CN117374259A - Modification method of high-nickel positive electrode material, positive electrode plate and lithium battery - Google Patents
Modification method of high-nickel positive electrode material, positive electrode plate and lithium battery Download PDFInfo
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- CN117374259A CN117374259A CN202311666741.9A CN202311666741A CN117374259A CN 117374259 A CN117374259 A CN 117374259A CN 202311666741 A CN202311666741 A CN 202311666741A CN 117374259 A CN117374259 A CN 117374259A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 59
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 15
- 238000002715 modification method Methods 0.000 title claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims abstract description 19
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000003513 alkali Substances 0.000 abstract description 11
- 229910017855 NH 4 F Inorganic materials 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 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 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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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
-
- 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
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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
- H01M4/52—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
The invention discloses a modification method of a high-nickel positive electrode material, a positive electrode plate and a lithium battery, and relates to the technical field of lithium batteries. Modifying the high nickel positive electrode material by using ammonium fluotitanate, and decomposing the ammonium fluotitanate to generate NH by performing one-time heat treatment at a lower temperature 4 F and TiF 4 Generated NH 4 F can react with residual alkali on the positive electrode material and generate a LiF coating layer on the surface; remaining TiF 4 The Ti and F anions and cations are co-doped by diffusing into the crystal lattice of the anode material when the secondary heat treatment is carried out at high temperature, so that the structural stability of the material can be effectively improved. After the modification is carried out by adopting the modification method, the residual alkali can be effectively removed, and the electrochemical performance of the anode material can be improved.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a modification method of a high-nickel positive electrode material, a positive electrode plate and a lithium battery.
Background
The high-nickel anode material is a common material of lithium ion batteries, has high energy density and good electrochemical performance, and is widely applied to the fields of electric vehicles, wearable equipment and the like. High nickel positive electrode materials are typically mixtures of nickel, manganese, cobalt, etc., with nickel being the major constituent. The main high-nickel positive electrode materials comprise nickel cobalt lithium manganate, nickel cobalt lithium aluminate, nickel lithium manganate and the like.
Nickel cobalt lithium manganate (NCM) is the most commonly used high nickel positive electrode material at present, and has higher discharge capacity and cycle life. NCM materials are usually composed of nickel, cobalt, manganese and other metal ions, and different discharge capacities and cycle lives can be realized through proper proportion. The NMC material has the advantages of higher energy density and better thermal stability.
The following problems are common in the current high nickel cathode materials:
(1) The high nickel material has high residual alkali content on the surface, and can be effectively removed by water washing, but the surface structure is destroyed, and the capacity exertion is affected.
(2) The high nickel surface forms Ni with high activity during charging 4+ Side reactions are easy to occur when the catalyst is in direct contact with electrolyte, so that transition metal is dissolved out, the electrolyte is consumed and the surface is passivated, and the cycle performance is reduced. The material needs to be protected by surface coating.
(3) The high nickel material phase undergoes repeated phase change in the lithium intercalation and deintercalation process, and in the process, the lithium diffusion rate is slow to lead the distribution of lithium to be uneven, so that the phase change of crystal grains is uneven, primary particles are easy to generate microcracks, the diffusion coefficient of lithium ions is required to be improved through element doping, the phase change is uneven, and the structural integrity is maintained.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a modification method of a high-nickel positive electrode material, a positive electrode plate and a lithium battery, and aims to remarkably reduce residual alkali and improve electrochemical performance.
The invention is realized in the following way:
in a first aspect, the present invention provides a method for modifying a high nickel positive electrode material, comprising: the mixture formed by the high nickel anode material and the ammonium fluotitanate is firstly subjected to primary heat treatment at the temperature of 280-450 ℃, and then is subjected to secondary heat treatment at the temperature of 600-800 ℃.
In an alternative embodiment of the invention, the temperature of the primary heat treatment is 300-400 ℃ and the treatment time is 1-3 h.
