CN113809280B - Cathode material and preparation and application thereof - Google Patents

Cathode material and preparation and application thereof Download PDF

Info

Publication number
CN113809280B
CN113809280B CN202111013570.0A CN202111013570A CN113809280B CN 113809280 B CN113809280 B CN 113809280B CN 202111013570 A CN202111013570 A CN 202111013570A CN 113809280 B CN113809280 B CN 113809280B
Authority
CN
China
Prior art keywords
positive electrode
coating agent
sintering
coating
strong acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111013570.0A
Other languages
Chinese (zh)
Other versions
CN113809280A (en
Inventor
李嘉俊
崔军燕
李子郯
任海朋
陈婷婷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Svolt Energy Technology Co Ltd
Original Assignee
Svolt Energy Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Svolt Energy Technology Co Ltd filed Critical Svolt Energy Technology Co Ltd
Priority to CN202111013570.0A priority Critical patent/CN113809280B/en
Publication of CN113809280A publication Critical patent/CN113809280A/en
Application granted granted Critical
Publication of CN113809280B publication Critical patent/CN113809280B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application discloses a positive electrode material and preparation and application thereof. The positive electrode material with the approximate surface-shaped coating effect is prepared by changing the sintering technical means and applying the interaction between the coating agents. The coverage range of the surface coating layer of the anode material prepared by the method is larger, the erosion degree of electrolyte to material particles is obviously reduced, the probability of side reaction is effectively reduced, the improvement of the cycling stability of the material is facilitated, and meanwhile, the gas generation problem of soft package can be relieved to a certain extent, so that the safety of the material is improved.

