP / PE film generally used in the industry to isolate the positive electrode and the negative electrode from each other, and the aluminum laminate film is a coating material for the positive electrode, the negative electrode, the separator, and the electrolyte.

[0052] The adhesive includes polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, poly(vinylidene fluoride), polyethylene, polypropylene, styrene-butadiene rubber, acrylate-modified styrene-butadiene rubber, epoxy resin, nylon, etc., and combinations thereof. Its role is to improve the adhesiveness between the positive electrode active material particles and between the positive electrode active material particles and the current collector.

[0053] The conductive assistant includes one or more of a carbon-based material, a metal-based material, and a conductive polymer. The carbon-based material is one or more of natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, and carbon fiber. The metal-based material is a metal powder or metal fiber of copper, nickel, aluminum, or silver. The conductive polymer is a polyphenylene derivative.

[0054] The present invention further provides the high-nickel cathode material for lithium-ion batteries, or the cathode of the lithium-ion battery, or the use of the lithium-ion battery in the field of digital batteries, power batteries or storage batteries.

[0055] Hereinafter, the beneficial effects of the present invention will be further described with specific examples.

[0056] The information on the reagents and equipment used in the following examples is as shown in Table 1-1, Table 1-2 and Table 2.

[0057]

Table 1-1

[0058]

Table 1-2

[0059]

Table 2

[0060] (Example 1) Mixing of raw materials: Using a 200L plowshare mixer, start it and stir, add 31.78 kg of anhydrous lithium hydroxide, 3.44 kg of cerium oxide, and 100 kg of nickel-manganese hydroxide precursor Ni 0.9 Mn 0.1 (OH)2 (purchased from Guangdong Yingde Jiana Energy Co., Ltd.) and stir for 2 hours in preparation for use. First firing: Using a 36-meter roller hearth kiln, set the temperature to 840 °C, flow in oxygen, the gas flow rate is 10 L / min, put the mixed raw materials into a crucible, send them into the roller hearth kiln for firing, set the isothermal time to 35 hours, cool the raw materials to room temperature, and grind them with a jet mill to obtain the semi-finished product of the first firing. Second firing: Using a 36-meter roller hearth kiln, set the temperature to 700 °C, introduce oxygen, the gas flow rate is 10 L / min. Put the semi-finished product of the first firing into a sagger, send it into the roller hearth kiln for firing, set the isothermal time to 8 hours, cool the raw material to room temperature, grind it with a jet mill to obtain the semi-finished product of the second firing. Coating treatment: Put the semi-finished product of the second firing into a stirring tank, start stirring, add 150 kg of deionized water, add 1.05 kg of tetrabutyl titanate, mix for 50 minutes, and filter to obtain a cake. Third firing: Using a 36-meter roller hearth kiln, set the temperature to 600 °C, introduce oxygen, the gas flow rate is 10 L / min. Put the cake after coating treatment into a sagger, send it into the roller hearth kiln for firing, set the isothermal time to 4 hours, cool the raw material to room temperature, grind it with a jet mill, demagnetize and screen to obtain the cathode material.

[0061] Digest with dilute hydrochloric acid and verify by ICP analysis. The chemical formula of the cathode material is Li 1.24 Ni 0.9 Mn 0.1 Ti 0.0051 Ce 0.02 O2.

[0062] (Example 2) Mixing of raw materials: Using a 200 L plowshear mixer, start stirring, add 48.99 kg of lithium hydroxide monohydrate, 1.2 kg of cobalt oxide, 100 kg of nickel-manganese precursor Ni 0.8 Mn 0.2 (OH)2 (purchased from Guangdong Yingde Jiana Energy Co., Ltd.), stir for 2 hours in preparation for use. First firing: Using a 36-meter roller hearth kiln, set the temperature to 890 °C, introduce oxygen, the gas flow rate is 8 L / min. Put the mixed raw materials into a sagger, send it into the roller hearth kiln for firing, set the isothermal time to 28 hours, cool the raw material to room temperature, grind it with a jet mill to obtain the semi-finished product of the first firing. Second firing: Using a 36-meter roller hearth kiln, set the temperature to 750 °C, introduce oxygen, the gas flow rate is 8 L / min. Put the semi-finished product of the first firing into a sagger, send it into the roller hearth kiln for firing, set the isothermal time to 6 hours, cool the raw material to room temperature, pulverize it with a jet mill to obtain the semi-finished product of the second firing. Coating treatment: Put the semi-finished product of the second firing into a stirring tank, start stirring, add 120 kg of deionized water, add 1.02 kg of tetrabutyl titanate, mix for 60 minutes, and filter to obtain a cake. Third firing: Using a 36-meter roller hearth kiln, set the temperature to 700 °C, introduce oxygen, the gas flow rate is 8 L / min. Put the cake after coating treatment into a sagger, send it into the roller hearth kiln for firing, set the isothermal time to 5 hours, cool the raw material to room temperature, pulverize it with a jet mill, demagnetize and screen it to obtain the cathode material.