In an alternative embodiment of the invention, the temperature of the secondary heat treatment is 650-750 ℃ and the treatment time is 6-10 h.
In an alternative embodiment of the invention, the primary heat treatment and the secondary heat treatment are carried out in an oxygen atmosphere.
In an alternative embodiment of the invention, the mass fraction of the high nickel positive electrode material in the mixture is 95.0% -99.8%.
In an alternative embodiment of the invention, the mass fraction of the high nickel positive electrode material in the mixture is 95% -97%.
In an alternative embodiment of the present invention, in the chemical formula of the high nickel positive electrode material, the molar ratio of the nickel content to the total amount of the transition metal is 0.8 or more.
In a second aspect, the present invention also provides a positive electrode material prepared by the modification method of any of the above embodiments.
In a third aspect, the present invention also provides a positive electrode sheet, including the positive electrode material of any of the above embodiments.
In a fourth aspect, the present invention also provides a lithium battery, including the positive electrode sheet of any of the above embodiments.
The invention has the following beneficial effects: modifying the high nickel positive electrode material by using ammonium fluotitanate, and decomposing the ammonium fluotitanate to generate NH by performing one-time heat treatment at a lower temperature 4 F and TiF 4 Generated NH 4 F can react with residual alkali on the positive electrode material and generate a LiF coating layer on the surface; remaining TiF 4 The Ti and F anions and cations are co-doped by diffusing into the crystal lattice of the anode material when the secondary heat treatment is carried out at high temperature, so that the structural stability of the material can be effectively improved. After the modification is carried out by adopting the modification method, the residual alkali can be effectively removed, and the electrochemical performance of the anode material can be improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows modified LiNi of ammonium fluorotitanate 0.92 Co 0.05 Mn 0.03 O 2 SEM of positive electrode material (×3.00 k);
FIG. 2 shows modified LiNi of ammonium fluorotitanate 0.92 Co 0.05 Mn 0.03 O 2 SEM of positive electrode material (×5.00 k);
FIG. 3 shows modified LiNi of ammonium fluorotitanate 0.92 Co 0.05 Mn 0.03 O 2 Positive electrode material XRD.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a modification method of a high-nickel positive electrode material, which utilizes ammonium fluotitanate to modify the high-nickel positive electrode material, and comprises the following specific operation steps:
s1, mixing materials
The ammonium fluotitanate and the high-nickel cathode material are uniformly mixed to obtain a mixture, and the mixing mode is not limited and can be general stirring, ball milling and other modes.
In some embodiments, the mass fraction of the high nickel positive electrode material in the mix is 95.0% to 99.8%, preferably 95% to 97%. The recycling performance of the product is further improved by further controlling the dosage of the ammonium fluotitanate.
Specifically, the total amount of ammonium fluotitanate and the high-nickel cathode material is 100%, and the mass fraction of the high-nickel cathode material in the mixture may be 95.0%, 96.0%, 97.0%, 98.0%, 99.0%, 99.5%, 99.8%, or any value between the above adjacent values.
In some embodiments, the high nickel positive electrode material has a molar ratio of nickel content to total transition metal content of 0.8 or more. The specific type of the high nickel positive electrode material is not limited, and the high nickel positive electrode material is not limited to nickel cobalt lithium manganate positive electrode material, and can be specifically LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.9 Co 0.05 Mn 0.05 O 2 、LiNi 0.92 Co 0.05 Mn 0.03 O 2 、LiNi 0.96 Co 0.03 Mn 0.01 O 2 、LiNiO 2 . The high nickel positive electrode material is a commercial material, and the particle size of the high nickel positive electrode material can be 2-14 mu m.
S2, primary heat treatment
The mixture formed by the high-nickel positive electrode material and the ammonium fluotitanate is subjected to primary heat treatment at the temperature of 280-450 ℃, and the ammonium fluotitanate reacts at a lower temperature as follows:
；
decomposition of ammonium fluorotitanate to NH 4 F and TiF 4 Generated NH 4 F reacts with LiOH to consume residual alkali and generate a LiF coating layer on the surface; generated TiF 4 And the anion and cation co-doping is formed during the secondary heat treatment, so that the structural stability of the material can be improved.
