CN112018345A - High-nickel composite positive electrode material and preparation method and application thereof - Google Patents

High-nickel composite positive electrode material and preparation method and application thereof Download PDF

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CN112018345A
CN112018345A CN202010673140.0A CN202010673140A CN112018345A CN 112018345 A CN112018345 A CN 112018345A CN 202010673140 A CN202010673140 A CN 202010673140A CN 112018345 A CN112018345 A CN 112018345A
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nickel
positive electrode
lithium
transition metal
nickel composite
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陈敏
唐泽勋
商士波
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Hunan Sangrui New Material Co ltd
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Thornton New Energy Technology Changsha Co ltd
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Abstract

The invention relates to a high-nickel composite anode material and a preparation method and application thereof, wherein the high-nickel composite anode material comprises the following components: a lithium nickel-based transition metal oxide; and a composite oxide represented by formula I coated on the surface of the lithium nickel-based transition metal oxide: a. the1‑xBxCO3‑z(I); wherein, A in the formula I is selected from rare earth elements, B is selected from alkaline earth metal elements, C is selected from one transition metal element or the combination of a plurality of transition metal elements, and 0X is more than 05 and less than or equal to 0.4, and z is more than 0.02 and less than 0.2. According to the high-nickel composite cathode material provided by the invention, the composite oxide is coated on the surface of the lithium-nickel-based transition metal oxide, so that the high-nickel composite cathode material has good electron and secondary transmission capabilities; also, in the use in a lithium secondary battery, the cycle performance and rate performance of the lithium secondary battery can be improved.

Description

High-nickel composite positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium secondary batteries, in particular to a high-nickel composite positive electrode material and a preparation method and application thereof.
Background
The lithium secondary battery has the advantages of high voltage, high specific energy, good cycle performance and the like, and is widely applied to the fields of electronic products, medical products, wearable products and the like. As the social life relationship between the above products and people becomes more compact, the demand for the electrochemical performance of the lithium secondary battery is also higher and higher. The positive electrode active material is an important component of the lithium secondary battery and can provide lithium secondary reciprocating movement to the positive electrode and the negative electrode in the charging and discharging processes of the battery, so that the positive electrode active material is important for improving the electrochemical performance of the lithium secondary battery.
The nickel-cobalt-manganese (NCM) ternary positive active material has the characteristics of high specific capacity, long cycle life, low toxicity, low price and the like, so that the nickel-cobalt-manganese ternary positive active material becomes the most widely applied positive active material in the lithium secondary battery. The Chinese patent application No. CN201911251189.0, entitled high-nickel anode material with composite coating layer and its preparation method, describes that the high-nickel anode material coated with nano material is mixed with secondary water and soluble phosphate dissolved with soluble lithium compound, stirred uniformly, vacuum filtered, dried and burned in a kiln, cooled, crushed and sieved to obtain the high-nickel anode material with composite coating layer.
However, the above-mentioned high nickel cathode material is easy to generate oxygen during charging and discharging, especially at high temperature, and further the structure of the material is changed, which affects the cycle performance and rate capability, and further limits the application.
Disclosure of Invention
In view of the above problems, the present invention provides a high nickel composite positive electrode material, and a preparation method and an application thereof, wherein a lithium nickel-based transition metal oxide and a composite oxide coated on the surface of the lithium nickel-based transition metal oxide are used as positive electrode active materials, and when the positive electrode active materials are applied to the charge and discharge processes of a lithium secondary battery, the generation of oxygen can be inhibited, the phase change of the materials can be avoided, and the cycle performance and the rate capability of the materials can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a first aspect of the present invention provides a high nickel composite positive electrode material, comprising:
a lithium nickel-based transition metal oxide; and
a composite oxide represented by formula i coated on the surface of the lithium nickel-based transition metal oxide:
A1-xBxCO3-z (Ⅰ)；
wherein, A in the formula I is selected from rare earth elements, B is selected from alkaline earth elements, C is selected from one transition metal element or the combination of a plurality of transition metal elements, x is more than 0.05 and less than or equal to 0.4, and z is more than 0.02 and less than 0.2.
In some alternative embodiments, a in formula i is selected from La, B is selected from Sr, and C is selected from a combination of Co and Fe.
In some alternative embodiments, the formula i is:
La1-xSrxCo1-yFeyO3-z；
wherein x is more than 0.05 and less than or equal to 0.4, y is more than 0 and less than or equal to 0.9, and z is more than 0.02 and less than 0.2.
In some alternative embodiments, the particle size of the composite oxide is 20 to 200 nm.
In some alternative embodiments, the coating amount of the composite oxide is 0.1 to 2%.
In some alternative embodiments, the lithium nickel-based transition metal oxide is represented by formula ii:
LiNiσCoλMn1-σ-λO2 (Ⅱ)；
wherein, the sigma is more than or equal to 0.6 and less than 1, and the lambda is more than 0 and less than 0.4.