Description

Cathode material and preparation and application thereof
Technical Field
The present disclosure relates to, but not limited to, the field of new energy, and in particular, to, but not limited to, a positive electrode material for a lithium ion battery, and a preparation method and an application thereof.
Background
In recent years, with the rapid development of the lithium ion battery industry, a large number of lithium ion batteries are continuously emerging, and by virtue of the advantages of high energy density, long cycle life, high safety, environmental friendliness and the like, the lithium ion batteries are widely applied to a plurality of fields such as mobile phones, electric vehicles, electronic products and the like, and play an important role in daily production and life of people.
The anode material is an important component of the lithium ion battery and is an important factor for restricting the development of the lithium ion battery with high power and long service life. The nickel-cobalt-manganese ternary cathode material integrates respective advantages of three elements of nickel, cobalt and manganese, and is a cathode material with great development potential. The high-nickel ternary material has high specific capacity due to high nickel content, and can meet higher requirements of people. However, the self cycle of the high nickel material is unstable, and the safety is not high, which is a technical problem to be solved at present. The medium nickel ternary material is also concerned by people due to higher safety performance, although the capacity of the medium nickel material is not as good as that of the high nickel material, the capacity disadvantage of the medium nickel material can be made up by some modification methods, and the electrochemical performance of the material is improved by adopting modification means such as surface coating and ion doping, and increasing the cut-off voltage.
At present, two modes of ion doping and cutoff voltage increasing are proved to improve the charge-discharge specific capacity of a medium nickel material to a certain extent, but the modes often bring the problem of capacity accelerated attenuation to the material while improving the specific capacity, so that surface coating is needed to maintain the cycling stability of the material and ensure the durability of the material. The conventional coating method is to uniformly mix the coating agent and the anode material, and then sinter the mixture at a certain temperature to ensure that the coating agent is adhered to the surface of the anode material, thereby achieving the coating effect. However, most coating layers formed by the coating agent under the sintering action are usually point-shaped coating, that is, coating agent particles form one point-shaped object and are densely distributed on the surface of the anode material particles, and the coating effect can reduce the erosion speed of the electrolyte to the material particles to a certain extent and plays a role in improving the cycle performance of the material. It is clear that this effect is limited because a large part of the surface of the particles remains exposed, which still increases the probability of side reactions of the material particles with the electrolyte.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the present application.
The positive electrode material with the approximate surface-shaped coating effect is prepared by changing the sintering technical means and applying the interaction between the coating agents. The coverage range of the surface coating layer of the anode material prepared by the method is larger, the erosion degree of electrolyte to material particles is obviously reduced, the probability of side reaction is effectively reduced, the improvement of the cycling stability of the material is facilitated, and meanwhile, the gas generation problem of soft package can be relieved to a certain extent, so that the safety of the material is improved.
The application provides a preparation method of a lithium ion battery anode material, which comprises the following steps:
uniformly mixing the positive electrode active material, the low-melting-point strong acid weak base salt and the coating agent 2, and then performing primary sintering and secondary sintering;
the sum of the weight of the low-melting-point strong acid weak base salt and the coating agent 2 is 0.2-0.5% of the positive electrode active material;
or uniformly mixing the positive electrode active material, the coating agent 1, the low-melting-point strong acid weak base salt and the coating agent 2, and then performing primary sintering and secondary sintering;
the weight sum of the coating agent 1, the low-melting-point strong acid weak base salt and the coating agent 2 accounts for 0.2-0.5% of the positive electrode active material;
in one embodiment provided herein, the sintering temperature of the first sintering is 180 ℃ to 300 ℃, the sintering time of the first sintering is 1h to 4h, and the temperature rise rate of the first sintering is 3 ℃/min to 6 ℃/min;
in one embodiment provided herein, the sintering temperature of the second sintering is 500 ℃ to 750 ℃, the sintering time of the second sintering is 6h to 10h, and the temperature rise rate of the first sintering is 1 ℃/min to 3 ℃/min.
In one embodiment provided herein, the capping agent 1 is selected from any one or more of compounds of any one or more elements of Zn, mg, B, ti, ba, zr, al, W, co, ta, and Nb;
in one embodiment provided herein, the coating agent 1 is any one or more of an oxide, a hydroxide, a sulfate, and a lithium salt containing an acid ion of the above element.
In one embodiment provided herein, the coating agent 2 is selected from the group consisting of coating agents that are soluble in the low melting point weak base and that do not chemically react at the decomposition temperature of the low melting point weak base;