[0063] Digest with dilute hydrochloric acid and verify by ICP analysis. The chemical formula of the cathode material is Li 1.01 Ni 0.8 Mn 0.2 Co 0.016 Ti 0.0046 O2.

[0064] (Example 3) Mixing of raw materials: Using a 200L plowshear mixer, start stirring, add 48.18 kg of lithium hydroxide monohydrate, 2.319 kg of tungsten oxide, 2 kg of cobalt carbonate, 100 kg of D v Nickel-manganese precursor Ni with a particle size of 15 μm 0.9 Mn 0.1 (OH)2 (purchased from Guangdong Yingde Jiana Energy Co., Ltd.) was added and stirred for 2 hours in preparation for use. First firing: Using a 36-meter roller hearth kiln, set the temperature to 830 °C, introduce oxygen, the gas flow rate is 15 L / min. Put the mixed raw materials into a sagger, send it into the roller hearth kiln for firing, set the isothermal time to 30 hours, cool the raw material to room temperature, pulverize it with a jet mill to obtain the semi-finished product of the first firing. Coating treatment: The semi-finished product after the first firing was put into a stirring tank, started and stirred, 100 kg of deionized water was added, 25.4 kg of rubidium carbonate solution (a mixture of rubidium carbonate and water in a ratio of 1:10) was added, mixed for 40 minutes, and filtered to obtain a cake. Second firing: Using a 36-meter roller hearth kiln, the temperature was set at 700 °C, oxygen was introduced, the gas flow rate was 15 L / min, the cake after the coating treatment was put into a crucible, sent into the roller hearth kiln for firing, the isothermal time was 9 hours, the raw material was cooled to room temperature, pulverized by a jet mill, demagnetized and sieved to obtain a cathode material.

[0065] Digested with dilute hydrochloric acid and verified by ICP analysis, the chemical formula of the cathode material is Li 1.06 Ni 0.9 Mn 0.1 Co 0.02 W 0.01 Rb 0.02 O2.

[0066] (Example 4) Mixing of raw materials: Using a 200L plowshear mixer, started and stirred, 46.06 kg of lithium hydroxide monohydrate, 100 kg of nickel-manganese hydroxide precursor Ni 0.85 Mn 0.15 (OH)2 (purchased from Guizhou Zhongwei Zhengyuan New Materials Co., Ltd.) was added and stirred for 2 hours in preparation for use. First firing: Using a 36-meter roller hearth kiln, the firing temperature was set at 840 °C, oxygen (oxygen flow rate 12 L / min) was introduced, the mixed raw material was put into the device for the first firing, the isothermal time was 16 hours, the raw material was cooled to room temperature, pulverized by a jet mill to obtain a semi-finished product after the first firing. Second firing: Using a 36-meter roller hearth kiln, the firing temperature was set at 800 °C, oxygen (oxygen flow rate 8 L / min) was introduced, the semi-finished product after the first firing was put into a 36-meter roller hearth kiln for the second firing, the isothermal time was 18 hours, the raw material was cooled to room temperature, pulverized by a jet mill, and then demagnetized to obtain a semi-finished product after the second firing. Coating treatment: Put the semi-finished product after the second firing into the stirring tank, start and stir, add 100 kg of deionized water, stir for 10 minutes, perform suction filtration, bake, put the semi-finished product after baking into the mixer, start and stir, add 1.77 kg of ammonium heptamolybdate, and mix for 30 minutes. Third firing: Utilize a 36-meter roller hearth kiln, set the firing temperature at 600 °C, flow in oxygen (oxygen flow rate 5 L / min), put the raw material after coating treatment into the 36-meter roller hearth kiln for the third firing, set the constant temperature for 10 hours, cool the raw material to room temperature, grind it with a jet mill, demagnetize and screen it to obtain the cathode material.

[0067] Digest with dilute hydrochloric acid and verify by ICP analysis. The chemical formula of the cathode material is Li 1.04 Ni 0.85 Mn 0.15 Mo 0.01 O2.

