CN118221177A - Positive electrode material precursor, positive electrode material, preparation method and application of positive electrode material precursor and positive electrode material - Google Patents
Positive electrode material precursor, positive electrode material, preparation method and application of positive electrode material precursor and positive electrode material Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 112
- 239000002243 precursor Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011164 primary particle Substances 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 21
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 14
- 238000004321 preservation Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 53
- 238000001816 cooling Methods 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- 239000010405 anode material Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 23
- 229910052759 nickel Inorganic materials 0.000 description 18
- 239000011812 mixed powder Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
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- 238000005336 cracking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
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- 239000012798 spherical particle Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000006258 conductive agent Substances 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a positive electrode material precursor, a positive electrode material, a preparation method and application thereof, wherein the preparation method of the positive electrode material precursor comprises the following steps: heating the primary particle precursor to 200-600 ℃ at a speed of 6-10 ℃/min, and preserving heat for 1-4 hours to obtain a positive electrode material precursor; the primary particle precursor comprises nickel cobalt manganese hydroxide and water, wherein the mass of the water accounts for 8% -12% of the mass of the primary particle precursor, and the particle size D50 of the nickel cobalt manganese hydroxide is larger than 1 mu m. The method comprises the steps of depolymerizing a precursor by utilizing air flow generated by water evaporation of a primary particle precursor caused by rapid temperature rise by controlling the water content of the primary particle precursor, the temperature rising rate in the sintering process, the sintering temperature and the heat preservation time, so as to obtain a positive electrode material precursor; and then the positive electrode material precursor is used for preparing the positive electrode material, so that the capacity of the traditional polycrystal can be exerted, and the cycle performance of the traditional polycrystal can be ensured.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a positive electrode material precursor, a positive electrode material, a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life and the like, and is widely applied to power supply systems such as portable electronic equipment, electric automobiles, energy storage power stations and the like, so that the society is continuously promoted to develop towards intellectualization and cleanliness. However, as the energy density of lithium batteries is continuously improved in the market, one of the more effective solutions at present is to improve the Ni content to prepare the high-nickel NCM ternary cathode material. However, with the increase of Ni content, the gas production, circulation and safety performance of the high-nickel NCM ternary positive electrode material are correspondingly deteriorated.
The nickel-cobalt-manganese ternary positive electrode material in the current market is mainly made of polycrystalline materials, is secondary particles formed by agglomerating a large number of primary micro-nano particles, has large surface area, can increase the contact area between the positive electrode and electrolyte, and improves the energy storage capacity and the charge-discharge rate of the battery, but in the circulation process of the battery, the electrolyte can infiltrate and erode the positive electrode material along gaps between the secondary particles, so that the generation of microcracks is aggravated due to volume expansion, and the lithium ion battery is more serious under the conditions of high voltage and high current charge-discharge, so that the lithium ion battery is attenuated too quickly in the subsequent circulation process. The high-nickel monocrystal ternary material is obtained by the growth of primary particles through high-temperature crystallization, has no particle aggregation and microcrack, has good mechanical properties, and almost does not generate microcrack in the charge-discharge cycle process, so that the cycle stability is better than that of a polycrystalline material, but the preparation of the monocrystal material requires higher sintering temperature, and the high temperature is easy to cause material overburning and grain boundary fusion, so that the initial capacity is greatly reduced.
Therefore, how to increase the first efficiency of the nickel monocrystal material, the discharge capacity of the material is close to that of the secondary particles under the condition of ensuring the charge capacity, and the gas production, circulation and safety performance of the material are superior to those of the secondary particles, so that the material becomes a bottleneck for developing monocrystal materials in the industry. In view of the above, the invention provides a positive electrode material precursor, a positive electrode material, and a preparation method and application thereof.
Disclosure of Invention
Aiming at the problems that the existing polycrystalline positive electrode material has poor circulation performance, and the existing single crystal positive electrode material has low capacity due to the adoption of a high sintering temperature although the existing single crystal positive electrode material has good circulation, the invention provides a positive electrode material precursor, a positive electrode material and a preparation method and application thereof.