in one embodiment provided herein, the coating agent 2 is selected from one or both of titanate and carbonate; optionally, the titanate is selected from magnesium titanate; optionally, the carbonate is selected from one or both of magnesium carbonate and zinc carbonate.
In one embodiment provided herein, the low melting point strong acid weak base salt is selected from any one or more of ammonium sulfate, ammonium phosphate, ammonium bisulfate, and ammonium bisulfate;
in one embodiment provided herein, the melting point of the low melting point strong acid weak base salt is 180 ℃ to 300 ℃, and the second sintering temperature exceeds the decomposition temperature of the low melting point strong acid weak base salt until the decomposition is complete.
In one embodiment provided herein, the positive electrode active material is selected from a positive electrode material precursor or an uncoated positive electrode material;
in one embodiment provided herein, comprising nickel, cobalt, manganese and an element a, the molar ratio of the sum of the moles of manganese and element a to nickel, cobalt is (1-x-y): x: y; wherein the values of x and y are as follows: x is more than or equal to 0.5 and less than 0.8,0 yarn woven fabric y is less than or equal to 0.2,0 yarn woven fabric x + y yarn woven fabric 1, or high nickel: x is more than or equal to 0.8 and less than 1,0 yarn-over y yarn-over 0.2,0 yarn-over x + y yarn-over 1;
optionally, the element a is selected from any one or more of Al, W and Zr.
The definition of the positive electrode material precursor is as follows: hydroxides containing the above metal elements synthesized from metal salts of the above elements as raw materials;
for example, ni-Co-Mn hydroxide Ni synthesized from a material containing a nickel salt, a cobalt salt, and a manganese salt x Co y Mn 1-x-y (OH) 2 。
The uncoated positive electrode material is defined as: uniformly mixing and sintering a precursor of the positive electrode material and lithium salt to obtain the positive electrode material;
for example, liNi lithium nickel cobalt manganese oxide formed by calcining Ni cobalt manganese hydroxide and lithium salt as described above x Co y Mn 1-x-y O 2 。
In one embodiment provided herein, the weight ratio of the positive electrode active material, the coating agent 1, the low melting point strong acid weak base salt, and the coating agent 2 is 100% (0 to 0.2%); optionally, the weight ratio of the positive electrode active material, the coating agent 1, the low melting point strong acid weak base salt, and the coating agent 2 is (100): (0.05% to 0.2%): (0.05% to 0.2%): 0.05% to 0.2%); preferably, the sum of the amounts of the coating agent 1, the low-melting strong acid weak base salt, and the coating agent 2 is 0.2% to 0.5% of the positive electrode active material.
In yet another aspect, the present application provides a positive electrode material for a lithium ion battery, including a positive electrode active material and a coating material coating the positive electrode active material; the coating material forms a layered structure to coat the surface of the positive electrode active material, and the layered structure does not comprise a coating agent with a particle structure;
in one embodiment provided by the application, the lithium ion battery cathode material is prepared according to the preparation method.
In another aspect, the present application provides a use of the above-mentioned cathode material in a lithium battery, wherein the thickness of the coating material is 50nm to 200nm;
in one embodiment provided herein, the positive electrode material has a particle size of 1.5 μm to 3.5 μm.
In still another aspect, the present application provides a method of coating a positive active material for a lithium battery, including the steps of:
dissolving a coating agent in a molten state of a low-melting-point strong acid weak base salt, then coating the molten state of the low-melting-point strong acid weak base salt in which the coating agent is dissolved on the surface of the lithium battery positive electrode active material, and then removing the low-melting-point strong acid weak base salt to ensure that the coating agent is coated on the surface of the lithium battery positive electrode active material, thereby completing the coating of the lithium battery positive electrode active material;
alternatively, the low melting point strong acid weak base salt can decompose into a gas at high temperature; optionally, the weak base salt of a strong acid with a low melting point does not chemically react with the coating agent.
In another aspect, the present application provides a method for reducing lithium hydroxide in a positive electrode material of a lithium battery, comprising the steps of:
the method comprises the following steps of uniformly mixing a low-melting-point strong acid weak base salt with a positive electrode active material to be sintered, and heating to melt the low-melting-point strong acid weak base salt, so that the content of lithium hydroxide in the positive electrode active material or the positive electrode material of the lithium battery can be reduced; and sintering the positive active material to obtain the positive material.
In embodiments provided herein, a method of reducing lithium hydroxide in a positive active material of a lithium battery includes: dissolving a coating agent in a molten state of a low-melting-point strong acid weak base salt, then coating the molten state of the low-melting-point strong acid weak base salt in which the coating agent is dissolved on the surface of the lithium battery positive electrode active material, and then removing the low-melting-point strong acid weak base salt to ensure that the coating agent is coated on the surface of the lithium battery positive electrode active material, thereby completing the coating of the lithium battery positive electrode active material;