Specifically, the temperature of the primary heat treatment may be 280 ℃, 300 ℃, 320 ℃, 350 ℃, 370 ℃, 400 ℃, 420 ℃, 450 ℃, or the like.
In some embodiments, the temperature of the primary heat treatment is 300 ℃ to 400 ℃ and the treatment time is 1h to 3h to allow for adequate reaction. The treatment time may be 1h, 2h, 3h, etc.
In some embodiments, the primary heat treatment is performed in an oxygen atmosphere, which may be in high purity oxygen, with an oxygen purity of greater than 99%.
S3, secondary heat treatment
After the primary heat treatment is completed, the secondary heat treatment is carried out at 600-800 ℃. In this process, the TiF generated in S2 4 Can diffuse into the lattice of the positive electrode material to form Ti and F anion and cation co-doping, and can effectively improve the structural stability of the material.
Specifically, the temperature of the secondary heat treatment may be 600 ℃, 620 ℃, 650 ℃, 670 ℃, 700 ℃, 720 ℃, 750 ℃, 780 ℃, 800 ℃, or the like.
In some embodiments, the temperature of the secondary heat treatment is 650-750 ℃ and the treatment time is 6-10 h, so as to improve the effect of anion-cation doping and further improve the structural stability of the material. The treatment time may be 6h, 7h, 8h, 9h, 10h, etc.
In some embodiments, the secondary heat treatment is also performed in an oxygen atmosphere, which may be in high purity oxygen, with an oxygen purity of greater than 99%.
The embodiment of the invention also provides the positive electrode material which is prepared by the modification method, wherein the LiF coating layer is formed on the surface of the positive electrode material, ti and F ions are doped on the surface and the inside of the positive electrode material, and the positive electrode material has good stability and excellent cycle performance.
The invention also provides a positive electrode plate which comprises the positive electrode material, and the battery has excellent electrochemical performance after the positive electrode plate is assembled into the battery.
The invention also provides a lithium battery, which comprises the positive electrode plate, a negative electrode plate, electrolyte, a diaphragm and the like, so as to form a complete lithium battery.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a modification method of a high-nickel positive electrode material, which comprises the following steps:
(1) Mixing material
Taking a cathode material LiNi with the particle size of 2-3 mu m 0.92 Co 0.05 Mn 0.03 O 2 (produced by Yibin lithium materials Co., ltd.) and ammonium fluotitanate are mixed and stirred uniformly to obtain a mixture, and the mass ratio of the positive electrode material to the ammonium fluotitanate is controlled to be 99.8:0.2.
(2) One-time heat treatment
The mixture was heated for 2h under oxygen atmosphere at a temperature of 350 ℃.
(3) Secondary heat treatment
Raising the temperature to 700 ℃ and preserving the heat for 8 hours.
Example 2
The only difference from example 1 is that: in the step (1), the mass ratio of the positive electrode material to the ammonium fluotitanate is 99.5:0.5.
Example 3
The only difference from example 1 is that: in the step (1), the mass ratio of the positive electrode material to the ammonium fluotitanate is 99:1.
Example 4
The only difference from example 1 is that: in the step (1), the mass ratio of the positive electrode material to the ammonium fluotitanate is 97:3.
Example 5
The only difference from example 1 is that: in the step (1), the mass ratio of the positive electrode material to the ammonium fluotitanate is 95:5.
Example 6
The only difference from example 1 is that: in the step (1), the mass ratio of the positive electrode material to the ammonium fluotitanate is 92:8.
Example 7
The only difference from example 5 is that: the treatment temperature in the step (2) is 200 ℃.
Example 8
The only difference from example 5 is that: the treatment temperature in the step (2) is 250 ℃.
Example 9
The only difference from example 5 is that: the treatment temperature in the step (2) is 450 ℃.