The technical scheme for solving the technical problems is as follows:
in a first aspect, a method for preparing a precursor of a positive electrode material includes the steps of:
Heating the primary particle precursor to 200-600 ℃ at a speed of 6-10 ℃/min, and preserving heat for 1-4 hours to obtain a positive electrode material precursor;
The primary particle precursor comprises nickel cobalt manganese hydroxide and water, wherein the mass of the water accounts for 8-12% of the mass of the primary particle precursor, and the particle size D50 of the nickel cobalt manganese hydroxide is larger than 1 mu m.
The beneficial effects of the invention are as follows: the method comprises the steps of depolymerizing a precursor by utilizing air flow generated by water evaporation of the precursor of primary particles caused by rapid temperature rise by controlling the water content of the precursor of the primary particles (the particle size of the primary particles is more than or equal to 1 um) and the temperature rising rate, sintering temperature and heat preservation time in the presintering process; the positive electrode material precursor is prepared into a positive electrode material, so that the capacity of the traditional polycrystal can be exerted, and the cycle performance of the positive electrode material can be ensured; the method is simple to operate, environment-friendly, low in cost and potential for large-scale popularization.
Further, the particle size D50 of the nickel cobalt manganese hydroxide is 1-10 μm.
The beneficial effects of adopting the further scheme are as follows: the traditional polycrystal is a secondary spherical particle formed by agglomeration of primary particles, and the condition of spherical cracking can occur in the sintering process, so that microcracks are generated, and the secondary reaction occurs when the secondary spherical particle contacts with electrolyte in the charging and discharging processes, so that the cycle performance of the material is seriously affected; the single crystal precursor has better cycle performance than polycrystal because of being independent primary particles and not having the condition of ball cracking, but the sintering of the traditional single crystal requires too high temperature to burn through the material because of the structure, so that the capacity of the traditional single crystal is greatly influenced and is lower; the invention uses the polycrystal material with the granularity D50 of 1-10 mu m to depolymerize the polycrystal material from the inside to prepare the material similar to single crystal, which can greatly reduce the sintering temperature of the material, and prevent the problem of ball cracking, thereby avoiding the loss of cycle performance, and can also use the sintering temperature lower than the sintering temperature of the traditional single crystal to avoid the loss of capacity, thereby obtaining the anode material with good cycle performance and high capacity.
Further, the molecular formula of the nickel cobalt manganese hydroxide is Ni xCoyMn(1-x-y)(OH)2, wherein x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.2.
Further, the method also comprises the following steps: and after the primary particle precursor is subjected to heating and heat preservation treatment, after the positive electrode material precursor is cooled to room temperature, crushing the positive electrode material precursor.
The beneficial effects of adopting the further scheme are as follows: and (3) combining and crushing the prepared positive electrode material precursor to further depolymerize the positive electrode material precursor to obtain the single-crystal positive electrode material precursor.
In a second aspect, a positive electrode material is prepared from the positive electrode material precursor.
The beneficial effects of adopting above-mentioned scheme are: the positive electrode material prepared by the single crystal positive electrode material precursor can exert the capacity of the traditional polycrystal and can ensure the cycle performance.
In a third aspect, a method for preparing a positive electrode material includes the steps of: and mixing the positive electrode material precursor with lithium salt, and performing primary sintering, wherein the primary sintering temperature is lower than 800 ℃ to obtain the positive electrode material.
The beneficial effects of adopting above-mentioned scheme are: the monocrystal positive electrode material precursor is prepared into the positive electrode material by adopting a low-temperature sintering mode (the sintering temperature is lower than 800 ℃), so that the capacity of the traditional polycrystal can be exerted, and the cycle performance of the polycrystal can be ensured.
Further, the lithium salt comprises at least one of lithium hydroxide, lithium sulfate, lithium carbonate, lithium acetate and lithium nitrate; and/or
The molar ratio of the positive electrode material precursor to the lithium salt is 1:1.01-1:1.08; and/or
The specific process of the first sintering is as follows: and heating the mixture of the positive electrode material precursor and the lithium salt to 500-800 ℃ at a heating rate of 1-10 ℃ min -1 under an oxygen atmosphere, then preserving heat for 10-20 h, and cooling to room temperature to obtain the positive electrode material.