[0068] (Example 5) Mixing of raw materials: Utilize a 200L plowshear mixer, start and stir, add 46.94 kg of lithium hydroxide monohydrate and 100 kg of nickel-manganese precursor Ni 0.85 Mn 0.15 (OH)2 (purchased from Guizhou Zhongwei Zhengyuan New Materials Co., Ltd.), stir for 2 hours in preparation for use. First firing: Utilize a 36-meter roller hearth kiln, set the firing temperature at 810 °C, flow in oxygen (oxygen flow rate 12 L / min), put the mixed raw material into the device for the first firing, set the constant temperature for 12 hours, cool the raw material to room temperature, grind it with a jet mill to obtain the semi-finished product after the first firing. Coating treatment: Put the semi-finished product after the first firing into the stirring tank, start and stir, add 100 kg of deionized water, stir for 20 minutes, perform suction filtration, bake, put the semi-finished product after baking into the mixer, start and stir, add 0.4 kg of boron oxide, and mix for 30 minutes. Second firing: Using a 36-meter roller hearth kiln, set the firing temperature to 400 °C, flow in oxygen (oxygen flow rate 5 L / min), put the raw material after coating treatment into the 36-meter roller hearth kiln for the third firing, set the constant temperature for 5 hours, cool the raw material to room temperature, demagnetize and screen it to obtain the cathode material.

[0069] Digest with dilute hydrochloric acid and verify by ICP analysis. The chemical formula of the cathode material is Li 1.06 Ni 0.85 Mn 0.15 B 0.005 O2.

[0070] (Example 6) Mixing of raw materials: Using a 200 L plowshear mixer, start and stir, add 29.07 kg of anhydrous lithium hydroxide, 2.95 kg of strontium carbonate, and 100 kg of nickel-manganese hydroxide precursor Ni 0.95 Mn 0.05 (OH)2 (purchased from Guangdong Yingde Jiana Energy Co., Ltd.) and stir for 2 hours in preparation for use. First firing: Using a 36-meter roller hearth kiln, set the temperature to 790 °C, flow in oxygen, the gas flow rate is 10 L / min, put the mixed raw material into a crucible, send it into the roller hearth kiln for firing, set the constant temperature time to 40 hours, cool the raw material to room temperature, and grind it with a jet mill to obtain the first-fired semi-finished product. Coating treatment: Put the first-fired semi-finished product into a stirring tank, start and stir, add 100 kg of deionized water, then add 28.5 kg of magnesium acetate solution (a mixture of magnesium acetate and water in a ratio of 1:10), mix for 60 minutes, and filter to obtain a cake. Second firing: Using a 36-meter roller hearth kiln, set the temperature to 680 °C, flow in oxygen, the gas flow rate is 10 L / min, put the cake after coating treatment into a crucible, send it into the roller hearth kiln for firing, set the constant temperature time to 5 hours, cool the raw material to room temperature, grind it with a jet mill, demagnetize and screen it to obtain the cathode material.

[0071] Digested with dilute hydrochloric acid and verified by ICP analysis, the chemical formula of the positive electrode material is Li 1.14 Ni 0.95 Mn 0.05 Sr 0.02 Mg 0.02 O2

[0072] (Example 7) Mixing of raw materials: Using a 200L plowshare mixer, start it and stir, add 48.18 kg of lithium hydroxide monohydrate, 1.9 kg of strontium carbonate, and 100 kg of nickel-manganese precursor Ni 0.9 Mn 0.1 (OH)2 (purchased from Guangdong Yingde Jiana Energy Co., Ltd.) and stir for 2 hours in preparation for use. First firing: Using a 36-meter roller hearth kiln, set the temperature to 860 °C, flow in oxygen, the gas flow rate is 15 L / min, put the mixed raw materials into a crucible, send them into the roller hearth kiln for firing, set the isothermal time to 35 hours, cool the raw materials to room temperature, grind them with a jet mill to obtain the first-fired semi-finished product. Second firing: Using a 36-meter roller hearth kiln, set the temperature to 750 °C, flow in oxygen, the gas flow rate is 15 L / min, put the first-fired semi-finished product into a crucible, send them into the roller hearth kiln for firing, set the isothermal time to 7 hours, cool the raw materials to room temperature, grind them with a jet mill to obtain the second-fired semi-finished product. Coating treatment: Put the second-fired semi-finished product into a stirring tank, start it and stir, add 100 kg of deionized water, add 8.4 kg of aluminum nitrate nonahydrate solution (a mixture of aluminum nitrate nonahydrate and water in a ratio of 1:5), mix for 40 minutes, and filter to obtain a cake. Third firing: Using a 36-meter roller hearth kiln, set the temperature to 700 °C, flow in oxygen, the gas flow rate is 15 L / min, put the cake after coating treatment into a crucible, send them into the roller hearth kiln for firing, set the isothermal time to 9 hours, cool the raw materials to room temperature, grind them with a jet mill, demagnetize and screen to obtain the positive electrode material.

