CN113851641A - High-entropy solid solution cathode material and preparation method and application thereof - Google Patents
High-entropy solid solution cathode material and preparation method and application thereof Download PDFInfo
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- 239000006104 solid solution Substances 0.000 title claims abstract description 52
- 239000010406 cathode material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 22
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- 229910013172 LiNixCoy Inorganic materials 0.000 claims abstract description 6
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- 239000000126 substance Substances 0.000 claims abstract description 4
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
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- 239000007774 positive electrode material Substances 0.000 claims description 12
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- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
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- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
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- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052791 calcium Inorganic materials 0.000 claims description 6
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 11
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- 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
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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Abstract
The invention provides a high-entropy solid solution cathode material and a preparation method and application thereof. The high-entropy solid solution cathode material is secondary spherical particles or quasi-single crystal particles; the chemical formula of the high-entropy solid solution cathode material is LiNixCoyMn0.95‑x‑yM0.05O2Wherein, M comprises at least five metal elements x + y which are less than or equal to 0.95; the structural composition of the high-entropy solid solution cathode material at least comprises two layered material body structures. The invention forms a multi-element metal oxide system, 5 or more elements share the same atomic site to form a stable high-entropy solid solution, so that the anode material has good structural stability and thermal stabilityAnd the performance, the rate performance and the like of the anode material are realized, and when the anode material is prepared by adopting a spray drying method, the participation of ammonia water is not needed, and wastewater treatment equipment and process are not needed, so that the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a high-entropy solid solution cathode material, and a preparation method and application thereof.
Background
At present, the problems of environmental pollution and energy shortage are increasingly serious, sustainable renewable energy sources, novel power batteries and efficient energy storage systems are developed for reducing pollution in the use process of fossil fuels, and reasonable configuration of renewable resources is realized, so that the method becomes the key point of research. The lithium ion battery is a novel high-energy green battery which attracts much attention, and compared with other energy storage systems, the lithium ion battery has the outstanding advantages of high storage energy per unit volume, long cycle life, good safety, no memory effect and the like. The method has wide application prospect and potential huge economic benefit in various aspects such as portable electronic equipment, electric automobiles, space technology, national defense industry and the like, and quickly becomes the focus of wide attention in recent years.
The anode material is an important component of the lithium ion battery and has great influence on the performance of the lithium ion battery. The positive electrode materials of lithium ion batteries that have been put into practical use at present can be roughly classified into three groups according to their structures, including lithium metal oxides having a hexagonal layered structure, spinel materials, and compounds having a polyanion structure. Among them, the layered oxide is attracting attention because of its high energy density, easy preparation, strong structural stability, and excellent lithium ion deintercalation/intercalation reversibility.
Aiming at the intrinsic defects of the commercial layered cathode material in the current market, such as poor cycle stability caused by irreversible structural phase change caused by the cyclic phase change under high voltage; the electron conductivity is low and the multiplying power performance caused by Li/Ni mixed discharge is poor; in the highly delithiated state, Ni4+Has a strong oxidizing property tending to reduce to form Ni3+To release O2Resulting in poor thermal stability. At present, the main means for improving the material performance is ion doping, and the stability of the material structure is improved to a certain extent by doping some metal ions into the crystal lattices of the layered material through various processes. However, the doping material has less doping element species at each time, and only acts on the interior of the material transition metal layer, so that the performance improvement is limited.
Most of the current anode material precursors produced in commercial production adopt ammonia water as a precipitator, and an important problem of the adoption of the ammonia water is that the ammonia water has high volatility, generates a large amount of ammonia wastewater byproducts and causes serious pollution; in addition, the preparation of the lithium ion battery anode material by adopting a coprecipitation method has long required period and various working procedures, and inert gas needs to be introduced in the reaction process to prevent partial ions such as manganese ions from being oxidized.