The beneficial effects of adopting the further scheme are as follows: according to the positive electrode material obtained by adopting a mode that the sintering temperature of the precursor is lower than that of the traditional single crystal, the condition that the capacity of the traditional single crystal is lower due to the fact that the sintering temperature is too high can be avoided, and the high capacity of the traditional polycrystal can be reserved.
Further, the preparation method of the positive electrode material further comprises the following steps: and mixing the anode material with a coating material, and performing secondary sintering to obtain the coated anode material.
The beneficial effects of adopting the further scheme are as follows: the prepared positive electrode material and the coating material are mixed and sintered to obtain the coated positive electrode material, which has the circulation performance of the traditional single crystal, and meanwhile, the problem of poor capacity of the traditional single crystal caused by overburning can be avoided, namely, the coated positive electrode material has high circulation stability and large charge-discharge capacity.
Further, the coating material is a compound containing at least one element of Co, al, mg, ca, Y, ti, W, B, mo, nb, ta, S, sb, cr; the coating material is oxide, chloride or fluoride of the element; and/or
The coating material accounts for 0.1-1% of the mass of the positive electrode material; and/or
The specific process of the second sintering is as follows: and heating the mixture of the anode material and the coating material to 250-650 ℃ at a heating rate of 1-10 ℃ min -1 under an oxygen atmosphere, preserving heat for 2-10 h, and cooling to room temperature to obtain the coated anode material.
All sintering is carried out in oxygen, and the partial pressure of oxygen is 0.01-1 standard atmospheric pressure.
In a fourth aspect, a positive electrode material is used for the preparation of a lithium battery.
The beneficial effects of adopting above-mentioned scheme are: the positive electrode material obtained by the invention has the traditional single crystal cycle performance, and meanwhile, the problem of poor capacity caused by overburning of the traditional single crystal can be avoided, that is, the positive electrode material has high cycle stability and large charge-discharge capacity.
Drawings
FIG. 1 is a schematic illustration of a primary particle precursor of the present invention;
FIG. 2 is a schematic diagram of a process for obtaining a precursor of a positive electrode material by depolymerizing and jet milling a primary particle precursor at a high temperature; wherein, the positive electrode material precursor is uniformly dispersed in the square frame.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or apparatus used were conventional products commercially available through regular channels, with no manufacturer noted.
The embodiment relates to a preparation method of a positive electrode material precursor, which comprises the following steps:
Heating the primary particle precursor (figure 1) to 200-600 ℃ at a rate of 6-10 ℃/min, such as 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min to 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ and the like, and preserving the temperature for 1-4 hours, such as 1 hour, 2 hours, 3 hours, 4h and the like, so as to obtain a positive electrode material precursor;
The primary particle precursor comprises nickel cobalt manganese hydroxide and water, wherein the mass of the water accounts for 8-12%, such as 8%, 9%, 10%, 11%, 12% and the like, of the mass of the primary particle precursor, and the particle size D50 of the nickel cobalt manganese hydroxide is larger than 1 mu m; the particle size D50 of the nickel cobalt manganese hydroxide is preferably 1 μm to 10 μm, for example 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 8 μm, 9 μm, 10 μm, etc. in this example.
In this embodiment, preferably, after the primary particle precursor is heated and preserved, the temperature may be reduced to 200 ℃ at a cooling rate of 1-10 ℃ min -1, specifically, the temperature may be reduced to 200 ℃ at a cooling rate of 1℃·min-1、2℃·min-1、3℃·min-1、4℃·min-1、5℃·min-1、6℃·min-1、7℃·min-1、8℃·min-1、9℃·min-1、10℃·min-1 or the like, and finally, the primary particle precursor is naturally cooled to room temperature.
In this embodiment, the molecular formula of the nickel cobalt manganese hydroxide is preferably Ni xCoyMn(1-x-y)(OH)2, where x is greater than or equal to 0.6 and less than or equal to 1, y is greater than or equal to 0 and less than or equal to 0.2, and x may be 0.9, 0.94, etc., and y may be 0.06, 0.05, etc.