In some alternative embodiments, the lithium nickel-based transition metal oxide is selected from LiNi0.8Co0.1Mn0.1O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.85Co0.1Mn0.05O2At least one of;
the composite oxide is selected from La0.7Sr0.3Co0.2Fe0.8O2.9、La0.6Sr0.4Co0.2Fe0.8O2.85And La0.8Sr0.2Co0.3Fe0.7O2.93At least one of (1).
A second aspect of the present invention provides a method for preparing the high nickel composite positive electrode material according to any one of the above embodiments, including the following steps:
mixing the lithium-nickel-based transition metal oxide with the composite oxide to obtain a mixture;
and sintering the mixture to obtain the high-nickel composite cathode material.
In some alternative embodiments, the mixing is gravity-free mixing and the time of mixing is from 0.5 to 4 hours; the sintering temperature is 300-800 ℃, and the sintering time is 4-12 h.
A third aspect of the present invention provides a lithium secondary battery comprising:
a positive electrode comprising the high nickel composite positive electrode material described in any of the above embodiments;
a negative electrode; and
an electrolyte between the positive electrode and the negative electrode, and a separator.
The embodiment of the invention has at least the following advantages:
1) the high-nickel composite anode material provided by the invention can inhibit the generation of oxygen in the charge and discharge process of the anode, avoids the phase change of the material, and further improves the cycle performance and the rate capability of the lithium secondary battery.
2) The preparation method of the high-nickel composite anode material provided by the invention is simple and controllable, and is suitable for industrial production.
3) According to the lithium secondary battery provided by the invention, the positive electrode of the lithium secondary battery comprises the high-nickel composite positive electrode material, so that the lithium secondary battery has better cycle performance and rate capability.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the high nickel composite positive electrode material prepared in example 1 of the present application.
Detailed description of the preferred embodiments
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention firstly provides a high-nickel composite anode material, which comprises the following components:
a lithium nickel-based transition metal oxide;
a composite oxide represented by formula i coated on the surface of the lithium nickel-based transition metal oxide:
A1-xBxCO3-z (Ⅰ)；
wherein, A in the formula I is selected from rare earth elements, B is selected from alkaline earth elements, C is selected from one transition metal element or the combination of a plurality of transition metal elements, x is more than 0.05 and less than or equal to 0.4, and z is more than 0.02 and less than 0.2.
The high-nickel composite positive electrode material provided by the invention is used in a lithium secondary battery, and can improve the cycle performance and rate performance of the lithium secondary battery. The inventors have analyzed based on this phenomenon and have considered that it is possible: in the process of charging and discharging of the lithium secondary battery, the composite oxide represented by the formula I can generate a large number of oxygen vacancies with positive charges on the surface of the lithium-nickel-based transition metal oxide, and the oxygen vacancies are converged to form a potential well which is easy to capture oxygen ions, so that the generation of oxygen is inhibited, the phase change of the active material of the positive electrode is avoided, and the cycle performance and the rate capability of the lithium secondary battery are improved.
In order to be able to increase the energy density of the battery, the mole percent content of nickel in the NCM ternary positive active material is typically increased in the prior art methods. However, an increase in the nickel content results in deterioration of cycle performance and rate performance of the battery. In this embodiment, the mole percentage of nickel in the lithium-nickel-based transition metal oxide is generally controlled to be above 60%, and since the surface of the lithium-nickel-based transition metal oxide is coated with the composite oxide of formula i, the energy density of the lithium secondary battery is improved, and the cycle performance and the rate capability of the lithium secondary battery are also improved.
By way of example, the molar percentage of nickel in the lithium nickel-based transition metal oxide may be, but is not limited to, 60%, 65%, 70%, 75%, 80%, 85%, and 90%. The specific content of nickel can be selected according to the application.
In the present embodiment, the molar percentages of the other elements in the lithium nickel-based transition metal oxide are not particularly limited as long as the sum of the molar percentages of the elements is 100%.
In an alternative embodiment of the present invention, the transition metal in the lithium nickel-based transition metal oxide may be selected from Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn, Mn, or a combination thereof. In a specific embodiment of the present invention, the transition metal is selected from the group consisting of Co and Mn.
Further, the lithium nickel-based transition metal oxide is a compound represented by formula II:
LiNiσCoλMn1-σ-λO2 (Ⅱ)；
wherein, the sigma is more than or equal to 0.6 and less than 1, and the lambda is more than 0 and less than 0.4.
In formula ii, for example, σ may be, but not limited to, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, and λ may be, but not limited to, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35.
In an alternative embodiment of the present invention, the lithium nickel-based transition metal oxide may be obtained by any combination of the above values. In a specific embodiment of the present invention, σ is 0.6, 0.8, 0.85 and λ is 0.1, 0.2, i.e., the lithium nickel-based transition metal oxide may be, but is not limited to, LiNi0.8Co0.1Mn0.1O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.85Co0.1Mn0.05O2。
In the high-nickel composite positive electrode material provided by the invention, the composite oxide coated on the surface of the lithium-nickel-based transition metal oxide can provide a sufficient reaction area for the lithium-nickel-based transition metal oxide and an electrolyte, and can form oxygen vacancies on the surface of the lithium-nickel-based transition metal oxide to inhibit the generation of oxygen, thereby being beneficial to improving the cycle performance and rate capability of a lithium secondary battery.
