CN114906884A - Preparation method of fluorine-niobium double-doped lithium niobate-coated ternary material - Google Patents
Preparation method of fluorine-niobium double-doped lithium niobate-coated ternary material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 94
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- TTXOCPWHRPZIJA-UHFFFAOYSA-N [F].[Nb] Chemical compound [F].[Nb] TTXOCPWHRPZIJA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 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 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 239000011572 manganese Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 claims description 9
- 241000080590 Niso Species 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000004080 punching Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012982 microporous membrane Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000011156 evaluation Methods 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000012216 screening Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000007873 sieving Methods 0.000 description 6
- -1 Ni3+ ions Chemical class 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
Images
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- 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 discloses a preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material, which comprises the following steps: (1) preparing a nickel-cobalt-manganese hydroxide precursor by utilizing a coprecipitation reaction; (2) uniformly stirring fluoroniobate and nickel-cobalt-manganese hydroxide precursors, and then adding ammonia water or introducing ammonia gas to generate niobium hydroxide and ammonium fluoride to obtain a composite material of the modified precursors; (3) mixing the composite material obtained in the step (2) with lithium hydroxide, and calcining at high temperature in an oxygen atmosphere to obtain a fluorine-niobium double-doped lithium niobate-coated ternary material; and (4) carrying out crushing, grading and screening on the fluorine-niobium double-doped lithium niobate coated ternary material generated in the step (3) by using a jet mill to obtain a finished ternary material. According to the invention, the in-situ fluorine-niobium double-doped ternary material is utilized, lithium niobate is generated on the surface of the in-situ fluorine-niobium double-doped ternary material, the fluorine-niobium double-doped ternary material and the lithium niobate-coated ternary material are formed, the interface stability and the cycle performance of the ternary material are improved, the problem of residual alkali is solved by adopting a waterless washing process, and the loss of electrical performance is reduced.
Description
Technical Field
The invention belongs to the technical field of new energy lithium ion battery materials, and mainly relates to a preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material.
Background
The long-term development planning in the automobile industry is clearly planned, and by 2020, the energy density of a power battery monomer reaches over 300Wh/kg, and the aim is to achieve 350 Wh/kg. By 2025, power battery systems reached an energy density of 350 Wh/kg. To achieve the above objective, one of the solutions is to use a high nickel ternary positive electrode. Due to the instability of Ni3+, the reduction of Ni3+ ions can occur in the material during the battery synthesis process, which leads to the increase of the surface alkalinity of the material, and the reduction of Ni3+ ions during the circulation process can lead to lattice oxygen release, gas generation at the positive electrode side and metal dissolution, which seriously affect the cycle life and safety performance of the battery. The currently effective measure is doping and cladding of ternary materials. For example, CN113851633A A niobium-doped high-nickel ternary cathode material coated with niobium phosphate and a preparation method thereof adopt an in-situ doping mode, but the problem of alkali residue is not well solved; although the preparation method of the CN113611862A lithium niobate-coated cathode material, the lithium niobate-coated cathode material and the application thereof have obvious improvement on the problem of residual alkali, the coating uniformity is poor.
The present invention has been made to solve these problems.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material comprises the following steps:
(1) preparing a nickel-cobalt-manganese hydroxide precursor by utilizing a coprecipitation reaction;
(2) uniformly stirring the fluoroniobate and nickel-cobalt-manganese hydroxide precursors, and then adding ammonia water (or introducing ammonia gas) to generate niobium hydroxide and ammonium fluoride to obtain a composite material of the modified precursors;
(3) and (3) mixing the composite material obtained in the step (2) with lithium hydroxide, and calcining at high temperature in an oxygen atmosphere to obtain the fluorine-niobium double-doped lithium niobate-coated ternary material.
And (3) further, carrying out crushing and grading on the fluorine-niobium double-doped lithium niobate-coated ternary material generated in the step (3) by using an airflow pulverizer, and sieving to obtain a finished ternary material.