CN102881876A discloses a method for preparing a lithium-rich solid solution cathode material by a reduction coprecipitation method, which comprises the following steps of according to the molar ratio of lithium, nickel, manganese, cobalt and a reducing agent of (1+ x) to (1-x) y (x + z-x.z) to (1-x) k: and q, respectively weighing lithium, nickel, manganese, cobalt and a reducing agent. Mixing the measured wet grinding medium with nickel, manganese and cobalt, adding a reducing agent, stirring and mixing, adding an alkali liquor, carrying out wet grinding, aging, filtering and washing treatment, adding the wet grinding medium and a lithium compound, carrying out wet grinding and drying to prepare a precursor, placing the precursor in air, oxygen-enriched gas or pure oxygen atmosphere, and sintering to prepare the lithium-enriched solid solution cathode material.
CN102351253A discloses a preparation method of a manganese-based high-energy solid solution cathode material of a lithium ion battery, which comprises the following steps: (1) preparing a solution from a manganese source compound, a nickel source compound and a cobalt source compound according to a stoichiometric ratio; (2) preparing a precipitant, and adding ammonia water to prepare a mixed solution of the ammonia water and the precipitant; (3) adding the solution obtained in the step (1) and the solution obtained in the step (2) into inert gas for protection to obtain a precipitate; (4) filtering and washing the precipitate obtained in the step (3), drying in vacuum, adding a dispersing agent into the coprecipitate and a lithium-containing compound, grinding and mixing uniformly to obtain a manganese-based solid solution Li [ Li ]0.2Mn0.54Ni0.13Co0.13]O2A precursor; (4) putting the precursor obtained in the step (4) into a muffle furnace, roasting, and cooling to room temperature by liquid nitrogen; and crushing and granulating for the second time to obtain a sample.
In the two documents, a coprecipitation method is adopted to prepare the anode solid solution material, but an important problem of adopting the ammonia water is that the ammonia water has high volatility, a large amount of ammonia wastewater byproducts are generated, and a serious pollution problem is caused; in addition, the preparation of the lithium ion battery anode material by adopting a coprecipitation method has long required period and various working procedures, and inert gas needs to be introduced in the reaction process to prevent partial ions such as manganese ions from being oxidized.
Therefore, how to obtain a solid solution cathode material with stable structure and good electrochemical performance is a technical problem which needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a high-entropy solid solution cathode material and a preparation method and application thereof. According to the invention, other metal elements capable of improving the performance are introduced into the layered Transition Metal (TM) layer of the traditional ternary anode precursor material to form a multi-element metal oxide system, 5 or more elements share the same atomic site to form a stable high-entropy solid solution, so that the anode material has good structural stability, thermal stability, rate capability and the like, and ammonia water is not required to participate in the preparation of the anode material by adopting a spray drying method, so that wastewater treatment equipment and process are not required, and the cost is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-entropy solid solution cathode material, wherein the high-entropy solid solution cathode material is spherical secondary particles or single crystal-like particles; the chemical formula of the high-entropy solid solution cathode material is LiNixCoyMn0.95-x-yM0.05O2Wherein M comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er, x is more than 0, Y is more than 0, and x + Y is less than or equal to 0.95; the structural composition of the high-entropy solid solution cathode material at least comprises two layered material structures.
In the invention, the structural composition of the high-entropy solid solution cathode material at least comprises two layered material structures, namely:
LiNixCoyMn0.95-x-yM0.05O2is only the chemical formula of the whole positive electrode material, and the high-entropy solid solution positive electrode material is a solid solution material consisting of at least two layered structure materials, such as LiNixCoyMn0.95-x-yA0.05O2、LiNixCoyMn0.95-x- yB0.05O2At least two or more elements may be present in A, at least two or more metal elements may be present in B, and the sum of the elements in A and B is MAll of the elements of (a).
In the invention, the theoretical calculation shows that less than five elements in M are not beneficial to the formation of a solid solution structure, and are more prone to a single layered structure material and are not beneficial to the structural stability.
According to the invention, other metal elements capable of improving the performance are introduced into the TM layer of the traditional ternary anode precursor material to form a multi-element metal oxide system, 5 or more elements share the same atomic site to form a stable high-entropy solid solution, so that the anode material has good structural stability, thermal stability, rate capability and the like.
Preferably, the single crystal particles have a D50 of 1 to 25 μm, such as 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, or 18 μm.