In this embodiment, the preparation method of the primary particle precursor preferably includes the following steps: adding nickel sulfate, cobalt sulfate, manganese sulfate, sodium hydroxide solution and ammonia water in a certain molar ratio into a reaction kettle according to a general flow rate, and controlling the ammonia value and pH of the solution to obtain a mixed solution containing precursor particles; when the particle size D50 of the precursor particles in the mixed solution rises to be more than 1 mu m, obtaining a primary particle precursor solution; and (3) aging, washing and centrifuging the solution of the primary particle precursor solution to obtain the primary particle precursor, wherein the water content is controlled to be 8-12%.
The preferred embodiment further comprises the following steps: after the primary particle precursor is subjected to heating and heat preservation treatment, the positive electrode material precursor is crushed after being cooled to room temperature (fig. 2). Wherein the crushing is jet milling, the crushing pressure is 0.7-0.9MPa, and the feeding pressure is 0.3-0.5MPa.
The embodiment also relates to a positive electrode material, which is prepared from the positive electrode material precursor.
The preferred preparation method of the positive electrode material in this embodiment comprises the following steps: the positive electrode material precursor is mixed with lithium salt and subjected to a first sintering at a temperature lower than 800 ℃, for example 650 ℃, 700 ℃, 800 ℃, etc., to obtain a positive electrode material.
Preferably, the lithium salt includes at least one of lithium hydroxide, lithium sulfate, lithium carbonate, lithium acetate, and lithium nitrate; and/or
The molar ratio of the positive electrode material precursor to the lithium salt is 1:1.01-1:1.08, for example, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, and the like; and/or
The specific process of the first sintering is as follows: the mixture of the positive electrode material precursor and the lithium salt is heated to 500-800 ℃ at a heating rate of 1-10 ℃ min -1, such as to 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ at a heating rate of 1-10 ℃ min -1、3℃·min-1、5℃·min-1、7℃·min-1、9℃·min-1, and then is kept for 10-20 hours, such as 10 hours, 12 hours, 15 hours, 17 hours, 19 hours, 20 hours, cooled to room temperature, specifically cooled to 200 ℃ at a cooling rate of 1-10 ℃ min -1, specifically cooled to 200 ℃ at a cooling rate of 1-10 ℃ min -1、2℃·min-1、4℃·min-1、6℃·min-1、8℃·min-1, and finally naturally cooled to room temperature; and obtaining the positive electrode material.
Preferably, the preparation method of the positive electrode material further includes the following steps: and mixing the anode material with a coating material, and performing secondary sintering to obtain the coated anode material.
In this embodiment, preferably, the coating material is a compound containing at least one element of Co, al, mg, ca, Y, ti, W, B, mo, nb, ta, S, sb, cr, and the coating material is an oxide, chloride or fluoride of the element; for example, the coating material may be TiO 2、Al2O3、CaCl2、CoCl2; and/or
The coating material accounts for 0.1-1% of the mass of the positive electrode material, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% and 1%; and/or
The specific process of the second sintering is as follows: and heating the mixture of the anode material and the coating material to 250-650 ℃ at a heating rate of 1-10 ℃ min -1 under an oxygen atmosphere, specifically heating to 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and the like at a heating rate of 1-10 ℃ min -1、3℃·min-1、5℃·min-1、7℃·min-1、9℃·min-1 and the like, preserving heat for 2-10 h, specifically 2h, 4h, 6h, 8h, 10 h and the like, cooling to room temperature, specifically cooling to 200 ℃ at a cooling rate of 1-10 ℃ min -1, specifically cooling to 200 ℃ at a cooling rate of 1-10 ℃ min -1、2℃·min-1、4℃·min-1、6℃·min-1、8℃·min-1 and the like, and naturally cooling to room temperature to obtain the coated anode material.
All sintering reactions are performed in oxygen, and the partial pressure of oxygen is 0.01-1 standard atmospheric pressure.
The present embodiment also relates to an application of the positive electrode material, and the positive electrode material is used for preparing a lithium battery.