[0073] Digested with dilute hydrochloric acid and verified by ICP analysis, the chemical formula of the positive electrode material is Li 1.1 Ni 0.9 Mn 0.1 Sr 0.015 Al 0.003 O2

[0074] (Example 8) The positive electrode materials of Example 3 and Example 7 were mixed at a mass ratio of 1:1 to obtain a mixed positive electrode material

[0075] (Example 9) The positive electrode materials of Example 3 and Example 7 were mixed at a mass ratio of 7:3 to obtain a mixed positive electrode material

[0076] (Test Example 1) The characteristic parameters of the high-nickel positive electrode materials manufactured in Examples 1 to 9 were measured by the following method

[0077] (1) Measurement method of pore size distribution curve Using an automatic specific surface area and pore size distribution measuring device (TriStarII3020), 4 g of the positive electrode powder material was placed in a sample tube for measurement, and degassing treatment was performed at 200 °C for 1 hour to sufficiently remove moisture from the measurement sample. Subsequently, using the nitrogen adsorption method with liquid nitrogen, isotherms on the adsorption side and desorption side were measured in the range where the relative pressure P / P0 (P0 ≒ 665 mmHg) was 0.01 to 0.995. Using the desorption side isotherm and calculating by the BJH method, a pore size distribution curve with the pore size on the horizontal axis and the pore volume on the vertical axis was obtained. The pore size distribution curve of the high-nickel positive electrode material manufactured in Example 7 is as shown in Figure 1. As can be seen from Figure 1, in the pore size distribution curve, there is a single peak within the range of pore sizes of 1.5 to 20 nm. The pore size ranges of the high-nickel positive electrode materials manufactured in Examples 1 to 9, and the measurement results of the total pore volume by the one-point adsorption method where the pore size is 1.5 to 20 nm are as shown in Table 3

[0078] (2) Measurement method of specific surface area In the present invention, the specific surface area was measured by an automatic specific surface area and pore size distribution measuring device (TriStarII 3020) with reference to the gravimetric method of the gas adsorption BET method of GB / T 19587-2004, and the measurement results are as shown in Table 3.

[0079] (3) Particle size measurement method In the present invention, the particle size was measured by a Malvern Master Size 2000 laser particle size distribution measuring device with reference to the laser diffraction method for particle size distribution analysis of GB / T 19077-2016. 1 g of the powder was weighed, added to 60 mL of pure water, ultrasonicated for 5 minutes, the sample was injected into the sample injector for measurement, and the measurement data was recorded. The measurement results are as shown in Table 3.

[0080] The Malvern Master Size 2000 laser particle size distribution measuring device was used, the detection angle was set to 0 - 135°, the test principle was the Mie theory, the ultrasonic intensity was 40 kHz 180 W, the particle refractive index was 1.692, the particle absorption rate was 1, the sample measurement time was 6 seconds, the number of snapshots for background measurement was 6000 times, and the light obscuration rate was 8 - 12%.

[0081] (4) XRD measurement method The X’Pert PRO MPD diffractometer was used, with a Cu tube target, a wavelength of 1.54060, and a Be window. In the incident optical path, the soller slit was 0.04 rad, the divergence slit was 1 / 2°, the anti-scatter slit was 10 mm, and the anti-scatter slit was 1°. In the diffraction optical path, the anti-scatter slit was 8.0 mm, the soller slit was 0.04 rad, and a large Ni filter was used. The scanning range was 10 - 80°, the scanning step width was 0.013°, the measurement time per step was 30.6 seconds, the voltage was 40 kV, the current was 40 mA, and the analysis software was High-Score Plus. The X-ray diffraction pattern of the high-nickel cathode material produced in Example 6 was as shown in Figure 2, and the measurement results of the full width at half maximum FWHM(101) corresponding to the (101) diffraction peak near the diffraction angle 2θ of the high-nickel cathode materials produced in Examples 1 - 9 were as shown in Table 3.