In an embodiment of the invention, a in formula i is selected from rare earth metals, which may be lanthanides or combinations between lanthanides. Specifically, the lanthanoid is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).
B in the formula I is selected from alkaline earth metal elements, and concretely, the alkaline earth metal elements are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra).
C in the formula I is selected from one transition metal element or a combination of a plurality of transition metal elements, wherein the transition metal elements can be scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn).
In an alternative embodiment of the present invention, when a in formula i is selected from La, B is selected from Sr, and C is selected from the combination of Co and Fe, the formation of a composite oxide having the following general formula can further improve the cycle performance and rate performance of a lithium secondary battery.
La1-xSrxCo1-yFeyO3-z；
Wherein x is more than 0.05 and less than or equal to 0.4, y is more than 0 and less than or equal to 0.9, and z is more than 0.02 and less than 0.2.
Illustratively, in the general formula of the complex oxide, x may be, but is not limited to, 0.1, 0.2, 0.3, 0.4, y may be, but is not limited to, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and z may be, but is not limited to, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19.
In an alternative embodiment of the present invention, the composite oxide may be obtained by any combination of the above values. In a specific embodiment of the present invention, x is 0.2, 0.3, y is 0.7, 0.8, and z is 0.07, 0.1, 0.15, i.e., the composite oxide may be, but is not limited to, La0.7Sr0.3Co0.2Fe0.8O2.9、La0.6Sr0.4Co0.2Fe0.8O2.85And La0.8Sr0.2Co0.3Fe0.7O2.93。
The inventor finds out through experimental research that the doping amount of Sr can influence the formation of oxygen vacancies, and further influence the cycle performance and rate performance of the battery. When the value of x is lower than the range, enough oxygen vacancies cannot be formed, so that the generation of oxygen cannot be effectively inhibited, and the cycle performance and the rate performance of the battery are reduced; when the value of x exceeds the above range, an excessive amount of oxygen vacancies may be formed, which may result in a decrease in the conductive properties of the composite oxide, thereby causing a decrease in the cycle performance and rate capability of the lithium secondary battery.
In an alternative embodiment of the present invention, the composite oxide has a particle size of 20 to 200nm, which can further improve cycle performance and rate performance of the lithium secondary battery.
In addition, the coating amount of the composite oxide may also contribute to improvement of cycle performance and rate performance of the lithium secondary battery. In an alternative embodiment, the coating amount of the composite oxide is 0.1 to 2%, that is, the amount of the composite oxide coated on the surface of the lithium nickel-based transition metal oxide is 0.1 to 2% of the amount of the lithium nickel-based transition metal oxide.
Illustratively, the coating amount of the composite oxide may be, but is not limited to, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%. In a specific embodiment of the present invention, the coating amount of the composite oxide is 0.1%, 0.5%, 1%.
A second aspect of the present invention provides a method for preparing a high nickel composite positive electrode material in any one of the above embodiments, including the following steps:
1) mixing lithium-nickel-based transition metal oxide with composite oxide to obtain a mixture;
wherein the lithium nickel-based transition metal oxide is a compound represented by formula II: LiNiσCoλMn1-σ-λO2(Ⅱ)，0.6≤σ＜1，0＜λ＜0.4。
The lithium nickel-based transition metal oxide can be prepared by the following method or directly purchased, and the method specifically comprises the following steps:
the precursor containing the transition metal and a lithium source (for example, lithium hydroxide, lithium carbonate, etc.) are mixed in a certain molar ratio, and sintered in an oxygen-containing atmosphere (for example, air, oxygen, etc.) or an inert atmosphere (for example, argon, etc.), to obtain the lithium-nickel-based transition metal oxide.
2) And sintering the mixture to obtain the high-nickel composite cathode material.
In a specific operation, the mixing of the lithium nickel-based transition metal oxide and the composite oxide in the step 1) can be carried out in a gravity-free mixing kettle for 0.5-4h, so that the lithium nickel-based transition metal oxide and the composite oxide are mixed; in the step 2), the sintering temperature is 300-800 ℃, and the sintering time is 4-12 h.
The preparation method of the high-nickel composite anode material provided by the invention is simple and controllable, and is suitable for industrial production.
A third aspect of the present invention provides a positive electrode comprising the high nickel composite positive electrode material according to any one of the above embodiments or the high nickel composite positive electrode material obtained by the production method according to any one of the above embodiments.
A fourth aspect of the present invention provides a lithium secondary battery comprising: the positive electrode, the negative electrode, and the electrolyte and the separator between the positive electrode and the negative electrode in the above embodiments.