Further, the specific steps of the step (1) are as follows: will contain NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 The total concentration of O is 2.0mol L -1 Pumping the aqueous solution into a continuous stirring reactor under nitrogen, wherein the reaction temperature is 50-60 ℃; then 10 wt.% NaOH solution and 5.0mol L of NaOH were added separately -1 NH 4 OH solution, controlling the pH value of a reaction system to be 11.8, generating precipitate after the reaction is finished, filtering and washing with deionized water to finally obtain a ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 。
Preferably, the NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 The total concentration of O is 2.0mol L -1 In an aqueous solution of (2) at a molar ratio of Ni 2+ :Co 2+ :Mn 2+ ＝8:1:1。
Preferably, the reaction temperature in step (1) is 50-60 ℃.
Further, the specific steps in the step (2) are as follows: in a closed reactor, 0.027g fluoroniobic acid and 1.0g ternary precursor Ni were added 0.8 Co 0.1 Mn 0.1 (OH) 2 Uniformly stirring, adding a mixed solution of water and ethanol as a solvent, introducing ammonia gas, and controlling the ammonia gas and the fluoroniobateThe mass molar ratio is 9: 1, continuously stirring for 4 hours at the temperature of 10 ℃ to obtain the modified precursor composite material.
Preferably, 0.027g fluoroniobic acid and 1.0g ternary precursor Ni are charged in a closed reactor 0.8 Co 0.1 Mn 0.1 (OH) 2 Then, the mixture was stirred uniformly for 30 min.
Further, the specific steps in the step (3) are as follows: uniformly mixing the composite material in the step (2) with lithium hydroxide, then placing the mixture in a tubular furnace for staged sintering, firstly introducing nitrogen, heating to 470-490 ℃ at the speed of 5 ℃/min for presintering, and preserving heat for 1.5-2.5 h; then the temperature is increased to 740 and 760 ℃, and the temperature is kept for 3.5 to 4.5 hours; and cutting off the nitrogen atmosphere after the heat preservation is finished, introducing the oxygen atmosphere, preserving the heat at the temperature of 740-760 ℃ for 11-13h, and naturally cooling to obtain the fluorine-niobium double-doped lithium niobate-coated ternary material.
Description of the reaction mechanism or working principle
H 2 NbF 7 +7NH 4 OH→Nb(OH) 5 +7NH 4 F+2H 2 O
2Nb(OH) 5 →Nb 2 O 5 +5H 2 O
Nb 2 O 5 +Li 2 CO 3 →2LiNbO 3 +CO 2
Nb 2 O 5 +2LiOH→2LiNbO 3 +H 2 O。
Preferably, the temperature is raised to 480 ℃ at the speed of 5 ℃/min for presintering, and the temperature is kept for 2 h; then heating to 750 ℃, and preserving heat for 4 hours; cutting off the nitrogen atmosphere after the heat preservation is finished, introducing the oxygen atmosphere, preserving the heat at 750 ℃ for 12h, and naturally cooling.
Further, the electrochemical performance of the cathode material is evaluated by using a CR2032 button cell; the positive electrode adopts a finished ternary material, a conductive agent acetylene black and a binder polyvinylidene fluoride, and the mass ratio of the conductive agent acetylene black to the binder polyvinylidene fluoride is 90: 5: 5, the specific preparation process comprises the following steps: firstly, taking 0.18g of finished ternary material, 0.01g of conductive agent acetylene black and 0.01g of polyvinylidene fluoride, putting the materials into a 10mL small beaker, uniformly mixing, then dropwise adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on a dried carbon-coated aluminum foil by using a scraper 150mm, firstly putting the dried carbon-coated aluminum foil in a blast drying box, drying for 8 hours at 80 ℃, then transferring the dried carbon-coated aluminum foil into a vacuum drying box, drying for 12 hours at 120 ℃, weighing and transferring the completely dried electrode plate into a glove box after punching into a circular positive electrode plate with the diameter of 12mm by using a punching machine, taking the prepared positive electrode plate as a positive electrode, taking metal lithium as a negative electrode, taking a mixture of 1.1mol/L LiPF6 dissolved in an EC/DMC/EMC mixed solvent as an electrolyte, taking a Celgard 2400 microporous membrane as a diaphragm, putting all the materials into the glove box to assemble a CR2032 button cell, and sealing by using a sealing machine; and finally standing and activating the assembled CR2032 button cell for 12h at room temperature for later use.