alternatively, the low melting point strong acid weak base salt can decompose into a gas at high temperature; optionally, the low melting point strong acid weak base salt does not chemically react with the coating agent.
The medium nickel anode material with the approximate surface-shaped coating effect is prepared by changing the sintering technical means and applying the interaction between the coating agents. The coverage area of the surface coating layer of the anode material prepared by the application is large, the corrosion degree of electrolyte to material particles is obviously reduced, the probability of side reaction is effectively reduced, the circulation stability of the material is promoted more favorably, and meanwhile, the gas production problem of soft package can be relieved to a certain extent, so that the safety of the material is improved.
In addition, the sheet-like coating state formed in the molten state can better combine the coating agent with the surface of the positive active material particles, prevent the coating agent from falling off due to the action of external force, and better play the role of the coating agent, so that the electrochemical performance of the material is stably improved.
Additional features and advantages of the present application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the present application. Other advantages of the present application can be realized and attained by the invention in the aspects illustrated in the description.
Drawings
The accompanying drawings are included to provide an understanding of the present disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the examples serve to explain the principles of the disclosure and not to limit the disclosure.
FIG. 1 is SEM images of example 1 and comparative example 3, wherein the left image is example 1 and the right image is comparative example 3; the left picture is like surface shape cladding, the cladding layer covers most surfaces of the particles, the right picture is point-shaped cladding, and the cladding layer is composed of dense cladding points;
FIG. 2 is a graph of the capacity cycling of example 1 and comparative example 3;
fig. 3 is a graph of cycle retention for example 1 and comparative example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application are described in detail below. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The method comprises the following process steps:
weighing the positive electrode precursor and the lithium salt according to a certain lithium salt ratio, putting the positive electrode precursor and the lithium salt into a high-speed mixer, uniformly mixing at a certain speed, putting the mixture into an atmosphere furnace, introducing oxygen for sintering, cooling along with the furnace, taking out the material, crushing, grinding and sieving the material to obtain a positive electrode material primary sintering product (positive electrode active material) with a certain particle size. The method comprises the following specific steps:
1) Putting the crushed and sieved medium nickel material calcined product, a certain amount of low-temperature meltable coating agent, magnesium titanate and other coating agents into a high-speed mixer, and fully stirring and mixing.
2) And placing the mixed material into an atmosphere furnace for presintering and sintering treatment, cooling along with the furnace, and sieving the material to obtain the planar coated medium nickel anode material.
The chemical formula of the precursor of the medium nickel ternary cathode material in the step 1) can be Ni x Co y Mn 1-x-y (OH) 2 。
The particle size D50 may be 3.2 μm to 3.7 μm; the lithium salt may be lithium hydroxide or lithium carbonate; according to the ratio of the sum of the mole numbers of nickel, cobalt and manganese to the mole number of lithium of 1.02 to 1.06, the rotating speed of 8m/s to 18m/s, the sintering temperature of 880 ℃ to 1000 ℃ and the sintering time of 6h to 12h; the heating rate is 3 ℃/min to 5 ℃/min; the D50 of the calcined product is 1.5 μm to 3.5. Mu.m.
Example 1:
in this embodiment, the medium nickel material is LiNi 0.6 Co 0.1 Mn 0.3 O 2 (ii) a The single firing condition of the medium nickel material is as follows: weighing a ternary positive electrode precursor with the granularity D50 of 3.3 mu m and lithium hydroxide according to the ratio of the sum of the mole numbers of nickel, cobalt and manganese to the mole number of lithium of 1.02, putting the three-element positive electrode precursor and the lithium hydroxide into a high-speed mixer, uniformly mixing at the speed of 15m/s, putting the mixture into an atmosphere furnace, introducing oxygen, sintering at 920 ℃ for 12 hours at the heating rate of 5 ℃/min, cooling along with the furnace, taking out the material, crushing, grinding and sieving the material to obtain a ternary material calcined product with the granularity D50 of 2.8 mu m.
1) 0.12wt.% of ammonium bisulfate, 0.15wt.% of magnesium titanate and 0.1wt.% of aluminum oxide based on the weight of the medium nickel material calcined product are put into a high-speed mixer to be fully stirred and uniformly mixed with the crushed and sieved medium nickel material calcined product.
2) Putting the mixed material obtained in the step 1) into an atmosphere furnace, sintering for 3h at 200 ℃ (heating to 200 ℃ and then preserving heat for 3 h), heating at the rate of 3 ℃/min, then heating to 600 ℃ and sintering for 7h (heating to 600 ℃ and then preserving heat for 7 h), heating at the rate of 2 ℃/min, cooling along with the furnace, and sieving the material to obtain the surface-like coated type medium-nickel ternary positive electrode material LiNi 0.6 Co 0.1 Mn 0.3 O 2 。
The surface of the material is coated with magnesium titanate and aluminum oxide.