In the lithium secondary battery provided by the invention, the positive electrode specifically comprises a positive electrode current collector and a positive electrode diaphragm arranged on the surface of the positive electrode current collector. The positive electrode current collector may be a current collector known to those skilled in the art, such as a metal foil. In particular, the metal foil may be selected from copper, aluminum, nickel, titanium, iron, silver, gold, or alloys thereof. In a specific embodiment of the present invention, the positive electrode current collector is selected from aluminum foil. The positive electrode diaphragm is formed by the high-nickel composite positive electrode material, the conductive agent and the binder.
When preparing the positive electrode, the high nickel composite positive electrode material in the above embodiment, the conductive agent and the binder may be dispersed in a solvent, and fully stirred and mixed to form a uniform positive electrode slurry; and uniformly coating the positive electrode slurry on a positive electrode current collector, and drying, rolling and slitting to obtain the positive electrode.
In some alternative embodiments of the present invention, the conductive agent is selected from at least one of carbon black, acetylene black, graphene, ketjen black, and carbon fiber.
The binder is at least one selected from polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyethylene, polypropylene, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, ethylene oxide-containing polymer, polyvinylpyrrolidone and polyurethane.
In the lithium secondary battery provided by the invention, the negative electrode adopts metal foil, and the metal foil can be selected from copper, aluminum, nickel, titanium, iron, silver, gold, lithium or alloy thereof. In an embodiment of the present invention, the metal foil is a lithium metal foil.
In addition, the negative electrode may be provided with a conductive layer formed of a conductive agent and a binder. Specifically, the conductive agent is selected from at least one of natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, and graphene.
The binder is at least one selected from sodium carboxymethylcellulose, styrene-butadiene rubber, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyvinyl alcohol and sodium polyacrylate.
When the cathode is prepared, the conductive agent and the binder can be dispersed in a proper amount of deionized water, and the mixture is fully stirred and mixed to form uniform cathode slurry; and uniformly coating the cathode slurry on a metal foil, and drying, rolling and slitting to obtain the cathode.
The electrolyte solution in the lithium ion secondary battery of the present invention is not particularly limited, and may be any electrolyte solution known to those skilled in the art, for example, a nonaqueous electrolyte solution. In some alternative embodiments of the present invention, the nonaqueous electrolytic solution includes an electrolyte and an organic solvent.
In the practice of the present invention, the electrolyte may be selected from lithium salts including lithium hexafluorophosphate (LiPF)6) At least one of lithium difluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bis (fluorosulfonylimide), lithium bis (trifluoromethanesulfonylimide), lithium bis (oxalato) borate, and lithium difluoro (oxalato) borate.
The organic solvent is selected from Ethylene Carbonate (EC), propylene carbonate, butylene carbonate, gamma-butyrolactone, pentylene carbonate, dimethyl carbonate (DMC), diethyl carbonate, dipropyl carbonate, and ethyl methyl carbonate. The carboxylic acid ester may be, but is not limited to, at least one of ethyl butyrate, methyl butyrate, propyl propionate, ethyl propionate, methyl propionate, ethyl acetate, and methyl acetate.
In addition, additives can be added into the nonaqueous electrolyte solution to improve the electrochemical performance of the lithium secondary battery. The additive may be one well known to those skilled in the art, and illustratively, the additive may be at least one selected from the group consisting of an SEI film forming additive, a flame retardant additive, an anti-overcharge additive, and a conductive additive.
The separator material in the lithium ion secondary battery of the present invention is not particularly limited, and may be a separator material known to those skilled in the art, and for example, the separator material may be one selected from a polypropylene separator, a polyethylene separator, and a polyvinylidene fluoride separator.
The form of the lithium secondary battery of the present invention is not particularly limited, and may be button-shaped, cylindrical, or square.
Hereinafter, the high nickel composite positive electrode material, the method for preparing the same, and the lithium secondary battery (button cell) according to the present invention will be described in detail with reference to specific examples.
Unless otherwise specified, the chemical materials and instruments used in the following examples and comparative examples are all conventional chemical materials and conventional instruments, and are commercially available.
Example 1
The preparation method of the high-nickel composite cathode material provided by the embodiment comprises the following steps:
1) mixing Ni0.8Co0.1Mn0.1(OH)2Mixing with lithium hydroxide, sintering at 810 deg.C for 12 hr in oxygen atmosphere, and naturally cooling to obtain LiNi-based transition metal oxide0.8Co0.1Mn0.1O2(ii) a Wherein Li: the molar ratio of (Ni + Co + Mn) was 1.03: 1;
2) reacting LiNi0.8Co0.1Mn0.1O2And La0.7Sr0.3Co0.2Fe0.8O2.9Adding the mixture into a gravity-free mixing kettle, and mixing for 1 hour to uniformly mix the lithium-nickel-based transition metal oxide and the composite oxide to obtain a mixture; wherein, LiNi0.8Co0.1Mn0.1O2And La0.7Sr0.3Co0.2Fe0.8O2.9The mass ratio of (A) to (B) is 1000: 1, La0.7Sr0.3Co0.2Fe0.8O2.9Has a particle size of about 30 nm;
3) sintering the mixture at 600 ℃ for 6h, taking out, and sieving to obtain the high-nickel composite cathode material which can be expressed as LiNi0.8Co0.1Mn0.1O2@La0.7Sr0.3Co0.2Fe0.8O2.9(ii) a Wherein, La0.7Sr0.3Co0.2Fe0.8O2.9The coating amount of (3) was 0.1%.