[0082] (5) Method for measuring tap density Using a 100 mL graduated cylinder, weigh m (50 ± 0.5) g of the powdery substance, put the raw material into the graduated cylinder so as to spread it at the bottom of the graduated cylinder, read and record the scale at the upper edge of the raw material as V1. Place the graduated cylinder containing the powdery substance on a BT-303 tap density tester and fix it. Set the parameters of amplitude 3 ± 0.1 mm and vibration frequency 3000 times. Start the device. After the vibration is completed, remove the graduated cylinder and read the scale V2 at the upper edge of the powdery substance. The tap density was (V1 - V2) / m. The measurement results were as shown in Table 3.

[0083] (6) Method for measuring the total amount of free lithium Accurately weigh a 30 g ± 0.01 g sample, add the sample to a 250 mL Erlenmeyer flask, place a magnetic stirrer in it, and add 100 mL of deionized water. Place the Erlenmeyer flask on the magnetic stirrer, start the device, and stir for 30 minutes. Filter the mixed solution with qualitative filter paper and a funnel. Take out 50 mL of the filtrate with a 50 mL pipette and add it to a 100 mL beaker, and place a stir bar in it. Place the beaker on the magnetic stirrer, add 2 drops of phenolphthalein indicator. Titrate with 0.05 mol / L hydrochloric acid standard solution until the color of the solution changes from red to colorless, and record the volume V1 (end point 1) of the 0.05 mol / L hydrochloric acid standard solution. Add 2 drops of methyl red indicator, and the color of the indicator changes from colorless to yellow. Titrate with 0.05 mol / L hydrochloric acid standard solution until the color of the solution changes from yellow to orange. Place the beaker on a heating furnace and heat until the solution boils (the color of the solution changes from orange to yellow). Remove the beaker and cool it to room temperature. Further place the beaker on the magnetic stirrer, and titrate with 0.05 mol / L hydrochloric acid standard solution until the color of the solution changes from yellow to light red, and record the volume V2 (end point 2) of the 0.05 mol / L hydrochloric acid standard solution. Calculate the total amount of free lithium according to the following formula, and the measurement results are as shown in Table 3.

[0084] Total amount of free lithium = V2 × 0.05 × 6.94 × 2 × 100% / (m × 1000), The total amount of free lithium is in units of 100%, m is the mass of the sample, in units of g, V2 is at the second titration end point, in units of mL, 6.94 is the atomic weight of lithium.

[0085]

Table 3

[0086] (Test Example 2) Manufacture and performance evaluation of lithium-ion batteries: Manufacture a pouch cell 454261 by the following method. Manufacture of the positive electrode: Each of the high-nickel positive electrode materials manufactured in Examples 1 to 9 of the present invention, conductive carbon black (S.P), and adhesive polyvinylidene fluoride (PVDF) were added to N-methylpyrrolidone (NMP) at a weight ratio of 94:3:3 (the weight ratio of the positive electrode material to NMP was 2.1:1), and sufficiently mixed and stirred to form a uniform slurry, which was coated on an aluminum foil current collector, dried, and pressed to obtain a positive electrode plate.

[0087] Manufacture of the negative electrode: Artificial graphite for the negative electrode, conductive carbon black (S.P), carboxymethyl cellulose (CMC), and adhesive (SBR) were added to a sufficient amount of pure water at a weight ratio of 95:1:1:3, mixed and stirred to form a uniform slurry, which was coated on a copper foil current collector, dried, and pressed to obtain a negative electrode plate.

[0088] The separator was a PP / PE composite film material. Tabs were spot welded to the pressed positive and negative electrode plates. After inserting the separator, it was wound in a winding machine and then placed in a pouch jig, and the upper and side surfaces were sealed. Next, it was placed in an oven for heating and drying. Then, 9 g of electrolyte solution was injected in an environment with a relative humidity of less than 1.5%. A mixed solvent with a mass ratio of EC:DEC:DMC = 1:1:1 was used as the electrolyte solution, and the electrolyte was 1 M lithium hexafluorophosphate. After injection and formation for 48 hours, it was evacuated and sealed. The cell model number was 454261.

[0089] The battery characteristic test was carried out on a battery tester (provided by Zhejiang Hangke Technology) by the following method.

[0090] 1) Capacity test The manufactured pouch cell was connected to the test track, and the test program was started. The steps were set as follows. The test temperature was set to 25 °C, and it was left standing for 4 hours, then charged at a constant current and constant voltage for 4 hours (for example, charged to 4.2 V at 1 / 3C), once stopped, left standing, and discharged at a constant current (for example, until the voltage reached 3.0 V at 1 / 3C). The capacity under the said current and voltage was obtained, and by repeating the said steps, capacity data under different current and voltage conditions could be obtained.