The beneficial technical effects are as follows:
1. according to the invention, liquid-phase in-situ coating is adopted, the lithium niobate serving as a coating material is uniformly dispersed on the surface of the ternary material after sintering, the ternary material is prevented from reacting with trace HF in an electrolyte in a high lithium removal state to isolate and reduce the pH value, the cycling stability of the material is improved, the lithium niobate has higher ionic conductivity, the Li & lt + & gt diffusion rate is 10 & lt-5 & gtS & cm & lt-1 & gt at room temperature, the interface resistance can be effectively reduced, and the rate capability of the material is improved; the doped niobium partially replaces the position of the transition metal ion, and the outer shell layer of the doped niobium partially has a d0 electronic configuration which can minimize the distortion of Ni2+, Ni2+ more stably occupies the position of the transition metal layer 3a, and the mixed arrangement of lithium and nickel cations is reduced; meanwhile, fluorine anions are cooperatively doped, and F is used for replacing a lattice part O2-so as to reduce the redox activity of O2-and stabilize the material structure; the ternary material can react to remove residual lithium on the surface during sintering, and can be subjected to a waterless washing process.
2. According to the invention, the in-situ fluorine-niobium double-doped ternary material is utilized, and lithium niobate is generated on the surface of the ternary material to form the fluorine-niobium double-doped and lithium niobate-coated ternary material, so that the interface stability, the cycle performance and the residual alkali problem of the ternary material are improved, and meanwhile, the residual alkali problem can be solved by adopting a waterless washing process, so that the loss of the electrical property is reduced.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is an SEM image of the fluorine niobium double doped lithium niobate coated ternary material of example 4.
FIG. 2 is the XRD spectrum of the fluorine niobium double doped lithium niobate coated ternary material of example 4.
FIG. 3 is a graph comparing the discharge gram capacities at different rates for example 1 and example 4.
Fig. 4 is a comparison of cycles for each example, with the base group being a fluorine-free niobium double-doped lithium niobate-free clad ternary material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material comprises the following steps:
(1) will contain NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 The total concentration of O is 2.0mol L -1 Aqueous solution (molar ratio Ni) 2+ :Co 2+ :Mn 2+ No. 8:1:1) was pumped into a continuous stirred tank reactor under nitrogen at 55 ℃; then 10 wt.% NaOH solution and 5.0mol L of NaOH were added separately -1 NH 4 OH solution, controlling the pH value of a reaction system to be 11.8, generating a precipitate after the reaction is finished, filtering and washing with deionized water to finally obtain a ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ；
(2) 0.027g fluoroniobic acid and 1.0g ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Adding the mixture into a reactor, uniformly stirring for 30min, then adding ammonia water, and controlling the mass molar ratio of the ammonia water to the fluoroniobate to be 9: 1, continuously stirring for 4 hours at the temperature of 10 ℃ to obtain a modified precursor composite material;
(3) uniformly mixing the composite material obtained in the step (2) with lithium hydroxide (molar ratio Mn) 2+ ：Li＝1:1.05) Then the mixture is placed in a tube furnace for sectional sintering. Under the oxygen atmosphere, firstly heating to 480 ℃ at the speed of 5 ℃/min for presintering, and preserving heat for 2 h; then heating to 750 ℃ at the speed of 5 ℃/min, sintering, preserving heat for 12h, and naturally cooling to obtain the fluorine-niobium double-doped lithium niobate coated ternary material;
(4) and (3) crushing, grading and sieving the fluorine-niobium double-doped lithium niobate coated ternary material by using an airflow crusher to obtain the finished ternary material.
Mn 2+ Refers to composite materials.
The electrochemical performance of the cathode material is evaluated by using a CR2032 button cell. The anode adopts the finished ternary material in the embodiment 1, the conductive agent adopts acetylene black, the binder adopts polyvinylidene fluoride, and the mass ratio of the conductive agent to the binder is 90: 5: 5.
the specific preparation process comprises the following steps: first, 0.18g of the ternary material prepared in example 1, 0.01g of acetylene black as a conductive agent and 0.01g of polyvinylidene fluoride are put into a 10mL beaker and mixed uniformly, and then a proper amount of N-methyl pyrrolidone is added dropwise and stirred into uniform slurry. Coating the dried carbon-coated aluminum foil with a scraper of 150mm, drying the carbon-coated aluminum foil in a blast drying oven at 80 ℃ for 8h, transferring the carbon-coated aluminum foil into a vacuum drying oven at 120 ℃ for vacuum drying for 12h, weighing and transferring the completely dried pole piece into a glove box for later use after the pole piece is made into a circular positive pole piece with the diameter of 12mm by a punching machine.