In a word, the method controls the water content of the precursor, the heating rate in the presintering process, the presintering temperature and the heat preservation time, and depolymerizes the primary particles again in combination with the crushing mode to obtain a uniform positive electrode material precursor of single crystal particles, so that sintering can be performed at a sintering temperature lower than that of the traditional single crystal, the conventional single crystal has the circulation performance, the problem of poor capacity of the traditional single crystal caused by the presintering can be avoided, and the positive electrode material with high circulation stability and large charge-discharge capacity is obtained; the preparation method is simple, is environment-friendly, and has the potential of large-scale popularization. Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
The embodiment relates to a preparation method of a positive electrode material, which comprises the following steps:
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to a mole ratio of 94:5:1 is fully dissolved in hot water at 60 ℃, after the dissolution is finished, the mixture is pumped into a reaction kettle, sodium hydroxide solution and ammonia water are added simultaneously to form a mixed solution, the ammonia value of the mixed solution is controlled to be 3g/L, the pH value is 10.5, the stirring linear speed is controlled to be 8m/s, and when the particle size D50 of precursor particles in the mixed solution is expanded to 10 mu m, the synthesis of the high-nickel precursor material is finished. And (3) aging, washing and centrifuging the solution containing the high-nickel precursor material to obtain the high-nickel precursor material, controlling the water content of the precursor to be 10%, heating the prepared Ni 0.94Co0.05Mn0.01(OH)2 polycrystal precursor to 500 ℃ at the rate of 8 ℃ for -1, preserving heat for 1h, and cooling to 200 ℃ at the rate of 5 ℃ for -1. And cooling to room temperature, taking out the sample, and crushing by combining with air flow to obtain the uniform high-nickel monocrystal precursor.
(2) And uniformly mixing the obtained precursor with LiOH according to the molar ratio of 1:1.06 to obtain mixed powder A. And heating the mixed powder A to 650 ℃ in an oxygen atmosphere, preserving heat for 5 hours, and then cooling to room temperature at a cooling rate of 5 ℃ min -1 to obtain the anode material B. Adding 3000ppmTiO 2 to the obtained positive electrode material B, uniformly mixing to obtain mixed powder C, heating the mixed powder C to 500 ℃ under the oxygen atmosphere, preserving heat for 2 hours, and then cooling to room temperature at the cooling rate of 5 ℃ min -1 to obtain the coated positive electrode material D.
Example 2:
The embodiment relates to a preparation method of a positive electrode material, which comprises the following steps:
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to a mole ratio of 90:6:4 fully dissolving in hot water at 60 ℃, pumping into a reaction kettle after the dissolution is completed, simultaneously adding sodium hydroxide solution and ammonia water to form a mixed solution, controlling the ammonia value of the mixed solution to be 3g/L and the pH value to be 10.5, controlling the stirring linear speed to be 9m/s when stirring, and finishing the synthesis of the high-nickel precursor material when the particle size D50 of the precursor particles in the mixed solution is increased to 10 mu m. And (3) aging, washing and centrifuging the solution containing the high-nickel precursor material to obtain the high-nickel precursor material, controlling the water content of the precursor to be 10%, heating the prepared Ni 0.9Co0.06Mn0.04(OH)2 polycrystal precursor to 400 ℃ at the rate of 8 ℃ for -1, preserving heat for 3 hours, and cooling to 200 ℃ at the rate of 5 ℃ for -1. And cooling to room temperature, taking out the sample, and crushing by combining with air flow to obtain the uniform high-nickel monocrystal precursor.
(2) And uniformly mixing the obtained precursor with LiOH according to the molar ratio of 1:1.05 to obtain mixed powder A. And heating the mixed powder A to 660 ℃ in an oxygen atmosphere, preserving heat for 10 hours, and then cooling to room temperature at a cooling rate of 5 ℃ min -1 to obtain the anode material B. Adding 3000ppmTiO 2 to the obtained positive electrode material B, uniformly mixing to obtain mixed powder C, heating the mixed powder C to 500 ℃ under the oxygen atmosphere, preserving heat for 8 hours, and then cooling to room temperature at the cooling rate of 5 ℃ min -1 to obtain the coated positive electrode material D.