[0091] 2) Cycle Test The battery that had undergone the capacity test was connected to a test track, the test program was started, and the steps were set as follows. The test temperature was set to 45°C, left standing for 4 hours, charged at a constant current for 4 hours (for example, charged to 4.2V at 1C or charged to 4.3V at 1C), switched to a constant voltage for charging (for example, charged to 4.2V in 2 hours or charged to 4.3V in 2 hours), left standing for 5 minutes, discharged at a constant current for 4 hours (for example, to a voltage of 3.0V at 1C), left standing for 5 minutes, and the steps starting from the constant current charging were repeated to conduct a cycle test, whereby the capacity retention rate at different voltages and different cycle numbers can be obtained.

[0092] 3) Post-Cycle DC Internal Resistance (DCR) Increase Test In the cycle test steps of 2), before the constant current discharge, a step of discharging at a constant current for 30 seconds was added (the voltage difference within 30 seconds was recorded and divided by the current to obtain the DCR), and the rest was the same. The steps starting from the constant current charging were repeated to conduct a cycle test, whereby the DCR increase rate at different cycle numbers (the difference between the DCR after that cycle and the DCR after the first cycle divided by the DCR after the first cycle) can be obtained, and the test results are as shown in Table 4.

[0093] 4) Rate Performance The manufactured pouch cell was connected to a test track and the test program was started. The steps were set as follows. The test temperature was set to 25°C, left standing for 4 hours, charged to 4.2V at a constant current and constant voltage at 1 / 3C, once the current reached 0.02C, stopped once and left standing, discharged to a voltage of 3.0V at 1 / 3C, and the 1 / 3C discharge capacity of the battery was recorded. Left standing for 4 hours, charged to 4.2V at a constant current and constant voltage at 1C, once the current reached 0.02C, stopped once and left standing, discharged at a constant current to a voltage of 3.0V at 1C, and the 1C discharge capacity of the battery was recorded. Left standing for 4 hours, charged to 4.2V at a constant current and constant voltage at 2C, once the current reached 0.02C, stopped once and left standing, discharged at a constant current to a voltage of 3.0V at 2C, and the 2C discharge capacity of the battery was recorded.

[0094]

Table 4

[0095] As can be seen from Table 3, when the high-nickel cathode material for lithium-ion batteries manufactured in Examples 1 to 9 of the present invention was measured by the nitrogen adsorption method, the total pore volume of the one-point adsorption method at a pore diameter of 1.5 to 20 nm was 0.0043 cm 3 / g or less. Therefore, the cathode material has a porous structure, and the pore diameter range is within 1.7 to 19 nm. The tap density of the high-nickel cathode material manufactured in the present invention exceeds 1.9 g / cm 3 and the specific surface area is 0.33 to 0.95 m 2 / g, and the Dv50 particle size is 3.3 to 17.3 μm. In the XRD diffraction pattern, it is shown that the full width at half maximum FWHM(101) of the diffraction peak at a diffraction angle 2θ of around 36.6° in the powder X-ray diffraction pattern of the cathode material is 0.093 to 0.133.

[0096] As can be seen from Table 4, the lithium-ion batteries manufactured using the high-nickel cathode materials for lithium-ion batteries produced in Examples 1 to 9 of the present invention had a capacity of 181 to 200.7 mAh / g at a current of 1 / 3C and a voltage of 4.2V, a discharge capacity of 175.3 to 194.6 mAh / g at a current of 2C, a capacity retention rate of 87 to 94% after 200 cycles at 4.2V, and a DCR increase rate of 19 to 30% after 200 cycles at 4.2V. The high-nickel cathode material manufactured in the present invention has small pore diameters, provides many paths for the movement of lithium ions, and the paths are short. Therefore, high capacity and good rate characteristics are obtained. Since the full width at half maximum FWHM(101) of the diffraction peak at a diffraction angle 2θ of around 36.6° in the powder X-ray diffraction pattern of the cathode material is 0.093 to 0.133, the structural stability of the material is good, it has a good capacity retention rate, and the increase in DC internal resistance is small. In Examples 8 and 9 of the present invention, by mixing cathode materials with different particle sizes, the tap density of the high-nickel cathode material for lithium-ion batteries is further increased, a good balance is achieved between capacity and cycle characteristics, and the increase in DC internal resistance is also reduced.