Fig. 1 is an SEM image of the high nickel composite positive electrode material prepared in example 1, and it can be seen from fig. 1 that the high nickel composite positive electrode material is in a spherical shape and has a particle size of about 15 μm.
The embodiment also provides a preparation method of the button cell (model number is CR2032), which comprises the following specific steps:
1) preparing a positive pole piece: preparing the high-nickel composite cathode material prepared in the example 1, acetylene black and a binder into pasty cathode slurry according to the mass ratio of 88:6: 6;
uniformly coating the slurry on an aluminum foil, then placing the aluminum foil in a vacuum drying oven, drying at 100 ℃ for 12 hours, and compacting under 20MPa to obtain a positive pole piece; wherein the amount of the active material loaded on the positive electrode sheet is 4-5mg cm-2；
2) Placing the positive pole piece in a lower cover of a button cell, placing a diaphragm (model number is cell-gard 2300) on the positive pole piece, and injecting 300 mu l of electrolyte into the positive pole piece, wherein the volume ratio of the electrolyte to Ethylene Carbonate (EC) to dimethyl carbonate (DMC) is 1: 1, LiPF at a concentration of 1mol/L6A solution dissolved in the above solvent.
3) Using metal lithium as a negative electrode, placing the metal lithium on the upper side of the separator, covering the upper cover with a sealing gasket, and riveting with a riveting machine to obtain the button cell.
The battery is assembled in a glove box under an argon atmosphere.
Example 2
The preparation method of the high-nickel composite cathode material provided by the embodiment comprises the following steps:
1) mixing Ni0.6Co0.2Mn0.2(OH)2Mixing with lithium hydroxide, sintering at 880 deg.C for 10 hr in oxygen atmosphere, and naturally cooling to obtain LiNi-based transition metal oxide0.6Co0.2Mn0.2O2(ii) a Wherein Li: the molar ratio (Ni + Co + Mn) was 1.06: 1;
2) reacting LiNi0.6Co0.2Mn0.2O2And La0.6Sr0.4Co0.2Fe0.8O2.85Adding into a gravity-free mixing kettle, and mixing for 1.5h to obtain lithium-nickel-based transition metal oxide and composite oxideUniformly mixing the materials to obtain a mixture; wherein, LiNi0.6Co0.2Mn0.2O2And La0.6Sr0.4Co0.2Fe0.8O2.85The mass ratio of (A) to (B) is 1000: 1, La0.6Sr0.4Co0.2Fe0.8O2.85Has a particle size of about 20 nm;
3) sintering the mixture at 630 ℃ for 6h, taking out, and sieving to obtain the high-nickel composite cathode material which can be expressed as LiNi0.6Co0.2Mn0.2O2@La0.6Sr0.4Co0.2Fe0.8O2.85(ii) a Wherein, La0.6Sr0.4Co0.2Fe0.8O2.85The coating amount of (3) was 0.5%.
The button cell provided in this example was prepared in substantially the same manner as in example 1, except that: the high nickel composite positive electrode material prepared in example 2 was used as a positive electrode active material.
Example 3
The preparation method of the high-nickel composite cathode material provided by the embodiment comprises the following steps:
1) mixing Ni0.85Co0.1Mn0.05(OH)2Mixing with lithium hydroxide, sintering at 785 deg.C for 15h in oxygen atmosphere, and naturally cooling to obtain LiNi-based transition metal oxide0.85Co0.1Mn0.05O2(ii) a Wherein Li: the molar ratio of (Ni + Co + Mn) was 1.02: 1;
2) reacting LiNi0.85Co0.1Mn0.05O2And La0.8Sr0.2Co0.3Fe0.7O2.93Adding the mixture into a gravity-free mixing kettle, and mixing for 1.5 hours to uniformly mix the lithium-nickel-based transition metal oxide and the composite oxide to obtain a mixture; wherein, LiNi0.85Co0.1Mn0.05O2And La0.8Sr0.2Co0.3Fe0.7O2.93The mass ratio of (A) to (B) is 100: 1, La0.8Sr0.2Co0.3Fe0.7O2.93Has a particle diameter of about50nm；
3) Sintering the mixture at 630 ℃ for 6h, taking out, and sieving to obtain the high-nickel composite cathode material which can be expressed as LiNi0.85Co0.1Mn0.05O2@La0.8Sr0.2Co0.3Fe0.7O2.93(ii) a Wherein, La0.8Sr0.2Co0.3Fe0.7O2.93The coating amount of (2) was 1%.
The button cell provided in this example was prepared in substantially the same manner as in example 1, except that: the high nickel composite positive electrode material prepared in example 3 was used as a positive electrode active material.