The prepared positive plate is used as a positive electrode, metal lithium is used as a negative electrode, a mixture of 1.1mol/L LiPF6 dissolved in an EC/DMC/EMC mixed solvent is used as an electrolyte, a Celgard 2400 polypropylene microporous membrane is used as a diaphragm, all materials are placed in a glove box to be assembled into a CR2032 button cell, a sealing machine is used for sealing, and finally the assembled CR2032 button cell is stood and activated for 12 hours at room temperature for standby.
As shown in FIG. 3, the gram volume discharged of the material obtained in this example 1 at 0.33C was 189.2 mAh/g.
Example 2:
the embodiment provides a preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material, which comprises the following specific steps:
(1) will contain NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 The total concentration of O is 2.0mol L -1 Aqueous solution (molar ratio Ni) 2+ :Co 2+ :Mn 2+ No. 8:1:1) was pumped into a continuous stirred reactor under nitrogen at 55 ℃; then 10 wt.% NaOH solution and 5.0mol L of NaOH were added separately -1 NH 4 OH solution, controlling the pH value of a reaction system to be 11.8, generating a precipitate after the reaction is finished, filtering and washing with deionized water to finally obtain a ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ；
(2) In a closed reactor, 0.027g fluoroniobic acid and 1.0g ternary precursor Ni were added 0.8 Co 0.1 Mn 0.1 (OH) 2 Uniformly stirring for 30min, adding a mixed solution of water and ethanol as a solvent, introducing ammonia gas, and controlling the mass molar ratio of the ammonia gas to the fluoroniobate to be 9: 1, continuously stirring for 4 hours at the temperature of 10 ℃ to obtain a modified precursor composite material;
(3) uniformly mixing the composite material obtained in the step (2) with lithium hydroxide (molar ratio Mn) 2+ : li ═ 1:1.05), and then placed in a tube furnace for staged sintering. Under the oxygen atmosphere, firstly heating to 480 ℃ at the speed of 5 ℃/min for presintering, and preserving heat for 2 h; then heating to 750 ℃ at the speed of 5 ℃/min, sintering, preserving heat for 12h, and naturally cooling to obtain the fluorine-niobium double-doped lithium niobate coated ternary material;
(4) and (3) crushing, grading and sieving the fluorine-niobium double-doped lithium niobate coated ternary material by using an airflow crusher to obtain the finished ternary material.
The same assembly fastening method as the embodiment is adopted, except that the ternary material of the embodiment 2 is adopted as the positive electrode, and other parts are not changed.
Example 3:
the embodiment provides a preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material, which comprises the following specific steps:
(1) will contain NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 The total concentration of O is 2.0mol L -1 Aqueous solution (molar ratio Ni) 2+ :Co 2+ :Mn 2+ 8:1:1) continuous stirring with nitrogen pumpingIn the reactor, the reaction temperature is 55 ℃; then 10 wt.% NaOH solution and 5.0mol L of NaOH were added separately -1 NH 4 OH solution, controlling the pH value of a reaction system to be 11.8, generating a precipitate after the reaction is finished, filtering and washing with deionized water to finally obtain a ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ；
(2) 0.027g fluoroniobic acid and 1.0g ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Adding the mixture into a reactor, uniformly stirring for 30min, then adding ammonia water, and controlling the mass molar ratio of the ammonia water to the fluoroniobate to be 9: 1, continuously stirring for 4 hours at the temperature of 10 ℃ to obtain the modified precursor composite material
(3) Uniformly mixing the composite material obtained in the step (2) with lithium hydroxide (Mn) 2+ : li ═ 1:1.05), and then placed in a tube furnace for staged sintering. Firstly, introducing nitrogen, heating to 480 ℃ at the speed of 5 ℃/min, performing presintering, and keeping the temperature for 4 hours; then heating to 750 ℃ and preserving the heat for 4 h; cutting off the nitrogen atmosphere after the heat preservation is finished, introducing the oxygen atmosphere, preserving the heat at 750 ℃ for 12 hours, and naturally cooling to obtain the fluorine-niobium double-doped lithium niobate coated ternary material;
(4) and (3) crushing, grading and sieving the fluorine-niobium double-doped lithium niobate coated ternary material by using an airflow crusher to obtain the finished ternary material.