[0097] In summary, compared with the conventional cathode materials for lithium-ion batteries, the present invention obtains a cobalt-free modified high-nickel cathode material for lithium-ion batteries by adding a modifying element and performing at least two firings and one coating treatment. It has a unique porous structure and crystal structure. Since the porous structure of the cathode material provides many paths for the movement of lithium ions and the paths are short, the lithium-ion battery not only has a higher capacity and good rate characteristics, but also the material has excellent structural stability due to the crystal structure. During the charge and discharge of the lithium-ion battery, the decrease in capacity is small, the cycle characteristics are excellent, the increase in DC internal resistance is small, and an effective balance is achieved among the capacity, rate characteristics, and cycle characteristics of the cobalt-free cathode material.

[0098] The above are only preferred embodiments of the implementation of the present invention and are not any limitation to the present invention. Any modifications, equivalent substitutions, or improvements made without departing from the spirit and principle of the present invention shall be included in the protection scope of the present invention.

[0099] (Supplementary Note) (Supplementary Note 1) It has a porous structure, and its chemical formula 1 is Li 1+a Ni b Mn c A d The elemental composition shown in O2, provided that 0.01 ≦ a ≦ 0.24, 0.79 < b ≦ 0.96, 0.01 < c ≦ 0.20, 0 < d ≦ 0.06, and A is any one or more elements selected from Mn, Co, Al, Zr, Y, Rb, Cs, W, Ce, Mo, Ba, Ti, Mg, Ta, Nb, Ca, V, Sc, Sr, and B, or is selected from a phosphorus-containing compound containing at least one element of Ti, Al, Mg, Zr, La, and Li A high-nickel cathode material for a lithium-ion battery, characterized in that

[0100] (Supplementary Note 2) When measured by the nitrogen adsorption method, in the BJH pore size distribution curve, it has a single-peak or multi-peak pore size distribution within the range of pore sizes of 1.5 to 20 nm, and the high-nickel cathode material has a one-point adsorption total pore volume of 0.01 cm 3 / g or less in the range of pore sizes of 1.5 to 20 nm The high-nickel cathode material for a lithium-ion battery according to Supplementary Note 1, characterized in that

[0101] (Supplementary Note 3) The high-nickel cathode material has a one-point adsorption total pore volume of 0.007 cm 3 / g or less in the range of pore sizes of 1.5 to 20 nm The high-nickel cathode material for a lithium-ion battery according to Supplementary Note 2, characterized in that

[0102] (Supplementary Note 4) The full width at half maximum FWHM(101) of the (101) diffraction peak at a diffraction angle 2θ of around 36.6° in the powder X-ray diffraction pattern of the cathode material is 0.080 to 0.180 The high-nickel cathode material for a lithium-ion battery according to Supplementary Note 1, characterized in that

[0103] (Appendix 5) The Dv50 particle size of the positive electrode material is 3 to 20 μm, The high-nickel positive electrode material for lithium-ion batteries according to Appendix 1, characterized in that.

[0104] (Appendix 6) The specific surface area of the positive electrode material is 0.33 to 1.5 m 2 / g, The high-nickel positive electrode material for lithium-ion batteries according to Appendix 1, characterized in that.

[0105] (Appendix 7) The tap density of the positive electrode material is 1.9 g / cm 3 or more, The high-nickel positive electrode material for lithium-ion batteries according to Appendix 1, characterized in that.

[0106] (Appendix 8) The total amount of free lithium in the positive electrode material is less than 1800 ppm, The high-nickel positive electrode material for lithium-ion batteries according to Appendix 1, characterized in that.

[0107] (Appendix 9) In Chemical Formula 1, 0.001 ≤ d ≤ 0.04, The high-nickel positive electrode material for lithium-ion batteries according to Appendix 1, characterized in that.

[0108] (Appendix 10) Including performing at least two firings and one coating treatment after mixing the raw materials, The method for manufacturing a high-nickel positive electrode material for lithium-ion batteries according to Appendix 1, characterized in that.

[0109] (Appendix 11) The temperature of the first firing is 700 to 900 °C, The temperature of the second firing is 400 to 800 °C, The manufacturing method according to Appendix 10, characterized in that.

[0110] (Appendix 12) The firing temperature of the first firing is 790 to 890 °C, and the firing temperature of the second firing is 680 to 800 °C. The manufacturing method according to Appendix 10, characterized in that.

[0111] (Appendix 13) The isothermal time of the first firing is 8 to 40 hours, and the isothermal time of the second firing is 5 to 20 hours. The manufacturing method according to Appendix 10, characterized in that.

[0112] (Appendix 14) The firing atmosphere is oxygen, The manufacturing method according to Appendix 10, characterized in that.