Comparative example 1
The preparation method of the high-nickel composite cathode material provided by the comparative example comprises the following steps:
1) mixing Ni0.8Co0.1Mn0.1(OH)2Mixing with lithium hydroxide, sintering at 810 deg.C for 12 hr in oxygen atmosphere, and naturally cooling to obtain LiNi-based transition metal oxide0.8Co0.1Mn0.1O2(ii) a Wherein Li: the molar ratio of (Ni + Co + Mn) was 1.03: 1;
2) reacting LiNi0.8Co0.1Mn0.1O2And La0.95Sr0.05Co0.2Fe0.8O2.98Adding the mixture into a gravity-free mixing kettle, and mixing for 1 hour to uniformly mix the lithium-nickel-based transition metal oxide and the composite oxide to obtain a mixture; wherein, LiNi0.8Co0.1Mn0.1O2And La0.95Sr0.05Co0.2Fe0.8O2.98The mass ratio of (A) to (B) is 1000: 1, La0.95Sr0.05Co0.2Fe0.8O2.98Has a particle size of about 30 nm;
3) sintering the mixture at 600 ℃ for 6h, taking out, and sieving to obtain the high-nickel composite cathode material which can be expressed as LiNi0.8Co0.1Mn0.1O2@La0.7Sr0.3Co0.2Fe0.8O2.98(ii) a It is composed ofIn La0.95Sr0.05Co0.2Fe0.8O2.98The coating amount of (3) was 0.1%.
The button cell provided by this comparative example was prepared essentially the same as example 1, except that: the high nickel composite positive electrode material prepared in comparative example 1 was used as the positive electrode active material.
Comparative example 2
The preparation method of the high-nickel composite cathode material provided by the comparative example comprises the following steps:
1) mixing Ni0.8Co0.1Mn0.1(OH)2Mixing with lithium hydroxide, sintering at 810 deg.C for 12 hr in oxygen atmosphere, and naturally cooling to obtain LiNi-based transition metal oxide0.8Co0.1Mn0.1O2(ii) a Wherein Li: the molar ratio of (Ni + Co + Mn) was 1.03: 1;
2) reacting LiNi0.8Co0.1Mn0.1O2And La0.5Sr0.5Co0.2Fe0.8O2.78Adding the mixture into a gravity-free mixing kettle, and mixing for 1 hour to uniformly mix the lithium-nickel-based transition metal oxide and the composite oxide to obtain a mixture; wherein, LiNi0.8Co0.1Mn0.1O2And La0.5Sr0.5Co0.2Fe0.8O2.78The mass ratio of (A) to (B) is 1000: 1, La0.5Sr0.5Co0.2Fe0.8O2.78Has a particle size of about 30 nm;
3) sintering the mixture at 600 ℃ for 6h, taking out, and sieving to obtain the high-nickel composite cathode material which can be expressed as LiNi0.8Co0.1Mn0.1O2@La0.5Sr0.5Co0.2Fe0.8O2.78(ii) a Wherein, La0.5Sr0.5Co0.2Fe0.8O2.78The coating amount of (3) was 0.1%.
The button cell provided by this comparative example was prepared essentially the same as example 1, except that: the high nickel composite positive electrode material prepared in comparative example 2 was used as the positive electrode active material.
Comparative example 3
The preparation method of the positive electrode active material provided by the comparative example comprises the following steps:
1) mixing Ni0.8Co0.1Mn0.1(OH)2Mixing with lithium hydroxide, sintering at 810 deg.C for 12 hr in oxygen atmosphere, and naturally cooling to obtain LiNi-based transition metal oxide0.8Co0.1Mn0.1O2(ii) a Wherein Li: the molar ratio of (Ni + Co + Mn) was 1.03: 1;
2) subjecting the above LiNi to a reaction0.8Co0.1Mn0.1O2Sintering at 600 deg.C for 6h, taking out, and sieving to obtain positive active material
The button cell provided by this comparative example was prepared essentially the same as example 1, except that: the positive electrode active material prepared in comparative example 3 was used.
Comparative example 4
The preparation method of the high-nickel composite cathode material provided by the comparative example comprises the following steps:
1) mixing Ni0.8Co0.1Mn0.1(OH)2Mixing with lithium hydroxide, sintering at 810 deg.C for 12 hr in oxygen atmosphere, and naturally cooling to obtain LiNi-based transition metal oxide0.8Co0.1Mn0.1O2(ii) a Wherein Li: the molar ratio of (Ni + Co + Mn) was 1.03: 1;
2) reacting LiNi0.8Co0.1Mn0.1O2With TiO2Adding the mixture into a gravity-free mixing kettle to mix for 1 hour to ensure that the LiNi is mixed0.8Co0.1Mn0.1O2With TiO2Uniformly mixing to obtain a mixture; wherein the above TiO2Can be prepared by the method described in Chinese patent publication No. CN109192969A, and the TiO2Has oxygen vacancies and has a particle size of about 30 nm; LiNi0.8Co0.1Mn0.1O2With TiO2The mass ratio of (A) to (B) is 1000: 1;
3) sintering the mixture at 600 deg.C for 6 hr, taking out, and sieving to obtain the final productTo high nickel composite positive electrode materials, which may be denoted as LiNi0.8Co0.1Mn0.1O2@TiO2。
The button cell provided by this comparative example was prepared essentially the same as example 1, except that: the high nickel composite positive electrode material prepared in comparative example 4 was used as the positive electrode active material.