The same assembly fastening method as the embodiment is adopted, except that the ternary material of the embodiment 3 is adopted as the positive electrode, and other parts are not changed.
Example 4:
the embodiment provides a preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material, which comprises the following specific steps:
(1) will contain NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 The total concentration of O is 2.0mol L -1 Aqueous solution (molar ratio Ni) 2+ :Co 2+ :Mn 2+ No. 8:1:1) was pumped into a continuous stirred reactor under nitrogen at 55 ℃; then 10 wt.% NaOH solution and 5.0mol L of NaOH were added separately -1 NH 4 OH solution, controlling the pH value of a reaction system to be 11.8, and generating after the reaction is finishedFiltering the precipitate, and washing with deionized water to obtain a ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ；
(2) In a closed reactor, 0.027g fluoroniobic acid and 1.0g ternary precursor Ni were added 0.8 Co 0.1 Mn 0.1 (OH) 2 Uniformly stirring for 30min, adding a mixed solution of water and ethanol as a solvent, introducing ammonia gas, and controlling the mass molar ratio of the ammonia gas to the fluoroniobate to be 9: 1, continuously stirring for 4 hours at the temperature of 10 ℃ to obtain a modified precursor composite material;
(3) uniformly mixing the composite material obtained in the step (2) with lithium hydroxide (Mn) 2+ : li ═ 1:1.05), and then placed in a tube furnace for staged sintering. Firstly, introducing nitrogen, heating to 480 ℃ at the speed of 5 ℃/min, performing presintering, and keeping the temperature for 2 hours; then heating to 750 ℃ and preserving the heat for 4 h; cutting off the nitrogen atmosphere after the heat preservation is finished, introducing the oxygen atmosphere, preserving the heat at 750 ℃ for 12h, and naturally cooling to obtain the fluorine-niobium double-doped lithium niobate coated ternary material;
(4) and (3) crushing, grading and sieving the fluorine-niobium double-doped lithium niobate-coated ternary material by using an airflow crusher to obtain a finished ternary material.
The same assembly fastening method as the embodiment is adopted, except that the ternary material of the embodiment 4 is adopted as the positive electrode, and other parts are not changed.
As shown in fig. 1, the fluorine niobium double-doped lithium niobate-coated ternary material of embodiment 4 has a good morphology, wherein the secondary particles are spheroidal, and the average particle size is 10 um.
As shown in FIG. 2, the fluorine-niobium double-doped lithium niobate-coated ternary material of example 4 has the strongest peak at 18.65-18.85 degrees, which is the (003) peak, the second strongest peak at 44.40-44.60 degrees, which is the (104) peak, and the third strongest peak at 36.65-38.85 degrees, which is the (101) peak, and the above-mentioned map conforms to the crystal peak of the high-nickel ternary material and conforms to the α -NaFeO 2 And (5) structure.
As shown in fig. 3, the gram-discharged capacity of the material of the button cell prepared in example 1 and example 4 was measured at 0.2C, 0.33C, 0.5C and 1C rates, respectively, and the gram-discharged capacity of the material of example 4, 0.33C, was 191.5 mAh/g.
As shown in fig. 4, the cycle of this example 4 is the best, mainly due to the fact that ammonia gas can synthesize a better modified ternary precursor than ammonia water, and meanwhile, a multistage sintering mode of pre-sintering with nitrogen gas and then sintering with oxygen gas is adopted, so that the purity and crystallinity of the ternary material obtained by sintering are higher.
As shown in Table 1, the total residual alkali was controlled to be within 2500ppm, which is a preferable level, by using the anhydrous washing process of example IV.