[0113] (Appendix 15) The coating treatment is performed before the final firing, The manufacturing method according to Appendix 10, characterized in that.

[0114] (Appendix 16) The Li source is a lithium-containing oxide, a lithium-containing fluoride, or a lithium-containing salt, The manufacturing method according to Appendix 10, characterized in that.

[0115] (Appendix 17) The Li source is selected from one or more of anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium acetate, and lithium fluoride, The manufacturing method according to Appendix 16, characterized in that.

[0116] (Appendix 18) Manufactured from the manufacturing method according to any one of Appendices 10 to 17, The high-nickel cathode material for a lithium-ion battery, characterized in that.

[0117] (Appendix 19) Two or more kinds of positive electrode materials manufactured from the manufacturing method described in any one of Supplementary Notes 1 to 9 or any one of Supplementary Notes 10 to 17 are included, A high-nickel positive electrode material for a lithium-ion battery, characterized in that.

[0118] (Supplementary Note 20) It includes a current collector and a positive electrode material supported on the current collector, and the positive electrode material is a high-nickel positive electrode material for a lithium-ion battery manufactured from the manufacturing method described in any one of Supplementary Notes 1 to 9 or any one of Supplementary Notes 10 to 17. A lithium-ion battery positive electrode, characterized in that.

[0119] (Supplementary Note 21) It includes a positive electrode, a negative electrode, and a lithium salt-containing electrolyte, and the positive electrode is the lithium-ion battery positive electrode described in Supplementary Note 20. A lithium-ion battery, characterized in that.

Claims

1. A high nickel positive electrode material for lithium ion batteries, having a porous structure, and represented by the chemical formula 1: Li １＋ａ Ni ｂ Mn ｃ A ｄ O ２ wherein, 0.01≦a≦0.24, 0.79<b≦0.96, 0.01<c≦0.20, and 0<d≦0.06, and A is one or more elements selected from Mn, Co, Al, Zr, Y, Rb, Cs, W, Ce, Mo, Ba, Ti, Mg, Ta, Nb, Ca, V, Sc, Sr, and B; When measured by nitrogen adsorption, the high nickel positive electrode material has a single-peak or multi-peak pore size distribution in the pore size range of 1.5 to 20 nm in the BJH pore size distribution curve, and the single-point adsorption total pore volume in the pore size range of 1.5 to 20 nm is 0.007 cm ３ / g, and the specific surface area of ​​the positive electrode material is 0.33 to 1.5 m ２ / g, A high nickel positive electrode material for lithium ion batteries.

2. The full width at half maximum (FWHM) (101) of the (101) diffraction peak at a diffraction angle 2θ of about 36.6° in the powder X-ray diffraction pattern of the positive electrode material is 0.080 to 0.

180.

2. The high nickel positive electrode material for lithium ion batteries according to claim 1.

3. The positive electrode material has a Dv50 particle size of 3 to 20 μm; 2. The high nickel positive electrode material for lithium ion batteries according to claim 1.

4. The tap density of the positive electrode material is 1.9 g / cm ３ That's all.

2. The high nickel positive electrode material for lithium ion batteries according to claim 1.

5. The total free lithium content of the positive electrode material is less than 1800 ppm; 2. The high nickel positive electrode material for lithium ion batteries according to claim 1.

6. In the formula 1, 0.001≦d≦0.04; 2. The high nickel positive electrode material for lithium ion batteries according to claim 1.

7. The cathode material according to any one of claims 1 to 6, A high nickel positive electrode material for lithium ion batteries.

8. A current collector and a positive electrode material supported on the current collector, the positive electrode material being the high nickel positive electrode material for lithium ion batteries according to any one of claims 1 to 6. A lithium ion battery positive electrode comprising:

9. A lithium ion battery comprising a positive electrode, a negative electrode, and a lithium salt-containing electrolyte, the positive electrode being the lithium ion battery positive electrode according to claim 8. A lithium-ion battery characterized by:

10. The positive electrode is made of a material including a positive electrode current collector, a positive electrode active material coated on the positive electrode current collector, an adhesive, and a conductive assistant, and the positive electrode active material is the positive electrode material for lithium ion batteries.

10. The lithium ion battery according to claim 9.

11. The adhesives include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, poly(vinylidene fluoride), polyethylene, polypropylene, styrene butadiene rubber, acrylated styrene butadiene rubber, epoxy resins, nylon, and the like, and combinations thereof.

11. The lithium ion battery of claim 10.

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