Comparative example 1:
The comparative example relates to a preparation method of a positive electrode material, comprising the following steps:
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to a mole ratio of 94:5:1 is fully dissolved in hot water at 60 ℃, after the dissolution is finished, the mixture is pumped into a reaction kettle, sodium hydroxide solution and ammonia water are added to form a mixed solution, the ammonia value of the mixed solution is controlled to be 3g/L, the pH value is 11, the stirring linear speed is controlled to be 10m/s, and when the particle size D50 of precursor particles in the mixed solution rises to 3 mu m, the synthesis of the high-nickel precursor material is finished. And (3) aging, centrifuging, washing and drying the solution containing the high-nickel precursor material, and sieving to remove iron to obtain the high-nickel precursor material Ni 0.94Co0.05Mn0.01(OH)2, wherein the water content of the precursor is controlled to be 0.5%.
(2) And uniformly mixing the prepared Ni 0.94Co0.05Mn0.01(OH)2 monocrystal precursor and LiOH according to the molar ratio of 1:1.06 to obtain mixed powder A. And heating the mixed powder A to 680 ℃ in an oxygen atmosphere, preserving heat for 5 hours, and then cooling to room temperature at a cooling rate of 5 ℃ min -1 to obtain the anode material B. Adding 3000ppmTiO 2 to the obtained positive electrode material B, uniformly mixing to obtain mixed powder C, heating the mixed powder C to 600 ℃ under the oxygen atmosphere, preserving heat for 2 hours, and then cooling to room temperature at a cooling rate of 5 ℃ min -1 to obtain the coated positive electrode material D.
Comparative example 2:
The embodiment relates to a preparation method of a positive electrode material, which comprises the following steps:
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to a mole ratio of 94:5:1 is fully dissolved in hot water at 60 ℃, after the dissolution is finished, the mixture is pumped into a reaction kettle, sodium hydroxide solution and ammonia water are added to form a mixed solution, the ammonia value of the mixed solution is controlled to be 3g/L, the pH value is 11, the stirring linear speed is controlled to be 10m/s, and when the particle size D50 of precursor particles in the mixed solution is expanded to 10 mu m, the synthesis of the high-nickel precursor material is finished. And (3) aging, centrifuging, washing and drying the solution containing the high-nickel precursor material, and sieving to remove iron to obtain the high-nickel precursor material Ni 0.94Co0.05Mn0.01(OH)2, wherein the water content of the precursor is controlled to be 0.5%.
(2) And uniformly mixing the prepared Ni 0.94Co0.05Mn0.01(OH)2 polycrystal precursor and LiOH according to the molar ratio of 1:1.06 to obtain mixed powder A. And heating the mixed powder A to 650 ℃ in an oxygen atmosphere, preserving heat for 5 hours, and then cooling to room temperature at a cooling rate of 5 ℃ min -1 to obtain the anode material B. Adding 3000ppmTiO 2 to the obtained positive electrode material B, uniformly mixing to obtain mixed powder C, heating the mixed powder C to 500 ℃ under the oxygen atmosphere, preserving heat for 2 hours, and then cooling to room temperature at the cooling rate of 5 ℃ min -1 to obtain the coated positive electrode material D.
Test example:
The coated positive electrode materials, conductive agent (Super P) and binder (dissolved in NMP mass fraction 5% PVDF) prepared according to examples 1 to 2 and comparative examples 1 to 2 were weighed in a mass ratio of 80:10:10 into a stirring box; placing the stirring box in a homogenizer with a set program, uniformly coating the material on an aluminum foil with the thickness of 0.25 mm by a coating machine, and drying, cutting, weighing and editing to obtain the positive plate with the diameter of 12 mm. The negative electrode was a metal lithium, and a KLD-1230C ternary electrolyte and a single-sided ceramic separator were used to assemble a CR2032 button cell.