Preferably, the D50 of the secondary spherical particles is 2-18 μm, such as 2 μm, 5 μm, 10 μm, 15 μm or 18 μm.
In a second aspect, the present invention provides a method for preparing a high-entropy solid-solution cathode material as described in the first aspect, the method comprising the steps of:
(1) mixing a lithium source, a metal salt solution and a polymer carrier, and then carrying out spray drying to obtain a precursor of the positive electrode material;
(2) performing primary sintering and secondary sintering on the anode material precursor in the step (1) in an oxygen atmosphere to obtain the high-entropy solid solution anode material;
wherein the metal salt solution comprises a primary metal salt solution and a secondary metal salt solution; the metal in the primary metal salt solution comprises nickel and cobalt, and the metal in the secondary metal salt solution comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er.
According to the invention, through a spray drying method and solution mixing, atomic-level mixing is realized, a multi-element metal solid solution system is obtained, five or more elements in the anode material share the same atomic sites, and a stable high-entropy solid solution is formed, and the high-entropy solid solution material has complex metal bond composition, and shows excellent structural stability, thermal stability, rate capability and the like.
Compared with the traditional ternary cathode material process, the method can stably produce 1-4 mu m single crystal or secondary particle materials at low cost, greatly shortens the process path of the cathode material, and reduces the time cost and the equipment investment cost.
Preferably, the metal in the primary metal salt solution further comprises manganese.
Preferably, the primary metal salt solution of step (1) comprises nitrate and/or acetate.
Preferably, the secondary metal salt solution of step (1) comprises nitrate and/or acetate.
Preferably, the polymer carrier in step (1) comprises any one of ethylene glycol, citric acid or polyvinyl alcohol or a combination of at least two thereof.
In the invention, ethylene glycol, citric acid or polyvinyl alcohol is selected as a polymer carrier, which is more beneficial to the uniform dispersion among different doped ions and reduces the segregation possibility of metal ions.
Preferably, the molar ratio of lithium in the lithium source, the metal in the metal salt solution and the polymer carrier in the step (1) is (0.95-1.13): (0.03-0.15): 0.95-1.13), such as 0.95:1:0.95, 1:1:1, 1.13:1:1, 1:1:1.13, 1.1:1:1 or 1.13:1: 1.13.
The metal in the metal salt solution comprises the metal in the primary metal salt solution and the metal in the secondary metal salt solution.
Preferably, in the spray drying in step (1), the pressure in the atomization process is 0.4 to 0.6MPa, such as 0.4MPa, 0.45MPa, 0.5MPa, 0.55MPa or 0.6 MPa.
Preferably, in the spray drying in the step (1), the flow rate of the solution is 1-15L/h, such as 1L/h, 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h, 8L/h, 9L/h, 10L/h, 11L/h, 12L/h, 13L/h, 14L/h or 15L/h, etc.
Preferably, in the spray drying in the step (1), the temperature at the inlet is 300 to 400 ℃, for example, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃ or 400 ℃, and the like.
Preferably, in the spray drying in the step (1), the temperature of the outlet is 140 to 160 ℃, for example, 140 ℃, 145 ℃, 150 ℃, 155 ℃ or 160 ℃, and the like.
Preferably, the temperature rise rate of the primary sintering in the step (2) is 2-10 ℃/min, such as 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, and the like.
Preferably, the temperature of the primary sintering in the step (2) is 300-500 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃.
Preferably, the time of the primary sintering in the step (2) is 3-6 h, such as 3h, 4h, 5h or 6 h.
Preferably, the temperature of the secondary sintering in the step (2) is 700-980 ℃, such as 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 980 ℃.