Comparative example 1
The positive electrode material in the example 1 is treated by adopting a method of washing residual alkali reduction, and the specific steps are as follows:
(1) Positive electrode material and deionized water were mixed at 1: mixing together at a mass ratio of 0.8, and stirring at a high speed for 10min at room temperature;
(2) Filtering out excessive water, drying the positive electrode material in a vacuum oven at 150 ℃ for 3 hours, and taking out for standby;
(3) And (3) carrying out heat treatment on the dried material at 400 ℃ for 2 hours in an oxygen atmosphere.
Comparative example 2
The only difference from example 5 is that: ammonium fluorotitanate is replaced with an equivalent amount of fluorotitanic acid.
Comparative example 3
The difference from example 5 is that the decomposition of ammonium fluorotitanate provides NH 4 F and TiF 4 Respectively directly using NH 4 F and TiF 4 Instead, the amount was kept the same as the amount of the theoretical decomposition product.
Test example 1
The positive electrode material prepared in example 1 was characterized, SEM images are shown in fig. 1 and 2, and XRD images are shown in fig. 3.
SEM results showed that the particles of the material were dispersed single crystal particles having a particle size of about 2-3 μm. The XRD measured shows that the prepared positive electrode material has alpha-NaFeO 2 The crystal structure is a typical layered oxide cathode material.
Test example 2
The performance of the positive electrode material was measured after the treatment of examples and comparative examples, and the untreated positive electrode material was used as a blank, and the results are shown in table 1.
TABLE 1 results summary of cathode material Performance test results
From the test results of table 1, it can be seen that the present embodiment can significantly reduce residual alkali while improving capacity and cycle performance of the positive electrode material. Compared with the mode of washing residual alkali with water, the electrochemical performance of the obtained product is more excellent.
Examples 1-6 examined the effect of modification under different raw material ratios, examples 4-5 were better in modification effect, lower in residual alkali content, better in cycle performance, and the mass fraction of the high-nickel positive electrode material in the mixture was preferably 95% -97%. Examples 7-9 examined the effect of the treatment temperature of step (2) on the modification effect, with the optimum treatment temperature of step (2) at 350 ℃.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The modification method of the high-nickel positive electrode material is characterized by comprising the following steps of: the mixture formed by the high nickel anode material and the ammonium fluotitanate is firstly subjected to primary heat treatment at the temperature of 280-450 ℃, and then is subjected to secondary heat treatment at the temperature of 600-800 ℃.
2. The method according to claim 1, wherein the temperature of the primary heat treatment is 300 ℃ to 400 ℃ and the treatment time is 1h to 3h.
3. The modification process according to claim 1 or 2, wherein the secondary heat treatment is carried out at a temperature of 650 ℃ to 750 ℃ for a treatment time of 6h to 10h.
4. The modification method according to claim 1 or 2, wherein the processes of the primary heat treatment and the secondary heat treatment are each performed in an oxygen atmosphere.
5. The modification method according to claim 1, wherein the mass fraction of the high-nickel positive electrode material in the mixture is 95.0% to 99.8%.
6. The method according to claim 5, wherein the mass fraction of the high nickel positive electrode material in the mixture is 95% to 97%.
7. The method according to claim 1, wherein a molar ratio of the nickel content to the total amount of the transition metal in the chemical formula of the high-nickel positive electrode material is 0.8 or more.
8. A positive electrode material, characterized by being prepared by the modification method according to any one of claims 1 to 7.
9. A positive electrode sheet comprising the positive electrode material according to claim 8.
10. A lithium battery comprising the positive electrode sheet of claim 9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311666741.9A CN117374259B (en) | 2023-12-07 | 2023-12-07 | Modification method of high-nickel positive electrode material, positive electrode plate and lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311666741.9A CN117374259B (en) | 2023-12-07 | 2023-12-07 | Modification method of high-nickel positive electrode material, positive electrode plate and lithium battery |
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