The assembled battery was tested for first discharge capacity, first charge-discharge efficiency, and cycle stability, and the results are shown in table 1:
TABLE 1 detection results
As can be seen from table 1, by comparing example 1 and example 2, it can be seen that the temperature sintering has a certain influence on the depolymerization of the primary particles during the precursor preparation process, and the higher the temperature, the better the depolymerization degree, the higher the cycle performance, and the higher the Ni content, and the higher the capacity. As can be seen by comparing example 1 with comparative examples 1 and 2, compared with comparative example 1, the same nickel cobalt manganese content is achieved, and the conventional single crystal has a larger influence on capacity due to higher sintering temperature, so that the capacity of the conventional single crystal is far lower than that of the prepared material of the invention, and the prepared material of the invention well maintains the cycle performance of the conventional single crystal; compared with comparative example 2, the conventional polycrystal has the advantages that the primary particles generate microcracks, and the secondary reaction with the electrolyte causes the cycle performance of the polycrystal to be damaged, and the material prepared by the method has the appearance of single crystals because the polycrystal material is depolymerized in the early stage, the microcracks are not generated, the cycle performance of the polycrystal is prevented from being damaged, and the material has the cycle performance higher than that of comparative example 2 and shows the high capacity of the polycrystal material.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. The preparation method of the positive electrode material precursor is characterized by comprising the following steps:
Heating the primary particle precursor to 200-600 ℃ at a speed of 6-10 ℃/min, and preserving heat for 1-4 hours to obtain a positive electrode material precursor;
The primary particle precursor comprises nickel cobalt manganese hydroxide and water, wherein the mass of the water accounts for 8-12% of the mass of the primary particle precursor, and the particle size D50 of the nickel cobalt manganese hydroxide is larger than 1 mu m.
2. The method for preparing a positive electrode material precursor according to claim 1, wherein the particle size D50 of the nickel cobalt manganese hydroxide is 1 μm to 10 μm.
3. The method for preparing a precursor of a positive electrode material according to claim 1, wherein the molecular formula of the nickel cobalt manganese hydroxide is Ni xCoyMn(1-x-y)(OH)2, wherein x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.2.
4. The method for preparing a positive electrode material precursor according to claim 1, further comprising the steps of: and after the primary particle precursor is subjected to heating and heat preservation treatment, after the positive electrode material precursor is cooled to room temperature, crushing the positive electrode material precursor.
5. A positive electrode material, characterized by being prepared from the positive electrode material precursor according to any one of claims 1 to 4.
6. The preparation method of the positive electrode material according to claim 5, comprising the following steps:
and mixing the positive electrode material precursor with lithium salt, and performing primary sintering, wherein the primary sintering temperature is lower than 800 ℃ to obtain the positive electrode material.
7. The method for preparing a positive electrode material according to claim 6, wherein,
The lithium salt comprises at least one of lithium hydroxide, lithium sulfate, lithium carbonate, lithium acetate and lithium nitrate; and/or
The molar ratio of the positive electrode material precursor to the lithium salt is 1:1.01-1:1.08; and/or
The specific process of the first sintering is as follows: and heating the mixture of the positive electrode material precursor and the lithium salt to 500-800 ℃ at a heating rate of 1-10 ℃ min -1 under an oxygen atmosphere, then preserving heat for 10-20 h, and cooling to room temperature to obtain the positive electrode material.
8. The method for preparing a positive electrode material according to claim 6, wherein,
The preparation method of the positive electrode material further comprises the following steps: and mixing the anode material with a coating material, and performing secondary sintering to obtain the coated anode material.
9. The method for preparing a positive electrode material according to claim 8, wherein,
The coating material is a compound containing at least one element of Co, al, mg, ca, Y, ti, W, B, mo, nb, ta, S, sb, cr; and/or
The coating material accounts for 0.1-1% of the mass of the positive electrode material; and/or
The specific process of the second sintering is as follows: and heating the mixture of the anode material and the coating material to 250-650 ℃ at a heating rate of 1-10 ℃ min -1 under an oxygen atmosphere, preserving heat for 2-10 h, and cooling to room temperature to obtain the coated anode material.
10. Use of the positive electrode material according to claim 5 or the positive electrode material produced by the production method according to any one of claims 6 to 9 for producing a lithium battery.
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