Table 1: comparative example four residual base amount by titration
| Sample(s) | LiOH(ppm) | Li 2 CO 3 (ppm) | FreeLi + (ppm) |
| Example four | 765 | 1247 | 500 |
Example 5:
the embodiment provides a preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material, which comprises the following specific steps:
(1) will contain NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 The total concentration of O is 2.0mol L -1 Aqueous solution (molar ratio Ni) 2+ :Co 2+ :Mn 2+ 8:1:1) continuous stirred reaction with pumping of nitrogenIn a reactor, the reaction temperature is 55 ℃; then 10 wt.% NaOH solution and 5.0mol L of NaOH were added separately -1 NH 4 OH solution, controlling the pH value of a reaction system to be 11.8, generating a precipitate after the reaction is finished, filtering and washing with deionized water to finally obtain a ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ；
(2) In a closed reactor, 0.027g fluoroniobic acid and 1.0g ternary precursor Ni were added 0.8 Co 0.1 Mn 0.1 (OH) 2 Uniformly stirring for 30min, adding a mixed solution of water and ethanol as a solvent, introducing ammonia gas, and controlling the mass molar ratio of the ammonia gas to the fluoroniobate to be 9: 1, continuously stirring for 4 hours at the temperature of 10 ℃ to obtain a modified precursor composite material;
(3) uniformly mixing (TM) the composite material obtained in the step (2) with lithium hydroxide 2+ : li ═ 1:1.05), and then placed in a tube furnace for staged sintering. Firstly, introducing nitrogen, heating to 480 ℃ at the speed of 5 ℃/min, performing presintering, and keeping the temperature for 2 hours; then heating to 750 ℃ and preserving the heat for 4 h; cutting off the nitrogen atmosphere after the heat preservation is finished, introducing oxygen atmosphere, preserving the heat at 750 ℃ for 12h, naturally cooling to obtain the fluorine niobium double-doped lithium niobate-coated ternary material, adding water to the rear of the fluorine niobium double-doped lithium niobate-coated ternary material, and drying at 120 ℃;
(4) and (4) carrying out crushing, grading and sieving on the fluorine-niobium double-doped lithium niobate coated ternary material subjected to water washing and drying in the step (3) by using a jet mill to obtain a finished ternary material.
The same assembly fastening method as the embodiment is adopted, except that the ternary material of the embodiment 5 is adopted as the positive electrode, and other parts are not changed.
Detection method
The circulation comparison chart of each embodiment is shown in fig. 4, a blue test system is adopted to carry out electric performance test on the deduction electricity, the test voltage is 3.0-4.3V, the working step is 1C constant current charging to 4.3V, and the stand is kept for 5 min; 1C was discharged to 3.0V and cycled for 300 weeks.
As shown in Table 2, the residual base amounts of example four and example five were compared by titration.
| Sample (I) | LiOH(ppm) | Li 2 CO 3 (ppm) | FreeLi + (ppm) |
| Example four | 765 | 1247 | 500 |
| EXAMPLE five | 672 | 1056 | 339 |
It can be seen by comparison that the residual alkali amount after washing is reduced compared with that after washing without water (example four), and after washing with water, as shown in fig. 4, the cycle performance is much worse than that of washing without water (example four), mainly because the washing with water damages the structure of the material.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of a fluorine-niobium double-doped lithium niobate-coated ternary material is characterized by comprising the following steps:
(1) preparing a nickel-cobalt-manganese hydroxide precursor by utilizing a coprecipitation reaction;
(2) uniformly stirring the fluoroniobate and nickel-cobalt-manganese hydroxide precursors, and then adding ammonia water or introducing ammonia gas to generate niobium hydroxide and ammonium fluoride to obtain a composite material of the modified precursors;
(3) and (3) mixing the composite material obtained in the step (2) with lithium hydroxide, and calcining at high temperature in an oxygen atmosphere to obtain the fluorine-niobium double-doped lithium niobate-coated ternary material.
2. The method for preparing the fluorine niobium double-doped lithium niobate-coated ternary material according to claim 1, wherein the fluorine niobium double-doped lithium niobate-coated ternary material generated in the step (3) is crushed, graded and sieved by a jet mill to obtain a finished ternary material.
3. The method for preparing the fluorine-niobium double-doped lithium niobate-coated ternary material according to claim 2, wherein the step (1) comprises the following steps: will contain NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 The total concentration of O is 2.0mol L -1 Pumping the aqueous solution into a continuous stirring reactor under nitrogen, wherein the reaction temperature is 50-60 ℃; then 10 wt.% NaOH solution and 5.0mol L of NaOH were added separately -1 NH 4 OH solution, controlling the pH value of a reaction system to be 11.8, generating a precipitate after the reaction is finished, filtering and washing with deionized water to finally obtain a ternary precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 。
4. The method for preparing the fluorine-niobium double-doped lithium niobate-coated ternary material according to claim 3, wherein the NiSO is used as a precursor 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 The total concentration of O is 2.0mol L -1 In an aqueous solution of (2) at a molar ratio of Ni 2+ :Co 2+ :Mn 2+ ＝8:1:1。
5. The method for preparing the fluorine niobium double-doped lithium niobate-coated ternary material according to claim 3, wherein the reaction temperature in the step (1) is 50-60 ℃.