Comparative example 5
The preparation method of the high-nickel composite cathode material provided by the comparative example comprises the following steps:
1) mixing Ni0.8Co0.1Mn0.1(OH)2Mixing with lithium hydroxide, sintering at 810 deg.C for 12 hr in oxygen atmosphere, and naturally cooling to obtain LiNi-based transition metal oxide0.8Co0.1Mn0.1O2(ii) a Wherein Li: the molar ratio of (Ni + Co + Mn) was 1.03: 1;
2) reacting LiNi0.8Co0.1Mn0.1O2Adding MgO into a gravity-free mixing kettle to mix for 1h to ensure that LiNi0.8Co0.1Mn0.1O2Uniformly mixing the MgO with the mixture to obtain a mixture; wherein the MgO is prepared by a method described in Chinese patent publication No. CN109192969A, and the MgO has oxygen vacancy and has a particle size of about 30 nm; LiNi0.8Co0.1Mn0.1O2The mass ratio of MgO to MgO is 1000: 1;
3) sintering the mixture at 600 ℃ for 6h, taking out, and sieving to obtain the high-nickel composite cathode material which can be expressed as LiNi0.8Co0.1Mn0.1O2@MgO。
The button cell provided by this comparative example was prepared essentially the same as example 1, except that: the high nickel composite positive electrode material prepared in comparative example 5 was used as the positive electrode active material.
Comparative example 6
The preparation method of the high-nickel composite cathode material provided by the comparative example comprises the following steps:
1) mixing Ni0.8Co0.1Mn0.1(OH)2And hydrogenAfter lithium oxide is evenly mixed, the mixture is sintered for 12 hours at 810 ℃ in the oxygen atmosphere, and after natural cooling, the lithium nickel base transition metal oxide LiNi is prepared0.8Co0.1Mn0.1O2(ii) a Wherein Li: the molar ratio of (Ni + Co + Mn) was 1.03: 1;
2) reacting LiNi0.8Co0.1Mn0.1O2And ZrO2Adding the mixture into a gravity-free mixing kettle to mix for 1 hour to ensure that the LiNi is mixed0.8Co0.1Mn0.1O2And ZrO2Uniformly mixing to obtain a mixture; wherein, the above-mentioned ZrO2Can be prepared by the method described in Chinese patent publication No. CN109192969A, and the ZrO2Has oxygen vacancies and has a particle size of about 30 nm; LiNi0.8Co0.1Mn0.1O2And ZrO2The mass ratio of (A) to (B) is 1000: 1;
3) sintering the mixture at 600 ℃ for 6h, taking out, and sieving to obtain the high-nickel composite cathode material which can be expressed as LiNi0.8Co0.1Mn0.1O2@ZrO2。
The button cell provided by this comparative example was prepared essentially the same as example 1, except that: the high nickel composite positive electrode material prepared in comparative example 6 was used as the positive electrode active material.
The following tests were performed on the button cells of the above examples and comparative examples, and the test results are shown in table 1.
1. Cycle testing at Normal and high temperatures
Placing the battery in an environment with the temperature of 25 ℃ and the temperature of 55 ℃, performing charge-discharge circulation by using 1C current in a charge-discharge voltage interval of 2.8-4.3V, recording the initial capacity as Q1, recording the capacity as Q2 after circulation to 200 weeks, and calculating the capacity retention rate of the battery after circulation according to the following formula:
capacity retention (%) ═ Q2/Q1 × 100%.
2. Rate capability test
Placing the battery in an environment at 25 ℃, and carrying out first-week charging and discharging by using 0.2C current in a charging and discharging voltage interval of 2.8-4.3V, wherein the recording capacity is W1; the second cycle of charging and discharging was carried out at a current of 0.5C and recorded as capacity W2; the third cycle of charge and discharge was carried out at a current of 1C, and the recording capacity was W3; the capacity retention rate was calculated from the following formula:
capacity retention (%) (W1 or W2)/W3 × 100%.
TABLE 1
Figure BDA0002583074870000131
Figure BDA0002583074870000141
Referring to table 1, it can be seen from the results of the cycle performance and rate performance tests of comparative example 1 and comparative examples 1-2 that when x is more than 0.05 and less than 0.4 and z is more than 0.02 and less than 0.2 in formula i, the battery with the high nickel cathode material can have better cycle performance and rate performance. When the value of x in the general formula of the composite oxide is lower than the range defined by the invention, enough oxygen vacancies cannot be formed, and further, the generation of oxygen cannot be effectively inhibited, so that the cycle performance and the rate capability of the battery are reduced; when the value of x exceeds the range defined by the invention, excessive oxygen vacancies can be formed, and further the conductivity of the composite oxide is reduced, so that the cycle performance and the rate capability of the battery are reduced.