The thickness of the coating layer is 80nm; the value of the D50 of the calcined product is the particle size of the finished material.
Example 2:
in this embodiment, the nickel-containing quaternary material is LiNi 0.65 Co 0.05 Mn 0.28 Al 0.02 O 2 (ii) a The medium nickel material has the following primary sintering conditions: the quaternary positive electrode precursor Ni with the granularity D50 of 3.7 mu m 0.65 Co 0.05 Mn 0.28 Al 0.02 (OH) 2 And lithium hydroxide is weighed according to the ratio of the sum of the mole numbers of nickel, cobalt, manganese and aluminum to the mole number of lithium of 1.06, the lithium salt is put into a high-speed mixer, the lithium salt and the lithium salt are uniformly mixed at the speed of 10m/s, then the mixture is put into an atmosphere furnace, oxygen is introduced, the mixture is sintered for 6 hours at the temperature of 970 ℃, the temperature rise rate is 3 ℃/min, the mixture is taken out after furnace cooling, and the material is crushed, ground and sieved to obtain a quaternary material primary combustion product with the granularity D50 of 3 mu m.
1) 0.05wt.% of ammonium hydrogen phosphate, 0.1wt.% of ammonium phosphate, 0.2wt.% of magnesium titanate and 0.05wt.% of zirconium hydroxide, which are based on the weight of the primary sintered product of the medium nickel material, and the crushed and sieved primary sintered product of the medium nickel material are put into a high-speed mixer to be fully stirred and uniformly mixed.
2) Putting the mixed material obtained in the step 1) into an atmosphere furnace, sintering for 2h at 260 ℃ (heating to 260 ℃ and then preserving heat for 2 h), heating at a rate of 5 ℃/min, then heating to 750 ℃ and sintering for 6h (heating to 750 ℃ and then preserving heat for 7 h), heating at a rate of 1.5 ℃/min, cooling along with the furnace, and sieving the material to obtain the surface-like coated type medium-nickel quaternary positive electrode material LiNi 0.65 Co 0.05 Mn 0.28 Al 0.02 O 2 。
The surface of the material is coated with magnesium titanate and zirconium hydroxide.
The thickness of the coating layer is 120nm; the value of the D50 of the calcined product is the particle size of the finished material.
Example 3:
in this embodiment, the medium nickel cobalt-free material is LiNi 0.75 Mn 0.25 O 2 (ii) a The medium nickel cobalt-free material has the following conditions: adding lithium salt and the positive electrode precursor with the granularity D50 of 3.6 mu m according to the sum of the mole numbers of nickel and manganese in the lithium saltWeighing the raw materials in a molar ratio of 1.03, putting the raw materials into a high-speed mixer, uniformly mixing the raw materials at a speed of 12m/s, putting the raw materials into an atmosphere furnace, introducing oxygen, sintering the raw materials at 900 ℃ for 10 hours at a heating rate of 4 ℃/min, cooling the raw materials along with the furnace, taking out the raw materials, crushing, grinding and sieving the raw materials to obtain a cobalt-free material calcined product with the granularity D50 of 3.2 mu m.
1) 0.2wt.% of ammonium sulfate and 0.25wt.% of magnesium titanate based on the weight of the calcined product of the medium nickel material and the crushed and sieved calcined product of the medium nickel material are put into a high-speed mixer to be fully stirred and uniformly mixed.
2) Putting the mixed material obtained in the step 1) into an atmosphere furnace, sintering at 300 ℃ for 4h (heating to 300 ℃ and then preserving heat for 4 h), heating at a rate of 6 ℃/min, then heating to 550 ℃ and sintering for 10h (heating to 550 ℃ and then preserving heat for 10 h), heating at a rate of 3 ℃/min, cooling along with the furnace, and sieving the material to obtain the face-like coated medium-nickel cobalt-free cathode material LiNi 0.75 Mn 0.25 O 2 。
The surface of the material is coated with magnesium titanate.
The thickness of the coating layer is 150nm; the value of the D50 of the calcined product is the particle size of the finished material.
Example 4:
in this example, the source and the one-firing conditions of the medium nickel material were the same as those in example 1.
1) Essentially the same as step 1) of example 1), except that: coating agent 1 is B 2 O 3 (the amount of the coating agent 1 used was the same as in example 1).
2) Same as step 2 of example 1).
Example 5:
in this example, the source and the one-firing conditions of the medium nickel material were the same as those in example 1.
1) Essentially the same as step 1) of example 1, except that: cladding agent 1 is Nb 2 O 5 (the amount of the coating agent 1 used was the same as in example 1).
2) Same as step 2 of example 1).
Example 6:
in this example, the source and the one-firing conditions of the medium nickel material were the same as those in example 1.
1) Essentially the same as step 1) of example 1, except that: coating agent 1 is Co (OH) 2 (the amount of the coating agent 1 used was the same as in example 1).
2) Same as step 2) of example 1.
Example 7:
in this example, the source and the one-firing conditions of the medium nickel material were the same as those in example 1.
1) Essentially the same as step 1) of example 1), except that: coating agent 1 is BaSO 4 (the amount of the coating agent 1 used was the same as in example 1).
2) Same as step 2 of example 1).
Example 8:
in this example, the source and the one-firing conditions of the medium nickel material were the same as those in example 1.
1) Essentially the same as step 1) of example 1), except that: coating agent 1 is Li 4 Ti 5 O 12 (the amount of the coating agent 1 used was the same as in example 1).
2) Same as step 2) of example 1.
Example 9:
in this example, the source and the one-firing conditions of the medium nickel material were the same as those in example 1.
1) Essentially the same as step 1) of example 1), except that: coating agent 1 is WO 3 (the amount of the coating agent 1 used was the same as in example 1).