Preferably, the time of the secondary sintering in the step (2) is 15-30 h, such as 15h, 20h, 25h or 30 h.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing a lithium source, a main metal salt solution, an auxiliary metal salt solution and a polymer carrier, carrying out spray drying at an atomization pressure of 0.4-0.6 MPa and a solution flow rate of 1-15L/h, and keeping the temperature of an inlet at 300-400 ℃ and the temperature of an outlet at 140-160 ℃ to obtain a precursor of the positive electrode material;
(2) heating the precursor of the cathode material in the step (1) to 300-500 ℃ at a heating rate of 2-10 ℃/min in an oxygen atmosphere for primary sintering for 3-6 h, and then continuously heating to 700-980 ℃ for secondary sintering for 15-30 h to obtain the high-entropy solid solution cathode material;
wherein the metal in the primary metal salt solution comprises nickel, cobalt and manganese, and the metal in the secondary metal salt solution comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er; the molar ratio of the lithium in the lithium source, the metal in the metal salt solution and the polymer carrier in the step (1) is (0.95-1.13): (0.03-0.15): 0.95-1.13).
In a third aspect, the invention further provides a lithium ion battery, which includes the high-entropy solid solution cathode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, other metal elements capable of improving the performance are introduced into the TM layer of the traditional ternary anode precursor material to form a multi-element metal oxide system, 5 or more elements share the same atomic site and become a stable high-entropy solid solution, so that the anode material has good structural stability, thermal stability, rate capability and the like, and ammonia water is not required to participate in the preparation of the anode material by adopting a spray drying method, so that wastewater treatment equipment and process are not required, and the cost is reduced.
Drawings
Fig. 1 is an SEM image of the material provided in example 1.
Fig. 2 is a first charge and discharge curve of the battery provided in example 1.
Fig. 3 is a graph of the cycle performance of the battery provided in example 1.
Fig. 4 is an XRD pattern of the high-entropy cathode material provided in example 2.
Fig. 5 is a first charge-discharge curve diagram of the battery provided in example 2.
FIG. 6 is an SEM image of the material provided in example 3
Fig. 7 is a rate performance plot for the battery provided in example 3.
Fig. 8 is a graph showing the first charge and discharge curves of the battery provided in example 3.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a high-entropy solid solution cathode material, which comprises the following steps:
(1) preparing a main metal acetate solution and an auxiliary metal acetate solution with the concentration of 1mol/L by using a salt solution prepared by the molar ratio of Ni, Co, Sn, Zn, Mg, W, Cr and Al of 0.83:0.12:0.01:0.01:0.01:0.01:0.005:0.005, weighing lithium hydroxide according to the molar ratio of Li to all metals of 1.05:1, and preparing a polymer carrier of 0.3mol/L, wherein the polymer carrier is formed by mixing ethylene glycol and citric acid in a mass ratio of 1: 1; uniformly mixing the polymer carrier solution and a salt solution (the molar ratio of lithium to the polymer carrier is 1:1), feeding the mixture into a spray dryer, atomizing the mixture by using a nozzle under the air pressure of 0.4MPa, and drying the mixture by using hot air; the total flow rate of the solution is controlled to be 10L/h in the process; the inlet hot air temperature is 350 ℃, and the outlet hot air temperature is 150 ℃, so as to obtain a precursor of the anode material;
(2) placing the precursor of the anode material in the step (1) in a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, preserving heat for 6h, heating to 780 ℃ and preserving heat for 24h, cooling and sieving,
obtaining the spherical layered high-entropy chemically stable cathode material LiNi0.83Co0.12(Sn0.01Zn0.01Mg0.01W0.01Cr0.005Al0.005)O2. The appearance is shown in figure 1
The positive electrode material was assembled into a 2032 button cell.
The battery is subjected to relevant performance verification, and the first discharge specific capacity and the first charge-discharge efficiency at 3-4.3V and 0.1C are respectively as follows: 210.5mAh/g and 84.2%, the discharge curve is shown in FIG. 2; the capacity retention rate after 60 cycles at room temperature is 95.52% at 3-4.3V and 0.2C, and the discharge curve is shown in FIG. 3.