Comparing example 1 with comparative example 3 in which the composite oxide was not added, example 1 can significantly improve the cycle performance and rate performance of the battery. Based on this phenomenon, the possible principles are: in the process of charging and discharging of the lithium secondary battery, the composite oxide can generate a large amount of oxygen vacancies with positive charges on the surface of the lithium-nickel-based transition metal oxide, the oxygen vacancies are converged to form a potential well, the potential well is easy to capture oxygen ions, further the generation of oxygen is inhibited, the phase change of the active material of the positive electrode is avoided, and the cycle performance and the rate capability of the lithium secondary battery are improved.
From the results of the cycle performance and rate performance tests in example 1 and comparative examples 4 to 6, it can be seen that the composite oxide of the present invention can significantly improve the cycle performance and rate performance of a battery, compared to magnesium oxide, titanium oxide, and zirconium oxide.
Based on the above results, it can be seen that when the composite oxide represented by formula i of the present application is coated on the surface of the lithium-nickel-based transition metal oxide, and x is greater than 0.05 and less than or equal to 0.4, and z is greater than 0.02 and less than 0.2, the battery with the high-nickel cathode material can have better cycle performance and rate capability.
Finally, it should be noted that: the above experimental examples are only used to illustrate the technical solution of the present invention, but not to limit the same; although the present invention has been described in detail with reference to the foregoing experimental examples, it will be understood by those skilled in the art that: the technical scheme recorded in each experimental example can be modified, or part or all of the technical features can be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical scheme depart from the scope of the technical scheme of each experimental example of the invention.

Claims (10)

1. A high nickel composite positive electrode material, comprising:
a lithium nickel-based transition metal oxide; and
a composite oxide represented by formula i coated on the surface of the lithium nickel-based transition metal oxide:
A1-xBxCO3-z (Ⅰ)；
wherein, A in the formula I is selected from rare earth elements, B is selected from alkaline earth elements, C is selected from one transition metal element or the combination of a plurality of transition metal elements, x is more than 0.05 and less than or equal to 0.4, and z is more than 0.02 and less than 0.2.
2. The high nickel composite positive electrode material as claimed in claim 1, wherein A in the formula I is selected from La, B is selected from Sr, and C is selected from a combination of Co and Fe.
3. The high nickel composite positive electrode material according to claim 2, wherein the formula i is:
La1-xSrxCo1-yFeyO3-z；
wherein x is more than 0.05 and less than or equal to 0.4, y is more than 0 and less than or equal to 0.9, and z is more than 0.02 and less than 0.2.
4. The high-nickel composite positive electrode material according to claim 1, wherein the particle diameter of the composite oxide is 20 to 200 nm.
5. The high-nickel composite positive electrode material according to claim 1, wherein the coating amount of the composite oxide is 0.1 to 2%.
6. The high nickel composite positive electrode material according to any one of claims 1 to 5, wherein the lithium nickel based transition metal oxide is represented by formula II:
LiNiσCoλMn1-σ-λO2 (Ⅱ)；
wherein, the sigma is more than or equal to 0.6 and less than 1, and the lambda is more than 0 and less than 0.4.
7. The high nickel composite positive electrode material according to claim 6, wherein the lithium nickel based transition metal oxide is selected from LiNi0.8Co0.1Mn0.1O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.85Co0.1Mn0.05O2At least one of;
the composite oxide is selected from La0.7Sr0.3Co0.2Fe0.8O2.9、La0.6Sr0.4Co0.2Fe0.8O2.85And La0.8Sr0.2Co0.3Fe0.7O2.93At least one of (1).
8. A preparation method of the high-nickel composite positive electrode material as defined in any one of claims 1 to 7, comprising the steps of:
mixing the lithium-nickel-based transition metal oxide with the composite oxide to obtain a mixture;
and sintering the mixture to obtain the high-nickel composite cathode material.
9. The method of claim 8, wherein the mixing is gravity-free mixing and the mixing time is 0.5-4 hours; the sintering temperature is 300-800 ℃, and the sintering time is 4-12 h.
10. A lithium secondary battery, characterized in that the lithium secondary battery comprises:
a positive electrode comprising the high nickel composite positive electrode material of any one of claims 1 to 7;
a negative electrode; and
an electrolyte between the positive electrode and the negative electrode, and a separator.
CN202010673140.0A 2020-07-14 2020-07-14 High-nickel composite positive electrode material and preparation method and application thereof Pending CN112018345A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114975968A (en) * 2022-06-29 2022-08-30 贝特瑞（江苏）新材料科技有限公司 Cathode material, preparation method thereof and lithium ion battery
EP4057381A1 (en) * 2021-03-08 2022-09-14 SK On Co., Ltd. Lithium secondary battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4057381A1 (en) * 2021-03-08 2022-09-14 SK On Co., Ltd. Lithium secondary battery
CN114975968A (en) * 2022-06-29 2022-08-30 贝特瑞（江苏）新材料科技有限公司 Cathode material, preparation method thereof and lithium ion battery

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