2) Same as step 2 of example 1).
Example 10:
in this example, the source and the one-firing conditions of the medium nickel material were the same as those in example 1.
1) Essentially the same as step 1) of example 1), except that: the coating agent 2 is MgCO 3 (the amount of the coating agent 2 used was the same as in example 1).
2) Same as step 2 of example 1).
Example 11:
in this example, the source and the one-firing conditions of the medium nickel material were the same as those in example 1.
1) Essentially the same as step 1) of example 1, except that: coating agent 2 is ZnCO 3 (the amount of the coating agent 2 used was the same as in example 1).
2) Same as step 2) of example 1.
Example 12:
in this embodiment, the high nickel material is LiNi 0.83 Co 0.11 Mn 0.06 O 2 (ii) a The high nickel material has the following conditions: weighing a positive electrode precursor with the granularity D50 of 3.6 mu m and lithium carbonate according to the condition that the ratio of the sum of the mole numbers of nickel, cobalt and manganese to the mole number of lithium is 1.03, putting the positive electrode precursor and the lithium carbonate into a high-speed mixer, uniformly mixing at the speed of 12m/s, putting the mixture into an atmosphere furnace, introducing oxygen, sintering at 750 ℃ for 10 hours, cooling along with the furnace at the heating rate of 4 ℃/min, taking out the material, crushing, grinding and sieving the material to obtain a material primary combustion product with the granularity D50 of 3.2 mu m. (the higher the nickel content, the lower the calcination temperature)
1) Same as in step 1 of example 1).
2) Same as step 2) of example 1.
Comparative example 1:
in this comparative example, the source and the one-shot conditions of the nickel material were the same as in example 3.
1) 0.15wt.% of ammonium bisulfate, 0.25wt.% of magnesium titanate and 0.2wt.% of aluminum oxide based on the weight of the calcined product of the medium nickel material are put into a high-speed mixer to be fully stirred and uniformly mixed with the crushed and sieved calcined product of the medium nickel material.
2) Same as step 2 of example 1).
The surface of the material is coated with magnesium titanate and aluminum oxide.
The thickness of the coating layer is 100nm; the value of the D50 of the calcined product of example 3 is the particle size of the finished material.
Comparative example 2:
in this comparative example, the source and the one-shot conditions of the nickel material were the same as those of example 1.
1) Same as step 1) of example 1.
2) The mixed materials are put into an atmosphere furnace and sintered for 3 hours at 400 ℃ (after the temperature is raised to 400℃)Keeping the temperature for 3 hours), heating up to 600 ℃ at the rate of 3 ℃/min, sintering for 7 hours (keeping the temperature for 7 hours after heating up to 600 ℃), heating up to the rate of 2 ℃/min, cooling along with the furnace, and sieving the material to obtain the dot-coated medium-nickel ternary cathode material LiNi 0.6 Co 0.1 Mn 0.3 O 2 。
The surface of the material is coated with magnesium titanate and aluminum oxide.
The thickness of the coating layer is 95nm; the value of D50 of the one-shot product of example 1 is the particle size of the finished material.
Comparative example 3:
comparative example 3 the medium nickel-fired product of example 1 was selected.
1) Putting 0.1wt.% of aluminum oxide and crushed and sieved medium nickel material calcined product into a high-speed mixer, and fully stirring and uniformly mixing the aluminum oxide and the crushed and sieved medium nickel material calcined product.
2) The mixed material is put into an atmosphere furnace to be sintered for 7 hours at the temperature of 600 ℃, the heating rate is 4 ℃/min, after the material is cooled along with the furnace, the material is sieved, and the dot-shaped coated medium-nickel ternary positive electrode material LiNi is obtained 0.6 Co 0.1 Mn 0.3 O 2 。
Comparative example 3 cannot consume residual alkali such as LiOH in the material, and the content of residual alkali in the prepared cathode material was more than that in example and comparative example 1. As can be seen from fig. 1, the positive electrode material prepared in example 1 is similar-surface-shaped coating, and the positive electrode material prepared in this comparative example is point-shaped coating, and the coating effect is inferior to that of the similar-surface-shaped coating in example 1. The effect of the difference in the coating effect on the performance of the positive electrode material can be seen from fig. 2 and 3.
Comparative example 4:
this comparative example 4 selects the high nickel one-shot product of example 12.
1) Same as in step 1) of comparative example 3.
2) Same as in step 2) of comparative example 3.
The samples prepared in the above examples and comparative examples were uniformly mixed with a medium nickel positive electrode material, a carbon black conductive agent SP (VXC 72, a new color material of Anhui essence) and a binder polyvinylidene fluoride PVDF (Shanghai plastic new material, 6008) in a mass ratio of 92. The electrochemical performance of the alloy is tested, and the result is shown in table 1:
TABLE 1
Figure BDA0003239653130000111
Figure BDA0003239653130000121
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and the object of the present invention can be accomplished by changing the kind of the positive electrode material, such as the cobalt-free positive electrode material, the quaternary positive electrode material, etc., or changing the kind of the coating agent.
Although the embodiments disclosed in the present application are described above, the descriptions are only for the convenience of understanding the present application, and are not intended to limit the present application. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure as defined by the appended claims.