Example 2
The embodiment provides a preparation method of a high-entropy solid solution cathode material, which comprises the following steps:
(1) preparing a main metal acetate solution and an auxiliary metal acetate solution with the concentration of 1mol/L by using a salt solution prepared by the molar ratio of Ni, Co, Mn, Sn, W, Al, Mg and Zr of 0.75:0.1:0.15:0.01:0.02:0.01:0.005:0.005, weighing lithium hydroxide according to the molar ratio of Li to all metals of 1.13:1, and preparing a polymer carrier of 0.3mol/L, wherein the polymer carrier is polyvinyl alcohol; uniformly mixing the polymer carrier solution and a salt solution (the molar ratio of lithium to the polymer carrier is 1:1), feeding the mixture into a spray dryer, atomizing the mixture by using a nozzle under the air pressure of 0.6MPa, and drying the mixture by using hot air; the total flow rate of the solution is controlled to be 15L/h in the process; the inlet hot air temperature is 400 ℃, and the outlet hot air temperature is 160 ℃, so as to obtain a precursor of the anode material;
(2) placing the precursor of the positive electrode material in the step (1) in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/min under an oxygen atmosphere, preserving heat for 6h, heating to 700 ℃ again, preserving heat for 30h, cooling and sieving to obtain the spherical layered high-entropy chemically stable positive electrode material LiNi0.75Co0.1Mn0.15Sn0.025W0.025Al0.01Mg0.005Zr0.005O2(ii) a The XRD diagram is shown in figure 4, and is a typical layered structure.
And (3) homogenizing and coating the positive electrode material, a certain amount of conductive agent and binder according to a certain mass ratio, drying, and cutting into pieces to prepare the button cell.
The battery is subjected to relevant performance verification, and the first discharge specific capacity and the first charge-discharge efficiency at 3-4.3V and 0.1C are respectively as follows: 188.9mAh/g and 87.1%, the discharge curve is shown in FIG. 5; 3-4.3V, 0.2C, and the capacity retention rate is 96.8% after 60 cycles at room temperature.
Example 3
The embodiment provides a preparation method of a high-entropy solid solution cathode material, which comprises the following steps:
(1) preparing a main metal acetate solution and an auxiliary metal acetate solution with the concentration of 1mol/L by using a salt solution prepared by the molar ratio of Ni, Co, Mn, W, Al, Mg, Y and Mo of 0.75:0.07:0.1:0.01:0.02:0.02:0.05:0.05, weighing lithium hydroxide according to the molar ratio of Li to all metals of 1:1, and preparing a polymer carrier of 0.3mol/L, wherein the polymer carrier is formed by mixing ethylene glycol and citric acid in a mass ratio of 1: 1; uniformly mixing the polymer carrier solution and a salt solution (the molar ratio of lithium to the polymer carrier is 1:1.13), feeding the mixture into a spray dryer, atomizing the mixture by using a nozzle under the air pressure of 0.5MPa, and drying the mixture by using hot air; the total flow rate of the solution is controlled to be 1L/h in the process; the inlet hot air temperature is 300 ℃, and the outlet hot air temperature is 140 ℃ to obtain a precursor of the anode material;
(2) placing the precursor of the cathode material in the step (1) in a tube furnace, heating to 450 ℃ at a heating rate of 10 ℃/min under an oxygen atmosphere, preserving heat for 6h, heating to 920 ℃ again, preserving heat for 20h, cooling and sieving to obtain the high-entropy chemically stable cathode material LiNi with the appearance similar to single crystal0.75Co0.07Mn0.1 W0.01Al0.02Mg0.02Y0.05Mo0.05O2. The morphology is shown in fig. 6.
The above-described positive electrode materials were assembled into 2032 coin cells. The battery is subjected to relevant performance verification, and the rate performance result is shown in fig. 7; the first discharge specific capacity and the first charge-discharge efficiency at 3-4.3V and 0.1C are respectively as follows: 167mAh/g and 77.7%, the discharge curve is shown in FIG. 8.
In conclusion, other metal elements capable of improving performance are introduced into the TM layer of the traditional ternary cathode precursor material to form a multi-element metal oxide system, 5 or more elements share the same atomic site and become a stable high-entropy solid solution, so that the cathode material has good structural stability, thermal stability, rate capability and the like, ammonia water is not needed when the cathode material is prepared by adopting a spray drying method, and wastewater treatment equipment and a process are not needed, so that the cost is reduced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The high-entropy solid solution cathode material is characterized in that the high-entropy solid solution cathode material is quadratic spherical particles or quasi-single crystal particles; the chemical formula of the high-entropy solid solution cathode material is LiNixCoyMn0.95-x-yM0.05O2Wherein M comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er, x is more than 0, Y is more than 0, and x + Y is less than or equal to 0.95; the structural composition of the high-entropy solid solution cathode material at least comprises two layered material body structures.