6. The method for preparing the fluorine-niobium double-doped lithium niobate-coated ternary material according to claim 1, wherein the step (2) comprises the following specific steps: in a closed reactor, 0.027g fluoroniobic acid and 1.0g ternary precursor Ni were added 0.8 Co 0.1 Mn 0.1 (OH) 2 Uniformly stirring, adding a mixed solution of water and ethanol as a solvent, introducing ammonia gas, and controlling the mass molar ratio of the ammonia gas to the fluoroniobate to be 9: 1, continuously stirring for 4 hours at the temperature of 10 ℃ to obtain the modified precursor composite material.
7. The method for preparing the fluorine-niobium double-doped lithium niobate-coated ternary material according to claim 6, wherein 0.027g of fluorine-niobium and 1.0g of ternary precursor Ni are added into a closed reactor 0.8 Co 0.1 Mn 0.1 (OH) 2 Then, the mixture was stirred uniformly for 30 min.
8. The method for preparing the fluorine-niobium double-doped lithium niobate-coated ternary material according to claim 1, wherein the step (3) comprises the following steps: uniformly mixing the composite material in the step (2) with lithium hydroxide, then placing the mixture in a tubular furnace for staged sintering, firstly introducing nitrogen, heating to 470-490 ℃ at the speed of 5 ℃/min for presintering, and preserving heat for 1.5-2.5 h; then the temperature is increased to 740 and 760 ℃, and the temperature is kept for 3.5 to 4.5 hours; and cutting off the nitrogen atmosphere after the heat preservation is finished, introducing the oxygen atmosphere, preserving the heat for 11-13h at the temperature of 740-760 ℃, and naturally cooling to obtain the fluorine-niobium double-doped lithium niobate coated ternary material.
9. The method for preparing the fluorine niobium double-doped lithium niobate-coated ternary material according to claim 8, wherein the temperature is raised to 480 ℃ at a rate of 5 ℃/min for presintering, and the temperature is kept for 2 hours; then heating to 750 ℃ and preserving the heat for 4 h; cutting off the nitrogen atmosphere after the heat preservation is finished, introducing the oxygen atmosphere, preserving the heat at 750 ℃ for 12h, and naturally cooling.
10. The method for preparing the fluorine-niobium double-doped lithium niobate-coated ternary material according to claim 1, wherein the evaluation of the electrochemical performance of the cathode material adopts a CR2032 button cell; the positive electrode adopts a finished ternary material, a conductive agent acetylene black and a binder polyvinylidene fluoride, and the mass ratio of the conductive agent acetylene black to the binder polyvinylidene fluoride is 90: 5: 5, the specific preparation process comprises the following steps: firstly, taking 0.18g of finished ternary material, 0.01g of conductive agent acetylene black and 0.01g of polyvinylidene fluoride, putting the materials into a 10mL small beaker, uniformly mixing, then dropwise adding a proper amount of N-methyl pyrrolidone, stirring to form uniform slurry, coating the uniform slurry on a dried carbon-coated aluminum foil by using a scraper 150mm, firstly putting the dried carbon-coated aluminum foil in a blast drying box, drying for 8 hours at 80 ℃, then transferring the dried carbon-coated aluminum foil into a vacuum drying box, drying for 12 hours at 120 ℃, weighing and transferring the completely dried electrode plate into a glove box after punching into a circular positive electrode plate with the diameter of 12mm by using a punching machine, taking the prepared positive electrode plate as a positive electrode, taking metal lithium as a negative electrode, taking a mixture of 1.1mol/L LiPF6 dissolved in an EC/DMC/EMC mixed solvent as an electrolyte, taking a Celgard 2400 microporous membrane as a diaphragm, putting all the materials into the glove box to assemble a CR2032 button cell, and sealing by using a sealing machine; and finally standing and activating the assembled CR2032 button cell for 12h at room temperature for later use.
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