Claims (11)

1. A preparation method of a lithium ion battery positive electrode material comprises the following steps:
uniformly mixing the positive electrode active material, the low-melting-point strong acid weak base salt and the coating agent 2, and then performing primary sintering and secondary sintering;
the sum of the weight of the low-melting-point strong acid weak base salt and the coating agent 2 is 0.2-0.5% of the positive electrode active material;
or, uniformly mixing the positive electrode active material, the coating agent 1, the low-melting-point strong acid weak base salt and the coating agent 2, and then performing primary sintering and secondary sintering;
the weight sum of the coating agent 1, the low-melting-point strong acid weak base salt and the coating agent 2 accounts for 0.2-0.5% of the positive electrode active material;
the sintering temperature of the first sintering is 180-300 ℃, the sintering time of the first sintering is 1-4 h, and the heating rate of the first sintering is 3-6 ℃/min;
the sintering temperature of the second sintering is 500-750 ℃, the sintering time of the second sintering is 6-10 h, and the heating rate of the second sintering is 1-3 ℃/min;
the coating agent 1 is selected from any one or more of compounds of any one or more elements of Zn, mg, B, ti, ba, zr, al, W, co, ta and Nb;
the coating agent 2 is selected from the coating agents which are dissolved in the low-melting-point strong acid weak base salt and do not generate chemical reaction at the melting temperature of the low-melting-point strong acid weak base salt;
the melting point of the low-melting strong acid weak base salt is between 180 and 300 ℃;
the coating agent 2 is one or two selected from titanate and carbonate.
2. The method according to claim 1, wherein the titanate is selected from magnesium titanate.
3. The production method according to claim 1, wherein the carbonate is one or both of magnesium carbonate and zinc carbonate.
4. The preparation method according to claim 1, wherein the low melting point strong acid weak base salt is selected from any one or more of ammonium sulfate, ammonium phosphate, ammonium hydrogen sulfate and ammonium hydrogen phosphate.
5. The production method according to claim 1, wherein the positive electrode active material contains nickel, cobalt, manganese and an element a, and the molar ratio of the sum of the number of moles of manganese and the element a to nickel and cobalt is (1-x-y): x: y; wherein the values of x and y are more than or equal to 0.5 and less than x <1,0< -y <0.2,0< -x < +y < -1, or more than or equal to 0.8 and less than 1,0< -y <0.2, and 0< -x < +y < -1.
6. The production method according to claim 1, wherein the element a is selected from any one or more of Al, W, and Zr.
7. The production method according to claim 1, wherein the weight ratio of the positive electrode active material, the coating agent 1, the low-melting point strong acid weak base salt, and the coating agent 2 is 100 (0 to 0.2%): 0.05 to 0.2%): 0.1 to 0.3%.
8. The production method according to claim 1, wherein the weight ratio of the positive electrode active material, the coating agent 1, the low-melting point strong acid weak base salt, and the coating agent 2 is 100% (0.05% to 0.2%).
9. A lithium ion battery positive electrode material comprises a positive electrode active material and a coating material for coating the positive electrode active material; the coating material forms a layered structure to coat the surface of the positive electrode active material, and the layered structure does not comprise a coating agent with a particle structure;
the lithium ion battery cathode material is prepared according to the preparation method of any one of claims 1 to 8.
10. Use of the positive electrode material according to claim 9 in a lithium ion battery, wherein the coating material has a thickness of 50 to 200nm.
11. Use according to claim 10, wherein the particle size of the positive electrode material is 1.5 to 3.5 μm.
CN202111013570.0A 2021-08-31 2021-08-31 Cathode material and preparation and application thereof Active CN113809280B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111013570.0A CN113809280B (en) 2021-08-31 2021-08-31 Cathode material and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111013570.0A CN113809280B (en) 2021-08-31 2021-08-31 Cathode material and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN113809280A CN113809280A (en) 2021-12-17
CN113809280B true CN113809280B (en) 2023-03-14