2. A high entropy solid solution cathode material according to claim 1, wherein D50 of the single crystal particles is 1-25 um;
preferably, the D50 of the secondary spherical particles is 2-18 μm.
3. A production method of a high-entropy solid-solution cathode material according to claim 1 or 2, characterized by comprising the steps of:
(1) mixing a lithium source, a metal salt solution and a polymer carrier, and then carrying out spray drying to obtain a precursor of the positive electrode material;
(2) performing primary sintering and secondary sintering on the anode material precursor in the step (1) in an oxygen atmosphere to obtain the high-entropy solid solution anode material;
wherein the metal salt solution comprises a primary metal salt solution and a secondary metal salt solution; the metal in the primary metal salt solution comprises nickel and cobalt, and the metal in the secondary metal salt solution comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er.
4. A method of producing a high entropy solid solution cathode material according to claim 3, wherein the metal in the primary metal salt solution further includes manganese;
preferably, the primary metal salt solution of step (1) comprises nitrate and/or acetate;
preferably, the secondary metal salt solution of step (1) comprises nitrate and/or acetate.
5. A method for preparing a high entropy solid solution cathode material according to claim 3 or 4, wherein the polymer carrier in step (1) comprises any one of ethylene glycol, citric acid or polyvinyl alcohol or a combination of at least two thereof.
6. A method for preparing a high entropy solid solution cathode material according to any of claims 3-5, wherein the molar ratio of lithium in the lithium source, metal in the metal salt solution and polymer carrier in step (1) is (0.95-1.13): (0.03-0.15): (0.95-1.13).
7. A preparation method of the high-entropy solid-solution cathode material according to any one of claims 3 to 6, wherein in the spray drying in the step (1), the pressure of the atomization process is 0.4-0.6 MPa;
preferably, in the spray drying in the step (1), the flow rate of the solution is 1-15L/h;
preferably, in the spray drying in the step (1), the temperature of an inlet is 300-400 ℃;
preferably, in the spray drying in the step (1), the temperature of the outlet is 140-160 ℃.
8. A preparation method of the high-entropy solid-solution cathode material according to any one of claims 3 to 7, wherein the temperature rise rate of the primary sintering in the step (2) is 2-10 ℃/min;
preferably, the temperature of the primary sintering in the step (2) is 300-500 ℃;
preferably, the time of the primary sintering in the step (2) is 3-6 h;
preferably, the temperature of the secondary sintering in the step (2) is 700-980 ℃;
preferably, the time of the secondary sintering in the step (2) is 15-30 h.
9. A method of producing a high entropy solid solution cathode material according to any one of claims 3 to 8, characterized in that the production method includes the steps of:
(1) mixing a lithium source, a main metal salt solution, an auxiliary metal salt solution and a polymer carrier, carrying out spray drying at an atomization pressure of 0.4-0.6 MPa and a solution flow rate of 1-15L/h, and keeping the temperature of an inlet at 300-400 ℃ and the temperature of an outlet at 140-160 ℃ to obtain a precursor of the positive electrode material;
(2) heating the precursor of the cathode material in the step (1) to 300-500 ℃ at a heating rate of 2-10 ℃/min in an oxygen atmosphere for primary sintering for 3-6 h, and then continuously heating to 700-980 ℃ for secondary sintering for 15-30 h to obtain the high-entropy solid solution cathode material;
wherein the metal in the primary metal salt solution comprises nickel, cobalt and the metal in the secondary metal salt solution comprises at least five of Ti, V, Cr, Fe, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er; the molar ratio of the lithium in the lithium source, the metal in the metal salt solution and the polymer carrier in the step (1) is (0.95-1.13): (0.03-0.15): 0.95-1.13).
10. A lithium ion battery, characterized in that the lithium ion battery comprises the high-entropy solid-solution cathode material according to claim 1 or 2.
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