Family

ID=78894501

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111013570.0A Active CN113809280B (en) 2021-08-31 2021-08-31 Cathode material and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN113809280B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106876686A (en) * 2017-04-14 2017-06-20 中南大学 A kind of method for carrying out surface modification with positive electrode active materials to lithium ion battery
CN108598382A (en) * 2018-03-07 2018-09-28 电子科技大学 A kind of method of watery fusion coated lithium ion battery positive electrode
CN109360969A (en) * 2018-11-16 2019-02-19 广东佳纳能源科技有限公司 A kind of alumina-coated anode material for lithium-ion batteries and preparation method thereof
CN111916702A (en) * 2020-07-24 2020-11-10 惠州亿纬锂能股份有限公司 Coated modified cathode material, preparation method thereof and lithium ion battery

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105098188B (en) * 2014-04-28 2017-09-01 比亚迪股份有限公司 A kind of anode material for lithium-ion batteries additive and preparation method thereof, positive electrode and lithium ion battery containing the additive
CN110890542B (en) * 2020-01-14 2020-06-26 桑顿新能源科技有限公司 Lithium ion battery anode material and preparation method thereof, lithium ion battery anode, lithium ion battery and power utilization equipment

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106876686A (en) * 2017-04-14 2017-06-20 中南大学 A kind of method for carrying out surface modification with positive electrode active materials to lithium ion battery
CN108598382A (en) * 2018-03-07 2018-09-28 电子科技大学 A kind of method of watery fusion coated lithium ion battery positive electrode
CN109360969A (en) * 2018-11-16 2019-02-19 广东佳纳能源科技有限公司 A kind of alumina-coated anode material for lithium-ion batteries and preparation method thereof
CN111916702A (en) * 2020-07-24 2020-11-10 惠州亿纬锂能股份有限公司 Coated modified cathode material, preparation method thereof and lithium ion battery

Also Published As

Publication number Publication date
CN113809280A (en) 2021-12-17

Similar Documents

Publication Publication Date Title
CN108091843B (en) Lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof
JP5712544B2 (en) Positive electrode active material particle powder, method for producing the same, and nonaqueous electrolyte secondary battery
US20210367233A1 (en) Ternary positive electrode material and preparation method therefor, and lithium-ion battery
CN102844914B (en) Positive electrode active material for non-aqueous electrolyte secondary battery and process for production thereof, and non-aqueous electrolyte secondary battery produced using the positive electrode active material
CN103765658B (en) There is the positive electrode of the composition relying on size
CN103066261B (en) The synthetic method of the nickelic multi-element metal oxide positive electrode of high power capacity
CN103794773B (en) A kind of method of producing high power capacity 523 type tertiary cathode material
CN110931768A (en) Ternary positive electrode material of high-nickel monocrystal lithium ion battery and preparation method
CN109461891B (en) High-voltage lithium cobalt oxide cathode material and preparation method thereof
KR20190006907A (en) Spherical or spherical-like cathode material for lithium-ion battery and lithium-ion battery
AU2007360837A1 (en) Cathode active material for lithium secondary batteries with high safety, method of preparing the same, and lithium secondary batteries comprising the same
KR20240013213A (en) Sodium-containing oxide anode material and its manufacturing method and application, anode plate and its application
CN102386388A (en) Positive electrode materials combining high safety and high power in a Li rechargeable battery
JP2006253140A (en) Positive electrode active material for nonaqueous electrolyte secondary batteries, its manufacturing method and lithium secondary battery containing the same
JPWO2012133113A1 (en) Positive electrode active material particle powder, method for producing the same, and nonaqueous electrolyte secondary battery
CN114920306A (en) Positive electrode material precursor, positive electrode material, preparation method of positive electrode material and sodium ion battery
CN105406053A (en) Preparation method for cathode material and cell
CN113991079A (en) Composite cathode material and preparation method thereof
CN113603154A (en) High-voltage nickel-cobalt-manganese ternary precursor and preparation method thereof
CN113497227A (en) Full-concentration-gradient-adjustable mono-like lithium-rich layered oxide cathode material and preparation method thereof
CN110620230A (en) Positive active material, preparation method thereof, positive plate and lithium battery
CN111540890A (en) Nickel cobalt lithium manganate ternary cathode material and preparation method thereof
CN110863245A (en) Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile
CN111592053A (en) Nickel-based layered lithium ion battery positive electrode material and preparation method and application thereof
CN114447297A (en) Nickel-cobalt lithium manganate high-nickel single crystal positive electrode material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant